Method of depositing tin oxide coatings on flat glass and the resulting coated glass

Description: TECHNICAL FIELD [Detailed description of the invention]

Tin oxide coating and titanium oxide coating on flat glass The method of deposition and the coated glass obtained by this method Background of the invention 1. Field of invention The present invention presents a titanium oxide coating and tin oxide coating on a flat glass substrate. Regarding the method of depositing ting and the coated glass obtained by this method To do. More particularly, the present invention is a titanium oxide coaty on flat glass. Coating with tin oxide and corresponding metal tetrachloride and organic oxides Concerning chemical vapor deposition methods for obtaining using a coating precursor gas mixture containing It is a thing. 2. Overview of related technologies Titanium oxide coating and tin oxide coating can be applied to glass containers such as Used in jars, it has been proposed to improve the mechanical strength of this container. Also, Both titanium oxide coating and tin oxide coating on flat glass It is also proposed to use it to modify the properties of glass for use in architectural applications. Titanium oxide coaty provided under vacuum (by reactive sputtering) Is used as a component of sputtered multi-layer infrared reflective coatings On the other hand, tin oxide coating is used as a layer of multi-layer sputtered coating. Not only used, but also infrared reflective coating and / or Or as a conductive coating, it is deposited by thermal decomposition. British Patent No. 1 115 342 states that it has good intrinsic strength and good resistance. Abrasionable glass containers for containers that are still hot from the manufacturing process Then, the secondary soot chloride in the organic liquid, preferably isopropyl alcohol (ie, Disclosure of process for production by spraying a solution or dispersion of tin tetrachloride) Has been done. A small amount of titanium chloride can be introduced as a denaturant. Jet Can be the type of injection, the tunnel above the conveyor for high temperature glass bottles A liquid solution was supplied to a nebulizer placed on either side of the "Liquid Reagent Mi". A strike is obtained, which forms a layer of liquid over the entire outer surface of the bottle, where this liquid Layers react to form a layer of tin oxide. UK Pat. No. 1 187 784, UK Pat. No. 1 115 342 An improvement to the process described in the specification and the normal practice of such a process. During the automatic manufacturing process of glassware, which does not affect and does not require additional monitoring Clearly more suitable methods are described for introduction to. In this patent specification Proposed to treat glass containers at high temperatures with a liquid solution of an organic compound of tin. "This compound is divided into two substances by applying heat. One of them is an organic compound of tin that has a high decomposition temperature. The organic compound reacts with the glass surface to form a diffusion layer of tin oxide on the glass surface. The other material, however, is of tin, such that a significant proportion of the vapors of the aforementioned chemicals can be obtained. A volatile compound, heat treated the container to glass at least on the surface of the container It has the property that a reaction occurs between the tin compound and the tin compound. " Process glass containers The substance used for this is tin tetrachloride, which has a carbonyl group with moderate activity. Organic substances such as ethyl alcohol, n-propyl alcohol, isopropi Lu alcohol, n-butyl alcohol and iso butyl alcohol and acetic acid, pro Can be provided by reacting with organic esters of pionic acid and butyric acid it can. The resulting solution is applied to a hot container in the presence of an ambient atmosphere, for example. In the form of fine mist, after the high temperature container has advanced from the molding machine, Anneli It can be sprayed before it enters the slow cooling tank. British Patent No. 1 1877 In the specification 83, the method described in the specification of British Patent No. 1 187 784 and A similar method is described, where titanium instead of tin organic compounds The organic compound is sprayed onto a hot glass container. Organic titanium compound, tin Titanium tetrachloride is organically esterified, eg vinegar, in a manner similar to that of organic compounds in It can be obtained by reacting with n-butyl acid. Again, the resulting solution Is sprayed onto the glass in the container production line in the ambient atmosphere. It has also been applied either as a liquid spray or, more recently, in a gaseous form. A tin oxide coating was applied to high-temperature flat glass using tin tetrachloride. Forming a conductive, infrared-reflecting coating on the surface of hot glass And was proposed; for water to hydrolyze tin tetrachloride to form tin oxide. It was used as an oxygen source. Processes involving the use of reactants in gaseous form (also CVD or chemical vapor deposition) (Also called the dressing method), in particular the reactants are premixed prior to application to the glass. If possible, it has advantages over spraying methods for coating flat glass. There are some. Unfortunately, tin tetrachloride reacts easily with water and therefore tetrachloride. Previous proposals to use tin and water vapor in gaseous form usually squeeze the gas. Supply separately to the surface and mix these gases while in contact with the glass Was accompanied by. UK Pat. No. 2,044, 137A creates a separate laminar flow for each reactant. High by bringing these streams together tangentially to each other on the glass It relates to the process of discharging onto a hot glass substrate. Titanium tetrachloride, the cost of tin tetrachloride Instead, it is used as a type of gaseous reactant to form a titanium oxide coating. be able to. The patent specification also provides hydrogen to one of the gas streams. It has been suggested that this weakens the violent reaction between tin tetrachloride and water vapor. This This is the desired reaction by adding gaseous