TWI245024B

TWI245024B - Compositions, apparatus and methods for forming coatings of selected color on a substrate and articles produced thereby

Info

Publication number: TWI245024B
Application number: TW093115444A
Authority: TW
Inventors: Luke A Kutilek; Roger L Scriven; Patricia Ruzakowski Athey; Charles B Greenberg; John B Slobodnik
Original assignee: Ppg Ind Ohio Inc
Priority date: 1998-08-13
Filing date: 1999-09-15
Publication date: 2005-12-11
Also published as: CA2340044A1; WO2000009457A3; TWI222960B; KR20010079644A; CZ2001554A3; ID28206A; AU5482699A; AU748247B2; CN1331661A; JP2002522347A; WO2000009457A2; TW200427642A; EP1119525A2; CN1272270C; BR9914310A

Abstract

A copper containing component and a manganese containing component are applied onto the surface of a substrate to form a coating having a selected ratio of copper to manganese to form a desired color. Further, color shifting of a multi-component coating upon subsequent heat treatment is minimized or prevented by determining the most mobile species in the coating and then placing a concentration gradient layer of an oxide of that mobile species between the substrate and the coating. Upon subsequent heat treatment, the mobile species in the gradient layer diffuses into the substrate more readily than the mobile species in the coating. Still further, color shifting due to heating, e.g. tempering operations, is minimized by adding calcium to an FeOx system to prevent darkening of the film after heating. An apparatus for forming a graduated coating on a substrate includes o coating station positioned along a conveyor. The coating station includes a first coating dispenser pivotally mounted on a first support and at least one exhaust hood. The first coating dispenser is positioned such that an axis through the delivery end of the first coating dispenser subtends the substrate at a predetermined angle.

