經濟部中央標準局員工消費合作社印装 A 7 B7 五、發明説明（1 ) 發明背景 1. 發明領域 本發明係關於於平坦玻璃基材上沈積鈦氧化物及錫氧 化物塗層之方法及結果所得之塗覆玻璃。特別本發明係關 於一種使用包括對應金屬四氣化物及有機氧化劑塗覆前驅 物氣體混合物於平板玻璃上生產鈦氧化物及錫氧化物塗層 之化學蒸氣沈積方法。 2. 先前技術之概述 欽氧化物及錫氧化物塗層曾經提議用於玻璃容器例如 瓶來改良容器的機械強度》也曾提議使用鈦氧化物及錫氧 化物塗層於平板玻璃來修改建築用玻璃特性於真空下（經 由反應性滅鍵）沈積的鈦氧化物塗層用作濺鍍多層紅外線 反射塗層組分；而錫氧化物塗層不僅用作多層濺鍍塗層， 同時也以攙雜劑熱解沈積作為紅外線反射及或導電塗層。 英國專利說明書1 115 342敘述一種生產具有良好特 性強度及良好耐磨性之玻璃容器之方法，其經由使用氣化 錫（亦即四氣化錫於有機液體以異丙醇為佳）之溶液或分散 液於容器得知製造過程時趁熱喷霧容器生產》可攙混小量 氣化鈦作為改質劑。液體溶液飯至設置於熱玻璃報輸送帶 上方隧道兩側的霧化氣（可屬於加壓喷射類型）而產生‘液 體反應劑霧’而於瓶之全部外表面形成一層液體，於此處 反應形成錫氧化物層。 英國專利說明書1 1 87 784敘述英國專利說明書 1 115 342敘述方法之改良’且顯然更適合合併入自動化 本紙張尺度逋用中國國家標準（CNS ) A4規格（210X297公釐） 4 (請先閱讀背面之注意事項再填寫本頁) 裝. '*7· 經濟部中央標準局貝工消費合作社印製 410214 A7 --------- B7 五、發明説明（2 ) 生產破璃器皿之製程而未干擾此種製程之運作且無需額外 監督。該說明書提議使用有機踢化合物液體溶液處理於高 溫之玻璃容器“該化合物之性f當濕熱時分解成兩種材料 ’其中-種為具有高分解溫度的有機錫化合物，其於玻璃 表面反應而形成於玻璃表面内部的錫氧化物擴散成而另一 ，材料為揮發性錫化合物故產生大半比例之該種化合物蒸 氣’將容器置於加熱處理引起介於玻璃間至少與容器表面 與錫化合物間之反應”。用於處理玻璃容器的材料可經由 四氣化錫與含中等活性之幾基之有機物質反應提供，該有 機物質例如為乙醇、正丙醇、異丙醇、正丁醇及異丁醇與 乙酸、丙酸及丁酸之有機物質。所得溶液可於周圍大氣壓 存在下喷霧於熱容器上，例如於熱容器離開成形機器而進 入退火窯之前呈細霧形式反應。英國專利說明書i 187 783 敘述類似1 187 784所述方法，其中鈦有機化合物喷霧於 熱容器上替代錫有機化合物。有機鈦化合物可以類似於有 機錫化合物之方式經由四氣化鈦於有機酯例如乙酸正丁酯 。再度所得溶液於周圍氣氛下喷霧於露容器生產線上的玻 璃上方。 也曾經提議使用四氣化錫呈液體喷霧施用，或更為晚 近呈氣態形式施用錫氧化物塗層至熱平板玻璃上，而於熱 平板玻璃面形成導電性紅外光反射塗層；使用水分解四氣 化錫其作為形成錫氧化物的氧來源。 包括使用氣態形式反應物之方法（亦名CVD或化學蒸 氣沈積方法）具有某些優於塗覆平板玻璃之喷霧方法之優 本紙张纽適用中S國家橾準（c叫Α4^ ( 21()χ297公慶） (請先閱讀背面之注意事項再填寫本頁) 年 410214 A7 B7 五、發明説明（3 ) 點，特別當反應物於施用至玻璃之前預先混合時尤為如此 。不幸四氯化錫易與水反應’而先前提議使用四氣化錫及 水蒸氣成氣態形式通常需要分別供應氣髋至玻璃表面而與 玻璃接觸時混合之。 英國專利說明書2 044 137A係有關—種方法其中各種 反應物質分立層流經形成’並經由呈住復切線方向接觸玻 璃合併成流投射至熱玻璃基材上。四氣化鈦可用作其中一 種氣體反應物替代四氣化錫必形成鈦氧化物塗層。該專利 案也提示供應氫至其中一股風·體流而緩和四氣化踢與水蒸 氣間之激烈反應。可經由直接加入氣態氫加入甲醇，其據 稱可於原位反應產生所需氣態氩進行。 英國專利說明書2 026 454B敘述一種方法其中塗層室 設置於熱浮面玻璃帶上，當帶由浮面浴前進時及（1)預熱 氮載氣，（2)夾帶於預熱氮之四氣化錫，及(3)空氣、水蒸 氣及氩氟酸之連續氣體流引入塗層室内，使其呈大體不含 湍動層順著有待塗覆的玻璃基材表面流動。該專利規定於 玻璃上方於氣態介質内之水蒸氣及四氣化錫濃度。 經濟部中央標準局員工消費合作社印裝 歐洲專利說明書〇 3幻239B1及0 3了6 240B1敘述一種 於熱玻璃帶上沈積錫氧化物塗層之方法及裝置。四氣化錫 於預熱乾空氣之第一氣態流沿著於塗層室下方前進的熱玻 璃帶表面流動，第二氫氟酸及水蒸氣湍動流以垂直玻璃面 積第一氣態流流動方向之直角引進塗層室内’合併第一及 第二氣體流於湍動流條件下抽取通過玻璃上方的塗層室。 該方法及裝置也可使用四氣化鈦代替四氯化錫用於施用鈦 6 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度逋用中國國家橾準（CNS ) A4规格（210 X 2的公釐） 410214 A7 B7 五、發明説明（4 ) 氧化物塗層。 美國專利4 590 096敘述一種方法其中包括大體不含 溶劑之有機錫氣化物及反應性有機氟化合物其可溶於或可 溶混於有機錫氯化物之混合物引進預熱載氣流，在氣流含 有足量水蒸氣使氣體流之相對濕度於18eC約為6%至約 100%。所得氣艎流通過熱玻璃面而沈積氟攙雜錫氧化物 塗層於熱玻璃上。可使用廣泛多種有機錫化合物並敘述使 用四氯化錫之可能性。同理可使用廣泛多種有機氟化合物 包含含氧化合物例如三氟乙酸及三氟乙酸乙酯。若干含氟 攙雜劑於有機錫化合物之溶解度有限，可使用選擇性增溶 劑來提高氟攙雜劑於有機錫化合物之溶解度；可使用乙針 、乙酸乙酯、己烧、甲基異丁基甲網及丁搭作為增溶劑之 非限制例。但該美國專利案與其他專利案共通利用化學蒸 氣沈積法由氣態金屬四氯化物沈積金屬氧化物，使用水蒸 氣作為氧來源。 經濟部中央標準局負工消费合作社印製 {請先閱讀背面之注意事項再填寫本頁)Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A 7 B7 V. Description of the invention (1) Background of the invention 1. Field of the invention The present invention relates to a method and result of depositing titanium oxide and tin oxide coatings on a flat glass substrate The resulting coated glass. In particular, the present invention relates to a chemical vapor deposition method for producing titanium oxide and tin oxide coatings on flat glass using a precursor gas mixture including a corresponding metal tetragas and an organic oxidant. 2. Overview of the prior art. Chin oxide and tin oxide coatings have been proposed for glass containers such as bottles to improve the mechanical strength of the container. It has also been proposed to use titanium oxide and tin oxide coatings on flat glass to modify architectural applications. Glass properties: Titanium oxide coatings deposited under vacuum (via reactive debonding) are used as components for sputtered multilayer infrared reflective coatings; while tin oxide coatings are not only used as multilayer sputtered coatings, but also doped with The agent is pyrolytically deposited as an infrared reflective and / or conductive coating. British Patent Specification 1 115 342 describes a method for producing a glass container with good characteristic strength and good abrasion resistance by using a solution of vaporized tin (that is, tetra-gasified tin in an organic liquid, preferably isopropyl alcohol) or The dispersion can be produced in the container while the container is being manufactured while the manufacturing process is being learned. "A small amount of titanium gasified can be mixed as a modifier. Liquid solution rice to the atomized gas (which can be a type of pressurized spray) placed on both sides of the tunnel above the hot glass newspaper conveyor belt to generate a 'liquid reactant mist' and form a layer of liquid on the entire outer surface of the bottle, where it reacts A tin oxide layer is formed. The British Patent Specification 1 1 87 784 describes the improvement of the method described in the British Patent Specification 1 115 342, and it is obviously more suitable to be incorporated into the automation. This paper standard uses the Chinese National Standard (CNS) A4 specification (210X297 mm) 4 (Please read the back first Note: Please fill in this page again.) Packing. '* 7 · Printed by Shelley Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs, 410214 A7 --------- B7 V. Description of the invention (2) Production process of glass-breaking utensils It does not interfere with the operation of this process and requires no additional supervision. The specification proposes to use a liquid solution of an organic kick compound to treat a high temperature glass container. "The nature of the compound f decomposes into two materials when moist and hot ', one of which is an organic tin compound with a high decomposition temperature, which is formed by reacting on the glass surface. Tin oxide diffuses inside the glass surface and another, the material is a volatile tin compound, which generates a large proportion of the compound vapor. 'Place the container in a heat treatment to cause a gap between the glass and at least between the container surface and the tin compound. reaction". Materials for processing glass containers can be provided by reacting tin tetraoxide with organic substances containing moderately active groups such as ethanol, n-propanol, isopropanol, n-butanol, and isobutanol and acetic acid. , Propionic and butyric organic substances. The resulting solution can be sprayed on a hot container in the presence of ambient atmospheric pressure, for example, it reacts in the form of a fine mist before the hot container leaves the forming machine and enters the annealing kiln. British patent specification i 187 783 describes a method similar to that described in 1 187 784, in which a titanium organic compound is sprayed on a hot container instead of a tin organic compound. Organic titanium compounds can be similar to organic tin compounds via tetragasification of titanium to organic esters such as n-butyl acetate. The resulting solution was sprayed again on the glass in the dew container production line in the surrounding atmosphere. It has also been proposed to use four gaseous tin as a liquid spray application, or more recently in a gaseous form, to apply a tin oxide coating to hot flat glass, and to form a conductive infrared light reflective coating on the surface of the hot flat glass; use water Decomposes four gaseous tin as a source of oxygen to form tin oxide. Methods that include the use of reactants in gaseous form (also known as CVD or chemical vapor deposition methods) have certain advantages over the spray method of coating flat glass. This paper is suitable for use in S countries (c is A4 ^ (21 ( ) 297 public holiday) (Please read the notes on the back before filling this page) Year 410214 A7 B7 V. Description of the invention (3) Point, especially when the reactants are pre-mixed before applying to the glass. Unfortunately tetrachloride Tin is susceptible to reaction with water ', and the previous proposal to use four gaseous tin and water vapor to form a gaseous form usually requires separate supply of gas to the glass surface and mixing when contacting the glass. British Patent Specification 2 044 137A is related to a method of various A discrete layer of reactive material flows through the formation 'and contacts the glass in the direction of the complex tangent to merge into a stream and project it onto the hot glass substrate. Titanium tetragas can be used as one of the gas reactants instead of tin tetragas and must form titanium oxide. Coating. This patent also suggests the supply of hydrogen to one of the wind and body currents to alleviate the intense reaction between the four gasification kick and water vapor. Methanol can be added directly by adding gaseous hydrogen, It is said that it can be carried out in situ to produce the required gaseous argon. British Patent Specification 2 026 454B describes a method in which the coating chamber is set on a hot-floating surface