201249764 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種玻璃板之製造方法。 【先前技術】 目前，作為液晶顯示裝置或電漿顯示裝置等平板顯示器 之顯不部之零件，使用平面玻璃板。於液晶顯示裝置之情 形時，玻璃板例如用作構成薄膜電晶體驅動液晶顯示裝置 (TFT-LCD)之玻璃基板，除此以外亦用作覆蓋顯示部之覆 蓋玻璃》 玻璃製造業者煩惱製造過程中於玻璃中所形成之氣泡。 尤其是液晶顯示裝置之玻璃基板用或覆蓋玻璃用之玻璃板 要求極少之氣泡含量。因此’於玻璃之製造過程中，為了 去除氣泡而於玻璃原料中添加氧化砷或氧化綈作為澄清 劑。又’由於該等澄清劑對環境之影響令人擔憂，故作為 不使用該等澄清劑之氣泡之去除方法，例如提出有如專利 文獻1(曰本專利特表2001-503008號公報）中所揭示之藉由 控制環境中之氫分壓而抑制氣泡之形成的技術。 【發明内容】 [發明所欲解決之問題] 但是’玻璃中所形成之氣泡有多種多樣，有即便使用如 上所述之先前之方法亦無法將氣泡充分去除之氣泡。因 此，依然要求尋找有效抑制玻璃中所形成之氣泡之方法。 本發明係鑒於上述課題而成者，提供一種可有效抑制玻 璃中之氣泡之玻璃板之製造方法。 163495.doc 201249764 [解決問題之技術手段] 本發明之發明者針對抑制玻璃中之氣泡之形成之方法， 進行努力研究，結果發現： (i)尺寸為300 μηι以下之氣泡較多於將新的未使用之銘或 舶合金製之攪拌翼（亦稱為攪拌器）導入製造線中時形成， 邊為氣泡係於澄清步驟之後所產生； (11)於玻璃中所形成之氣泡中有以A、A、s〇2、c〇2為 成分者，尺寸為3〇〇 μίη以下之氣泡主要係以c〇2為成分 者； (111)認為以C〇2為成分之氣泡係源自有機物者，且認為 該有機物為油、樹脂或灰塵等攪拌翼之製造過程中所使用 者之殘留物，或者源自外部之飛來物附著於攪拌翼之表面 而成者。 因此’本發明之發明者認為只要去除㈣翻合金製之搜 拌翼之與溶融玻璃接觸之表面的附著物，則可有效抑 泡之形成。 本發明係根據上述觀點而成者，本發明之玻璃板之製造 方法之特徵在於··包括如下準備步驟：於使玻璃製造線正 式運轉之前，對鉑或始合 去除_之與炫融= 翼進订熱處理，藉此 3玻璃接觸之表面的附著物。 藉此可有效抑制因該附著物而於玻璃中形成氣泡。 又’本發明之破璃^ 將_浸於較二=法較佳為，準備步驟包括 璃十。 切轉時以上之溫度之炫融玻 163495.doc 201249764 又’本發明之玻璃板之製造方法較佳為，準備步驟包括 將攪拌翼浸於黏度為120 Pa . S以下之溶融玻璃中》 又’本發明之玻璃板之製造方法較佳為，準備步驟包 括’將攪拌翼於偏離玻璃製造線之生產線外之狀態下，浸 於加熱為較正式運轉時與攪拌翼之表面所接觸之熔融玻璃 之溫度高出50°C以上的環境中。 [發明之效果] 依據本發明之玻璃板之製造方法，可有效抑制於玻璃中 形成氣泡。 【實施方式】 以下，參照隨附之圖式說明本發明之一實施形態。再 者’以下之說明係關於本發明之一例者，本發明並不限定 於該等。 (1)整體構成 U-1)玻璃之原料 本發明之玻璃板之製造方法可應用於所有玻璃板之製 知·，尤其是較佳用於製造液晶顯示裝置或電漿顯示裝置等 平板顯不器用之玻璃基板、或者覆蓋顯示部之覆蓋玻璃。 於依據本發明製造玻璃板時，首先以成為所期望之玻璃 組成之方式，調配玻璃原料。例如，於製造平板顯示器用 之玻璃基板之情形時，較佳為以具有如下組成之方式調配 原料。 (a) Si〇2 : 50〜70 質量 〇/〇、 (b) B2〇3 : 5〜18 質量。/〇、 163495.doc 201249764 (c) ai2〇3 : 10〜25 質量 ％、 (d) MgO : 〇〜1〇質量 ％、 O) CaO : 〇〜2〇 質量 0/〇、 (f) SrO . 〇〜2〇質量％、 (〇) Ba〇 : 〇〜1〇f 量％、 (P) RO . 5〜20質量％(其中，R為選自峋、c 之至少1種）， ^ (q) r2〇 .超過〇·10質量％且為2 〇質量％以下（其中，] 為選自Li、Na、及K中之至少旧)， '、 ⑴選自氧化錫、氧化鐵、及氧化鈽等中之至少!種金/ 氧化物合計為0.054 5質量％。 再者，上述之液晶基板用玻璃較佳為實質上不含砷及 H即便含有該等物質，該等亦作為雜質，具體而 吕’該等物質亦包括As2〇3、及叫〇3等氧化物在内較佳為 0.1質量％以下。 除上述成分以外，為了調節玻璃之各種物理性、熔融、 澄清、及成形之特性，本發明之玻璃可含有各種其他氧化 物。作為如上所述之其他氧化物之例，可列舉如下者但不 限定於該等：Sn〇2、Ti02、MnO、ZnO、Nb205、MoCh、 Ta205、W03、Y2〇3、及 La2〇3。 上述（a)〜(r)中之（p)之R〇之供給源可使用硝酸鹽或碳酸 鹽°再者’為了提高熔融玻璃之氧化性，更理想為以適合 於步驟之比例使用硝酸鹽作為RO之供給源。 與將一定量之玻璃原料供給至熔解用之爐中而進行批次 I63495.doc 201249764 處理之方式不同’本實施形態中所製造之玻璃板係連續地 進行製造。本發明之製造方法中所應用之玻璃板亦可為具 有任意厚度及寬度之玻璃板。 (1-2)玻璃製造步驟之概要 本發明之一實施形態之玻璃板之製造方法包括圖1之流 程圖所示的一系列步驟，且使用圖2所示之玻璃板製造線 100 ° 以成為上述組成之方式所調配之玻璃之原料係首先於溶 解步驟（步驟S101)中熔解。原料係投入熔解槽1〇1中並 加熱直至特定之溫度。於例如具有上述組成之平板顯示器 用之玻璃基板之情形時，特定之溫度較佳為丨55〇〇C以上。 經加熱之原料熔解而形成熔融玻璃。熔融玻璃係通過第！ 輸送官（transfer tube)l〇5a而運送至進行後續之澄清步驟 (步驟S102)之澄清槽1〇2中。 於後續之澄清步驟（步驟Sl〇2)中，澄清熔融玻璃。具體 而言，若於澄清槽1〇2中加熱熔融玻璃直至特定之溫度， 則熔融玻璃中所含之氣體成分形成氣泡，或者汽化而排出 於熔融玻璃之外。於例如具有上述組成之平板顯示器用之 玻璃基板之情形時’特定之溫度較佳為161〇t以上。經澄 >月之熔融玻璃係通過第2輸送管1〇5b，而運送至進行作為 後續之步驟之均質化步驟（步驟S103)之攪拌槽103中。 於後續之均質化步驟（步驟S103)中，熔融玻璃均質化。 圖3表不攪拌槽1〇3。具體而言，熔融玻璃係藉由於攪拌槽 1〇3中，利用攪拌槽1〇3所具備之下述攪拌翼103a進行攪拌 163495.doc 201249764 而均質化。運送至攪拌槽1〇3中之熔融玻璃係加熱至特定 y度範圍。於例如具有上述組成之平板顯示器用之玻璃 板之情形時，特定之溫度範圍較佳為續(黏度約為 〃 S) 15〇〇 C (黏度約為6〇 pa · s)。經均質化之熔融 玻璃係自攪拌槽103運送至第3輸送管1〇九中。 、於後續之供給步驟(步驟sl〇4)中，熔融玻璃係於第3輸 送s 1〇5。巾加熱至適合於成形之溫度，並運送至進行後續 之成形步驟（步驟_)之成形裝置1〇4中。於例如且有上 述組成之平板顯示器用的玻璃基板之情形時，適合於成形 之溫度較佳為約12 〇 〇。〇。 於後續之成形步驟（步驟咖）中，熔融玻璃成形為板狀 之玻璃。於本實施形態中’、熔融玻璃係利用溢流下拉法連 續地成形為帶狀。所成形之帶狀之玻璃經切割而成為玻璃 板。溢流下拉法其本身為公知之方法，例如為如美國專利 第3,338,696號說明書中所記載之方法：流入成形體中而溢 出之熔融玻璃沿著該成形體之各外表面溢流，並於在該成 形體之底面合流之處向下方延伸而成形為帶狀之玻璃。 (1-3)攪拌槽及攪拌翼 圖3表示攪拌槽103 〇攪拌槽1〇3係收容鉑或鉑合金製之 熔融玻璃之容器，具備麵或麵合金製之攪拌翼ι〇3&/於翻 合金之情形時，較佳為使用例如具有鉑9〇質量％ '铑⑺質 量％之成分之合金。又’亦可使用將氧化料金属氧 化物分散於鉑中而得之作為強化鉑之鉑_鍺_鍅合金。攪拌 翼l〇3a具有旋轉軸、及安裝於該旋轉軸上之複數個翼。旋 163495.doc 201249764 轉軸係自容器之頂部垂直插入容器内。複數個翼係以旋轉 軸為中心成放射狀安裝於旋轉軸上。旋轉軸係藉由馬達等 驅動部而旋轉。若旋轉軸旋轉，則安裝於旋轉軸上 個翼攪拌熔融玻璃。 (2)準備步驟詳細情況 未使用之新裝置有可能於與熔融玻璃接觸之表面上附有 附著物。認為附著物有於攪拌翼1〇3a之製造過程或完成時 附著於其表面之灰塵或樹脂、油等有機物等各種者，由於 該等附著物通常對於玻璃成分成為雜質，故藉由清洗而極 力將其去除。但是’本發明之發明者在調查玻璃中形成極 微細之氣泡之原因的過程中，發現於以目視觀察為平滑之 攪拌翼103a之表面存在非常微細之研磨痕或凹凸於該研 磨痕或凹凸中殘留有無法由通常之清洗而完全去除之附著 物。尤其是，於附著物之中有機物很有可能成為玻璃中之 氣泡形成之原因·» gp，認為有機物中所含之碳與氧結合而 生成二氧化碳氣體，且該氣體被封閉於玻場中而形成氣 包因此於將攪拌翼l〇3a等新的未使用之裝置投入玻璃 板製造線100中時’較佳為於進行去除該等附著物之準備 步驟之後使玻璃板製造線! 〇〇正式運轉。準備步驟係如 乂下所說明’對授拌翼1()33之與嫁融玻璃接觸之表面進行 熱處理，去除該表面之附著物。具體而言，較佳為進行後 續之生產線外熱處理或生產線上熱處理中之任—者。又， 亦可進行兩者之熱處理。 (2-1)生產線上熱處理 163495.doc 201249764 生產線上熱處理係於將攪拌翼1 〇3a設置於玻璃板製造線 1〇〇中之狀態下（生產線上），對攪拌翼l〇3a進行熱處理。具 體而言’較佳為使較正式運轉時溫度更高之熔融玻璃流入 攪拌槽103中並使攪拌翼i〇3a旋轉，藉此使攪拌翼1〇3&之 與熔融玻璃接觸之表面浸於該熔融玻璃中。熔融玻璃係藉 由使玻璃板製造線100上之上述各裝置運轉而生成。即， 以與正式運轉時相同之方式依據圖1所示之上述玻璃板之 製造步驟’使玻璃之原料於熔解槽1〇1中熔解而生成炼融 玻璃’進而使該熔融玻璃依序流入第1輸送管1〇5a'澄清 槽102、第2輸送管l〇5b以及攪拌槽103中。然而，如上所 述與攪拌翼103 a所接觸之熔融玻璃之溫度以高於正式運轉 時為佳。較佳為熔融玻璃之溫度較正式運轉時與攪拌翼 l〇3a所接觸之溫度高出3〇〇c左右以上。例如，若將正式運 轉時與攪拌翼l〇3a所接觸之熔融玻璃之溫度設為約 1440 C則較佳為較該溫度南出30°C以上，即，較佳為使 1470°C以上之熔融玻璃流入攪拌槽1〇3中。但是，若熔融 玻璃之溫度過高，則有時縮短攪拌槽103及位於其下游之 玻璃板製造線100上之其他裝置之壽命，故而較佳為與攪 拌翼103a所接觸之熔融玻璃之溫度並未較正式運轉時之溫 度尚出100C以上。 又，熔融玻璃之黏度以低於正式運轉時為佳，較佳為 120 Pa . S以下。熔融玻璃係隨著溫度變高而黏度變低。 藉由使攪拌翼103a之表面浸於黏度較低即流動之熔融玻璃 中’可使殘留於其表面之附著物浸於高溫下，藉由對其表 163495.doc 10· 201249764 面擦塗熔融玻璃’亦可更確實地沖洗進入細小凹處之附著 物’故而較佳。