Description

1245024 玖、發明說明：相關申請案參考本申凊案為美國專利申請案序列號第08/992,484號[歸檔於1997年12月18日，名稱為”於基質上沈積具有褪色區域之熱解性塗層之方法及設備，及由之而得之物件，，（，，Meth〇ds and Apparatus for Depositing Pyrolytic Coatings Having a Zone Over a Substrate and Articles Produced Thereby,f)] 的延續部分。本案亦得益於美國臨時申請案序列號第 60/0965415^(U.S. Provisional Application Serial NO.60/096,415) [歸檔於1998年8月13日，名稱為"於基質上形成分級褪色區域之方法及設備，及由之而得之物件”]。以上揭示申請案併於本文，以供參考。【發明所屬之技術領域】本發明全面闡述了在基質上形成經選擇顏色塗層之組合物、設備及方法，特別闡述了變動有機金屬組合物之水性懸〉予液中的組份。將懸浮液沈積於玻璃基質上，以在玻璃基質上熱解產生經選擇顏色的穩定塗覆薄膜。在本發明的一個具體實施例中，該塗層在基質[如浮法（float)玻璃條]表面上具有分級褪色區域。【先前技術】在各種工業應用中，常需要在玻璃表面上形成塗層。例如，飞車擋風屏具有名為，，色帶，，或，，褪色區域”的經塗覆區域。在很多客車中，後座和後窗玻璃系以均勻厚度的塗層塗覆。這些塗覆區域減少了可見光、紅外光或紫外光的透 93611.doc 1245024 射率，從而減小刺目的強光、車輛的能見度和/或太陽能的透過率，進而減少車輛内部能量的獲得。名稱，，褪色區域，，一般指透明邊緣的相鄰區域（如汽車擋風屏的頂端），其中通過透明部分的能見度自較低透明區域至較高透明區域變化。美國專利第3,660,061號將有機金屬鹽溶於有機溶液，使之喷到熱玻璃表面上，形成金屬氧化物薄膜。美國專利第 4,719,127號揭示將有機金屬鹽之水性懸浮液噴到熱玻璃表面上，於5亥表面上熱解形成金屬氧化物塗層。目丽，可用之塗覆工藝係用於灰色或暗灰色塗層，尤其用於汽車工業，該經塗覆玻璃可與大多數汽車體顏色配用，沒有對汽車體顏色產生”不合”。但在對經塗覆基質回火及成型期間加熱時，很多已知經塗覆基質改變了顏色或色調。這種引起顏色改變的加熱很難產生顏色穩定度一致的經塗覆材料。另外，很多已知經塗覆基質不具有化學耐性’例如與具有檸檬酸之溶液接觸。美國專利第2,676,1 14號揭示使用多個相對於多個蒸發塗覆源以幾何方式安置之固定屏護，以於基質上形成一系列相鄰但彼此分離之不同厚度帶。該技術之一限制為，該分離塗覆帶使得該被塗覆基質具不悅的條紋或色條外觀。美國專利第3,004,875號揭示於護屏上方以多個噴搶向基質邊緣塗以分級塗層。遠離喷搶的塗帶具有厚面，與喷槍相鄰的塗帶具有薄面。這種工藝的限制為，其設備需要複雜的屏護噴射裝置，且由於塗覆操作時護屏下方接近護屏邊緣產生渦流，使生成塗帶具有斑狀外觀。 93611.doc 1245024 美國專利第4，138,284號鮑托帕(〜叫揭示以—種汰料組合物沿玻璃基質的-邊塗覆。得到的塗帶且有厚声: 本均句的相對較寬面，而基質之塗覆和未塗覆部分之= 一窄且分級的邊界區域。就此我們瞭解，將經選擇透射顏色的塗層塗於基質表面減少或消除與目前已知組合物和方法有關的限二貝提供這樣的組合物、方法和設備將大有益處。【發明内容】本發明係關於形成塗層之方法，例如在基質上形成所需顏色的含銅㈣之塗層，即，將含銅組份和含猛組份以^ -經選擇比例塗到（如玻璃）基質上，形減有銅對猛經選擇比例之塗層。尤其是，當含銅組份和含猛組份之比為1時，塗層透射藍色。含銅組份和含缝份之比小於約丨時，顏色隨比例的降低自灰藍至琥J白色（黃褐）變4。在含銅㈣和含短組份約大於W，顏色隨比例的增加自灰藍至棕色變化。本發明進一步關於在基質上形成經選擇顏色塗層之組合物γ含銅和錳之塗層依銅對錳之比形成自琥珀色（黃褐色）至監色再至淺棕色變化之塗層。鉻、銅和錳之物系提供了透射中灰色之塗層。可向該銅和猛之物系、加人始，以增加化=耐性，如塗層對擰檬酸的化學耐性。氧化鐵物系提供了金色塗層。可向該氧化物系加入銅，提供透射淺灰棕色塗層。可向氧化鐵銅物系加入鉻，提供透射深灰棕色之塗層。虱化錳（Mn2〇3)塗層提供了淡紫色/薰衣草色塗層，而具有（Mn++)(Mnw)2〇4相的薄膜提供了淺琥轴色薄膜。 93611.doc !245〇24 (Mn++)(Mn+++)204將被指定為”Mn3〇4，，。本發明尚進一步關於防止隨後加熱處理時多組份和多層經塗覆基質顏色改變之方法，其步驟包括，測定塗層中二最易移動種類’向基質（如玻璃片）和塗層之間置入易移動種類氧化物之濃度梯度層，該濃度梯度層較佳直接塗於玻璃基質上，亦可在玻璃基質上形成的塗覆層上塗覆。隨後加熱處理時，該濃度梯度層中的易移動種類較塗層中的易移動種類更易於擴散到基質中，使塗層易移動種類的消耗最小，減少或消除透射率的增加。本發明進-步關於在基質（如玻璃片）表面上形成分級塗層之設備。該設備包括-個塗覆臺和相對移動玻璃片之裝置。該塗覆臺包括於第一技撐物上安裝的塗料分配器，較麵可旋轉性安裝。吸除蓋於該塗料分配器的一側或雙側安置。塗料源和加壓流體源與塗料分配器相連。塗料分配器相對於玻璃移動裝置安裳，使通過塗料分配器送孔刀(如賀嘴）的假想軸或（如使用多於丨個喷嘴）假想的塗料喷射中線以某—預以度與玻璃移動裝置交又，使塗料分配运末端的塗料噴射σ於玻璃表面上提供分級塗層。靠近: 料分配器輸送末端的分級塗層較厚，而遠離塗料分配哭: ==塗層較薄。塗層厚度較佳隨塗料分配器輸料減’或者說靠近塗料分配器破璃片邊緣的塗 ^又備可於第二支撐物上旋轉性安裝第二兩個塗料分配器之-或二者可垂直或水平移動。… 93611.doc -10 - 1245024 在本發明另-個較佳具體實施例中，該㈣包括於待塗基質表面上成線或迂回安置的多個彼此分離的塗料分配器或噴嘴。各塗料分配器將塗料以圓椎形或扇形(如橢圓形) 噴射圖形刀配到基質的表面區域上。—個噴嘴的塗覆區域與另-個喷嘴的塗覆區域重疊，形成中心區域厚度大體均勻且中心區域各侧有分級區域之塗層。本發明進-步關於在基質表面上形成褪色區域之方法，即，使塗料分配器與基質表面的一側相鄰，且與基質表面的相反-側形成角纟’使來自該塗料分配器的塗料以分級褪色區域沈積於基質上。在本發明之實施例中，較佳用教解形成塗層之有機金屬材料。製造之物另外，本發明進一步敘述了用以上方法和設備件，如建築窗或汽車透明物。較佳具體實施例詳述〜必同，隹以下說到"靠近"遠離"較上” ”較下"右”"左"，，垂直”"水平頂部”"底部” ”高於""低於”及其衍生詞。除明確另外說外’本發明可採用各種選擇性變異方法和步驟系列。以說明書中描述的具體方法、組合物、設備和物件為轉之間早具體實施例。因此，與本文揭w體實具體大小尺寸和物理特性不應認作對本發明的限制。對於基質上形成的色調帶或褪色區域，較佳透射顏色的褪色區域。這也許對汽車車窗特二車窗顏色產生了與汽車顏色有關的審美愉悅性。因此^ 93611.doc 1245024 發明之具體實施例包括用於在玻璃基質上形成具經選擇透射顏色或顏色之塗料組合物及方法。此等組合物及方法可使用習用塗覆設備，例如（非限定性）習用化學氣相澱積 (CVD)、PVD、MSVD或熱解性塗覆設備。此等習用塗覆設備貫例揭示於美國專利第2,676，114號、第3,〇〇4,875號以及第4，138,284號，其揭示内容併於本文以供參考。關於圖1，圖1顯示了結合本發明特徵之塗覆設備1〇。塗覆設備10包括塗覆臺14，用於在基質上澱積分級塗層。在圖1和圖2中，本發明之分級塗層以厚度減小的分隔線表示。但應瞭解，此種表示僅為象徵性，事實上，本發明之塗層具有非條紋的分級外觀。在本發明的討論中，雖然未對其限制，但熱解性塗層係澱積經加熱之基質上。因此，在以下討論中，加熱室（如加熱爐丨2)和輪送機丨6與塗覆臺Μ 一起使用。輸送機16自加熱爐12延伸通過塗覆臺14，且以某一經選擇速度將待塗覆基質18(如待塗覆的浮法玻璃片）自加熱爐12輸送通過塗覆臺14。輸送機16可為任何習用類型，如多個可旋轉的金屬㈣陶竟輥。由此我們能夠白瞭解^ 加熱爐12可以為已知技藝類型的平玻璃形成室，室中自、々融玻璃於金屬浴上移動’形成提供平玻璃長條。輪送= 可使玻璃條自形成室至所用技藝類型的退火爐移動，將平玻璃條退火。 ^ 塗覆臺u包括塗料分配器20,如習用空氣霧化賓克夷姆 (Bmk、S-Sames)95型㈣。在塗覆臺14中，塗料分配器謂務化液體物質以扇形或圓錐形喷向基質表面。涂：土料分配器 93611.doc -12- 1245024 20經撓性可彎曲導管24與塗料源22相連，較佳為一種或多種乙醯丙酮金屬鹽的水性懸浮液，或其他習用塗料。適用的塗料於美國專利第4,719，127號由格林伯哥（(31^111^]^)所揭示，其揭示内容併於本文以供參考。計量泵26與導管24 相連如4用考爾帕莫瑪斯特萊（Cole-Parmer MasterFlex) 07523-20泵。塗料分配器亦經撓性導管3〇與壓縮流體源μ 相連。塗料分配器20較佳用常用方法安裝於支撐物料上（如金屬忙木）卩便轴向、橫向和垂直運動。塗料分配器2〇較佳相對於待塗玻璃片或輸送機16承載表面安裝，使（延伸通過塗料分配器2()的噴嘴或卸料端喷射中心的）假想軸或線⑶ (基本上垂直於待塗基質18表面或承載表面的）垂直延伸軸 V之間的夾角僅在圖丨顯示）介於約〇至9〇。之間較佳介於約20-40之間。該塗料分配器2()亦m g + 使塗料分配器20高於輪送機16的高度、分配器2〇沿循輸送 ②的位置和塗料分配益2〇與輸送機的側向位置能夠選擇 L 口定雖然圖1中只顯不了一個塗料分配器，但安裝於第-支撐物34上的此類塗料分配器2〇可有多個，例如，安裝於第一塗料分配器2〇的旁側、上方或下方。弟一吸除蓋40位於有關輸送機㈣行方向（如以數字μ 指明的箭頭線)的塗料分配器2〇的上流，第二吸除蓋Ο位於哭4 V輸I機Μ運订方向的塗料分配器2〇的下流。溫度傳感白用紅外溫度計）視情形及較佳位於輸送機Μ上方且與第—吸除蓋4〇相鄰的位置，以檢測基質聰解塗層的 93611 .doc -13- 1245024 *度。吸除蓋40和42分別與各自的吸除導管44或45相連。輔助吸除蓋49位於離開塗料分配器20的基質遠側，以提供 7卜的吸除％力。為避免在玻璃表面上發生不需要的過量噴射，可提供圖2所示的阻擋層51和/或使用蓋的。以此方法，來自塗料分配器20的喷霧不受傳播，防止了喷霧間的干擾同日守防止無規空氣浮游塗料自塗料分配器2〇立刻傳载和沈積在玻璃部分上。現在繼續參考圖2，圖2顯示了結合本發明特徵之塗覆設備1〇〇。塗覆設備100包括具有塗料分配器120的第二塗覆堂，該第二塗料分配器丨2〇可旋轉地安裝在第二支撐物134 上。第三吸除蓋47位於第二吸除蓋42的下流。雖然圖2中未顯示，但圖1所示的輔助吸除蓋49可分別於第一塗覆臺丨斗和第二塗覆臺114中安裝。第二支撐物134與第一支撐物“側向離開，以便第二塗料分配器12〇介於第二吸除蓋42和第三示二4 7之間。如圖2緩衝線（即虛線）所示，可在第二塗覆堂Π4安裝附加的塗料分配器121，例如安裝於第二塗料分配态120的旁側、上方或下方。在設備1〇和1〇〇中，來自塗料分配器的噴射和待塗目標物之間未安裝護屏或擋板。第一塗料分配器120可與第一塗料分配器2〇的壓縮流體源28和塗料源22相連，以將相同的塗料喷到基質丨8上。或者如圖2所示，使第二塗料分配器12〇經導管13〇與單獨的壓縮流體源128相連，以及經具有計量泵126的導管124與單獨的塗料源122相連，以將相同或不同的塗料喷到基質18上。附加塗料分配器12ι可以塗料分配器2〇和12〇類似的方式與 9361 l.doc 1245024 相同或不同的壓縮流體源和塗料相連。圖3顯示了體現本發明特徵之習用浮法破璃系統仏。由浮法玻璃製造技藝的一般技藝，我們很容易瞭解，習用浮法玻璃系統46包括加熱爐48，熔融玻璃在加熱爐中形成。然後將熔融玻璃轉移到包含於形成室5〇中的熔融金屬浴上：玻璃板在金屬浴表面上形成。玻璃板移出室5〇，藉助輸送機54進入退火爐52。如圖3所示，塗覆臺（如圖工的塗覆臺μ 或圖2的系列塗覆臺1〇〇)可安裝於室5〇和退火爐^之間。現在特別參考圖1所示的具體部件，描述塗覆臺14的操作。在以下的討論中，圖丨的加熱室或加熱爐12，可認為是產生連續玻璃片（如玻璃條）的圖3之室5〇或產生單獨玻璃片的習用加熱爐。連續基質（如玻璃條）或不連續待塗基質18(如平板玻璃片）分別於室50或加熱爐12中加熱至所需溫度。輸送機16將經加熱之基質1 8運送到塗覆臺14。塗料分配器2〇以所需高度和側向位置（如與輸送機16側邊的距離）以及角度“選擇性女t，使基貝18經輸送通過塗覆臺14時，塗料分配器2 〇將塗料喷到基質18的上表面上。該塗料分配器2〇的定位可人工進行，或以習用自動定位裝置自動連接。在基質1 8移動通過塗覆臺14時，塗料自塗料源22移至塗料分配器20，與來自壓縮流體源28的壓縮空氣混合，以圓錐噴射圖形從塗料分配器20的喷嘴噴向熱基質1 8。第一吸除蓋40和弟一吸除蓋42自塗覆臺14吸除多餘的塗料，以提供基本沒有缺陷或次品的均勻塗層。亦可使用輔助吸除蓋 93611.doc -15 - 1245024 49，進一步增強塗覆臺14的吸除作用。如以上討論，為防止空軋中的塗料顆粒自塗料分配器移過及沈積在板條的最遂部分上，可以使用圖2所示的阻擋層5 1。在基質1 8移動通過塗覆臺14時，塗料分配器2〇將塗料喷到熱基質18上部，塗料於此熱解形成相當耐用的分級熱解性塗層。於玻璃表面測得的喷扇大小、輸送機16的速度以及塗料分配為20的噴嘴和基質1 8的距離經過固定，使喷射圖形於基質18上形成所需的塗層分佈或分級。選擇性控制塗料通過塗料分配器20的壓力和體積，以便在基質18的表面上沈積所需的塗層梯度和厚度。因為塗料分配器2〇對基質“的遠側成一角度，較厚的塗料層沈積於基質18的近側上（即，相對於塗料分配器20的基質最近側），而沈積於基質Μ上的塗層厚度隨與基質反向邊緣（離塗料分配器的最遠邊緣）的距離減小而降低，且其間產生了大體上連續的厚度梯度，即，與塗料分配器20的距離增加，塗層厚度降低。因此，跨越基質18表面的所需寬度上塗上一層平滑且大體上連續分級的塗料60。由於實施本發明不需先前技藝中的護屏或擋板，得到的塗層於基質18形成平滑連續的梯度，沒有先前技藝普通塗覆設備的條紋或麻點限制。而且，通過使用熱解性塗料而不是先前技藝的一般染料，本發明製得之經塗覆基質可直接使用（如汽車透明物），不需要先前技藝的染料塗覆基質一般要求的保護性步驟，如保護衣或保護層。' 通過一般玻璃塗覆技藝方法可瞭解，塗覆系統參數可影響所得之塗層。例如，在所有其他條件相同時，基質丨8移 93611.doc -16 - 1245024 動通過塗覆堂越快，塗層的總體厚度越薄。角产越大，靠㈣料分配n獅㈣愈薄，遠離塗❹配請的塗層愈尽。在塗料分配器20高於基質18的距離增加時，整體塗層變薄。塗料通過塗料分配哭2〇的户# 土曰口口2m瓜逑越大，整體塗層越厚。【實施方式】實例# 1 將約〇·157英时（4.0毫米）厚、24英寸（60.1厘米）寬及30英寸(:6.2厘米）長的平玻璃片或基質用圖1所示的本發明之塗覆堂塗覆’其中的平玻璃片或基質在商業上從賓夕法尼亞，匹次堡的PPU業公司得到㈣IndustHes，Inc ^1245024 发明 Description of the invention: For related applications, refer to this application for US Patent Application Serial No. 08 / 992,484 [Archived on December 18, 1997, entitled "Pyrolytic property of a faded area deposited on a substrate" Coating methods and equipment, and objects derived therefrom, (, Meth〇ds and Apparatus for Depositing Pyrolytic Coatings Having a Zone Over a Substrate and Articles Produced Thereby, f)]. The case also benefits US Provisional Application Serial No. 60/0965415 ^ (US Provisional Application Serial No. 60 / 096,415) [Archived on August 13, 1998, named " Method and Equipment for Forming Graded Faded Areas on a Substrate, and Objects derived from it "]. The above-disclosed applications are incorporated herein by reference. [Technical field to which the invention belongs] The present invention comprehensively describes the composition, equipment, and method for forming a selected color coating on a substrate, and particularly describes the components in the aqueous suspension of a modified organometallic composition. The suspension is deposited on a glass substrate to pyrolyze on the glass substrate to produce a stable coated film of selected color. In a specific embodiment of the invention, the coating has graded faded areas on the surface of a substrate [e.g. a float glass strip]. [Prior art] In various industrial applications, it is often necessary to form a coating on the glass surface. For example, a speeding windshield has a coated area named ", ribbon, or, faded area". In many passenger cars, the rear seat and rear window glass are coated with a uniform thickness coating. These The coating area reduces the transmittance of visible light, infrared light, or ultraviolet light by 93611.doc 1245024, thereby reducing glare, vehicle visibility, and / or solar transmittance, which in turn reduces energy harvesting inside the vehicle. Name, The faded area generally refers to the adjacent area with transparent edges (such as the top of a car windshield), in which the visibility through the transparent portion varies from a lower transparent area to a higher transparent area. US Patent No. 3,660,061 applies organic metal salts Dissolve in organic solution and spray it on the surface of hot glass to form a metal oxide film. U.S. Patent No. 4,719,127 discloses spraying an aqueous suspension of an organic metal salt on the surface of hot glass and pyrolyzes on the surface to form a metal Oxide coating. The coating process that can be used is gray or dark gray coating, especially for the automotive industry. The use of body color does not cause a "mismatch" in the color of the car body. However, when tempering and heating the coated substrate, many known coated substrates change the color or hue. This heating causes color changes It is difficult to produce a coated material with consistent color stability. In addition, many known coated substrates are not chemically resistant, such as contact with a solution with citric acid. US Patent No. 2,676,1 14 discloses the use of multiple A plurality of evaporative coating sources are geometrically arranged fixed screens to form a series of adjacent but separated strips of different thicknesses on the substrate. One limitation of this technique is that the separated coating strips make the coated substrate It has an unpleasant streak or color stripe appearance. US Patent No. 3,004,875 discloses that a plurality of spray guns are applied to the edge of the substrate to apply a graded coating on the screen. The coating tape has a thin surface. The limitation of this process is that its equipment requires a complicated screen spraying device, and because the eddy current is generated near the edge of the screen under the screen during the coating operation, the coating is generated. It has a speckle-like appearance. 93611.doc 1245024 US Patent No. 4,138,284 Botopa (~ is called to disclose a coating composition along the edge of the glass substrate. The resulting coated tape has a thick sound: The relatively wide surface of the sentence, and the coated and uncoated parts of the substrate = a narrow and graded boundary area. In this connection, we understand that applying a coating of a selected transmission color to the surface of the substrate reduces or eliminates the current known Compositions and methods related to edible shellfish It would be of great benefit to provide such compositions, methods, and equipment. SUMMARY OF THE INVENTION The present invention relates to a method for forming a coating, such as a copper-containing substrate that forms a desired color on a substrate. Coating, that is, the copper-containing component and the fibrous component are applied to a substrate (such as glass) in a selected ratio, such as a coating having a copper-to-fibre selected ratio. In particular, when the ratio of the copper-containing component to the fibrous component is 1, the coating transmits blue. When the ratio between the copper-containing component and the seam-containing component is less than about 丨, the color decreases from gray blue to white (yellowish brown) with hues 4 as the ratio decreases. In copper-containing tinctures and short-components, they are larger than W, and the color changes from gray-blue to brown with increasing proportion. The present invention further relates to forming a composition of a selected color coating on a substrate. A coating containing copper and manganese is formed from a amber (yellow-brown) to a monitor color to a light brown coating in accordance with the copper to manganese ratio. The chromium, copper and manganese systems provide a transmission medium gray coating. It can be added to the copper and fierce material system to increase chemical resistance, such as the chemical resistance of the coating to citric acid. The iron oxide system provides a golden coating. Copper can be added to this oxide system to provide a light grayish brown coating. Chromium can be added to the iron oxide copper system to provide a dark grey-brown coating. The manganese (Mn203) coating provided a lavender / lavender-colored coating, while the film with the (Mn ++) (Mnw) 204 phase provided a light-hued axis film. 93611.doc! 245〇24 (Mn ++) (Mn +++) 204 will be designated as "Mn304". The present invention further relates to a method for preventing the color change of multicomponent and multilayer coated substrates during subsequent heat treatment, which The steps include determining the two most mobile species in the coating, and placing a concentration gradient layer of the mobile species oxide between the substrate (such as a glass sheet) and the coating. The concentration gradient layer is preferably directly coated on the glass substrate. It can also be applied on the coating layer formed on the glass substrate. When subsequently heat-treated, the mobile species in the concentration gradient layer are more easily diffused into the substrate than the mobile species in the coating, making the coatings easier to move. The consumption is minimal, and the increase in transmittance is reduced or eliminated. The present invention further relates to a device for forming a graded coating on the surface of a substrate such as a glass sheet. The device includes a coating table and a device for relatively moving the glass sheet. The coating station includes a paint dispenser installed on the first support and can be rotatably installed. The suction cover is arranged on one or both sides of the paint dispenser. The paint source and pressurized fluid source and paint distribution Device The paint dispenser is relative to the glass moving device Ansang, so that the imaginary axis of the hole cutter (such as a nozzle) or the imaginary paint spray center line (such as using more than 丨 nozzles) is sent through the paint dispenser— It intersects with the glass moving device, so that the paint spraying at the end of the paint distribution can be sprayed on the glass surface to provide a graded coating. Close to: The graded coating at the end of the material dispenser is thicker, and away from the paint distribution: == coating Thinner. The thickness of the coating is preferably reduced as the paint dispenser feeds, or the coating near the edge of the broken glass chip of the paint dispenser is ready for the second support to be rotatably installed on the second or second paint dispenser- Or both can be moved vertically or horizontally .... 