hydrogen directly or in-situ. It can be done by adding methanol, which is said to produce gaseous hydrogen. Wear. UK Pat. No. 2,026, 454B states that the cladding is hot float glass. Place it on the ribbon as it advances from the float bath, (1) Preheated nitrogen carrier gas, (2) Four salts taken into preheated nitrogen Subject to tin, and (3) continuous gaseous flows of air, water vapor and hydrofluoric acid. Introduced into the encapsulation, these flow along the surface of the glass substrate and are almost undisturbed The method of coating as a layer is described. In this patent specification, glass The concentrations of water vapor and tin tetrachloride in the above gaseous medium have been identified. European Patent No. 0 365 239 B1 and No. 0 376 240 B1 The details include how and how to deposit a tin oxide coating on a hot glass ribbon. The place is described. First gas flow of tin tetrachloride in preheated dry air Hydrofluoric acid, flowing along the surface of a hot ribbon of glass traveling under the cladding. O And a second turbulent flow of water vapor in the cladding chamber, the flat surface of the glass and the flow of the first gas flow. Introduce the first gas flow and the second gas flow together at right angles to the direction of , Pull out under turbulent conditions through the cladding chamber above the glass. This method and equipment Also coats titanium oxide with titanium tetrachloride instead of tin tetrachloride Can be used to provide. U.S. Pat. No. 4,590 096 states that the bite is soluble in organotin chloride. Or, a mixture of organochloride soot and reactive organofluorine compounds, which are miscible with organotin chloride. A coating solution containing a mixture containing almost no solvent, gas at 18 ° C. Preheated, containing enough water vapor for the relative humidity of the stream to be about 6% to about 100% A method of introducing into a carrier gas stream is described. The obtained gas flow is high A fluorine-doped tin oxide coating is applied over the surface of the hot glass at a high temperature. Accumulate on the lath. A wide range of organotin compounds can be used, and tin tetrachloride can be used. It is stated that it can be used. Similarly, a wide range of oxygen-containing compounds Organofluorine compounds in the enclosure, such as trifluoroacetic acid and ethyl trifluoroacetate Can be used. Some fluorine-containing dopants are the organotins used Organic tin compounds with low solubility in compounds and with optional solubilizers Can increase the solubility of fluorine dopants in: acetic anhydride, acetic acid Used by ethyl, hexane, methyl isobutyl ketone and butyraldehyde Listed as non-limiting examples of solubilizers that can be. But this United States In the patent specification, metal oxidation from gaseous metal tetrachloride using a chemical vapor deposition method. Like other patent specifications that deposit objects, water vapor is used as the oxygen source. U.S. Pat. No. 4,751 149 by Vijaykumar et al. Smell the ting at low temperatures (60 ° C to 350 ° C, preferably 100 ° C to 200 ° C). It is related to the deposition by chemical vapor deposition on the heat-sensitive photoconductor substrate. And organic zinc compounds and oxygen-containing organic compounds, such as esters. Zinc oxide coating is deposited from the oxidant and inert carrier gas that can be produced. It is proposed to stack. This patent specification is not completely clear, but Obviously, separate streams of organozinc compounds and oxidants in the patent specification of Has been proposed to be introduced into the deposition chamber and a mixture of these is delivered to the cladding chamber. It is a fact that it has not been proposed to premix these ingredients before To. Tin oxide coating or titanium oxide coating, high temperature flat glass Corresponding metal tetrasalt as a low cost reactant by the CVD method used for Using a premixture of compound and oxygen source, metal tetrachloride and oxygen source (formerly water) In the meantime, a premature reaction occurs and metal oxides are formed in the coating, resulting in problems. And it is advantageous to provide a method of deposition without causing inefficiencies. On the way This allows for high speed deposition of the coating and transfer during the glass manufacturing process. It is possible to deposit the required coating thickness on a moving glass ribbon It is especially advantageous when it becomes. Outline of the invention In the present invention, the tin oxide coating or the titanium oxide coating is heated at a high temperature. Includes corresponding metallic tetrachloride and organic oxygen sources for installation on glass substrates Using a precursor gas mixture, no need to introduce water vapor, this result is too early Provide a chemical vapor deposition method that is not dangerous. The present invention applies a tin oxide coating or a titanium oxide coating to a high temperature flat surface. Provides a method of depositing on a glass, this method (a) As an oxygen source for producing the corresponding metal tetrachloride and metal oxides To produce a precursor gas mixture containing an organic oxygen-containing compound of (b) Metal tetrachloride reacts with the above-mentioned precursor gas mixture to form a metal oxide. Keeping the temperature below the temperature, at the same time opening the mixture onto hot glass. Send to the coating room (c) This precursor gas mixture is introduced into the cladding, thereby allowing the mixture to be introduced. Hot glass surface of the corresponding metal oxide containing oxygen from organic compounds when heated Causes deposits on Including the process. Surprisingly, a wide range of oxygen-containing organic compounds, of water vapor or gaseous oxygen It can be used as an oxygen source without the need for presence, which is usually an oxidant. Rather, it includes compounds that are considered reducing agents, such as alcohol. Deer However, preferred organic compounds are carbonyl compounds, especially esters: β-hydrogen. Particularly good results were obtained using the ester having an alkyl group. β water Alkyl groups with elements