但是，若熔融玻璃之黏度過低，則對搜摔 翼l〇3a之表面之摩擦力過小，無法獲得擦落附著物之效 果。熔融玻璃之黏度較佳為50 Pa · S以上。 (2-2)生產線外熱處理 生產線外熱處理係於攪拌翼l〇3a偏離玻璃板製造線1〇〇 之狀態（生產線外）下，對攪拌翼103a進行熱處理。具體而 言’較佳為將攪拌翼103a放入生產線外狀態之鉑或鉑合金 等耐火金屬製之爐中，並對該爐内之環境加熱，使攪拌翼 103a之與熔融玻璃接觸之表面浸於高溫之環境中。爐内之 環境之加熱較佳為藉由利用氣體燃燒器對環境加熱而進 行又進而’較佳為藉由利用電源設備使該爐通電而進 灯加熱。環境之溫度較佳為較正式運轉時與攪拌翼1〇3a所 接觸之熔融玻璃之溫度高出5(rc以上的溫度。例如，若正 式運轉時與攪拌翼1〇3a所接觸之熔融玻璃之溫度為 1445°C ’則較佳為較其高出5〇<t以上之溫度（例如， 1 5〇〇°C )。較佳為使攪拌翼1〇3a之與熔融玻璃接觸之表面 浸於該高溫之環境下至少24小時。 再者，作為生產線外熱處理，對於上述攪拌翼1 03 a之利 用尚溫之環境之熱處理並非必需於生產線外之爐中進行， 亦可在°又置於玻璃板製造線丨〇〇上之狀態之攪拌槽103中進 行。 (3)實施例 (3 -1)生產線上熱處理之實施例 163495.doc 201249764 利用未使用且新品之攪拌翼103a，依據圖1之流程圖所 示之上述一系列玻璃板製造步驟，使圖2所示之上述玻璃 板製造線100運轉而製造玻璃板。再者，玻璃原料係以所 製造之玻璃板之組成成為如下所示之方式進行調配： Si02 : 60.9 質量 〇/〇、b203 : 1 1.6 質量。/〇、Al2〇3 : 16.9 質量 %、MgO : 1.7 質量。/〇、CaO : 5.1 質量 ％、SrO : 2.6 質量 %、BaO : 0.7 質量。/。、K20 : 0.25 質量％、Fe203 : 0.15 質量 %、Sn〇2 : 0.13質量％ »與攪拌翼l〇3a所接觸之熔融玻璃 之溫度與玻璃板製造線100之正式運轉時相同約為 1445 C (黏度約為113 Pa · S)。測量所製造之玻璃板中之氣 泡之數量，首先確認尺寸為300 μιη以下之氣泡之數量於1 kg之玻璃中約為0.24個。又，分析尺寸為3〇〇 μπι以下之氣 泡之成分’確認成分主要為C02。 繼而’使與攪拌翼103a所接觸之熔融玻璃之溫度較玻璃 板製造線100之正式運轉時之約1445。(：高出30。(：以上，約 為1484°C (黏度約為71 Pa · S)。於持續該狀態3天之後，製 造玻璃板’若測量所製造之玻璃板中所含之氣泡之數量， 則尺寸為300 μηι以下之氣泡之數量於i kg之玻璃中約為 0 · 1 6 個。 (3-2)比較例 利用未使用且新品之攪拌翼1 〇3a，依據圖1之流程圖所 示之上述一系列玻璃板製造步驟，使圖2所示之上述玻璃 板製造線100運轉而製造玻璃板。再者，玻璃原料係以所 製造之玻璃板之組成成為如下所示之方式進行調配： 163495.doc •12* 201249764201249764 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method of manufacturing a glass sheet. [Prior Art] At present, a flat glass plate is used as a part of a display portion of a flat panel display such as a liquid crystal display device or a plasma display device. In the case of a liquid crystal display device, the glass plate is used, for example, as a glass substrate constituting a thin film transistor-driven liquid crystal display device (TFT-LCD), and is also used as a cover glass covering the display portion. Bubbles formed in the glass. In particular, a glass substrate for a liquid crystal display device or a glass plate for covering a glass requires a very small bubble content. Therefore, in the manufacturing process of glass, arsenic oxide or cerium oxide is added as a clarifying agent to the glass raw material in order to remove bubbles. Further, since the influence of the clarifying agents on the environment is a concern, as a method of removing the bubbles which does not use the clarifying agents, for example, it is disclosed in Patent Document 1 (Japanese Patent Laid-Open Publication No. 2001-503008). A technique for suppressing the formation of bubbles by controlling the partial pressure of hydrogen in the environment. SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] However, there are various types of bubbles formed in the glass, and there are bubbles which cannot sufficiently remove the bubbles even by the prior method as described above. Therefore, it is still required to find a method for effectively suppressing bubbles formed in the glass. The present invention has been made in view of the above problems, and provides a method for producing a glass sheet which can effectively suppress bubbles in a glass. 163495.doc 201249764 [Technical means for solving the problem] The inventors of the present invention conducted an effort to suppress the formation of bubbles in the glass, and found that: (i) bubbles having a size of 300 μη or less are more likely to be new. When the unused agitator or alloyed agitator (also known as a stirrer) is introduced into the manufacturing line, the bubble is formed after the clarification step; (11) the bubble formed in the glass is A , A, s〇2, c〇2 are components, and the bubbles below 3〇〇μίη are mainly composed of c〇2; (111) The bubbles with C〇2 as the constituents are derived from organic matter. Further, it is considered that the organic substance is a residue of a user in the manufacturing process of a stirring blade such as oil, resin, or dust, or a foreign matter is attached to the surface of the stirring blade. Therefore, the inventors of the present invention considered that it is possible to effectively suppress the formation of bubbles as long as the attachment of the surface of the searched wing made of the alloyed alloy to the molten glass is removed. The present invention has been made in view of the above-described viewpoints, and the method for producing a glass sheet according to the present invention is characterized in that it includes the following steps: removing the platinum or the start-up before the glass-making line is officially operated. Adhesive heat treatment, whereby the adhesion of the surface of the glass contact is made. Thereby, it is possible to effectively suppress the formation of bubbles in the glass due to the deposit. Further, the breaking of the present