glass ribbon when the belt is advanced from the floating surface bath and (1) preheated nitrogen load Gas, (2) four gaseous tin entrained in preheated nitrogen, and (3) a continuous gas stream of air, water vapor, and argon fluoride acid is introduced into the coating chamber so that it is substantially free of turbulent layers and is to be coated The surface of the covered glass substrate flows. The patent stipulates the concentration of water vapor and tetragas tin in a gaseous medium above the glass. The European Union's Patent Specification printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, 03, 239B1 and 0.3 240B1 describes a method and device for depositing a tin oxide coating on a hot glass ribbon. The first gaseous flow of four gasified tin in the preheated dry air flows along the surface of the hot glass ribbon advancing below the coating chamber, and the second The turbulent flow of hydrofluoric acid and water vapor is introduced into the coating chamber at a right angle to the first gaseous flow direction of the vertical glass area. The first and second gas streams are merged under the conditions of turbulent flow and drawn through the coating chamber above the glass. Method and It is also possible to use titanium tetrachloride instead of tin tetrachloride for the application of titanium 6 (Please read the precautions on the back before filling this page) This paper size uses the Chinese National Standard (CNS) A4 size (210 X 2 (410 mm) 410214 A7 B7 V. Description of the invention (4) Oxide coating. US Patent No. 4 590 096 describes a method which includes an organic tin gaseous agent and a reactive organic fluorine compound which are substantially free of solvents and which are soluble or soluble The mixture mixed with organotin chloride is introduced into a preheat carrier gas stream, and the gas stream contains sufficient water vapor to make the relative humidity of the gas stream from 18eC to about 6% to about 100%. The resulting gas stream passes through the hot glass surface to deposit fluorodoped tin Oxide coating on hot glass. A wide variety of organotin compounds can be used and the possibility of using tin tetrachloride is described. Similarly, a wide variety of organic fluorine compounds can be used, including oxygenates such as trifluoroacetic acid and ethyl trifluoroacetate. Some fluorinated dopants have limited solubility in organotin compounds. Selective solubilizers can be used to increase the solubility of fluorinated dopants in organotin compounds. Acetate, ethyl acetate, hexane, methyl isobutyl methyl ether, and butyl can be used. Non-limiting examples of solubilizers. However, this U.S. patent and other patents commonly use chemical vapor deposition to deposit metal oxides from gaseous metal tetrachloride, using water vapor as a source of oxygen. Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperatives (Please read the precautions on the back before filling this page)
Vijaykumar等美國專利4 751 149係關於經由於低溫 (60至350t：較佳100至20(TC)藉化學蒸氣沈積而於感熱光 導體基材上沈積辞氧化物塗層，並提議由有機鋅化合物及 氧化基沈積辞氧化物塗層’氧化劑可為含氧有機化合物例 如酯及惰性載氣。雖然該專利尚未完全清楚，但顯然提議 將有機鋅化合物及氧化劑之分開流引進沈積室内，且確實 未曾提議於輸送至塗層室之前預先混合該等成份。 較佳提供一種沈積錫或鈦氧化物塗層之方法，經由使 用對應金屬四氯化物作為低成本反應物與氧來源之預混合 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0X2W公| ) 410214 :77 五、發明説明（5 ) 物藉CVD方法施用至熱平板玻璃上，而介於金屬四氣化 物於氧來源(過去為水）間不會出現過早反應，結果導致於 塗層設備形成金屬氧化物，造成隨後之問題及效率不佳。 若該方法可以高速沈積塗層，於玻璃生產製程中時所需塗 層厚度沈積於移動中的玻璃帶上則特佳。 發明概述 根據本發明提供一種使用含對應金屬四氣化物及有機 氧來源之前驅氣體混合物於熱玻璃基材上鋪上錫氧化物或 鈦氧化物塗層之化學蒸氣沈積方法，而無需包含水蒸氣及 隨後造成過早反應之風險。 本發明提供一種於熱平板玻璃上沈積一層錫氧化物或 鈦氧化物塗層之方法包括下列步驟： (a) 製備含對應金屬四氣化物及有機含氧化合物作為形成 金屬氧化物之氧來源之前驅氣體混合物； (b) 將該前驅氣體混合物維持於低於金屬四氣化物可反應 而形成金屬氧化物溫度之溫度，同時將該混合物輸送 至開口於熱玻璃上方的塗層室； (c) 將前驅氣體混合物引進塗層室内，藉此混合物被加熱 經濟部中央標準局負工消费合作社印製 {請先閱讀背面之注意事項再填寫本頁) ’引起合併有來自有機化合物之氧的對應金屬氧化物 沈積至熱玻璃表面上。 出乎意外’可使用廣泛多種含氧有機化合物作為氧來 源而無需存在有水蒸氣或氣態氧，包含通常視為還原劑而 非氧化劑之化合物例如醇類。但較佳有機化合物為幾基化 合物特別酯；使用含有一個々氫之烷基之酯可獲得特佳結 本紙張尺度逋用中國國家標準（CNS ) A4規格（210X297公釐） 經濟部中央橾隼局貝工消费合作社印製 __410214 ^ _ 五、發明説明（6 ) ' ~~ 果β具一個/3氩之烷基通常含2至1〇個碳原子。 較佳使用含2至10個碳原子之有機化合物，特別酯類 ’原因為分子更大則揮發性較低，因而較不方便用於本發 明之CVD製程。 特佳用於實施本發明之酯類包含甲酸乙酯、乙酸乙酯 、丙酸乙酯、甲酸異丙酯、乙酸異丙酯、乙酸正丁醋、及 乙酸第三丁酯。 本發明方法通常是與連續玻璃帶基材之形成例如浮面 玻璃生產製程共同實施》但本發明方法可於線上或離線用 於塗覆其他平板玻璃基材。 本發明包括製備前驅氣體混合物其包含錫或鈦四氣化 物及有機含氧化合物；載氣或稀釋劑例如氮空氣或氦通常 亦含於氣體混合物’由於有機含氧化合物之熱分解可以高 迷引發金屬氧化物沈積反應故需要前驅混合物維持於有機 氧化合物之熱分解溫度之溫度，以防氣體混合物過早反應 而形成金屬氧化物。 氣態混合物維持於低於可反應形成金屬氧化物之溫度 ，並輸送至接近有待塗層之平板玻璃基材位置，該基材之 溫度（高於反應溫度）其高於前驅氣體混合物内有機氧化合 物之分解溫度。 隨後前驅氣體混合物引進基材正上方之蒸氣空間。來 自基材的熱量升高前驅氣體溫度高於有機氧化合物之熱分 解溫度。然後有機氧化合物分解並與金屬四氣化物反應產 生金屬氧化物塗層於基材上。 本紙張尺度適用中國國家標华（CNS ) A4規格（210X297公釐） {讀先閲讀背面之注意事項再填寫本頁j -β 政· 410214 A7 B7 五、發明説明（7 ) 本發明可以高枕積速率例如超過130A/秒，及於較 佳具體例超過25〇A/秒生產沈積於熱玻璃上的锡及欽氧 塗層。 沈積速率是於使用特定含氧有機化合物，及有機含氧 化合物及金屬氣化物濃度以及玻璃溫度有關。對任何特定 化合物組合’供快速塗層沈積之最佳濃度(特別）有機含氧 化合物對金屬四氯化物之最佳比例及流速可經由簡單試驗 得知β但須了解使用較高濃度反應物及高氣體流速可能導 致反應物轉成塗層之整體轉化率效率較低，故商業操作之 最佳條件可能與可獲得最高之沈積速率不同。 較佳有機含氧化物之濃度以體積計為金屬四氣化物之 體積比濃度之約0·5特別I至5倍。常使用至少佔金屬氣化 物重量之30%重量比。 本發明方法可於玻璃生產過程中於線上以高速於熱平 板玻璃基材上生產鈦氧化物及錫氧化物塗層，鈦氧化物塗 層可以高折射指數(至少14)生產，而達成所需光學效果， 特別當與其他塗層合併使用時尤為如此。錫氧化物塗層可 攙雜例如攙雜氟’是經由攙混適當攙雜劑前驅物至前驅氣 體混合物内’提高塗層的導電率及紅外光反射率因此可用 作建築上釉及其他用途作為導電塗層及/或低發射率塗層 〇 圊示之簡單說明 本發明之前述及其他優點對業界人士由下文較佳具體 例之詳細說明同時鑑於附囷考慮將顯然知明，附圖中： 本紙張尺度適用中國囷家榇準（<^5)八4規格（210父297公釐} (請先閱讀背面之注意事項再填寫本頁) 丁 _ -3 經濟部中央標準局員工消費合作社印製 10 41Q2U at _____ B7 五、發明説明（8 ) 第1圖為實施浮面玻璃製程之裝置之垂直剖面示意圖 ，該裝置包含適當設置的氣體配送器而可用於實施本發明 之方法； 第2圖為根據本發明塗覆之物件之分解剖面圖； 第3圖為適用於實施本發明之氣體配送梁之放大示意 端視圖；及 第4圖為適用於實施本發明之另一種氣體配送梁之放 大示意端示圖。 放大示意端示圖 現在特別參照附圖第1囷10概略說明用作實施本發明 方法之手段之浮面玻璃裝置》浮面玻璃裝置特別包括通道 區段12 ’沿此通道區段熔融玻璃14由熔爐（未顯示出）輸送 至浮面浴區段16，其中眾所周知之浮面方法形成連續玻璃 帶18。玻璃帶18由浴區段16前進通過比鄰的退火窯2〇及冷 卻區段22。連續玻璃帶18作為基材，根據本發明之金屬氧 化物塗層沈積於該基材上。 浮面區段16包含一個底區段24，於其内部容納熔融錫 .浴26頂28相對側壁30及端壁32。項28側壁30及端壁32共同 經濟部中央標隼局負工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 界定一個包圍體34 ’其中維持非氧化氣氛以防熔融錫氧化 〇 此外氣體配送器梁64、66及68位於浴區段16。於浴區 段之氣趙配送氣梁60及66用以於藉本發明方法施用锡或欽 氧化物之前施用額外塗層至基材上β額外塗層包含石夕及氣 化矽。 本紙張尺度適用中國國家榇準（CNS ) Α4規格（210X297公釐） 11 經濟部中央標準局員工消費合作社印裝 A7 B7_ 五、發明説明（9 ) 操作時熔融玻璃實施沿調節閘門38下方的通道36以控 制量向下流至錫浴26表面上。於錫浴上方熔融玻璃受重力 及表面張力以及某些機械影響力影響向側方向展開，前進 跨越浴而形成帶18 ^帶於舉出輥40上移動隨後輸送通過退 火窯20及於排齊輥42上的冷卻區段22。施用本發明之塗層 可於浮面浴區段16進行又可沿著生產線例如於介於浮面浴 與退火窯間之間隙進行或於退火窯進行。 適當非氧化氣乱通常為氣或氛與氣之氧化物而氪^占大 半維持於浴包圍體34内部以防錫浴氧化。氣氛氣體通過以 操作式偶合至分布歧管46的導管44。非氧化氣體已足夠彌 補正常損失並維持於略為正壓，約高於周圍積大氣壓〇,〇01 至0.01大氣壓之壓力之速率引進故可防止外侧氣氛的滲入 。維持錫浴26及包圍體24於所需溫度之熱量是由包圍體内 部的輻射加熱器48提供β退火窯20内部氣氛典型為大氣而 冷卻區段22並未封閉，玻璃帶開放至周圍大β周圍空氣例 如可藉冷卻區段風扇50導引至玻璃帶。加熱器（未顯示出） 也可設於退火窯内部使玻璃帶輸送通過其中時玻瑜帶溫度 根據預定計劃緩慢下降。 第1圖示例說明使用位於浮面浴16之氣艘配送器梁64 、66及68沈積多種塗層於玻璃帶基材上》氣體配送器梁為 一型可用於實施本發明方法之反應器。 根據本發明適合供應前驅材料之配送器梁的方便構造 概略示意於第3囷。由間隔的内壁外壁72及74形成的顛倒 概略通道形骨架7〇界定封閉穴76及78。適當熱交換介質循 本紙張尺度邊用中國國家楳準（CNS ) Α4規格（2! 0 χ 297公釐） 12 (請先鬩讀.背面之注意事項再填寫本頁) 、1 Μ 經濟部中央標準局貝工消費合作社印製 410214 A7 ___B7 _____ 五、發明説明（i〇) 環通過封閉穴76、78以維持配送氣梁於所需溫度。 前驅氣逋混合物通過流體冷卻時供應管路80供應。供 應管路80沿配送氣梁延伸並容納與供應管路隔開’滴路管 路80送來的氣體。供應管路80前進至由骨架攜載之露頭碑 86内部之輸送室84。經由滴落管路82接受的前驅氣體由輸 送室84通過通道88朝向塗層室排放，塗層室於玻璃上方界 定一個蒸氣空間開口，於此處於第3圖箭頭所示方向沿玻 璃18表面流動。 擋板90可設於輸送室84内部供平衡跨越配送器梁流動 的前驅材料以確保各材料以光滑層流均衡流跨越整個配送 氣梁排放至玻璃18上。用過的前驅材料均收集並通過排放 室92沿配送氣梁旁侧排放β 各型用於化學蒸氣沈積之配送器梁皆適用於本方法且 為先前技術已知。 其中一種替代配送器梁構造示意說明於附圖之第4圖 。使用此種配送器（概略標示為100，更完整欽述於歐洲專 利03 05 102Β)前驅氣體混合物通過氣趙供應導管1〇1，於 此處解通過導管102及103循環之流體冷卻β氣艘供應導管 101經由細長孔口 104開放入氣體流約束器1〇5。 氣體流約束器105更完整敘述於英國專利說明書} 5〇7 ’該種包括多根金屬長條沿縱向全區呈正弦波形而沿配送 器長度方向以彼此毗鄰關係垂直安裝。毗鄰的金屬長條“ 離相”設置而介於其間界定多條垂直通道。垂直通道之剖 面積比較氣體供應導管101之剖面積小，故沿配送器之長 本紙張尺度逋用中國囤家標率（CNS ) A4規格（210X297公" ----- -13 - ----„--------------ir------Μ (請先Μ讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印裝 410214 A7 ~-------- B7 五、發明説明（U) 度方向氣體大趙穩壓由氣趙流約束器105釋放。 塗覆氣趙由氣體流約束器釋放人大趙U型導引通道( 概略標示為_之入口側1〇7，導引通道包含入口腳阳， 塗層室H>8其開放之有待塗層的熱玻璃基材iu)，及排放腳 1〇9因此用過的塗層氣體由玻璃撤出。界定塗覆通道之碑 塊圓角可促成跨越有待塗覆之玻璃表面平行玻璃表 面之塗 層形成均勻層流。 下例實例（其中氣體體積是於標準條件標示，亦及除 非另行陳述是於-大氣壓及周圍溫度戌供進一步舉例說 明及監視本發明但絕非意圖限制本發明。 實例1至5 此等實例中，於實驗室使用第3圖所示該型雙向塗覆 反應器來沈積鈦氧化物塗層。 實例1、2及3中，破螭於輸送帶如上加熱而模擬浮面 玻璃製程之塗覆反應條件俾測試本發明方法。如使用線上 親而於實施本發明方法之前輸送玻璃基材通過加熱區段。 實例1中破璃基材為初步已經提供氧化石夕塗層之浮面玻璃 。氧化矽塗層經由已知化學蒸氣沈積法利用單矽烷前驅物 於富氡氣氛沈積於浮面玻璃上。氧化矽沈積會構成本發明 之一部分β 根據本發明鈦氧化物塗層沈積於經氧化砂塗覆之基材 上。基材是於1170°F/630°C及基材線性速度為300吋/8 米/分。 欲沈積鈦氧化物，開發一種包括四氣化鈦、乙酸乙酯 本紙張尺度適用中國囤家梂準（CNS ) A4规格（2丨0X297公釐） 14 ----.--.---^襞-------、17------Μ I . (請先閲讀背面之;i意事項再填寫本頁) 410214 A7 B7 五、發明説明（12) 、氧及氦之前驅氣體混合物β氦包含於前軀混合物作為反 應物之載氣。前驅混合物是經由將四種氣體流經過單一歧 管系統同時引進製備β線上靜態混合氣用來確保均質前驅 混合物。前驅混合物之體積百分組成為〇7%四氣化鈦、 17.2%乙酸乙酯、7.2%氧及74.9%氦，各成份於歧管之流 速示於附表1。 前驅混合物溫度維持高於3〇〇°f/150°C以防四氣化鈦 於乙酸乙酯之加合反應。前驅物溫度也維持低於乙酸乙酯 之熱分解溫度範圍950T-1130eF(510°〇61(TC)以防混合物 過早反應。 前媒混合物引進恰位於移動中的基材上方的反應器内 β前驅物塔之溫度為250°F/120°〇反應器面之溫度為350 F/175 C。基材溫度較高引發乙酸乙酯熱分解隨後導致 鈦氧化物沈積。 經濟部中央榡準局員工消费合作社印製 所得塗層玻璃於空氣中冷卻並分析塗層，發現鈦氧化 物之鈦含量為2·5·3·5原子。/。》鈦氧化物塗層厚度測得為490 Α及厚度及生長速率（150Α/秒)示於表i。所得產物之光 學性質包含照明劑C透射率觀察值（10。觀察)623。/。及照明 劑反射率觀察值35.6% »消光係數於500nm為0.008，而鈦 氧塗層之折射指數為2,44。 實例2及3重覆實例1陳述之塗復過程，但實例2使用甲 酸乙酯作為氧之有機來源，而實例3使用異丙醇作為氧之 有機來源及使用未經塗覆玻璃（替代實例1及2之氧化矽塗 層玻璃）作為基材。使用氣體流速及實例2之例生產的鈦氧 15 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標隼（C»S )八4規格（210X 2^7公釐） 經濟部中央棣孪局負工消費合作杜印t 410214 A7 B7 ____ 五、發明説明（13) 化物塗層厚度及生長速率示於表1。