TW201139303A - Glass plate manufacturing method and glass plate manufacturing apparatus - Google Patents

Abstract

Disclosed is a glass plate manufacturing method which includes: a melting step wherein a molten glass is obtained by melting a glass raw material; a forming step wherein a glass ribbon is formed of the molten glass by means of a down-draw method; a vaporization promoting step wherein vaporization of vaporization components from the molten glass surface and/or the glass ribbon surface is promoted; a cooling step wherein the glass ribbon is cooled; and a cutting step wherein a glass plate is obtained by cutting the glass ribbon.

Description

201139303 六、發明說明： 【發明所屬之技術領域】 本發明係有關玻璃板及製造玻璃板的方法。 【先前技術】 在液晶顯示器或電漿顯示器等之平板顯示器（以下， 稱作「FPD」）中，作爲玻璃基板，使用厚度爲例如 1.0 mm以下之薄的玻璃板。在近年來，FPD玻璃基板之大 型化進展，例如使用尺寸2200mmx25 00mm之稱作第8代之 玻璃板。 對於製造如此之FDP玻璃基板，最常使用下拉法。在 下拉法中，由使熔融玻璃，從成形裝置的溝溢流者，連續 地成形帶狀之玻璃帶。此時，將玻璃帶，經由滾輪等而拉 下至下方。此時，經由玻璃帶之拉下速度而進行玻璃帶的 厚度調整。之後以特定長度切斷玻璃帶而製造玻璃板。 例如，對於專利文獻1係揭示有圖11所示之玻璃板製 造裝置。其玻璃板製造裝置係具備：成形裝置7，和圍繞 成形裝置7之斷熱構造體8。斷熱構造體8係爲經由保持高 溫的空氣於成形裝置7之周圍之時，爲了維持從成形裝置7 溢流之熔融玻璃的溫度的構成，通常，通過玻璃帶之閘門 8 1以外係作爲密閉構造。 具體而言，在揭示於專利文獻1之玻璃板之製造裝置 中，斷熱構造體8則由於下方開口之容器狀的主體8A，和 呈封塞主體8 A之開口地加以配置之閘門構成體8B加以構 201139303 成。閘門構成體8B的內部係成爲空洞，對於其閘門構成體 8B的內部係成爲通過冷卻管82而供給冷卻用空氣》經由此 ，在揭示於專利文獻1之玻璃板之製造裝置中，成爲可形 成玻璃帶9之後進行冷卻》 在如此之狀況下，知道有例如，可薄型化，輕量化， 機械性強度或透明性高，並且可以短時間製造之顯示器用 玻璃基板（專利文獻2 )。其玻璃基板係由含有40〜70重量 %Si〇2，含有〇.1~20重量％八丨2〇3，含有〇〜20重量％Na2〇， 含有0〜15重量。/〇Li20，含有0.1〜9重量％Zr02，Li20與Na20 之合計含有量爲3〜20重量％之玻璃材料加以形成。對於玻 璃基板的表面係經由化學強化處理而形成深度50μηι以上 之壓縮應力層。 另外，知道有從較退火點爲高之第1之溫度，急冷成 較應變點爲低之第2之溫度，經由離子交換而進行化學強 化處理，具有至少從表面具有2 Ομπι深度的離子交換表面 層之玻璃（專利文獻3 )。 更且’知道有呈可得到高機械性強度地，可將玻璃內 的壓縮應力層的壓縮應力値與厚度作爲最佳化，並且可容 易地進行熱加工之強化玻璃的製造方法（專利文獻4 )。 在此製造方法中’將從緩冷點至應變點之溫度域，以 2 0 0 °C /分以下，理想爲5 0 °C /分以下的冷卻速度進行冷卻 之後，進行化學強化處理。 以往技術文獻 -6- 201139303 [專利文獻] [專利文獻1]日本特表2009-519884號公報 [專利文獻2]日本特開2002-174810號公報 [專利文獻 3]US 2009/0220761 號 A1 [專利文獻4]日本特開2010_168252號公報 【發明內容】 [發明欲解決之課題] 但從熔融玻璃係在與空氣接觸的邊界面，揮發成分產 生揮發。本申請發明之發明者們係認爲如以下拉法有效地 利用此揮發，是否可於玻璃板之表背兩面形成所期望之壓 縮應力層。 (第1之問題） 但如揭示於專利文獻1之製造裝置，對於斷熱構造體8 爲密閉構造之情況’從成形裝置抑制來自溢流之熔融玻璃 的揮發成分之揮發之故，無法形成應力値高之壓縮應力層 〇 然而，對於專利文獻1係亦揭示有於閘門構成體8B， 設置將來自冷卻管的冷卻用冷氣噴出於由主體8A所被 覆之空間內的噴出口 83，經由從噴出口 83流動冷卻用空氣 至閘門8 1而冷卻玻璃帶9之情況。但如此，即使於閘門8 1 附近使強制對流產生’從此上側的空氣，即由主體8A所 被覆之空間內的大部分空氣係留在其場所之故，對於抑制 201139303 來自熔融玻璃之揮發成分的揮發亦未改變。 (第2之問題） 在揭示於專利文獻2之玻璃基板中，由進行離子交換 而進行化學強化處理者，於玻璃板的表面形成壓縮應力層 。但採用使用於離子交換的鹼離子而將玻璃基板進行化學 強化處理之情況，係例如，對於形成於液晶顯示裝置玻璃 基板上之TFT(Thin Film Transistor)特性帶來影響，更且 在污染液晶材料的點，並不理想。因此，經由離子交換所 化學強化之強化玻璃係不易使用於液晶顯示裝置玻璃基板 。即使作爲可經由離子交換之化學強化處理，在化學強化 處理之前工程中，亦無法避免傷痕附著於玻璃板的表面。 另一方面，於玻璃板之成形之後進行上述化學強化處理時 ，之後進行之玻璃表面的切斷或玻璃板之硏削·硏磨或包 含形狀加工之加工處理的效率則下降。 揭示於專利文獻3之玻璃板係因在緩冷工程中急冷玻 璃之故’有於玻璃表面形成小壓縮應力層之情況。但只在 緩冷工程中，由急冷玻璃所得到之壓縮應力層的應力値係 極低之故，亦在化學強化處理之前工程中，於玻璃的表面 附著有傷痕。另外，在厚度爲薄之玻璃板中，因沿著厚度 方向顯示拋物線形狀之內部應力分布引起，形成於玻璃板 內部之拉伸應力層的應力値變大。拉伸應力層的應力値大 的情況，例如，於切斷玻璃板之情況，爲了切斷而加入之 特定深度切割線則想定外地伸長於玻璃板的厚度方向，而 -8- 201139303 在有分割玻璃板爲所期望尺寸變爲困難之情況的點，並不 理想。 在專利文獻4中，由將徐緩冷卻玻璃所成形之玻璃板 ，進行化學強化者，壓縮應力層的應力値係變高。但玻璃 板係於成形後，加以化學強化之前，裁切成特定尺寸加以 形狀加工。玻璃板係在如此之工程間的搬送中或切斷或形 狀加工中，有著於表面附著傷痕情況。玻璃板係於進行化 學強化之前，於玻璃表面附著傷痕時，即使之後加以化學 強化而得到高強度，對於玻璃表面係亦殘留有傷痕。 本發明係有鑑於如此情事，其第1之目的爲提供可從 成形裝置促進來自溢流之熔融玻璃的揮發成分之揮發的玻 璃板製造裝置及使用其玻璃板製造裝置之玻璃板製造方法 同時’提供經由前述之玻璃板製造方法所得到之玻璃板。 另外’本發明之第2之目的係提供於玻璃板製造時， 未對於玻璃成形後之加工處理的效率帶來不良影響，於不 易附著傷痕於玻璃表面之程度，強化玻璃表面之玻璃板， 和玻璃板之製造方法。 [爲解決課題之手段] (第1之發明） 爲了達成上述第1之目的，本發明之一形態係經由下 拉法而製造玻璃板之裝置，其中，提供具備：從溝的兩側 使熔融玻璃溢流，經由在壁面使其溢流之熔融玻璃彼此融 合之時而形成玻璃帶之成形裝置，和具有圍繞前述成形裝 -9- 201139303 置之同時’通過經由前述成形裝置所形成之前述玻璃帶的 閘門之斷熱構造體，對於前述斷熱構造體，係設置有從前 述斷熱構造體外導入至前述斷熱構造體內，將沿著流下在 前述成形裝置之壁面上的熔融玻璃而上升之氣體，排出於 前述斷熱構造體外之排出口的玻璃板製造裝置。 另外，本發明之一形態係經由下拉法而製造玻璃板之 方法’其中，提供含有：從以斷熱構造體所圍繞之成形裝 置的溝兩側，使熔融玻璃溢流同時，使從前述斷熱構造體 外導入至前述斷熱構造體內之氣體，沿著流下在前述成形 裝置之壁面上的熔融玻璃而上升之後，排出於前述斷熱構 造體外之工程的玻璃板製造方法。 更且，本發明之一形態係經由上述之玻璃板製造方法 所得到之玻璃板，其中，提供於表背兩面具有壓縮應力層 之玻璃板。 (第2之發明） 爲了達成前述第2之目的，本發明之一形態係提供以 下拉法加以成形之玻璃板。 對於在前述玻璃板之厚度方向的中心位置之Si的原子 濃度（原子％ )而言之Si的原子濃度（原子％ )的濃度比 率爲高之5 %以上之S i高濃度範圍，則從玻璃表面沿著厚度 方向，形成於較〇爲大而30nm以下深度之範圍。 前述S i高濃度範圍係具有S i原子濃度之最大峰値，沿 著前述玻璃板之厚度方向的Si原子濃度係從前述最大峰値 -10- 201139303 位置至前述玻璃板的表面及前述中心位置連續性減少。 本發明之其他一形態係提供以下拉法加以成形之玻璃 板。 該玻璃板係具有形成於前述玻璃板之內部的拉伸應力 層，和形成於前述拉伸應力層兩側之壓縮應力層。 前述壓縮應力層之應力値的絕對値係4MPa以下，前 述壓縮應力層係形成於較從前述玻璃板的表面沿著前述玻 ζ 璃板之厚度方向之ΙΟμιη爲大而50μηι以下之深度範圍，前 述壓縮應力層之厚度係不足前述玻璃板之厚度的13分之1 〇 前述拉伸應力層之應力値的絕對値係0.4MPa以下，前 述拉伸應力層之應力値的偏差係〇.2MPa以下。 本發明之又其他一形態係提供玻璃板之製造方法。該 製造方法係具備： 熔融玻璃原料之工程； C 和使用下拉法，從熔融之玻璃成形玻璃帶之工程； 和切斷前述玻璃帶，形成玻璃板之工程。 此時，前述玻璃帶係對於在前述玻璃板之厚度方向的 中心位置之s i的原子濃度（原子％ )而言之s i的原子濃度 (原子％ )的濃度比率爲高之5%以上之Si高濃度範圍，則 從玻璃表面沿著厚度方向，形成於較〇爲大而30nm以下深 度之範圍，前述Si高濃度範圍係具有Si原子濃度之最大峰 : 値，沿著前述玻璃板之厚度方向的Si原子濃度係從前述最 * 大峰値位置至前述玻璃板的表面及前述中心位置連續性減 -11 - 201139303 少地加以成形。 本發明之又其他一形態係提供玻璃板之製造方法。該 製造方法係具備： 熔融玻璃原料之工程； 和使用下拉法’從熔融之玻璃成形玻璃帶之工程； 和切斷前述玻璃帶，形成玻璃板之工程。 此時，形成於從前述玻璃帶的表面沿著前述玻璃帶之 厚度方向之ΙΟμηι爲大而50μηι以下之深度範圍之壓縮應力 層，其中，具有不足前述玻璃帶之厚度的13分之丨之厚度 ，呈具有壓縮應力値之絕對値爲4MPa以下之2個壓縮應力 層，和夾持於前述2個壓縮應力層，拉伸應力値的絕對値 爲0.4MPa以下之拉伸應力層地，成形前述玻璃帶。 [發明效果] 如根據上述第1之發明，經由通過斷熱構造體之氣體 ，沿著流下在成形裝置之壁面上的熔融玻璃而上升之時， 可促進來自熔融玻璃之揮發成分的揮發。由此，可得到於 表背兩面形成應力値高之壓縮應力層的玻璃板。 上述第2之發明的玻璃板係於玻璃板之製造時，未對 於玻璃成形後之加工處理的效率帶來不良影響，而強化玻 璃表面爲不易附著傷痕於玻璃表面之程度。本發明之玻璃 製造方法係可效率佳地製造上述玻璃板。 【實施方式】 -12- 201139303 以下’對於本發明之玻璃板及玻璃板之製造方法加以 說明。 (玻璃板之槪略說明） 圖1係顯示本實施形態之玻璃板〗〇之內部應力分布的 剖面圖。 玻璃板1 0係由下拉法加以製造，例如，使用於FPD玻 (' 璃基板。玻璃板1 〇係厚度或尺寸係無特別加以限定。強化 玻璃板1 0之強化玻璃係例如，使用於電子機器之顯示畫面 的玻璃蓋。 玻璃板1 0係如圖1所示，具有形成於玻璃板之內部的 拉伸應力層12，和形成於拉伸應力層12之兩側的壓縮應力 層1 4 〇 壓縮應力層1 4係形成於從玻璃板1 〇的表面沿著玻璃板 1〇之厚度方向之10 μπι爲大而50 μιη以下之滦度範圍，壓縮 ( 應力層14厚度係不足玻璃板10之厚度的1/13。壓縮應力層 14之應力値之絕對値爲4MPa以下，拉伸應力層12之應力 値的絕對値爲〇 . 4 Μ P a以下。 具體而言，壓縮應力層14之厚度作爲^時，厚度 係較Ομηι爲大而50μηι以下，不足玻璃板10之厚度W〇的1/13 。壓縮應力層14之應力値（絕對値）的最大値31係4MPa 以下，拉伸應力層1 2之應力値（絕對値）的最大値S2係 0.4 Μ P a以下。 圖1中的粗實線係顯示沿著玻璃板1 0之厚度方向的內 -13- 201139303 部應力分布，即壓縮·拉伸應力曲線圖。圖2係顯示在緩 冷工程急冷玻璃情況所得到之以往的玻璃板之內部應力分 布的圖。 在緩冷工程急冷玻璃情況所得到之壓縮·拉伸應力曲 線圖係呈描繪拋物線之曲線圖。於急冷玻璃之情況，形成 於玻璃板之壓縮應力層係經由玻璃表面與內部之熱膨脹的 差而產生的構成。其熱膨脹率的差係因玻璃的熱傳導率引 起而產生。另外，在緩冷工程中，以往所得到之壓縮應力 層之厚度w’,（參照圖2)係玻璃板的厚度W’G之1/10以上 〇 對此，在玻璃板10中，經由因形成於玻璃表面之Si高 濃度範園引起之熱膨脹的差，於玻璃板1 〇之表面附近，形 成厚度薄之壓縮應力層14。Si高濃度範圍係如後述，在玻 璃帶之成形工程中，經由從熔融玻璃或者玻璃帶之表面促 進揮發成分的揮發或者增大揮發量之時加以形成。此時， 拉伸應力層12係於玻璃板10之厚度方向，具有略一定低之 應力値，以往之拉伸應力層之拉伸應力値則與於玻璃板之 厚度方向呈描繪拋物線地分布情況不同。 另外，在玻璃板10之全體中，因經由壓縮應力層14之 壓縮與經由拉伸應力層1 2之拉伸則相抵之故，壓縮應力層 14變薄時，與拉伸應力相抵之故而壓縮應力層14之應力値 (絕對値）係變高。因此，壓縮應力層1 4係例如，具有在 緩冷工程中，只在急冷玻璃之情況所得到之壓縮應力層之 應力値爲大之應力値。也就是，對於玻璃板10係具有大的 -14- 201139303 應力値之壓縮應力層14則形成於玻璃表面之故，玻璃板10 之玻璃表面係比較於只在緩冷工程強化玻璃表面之以往的 玻璃板，不易附著傷痕。 以下，更詳細地說明玻璃板1 0。 (玻璃板之詳細說明） 形成於玻璃板10之壓縮應力層14之厚度W,係較Ομηι爲 大而5 0 μηι以下。壓縮應力層1 4係形成於玻璃表面。即， 壓縮應力層14係從玻璃表面形成於最大5 Ομιη之深度的範 圍。更且以其他說法時，從壓縮應力層14之表面的深度係 5 0μηι以下。壓縮應力層之深度係可經由促進從在成形工 程之熔融玻璃或玻璃帶之表面的揮發之時而加深，但壓縮 應力層14之深度當超過50μηι時，由此，產生超出成形適 當條件的脫離，或生產性之下降。因此，從壓縮應力層1 4 之表面的深度係50μπι以下。因此，壓縮應力層14之深度 係45μιη以下’ 40μιη以下，38μηι以下爲佳。如此理想的形 態係可由調整包含從熔融玻璃或成形中的玻璃帶之表面促 進揮發成分之揮發’或者增大揮發量之條件的玻璃板之製 造條件及玻璃板的組成者而實現。 然而’在本說明書的壓縮應力層14之深度係顯示玻璃 丰反10的表背之中’在一方的面加以形成之壓縮應力層之最 深部’從玻璃表面之深度。也就是，玻璃板丨0之表背表面 ’各形成有具有上述深度之壓縮應力層14。 另外’壓縮應力層14之深度係超過ΙΟμίΏ。由將壓縮 -15- 201139303 應力層14之深度作爲超過ΙΟμιη者，可防止經由因處理引 起之細微的傷痕而容易刮傷玻璃之情況。壓縮應力層14之 深度係考慮即使附著深的傷痕，玻璃板1 0亦不易產生破損 的點，而爲15μιη以上，20μηι以上，25μπι以上，30μιη以上 ，35μηι以上爲更佳。 形成於玻璃表面之壓縮應力層14的深度係不足玻璃板 10的厚度W〇之1/13，但不足1/15，不足1/17，不足1/20, 不足1/22，不足1/24爲佳。 如此理想的形態亦可由調整包含從熔融玻璃或成形中 的玻璃帶之表面促進揮發成分之·揮發，或者增大揮發量之 條件的玻璃板之製造條件及玻璃板的組成者而實現。 形成於玻璃板1 〇之表面附近的壓縮應力層1 4之應力値 (絕對値）係在最大亦爲4MPa。上述應力値（絕對値） 之最大値當超過4MPa時，壓縮應力層14之應力値的總和 變大，玻璃板1 〇之加工，例如形狀加工變爲困難。因此， 壓縮應力層14之應力値（絕對値）之最大値係3.7MPa以下 ，3.5MPa以下，3.0MPa以下，2.8MPa以下爲佳。另外， 壓縮應力層14之應力値（絕對値）之最大値係〇. 1 μPa以上 ’ 0.5MPa以上IMPa以上，l.5MPa以上，2MPa以上爲佳 。壓縮應力層14係因應力値（絕對値）爲超過〇MPa的層 之故，由壓縮應力層14形成於玻璃板1〇之玻璃表面者，玻 璃板10之機械性強度則提昇。 然而’在本說明書之「應力値」係顯示在從玻璃板10 之玻璃表面削去各特定之深度的試料中，從其試料的表面 -16- 201139303 0~1 0 μπι之平均値。因此，對於局部性，壓縮應力層14具 有呈超過上述應力値之範圍的應力値之玻璃板，亦作爲玻 璃板10而包含。 形成於玻璃板1 〇內部之拉伸應力層1 2之應力値係如上 述，於玻璃板1〇之厚度方向爲略一定。其拉伸應力層12之 應力値係如上述爲〇.4MPa以下。當拉伸應力層12之應力値 (絕對値）的最大値超過〇 . 4 Μ P a時，例如於切斷玻璃板之 情況，爲了切斷而放入之特定深度之切割線則想定外地伸 長於玻璃板之厚度方向，有著分割玻璃板10爲所期望之尺 寸則變爲困難之情況。因此，拉伸應力層1 2之應力値之最 大値（絕對値）係〇.3MPa以下，〇.2MPa以下，0.15MPa， 0 · 1 0 Μ P a以下爲佳。在本實施形態中，可將玻璃表面之壓 縮應力層14之應力値（絕對値）的最大値/拉伸應力層12 之應力値（絕對値）的最大値作爲6以上。 另外，在玻璃板10之厚度方向，在兩側除了各1/10之 拉伸應力層12中心部分4/5(以下，單稱作「拉伸中心範圍 」）之玻璃板10之拉伸應力層12的應力値之變動，即應力 値（絕對値）之最大値與最小値的差係0.1 2 MPa以下爲佳 。由此，可使玻璃板之切斷性提昇。更理想爲0. 1 0MPa以 下，0.05MPa以下，0.02MPa以下。如此理想的形態亦可 由調整包含從熔融玻璃或成形中的玻璃帶之表面促進揮發 成分之揮發，或者增大揮發量之條件的玻璃板之製造條件 及玻璃板的組成者而實現。 形成於玻璃板10之內部的拉伸應力層12之應力値係於 -17- 201139303 玻璃板ι〇之厚度方向爲略一定之故，比較於拉伸應力層之 應力値則於玻璃板之厚度方向呈描繪拋物線地加以形成之 情況，可將拉伸應力層1 2保持爲薄。 更詳細爲，玻璃板10之拉伸應力層12之應力値係於玻 璃板10之厚度方向爲略一定，比較於其應力値之最大値（ 絕對値），只在緩冷工程所得到之以往之玻璃板的拉伸應 力値之最大値（絕對値）爲大。即，在以往之玻璃板中， 呈對於形成於玻璃表面之壓縮應力層的壓縮應力而言相抵 地，以拋物線形狀之曲線圖而形成拉伸應力層。因此，玻 璃板的厚度變薄時，因爲了相抵玻璃表面之壓縮應力層的 壓縮應力之拉伸應力層之厚度亦變薄之故，在以往之玻璃 板中，拉伸應力層之應力値係極端地變高，例如，於切斷 玻璃板之情況，爲了切斷而放入之特定深度之切割線則想 定外地伸長於玻璃板之厚度方向，有著分割玻璃板1 0爲所 期望之尺寸則變爲困難之情況。但本實施形態之玻璃板1 0 之拉伸應力層12之應力値係因於玻璃板1〇之厚度方向爲略 —定之故，拉伸應力層之應力値的最大値係不易變高，亦 可精確度佳地進行玻璃板之加工。 從玻璃的組成而視玻璃板1 0時，對於玻璃板1 0係於從 玻璃表面沿著厚度方向較0爲大而30nm以下之深度範圍， 形成Si高濃度範圍（以後，稱作富Si層）。富Si層係對於 在玻璃板10之厚度方向之中心位置的Si之原子濃度（原子 % )而言之S i之原子濃度（原子％ )的濃度比率爲高之5 % 以上的範圍。富Si層所位置之範圍係理想爲超過〇〜25nm、 -18- 201139303 2〜20nm、5〜16nm、8〜16nm。另一方面，富Si層之深度係 可經由促進從在成形工程之熔融玻璃或玻璃帶之表面的揮 發而加深，但由此，產生有脫離成形適當條件，或者生產 性之下降。或者，當富Si層的深度超過30nm時，於玻璃板 1 〇之玻璃表面實施蝕刻處理之情況，蝕刻則變爲困難。另 外，當富Si層的深度超過30nm時，形成於玻璃表面之壓縮 應力層1 4之應力値（絕對値）變大，產生有玻璃板之切斷 性則下降之不良情況。因此，富Si層的深度爲30nm以下爲 佳。 富Si層係具有Si原子濃度之最大峰値，沿著玻璃板1〇 之厚度方向的Si原子濃度係從上述最大峰値之位置朝向兩 側而減少。經由具有如此之玻璃之組成之時，形成上述之 壓縮應力層Μ及拉伸應力層12。Si原子濃度係意味對於除 了氧原子之玻璃成分全體（除了 Si，Al，B，Ca，Sr，Ba 等之氧原子的玻璃全成分）而言之Si的原子％。 此時’在玻璃熔融狀態（例如，玻璃的黏性爲1 04 +5 〜105poise，或者溫度1 1〇〇〜1 3 00 °C )，比較於Si02，蒸氣 壓（飽和蒸氣壓）高之揮發成分則在玻璃板的厚度方向之 中心位置，含有30質量％以上則在形成上述富Si層的點爲 佳。 在此’上述濃度比率成爲不足5 %時，在玻璃表面與 內部無法得到充分之熱膨脹率的差，而無法有效形成壓縮 應力層1 4。或者，無法得到充分之維氏硬度或耐久性。 另一方面，上述濃度比率當超過3 0%時，玻璃板之品 201139303 ’ 期 如所 例於 ’ 用 化使 變法 生無 產著 }有 生 ’ 特難 學困 化爲 ’ 變 ,111 m-l s 特處 的刻 熱蝕 ’ 或 性斷 特切 理之 物板 C璃 質玻 望之用途的情況。從此點，上述濃度比率係將30%作爲上 限爲佳。 另外，在富Si層中，Si原子含有量或Si原子濃度爲最 高之峰値位置係位置於從玻璃表面〇〜5 nm之深度範圍。 由將富Si層，形成於從玻璃表面沿著厚度方向較〇爲 大而30nm以下之深度範圍者，可在玻璃表面與內部得到 充分之熱膨脹率的差，可於玻璃表面形成壓縮應力層14。 另外，亦可提昇玻璃表面之維氏硬度或耐久性，可防止玻 璃板10破損。即，Si係因可使維氏硬度提昇之成分之故， 經由形成於玻璃表面之富Si層，玻璃板10之玻璃表面之維 氏硬度係變高。另外，Si係對於耐藥品性優越之故，形成 富Si層於玻璃表面之玻璃板1 0的耐久性亦提昇。另外，玻 璃表面之維氏硬度係比較於以往之玻璃板而提昇之故，可 得到龜裂產生率則下降，更不易附著傷痕，不易破損之效 果。 玻璃板10之玻璃表面之維氏硬度係例如爲4GPa以上 ，而5GPa以上，5.3GPa以上爲佳。或者，玻璃表面之維 氏硬度則在與玻璃內部之維氏硬度的比，加以提昇〇.〇 1 % 以上，而作爲0.02%以上，0.05%以上，0.10%以上，1%以 上爲佳。 如此，玻璃板1 0係在內部應力的點中，具有拉伸應力 層1 2及壓縮應力層1 4，在組成的點中，於玻璃表面附近具 -20- 201139303 有富Si層。玻璃板10係在後述之玻璃帶之成形工程中，從 熔融玻璃或玻璃帶的表面，例如在玻璃的黏性爲 1045~105poise，或者溫度1100〜1300 °C之玻璃熔融狀態中 ，比較於Si02，經由促進飽和蒸氣壓高之揮發成分的揮發 而可得到。 如此理想的數値範圍之各形態亦可由調整包含從熔融 玻璃或成形中的玻璃帶之表面促進揮發成分之揮發，或者 增大揮發量之條件的玻璃板之製造條件及玻璃板的組成者 而實現。 如此之玻璃板1 〇係更加地進行經由離子交換之化學強 化處理而強化玻璃表面亦可。玻璃板1 0係未進行經由離子 交換之化學強化處理亦可。本發明之實施形態係亦包含經 由離子交換，化學強化玻璃板1 0之玻璃表面的強化玻璃。 此情況，上述之富Si層與經由離子交換的離子交換處理範 圍則並存形成於玻璃表面。離子交換處理範圍係指玻璃表 面中的成分之Li，N a等之離子交換成分則與離子交換用之 處理液中的K等之離子交換成分加以交換之範圍。此時， 對於化學強化之玻璃板1 0，係經由化學強化處理之壓縮應 力層則重疊於因富Si層引起之壓縮應力層14形成大的壓縮 應力層。經由離子交換，從玻璃表面朝向內部加以形成之 壓縮應力層的厚度係成爲2 0〜ΙΟΟμπι。 經由離子交換加以擴大之壓縮應力層之應力値（絕對 値）的最大値係300MPa以上爲佳，400MPa以上爲更佳。 由將應力値（絕對値）的最大値作爲3 00MPa以上者，化 -21 - 201139303 學強化之玻璃板1 〇，係例如因保護顯示器等而可得到充分 之強度。然而，上述應力値（絕對値）越高，玻璃的強度 係提昇，但強化之玻璃產生破損時之衝擊亦變大。爲了防 止經由上述衝擊之事故，加以化學強化處理之玻璃板1 〇， 係壓縮應力層之應力値（絕對値）的最大値爲9 5 0MPa以 下爲佳，而800MPa以下爲更佳，700MPa以下爲又更佳。 另一方面，與由急冷玻璃而於玻璃表面形成壓縮應力層之 以往的玻璃板做比較，拉伸應力層之應力値（絕對値）係 不易變大。 化學強化處理後之壓縮應力層之厚度爲20μιη以上， 而30μηι以上，40μη!以上爲佳。壓縮應力層之厚度越大程 度，即使於強化玻璃附著有深的傷痕，強化玻璃亦不易破 損，機械性強度的不勻變小。另一面，壓縮應力層之厚度 係10 0 μιη以下。壓縮應力層之厚度係當考慮強化玻璃之加 工之容易度時，作爲90μηι以下，80μιη以下爲佳。 然而，玻璃板1 〇，適用化學強化玻璃板1 0之強化玻璃 的玻璃蓋厚度係1.5mm以下爲佳。在此，在i.5mm以上之 玻璃板中，玻璃板其本身強度變大，形成於玻璃表面附近 之壓縮應力層14則未能充分發揮機能。也就是，在本實施 形態所形成之玻璃板1 0或玻璃蓋的厚度係1 . 〇mm以下、 0.7mm以下、0.5mm以下、〇.3mm以下爲佳，玻璃板10之 厚度越薄，本發明之效果越顯著。 另外’本實施形態之玻璃板製造方法係最佳爲大的玻 璃板。此係越大的玻璃板，經由彎曲量爲大，因處理引起 -22- 201139303 之細微的傷痕，玻璃板則容易破損，但因經由於玻璃表面 形成壓縮應力層14之時，可降低上述問題之發生。因此， 玻璃板10之寬度方向爲1 000mm以上，2000mm以上之玻璃 板之情況，本發明之效果成爲顯著。 (玻璃板之玻璃的種類） 作爲使用於玻璃板10之玻璃，可使用硼矽玻璃，矽酸 鋁玻璃，硼矽酸鋁玻璃，鈉鈣玻璃，鹼金屬矽酸鹽玻璃， 鹼金屬矽酸鋁玻璃，鹼金屬鋁鍺酸鹽玻璃等之種類。然而 ，可適用於本發明之玻璃板的玻璃係不限定於上述種類， 如至少含有Si〇2，和在玻璃熔融溫度（玻璃的黏性爲 1 04 5〜l〇5poise，或者溫度1 100〜1 3 00 °c )之飽和蒸氣壓則 較Si02爲高之揮發成分的種類之玻璃即可。然而，ai2o3 係網目形成氧化物，在玻璃之成分之中，比較而言飽和蒸 氣壓爲低之成分。但在本實施形態中，較Si〇2，飽和蒸氣 壓爲高之故，作爲將Al2〇3含於揮發成分。 然而，玻璃組成中的揮發成分之含有量係30質量％以 上更佳，而35質量％以上，40質量％以上爲又更佳。隨之 ，在未揮發有玻璃板10之揮發成分的玻璃板1〇之拉伸應力 層12中，揮發成分之含有量係成爲30質量％以上。玻璃組 成中的揮發成分之含有量不足30質量％時，未促進揮發成 分之揮發，而於玻璃表面不易形成富Si層或壓縮應力層。 另外，多含有揮發成分時，揮發則過於增加，而玻璃的均 質化則變爲困難。因此，玻璃組成中的揮發成分之含有量 -23- 201139303 係60質量％以下，50質量％以下爲佳’而45質量％以下爲 更佳。 (各玻璃之組成例） 例如，硼矽酸鋁玻璃係例示含有以下成分之構成。然 而，在以下記載之組成的％顯示係顯示質量％。硼矽酸錨 玻璃係例如使用於平板顯示器玻璃基板。下記括弧內之顯 示係各成分之理想含有率。 （）201139303 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a glass sheet and a method of manufacturing the same. [Prior Art] In a flat panel display (hereinafter referred to as "FPD") such as a liquid crystal display or a plasma display, a thin glass plate having a thickness of, for example, 1.0 mm or less is used as the glass substrate. In recent years, the miniaturization of FPD glass substrates has progressed, for example, a glass plate of the eighth generation using a size of 2200 mm x 25 00 mm. For the manufacture of such FDP glass substrates, the down-draw method is most often used. In the down-draw method, a strip-shaped glass ribbon is continuously formed by overflowing the molten glass from the groove of the molding apparatus. At this time, the glass ribbon is pulled down to the lower side via a roller or the like. At this time, the thickness of the glass ribbon was adjusted by the pulling speed of the glass ribbon. Thereafter, the glass ribbon is cut at a specific length to produce a glass plate. For example, Patent Document 1 discloses a glass sheet manufacturing apparatus shown in Fig. 11. The glass sheet manufacturing apparatus includes a molding device 7, and a heat-dissipating structure 8 surrounding the molding device 7. The heat-dissipating structure 8 is a structure in which the temperature of the molten glass overflowing from the molding device 7 is maintained while maintaining the temperature of the molten glass by the high-temperature air, and is normally sealed by the gate of the glass ribbon 8 1 . structure. Specifically, in the manufacturing apparatus of the glass sheet disclosed in Patent Document 1, the heat-dissipating structure 8 has a container-shaped main body 8A that is opened at the lower side and a gate structure that is disposed in the opening of the plugging main body 8A. 8B is constructed into 201139303. The inside of the shutter structure 8B is a hollow, and the inside of the shutter structure 8B is supplied with cooling air through the cooling pipe 82. Thus, it can be formed in the manufacturing apparatus of the glass plate disclosed in Patent Document 1. After the glass ribbon 9 is cooled, it is known that, for example, a glass substrate for a display which can be made thinner, lighter, has higher mechanical strength or transparency, and can be manufactured in a short period of time (Patent Document 2). The glass substrate is composed of 40 to 70% by weight of Si〇2, containing 0.1 to 20% by weight of octagonal 2〇3, containing 〇20% by weight of Na2〇, and containing 0 to 15 parts by weight. /〇Li20, which is formed by containing 0.1 to 9% by weight of ZrO 2 and a total amount of Li20 and Na20 in an amount of 3 to 20% by weight. The surface of the glass substrate is subjected to a chemical strengthening treatment to form a compressive stress layer having a depth of 50 μm or more. Further, it is known that there is a temperature from the first point higher than the annealing point, and the temperature is quenched to a second temperature lower than the strain point, and chemical strengthening treatment is performed by ion exchange, and has an ion exchange surface having a depth of at least 2 μm from the surface. Glass of the layer (Patent Document 3). Furthermore, it is known that a method of producing a tempered glass in which the compressive stress 压缩 and the thickness of the compressive stress layer in the glass can be optimized and the hot working can be easily performed (Patent Document 4) ). In this manufacturing method, the chemical strengthening treatment is carried out after cooling from a slow cooling point to a strain point in a temperature range of 200 ° C / min or less, preferably 50 ° C / min or less. [Patent Document 1] [Patent Document 1] Japanese Patent Publication No. 2009-519884 [Patent Document 2] JP-A-2002-174810 (Patent Document 3) US 2009/0220761 No. A1 [Patent [Problem to be Solved by the Invention] However, the volatile component is volatilized from the boundary surface of the molten glass which is in contact with the air. The inventors of the present invention considered that it is possible to form the desired compressive stress layer on both sides of the front and back sides of the glass sheet by effectively utilizing the volatilization by the following drawing method. (Problem of the first aspect) However, in the case of the manufacturing apparatus disclosed in Patent Document 1, when the heat-dissipating structure 8 is in a sealed structure, the volatilization of the volatile component from the overflow molten glass is suppressed from the molding device, and the stress cannot be formed. Further, the patent document 1 discloses a gate structure 8B, and a discharge port 83 for spraying cooling air from the cooling pipe into a space covered by the main body 8A is provided, and the discharge port 83 is provided. The outlet 83 flows the cooling air to the gate 81 to cool the glass ribbon 9. However, even if forced convection occurs near the gate 8 1 , the air from the upper side, that is, most of the air in the space covered by the main body 8A remains in the place, suppresses the volatilization of the volatile components from the molten glass of 201139303. It has not changed. (Second Problem) In the glass substrate disclosed in Patent Document 2, a chemical stress enhancement treatment is performed by ion exchange, and a compressive stress layer is formed on the surface of the glass plate. However, when the glass substrate is subjected to chemical strengthening treatment using an ion ion for ion exchange, for example, it affects TFT (Thin Film Transistor) characteristics formed on a glass substrate of a liquid crystal display device, and is more contaminated with liquid crystal material. The point is not ideal. Therefore, the tempered glass chemically strengthened by the ion exchange is not easily used for the liquid crystal display device glass substrate. Even in the case of chemical strengthening treatment by ion exchange, it is impossible to prevent the flaw from adhering to the surface of the glass sheet in the process before the chemical strengthening treatment. On the other hand, when the above-described chemical strengthening treatment is performed after the formation of the glass sheet, the efficiency of the cutting of the glass surface or the boring and honing of the glass sheet or the processing including the shape processing is lowered. The glass plate disclosed in Patent Document 3 has a small compressive stress layer formed on the surface of the glass due to the quenching of the glass in the slow cooling process. However, in the slow cooling process, the stress 値 of the compressive stress layer obtained from the quenched glass is extremely low, and the surface of the glass is attached with scratches before the chemical strengthening treatment. Further, in the glass plate having a small thickness, the stress 値 of the tensile stress layer formed inside the glass sheet becomes large due to the internal stress distribution showing the parabolic shape along the thickness direction. When the stress of the tensile stress layer is large, for example, in the case of cutting the glass plate, the specific depth cutting line added for cutting is intended to be elongated in the thickness direction of the glass plate, and -8-201139303 is divided. The glass plate is a point where the desired size becomes difficult, which is not preferable. In Patent Document 4, when the glass plate formed by slowly cooling the glass is chemically strengthened, the stress 値 of the compressive stress layer becomes high. However, after the glass sheet is formed, it is cut into a specific size and shaped before being chemically strengthened. The glass plate is attached to the surface during the transfer or cutting or shape processing of such a project. When the glass plate is attached to the surface of the glass before chemical strengthening, even if it is chemically strengthened to obtain high strength, there is a flaw on the glass surface. In view of the above, the first object of the present invention is to provide a glass sheet manufacturing apparatus capable of promoting volatilization of volatile components from molten glass from a molding apparatus, and a glass sheet manufacturing method using the same. A glass plate obtained by the aforementioned glass plate manufacturing method is provided. Further, the second object of the present invention is to provide a glass sheet which does not adversely affect the efficiency of processing after glass forming, and which is less likely to adhere to scratches on the surface of the glass, and which strengthens the glass surface of the glass surface, and A method of manufacturing a glass plate. [Means for Solving the Problem] (Invention No. 1) In order to achieve the above-described first object, an aspect of the present invention provides an apparatus for producing a glass sheet by a down-draw method, wherein the provision of the molten glass is provided from both sides of the groove Overflow, a forming device for forming a glass ribbon by fusing the molten glass that overflows the wall surface, and having the aforementioned glass ribbon formed by the aforementioned forming device while being disposed around the forming device -9-201139303 The heat-insulating structure of the gate is provided with a gas that is introduced into the heat-insulating structure from the heat-insulating structure outside the heat-insulating structure, and that is raised along the molten glass flowing down the wall surface of the molding device. A glass plate manufacturing apparatus that discharges the discharge port outside the heat-insulating structure. Further, a mode of the present invention is a method for producing a glass sheet by a down-draw method, wherein a method of supplying a molten glass from both sides of a groove of a molding device surrounded by a heat-insulating structure is provided, and the molten glass is simultaneously discharged from the foregoing A method of manufacturing a glass sheet in which a gas introduced into the heat-insulating structure in vitro is introduced into the body of the heat-dissipating structure, and then ejected from the molten glass on the wall surface of the forming apparatus, and then discharged to the outside of the heat-insulating structure. Furthermore, one aspect of the present invention is a glass sheet obtained by the above-described method for producing a glass sheet, which is provided with a glass sheet having a compressive stress layer on both sides of the front and back. (Second Invention) In order to achieve the above second object, an aspect of the present invention provides a glass sheet formed by a down-draw method. The concentration ratio of the atomic concentration (atomic %) of Si in the atomic concentration (atomic %) of Si at the center position in the thickness direction of the glass plate is 5% or more of the high concentration range of S i, and the glass is from the glass. The surface is formed along the thickness direction in a range in which the crucible is large and the depth is 30 nm or less. The high concentration range of the S i has a maximum peak value of the concentration of Si atoms, and the concentration of Si atoms along the thickness direction of the glass plate is from the position of the maximum peak 値-10-201139303 to the surface of the glass plate and the center position. The continuity is reduced. Another aspect of the present invention provides a glass sheet which is formed by the following drawing method. The glass sheet has a tensile stress layer formed inside the glass sheet and a compressive stress layer formed on both sides of the tensile stress layer. The compressive stress layer has an absolute enthalpy of 4 MPa or less, and the compressive stress layer is formed in a depth range from the surface of the glass sheet to the thickness direction of the glass sheet, which is 50 μm or less. The thickness of the compressive stress layer is less than 1/13 of the thickness of the glass plate. The absolute value of the stress 値 of the tensile stress layer is 0.4 MPa or less, and the variation of the stress 値 of the tensile stress layer is 22 MPa or less. Still another aspect of the present invention provides a method of producing a glass sheet. The manufacturing method includes: a process of melting a glass raw material; C and a process of forming a glass ribbon from molten glass using a down-draw method; and a process of cutting the glass ribbon to form a glass plate. In this case, the concentration ratio of the atomic concentration (atomic %) of si to the atomic concentration (atomic %) of si at the center position in the thickness direction of the glass plate is higher than 5% or more. The concentration range is formed from the surface of the glass along the thickness direction in a range of greater than 30 nm below the depth of the crucible, and the high concentration range of Si has a maximum peak of Si atom concentration: 値, along the thickness direction of the glass plate The Si atomic concentration is formed from the most *large peak position to the surface of the glass sheet and the continuity of the center position is reduced by -11 - 201139303. Still another aspect of the present invention provides a method of producing a glass sheet. The manufacturing method includes: a process of melting a glass raw material; and a process of forming a glass ribbon from a molten glass using a down-draw method; and a process of cutting the glass ribbon to form a glass sheet. At this time, a compressive stress layer formed in a depth range from the surface of the glass ribbon along the thickness direction of the glass ribbon to a depth of 50 μm or less, wherein the thickness of the glass ribbon is less than 13% of the thickness of the glass ribbon. And two compressive stress layers having an absolute enthalpy of compressive stress 4 of 4 MPa or less, and a tensile stress layer sandwiched between the two compressive stress layers and having an absolute enthalpy of tensile stress 0.4 of 0.4 MPa or less, forming the aforementioned Glass belt. [Effect of the Invention] According to the first aspect of the invention, when the gas passing through the heat-insulating structure rises along the molten glass flowing down the wall surface of the molding apparatus, volatilization of the volatile component from the molten glass can be promoted. Thereby, a glass plate in which a compressive stress layer having a high stress is formed on both sides of the front and back sides can be obtained. In the glass sheet of the second aspect of the invention, the glass sheet is not adversely affected by the efficiency of the processing after the glass is formed, and the surface of the reinforced glass is less likely to adhere to the surface of the glass. The glass manufacturing method of the present invention can efficiently produce the above glass sheet. [Embodiment] -12-201139303 Hereinafter, a method for producing a glass plate and a glass plate of the present invention will be described. (Brief Description of Glass Plate) Fig. 1 is a cross-sectional view showing the internal stress distribution of the glass plate of the present embodiment. The glass plate 10 is manufactured by a down-draw method, for example, for FPD glass ('glass substrate. The glass plate 1 is not particularly limited in thickness or size. The tempered glass of the tempered glass plate 10 is used, for example, in electronics. The glass cover of the display screen of the machine. The glass plate 10 has a tensile stress layer 12 formed inside the glass plate and a compressive stress layer 14 formed on both sides of the tensile stress layer 12 as shown in FIG. The compressive stress layer 14 is formed on the surface of the glass plate 1 from the surface of the glass plate 1 in the thickness direction of 10 μm to a thickness range of 50 μm or less, and is compressed (the thickness of the stress layer 14 is insufficient for the glass plate 10). 