201200482 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種熔融玻璃處理裝置、其製造方法、及 其用途。 【先前技術】 於熔融玻璃處理裝置中，熔融玻璃所接觸之構件之材料 通常使用鉑或鉑合金。鉑合金係除了鉑（Pt)以外亦含有鍺 (Rh)、銥（Ir)、釕（RU)、金（Au)等之合金。鉑及鉑合金具有 熔點較局、於大氣中難以氧化、與熔融玻璃之反應性較低 之特徵，故而適宜作為熔融玻璃所接觸之構件之材料。 然而，於使用鉑或鉑合金之情形時，存在於熔融玻璃中 產生氣泡之問題。該氣泡係由溶存於熔融玻璃中之水分而 引起者。-般認為’若水分分解成氫氣與氧氣，則氫氣穿 透翻散逸至外部’氧氣殘存於溶融玻璃中而形成氣泡。又， 亦存在以下問胃：由於翻與外部空氣中之氧氣進行反應而 生成翻氧化物_2)之氣體，或由於財身因熱而揮散，而 導致翻製或翻合金製之構件緩緩揮散。 因此，為解決上述問題’提出於始製或翻合金製之構件 之外表面設置氫氣低穿透層。作為氫氣低穿透層之材料， 而使用玻璃或陶瓷（例如參考專利文獻丨）。 先前技術文獻 專利文獻 專利文獻1 :曰本專利特± J付表2004-523449號公報 【發明内容】 155916.doc201200482 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a molten glass processing apparatus, a method of manufacturing the same, and uses thereof. [Prior Art] In the molten glass processing apparatus, the material of the member to which the molten glass is contacted is usually platinum or a platinum alloy. The platinum alloy contains alloys of rhodium (Rh), iridium (Ir), rhodium (RU), and gold (Au) in addition to platinum (Pt). Platinum and platinum alloys are characterized by their relatively high melting point, difficulty in oxidation in the atmosphere, and low reactivity with molten glass, and are therefore suitable as materials for members to be contacted by molten glass. However, in the case of using platinum or a platinum alloy, there is a problem that bubbles are generated in the molten glass. This bubble is caused by moisture dissolved in the molten glass. It is generally believed that if water decomposes into hydrogen and oxygen, the hydrogen permeates and scatters to the outside. Oxygen remains in the molten glass to form bubbles. In addition, there are also the following stomachs: due to the reaction of oxygen in the outside air to generate a gas that turns oxides, or because the body is volatilized by heat, the components of the turned or alloyed alloy are slowly slowed down. Fluttering. Therefore, in order to solve the above problem, it is proposed to provide a hydrogen gas low permeability layer on the outer surface of the member which is formed or alloyed. As a material of the hydrogen gas low permeability layer, glass or ceramic is used (for example, refer to the patent document 丨). PRIOR ART DOCUMENT Patent Document Patent Document 1: Japanese Patent Application No. JP-A No. 2004-523449 [Abstract] 155916.doc
I 201200482 發明所欲解決之問題 然而’於使用玻域β _ 等作為氫氣低穿透層之材料之情形 時，有時玻璃因自身番Α 置而向下方熱流動，從而自構件之 外表面脫離β 又於單獨使用陶究作為氣氣低穿透層之材料之情形 時，若將陶究粒子喷敷於構件之外表面，則由於陶曼與翻 之熱膨脹差而容易於陶瓷或鉑中產生龜裂。 尤其是近年來，面向液晶顯示器（LCD，Liquid Crystal Disp㈣等平板顯示器（FPD，Flat panel叫㈣）而使用無 鹼玻璃。無驗玻璃係實質上不含驗金屬之玻璃，且斑通常 之鈉鈣玻璃相比，熔解溫度高Al〇(rc以上。因此，上述構 件之使用溫度升高，上述問題變得容易顯在化。 又，近年來，存在於熔解玻璃原料之熔解槽中，使用氧 氣燃燒燃燒器作為破璃原料之加熱源之傾向。與空氣燃燒 燃燒器相比，氧氣燃燒燃燒器之加熱效率更加良好。然而二 若使用氧氣燃燒燃燒器，則由於熔解槽内之上部空間之水 分濃度升高，故而溶存於熔融玻璃中之水分濃度升高。因 此’上述問題變得容易顯在化。 本發明係鑒於上述課題而完成者，其目的在於提供一種 可更有效地抑制於熔融玻璃中生成氣泡之熔融玻璃處理裝 置。 ’ 解決問題之技術手段 為解決上述目的，本發明提供一種熔融玻璃處理裝置， 其係包含内表面與熔融玻璃接觸之鉑製或鉑合金製之構 155916.doc 201200482 件、覆蓋該構件之外表面之至少一部分的玻璃層、以及該 玻璃層之至少外側滲透於其中之耐熱性纖維體者，且 上述耐熱性纖維體含有玻璃纖維或陶瓷纖維，以氧化物 基準之質量％表示計，Si02之含量為50%以上， 形成上述玻璃層之玻璃於使用溫度下具有1〇2.5 dPa.sW 上之黏度， 上述玻璃層中包含與外部空氣不連通之空隙。 發明之效果 根據本發明’可提供一種能夠更有效地抑制於熔融玻璃 中生成氣泡之熔融玻璃處理裝置。 【實施方式】 以下，參考圖式，對用以實施本發明之形態加以說明， 但本發明並不受下述實施形態限制，可不偏離本發明之範 圍而對下述實施形態進行各種變形及置換。 (熔融玻璃處理裝置） 炫融玻璃處理裝置係處理熔融玻璃之裝置，例如為用於 熔融玻璃之炫解、澄清、調溫、輸送、攪拌等之裝置。再 者’本發明之熔融玻璃處理裝置並不限定於此。 圖1係本發明之一實施形態之熔融玻璃處理裝置之使用 狀態的剖面圖。例如，如圖i所示，熔融玻璃處理裝置^包 含：内表面31與熔融玻璃2接觸之鉑製或鉑合金製之構件 3、覆蓋該構件3之外表面32之至少一部分的玻璃層彳、以及 該玻璃層4之至少外側（與構件3為相反側）滲透於其中之耐 熱性纖維體卜玻璃層4藉由覆蓋構件3之外表面32之至少— 155916.doc 201200482 部分，巾抑制熔融玻璃2中所含之氫氣穿透構件3散逸至外 部。耐熱性纖維體5抑制玻璃層4之熱流動。以下，對各構 成加以說明。 構件3係由鉑或鉑合金所構成。鉑合金係除了鉑（pt)以外 亦含有铑（Rh)、銥（ir)、釕（Ru)、金（Au)等之合金。鉑及鉑 合金具有熔點較高、於大氣中難以氧化、與熔融玻璃2之反 應性較低之特徵，故而適宜作為熔融玻璃2所接觸之構件3 之材料。 構件3之形狀係根據熔融玻璃處理裝置丨之種類或用途等 而設定。例如，構件3之形狀可設定為箱形或管形。構件3 之内表面31與熔融玻璃2接觸，構件3之外表面32與玻璃層4 接觸。 玻璃層4藉由覆蓋構件3之外表面32之至少一部分，而抑 制熔融玻璃2中所含之氫氣穿透構件3散逸至外部’進而抑 制溶存於熔融玻璃2十之水分之分解。因此，可抑制由水分 之分解而引起的氣泡之生成。又，可抑制鉑等之揮散。 形成玻璃層4之玻璃並無特別限制，例如，以氧化物基準 之質量％表示計，含有Si02 : 50〜72%、Al2〇3 : 〇 5〜24〇/〇較 佳為 0.5〜23%、B2〇3 : 0〜12%、MgO: 0〜8%、CaCK 〇〜14.5。/。、 SrO : 0〜24。/。、BaO : 0〜13·5〇/。、Na2〇+Li2〇+K2〇 : 〇〜15%， 且MgO+CaO+SrO+BaO為9〜29.5%。此時，可進而含有 Zr〇2 : 0〜5% 〇 於熔融玻璃2為無鹼玻璃之情形時，形成玻璃層4之玻璃 較理想為同樣為無驗玻璃。其原因在於，於構件3損傷之情 155916.doc 201200482 形時，防止玻璃層4中之鹼金屬混入熔融玻璃2中。 形成玻璃層4之無鹼玻璃並無特別限制，例如，以氧化物基 準之質量％表示計’含有81〇2:50~66%、八12〇3:10.5~24%較 佳為 10.5〜22%、B2〇3 : 〇~12%、MgO : 0~8%、CaO : 0~14.5%、 SrO : 〇〜24%、BaO : 0-13.5%，且 MgO+CaO+SrO+BaO 為 9〜29.5%。此時，可進而含有Zr〇2 : 0-5%。較佳為以氧化 物基準之質量％表示計，含有Si02 : 58〜66%、A1203 : 15〜22%、B2〇3 : 5〜12%、MgO : 0〜8%、CaO : 〇〜9%、SrO : 3〜12.5%、BaO : 0〜2%，且 MgO+CaO+SrO+BaO為 9〜18%。 形成玻璃層4之玻璃於使用溫度下具有1〇2·5 dPa.s以上 (較佳為102·8 dPa.s以上，更佳為1〇3.5 dPa.s以上）之黏度η。 於該黏度η過低之情形時，玻璃因自身重量而向下方熱流 動，或玻璃通過耐熱性纖維體5流出至外部，而使玻璃層4 自構件3脫離。另一方面，於該黏度η過高之情形時，難以 形成連續之玻璃層4，又，難以於玻璃層4之内部形成與外 部空氣不連通之空隙7(詳見下述）。因此，該黏度η較佳為 於使用溫度下為104·8 dPa.s以下，更佳為1〇4.5 dPa.s以下。 此處’所謂使用溫度，係指構件3與熔融玻璃2接觸之狀 態下之溫度。熔融玻璃2、構件3、玻璃層4之使用溫度通常 大致相等。 形成玻璃層4之玻璃之至少一部分於使用溫度下滲透至 耐熱性纖維體5中。玻璃層4向耐熱性纖維體5之滲透深度D2 較理想為0.1 mm以上。此處，滲透深度係指平均值。若 滲透深度D2過小’則難以藉由耐熱性纖維體5而抑制玻璃層 155916.doc 201200482 4之熱流動。 再者’如圖1所示，於本實施形態中，形成玻璃層4之玻 璃之僅一部分滲透至耐熱性纖維體5中，但只要玻璃層4與 構件3接觸，則形成玻璃層4之玻璃亦可全部滲透至耐熱性 纖維體5中。 形成玻璃層4之玻璃較理想為於使用溫度下，對構件3之 潤濕性高於對耐熱性纖維體5之潤濕性者。藉此，可提高玻 璃層4與構件3之密接性。 形成玻璃層4之玻璃與構成構件3之材料（例如鉑或鉑合 金）的接觸角0a亦取決於玻璃之種類等，於使用溫度下例如 為30〜60。，較佳為45〜55。》 此處’所謂接觸角’係指依據jIS R 3257-1999中所規定 之接觸角者。於本發明中，接觸角0a係水平設置由構成構 件3之材料（例如鉑或鉑合金）所形成之試驗板，並將形成玻 璃層4之玻璃之液滴靜置於試驗板上而測定。該接觸角可藉 由市售之裝置而測定。 另一方面，形成玻璃層4之玻璃與構成耐熱性纖維體5之 材料（例如玻璃或陶瓷）的接觸角的於使用溫度下例如為 60〜110° ’較佳為7〇〜11〇。。若接觸角扑過小，則玻璃層4與 構件3之密接性變差。又，若接觸角扑過大，則玻璃層斗與 财熱性纖維體5之密接性變差。 於本發明中，接觸角扑係水平設置由與構成耐熱性纖維 體5之材料（例如玻璃或陶瓷）相同之組成所形成的試驗板 (例如玻璃板或陶瓷板），並將形成玻璃層4之玻璃之液滴靜 155916.doc 201200482 置於試驗板上而測定。 玻璃層4之厚度Dl(包括滲透深度D2)較理想為ο』 上。此處，厚度D1係指平均值。右厚度D1過小，則設置玻 璃層4之效果未充分體現。另一方面，若厚度di過大，則形 成玻璃層4之玻璃因自身重量而向下方熱流動，而使玻璃層 4自構件3脫離。因此，厚度D1較佳為3 mm以下，更佳為未 達1 mm，進而更佳為0.9 mm以下，尤佳為〇,8 mm以下。 如圖1所示，本實施形態之玻璃層4包含與外部空氣不連 通之空隙7、9。空隙7、9分散配置於玻璃層4中。空隙7對 構件3之外表面32開放，且空隙7内之氣體與構件3之外表面 32接觸。空隙7抑制氫氣自内側向外側穿透構件3，進而抑 制熔融玻璃2中之氣泡生成等。關於其理由，仍未充分把 握，但可考慮以下（1)〜(3)之理由。 (1) 於空隙7内之氣體中蓄積有自内側向外側穿透構件3 之氣氣。因此’由於氫氣濃度較高之氣體與構件3之外表面 32接觸’故而可抑制氫氣自内側向外側穿透構件3。 (2) 氫於構件3或玻璃層4等固體或液體中係以原子之形 式含有，於空隙7内之氣體中則以分子之形式含有。因此， 為使氫氣經由空隙7自構件3向玻璃層4移動，必需於原子進 仃鍵結而形成分子後’再使分子分解為原子。於該等鍵結 或刀解中’必需特定之能量，故而可抑制氫氣之移動。 (3) 空隙7藉由在形成玻璃層4之玻璃與構件3之間形成 面而表現玻璃對構件3之表面張力，抑制玻璃相對 於構件3進行熱流動。 