invention is preferably carried out by immersing in the second method, and the preparation step comprises the glass ten. The temperature of the above-mentioned temperature is 163495.doc 201249764 Further, the manufacturing method of the glass plate of the present invention is preferably that the preparation step comprises immersing the stirring blade in a molten glass having a viscosity of 120 Pa·s or less. Preferably, the method for preparing the glass sheet of the present invention comprises the steps of: preparing the stirring blade to be out of the production line of the glass manufacturing line, and immersing the molten glass in contact with the surface of the stirring wing during the normal operation. The temperature is higher than 50 °C. [Effects of the Invention] According to the method for producing a glass sheet of the present invention, it is possible to effectively suppress the formation of bubbles in the glass. [Embodiment] Hereinafter, an embodiment of the present invention will be described with reference to the accompanying drawings. Further, the following description is directed to an example of the present invention, and the present invention is not limited thereto. (1) Overall composition U-1) Raw material of glass The method for producing a glass plate of the present invention can be applied to the production of all glass plates, and is particularly preferably used for manufacturing flat panel displays such as liquid crystal display devices or plasma display devices. The glass substrate or the cover glass covering the display portion. In the production of a glass sheet according to the present invention, the glass raw material is first formulated in such a manner as to have a desired glass composition. For example, in the case of producing a glass substrate for a flat panel display, it is preferred to formulate a raw material in such a manner as to have the following composition. (a) Si〇2: 50~70 mass 〇/〇, (b) B2〇3: 5~18 mass. /〇, 163495.doc 201249764 (c) ai2〇3: 10~25 mass%, (d) MgO: 〇~1〇% by mass, O) CaO: 〇~2〇 mass 0/〇, (f) SrO. 〇~2〇% by mass, (〇) Ba〇: 〇~1〇f amount %, (P) RO . 5 to 20% by mass (where R is at least one selected from 峋 and c), ^ (q R2〇. more than 〇·10 mass% and 2 〇 mass% or less (wherein is at least the old one selected from the group consisting of Li, Na, and K), ', (1) is selected from the group consisting of tin oxide, iron oxide, and cerium oxide. At least, etc.! The total amount of gold/oxide is 0.054 5 mass%. Further, it is preferable that the glass for a liquid crystal substrate is substantially free of arsenic and H, and even if such a substance is contained, these are also impurities. Specifically, the materials include As2〇3 and 〇3. The content is preferably 0.1% by mass or less. In addition to the above components, the glass of the present invention may contain various other oxides in order to adjust various physical, melting, clarifying, and forming properties of the glass. Examples of the other oxides as described above include, but are not limited to, Sn2, TiO2, MnO, ZnO, Nb205, MoCh, Ta205, W03, Y2〇3, and La2〇3. In the above (a) to (r), the supply source of R〇 of (p) may be a nitrate or a carbonate. Further, in order to increase the oxidizing property of the molten glass, it is more preferable to use the nitrate in a ratio suitable for the step. As a source of supply for RO. The glass plate produced in the present embodiment is continuously produced by supplying a predetermined amount of the glass raw material to the melting furnace and performing the batch I63495.doc 201249764. The glass plate to which the production method of the present invention is applied may also be a glass plate having any thickness and width. (1-2) Outline of Glass Manufacturing Step The method for producing a glass sheet according to an embodiment of the present invention includes a series of steps shown in the flow chart of Fig. 1, and uses the glass sheet manufacturing line shown in Fig. 2 to become 100 ° The raw material of the glass blended in the above-described composition is first melted in the dissolution step (step S101). The raw material is placed in the melting tank 1〇1 and heated up to a specific temperature. For example, in the case of a glass substrate for a flat panel display having the above composition, the specific temperature is preferably 丨55 〇〇C or more. The heated raw material is melted to form molten glass. The molten glass system passes the first! The transfer tube 10a is transported to the clarification tank 1〇2 which performs the subsequent clarification step (step S102). In the subsequent clarification step (step S1〇2), the molten glass is clarified. Specifically, when the molten glass is heated