1/13 of the thickness. The absolute 値 of the stress 値 of the compressive stress layer 14 is 4 MPa or less, and the absolute 値 of the stress 値 of the tensile stress layer 12 is 〇. 4 Μ P a or less. Specifically, the compressive stress layer 14 When the thickness is φ, the thickness is larger than Ομηι and is less than 50 μm, which is less than 1/13 of the thickness W 玻璃 of the glass sheet 10. The stress 値 (absolute 値) of the compressive stress layer 14 is 値31, 4 MPa or less, tensile stress. The most stress 値 (absolute 値) of layer 1 2値S2 is 0.4 Μ P a or less. The thick solid line in Fig. 1 shows the stress distribution of the inner-13-201139303 along the thickness direction of the glass plate 10, that is, the compression/tensile stress curve. Fig. 2 shows The internal stress distribution of the conventional glass plate obtained in the case of the quenching glass in the slow cooling process. The compression/tensile stress curve obtained in the case of the quenching glass in the slow cooling process is a graph depicting the parabola. In other cases, the compressive stress layer formed on the glass sheet is formed by the difference in thermal expansion between the surface of the glass and the inside. The difference in thermal expansion coefficient is caused by the thermal conductivity of the glass. The thickness w' of the obtained compressive stress layer (see FIG. 2) is 1/10 or more of the thickness W'G of the glass plate. In this case, in the glass plate 10, the high concentration of Si is formed by the surface of the glass. The difference in thermal expansion caused by the formation of a thin compressive stress layer 14 near the surface of the glass sheet 1. The high concentration range of Si is as follows, in the forming process of the glass ribbon, from the molten glass or glass. The surface of the ribbon is formed by promoting the volatilization of the volatile component or increasing the amount of volatilization. At this time, the tensile stress layer 12 is in the thickness direction of the glass plate 10, and has a slightly lower stress 値, the conventional tensile stress layer The tensile stress 不同 is different from the case where the thickness direction of the glass plate is parabolically distributed. Further, in the entire glass plate 10, the compression through the compressive stress layer 14 and the stretching through the tensile stress layer 12 When the compressive stress layer 14 is thinned, the stress 値 (absolute 値) of the compressive stress layer 14 becomes higher than the tensile stress. Therefore, the compressive stress layer 14 has, for example, a slow cooling project. Among them, the stress 値 of the compressive stress layer obtained only in the case of quenched glass is a large stress 値. That is, for the glass sheet 10, the compressive stress layer 14 having a large -14-201139303 stress 形成 is formed on the glass surface, and the glass surface of the glass sheet 10 is compared with the conventional tempered glass surface only in the slow cooling process. Glass plate, it is not easy to attach scratches. Hereinafter, the glass plate 10 will be described in more detail. (Detailed Description of Glass Plate) The thickness W of the compressive stress layer 14 formed on the glass sheet 10 is larger than Ομηι and is less than 50 μm. The compressive stress layer 14 is formed on the surface of the glass. That is, the compressive stress layer 14 is formed from the surface of the glass to a depth of at most 5 Ο μηη. Further, in other words, the depth from the surface of the compressive stress layer 14 is less than 50 μm. The depth of the compressive stress layer may be deepened by facilitating volatilization from the surface of the molten glass or glass ribbon during the forming process, but the depth of the compressive stress layer 14 exceeds 50 μm, thereby causing detachment beyond the appropriate conditions for forming. , or a decline in productivity. Therefore, the depth from the surface of the compressive stress layer 14 is 50 μm or less. Therefore, the depth of the compressive stress layer 14 is preferably 45 μm or less and less than 40 μmη, preferably 38 μηη or less. Such an ideal state can be achieved by adjusting the manufacturing conditions of the glass plate including the conditions for promoting the volatilization of the volatile component from the surface of the glass ribbon or the glass ribbon being formed or increasing the amount of volatilization. However, the depth of the compressive stress layer 14 in the present specification indicates the depth from the surface of the glass at the deepest portion of the compressive stress layer formed on one surface of the front and back of the glass. That is, the front and back surfaces of the glass sheets ’0 are each formed with a compressive stress layer 14 having the above-described depth. Further, the depth of the compressive stress layer 14 exceeds ΙΟμίΏ. By using the depth of the stress layer 14 of the compression -15-201139303 as the value exceeding ΙΟμιη, it is possible to prevent the glass from being scratched easily by the minute flaw caused by the treatment. The depth of the compressive stress layer 14 is such that the glass plate 10 is less likely to be damaged even if it is deeply adhered, and is preferably 15 μm or more, 20 μm or more, 25 μm or more, 30 μm or more, and 35 μm or more. The depth of the compressive stress layer 14 formed on the surface of the glass is less than 1/13 of the thickness W of the glass plate 10, but less than 1/15, less than 1/17, less than 1/20, less than 1/22, less than 1/24. It is better. Such an ideal form can also be achieved by adjusting the manufacturing conditions of the glass plate and the composition of the glass plate, which are required to promote the volatilization of the volatile component from the surface of the glass ribbon or the glass ribbon during molding, or to increase the amount of volatilization. The stress 値 (absolute 値) of the compressive stress layer 14 formed near the surface of the glass sheet 1 is also at a maximum of 4 MPa. When the maximum stress of the above stress 値 (absolute 値) exceeds 4 MPa, the total stress 値 of the compressive stress layer 14 becomes large, and processing of the glass sheet 1 ,, for example, shape processing becomes difficult. Therefore, the maximum enthalpy of stress 値 (absolute 値) of the compressive stress layer 14 is 3.7 MPa or less, 3.5 MPa or less, 3.0 MPa or less, and 2.8 MPa or less. Further, the stress 値 (absolute 値) of the compressive stress layer 14 is the largest 値 system. 1 μPa or more ～ 0.5 MPa or more and IMPa or more, and 1.5 MPa or more, preferably 2 MPa or more. The compressive stress layer 14 is formed by the compressive stress layer 14 on the glass surface of the glass sheet 1 because the stress 値 (absolute 値) is a layer exceeding 〇 MPa, and the mechanical strength of the glass sheet 10 is improved. However, the "stress 値" in the present specification is shown as an average 値 from the surface of the sample -16 - 201139303 0 to 10 μπι in the sample which is cut from the glass surface of the glass plate 10 at a specific depth. Therefore, for the locality, the compressive stress layer 14 has a glass plate having a stress 超过 exceeding the range of the stress ,, and is also included as the glass plate 10. The stress 値 of the tensile stress layer 12 formed inside the glass sheet 1 is as described above, and is slightly constant in the thickness direction of the glass sheet 1 。. The stress enthalpy of the tensile stress layer 12 is 〇4 MPa or less as described above. When the maximum enthalpy of the stress 値 (absolute 値) of the tensile stress layer 12 exceeds 4 4 Μ P a , for example, in the case of cutting the glass plate, the cutting line of a specific depth placed for cutting is intended to be externally elongated. In the thickness direction of the glass sheet, it is difficult to have the divided glass sheet 10 in a desired size. Therefore, the maximum 値 (absolute 値) of the stress 拉伸 of the tensile stress layer 12 is 33 MPa or less, 〇. 2 MPa or less, 0.15 MPa, 0 · 1 0 Μ P a or less. In the present embodiment, the maximum enthalpy of the stress 値 (absolute 値) of the maximum 値/tensile stress layer 12 of the stress 値 (absolute 値) of the compressive stress layer 14 on the glass surface can be 6 or more. Further, in the thickness direction of the glass sheet 10, tensile stress of the glass sheet 10 of the center portion 4/5 (hereinafter, simply referred to as "stretching center range") of the tensile stress layer 12 of each of 1/10 is formed on both sides. The variation of the stress 层 of the layer 12, that is, the difference between the maximum 値 and the minimum 値 of the stress 値 (absolute 値) is preferably 0.1 2 MPa or less. Thereby, the cutting property of the glass plate can be improved. More preferably, it is 0.10 MPa or less, 0.05 MPa or less, and 0.02 MPa or less. Such an ideal form can also be achieved by adjusting the manufacturing conditions of the glass sheet containing the volatilization of the volatile component from the surface of the molten glass or the formed glass ribbon, or increasing the amount of volatilization. The stress 値 of the tensile stress layer 12 formed inside the glass sheet 10 is slightly different in the thickness direction of the glass sheet -17-201139303, and the stress 値 of the tensile stress layer is the thickness of the glass sheet. When the direction is formed by drawing a parabola, the tensile stress layer 12 can be kept thin. More specifically, the stress 値 of the tensile stress layer 12 of the glass sheet 10 is slightly constant in the thickness direction of the glass sheet 10, compared to the maximum 値 (absolute 値) of the stress ,, which is only obtained in the slow cooling project. The maximum tensile strength (absolute 値) of the tensile stress of the glass plate is large. That is, in the conventional glass plate, the tensile stress layer is formed in a parabolic shape as a function of the compressive stress of the compressive stress layer formed on the glass surface. Therefore, when the thickness of the glass sheet is thinned, the thickness of the tensile stress layer due to the compressive stress of the compressive stress layer against the glass surface is also thinned. In the conventional glass sheet, the stress of the tensile stress layer is Extremely high, for example, in the case of cutting the glass sheet, the cutting line placed at a specific depth for cutting is intended to be elongated in the thickness direction of the glass sheet, and the split glass sheet 10 is the desired size. It becomes a difficult situation. However, the stress 値 of the tensile stress layer 12 of the glass plate 10 of the present embodiment is slightly determined by the thickness direction of the glass plate 1 ,, and the maximum 値 of the stress 値 of the tensile stress layer is not easily increased. The glass sheet can be processed with high precision. When the glass plate 10 is viewed from the composition of the glass, the glass plate 10 is formed to have a high concentration range of Si from the surface of the glass in the thickness direction from 0 to 30 nm (hereinafter referred to as a Si-rich layer). ). The concentration ratio of the atomic concentration (atomic %) of Si in the atomic concentration of Si (atomic %) at the center of the thickness direction of the glass plate 10 in the Si-rich layer is in the range of 5 % or more. The range of the position of the Si-rich layer is desirably more than 〇25 nm, -18-201139303 2~20 nm, 5-16 nm, and 8-16 nm. On the other hand, the depth of the Si-rich layer can be deepened by promoting the volatilization from the surface of the molten glass or the glass ribbon in the forming process, but the appropriate conditions for the release molding or the decrease in productivity are caused. Alternatively, when the depth of the Si-rich layer exceeds 30 nm, etching is performed on the glass surface of the glass plate 1 , and etching becomes difficult. Further, when the depth of the Si-rich layer exceeds 30 nm, the stress 値 (absolute 値) of the compressive stress layer 14 formed on the surface of the glass becomes large, and the chipability of the glass plate is lowered. Therefore, the depth of the Si-rich layer is preferably 30 nm or less. The Si-rich layer has a maximum peak of Si atom concentration, and the concentration of Si atoms in the thickness direction of the glass sheet 1 减少 decreases from the position of the maximum peak 朝向 toward both sides. The compressive stress layer Μ and the tensile stress layer 12 described above are formed by having such a composition of glass. The Si atom concentration means the atomic % of Si for the entire glass component excluding the oxygen atom (except for the glass total component of oxygen atoms such as Si, Al, B, Ca, Sr, Ba, etc.). At this time 'in the molten state of the glass (for example, the viscosity of the glass is 1 04 +5 ~ 105poise, or the temperature is 1 1 〇〇~1 3 00 °C), compared with SiO2, the vapour pressure (saturated vapor pressure) is high. The component is preferably 30% by mass or more in the center of the thickness direction of the glass sheet, and is preferably formed at the point where the Si-rich layer is formed. When the concentration ratio is less than 5%, a sufficient difference in thermal expansion coefficient cannot be obtained on the surface and the inside of the glass, and the compressive stress layer 14 cannot be effectively formed. Or, sufficient Vickers hardness or durability cannot be obtained. On the other hand, when the above concentration ratio exceeds 30%, the glass plate product 201139303' period is as described in the 'use of the chemical process to make the production unproductive} and there is a 'special difficulty to learn to become a change, 111 ml s special The case of the engraved thermal eclipse' or the use of the slab of the slab. From this point of view, the above concentration ratio is preferably 30% as the upper limit. Further, in the Si-rich layer, the peak position of the Si atom or the Si atom concentration is the highest in the range of 〇 5 5 nm from the surface of the glass. When the Si-rich layer is formed on a surface of the glass surface which is relatively large in the thickness direction and has a depth of 30 nm or less, a sufficient difference in thermal expansion ratio can be obtained on the surface and inside of the glass, and a compressive stress layer 14 can be formed on the surface of the glass. . In addition, the Vickers hardness or durability of the glass surface can be improved to prevent the glass plate 10 from being damaged. That is, since Si is a component which can increase the Vickers hardness, the Vickers hardness of the glass surface of the glass plate 10 becomes high via the Si-rich layer formed on the glass surface. Further, since the Si system is excellent in chemical resistance, the durability of the glass plate 10 in which the Si-rich layer is formed on the glass surface is also improved. Further, the Vickers hardness of the glass surface is improved compared with the conventional glass plate, and the crack generation rate is lowered, and it is less likely to adhere to the flaw and is less likely to be broken. The Vickers hardness of the glass surface of the glass plate 10 is, for example, 4 GPa or more, and preferably 5 GPa or more and 5.3 GPa or more. Alternatively, the Vickers hardness of the glass surface is increased by 〇. 〇 1% or more with respect to the Vickers hardness inside the glass, and is preferably 0.02% or more, 0.05% or more, 0.10% or more, and more preferably 1% or more. Thus, the glass sheet 10 is a point of internal stress, and has a tensile stress layer 12 and a compressive stress layer 14 having a Si-rich layer in the vicinity of the glass surface in the vicinity of the glass surface. The glass plate 10 is formed from a surface of a molten glass or a glass ribbon, for example, a glass having a viscosity of 1045 to 105 poise or a molten glass having a temperature of 1100 to 1300 ° C in a molding process of a glass ribbon to be described later, compared with SiO 2 . It is obtained by volatilization of a volatile component which promotes a high saturated vapor pressure. Each of the forms of the desired number range may be adjusted by the production conditions of the glass plate including the conditions for promoting the volatilization of the volatile component from the surface of the molten glass or the formed glass ribbon, or increasing the amount of volatilization. achieve. Such a glass plate 1 can be further strengthened by chemical strengthening treatment by ion exchange to strengthen the glass surface. The glass plate 10 may not be subjected to chemical strengthening treatment by ion exchange. Embodiments of the present invention also include tempered glass that chemically strengthens the glass surface of the glass sheet 10 by ion exchange. In this case, the Si-rich layer described above and the ion exchange treatment range via ion exchange are coexisted on the surface of the glass. The ion exchange treatment range is a range in which an ion exchange component such as Li, Na or the like in the surface of the glass is exchanged with an ion exchange component such as K in the treatment liquid for ion exchange. At this time, for the chemically strengthened glass plate 10, the compressive stress layer subjected to the chemical strengthening treatment is superposed on the compressive stress layer 14 due to the Si-rich layer to form a large compressive stress layer. The thickness of the compressive stress layer formed from the glass surface toward the inside via ion exchange is 20 to ΙΟΟμπι. The maximum enthalpy of stress 値 (absolute 値) of the compressive stress layer which is enlarged by ion exchange is preferably 300 MPa or more, and more preferably 400 MPa or more. When the maximum enthalpy of stress 値 (absolute 値) is 300 MPa or more, the glass plate reinforced by -21 - 201139303 can be sufficiently reinforced by, for example, a protective display. However, the higher the stress 値 (absolute 値), the higher the strength of the glass, but the greater the impact of the reinforced glass. In order to prevent the glass plate 1 which is chemically strengthened by the above-mentioned impact, the maximum enthalpy of the stress 値 (absolute 値) of the compressive stress layer is preferably 950 MPa or less, and more preferably 800 MPa or less, and 700 MPa or less. Better yet. On the other hand, compared with the conventional glass plate which forms a compressive stress layer on the surface of the glass by quenching glass, the stress 値 (absolute 値) of the tensile stress layer is not easily increased. The thickness of the compressive stress layer after the chemical strengthening treatment is 20 μm or more, and 30 μηι or more and 40 μη· or more are preferable. The thickness of the compressive stress layer is as large as possible, and even if the tempered glass is attached with a deep flaw, the tempered glass is not easily broken, and the mechanical strength unevenness is small. On the other hand, the thickness of the compressive stress layer is 10 or less. When the thickness of the compressive stress layer is considered to be easy to handle the tempered glass, it is preferably 90 μm or less and 80 μm or less. However, the thickness of the glass cover of the tempered glass to which the chemically strengthened glass plate 10 is applied is preferably 1.5 mm or less. Here, in the glass plate of i. 5 mm or more, the strength of the glass plate itself is increased, and the compressive stress layer 14 formed near the surface of the glass is not sufficiently functional. That is, the thickness of the glass plate 10 or the glass cover formed in the present embodiment is 1. 〇 mm or less, 0.7 mm or less, 0.5 mm or less, or 〇. 3 mm or less, and the thickness of the glass plate 10 is thinner. The effect of the invention is more remarkable. Further, the method for producing a glass sheet of the present embodiment is preferably a large glass sheet. The glass plate which is larger in this system has a large amount of bending, and the glass plate is easily broken due to the slight flaw of -22-201139303 caused by the treatment, but the above problem can be reduced when the compressive stress layer 14 is formed on the surface of the glass. It happened. Therefore, the effect of the present invention is remarkable in the case where the width direction of the glass plate 10 is 1 000 mm or more and 2000 mm or more. (Type of Glass for Glass Plate) As the glass used for the glass plate 10, borosilicate glass, aluminum silicate glass, aluminum borosilicate glass, soda lime glass, alkali metal silicate glass, alkali metal silicate Glass, alkali metal aluminosilicate glass, etc. However, the glass system which can be applied to the glass plate of the present invention is not limited to the above types, such as containing at least Si〇2, and at the glass melting temperature (the viscosity of the glass is 1 04 5 to l 〇 5 poise, or the temperature is 1 100 〜 The saturated vapor pressure of 1 3 00 °c) may be a type of glass having a higher volatile component than SiO 2 . However, the ai2o3 system forms an oxide, and among the components of the glass, the saturated vapor pressure is relatively low. However, in the present embodiment, since the saturated vapor pressure is higher than that of Si 2 , Al 2 〇 3 is contained in the volatile component. However, the content of the volatile component in the glass composition is preferably 30% by mass or more, and more preferably 35% by mass or more, and more preferably 40% by mass or more. In the tensile stress layer 12 of the glass plate 1 of the glass plate 10 in which the volatile component of the glass plate 10 is not volatilized, the content of the volatile component is 30% by mass or more. When the content of the volatile component in the glass composition is less than 30% by mass, the volatilization of the volatilization component is not promoted, and the Si-rich layer or the compressive stress layer is less likely to be formed on the surface of the glass. Further, when a volatile component is contained in a large amount, volatilization is excessively increased, and homogenization of glass becomes difficult. Therefore, the content of the volatile component in the glass composition -23-201139303 is 60% by mass or less, preferably 50% by mass or less, and more preferably 45% by mass or less. (Composition Example of Each Glass) For example, the aluminum borosilicate glass is exemplified by the following components. However, the % display of the composition described below shows the mass %. Boric acid anchor glass is used, for example, in a flat panel display glass substrate. The following shows the ideal content of the components in the brackets. ()