155916.doc -9- 201200482 空隙9係以空隙9内之氣體與構件3之外表面32不接觸之 方式而構成。空隙9以與上述（2)相同之理由抑制氫氣自内側 向外側穿透構件3，進而抑制熔融玻璃2中之氣泡生成等。 與外部空氣不連通之空隙7、9較理想為合計占玻璃層4 之剖面之2〜70% ^若空隙7、9所占之比例過低，則無法充 刀獲知·上述（1)〜(3)之效果。另一方面，若空隙7、9所占之 比例過高，則空隙7、9會與外部空氣連通，或玻璃層4之機 械強度降低。更佳之範圍為5〜65%，進而更佳之範圍為 10〜60%，尤佳之範圍為2〇〜5〇0/〇。 再者，本實施形態之玻璃層4包含空隙7、9之兩者，但本 發明並不限定於此。例如，玻璃層4亦可僅包含空隙7。 又’如圖1所示’本實施形態之空隙7、9於玻璃層4中， 形成於未滲透至耐熱性纖維體5中之部分，但只要與外部空 氣不連通’則亦可形成於滲透至耐熱性纖維體5令之部分。 另外，於s亥情形時，空隙7、9内之氣體與耐熱性纖維體5 接觸。 耐熱性纖維體5抑制玻璃層4之熱流動。又，财熱性纖維 體5藉由自玻璃層4向外側延伸，而阻斷與玻璃層4接觸之外 部空氣之流動。其原因在於，若玻璃層4與新鮮之外部空氣 接觸，則空隙7、9内之氣體之氫氣濃度或水分濃度降低。 耐熱性纖維體5含有玻璃纖維或陶瓷纖維。此處，所謂耐 熱性’於玻璃纖維之情形時，係指玻璃纖維具有高於使用 溫度之軟化點’於陶瓷纖維之情形時，係指陶瓷纖維具有 馬於使用溫度之熔點。該等纖維難以於使用溫度下發生熱 155916.doc •10· 201200482 變形’故而可抑制玻璃層4之熱流動。 耐熱性纖維體5係該等纖維之集合體。耐熱性纖維體5之 形態並無特別限制，可為將複數之纖維編織成布狀者，亦 可為將複數之纖維纏繞成塊狀者。將複數之纖維編織成布 狀者於可撓性及加工性方面優異。纖維之平均長度較佳為 10 mm以上。 耐熱性纖維體5以氧化物基準之質量％表示計，Si〇2之含 量為50%以上。於Si〇2之含量未達5〇%之情形時，由於形成 玻璃層4之玻璃對耐熱性纖維體5之潤濕性過高，故而玻璃 會通過耐熱性纖維體5流出至外部，而使玻璃層4自構件3 脫離。 耐熱性纖維體5之厚度D3(包括滲透深度D2)較佳為〇 5 mm 以上。此處，厚度D3係指平均值。若厚度1)3未達〇 5爪爪， 則耐熱性纖維體5之剛度不充分，無法充分獲得抑制玻璃層 4之熱流動之效果。 於該耐熱性纖維體5之外側亦可設置隔熱構件6。隔熱構 件6係由耐火物等構成，隔熱構件6可緩和由外部空氣引起 之冷部，同時抑制構件3及耐熱性纖維體5等因熔融玻璃2 之液壓而發生變形。 (熔融玻璃處理裝置之製造方法） 繼而，對上述熔融玻璃處理裝置丨之製造方法加以說明。 該製造方法包括藉由在構件3與耐熱性纖維體5之間形成 含有玻璃粉末之塗層並進行焙燒，而形成玻璃層4之步驟。 具體而言，首先，如圖2所示，於構件3之外表面32之至 155916.doc 201200482 少—部分塗佈含有 塗層8。 々不之浆枓並加以乾燥，藉此形成I 201200482 The problem to be solved by the invention However, when the glass domain β _ or the like is used as the material of the hydrogen low-permeability layer, sometimes the glass flows downward due to its own heat, thereby detaching from the outer surface of the member. When β is used alone as the material of the gas-permeable low-penetration layer, if the ceramic particles are sprayed on the outer surface of the member, it is easy to be produced in ceramic or platinum due to the difference in thermal expansion between Tauman and the turn-over. Cracked. In particular, in recent years, non-alkali glass has been used for liquid crystal displays (LCD, Liquid Crystal Disp (4), etc.), and the non-alkali glass is substantially free of metal glass, and the spot is usually sodium calcium. Compared with glass, the melting temperature is higher than Al 〇 (rc or more. Therefore, the above-mentioned problem becomes easy to become apparent when the use temperature of the above-mentioned members is increased. In addition, in recent years, it is present in a melting tank for melting glass raw materials, and is burned with oxygen. The burner has a tendency to be a heating source for the raw material of the glass. Compared with the air combustion burner, the heating efficiency of the oxygen combustion burner is better. However, if the oxygen combustion burner is used, the water concentration in the upper space of the melting tank is used. When the temperature is increased, the concentration of water dissolved in the molten glass is increased. Therefore, the above problem is easily manifested. The present invention has been made in view of the above problems, and an object thereof is to provide a method which can be more effectively suppressed in molten glass. A molten glass processing apparatus for generating bubbles. 'Technical means for solving the problem. To solve the above object, the present invention provides a A molten glass processing apparatus comprising a platinum or platinum alloy having an inner surface in contact with molten glass, 155916.doc 201200482, a glass layer covering at least a portion of an outer surface of the member, and at least an outer side of the glass layer In the heat-resistant fibrous body, the heat-resistant fibrous body contains glass fibers or ceramic fibers, and the content of SiO 2 is 50% or more based on the mass % of the oxide, and the glass forming the glass layer is used. The viscosity has a viscosity of 1 〇 2.5 dPa.sW, and the glass layer contains a void which does not communicate with the outside air. Advantageous Effects of Invention According to the present invention, it is possible to provide a molten glass treatment capable of more effectively suppressing generation of bubbles in molten glass. [Embodiment] The embodiments of the present invention are described below with reference to the drawings, but the present invention is not limited by the following embodiments, and various modifications may be made to the following embodiments without departing from the scope of the invention. And replacement. (Molten glass processing equipment) The glass processing equipment is a device for processing molten glass. The apparatus for use in melting, clarifying, tempering, conveying, stirring, etc. of the molten glass. The molten glass processing apparatus of the present invention is not limited thereto. Fig. 1 is a molten glass treatment according to an embodiment of the present invention. A cross-sectional view of the state of use of the apparatus. For example, as shown in Fig. i, the molten glass processing apparatus comprises: a member made of platinum or platinum alloy having an inner surface 31 in contact with the molten glass 2, and an outer surface 32 covering the member 3. At least a portion of the glass layer 彳, and at least the outer side of the glass layer 4 (on the opposite side from the member 3), the heat-resistant fibrous body glass layer 4 is covered by at least the outer surface 32 of the covering member 3 - 155916. In the portion of doc 201200482, the towel suppresses the escape of the hydrogen gas penetrating member 3 contained in the molten glass 2 to the outside. The heat resistant fibrous body 5 suppresses the heat flow of the glass layer 4. Hereinafter, each configuration will be described. The member 3 is composed of platinum or a platinum alloy. The platinum alloy contains alloys of rhodium (Rh), iridium (ir), ruthenium (Ru), and gold (Au) in addition to platinum (pt). Platinum and platinum alloys are preferred as the material of the member 3 to which the molten glass 2 is contacted because of its high melting point, difficulty in oxidation in the atmosphere, and low reactivity with the molten glass 2. The shape of the member 3 is set in accordance