in the clarification tank 1〇2 to a specific temperature, the gas components contained in the molten glass form bubbles or are vaporized and discharged outside the molten glass. For example, in the case of a glass substrate for a flat panel display having the above composition, the specific temperature is preferably 161 〇t or more. The molten glass of Jingcheng > month passes through the second transfer pipe 1〇5b, and is transported to the stirring tank 103 which performs the homogenization step (step S103) as a subsequent step. In the subsequent homogenization step (step S103), the molten glass is homogenized. Figure 3 shows the stirring tank 1〇3. Specifically, the molten glass is homogenized by stirring 163495.doc 201249764 by the following stirring blade 103a provided in the stirring tank 1〇3 in the stirring tank 1〇3. The molten glass conveyed into the stirring tank 1〇3 is heated to a specific y degree range. For example, in the case of a glass plate for a flat panel display having the above composition, the specific temperature range is preferably continuous (viscosity is about 〃 S) 15 〇〇 C (viscosity is about 6 〇 pa · s). The homogenized molten glass is transported from the agitation tank 103 to the third transfer pipe. In the subsequent supply step (step sl4), the molten glass is attached to the third transport s 1〇5. The towel is heated to a temperature suitable for forming and conveyed to a forming device 1〇4 for performing a subsequent forming step (step_). For example, in the case of a glass substrate for a flat panel display having the above composition, the temperature suitable for forming is preferably about 12 Å. Hey. In the subsequent forming step (step coffee), the molten glass is formed into a plate-shaped glass. In the present embodiment, the molten glass is continuously formed into a strip shape by an overflow down-draw method. The formed ribbon-shaped glass is cut into a glass plate. The overflow down-draw method is known per se, and is, for example, a method as described in the specification of U.S. Patent No. 3,338,696: the molten glass flowing into the formed body overflows along the outer surfaces of the formed body, and The bottom surface of the formed body is joined downward to form a strip-shaped glass. (1-3) Stirring tank and stirring blade Fig. 3 shows a stirring tank 103. The stirring tank 1〇3 is a container for storing molten glass made of platinum or platinum alloy, and is provided with a stirring blade ι〇3&/ In the case of alloying, it is preferred to use, for example, an alloy having a composition of platinum 〇 mass% '铑(7)% by mass. Further, a platinum-ruthenium-iridium alloy which is obtained by dispersing an oxide metal oxide in platinum may be used. The agitating blade 10a has a rotating shaft and a plurality of wings attached to the rotating shaft. Spin 163495.doc 201249764 The shaft is inserted vertically into the container from the top of the container. A plurality of wing systems are radially mounted on the rotating shaft about the rotating shaft. The rotating shaft is rotated by a driving portion such as a motor. When the rotating shaft rotates, the wing is attached to the rotating shaft to agitate the molten glass. (2) Details of the preparation steps The new device that is not used may have attached matter on the surface in contact with the molten glass. It is considered that the deposits are various such as dust, resin, oil, or the like adhered to the surface of the stirring blade 1〇3a during the manufacturing process or completion of the stirring blade 1〇3a, and since these deposits generally become impurities to the glass component, it is highly effective by cleaning. Remove it. However, in the process of investigating the cause of the formation of extremely fine bubbles in the glass, the inventors of the present invention found that there is a very fine polishing mark or unevenness in the surface of the stirring blade 103a which is visually observed to be smooth. There are residues attached that cannot be completely removed by normal cleaning. In particular, organic matter in the deposits is likely to be a cause of bubble formation in the glass. » gp, it is considered that carbon contained in the organic matter combines with oxygen to form carbon dioxide gas, and the gas is sealed in the glass field to form Therefore, when the new unused device such as the stirring blade 10a is put into the glass sheet manufacturing line 100, it is preferable to make the glass sheet manufacturing line after the preparation step of removing the deposits! . The preparation step is performed by heat-treating the surface of the mixing blade 1 () 33 which is in contact with the graft glass, as described in the