實例3中異丙醇於反應 器内燃燒僅留下粒狀鈦氧化物於玻璃上，故對應沈積速率 引述為〇A/秒。 實例4及5之程序如先前實例（反應器溫度及基材同實 例1)但基材為靜態而非動態。靜態樣品置於反應器内10秒 °於靜態條件下基材於反應器内停留時間比較動態條件增 加因數5。 實例4用於乙酸甲酯作為有機氧來源而實例5使用乙酸 正丁酯；各例中生產鈦氧化物塗層。氣體流速，結果所得 欽氧化物塗層厚度及塗層生長速率示於表〗。使用乙酸甲 醋達成生長速率相對緩慢討論如後。 實例6 浮面玻璃製程用於以線上數度434吋/11米/分生產 0.125吋/3毫米之連續玻璃帶。破璃溫度於浮面浴之鈦氧 化物塗層區段之期望施用點，使用塗層 反應器類似第3圖所示。前驅物塔溫度為4〇〇°f/205°C及 反應器面溫度為500°F/260°C。實施本發明方法前氧化矽 塗層於浮面浴區段於玻璃基材上沈積層厚約339人。使用 如實例I所說化學蒸氣沈積法來沈積氧化矽塗層。氧化矽 之沈積未構成本發明之一部分。 開發前驅氣體混合物包括四氣化鈦及乙酸乙醋於氦載 氣。於前驅物未使用氧，由於先前實例結果指示塗覆反應 對氧濃度不敏感。前驅混合物其將三種成分同時引進通過 歧管系統製備。前驅混合物之體積百分組成為〇6%四氣 本紙張尺皮逋用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂 Μ- 16 410214 A7 B7_______ 五、發明説明（14) 化鈦、1.8%乙酸乙酯及97.5°/。氦。成分流速分別為480.0 1/m 氦、3.0 1/m四氣化鈦、9.2 Ι/m乙酸乙酯。前驅混合物種流 速為492.2 Ι/m。 所得鈦氧化物塗層厚度684A。塗層之碳含量小於2原 子％。塗層生長速率為每秒309A。 實例7 實例6之進行程序用於本例。基材包括矽塗層然後為 氧化矽於玻璃基材上。塗層是於浮面浴區段藉以化學蒸氣 沈積法沈積。矽塗層是由單矽烷與非氧化載氣藉CVD沈 積。然後氧化矽塗層使用實例1之相同程序沈積於矽塗層 上。 鈦氧化物塗層前驅物包含四氣化鈦及乙酸乙酯於氦載 氣。前驅物之體積百分組成為〇.5°/。四氣化鈦、1.9%乙酸 乙酯及97.6%氦。各成分之對應流速為480·0 Ι/m氦、2.4 1/m 四氣化鈦、9.2 1/m乙酸乙酯。前驅混合物之種流速為491.6 Ι/m。 所得塗覆件52示例說明於第2囷。玻璃基材54闡明具 有一堆多層塗層56。塗層包括一層矽58、一層氧化石夕， 然後一層鈦氧化物塗層62於物件頂上。於所得物件頂上之 欽氧化物塗層厚度為836Α β所得塗層堆之光學性質包含 照明劑C透射率觀察值13,1°/。及照明劑前c反射率觀察值 82.5% »鈦氧化物塗層之生長速率為378人/秒。 本紙張尺度適用中國國家標準（CNS ) Α4规格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央標準扃貝工消费合作社印製 17 ^l〇2l4 A7 --------- —_B7 五、發明説明（15) 表1 T例 流速(升/分） 四氣化鈦 有機氧化合物 氧 氦 厚度 A 生長速率 A/秒 1 0.2 4,8乙酸乙酯 2.0 20.9 490 150 2 0.5 1.6甲酸乙酯 6.0 17.4 800 250 3 0,45 異丙醇 4.0 15.45 0 0 4 0.5 L2曱酸甲酯 6.0 17.4 <100 <10 5 0.5 〇_5乙酸第三丁酯 6.0 16.5 1300 130 實例8至13 (請先閱讀背面之注意事項再填寫本頁} 此等實例中於實驗室使用靜態塗覆機來施用錫氧化物 塗層於如歐洲專利EP 〇 275 662B所述生產的載有色彩壓 抑矽氧化物塗層之浮面玻璃基材上β 有待塗覆之浮面玻璃支載於反應容器之鎳碑上，而碑 由下方藉電熱源漸加熱提供溫度1085«F/585^。平坦石 墨板安裝於玻璃上方約〇.4吋/10毫米且與玻璃平行而提 供介於載有矽氡化層之玻璃面於平板間之氣體流經深度 〇_4吋/10毫米。 含四氣化錫及有機氧來源於空氣及小比例額外氮氣周 圍載氣之前驅氣艘混合物通過於維持溫度435卞±25卞/ 225°C±15°C之氣體管路輸送並設有魚尾喷嘴開口於平行 玻璃面之概略方向於熱玻璃上方之氣體流徑。總載氣流速 為13 m3/h〇四氱化錫流速及有機化合物性質及流速示於 本紙張尺度適用中國國家標準（CNS ) A4規格（210ΧΪ97公缝） ~~ -Vijaykumar et al. U.S. Patent No. 4,751,149 is related to the deposition of oxide coatings on thermosensitive photoconductor substrates by chemical vapor deposition at low temperatures (60 to 350t: preferably 100 to 20 (TC)), and proposes to use organic zinc compounds The oxide coating can be an oxygen-containing organic compound such as an ester and an inert carrier gas. Although the patent is not completely clear, it is clearly proposed to introduce a separate stream of the organic zinc compound and the oxidant into the deposition chamber, and it has never been It is proposed to premix the ingredients before delivery to the coating chamber. It is preferred to provide a method for depositing a tin or titanium oxide coating by premixing the paper using the corresponding metal tetrachloride as a low cost reactant and oxygen source. Applicable to China National Standard (CNS) A4 specification (2 丨 0X2W male |) 410214: 77 V. Description of the invention (5) The material is applied to the hot flat glass by CVD method, and the metal four gaseous material is in the source of oxygen (formerly Water) will not react prematurely, resulting in the formation of metal oxides in the coating equipment, resulting in subsequent problems and poor efficiency. If this method can be high The coating is deposited, and the thickness of the desired coating is particularly preferably deposited on the moving glass ribbon during the glass production process. SUMMARY OF THE INVENTION According to the present invention, a precursor gas mixture containing a corresponding metal tetragas and an organic oxygen source is provided. Chemical vapor deposition method of tin oxide or titanium oxide coating on hot glass substrate without the need to include water vapor and the risk of subsequent premature reaction. The present invention provides a layer of tin oxide deposited on hot flat glass. The method for coating titanium or titanium oxide includes the following steps: (a) preparing a precursor gas mixture containing the corresponding metal tetragas and organic oxygenates as an oxygen source for forming the metal oxide; (b) maintaining the precursor gas mixture at A temperature lower than the temperature at which metal tetragases can react to form metal oxides, and at the same time convey the mixture to the coating chamber opened above the hot glass; (c) introduce the precursor gas mixture into the coating chamber, thereby heating the mixture Printed by the Central Laboratories of the Ministry of Economic Affairs, Consumer Cooperatives (Please read the notes on the back before filling this page) The corresponding metal oxide incorporating oxygen from the organic compound is deposited onto the hot glass surface. Surprisingly, a wide variety of oxygen-containing organic compounds can be used as a source of oxygen without the presence of water vapor or gaseous oxygen, including compounds such as alcohols which are generally regarded as reducing agents and not oxidizing agents. However, the preferred organic compound is a special ester of several bases; an excellent paper size can be obtained by using an ester containing an alkyl group of hydrogen, using Chinese National Standard (CNS) A4 (210X297 mm) Central Ministry of Economic Affairs. Printed by the local shellfish consumer cooperative __410214 ^ _ V. Description of the invention (6) '~~ Fruit β has a / 3 argon alkyl group usually containing 2 to 10 carbon atoms. It is preferred to use organic compounds containing 2 to 10 carbon atoms, especially esters because the larger the molecule, the lower the volatility, and therefore it is less convenient to use in the CVD process of the present invention. The esters particularly preferably used in the practice of the present invention include ethyl formate, ethyl acetate, ethyl propionate, isopropyl formate, isopropyl acetate, n-butyl acetate, and tert-butyl acetate. The method of the present invention is usually implemented in conjunction with the formation of a continuous glass ribbon substrate, such as a floating glass production process. However, the method of the present invention can be used online or offline to coat other flat glass substrates. The invention includes the preparation of a precursor gas mixture which contains tin or titanium tetragases and organic oxygenates; a carrier gas or diluent such as nitrogen air or helium is usually also contained in the gas mixture. 'It can be triggered by thermal decomposition of organic oxygenates. The metal oxide deposition reaction requires the precursor mixture to be maintained at the temperature of the thermal decomposition temperature of the organic oxygen compound to prevent the gas mixture from reacting prematurely to form a metal oxide. The gaseous mixture is maintained below the temperature at which it can react to form metal oxides and is transported to a position near the flat glass substrate to be coated. The temperature of the substrate (above the reaction temperature) is higher than the organic oxygen compounds in the precursor gas mixture. Decomposition temperature. The precursor gas mixture is then introduced into the vapor space directly above the substrate. The heat from the substrate increases the temperature of the precursor gas above the thermal decomposition temperature of the organic oxygen compound. The organic oxygen compound then decomposes and reacts with the metal tetragas to produce a metal oxide coating on the substrate. This paper size applies to China National Standards (CNS) A4 specifications (210X297 mm) {Read the precautions on the back before filling in this page j -β Government · 410214 A7 B7 V. Description of the invention (7) The rate is, for example, more than 130 A / second, and in a preferred embodiment more than 250 A / second, a tin and oxin coating deposited on hot glass is produced. The deposition rate is related to the use of specific oxygen-containing organic compounds, the concentration of organic oxygenates and metal vapors, and the glass temperature. For any specific compound combination, the best concentration for rapid coating deposition (especially) the optimal ratio and flow rate of organic oxygenates to metal tetrachloride can be obtained through simple experiments, but it is important to understand the use of higher concentrations of reactants and High gas flow rates may result in lower overall conversion efficiency of reactants to coatings, so the optimal conditions for commercial operations may differ from the highest deposition rates that can be obtained. It is preferable that the concentration of the organic oxide-containing compound is about 0.5 to 1 to 5 times the volume-to-volume concentration of the metal tetragas in terms of volume. Often used at