with the type or use of the molten glass processing apparatus. For example, the shape of the member 3 can be set to a box shape or a tubular shape. The inner surface 31 of the member 3 is in contact with the molten glass 2, and the outer surface 32 of the member 3 is in contact with the glass layer 4. The glass layer 4 suppresses the decomposition of moisture dissolved in the molten glass by inhibiting at least a part of the outer surface 32 of the member 3, and suppressing the hydrogen gas penetrating member 3 contained in the molten glass 2 from escaping to the outside. Therefore, generation of bubbles caused by decomposition of moisture can be suppressed. Further, it is possible to suppress the volatilization of platinum or the like. The glass forming the glass layer 4 is not particularly limited, and is, for example, SiO 2 : 50 to 72%, and Al 2 〇 3 : 〇 5 to 24 〇 / 〇 is preferably 0.5 to 23%, based on the mass % of the oxide. B2〇3: 0~12%, MgO: 0~8%, CaCK 〇~14.5. /. , SrO: 0~24. /. , BaO: 0~13·5〇/. , Na2〇+Li2〇+K2〇 : 〇~15%, and MgO+CaO+SrO+BaO is 9~29.5%. In this case, Zr 〇 2 : 0 to 5% 〇 may be further contained. When the molten glass 2 is an alkali-free glass, the glass forming the glass layer 4 is preferably a non-glass. The reason for this is that the alkali metal in the glass layer 4 is prevented from being mixed into the molten glass 2 in the case of the damage of the member 3 155916.doc 201200482. The alkali-free glass forming the glass layer 4 is not particularly limited, and for example, it is represented by mass % of oxides, and contains 81 〇 2: 50 to 66%, 八 12 〇 3: 10.5 to 24%, preferably 10.5 to 22 %, B2〇3 : 〇~12%, MgO: 0~8%, CaO: 0~14.5%, SrO: 〇~24%, BaO: 0-13.5%, and MgO+CaO+SrO+BaO is 9~ 29.5%. In this case, Zr〇2 may further be contained: 0-5%. Preferably, it is SiO2: 58 to 66%, A1203: 15 to 22%, B2〇3: 5 to 12%, MgO: 0 to 8%, and CaO: 〇 to 9%, based on the mass% of the oxide. , SrO: 3 to 12.5%, BaO: 0 to 2%, and MgO+CaO+SrO+BaO is 9 to 18%. The glass forming the glass layer 4 has a viscosity η of 1 〇 2·5 dPa·s or more (preferably 102·8 dPa·s or more, more preferably 1 〇 3.5 dPa·s or more) at the use temperature. When the viscosity η is too low, the glass flows downward due to its own weight, or the glass flows out to the outside through the heat-resistant fibrous body 5, and the glass layer 4 is detached from the member 3. On the other hand, when the viscosity η is too high, it is difficult to form the continuous glass layer 4, and it is difficult to form the void 7 which is not in communication with the outside air inside the glass layer 4 (see below). Therefore, the viscosity η is preferably at a use temperature of 104·8 dPa·s or less, more preferably 1 〇 4.5 dPa·s or less. Here, the term "use temperature" means the temperature of the member 3 in contact with the molten glass 2. The use temperatures of the molten glass 2, the member 3, and the glass layer 4 are generally substantially equal. At least a portion of the glass forming the glass layer 4 penetrates into the heat resistant fibrous body 5 at the use temperature. The penetration depth D2 of the glass layer 4 to the heat-resistant fibrous body 5 is desirably 0.1 mm or more. Here, the depth of penetration refers to the average value. If the penetration depth D2 is too small, it is difficult to suppress the heat flow of the glass layer 155916.doc 201200482 4 by the heat resistant fibrous body 5. Further, as shown in Fig. 1, in the present embodiment, only a part of the glass forming the glass layer 4 penetrates into the heat-resistant fibrous body 5, but as long as the glass layer 4 is in contact with the member 3, the glass of the glass layer 4 is formed. It is also possible to completely infiltrate into the heat resistant fibrous body 5. The glass forming the glass layer 4 is preferably one which has higher wettability to the member 3 than the heat-resistant fibrous body 5 at the use temperature. Thereby, the adhesion between the glass layer 4 and the member 3 can be improved. The contact angle 0a of the glass forming the glass layer 4 and the material constituting the member 3 (e.g., platinum or platinum alloy) is also dependent on the type of the glass, etc., and is, for example, 30 to 60 at the use temperature. Preferably, it is 45 to 55. Here, the term "contact angle" means a contact angle as defined in jIS R 3257-1999. In the present invention, the contact angle 0a is horizontally provided with a test plate formed of a material constituting the member 3 (e.g., platinum or platinum alloy), and the droplets of the glass forming the glass layer 4 are placed on a test plate to be measured. The contact angle can be determined by means of a commercially available device. On the other hand, the contact angle of the glass forming the glass layer 4 and the material constituting the heat-resistant fibrous body 5 (e.g., glass or ceramic) is, for example, 60 to 110 °' at the use temperature, preferably 7 Å to 11 Å. . If the contact angle is too small, the adhesion between the glass layer 4 and the member 3 is deteriorated. Further, if the contact angle is too large, the adhesion between the glass layer bucket and the heat-generating fibrous body 5 is deteriorated. In the present invention, the contact angle flap is horizontally provided with a test plate (for example, a glass plate or a ceramic plate) formed of the same composition as the material constituting the heat resistant fibrous body 5 (for example, glass or ceramic), and the glass layer 4 is formed. The glass droplets were measured on a test plate by placing 155916.doc 201200482. The thickness D1 of the glass layer 4 (including the penetration depth D2) is preferably ο". Here, the thickness D1 means an average value. If the right thickness D1 is too small, the effect of setting the glass layer 4 is not fully reflected. On the other hand, if the thickness di is too large, the glass forming the glass layer 4 flows downward due to its own weight, and the glass layer 4 is detached from the member 3. Therefore, the thickness D1 is preferably 3 