Si02 : 50〜70% ( 55〜65%，57〜64%，58〜62%) >Si02 : 50~70% (55~65%, 57~64%, 58~62%) >

Al2〇3 : 5~20% ( 10〜20%，12-18% » 15〜18%)， B2〇3 : 0〜15% ( 5〜15%，6〜13%，7〜12%)， 此時，作爲任意成分，含有下記之組成亦可。 M g Ο : 0 ~ 1 0 °/〇 (下限係0.0 1 %，下限係0.5 %，上限係 5%，上限係4% ’上限係2% )，Al2〇3: 5~20% (10~20%, 12-18% » 15~18%), B2〇3: 0~15% (5~15%, 6~13%, 7~12%), In this case, as an optional component, the composition described below may be included. M g Ο : 0 ~ 1 0 ° / 〇 (the lower limit is 0.01%, the lower limit is 0.5%, the upper limit is 5%, the upper limit is 4% ‘the upper limit is 2%),

CaO : 0〜10% (下限係1%，下限係3%，下限係4%， 上限係9%，上限係8%，上限係7%，上限係6% )， (:'CaO : 0 to 10% (lower limit is 1%, lower limit is 3%, lower limit is 4%, upper limit is 9%, upper limit is 8%, upper limit is 7%, upper limit is 6%), (:'

SrO : 0~10°/。（下限係0.5%，下限係3%，上限係9%， 上限係8%，上限係7%，上限係6% )，SrO : 0~10°/. (The lower limit is 0.5%, the lower limit is 3%, the upper limit is 9%, the upper limit is 8%, the upper limit is 7%, and the upper limit is 6%).