usually contain 2 to 10 carbon atoms. It is preferable to use organic compounds with 2 to 10 carbon atoms, especially esters. I. The reason is that larger molecules tend to be less volatile, so this This is because it is more inconvenient to use in the Ming CVD method. Particularly preferred esters for use in the practice of the present invention are ethyl formate, vinegar. Ethyl acid acid, ethyl propionate, isopropyl formate, isopropyl acetate, n acetate -Includes butyl and t-butyl acetate. The methods of the invention are generally continuous, eg, during a float glass manufacturing process. It is carried out in connection with forming a glass ribbon substrate. However, the method of the present invention Covered with other flat glass substrates, either online or offline It can be used to overturn. The present invention contains tin tetrachloride or titanium tetrachloride and an organic oxygen-containing compound before Accompanied by producing a vehicle gas mixture; carrier gas or diluent such as nitrogen Element, air or helium is usually contained in the gas mixture. Organic oxygen-containing compounds Since the metal oxide deposition reaction can be initiated at high speed by the thermal decomposition of the precursor mixture, Keeping the temperature lower than the thermal decomposition temperature of organic oxygen compounds to generate metal oxides It is desirable to prevent the accompanying pre-reaction of the gaseous mixture. Bring the gaseous mixture to a temperature below the temperature at which it reacts to form metal oxides. Maintained and delivered to a location near the coated flat glass substrate, which substrate is described above. A temperature higher than the reaction temperature (and the decomposition temperature of the organic oxygen compound in the precursor gas mixture) Temperature above degrees). The precursor gas mixture is then introduced into the vapor space just above the substrate. substrate Due to the heat from, the temperature of the precursor gas is higher than the pyrolysis temperature of the organic oxygen compound. Rise to temperature. Next, the organic oxygen compound decomposes with the reaction with the metal tetrachloride. , Produces a metal dioxide coating on the substrate. According to the present invention, tin oxide coating and titanium oxide coating on high temperature glass The ing has a high deposition rate, eg, a rate of over 130 Å / sec, and a preferred fruit. In the embodiment, it is possible to deposit at a rate of more than 250 Å / sec. The deposition rate is the specific organic oxygen-containing compound used, as well as the organic oxygen-containing compound. It depends on the concentration of both the substance and the metal chloride, as well as the temperature of the glass. Any specific Optimal concentrations (and especially organic oxygen-containing compound pairs) for the combination of compounds Optimal ratio of metal tetrachloride) and flow rate for rapid coating deposition, It can be determined by a simple test. However, higher concentrations of reactants and As a result of using a high gas flow rate, the overall efficiency of conversion of the reactants to the coating is ratio It tends to be relatively low, so the optimum conditions for industrial operation are the best deposits. It should be understood that the conditions that provide the product velocity may differ. Preferably, the volumetric concentration of the organic oxygen-containing compound is about the volume concentration of the metal chloride. 0.5 times, especially 1 to 5 times. Generally, organic oxygen-containing compounds are metal It can be used in an amount of at least 30% by weight based on the weight of chloride. Titanium oxide coating and tin oxide coating by the method of the present invention Made online at high speed during the glass manufacturing process, on a hot flat glass substrate Can be built. Titanium oxide coating, high index of refraction (at least 2. Can be manufactured in 4), which makes it especially in combination with other coating layers The desired optical effect can be achieved when used in the above. Oxidized tin coating For example, fluorine is introduced into the precursor gas mixture as a suitable precursor for the dopant. By entering, it can be doped, which leads to the coating. Increases electrical and infrared reflectance, which makes it suitable for building polish and other uses The coating as a conductive coating and / or low emissivity coating in The usefulness of ting can be enhanced. A brief description of the drawing The aforementioned advantages and other advantages of the present invention are taken into account with reference to the accompanying drawings. The following description of preferred embodiments will be readily apparent to those of skill in the art. here: FIG. 1 shows a gas distributor appropriately arranged to enable the implementation of the method of the present invention. Schematic diagram of a vertical cross section of an apparatus for carrying out the float gas process of the present invention. And FIG. 2 is a partial cross-sectional view of the article covered by the present invention. FIG. 3 is an enlarged diagram of a gas distributor beam suitable for use in the practice of the present invention. It is an end view FIG. 4 shows of other gas distributor beams that can be used to carry out the present invention. Enlarged diagram end view. Description of preferred embodiments Here, as a means for carrying out the method of the present invention with reference to the drawings more specifically. Float glass equipment used in the above is generally shown in FIG. This flow The glass device, more specifically, comprises a canal portion 12, along which a melt The glass 14 is sent from the melting furnace (not shown) to the float bath portion 16 and is connected here. The continuous glass ribbon 18 is formed by a well-known float process. .. The glass ribbon 18 starts from the bath portion 16 and is adjacent to the annealing slow cooling machine 20. And proceed through the cooling section 22. Continuous glass ribbon 18 on top of metal oxide The coating acts as a substrate to be deposited according to the methods