mm or less, more preferably less than 1 mm, still more preferably 0.9 mm or less, and particularly preferably 〇, 8 mm or less. As shown in Fig. 1, the glass layer 4 of the present embodiment includes voids 7, 9 which are not connected to the outside air. The voids 7 and 9 are dispersedly disposed in the glass layer 4. The void 7 is open to the outer surface 32 of the member 3, and the gas in the void 7 is in contact with the outer surface 32 of the member 3. The void 7 suppresses the passage of hydrogen gas from the inside to the outside of the member 3, thereby suppressing generation of bubbles in the molten glass 2. The reason for this is still not fully grasped, but the following reasons (1) to (3) can be considered. (1) The gas that penetrates the member 3 from the inside to the outside is accumulated in the gas in the gap 7. Therefore, since the gas having a higher hydrogen concentration is in contact with the outer surface 32 of the member 3, the hydrogen gas can be prevented from penetrating the member 3 from the inside to the outside. (2) Hydrogen is contained in the form of atoms in a solid or liquid such as the member 3 or the glass layer 4, and is contained as a molecule in the gas in the void 7. Therefore, in order to move hydrogen gas from the member 3 to the glass layer 4 via the void 7, it is necessary to form a molecule after the atom is bonded to bond, and then the molecule is decomposed into atoms. In the bonding or knife solution, specific energy is required, so that the movement of hydrogen gas can be suppressed. (3) The void 7 expresses the surface tension of the glass-to-member 3 by forming a surface between the glass forming the glass layer 4 and the member 3, and suppresses heat flow of the glass with respect to the member 3. 155916.doc -9-201200482 The gap 9 is formed such that the gas in the gap 9 does not contact the outer surface 32 of the member 3. The gap 9 suppresses the passage of hydrogen gas from the inside to the outside of the member 3 for the same reason as in the above (2), and further suppresses generation of bubbles or the like in the molten glass 2. The gaps 7 and 9 which are not connected to the outside air are preferably 2 to 70% of the cross section of the glass layer 4 in total. If the ratio of the gaps 7 and 9 is too low, the above-mentioned (1) to 3) The effect. On the other hand, if the ratio of the voids 7 and 9 is too high, the voids 7 and 9 communicate with the outside air, or the mechanical strength of the glass layer 4 may decrease. A more preferable range is 5 to 65%, and a more preferable range is 10 to 60%, and a particularly preferable range is 2 to 5 to 0/〇. Further, the glass layer 4 of the present embodiment includes both of the voids 7 and 9, but the present invention is not limited thereto. For example, the glass layer 4 may also contain only the voids 7. Further, as shown in Fig. 1, the gaps 7 and 9 of the present embodiment are formed in the glass layer 4 in a portion that does not penetrate into the heat-resistant fibrous body 5, but may be formed in the penetration as long as it is not connected to the outside air. To the heat-resistant fibrous body 5 parts. Further, in the case of shai, the gas in the voids 7, 9 is in contact with the heat-resistant fibrous body 5. The heat resistant fibrous body 5 suppresses the heat flow of the glass layer 4. Further, the heat-generating fiber 5 extends outward from the glass layer 4 to block the flow of air outside the glass layer 4. The reason for this is that if the glass layer 4 comes into contact with fresh outside air, the hydrogen concentration or the water concentration of the gas in the voids 7 and 9 is lowered. The heat resistant fibrous body 5 contains glass fibers or ceramic fibers. Here, the term "heat resistance" in the case of glass fibers means that the glass fibers have a softening point higher than the use temperature in the case of ceramic fibers, and means that the ceramic fibers have a melting point at the use temperature. These fibers are difficult to generate heat at the use temperature, so that the heat flow of the glass layer 4 can be suppressed. The heat resistant fibrous body 5 is an aggregate of these fibers. The form of the heat-resistant fibrous body 5 is not particularly limited, and may be one in which a plurality of fibers are woven into a cloth, or a plurality of fibers may be wound into a block. The fiber which is woven into a plurality of fibers is excellent in flexibility and workability. The average length of the fibers is preferably 10 mm or more. The heat-resistant fibrous body 5 is expressed by mass% of the oxide standard, and the content of Si〇2 is 50% or more. When the content of Si〇2 is less than 5%, the wettability of the glass forming the glass layer 4 to the heat-resistant fibrous body 5 is too high, so that the glass flows out to the outside through the heat-resistant fibrous body 5, so that The glass layer 4 is detached from the member 3. The thickness D3 (including the penetration depth D2) of the heat-resistant fibrous body 5 is preferably 〇 5 mm or more. Here, the thickness D3 means an average value. When the thickness 1)3 is less than the 爪5 claw, the rigidity of the heat-resistant fibrous body 5 is insufficient, and the effect of suppressing the heat flow of the glass layer 4 cannot be sufficiently obtained. A heat insulating member 6 may be provided on the outer side of the heat resistant fibrous body 5. The heat insulating member 6 is made of a refractory or the like, and the heat insulating member 6 can alleviate the cold portion caused by the outside air, and at the same time, the member 3 and the heat resistant fibrous body 5 can be deformed by the hydraulic pressure of the molten glass 2. (Manufacturing Method of Molten Glass Processing Apparatus) Next, a method of manufacturing the molten glass processing apparatus 加以 will be described. This manufacturing method includes the step of forming the glass layer 4 by forming a coating containing a glass powder between the member 3 and the heat resistant fibrous body 5 and baking. Specifically, first, as shown in Fig. 2, the outer surface 32 of the member 3 is 155916.doc 201200482 less-partially coated with the coating 8. Rinse and dry, thereby forming