least 30% by weight of the weight of the metal vapor. The method of the present invention can produce titanium oxide and tin oxide coatings on a glass substrate during the glass production process at a high speed on a hot flat glass substrate. The titanium oxide coating can be produced with a high refractive index (at least 14) to achieve the required Optical effects, especially when combined with other coatings. Tin oxide coatings can be doped with, for example, doped with fluorine 'by mixing appropriate dopant precursors into the precursor gas mixture' to increase the coating's electrical conductivity and infrared light reflectance, so it can be used as architectural glazing and other uses as a conductive coating Layer and / or low-emissivity coating. Brief description of the above and other advantages of the present invention will be made clear to those skilled in the art from the following detailed specific examples and will be apparent in view of the accompanying considerations. In the drawings: Applicable to China's Family Standard (&^; 5) 8-4 specifications (210 father 297 mm) (Please read the precautions on the back before filling this page) Ding _3 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 10 41Q2U at _____ B7 V. Description of the invention (8) Figure 1 is a schematic vertical sectional view of a device for implementing a floating glass process. The device includes a gas distributor that is appropriately arranged and can be used to implement the method of the present invention. Figure 2 is based on this An exploded cross-sectional view of an object coated by the invention; FIG. 3 is an enlarged schematic end view of a gas distribution beam suitable for implementing the present invention; and FIG. 4 is another view suitable for implementing the present invention An enlarged schematic end view of a gas distribution beam. The enlarged schematic end view will now be described in particular with reference to Figures 1 to 10 of the accompanying drawings. A floating glass device used as a means of implementing the method of the present invention "a floating glass device specifically includes a channel section 12 ' The molten glass 14 is conveyed along this channel section by a furnace (not shown) to a floating surface bath section 16, wherein a well-known floating surface method forms a continuous glass ribbon 18. The glass ribbon 18 is advanced from the bath section 16 through the adjacent annealing kiln 2. And cooling section 22. A continuous glass ribbon 18 is used as a substrate on which the metal oxide coating according to the invention is deposited. The floating surface section 16 comprises a bottom section 24, which contains molten tin inside. Bath 26 The top 28 is opposite to the side wall 30 and the end wall 32. Item 28 The side wall 30 and the end wall 32 are printed by the Consumers ’Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling this page). The non-oxidizing atmosphere is maintained to prevent the molten tin from being oxidized. In addition, the gas distributor beams 64, 66, and 68 are located in the bath section 16. The gas Zhao distributor gas beams 60 and 66 in the bath section are used to apply the method of the present invention. Apply an additional coating to the substrate before tin or zinc oxide. The β additional coating contains Shi Xi and fumed silicon. This paper size applies to China National Standards (CNS) A4 (210X297 mm) 11 Central Bureau of Standards, Ministry of Economic Affairs A7 B7_ printed by employee consumer cooperatives V. Description of the invention (9) During operation, the molten glass shall flow down the surface of the tin bath 26 along the channel 36 below the regulating gate 38 to the tin bath 26. The molten glass above the tin bath is subject to gravity and surface tension And certain mechanical influences affect the lateral deployment, advance across the bath to form a belt 18, and the belt is moved on the take-up roller 40 and then conveyed through the annealing kiln 20 and the cooling section 22 on the alignment roller 42. The application of the coating of the present invention can be performed in the floating surface bath section 16 or along the production line, for example, in the gap between the floating surface bath and the annealing kiln or in the annealing kiln. Appropriate non-oxidizing gas disturbance is usually gas or the oxide of atmosphere and gas, and most of it is maintained inside the bath enclosure 34 to prevent oxidation of the tin bath. The atmosphere gas passes through a conduit 44 operatively coupled to a distribution manifold 46. The non-oxidizing gas is sufficient to compensate for the normal loss and is maintained at a slightly positive pressure, which is introduced at a rate of about 0.001 to 0.01 atmospheres higher than the ambient pressure so that the infiltration of the outside atmosphere can be prevented. The heat that maintains the tin bath 26 and the enclosure 24 at the required temperature is provided by the radiant heater 48 inside the enclosure. The interior atmosphere of the beta annealing kiln 20 is typically the atmosphere, and the cooling section 22 is not closed. The glass ribbon is opened to the surrounding area. The ambient air can be guided to the glass ribbon by the cooling section fan 50, for example. A heater (not shown) may also be provided inside the annealing kiln to allow the glass ribbon temperature to slowly decrease as the glass ribbon is conveyed through it. Figure 1 illustrates the use of gas vessel distributor beams 64, 66, and 68 on a floating surface bath 16 to deposit various coatings on a glass ribbon substrate. The gas distributor beam is a type of reactor that can be used to implement the method of the present invention. A convenient structure of a dispenser beam suitable for supplying precursor materials according to the present invention is schematically illustrated in the third figure. The upside-down outline channel-shaped skeleton 70 formed by the spaced inner and outer walls 72 and 74 defines closed cavities 76 and 78. Appropriate heat exchange media follow the Chinese paper standard (CNS) Α4 specification (2! 0 χ 297 mm) 12 (Please read it first. Please note on the back before filling out this page), 1 Μ Central Ministry of Economic Affairs Printed by the Bureau of Standardization and Shellfish Consumer Cooperatives 410214 A7 ___B7 _____ V. Description of the Invention (i〇) The ring passes through the closed holes 76, 78 to maintain the distribution gas beam at the required temperature. The precursor gas radon mixture is supplied through a supply line 80 when the fluid is cooled. The supply pipe 80 extends along the distribution gas beam and contains the gas sent from the drip pipe 80 separated from the supply pipe. The supply line 80 advances to a transfer chamber 84 inside the outcrop 86 carried by the skeleton. The precursor gas received through the drip line 82 is discharged from the conveying chamber 84 through the passage 88 toward the coating chamber. The coating chamber defines a vapor space opening above the glass, and flows here along the surface of the glass 18 in the direction shown by the arrow in FIG. 3. . The baffle 90 may be provided inside the conveying chamber 84 to balance the precursor material flowing across the distributor beam to ensure that each material is discharged to the glass 18 across the entire distribution gas beam in a smooth laminar and balanced flow. The used precursor materials are collected and discharged along the side of the distribution gas beam through the discharge chamber 92. All types of distributor beams for chemical vapor deposition are suitable for this method and are known in the prior art. One alternative dispenser beam structure is illustrated schematically in Figure 4 of the accompanying drawings. Using this type of dispenser (shown generally as 100, more fully described in European Patent 03 05 102B), the precursor gas mixture is passed through the gas supply pipe 101, where the fluid circulating through the pipes 102 and 103 is used to cool the β gas vessel. The supply conduit 101 opens into the gas flow restrictor 105 via an elongated orifice 104. The gas flow restrictor 105 is described more fully in the British Patent Specification} 507 'This type includes a plurality of metal strips which are sinusoidal in shape along the entire longitudinal direction and are vertically installed in abutting relationship with each other along the length of the dispenser. Adjacent metal strips are arranged "out of phase" with multiple vertical channels defined between them. The cross-sectional area of the vertical channel is smaller than the cross-sectional area