93611.doc -10-1245024 In another preferred embodiment of the present invention, the puppet includes a plurality of separated from each other which are arranged in a line or a circuit on the surface of the substrate to be coated. Paint dispenser or nozzle. Each paint dispenser applies paint to the surface area of the substrate in the shape of a circular cone or fan (such as an oval) spray pattern knife.-The coating area of one nozzle and the coating area of another nozzle Overlap The thickness of the area is substantially uniform and there is a coating of graded areas on each side of the central area. The invention further relates to a method for forming a faded area on the surface of the substrate, that is, the paint dispenser is adjacent to one side of the surface of the substrate and to the substrate Opposite-side corners of the surface cause the paint from the paint dispenser to be deposited on the substrate in graded faded areas. In the embodiment of the present invention, the organometallic material used to form the coating is preferably taught. In addition, the present invention further describes the use of the above methods and equipment, such as building windows or automobile transparent objects. The detailed description of the preferred embodiments is the same, as described below " close " away " Bottom " right " left ", vertical " horizontal top " bottom " "above " " below" and its derivatives. Except where explicitly stated, the present invention may employ a variety of selective mutation methods and series of steps. The specific methods, compositions, equipment, and articles described in the specification are specific examples. Therefore, the specific size and physical characteristics as disclosed herein should not be considered as a limitation to the present invention. For tone bands or faded areas formed on a substrate, faded areas that transmit color are preferred. This may have a special effect on the color of the car window. Therefore, 93611.doc 1245024 embodiments of the invention include coating compositions and methods for forming a selected transmission color or colors on a glass substrate. These compositions and methods can use conventional coating equipment, such as (non-limiting) conventional chemical vapor deposition (CVD), PVD, MSVD, or pyrolytic coating equipment. Examples of such conventional coating equipment are disclosed in U.S. Patent Nos. 2,676,114, 3,004,875, and 4,138,284, the disclosures of which are incorporated herein by reference. With regard to Fig. 1, Fig. 1 shows a coating apparatus 10 incorporating features of the present invention. The coating apparatus 10 includes a coating station 14 for depositing an integral coating on a substrate. In Figures 1 and 2, the graded coatings of the present invention are shown as dividing lines of reduced thickness. It should be understood, however, that this representation is merely symbolic, and in fact, the coatings of the present invention have a non-striped graded appearance. In the discussion of the present invention, although not limited thereto, a pyrolytic coating is deposited on a heated substrate. Therefore, in the following discussion, a heating chamber (such as a heating furnace 2) and a carousel 6 are used together with the coating station M. A conveyor 16 extends from the heating furnace 12 through the coating station 14 and conveys the substrate 18 to be coated (such as a float glass sheet to be coated) from the heating furnace 12 through the coating station 14 at a selected speed. The conveyor 16 may be of any conventional type, such as a plurality of rotatable metal concrete rollers. From this, we can understand that the heating furnace 12 can provide a flat glass strip for the formation of flat glass of known technology type. The flat glass strip can be formed by moving the molten glass on the metal bath. Carousel = Allows the glass strip to be moved from the forming chamber to the type of annealing furnace used to anneal the flat glass strip. ^ The coating station u includes a coating dispenser 20, such as a conventional air atomizing Bink (95, S-Sames) type ㈣. In the coating station 14, the paint dispenser sprays the liquidized substance in a fan or cone shape onto the surface of the substrate. Coating: Soil distributor 93611.doc -12- 1245024 20 is connected to the coating source 22 via a flexible bendable conduit 24, preferably an aqueous suspension of one or more acetoacetone metal salts, or other conventional coatings. A suitable coating is disclosed in U.S. Patent No. 4,719,127 by Greenberg ((31 ^ 111 ^) ^), the disclosure of which is incorporated herein by reference. A metering pump 26 is connected to the conduit 24, such as a Kalppa Cole-Parmer MasterFlex 07523-20 pump. The paint dispenser is also connected to the compressed fluid source μ through a flexible conduit 30. The paint dispenser 20 is preferably installed on a supporting material (such as metal) by common methods. (Busy wood) to move axially, laterally and vertically. The paint dispenser 20 is preferably mounted relative to the bearing surface of the glass sheet to be coated or the conveyor 16 so that (extending through the nozzle or discharge end of the paint dispenser 2 () The angle between the imaginary axis or line (of the spray center) ⑶ (which is substantially perpendicular to the surface of the substrate 18 to be coated or the bearing surface) of the vertical extension axis V is only shown in FIG. It is preferably between about 20-40. The paint dispenser 2 () is also mg + to make the paint dispenser 20 higher than the height of the carousel 16, the position of the dispenser 20 along the conveyor ② and the paint distribution benefit 20 and the lateral position of the conveyor can be selected L Although only one paint dispenser is not shown in FIG. 1, there may be multiple such paint dispensers 20 installed on the first support 34, for example, installed on the side of the first paint dispenser 20. , Above or below. The first suction cover 40 is located upstream of the paint dispenser 2o in the direction of the conveyor (such as the arrow line indicated by the number μ), and the second suction cover 0 is located in the direction of the 4V delivery machine. Downstream of the paint dispenser 20. Temperature sensor (infrared thermometer for white use) Depending on the situation and preferably located above the conveyor M and adjacent to the first suction cover 40, to detect the 93611.doc -13-1245024 * degree of the matrix clastic coating. The suction caps 40 and 42 are connected to respective suction ducts 44 or 45, respectively. An auxiliary suction cap 49 is located far from the substrate away from the paint dispenser 20 to provide a suction force of 7%. In order to avoid unnecessary excessive spraying on the glass surface, a barrier layer 51 and / or a cover may be provided as shown in FIG. 2. In this way, the spray from the paint dispenser 20 is not spread, preventing interference between spray booths and preventing random airborne paint from being carried and deposited on the glass portion from the paint dispenser 20 immediately. Reference is now continued to FIG. 2, which illustrates a coating apparatus 100 incorporating features of the present invention. The coating apparatus 100 includes a second coating hall having a paint dispenser 120 that is rotatably mounted on a second support 134. The third suction cover 47 is located downstream of the second suction cover 42. Although not shown in FIG. 2, the auxiliary suction cover 49 shown in FIG. 1 may be installed in the first coating station hopper and the second coating station 114, respectively. The second support 134 is separated from the first support "laterally, so that the second paint dispenser 120 is between the second suction cover 42 and the third display 47, as shown in Fig. 2 (the dashed line) As shown, an additional paint dispenser 121 may be installed in the second coating hall Π4, for example, beside, above, or below the second paint distribution state 120. In the equipment 10 and 100, from the paint dispenser There is no shield or baffle installed between the spray and the target to be coated. The first paint dispenser 120 may be connected to the compressed fluid source 28 and the paint source 22 of the first paint dispenser 20 to spray the same paint to Substrate 8. Alternatively, as shown in FIG. 2, a second paint dispenser 120 is connected to a separate source of compressed fluid 128 via a conduit 13o, and is connected to a separate paint source 122 via a conduit 124 having a metering pump 126, The same or different paint is sprayed onto the substrate 18. The additional paint dispenser 12m can be connected to the same or different compressed fluid source and paint as 9361 l.doc 1245024 in a similar manner to the paint dispensers 20 and 120. Figure 3 shows The conventional float glass breaking system embodying the features of the present invention仏. The general skill of the float glass manufacturing technique is easy to understand. The conventional float glass system 46 includes a heating furnace 48 in which the molten glass is formed. The molten glass is then transferred to the glass contained in the forming chamber 50. On the molten metal bath: A glass plate is formed on the surface of the metal bath. The glass plate is removed from the chamber 50 and entered into the annealing furnace 52 by means of a conveyor 54. As shown in FIG. The 2 series coating station 100) can be installed between the chamber 50 and the annealing furnace ^. Now referring to the specific components shown in FIG. 1, the operation of the coating station 14 will be described. In the following discussion, FIG. The heating chamber or heating furnace 12 can be considered as the conventional heating furnace of the room 50 of Fig. 3 which produces continuous glass sheets (such as glass strips) or separate glass sheets. Continuous substrates (such as glass strips) or discontinuous substrates to be coated 18 (such as a flat glass sheet) are heated to the required temperature in the chamber 50 or the heating furnace 12, respectively. The conveyor 16 transports the heated substrate 18 to the coating station 14. The coating dispenser 20 is at the required height and side To the position (such as the distance from the side of the conveyor 16 ) And the angle "selective female t", when the base 18 is transported through the coating table 14, the coating dispenser 20 sprays the coating onto the upper surface of the substrate 18. The positioning of the paint dispenser 20 can be performed manually or automatically connected with a conventional automatic positioning device. As the substrate 18 moves through the coating station 14, the coating is moved from the coating source 22 to the coating dispenser 20, mixed with compressed air from the compressed fluid source 28, and sprayed from the nozzle of the coating dispenser 20 toward the hot substrate in a conical spray pattern. 1 8. The first suction cover 40 and the first suction cover 42 remove excess paint from the coating station 14 to provide a uniform coating with substantially no defects or defective products. The auxiliary suction cover 93611.doc -15-1245024 49 can also be used to further enhance the suction effect of the coating table 14. As discussed above, in order to prevent paint particles in the air rolling from moving from the paint dispenser and accumulating on the fastest part of the slat, the barrier layer 51 shown in Fig. 2 can be used. As the substrate 18 moves through the coating station 14, the coating dispenser 20 sprays the coating onto the upper portion of the thermal substrate 18, where it is pyrolyzed to form a relatively durable graded pyrolytic coating. The size of the spray fan measured on the glass surface, the speed of the conveyor 16 and the distance between the nozzle for coating distribution 20 and the substrate 18 are fixed, so that the spray pattern forms a desired coating distribution or classification on the substrate 18. The pressure and volume of the paint through the paint dispenser 20 are selectively controlled to deposit the required coating gradient and thickness on the surface of the substrate 18. Because the paint dispenser 20 is at an angle to the distal side of the substrate, a thicker coating layer is deposited on the proximal side of the substrate 18 (ie, relative to the substrate's nearest side relative to the paint dispenser 20), while the The coating thickness decreases as the distance from the opposite edge of the substrate (the farthest edge from the paint dispenser) decreases, and a generally continuous thickness gradient is created, that is, as the distance from the paint dispenser 20 increases, the coating The thickness is reduced. Therefore, a smooth and substantially continuously graded coating 60 is applied over a desired width across the surface of the substrate 18. Since the present invention does not require a screen or barrier in the prior art, the resulting coating is formed on the substrate 18 Smooth continuous gradients without the streak or pitting limitations of conventional coating equipment of the prior art. Furthermore, by using a pyrolytic coating instead of the conventional dyes of the prior art, the coated substrate prepared by the present invention can be used directly (such as automotive Transparent), which does not require the protective steps normally required for dye-coating substrates of prior art, such as protective clothing or protective layers. 'By general glass coating techniques Understand that the parameters of the coating system can affect the resulting coating. For example, when all other conditions are the same, the faster the substrate moves through the coating hall, the thinner the overall thickness of the coating. The larger the production, the thinner the griffin is distributed by the material, and the more the coating away from the coating is, the more the coating becomes thinner as the distance of the paint dispenser 20 above the substrate 18 increases. The paint is distributed through the paint. 2〇的户 # The larger the size of the mouth 2m, the thicker the overall coating. [Embodiment] Example # 1 will be about 0.157 inches (4.0 mm) thick, 24 inches (60.1 cm) wide, and 30 An inch (: 6.2 cm) flat glass sheet or substrate was coated with the coating hall of the present invention shown in FIG. 1 where the flat glass sheet or substrate was commercially available from PPU Industries, Pittsburgh, Pennsylvania. IndustHes , Inc ^