following section, to remove the adhering matter on the surface. Specifically, it is preferred to carry out any of the subsequent production line heat treatment or heat treatment on the production line. Moreover, heat treatment of both can also be performed. (2-1) Heat treatment on the production line 163495.doc 201249764 The heat treatment on the production line is performed by heating the stirring blade l〇3a while the stirring blade 1 〇3a is placed in the glass sheet manufacturing line 1 (production line). Specifically, it is preferable that the molten glass having a higher temperature than that during the normal operation flows into the agitation vessel 103 and rotates the agitating blades i 〇 3a, thereby immersing the surface of the agitation blades 1 〇 3 & In the molten glass. The molten glass is produced by operating the above-described respective devices on the glass sheet manufacturing line 100. That is, in the same manner as in the case of the main operation, the raw material of the glass is melted in the melting tank 1〇1 to form a molten glass in the same manner as in the manufacturing process of the glass sheet shown in Fig. 1 , and the molten glass is sequentially flowed into the first step. 1 The conveying pipe 1〇5a' clarification tank 102, the second conveying pipe 10b5b, and the stirring tank 103. However, it is preferable that the temperature of the molten glass which is in contact with the stirring blade 103a as described above is higher than that of the official operation. Preferably, the temperature of the molten glass is higher than the temperature at which the stirring blade l〇3a is in contact with the temperature of about 3 〇〇c or more. For example, when the temperature of the molten glass that is in contact with the stirring blade 10a in the main operation is about 1440 C, it is preferably 30 ° C or more above the temperature, that is, preferably 1470 ° C or more. The molten glass flows into the stirring tank 1〇3. However, if the temperature of the molten glass is too high, the life of the stirring tank 103 and other devices on the glass sheet manufacturing line 100 located downstream thereof may be shortened, so that the temperature of the molten glass that is in contact with the stirring blade 103a is preferably The temperature is not more than 100C when it is not officially operated. Further, the viscosity of the molten glass is preferably lower than the actual operation, and is preferably 120 Pa·s or less. The molten glass system has a lower viscosity as the temperature becomes higher. By immersing the surface of the agitating blade 103a in a molten glass which has a low viscosity, that is, flowing, the adhering matter remaining on the surface thereof can be immersed at a high temperature, and the molten glass is wiped by surface 163495.doc 10· 201249764 It is also preferable to wash the deposits into the small recesses more reliably. However, if the viscosity of the molten glass is too low, the frictional force on the surface of the searched wing l3a is too small, and the effect of rubbing off the attachment cannot be obtained. The viscosity of the molten glass is preferably 50 Pa·s or more. (2-2) Out-of-line heat treatment The production line heat treatment is performed by heat-treating the stirring blade 103a in a state where the stirring blade 10a is offset from the glass sheet manufacturing line 1 (outside the production line). Specifically, it is preferable that the stirring blade 103a is placed in a furnace made of a refractory metal such as platinum or a platinum alloy in a state outside the production line, and the environment in the furnace is heated to dip the surface of the stirring blade 103a in contact with the molten glass. In a high temperature environment. The heating of the environment in the furnace is preferably carried out by heating the environment with a gas burner and, more preferably, heating the lamp by energizing the furnace with a power supply. The temperature of the environment is preferably a temperature higher than 5 (rc or higher) than the temperature of the molten glass that is in contact with the stirring blade 1〇3a during the normal operation. For example, if the molten glass is in contact with the stirring blade 1〇3a during the normal operation. The temperature is 1445 ° C. It is preferably a temperature higher than 5 〇 < t (for example, 15 ° C). It is preferred to dip the surface of the stirring blade 1 〇 3a in contact with the molten glass. In the high-temperature environment, at least 24 hours. Further, as the production line heat treatment, the heat treatment of the above-mentioned stirring blade 101 a using the temperature is not necessary in the furnace outside the production