of the gas supply duct 101, so the Chinese paper standard (CNS) A4 size (210X297 male " ----- -13-- --- „-------------- ir ------ Μ (please read the notes on the back before filling in this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 410214 A7 ~ -------- B7 V. Description of the invention (U) The direction of gas pressure in the direction of U is released by the gas flow restrictor 105. The coated gas is released by the gas flow restrictor U-shaped guide The guide channel (the inlet side is roughly marked as _10, the guide channel contains the entrance foot, the coating chamber H > 8 is open and the hot glass substrate iu to be coated), and the discharge foot 10 is used for this purpose. The passing coating gas is withdrawn from the glass. The rounded corners of the stele block defining the coating channel can promote a uniform laminar flow of the coating across the glass surface to be coated parallel to the glass surface. The following example (where the gas volume is under standard conditions) Labeled, and unless otherwise stated, are at atmospheric pressure and ambient temperature for further illustration and monitoring of the invention but are by no means intended to limit the invention Examples 1 to 5 In these examples, a two-way coating reactor of the type shown in Fig. 3 was used in a laboratory to deposit a titanium oxide coating. In Examples 1, 2 and 3, the breakage was heated on the conveyor belt as above The coating reaction conditions of the floating glass process are simulated, and the method of the present invention is tested. For example, the glass substrate is transported through the heating section before the method of the present invention is carried out online. Coated floating glass. A silicon oxide coating is deposited on floating glass using a single silane precursor in a hafnium-rich atmosphere via a known chemical vapor deposition method. Silicon oxide deposition forms part of the present invention β A titanium oxide coating according to the present invention Deposited on oxidized sand-coated substrate. The substrate is at 1170 ° F / 630 ° C and the linear velocity of the substrate is 300 inches / 8 m / min. To deposit titanium oxide, develop a titanium oxide 2. The paper size of ethyl acetate is applicable to China Standards (CNS) A4 (2 丨 0X297mm) 14 ----.--.--- ^ 襞 -------, 17-- ---- Μ I. (Please read the back; please fill in this page before I) 410214 A7 B7 Explanation (12), β and helium precursor gas mixture β helium is contained in the precursor mixture as a carrier gas for the reactant. The precursor mixture is prepared by simultaneously introducing four gas streams through a single manifold system to prepare a static mixture on the β line. Ensure a homogeneous precursor mixture. The volume percentage of the precursor mixture is 07% titanium tetragas, 17.2% ethyl acetate, 7.2% oxygen, and 74.9% helium. The flow rates of the components in the manifold are shown in Appendix 1. Temperature of the precursor mixture Maintain above 300 ° f / 150 ° C to prevent the addition reaction of titanium tetragas to ethyl acetate. The precursor temperature is also maintained below the thermal decomposition temperature range of ethyl acetate of 950T-1130eF (510 ° 〇61 (TC) to prevent the mixture from reacting prematurely. The precursor mixture is introduced into the reactor just above the moving substrate β. The temperature of the precursor tower is 250 ° F / 120 °. The temperature of the reactor surface is 350 F / 175 C. The higher temperature of the substrate causes the thermal decomposition of ethyl acetate and then causes the deposition of titanium oxide. The coated glass printed by the consumer cooperative was cooled in the air and the coating was analyzed. It was found that the titanium content of the titanium oxide was 2.5 · 3.5 · 5 atoms. "" The thickness of the titanium oxide coating was measured to be 490 Å and the thickness And the growth rate (150A / sec) is shown in Table i. The optical properties of the obtained product include the observed value of the illuminant C transmittance (10. observation) 623. The observed value of the illuminant reflectance 35.6% »The extinction coefficient at 500nm is 0.008, and the refractive index of the titanium oxide coating is 2,44. Examples 2 and 3 repeat the coating process stated in Example 1, but Example 2 uses ethyl formate as the organic source of oxygen and Example 3 uses isopropanol as the organic source. Organic sources of oxygen and use of uncoated glass (replacement The silicon oxide-coated glass of Examples 1 and 2) was used as the substrate. The gas flow rate and the titanium oxide 15 produced in the example of Example 2 were used (please read the precautions on the back before filling this page). C »S) 8 size (210X 2 ^ 7 mm) Du Yint, Central Government Bureau of Ministry of Economic Affairs, Consumer Cooperation Du 410 214 A7 B7 ____ 5. Description of the invention (13) The thickness and growth rate of the compound coating are shown in Table 1. In Example 3, the combustion of isopropanol in the reactor left only the granular titanium oxide on the glass, so the corresponding deposition rate was quoted as 0 A / sec. The procedures of Examples 4 and 5 are the same as the previous examples (reactor temperature and temperature). The material is the same as Example 1), but the substrate is static rather than dynamic. The static sample is placed in the reactor for 10 seconds. Under static conditions, the residence time of the substrate in the reactor is increased by a factor of 5. Compared with the dynamic condition, Example 4 is used for methyl acetate. As the source of organic oxygen, Example 5 used n-butyl acetate; titanium oxide coatings were produced in each example. The gas flow rate, the thickness of the obtained Qin oxide coating, and the growth rate of the coating are shown in the table. Growth was achieved using methyl acetate. The rate is relatively slow. Example 6 The float glass process is used to produce a continuous glass ribbon of 0.125 inches / 3 mm at a number of 434 inches / 11 meters / minute on the line. The glass breaking temperature is at the desired application point of the titanium oxide coating section of the float surface bath. The layer reactor is similar to that shown in Figure 3. The precursor tower temperature is 400 ° f / 205 ° C and the reactor surface temperature is 500 ° F / 260 ° C. The silicon oxide coating is applied to a floating surface bath before implementing the method of the present invention. The layer deposited on the glass substrate was about 339 people thick. The chemical vapor deposition method as described in Example I was used to deposit a silicon oxide coating. The deposition of silicon oxide did not form part of the present invention. The development of a precursor gas mixture included four gasification Titanium and ethyl acetate in a helium carrier gas. No oxygen was used for the precursor, as the results of previous examples indicate that the coating reaction is not sensitive to oxygen concentration. The precursor mixture is prepared by introducing three components simultaneously through a manifold system. The volume of the precursor mixture is grouped into 06% of the four-gauge paper ruler. Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling out this page) Order M- 16 410214 A7 B7_______ 5. Description of the invention (14) Titanium oxide, 1.8% ethyl acetate and 97.5 ° /. helium. The component flow rates were 480.0 1 / m helium, 3.0 1 / m titanium tetragas, and 9.2 1 / m ethyl acetate. The precursor mixture seed flow rate was 492.2 l / m. The resulting titanium oxide coating had a thickness of 684A. The carbon content of the coating is less than 2 atomic%. The coating growth rate was 309A per second. Example 7 The procedure of Example 6 is used in this example. The substrate includes a silicon coating and then silicon oxide on a glass substrate. The coating is deposited in the floating bath section by chemical vapor deposition. The silicon coating is deposited by mono-silane and non-oxidizing carrier gas by CVD. A silicon oxide coating was then deposited on the silicon coating using the same procedure as in Example 1. Titanium oxide coating precursors include titanium tetraoxide and ethyl acetate in a helium carrier gas. The volume percentage of the precursors was 0.5 ° /. Tetragas titanium, 1.9% ethyl acetate and 97.6% helium. The corresponding flow rate of each component is 48.0 I / m helium, 2.4 1 / m titanium tetragas, and 9.2 1 / m ethyl acetate. The seed mixture flow rate was 491.6 l / m. The resulting coating 52 is exemplified in Section 2A. The glass substrate 54 is illustrated with a stack