Pittsburgh, Pennsylvania) ^ # ^ # ^ SOLARBRONZE® 〇該基質用稀洗蘇劑溶液洗務，再用蒸镏水清洗，然後以空氣乾燥。將該潔淨的玻璃基質以約115(TF(62rC)爐溫於臥式電輥式爐床加熱爐中加熱。受加熱之基質以約25〇英寸 (635厘米）/分鐘的線速度經輸送機自加熱爐運送通過塗覆，。經位於輸送機上第-吸除蓋40上流的紅外溫度計43測里進入塗覆$的基質溫度約為Π35-1 139T (613-61 5。(：）。所用塗料為磨細的乙醯丙_金屬鹽混合物混於水（ΐ6·5重量 %)之水性懸浮液，該乙醯丙鲷金屬鹽於72卞（22。〇具有 1_〇25之比重。該乙醯丙酮金屬鹽由％重量％之 Co(C5H7〇2)3(以後指作”乙醯丙酮鈷”）和$重量％之 Fe(C5H7〇2)3(以後指作”乙醯丙鲷鐵”）組成。將該水性懸浮液放入具有葉輪式攪拌機的容器中，該攪拌機以 352轉/刀鐘運轉，以保持懸浮液狀態。該懸浮液通過實 93611.doc 1245024 驗至用螺動計ϊ栗（考爾-帕莫馬特弗萊〇乃23-20) (Cole-Parmer MasterFlex 07523-20)以 85 毫升/分鐘之速率輸至喷嘴。喷嘴為習用空氣霧化型（賓克-塞姆95型） (Binks-Sames Model 95)，壓縮空氣用50磅/平方英寸表壓壓力（3 ·5千克/平方厘米）。喷嘴位於基質近側側向約7英寸 (17.8厘米）處，且垂直高於待塗玻璃基質表面約u英寸（27 9 厘米）。喷嘴所成角度使喷嘴中心以約25。之夾角α交又於基質上部。該設置使玻璃基質上產生了分級且基本為青銅色的褪色區域。如圖2所示，若干個塗覆臺14、i 14可連續安置，於各塗覆臺14、114將相同或不同的塗料塗到基質18上。例如，可期望在基質上產生層疊或堆疊式塗層，或在基質上產生經選擇之顏色，或在相同基質上形成多種顏色，其使用組合物及方法描述於同在申請中的美國專利申請案，標題為，，於基質上形成經選擇顏色之塗層之組合物及方法，及由之而付物件（Compositions and Methods for Forming Coatings of Selected Color 〇n a Substrate and Articles Produced Thereby’’）’其内容併於本文以供參考。雖然以上討論集中於以使用習用空氣霧化喷嘴之塗覆設備實施本發明，但本發明不限於使用該塗覆設備，亦可用匕颂i的塗覆设備貫施，例如使用氣相殿積塗層的塗覆為（’CVD塗覆器。由CVD塗覆的一般技藝，我們瞭解， CVD塗覆器通常位於移動基質的上方。其塗覆區包括橫向於基質運動方向定向的輸送槽（塗料通過輸送橫向排放） 93611.doc -18- 1245024 、及個或夕個吸除槽。結合本發明方法的cvd型塗覆區氐I5 13 8如圖5所示。可（例如）位於浮法玻璃系統μ的 v成至中如圖3緩衝線所示。如圖5所示，cvd塗覆區 I40可具有至少—個錐形塗料輸送槽142(自較窄寬度的一端至較寬寬度的另—端成錐形），塗料通過該錐形塗料輸送槽=以習知方式流向基質表面上，且該基質以塗覆區140 下的前頭X方向移動。吸除槽144位於輸送槽142的兩側。吸除槽144可具有相等寬度（如圖5所示）或製成錐形（如以輸送槽142類似方式）。或者使輸送槽142具有相等寬度，而吸除槽144製成錐形。在輸送槽142的較窄部分塗到基質表面的塗層比輸送槽142較寬部分下的塗層厚，且其間具有殺積厚度分級的塗層。圖6展示了本發明塗覆臺148之進一步具體實施例。該塗覆至148_有第—吸除盍4〇，且該第一吸除蓋與第二吸除盍42相離’其間具有多個錯開相離的塗料分配器200,如習用空氣霧化喷嘴。圖6所示的具體實施例展示了三個此類塗料分配器200,但不應認作對本發明的限制。塗料分配器綱較佳可移動或可旋轉安裝到高於輸送機㈣靜止框架上，該輸送機16用於將待塗基f 18送人塗覆臺148中。當:，塗料分配器200亦可選擇性安裝到可移動框架或橋形將塗料分配器200相對於基質18移動。塗料分配係與一個或多個塗料源和/或加壓流體源相連。如圖6所示，塗料分配器2〇〇較佳向下朝向基質a，以於基質18上形成喷射圖形，如橢圓形或伸長型喷射圖形。如 9361 l.doc -19- 1245024 圖7所示，各伸長圖形15〇具有主軸152、中心154以及外周邊或外邊緣156。塗料分配器2〇〇排列成，使其一個塗料分配器200的喷射圖形不干擾另一個塗料分配器2〇〇的喷射圖形。例如，可將塗料分配器2〇〇以拐折形式排列，使所有主軸152大體上平行且相互離開。如圖7所示，在基質18移動通過塗覆臺148時，塗料分配器2〇〇分別於基質18上噴射形成塗覆區域158。塗料分配器2〇〇應較佳定位，使一個塗料分配器20形成的塗覆區域158不延伸超過相鄰塗料分配器 200的圖形中心154。因此，塗覆區域158重疊形成圖8所示之塗層，該塗層具有大體上等厚的中心區域162、塗層各側具有錐形或分級的側區164。若需要，可將經塗覆基質“切成兩片或多片。例如，可將基質18沿圖8所示的垂直軸冗於一半處切成兩塊單獨的塗片，且各片具有分級的側區μ/，或將片18切成3片，其中間片具有均句的塗層，而外片具有分級區域。儘管在以上討論的具體實施例中討論了形成橢圓塗覆圖形的塗料分配器，但本發明不受此_圓形塗覆圖形的限制。例如，塗覆圖形可為任何形狀，如圓形、㈣等。另外，可連續安裝多個此類塗覆臺148 /、塗料噴到基質上。謂相以不同的塗覆坡螭基質的塗以及透射百分率。 ^ 具有兩個塗另—個側向旁支離圖9顯示了應用本發明方法之塗覆臺覆面反射百分率、未塗覆面反射百分率所用塗覆臺與圖6所示的塗覆臺148相料分配器200，且一個塗料分配器2〇〇與 93611.doc -20- 1245024 _5英寸（12·7厘米）距離。將約〇i57英寸（4〇毫幻厚α 央寸（6〇·1厘幻寬以及3〇英寸（76·2厘米）至4〇英寸（⑻6厘 ^ ^ ^ ^ ^ f ^ ^ ^ ^ ^ ^ ^ PPGi # △司侍到’其註冊商標為SQLEXTRA⑧）用乙醯丙嗣的銅 :結鹽和猛鹽混合物之水性懸浮液喷覆，將塗層熱解殿積於玻璃表面上。該殿積塗層具有約400-600A(埃）最大厚度，且經塗覆玻璃片各側具有錐形區域。橫跨塗覆玻璃片一個錐形邊或玻璃邊緣向另一個錐形邊，於經選擇位置測疋反射百分率〜和〜以及透射百分率。圖9橫坐標上的，，〇” 位置相虽於經塗覆玻璃片的一邊(如左邊》其他橫坐標位置表示離該邊的距離，於各位置敎反射百分率R^R2以及透射百2率。塗層於基質邊具有較高透射區域（如錐形區域）’而罪近基質18中間具有較低透射區域（如較厚的中心區域）’且其間具有平滑分級的透射區域。另一方面，塗層於基質邊具有較低的反射率1和1，而接近基質中部具有較高的反射率。分別測量時，Ri值較R2值高。如上討論，相鄰塗料分配器200的位置應使一個塗料分配為200的噴射圖形150不干擾另一個塗料分配器2⑼的噴射圖形150。圖1〇展示類似於上述塗層的反射百分率&和& 以及透射百分率，但兩個相鄰塗料分配器2〇〇的各個喷射與玻璃邊垂直沈積成一條線，使相鄰的喷射介於兩個喷射圖形間產生干擾。來自塗料分配器2〇〇的兩個噴射圖形間的干擾形成了具有重斑、不均勻厚度的中心區域。反射百分率和透射百分率係通過使用CU_E(國際照明委員會）標準、照 93611.doc -21 - 1245024 明物C、光線2度觀測器測量。圖11展示了一般車輛210。車輛210包括播風屏212、後窗 214以及側窗216、21 8和2 2 0。按照本文之討論，此等將被集體簡單指作π窗”。側窗216和218係用本發明之經塗覆玻璃製成，形成的分級褪色區域222自塗層較薄且基本透明靠近底部的第一區域224至塗層較厚且透明度差靠近頂部的第二區域226逐漸變化。在較佳的具體實施例中，安裝於車輛210的窗子具有垂直定向的褪色區域222，如有關的侧窗 216和218所示。然而，褪色區域222亦可視需要水平定向，如有關側窗220所示。若如此，褪色區域222亦可於具有第一區域224的窗頂定向。另外，如有關塗覆設備丨〇〇中所述，通過在褪色區域222形成期間以相鄰的塗覆臺給予不同的塗料，可使形成的褪色區域222於第一區域 224具有第一種顏色，第二區域226具有不同的第二種顏色。現在將描述獲得經選擇透射顏色塗層之具體塗料組合物和方法。為易於討論，這些混合物和方法一般按照所產生的顏色分類。但這些具體分類不應認作對本發明的限制。氧化鋼猛塗層我們發現，用具有含銅和含錳組份之懸浮液形成的塗層 (特別是熱解沈積塗層）提供了極佳的塗層，其透射顏色依所用懸浮液中銅對錳之莫耳比自琥珀色（黃褐色）至淺棕色至藍灰色至藍色變化。詳細而言，含有含錳乙醯丙酮鹽 [P Mn(C5H702)2(以後稱為乙醯丙酮亞錳）或 9361 l.doc -22- 1245024 (以後稱為乙醯丙酮般）]和含銅乙醯丙酮鹽[即， Cu(C5H7〇2M亦稱為π乙醯丙酮銅，，）]混合物之水性懸浮液產生了透射顏色自某範圍變化的塗層，該塗層之透射顏色自淺棕色（具有高含量銅）或琥站色（具有高含量錳）至藍色（塗層中銅對锰之莫耳比為1)和藍灰色（莫耳比微大於1或小於 1)。銅對猛之莫耳比增加或減小時的顏色變化列在表I中，以下詳細討論於圖12顯示。經塗覆基質係以含銅和錳的混合乙醯丙酮鹽（如乙醯丙酮銅和乙醯丙酮亞錳）之水性懸浮液手工喷射到潔淨的浮法玻璃基質[切成4英寸χ4英寸（1〇·2厘米χ1〇·2厘米）見方]而成。將基質以稀洗滌劑溶液洗滌，用蒸餾水清洗後經空氣乾燥。以習用濕法磨細技術產生乙醯丙酮銅cu(C5H7〇2)d0 乙醯丙酮亞錳Mn(C5H7〇2)2之水性懸浮液，且使含銅和錳之乙酸丙酮鹽以所需比例與去離子水和化學濕潤劑混合，將乙醯丙酮之金屬鹽顆粒分散、脫氣和懸浮。將基質以習用臺上隔焰爐加熱至足夠溫度，以保證使應用的懸浮液熱解 (如約600。(：），然後用裝配重力自流進料儲器的賓克 (Binks)95型喷搶手工噴射。矣二塗覆基質的透射和反射顏色範圍（作為組合物的函數）顯不於表I中，而樣品顏色顯示於圖7中。經塗覆基質的反射和透射顏色係使用國際照明委員會（c〇mmissi〇n International de 確定的照明物a，2。觀測器以習知標準色度坐標γ，x，y，形式說明。該經塗覆基質用X射線衍射法分析。經χ-射線螢光分析法（，，XRF，，）測定發 93611.doc -23- 1245024 現，表I的樣品A6至A8主要含立方晶系的Cu^Mn^CU尖晶石類型相，該相一般在塗層Cu/Mn之莫耳比為0.8至1.1範圍時發生，見表I。樣品A1和A2之富銅塗層透射棕色，而富猛塗層透射琥珀色（如樣品A13和A14)。 1 A14 I ΙΑΠ....... Lai2..... |ΑΠ| ΐΑΙΟ... > 樣品只有錳 0.11 0.25 0.33 0.49 0.54 0.67 0.82 1.00 1.50 2.03 4.00 9.00 只有銅懸浮液中 Οα(Π)/Μη(Π)之莫耳比只有錳 0.12 0.28 0.38 0.61 0.86 0.79 0.91 1.10 1.75 2.42 5.48 20.57 只有銅 § 1蒎 1 31.17 1 1 25.23 1 1 24.90 1 1 27.07 1 1 27.00 ί 23.97 1 28.52 1 24.56 1 [28.22 1 1 24.87 1 1 26.92 1 1 19.06 1 1 26.27 1 23.81 氺 (照明物A，2° ) 0.4294 1 0.4235 1 1 0.4355 1 1 0.4452 1 1 0.4641 1 1 0.4597 1 1 0.4734 1 1 0.4734 1 1 0.4778 1 1 0.4610 1 1 0.4517 1 1 0.4338 1 1 0.4389 1 0.4350 X 0.4076 1 0.4019 1 1 0.4009 1 1 0.4021 丨 0:4036 0.4027 ! 0.4067 1 ! 0.4057 1 1 0.4075 1 1 0.4044 1 1 0.4047 1 1 0.4047 1 1 0.4092 1 0.4084 'C 28.89 1 20.52 1 15.14 13.88 12.74 9.71 13.09 1 9.82 1 1 13.61 1 1 10.83 1 1 12.04 1 1 11.38 1 1 19.61 1 17.41 氺氺 (照明物A，2° ) 0.4266 1 0.4177 1 1 0.4146 1 0.4203 ! 0.4500 1 1 0.4432 1 1 0.4698 1 1 0.4722 1 1 0.4769 1 1 0.4460 1 1 0.4312 1 1 0.4347 1 1 0.4400 1 0.4419 X 1 0.4114 ] 1 0.4045 1 1 0.3950 1 ! 0.3915 1 I 0.3932 1 ! 0.3887 1 ! 0.3978 1 1 0.3960 1 1 0.4009 1 1 0.3937 1 0.3945 0.4072 0.4122 0.4131 1 61.68 1 1 61.80 1 1 49.09 1 1 40.13 1 1 31.37 1 1 38.16 1 1 27.85 1 1 34.78 1 1 27.46 1 1 35.78 1 1 37.26 ] 「58.87 1 1 52.71 1 57.13 氺氺氺 (照明物A，2° ) 0.4650 1 0.4600 1 1 0.4478 1 Γ 0.4389 1 1 0.4213 1 1 0.4266 1 Γ〇·4107 1 1 0.4149 1 1 0.4065 1 [0.4290 1 1 0.4399 1 1 0.4576 ί 0.4676 0.4679 X 0.4150 1 0.4147 [0.4125 1 1 0.4109 1 1 0.4075 1 1 0.4083 1 1 0.4039 1 [0.4058 1 1 0.4029 1 1 0.4090 1 1 0.4115 1 1 0.4131 1 1 0.4135 1 0.4139 1 ίPittsburgh, Pennsylvania) ^ # ^ # ^ SOLARBRONZE® 〇 The substrate is washed with a dilute detergent solution, rinsed with distilled water, and dried in air. The clean glass substrate was heated in a horizontal electric roller hearth furnace at a temperature of about 115 (TF (62rC)). The heated substrate was passed through a conveyor at a line speed of about 25 inches (635 cm) / minute. The self-heating furnace is transported through the coating. The temperature of the substrate entering the coating through an infrared thermometer 43 measured upstream of the first-removing cover 40 on the conveyor is about Π35-1 139T (613-61 5. (:)). The coating used was an aqueous suspension of a finely divided mixture of acetamidine metal salt and water (6.5% by weight), and the acetamium metal salt at 72% (22.0%) had a specific gravity of 1-25. The acetoacetone metal salt is composed of% by weight of Co (C5H7〇2) 3 (hereinafter referred to as "cobalt acetone acetone") and $ (%) by weight of Fe (C5H7〇2) 3 (hereinafter referred to as "acetamidine bream" Iron ") composition. The aqueous suspension was put into a container with an impeller mixer, which was operated at 352 revolutions / knife clock to maintain the suspension state. The suspension passed the test of 93611.doc 1245024 and was tested with a screw. Ji Lili (Cole-Parmer Master Fry No. 23-20) (Cole-Parmer MasterFlex 07523-20) is delivered to the spray at a rate of 85 ml / min. The nozzle is a conventional air atomizing type (Binks-Sames Model 95). The compressed air uses a pressure of 50 psig (3.5 kg / cm2). The nozzle is located near the substrate. It is about 7 inches (17.8 cm) laterally and vertically about u inches (27 9 cm) above the surface of the glass substrate to be coated. The angle formed by the nozzle makes the center of the nozzle intersect at an angle α of 25 ° to the upper part of the substrate. This setting produces a graded and substantially bronze-colored faded area on the glass substrate. As shown in FIG. 2, several coating stations 14, i 14 can be placed continuously, and each coating station 14, 114 will have the same or different The coating is applied to the substrate 18. For example, it may be desired to produce a layered or stacked coating on the substrate, or to produce a selected color on the substrate, or to form multiple colors on the same substrate, using compositions and methods described in the same Compositions and methods for forming coatings of selected colors on substrates and compositions and methods (Compositions and Methods for Forming Coatings of Selected Color) ate and Articles Produced Thereby ") and its contents are incorporated herein by reference. Although the foregoing discussion has focused on implementing the present invention with a coating apparatus using a conventional air atomizing nozzle, the present invention is not limited to using the coating apparatus, but also It can be applied with a coating device such as a CVD coater using a vapor phase coating. From the general art of CVD coating, we understand that CVD applicators are usually located above a moving substrate. The coating area includes a conveying trough (the coating is discharged laterally through the conveying direction) 93611.doc -18-1245024, and a suction trough. The cvd-type coating area 氐 I5 13 8 incorporating the method of the present invention is shown in FIG. 5. It can be, for example, located in the float glass system μ as shown in the buffer line of FIG. 3. As shown in FIG. 5, the cvd coating area I40 may have at least one tapered paint conveying groove 142 (from one end of the narrower width to the other end of the wider width being tapered) through which the paint passes. = It flows onto the surface of the substrate in a conventional manner, and the substrate moves in the front X direction under the coating area 140. The suction tank 144 is located on both sides of the transport tank 142. The suction grooves 144 may have equal widths (as shown in FIG. 5) or be tapered (as in a similar manner to the conveying grooves 142). Alternatively, the conveying grooves 142 have equal widths, and the suction grooves 144 are tapered. The coating applied to the surface of the substrate at the narrower portion of the transfer groove 142 is thicker than the coating at the wider portion of the transfer groove 142, and there is a coating with a grading of the thickness of the substrate therebetween. FIG. 6 shows a further specific embodiment of the coating station 148 of the present invention. The coating to 148_ has the first suction 盍 40, and the first suction cover is separated from the second suction 盍 42 'with a plurality of staggered and separated paint dispensers 200, such as conventional air atomization. nozzle. The specific embodiment shown in Figure 6 illustrates three such paint dispensers 200, but should not be considered as limiting the invention. The paint dispenser is preferably movable or rotatable mounted on a stationary frame higher than the conveyor ㈣, the conveyor 16 for feeding the substrate to be coated f18 into a coating station 148. When: The paint dispenser 200 can also be selectively mounted to a movable frame or bridge to move the paint dispenser 200 relative to the substrate 18. The paint distribution system is connected to one or more paint sources and / or pressurized fluid sources. As shown in FIG. 6, the paint dispenser 200 is preferably directed downward to the substrate a to form a spray pattern on the substrate 18, such as an oval or elongate spray pattern. As shown in FIG. 7 of 9361 l.doc -19-1245024, each of the elongated patterns 150 has a major axis 152, a center 154, and an outer periphery or outer edge 156. The paint dispensers 200 are arranged so that the spray pattern of one paint dispenser 200 does not interfere with the spray pattern of the other paint dispenser 200. For example, the paint dispensers 200 may be arranged in a turn so that all the main shafts 152 are substantially parallel and away from each other. As shown in FIG. 7, as the substrate 18 moves through the coating table 148, the coating dispenser 200 sprays on the substrate 18 to form coating areas 158, respectively. The paint dispenser 2000 should be positioned so that the coating area 158 formed by one paint dispenser 20 does not extend beyond the graphic center 154 of the adjacent paint dispenser 200. Therefore, the coating regions 158 overlap to form the coating shown in FIG. 8, which has a central region 162 of substantially equal thickness and tapered or graded side regions 164 on each side of the coating. If desired, the coated substrate can be "cut into two or more pieces. For example, the substrate 18 can be cut into two separate smears halfway along the vertical axis shown in Fig. 8 with each piece having a grade The side area μ /, or slice 18 is cut into 3 pieces, the middle piece has a uniform coating, and the outer piece has a graded area. Although the coatings forming the elliptical coating pattern are discussed in the specific embodiments discussed above Dispenser, but the present invention is not limited by this _ circular coating pattern. For example, the coating pattern can be any shape, such as circle, ㈣, etc. In addition, multiple such coating stations can be installed in succession 148 /, The coating is sprayed onto the substrate. It is said that the coating and the transmission percentage of the coating slope substrate are different. ^ There are two coatings and one lateral branching. Figure 9 shows the reflection percentage, The coating station used for the percentage of uncoated surface reflection is the same as the coating station 148 shown in FIG. 6, and a coating dispenser 200 is at a distance of 5 inches (12 · 7 cm) from 93611.doc -20-1245024. .Approximately 〇i57 inches (40 millimeters thick α central inches (60.1 Magic width and 30 inches (76 · 2 cm) to 40 inches (⑻6 centimeters ^ ^ ^ ^ ^ f ^ ^ ^ ^ ^ ^ ^ ^ PPGi # △ Secretary to 'its registered trademark is SQLEXTRA⑧) for use Copper: spraying on an aqueous suspension of salt and fibrous salt mixture to pyrolyze the coating on the glass surface. The coating has a maximum thickness of about 400-600A (Angstroms) and is coated on each side of the glass sheet It has a tapered area. Measure the reflection percentages ~ and ~ and transmission percentages at selected positions across one tapered edge or glass edge of the coated glass sheet to the other tapered edge. On the abscissa of Figure 9, "0" Although the position phase is on one side of the coated glass sheet (such as the left side), the other abscissa positions indicate the distance from the side, and the reflection percentage R ^ R2 and transmission percentage 2 are at each position. The coating has higher transmission on the substrate edge. Area (such as a tapered area) 'and the lower transmission area (such as a thicker central area) in the middle of the substrate 18' and a smooth gradation transmission area in between. On the other hand, the coating has a lower Reflectances 1 and 1, while higher near the middle of the matrix Reflectivity. When measured separately, the Ri value is higher than the R2 value. As discussed above, the position of the adjacent paint dispenser 200 should be such that the spray pattern 150 of one paint distribution 200 does not interfere with the spray pattern 150 of the other paint dispenser 2⑼. 10 shows the reflection percentages & and & transmission percentages similar to the above coatings, but each spray of two adjacent paint dispensers 200 is deposited in a line perpendicular to the glass edge so that adjacent sprays are between Interference between two spray patterns. Interference between two spray patterns from the paint dispenser 200 forms a central area with heavy spots and uneven thickness. The reflection and transmission percentages are obtained by using CU_E (International Commission on Illumination) Standard, according to 93611.doc -21-1245024 Brightness C, light 2 degree observer. FIG. 11 illustrates a general vehicle 210. The vehicle 210 includes a wind screen 212, a rear window 214, and side windows 216, 218, and 220. According to the discussion in this article, these will be referred to collectively as π windows. "The side windows 216 and 218 are made of the coated glass of the present invention, forming a graded faded area 222 that is thinner and substantially transparent near the bottom. The first region 224 to the second region 226 with a thick coating and poor transparency near the top gradually changes. In a preferred embodiment, the window mounted on the vehicle 210 has a vertically-oriented faded region 222, such as the relevant side Windows 216 and 218 are shown. However, the faded area 222 can also be oriented horizontally as required, as shown in the relevant side window 220. If so, the faded area 222 can also be oriented at the top of the window with the first area 224. In addition, as related As described in the coating device, by applying different coatings to adjacent coating stations during the formation of the faded region 222, the formed faded region 222 can have a first color in the first region 224 and a second region 226 Has a different second color. Specific coating compositions and methods to obtain a selected transmission color coating will now be described. For ease of discussion, these mixtures and methods generally follow the resulting color Classification. However, these specific classifications should not be considered as limiting the invention. Oxidized steel coatings We have found that coatings (especially pyrolytically deposited coatings) formed from suspensions with copper and manganese containing components provide Excellent coating, its transmission color varies from amber (yellow brown) to light brown to blue gray to blue according to the molar ratio of copper to manganese in the suspension used. In detail, it contains manganese-containing acetone salt [P Mn (C5H702) 2 (hereinafter referred to as manganese acetoacetone) or 9361 l.doc -22-1245024 (hereinafter referred to as acetoacetone)] and copper-containing acetamone acetone salt [ie, Cu (C5H7. 2M is also called π-acetamidine copper acetone,)] The aqueous suspension of the mixture produces a coating with a change in transmission color from a certain range, the transmission color of the coating is from light brown (with high content of copper) or huzu color ( High content of manganese) to blue (copper to manganese molar ratio of 1 in coating) and blue-gray (molar ratio is slightly greater than 1 or less than 1). Color when copper to fierce molar ratio is increased or decreased The changes are listed in Table I, and are discussed in detail below in Figure 12. The coated substrates were mixed with copper and manganese Aqueous suspensions of acetone salts (such as copper acetate and manganese acetate) are manually sprayed onto a clean float glass substrate [cut into 4 inches x 4 inches (10.2 cm x 10.2 cm) square] The substrate is washed with a dilute detergent solution, washed with distilled water, and then air-dried. Copper acetoacetone cu (C5H7〇2) d0 is produced using conventional wet milling techniques. Mn (C5H7〇2) 2 and an aqueous acetone salt containing copper and manganese, mixed with deionized water and a chemical wetting agent in the required ratio, dispersing, degassing and suspending the metal salt particles of acetone acetone. The upper muffle furnace is heated to a sufficient temperature to ensure that the applied suspension is pyrolyzed (e.g. about 600). (:), then manually spray with a Binks 95 spray gun equipped with a gravity gravity feed reservoir. The transmission and reflection color ranges (as a function of the composition) of the second coated substrate are not shown in Table I, and the sample colors are shown in FIG. The reflection and transmission colors of the coated substrates are determined using the illumination objects a, 2 determined by the International Commission on Illumination (commmission International de). The observer is described in the form of conventional standard chromaticity coordinates γ, x, y. The coated substrate was analyzed by X-ray diffraction. The X-ray fluorescence analysis (,, XRF ,,) was used to determine the 93611.doc -23-1245024. Now, samples A6 to A8 of Table I mainly contain Cu in cubic system. ^ Mn ^ CU spinel-type phase, which generally occurs when the molar ratio of Cu / Mn of the coating ranges from 0.8 to 1.1, as shown in Table I. The copper-rich coatings of samples A1 and A2 are transmitted brown and rich The coating transmits amber (such as samples A13 and A14). 1 A14 I ΙΑΠ ....... Lai2 ..... | ΑΠ | ΐΑΙΟ ... > Sample only manganese 0.11 0.25 0.33 0.49 0.54 0.67 0.82 1.00 1.50 2.03 4.00 9.00 Only the molar ratio of 〇α (Π) / Μη (Π) in copper suspension is only manganese 0.12 0.28 0.38 0.61 0.86 0.79 0.91 1.10 1.75 2.42 5.48 20.57 only copper§ 1 蒎 1 31.17 1 1 25.23 1 1 24.90 1 1 27.07 1 1 27.00 ί 23.97 1 28.52 1 24.56 1 [28.22 1 1 24.87 1 1 26.92 1 1 19.06 1 1 26.27 1 23.81氺 (Illuminator A, 2 °) 0.4294 1 0.4235 1 1 0.4355 1 1 0.4452 1 1 0.4641 1 1 0.4597 1 1 0.4734 1 1 0.4734 1 1 0.4778 1 1 0.4610 1 1 0.4517 1 1 0.4338 1 1 0.4389 1 0.4350 X 0.4076 1 0.4019 1 1 0.4009 1 1 0.4021 丨 0: 4036 0.4027! 0.4067 1! 0.4057 1 1 0.4075 1 1 0.4044 1 1 0.4047 1 1 0.4047 1 1 0.4092 1 0.4084 'C 28.89 1 20.52 1 15.14 13.88 12.74 9.71 13.09 1 9.82 1 1 13.61 1 1 10.83 1 1 12.04 1 1 11.38 1 1 19.61 1 17.41 氺氺 (illuminator A, 2 °) 0.4266 1 0.4177 1 1 0.4146 1 0.4203! 0.4500 1 1 0.4432 1 1 0.4698 1 1 0.4722 1 1 0.4769 1 1 0.4460 1 1 0.4312 1 1 0.4347 1 1 0.4400 1 0.4419 X 1 0.4114] 1 0.4045 1 1 0.3950 1! 0.3915 1 I 0.3932 1! 0.3887 1! 0.3978 1 1 0.3960 1 1 0.4009 1 1 0.3937 1 0.3945 0.4072 0.4122 0.4131 1 61.68 1 1 61.80 1 1 49.09 1 1 40.13 1 1 31.37 1 1 38.16 1 1 27.85 1 1 34.78 1 1 27.46 1 1 35.78 1 1 37.26] "58.87 1 1 52.71 1 57.13 氺氺氺 (Illumination A, 2 °) 0.4650 1 0.4600 1 1 0.4478 1 Γ 0.4389 1 1 0.4213 1 1 0.4266 1 Γ 0.4107 1 1 0.4149 1 1 0.4065 1 [0.4290 1 1 0.4399 1 1 0.4576 liter 0.4676 0.4679 X 0.4150 1 0.4147 [0.4125 1 1 0.4109 1 1 0.4075 1 1 0.4083 1 1 0.4039 1 [0.4058 1 1 0.4029 1 1 0.4090 1 1 0.4115 1 1 0.4131 1 1 0.4135 1 0.4139 1