of the invention. The float portion 16 has a bottom 24, inside which a bath of molten tin 26 and a top. 28, including opposing side walls 30 and end walls 32. Top 28, side wall 30 and The end walls 32 together form a siege 34, in which a non-oxidizing atmosphere is maintained, Prevents oxidation of molten tin. In addition, gas distributor beams 64, 66 and 68 are placed in the bus section 16. To. By the method of the present invention, using the gas distributor beams 64 and 66 in the bus section. Before applying a tin oxide coating or a titanium oxide coating, The coating is provided on the substrate. Additional coatings are silicon and silica Can include. In operation, the molten glass 14 is a controlled amount of regulated twill (regulat). Along the canal 36 under the ing tweel) 38 and down on the surface of the tin bath 26 It flows. On the tin bath, the molten glass has gravity and surface tension, as well as some mechanical Under the influence, it diffuses laterally, which travels across the bath and forms the ribbon 18. To be done. Remove this ribbon onto the lift out roll 40 An aligned roll is then passed through the annealing slow cooling chamber 20 and the cooling section 22. 42 Transport through above. The application of the coating of the present invention applies to the float bath portion 1 6 Medium or other production lines, such as float baths and annealing slow cooling It can be done in the intervening space or in the annealing slow cooling. With a suitable non-oxidizing atmosphere, generally a room atmosphere or nitrogen high in nitrogen Maintaining the atmosphere of the mixture with hydrogen in the siege 34 of the bath prevents oxidation of the tin bath To do. Ambient gas, conduit 44 operatively combined with distribution manifold 46 Let it enter through. Derivation of non-oxidizing gas at a rate sufficient to compensate for normal losses Enter and slightly positive pressure, that is, about 0.001 to about 0.0 than the surrounding atmospheric pressure Maintain at 1 atm higher to prevent permeation of the outside atmosphere. Tin bath 26 and parcel The heat to maintain the desired temperature conditions in the enclosure 34, the radiant heater in the enclosure 4 Provided by 8. While the atmosphere inside the slow cooling machine 20 is typically ambient air , Cooling part 22 is not surrounded and the glass ribbon is exposed to the surrounding atmosphere To. The ambient air is directed toward the glass ribbon, for example, by the fan 50 in the cooling part. Kake. In addition, a heater (not shown) is installed in the annealing slow cooling machine to make a glass. The temperature of the ribbon, the surroundings as this ribbon is transported through a slow cooling cage Therefore, it can be gradually lowered. Figure 1 shows the gas distributor beams 64, 66 and located in the float bus 16. 68 is used to illustrate the deposition of various coatings on a glass ribbon substrate. To do. The gas distributor beam can be used in the practice of the method of the invention. It is a form of response. In the present invention, advantages for distributor beams suitable for supplying precursors. The various forms are generally diagrammatically shown in FIG. By the separated inner wall 72 and outer wall 74 Formed, inverted, generally grooved skeleton 70, closed empty Define caves 76 and 78. A suitable heat exchange medium in a closed space 76, 78 Circulate through to keep the distributor beam at the desired temperature. The precursor gas mixture is fed through a fluid-cooled supply conduit 80. Supply The conduit 80 extends along the distributor beam and separates the gas along the supply conduit. Proceed through the descent line 82. Supply conduit 80 is supported by a skeleton It leads to the delivery chamber 84 in the header 86. Before being transported by descent line 82 Steam air that opens the vehicle gas from the delivery chamber 84 through the passage 88 onto the glass. Discharge in the direction of the cladding chamber, where these precursor gases are glass 18 It flows along the surface of the in the direction of the arrow shown in FIG. A deflector 90 is provided in the delivery chamber 84 to provide a precursor beam across the distributor beam. Equalizing the flow, this material completely lateralizes the distributor beam against the glass 18. Ensuring that it is discharged in a smooth, layered and uniform flow that breaks. Consumed precursor The material is collected and removed along the sides of the distributor beam through the discharge chamber 92. Various forms of distributor beams used for chemical vapor deposition are suitable for the methods of the invention and are conventionally used. Known in technology. One such alternative form of distributor beam is shown graphically in FIG. general Indicated by reference numeral 100 (also in European Patent EP 0 305 102B) (More fully described), this distributor is used to gas the precursor gas mixture. Introduced through supply duct 101, where this mixture is passed through ducts 102 and 1 It is cooled by the cooling fluid that circulates through 03. The gas supply duct 101 is long It is opened in the gas flow throttle 105 by the opening 104 of. The gas flow throttle 105 is further described in UK Pat. No. GB 1 507 996. Of the type described in minutes, this is a longitudinal waveform in the form of a sine wave Vertically in contact with each other so that they extend along the length of the distributor It has multiple metal strips mounted. Metal strips with adjacent waveforms Place the pipes "out of phase" to create multiple vertical grooves between them. these The vertical groove has a cross-sectional area smaller than the cross-sectional area of the gas supply duct 101. From the gas flow throttle 105, the gas has an almost constant pressure along the length direction of the distributor. Released in force. Coating gas from the gas flow throttle, inlet leg 107, high temperature to be coated It has a cladding 108 open on the glass substrate 110 and a discharge leg 109. , Generally emitted into the inlet side 107 of the approximately U-shaped guide groove, indicated by 106, which Withdraws used coating gas from the glass. Determine the covering