BaO : 〇〜1 〇% (上限係8%，上限係3%，上限係1 %， 上限係0.2%) ’BaO : 〇~1 〇% (upper limit is 8%, upper limit is 3%, upper limit is 1%, upper limit is 0.2%) ’

Zr〇2 : 0-10% ( 0-5% > 〇~4% > 0-1% . 〇~〇.1%)， 更且，作爲硼矽酸鋁玻璃係例示下記組成。下記括弧 內之顯示係各成分之理想含有率。Zr〇2 : 0-10% (0-5% > 〇~4% > 0-1% . 〇~〇.1%), and more, as an example of the composition of the aluminum borosilicate glass. The display in the brackets below shows the ideal content of each component.

Si〇2 : 50-70% ( 55-65 % > 58-62%)， • 24 - 201139303 A12 Ο 3 : 1 0 ~ 2 5 % ( 1 5 〜2 0 %，15-18%)， B 2 0 3 : 5- 1 8% ( 8-14% - 10-13%) >Si〇2 : 50-70% ( 55-65 % > 58-62%), • 24 - 201139303 A12 Ο 3 : 1 0 ~ 2 5 % ( 1 5 ～2 0 %, 15-18%), B 2 0 3 : 5- 1 8% ( 8-14% - 10-13%) >

MgO : 0〜1 0% ( 1 ~5 %，1 ~2% )，MgO : 0~1 0% (1 ~ 5 %, 1 ~ 2% ),

CaO : 0〜20% ( 1 〜7%，4〜7% )， S r Ο : 0 ~ 2 0 % ( 1 ~ 1 〇 %，1 ~ 3 % )， B a Ο : 0-10% ( 〇 ~ 2 % > 0 ~1 % ) > K20 ： 0-2% ( 0.1-2% - 0.1-0.5%)， S η Ο 2 _· 0 〜1 〇/〇 ( 〇 · 〇 1 〜〇 · 5 %，0 _ 0 1 〜0 · 3 % )。 另外’鹼金屬矽酸鋁玻璃係例示含有以下成分之構成 。鹼金屬矽酸鋁玻璃係例如使用於電子機器之顯示畫面的 玻璃蓋。下記括弧內之顯示係各成分之理想含有率。CaO : 0~20% (1~7%, 4~7%), S r Ο : 0 ~ 2 0 % (1 ~ 1 〇%, 1 ~ 3 % ), B a Ο : 0-10% ( 〇 ~ 2 % > 0 ~1 % ) > K20 : 0-2% ( 0.1-2% - 0.1-0.5%), S η Ο 2 _· 0 〜1 〇/〇( 〇· 〇1 〇〇· 5 %, 0 _ 0 1 〜 0 · 3 % ). Further, the alkali metal silicate glass is exemplified by the following components. The alkali metal silicate glass is used, for example, as a glass cover for a display screen of an electronic device. The display in brackets below shows the ideal content of each component.

Si〇2 : 50〜70% ( 55〜65%，57〜64%，5 7-62 %), A12 Ο 3 : 5 〜2 0 0/〇 ( 9 〜1 8 %，1 2 〜1 7 % )，Si〇2: 50~70% (55~65%, 57~64%, 5 7-62%), A12 Ο 3 : 5 〜2 0 0/〇 (9 〜1 8 %, 1 2 〜1 7 % ),

Na2〇 : 6〜30% ( 7〜20%，8〜1 8%，1 〇〜1 5% )， 此時，作爲任意成分，含有下記之組成亦可。Na2〇 : 6~30% (7~20%, 8~1 8%, 1 〇~1 5%). In this case, as an optional component, the following composition may be included.

Li20 : 0〜8% ( 0~6%，0〜20/〇，0〜0.6%，0〜0.4% , 0~0.2%) > B 2 〇 3 · 0 〜5 0/〇 ( 0 ~ 2 %，0 ~ 1 %，0 ~ 0.8 % )， K20 : 0~10% (下限係1 %，下限係2%，上限係6%， 上限係5%，上限係4%)，Li20 : 0~8% (0~6%, 0~20/〇, 0~0.6%, 0~0.4%, 0~0.2%) > B 2 〇3 · 0 ～5 0/〇 ( 0 ~ 2 %,0 ~ 1 %, 0 ~ 0.8 % ), K20 : 0~10% (the lower limit is 1%, the lower limit is 2%, the upper limit is 6%, the upper limit is 5%, and the upper limit is 4%).

MgO : 0〜10% (下限係1%，下限係2%，下限係3%， 下限係4 %，上限係9 %，上限係8 %，上限係7 % )， C aO : 〇~2 0 % (下限係〇 · 1 % ’下限係1 %，下限係2 %， 上限係1 〇%，上限係5%，上限係4%，上限係3% )， -25- 201139303 Z r Ο 2 : 0 〜1 0 % ( 0 〜5 %，0 〜4 %，0 〜1 %，〇〜〇·”/〇) ’ 更且，作爲鹼金屬矽酸鋁玻璃係例示下記組成。MgO : 0 to 10% (lower limit is 1%, lower limit is 2%, lower limit is 3%, lower limit is 4%, upper limit is 9%, upper limit is 8%, upper limit is 7%), C aO : 〇~2 0 % (lower limit system 1 1 % 'lower limit 1 %, lower limit 2 %, upper limit 1 〇%, upper limit 5%, upper limit 4%, upper limit 3%), -25- 201139303 Z r Ο 2 : 0 〜1 0 % (0 〜5 %, 0 〜4 %, 0 〜1 %, 〇~〇·"/〇) ' Further, as an alkali metal silicate glass system, the composition is as follows.

Si02 ·· 5 0〜70%， AI2O3 : 5〜20% ’ N a 2 0 · 6〜20%， K 2 Ο : 0 〜1 0 %，Si02 ·· 5 0~70%, AI2O3 : 5~20% ‘ N a 2 0 · 6~20%, K 2 Ο : 0 ～1 0 %,

MgO : 0〜10%，MgO : 0~10%,

C a 0 :超過2〜2 0 % ,C a 0 : more than 2~2 0 %,

Zr〇2 : 0^4.8%， 更且，理想爲Zr〇2 : 0^4.8%, more, ideally

Si02 含有率—1/2. Al2〇3 之含有率：46_5~59%’ CaO/RO (但R係選自Mg、Ca、Sr及Ba之中之至少1種 )含有量比爲超過〇 · 3 %，Si02 content rate - 1/2. Al2〇3 content rate: 46_5~59% 'CaO/RO (but R is selected from at least one of Mg, Ca, Sr, and Ba). The content ratio is more than 〇· 3 %,

Sr〇含有率+ BaO含有率不足10%， (Zr02+Ti02) /Si02 含有量比不足 〇~〇·〇7’Sr〇 content rate + BaO content rate is less than 10%, (Zr02+Ti02) /Si02 content ratio is insufficient 〇~〇·〇7’

B203/Rl2〇 (但R1係選自Li，Na及Κ之中之至少1種） 含有量比爲不足〇〜〇·〗％。 更且，作爲另外之鹼金屬矽酸鋁玻璃係例示下記組成 S i 0 2 * 58 〜68%， AI2O3 : 8〜15%， Na2〇 ; 10〜20%， Li20 : 〇〜1 % K20 : 1 〜50/0， -26- 201139303B203/Rl2〇 (but R1 is at least one selected from the group consisting of Li, Na, and yttrium). The content ratio is less than 〇~〇·〗 〖%. Further, as an additional alkali metal silicate glass system, the composition is as follows: S i 0 2 * 58 to 68%, AI2O3: 8 to 15%, Na2〇; 10 to 20%, Li20: 〇~1% K20 : 1 ~50/0, -26- 201139303

MgO ： 2〜10%， (各成分） S i Ο 2係構成玻璃板1 0之玻璃的結構的成分，具有提昇 玻璃的化學耐久性與耐熱性的效果。對於s i0 2含有率過低 的情況，無法充分得到化學耐久性與耐熱性的效果’而 Si02含有率過高時，容易引發玻璃失透’成形變爲困難的 同時，黏性上升，玻璃的均質化變爲困難。 ai2o3係構成玻璃的結構的成分，具有提昇玻璃的化. 學耐久性與耐熱性的效果。另外，具有提昇離子交換性能 或蝕刻速度的效果。對於A1203含有率過低的情況，無法 充分得到玻璃的化學耐久性與耐熱性的效果。另一方面， ai2o3含有率過高時，玻璃的黏性上升，而溶解變爲困難 同時，耐酸性降低。 B2〇3係降低玻璃的黏性，促進玻璃的熔解及清澈之成 分。B2〇3含有率過低時，玻璃的黏性變高，玻璃的均質化 變爲困難。MgO: 2 to 10%, (components) S i Ο 2 is a component constituting the glass of the glass plate 10, and has an effect of improving the chemical durability and heat resistance of the glass. When the content ratio of s i0 2 is too low, the effects of chemical durability and heat resistance cannot be sufficiently obtained. When the SiO 2 content is too high, the glass is devitrified, and the molding becomes difficult, and the viscosity increases. Homogenization becomes difficult. Ai2o3 is a component constituting the structure of the glass, and has an effect of improving the durability and heat resistance of the glass. In addition, it has the effect of improving ion exchange performance or etching speed. When the content of A1203 is too low, the effects of chemical durability and heat resistance of the glass cannot be sufficiently obtained. On the other hand, when the content ratio of ai2o3 is too high, the viscosity of the glass rises, and dissolution becomes difficult, and the acid resistance is lowered. The B2〇3 system reduces the viscosity of the glass and promotes the melting and clearing of the glass. When the content of B2〇3 is too low, the viscosity of the glass becomes high, and the homogenization of the glass becomes difficult.

MgO及CaO係降低玻璃的黏性，促進玻璃的熔解及清 澈之成分。另外，Mg及Ca係在鹼土類金屬之中，使玻璃 的密度上升之比例爲小之故，爲了將所得到之玻璃輕量化 同時，提昇溶解性而爲有利的成分。但，MgO及CaO含有 率過高時，玻璃的化學耐久性則降低。 S rO及B aO係降低玻璃的黏性，促進玻璃的熔解及清 澈之成分。另外’亦爲提昇玻璃原料之氧化性而提高清澈 -27- 201139303 性的成分。但，SrO及BaO含有率過高時，玻璃的密度則 上升，無法謀求玻璃板之輕量化同時，玻璃的化學耐久性 降低。MgO and CaO reduce the viscosity of the glass and promote the melting and clearing of the glass. Further, Mg and Ca are among the alkaline earth metals, and the ratio of the increase in the density of the glass is small, and it is an advantageous component in order to reduce the solubility of the obtained glass while improving the solubility. However, when the MgO and CaO content are too high, the chemical durability of the glass is lowered. S rO and B aO reduce the viscosity of the glass and promote the melting and clearing of the glass. In addition, it also enhances the oxidative properties of glass raw materials to improve the clarity of ingredients. However, when the content ratio of SrO and BaO is too high, the density of the glass increases, and the weight of the glass sheet cannot be reduced, and the chemical durability of the glass is lowered.

Li20係使玻璃的黏度降低，提昇玻璃之熔解性或成形 性之成分。另外，Li20係提昇玻璃的楊氏模數之成分。更 且，Li20係離子交換成分之一，在鹼金屬氧化物之中，加 大壓縮應力層14之深度的效果爲高。但Li20含有率過高時 ，液相黏度降低，玻璃容易失透之故，利用下拉法，安定 玻璃之大量生產性變爲困難。另外，玻璃之熱膨脹係數過 高，玻璃的耐熱衝擊性降低，金屬或有機系黏著劑等之周 邊材料與熱膨脹係數則不易整合。更且，爲了進行玻璃板 的強化而進行離子交換處理之情況，有著在離子交換處理 之離子交換鹽的劣化變快之不良情況。另外，Li20之含有 率過高時，由於玻璃的低溫黏度過度下降，在化學強化後 之加熱工程，產生應力緩和，而壓縮應力値降低之故，無 法得到充分之強度。Li20 is a component that lowers the viscosity of glass and improves the meltability or formability of glass. In addition, Li20 is a component that increases the Young's modulus of the glass. Further, among the Li20-based ion exchange components, the effect of increasing the depth of the compressive stress layer 14 among the alkali metal oxides is high. However, when the Li20 content is too high, the viscosity of the liquid phase is lowered, and the glass is easily devitrified. By using the down-draw method, the mass productivity of the glass is difficult. Further, the thermal expansion coefficient of the glass is too high, and the thermal shock resistance of the glass is lowered, and the peripheral material such as a metal or an organic adhesive is not easily integrated with the thermal expansion coefficient. Further, in the case where the ion exchange treatment is carried out in order to strengthen the glass sheet, the deterioration of the ion exchange salt in the ion exchange treatment becomes high. Further, when the content of Li20 is too high, since the low-temperature viscosity of the glass is excessively lowered, the stress is relieved by the heating process after the chemical strengthening, and the compressive stress 値 is lowered, so that sufficient strength cannot be obtained.

Na20係使玻璃的高溫黏度降低，提昇玻璃之熔融性 或成形性之必須成分。另外，改善玻璃之耐失透性的成分 。在Na20含有率不足6質量％之中，玻璃的熔解性降低， 爲了熔解之成本變高。另外，Na20係離子交換成分，於 進行化學強化處理之情況，在Na20含有率不足6質量％之 中，離子交換性能亦下降之故，無法得到充分之強度。另 外，熱膨脹率過度降低，金屬或有機系黏著劑等之周邊材 料與熱膨脹係數則不易整合。更且，因容易引起玻璃失透 -28- 201139303 ，耐失透性亦降低’使玻璃溢流之下拉法的適用變爲不可 能之故，安定之玻璃的大量生產變爲困難。另一方面’ Na20含有率過高時，低溫黏度降低，熱膨脹率變爲過剩 ，而耐衝擊性降低，金屬或有機系黏著劑等之周邊材料與 熱膨脹係數則不易整合。另外，亦產生經由玻璃平衡之惡 化的耐失透性降低之故，利用下拉法，安定玻璃之大量生 產變爲困難。 κ2ο係亦爲使玻璃之高溫黏度下降，提昇玻璃之熔解 性或成形性之同時，改善耐失透性之成分。另外，Κ20係 離子交換成分，由於含有Κ20而可使玻璃之離子交換性能 之成分。但Κ20之含有率過高時，低溫黏度降低，熱膨脹 率變爲過剩，耐衝擊性降低之故，對於作爲玻璃蓋而適用 之情況並不理想。另外，Κ2 0含有率過高時，金屬或有機 系黏著劑等之周邊材料與熱膨脹係數則不易整合。另外， 亦產生經由玻璃平衡之惡化的耐失透性降低之故，利用下 拉法’安定玻璃之大量變爲困難。Na20 is a component that reduces the high-temperature viscosity of glass and enhances the meltability or formability of glass. In addition, it improves the resistance of glass to devitrification. When the Na20 content is less than 6% by mass, the meltability of the glass is lowered, and the cost for melting is increased. Further, in the case where the Na20-based ion exchange component is subjected to the chemical strengthening treatment, the Na20 content is less than 6% by mass, and the ion exchange performance is also lowered, so that sufficient strength cannot be obtained. In addition, the coefficient of thermal expansion is excessively lowered, and the peripheral materials such as metal or organic adhesives are not easily integrated with the coefficient of thermal expansion. Furthermore, it is easy to cause devitrification of the glass -28-201139303, and the resistance to devitrification is also lowered. 'The application of the pulling method under the glass overflow becomes impossible, and mass production of stable glass becomes difficult. On the other hand, when the Na20 content is too high, the low-temperature viscosity is lowered, the thermal expansion coefficient is excessive, and the impact resistance is lowered, and the surrounding materials such as metal or organic adhesives are not easily integrated with the thermal expansion coefficient. In addition, the devitrification resistance due to the deterioration of the glass balance is also lowered, and the mass production of the stabilized glass becomes difficult by the down-draw method. Κ2ο is also a component that improves the resistance to devitrification while reducing the high-temperature viscosity of the glass, improving the meltability or formability of the glass. Further, the Κ20 series ion exchange component is a component which can impart ion exchange performance of glass due to the inclusion of ruthenium 20. However, when the content of bismuth 20 is too high, the low-temperature viscosity is lowered, the coefficient of thermal expansion is excessive, and the impact resistance is lowered, which is not preferable as a glass cover. Further, when the content of Κ20 is too high, the surrounding material such as a metal or an organic adhesive is not easily integrated with the thermal expansion coefficient. In addition, the deterioration of the devitrification resistance due to the deterioration of the glass balance is also caused, and it is difficult to stabilize the glass by the pull-down method.

Li20，Na2〇及Κ20係從玻璃熔出而使TFT特性劣化， 另外’於增加玻璃之熱膨漲係數熱處理時，破損基板之成 分情況’對於作爲平板顯示器玻璃基板而適用之情況，多 量含有係並不理想。但經由特別含有特定量上述成分於玻 璃中之時’抑制TFT特性之劣化或玻璃之熱膨脹爲一定範 圍I內同時’提昇玻璃之熔融性，且提昇玻璃之鹽基性度， 而容易進行價數變動之金屬的氧化，可發揮清澈性。Li20, Na2〇, and Κ20 are melted from the glass to deteriorate the TFT characteristics. In addition, when the heat-expanding coefficient of the glass is increased, the composition of the damaged substrate is used as a flat-panel display glass substrate. Not ideal. However, it is easy to carry out the valence by suppressing the deterioration of the TFT characteristics or the thermal expansion of the glass within a certain range I while increasing the specificity of the above-mentioned components in the glass while simultaneously increasing the melting property of the glass and increasing the basicity of the glass. The oxidation of the changing metal can be made clear.

Zr〇2係提高玻璃之失透溫度附近的黏性或應變點之成 -29 - 201139303 分。另外，Zr02係亦爲使玻璃之耐熱性提昇的成分。另外 ，Zr02係顯著使離子交換性能提昇的成分。但Zr02之含有 率過高時，失透溫度則上升，耐失透性則下降。The Zr〇2 system increases the viscosity or strain point near the devitrification temperature of the glass -29 - 201139303 points. In addition, the ZrO 2 system is also a component that enhances the heat resistance of the glass. In addition, Zr02 is a component that significantly improves ion exchange performance. However, when the content of Zr02 is too high, the devitrification temperature rises and the devitrification resistance decreases.

