200838815 九、發明說明 【發明所屬之技術領域】 本發明是關於浮法平板玻璃之製造方法，尤其是關於 伸張經由熔融錫浴所成形之帶狀玻璃（glass rib bo η)之頂輥 (top roll)。 【先前技術】 以浮法製造平板玻璃的情況，配合玻璃製品的組成來 調配，將溶解混合過的批料之熔融玻璃導入到熔融錫浴， 讓熔融玻璃在熔融錫錫上移動，成形爲特定厚度及特定寬 度之熔融玻璃的帶（以下，稱爲帶狀玻璃（glass ribbon))。 該成形中，爲了要將比熔融錫上之帶狀玻璃的平衡厚度還 要更薄的帶狀玻璃予以成形，而採用被稱爲頂輥之在與帶 狀玻璃接觸的前端設有溝和齒之迴轉的輥子。採用：當要 成形時將該頂輥的前端押壓到與帶狀玻璃的行進方向成垂 直之寬度方向的兩端部，對帶狀玻璃朝向與行進方向大致 成垂直的方向施加張力，抑制帶狀玻璃縮幅受並且也朝向 行進方向伸張的方法。頂輥則是如同日本專利文獻1中所 揭示由鋼所作成，或如同日本專利文獻1中所揭示由耐熱 合金所作成。 隨著時間經過在熔融錫浴內的頂輥主要會附著熔融錫 。該原因係因在頂輥的內部設置空間，使該空間與迴轉軸 部連通，經過軸部從浴外來讓液體或氣體流通，形成爲可 冷卻的構造來防止溫度上升之故。即是頂輥爲熔融錫浴內 -4- 200838815 較低溫度的構件，故會在頂輥表面凝聚熔融錫浴內所揮發 的錫等、或因其他的原因而直接附著熔融錫浴內的熔融錫 之故。附著在頂輥與帶狀玻璃的接觸部之錫增加的話，受 到該錫厚度的影響而導致利用頂輥來擠壓帶狀玻璃的壓力 變動、或導致該錫容易附著在帶狀玻璃、或導致帶狀玻璃 與頂輥不容易分離。因此，會有帶狀玻璃的厚度變動，很 難製造出均等厚度的平板玻璃的問題。另外，即使在頂輥 未與帶狀玻璃接觸的部分，仍會有一度附著之錫的一部分 受到來自熔融錫的輻射熱等而再度熔解，掉落在帶狀玻璃 上，成爲往後步驟造成故障原因的事態。進而，附著在頂 輥的錫會引起上述的問題，故必須進行除去附著的錫的維 護作業，該作業造成熔融錫浴內的環境狀態變化，因而會 有除了穩定作業之外的問題。 爲了要減輕錫附著在頂輥，採用如同日本專利文獻3 中所揭示之碳素材的頂輥。此情況下，錫附著在頂輥所引 起的缺點可以大幅減少。另則，碳素材非常不容易實施熔 接等的連結加工，即使作爲頂輥使用時，要形成爲從軸部 使液體或氣體流通來進行冷卻的構造極爲困難。 專利文獻1 :日本專利特表2002-544 1 04號公報 專利文獻2 :日本專利特開平7 - 1 0 5 6 9號公報 專利文獻3:日本專利特開昭64-5921號公報 【發明內容】 <發明所欲解決之課題> -5- 200838815 熔融錫浴內雖設計成保持在還原雰圍，但要與外氣完 全阻隔並不容易，不可避免會在雰圍內含有些微的氧。有 些情況會因某些原因而局部性地升高氧濃度。碳素材在高 溫下與氧接觸的話會急遽地氧化並揮發。因而，些微的氧 導致碳的揮發，故會有失去表面的平滑性而改變與帶狀玻 璃（glass ribbon)的接觸性，失去帶狀玻璃厚度的均等性的 問題。或者局部地引起氧濃度的增加的話，會有大幅侵蝕 頂輥的問題。尤其，碳素材的頂輥的情況，因沒有冷卻構 造，所以成爲與接觸的帶狀玻璃極接近的高溫度，與氧的 反應因而較快速進展。 另外，碳素材比金屬材還要脆，故頂輥本身之前端部 的齒或溝不容易加工。進而，還會有受到帶狀玻璃之黏度 的局部變動等，容易引起斷齒等的問題。此外，如同電漿 顯示器或TFT面板用的玻璃，必須經過薄板化之平板玻 璃的製造，尤其，朝向頂輥的與帶狀玻璃的行進方向成垂 直之寬度方向的兩端部之施加押壓力、或帶狀玻璃往與行 進方向大致垂直的方向之施加張力則變成更加必要，由於 齒或溝的脆度或輥子前端與迴轉軸之連接部的脆弱度等’ 故會有碳製的頂輥無法施加充足的押壓力或張力的問題。 本發明係鑒於上述問題而提案，具備有與碳製頂輥相 匹敵之錫的非附著性，會減輕與氧的急遽反應性或機械性 脆度的問題。即是本發明的目的是提供不僅頂輥與錫的附 著性很小，還可以抗熔融錫浴內的微量氧，可對薄板化施 加充分的押壓力或張力之具有高度耐久性之頂輥、及使用 -6 - 200838815 該頂輥的平板玻璃之製造方法。 <用以解決課題之手段> 本發明是一種平板玻璃之製造方法，其特徵爲：防止 用來以浮法製造平板玻璃之熔融錫浴所利用之頂輥所附著 的熔融錫等的異物附著至頂輥表面、克服頂輥的齒或溝的 脆弱度、以及高耐久化，藉由設置在金屬製的頂輥的表面 之類鑽碳（diamond-like carbon)的薄膜來實現及有關適於 該方法之上述的頂輥，主要有下述的發明。 (1) 一種平板玻璃之製造方法，是使用頂輥，對熔融 錫上的帶狀熔融玻璃，朝向與該流動方向大致成垂直的方 向，施加張力的浮法平板玻璃之製造方法，其特徵爲：使 用頂輥，該頂輥則是在母材由金屬材料所構成且與熔融玻 璃接觸的表面，具有類鑽碳（diamond-like carbon)的薄膜 • (2) —種頂輥，是在以浮法進行平板玻璃製造時，對 熔融錫上的帶狀熔融玻璃，朝向與該流動方向成垂直的方 向，施加張力之頂輥，其特徵爲：在母材由金屬材料所構 成且與熔融玻璃接觸的表面，具有類鑽碳（diamond-like carbon)的薄膜。 (3)前述的製造方法或頂輥，是在前述薄膜與母材之 間，具有鉻、鈦、鋁、矽、鎳、鈷當中至少含有1種以上 的成分之氮化物、氧化物、碳化物或與母材不同之金屬的 200838815 [發明效果] ~ 本發明的頂輥，由於在表面具有類鑽碳（diamond-like carbon)的薄膜，故薄膜與錫的附著性很小，熔融錫浴內 的屬於熔融金屬的錫不容易固著在頂輥表面。可以減少被 認爲是錫的原因造成之帶狀玻璃的厚度變動等。另外，可 以減少因錫從與頂輥與熔融錫浴內的雰圍接觸的表面掉落 到帶狀玻璃上，附著在玻璃而造成之裝置故障。進而，因 p 錫不容易固著在頂輥表面，所以可以削減除去附著的錫之 維護作業。 頂輥的母材爲金屬，可以對帶狀玻璃施加強力的押壓 力或張力，還可以對應於製造厚度很薄的玻璃。 類鑽碳的薄膜，因具有既高硬度又優異的耐磨耗性/ 耐擦傷性，所以以帶狀玻璃的較低溫與硬質的部分接觸， 頂輥表面受到損傷或表面的平滑性下降的事態很少，可以 減少頂輥表面的凹凸造成帶狀玻璃之附著性的變化。 • 在前述薄膜與母材之間，含有金屬氮化物等的層，該 金屬氮化物爲含有鉻來作爲金屬元素的情況，該層因熱膨 脹差等造成的畸變，所以可以提高薄膜與母材的密貼力。 【實施方式】 以下，根據圖面（第1〜2圖）來針對本發明浮法平板玻 璃之製造方法及頂輥的理想實施形態進行說明。第1圖爲 用來實施本發明之熔融錫浴之槪略水平剖面圖。第2圖爲 包含第1圖的頂輥的部分之說明圖的一個例子。此外，以 -8- .200838815 下的說明中，列舉玻璃板屬於建築用平板玻璃或汽車用平 板玻璃的材料之鈉玻璃（soda-lime glass)來當作例子， 不過本發明的玻璃並不侷限於鈉鈣玻璃。熔融玻璃或帶狀 玻璃（glass ribbon)的溫度等的條件得以依照玻璃的種類來 改變，並不侷限於下述的條件。 以浮法來製造平板玻璃的方法，主要是由將原材料予 以熔融來獲得熔融玻璃之熔解步驟、將熔融玻璃導入到熔 融錫浴來成形爲帶狀玻璃之成形步驟、以及將帶狀玻璃的 溫度予以漸漸地降低來變成接近常溫之徐冷步驟所構成。 熔解步驟爲將矽砂、石灰石或鈉石灰等的原材料，配 合玻璃製品的組成來調配，將熔解混合過後的批料投入由 耐火性的磚塊等所組成之熔解窯，依照玻璃的種類，藉由 設置在熔解窯內部之大約1 400 °C以上的燃燒器等來進行加 熱熔融，以獲得熔融玻璃的步驟。例如，從爐的其中一端 ，將批料投入眾知的溶解爐內，將燃燒重油所獲得的火焰 ，吹向該投入的批料，又還噴吹將天然瓦斯與空氣混合進 行燃燒所獲得的火焰，經由加熱到大約1 5 5 0 °C以上來熔解 批料，以獲得熔融玻璃。另外，有些情況，使用眾知的電 容解爐來獲得熔融玻璃。 徐冷步驟爲在成形後藉由推出輥8，從熔融錫2取得帶 狀玻璃4之後的步驟。徐冷主要是以具備有作爲帶狀玻璃4 的搬運機構之金屬輥9、及用來將帶狀玻璃4的溫度予以漸 漸地下降之機構（未圖示）之徐冷爐10來進行。漸漸地下降 溫度的機構係利用燃燒瓦斯或電熱器，將該輸出受到控制 -9- 200838815 的熱量，供應至爐內的必要位置，直到帶狀玻璃4接近常 溫的溫度帶爲止，慢慢地進行冷卻。因此，可以消除帶狀 玻璃4內部存在的殘留應力。 以下，針對含有本發明的特徵部分之成形步驟進行說 明。成形步驟係將熔融玻璃，從熔解窯下游部1，導入第1 圖所示的熔融錫浴3，讓帶狀玻璃4浮在熔融錫2上並行進 來進行成形。成形步驟中，爲了要將比熔融玻璃的平衡厚 度還要薄的帶狀玻璃4予以成形，在行進方向所成垂直之 寬度方向的兩端部，押壓頂輥5所迴轉的輥子，朝向寬度 方向施加張力，抑制熔融錫上2的帶狀玻璃4縮幅，也朝向 行進方向伸張。 爲了要呈現頂輥5的形狀，第2圖中表示該部分側面。 第2圖中係以剖面來顯示熔融錫2和帶狀玻璃4。頂輥5具有 :具有與游熔融玻璃所組成之帶狀玻璃4接觸的表面之滾 輪部51、迴轉軸部52、覆蓋迴轉軸部52之保護構件部53、 以及覆蓋滾輪部5 1的頭部之保護構件部54。滾輪部5 1和迴 轉軸部52則是由以金屬材料組成的母材所構成，保護構件 部53、54也可以由金屬材料或除此之外的鋼材所來組成。 母材的金屬材料係由鋼或耐熱合金等所組成，可以使用不 銹鋼等眾知的金屬材料。 滾輪部5 1的外周表面係如第2圖所示與由熔融玻璃所 組成之帶狀玻璃4接觸。第2圖中該部分的形狀爲例中所示 的形狀，並不侷限於該形狀。例如也可是齒輪狀的形狀。 此外’第2圖中的滾輪部51或頂輥5全體的大小或形狀，則 -10- 200838815 依照根據熔融錫浴內之頂輥所推測的設置位置上之帶狀玻 璃的組成之溫度與黏性的關係有所不同。頂輥5係以經由 齒輪減速機構等’與馬達的輸出軸相連結，以特定的迴轉 速進行迴轉的方式構成。 頂輥5的滾輪部5 1與熔融錫浴3內之高溫的帶狀玻璃4 接觸，又迴轉軸部5 2的前端存在於高溫的雰圍內，故通常 是形成爲在頂輥5的迴轉軸部5 2或甚至於在滾輪部5 1，內 部設有空間，在該處流通液體或氣體，而能夠予以冷卻的 構造。另外，頂輥5的迴轉軸部5 2表面和滾輪部5 1的頭部 等的與帶狀玻璃沒有直接接觸的表面，最好是用隔熱材料 •等的非金屬材料所組成之保護構件或由金屬材料作爲殼體 材所組成之保護材來覆蓋。尤其，如同第2圖所示，除了 前端部分之外，滾輪部51的頭部或迴轉軸部52最好是用保 護構件5 3、5 4所覆蓋。因此，頂輥與熔融錫浴內的雰圍接 觸之母材表面部分可以減少，且錫附著的範圍可以減少。 ，1 Λ > 頂輥5的最佳狀況爲頂輥的前端（滾輪部5 1與迴轉軸部 52的滾輪部附近）的最高溫度保持在ll〇〇°C以下。這點是 因熔融錫浴內備設計成保持在還原雰圍內，但會有不容易 與外氣完全阻隔，不可避免地會在雰圍內含有氣體，有些 時候氧濃度會局部變高的情形，故高溫氧化雰圍則會有類 鑽碳的薄膜受到氧化的可能性之故。更理想的是以抑制氧 化爲前提，頂輥5之前端的最高溫度保持在1 000 °C以下較 佳。