OHOH

QslflstIe-I_ J I I ϊ*I 93611.doc -24- 1245024 實例#2 在該實例中，基質係如下製備和塗覆。將4毫米厚、4英寸X4央寸（1〇·2厘米χ1〇·2厘米）方形的浮法玻璃片通過稀洗滌劑溶液洗淨，用蒸顧水清洗，然後將基f經空氣乾燥。將淨化的玻璃基質用2_丙醇和㈣水之溶液（湖q體積百分比）喷上，以纖維素性聚酯布擦乾、除去髒物、不含需要的薄膜、手印和/或碎屑。以習用濕化研磨技術提供乙酿丙酮銅和乙酸丙舰之含水懸浮液。將這些單-的乙酸丙酮金屬鹽之懸洋液一起混合，產生具有〇^/^^11莫耳比為9 〇9 至0.43的二元懸浮液。將玻璃基質送人臺上隔焰加熱爐，加熱至約_°(：。將經加熱的玻璃基f㈣備重力自流進料儲抑的喷％手工噴上塗料的水性懸浮液。實驗所使用喷槍包括賓克（BinkS)63型PB氣帽、賓克63型“流體噴嘴和賓克 663型針。喷％的霧化空氣壓力設定於5〇磅/平方英寸。水性懸洋液以離玻璃表面約1〇英寸（25·4厘米）距離向基質喷射約8秒鐘。如表II所示，Cu/Mn莫耳比大於或等於1513的薄膜產生了透射棕色的經塗覆基片。對於表„中扪49樣品，隨著薄膜中Cu/Mn莫耳比（用X射線螢光法測定）的減小，其透射色自淺棕至灰監至深藍再至淺藍色變化。經χ射線螢光分析法測定，表II中B6-B8樣品的深藍色塗層主要含立方品系 CuuMnuO4大晶石類型相，且一般發生於薄膜中α/Μη莫耳比自0.8至1.2之範圍（χ射線螢光法測定）。沈積後，將經塗覆基貝加熱至650 C約10分鐘。該加熱導致了發光透射百 93611.doc -25- 1245024 分率的變化（△ Y)及顏色的變化（在表II中顯示為△ E (FMCII))。為便於討論，加熱處理後的透射率增加在本文中稱為’’漂白’’。表II中的△ E(FMCII)係指經塗覆基質於加熱前和加熱後的顏色差。△ E(FMCII)係根據CIE(國際照明委員會）的比色計委員會（Colorimetry Committee)確定的習用公式測定。我們應注意到，CiMjMn^CU的藍色尖晶石類型相能夠通過使用Cu(II)/Mn(II)的乙醯丙酮鹽懸浮液產生，如表I中的樣品A6-A8。同樣的尖晶石類型相係於使用Cu(II)/Mn(III) 乙烯丙酮鹽懸浮液的表Π樣品B6-B8中觀察到。雖然表I未展示樣品A6-A8加熱處理後的結果，但可以預見，此等樣品係以表II樣品B6-B8相似的方式漂白。QslflstIe-I_ J I I ϊ * I 93611.doc -24-1245024 Example # 2 In this example, the substrate was prepared and coated as follows. A 4 mm thick, 4 inch x 4 inch (10.2 cm x 10.2 cm) square float glass sheet was washed with a dilute detergent solution, washed with distilled water, and then the substrate was air-dried. Spray the purified glass substrate with a solution of 2-propanol and water in water (percentage by volume of lake q), wipe dry with a cellulose polyester cloth, remove dirt, and contain no needed films, fingerprints, and / or debris. Provides an aqueous suspension of copper acetoacetone and acetic acid propane using conventional wet grinding technology. These mono-acetic acid acetone metal salt suspensions are mixed together to produce a binary suspension having a Mo / r ratio of 109 / 0.43. The glass substrate was sent to a flame-retarding heating furnace on the table, and heated to about _ ° (:. The heated glass substrate was prepared by gravity gravity feed storage spraying and sprayed by hand with an aqueous suspension of the coating. The spray used in the experiment was The gun includes a BinkS Type 63 PB air cap, a Bink Type 63 "fluid nozzle, and a Bink Type 663 needle. The spraying atomization air pressure is set at 50 psi. The surface was sprayed toward the substrate at a distance of about 10 inches (25.4 cm) for about 8 seconds. As shown in Table II, a film having a Cu / Mn molar ratio greater than or equal to 1513 produced a coated substrate that was transmissive brown. For Table „Medium 扪 49 sample, with the decrease of Cu / Mn molar ratio (measured by X-ray fluorescence method) in the film, its transmission color changes from light brown to gray monitor to dark blue to light blue. Χ According to the ray fluorescence analysis method, the dark blue coatings of the B6-B8 samples in Table II mainly contain cubic CuuMnuO4 large crystal type phases, and generally occur in the range of α / Μη Mor ratio from 0.8 to 1.2 in the film (χ X-ray fluorescence method). After deposition, the coated substrate was heated to 650 C for about 10 minutes. This heating guide The change in light transmittance percentage (△ Y) and color change (shown as △ E (FMCII) in Table II) are shown. For the sake of discussion, the transmittance after heat treatment is increased in this article. It is called bleaching. △ E (FMCII) in Table II refers to the color difference between the coated substrate before heating and after heating. △ E (FMCII) refers to the colorimetric according to CIE (International Commission on Illumination) It is determined by the conventional formula determined by the Colorimetry Committee. We should note that the blue spinel-type phase of CiMjMn ^ CU can be generated by using the acetamidine acetone salt suspension of Cu (II) / Mn (II), such as Samples A6-A8 in Table I. The same spinel type phase was observed in Table II samples B6-B8 using a Cu (II) / Mn (III) ethylene acetone salt suspension. Although Table I does not show samples Results of A6-A8 after heat treatment, but it is foreseeable that these samples were bleached in a similar manner to Table B samples B6-B8.

表II 樣品編號 Cu(II)/ Mn(III) 懸浮液之莫耳比經沈積薄膜中的 Cu/Mn 莫耳比尤積薄膜之透射色度值(照明物A，2°) 於650°C，10分鐘加熱處理後的透射色度值變化 (照明物A，2°) ΔΕ (FMCII) Y X y ΔΥ △ X △y B1 9.09 15.13 50.59 0.4713 0.4135 2.56 -0.0049 0.0001 6·56_ B2 4.00 5.93 47.98 0.4644 0.4138 2.95 -0.0111 -0.0009 12.81 B3 2.33 3.31 38.66 0.4538 0.4135 1.90 -0.0130 -0.0020 13.13 B4 1.49 2.11 38.56 0.4417 0.4188 2.14 0.0123 -0.0020 12.48 B5 1.00 1.41 37.15 0.4288 0.4089 6.42 -0.0058 -0.0016 13.33 B6 0.82 1.15 31.57 0.4164 0.4058 7.07 0.0041 0.0012 15.54 B7 0.67 0.94 29.57 0.4112 0.4043 7.10 0.0103 0.0029 19.19 B8 0.54 0.78 23.55 0.4044 0.4009 8.13 0.0167 0.0059 27.14 B9 0.43 0.60 39.38 0.4266 0.4082 6.88 0.0100 0.0027 16.61 擴散偶合實驗在Cu-Mn系統中，銅為易移動種類’其測定係基於以下實驗完成。將CuO薄膜喷塗到經加熱的第一塊石英基質表 93611.doc -26- 1245024 面上。在以下的討論中，基質塗覆時約為600°C。將Μη304 薄膜喷到第二塊經加熱的石英基質表面上。然後將兩塊基質面對面連在一起，使部分經塗覆表面彼此接觸，而經塗覆表面的剩餘部分與另一塊不接觸，即，部分經塗覆表面彼此不接觸。將該基質加熱至650°c，且保持16.2小時。分開時’直接與第一塊基質經塗覆表面銅薄膜接觸的第二塊基質經塗覆蓋表面部分用裸眼觀察，呈暗藍色。可以相信，此係由於銅離子自CuO薄膜遷移到Mn3〇4薄膜，形成具有 CuuMn^O4尖晶石類型相的暗藍色塗層。對應的cu〇薄膜區域在加熱時更淺，表明消耗了銅離子。第二塊基質上未與CuO薄膜接觸的Mho#薄膜部分在加熱時自琥珀色薄膜轉化為淡紫色/薰衣草色。在進的貫驗中，CuO薄膜沈積於經加熱的石英基質上，而Μϋ3〇4薄膜沈積於經加熱的玻璃基質上。然後將兩塊基質面對面連在一起，且部分經塗覆表面與另一塊相連，剩餘部分與另一塊不接觸。將該基質加熱至65〇t：保持％分鐘。分開時，直接與第一塊基質經塗覆表面Cu〇薄膜接觸的第二塊基質經塗覆表面以裸眼觀察，透射暗藍色。可以相信，此係由於銅離子自氧化銅（Cu〇)薄膜遷移到％〜山，幵y成日日監色CuuMnuO4的尖晶石類型相。石英基質上的對應膜很淺，表示耗盡了銅離子。薄膜的剩餘部分變化很小，表不銅離子不易擴散進入石英，而優先擴散進入沈積於玻璃基質的Mn3〇4薄膜巾，形成暗藍色Cu"Mn“〇4的尖晶石類型相。這又表明，錳離子不優先擴散進入玻璃， 93611.doc -27- 1245024 或者說錳離子較銅離子擴散更為緩慢。將CuO薄膜沈積於經加埶的玻璃 …、旧敬嘴I貝上，而Mn3〇4薄膜沈積於經加熱的石英基質上。接著將兩塊基質面對面偶合，加熱到65Gt且保持30分鐘。分離時，不與玻璃上氧化銅薄膜接觸的石英上’琥珀色—A薄膜表面轉化為淡紫色 Μη304薄膜。石英基質的―小部分顯示出—片藍色區域，表示存在暗藍色CUl.4Mni.6〇4尖晶石類型相。然而，大多數銅擴散入玻璃，而未進入沈積於石英上的Mho#薄臈。因此從这些貫驗得出結論，銅離子為CuMn〇x物系中的最易移動種類，且為必須防止擴散進入玻璃基質的主要種類。防止漂白如以上實例#2的有關討論，玻璃基質上的沈積薄膜在隨後加熱處理後趨向於改變顏色，如回火或退火。可以相信，這是由於塗層和玻璃基質之間易移動種類發生離子交換的結果。我們知道，於玻璃基質和塗層之間置入惰性層作為阻擋層，將有助於防止此等擴散。然而，這些阻擋並非總是有效。因此，現已研究出一種替代方法，該方法用一種濃度梯度層置於塗層和基質之間，阻止或減慢擴散。這一概念通常可如下解釋：如果已知單層氧化物塗層[為便於討論，用ABCOx表示（其中A、B、C為塗層中的金屬離子）]改變顏色（如，加熱處理後漂白），例如由B離子擴散進入玻璃基質交換出D 離子（如驗離子）]，那麼BOx薄膜可沈積於玻璃基質和ABc〇塗層之間。就此我們瞭解，可用具有兩種或多種金屬離子 93611.doc -28 - 1245024 之單層氧化物塗層實施本發明。為防止漂白，Β〇χ層提供了犧牲性或濃度梯度層。該犧牲性層的B離子比ABCOx塗層的 B離子更易於擴散進入玻璃。因而，通過於ABC〇x層和玻璃之間置入BOx夾層，BOx内襯層中的b離子將部分或全部擴政進入玻璃。BOx層作為濃度梯度層防止或減慢B離子自外塗層或ABCOx塗層擴散進入玻璃基質。結果是，ABC〇x外衣層中的B離子較為緩慢地進入Β〇χ内襯層，使ABC〇x層遞減最小，而BOx内襯層的B離子大部分擴散進入玻璃（可能有少量進入外衣層）。因此，通過調節Β〇χ層的厚度和組份以及ABCOx外衣層的厚度和組份，能夠控制經塗覆玻璃的透射顏色。此係由時間、溫度和薄膜厚度作用，將大部分或全部BOx層破壞，使實f上只有所需的胤匕外衣層留在外面。BOx層較佳直接沈積於玻璃基質上，但亦可沈積於基質的另一種塗層上。為充當濃度梯度阻擋層，沈積B〇x層應使經塗覆玻璃内的顏色變化以及自外衣層進人玻璃❹料擴散均達到最 J例如，加熱處理時，上述CuuMnuO4藍色薄膜可能漂白導致發色團的晶體結構破壞，以至斑點處的顏色不再出現（例如，於65(TC加熱16小時），而且銅和轉子擴散進入玻璃。如上討論’銅為該系統的最易移動種類。因此，製得的雙層物系包括玻璃/CuQ/Cui4Mni6〇4。沈積厚度變化Cu0層的實驗結果顯示於以下的表m中。製造f層期間’塗料係沈積於未支撐於錫洛上玻璃面的經、予法玻璃面上。未切表面經塗覆，於熱解流水線上 93611.doc -29- 1245024 完成，或於浮法條板上形成CVD塗層。自浮法條板切成的玻璃片之富錫表面尚於實驗室實驗階段塗覆。但經測定，玻璃之富錫表面於加熱處理期間充當阻擋層，阻止離子自，層擴散進入玻璃，且錫離子充當了阻播層。Cu〇層在破璃上沈積後，將CuuMn】6〇4層沈積於Cu〇層上。層的厚度隨乙醢丙酮銅鹽懸浮液喷向玻璃基質的噴射時間^化 :變化，例如’ 2秒鐘喷射時間產生的Cu〇層較時鐘噴射日寸間產生的CuO層薄。Cu〇層的厚度自約5〇A(2秒鐘噴射時間)至約200人(8秒鐘噴射時間)變化。就此我們能夠瞭* ^⑩ 本發明不受氧化銅層厚度的限制，在本發明的實施中，h 埃α)至26〇a範圍的厚度均可接受。Cui為6〇4層的厚度不變’約為3〇〇A。cUl.4Mni.6〇4薄膜係通過將鋼（11)和猛（πι) 之乙醯丙《鹽以0.54之莫耳比噴射8秒鐘沈積，沈積層具有_ 約300A厚度。就此我們又能夠瞭解，本發明不受 CuuMnuO4薄膜厚度的限制，1〇〇人至7〇〇入範圍的厚度均可接叉。樣品的薄膜厚度係通過分光橢圓光度法測定。我們清楚地注意到於玻璃上沈積塗層的漂白效應，如浮法工藝製造玻璃；然而在石英上沈積塗層，漂白效應不像玻璃基質那樣，因為石英基質僅存在百萬分計的離子，離子交換減少，以致石英基質上幾乎沒有離子交換。Table II Sample No. Cu (II) / Mn (III) Suspension Molar Ratio Cu / Mn Molybdenum Film Deposited Film Transmittance Chromaticity Value (Illumination Object A, 2 °) at 650 ° C The change in transmission chromaticity value after 10 minutes heat treatment (illumination object A, 2 °) ΔΕ (FMCII) YX y ΔΥ △ X △ y B1 9.09 15.13 50.59 0.4713 0.4135 2.56 -0.0049 0.0001 6 · 56_ B2 4.00 5.93 47.98 0.4644 0.4138 2.95 -0.0111 -0.0009 12.81 B3 2.33 3.31 38.66 0.4538 0.4135 1.90 -0.0130 -0.0020 13.13 B4 1.49 2.11 38.56 0.4417 0.4188 2.14 0.0123 -0.0020 12.48 B5 1.00 1.41 37.15 0.4288 0.4089 6.42 -0.0058 -0.0016 13.33 B6 0.82 1.15 31.57 0.4164 0.4058 7.07 0.0041 0.0012 0.0012 15.54 B7 0.67 0.94 29.57 0.4112 0.4043 7.10 0.0103 0.0029 19.19 B8 0.54 0.78 23.55 0.4044 0.4009 8.13 0.0167 0.0059 27.14 B9 0.43 0.60 39.38 0.4266 0.4082 6.88 0.0100 0.0027 16.61 In the Cu-Mn system, copper is a mobile species' its measurement system Based on the following experiments. A CuO film was sprayed onto the first heated quartz substrate surface 93611.doc -26-1245024. In the following discussion, the substrate is coated at approximately 600 ° C. A Mη304 film was sprayed onto the surface of a second heated quartz substrate. The two substrates are then joined face to face so that part of the coated surface is in contact with each other, and the remainder of the coated surface is not in contact with the other, i.e., part of the coated surface is not in contact with each other. The substrate was heated to 650 ° C and held for 16.2 hours. At the time of separation ', the second substrate directly in contact with the copper film on the coated surface of the first substrate was observed with the naked eye after coating the surface portion of the second substrate, showing a dark blue color. It is believed that this is due to the migration of copper ions from the CuO film to the Mn304 film, forming a dark blue coating with a CuuMn ^ O4 spinel type phase. The corresponding cuO film area is shallower when heated, indicating that copper ions are consumed. The portion of the Mho # film on the second substrate that was not in contact with the CuO film was converted from an amber film to a lavender / lavender color when heated. In further tests, CuO films were deposited on a heated quartz substrate, and Mϋ304 films were deposited on a heated glass substrate. The two substrates are then joined face-to-face, with a portion of the coated surface connected to the other, and the remaining portion is not in contact with the other. The substrate was heated to 6Ot: held for% minutes. When separated, the coated surface of the second substrate directly in contact with the Cu film of the coated surface of the first substrate was observed with the naked eye and transmitted dark blue. It is believed that this is a spinel-type phase of CuuMnuO4 due to the migration of copper ions from the copper oxide (Cu0) film to% ~ Mo. The corresponding film on the quartz substrate is shallow, indicating that the copper ions are depleted. The remaining part of the film changes little, indicating that copper ions do not easily diffuse into the quartz, but preferentially diffuse into the Mn304 film towel deposited on the glass substrate, forming a dark blue Cu " Mn "〇4 spinel type phase. This It also shows that manganese ions do not diffuse into glass preferentially, 93611.doc -27-1245024 or manganese ions diffuse more slowly than copper ions. CuO thin film is deposited on the glass to be added ... The Mn304 film was deposited on a heated quartz substrate. Then the two substrates were coupled face to face, heated to 65Gt and held for 30 minutes. When separated, the surface of the amber-A film on the quartz that was not in contact with the copper oxide film on the glass was separated. Converted to lilac Mn304 film. A small portion of the quartz matrix shows a blue area, indicating the presence of a dark blue CU1.4Mni.604 spinel type phase. However, most copper diffuses into the glass without Enter Mho # 臈, which is deposited on quartz. Therefore, it is concluded from these experiments that copper ions are the most mobile species in the CuMnox system, and are the main species that must be prevented from diffusing into the glass matrix. Preventing bleaching As discussed in Example # 2 above, the deposited film on the glass substrate tends to change color, such as tempering or annealing, after subsequent heat treatment. It is believed that this is due to the species that are easy to move between the coating and the glass substrate The result of ion exchange. We know that placing an inert layer between the glass substrate and the coating as a barrier will help prevent such diffusion. However, these barriers are not always effective. Therefore, an alternative has been developed Method, which uses a concentration gradient layer placed between the coating and the substrate to prevent or slow diffusion. This concept can usually be explained as follows: If a single-layer oxide coating is known [for ease of discussion, use ABCOx ( Where A, B, and C are metal ions in the coating)] change the color (such as bleaching after heat treatment), for example, the diffusion of B ions into the glass matrix to exchange D ions (such as test ions)], then the BOx film can be deposited Between the glass substrate and the ABc0 coating. For this we understand that a single-layer oxide coating with two or more metal ions 93611.doc -28-1245024 can be used. Invention. To prevent bleaching, the BOX layer provides a sacrificial or concentration gradient layer. The B ions of the sacrificial layer diffuse into the glass more easily than the BCOx coated B ions. Therefore, the A BOx interlayer is interposed, and part or all of the b ions in the BOx inner layer will expand into the glass. The BOx layer acts as a concentration gradient layer to prevent or slow the diffusion of B ions from the outer coating or ABCOx coating into the glass matrix. The result is The B ions in the ABC〇x outer coating layer enter the B 0χ inner liner relatively slowly, so that the ABC 0x layer decreases gradually, while most of the B ions in the BOx inner liner diffuse into the glass (a small amount may enter the outer coating layer) Therefore, by adjusting the thickness and composition of the B0x layer and the thickness and composition of the ABCOx coating layer, the transmission color of the coated glass can be controlled. This system is affected by time, temperature and film thickness, and destroys most or all of the BOx layers, so that only the required outer coat layer is left on the outside. The BOx layer is preferably deposited directly on the glass substrate, but may also be deposited on another coating on the substrate. In order to act as a concentration gradient barrier, the deposition of the B0x layer should maximize the color change in the coated glass and the diffusion of the glass material from the outer layer into the glass material. For example, during heat treatment, the above-mentioned CuuMnuO4 blue film may cause bleaching. The crystal structure of the chromophore is broken, so that the color at the spots no longer appears (for example, at 65 (TC heated for 16 hours), and copper and the rotor diffuse into the glass. As discussed above, 'copper is the most mobile species of this system. Therefore The obtained double-layer system includes glass / CuQ / Cui4Mni60. The experimental results of the deposited Cu0 layer with varying thickness are shown in the following table. During the manufacture of the f-layer, the coating system was deposited on the glass surface not supported on the silo. Warp and pre-processed glass surface. The uncut surface is coated and completed on the pyrolysis line 93611.doc -29-1245024, or a CVD coating is formed on the float strip. Cut from the float strip The tin-rich surface of the glass sheet is still coated in the laboratory experimental stage. However, it has been determined that the tin-rich surface of the glass acts as a barrier layer during heat treatment to prevent the ions from self-diffusing, the layer diffuses into the glass, and the tin ions act as a propagation barrier layer After the Cu0 layer is deposited on the broken glass, a CuuMn] 604 layer is deposited on the Cu0 layer. The thickness of the layer varies with the spray time of the acetone-acetone copper salt suspension to the glass substrate: change, for example, ' The Cu0 layer produced by the 2 second spray time is thinner than the CuO layer produced by the clock injection day. The thickness of the Cu0 layer ranges from about 50A (2 second spray time) to about 200 people (8 second spray time). In this regard, we are able to realize that the present invention is not limited by the thickness of the copper oxide layer. In the practice of the present invention, thicknesses ranging from h Angstrom α) to 260a are acceptable. Cui has a constant thickness of 604 layers' and is about 300A. The cUl.4Mni.604 film is deposited by spraying steel (11) and acetonitrile (salt) at a molar ratio of 0.54 for 8 seconds, and the deposited layer has a thickness of about 300A. In this regard, we can understand that the present invention is not limited by the thickness of the CuuMnuO4 film, and the thickness can range from 100 to 700 mm. The film thickness of the sample was measured by spectroscopic ellipsometry. We clearly notice the bleaching effect of depositing coatings on glass, such as in the float process. However, when depositing coatings on quartz, the bleaching effect is not the same as that of glass substrates, which have only millions of ions. Ion exchange is reduced so that there is almost no ion exchange on the quartz matrix.