Ti02係使玻璃之高溫黏度降低之成分。另外，1^02係 使離子交換性能提昇的成分。但Ti02之含有率過高時，耐 失透性則下降。更且，玻璃進行著色，對於FPD玻璃基板 或電子機器之顯示遨面的玻璃蓋等之適用係並不理想。另 外，從玻璃進行著色之情況，因紫外線透過率降低之故， 於進行使用紫外線硬化樹脂之處理情況，產生有無法充分 硬化紫外線硬化樹脂之不良情況。 在玻璃板1 〇之玻璃中，作爲使玻璃中之氣泡脫泡之成 分而可添加清澈劑。作爲清澈劑，如爲環境負荷小，對於 玻璃之清澈性優越之構成，並無特別限制，但例如可舉出 選自氧化錫，氧化鐵，氧化鈽，氧化铽，氧化鉬及氧化鎢 之金屬氧化物之至少1種。 然而，As2〇3及Sb203係在熔融玻璃中產生伴隨價數變 動的反應，具有清澈玻璃之效果的物質，但As203及Sb203 係從環境負荷爲大之物質之情況，在本實施形態之玻璃板 10中，於玻璃中，實質上未含有As203及Sb203。然而，在 本說明書中，實質上未含有As203及Sb203係意味不足 〇.〇1 %質量，除了不純物而未特意含有者。 (玻璃板之製造方法） 如此之玻璃板1 〇係使用下拉法而加以製造。圖3係說 -30- 201139303 明本實施形態之玻璃板之製造方法的流程之一例圖。玻璃 板之製造方法係主要具有熔解工程（步驟S10) ’和清澈 工程（步驟S20 )，和攪拌工程（步驟S30 )，和成形工程 (步驟S40 )，和緩冷工程（步驟S50 ) ’和裁板工程（步 驟S60 )，和形狀加工工程（步驟S70 )，和化學強化處理 工程（步驟S 8 0 )。 在熔解工程（步驟S 1 0 )中，以未圖示之熔解爐，玻 璃原料則根據經由化石燃料之燃燒的間接加熱及經由電性 通電之直接加熱加以加熱，製作熔融玻璃。玻璃的熔解係 亦可以除此之外的方法進行。 接著，進行清澈工程（步驟S20 )。在清澈工程中， 在儲留熔融玻璃於未圖示之液槽的狀態，熔融玻璃中的氣 泡則利用上述之清澈劑而加以去除。具體而言，經由在熔 融玻璃中價數變動之金屬氧化物的氧化還元反應而加以進 行。在高溫時之熔融玻璃中，金屬氧化物係經由還元反應 而放出氧，此氧係成爲氣體，使熔融玻璃中的氣泡成長而 浮上於液面。由此，將熔融玻璃中的氣泡係加以脫泡。或 者，氧氣之氣泡係進入熔融玻璃中之其他的氣泡中的氣體 而成長，浮上於熔融玻璃之液面。由此，將熔融玻璃中的 氣泡係加以脫泡。另外，脫泡後，玻璃的溫度降低時，金 屬氧化物則引發氧化反應，而未浮上吸收殘留於玻璃中之 小泡中的氧。吸收氧，小泡係變更小而再吸收於玻璃中。 接著，進行攪拌工程（步驟S30 )。在攪拌工程中， 爲了保持玻璃之化學性及熱均一性，於朝向垂直之未圖示 -31 - 201139303 的攪拌槽，通過有熔融玻璃。經由設置於攪拌槽的攪拌器 ，攪拌熔融玻璃同時，移動至垂直下方向底部，引導至之 後工程。經由此，可抑制脈理等之玻璃的不均一性。 接著，進行成形工程（步驟S40 )。在成形工程中， 使用下拉法。包含溢流下拉或縫隙下拉等之下拉法係有著 使用例如日本特開20 1 0-1 89220號公報，日本特許第 3 5 86 1 42號公報或圖5所示之裝置的公知方法。對於在下拉 法之成形工程係後述之。由此，成形具有特定的厚度，寬 度之薄片狀的玻璃帶。作爲成形方法，在下拉法之中，最 佳爲溢流下拉法，但亦可爲縫隙下拉法。但對於促進揮發 成分之揮發或者增大揮發量而提高壓縮應力層14之應力値 (絕對値），係揮發量多之溢流下拉法爲佳。 接著，進行緩冷工程（步驟S50)。具體而言，成形 爲薄片狀之玻璃帶係不會產生偏差地控制冷卻速度，由未 圖示之緩冷爐而冷卻至緩冷點以下。由此，玻璃帶係與最 終製品之玻璃板1 〇同樣地，在應力的點具有壓縮應力層1 4 及拉伸應力層12，在組成的點具有富Si層。 接著，進行裁板工程（步驟S 60)。具體而言，連續 性所生成之玻璃帶係裁板成各一定長度，得到玻璃板。 之後，進行形狀加工工程（步驟S70 )。在形狀加工 工程中，除了切出成特定的玻璃板之尺寸或形狀之外，進 行玻璃表面及端面的硏削♦硏磨。形狀加工係採用噴砂處 理，使用切刀或雷射之物理性手段亦可，而亦可使用蝕刻 等之化學的手段。然而，對於將玻璃板形成加工成複雜的 -32- 201139303 形狀時，於化學強化處理前，實施上述鈾刻處理爲佳。 作爲玻璃板1 〇之形狀加工的一例，係可舉出於如圖4 所示之玻璃板1 0開孔1 1，加工成含有曲線及直線的外形形 狀之蝕刻處理。加工成如此之外形形狀的玻璃板1 0係使用 於電子機器之顯示畫面的玻璃蓋。 此情況，首先，於玻璃板的兩主表面上，塗佈光阻劑 材料。接著，藉由具有所期望之外形形狀圖案之光罩而將 光阻劑材料進行曝光。上述外形形狀並無特別加以限定， 但例如包含具有負的曲率部分（沿著外形形狀的端而於左 側而視外形形狀的範圍內部同時前進時，隨著前進而彎曲 於右側的部分）之外形形狀。接著，將曝光後的光阻劑材 料進行顯像，於玻璃板的被蝕刻範圍以外之範圍，形成光 阻劑圖案，蝕刻玻璃板之被蝕刻範圍。此時，作爲蝕刻劑 使用濕蝕刻液之情況，玻璃板係等向性地加以蝕刻。由此 ，玻璃板的端面係中央部則朝向外方最爲突出，從其中央 部朝向兩主表面側形成徐緩彎曲的傾斜面。然而，傾斜面 與主表面的邊界及傾斜面彼此的邊界係最佳作爲帶有圓滑 的形狀。 在蝕刻工程所使用之光阻劑材料係並無特別加以限定 ，但可適用對於在將光阻劑圖案作爲光罩而蝕刻玻璃時所 使用之蝕刻劑而言具有耐性之材料。例如，玻璃係一般經 由含有氟酸之水溶液的濕蝕刻，或氟素系氣體之乾蝕刻而 加以腐蝕之故，對於氟酸耐性優越之光阻劑材料等最佳。 另外，作爲上述蝕刻劑，係可適用含有氟酸，硫酸，硝酸 -33- 201139303 ，鹽酸，六氟矽酸之中至少1種的酸之混酸。 經由作爲蝕刻劑而使用氟酸或上述混酸水溶液之時， 可得到所期望形狀之玻璃蓋。 另外，在利用蝕刻而進行形狀加工時，只由調整光罩 圖案，亦可容易實現複雜之外形形狀。更且，由經由蝕刻 而進行形狀加工者，亦可更提昇生產性，亦可降低加工成 本。然而，作爲爲了將光阻劑材，從玻璃板剝離之剝離液 ，係可使用ΚΟΗ或NaOH等之鹼溶液。上述光阻劑材，蝕 刻劑，剝離液之種類係可對應於玻璃板之材料而作適宜選 擇。 然而，作爲蝕刻的方法，不單只有浸漬於蝕刻液之方 法，而亦可使用噴霧蝕刻液之噴射蝕刻法等。由利用如此 蝕刻而形狀加工玻璃板者，可得到表面粗度具有高平滑性 之端面的玻璃蓋。也就是，可防止在經由機械加工而形狀 加工時必定產生之微細龜裂的發生，更可提昇玻璃蓋之機 械性強度。 最後，進行經由離子交換之化學強化處理（步驟S80 )。然而，化學強化處理係根據情況而未進行、例如，使 用於平板顯示器之硼矽酸鋁玻璃等之玻璃板係未進行化學 強化處理。另一方面，對於適合使用於如鹼金屬矽酸鋁玻 璃之電子機器之表示畫面的玻璃蓋之玻璃板，係進行化學 強化處理。 由在玻璃表面附近更將形成有富Si層或壓縮應力層14 之玻璃板1 0進行化學強化者，可更提昇玻璃板1 〇之強度。 -34 - 201139303 另外，與由急冷玻璃而於表面形成壓縮應力層之以往的玻 璃板做比較，本實施形態之玻璃板的拉伸應力層之應力値 (絕對値）係不易變大。 然而，爲了進行離子交換而於玻璃成分中’含有離子 交換成分之Na20或Li20爲佳。本實施形態之化學強化的強 化玻璃係除了電子機器之顯示畫面的玻璃蓋之外’可適用 於攜帶終端裝置之框體，太陽能電池之玻璃蓋’顯示器用 之玻璃基板，觸控面板顯示器之玻璃蓋，觸控面板顯示器 之玻璃基板等。 例如，化學強化處理係可使用如下述之方法而進行之 〇 在化學強化處理中，將玻璃板1 〇，浸漬約1 ~2 5小時於 例如保持在350〜5 5 0 °C程度之KN03 1 00%的處理浴中。此時 ，玻璃表層之Na +離子或Li +離子則由離子交換爲處理浴 中的K +離子或Li +離子者，化學強化玻璃板。然而，離子 交換處理時之溫度，時間，離子交換溶液等係可做適宜變 更。例如，離子交換溶液係亦可爲2種類以上之混合溶液 〇 玻璃板之製造方法係除此之外，有洗淨工程及檢查工 程，但省略此等工程之說明。然而，形狀加工工程係於化 學強化處理工程之前進行，而亦可爲於化學強化處理工程 之後進行。 在本實施形態之玻璃板1 0的製造之成形工程中，由從 玻璃帶促進揮發成分之揮發，或揮發量增大者，形成富Si -35- 201139303 層，因其富Si層引起，緩冷後，於裁板工程前，形成壓縮 應力層14及拉伸應力層12。揮發成分係指較5102容易揮發 的成分，換言之，顯示在熔融玻璃中（例如，玻璃的黏性 爲1045〜105poise，或溫度1100〜1300 °c )，飽和蒸氣壓較 si〇2爲高的成分。作爲揮發成分，係例如可舉出ai2o3， B2O3 ' L12O > Na2〇 · K2O ' MgO > CaO > SrO > BaO » Zr〇2 ，Sn02等，但並不限定於此等。然而，B203，鹼氧化物（ L12O * Na2〇 > K2O)，驗土 類金屬氧化物（MgO，CaO， SrO，BaO )係揮發性高之故，作爲玻璃成分，至少含有1 種爲佳。Sn02係作爲SnO而揮發。 揮發過度時，無法適當玻璃板的成形之故，例如B2〇3 之含有率的上限爲14質量％更佳，而13質量％特別佳。另 外，Sn02之含有率高時，有著對於玻璃產生失透。隨之， 從防止玻璃之失透的觀點，Sn02之含有率的上限係〇.5質 量％更佳，而0.3質量％特別佳。更且，作爲玻璃之熔解促 進劑所使用之κ20係添加多量時，從玻璃板熔出。因此， 對於使用於液晶顯示裝置用玻璃基板等之平板顯示器玻璃 基板的情況，κ20之含有率的上限爲0.5質量％更佳。 此等之揮發成分係在熔融玻璃中，飽和蒸氣壓較Si02 爲高之故，於成形時（玻璃熔融之狀態），從熔融玻璃或 玻璃帶揮發。也就是，在從熔融玻璃形成玻璃帶之成形工 程中，在玻璃帶表面，Si02以外的成分揮發之故，結果， 對於成形後之玻璃表面’係形成s i原子濃度較玻璃內部之 Si原子濃度爲高之富Si層。另外，於玻璃板之玻璃表面形 -36- 201139303 成富Si層時，經由與玻璃內部之熱膨脹率的差，形成壓縮 應力層14於玻璃表面。 (成形裝置） 圖5係說明實施經由下拉法之成形方法的成形裝置之 一例圖。 成形裝置101係構成下方向尖的五角形楔状（寬度窄、 棒球本壘板形狀）之剖面形狀。成形裝置1 01係具有：設置 有直線延伸的溝1 1 1之上面，和設置於此上面的溝1 Π，和 從平行之兩端部朝向下方之一對的壁面112。然而，在本 說明書中，爲了說明之方便，將在水平面上溝Π 1的延伸 方向（圖5之紙面垂直方向）稱作X方向，將在水平面上 與X方向垂直交叉的方向稱作Y方向，將垂直方向稱作z方 向（參照圖6 )。 溝1 11係使從未圖示之供給管供給至一端的熔融玻璃 103，呈遍佈全長均一地溢流地，隨著從一端朝向於另一 端，深度緩緩變淺。一對之壁面112之各自係具有：從上 面之Y方向的端部垂直地垂下之垂直面，和從此垂直面之 下端部呈相互接近地傾斜於內方向之傾斜面。此等之傾斜 面的下端部彼此係交錯形成延伸於X方向之稜線。 成形裝置1 01係經由使熔融玻璃103，從溝1 1 1之兩側 溢流，在壁面1 1 2上誘導其溢流之熔融玻璃彼此而在傾斜 面之下端部融合之時，連續地形成帶狀之玻璃帶1 04。 斷熱構造體102係形成收容成形裝置101之成形空間（ -37- 201139303 處理室）。具體而言，斷熱構造體102係由對於斷熱性優 越之材料加以構成，具有於上下方向夾持成形裝置101而 相互對向之底壁1 2 1及天頂壁1 2 3，和連結底壁1 2 1與天頂 壁123之周緣彼此的矩形筒狀的周壁122。對於底壁121之 中央，係設置有通過經由成形裝置1 〇 1所形成之玻璃帶1 04 之閘門125。然而，斷熱構造體102係呈成爲中空構造’供 給加熱用或冷卻用之空氣於內部亦可。 在本實施形態中，如圖5所示，對向於成形裝置1〇1之 壁面112，朝向Y方向，於周壁122之長壁部之上部，設置 貫通周壁122之複數的排出口 126。更且，朝向周壁122之 Y方向，於長壁部之下部，設置貫通周壁122之複數的導 入口 1 2 7。因此，經由自然對流，形成如於圖5中箭頭a，b ，c所示之空氣的流動。即，斷熱構造體102外之空氣則通 過導入口 127而導入於斷熱構造體102內》所導入的空氣係 沿著流下在成形裝置101之壁面112上的熔融玻璃103而上 升，之後，通過排出口 126而排出於斷熱構造體102外。如 此，經由在斷熱構造體102內，使從外部導入之新鮮的空 氣上升之時，可促進來自熔融玻璃1 03之揮發成分（例如 ，A12 〇 3，B 2 〇 3，L i 2 Ο，N a 2 Ο，K 2 〇，M g 0，C a Ο，S r 0， BaO，Zr02，Sn02等）的揮發。對於其揮發成分揮發的部 分，即與上升之空氣接觸之熔融玻璃103的表面，係於冷 卻玻璃帶104時而形成富Si層，經由其富Si層之生成，形 成壓縮應力層14。爲了提高壓縮應力層14之應力値（絕對 値），熔融玻璃1〇3含有多的揮發成分爲佳❶ -38- 201139303 然而，排出口 126及導入口 127係亦可朝向在周壁122 之X方向而設置於短壁部亦可。或者朝向於周壁122之X方 向，只於短壁部設置排出口 126及導入口 127亦可。但對於 遍佈於熔融玻璃1 〇 3之全幅均一地揮發揮發成分，排出口 126及導入口 127係朝向周壁122之Y方向，只於長壁部， 以一定的間距加以設置爲佳。 另外，排出口 126及導入口 127之形狀及數量係對於周 壁1 22只要保持必要的強度而可做適宜選定。例如亦可將 排出口 1 2 6及導入口 1 2 7之形狀，如圖6所示，作爲圓形， 而亦可作爲延伸於X方向之縫隙狀而降低數量。然而，對 於爲了均一地，且有效率佳地從斷熱構造體102排出氣體 ，使用遍佈玻璃帶之寬度方向全體延伸之縫隙則更有效果 。但產生有越擴大縫隙之開口面積，氣體流量越增加，玻 璃板之表面缺點的增加，或玻璃表面凹凸之惡化，成形溫 度的確保變爲困難之問題。但此問題係如以下所示，將從 導入口 127導入至斷熱構造體1〇2內之空氣或非活性氣體之 溫度’作爲斷熱構造體102內之目標溫度，且斷熱構造體 1 02內之壓力則呈可維持爲特定的壓力地經由調整氣體的 流量之時而可解決。 更且，通過導入口 12 7而導入至斷熱構造體102內之空 氣係例如’未降低熔融玻璃1 〇 3或玻璃帶1 04之溫度的程度 之溫度爲佳。在此’所導入之空氣的量如爲少量，即使導 入常溫的空氣，溶融玻璃1 〇 3或玻璃帶1 〇 4之溫度亦未降低 那樣程度。因此’導入常溫的空氣亦可。另一方面，導入 • 39 - 201139303 於斷熱構造體102內之空氣的if如爲多量，當導入常溫的 空氣時，熔融玻璃103或玻璃帶104之溫度係大幅降低。對 於此情況，將通過導入口 127所導入之空氣加熱成特定的 溫度之未圖示之加熱裝置，則加以設置於斷熱構造體1 〇2 之外側或內側爲佳。 在以上說明之成形裝置1 0 1中，從經由斷熱構造體1 02 所圍繞之成形裝置1 0 1的溝1 1 1之兩側，熔融玻璃1 03則溢 流之另一方面，沿著流下在成形裝置101之壁面112上的熔 融玻璃103而空氣則上升之後，排出於斷熱構造體102外。 在此，上述空氣係從斷熱構造體102外導入至斷熱構造體 1 02內。如此，斷熱構造體1 02內之空氣則經由沿著流下在 成形裝置101之壁面112上的熔融玻璃而流動之時，促進來 自溶融玻璃1 03之揮發成分的揮發。經由此，可得到於玻 璃板10之玻璃表背兩面形成應力値高的壓縮應力層14之玻 璃板1 〇。 然而，在本實施形態中，排出口 1 26則加以設置於周 壁122之上部，但排出口 126之位置並無特別加以限定。例 如，如圖7所示，將排出口 1 2 6設置於在天頂壁1 2 3之成形 裝置1 〇 1之正上方部分亦可。即使如此作爲，經由自然對 流，可將從斷熱構造體102外導入至斷熱構造體102內之空 氣沿著流下在成形裝置1〇1之壁面112上的熔融玻璃1〇 3而 上升之後，通過排出口 12 6而排出於斷熱構造體1〇2外。另 外，對於此情況，在成形裝置101之上部，熔融玻璃103亦 與通過斷熱構造體102之空氣接觸之故，較將排出口 126設 -40- 201139303 置於周壁1 2 2之上部的情況，揮發成分之揮發係更加促進 〇 但對於將排出口 1 2 6設置於天頂壁1 2 3之情況’有著來 自斷熱構造體102之上方的落塵等之落下物’通過排出口 1 2 6而落下於熔融玻璃1 〇 3之情況。從此觀點’係如圖5 ’ ό 所示之實施形態，將排出口丨26設置於周壁122之上部者爲 佳。 另外，在圖5，6所示之實施形態中，導入口 127則加 以設置於周壁1 2 2之下部’但導入口 1 2 7之位置係無特別加 以限制。例如如圖8所示’亦可將導入口 1 2 7設置於底壁 1 2 1。此情況，當導入口 1 2 7位於成形裝置1 〇 1正下方之範 圍R內時，來自導入口 127之空氣的流動則有對於玻璃帶 104之形狀安定性帶來影響之虞。因此’導入口 127係設置 於範圍R之外側爲佳。 另外，如圖7所示，亦可未設置導入口 1 2 7。即使如此 作爲，斷熱構造體102外之空氣亦通過閘門〗25而導入至斷 熱構造體102內。但對於此情況，閘門125朝向與玻璃帶 104相反方向而空氣通過，有損玻璃帶1〇4之形狀安定性之 虞之故，設置與閘門125不同之導入口 127爲佳。 另外，在圖5〜8所示之實施形態中，經由自然對流而 進行對於斷熱構造體102內之空氣的導入及對於斷熱構造 體1 02外之空氣的排出，但經由強制對流而進行空氣的導 入及排出亦可。例如，於斷熱構造體1 〇2之下部貫通有供 給管之同時，於斷熱構造體1〇2之上部貫通有排出管，於 -41 - 201139303 供給管或排出管連接有風扇即可。此情況，開口於斷熱構 造體1 02內之空間的供給管及排出管之端部則成爲各構成 導入口及排出口。然而，空氣的導入方法係除此之外，亦 有例如’將加壓氣體，藉由過濾器而減壓導入等之方法。 然而’空氣的導入方法係未限定於上述，而亦可採取其他 的空氣導入方法。 另外’通過導入口 127或閘門125而導入至斷熱構造體 1 02內之氣體係未必必須爲空氣，亦可爲非活性氣體。作 爲非活性氣體係從防止成形裝置101或斷熱構造體102之腐 蝕的觀點，特別使用氮爲佳。 在圖5〜8所示之實施形態中，由將氣體導入至斷熱構 造體102內，沿著熔融玻璃1〇3或玻璃帶104之流動方向而 流動氣體’可使在斷熱構造體102內之加以氣化之揮發成 分的濃度降低。未流動氣體之情況，在斷熱構造體102內 ，揮發成分因成爲飽和狀態之故，更無法促進揮發成分之 揮發。即，導入於斷熱構造體102內之氣體係爲了降低在 斷熱構造體102內之加以氣化之揮發成分的濃度而發揮機 能。隨之，從外部所導入之氣體的流動係不只限定於上升 ，而亦可爲下降。 另外，作爲促進熔融玻璃103或玻璃帶104之揮發成分 之揮發的另外方法，亦可將斷熱構造體102內之成形空間 內做成減壓環境。如將斷熱構造體1 02內之成形空間進行 減壓，促進揮發成分之揮發。 例如，由設置吸引裝置於圖5所示之排出口 126者，可 -42 - 201139303 將斷熱構造體102內進行減壓。然而，設置於斷熱構造體 1 〇 2之排出口 1 2 6或所設置之吸引裝置之數量係無特別加以 限定，而如設置1以上即可。 然而，當將斷熱構造體1〇2內之成形空間過於減壓時 ，從閘門125，導入較斷熱構造體1〇2內爲低溫度之氣體’ 玻璃帶1 04則未加以均一，對於玻璃板1 〇之厚度產生不均 ，亦更發生有偏差。 因此，斷熱構造體1〇2內之成形空間，比較於減壓前 之斷熱構造體102內，減壓在10分之1以下的範圍爲佳。也 就是，對於斷熱構造體102內之成形空間的氣壓爲1氣壓之 情況，將壓力的上限作爲0.9氣壓而減壓爲佳。 如此作爲，經由調整斷熱構造體1 02內之成形空間的 環境之時，形成玻璃帶104。 更且，作爲促進熔融玻璃103或玻璃帶104之揮發成分 之揮發的另外方法，亦可將斷熱構造體102內之成形空間 的環境溫度提昇。如斷熱構造體1 02內之成形空間的環境 溫度上升，揮發成分之飽和蒸氣氣壓亦上升之故，促進揮 發成分之揮發。 然而，斷熱構造體1 02內之成形空間的環境溫度過於 上升時’玻璃帶104之成形變爲困難，更且能量消耗量則 增加。因此，上升之斷熱構造體102內之成形空間的環境 溫度的上升範圍係超過0〜loot爲佳，而超過〇〜50 t爲更 佳’而超過0 ~ 1 0 °c爲更佳。 如此作爲而調整斷熱構造體102內之成形空間的環境 -43- 201139303 ，增加面對於斷熱構造體1 02內之熔融玻璃1 03或玻璃帶 104之表面的環境之揮發成分的分壓與揮發成分之飽和蒸 氣壓的差。由此，促進揮發成分的揮發同時，形成玻璃帶 104。從如此之熔融的玻璃及玻璃帶表面促進揮發成分的 揮發之方法，係除了熔融之玻璃及玻璃帶之兩表面之外， 只對於一方之表面亦可適用。 更且，作爲增加熔融玻璃103或玻璃帶104之揮發成分 的揮發量之方法，可加長從在成形工程之成形裝置101的 Q 下端部至閘門1 25之上端部的距離。經由加長此距離之時 ，玻璃帶1 04則可加長通過成形空間內之通過時間。其結 果，在斷熱構造體102內之空間，玻璃帶104曝露於高溫的 時間變長，揮發時間增加。因此，玻璃帶1 04之揮發成分 的揮發量則增加。 當將上述距離作爲過長時，所成形之玻璃帶1 04的厚 度則產生變化。因此，上述距離之增加分係超過〇〜2 0mm ，超過0〜l〇mm，超過〇~5mm，超過0〜1mm，超過0〜0.1mm () 更佳。 另外，加大成形體裝置101本身的尺寸，加長流動有 熔融玻璃103之壁面11 2之流動長度亦可。由此，在斷熱構 造體102內之空間，熔融玻璃103曝露於高溫的時間變長， 揮發時間增加。因此，熔融玻璃1 03之揮發成分的揮發量 則增加。 將從通過斷熱構造體102內之熔融玻璃促進揮發成分 之揮發或爲了增加揮發量之方法，做過種種說明，但此等 -44- 201139303 方法係可以單獨或組合而使用。 由如此作爲所製造之玻璃板1 〇係因可將壓縮應力層1 4 薄化形成於玻璃表面之故，可保持玻璃板之加工性同時， 可防止傷痕附著於玻璃表面。 特別係將玻璃板1 〇使用於液晶顯示裝置用玻璃基板等 之FDP玻璃基板之情況，無法多含有離子交換成分之鹼金 屬離子。因此，玻璃板1 〇係在未進行離子交換而得到壓縮 應力層14的點爲有效。更且，因得到較在緩冷工程中由急 冷玻璃所得到之以往的玻璃板之壓縮應力層爲薄，且應力 値（絕對値）爲大之壓縮應力層14之故，玻璃板10係可作 爲形狀加工前之薄的玻璃板而有效使用。 以往的玻璃板係在工程間的搬送中或切斷或形狀加工 中，有著於表面附著傷痕情況。但玻璃板1 〇係可防止於進 行化學強化之前，附著傷痕於玻璃表面之故，可防止玻璃 蓋表面的傷痕，進而可使表面品質提昇。 (實施例） 圖9係顯示對於硼矽酸鋁玻璃之玻璃板1 〇而言進行實 測之s i的原子濃度（％ )之分布圖。S i的原子濃度（％ ) 係使用X線光電子分光裝置（UL VAC-PHI公司製Quant era SXM )，測定表面附近之Si原子濃度。具體而言’經由濺 鍍法而將玻璃板的表面挖深至各種深度，測定在各深度之 原子濃度。作爲測定元素，與S i同時’指定含有率相對高 之揮發成分之A丨，B，Ca，Sr’ Ba’求取佔於測定元素中 -45- 201139303 之S i的比率，此等成分係在玻璃帶之成形工程中，從玻璃 帶之表面揮發的揮發成分。然而，在揮發成分之中，κ及 Sn的含有率爲小，此等的量對於Si原子濃度帶來的影響係 認爲少之故，此等未含於測定元素。圖9所示之玻璃板A ，玻璃板B係使用圖5所示之裝置，改變流動之空氣的條件 所製作之玻璃板。 如圖9所示，在玻璃板A，玻璃板B中，均比較於玻璃 中心位置’ S i原子濃度爲5 %以上之高範圍則從玻璃表面沿 著厚度方向，形成於較0爲大30nm以下之深度範圍。此係 在玻璃板A，玻璃板B中，認爲根據在玻璃表面附近，揮 發成分的量比較於內部爲少者。 然而’上述玻璃板A及玻璃板B之各成文之含有率（ 質量％ )係如下。Ti02 is a component that lowers the high temperature viscosity of glass. In addition, 1^02 is a component that enhances ion exchange performance. However, when the content of Ti02 is too high, the resistance to devitrification decreases. Further, the glass is colored, and it is not preferable for the FPD glass substrate or the glass cover of the electronic device to display the surface. Further, in the case of coloring from glass, the ultraviolet transmittance is lowered, and the treatment with the ultraviolet curable resin causes a problem that the ultraviolet curable resin cannot be sufficiently cured. In the glass of the glass plate, a clearing agent can be added as a component for defoaming bubbles in the glass. The clearing agent is not particularly limited as long as it has a small environmental load and is excellent in the clarity of the glass, and examples thereof include metals selected from the group consisting of tin oxide, iron oxide, cerium oxide, cerium oxide, molybdenum oxide and tungsten oxide. At least one of oxides. However, As2〇3 and Sb203 are substances which have a effect of clarifying the valence fluctuation in the molten glass, and have the effect of clearing the glass. However, when As203 and Sb203 are substances having a large environmental load, the glass plate of the present embodiment is used. In 10, in the glass, substantially no As203 and Sb203 were contained. However, in the present specification, the fact that As203 and Sb203 are not substantially contained means that the mass is not enough, and the mass is not intentionally contained except for impurities. (Manufacturing Method of Glass Plate) Such a glass plate 1 is manufactured by a down-draw method. Fig. 3 is a view showing an example of the flow of a method for producing a glass sheet according to the embodiment of the present invention. The manufacturing method of the glass plate mainly has a melting process (step S10)' and a clearing process (step S20), and a stirring process (step S30), and a forming process (step S40), and a slow cooling process (step S50)' and a paneling process. (Step S60), and shape processing engineering (Step S70), and chemical strengthening treatment engineering (Step S80). In the melting process (step S10), the glass raw material is heated by indirect heating by combustion of fossil fuel and direct heating by electrical conduction in a melting furnace (not shown) to produce molten glass. The melting of the glass can also be carried out by other methods. Next, a clearing process is performed (step S20). In the clearing process, the bubbles in the molten glass are removed by the above-described clearing agent in a state where the molten glass is stored in a liquid tank (not shown). Specifically, it is carried out by an oxidation-reduction reaction of a metal oxide having a valence in the molten glass. In the molten glass at a high temperature, the metal oxide releases oxygen through a reductive reaction, and this oxygen becomes a gas, and the bubbles in the molten glass grow and float on the liquid surface. Thereby, the bubbles in the molten glass are defoamed. Alternatively, the bubble of oxygen grows into the gas in the other bubbles in the molten glass and floats on the liquid surface of the molten glass. Thereby, the bubbles in the molten glass are defoamed. Further, after the defoaming, when the temperature of the glass is lowered, the metal oxide initiates an oxidation reaction, and does not float up the oxygen remaining in the vesicles remaining in the glass. Oxygen is absorbed, and the small bubble system is changed little and absorbed in the glass. Next, a stirring process is performed (step S30). In the stirring process, in order to maintain the chemical and thermal uniformity of the glass, molten glass is passed through the stirring tank which is oriented vertically -31 - 201139303. The molten glass is stirred while passing through the agitator provided in the agitation tank, and moved to the bottom in the vertical direction, and then guided to the subsequent work. Thereby, the unevenness of the glass such as the pulse can be suppressed. Next, a forming process is performed (step S40). In the forming process, a pull-down method is used. There is a well-known method using a lower pull-down method, such as an overflow pull-down or a slit pull-down method, using a device shown in, for example, Japanese Patent Laid-Open No. Hei. No. Hei. This will be described later in the forming engineering department of the pull-down method. Thereby, a glass ribbon having a specific thickness and a width is formed. As the forming method, among the down-draw methods, the overflow down-draw method is preferable, but the slit down method can also be used. However, it is preferable to increase the stress 値 (absolute 値) of the compressive stress layer 14 by promoting the volatilization of the volatile component or increasing the amount of volatilization, and it is preferable to use an overflow down-draw method in which the amount of volatilization is large. Next, a slow cooling process is performed (step S50). Specifically, the glass ribbon formed into a sheet shape is controlled to have a cooling rate without variation, and is cooled to a temperature below the slow cooling point by a slow cooling furnace (not shown). Thereby, the glass ribbon system has the compressive stress layer 14 and the tensile stress layer 12 at the point of stress similarly to the glass plate 1 of the final product, and has a Si-rich layer at the point of composition. Next, a paneling process is performed (step S60). Specifically, the glass ribbon produced by the continuity is cut into a predetermined length to obtain a glass plate. Thereafter, a shape processing project is performed (step S70). In the shape processing project, in addition to cutting out the size or shape of a specific glass plate, boring and honing of the glass surface and the end surface are performed. The shape processing system is sandblasted, and a physical means such as a cutter or a laser may be used, and a chemical means such as etching may be used. However, when the glass sheet is formed into a complicated shape of -32 to 201139303, it is preferable to carry out the above-described uranium engraving treatment before the chemical strengthening treatment. An example of the shape processing of the glass plate 1 is an etching process in which the glass plate 10 is opened as shown in Fig. 4 and processed into an outer shape including a curved line and a straight line. The glass plate 10 processed into such an outer shape is a glass cover used for a display screen of an electronic device. In this case, first, a photoresist material is coated on both main surfaces of the glass plate. Next, the photoresist material is exposed by a photomask having a desired outer shape pattern. The outer shape is not particularly limited, and includes, for example, a shape having a negative curvature (a portion that is curved toward the right side when advancing toward the left side and the outer shape while advancing toward the left side along the end of the outer shape) shape. Next, the exposed photoresist material is developed to form a photoresist pattern in a range outside the etched range of the glass plate, and the etched range of the glass plate is etched. At this time, in the case where a wet etching liquid is used as an etchant, the glass plate is isotropically etched. As a result, the center portion of the end surface of the glass sheet protrudes most outward, and an inclined surface that is gently curved is formed from the center portion toward the both main surface sides. However, the boundary between the inclined surface and the main surface and the boundary between the inclined surfaces are preferably as a rounded shape. The photoresist material used in the etching process is not particularly limited, but a material which is resistant to an etchant used for etching a glass using a photoresist pattern as a mask can be applied. For example, the glass system is generally etched by wet etching using an aqueous solution containing hydrofluoric acid or dry etching of a fluorine-based gas, and is preferably optimized for a photoresist material excellent in hydrofluoric acid resistance. Further, as the etchant, a mixed acid containing at least one of hydrofluoric acid, sulfuric acid, nitric acid-33-201139303, hydrochloric acid, and hexafluoroantimonic acid can be used. When a hydrofluoric acid or the above mixed acid aqueous solution is used as an etchant, a glass cover having a desired shape can be obtained. Further, when the shape is processed by etching, it is also possible to easily realize a complicated outer shape by merely adjusting the mask pattern. Further, if the shape is processed by etching, the productivity can be further improved, and the processing cost can be reduced. However, as the stripping liquid for peeling the photoresist material from the glass sheet, an alkali solution such as hydrazine or NaOH can be used. The types of the above-mentioned photoresist, etchant, and stripper may be appropriately selected in accordance with the material of the glass plate. However, as a method of etching, not only a method of immersing in an etching liquid but also a spray etching method using a spray etching liquid or the like can be used. A glass cover having a surface having a high surface smoothness can be obtained by processing a glass sheet by such etching. That is, it is possible to prevent the occurrence of fine cracks which are necessarily generated when the shape is processed by machining, and to improve the mechanical strength of the glass cover. Finally, a chemical strengthening treatment by ion exchange is performed (step S80). However, the chemical strengthening treatment is not carried out depending on the case, for example, the glass plate of the borosilicate glass or the like used for the flat panel display is not subjected to chemical strengthening treatment. On the other hand, a glass plate of a glass cover suitable for use in an image display of an electronic device such as an alkali metal silicate glass is subjected to a chemical strengthening treatment. The chemical strengthening of the glass sheet 10 in which the Si-rich layer or the compressive stress layer 14 is formed in the vicinity of the glass surface can further enhance the strength of the glass sheet 1 . In addition, the stress 値 (absolute 値) of the tensile stress layer of the glass sheet of the present embodiment is less likely to be larger than the conventional glass sheet in which the compressive stress layer is formed on the surface by the quenched glass. However, it is preferred that Na20 or Li20 containing an ion exchange component in the glass component for ion exchange. The chemically strengthened tempered glass of the present embodiment is applicable to a casing that carries a terminal device, a glass cover for a solar cell, a glass substrate for a display, and a glass for a touch panel display, in addition to a glass cover of a display screen of an electronic device. Cover, glass substrate of touch panel display, etc. For example, the chemical strengthening treatment can be carried out by a method as follows. In the chemical strengthening treatment, the glass plate is immersed for about 1 to 25 hours, for example, KN03 1 which is maintained at a temperature of 350 to 550 °C. 00% in the treatment bath. At this time, the Na + ions or Li + ions in the surface layer of the glass are ion-exchanged into K + ions or Li + ions in the treatment bath to chemically strengthen the glass plate. However, the temperature, time, ion exchange solution, etc. during the ion exchange treatment can be suitably changed. For example, the ion exchange solution may be a mixed solution of two or more types. In addition to the manufacturing method of the glass plate, there are cleaning processes and inspection procedures, but the description of these processes is omitted. However, the shape processing engineering is performed before the chemical strengthening treatment project, or after the chemical strengthening treatment engineering. In the molding process for manufacturing the glass sheet 10 of the present embodiment, the Si-35-201139303 layer is formed by volatilization of the volatile component from the glass ribbon, or the amount of volatilization is increased, which is caused by the Si-rich layer. After cooling, the compressive stress layer 14 and the tensile stress layer 12 are formed before the paneling process. Volatile component means a component which is more volatile than 5102, in other words, it is shown in molten glass (for example, the viscosity of glass is 1045~105poise, or the temperature is 1100~1300 °c), and the saturated vapor pressure is higher than that of si〇2. . Examples of the volatile component include ai2o3, B2O3' L12O > Na2〇 · K2O 'MgO > CaO > SrO > BaO » Zr〇2 , Sn02 and the like, but are not limited thereto. However, B203, an alkali oxide (L12O*Na2〇 > K2O), and a soil-like metal oxide (MgO, CaO, SrO, BaO) have high volatility, and it is preferable to contain at least one kind as a glass component. Sn02 is volatilized as SnO. When the volatilization is excessive, the glass sheet cannot be formed properly. For example, the upper limit of the content of B2〇3 is preferably 14% by mass, and particularly preferably 13% by mass. In addition, when the content of Sn02 is high, there is devitrification of the glass. Accordingly, from the viewpoint of preventing devitrification of the glass, the upper limit of the content of Sn02 is preferably 5% by mass, and particularly preferably 0.3% by mass. Further, when a large amount of κ20 is used as a melting accelerator for glass, it is melted from the glass plate. Therefore, in the case of a flat panel display glass substrate used for a glass substrate for a liquid crystal display device or the like, the upper limit of the content ratio of κ20 is preferably 0.5% by mass. These volatile components are in molten glass, and the saturated vapor pressure is higher than that of SiO 2 , and is volatilized from the molten glass or the glass ribbon at the time of molding (the state in which the glass is melted). That is, in the molding process of forming a glass ribbon from molten glass, the components other than SiO 2 are volatilized on the surface of the glass ribbon, and as a result, the concentration of Si atoms formed on the surface of the glass after molding is smaller than the concentration of Si atoms in the interior of the glass. High-rich Si layer. Further, when the Si layer is formed on the glass surface of the glass sheet from -36 to 201139303, the compressive stress layer 14 is formed on the surface of the glass via the difference in thermal expansion rate from the inside of the glass. (Molding Apparatus) Fig. 5 is a view showing an example of a molding apparatus which performs a molding method by a down-draw method. The molding apparatus 101 is formed in a cross-sectional shape of a pentagonal wedge shape (a narrow width and a baseball home plate shape) in a downward direction. The forming apparatus 101 has a groove 1 1 provided on a straight line extending therethrough, a groove 1 设置 provided on the upper surface, and a wall surface 112 facing from the opposite end portions to the lower side. However, in the present specification, for the convenience of explanation, the extending direction of the groove 1 in the horizontal plane (the vertical direction of the paper in FIG. 5) is referred to as the X direction, and the direction perpendicularly intersecting the X direction in the horizontal plane is referred to as the Y direction. The vertical direction is referred to as the z direction (refer to FIG. 6). The groove 1 11 is such that the molten glass 103 supplied to the one end from the supply pipe (not shown) overflows uniformly over the entire length, and gradually becomes shallower as it goes from one end toward the other end. Each of the pair of wall faces 112 has a vertical surface that hangs vertically from the end portion in the Y direction of the upper surface, and an inclined surface that is inclined toward the inner direction from the lower end portion of the vertical surface. The lower end portions of the inclined faces are alternately formed with each other to form a ridge line extending in the X direction. The molding apparatus 101 is continuously formed by causing the molten glass 103 to overflow from both sides of the groove 1 1 1 and inducing the molten glass which overflows on the wall surface 112 to merge with each other at the lower end portion of the inclined surface. Ribbon glass belt 104. The heat-dissipating structure 102 forms a molding space (-37-201139303 processing chamber) in which the forming apparatus 101 is housed. Specifically, the heat-dissipating structure 102 is made of a material excellent in heat-breaking property, and has a bottom wall 1 2 1 and a zenith wall 1 2 3 which are opposed to each other in the vertical direction, and the bottom wall is joined to the bottom wall. 1 2 1 is a rectangular cylindrical peripheral wall 122 that is adjacent to the periphery of the zenith wall 123. For the center of the bottom wall 121, a shutter 125 through the glass ribbon 104 formed through the forming device 1 〇 1 is provided. However, the heat-dissipating structure 102 may be a hollow structure for supplying air for heating or cooling to the inside. In the present embodiment, as shown in Fig. 5, the wall surface 112 of the molding apparatus 1A1 faces the Y direction, and a plurality of discharge ports 126 penetrating the peripheral wall 122 are provided in the upper portion of the long wall portion of the peripheral wall 122. Further, a plurality of lead-in ports 1 2 7 penetrating the peripheral wall 122 are provided in the Y direction of the peripheral wall 122 at a lower portion of the long wall portion. Therefore, the flow of air as indicated by arrows a, b, c in Fig. 5 is formed via natural convection. In other words, the air introduced outside the heat-dissipating structure 102 is introduced into the heat-dissipating structure 102 through the introduction port 127. The air introduced is raised along the molten glass 103 flowing down the wall surface 112 of the molding apparatus 101, and then, The discharge port 126 is discharged to the outside of the heat-dissipating structure 102. In this way, when the fresh air introduced from the outside is raised in the heat-dissipating structure 102, the volatile components from the molten glass 103 (for example, A12 〇3, B 2 〇 3, L i 2 Ο, can be promoted, Volatilization of N a 2 Ο, K 2 〇, M g 0, C a Ο, S r 0, BaO, Zr02, Sn02, etc.). The portion where the volatile component is volatilized, i.e., the surface of the molten glass 103 that is in contact with the rising air, forms a Si-rich layer when the glass ribbon 104 is cooled, and the compressive stress layer 14 is formed by the formation of the Si-rich layer. In order to increase the stress 値 (absolute 値) of the compressive stress layer 14, the molten glass 1 〇 3 contains a large amount of volatile components - 38-201139303. However, the discharge port 126 and the inlet port 127 may also face the X direction of the peripheral wall 122. It can also be placed in the short wall. Alternatively, the discharge port 126 and the introduction port 127 may be provided only in the short wall portion in the X direction of the peripheral wall 122. However, it is preferable that the discharge port 126 and the introduction port 127 are oriented in the Y direction of the peripheral wall 122 in the entire width of the molten glass 1 〇 3, and are disposed at a constant pitch only in the long wall portion. Further, the shape and the number of the discharge port 126 and the introduction port 127 can be appropriately selected as long as the peripheral wall 1 22 maintains the necessary strength. For example, the shape of the discharge port 1 2 6 and the introduction port 1 27 can be reduced as a circular shape as shown in Fig. 6 as a slit extending in the X direction. However, in order to uniformly discharge the gas from the heat-dissipating structure 102 in a uniform manner, it is more effective to use a slit extending over the entire width direction of the glass ribbon. However, as the opening area of the slit is increased, the gas flow rate is increased, the surface defects of the glass sheet are increased, or the unevenness of the glass surface is deteriorated, and the formation temperature is difficult to be secured. However, the problem is as follows, the temperature of the air or the inert gas introduced into the heat-dissipating structure 1〇2 from the inlet 127 is taken as the target temperature in the heat-dissipating structure 102, and the heat-dissipating structure 1 is The pressure in 02 can be solved by adjusting the flow rate of the gas while maintaining a specific pressure. Further, it is preferable that the air introduced into the heat-dissipating structure 102 through the introduction port 12, for example, the temperature at which the temperature of the molten glass 1 〇 3 or the glass ribbon 104 is not lowered is preferable. Here, the amount of air introduced is such a small amount that the temperature of the molten glass 1 〇 3 or the glass ribbon 1 〇 4 is not lowered even if air of normal temperature is introduced. Therefore, it is also possible to introduce air at normal temperature. On the other hand, when the air in the heat-dissipating structure 102 is introduced as a large amount, the temperature of the molten glass 103 or the glass ribbon 104 is greatly lowered when air of normal temperature is introduced. In this case, it is preferable that the air introduced through the inlet port 127 is heated to a heating device (not shown) having a specific temperature, and is provided outside or inside the heat-dissipating structure 1 〇2. In the molding apparatus 100 described above, from the both sides of the groove 1 1 1 of the forming apparatus 10 1 surrounded by the heat-dissipating structure 102, the molten glass 103 overflows on the other hand, along the other side. The molten glass 103 on the wall surface 112 of the molding apparatus 101 flows down and the air rises, and is discharged to the outside of the heat-dissipating structure 102. Here, the air is introduced into the heat-dissipating structure 102 from the outside of the heat-dissipating structure 102. As a result, the air in the heat-dissipating structure 102 is caused to volatilize from the volatile component of the molten glass 103 by flowing along the molten glass flowing down the wall surface 112 of the molding apparatus 101. Thereby, a glass plate 1 of a compressive stress layer 14 having a high stress is formed on both sides of the glass back of the glass plate 10. However, in the present embodiment, the discharge port 1 26 is provided on the upper portion of the peripheral wall 122, but the position of the discharge port 126 is not particularly limited. For example, as shown in Fig. 7, the discharge port 1 2 6 may be disposed at a portion directly above the forming device 1 〇 1 of the zenith wall 1 2 3 . Even in this case, the air introduced into the heat-dissipating structure 102 from the outside of the heat-dissipating structure 102 can be raised along the molten glass 1〇3 flowing down the wall surface 112 of the forming apparatus 1〇1 via natural convection. It is discharged through the discharge port 12 6 outside the heat-dissipating structure 1〇2. Further, in this case, in the upper portion of the forming apparatus 101, the molten glass 103 is also in contact with the air passing through the heat-dissipating structure 102, and the discharge port 126 is placed on the upper side of the peripheral wall 1 22 instead of the -40-201139303. The volatilization of the volatile component further promotes the enthalpy, but in the case where the discharge port 1 2 6 is placed on the zenith wall 1 2 3, the drop of the dust or the like from the heat-dissipating structure 102 passes through the discharge port 1 2 6 Dropped in the case of molten glass 1 〇3. From this point of view, as shown in Fig. 5'', the discharge port 26 is preferably provided above the peripheral wall 122. Further, in the embodiment shown in Figs. 5 and 6, the introduction port 127 is provided at the lower portion of the peripheral wall 1 2 2, but the position of the introduction port 1 27 is not particularly limited. For example, as shown in Fig. 8, the inlet port 1 2 7 may be disposed on the bottom wall 1 2 1 . In this case, when the inlet port 127 is located in the range R immediately below the forming apparatus 1 〇 1, the flow of air from the inlet port 127 has an effect on the shape stability of the glass ribbon 104. Therefore, it is preferable that the inlet port 127 is disposed outside the range R. Further, as shown in Fig. 7, the inlet port 1 27 may not be provided. Even in this case, the air outside the heat-insulating structure 102 is introduced into the heat-dissipating structure 102 through the gates 25. However, in this case, it is preferable that the gate 125 faces the direction opposite to the glass ribbon 104 and the air passes therethrough, and the shape of the glass ribbon 1〇4 is deteriorated, and the inlet port 127 different from the gate 125 is preferably provided. Further, in the embodiment shown in FIGS. 5 to 8, the introduction of the air in the heat-insulating structure 102 and the discharge of the air outside the heat-dissipating structure 102 are performed by natural convection, but the convection is performed by forced convection. Air can also be introduced and discharged. For example, a supply pipe is penetrated through the lower portion of the heat-dissipating structure 1 〇2, and a discharge pipe is inserted through the upper portion of the heat-dissipating structure 1〇2, and a fan is connected to the supply pipe or the discharge pipe at -41 - 201139303. In this case, the supply pipe and the end portion of the discharge pipe which are opened in the space in the heat-dissipating structure 102 become the respective guide inlets and discharge ports. However, in addition to the air introduction method, for example, a method of introducing a pressurized gas into a reduced pressure by a filter or the like may be employed. However, the method of introducing the air is not limited to the above, and other air introduction methods may be employed. Further, the gas system introduced into the heat-dissipating structure 102 through the inlet port 127 or the gate 125 is not necessarily required to be air, and may be an inert gas. From the viewpoint of preventing corrosion of the forming device 101 or the heat-insulating structure 102 as the inert gas system, it is preferable to use nitrogen in particular. In the embodiment shown in FIGS. 5 to 8, the gas is introduced into the heat-dissipating structure 102, and the gas flows along the flow direction of the molten glass 1〇3 or the glass ribbon 104, so that the heat-dissipating structure 102 can be formed. The concentration of the volatile component that is vaporized therein is lowered. In the case of a non-flowing gas, in the heat-dissipating structure 102, since the volatile component is saturated, the volatilization of the volatile component is not promoted. In other words, the gas system introduced into the heat-dissipating structure 102 functions to reduce the concentration of the volatile component that is vaporized in the heat-dissipating structure 102. Accordingly, the flow of the gas introduced from the outside is not limited to the rise, but may be decreased. Further, as another method of promoting volatilization of the volatile component of the molten glass 103 or the glass ribbon 104, the molding space in the heat-dissipating structure 102 may be made into a reduced pressure environment. When the molding space in the heat-dissipating structure 102 is decompressed, volatilization of the volatile component is promoted. For example, by providing the suction means 126 at the discharge port 126 shown in Fig. 5, the inside of the heat-dissipating structure 102 can be decompressed at -42 - 201139303. However, the number of the suction means provided at the discharge port 1 2 6 of the heat-dissipating structure 1 〇 2 or the number of suction means provided is not particularly limited, and may be set to 1 or more. However, when the molding space in the heat-dissipating structure 1〇2 is excessively decompressed, the gas which is a low temperature in the heat-dissipating structure 1〇2 is introduced from the gate 125, and the glass ribbon 104 is not uniform. The thickness of the glass plate 1 is uneven, and there is a deviation. Therefore, the molding space in the heat-dissipating structure 1〇2 is preferably in the range of 1/10 or less in the heat-dissipating structure 102 before the pressure reduction. That is, in the case where the gas pressure in the molding space in the heat-dissipating structure 102 is 1 atmosphere, it is preferable to set the upper limit of the pressure to 0.9 atm. In this manner, the glass ribbon 104 is formed by adjusting the environment of the molding space in the heat-dissipating structure 102. Further, as another method of promoting volatilization of the volatile component of the molten glass 103 or the glass ribbon 104, the ambient temperature of the molding space in the heat-dissipating structure 102 can be increased. When the ambient temperature of the molding space in the heat-insulating structure 102 increases, the saturated vapor pressure of the volatile component also rises, thereby promoting the volatilization of the volatile component. However, when the ambient temperature of the forming space in the heat-insulating structure 102 is excessively increased, the formation of the glass ribbon 104 becomes difficult, and the amount of energy consumption increases. Therefore, the rising range of the ambient temperature of the forming space in the rising heat-dissipating structure 102 is preferably more than 0 toloot, and more preferably 〇~50 t is more than more than 0 to 10 °c. In this way, the environment of the molding space in the heat-dissipating structure 102 is adjusted - 43-201139303, and the partial pressure of the volatile component of the environment of the surface of the molten glass 103 or the glass ribbon 104 in the heat-dissipating structure 102 is increased. The difference in saturated vapor pressure of the volatile component. Thereby, the volatilization of the volatile component is promoted, and the glass ribbon 104 is formed. The method of promoting volatilization of volatile components from the surface of such molten glass and glass ribbon is applicable to only one surface except for the surfaces of the molten glass and the glass ribbon. Further, as a method of increasing the amount of volatilization of the volatile component of the molten glass 103 or the glass ribbon 104, the distance from the lower end portion Q of the molding apparatus 101 of the forming process to the upper end portion of the shutter 135 can be lengthened. By lengthening this distance, the glass ribbon 104 can lengthen the passage time through the forming space. As a result, in the space inside the heat-insulating structure 102, the time during which the glass ribbon 104 is exposed to a high temperature becomes long, and the evaporation time increases. Therefore, the amount of volatilization of the volatile component of the glass ribbon 104 is increased. When the above distance is made too long, the thickness of the formed glass ribbon 104 changes. Therefore, the increase in the above distance is more than 〇~20 mm, more than 0~l〇mm, more than 〇~5mm, more than 0~1mm, more than 0~0.1mm (). Further, the size of the molded body apparatus 101 itself may be increased, and the flow length of the wall surface 11 2 on which the molten glass 103 flows may be lengthened. Thereby, in the space inside the heat-dissipating structure 102, the time during which the molten glass 103 is exposed to a high temperature becomes long, and the volatilization time increases. Therefore, the amount of volatilization of the volatile component of the molten glass 103 is increased. Various methods for promoting the volatilization of the volatile component or the method of increasing the amount of volatilization from the molten glass passing through the heat-dissipating structure 102 have been described, but the methods of -44-201139303 can be used singly or in combination. Since the glass sheet 1 thus produced can be formed by thinning the compressive stress layer 14 on the glass surface, the workability of the glass sheet can be maintained, and the flaw can be prevented from adhering to the glass surface. In particular, when the glass plate 1 is used for an FDP glass substrate such as a glass substrate for a liquid crystal display device, it is not possible to contain an alkali metal ion of an ion exchange component. Therefore, it is effective that the glass plate 1 is a point at which the compressive stress layer 14 is obtained without ion exchange. Further, since the compressive stress layer of the conventional glass sheet obtained from the quenched glass in the slow cooling process is thin and the stress 値 (absolute 値) is the large compressive stress layer 14, the glass sheet 10 can be obtained. It is effectively used as a thin glass plate before shape processing. Conventional glass sheets have scratches on the surface during transportation or cutting or shape processing between projects. However, the glass plate 1 can prevent the surface from being scratched on the surface of the glass before chemical strengthening, thereby preventing the surface of the glass cover from being damaged, thereby improving the surface quality. (Example) Fig. 9 is a graph showing the atomic concentration (%) of s i measured for a glass plate 1 〇 of aluminoborosilicate glass. Atomic concentration (%) of S i The concentration of Si atoms in the vicinity of the surface was measured using an X-ray photoelectron spectroscope (Quantera SXM manufactured by UL VAC-PHI Co., Ltd.). Specifically, the surface of the glass plate was dug to various depths by sputtering, and the atomic concentration at each depth was measured. As a measurement element, A丨, B, Ca, and Sr' Ba' of the volatile component having a relatively high content rate are simultaneously specified with S i , and the ratio of S i of -45 to 201139303 in the measurement element is determined. In the forming process of the glass ribbon, volatile components volatilized from the surface of the glass ribbon. However, among the volatile components, the content of κ and Sn is small, and the influence of these amounts on the concentration of Si atoms is considered to be small, and these are not included in the measurement elements. The glass plate A and the glass plate B shown in Fig. 9 are glass plates produced by changing the conditions of the flowing air using the apparatus shown in Fig. 5. As shown in FIG. 9, in the glass plate A and the glass plate B, the high range of the S i atomic concentration of the glass center position is 5% or more from the glass surface along the thickness direction, and is formed at 30 nm larger than 0. The following depth range. In the glass plate A and the glass plate B, it is considered that the amount of the volatile component is smaller than the inside in the vicinity of the glass surface. However, the content ratio (% by mass) of each of the above-mentioned glass plate A and glass plate B is as follows.