漿料較佳為含右I 合劑而使用膠體二望機“㈣有機黏合劑°作為無機黏 性高分子（例如_越化7等。作為有㈣合劑而使用水溶 ㈣之塗佈二商品名: 塗法、網版印刷法、二二：例如使用喷塗法或旋 燥而成之^ 亦可貼喊毀料乾 乂 <膜來代替塗佈漿料。 對^塗佈之浆料進行乾燥之溫度較佳為4㈡3(TC。 ^者:如圖3所示’於塗層8之外側貼附财熱性纖維體5。 所不之隔熱構件6保持耐熱性纖維體5之外 側。Preferably, the slurry contains a right-handed mixture and a colloidal two-dimensional machine "(4) organic binder ° is used as an inorganic adhesive polymer (for example, _Changhua 7 or the like. As a (four) mixture, water-soluble (four) coating is used. Coating method, screen printing method, 22: For example, using spray coating or swirling, it can also be used to replace the coating slurry by smashing the dry film. The temperature is preferably 4 (two) 3 (TC. ^: As shown in Fig. 3, the heat-generating fibrous body 5 is attached to the outer side of the coating layer 8. The heat insulating member 6 is not provided on the outer side of the heat-resistant fibrous body 5.
最後’培燒圖3所示之紐驻艘 ^ lL 又，，且裝體藉此，塗層8中所含之玻 璃粉末進行熱流動而形忐阁，张-士 * 初叩4成圖1所不玻璃層4，同時玻璃粉末 之間隙形成圖1所示之空隙7、9。 培燒條件係根據玻璃粉末之種類或空隙7、9之比例等而 適當設^。例如培燒可於大氣中，在與使用溫度大致相同 之溫度下實施》 乂上述方式獲得圖1所示之熔融玻璃處理裝置1。於該製 造方法中’由於不需要喷敷裝置等，故而可於現有設備之 構件3上设置玻璃層4及耐熱性纖維體5。 再者，於本實施形態中，形成塗層8之後，於塗層8之外 側貼附耐熱性纖維體5，但本發明並不限定於此。例如，亦 可將含有玻璃粉末之漿料塗佈於耐熱性纖維體5之内側 1559l6.doc -12· 201200482 後’將耐熱性纖維體5之内側貼附於構件3之外表面32並加 以乾燥，藉此形成塗層8。 (玻璃製造裝置） 繼而’對包含上述熔融玻璃處理裝置1之玻璃製造裝置加 以說明。 圖4係包含熔融玻璃處理裝置丨之玻璃製造裝置之方塊 圖。如圖4所示，玻璃製造裝置1〇包含熔解槽u、澄清槽12、 攪拌槽13、及成形裝置14。熔解槽丨丨、澄清槽〗2、攪拌槽 U、及成形裝置14係藉由輸送管15〜17而連接。 熔解槽11係熔解玻璃原料而製造熔融玻璃。於熔解槽u 之内壁設有原料投入口、複數個燃燒器等。作為燃燒器， 有空氣燃燒燃燒器及氧氣燃燒燃燒器，就保護環境之觀點 而言’較理想為氧氣燃燒燃燒器。 自原料投入口投入之玻璃原料藉由燃燒器喷出之火焰之 輻射熱而加熱’形成溶融玻璃。該熔融玻璃經由輸送扣 而輸送至澄清槽12中。 槽12係使熔融玻璃中所含之氣泡上浮而加以去除。 該氣泡主要為熔解粉末狀之玻璃原料時所生成者。為促進 氣泡之上浮，例如亦可對澄清槽12内之上部空間進行減 壓。澄清槽I2内之㈣玻璃㈣輸送f Μ而輸送至授掉槽 1 3中。 曰 ;搜拌和攪拌熔融玻璃τρ㈣拌炼融玻 璃之裝置，使用例如擾拌器等旋轉構件。檀掉㈣内之溶 融玻璃經由輸送管丨7而輸送至成形裝置丨4令。 1559I6.doc •13- 201200482 成形裝置14係使㈣麵成形為特定形狀^成形裝μ 可為溶融玻璃之成形中所使用之通常裝置^例如於使溶 融玻璃成形為帶板狀之情形時，成形裝置14可使用浮式成 形裝置或融合成形裝置。又，於使熔融玻璃成形為瓶狀之 情形時’成形裝置U可使用鑄激成形裝置。成形後之熔融 玻璃經緩冷後，視需要切割成特定尺寸而形成製品。 於該玻璃製造裝置1〇中，熔融玻璃處理裝置丨用於熔解槽 11、澄清槽12、攪拌槽13、及輸送管15〜17之至少一部分之 内壁（尤其是側壁或底壁）。 如此般，本實施形態之玻璃製造裝置10包含熔融玻璃處 理裝置1、及使自熔融玻璃處理裝置丨所供給之熔融玻璃形 成特定形狀之成形裝置14，故而可抑制於熔融玻璃中生成 氣泡。其結果’可製造品質較高之玻璃製品。 (玻璃製造方法） 繼而，對使用上述玻璃製造裝置10之玻璃製造方法加以 說明。 首先’調配複數種原料，製備玻璃原料。例如，以形成 如下玻璃之方式調配複數種原料：以氧化物基準之質量％ 表示計’含有Si〇2 : 50〜72°/。、Al2〇3 : 〇.5〜24%，較佳為 0.5〜230/〇、B2〇3 : 〇〜120/〇、MgO : 0〜8%、CaO : 0〜14.5%、 SrO : 0〜24%、BaO : 0〜13.5%、Na2〇+Li2〇+K2〇 ·· 0〜15%， 且]\4呂0+€&0+81*0+83〇為9~29.5%(此時，可進而含有21*02: 0-5%) » 於製備無驗玻璃之原料之情形時，例如，以形成如下無 14 155916.doc 201200482 驗玻璃之方式調配複數種原料：以氧化物基準之質量％表 示計’含有8丨02:50~66%、人1203:10.5〜24°/。，較佳為 10.5-22% ^ b2〇3 ： 0-12% ' MgO ： 0-8% ' CaO : 0-14.5% ' SrO : 〇〜24%、BaO : 0~13.5%，且 MgO+CaO+SrO+BaO為 ^。^。/。（此時’可進而含有心仏：❹〜㈣卜較佳為以形成如 下無驗玻璃之方式調配複數種原料：以氧化物基準之質量 0/〇表示計’含有 Si〇2 : 58〜66%、Al2〇3 : 15〜22%、B203 : 5〜12%、MgO : 〇〜8%、CaO : 0〜9%、SrO : 3〜12.50/〇、BaO : 0〜2%，且 Mg〇 + CaO+SrO+BaO為 9〜18%。 接著，將所製備之玻璃原料投入熔解槽〖丨中，製造溶融 玻璃。繼而，將所製造之熔融玻璃經由輸送管15輸送至澄 清槽12中’使内部所含之氣泡上浮而加以去除。該氣泡主 要為熔解粉末狀之玻璃原料時所生成者。為促進氣泡之上 浮，例如亦可對澄清槽丨2内之上部空間進行減壓。繼而， 將澄清槽12内之熔融玻璃經由輸送管16輸送至攪拌槽13 中，攪拌炼融玻璃使其均質化。其後，將攪拌槽丨3内之溶 融破璃經由輸送管17輸送至成形裝置14中，成形為特定形 狀。成形方法例如有浮式法或融合法、鑄漿成形法等。成 形後之熔融玻璃經缓冷後，視需要切割成特定尺寸而形成 製品。 於該玻璃製造方法中’溶融玻璃處理裝置丨用於炼解槽 U、澄清槽12、攪拌槽13、及輸送管15〜17之至少一部分之 内壁（尤其是側壁或底壁）。 如此般，本實施形態之玻璃製造方法使自溶融玻璃處理 155916.doc -15- 201200482 裝置1所供給之熔融玻璃成形為特定形狀，故而可抑制於熔 融玻璃中生成氣泡。其結果，可製造品質較高之玻璃製品。 實施例 以下，藉由實施例等對本發明進行具體說明，但本發明 並非受該等例所限定者。 [例1〜例12] (熔融玻璃處理裝置） 首先，準備鉑合金製（鉑9〇質量。/。、鍺丨〇質量％)之坩堝作 為熔融玻璃所接觸之構件。該坩堝係依據JIS H 62〇1_1986 者，且具有特定形狀（高度：27 mm、上部外徑：25 mm、 底部外徑：15 mm、容量：1〇 cc、質量：8.0 g)。 於所準備之坩堝之外表面塗佈漿料，並於大氣中以9〇艺 乾燥2小時，形成塗層。漿料係使用將玻璃粉末（粒度：“π 以下）67質量份、與Met〇1〇se水溶液（濃度：〇3質量％)33質 量份加以混合而製備者。玻璃粉末係使用表〗所示之玻璃 A〜D中之任—者。玻璃A〜c係無驗玻璃。將各玻璃μ之組 成不於表1中。Finally, 'burning the new station in the figure shown in Figure 3, l lL, and the body, by means of the glass powder contained in the coating 8 for heat flow, the shape of the pavilion, Zhang - Shi * Chu Wei 4 into Figure 1 The glass layer 4 is not formed, and the gaps of the glass powder form the voids 7, 9 shown in Fig. 1. The firing conditions are appropriately set depending on the type of the glass powder, the ratio of the voids 7, 9 and the like. For example, the molten glass processing apparatus 1 shown in Fig. 1 can be obtained by performing the above method in the atmosphere at a temperature substantially the same as the use temperature. In the manufacturing method, since the coating device or the like is not required, the glass layer 4 and the heat-resistant fibrous body 5 can be provided on the member 3 of the conventional equipment. Further, in the present embodiment, after the coating layer 8 is formed, the heat-resistant fibrous body 5 is attached to the outer side of the coating layer 8, but the present invention is not limited thereto. For example, the slurry containing the glass powder may be applied to the inner side of the heat-resistant fibrous body 5, 1559l6.doc -12·201200482, and the inner side of the heat-resistant fibrous body 5 is attached to the outer surface 32 of the member 3 and dried. Thereby, the coating 8 is formed. (Glass manufacturing apparatus) Next, the glass manufacturing apparatus including the above-described molten glass processing apparatus 1 will be described. Fig. 4 is a block diagram of a glass manufacturing apparatus including a molten glass processing apparatus. As shown in FIG. 4, the glass manufacturing apparatus 1A includes a melting tank u, a clarification tank 12, a stirring tank 13, and a forming apparatus 14. The melting tank, the clarification tank 2, the stirring tank U, and the forming device 14 are connected by the conveying pipes 15 to 17. The melting tank 11 melts the glass raw material to produce molten glass. A raw material input port, a plurality of burners, and the like are provided on the inner wall of the melting tank u. As a burner, there are an air combustion burner and an oxygen combustion burner, and it is preferable to be an oxygen combustion burner from the viewpoint of environmental protection. The glass raw material input from the raw material input port is heated by the radiant heat of the flame ejected from the burner to form a molten glass. The molten glass is conveyed to the clarification tank 12 via a conveyance buckle. The groove 12 floats and removes the bubbles contained in the molten glass. This bubble is mainly generated when the powdery glass material is melted. In order to promote the floating of the bubble, for example, the upper space in the clarification tank 12 may be depressurized. The (four) glass (four) in the clarification tank I2 is transported to the transfer tank 13 by the transfer of f Μ.