頂輥5之前端的最高溫度，則是依據接觸的帶狀玻璃 的物性、溫度和雰圍溫度；頂輥素材的種類或壁厚；以及 -11 - 200838815 冷卻液體或氣體的特性、溫度和流通量等而有所變化。 成形後，帶狀玻璃4利用冷卻器6和7來冷卻到大約6 0 0 °C，運送到前述的徐冷爐1 0。 此外，前述中已針對包含屬於本發明的特徵部分之頂 輥的平板玻璃之製造方法進行說明過，不過平板玻璃之製 造方法、製造條件以及頂輥的基本構造等，即使採用以下 所示之本發明的頂輥，仍會在眾知的範圍內，本質上並不 會受到影響。 以下，針對本發明的頂輥進行說明，類鑽碳的薄膜形 成在頂輥的至少與熔融玻璃接觸的表面。例如，第2圖所 示的頂輥則是形成在滾輪部5 1的外周表面。最好是滾輪部 5 1之露出金屬材料的表面也形成有類鑽碳的薄膜。另外， 最好是迴轉軸部5 2的前端部之露出金屬材料的表面也形成 有類鑽碳的薄膜。滾輪部5 1的與熔融玻璃接觸的表面用保 護材料來覆蓋的情況，該母材表面也可以不形成類鑽碳的 莫。同樣，用保護構件部53保護著之迴轉軸部52的母材 表面’也可以不形成類鑽碳的薄膜。此外，保護構件部5 3 表面或保護材料表面，因應於情況，也可以形成類鑽碳的 薄膜。 本發明中，類鑽碳的薄膜不僅形成在頂輥的與熔融玻 璃接觸的表面，還形成在容易凝聚錫蒸氣之部位的表面或 容易附著熔融錫浴內的錫之部位的表面，再則最好是形成 在會有凝聚的錫或附著的錫剝離而到落在帶狀玻璃上之虞 之部位的表面。這樣的表面即是由金屬材料所組成的母材 -12- 200838815 露出的部分且是在熔融錫浴內的高溫雰圍內（在帶狀玻璃 附近）的表面。 類鑽碳的薄膜爲具有與鑽石所具有的密度相同程度的 密度且實質上由碳原子所組成之膜的統稱。非晶質碳、硬 質碳膜、碳氫化合物膜（a-C : H)、以及i-碳膜（類鑽碳的 另一種稱呼）等也包含在當中。 形成之類鑽碳的膜厚並沒有特別的限定，不過最好是 設定爲0.1 μπι〜50 μιη。以更長期使用爲目的的情況，因想 像的到熔融錫浴內雰圍的條件變動會導致壁厚變薄，所以 也可以更厚地形成膜厚，不過厚膜化容易導致膜質的降低 或剝離的原因，或成膜時間變長，所以實用上並不可行。 因此，0.5〜20μηι的膜厚較爲適當’最好是1〜ΙΟμιη。 類鑽碳的膜厚的狀態也可是均等的單一膜，不過還可 以是微細的類鑽碳的層片形成爲摺疊狀的膜厚或形成爲皺 紋狀。 類鑽碳的薄膜之形成方法，可以以蒸鍍法，例如物理 蒸鍍法（PVD 法：physical vapor deposition)、化學蒸鍍法 (CVD 法：chemical vapor deposition)等、或以液相來進行 反應等之眾知的方法來進行製作。PVD法包括有離子鍍法 (ion plating method )、雷射消熔法（la sera blati on method) 、以及濺鍍法（sputtering method)等，使用石墨等的碳材 料來作爲標靶。CVD法常被使用的是使用碳化合物來做 爲原料氣體之電漿CVD法。電漿原料氣體可以使用用來 形成類鑽碳的處理層之甲烷（CH4)、乙烷（C2H6)、丙烷 -13- 200838815 (C3H8)、丁烷（C4HlG)、乙炔（c2H2)、苯（(：6116)等，因應於 需要’使用在這些碳氫化合物氣體中混合了氫氣、惰性氣 體等來作爲載體氣體之氣體。要將薄膜形成在頂輥的尖銳 端部最好是採用離子鍍法或電漿CVD法，這兩當中CVD 法因比較容易取得成膜控制的範圍所以更加理想。 提高類鑽碳的薄膜與由金屬材料所組成的母材之密貼 力’爲了要獲得該效果，最好是在母材與類鑽碳的薄膜之 間設置中間層。中間層的材料最好是與鉻、鈦、鋁、矽、 鎳、鈷當中至少含有1種以上的成分之氮化物、氧化物、 碳化物或與母材不同之金屬。類鑽碳一般比金屬還要更硬 且脆，故會有連母材之金屬的微小變形都不容易追隨而導 致剝離的原因的情形。因而，中間層的材料，即使類鑽碳 剝離的情況仍要保護母材，故最好是比母材還要更硬質， 最好是將硬質的氮化物、氧化物、或是碳化物作爲中間層 材料還使用。例如CrAIN、TiCN等也可以作爲適當的中 間材料來使用。 另外，這些當中，含有鉻來作爲金屬元素之金屬氮化 物當作中間層材料則更加理想。金屬氮化物中的金屬元素 也可只由鉻來組成。除了鉻以外也可含有其他的金屬元素 。最好是實質上金屬原子全體由鉻原子所組成。鉻氮化物 功能上是作爲即使是局部變成氧化雰圍且類鑽碳氧化揮發 了，仍會對錫有良好的耐侵蝕性且對母材的保護性也很高 的膜，進而含有鉻的金屬氮化物也與類鑽碳同樣’與錫在 高溫下的非附著性良好’故若是殘留著金屬氮化物中間層 -14- 200838815 的話，可以保持非附著性。 形成中間層可以採用各種的乾式蝕刻、濕式蝕刻。這 些當中，最好是採用成膜上限制比較少的PVD法。進而 ，離子鍍法因對前端部的成膜特別良好，所以較爲理想。 中間層的厚度即使是0.1 μπι程度也具有效果。例如，中間 層爲含有鉻氮化物的單層的情況，即使是0.1 μ m〜5 5 μ m都 會發揮效果。中間層也可以更厚地形成，但因成膜時間很 長，實用上並不可行。另外，即使過度薄，設置中間層的 意義則會衰減。因此，中間層適當厚度爲0.1〜ΙΟμηι，最好 是0.5〜5μιη。最理想的是1〜3μηι。 類鑽碳的薄膜與錫的非附著性，即使在高溫下仍會維 持，若爲類鑽碳不會發揮氧化的溫度/氧濃度範圍的話， 可以大幅減少經長期地錫對頂輥的附著。另外，頂輥表面 的傷痕或平坦鍍度的下降，導致錫或異物附著的原因，來 會因改變接觸性，而成爲變化帶狀玻璃的平板厚度的原因 。然則，類鑽碳的薄膜因具有既高硬度又優異的耐磨損性 /耐摩擦性，所以即使在帶狀玻璃的較低溫下接觸到硬質 的部分，對頂輥表面造成傷痕，仍不太會使平坦度降低， 也不會在短時間內就受到磨損。 以下，針對爲了要證實這些效果而施行的實施例進行 說明。 (實施例1)200838815 IX. INSTRUCTIONS OF THE INVENTION [Technical Field] The present invention relates to a method for producing a float glass, and more particularly to a top roll for stretching a glass rib bo η formed through a molten tin bath. ). [Prior Art] When a flat glass is produced by a float method, it is blended with the composition of the glass product, and the molten glass in which the mixed batch is dissolved is introduced into a molten tin bath, and the molten glass is moved on the molten tin to form a specific A belt of molten glass having a thickness and a specific width (hereinafter referred to as a glass ribbon). In the forming, in order to form a strip glass which is thinner than the balance thickness of the ribbon glass on the molten tin, a groove and a tooth are provided at the front end which is called the top roll in contact with the strip glass. The rotating roller. When the forming is performed, the tip end of the top roll is pressed to both end portions in the width direction perpendicular to the traveling direction of the strip glass, and the belt glass is applied with a tension in a direction substantially perpendicular to the traveling direction, and the belt is restrained. A method in which the glass is contracted and also stretched toward the direction of travel. The top roll is made of steel as disclosed in Japanese Patent Laid-Open No. 1, or is made of a heat-resistant alloy as disclosed in Japanese Patent Publication 1. The top roller in the molten tin bath will mainly adhere to the molten tin as time passes. This is because the space is provided inside the top roller, and the space is communicated with the rotary shaft portion, and the liquid or gas is allowed to flow from the outside of the bath through the shaft portion to form a coolable structure to prevent the temperature from rising. That is, the top roll is a member having a lower temperature in the molten tin bath -4-200838815, so that the tin volatilized in the molten tin bath is condensed on the surface of the top roll, or the molten in the molten tin bath is directly adhered to other reasons. The reason of tin. When the amount of tin attached to the contact portion between the top roll and the strip glass increases, the