表III 在加熱丽及於650。(：加熱處理1〇分鐘後，淨玻璃/Cu〇/ CUl.4Mni.604樣品的Cu0層厚度變化效應。π 薄膜·. 係以Cu(n)/Mn(III)莫耳比為〇 54的懸浮液用8秒鐘喷射時' 93611.doc -30 - 1245024 間沈積。實例編號喷射時間(秒) CuO/ Cui.4Mni.6〇4 沈積薄膜之透射色度值 (照明物A，2°) 於650°C加熱處理10分鐘後之透射色度值變化 (照明物A，2°) Y X y ΔΥ Δχ △y D1 2/8 加熱前 47.20 0.4271 0.4086 加熱後 53.03 0.4317 0.4092 5.83 0.0046 0.0006 D2 3/8 加熱前 42.97 0.4279 0.4088 加熱後 44.78 0.4245 0.4076 1.81 -0.0034 -0.0012 D3 4/8 加熱前 40.09 0.4328 0.4099 加熱後 40.83 0.4273 0.4085 0.74 -0.0055 -0.0014 D4 6/8 加熱前 33.01 0.4333 0.4111 加熱後 33.55 0.4280 0.4096 0.54 0.0052 -0.0015 D5 8/8 加熱前 34.03 0.4444 0.4126 加熱後 34.72 0.4408 0.4119 0.69 -0.0036 -0.0008 由於雙層物系（玻璃/CuO/CuuMn^CU)中存在淺棕色 CuO底層，所以沒有與CuuMnuCU尖晶石類型相有關的典型藍色。該雙層物系於650 °C加熱10分鐘，與具有 CuuMnuC^尖晶石類型相塗層的單層沈積且未力口熱之樣品比較。具有相同CuO底層（靠近玻璃）的上層Cu/Mn莫耳比 (自0.82至1.49)之變化結果以及經沈積的雙層物系與相同經加熱處理的雙層物系之比較結果於表IV顯示。對各雙層物系加熱後，由於濃度梯度阻止性CuO層的銅離子擴散進入玻璃，其後剩留所需的CiiuMn^CU藍色尖晶石類型的外層，透射顏色又為藍色。加熱處理前和加熱處理後，雙層物系的透射率發生變化（漂白）△ Y，Cu/Mn之比為0.82時，自11%減小至 0.75%; Cu/Mn 之比為 1.00時，自 6.4% 減小至 0.26%;而 Cu/Mn 之比為1.49時，自3.4%減小至-0.32%(加熱處理後變暗）。而且，△ E(FMCII)[上述三個樣品的顏色變化，用麥阿丹裝置 93611.doc -31 - 1245024 (Mac Adam Units)測定]分別自1 8· 1減小至3 ·4 ’ 1 7·8減小至 3.7以及自15.1減小至4.9，因為玻璃的經承載表面上存在 CuO 層0Table III is heated at 650 ° C. (: After 10 minutes of heat treatment, the effect of Cu0 layer thickness change of the clear glass / Cu0 / CU1.4Mni.604 sample. Π thin film.. Based on Cu (n) / Mn (III) molar ratio of 54 When the suspension is sprayed for 8 seconds, '93611.doc -30-1245024 is deposited. Example No. Spray time (seconds) CuO / Cui.4Mni.6〇4 Transmission chromaticity value of the deposited film (illuminant A, 2 °) Change in transmission chromaticity value after heating at 650 ° C for 10 minutes (illumination object A, 2 °) YX y ΔΥ Δχ △ y D1 2/8 before heating 47.20 0.4271 0.4086 after heating 53.03 0.4317 0.4092 5.83 0.0046 0.0006 D2 3/8 Before heating 42.97 0.4279 0.4088 After heating 44.78 0.4245 0.4076 1.81 -0.0034 -0.0012 D3 4/8 Before heating 40.09 0.4328 0.4099 After heating 40.83 0.4273 0.4085 0.74 -0.0055 -0.0014 D4 6/8 Before heating 33.01 0.4333 0.4111 After heating 33.55 0.4280 0.4096 0.54 0.0052 -0.0015 D5 8/8 Before heating 34.03 0.4444 0.4126 After heating 34.72 0.4408 0.4119 0.69 -0.0036 -0.0008 Because there is a light brown CuO underlayer in the double-layer system (glass / CuO / CuuMn ^ CU), it is not the same as CuuMnuCU spinel type Relative Typical blue color. The double layer is heated at 650 ° C for 10 minutes, compared with a single-layer deposited and unheated sample with a CuuMnuC ^ spinel type phase coating. It has the same CuO bottom layer (close to the glass) The results of the change in the Cu / Mn molar ratio of the upper layer (from 0.82 to 1.49) and the comparison of the deposited double-layer system and the same heat-treated double-layer system are shown in Table IV. Each double-layer system was heated Later, due to the concentration gradient preventing the copper ions of the CuO layer from diffusing into the glass, the required CiuMn ^ CU blue spinel type outer layer remained, and the transmission color was blue again. Before and after heat treatment, The transmittance of the double-layer system changes (bleaching) △ Y, when the Cu / Mn ratio is 0.82, it decreases from 11% to 0.75%; when the Cu / Mn ratio is 1.00, it decreases from 6.4% to 0.26% When the Cu / Mn ratio is 1.49, it decreases from 3.4% to -0.32% (darkness after heat treatment). Moreover, ΔE (FMCII) [color change of the above three samples, measured with a Macadam apparatus 93611.doc -31-1245024 (Mac Adam Units)] was reduced from 1 8 · 1 to 3 · 4 '1 7 · 8 to 3.7 and 15.1 to 4.9 because of the CuO layer on the loaded surface of the glass 0

Η—i K) W Η—* h—ι W ο W ν〇 W 00 W w ON w Ui w w LO Μ to Μ 綠Sq C ρ ο ο C ί>< *1 ο 1 ?? si C ρ ο ο C ρ ο *1 0 1 i o g o o c ¥g *1 ο I 端紅濟: 蒎淼含 S障 Η—ι ο Η—1 o ο bo K) ο 00 κ> 00 ο οο o 00 ο a Μ ^ ^ =淨V a 交 ^ a w ^ 00 00 00 00 οο 00 ^ a Η t Ρ -Κ a U) 〇 LO 1—ι u> 00 to U) U) to 00 Κ) σ> Uj to o ’Ό Lk) LO CO *00 U) u> 00 § Ον 一 00 iS -¾ 爹氣 > S to聲 0 [B> 〇 *4^ ο ί: to ο 6 ί—1 ο ο ο 00 to ο to o 2 o U) VO <1 o to ο 'ί; S ο ο to <1 Ρ>< 〇 to ο U) ο έ ο 4^ ο *4^ ίο ο 占 U) U) o •会 VO o to P o ο H-i ο ο \〇 ο 4^ ο Ό ρ Lk> U) ο to ON U) o Κ—k •ο Η-Α [> ►-< 海S琴 :辩a §：驾：〇 > 「） ^ )¾ ^ 。瞬磬 ms CT ρ ο Lr\ <1 ό ο U) νο ό ο ο to ό o )—J LO o ό o s ρ ο Η—i 00 > X ό Ο Η—1 1—ι ρ ο S U) 6 ο ο ό o s LO p o o ρ ο ο > 4^ 00 Ό § U) Ον 1—t o U) 6 οο § > % W G -32- 93611.doc 1245024 加入其他含金屬組份（如含過渡金屬的乙醯丙酮鹽）改良了塗層的反射和透射性能，進而改變塗層的顏色吸收。例如’氧化MnCuCr之薄膜趨向於中灰色。雖然在上述實例中含銅的乙醯丙酮鹽和含錳的乙醯丙酮鹽係作為混合物噴到經加熱基質上，但為獲得相同的所需顏色亦可將單個的乙醯丙酮鹽懸浮液依次喷到經加熱的基質上。例如應用圖2所示的塗覆設備，將含銅物質之懸浮液 (如乙醯丙酮銅）噴到經加熱的玻璃基質上，該基質經冷卻和重新加熱，然後用含錳物質（如乙醯丙酮亞錳和乙醯丙酮錳）噴塗，產生Cu-Mn發色團的所需顏色（如藍色）。亦可首先將乙醯丙酮亞錳或乙醯丙酮錳喷到基質上，隨後噴上單獨的乙醯丙酮銅塗料，以獲得所需之顏色。而且，我們瞭解，本發明未限制塗覆期間的基質溫度，能夠使塗層熱解的任一溫度均可接受，如400°C和900°C。另外，二元或三元金屬的乙醯丙酮鹽亦可用於沈積薄膜，如AxB/CsHvOJi，其中A或B為金屬離子（如銅或錳），χ、丫和丨為使所需二元乙醯丙明鹽化合物之式達到平衡的莫耳數。雖然上述錳或亞錳和銅的乙醯丙酮鹽物系產生了藍色生色團’但所得之藍色塗層具有相對不良的耐酸性。進行以下實驗是為了發現產生所需具有耐久性顏色的銅 /錳物系之莫耳比。將基質用以前實例#1對基質的討論方法淨化。其塗料為磨細的乙醯丙酮錳鹽、銅鹽和鈷鹽之混合物。磨細物質懸浮於水性懸浮液，具有起始組合物之懸浮液列於表V中。懸浮液中不同Cu(II)/Mn(III)莫耳比的8個樣 93611.doc -33- 1245024 品結果展示於表v中。起始混合物的組份以及所生成的薄膜係經D. C.等離子體法分析。我們發現，透射藍灰色的薄膜具有約為1的銅/錳之莫耳比。其他組合物外觀呈琥珀色。表V右欄給出了根據習知ASTM(美國材料實驗學會標準）2 8 2 - 6 7檢驗方法檢驗的塗層結果[ί法鄉（ename 1)财酸性標準檢驗方法，檸檬酸點滴實驗]。’’是’’表示耐久性可以接受。Η—i K) W Η— * h—ι W ο W ν〇W 00 W w ON w Ui ww LO Μ to Μ green Sq C ρ ο ο C ί > < * 1 ο 1 ?? si C ρ ο ο C ρ ο * 1 0 1 iogooc ¥ g * 1 ο I terminal red economy: 蒎 miao with S obstacle Η—ι ο Η—1 o ο bo K) ο 00 κ > 00 ο οο o 00 ο a Μ ^ ^ = Net V a ^ aw ^ 00 00 00 00 οο 00 ^ a Η t Ρ -Κ a U) 〇LO 1—ι u > 00 to U) U) to 00 Κ) σ > Uj to o 'Ό Lk) LO CO * 00 U) u > 00 § Ον one 00 iS -¾ Daddy > S to sound 0 [B > 〇 * 4 ^ ο ί: to ο 6 ί—1 ο ο ο 00 to ο to o 2 o U) VO < 1 o to ο 'ί; S ο ο to < 1 Ρ > < 〇to ο U) ο ο ο 4 ^ ο * 4 ^ ίο ο account vo o to P o ο Hi ο ο \ 〇ο 4 ^ ο ρ ρ Lk > U) ο to ON U) o Κ—k • ο Η-Α [> ►- < Hai Sqin: Debate a §: Driving: 〇 > ") ^) ¾ ^. Instantaneous ms ms CT ρ ο Lr \ < 1 ό ο U) νο ό ο ο to ό o) —J LO o ό os ρ ο Η—i 00 > X ό Ο Η Η —1 1—ι ρ ο SU) 6 ο ο os LO poo ρ ο ο > 4 ^ 00 Ό § U) Ον 1—to U) 6 οο § >% WG -32- 93611.doc 1245024 Improved by adding other metal-containing components (such as transition metal-containing acetamidine acetone salt) The reflection and transmission properties of the coating change the color absorption of the coating. For example, the film of oxidized MnCuCr tends to be medium gray. Although the copper-containing acetoacetone salt and manganese-containing acetoacetone salt are used as a mixture in the above examples. Spray onto a heated substrate, but individual acetamidine suspensions can also be sprayed onto the heated substrate in order to obtain the same desired color. For example, using the coating equipment shown in FIG. 2, a suspension of a copper-containing substance (such as copper acetoacetone) is sprayed onto a heated glass substrate, the substrate is cooled and reheated, and then a manganese-containing substance (such as B (Manganese acetone manganese and ethyl acetomanganese acetone)) spray to produce the desired color (such as blue) of the Cu-Mn chromophore. Alternatively, first spray manganese acetoacetone or manganese acetoacetone onto the substrate, and then spray a separate copper acetoacetone coating to obtain the desired color. Moreover, we understand that the present invention does not limit the substrate temperature during coating, and any temperature capable of pyrolyzing the coating is acceptable, such as 400 ° C and 900 ° C. In addition, acetoacetone salts of binary or ternary metals can also be used to deposit thin films, such as AxB / CsHvOJi, where A or B is a metal ion (such as copper or manganese), and χ, γ, and 丨 are the required binary ethyl The molar number of the formula of the hydrazone salt compound reaches equilibrium. Although the above-mentioned acetoacetone salt system of manganese or manganese and copper generates a blue chromophore ', the resulting blue coating has relatively poor acid resistance. The following experiments were performed to find the molar ratio of copper / manganese systems that produce the desired durable color. The substrate was purified using the method discussed previously for substrate # 1. The coating is a mixture of finely ground acetoacetone manganese salt, copper salt and cobalt salt. The ground material is suspended in an aqueous suspension, and the suspension with the starting composition is listed in Table V. Eight samples with different Cu (II) / Mn (III) molar ratios in the suspension 93611.doc -33-1245024 The results are shown in Table v. The composition of the starting mixture and the resulting film were analyzed by D. C. plasma method. We found that the transmission blue-gray film had a copper / manganese molar ratio of about 1. Other compositions were amber in appearance. The right column of Table V shows the coating results tested according to the conventional ASTM (American Society of Materials Testing Standards) 2 8 2-6 7 inspection method [ί 法乡 (ename 1) acid acid standard inspection method, citric acid drip test] . "'Yes'" indicates that the durability is acceptable.