of multilayer coatings 56. The coating includes a layer of silicon 58, a layer of oxidized stone, and then a layer of titanium oxide 62 on top of the object. The optical properties of the coating stack obtained when the thickness of the anodic oxide coating on the top of the obtained object was 836A β included the observed value of illuminant C transmittance of 13.1 ° /. Observed c reflectance before illuminator 82.5% »The growth rate of titanium oxide coating was 378 persons / second. This paper size applies the Chinese National Standard (CNS) Α4 size (210X297 mm) (Please read the precautions on the back before filling this page) Ordered by the Central Standard of the Ministry of Economic Affairs Printed by Shellfish Consumer Cooperative 17 ^ l〇2l4 A7- ------- —_B7 V. Explanation of the invention (15) Table 1 Flow rate of T example (liters / minute) Titanium organic oxide compound oxygen helium thickness A Growth rate A / second 1 0.2 4,8 Ethyl acetate 2.0 20.9 490 150 2 0.5 1.6 Ethyl formate 6.0 17.4 800 250 3 0, 45 Isopropanol 4.0 15.45 0 0 4 0.5 L2 Methyl acetate 6.0 17.4 < 100 < 10 5 0.5 〇_5 tert-butyl acetate 6.0 16.5 1300 130 Examples 8 to 13 (Please read the notes on the back before filling this page} In these examples, a static coater is used in a laboratory to apply a tin oxide coating as described in European Patent EP 0275 662B Produced with color-repressed silicon oxide coating on floating glass substrate β The floating glass to be coated is supported on the nickel tablet of the reaction vessel, and the tablet is gradually heated by the electric heat source below to provide a temperature of 1085 «F / 585 ^ .A flat graphite plate is mounted about 0.4 inches / 10 mm above the glass and The gas passing between the glass surface carrying the silicidation layer and the flat plate is passed through to a depth of 4 inches / 10 mm. Contains four gaseous tin and organic oxygen sourced from air and a small proportion of additional nitrogen before the surrounding carrier gas The purge vessel mixture is transported through a gas pipeline maintained at a temperature of 435 卞 ± 25 卞 / 225 ° C ± 15 ° C and is provided with a fishtail nozzle opening parallel to the general direction of the glass surface and the gas flow path above the hot glass. Total load The air flow rate is 13 m3 / h. The flow rate of tin tetraoxide and the properties and velocity of organic compounds are shown on the paper scale. Applicable to China National Standard (CNS) A4 specification (210 × Ϊ97 stitches) ~~-
1T 經濟部中夬標準局員工消費合作社印装 410214 A7 ____B7 五、發明説明（16) 附表2。實例9至U中小量40%氟化氩挽混於前驅氣體混合 物而使所得錫氧化物塗層攙雜氟，如表所示。 含反應物氣體之氣體流供應約8秒，然後使塗覆裝置 機塗覆妥的玻璃於345T/2251之空氣流下方冷卻。拆卸 塗覆裝置時輸送氣體管路喷嘴及界定破璃上方氣體流徑的 平板於各例中皆不含沈積物’指示不存在有非期望的預先 反應。各例中玻璃含有錫氧化物塗層施用於矽氡化物上方 而塗層厚度隨距離魚尾喷嘴的距離改變，各前驅氣體混合 物之最大厚度及對應生長速率示於表2。使用氟化氫攙混 氟纔雜劑（實例9及11)生產樣品之發射率、電阻率、及、、蜀 度經測量而結果報告於表2。 本系列實例顯示有機氧來源可作為包括四氣化錫之預 混之前驅氣體混合物來沈積踢氧化物塗層而無對塗覆過程 具有有害影響之非期望預反應，例如錫氧化物沈積於供氣 導管。此外若有所需攙雜劑來源例如氟化氩可攙混於氣態 預混合物來降低塗層的發射率及電阻率同時仍可避免顯著 有害預反應。 實例14 經濟部中央橾準局员工消费合作社印製 本實例中第4圖示意說明之塗層配送氣用於浮面浴藉 本發明方法施用錫氧化物塗層。帶速度為約莓分鐘233吋 /每小時350米及玻璃厚度為〇.〇5吋/1.2毫米。玻璃溫度 為約1170°F/630°C。作為主要氣體混合室之供氣導管101 之溫度維持於300T/150°C，而靜態圓餅形氣體配送器105 之溫度為約645°F/340eC。四氣化錫及乙酸丁酯蒸氣經由 19 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度逋用中國國家標率（CNS ) A4規格（210X297公釐） 410214 at B7 五、發明説明（17) 於冒泡器將氮氣通過維持於175°F/80°C之液體輸送，如 此通過各別加熱的導管輸送至供氣導管101。蒸氣於主要 室混合，通過圓餅形包氣體配送器然後於成流條件下通過 U字型導引通道106，該通道包括塗層室108開口於熱玻璃 帶上。 (請先閱讀背面之注意事項再填寫本頁) 丁 -5 經濟部中央標準局員工消費合作社印製 20 本紙張尺度適用中國國家標準（CNS ) A4規格（2【〇Χ297公釐） 410214 A7 B7五、發明説明（IS) 13 10 11 12 ί 17 12 12 12 12 6 snp (ml/min) π=命芽 C*瘅(>舔 6瘅7-溫 0*漭 Tsi加^溫 16·2 (Tnl/min) 10 ο 13.4 13.4 120 1.3 so ΚΜ- (ml/ min) (請先閱讀背面之注意事項再填寫本頁) 2840 2750 2680 3460 2380 2284 ^命聲 k 335 344 335 432 360 262 S hs' 經濟部中央榡隼局員工消費合作社印製 Ρ251T Printed by the Consumers' Cooperative of Zhongli Standards Bureau of the Ministry of Economic Affairs 410214 A7 ____B7 V. Description of Invention (16) Schedule 2. In Examples 9 to U, a small amount of 40% argon fluoride was mixed with the precursor gas mixture so that the resulting tin oxide coating was doped with fluorine, as shown in the table. A gas stream containing the reactant gas is supplied for about 8 seconds, and then the coated glass is cooled by the coating device under the air stream of 345T / 2251. When the coating device was disassembled, the nozzle of the conveying gas pipeline and the plate defining the gas flow path above the broken glass did not contain deposits in each case ', indicating that there was no undesired pre-reaction. In each example, the glass contains a tin oxide coating applied on top of the silicide, and the coating thickness varies with the distance from the fish tail nozzle. The maximum thickness of each precursor gas mixture and the corresponding growth rate are shown in Table 2. The emissivity, resistivity, and degree of measurement of the samples produced using hydrogen fluoride mixed with a fluorine compound (Examples 9 and 11) are reported in Table 2. This series of examples shows that organic oxygen sources can be used as a premixed precursor gas mixture including four gaseous tin to deposit kick oxide coatings without undesired pre-reactions that have a detrimental effect on the coating process, such as tin oxide deposited on a supply Air duct. In addition, if a source of desired dopants such as argon fluoride can be blended with the gaseous premix to reduce the emissivity and resistivity of the coating while still avoiding significant harmful pre-reactions. Example 14 Printed by the Consumer Cooperative of the Central Bureau of Standards and Commerce of the Ministry of Economic Affairs The coating distribution gas illustrated in Figure 4 of this example is used in a floating bath. The method of the present invention applies a tin oxide coating. The belt speed was about 233 inches per minute / 350 meters per hour and the glass thickness was 0.05 inches / 1.2 mm. The glass temperature is approximately 1170 ° F / 630 ° C. The temperature of the gas supply duct 101, which is the main gas mixing chamber, is maintained at 300T / 150 ° C, while the temperature of the static disc-shaped gas distributor 105 is about 645 ° F / 340eC. Four gasification tin and butyl acetate vapor via 19 (Please read the notes on the back before filling in this page) This paper uses China National Standard (CNS) A4 size (210X297 mm) 410214 at B7 V. Description of the invention (17) Nitrogen is transported through the liquid maintained at 175 ° F / 80 ° C in the bubbler, and then transported to the air supply duct 101 through the respective heated ducts. The vapours are mixed in the main chamber, passed through a circular cake-shaped gas distributor, and then pass through a U-shaped guide channel 106 under flow conditions. The channel includes a coating chamber 108 opening in a hot glass ribbon. (Please read the notes on the back before filling out this page) Ding-5 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 20 This paper size is applicable to Chinese National Standard (CNS) A4 specifications (2 [〇 × 297 mm) 410214 A7 B7 V. Description of the invention (IS) 13 10 11 12 ί 17 12 12 12 12 6 snp (ml / min) π = life bud C * 瘅 (> lick 6 瘅 7- 温 0 * 漭 Tsi 加 ^ 温 16 · 2 (Tnl / min) 10 ο 13.4 13.4 120 1.3 so KM- (ml / min) (Please read the notes on the back before filling in this page) 2840 2750 2680 3460 2380 2284 ^ Sound k 335 344 335 432 360 262 S hs '' Printed by the Consumer Affairs Cooperative of the Central Government Bureau of the Ministry of Economic Affairs P25
6.9 XOL 0¾ Ρ256.9 XOL 0¾ Ρ25
5.3 x 1CT p4sa0 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） ohm/cm 遍ίϊ& 21 經濟部中央標準局貝工消费合作社印製 410214 A7 _______B7___ 五、發明説明（19) 使用的流速足夠獲得四氣化錫：乙酸丁酯莫耳比1 : 1 至1 : 5。試驗進行5小時。拆下塗覆機之前發現冷卻面上 及相關導管有超過9〇°/c不含沈積物，如此顯示四氣化錫與 乙酸丁酯用於玻璃上生產二氧化矽塗層時可彼此預先混合 而大趙未出現預反應。薄錫氧化物塗層是於玻璃帶上獲得5.3 x 1CT p4sa0 This paper size applies to Chinese National Standard (CNS) Α4 size (210X297 mm) ohm / cm ϊ ϊ & 21 Printed by Shellfish Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs 410214 A7 _______B7___ V. Description of the invention (19) Use The flow rate is sufficient to obtain a tin tetragas: butyl acetate molar ratio of 1: 1 to 1: 5. The test was conducted for 5 hours. Before removing the coating machine, it was found that more than 90 ° / c of the cooling surface and related ducts were free of deposits. This shows that tin tetraoxide and butyl acetate can be pre-mixed with each other when used to produce a silicon dioxide coating on glass. There was no pre-response for Da Zhao. Thin tin oxide coatings are obtained on glass ribbons