groove The rounded corners of the block are flat on the glass surface across the glass substrate to be coated Promotes a uniform layered flow of the coating. In the following embodiment (here, unless otherwise stated, the gas volume is the standard condition, i.e. (Represented under 1 atm pressure and ambient temperature) further exemplifies and discloses the present invention. Shown for purpose. These examples should not be construed as limiting the invention. .. Examples 1 to 5 In this series of examples, the type of bidirectional coating reactor shown in FIG. A titanium oxide coating was deposited for use in the laboratory. In Examples 1, 2 and 3, the glass is heated on a conveyor furnace and flown. The method of the present invention was tested by simulating the coating reaction conditions of the glass process. Ta. Before practicing the method of the present invention, this furnace was made using an in-line roller. The lath substrate was transported through the heating zone. In the first embodiment, the glass substrate is the most Float glass with a silica coating was used for the first time. This silica coating Known chemical vapor deposition using a monosilane precursor in an oxygen-rich atmosphere. It was deposited on the float glass by the roses. Silica deposits are any of the present invention Does not form a part. According to the present invention, a titanium oxide coating is deposited on a silica-coated substrate. did. The temperature of this substrate is 1170 ° F (630 ° C) and the linear velocity of the substrate is It was 300 inches / minute (8 m / minute). Titanium tetrachloride, ethyl acetate, oxygen and helium to deposit titanium oxide A precursor gas mixture containing flatulence was generated. Use helium as a carrier for the reactants It was contained in the precursor mixture. This precursor mixture, all four gas streams Manufactured by simultaneous introduction with a manifold system. Inline static The precursor mixture was reliably homogenized using a conventional mixer. 100 volumes of precursor mixture The fractional composition is 0.7% titanium tetrachloride, 17.2% ethyl acetate, 7.2% oxygen. And helium is 74.9%, and the flow rate of the components in the manifold is shown in Attached Table 1. It was as shown in. Keeping the temperature of the precursor mixture above 300 ° F (150 ° C), The adduct reaction between tan and ethyl acetate was prevented. In addition, the temperature of the precursor is adjusted to that of ethyl acetate. The thermal decomposition temperature range of 950 ° F to 1130 ° F (510 ° C to 610 ° C). It was kept low to prevent the mixture from pre-reacting. The precursor mixture was introduced into the reactor just above the moving substrate. Precursor tower The temperature at was 250 ° F (120 ° C). The temperature on the surface of the reactor is , 350 ° F (175 ° C). Ethyl acetate at relatively high substrate temperatures Pyrolysis was initiated, which in turn resulted in the decomposition of titanium oxide. The resulting coated glass was allowed to cool in air and the coating was analyzed. this The coating appears to be titanium oxide with a carbon content of 2.5-3.5 atomic% I was struck. The thickness of the titanium oxide coating is measured to be 490 Å. The thickness and growth rate (150 Å / sec) of are shown in Table 1. Optics of the resulting product The characteristic is 62.3% observed Illuminant C transmittance (10 ° observer). And had an observed illuminant C reflectance of 35.6%. The extinction coefficient is , 0.008 at 550 nm, and the index of refraction of the titanium oxide coating is It was 2.44. In Examples 2 and 3, in Example 2, formic acid as an organic oxygen source. In Example 3, isopropanol was used as the organic oxygen source, and the subject was covered. Uncovered glass (instead of glass coated with silicon oxide in Examples 1 and 2) The coating procedure described in Example 1 was repeated except that (2) was used as the substrate. .. The gas flow rate used and, in the case of Example 2, the obtained titanium oxide coating. Table 1 shows the thickness and growth rate of the crop. In Example 3, isopropano Le burned in the reactor, leaving only fine-grained titanium oxide on the glass. Therefore, the corresponding deposition rate was estimated to be 0 Å / sec. The procedures of Examples 4 and 5 were carried out except that the substrate was made static and not dynamic. As used in Examples 1 to 3 (reactor temperature and substrate are the same as in Example 1) Met). The static sample was placed under the reactor for 10 seconds. Under static conditions, anti The residence time of the substrate under the response was extended 5 times compared to the dynamic conditions. In Example 4, methyl acetate was used as the organic oxygen source, and in Example 5, , T-butyl acetate was used as the source of organic oxygen; in each case titanium oxide A coating was obtained. Gas flow rate and the resulting titanium oxide coating The thickness of the coating and the growth rate of the coating are shown in Table 1. Obtained using methyl acetate The relatively slow growth rates that have occurred are discussed below. Example 6 Linear velocity of 434 inches / minute (11 m / min) using float glass process Manufactured a continuous glass ribbon with a thickness of 0.125 inches (3 mm) .. For the glass temperature, use a coating reactor similar to the coating reactor shown in Fig. 3. Desired location to use in the float bath portion of the titanium oxide coating. It was set to 1140 ° F (615 ° C). The temperature in the precursor tower is 400 ° F (205 ° C) and the temperature on the reactor surface is 500 ° F (260 ° C) there were. Prior to implementing the method of the invention, a silica coating is applied onto the glass substrate. In the funnel bath, it was deposited to a thickness of about 339 Å. As described in Example 1 The silica coating was deposited using the same chemical vapor deposition process. Silica deposit Does not constitute any part of the present invention. Precursor gas containing titanium tetrachloride and ethyl acetate in helium carrier gas The mixture was generated. For oxygen, the coating reaction is oxygen-rich according