pressure of the strip glass is pressed by the top roll due to the thickness of the tin, or the tin tends to adhere to the strip glass or cause the tin to easily adhere to the strip glass. The ribbon glass is not easily separated from the top roller. Therefore, there is a problem that the thickness of the strip glass varies, and it is difficult to produce a flat glass having a uniform thickness. In addition, even in the portion where the top roller is not in contact with the ribbon glass, a part of the tin which is once adhered is remelted by the radiant heat from the molten tin, and falls on the ribbon glass, causing a malfunction in the subsequent step. State of affairs. Further, since the tin adhered to the top roll causes the above problems, it is necessary to perform maintenance work for removing the adhered tin, which causes a change in the environmental state in the molten tin bath, and thus has problems other than stable operation. In order to reduce the adhesion of tin to the top roller, a top roller such as the carbon material disclosed in Japanese Patent Laid-Open No. 3 is used. In this case, the disadvantages caused by the adhesion of tin to the top roll can be greatly reduced. Further, the carbon material is extremely difficult to perform the joining process such as welding, and even when it is used as a top roll, it is extremely difficult to form a structure in which a liquid or a gas flows from the shaft portion to be cooled. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. <Problems to be Solved by the Invention> -5- 200838815 Although the molten tin bath is designed to be kept in a reducing atmosphere, it is not easy to completely block the outside air, and it is inevitable that a slight amount of oxygen is contained in the atmosphere. In some cases, the oxygen concentration is locally increased for some reason. When the carbon material is in contact with oxygen at a high temperature, it will oxidize and volatilize violently. Therefore, a slight amount of oxygen causes volatilization of carbon, so that the smoothness of the surface is lost, the contact with the glass ribbon is changed, and the problem of the uniformity of the thickness of the ribbon glass is lost. Or, if the oxygen concentration is locally increased, there is a problem that the top roll is greatly eroded. In particular, in the case of the top roll of the carbon material, since there is no cooling structure, it becomes a high temperature close to the contact glass ribbon, and the reaction with oxygen proceeds rapidly. In addition, the carbon material is more brittle than the metal material, so the teeth or grooves at the front end of the top roller itself are not easily processed. Further, there is a local fluctuation such as the viscosity of the ribbon glass, which may cause problems such as broken teeth. Further, as for a glass for a plasma display or a TFT panel, it is necessary to manufacture a thin plate glass, in particular, a pressing force toward both ends of the top roll in the width direction perpendicular to the traveling direction of the strip glass, Or the tension applied to the strip glass in a direction substantially perpendicular to the direction of travel becomes more necessary, and the top roller of the carbon cannot be formed due to the brittleness of the teeth or the groove or the fragility of the joint between the tip end of the roller and the rotary shaft. Apply sufficient pressure or tension. The present invention has been made in view of the above problems, and has a non-adhesive property of tin which is comparable to a carbon top roll, and which has a problem of reducing the rapid reactivity with oxygen or the mechanical brittleness. That is, it is an object of the present invention to provide a highly durable top roll which is capable of not only having a small adhesion between the top roll and tin but also a trace amount of oxygen in the molten tin bath, and which can apply sufficient pressing force or tension to the thin plate. And the use of -6 - 200838815 the manufacturing method of the flat glass of the top roll. <Means for Solving the Problem> The present invention relates to a method for producing flat glass, which is characterized in that foreign matter such as molten tin adhered to a top roller used for a molten tin bath for producing flat glass by a float method is prevented. Adhesion to the top roll surface, overcoming the fragility of the teeth or grooves of the top roll, and high durability, achieved by a diamond-like carbon film disposed on the surface of the metal top roll The above-mentioned top roll of this method mainly has the following invention. (1) A method for producing a flat glass, which