曰; search and stir the molten glass τρ (4) to smelt the glass device, using a rotating member such as a scrambler. The molten glass in the sand drop (4) is conveyed to the forming device by the transfer tube 7 . 1559I6.doc •13-201200482 The forming device 14 is formed by forming the (four) surface into a specific shape. The forming device is a conventional device used for forming molten glass. For example, when the molten glass is formed into a strip shape, the forming is performed. The device 14 can use a float forming device or a fusion forming device. Further, in the case where the molten glass is formed into a bottle shape, the forming apparatus U can use a casting apparatus. After the formed molten glass is slowly cooled, it is cut into a specific size as needed to form a product. In the glass manufacturing apparatus, the molten glass processing apparatus is used for the inner wall (especially the side wall or the bottom wall) of at least a part of the melting tank 11, the clarification tank 12, the stirring tank 13, and the conveying pipes 15 to 17. As described above, the glass manufacturing apparatus 10 of the present embodiment includes the molten glass processing apparatus 1 and the molding apparatus 14 for forming a specific shape from the molten glass supplied from the molten glass processing apparatus, so that generation of bubbles in the molten glass can be suppressed. As a result, a glass product having a higher quality can be produced. (Glass manufacturing method) Next, a glass manufacturing method using the glass manufacturing apparatus 10 described above will be described. First, a plurality of raw materials are prepared to prepare a glass raw material. For example, a plurality of kinds of raw materials are prepared in such a manner as to form a glass having an amount of Si?2: 50 to 72 °/. , Al2〇3 : 〇.5~24%, preferably 0.5~230/〇, B2〇3: 〇~120/〇, MgO: 0~8%, CaO: 0~14.5%, SrO: 0~24 %, BaO: 0~13.5%, Na2〇+Li2〇+K2〇·· 0~15%, and]\4吕0+€&0+81*0+83〇 is 9~29.5% (at this time) , which may further contain 21*02: 0-5%). In the case of preparing a raw material without glass, for example, a plurality of raw materials are prepared in such a manner as to form a glass as follows: on the basis of oxide The mass % means that the meter contains 8丨02:50~66%, and the person 1203:10.5~24°/. Preferably, it is 10.5-22% ^ b2〇3 : 0-12% 'MgO : 0-8% ' CaO : 0-14.5% ' SrO : 〇~24%, BaO : 0~13.5%, and MgO+CaO +SrO+BaO is ^. ^. /. (At this time, 'may further contain a heart: ❹ ~ (4) Bu is preferably prepared in such a manner as to form a non-inspective glass as follows: mass based on oxide 0 / 〇 'includes Si 〇 2 : 58 ~ 66 %, Al2〇3: 15~22%, B203: 5~12%, MgO: 〇~8%, CaO: 0~9%, SrO: 3~12.50/〇, BaO: 0~2%, and Mg〇 + CaO + SrO + BaO is 9 to 18%. Next, the prepared glass raw material is placed in a melting tank to produce molten glass. Then, the produced molten glass is conveyed to the clarification tank 12 via the conveying pipe 15' The air bubbles contained in the interior are floated and removed. The bubbles are mainly generated when the powdery glass material is melted. To promote the floating of the bubbles, for example, the upper space in the clarification tank 2 can be depressurized. The molten glass in the clarification tank 12 is sent to the stirring tank 13 via the conveying pipe 16, and the molten glass is stirred and homogenized. Thereafter, the molten glass in the stirring tank 3 is conveyed to the forming apparatus 14 via the conveying pipe 17. Formed into a specific shape. For example, there are floating method or fusion method, and slurry forming After the formed molten glass is slowly cooled, it is cut into a specific size as needed to form a product. In the glass manufacturing method, a 'melting glass processing apparatus is used for the refining tank U, the clarification tank 12, the stirring tank 13, and The inner wall (especially the side wall or the bottom wall) of at least a part of the conveying pipes 15 to 17. In this manner, the glass manufacturing method of the present embodiment forms the molten glass supplied from the molten glass treatment 155916.doc -15-201200482 device 1 into The specific shape is such that bubbles are formed in the molten glass. As a result, a glass product having a high quality can be produced. EXAMPLES Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited by the examples. [Examples 1 to 12] (Molten glass processing apparatus) First, a crucible made of a platinum alloy (platinum 9 〇 mass / 锗丨〇, 锗丨〇 mass %) is prepared as a member to be contacted by molten glass. JIS H 62〇1_1986, and has a specific shape (height: 27 mm, upper outer diameter: 25 mm, bottom outer diameter: 15 mm, capacity: 1 〇 cc, mass: 8.0 g). The slurry was coated on the surface and dried in the air for 2 hours to form a coating layer. The slurry was used as a glass powder (particle size: "π or less) 67 parts by mass, and Met〇1〇se 33 parts by mass of an aqueous solution (concentration: 〇3 mass%) was prepared and mixed. The glass powder was used in any of the glasses A to D shown in Table 〗. The glass A to c was a glass without a glass. The composition is not in Table 1.