表V 樣品編號起始組分％(DCP) CuII/Mnll 懸浮液莫耳比薄膜中 Cu/Mn 莫耳比透射顏色對檸檬酸之耐久性锰銅鈷 C1 34.7 31.7 33.6 0.79 0.95 藍灰色否 C2 55.3 11.9 32.8 0.19 0.25 琥珀色否 C3 55.2 31.4 13.5 0.49 0.62 琥拍色否 C4 26.8 24.1 49.1 0.78 1.09 藍灰色是 C5 44.6 30.5 24.9 0.59 0.76 琥拍色否 C6 22.8 20.9 56.3 0.79 1.25 藍灰色是 C7 26.8 17.8 55.4 0.57 0.88 藍灰色是 C8 36.2 9.6 54.2 0.23 0.32 琥玉白色是現在我們瞭解，向含錳和銅之乙醯丙酮鹽物系加入乙醯丙酮鈷Co(C5H702)3產生了所需藍灰色之熱解性塗層。該 Cu/Mn/Co混合物亦極大地改良了耐酸性。當混合物之鈷含量高於約50重量％時，其耐酸性增至最大。該耐酸性增加係根據習用ASTM(美國材料實驗學會標準）282-67方法直觀測定[琺瑯（enamels)耐酸性標準檢驗方法，擰檬酸點滴檢驗]。可以相信，對酸耐久性的增加係由於Co/Cu/Mn基質的穩定性高於Cu/Mn基質的穩定性。氧化鐵組合物熱解形成於玻璃上的氧化鐵塗層產生了透射青銅色或金 93611.doc 34- 1245024 色的薄膜，且通過某種其他方式部分吸收可視區域的太陽光譜，減少通過玻璃的熱量負載，進而增強玻璃的防太陽光性能。氧化鐵可通過噴射熱解或化學氣相澱積方法應用於熱玻璃上。對於熱解性塗層，其較佳方法是將含鐵物質 (如乙醯丙酮鐵的水性懸浮液）噴到玻璃上，形成氧化鐵塗層。含鐵生色團的顏色可通過加入額外金屬離子形成二元或三元金屬氧化物薄膜而發生變化。例如，二元Cu_Fe氧化物塗層在潔淨的玻璃基質上形成時，傾向於透射淺灰-破拍色。三元氧化物（如，用Cu、&和卜的乙醯丙酮鹽形成）於潔淨的玻璃基質上形成了吸收暗灰_號拍色的薄膜。另外，可用具有乙醯丙酉同的钻鹽、猛鹽、紹鹽、飾鹽、舞鹽、欽鹽、紀鹽、辞鹽、錯鹽和錫鹽之化合物改變經沈積薄膜的顏色。士具有一般氧化鐵塗層#問題{，塗層在進一步加熱處理柃（如回火或彎曲）趨向於變暗。可以相信，或·彎曲溫度下結晶增加和粒積引起。儘管於氧:=璃火之間加入阻擋層能有助於防止變暗，但此等變暗可通過向氣化鐵物系加入經選擇的第二種組份消除，如加入(不受本發明限制)鈣、銅、鋁、鈽、鎂、錳'鈦、釔、鋅、鉛等。防止變暗 °、將乙醯丙_懸浮液與不同莫耳比的乙酿丙綱鐵混合，且喷到經加熱的破璃基質上熱解，形成氧化句鐵薄膜。該玻璃如前述討論弄淨。將兩塊4英寸（沒2厘米）方的潔淨玻 93611.doc -35- 1245024 每按表νι所列時間以同等的莫耳數（見表νί)溶液噴射。將其中塊加熱處理。薄膜的厚度不測。樣品F2具有66·94% 的务光透射率LTA，如前討論方法測定。加熱處理後，口a 為66.85%，變小1%。將吨薄膜沈積於玻璃片上，形成樣品以，然後加熱處理，，1〇分鐘)，得到變暗塗声，该塗層LTA變化-7.65%(加熱前透射曰了 3·32/°，加熱後透射 55·67%)。氧化Fe-Mg和氧化Fe_Zr(樣品队〇)顯7K纟士要；to 似，其二元金屬氧化物之發光透射率較丁、…果相 (FeOx)(Fl)變化更小。 70 *屬氧化物 93611.doc -36 - 1245024 *障涔綠鹆蒎容鍈耸觭麻。**琴650o°皆漤黔ΪΝ 一〇今淼薛sit^&綷昧襻今。 F6(加熱）樣品 | F5(加熱）1 ^Tj Lh F4(加熱） 2 樣品 F3(加熱） U) 1 F2(加熱）1 ^τ) 樣品 F1(加熱） 1—λ 樣品 K) K) Fe(III)Zr(IV) 懸浮液之莫耳比 K) K) )—a Fe(III)/Mg(II) 懸浮液之莫耳比 4^ Κ) to Fe(III)/Ca(II) 懸浮液之莫耳比 3B 幾 3Β 梟曰 Fe(III)/X 懸浮液之莫耳比〇\ 噴射時間，秒 Μ 喷射時間，秒喷射時間，秒喷射時間，秒 75.83 I 75.31 I 68.05 I 68.22 1 75.54 76.66 1 75.02 | ί 76.15 1 66.85 I 66.94 1 55.67 1 63.32 | *照明物A，2° i 0.4687 0.4691 0.4734 1 0.4723 1 0.4647 0.4625 0.4714 0.4688 0.4791 0.4782 0.5009 0.4819 0.4175 1 0.4176 I | 0.4187 0.4183 0.4173 | 0.4165 I 丨 0.4168 1 0.4176 1 1 0.4182 0.4185 0.4136 0.4186 0.52 1 -0：17 1 丨二 i:.12—1 1 1—1 LO -0.09 -7.65 ! △ γ 1 **照明物A，2° -0.0004 0.0011 0.0022 0.0026 0.0009 0.0190 > 0.0000 0.0004 0.0008 -0.0008 -0.0003 -0.0050 >Table V Sample number Initial component% (DCP) CuII / Mnll Cu / Mn Mole ratio in the suspension film Mole ratio transmission color Durability to citric acid Manganese copper cobalt C1 34.7 31.7 33.6 0.79 0.95 Blue gray No C2 55.3 11.9 32.8 0.19 0.25 Amber No C3 55.2 31.4 13.5 0.49 0.62 Soap No C4 26.8 24.1 49.1 0.78 1.09 Blue-grey is C5 44.6 30.5 24.9 0.59 0.76 So-blue No is C6 22.8 20.9 56.3 0.79 1.25 Blue-grey is C7 26.8 17.8 55.4 0.57 0.88 blue-gray is C8 36.2 9.6 54.2 0.23 0.32 sapphire white is now we understand that adding acetoacetone cobalt Co (C5H702) 3 to the manganese and copper-containing acetoacetone salt system produces the required blue-gray pyrolytic coating Floor. This Cu / Mn / Co mixture also greatly improves acid resistance. When the cobalt content of the mixture is higher than about 50% by weight, its acid resistance is maximized. This increase in acid resistance is determined visually according to the customary ASTM (American Society of Materials Testing Standards) 282-67 method [enamels standard acid resistance test method, citric acid drop test]. It is believed that the increase in acid durability is due to the stability of the Co / Cu / Mn matrix being higher than that of the Cu / Mn matrix. The iron oxide coating formed on the glass by pyrolysis of the iron oxide composition produces a thin film of bronze or gold 93611.doc 34-1245024, and partially absorbs the solar spectrum of the visible area by some other means, reducing the The heat load enhances the solar protection of the glass. Iron oxide can be applied to hot glass by spray pyrolysis or chemical vapor deposition. For pyrolytic coatings, the preferred method is to spray an iron-containing substance (such as an aqueous suspension of iron acetoacetate) onto the glass to form an iron oxide coating. The color of the iron-containing chromophore can be changed by adding additional metal ions to form a binary or ternary metal oxide film. For example, when a binary Cu_Fe oxide coating is formed on a clean glass substrate, it tends to transmit a light gray-break color. The ternary oxide (for example, formed from acetone salt of Cu, & and Bu) formed a thin film that absorbed the dark gray color on a clean glass substrate. In addition, the color of the deposited film can be changed by using a compound of diamond salt, fierce salt, Shao salt, decorative salt, Mai salt, Chin salt, Kishi salt, rhenium salt, wrong salt, and tin salt with the same salt. Taxi have a general iron oxide coating #problem {, the coating tends to darken during further heat treatment (such as tempering or bending). It is believed that the increase in crystallization and particle size at the bending temperature. Although the addition of a barrier layer between oxygen: = glass can help prevent darkening, these darkenings can be eliminated by adding a second component of choice to the vaporized iron system. Limitations of the invention) Calcium, copper, aluminum, scandium, magnesium, manganese, titanium, yttrium, zinc, lead and the like. To prevent darkening, the acetonitrile-propanol suspension is mixed with acetonitrile iron of different molar ratios, and sprayed on a heated glass-breaking substrate to pyrolyze to form an oxide iron film. The glass was cleaned as previously discussed. Spray two pieces of 4 inch (not 2 cm) clean glass 93611.doc -35-1245024 with the same number of moles (see table νί) solution every time listed in table νι. The pieces were heat-treated. The thickness of the film is not measured. Sample F2 has an LTA of 66.94%, as determined by the method discussed previously. After heat treatment, the mouth a was 66.85%, which became 1% smaller. Tons of film were deposited on a glass sheet to form a sample, and then heat treated, 10 minutes) to obtain a darkened coating sound. The LTA of the coating changed -7.65% (the transmission before heating was 3.32 / °, after heating, Transmission 55.77%). The oxidized Fe-Mg and oxidized Fe_Zr (sample team 〇) showed a 7K value; similarly, the luminous transmittance of the binary metal oxide was smaller than that of D, ... fruit phase (FeOx) (Fl). 70 * belongs to the oxide 93611.doc -36-1245024 * The barrier is green and the capacity is high. ** Qin 650o ° are all Qian QianΪ 一一今今薛 Xue sit ^ & ambiguous. F6 (Heating) Sample | F5 (Heating) 1 ^ Tj Lh F4 (Heating) 2 Sample F3 (Heating) U) 1 F2 (Heating) 1 ^ τ) Sample F1 (Heating) 1—λ Sample K) K) Fe ( III) Mole ratio of Zr (IV) suspension K) K)) —a Fe (III) / Mg (II) Mole ratio of suspension 4 ^ K) to Fe (III) / Ca (II) suspension Moore ratio 3B and 3B 枭 Moore ratio of Fe (III) / X suspension 〇 \ spray time, second M spray time, second spray time, second spray time, second 75.83 I 75.31 I 68.05 I 68.22 1 75.54 76.66 1 75.02 | til 76.15 1 66.85 I 66.94 1 55.67 1 63.32 | * Illumination A, 2 ° i 0.4687 0.4691 0.4734 1 0.4723 1 0.4647 0.4625 0.4714 0.4688 0.4791 0.4782 0.5009 0.4819 0.4175 1 0.4176 I | 0.4187 0.4183 0.4173 | 0.4165 I 丨 0.4168 1 0.4176 1 1 0.4182 0.4185 0.4136 0.4186 0.52 1 -0: 17 1 丨 two i: .12-1 1 1-1 LO -0.09 -7.65! △ γ 1 ** Illumination A, 2 ° -0.0004 0.0011 0.0022 0.0026 0.0009 0.0190 > 0.0000 0.0004 0.0008 -0.0008 -0.0003 -0.0050 >

>VI 93611.doc -37- 1245024 其他透射顏色的氧化物薄膜 :/爭-破璃基質上形成的Μη203氧化物薄膜產生出透射狄I色/熏衣草色的薄膜。於潔淨玻璃基質或石英基質上形成的Μη3〇4化物薄膜透射淺•自色。該琥％色薄膜可經加 …轉化為/火系色/薰衣草色，如將經塗覆基質於650°C加熱8 至30刀鐘。為改良其審美性，可用含矽阻擋層形成更均勻的顏色。例如，在用含錳乙醯丙酮鹽懸浮液噴射於潔淨的 >于法玻璃前，首先將氧化矽層沈積到潔淨的浮法玻璃基質上。含矽層可為20毫微米厚。經χ射線衍射發現，該透射淡 I色/熏衣草色之塗層主要含Mhos。根據上述astm 282-67方法檢驗該淡紫色/薰衣草色之塗層的耐檸檬酸性，發現其可耐受摔樣酸。在本發明之實施例中可使用C〇_Mn氧化物物系[c〇(n)、 Co(III)、Mn(II)、Μη(ΙΙΙ)]混合之懸浮液。所用兩個物系為 Co(II)/Mn(II)物系和C〇(III)/Mn(II)物系。在螢光燈條件下裸眼觀察懸浮液Co對Μη莫耳比自9.0-0.1變化時發現，此等物系產生的塗層透射顏色自標色至灰標至淺綠至淡黃_綠色變化（見表VII)。在配製某些以上討論的懸浮液時使用了界面活性劑。熟諳此藝者瞭解，如果界面活性劑對所得結果產生影響，鹿使用最小量。 93611.doc -38- 1245024 *»Ι;*·*^>Ι;***£^Ι> VI 93611.doc -37- 1245024 Other transmission color oxide films: / continued-The Mn203 oxide film formed on the broken glass substrate produces a transmissive Di I / lavender color film. The Mn304 film formed on a clean glass substrate or a quartz substrate is light-transmitting and self-coloring. The succinic% film can be converted into / fire-based color / lavender color by adding, for example, heating the coated substrate at 650 ° C for 8 to 30 knife minutes. To improve its aesthetics, a more uniform color can be formed with a silicon-containing barrier layer. For example, before spraying a manganese-containing acetone salt suspension on clean > glass, a silicon oxide layer is first deposited on a clean float glass substrate. The silicon-containing layer can be 20 nanometers thick. It was found by X-ray diffraction that the translucent light I / lavender color coating mainly contained Mhos. The lavender / lavender-colored coating was tested for citric acid resistance according to the above-mentioned method astm 282-67, and was found to be resistant to drop-like acid. In the embodiment of the present invention, a suspension of a Co-Mn oxide system [co (n), Co (III), Mn (II), Mη (III)] can be used. The two systems used were the Co (II) / Mn (II) system and the Co (III) / Mn (II) system. Observation of the change in the Co to Mη molar ratio of the suspension Co from 9.0-0.1 with naked eyes under fluorescent lamp conditions revealed that the transmission color of the coatings produced by these systems changed from standard to gray to light green to light yellow_green ( (See Table VII). Surfactants were used in formulating some of the suspensions discussed above. Those skilled in the art understand that if surfactants have an effect on the results obtained, deer use is minimal. 93611.doc -38-1245024 * »Ι; * · * ^ >Ι; *** £ ^ Ι