is characterized in that a strip-shaped molten glass on molten tin is applied to a float glass having a tension in a direction substantially perpendicular to the flow direction by using a top roll, and is characterized in that : Using a top roll, the top roll is a surface made of a metal material and in contact with the molten glass, and has a diamond-like carbon film. (2) A top roll is When the float glass is used for the production of flat glass, the top-shaped roll is applied to the strip-shaped molten glass on the molten tin in a direction perpendicular to the flow direction, and is characterized in that the base material is composed of a metal material and is molten glass. The surface that is in contact with a diamond-like carbon film. (3) The above-mentioned production method or top roll is a nitride, an oxide, or a carbide containing at least one or more of chromium, titanium, aluminum, lanthanum, nickel, and cobalt among the film and the base material. Or a metal different from the base material 200838815 [Invention Effect] ~ The top roll of the present invention has a film of diamond-like carbon on the surface, so the adhesion of the film to tin is small, and the molten tin bath The tin belonging to the molten metal is not easily fixed to the surface of the top roll. It is possible to reduce variations in thickness of the ribbon glass which are considered to be caused by tin. In addition, it is possible to reduce the failure of the device caused by the tin falling from the surface in contact with the atmosphere in the top roll and the molten tin bath onto the strip glass. Further, since p tin is not easily fixed to the surface of the top roll, maintenance work for removing the adhered tin can be reduced. The base material of the top roll is made of metal, which can apply a strong pressing force or tension to the strip glass, and can also correspond to the manufacture of a thin glass. The carbon-like film has high hardness and excellent wear resistance/scratch resistance. Therefore, the lower temperature and the hard part of the strip glass are in contact with each other, and the surface of the top roll is damaged or the smoothness of the surface is lowered. Rarely, the unevenness of the surface of the top roll can be reduced to cause a change in the adhesion of the ribbon glass. • A layer containing a metal nitride or the like is contained between the film and the base material, and the metal nitride contains chromium as a metal element, and the layer is distorted by a difference in thermal expansion or the like, so that the film and the base material can be improved. Close to the force. [Embodiment] Hereinafter, a preferred embodiment of a method for producing a float plate glass of the present invention and a top roll will be described based on the drawings (Figs. 1 to 2). BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic horizontal sectional view showing a molten tin bath for carrying out the present invention. Fig. 2 is an example of an explanatory view of a portion including a top roll of Fig. 1. In addition, in the description of -8-.200838815, the glass plate belongs to the soda-lime glass of the flat glass for building or the flat glass for automobile as an example, but the glass of the present invention is not limited. In soda lime glass. The conditions of the temperature of the molten glass or the glass ribbon are changed depending on the type of the glass, and are not limited to the following conditions. The method for producing flat glass by a float method is mainly a melting step of melting a raw material to obtain a molten glass, a step of forming a molten glass into a molten tin bath to form a strip glass, and a temperature of the strip glass. It is gradually reduced to become a cold step close to normal temperature. The melting step is to mix the raw materials such as strontium sand, limestone or sodium lime with the composition of the glass product, and put the melted and mixed batch into a melting kiln composed of fire-resistant bricks, etc., according to the type of glass. The step of heating and melting is carried out by a burner or the like provided at a temperature of about 1 400 ° C or more inside the melting kiln to obtain a molten glass. For example, from one end of the furnace, the batch is put into a known dissolution furnace, the flame obtained by burning the heavy oil is blown to the input batch, and the natural gas is mixed with air for combustion. The flame is melted by heating to above about 550 ° C to obtain a molten glass. In addition, in some cases, a known capacitor is used to obtain a molten glass. The cold step is a step after the strip glass 4 is taken from the