Si02 6 0.9 % A 1 2 〇 3 1 6.9 % B 2 0 3 1 1.6 % M g 0 1 . 7 % CaO 5 . 1 % SrO 2.6 % BaO 0.7 % K2〇 0.2 5 % Sn02 0.1 3 % 圖1〇係顯示對於上述玻璃板A之玻璃板10而言進行實 測之內部應力之分布圖。內部應力係使用微小面積雙重折 -46- 201139303 射計（王子計測機器公司製 KOBRA-CCD/X )，對於將玻 璃板10朝厚度方向切斷的剖面，從表面於各特定之深度， 測定每1 cm之光路差率（光路差/光路長度），以光彈性定 數除以此而算出。然而，「內部應力」係顯示沿著玻璃板 之厚度方向之〇~1 Ομηι之厚度平均値。因此，一有局部性 形成有呈超過圖1 〇所示之結果的應力値之情況。 如圖1 0所示，了解到對於玻璃板1 〇之表背兩面，係形 成有壓縮應力層14，形成有於其內部具有略一定之拉伸應 力値之拉伸應力層1 4。另外，亦了解到，形成於玻璃板內 部之拉伸應力層1 4之應力値則於玻璃板厚度方向，以略一 定加以形成。此係在玻璃板1 〇之玻璃表背兩面附近，因揮 發成分變少引起之構成。 更且，取出複數片使用圖5所示之裝置而製作之玻璃 板1 〇，作爲實施例1〜5。更且，經由表面硏磨以與實施例1 同樣方法而製作之玻璃板的壓縮應力層14而除去之時，將 壓縮·拉伸應力曲線圖形狀與實施例1 ~5不同之玻璃板作 爲比較例1。玻璃板之製造時，將硼矽酸鋁玻璃之玻璃的 原料，使用具備耐火煉瓦製之熔解槽與白金製之邊框槽等 之連續溶解裝置，以1 5 8 0 °C進行熔解，以1 6 5 0 °C清澈，以 1500 °C攪拌之後，經由使用圖5所示之裝置的下拉法而成 形厚度0.7mm之薄板狀的玻璃板。將關於實施例^及比 較例1之玻璃板的S i原子濃度的實測與內部應力的實測， 以與上述玻璃板A，B同樣方法而進行。 另外’以刮擦荷重2 N，刮擦長度3 0 m m之條件，於 -47- 201139303Si02 6 0.9 % A 1 2 〇3 1 6.9 % B 2 0 3 1 1.6 % M g 0 1 . 7 % CaO 5 . 1 % SrO 2.6 % BaO 0.7 % K2〇0.2 5 % Sn02 0.1 3 % Figure 1 The distribution of the internal stress measured actually for the glass plate 10 of the above-mentioned glass plate A is shown. The internal stress is measured by using a micro-area double-fold-46-201139303 ray meter (KOBRA-CCD/X manufactured by Oji Scientific Instruments Co., Ltd.), and the cross section of the glass plate 10 cut in the thickness direction is measured from the surface to each specific depth. The optical path difference of 1 cm (optical path difference/optical path length) is calculated by dividing the photoelastic constant. However, the "internal stress" indicates the thickness average 値 of 〇~1 Ομηι along the thickness direction of the glass sheet. Therefore, there is a case where the stress 値 which exceeds the result shown in Fig. 1 is formed locally. As shown in Fig. 10, it is understood that for the front and back sides of the glass sheet 1 , a compressive stress layer 14 is formed, and a tensile stress layer 14 having a slightly tensile stress 内部 is formed therein. Further, it is also understood that the stress 値 of the tensile stress layer 14 formed in the inner portion of the glass sheet is formed in a slight direction in the thickness direction of the glass sheet. This is caused by the fact that the waving component is reduced in the vicinity of both sides of the glass back of the glass plate. Further, a glass plate 1 manufactured by using the apparatus shown in Fig. 5 was taken out as a plurality of sheets, and Examples 1 to 5 were used. Further, when the surface was honed and removed by the compressive stress layer 14 of the glass plate produced in the same manner as in Example 1, the compression/tensile stress profile shape was compared with the glass plates different from Examples 1 to 5 as a comparison. example 1. In the manufacture of the glass plate, the raw material of the glass of the aluminum borosilicate glass is melted at 1580 ° C using a continuous dissolution apparatus such as a melting tank made of refractory silicon and a frame groove made of platinum. After clearing at 50 ° C and stirring at 1500 ° C, a thin plate-shaped glass plate having a thickness of 0.7 mm was formed by a down-draw method using the apparatus shown in Fig. 5 . The actual measurement of the Si atom concentration of the glass plates of Example 1 and Comparative Example 1 and the actual measurement of the internal stress were carried out in the same manner as in the above glass plates A and B. In addition, the condition of scraping the load 2 N and scraping the length of 3 m m is at -47- 201139303