to the results of the previous example. It was not used in the precursor as it was shown to be unaffected by the degree. precursor To produce a body mixture, three components are introduced simultaneously through a manifold system. did. The volume percentage composition of the precursor mixture was 0.6% titanium tetrachloride, 1 ethyl acetate. It was .8% and helium 97.5%. The flow rate for these components is Rium 480.01 / m, titanium tetrachloride 3.01 / m, ethyl acetate 9.21 / m Met. The total flow rate for the precursor mixture was 492.21 / m. The thickness of the titanium oxide coating obtained was 684 Å. This coaty The carbon content of the drug was less than 2 atomic%. The growth rate of the coating is 309 It was Å / sec. Example 7 The same procedure as that used in Example 6 was used in this example. The board is It had a silicon coating, and then silica on a glass substrate. This Coating is deposited in the float bath portion by a known chemical vapor deposition process. did. Silicon coating from monosilane containing non-oxidizing carrier gas Deposited by CVD. Next, apply the silica coating on the silicon coating. , Accumulated by using the same procedure as described in Example 1. Precursors for titanium oxide coating are titanium tetrachloride and ethyl acetate , Helium carrier gas contained. The volume percentage composition of this precursor is four It was 0.5% titanium chloride, 1.9% ethyl acetate and 97.6% helium. The flow rates corresponding to these components are helium 480.01 / m and titanium tetrachloride 2. It was 41 / m and ethyl acetate 9.21 / m. Total flow for precursor mixture The amount was 491.61 / m. The obtained coated article 52 is illustrated in FIG. Multiple glass substrates 54 Illustrated as having a stack of coatings 56. This coating , Silicon layer 58, silica layer 60, then titanium oxide coaty on top of the article Has 62. The titanium oxide coating on the resulting article is 836 Å thick Had The optical properties of the resulting coating stacks are 13.1% Observed Illuminant C transmittance and 82.5% Observed Illuminant Included C reflectance. Titanium oxide coating grows at 378 Å / sec there were. table 1<img file="JP2001503005A_D0001.tif" />Examples 8 to 13 In this series of examples, a static coating machine was used in the laboratory to acid. The tin coating is described in European Patent EP 0 275 662B. A color-suppressing silicon oxide layer obtained as described above. It was provided on a funnel glass substrate. Float glass to be coated is supported on a nickel block in a reaction vessel. , The block is heated from below by an electric heating element at 1085 ° F (585). A glass temperature of ° C) was obtained. A flat graphite plate, about 0.4 inches of glass ( 10mm) Above, a glass surface mounted parallel to the glass and having a silicon oxide layer A 0.4 inch (10 mm) deep gas flow path was provided between the surface and this plate. Tin tetrachloride and present in air as carrier gas and a small amount of additional nitrogen Precursor gas mixture containing machine oxygen source, 435 ° F ± 25 ° F (225 ° C ± 15 ° C) ) And gas above the hot glass in a direction generally parallel to the glass surface It was delivered through a gas line having a fishtail nozzle opening on the flow path. Total carrier gas flow rate is 13m³/ It was time. Flow rate of tin tetrachloride and The properties and flow rates of the organic compounds used are shown in the attached Table 2. Examples 9 and 1 In 1, as shown in the table, a small amount of 40% hydrogen fluoride in the precursor gas mixture. The resulting tin oxide coating was doped with fluorine. A stream of gas containing the reactant gas was applied for about 8 seconds, then the coating device and the coated gas. The lath was allowed to cool under an air stream of 345 ° F (225 ° C). Remove the covering device At that time, the delivery gas line, nozzle and plate that define the gas flow path above the glass are each In each case, it was found that there was no deposit, which was an undesired pre-reaction. Indicates that it was not. In each case, the glass is provided on silicon oxide Has a tin oxide coating, the thickness of this coating is fish It changes with the distance from the tail nozzle. For each precursor gas mixture used The maximum thickness and the corresponding growth rate are shown in Table 2. With hydrogen fluoride Emissivity, emissivity of samples (Examples 9 and 11) obtained by introducing a fluorine dopant. The resistance and fogging are measured and the results are recorded in Table 2. In this series of examples, the organic oxygen source is a premixed precursor containing tin tetrachloride. Used as part of a gas mixture, for example tin oxide deposits in the gas supply duct Acids thereby without significant undesired prereactions that adversely affect the coating process It is shown that a tin-forming coating can be deposited. In addition, as required A source of dopant, such as hydrogen fluoride, is then introduced into the gaseous premixture. Reduces the emissivity and resistivity of the arting, while at the same time performing a prominent and undesired prereaction You can keep avoiding it.<img file="JP2001503005A_D0002.tif" />Example 14 In this embodiment, the coating distributor graphically illustrated in FIG. 4 is flown. Used in Tovas, a tin oxide coating was provided by the method of the invention. .. Ribbon speed is about 233 inches per minute / 350 minutes per hour, glass thickness is , 0.05 inch (1.2 mm). The glass temperature is about 1170 ° F (6) It was 3O ° C). Temperature of gas supply duct 101 acting as primary gas mixing chamber At 300 ° F (150 ° C), a "static" waffle gas distributor 105 was about 645 ° F (340 ° C). Of tin tetrachloride and butyl acetate A liquid in which nitrogen is maintained at 175 ° F (80 ° C) in a bubbler to deliver vapors. And thereby air bubbles into the gas supply duct 101 through a separate heated conduit. And let it pass. Waffle pack gas mixed steam in the primary chamber Covering chamber 1 that is threaded through a distributor and then open on a hot glass ribbon under layered flow conditions 1 Pass the U-shaped guide groove 106 provided with 