molten tin 2 by the ejection roller 8 after molding. The Xu cold is mainly performed by a metal roll 9 having a transport mechanism as the strip glass 4 and a quenching furnace 10 for gradually lowering the temperature of the strip glass 4 (not shown). The mechanism for gradually lowering the temperature uses the combustion gas or the electric heater to supply the output to the necessary position in the furnace by the heat of the control -9-200838815 until the ribbon glass 4 approaches the temperature zone of the normal temperature, and slowly proceeds. cool down. Therefore, the residual stress existing inside the strip glass 4 can be eliminated. Hereinafter, the forming step including the characteristic portion of the present invention will be described. In the molding step, the molten glass is introduced into the molten tin bath 3 shown in Fig. 1 from the downstream portion 1 of the melting furnace, and the strip glass 4 is floated on the molten tin 2 to be formed. In the forming step, in order to shape the strip-shaped glass 4 which is thinner than the equilibrium thickness of the molten glass, the rolls which are rotated by the top roller 5 are oriented in the width direction at both end portions in the width direction perpendicular to the traveling direction. The tension is applied to suppress the contraction of the ribbon glass 4 on the molten tin 2 and also to extend in the traveling direction. In order to present the shape of the top roll 5, the side of the portion is shown in Fig. 2. In Fig. 2, molten tin 2 and ribbon glass 4 are shown in cross section. The top roller 5 has a roller portion 51 having a surface in contact with the ribbon glass 4 composed of the molten glass, a rotary shaft portion 52, a protective member portion 53 covering the rotary shaft portion 52, and a head covering the roller portion 51. Protective member portion 54. The roller portion 5 1 and the revolving shaft portion 52 are made of a base material made of a metal material, and the protective member portions 53 and 54 may be composed of a metal material or a steel material other than the above. The metal material of the base material is composed of steel or a heat resistant alloy, and a known metal material such as stainless steel can be used. The outer peripheral surface of the roller portion 51 is in contact with the strip glass 4 composed of molten glass as shown in Fig. 2 . The shape of this portion in Fig. 2 is the shape shown in the example, and is not limited to this shape. For example, it may be a gear-like shape. Further, the size or shape of the entire roller portion 51 or the top roller 5 in Fig. 2 is -10-200838815 in accordance with the temperature and viscosity of the composition of the ribbon glass at the set position estimated by the top roller in the molten tin bath. Sexual relationships are different. The top roller 5 is configured to be coupled to the output shaft of the motor via a gear reduction mechanism or the like and to rotate at a specific rotational speed. The roller portion 51 of the top roller 5 is in contact with the high-temperature ribbon glass 4 in the molten tin bath 3, and the tip end of the rotary shaft portion 52 is present in a high-temperature atmosphere, so that it is usually formed as a rotary shaft of the top roller 5. The portion 5 2 or even a structure in which a space is provided inside the roller portion 5 1 and a liquid or a gas flows therethrough to be cooled. Further, the surface of the top surface of the rotating shaft portion 52 of the top roller 5 and the head portion of the roller portion 51, which is not in direct contact with the ribbon glass, is preferably a protective member composed of a non-metallic material such as a heat insulating material or the like. Or covered by a metal material as a protective material composed of a casing material. In particular, as shown in Fig. 2, in addition to the front end portion, the head portion or the rotary shaft portion 52 of the roller portion 51 is preferably covered by the protective members 53, 54. Therefore, the surface portion of the base material which is in contact with the atmosphere in the molten tin bath can be reduced, and the range of tin adhesion can be reduced. 