Eriksen model 3 18 ( Eriksen公司製）刮擦硬度計之前端， 設置直徑0.7mm(B〇Sch規格）之晶球，刮擦傷痕於實施例 1〜5，比較例1的玻璃板。之後，對於實施例1 ~5，比較例1 的玻璃板，以雷射顯微鏡觀察玻璃表面，經由傷痕的龜裂 進展之玻璃板，評估不佳，龜裂未進展之玻璃板，評估良 好。 對於下述表1係顯示實測結果及評估結果。 表1 a施例1 實施例2 實施例3 實施例4 實施例5 比較例1 Si濃溶液層之 最深深度(臟） 10 8 9 7 9 - 在Si原子濃度峰 値(％)/中心位置之 S源子濃度(％) 117.70% 116.4% 116.8% 116.2% 117.3% - 壓縮應力層之 厚度WKpm) 50 40 45 30 47 - 壓縮應力層之 應力値之最大値 2.2 1.6 2.1 1.5 2 - 拉伸應力層之 應力値之最大値 0.11 0.11 0.16 0.12 0.13 - 拉伸中心範圍 之應力値的變動 0.08 0.06 0.1 0.05 0.07 - 傷痕評估 良好 良好 良好 良好 良好 不佳 由上述表1，實施例1~5係均形成厚度50μηι以下之壓 縮應力層1 4。因此，對於玻璃成形後之加工處理之效率， 不易帶來不良影響。另外，實施例1〜5係均以傷痕的評估 評估爲良好。由此，了解到玻璃板1 〇係對於玻璃成形後之 -48- 201139303 加工處理之效率，未帶來不良影響，強化玻璃表面爲不易 附著傷痕於玻璃表面的程度。 另外’在實施例1〜5之拉伸應力層1 2之「拉伸中心範 圍」之應力値的變動，即應力値（絕對値）之最大値與最 小値的差係均爲0 · 1 2 Μ P a以下。 更且，以下述的條件而化學強化下述表2所示之組成 的實施例6〜8與比較例2之玻璃板。比較例2係硏磨以與形 成於實施例6〜8同樣方法所製造之玻璃板表面之壓縮應力 層1 4的部分之後，進行化學強化所得到之強化玻璃。 實施例6〜8及比較例2的玻璃板係將如下述表2所示之 組成而調配之玻璃原料，使用具備耐火煉瓦製之熔解槽與 白金製之邊框槽等之連續熔解裝置，以1 520 °C進行熔解， 以1 5 5 0 °C清澈，以1 3 5 0 °C攪拌之後，經由使用圖5所示之 裝置的下拉法而成形厚度0.7mm之薄板狀的玻璃板，得到 化學強化用玻璃板。比較例2之玻璃板係與比較例1同樣， 表面硏磨玻璃板10之壓縮應力層14的部分而去除。 接著，於實施例6〜8及比較例2的玻璃板之玻璃表面， 經由上述之方法而刮擦傷痕。 於將洗淨的玻璃板保持於4 0 0 °C之ΚΝ Ο 3 1 0 0 %之處理浴 中，進行約2.5小時浸漬，使存在於玻璃表層之Na+離子， 離子交換爲處理浴中的K +離子，化學強化玻璃板。化學 強化後之玻璃板係於洗淨槽依序浸漬而加以洗淨，得到乾 燥之強化玻璃。 以雷射顯微鏡而觀察如此所得到之實施例6〜8及比較 -49- 201139303 例2之玻璃表面。此時，經由傷痕的龜裂進展之玻璃板， 評估不佳’龜裂未進展之玻璃板，評估良好。 胃於下述表2係顯示組成與評估結果。Eriksen model 3 18 (manufactured by Eriksen Co., Ltd.) scratched the front end of the durometer, and provided a crystal ball having a diameter of 0.7 mm (B〇Sch size) to scratch the glass sheets of Examples 1 to 5 and Comparative Example 1. Then, in the glass sheets of Comparative Examples 1 to 5, the glass surface of the glass plate of Comparative Example 1 was observed by a laser microscope, and the glass plate which had progressed through the crack of the flaw was evaluated, and the glass plate which was not cracked was evaluated, and the evaluation was good. Table 1 below shows the measured results and the evaluation results. Table 1 a Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 The deepest depth of the Si concentrated solution layer (dirty) 10 8 9 7 9 - at the peak concentration (%) / center position of the Si atom concentration S source concentration (%) 117.70% 116.4% 116.8% 116.2% 117.3% - Thickness of compressive stress layer WKpm) 50 40 45 30 47 - Maximum stress 压缩 of compressive stress layer 値 2.2 1.6 2.1 1.5 2 - Tensile stress layer The maximum stress 値0.11 0.11 0.16 0.12 0.13 - The variation of the stress 値 in the tensile center range 0.08 0.06 0.1 0.05 0.07 - The flaw evaluation is good, good, good, good, good, poor, and the thickness is formed by the above Table 1 and Examples 1 to 5 A compressive stress layer of less than 50 μηι 14 . Therefore, the efficiency of the processing after the glass forming is less likely to cause adverse effects. Further, all of Examples 1 to 5 were evaluated as good by evaluation of the flaw. Thus, it was found that the efficiency of the processing of the glass sheet 1 on the -48-201139303 after the glass formation did not adversely affect the degree of adhesion of the surface of the tempered glass to the surface of the glass. Further, the variation of the stress 値 in the "stretching center range" of the tensile stress layer 12 of Examples 1 to 5, that is, the difference between the maximum 値 and the minimum 値 of the stress 値 (absolute 値) is 0 · 1 2 Μ P a below. Further, the glass plates of Examples 6 to 8 and Comparative Example 2 having the compositions shown in Table 2 below were chemically strengthened under the following conditions. In Comparative Example 2, the tempered glass obtained by chemical strengthening was subjected to honing with a portion of the compressive stress layer 14 formed on the surface of the glass plate produced in the same manner as in Examples 6 to 8. The glass sheets of Examples 6 to 8 and Comparative Example 2 were prepared by using a continuous melting apparatus including a melting tank made of refractory smelting and a frame groove made of platinum, and the like. Melting at 520 ° C, clearing at 155 ° C, stirring at 135 ° C, and then forming a thin plate-shaped glass plate having a thickness of 0.7 mm by using a down-draw method using the apparatus shown in FIG. Strengthen the glass plate. In the glass plate of Comparative Example 2, as in Comparative Example 1, the portion of the compressive stress layer 14 of the glass plate 10 was honed and removed. Next, on the glass surfaces of the glass sheets of Examples 6 to 8 and Comparative Example 2, scratches were scratched by the above method. The washed glass plate was kept in a treatment bath at 400 ° C in Ο 3 1 0 0 %, and immersed for about 2.5 hours to cause Na+ ions present on the surface layer of the glass to be ion exchanged into K in the treatment bath. + ion, chemically strengthened glass plate. The chemically strengthened glass plate is washed by sequentially immersing in a washing tank to obtain a dried tempered glass. The glass surfaces of Examples 2 to 8 thus obtained and Comparative Example 49-201139303 were observed by a laser microscope. At this time, the glass plate which had progressed by the crack of the flaw was evaluated, and the glass plate which was not cracked was evaluated, and the evaluation was good. The stomach shows the composition and evaluation results in Table 2 below.