08. The flow rate used is such that the molar ratio of tin tetrachloride to butyl acetate is between 1: 1 and 1: 5. The flow rate was sufficient for this. This test was performed for 5 hours. Coating machine When removing, the cooled surface and associated ducts are in excess of 90% It was found that there was no deposit, which is the tin dioxide coating on the glass. Tin tetrachloride and butyl acetate used to obtain syrup with little prereaction Indicates that they can be premixed with each other. A thin tin oxide coating, Obtained on a glass ribbon. Various changes and modifications are made from the specific details of the invention, including the examples described above. It is possible without departing from the idea and scope of the present invention specified in the appended claims. Should be understood. In an essential detail of the invention, the invention is a glass base. Tin oxide coating and titanium oxide coating on the plate, corresponding metal four Organic compounds used as oxygen source in chloride and precursor gas mixture By providing a continuous chemical vapor deposition process on the glass substrate at a high deposition rate Is. Metal tetrachloride is a good choice for each metal due to the availability and cost of the raw material It is a good source. Optimal deposits, especially when depositing titanium oxide coatings from titanium tetrachloride Sources derived from esters, especially alcohols, to produce metal oxides at volume rates Uses an organic oxygen-containing compound that is an ester whose offspring is an alkyl group having β-hydrogen. It was found that it is desirable to be there. Furthermore, the decomposition temperature of the ester is desired. Above the reaction temperature of the coating precursor gas mixture at the point of application of Must not be. Used in a precursor gas mixture with β-hydrogen and an appropriate decomposition temperature The ester deposits the coating at a high deposition rate. To carry out the present invention The preferred group of esters used in the above is ethyl formate, ethyl acetate, propionic acid d. Chill, isopropyl formate, isopropyl acetate, n-butyl acetate and t-bu acetate A group consisting of chills is included. Generally, the ester decomposes in a continuous manner over a predetermined temperature range. Book In the invention, the thermal decomposition temperature of the ester is determined by the single molecule decomposition rate constant of the ester being 0. It is defined as a temperature of 01 / sec. Common esters, such as acetate The single molecule decomposition rate constants for chill and t-butyl acetate are well known and chemical. It can be found in the literature. Before about ethyl acetate and t-butyl acetate Pyrolysis temperatures using the above definitions are 935 ° F (500 ° C) and 650, respectively. ° F (344 ° C). Those skilled in the art will select the ester to be used and the specific deposition temperature. We are aware that the determination determines the optimal coating growth rate. Reaction temperature below the specified pyrolysis temperature, but within the decomposition range of the selected ester As a result, the growth rate of the coating is low. In the present invention, the ester used in the coating precursor gas mixture a. The rukir group can be a carbon compound having a carbon atom in the range of 2 to 10. Wear. The lower limit of this range depends on the need for β-hydrogen on the alkyl group. upper limit Is ignitable and volatile when the alkyl group has more than 10 carbon atoms. This is to avoid sexual problems. In carrying out the method of the present invention, individual gas streams are connected using a manifold. And can be adjusted to formulate a coating precursor gas mixture. Common Precursor gas mixture from manifold to gas beam distributor using the delivery line of Can be sent. An in-line static mixer is used in the delivery line to level A single gas mixture can be ensured. In addition, the gas distributor illustrated in Figure 3 Precursor gas by a deflector in the beam or by the gas flow throttle described with reference to FIG. Can be further mixed at the reactor stage. In many of the examples, oxygen was introduced into the coating precursor gas mixture. .. However, the deposition rate of the metal oxide coating is not affected by the oxygen concentration and is actually In Example 6 or 7, oxygen gas is not used, thereby introducing oxygen. Was shown to be unnecessary. Optimal coating composition for the concentration of reactive components in the coating precursor gas mixture It can be selected so that a long speed can be obtained. Metal tetrachloride concentration is common Is 0.1-5.0% by volume in the precursor gas mixture. Concentration of metal tetrachloride Degree is required to obtain the desired coating thickness at the available residence time It is based on the amount of metal. Therefore, the metal tetrachloride concentration is a variable of the process, eg For example, it is adjusted according to the linear velocity of the ribbon in the float glass process. The concentration of organic oxygen compounds in the coating precursor gas mixture is generally gold. It is 1 to 5 times the concentration of genus tetrachloride, and is selected within this range based on the decomposition temperature. .. When using esters, the deposition temperature is relatively low, and as a result, the rate of ester decomposition is high. Higher ester concentration due to relatively low and therefore reaction with metal tetrachloride is required. In Examples 6 and 7, of ethyl acetate in the precursor gas mixture The optimum concentration is 1 to 3 times the concentration of titanium tetrachloride. Higher than the optimum range Depending on the degree or low concentration, the metal oxide coating is a relatively low coaty Produces at the growth rate. The temperature of the precursor gas mixture is non-volatile, especially in the precursor line, to control the reaction. To avoid unwanted prereactions or adduct formations that result in the formation of spontaneous products It is critically important. One preferred practice that is particularly applicable when using esters