1 Λ > The optimum condition of the top roller 5 is that the maximum temperature of the tip end of the top roller (near the roller portion 51 and the roller portion of the rotary shaft portion 52) is maintained at ll 〇〇 ° C or lower. This is because the molten tin bath is designed to remain in the reducing atmosphere, but it is not easy to completely block the outside air, inevitably contains gas in the atmosphere, and sometimes the oxygen concentration will locally become high, so In the high temperature oxidation atmosphere, there is a possibility that the carbon-like film is oxidized. More preferably, the maximum temperature of the front end of the top roll 5 is preferably kept below 1 000 °C on the premise of suppressing oxidation. The maximum temperature at the front end of the top roll 5 is based on the physical properties of the contact strip glass, temperature and ambient temperature; the type or wall thickness of the top roll material; and -11 - 200838815 characteristics, temperature and throughput of the cooling liquid or gas, etc. And there have been changes. After the forming, the ribbon glass 4 is cooled to about 60 ° C by the coolers 6 and 7, and transported to the aforementioned quench furnace 10 . Further, the method for producing flat glass including the top roll which is a characteristic portion of the present invention has been described above, but the manufacturing method of the flat glass, the manufacturing conditions, the basic structure of the top roll, and the like are as follows. The top roll of the invention will still be within the scope of the known and will not be affected in nature. Hereinafter, the top roll of the present invention will be described, and the film of the diamond-like carbon is formed on the surface of the top roll which is in contact with at least the molten glass. For example, the top roller shown in Fig. 2 is formed on the outer peripheral surface of the roller portion 51. Preferably, the surface of the exposed portion of the roller portion 5 1 is also formed with a film of diamond-like carbon. Further, it is preferable that a surface of the front end portion of the rotary shaft portion 52 is formed with a diamond-like carbon film on the surface on which the metal material is exposed. When the surface of the roller portion 51 which is in contact with the molten glass is covered with a protective material, the surface of the base material may not form diamond-like carbon. Similarly, the surface of the base material of the rotary shaft portion 52 protected by the protective member portion 53 may not form a film of diamond-like carbon. Further, the surface of the protective member portion 5 3 or the surface of the protective material may be formed into a film of diamond-like carbon depending on the case. In the present invention, the carbon-like carbon film is formed not only on the surface of the top roll which is in contact with the molten glass, but also on the surface of the portion where the tin vapor is easily aggregated or the surface of the tin which is easily adhered to the molten tin bath, and then the most It is preferable to form a surface in which agglomerated tin or adhered tin is peeled off to a portion of the crucible that falls on the ribbon glass. Such a surface is the exposed portion of the base material -12-200838815 composed of a metallic material and is a surface in a high temperature atmosphere (near the ribbon glass) in the molten tin bath. The carbon-like carbon film is a general term for a film having a density which is the same as the density of the diamond and consists essentially of carbon atoms. Amorphous carbon, a hard carbon film, a hydrocarbon film (a-C: H), and an i-carbon film (another name for diamond-like carbon) are also included. The film thickness of the formed carbon is not particularly limited, but is preferably set to 0.1 μm to 50 μm. In the case of use for a longer period of use, the thickness of the atmosphere in the molten tin bath is expected to be reduced, so that the film thickness can be formed thicker, but the film thickness is likely to cause a decrease in film quality or peeling. , or the film formation time becomes longer, so it is not practical. Therefore, the film thickness of 0.5 to 20 μm is appropriate, and it is preferably 1 to ΙΟμιη. The film thickness of the diamond-like carbon may be a uniform single film, but the layer of fine diamond-like carbon may be formed into a folded film thickness or formed into a wrinkle shape. The method for forming a carbon-like carbon film can be carried out by a vapor deposition method such as physical vapor deposition (PVD), chemical vapor deposition (CVD), or a liquid phase. And other well-known methods to make. The PVD method includes an ion plating method, a la sera blati on method, and a sputtering method, and a carbon material such as graphite is used as a target. The CVD method is often a plasma CVD method using a carbon compound as a raw material gas. The plasma raw material gas may be used to form a treatment layer of diamond-like carbon such as methane (CH4), ethane (C2H6), propane-13-200838815 (C3H8), butane (C4HlG), acetylene (c2H2), benzene (( :6116), etc., in response to the need to use a gas in which hydrogen, an inert gas or the like is mixed as a carrier gas in these hydrocarbon gases. It is preferable to form the film at the sharp end of the top roll by ion plating or In the plasma CVD method, the CVD method is more preferable because it is easier to obtain the range of film formation control. The adhesion between the diamond-like carbon film and the base material composed of the metal material is improved. It is preferable to provide an intermediate layer between the base material and the diamond-like carbon film. The material of the intermediate layer is preferably a nitride or oxide containing at least one component selected from the group consisting of chromium, titanium, aluminum, lanthanum, nickel, and cobalt. , carbide or metal different from the base metal. Drilling carbon is generally harder and brittle than metal, so there will be cases where the tiny deformation of the metal of the base metal is not easy to follow and causes the peeling. Layer material, even class In the case of carbon stripping, the base metal is still protected, so it is better to be harder than the base material. It is preferable to use hard nitride, oxide or carbide as the intermediate layer material. For example, CrAIN, TiCN It can also be used as a suitable intermediate material. Among them, it is more preferable to use chromium as a metal nitride of a metal element as an intermediate layer material. The metal element in the metal nitride may also be composed only of chromium. In addition to chromium, it may contain other metal elements. It is preferable that substantially all of the metal atoms are composed of chromium atoms. The chromium nitride functions as a tin even if it is partially oxidized and the diamond-like carbon is oxidized and volatilized. A film which has good corrosion resistance and is highly protective to a base material, and a metal nitride containing chromium also has the same non-adhesion property to tin at high temperatures as the diamond-like carbon, so if metal nitrogen remains The intermediate layer-14-200838815 can maintain non-adhesion. Various intermediate dry etching and wet etching can be used to form the intermediate layer. Among them, it is preferable to adopt Further, the PVD method is less restrictive on the film. Further, the ion plating method is particularly preferable because the film formation at the tip end portion is particularly good. The thickness of the intermediate layer is effective even at a level of 0.1 μm. For example, the intermediate layer contains chromium nitrogen. In the case of a single layer of a compound, even if it is 0.1 μm to 5 5 μm, the intermediate layer can be formed thicker, but since the film formation time is long, it is practically impossible. In addition, even if it is too thin, it is set. The meaning of the intermediate layer is attenuated. Therefore, the appropriate thickness of the intermediate layer is 0.1 to ΙΟμηι, preferably 0.5 to 5 μηη, and most preferably 1 to 3 μηι. The non-adhesion of the diamond-like film to tin, even at high temperatures It will still be maintained. If the diamond-like carbon does not exhibit the temperature/oxygen concentration range of oxidation, the adhesion of the tin to the top roller over a long period of time can be greatly reduced. In addition, the occurrence of scratches or flat plating on the surface of the top roll causes the adhesion of tin or foreign matter, which may change the contact thickness and cause variation in the thickness of the flat glass. However, the carbon-like film has high hardness and excellent wear resistance/friction resistance, so even if it touches the hard part at the lower temperature of the ribbon glass, it causes damage to the top roller surface, and it is still not very good. It will reduce the flatness and will not be worn out in a short time. Hereinafter, an embodiment to be performed in order to confirm these effects will be described. (Example 1)