line, and may be placed in the ° The glass plate is produced in the stirring tank 103 in the state of the wire. (3) Example (3 - 1) Example of heat treatment on the production line 163495.doc 201249764 Using the unused and new stirring blade 103a, according to Fig. 1 In the above-described series of glass sheet manufacturing steps shown in the flowchart, the glass sheet manufacturing line 100 shown in Fig. 2 is operated to produce a glass sheet. Further, the glass material is composed of the glass sheet produced as follows. Way of deployment: Si0 2 : 60.9 mass 〇 / 〇, b203 : 1 1.6 mass. / 〇, Al2 〇 3 : 16.9 mass %, MgO: 1.7 mass. / 〇, CaO: 5.1 mass%, SrO: 2.6 mass%, BaO: 0.7 mass. /., K20: 0.25 mass%, Fe203: 0.15 mass%, Sn〇2: 0.13 mass% » The temperature of the molten glass in contact with the stirring blade 10a is the same as that of the glass plate manufacturing line 100. C (viscosity is about 113 Pa · S). Measure the number of bubbles in the glass plate produced. First, confirm that the number of bubbles with a size of 300 μηη or less is about 0.24 in 1 kg of glass. The component of the bubble of 3 〇〇μπι or less is confirmed to be mainly C02. Then, the temperature of the molten glass which is in contact with the stirring blade 103a is about 1445 when it is in the normal operation of the glass sheet manufacturing line 100. (: 30 is higher. (: Above, about 1484 ° C (viscosity is about 71 Pa · S). After 3 days of continuous state, the glass plate is manufactured.] If the number of bubbles contained in the manufactured glass plate is measured, the size is 300. The number of bubbles below μηι is about 0 · 1 in the glass of i kg (3-2) Comparative Example Using the unused stirring blade 1 〇 3a of the new product, the above-mentioned series of glass plate manufacturing steps shown in the flow chart of Fig. 1 is used to make the above-mentioned glass plate manufacturing line shown in Fig. 2 The glass plate is manufactured by operation 100. Further, the glass raw material is blended in such a manner that the composition of the produced glass plate is as follows: 163495.doc •12* 201249764
Si02 : 60.9 質量 ％、b2〇3 : 11.6 質量 ％、Al2〇3 : 16.9 質量 °/〇、MgO : 1.7 質量 ％、CaO : 5.1 質量 ％、SrO : 2.6 質量 %、83〇:0.7質量％、〖2〇:0.25質量％、卩62〇3:0.15質量 °/〇、Sn〇2 : 0.13質量％。與攪拌翼i〇3a所接觸之熔融玻璃 之溫度與玻璃板製造線100之正式運轉時相同約為 1445°C (黏度約為113 pa。s)。若測量第1天所製造之玻璃 板中之氣泡之數量，則尺寸為3〇〇 μηι以下之氣泡之數量於 1 kg之玻璃中約為〇.24個。進而，使玻璃板之製造持續20 天，若測量第2 1天所製造之玻璃板中之氣泡之數量，則尺 寸為300 μηι以下之氣泡之數量於1 kg之玻璃中約為0.35 個。再者’分析尺寸為300 μπι以下之氣泡之成分，結果成 分主要為C02。 根據上述（3-1)及（3-2)之例可知，若使與攪拌翼l〇3a所接 觸之熔融玻璃的溫度高於玻璃板製造線100之正式運轉時 的溫度，又，黏度低於正式運轉時，則有所製造之玻璃板 中所含之300 μπι以下的氣泡之數量減少之傾向。 (3-3)生產線外熱處理之實施例 使攪拌翼a偏離製造玻璃板之玻璃板製造線1〇〇，上 述玻璃板包含超過作為製品之容許範圍之數量之尺寸為 300 μπι以下的氣泡，並對該攪拌翼103a進行上述之生產線 外熱處理。具體而言，將攪拌翼l〇3a放入生產線外之鉑合 金製之爐中’利用電源設備使爐通電，並且利用氧燃燒器 對爐内之環境進行加熱。於爐内之環境之溫度約為1500°C 之狀態下，將攪拌翼l〇3a放入爐内24小時。其後，再次將 -13· 163495.doc 201249764 攪拌翼103a投入玻璃板製造線loo中，使用與上述先前例 相同之原料及玻璃板製造線1〇〇，並利用相同之方法連續 製造玻璃板。流入玻璃板製造線1〇〇中之熔融玻璃之溫度 及黏度與正式運轉時相同。即，與攪拌翼103a所接觸之熔 融玻璃與正式運轉時相同’溫度約為1445°C，黏度約為 113 Pa . S。若測量所製造之玻璃板所含有之氣泡之數 量’則1 kg之玻璃中之尺寸為300 μηι以下之氣泡的個數於 1 kg之玻璃中約為〇.12個。 根據上述（3-2)及（3-3)之例可知，若使攪拌翼i〇3a之與熔 融玻璃接觸的表面在較玻璃板製造線1〇〇之正式運轉時與 該表面所接觸之熔融玻璃高出50度以上之溫度的環境下， 浸至少24小時，其後製造玻璃板，則可減少玻璃板中所含 之300 μιη以下之氣泡之數量。 (4)特徵 (4-1) 本發明之玻璃板之製造方法之特徵在於：包括如下準備 步驟：於使玻璃板製造線100正式運轉之前，對鉑或舶合 金製之攪拌翼103a進行熱處理’藉此去除攪拌翼1〇3&之與 熔融玻璃接觸之表面之附著物。 於本發明之上述（3-1)及（3-3)之實施例中，於對鉑或始合 金製之攪拌翼103a之與熔融玻璃接觸的表面進行熱處理之 後，製造玻璃板’藉此可有效抑制玻璃中所形成之氣泡。 (4-2) 又，本發明之玻璃板之製造方法較佳為，準備步驟包 I63495.doc 201249764 括.使搜拌翼103a浸於較正式運轉時高出3〇°C左右以上之 溫度之溶融玻璃中。 於本發明之上述（3-1)之實施例中，於將鉑或鉑合金製之 授拌翼103 a之與熔融玻璃接觸的表面浸於較在玻璃板製造 線1〇〇之正式運轉時與該表面所接觸之熔融玻璃的溫度 1445°C高出30°C以上的1484°C之熔融玻璃中，其後製造玻 璃板’藉此’可有效抑制於玻璃中形成氣泡。 (4-3) 又’本發明之玻璃板之製造方法較佳為，準備步驟包 括：使攪拌翼103a浸於黏度為120 Pa· S以下之熔融玻璃 中。 於本發明之上述（3-1)之實施例中，於使鉑或鉑合金製之 攪拌翼103a之與熔融玻璃接觸的表面浸於黏度約為71 Pa· S之熔融玻璃中之後，製造玻璃板，藉此可有效抑制 於玻璃中形成氣泡。 (4-4) 又’本發明之玻璃板之製造方法較佳為，準備步驟包 括.使授摔翼103a於偏離玻璃板製造線之生產線外之 狀態下，浸於加熱為較正式運轉時與攪拌翼1〇3&之表面所 接觸之熔融玻璃之溫度高出50°c以上的環境下。 於本發明之上述（3-3)之實施例中，於使鉑或鉑合金製之 擾拌翼103a之與熔融玻璃接觸之表面浸於較在玻璃板製造 線100之正式運轉時與該表面所接觸之熔融玻璃之溫度 1445°C高出50°C以上的1500。〇之環境，其後製造玻璃，藉 163495.doc -15- 201249764 此可有效抑制於玻璃中形成氣泡。