155916.doc -16 - 201200482 其次’於塗層之外側貼附含浸有上述Metolose水溶液之 耐熱性纖維體。作為耐熱性纖維體，使用以下之任一市售 品。即，作為將複數之纖維編織成布狀者，使用石英玻璃 布（Nichias公司製，Siltex Cloth，Si02 : 99 質量 ％ 以上）、帶 狀之陶瓷布（Nichias公司製，Si02 : 53質量％，Al2〇3 : 47 質量0/〇)、氧化鋁布（Nichias公司製，Al2〇3: 99質量％以上）、 氧化锆布（Zircar公司製，Zr〇2 :約90質量％，Y2〇3 :約1〇 質量％)、及矽鋁氧化物布（Denka公司製，Si02: 20質量％， Ah〇3 : 80質量。/〇中之任一者。又’作為將複數之纖維纏繞 成塊狀者，使用石英玻璃絨（Tosoh公司製，Si02 : 99質量％ 以上）。 繼而，於以隔熱構件包圍耐熱性纖維體之狀態下，於大 氣中以110°C將該耐熱性纖維體乾燥2小時。作為隔熱構 件，使用含有氧化鋁及二氧化矽之有底筒狀（外部尺寸：48 mmx48mmx48mm，凹部深度：26mm，凹部内徑：32mm) 之耐火物。 最後，於鉑合金製之坩堝内投入熔融玻璃，於水分濃度 較低之大氣環境中（絕對濕度：3 g/m3)，在使用溫度τ下熱 處理1小時後，冷卻至室溫，而製造熔融玻璃處理裝置。投 入坩堝内之熔融玻璃係使用無鹼玻璃（以氧化物基準之質 量％表示計，Si02: 59.4%、Al2〇3: 17.6%、β2〇3: 7>9%、155916.doc -16 - 201200482 Next, a heat-resistant fibrous body impregnated with the above aqueous solution of Metolose was attached to the outer side of the coating. As the heat resistant fibrous body, any of the following commercial products is used. In other words, a quartz glass cloth (Siltex Cloth, manufactured by Nichias Co., Ltd., SiO 2 : 99% by mass or more) and a band-shaped ceramic cloth (made by Nichias Co., Ltd., Si02: 53% by mass, Al2) are used as the cloth. 〇3 : 47 mass 0 / 〇), alumina cloth (made by Nichias, Al2 〇 3: 99% by mass or more), zirconia cloth (made by Zircar, Zr 〇 2: about 90% by mass, Y2 〇 3: about 1% by mass), and yttrium aluminum oxide cloth (manufactured by Denka, Si02: 20% by mass, Ah〇3: 80% by mass. / 〇. Also as a person who entangles a plurality of fibers into a block A quartz glass wool (Si02: 99% by mass or more, manufactured by Tosoh Co., Ltd.) was used. Then, the heat-resistant fibrous body was dried at 110 ° C for 2 hours in the air while the heat-resistant fibrous body was surrounded by the heat insulating member. As the heat insulating member, a refractory material having a bottomed cylindrical shape (outer dimensions: 48 mm x 48 mm x 48 mm, recess depth: 26 mm, inner diameter of the recess: 32 mm) containing alumina and cerium oxide was used. Finally, in a crucible made of platinum alloy. Put in molten glass in an atmosphere with a low water concentration In the environment (absolute humidity: 3 g/m3), after heat treatment at the use temperature τ for 1 hour, it is cooled to room temperature to produce a molten glass processing apparatus. The molten glass charged into the crucible is made of alkali-free glass (based on oxides). The mass % indicates, Si02: 59.4%, Al2〇3: 17.6%, β2〇3: 7> 9%,
Mg0: 3.3。/。、Ca0: 3.8%、Sr〇: 8 〇%)。該無驗玻璃於投 入坩堝内之前，表示水分量之β·〇Η之值B為0 5mm·、 之值Β係使用傅立葉轉換紅外分光光度計（ft_ir，F〇ur^ 155916.doc -17- 201200482Mg0: 3.3. /. , Ca0: 3.8%, Sr〇: 8 〇%). Before the non-test glass is placed in the crucible, the value B of the moisture content of the moisture content is 0 5 mm·, and the value is FT_ir, F〇ur^ 155916.doc -17- 201200482
Transform Infrared)測定玻璃之板厚C及穿透率T，並將該測 定結果代入下述式中而算出。B = (l/C)log10(Tl/T2)(再者， T1 :參考波數4000/cm處之玻璃之穿透率（單位：，T2 : 羥基吸收波數3570/cm附近之玻璃之最小穿透率（單位：％)) (熔融玻璃處理裝置之評價） 繼而’對熔融玻璃處理裝置加以評價。 熔融玻璃中所含氣泡之比例係以相機自上方對所製造之 熔融玻璃處理裝置之坩堝内進行拍攝，作為所拍攝圖像中 氣泡之面積S2相對於熔融玻璃上表面之面積S1的比例 (S2/S1X 100)而測定。若考慮近年來對電漿顯示器用或液晶 顯示器用之平板顯示器所要求的高品質之顯示品質，則該 氣泡之比例較佳為15°/。以下，更佳為3%以下，進而更佳為 1 %以下。 玻璃層之厚度、玻璃層之剖面中所占之空隙比例、玻璃 層與坩堝之密接性、耐熱性纖維體之厚度、玻璃層向耐熱 性纖維體之渗透深度係將所製造之溶融玻璃處理裝置縱向 切成兩半’以顯微鏡觀察切割面而研究。此處，玻璃層之 厚度、耐熱性纖維體之厚度、玻璃層向耐熱性纖維體之滲 透深度係於切割面之15個部位進行測定之平均值。 形成玻璃層之玻璃於使用溫度τ下之黏度力（單位：dpa.s) 係將與§亥玻璃為相同組成之玻璃投入鉑坩禍中進行熔融， 使用旋轉圓筒型黏度計（ΜΟΤ〇ΥΑΜΑ公司製）加以測定。 形成玻璃層之玻璃與構成構件之材料（鉑合金）的於使用 溫度T下之接觸角0a、以及形成玻璃層之玻璃與構成耐熱性 155916.doc 18· 201200482 纖’准體之材料（石英玻璃或陶幻的於使用溫度τ下之接觸 角扑係使用高溫接觸角計（Kruss公司製）而測定。 (評價結果） 將熔融玻璃處理裝置之評價結果示於表2〜表3中。此處， 例1〜例5為實施例，例6〜例12為比較例。再者，關於玻璃層 進行熱流動，其一部分自坩堝剝離之例7、9〜12，無法測定 玻璃層之特性（黏度η除外）。 155916.doc •19· 201200482 【(Νΐ 1350 玻璃A rn OO 約45 Ο 陶瓷布 Si02 ： 53% Al2〇3 : 47% m Ο) Ο JO 約50 m 寸 1430 玻璃B 〇〇 CN 約35 〇 石英玻璃布 Si02 : 99% 以上 CN OO Ο 1300 玻璃C (N 寸· o 〇 石英玻璃布 Si02 : 99% 以上 (Ν CN c5 (N 未達1 (N 革 1350 玻璃A cn o 約30 〇 石英玻璃絨 Si02 : 99% 以上 CO 寸 ο VO 未達1 1350 玻璃A κτί rn OO o 〇 石英玻璃布 Si02 : 99% 以上 CN m· ο 未達1 使用溫度T(°C) 種類 i〇gi〇n 厚度(mm) 空隙之比例(％) 與坩堝之密接性 種類 組成(質量％) 厚度(mm) 玻璃層向耐熱性纖維體之滲透深度(mm) 玻璃層之玻璃與钻合金之接觸角0a(°) cm 5 韜 费 Μ 主i 衾 ^ C 齋球 氣泡之比例(％) 玻璃層 耐熱性纖維體 -2〇. 155916.doc 201200482 【ε<】 例12 1350 玻璃A in rn 無法測定 無法測定 X 矽鋁氧化物布 Si〇2 ： 20% Al2〇3 ： 80% IT) oi 0.5以上 40以下 例11 1350 玻璃A CO 無法測定 無法測定 X 氧化锆布 Zr02 :約 90% Y203 :約 10% CN 0.5以上 例10 1350 玻璃A κη cn 無法測定 無法測定 X 氧化鋁布 Α12〇3 : 99% 以上 0.5以上 3 40以下 〇\ 1350 玻璃D m CN 無法測定 無法測定 X 石英玻璃布 Si02 : 99% 以上 \Τ) 0.5以上 未測定 40以下 00 cs 00 1350 1 1 1 1 I 石英玻璃布 Si02 : 99% 以上 CS 1 1 1 卜 1350 玻璃A cn |無法測定| 無法測定 X 1 1 1 1 »rj 1 5 1350 1 1 1 1 1 1 1 1 1 1 1 使用溫度T(°C) 種類 f 厚度(mm) 空隙之比例(％) 與坩堝之密接性 種類 組成(質量％) 厚度(mm) 韜 漤 ±1 _後 頌 η ^ Γ' 镅球 5虑ρ is： 铌幾· s 氣泡之比例(％) 玻璃層 财熱性 纖維體 155916.doc •21 · 201200482 於例卜例5中’於鉑合金製之坩堝之外表面形成玻璃層， 玻璃層之熱流動藉由耐熱性纖維體而得到抑制。又，破璃 層中包含與外部空氣不連通，且對構件開放之空隙。因此 可知，與例6〜例12相比，例1〜例5之熔融玻璃中所含之氣泡 比例較小。 再者’於例7中’由於未使用耐熱性纖維體，故而玻璃層 因自身重量而向下方熱流動，而使其一部分自坩堝脫離。 於例9中’由於形成玻璃層之玻璃於使用溫度τ下之黏度^ 未達1〇2·5 dPa.s，故而玻璃層因自身重量而向下方熱流動， 而使其一部分自坩堝脫離。 於例10〜例12中，由於隔熱性纖維體之Si〇2之含量未達 質量％ ’故而玻璃層對隔熱性纖維體之潤濕性過高，玻璃 層之一部分通過隔熱性纖維體流出至外部。又，玻璃層之 剩餘部分所包含之空隙與外部空氣連通。 以上，詳細且參考特定之實施樣態對本發明進行了說 明，但本領域人員清楚瞭解，可不脫離本發明之精神及範 圍而進行各種修正或變更。 本申請案係基於2010年4月28曰提出申請之日本專利申 請2010-104350者，其内容以參考之形式併入本文中。 【圖式簡單說明】 圖1係本發明之一實施形態之熔融玻璃處理裝置之使用 狀態的剖面圖； 圖2係熔融玻璃處理裝置丨之製造方法之說明圖〇); 圖3係熔融玻璃處理裝置丨之製造方法之說明圖（？）；及 155916.doc •22· 201200482 圖4係包含熔融玻璃處理裝置1之玻璃製造裝置之方塊 圖。 【主要元件符號說明】 1 熔融玻璃處理裝置 2 熔融玻璃 3 構件 4 玻璃層 5 耐熱性纖維體 6 隔熱構件 7 > 9 空隙 8 塗層 10 玻璃製造裝置 11 熔解槽 12 澄清槽 13 攪拌槽 14 成形裝置 15-17 輸送管 31 内表面 32 外表面 Dl、D3 厚度 D2 滲透深度 155916.doc -23-Transform Infrared) The thickness C and the transmittance T of the glass were measured, and the measurement results were calculated by substituting the results. B = (l/C)log10(Tl/T2) (Further, T1: penetration rate of glass at reference wave number 4000/cm (unit: T2: minimum of glass near the hydroxyl absorption wave number 3570/cm) Transmittance (unit: %)) (Evaluation of the molten glass processing apparatus) Then, the evaluation of the molten glass processing apparatus was carried out. The ratio of the bubbles contained in the molten glass is the same as that of the molten glass processing apparatus manufactured by the camera from above. The inside image is measured as a ratio (S2/S1X 100) of the area S2 of the bubble in the captured image to the area S1 of the upper surface of the molten glass. Considering the recent use of a flat panel display for a plasma display or a liquid crystal display. The high-quality display quality required is preferably 15° / or less, more preferably 3% or less, still more preferably 1% or