爲了要確認類鑽碳與錫的非附著性，將SUS 304(J I -15- 200838815 S G43 03 [2005年版]:熱軋不銹鋼板和鋼帶）裁切成1 〇 mm角，將CirN以離子鍍法形成爲大約3μπι的膜厚，再在 該膜上面，以CVD法形成大約Ιμιη之類鑽碳的薄膜膜厚 〇 將所製作的試樣載置在縱型透明石英管內，預先在氫 氣氣流中以1 200 °C進行還原處理過的大約1 mm(D之球狀 的錫放置在試樣中心部，一面在石英管中流通高純度氮氣 p ，一面以紅外線加熱爐加熱到8 00 °C爲止。加熱中之石英 管出口的氧濃度爲1 ppm以下。以8 00 °C經過8分鐘過後， 攝影試樣與錫球的狀態。接觸角係類鑽碳的薄膜上大約爲 164度，沒有塗佈的SUS 3 04上大約爲36度。此外，接觸 角的定義係試樣表面與錫球的接觸部分夾的角度，根據這 次的攝影像來進行測定。藉由此方式得知：高溫低氧氛圍 下之錫的附著性則是類鑽碳的薄膜的表面明顯低於金屬材 料的不銹鋼的表面。 (實施例2) 爲了要確認實際生產時與錫的非附著性、薄膜不會剝 離、不會斷齒、以及在熔融錫浴內的耐久性，在由S25C( J I S G4 051 [2 0 05年版]:機械構造用碳鋼鋼材）所製造之 頂輥的滾輪部分，與實施例1同樣，以離子鍍法將CrN形 成大約3μιη的膜厚。進而，將滾輪部分載置在CVD用處 理室，進行清潔處理，形成類鑽碳的1 μπι薄膜，成膜後的 滾輪部分與不銹鋼製迴轉軸藉由熔接來予以接合。在迴轉 -16- 200838815 軸內部設置1對配管，能夠利用水流通在配管內部來進行 冷卻。進而，頂輥則是以由陶瓷材料所組成的保護材來披 覆該迴轉軸表面，以不銹鋼的保護材來披覆滾輪部的頭部 ，在熔融錫浴內之與帶狀玻璃的行進方向成垂直之寬度方 向的兩端部設置2對合計4台。形成有類鑽碳的薄膜之頂輥 ’即使開始使用後經過3個月，在與帶狀玻璃接觸的部分 ’錫的附著很少，進而即使對帶狀玻璃增加押壓力或張力 仍沒有損傷。另外，在熔融錫浴內經過大約3個月使用後 ’取出頂輥與帶狀玻璃接觸的部分，以目視觀察該部分。 其結果，未發現錫等的固著或披膜的剝離或缺齒等。一方 面’經過相同時間使用過之碳製的頂輥，未發現錫的附著 ，但明顯有壁磨損或齒部的斷齒。 如同以上的結果，可以確認··不僅具有對於本發明之 類鑽碳的薄膜與錫的非附著性之有效性，即使將這點實際 應用在頂輥的情況，仍具有比碳製的頂輥還要優異的耐久 性。 【圖式簡單說明】 第1圖爲用來實施本發明的熔融錫浴之槪略水平剖面 圖。 第2圖爲包含第1圖的頂輥的部分之說明圖的一個例子 【主要元件符號說明】 -17- 200838815 1 :熔解窯下游部 2 :熔融錫 3 :熔融錫浴 4 :帶狀玻璃（glass ribbon) 5 :頂輥 6 :冷卻器 7 :冷卻器In order to confirm the non-adhesion of diamond-like carbon and tin, SUS 304 (JI -15-200838815 S G43 03 [2005 edition]: hot-rolled stainless steel plate and steel strip) was cut into 1 〇mm angle, and CirN was ionized. The plating method is formed to a film thickness of about 3 μm, and a film thickness of a carbon-like film of about Ιμηη is formed on the film by a CVD method. The prepared sample is placed in a vertical transparent quartz tube, previously in hydrogen gas. In the airflow, about 1 mm is reduced at 1 200 °C (the spherical tin of D is placed in the center of the sample, and high-purity nitrogen p is circulated in the quartz tube while heating to 800 ° in an infrared heating furnace. C. The oxygen concentration at the outlet of the quartz tube during heating is 1 ppm or less. The state of the photographic sample and the solder ball after 8 minutes at 800 ° C. The contact angle is about 164 degrees on the carbon-like film. The uncoated SUS 3 04 is approximately 36 degrees. In addition, the contact angle is defined as the angle between the surface of the sample and the contact portion of the solder ball, and is measured based on this photographic image. The adhesion of tin under a low oxygen atmosphere is a film of diamond-like carbon The surface is significantly lower than the surface of the stainless steel of the metal material. (Example 2) In order to confirm the non-adhesion property with tin in actual production, the film does not peel, the teeth are not broken, and the durability in the molten tin bath is In the roller portion of the top roll manufactured by S25C (JIS G4 051 [2005]: carbon steel material for machine structure), CrN was formed into a film thickness of about 3 μm by ion plating in the same manner as in Example 1. Further, The roller portion is placed in the processing chamber for CVD, and is cleaned to form a 1 μm film of diamond-like carbon, and the rolled roller portion and the stainless steel rotary shaft are joined by welding. In the shaft of the rotary-16-200838815 A pair of pipes is provided, and water can be circulated inside the pipe for cooling. Further, the top roll covers the surface of the rotary shaft with a protective material composed of a ceramic material, and the roller portion is covered with a stainless steel protective material. The head portion is provided in a total of four pairs at both end portions in the width direction perpendicular to the traveling direction of the strip glass in the molten tin bath. The top roll of the film in which the carbon-like carbon is formed is used even after the start of use. At 3 months, there is little adhesion of tin in the portion in contact with the ribbon glass, and there is no damage even if the pressure or tension is increased on the ribbon glass. In addition, it is taken out after about 3 months in the molten tin bath. The portion where the top roller was in contact with the ribbon glass was visually observed. As a result, no fixation of tin or the like, peeling of the film, or missing teeth was observed. On the one hand, the top roller which was used after the same time was used. No adhesion of tin was observed, but there was a significant wall wear or a broken tooth of the tooth. As a result of the above, it was confirmed that not only the non-adhesive property of the film of the carbon-impregnated carbon of the present invention but also the tin was obtained, even if When this is actually applied to the top roll, it still has superior durability than the carbon top roll. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic horizontal cross-sectional view of a molten tin bath for carrying out the present invention. Fig. 2 is an example of an explanatory view of a portion including a top roll of Fig. 1 [Explanation of main component symbols] -17- 200838815 1 : downstream portion of the melting furnace 2: molten tin 3: molten tin bath 4: ribbon glass ( Glass ribbon) 5 : top roller 6 : cooler 7 : cooler
8 :推出輥 9 :金屬輥 1 〇 :徐冷爐 5 1 :滾輪部 5 2 :迴轉軸部 5 3 :保護構件部 54 =保護構件部8 : ejection roller 9 : metal roller 1 〇 : Xu cold furnace 5 1 : roller portion 5 2 : rotary shaft portion 5 3 : protective member portion 54 = protective member portion
-18--18-