【表2 I 實施例6 實施例7 實施例8 比較例2 Si02 65.2 65.5 66.0 65.5 ai2o3 8.3 8.0 10.0 8.0 B2〇3 — — 1.0 V MgO 4.0 8.0 5.0 8.0 CaO 3.5 — 0.8 — U20 — 0.5 一 0.5 Na20 15.3 15.8 14.4 15.8 K20 2.0 1.5 2.8 1.5 Zr02 1.7 0.7 — 0.7 傷痕評估 良好 良好 良好 不佳[Table 2 I Example 6 Example 7 Example 8 Comparative Example 2 Si02 65.2 65.5 66.0 65.5 ai2o3 8.3 8.0 10.0 8.0 B2〇3 — — 1.0 V MgO 4.0 8.0 5.0 8.0 CaO 3.5 — 0.8 — U20 — 0.5 A 0.5 Na20 15.3 15.8 14.4 15.8 K20 2.0 1.5 2.8 1.5 Zr02 1.7 0.7 — 0.7 Scar assessment good good good bad

由上述表2 ’實施例6〜8的傷痕之評估係爲良好，但比 較例2之評估係爲不佳。由此，了解到化學強化具有壓縮 應力層1 4與拉伸應力層1 2之玻璃板1 0，但在防止強化玻璃 表面的傷痕產生的點爲有效。 以上’對於本發明之玻璃板及玻璃板之製造方法，做 過詳細說明’但本發明係未限定於上述實施形態，而在未 脫離本發明之主旨範圍，當然亦可做種種的改良或變更。 [產業上之利用可能性] -50- 201139303 本發明之玻璃板1 0係適合於平板顯示器玻璃基板。另 外，化學強化本發明之玻璃板的強化玻璃係最佳使用於行 動電話’數位相機，PDA (攜帶終端裝置），太陽能電池 ，平板顯示器之玻璃蓋。另外，本發明之玻璃板係例如， 可期待對於觸控面板顯示器之基板，窗玻璃，磁碟用基板 ，固體攝影元件用玻璃蓋等之應用。 ^ 【圖式簡單說明】 圖1係顯示本實施形態之玻璃板之內部應力分布的圖 〇 圖2係顯示在緩冷工程急冷玻璃情況所得到之以往的 玻璃板之內部應力分布的圖。 圖3係說明本實施形態之玻璃板之製造方法的流程之 一例圖。 圖4係說明在本實施形態之玻璃板之製造方法的形狀 ( 加工的圖。 圖5係製造本實施形態之玻璃板之玻璃板製造裝置的 剖面圖。 圖6係圖4所示之玻璃板製造裝置之斜視圖。 圖7係變形例之玻璃板製造裝置之剖面圖。 圖8係其他變形例之玻璃板製造裝置之剖面圖。 圖9係顯示實測本實施形態之玻璃板的內部應力之分 布圖。 圖1 0係顯示實測本實施形態之玻璃板的Si原子濃度（ -51 - 201139303 %)之分布圖。 圖1 1係以往之玻璃製造裝置之剖面圖。 【主要元件符號說明】 1 0 1 :成形裝置 102 :斷熱構造體 103 :熔融玻璃 104 :玻璃帶 1 1 1 :溝 1 1 2 :壁面 121 :底壁 1 22 :周壁 1 2 3 :天頂壁 1 2 5 :閘門 1 2 6 :排出口 1 27 :導入口 -52-The evaluation of the scars of Examples 6 to 8 of the above Table 2 was good, but the evaluation of Comparative Example 2 was not good. Thus, it has been found that the glass plate 10 having the compressive stress layer 14 and the tensile stress layer 12 is chemically strengthened, but it is effective at preventing the occurrence of scratches on the surface of the tempered glass. The above description of the method for producing the glass sheet and the glass sheet of the present invention has been described in detail. However, the present invention is not limited to the above-described embodiments, and various modifications and changes can be made without departing from the spirit and scope of the invention. . [Industrial Applicability] -50- 201139303 The glass plate 10 of the present invention is suitable for a flat panel display glass substrate. Further, the tempered glass which chemically strengthens the glass plate of the present invention is preferably used for a mobile phone 'digital camera, a PDA (portable terminal device), a solar cell, and a glass cover for a flat panel display. Further, the glass plate of the present invention can be expected to be applied to, for example, a substrate for a touch panel display, a window glass, a substrate for a magnetic disk, and a glass cover for a solid-state imaging device. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an internal stress distribution of a glass sheet of the present embodiment. Fig. 2 is a view showing an internal stress distribution of a conventional glass sheet obtained in the case of a quenching glass in a slow cooling process. Fig. 3 is a view showing an example of the flow of a method for producing a glass sheet of the embodiment. Fig. 4 is a view showing a shape (processed view) of a method for producing a glass sheet according to the present embodiment. Fig. 5 is a cross-sectional view showing a glass sheet manufacturing apparatus for manufacturing the glass sheet of the embodiment. Fig. 6 is a glass sheet shown in Fig. 4. Fig. 7 is a cross-sectional view showing a glass sheet manufacturing apparatus according to a modification. Fig. 8 is a cross-sectional view showing a glass sheet manufacturing apparatus according to another modification. Fig. 9 is a view showing the internal stress of the glass sheet of the embodiment. Fig. 10 is a distribution diagram showing the Si atom concentration ( -51 - 201139303 %) of the glass plate of the present embodiment. Fig. 1 is a cross-sectional view of a conventional glass manufacturing apparatus. 0 1 : forming device 102 : heat-dissipating structure 103 : molten glass 104 : glass ribbon 1 1 1 : groove 1 1 2 : wall surface 121 : bottom wall 1 22 : peripheral wall 1 2 3 : zenith wall 1 2 5 : gate 1 2 6 : Discharge port 1 27 : inlet -52-

Claims (1)

201139303 七、申請專利範園： 1 · 一種玻璃板，係以下拉法加以成形之玻璃板，其特 徵爲 對於在前述玻璃板之厚度方向的中心位置之S i的原子 濃度（原子％ )而言之Si的原子濃度（原子％ )的濃度比 率爲高之5%以上之Si高濃度範圍，則從玻璃表面沿著厚度 方向，形成於較0爲大而30nm以下深度之範圍， 前述S i高濃度範圍係具有S i原子濃度之最大峰値，沿 著前述玻璃板之厚度方向的S i原子濃度係從前述最大峰値 位置至前述玻璃板的表面及前述中心位置連續性減少。 2 .如申請專利範圍第1項記載之玻璃板，其中，含於 前述玻璃板的材料，在玻璃熔融狀態中，比較於Si02而飽 和蒸氣壓高的揮發成分則在前述玻璃板之厚度方向的中心 位置，含有30質量％以上。 3.如申請專利範圍第1項或第2項記載之玻璃板，其中 ，前述玻璃板係具有形成於前述玻璃板之內部的拉伸應力 層，和形成於前述拉伸應力層兩側之壓縮應力層， 前述壓縮應力層之應力値的絕對値係4MPa以下， 前述壓縮應力層係形成於較從前述玻璃板的表面沿著 前述玻璃板之厚度方向之ΙΟμηι爲大而50μπι以下之深度範 圍，前述壓縮應力層之厚度係不足前述玻璃板之厚度的13 分之1， 前述拉伸應力層之應力値的絕對値係〇 · 4ΜΡa以下，前 述拉伸應力層之應力値的偏差係〇.2MPa以下。 -53- 201139303 4.如申請專利範圍第1項或第2項記載之玻璃板，其中 ，對於前述玻璃板之玻璃表面，係形成經由離子交換加以 化學強化之離子交換處理範園， 具有形成於前述玻璃板之內部的拉伸應力層，和形成 於前述拉伸應力層兩側之壓縮應力層， 前述壓縮應力層係從玻璃表面，形成於沿著前述玻璃 板之厚度方向之20〜ΙΟΟμπι之深度範圍。 5 .如申請專利範圍第1項至第4項任一記載之玻璃板， 其係使用於平板顯示器面板玻璃基板。 6.—種玻璃板，係以下拉法加以成形之玻璃板，其特 徵爲 具有形成於前述玻璃板之內部的拉伸應力層，和形成 於前述拉伸應力層兩側之壓縮應力層， 前述壓縮應力層之應力値的絕對値係4MPa以下， 前述壓縮應力層係形成於較從前述玻璃板的表面沿著 前述玻璃板之厚度方向之10 μηι爲大而50 μιη以下之深度範 圍，前述壓縮應力層之厚度係不足前述玻璃板之厚度的13 分之1， 前述拉伸應力層之應力値的絕對値係0.4MPa以下，前 述拉伸應力層之應力値的偏差係0.2MPa以下。 7 .如申請專利範圍第6項記載之玻璃板，其中，前述 玻璃板之前述拉伸應力層係在前述玻璃板之熔融狀態，比 較於Si02而含有30質量％以上飽和蒸氣壓高的揮發成分。 8.如申請專利範圍第6項或第7項記載之玻璃板，其係 -54- 201139303 使用於平板顯示器面板玻璃基板。 9.一種玻璃板之製造方法，其特徵爲具備：熔融玻璃 原料之工程； 和使用下拉法，從熔融之玻璃成形玻璃帶之工程； 和切斷前述玻璃帶，形成玻璃板之工程； 前述玻璃帶係對於在前述玻璃板之厚度方向的中心位 置之Si的原子濃度（原子％ )而言之Si的原子濃度（原子％ )的濃度比率爲高之5%以上之Si高濃度範圍，則從玻璃表 面沿著厚度方向，形成於較〇爲大而30nm以下深度之範圍 ，前述Si高濃度範圍係具有Si原子濃度之最大峰値，沿著 前述玻璃板之厚度方向的Si原子濃度係從前述最大峰値位 置至前述玻璃板的表面及前述中心位置連續性減少地加以 成形。 1 0 ·如申請專利範圍第9項記載之玻璃板之製造方法， 其中，成形前述玻璃帶時，經由加大在面對於前述熔融之 玻璃及前述玻璃帶之至少一方表面之環境的前述揮發成分 之分壓與前述揮發成分之飽和蒸氣壓的差，促進來自前述 熔融之玻璃及前述玻璃帶之至少一方表面之揮發成分的揮 發，形成前述玻璃帶。 1 1 ·如申請專利範圍第1 0項記載之玻璃板之製造方法 ，其中，成形前述玻璃帶時，在前述熔融玻璃，比較於 Si02呈促進飽和蒸氣壓高之揮發成分的揮發地，調整成形 前述玻璃帶之空間內的壓力及溫度之至少一方。 1 2 ·如申請專利範圍第1 0項記載之玻璃板之製造方法 -55- 201139303 ，其中’成形前述玻璃帶時，於成形前述玻璃帶之空間， 沿著前述玻璃帶而形成氣體的流動》 1 3 ·如申請專利範圍第9項記載之玻璃板之製造方法， 其中，成形前述玻璃帶時，在前述熔融玻璃，比較於Si〇2 呈增加飽和蒸氣壓高之揮發成分的揮發量地，調整成形前 述玻璃帶之空間內的玻璃帶之通過時間。 14. 一種玻璃蓋之製造方法，其特徵爲具有：如申請 專利範圍第9項至第1 3項任一記載之玻璃板之製造方法的3 個工程； 和更具有將經由前述玻璃板之製造方法所製造之前述 玻璃板的表面，經由離子交換進行化學強化之工程。 15. —種玻璃板之製造方法，其特徵爲具備：熔融玻 璃原料之工程； 和使用下拉法，從熔融之玻璃成形玻璃帶之工程； 和切斷前述玻璃帶，形成玻璃板之工程； 形成於較從前述玻璃帶的表面沿著前述玻璃帶之厚度 方向之ΙΟμηι爲大而50μιη以下之深度範圍之壓縮應力層， 其中，具有不足前述玻璃帶之厚度的13分之1之厚度，呈 具有壓縮應力値之絕對値爲4MPa以下之2個壓縮應力層， 和夾持於前述2個壓縮應力層，拉伸應力値的絕對値爲 0.4MPa以下之拉伸應力層地，成形前述玻璃帶。 1 6.如申請專利範圍第1 5項記載之玻璃板之製造方法 ，其中，從熔融之前述玻璃成形前述玻璃帶時，經由加大 在面對於前述熔融之玻璃及前述玻璃帶之至少一方表面之 -56- 201139303 環境的前述揮發成分之分壓與前述揮發成分之飽和蒸氣壓 的差，促進來自前述熔融之玻璃及前述玻璃帶之至少一方 表面之揮發成分的揮發，成形前述玻璃帶。 17. 如申請專利範圍第16項記載之玻璃板之製造方法 ，其中，成形前述玻璃帶時，在前述熔融玻璃，比較於 Si02呈促進飽和蒸氣壓高之揮發成分的揮發地，調整前述 空間內的壓力及溫度之至少一方。 18. 如申請專利範圍第16項記載之玻璃板之製造方法 ，其中，成形前述玻璃帶時，於成形前述玻璃帶之空間， 沿著前述玻璃帶而形成氣體的流動。 1 9.如申請專利範圍第1 5項記載之玻璃板之製造方法 ，其中，成形前述玻璃帶時，在前述熔融玻璃，比較於 Si 〇2呈增加飽和蒸氣壓高之揮發成分的揮發量地，調整成 形前述玻璃帶之空間內的玻璃帶之通過時間。 2 0.—種玻璃蓋之製造方法，具有：如申請專利範圍 第9項至第13項任一記載之玻璃板之製造方法的3個工程； 和更具有將經由前述玻璃板之製造方法所製造之前述 玻璃板的表面，經由離子交換進行化學強化之工程。 2 1 . —種玻璃板製造裝置，係經由下拉法而製造玻璃 板之裝置，具備： 使熔融玻璃，從溝的兩側溢流’經由使其溢流之熔融 玻璃彼此，在壁面進行誘導而融合’形成玻璃帶之成形裝 置； 和具有圍繞前述成形裝置並且讓經由前述成形裝置所 -57- 201139303 形成之前述玻璃帶通過之閘門的斷熱構造體； 對於前述斷熱構造體，係設置有將從前述斷熱構造胃 外導入至前述斷熱構造體內，沿著在前述成形裝置之壁面 上流下的熔融玻璃而上升之氣體排出於前述斷熱構造體# 之排出口。 22.—種玻璃板製造方法，係經由下拉法而製造玻璃 板之方法，含有： 從由斷熱構造體所圍繞之成形裝置的溝之兩側，使熔 〇 融玻璃溢流同時，使從前述斷熱構造體外導入至前述斷熱 構造體內之氣體，沿著在前述成形裝置之壁面上流下的熔 融玻璃而上升之後，排出於前述斷熱構造體外之工程。 2 3 · —種玻璃板，係經由如申請專利範圍第22項記載 之玻璃板製造方法所得到之玻璃板，其特徵爲 於表背兩面具有壓縮應力層。 -58-201139303 VII. Patent application garden: 1 · A glass plate which is formed by the following drawing method, and is characterized in that the atomic concentration (atomic %) of S i at the center position in the thickness direction of the glass plate is When the concentration ratio of the atomic concentration (atomic %) of Si is 5% or more in the high concentration range of Si, the surface of the glass is formed in a range from 0 to 30 nm in depth in the thickness direction, and the above S i is high. The concentration range has a maximum peak value of the concentration of Si atoms, and the concentration of Si atoms in the thickness direction of the glass sheet decreases from the maximum peak position to the surface of the glass sheet and the center position. 2. The glass plate according to claim 1, wherein the material contained in the glass plate is in a molten state of the glass, and the volatile component having a higher saturated vapor pressure than the SiO 2 is in the thickness direction of the glass plate. The center position contains 30% by mass or more. 3. The glass sheet according to claim 1 or 2, wherein the glass sheet has a tensile stress layer formed inside the glass sheet, and a compression formed on both sides of the tensile stress layer. The stress layer has an absolute enthalpy of stress 値 of 4 MPa or less in the compressive stress layer, and the compressive stress layer is formed in a depth range from a surface of the glass plate to a thickness of 50 μm or less along a thickness direction of the glass plate. The thickness of the compressive stress layer is less than 1/13 of the thickness of the glass plate, the absolute stress of the tensile stress layer is less than or equal to 4 ΜΡa, and the stress 値 of the tensile stress layer is 〇. 2 MPa. the following. A glass plate according to the first or second aspect of the invention, wherein the glass surface of the glass plate is formed by ion exchange treatment by chemical strengthening of ion exchange, and is formed in a tensile stress layer inside the glass plate and a compressive stress layer formed on both sides of the tensile stress layer, wherein the compressive stress layer is formed on the glass surface from 20 to ΙΟΟμπι along the thickness direction of the glass plate. Depth range. 5. The glass plate according to any one of claims 1 to 4, which is used for a flat panel display panel glass substrate. 6. A glass plate, which is a glass plate formed by a pulling method, characterized by having a tensile stress layer formed inside the glass plate, and a compressive stress layer formed on both sides of the tensile stress layer, The compressive stress layer has an absolute enthalpy of 4 MPa or less, and the compressive stress layer is formed in a depth range from 10 μηι in a thickness direction of the glass plate to a thickness of 50 μm or less from the surface of the glass plate, and the compression is performed. The thickness of the stress layer is less than 1⁄2 of the thickness of the glass plate, the absolute enthalpy of the stress 値 of the tensile stress layer is 0.4 MPa or less, and the variation of the stress 値 of the tensile stress layer is 0.2 MPa or less. The glass plate according to the sixth aspect of the invention, wherein the tensile stress layer of the glass plate is in a molten state of the glass plate, and contains 30% by mass or more of a volatile component having a high saturated vapor pressure compared to SiO 2 . . 8. The glass plate according to Item 6 or Item 7 of the patent application, wherein -54-201139303 is used for a flat panel display panel glass substrate. A method for producing a glass sheet, comprising: a project of melting a glass raw material; and a process of forming a glass ribbon from the molten glass using a down-draw method; and a process of cutting the glass ribbon to form a glass sheet; When the concentration ratio of the atomic concentration (atomic %) of Si in the atomic concentration (atomic %) of Si at the center position in the thickness direction of the glass plate in the thickness direction of the glass plate is 5% or more in the high concentration range of Si, The surface of the glass is formed in a thickness range of 30 nm or less along the thickness direction, and the Si concentration range has a maximum peak of Si atom concentration, and the Si atom concentration along the thickness direction of the glass plate is from the foregoing. The maximum peak position is formed by reducing the continuity of the surface of the glass sheet and the center position. The method for producing a glass sheet according to claim 9, wherein when the glass ribbon is molded, the volatile component in the environment of at least one surface of the molten glass and the glass ribbon is increased. The difference between the partial pressure and the saturated vapor pressure of the volatile component promotes volatilization of volatile components from at least one surface of the molten glass and the glass ribbon to form the glass ribbon. In the method of producing a glass sheet according to the above aspect of the invention, the glass ribbon is formed by adjusting the volatilization of the volatile component having a higher saturated vapor pressure than the SiO2 in the molten glass. At least one of pressure and temperature in the space of the glass ribbon. 1 2 - The method for producing a glass sheet according to claim 10, wherein the forming of the glass ribbon forms a flow of gas along the glass ribbon in the space of forming the glass ribbon. The method for producing a glass sheet according to claim 9, wherein, in the case of molding the glass ribbon, the amount of volatilization of the volatile component having a higher saturated vapor pressure is higher in the molten glass than in Si〇2. The passage time of the glass ribbon in the space in which the aforementioned glass ribbon is formed is adjusted. A method of producing a glass cover, comprising: three steps of a method for producing a glass sheet according to any one of claims 9 to 13; and further comprising: manufacturing by the glass sheet The surface of the aforementioned glass plate produced by the method is subjected to chemical strengthening by ion exchange. A method for producing a glass sheet, comprising: a project of melting a glass raw material; and a process of forming a glass ribbon from the molten glass using a down-draw method; and a process of cutting the glass ribbon to form a glass sheet; a compressive stress layer having a depth ranging from a surface of the glass ribbon in a thickness direction of the glass ribbon to a depth of 50 μm or less, wherein the thickness of the glass ribbon is less than 1/3 of the thickness of the glass ribbon. The compressive stress 値 has two absolute compressive stress layers of 4 MPa or less, and the tensile stress layer sandwiched between the two compressive stress layers and the tensile enthalpy of the tensile stress 0.4 is 0.4 MPa or less, and the glass ribbon is molded. (1) The method for producing a glass sheet according to the fifth aspect of the invention, wherein, when the glass ribbon is molded from the molten glass, at least one surface of the molten glass and the glass ribbon is enlarged on the surface. -56-201139303 The difference between the partial pressure of the volatile component in the environment and the saturated vapor pressure of the volatile component promotes volatilization of volatile components from at least one surface of the molten glass and the glass ribbon to form the glass ribbon. 17. The method for producing a glass sheet according to claim 16, wherein, in the case of molding the glass ribbon, the molten glass is adjusted in a space in which the volatile component of the SiO2 is increased in vapour pressure is increased. At least one of the pressure and temperature. 18. The method for producing a glass sheet according to claim 16, wherein when the glass ribbon is molded, a flow of gas is formed along the glass ribbon in a space in which the glass ribbon is formed. The method for producing a glass sheet according to the fifth aspect of the invention, wherein, in the case of molding the glass ribbon, the molten glass has a volatilization amount of a volatile component having a higher saturated vapor pressure than Si 〇2. The passage time of the glass ribbon in the space in which the glass ribbon is formed is adjusted. A manufacturing method of a glass cover, comprising: three processes of a method for producing a glass sheet according to any one of claims 9 to 13; and a method of manufacturing the glass sheet through the glass sheet The surface of the aforementioned glass plate produced is subjected to chemical strengthening by ion exchange. A glass plate manufacturing apparatus is a device for producing a glass plate by a down-draw method, comprising: causing molten glass to overflow from both sides of the groove, and inducing the molten glass through the molten glass a heat-dissipating structure that incorporates a forming device that forms a glass ribbon; and a shutter that has a gate that passes through the aforementioned forming device and passes through the aforementioned glass ribbon formed by the forming device-57-201139303; The gas which is introduced from the stomach outside the heat-insulating structure into the heat-insulating structure, and which rises along the molten glass flowing down on the wall surface of the molding apparatus, is discharged to the discharge port of the heat-insulating structure #. 22. A method for producing a glass sheet, which is a method for producing a glass sheet by a down-draw method, comprising: overflowing a molten glass from both sides of a groove of a forming device surrounded by a heat-insulating structure; The gas introduced into the heat-insulating structure in vitro by the heat-insulating structure is raised along the molten glass flowing down the wall surface of the molding apparatus, and then discharged to the outside of the heat-insulating structure. A glass plate obtained by the method for producing a glass sheet according to claim 22, which has a compressive stress layer on both sides of the front and back surfaces. -58-