Q 據了解由先前各例敘述本發明之細節可做出多種變化 及修改而未背離如隨附之申請專利範圍界上之精髓及範圍 。重要細節中本發明為一種經由使用對應金屬四氮化物及 有機化合物作為氧來源呈預先形成的前驅氣體混合物而以 高沈積速率於玻璃基材上舖設錫氧化物及鈦氧化物塗層及 連續化學蒸氣沈積方法。 金屬四氣化物由於易得且原料成本低，故為個別金屬 之較佳來源。 發現特別當由四氣化鈦沈積鈦氡化物塗層時，欲以最 佳沈積速率形成金屬氧化物，需要使用有機含氧化合物’ 其為酯特別為其中衍生自醇之基為含一個沒氫之烷基之酯 。如此酯之分解溫度不可高於於期望施用點塗覆前驅氣體 混合物之反應溫度〇於前驅氣體混合物使用的酯含有一個 万氫而適當分解溫度卻可以高沈積速率沈積塗層。用於實 施本發明之較佳酯包含甲酸乙酯、乙酸乙酯、丙酸乙酯、 甲酸異丙酯、乙酸異丙酯、乙酸正丁酯、乙酸第三丁酯。 通常酯是以連續方式於特定溫度範圍分解β本發明中 酿之熱分解溫度定義為單分子酯分解速率常數為0.01/秒 本紙張歧逋用中國固家橾準（CNS )从胁（21()χ 297公们 (請先聞讀背面之注意事項再填寫本頁} 丁 -a 經濟部中失棣準局負工消费合作社印裂 410214 A7 ______B7_____ 五、發明説明（2〇) 之溫度。常見酯如乙酸乙酯及乙酸第三丁酯之單分子分解 速率常數為眾所周知（鑑於化學參考文獻）。對乙酸乙酯及 已酸第三丁酯而言使前述定義之熱分解溫度分別為935V 及650°F(500°C及344。〇。業界人士 了解酯及特定沈積溫 度的選擇可決定最佳塗層生長速率β低於界定的熱反應溫 度但於特選酯之分解溫度範圍以内的反應溫度將導致塗層 生長速率下降。 根據本發明塗層前驅物氣體混合物使用之酯之烷基可 為含2-10個碳原子之碳化合物。範圍之下限是由烷基上的 泠氫需求指示。上限則為避免烷基含多於10個碳原子時造 成可燃性及揮發性" 實施本發明方法時可使用歧管連接並調節個別氣體流 而配方塗層前驅氣鱧混合物。常用輸送管路可用來由歧管 輸送前驅氣體混合物至氣體梁配送器。線上靜態混合機可 用於輸送管路確保均質氣體混合物。此外第3圖示例說明 之氣體配送器梁内的擋板或第4圖敘述之氣體流約束器可 於反應器階段提供前驅氣體的進一步混合。 許多實例中氧包含於塗層前驅氣體混合物《但金屬氧 化物塗層之沈積速率對氧濃度不敏感，實例6或7會使用氧 氣體形式無需包含氧。 塗層前驅氣艘混合物之反應性成分濃度可經選擇獲得 最佳塗層生長速率。金屬四氣化物濃度於前驅氣體混合物 通常為0.1至5_0 ν%。金屬四氯化物濃度是基於可得停留 時間内提供所需塗層厚度需要的金屬量β如此金屬四氣化 本紙張尺度適用中國國家橾準（CNS ) Α4規格（2丨0X297公釐） 23 (請先閲讀背面之注意事項再填寫本頁) 訂 Μ. 經濟部中央標準局負工消费合作杜印策 410214 五、發明説明（21) 物濃度是根據製程變數如帶於浮面玻璃製程之線性速度調 整。 塗層前驅氣體混合物内有機氧化合物濃度通常為金屬 四氣化物濃度之1至5倍，基於沈積時間而於此範圍内選用 °使用酯時較低沈積溫度導致酯沈積速率較慢，因此需要 較南濃度酯來與金屬四氣化物反應。實例6及7中前驅氣體 混合物内之乙酸乙酯最佳濃度為四氣化鈦濃度之丨至3倍。 高於或低於最佳範圍之濃度可於較低塗層生長速率生 產金屬氧化物塗層。 前驅氣體混合物溫度對反應之控制相當要緊，特別避 免非期望的預反應或加合物形成結果導致於前驅物管路生 成非揮發性產物。較佳具體例中特別使用酯時前驅氣體管 路溫度維持高於300°F/150°C。前驅氣體混合物亦較佳維 持低於有機氧化合物之熱分解溫度以防混合物預反應。 本發明方法利用得自基材之熱量來引發塗覆反應。線 上情況下例如浮面玻璃製程，基材是於極高溫形成。因此 本發明方法可應用於洋面玻璃製程之一點，於此點基材溫 度下降但仍然高於塗層之形成溫度較佳於玻璃已經大體完 成拉幅之後亦即低於1380°F/750eC »離線應用本發明需 要基材加熱酯高於酯分解溫度之溫度。 於浮面玻璃法實施本發明方法，較佳施用點是於浮面 浴區段。塗層施用點之溫度範圍通常約U〇〇〇_132〇T/ 590°-715°C。溫度為主要操作參數，原因為其影響前驅氣 體混合物使用的有機化合物濃度。浮面浴區段之基材溫度 本紙張尺度通用中國國家標车（CNS ) Μ規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂 24 經濟部中央標率局負工消費合作社印策 41〇2j^ A7 ---—__B7_ 五、發明説明（22) 相當穩定因此於施用點極少變化。實例6及7使用乙酸乙醋 時較佳基材溫度範圍為1100。-1250下/590。-680。(：。 來自基材之熱量升高前驅氣體混合物溫度至高於塗層 形成所需溫度（而當酯用作有機化合物時高於酯之熱分解 溫度）。金屬沈積反應可經由有機氧化合物分解引發。當 四氣化欽於具有一個含卢氫之烷基之酯合併使用時，鈦氧 化物塗層於基材上形成而分解速率比較一致塗層方法高 倍。使用浮面玻璃帶製程於線上施用時帶以相當快速率通 過氣體配送氣梁下方。金屬氧化物塗層於帶通過塗覆機下 方時沈積於浮面玻璃帶上》 發明人提出下述理論有關使用具有一個含万氫之烷基 之酯時可能進行的化學反應。但發明人並不希望將本發明 限制於此種可能的解釋，因此僅提供作為輔助了解本發明 方法結果。 發明人提示當S旨分解時石氫上的碳-氮鍵斷裂而氫轉 移至羰基消除烯，形成硝酸。同時硝酸與金屬四氣化物進 行水解反應，結果導致於基材上形成金屬氧化物塗層。 概略而言，根據本發明的生產的物件包括一個具有鈦 氧化物或錫氧化物之基材。塗層可直接施用於基材或作為 基材上方多層塗層之一層。金屬氧化物塗層之沈積速率受 有機氧化合物之沈積速率影響》於穩定反應溫度不同有機 氧化合物可提供不同塗層生長速率，原因為分解溫度不同 之故。因此，特定系統之期望金屬氧化物塗層生長速率是 經由使用特定有機氧化合物匹配於施用點之前联氣體溫度 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公 25 ----^k 裝-----_——------d (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標隼局貝工消費合作杜印製 4 ⑽ 14 B7 五、發明説明（23) 及基材溫度選定。 本發明之鈦氧化物塗層分解速率可比較已知沈積方法 之速率高10倍。本發明方法可使沈積速率超過每粆130 A 而某些沈積速率遠超過每秒300A。鈦氧化物之沈積速率 與高獲得具有折射指數大約2.4之塗層》 除了可達成高塗覆速率之外，本發明之又一優點為其 使用低成本金屬前驅物化合物，特別當前驅氣體混合物於 較佳成流條件下導引至基材上時可達成高轉化效率（金屬 四氣化物之轉化）。 本發明中所得氧化物塗層含極少含有來自有機氧化物 之殘破，特別當使用s旨時尤為如此。破為塗覆反應之非期 望副產物，原因為沈積塗層内之高濃度碳導致塗層吸收問 題。有機氧化合物用於塗層前驅氣體混合物之擔憂為分解 所得碳濃度可能對玻璃成品的吸收性質產生不良影響"由 本發明方法生產塗層内之碳含量顯示低於4原子％碳。此 種低濃度碳不會顯著影響塗層之吸收性質。 據了解此處顯示及敘述之本發明態樣僅作為示例說明 性具體例’可對物件形狀、尺寸之配置做出多種變化以及 多種製程變化而未背離本發明之精髓。 本紙張尺度適用中國國家橾準（CNS ) A4規格（210X297公釐） (諳先聞讀背面之注意事項再填寫本頁) .η 26 A7 B7 經濟部中央橾準局負工消費合作社印製 410214 五、發明説明（24) 元件標號對照 10... .浮面玻璃裝置 52,…塗覆件 12... .通道區段 54....玻璃基材 14... .嫁融玻璃 56....—堆多層塗層 16... .洋面浴區段 58....矽層 18... .玻璃帶 60.…氧化矽層 20... .退火窯 62·...鈦氧化物塗層 22... .冷卻區段 64-68,,..氣體配送器梁 24....底區段 70....骨架 26... .熔融錫浴 72.…内壁 28... 頂 74....外壁 30... .側壁 76，78.…封閉穴 32... .端壁 80.…流體冷卻式供應導管 34... .浴包圍體 82....滴落管路 36... .通道 84....輸送室 38... .調節閘門 86.…露頭碑 40... .舉出輥 88... .1¾ 42... •輥 90....擋板 44... .導管 92....排放室 46... .分布歧管 100....配送器 48," .輻射加熱器 101 .…供氣導管 50... .風扇 102-3....導管 (請先鬩讀背面之注意事項再填寫本頁)Q It is understood that the details of the present invention described in the previous examples can be variously changed and modified without departing from the spirit and scope of the scope of patent application as attached. In important details, the present invention is a method for laying tin oxide and titanium oxide coatings on glass substrates at high deposition rates and continuous chemistry by using pre-formed precursor gas mixtures using corresponding metal tetranitrides and organic compounds as oxygen sources. Vapor deposition method. Metal tetragases are a better source of individual metals due to their availability and low raw material costs. It was found that, especially when depositing a titanium halide coating from tetra-titanium titanium, in order to form a metal oxide at an optimal deposition rate, an organic oxygenate is needed ', which is an ester, in particular a group derived from an alcohol, which contains a hydrogen atom. An alkyl ester. The decomposition temperature of the ester should not be higher than the reaction temperature at which the precursor gas mixture is applied at the desired point of application. The ester used in the precursor gas mixture contains one million hydrogen and the appropriate decomposition temperature can deposit the coating at a high deposition rate. Preferred esters for use in the practice of the present invention include ethyl formate, ethyl acetate, ethyl propionate, isopropyl formate, isopropyl acetate, n-butyl acetate, and third butyl acetate. The ester is usually decomposed in a continuous manner in a specific temperature range. The thermal decomposition temperature in the present invention is defined as a single molecular ester decomposition rate constant of 0.01 / sec. This paper is classified using CNS from China (21 ( ) χ 297 (please read the precautions on the back before filling out this page) Ding-a The Ministry of Economic Affairs, the Bureau of Work and Consumer Cooperatives of the Ministry of Economic Affairs 410214 A7 ______B7_____ 5. The temperature of the invention description (2〇). Common The single-molecule decomposition rate constants of esters such as ethyl acetate and third butyl acetate are well known (in view of chemical references). For ethyl acetate and third butyl caprylate, the thermal decomposition temperatures defined above are 935 V and 650 ° F (500 ° C and 344 °. Industry insiders understand that the choice of ester and specific deposition temperature can determine the optimal coating growth rate β below the defined thermal reaction temperature but within the decomposition temperature range of the selected ester. The growth rate of the coating will be reduced. The alkyl group of the ester used in the gas mixture of the coating precursor according to the present invention may be a carbon compound containing 2 to 10 carbon atoms. The lower limit of the range is the requirement of hydrogen on the alkyl group. The upper limit is to avoid flammability and volatility when the alkyl group contains more than 10 carbon atoms. "When implementing the method of the present invention, a manifold can be used to adjust and adjust individual gas flows to formulate the coating gas precursor mixture. Commonly used transportation The pipeline can be used to transport the precursor gas mixture from the manifold to the gas beam distributor. The on-line static mixer can be used to transport the pipeline to ensure a homogeneous gas mixture. In addition, the baffle in the gas distributor beam or the fourth The gas flow restrictor described in the figure can provide further mixing of the precursor gas in the reactor stage. In many examples, oxygen is contained in the coating precursor gas mixture, but the deposition rate of the metal oxide coating is not sensitive to the oxygen concentration, examples 6 or 7 The form of oxygen gas is used and does not need to contain oxygen. The reactive component concentration of the coating precursor gas mixture can be selected to obtain the optimal coating growth rate. The concentration of metal tetragas in the precursor gas mixture is usually 0.1 to 5_0 ν%. Metal 4 The chloride concentration is based on the amount of metal required to provide the required coating thickness within the available residence time. Applicable to China National Standards (CNS) Α4 specifications (2 丨 0X297 mm) 23 (Please read the notes on the back before filling this page) Order M. Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperation Du Yince 410214 V. Description of the invention (21) The substance concentration is adjusted according to the process variables such as the linear speed of the float glass process. The concentration of the organic oxygen compound in the coating precursor gas mixture is usually 1 to 5 times the concentration of the metal tetragas. In this range, the lower deposition temperature when using esters results in a slower ester deposition rate. Therefore, the souther concentration of the ester is required to react with the metal tetragas. The optimal concentration of ethyl acetate in the precursor gas mixture in Examples 6 and 7 is Tetragas titanium concentration is three to three times. Concentrations above or below the optimal range can produce metal oxide coatings at lower coating growth rates. The control of the temperature of the precursor gas mixture is quite important to control the reaction, in particular to avoid undesired pre-reactions or adduct formation results in the formation of non-volatile products in the precursor pipeline. In the preferred embodiment, when the ester is used, the temperature of the precursor gas pipeline is maintained above 300 ° F / 150 ° C. The precursor gas mixture is also preferably kept below the thermal decomposition temperature of the organic oxygen compound to prevent the mixture from pre-reacting. The method of the present invention utilizes heat from a substrate to initiate a coating reaction. In the case of an on-line process such as a float glass process, the substrate is formed at extremely high temperatures. Therefore, the method of the present invention can be applied to a point in the manufacturing process of ocean glass. At this point, the temperature of the substrate decreases but is still higher than the coating forming temperature. Offline application The present invention requires the substrate to heat the ester to a temperature above the ester decomposition temperature. The method of the present invention is implemented in the floating glass method, and the preferred application point is in the floating surface bath section. The temperature range of the application point of the coating is usually about 0000-132 ° T / 590 ° -715 ° C. Temperature is the main operating parameter because it affects the concentration of organic compounds used in the precursor gas mixture. The temperature of the substrate in the floating surface bath section. This paper is a standard Chinese National Standard Vehicle (CNS) M size (210X297 mm). (Please read the precautions on the back before filling this page.) Cooperative cooperative policy 41〇2j ^ A7 ----- __B7_ V. Description of the invention (22) It is quite stable, so it rarely changes at the application point. The preferred substrate temperature range for Examples 6 and 7 when ethyl acetate was used was 1100. -1250/590. -680. (:. The heat from the substrate raises the temperature of the precursor gas mixture above the temperature required for the formation of the coating (and higher than the thermal decomposition temperature of the ester when the ester is used as an organic compound). The metal deposition reaction can be initiated by the decomposition of the organic oxygen compound When the four gasification is used in combination with an ester containing a hydrogen atom, the titanium oxide coating is formed on the substrate and the decomposition rate is higher than that of the uniform coating method. When the floating glass ribbon process is used for online application The belt passes through the gas under the gas beam at a fairly rapid rate. The metal oxide coating is deposited on the floating glass ribbon as the belt passes under the coater. The inventor proposed the following theory regarding the use of an ester with a hydride-containing alkyl group Chemical reactions that may occur at the time. However, the inventors do not wish to limit the invention to such possible explanations, so they are only provided as an aid to understand the results of the method of the invention. The inventors have suggested that carbon-nitrogen on stone hydrogen when S is decomposed The bond is broken and the hydrogen is transferred to the carbonyl elimination ene to form nitric acid. At the same time, the nitric acid undergoes a hydrolysis reaction with the metal tetragas, resulting in the formation on the substrate. It is an oxide coating. In general, the object produced according to the present invention includes a substrate with titanium oxide or tin oxide. The coating can be applied directly to the substrate or as a layer of a multilayer coating on the substrate. The deposition rate of metal oxide coatings is affected by the deposition rate of organic oxygen compounds. In the stable reaction temperature, different organic oxygen compounds can provide different coating growth rates due to different decomposition temperatures. Therefore, the desired metal oxide for a particular system The growth rate of the coating is matched to the temperature of the gas before the application point by using specific organic oxygen compounds. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 male 25 ---- ^ k installed ----__---- ------ d (Please read the notes on the back before filling out this page) Printed by Shellfish Consumer Cooperation, Central Standards Bureau, Ministry of Economic Affairs 4 印 14 B7 V. Description of the invention (23) and selection of substrate temperature. The decomposition rate of the titanium oxide coating of the present invention can be 10 times higher than that of known deposition methods. The method of the present invention can make the deposition rate exceed 130 A per 而 and some deposition rates far exceed 300 A per second In addition to the high deposition rate of titanium oxide, a coating with a refractive index of about 2.4 is obtained. In addition to achieving a high coating rate, another advantage of the present invention is its use of low-cost metal precursor compounds, especially the current gas-flooding mixtures. High conversion efficiency (conversion of metal four gaseous compounds) can be achieved when guided to the substrate under better flow conditions. The oxide coating obtained in the present invention contains very little debris from organic oxides, especially when using s This is especially the case. It is an undesired by-product of the coating reaction, because the high concentration of carbon in the deposited coating causes the coating to absorb the problem. The concern of organic oxygen compounds used in the coating precursor gas mixture is that the carbon concentration of the decomposition may be The absorption properties of the glass finished product have an adverse effect " The carbon content in the coating produced by the method of the present invention shows less than 4 atomic% carbon. This low concentration of carbon does not significantly affect the absorption properties of the coating. It is understood that the aspect of the present invention shown and described herein is merely an illustrative specific example, which can make various changes in the shape and size of the object and various process changes without departing from the essence of the present invention. This paper size is applicable to China National Standards (CNS) A4 (210X297 mm) (read the notes on the back before filling out this page). Η 26 A7 B7 Printed by the Central Consumers Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 410214 V. Description of the invention (24) Component reference 10 ... Floating glass device 52, ... Coating 12 ... Channel section 54 ... Glass substrate 14 ... Graft glass 56. ...— stack of multi-layer coatings 16 .... Ocean surface bath section 58 ... Silicon layer 18 ... Glass ribbon 60 ... Silicon oxide layer 20 ... Annealing kiln 62 ... Titanium oxide coating 22 .... Cooling section 64-68, ... Gas distributor beam 24 .... Bottom section 70 .... Framework 26 .... Molten tin bath 72 .... Inner wall 28 ... Top 74 ... Outer wall 30 ... Side wall 76, 78 ... Closed cavity 32 ... End wall 80 ... Fluid-cooled supply conduit 34 ... Bath enclosure 82 ... .. dripping line 36 ... .channel 84 .... conveying room 38 .... adjustment gate 86 .... outcrop 40 .... list roller 88 .... 1¾ 42 ... • Roller 90 ... Baffle 44 ... Duct 92 ... Drain chamber 46 ... Distribution manifold 100 ... Distributor 48, " Radiant heater 101 ... Air supply duct 50 ... .Fan 102-3 .... Conduit (Please read the precautions on the back before filling this page)
---1T ,M_ 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0X29?公釐） 27 410214 五、發明説明（25) A7 B7 104....孔口 105. ·..氣體流約束器 106. ...U字形導引通道 107…‘入口腳 108. …塗層室 109. …排放腳 110....熱玻璃基材 (請先閱讀背面之注意事項再填寫本買) -----訂 0 經濟部中央樣準局員工消費合作社印製 28 本紙張尺度適用中國國家標準（CNS ) A4规格（2丨0X297公釐）--- 1T, M_ This paper size is applicable to Chinese National Standard (CNS) A4 (2 丨 0X29? Mm) 27 410214 V. Description of the invention (25) A7 B7 104 .... Orifice 105 ... Gas Flow restrictor 106 .... U-shaped guide channel 107 ... 'inlet foot 108 .... coating chamber 109 .... discharge foot 110 .... hot glass substrate (please read the precautions on the back before filling in this purchase ) ----- Order 0 Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economy 28 This paper size is applicable to China National Standard (CNS) A4 (2 丨 0X297 mm)