1 ΧΙΟ 1 樣品 X — 樣品 ο.ιι ! 0.43 1.00 1 2.33 1 1 9.00 1 懸浮液中乙醯丙銅 Co(m)/Mn(n) 之莫耳比 0.11 0.43 1.00 | 2.33 1 | 9.00 1 0.16 1 0.66 1.64 3.96 19.31 X 鹆捧K卡雕# η ^ | 0.24 0.81 | 2.02 | 5.78 48.73 齊批 ^ Μ η 决F 1 19.27 1 16.75 21.95 15_95 1 19.01 1 1 15.92 1 1 17.35 1 1 14.20 1 1 17.39 1 1 13.64 1 * 參 > to。 1 0.4132 i 1 0.4138 1 1 0.4269 I 1 0.4282 1 1 0.4242 1 1 0.4136 I I 0.4148 I | 0.4284 | 0.4280 | 0.4231 1 X 0.3977 0.3965 0.4020 0.4053 1 0.4092 1 | 0.3964 | 1 0.3969 1 | 0.4024 | _0—70 | 0.4058 | 1 16.32 1 13.03 ； 14.24 I 1 9.04 1 1 10.77 1 1 13.08 I 1 13.46 I LML] I 9.69 I | 8.56 ] 关 ύ 參 > t〇0 1 0.4134 1 0.4086 1 0.4202 1 1 0.43601 0.4329 X | 0.4152 I 1 0.4077 I | 0.4335 | I 0.4357 I | 0.4394 | X 0.4048 0.4052 0.4054 0.4115 0.4200 I 0.4047 I I 0.4053 I 0.4066 I 0,4143 I 1 0.4184 I 71.17 71.39 55.25 1 63.18 1 57.87 I 74.26 I I 68.98 I 67.91 I 60.37 I | 69.62 | K： ί * > b〇0 1 0.4592! 1 0.4547 1 1 0.4579 1 1 0.4568 1 1 0.4641」 I 0.4562 I | 0.4554 I | 0.4533 I I 0.4592 I | 0.4586 | X 1 0.41621 1 0.4168 1 1 0.41441 1 0.4122 1 1 0.4130 1 0.4157 I 0.4170 I 1 0.41231 0.4122 | 0.4135 | >νπ I ®^'·Λ、^ 卜 λ >r I Π I 93611.doc -39- 1245024 一叫此藝者將很各易瞭解，進行本發明之改良須遵守前文揭示之概念。此改良應認為包括在本發明之範圍内。因此，以上描述的特殊具體實施例僅用於說明，不應認作對本發明範圍的限制。以下將給出申請專利的全部範圍和其某些及所有相當含義。【圖式簡單說明】圖1為體現本發明特徵之塗覆臺之同功異構視圖。圖2為體現本發明特徵之塗覆臺之選擇性同功異構視圖。圖3為具有本發明塗覆臺之浮法（驗)玻璃製造設備之方_ 框示意流程圖。圖4為經本發明塗覆臺形成褪色區域之經塗覆基質之側圖5為結合本發明方法形成的CVD塗覆器之底部視圖。圖6為體現本發明另一塗覆襞置之透視圖。圖7為經圖6所示裝置形成塗層圖形之平面圖。1 ΧΙΟ 1 Sample X — Sample ο.ιι! 0.43 1.00 1 2.33 1 1 9.00 1 Molar ratio of acetopropyl copper Co (m) / Mn (n) in suspension 0.11 0.43 1.00 | 2.33 1 | 9.00 1 0.16 1 0.66 1.64 3.96 19.31 X 鹆 GPK 卡雕 # η ^ | 0.24 0.81 | 2.02 | 5.78 48.73 All approved ^ Μ η F 1 19.27 1 16.75 21.95 15_95 1 19.01 1 1 15.92 1 1 17.35 1 1 14.20 1 1 17.39 1 1 13.64 1 * See > to. 1 0.4132 i 1 0.4138 1 1 0.4269 I 1 0.4282 1 1 0.4242 1 1 0.4136 II 0.4148 I | 0.4284 | 0.4280 | 0.4231 1 X 0.3977 0.3965 0.4020 0.4053 1 0.4092 1 | 0.3964 | 1 0.3969 1 | 0.4024 | _0—70 | 0.4058 | 1 16.32 1 13.03; 14.24 I 1 9.04 1 1 10.77 1 1 13.08 I 1 13.46 I LML] I 9.69 I | 8.56] Guan Jug gin > t〇0 1 0.4134 1 0.4086 1 0.4202 1 1 0.43601 0.4329 X | 0.4152 I 1 0.4077 I | 0.4335 | I 0.4357 I | 0.4394 | X 0.4048 0.4052 0.4054 0.4115 0.4200 I 0.4047 II 0.4053 I 0.4066 I 0,4143 I 1 0.4184 I 71.17 71.39 55.25 1 63.18 1 57.87 I 74.26 II 68.98 I 67.91 I 60.37 I | 69.62 | K: ί * > b〇0 1 0.4592! 1 0.4547 1 1 0.4579 1 1 0.4568 1 1 0.4641 ″ I 0.4562 I | 0.4554 I | 0.4533 II 0.4592 I | 0.4586 | X 1 0.41621 1 0.4168 1 1 0.41441 1 0.4122 1 1 0.4130 1 0.4157 I 0.4170 I 1 0.41231 0.4122 | 0.4135 | > νπ I ® ^ '· Λ, ^ λ λ > r I Π I 93611.doc -39- 1245024 This artist will be easy to understand and proceed. The improvement of the present invention must comply with the concepts disclosed aboveThis improvement should be considered to be included in the scope of the present invention. Therefore, the specific embodiments described above are for illustration only and should not be considered as limiting the scope of the invention. The full scope of patent applications and some and all of their equivalent meanings are given below. [Brief description of the drawings] FIG. 1 is an isotactic view of a coating station embodying the features of the present invention. Figure 2 is a selective isotactic view of a coating station embodying the features of the present invention. FIG. 3 is a schematic flow chart of a method for manufacturing float (inspection) glass manufacturing equipment having a coating station according to the present invention. FIG. 4 is a side view of a coated substrate forming a faded area by a coating station of the present invention. FIG. 5 is a bottom view of a CVD coater formed in combination with the method of the present invention. Figure 6 is a perspective view of another coating arrangement embodying the present invention. FIG. 7 is a plan view of a coating pattern formed by the apparatus shown in FIG. 6. FIG.

置製圖8為經圖6塗覆裝置塗製基質末端之截面圖。 1圖9和圖10為反射百分率和透射百分率對圖6塗覆裳造塗覆破璃之橫向寬度之坐標繪製曲線圖。成窗之車輛之同功圖11為具有本發明經塗覆玻璃基質製異構視圖。圖12為表1之八1至人14樣品之平面圖。【圖式代表符號說明】 10 塗覆設備 12 爐 93611.doc 40- 1245024 14 塗覆臺 16 輸送機 18 基質 20 塗料分配器 22 塗料源 24 可彎曲導管 26 計量幫浦 28 壓縮流體源 30 可彎曲導管 34 支撐物 40 第一吸除蓋 42 第二吸除蓋 43 溫度傳感器 44 吸除導管 45 吸除導管 46 浮法玻璃系統 47 第三吸除蓋 48 爐 49 辅助吸除蓋 50 形成室 51 阻擋層 52 退火爐 54 輸送機 60 分級塗料 93611.doc -41 - 1245024 62 基質 100 塗覆設備 114 第二塗覆臺 120 第二塗料分配器 121 塗料分配器 122 單獨塗料源 124 導管 126 計量幫浦 128 單獨塗料源 130 導管 134 第二支撐物 138 底部 140 CVD塗覆區 142 錐形塗料輸送槽 144 吸除槽 148 塗覆臺 150 橢圓形或伸長型噴射圖形 152 主軸 154 中心 15 6 外周邊或外邊緣 158 塗覆區域 162 大體上等厚的中心區域 164 錐形或分級的侧區 200 錯開相離的塗料分配器 93611.doc -42- 1245024 210 車輛 212 檔風屏 214 後窗 216 側窗 218 侧窗 220 侧窗 222 分級褪色區域 224 塗層較薄且基本透明靠近底部的第一區域 226 塗層較厚且基本透明度較差靠近頂部的第二區域 93611.doc -43-Setup FIG. 8 is a cross-sectional view of the end of a substrate coated by the coating apparatus of FIG. 6. Fig. 9 and Fig. 10 are graphs plotting the percentage of reflection and the percentage of transmission as a function of the lateral width of the coated glass in Fig. 6. Identical work of a windowed vehicle Fig. 11 is a heterogeneous view made of a coated glass substrate with the present invention. FIG. 12 is a plan view of the samples from Table 1 to Table 8 to FIG. [Illustration of Symbols] 10 coating equipment 12 furnace 93611.doc 40- 1245024 14 coating station 16 conveyor 18 substrate 20 paint dispenser 22 paint source 24 flexible conduit 26 metering pump 28 compressed fluid source 30 flexible Duct 34 Support 40 First suction cap 42 Second suction cap 43 Temperature sensor 44 suction duct 45 suction duct 46 float glass system 47 third suction cap 48 furnace 49 auxiliary suction cap 50 forming chamber 51 blocking Layer 52 Annealing furnace 54 Conveyor 60 Grading paint 93611.doc -41-1245024 62 Substrate 100 Coating equipment 114 Second coating station 120 Second paint distributor 121 Paint distributor 122 Separate paint source 124 Conduit 126 Metering pump 128 Separate paint source 130 Conduit 134 Second support 138 Bottom 140 CVD coating zone 142 Conical paint delivery tank 144 Suction tank 148 Coating station 150 Oval or elongated spray pattern 152 Spindle 154 Center 15 6 Outer periphery or outer edge 158 Coated area 162 Central area of approximately equal thickness 164 Conical or graded side area 200 Staggered paint dispensers 93611.doc -42-1245024 210 Vehicle 212 Windshield 214 Rear window 216 Side window 218 Side window 220 Side window 222 Graded faded area 224 Thin coating and substantially transparent first area near the bottom 226 Thick coating and poor basic transparency Second near the top Area 93611.doc -43-

Claims

來 I細24 拾、申請專利範園： 1 ·種於基質表面上形成分級塗層之方有第—端和第一…方…方法，其中該基質具弟一知，该方法包括以下步驟· 著成室、從相對於該形成室訂游的方向，沿相對2移出定義為基#之連續破璃條⑽―；相對该基質的第一端，安裝一定之涂粗八π即義為弟一塗料分配器該美皙士 77阢為輪运端之延伸軸對 β丞貝成一預定斜角；朝該基質移動來自該塗料分配器 Ψ m 、，疋義為弟一塗料之皙卜而伙斗# χ 土復材枓沈積於該基、於该基質表面形成分級塗層。 2. -種於基質之表面上形成分級塗層步驟： /、匕祜U下自玻璃形成室、實質上水平之平面之連續玻璃條；從相對於該形成室為下游的方向，於移出具有_基質主表面且定義為基質、提供多個相離的塗料分配器，排列各個塗料分配器，、刀別於基貝表面上形成具有中心之噴射圖形；引導塗料通過該塗料分配器；以及安裝塗料分配器，使基質相對於塗料分配器移動時，於该基質上形成多個重疊的經塗覆區域，以於該基質上形成分級塗層。、 3. 根據申請專利範圍第1項之方法，其中該基質於自形成室退出時移人退火爐且隨後移出，且則導及提供步驟: 93611.doc 1245024 於在玻璃形成室與退火爐出口端間移動之基質部位進仃，以於該基質上熱解該第一經塗覆材料。進 4·根據申請專利範圍第3項之方法，苴中少八中该引導及提供步驟係於該基質部位進入該退火爐之前，在該部位進行。 5.根據申請專利範圍第4項之方法，其包括於該玻璃形成室與該第一塗料分配器之間安裝第一吸除蓋、於該退火爐入口端與該第一塗料分配器之間安裝第二吸除蓋之步驟0 6.根據申請專利範圍第5項之方法，其包括避免自該基質表面沈積因實施自該供應步驟噴射所致之不需要的過量噴射步驟。 ' 7·根據申請專利範圍第3項之方法，其包括安裝至少一與該第一塗料分配器相隔離之第二塗料分配器，及供應該第二塗料分配器第二塗料之步驟。 8. 根據申請專利範圍第7項之方法，其包括將該第二塗料分配器導向該基質，使得經過該第二塗料分配器分配端所延伸之軸線與該基質形成第二預定角度。 9. 根據申請專利範圍第7項之方法，其中該第二塗料係不同於該第一塗料。 10. 根據中請專利範圍第8項之方法，其中該第二預定角度係不同於該第一預定角度。 11. «中請專利範圍第3項之方法，另包括沿大致與該基質第側平行之路輕移動該第一塗料分配器之步驟。 12. 根據中請專利範圍之方法，其中該安裝步驟係於該 93611.doc 1245024 移出步驟之前進行。 13.根據申請專利範圍第2項之方法’其中該基質於自形成室 u出k移人退火爐减後移出，且該引導及提供步驟係 ^在玻璃形成室與退火爐出口端之間移動之基質部位進行以於β亥基質上熱解該第一經塗覆材料。 Μ.根據申請專利範圍第叫之方法，其中則導及提供牛驟係於該基質部位進入該退火爐之前，在該部位進行/ 15.根據申請專利範圍第14項之方法，其包括安裳該塗料分配器之步驟，使得於該基f上以—塗料分配器形成之塗覆區域不超過相鄰塗料分配器之噴射圖形中央，以避免來自塗料分配器之噴射彼此互相干擾。 16·«中請專利範圍第15項之方法，其中該噴射圖形係具二二：t型喷射圖形’該方法包括安裝該塗料分配口口使侍忒寺刀配器之主軸均實質上平行之步驟。 17·根據申料利範圍第13項之方法，其包括安裝該塗料分配器以使該塗料於每一側均具有錐形區域之步驟。 1 8·根據申請專利範圍第丨7項之笪所达把u ”包括分割該經塗覆基貝為數片且每一片均具錐形區域之步驟。 19·根據申請專利範圍第丨項之方法，直 ^ @ 1 /、亥基質之第一端係人5亥弟一 ir而相對，且塗料僅射鄰且與該第二端相分隔之經選取^表面與該第一端相 2。.=請專:項之方法’其中由該分配器_ 二"直配“出之塗料係具隨意不受限之路徑。 21.根據申§月專利範圍第2項之方法，其中該塗料分配器係固 93611.doc 1245024 定式。 22. 根據申請專利範圍第2項之方法，其中由該分配器到該基質表面之塗料路徑係不受限。 23. 根據申請專利範圍第1項之方法，其係包括：於該玻璃形成室與第一塗料分配器之間安裝第一吸除蓋；於該第一塗料分配器於該退火爐入口端之間安裝第二吸除蓋；於該第二吸除蓋與該退火爐入口端之間安裝第二塗料分配器，使得經過該第二塗料分配器分配端所延伸之軸線與該基質形成一斜角；於該第二塗料分配器與該退火爐入口端之間安裝第三吸除蓋；及自該第一塗料分配器將第一塗料移向該基質且自該第二塗料分配器將第二塗料移向該基質，以於一次移動中，在基質表面形成分級塗層。 93611.docHere are some examples of patent application parks: 1. The first and the last methods of forming a graded coating on the surface of a substrate include the following steps. The method includes the following steps: In the writing room, from the direction opposite to the formation room, move along the relative 2 to define the continuous broken glass bar 为, which is defined as the base #; relative to the first end of the substrate, install a certain coating thickness of 8π, meaning brother. A paint dispenser 77 美 is a predetermined oblique angle for the extension axis of the shipping end to β 丞; moving toward the substrate from the paint dispenser Ψ m ，, 疋为 for the younger paint's fair buer # The χ soil composite material is deposited on the substrate and forms a graded coating on the surface of the substrate. 2.-The step of forming a graded coating on the surface of the substrate: /, a continuous strip of glass from the glass forming chamber, a substantially horizontal plane under the dagger; from the direction downstream from the forming chamber, the _ The main surface of the substrate is defined as the substrate, providing multiple separated paint dispensers, arranging each paint dispenser, forming a centered spray pattern on the surface of the substrate; guiding the paint through the paint dispenser; and installing The paint dispenser moves a substrate relative to the paint dispenser to form a plurality of overlapping coated areas on the substrate to form a graded coating on the substrate. 3. The method according to item 1 of the scope of patent application, wherein the substrate is moved into the annealing furnace and then removed when exiting from the forming chamber, and the steps are provided and provided: 93611.doc 1245024 at the exit of the glass forming chamber and the annealing furnace The substrate portion moved between the ends is pushed in to pyrolyze the first coated material on the substrate. Progress 4. According to the method in the scope of patent application No. 3, the guidance and providing step of the eighth middle school is performed before the substrate part enters the annealing furnace at that part. 5. The method according to item 4 of the patent application scope, comprising installing a first suction cover between the glass forming chamber and the first paint dispenser, and between the inlet of the annealing furnace and the first paint dispenser Step 0 of installing the second suction cover 6. The method according to item 5 of the scope of the patent application, which includes avoiding an unnecessary excessive spraying step caused by depositing from the surface of the substrate due to spraying from the supplying step. '7. The method according to item 3 of the scope of patent application, comprising the steps of installing at least a second paint dispenser separated from the first paint dispenser, and supplying the second paint of the second paint dispenser. 8. The method according to item 7 of the patent application scope, which comprises directing the second paint dispenser to the substrate such that an axis extending past the dispensing end of the second paint dispenser forms a second predetermined angle with the substrate. 9. The method according to item 7 of the application, wherein the second coating is different from the first coating. 10. The method according to item 8 of the patent application, wherein the second predetermined angle is different from the first predetermined angle. 11. The method of «Applicable Scope Item 3" further includes the step of lightly moving the first paint dispenser along a path substantially parallel to the first side of the substrate. 12. The method according to the patent claim, wherein the installation step is performed before the 93611.doc 1245024 removal step. 13. The method according to item 2 of the scope of the patent application, wherein the substrate is removed from the annealing chamber and removed from the annealing furnace, and the guiding and providing steps are moved between the glass forming chamber and the exit end of the annealing furnace. The matrix site is performed to pyrolyze the first coated material on a beta-hai matrix. M. The method called according to the scope of the patent application, wherein the guidance and provision of the cattle is performed before the substrate part enters the annealing furnace / 15. The method according to the scope of the patent application item 14, which includes Ansang The step of the paint dispenser is such that the coating area formed by the paint dispenser on the base f does not exceed the center of the spray pattern of the adjacent paint dispenser, so as to prevent the sprays from the paint dispenser from interfering with each other. 16 · «A method of claim 15 in the patent scope, wherein the spray pattern has two or two: t-type spray pattern 'The method includes the step of installing the coating distribution opening so that the main axes of the Shiji Temple knife adapter are substantially parallel . 17. The method according to item 13 of the claim scope, including the step of installing the paint dispenser so that the paint has a tapered area on each side. 1 8 · According to 笪 7 of the scope of the patent application, including "u" includes the step of dividing the coated substrate into several pieces, each of which has a tapered area. 19. · Method according to the scope of the patent application Straight ^ @ 1 /, the first end of the helium matrix is opposite to the helium-iron, and the paint only shoots adjacent and separated from the second end. The selected surface is opposite to the first end .. = Please special: the method of the item 'where the distributor _ two " direct distribution "the paint system has a free and unlimited path. 21. The method according to item 2 of the patent application, wherein the paint dispenser is fixed to 93611.doc 1245024. 22. The method according to item 2 of the scope of patent application, wherein the paint path from the dispenser to the surface of the substrate is not limited. 23. The method according to item 1 of the scope of patent application, comprising: installing a first suction cover between the glass forming chamber and the first paint dispenser; and placing the first paint dispenser at the inlet end of the annealing furnace. A second suction cap is installed between the second suction cap and the inlet end of the annealing furnace, so that the axis extending through the distribution end of the second coating dispenser forms an oblique relation with the substrate; A third suction cover between the second paint dispenser and the inlet end of the annealing furnace; and moving the first paint from the first paint dispenser to the substrate and the first paint from the second paint dispenser Two coatings are moved to the substrate so that in one movement, a graded coating is formed on the surface of the substrate. 93611.doc