less. The thickness of the glass layer and the cross section of the glass layer The void ratio, the adhesion between the glass layer and the crucible, the thickness of the heat-resistant fibrous body, and the penetration depth of the glass layer to the heat-resistant fibrous body are such that the manufactured molten glass processing apparatus is longitudinally cut into two halves, and the cut surface is observed by a microscope. the study. Here, the thickness of the glass layer, the thickness of the heat-resistant fibrous body, and the penetration depth of the glass layer to the heat-resistant fibrous body are measured at the average of 15 portions of the cut surface. The glass forming the glass layer is used at the use temperature τ. Viscosity (unit: dpa.s) The glass of the same composition as §Hui glass was melted in a platinum crucible, and it was measured using a rotary cylindrical viscometer (manufactured by Nippon Co., Ltd.). The contact angle 0a at the use temperature T with the material constituting the member (platinum alloy), and the glass forming the glass layer and the material constituting the heat resistance 155916.doc 18· 201200482 fiber (quartz glass or terracotta) The contact angle of the use temperature τ was measured using a high-temperature contact angle meter (manufactured by Kruss Co., Ltd.) (Evaluation results) The evaluation results of the molten glass processing apparatus are shown in Tables 2 to 3. Here, Examples 1 to 1 5 is an example, and Examples 6 to 12 are comparative examples. Further, in the case of heat transfer of the glass layer, a part of the glass layer is peeled off from the crucible, and the characteristics of the glass layer cannot be measured (except for the viscosity η). 155916.doc •19· 201200482 [(Νΐ 1350 Glass A rn OO About 45 陶瓷 Ceramic cloth Si02 : 53% Al2〇3 : 47% m Ο) Ο JO Approx. 50 m Inch 1430 Glass B 〇〇CN Approx. 35 〇 Quartz Glass cloth Si02 : 99% or more CN OO Ο 1300 Glass C (N inch · o 〇 Quartz glass cloth Si02 : 99% or more (Ν CN c5 (N not up to 1 (N leather 1350 glass A cn o about 30 〇 quartz glass velvet Si02 : 99% or more CO inch ο VO not up to 1 1350 Glass A κτί rn OO o 〇 Quartz glass cloth Si02 : 99% or more CN m· ο Not up to 1 Use temperature T (°C) Type i〇gi〇n Thickness ( Mm) Proportion of voids (%) Adhesion to crucibles (% by mass) Thickness (mm) Depth of penetration of glass layer to heat-resistant fibrous body (mm) Contact angle of glass of glass layer with drill alloy 0a (°) Cm 5 韬费Μ Main i 衾^ C Proportion of bubbles (%) Glass layer heat-resistant fiber body-2〇. 155916.doc 201200482 [ε<] Example 12 1350 Glass A in rn Unmeasurable Unmeasured X 矽Aluminium Oxide cloth Si〇2 : 20% Al2〇3 : 80% IT) oi 0.5 or more 40 or less Example 11 1350 Glass A CO It is impossible to measure X zirconia cloth Zr02: about 90% Y203: about 10% CN 0.5 above Example 10 1350 Glass A κη cn Cannot measure X Alumina fabric 12Α3 : 99% or more 0.5 or more 3 40 or less 〇 1350 Glass D m CN Cannot be measured Cannot be measured X Quartz glass cloth Si02 : 99% or more \Τ) 0.5 or more Not measured 40 or less 00 cs 00 1350 1 1 1 1 I Quartz glass cloth Si02 : 99% or more CS 1 1 1 Bu 1350 Glass A cn | Unable to measure | Unable to measure X 1 1 1 1 »rj 1 5 1350 1 1 1 1 1 1 1 1 1 1 1 Operating temperature T (°C) Type f Thickness (mm) Ratio of voids (%) and 坩埚Type of adhesion (% by mass) Thickness (mm) 韬漤±1 _After 颂 ^ ^ Γ' 镅球5 consideration ρ is: 铌 · s ratio of bubbles (%) Glass layer of thermal fiber 155916.doc • 21 · 201200482 In the example 5, a glass layer was formed on the outer surface of the crucible made of platinum alloy, and the thermal flow of the glass layer was suppressed by the heat-resistant fibrous body. Further, the frit layer includes a gap which is not communicated with the outside air and which is open to the member. Therefore, it is understood that the proportion of the bubbles contained in the molten glass of Examples 1 to 5 is smaller than those of Examples 6 to 12. Further, in Example 7, since the heat-resistant fibrous body was not used, the glass layer was thermally flowed downward due to its own weight, and a part thereof was released from the crucible. In Example 9, the viscosity of the glass forming the glass layer at the use temperature τ was less than 1 〇 2·5 dPa·s, so that the glass layer was thermally flowed downward due to its own weight, and a part thereof was detached from the crucible. In Examples 10 to 12, since the content of Si〇2 of the heat insulating fibrous body is less than % by mass, the wettability of the glass layer to the heat insulating fibrous body is too high, and one part of the glass layer passes through the heat insulating fiber. The body flows out to the outside. Further, the space included in the remaining portion of the glass layer communicates with the outside air. The invention has been described in detail above with reference to the specific embodiments thereof, and it is understood that various modifications and changes may be made without departing from the spirit and scope of the invention. The present application is based on Japanese Patent Application No. 2010-104350, filed Apr. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a state of use of a molten glass processing apparatus according to an embodiment of the present invention; Fig. 2 is an explanatory view of a method for manufacturing a molten glass processing apparatus; Fig. 3 is a molten glass treatment; Description of the manufacturing method of the apparatus ? (?); and 155916.doc • 22· 201200482 Fig. 4 is a block diagram of a glass manufacturing apparatus including the molten glass processing apparatus 1. [Explanation of main component symbols] 1 Molten glass processing equipment 2 Molten glass 3 Member 4 Glass layer 5 Heat-resistant fibrous body 6 Thermal insulation member 7 > 9 Air gap 8 Coating 10 Glass manufacturing equipment 11 Melting tank 12 Clarification tank 13 Stirring tank 14 Forming device 15-17 Inner surface 32 of the conveying pipe 31 External surface Dl, D3 Thickness D2 Infiltration depth 155916.doc -23-