Si02 : 60.9 mass %, b2 〇 3 : 11.6 mass %, Al 2 〇 3 : 16.9 mass ° / 〇, MgO : 1.7 mass %, CaO : 5.1 mass %, SrO : 2.6 mass %, 83 〇: 0.7 mass %, 2〇: 0.25 mass%, 卩62〇3: 0.15 mass °/〇, Sn〇2: 0.13 mass%. The temperature of the molten glass in contact with the stirring blade i〇3a is about 1445 ° C (viscosity is about 113 pa·s) as in the case of the official operation of the glass sheet manufacturing line 100. If the number of bubbles in the glass plate manufactured on the first day is measured, the number of bubbles having a size of 3 〇〇 μη or less is about 2424 in 1 kg of glass. Further, the glass sheet was produced for 20 days. If the number of bubbles in the glass sheet produced on the 21st day was measured, the number of bubbles having a size of 300 μη or less was about 0.35 in 1 kg of glass. Furthermore, 'the composition of the bubbles having a size of 300 μm or less was analyzed, and the result was mainly C02. According to the above examples (3-1) and (3-2), it is understood that the temperature of the molten glass that is in contact with the stirring blade 10a is higher than the temperature at the time of the actual operation of the glass sheet manufacturing line 100, and the viscosity is low. At the time of the official operation, the number of bubbles of 300 μm or less contained in the glass plate to be manufactured tends to decrease. (3-3) The embodiment of the production line heat treatment causes the stirring blade a to deviate from the glass sheet manufacturing line for manufacturing the glass sheet, and the glass sheet contains bubbles exceeding 300 μm or less in a quantity exceeding the allowable range of the product, and The above-described production line heat treatment is performed on the stirring blade 103a. Specifically, the stirring blade 10a is placed in a furnace made of a platinum alloy outside the production line. The furnace is energized by a power source device, and the environment inside the furnace is heated by an oxygen burner. The stirring blade 10a was placed in the furnace for 24 hours in a state where the temperature in the furnace was about 1500 °C. Thereafter, the -13·163495.doc 201249764 stirring blade 103a was again put into the glass sheet manufacturing line loo, and the same raw material and glass sheet manufacturing line as the above-mentioned prior art were used, and the glass sheet was continuously produced by the same method. The temperature and viscosity of the molten glass flowing into the glass sheet manufacturing line 1 are the same as those in the normal operation. That is, the molten glass which is in contact with the stirring blade 103a is the same as that at the time of the actual operation, and the temperature is about 1445 ° C, and the viscosity is about 113 Pa. If the number of bubbles contained in the glass plate produced is measured, then the number of bubbles having a size of 300 μη or less in 1 kg of glass is about 〇12 in 1 kg of glass. According to the above examples (3-2) and (3-3), it is understood that the surface of the stirring blade i〇3a that is in contact with the molten glass is in contact with the surface when it is in the normal operation of the glass sheet manufacturing line 1〇〇. The glass is immersed for at least 24 hours in an environment where the molten glass is higher than 50 degrees, and thereafter, the number of bubbles of 300 μm or less contained in the glass plate can be reduced. (4) Characteristics (4-1) The method for producing a glass sheet according to the present invention is characterized in that it includes a preparation step of heat-treating the stirring blade 103a made of platinum or alloy before the glass sheet manufacturing line 100 is officially operated. Thereby, the attachment of the surface of the stirring blade 1〇3& which is in contact with the molten glass is removed. In the above embodiments (3-1) and (3-3) of the present invention, after the surface of the stirring blade 103a made of platinum or the initial alloy is heat-treated, the glass plate is manufactured. Effectively suppresses bubbles formed in the glass. (4-2) Further, in the method for producing the glass sheet of the present invention, the preparation step package I63495.doc 201249764 includes immersing the search blade 103a at a temperature higher than about 3 ° C above the official operation. Melted in the glass. In the above embodiment (3-1) of the present invention, the surface of the blending blade 103a made of platinum or platinum alloy in contact with the molten glass is immersed in the official operation of the glass sheet manufacturing line. In the molten glass of 1484 ° C which is higher than the temperature of the molten glass which is in contact with the surface at 1,445 ° C and is higher than 30 ° C, the glass plate is then made 'by this' to effectively suppress the formation of bubbles in the glass. (4-3) Further, in the method for producing a glass sheet according to the present invention, the preparation step includes immersing the stirring blade 103a in a molten glass having a viscosity of 120 Pa·s or less. In the embodiment (3-1) of the present invention, after the surface of the stirring blade 103a made of platinum or platinum alloy is in contact with the molten glass, the surface is immersed in molten glass having a viscosity of about 71 Pa·s to produce glass. The plate can thereby effectively suppress the formation of bubbles in