In an embodiment, the temperature in the precursor gas line is from 300 ° F (150 ° C). Keep high. Also, the precursor gas mixture is higher than the thermal decomposition temperature of the organic oxygen compound. It is preferable to keep it at a low temperature to prevent the pre-reaction of the mixture. The method of the present invention uses heat from a substrate to initiate a coating reaction. on Extremely high temperature of the substrate in line conditions, eg float glass processes Formed with. Therefore, the method of the present invention lowered the temperature of the substrate, but still coaty. The temperature at which the glass ribbon is formed (and preferably after the elongation of the glass ribbon is almost complete) Temperature above 1380 ° F (750 ° C)) It can be used at the site of the glass process. Offline of the present invention For the application of, it is necessary to heat the substrate to a temperature higher than the decomposition temperature of the ester. is there. In carrying out the method of the present invention in a float glass process, it is preferred. The place of application is in the float bus part. Where to apply the coating The temperature range of is usually about 1100 ° F to 1320 ° F (590 ° C to 715 ° C). To. This temperature is an important operating parameter. The reason is that this temperature is a precursor This is because it affects the concentration of the organic compound used in the body gas mixture. float The temperature of the substrate in the bath part is relatively stable, so it is mostly at the point of application. Does not show any change. Preferred groups in Examples 6 and 7 with ethyl acetate The plate temperature range is 1100 ° F to 1250 ° F (590 ° C to 680 ° C). Due to the heat from the substrate, the temperature of the precursor gas mixture produces a coating When using the ester as an organic compound at a temperature higher than the temperature required for , A temperature higher than the thermal decomposition temperature of the ester). Metal deposition reaction, organic acid It can be initiated by the decomposition of the elementary compound. Has titanium tetrachloride and β-hydrogen When used in combination with an ester having an alkyl group, a titanium oxide coat Ings form on the substrate at a decomposition rate 10 times faster than known coating methods To. In the online application of the float glass ribbon process, the ribbon Passes under the gas distributor beam at a relatively high speed. Metal oxide coating On the float glass ribbon as the ribbon passes under the coating machine accumulate. The present inventors generate when using an ester having an alkyl group having β hydrogen. We propose the following theories related to possible chemical reactions. However, the present inventors, etc. We do not want Ming to be limited to this possible explanation, so we simply do this. Provided as an aid in understanding the results of the methods of the invention. The present inventors propose that when the ester decomposes, one of the β-hydrogens is used. The carbon-hydrogen bond is broken and hydrogen moves to the carbonyl group, eliminating the alkene. , To produce a carboxylic acid. Hydrolysis reaction is carboxylic acid and metal tetrachloride Simultaneously with objects, which creates a metal oxide coating on the substrate To. Generally, the finished article produced according to the present invention is coated with titanium oxide or Provide a substrate with a tin oxide coating. Apply this coating directly to the substrate Can be contacted or provided as multiple coating layers on the substrate .. The rate of deposition of the metal oxide coating affects the rate of decomposition of organic oxygen compounds Is done. At a steady reaction temperature, various organic oxygen compounds differ in decomposition temperature. To this end, various coating growth rates are provided. Therefore, for a given system To select the desired growth rate of the metal oxide coating, specific organic oxygen Match the compound to the precursor gas mixture temperature and substrate temperature at the point of application. To. The deposition rate of the titanium oxide coating in the present invention is the deposition of known deposition methods. It can be 10 times faster than the speed. 130 Å / sec by the method of the invention Accumulation rates of over 300 Å / sec are possible, with some deposition rates well over 300 Å / sec. It was measured. When the deposition rate of titanium oxide becomes higher, the coating becomes 2 A refractive index greater than .4 is given. In addition to being able to achieve high coating rates, other benefits of the invention The point is that in the present invention, a low-priced metal precursor compound is used, and in particular, a precursor gas. According to the present invention, when the mixture is guided above the substrate under favorable layered flow conditions. It is possible to achieve high conversion efficiency (of metal tetrachloride). In the present invention, the obtained oxide coating is particularly when an ester is used. Contains almost no residual carbon from the decomposition of organic oxygen compounds. Carbon is high The presence of bell carbon in the deposited coating creates absorption problems in the coating Therefore, it is an undesired by-product of the coating reaction. Coat organic oxygen compounds Concerns about its use in ing precursor gas mixtures are completed as a result of decomposition This is the production of levels of carbon that adversely affect the absorption properties of the glass. Of the present invention The carbon content in the coating obtained from the method is less than 4 atomic% when measured. Was shown to have been. Depending on this low level of carbon, the absorption properties of the coating Does not have a significant effect on. The embodiments shown and described herein are merely exemplary embodiments of the invention. Various changes in shape, dimensions and arrangement of components, which should be interpreted, In addition, changes in various procedures can be adopted without departing from the idea of the present invention. You should understand that.