the glass. (4-4) Further, the manufacturing method of the glass sheet of the present invention is preferably such that the preparation step comprises: immersing the feeding wing 103a in a state of being out of the production line of the glass sheet manufacturing line, and immersing the heating into a more formal operation. The temperature of the molten glass contacted by the surface of the stirring blade 1〇3& is higher than 50 ° C. In the above embodiment (3-3) of the present invention, the surface of the spoiler blade 103a made of platinum or platinum alloy is immersed in the surface of the glass sheet manufacturing line 100 and the surface thereof. The temperature of the molten glass contacted is 1445 ° C higher than 1500 above 50 ° C. The environment of the enamel, followed by the manufacture of glass, by 163495.doc -15- 201249764 this can effectively inhibit the formation of bubbles in the glass.
(5)變形例 (5-1)變形例A 上述實施形態調配較佳用於製造平板顯示器用之玻璃基 板之原料’並使用本發明之玻璃板製造方法來製造玻璃 板。但是’於其他實施形態中，亦可將本發明之玻璃板製 造方法用於例如製造覆蓋玻璃用之玻璃板中。於該情形 時’較佳為以具有以Na20、K20或者Li20為代表之鹼金屬 氧化物之濃度之合計大於2.〇質量。之組成的方式，調配玻 璃原料。 於製造具有如上所述之組成之玻璃板之情形時，於玻璃 板製造線100正式運轉時’與攪拌翼1〇3&之表面所接觸熔 融玻璃之溫度較佳為約1350〇C (黏度約為74 pa · s)。因 此’為了有效抑制氣泡之形成，較佳為於將攪拌翼丨〇3&之 表面is:於較§亥溫度高出3 〇以上之溫度（例如，13 8 0。(3或 其以上）之溶融玻璃的上述生產線上熱處理，或於將攪拌 翼103a之表面浸於較該溫度高出5〇〇c以上之溫度（例如， 1400°C或其以上）之環境的上述生產線外熱處理，或者於 進行該等兩者之後，製造玻璃板。再者，於具有本變形例 之如上所述之組成之玻璃的情形時，於138〇£>c下黏度成為 約 56 Pa · S。 以上，以抑制因攪拌翼103a之表面之附著物所引起之氣 泡之形成的玻璃板之製造為例，詳細說明本發明，但本發 明之應用並不限定於I本發明例如亦可用於如下玻璃板 I63495.doc -16· 201249764 之製造：抑制由於第!輸送管105a、第2輸送管獅、第3 輸送管邮、澄清管1()2、成形裝置1()4等及其他玻璃製造 用裝置之與熔融玻璃接觸之表面的附著物所引起之氣泡之 形成。 【圖式簡單說明】 圖1係本發明之實施形態之玻璃板之製造方法的流程 圖。 圖2係本發明之實施形態之玻璃板製造線之概略圖。 【主要元件符號說明】 圖3係本發明之實施形態之攪拌槽之圖。 100 玻璃板製造線 101 熔解槽 102 澄清槽 103 攪拌槽 103a 攪拌翼 104 成形裝置 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特表2001-503008號公報 163495.doc • 17-(5) Modifications (5-1) Modification A The above embodiment is preferably used for producing a glass substrate for a flat panel display, and a glass sheet is produced by using the glass sheet manufacturing method of the present invention. However, in other embodiments, the glass sheet manufacturing method of the present invention can also be applied to, for example, the production of a glass sheet for covering glass. In this case, it is preferable that the total concentration of the alkali metal oxides represented by Na20, K20 or Li20 is more than 2. 〇 mass. In the way of composition, the glass raw materials are blended. In the case of manufacturing a glass plate having the composition as described above, the temperature of the molten glass which is in contact with the surface of the stirring blade 1〇3& is preferably about 1350 〇C when the glass plate manufacturing line 100 is officially operated (viscosity is about For 74 pa · s). Therefore, in order to effectively suppress the formation of bubbles, it is preferred that the surface of the stirring blade 3& is: a temperature higher than 3 〇 higher than the temperature (for example, 138 (3 or more)) Heat-treating the above-mentioned production line of the molten glass, or immersing the surface of the stirring blade 103a in an environment of the above-mentioned production line in an environment where the temperature is higher than 5 ° C (for example, 1400 ° C or higher), or After performing both of these, a glass plate is produced. Further, in the case of the glass having the composition as described above in the present modification, the viscosity becomes about 56 Pa · S at 138 Å > c. The invention is described in detail by taking the manufacture of a glass sheet which suppresses the formation of bubbles caused by the adhesion of the surface of the stirring blade 103a. However, the application of the present invention is not limited to the present invention, for example, it can also be used for the following glass plate I63495. Doc -16· 201249764 Manufacture: suppression of the first delivery tube 105a, the second delivery lion, the third delivery pipe, the clarification pipe 1 () 2, the forming device 1 () 4, and other glass manufacturing devices Attachment of the surface contacted by molten glass BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing a method for producing a glass sheet according to an embodiment of the present invention. Fig. 2 is a schematic view showing a glass sheet manufacturing line according to an embodiment of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 3 is a view showing a stirring tank according to an embodiment of the present invention. 100 Glass plate manufacturing line 101 Melting tank 102 Clarifying tank 103 Stirring tank 103a Stirring blade 104 Forming apparatus [Prior Art Document] [Patent Literature] [Patent Document 1] 专利本专利特表2001-503008号163163.doc • 17-