TW201136847A

TW201136847A - Glass plate manufacturing method and glass plate manufacturing apparatus

Info

Publication number: TW201136847A
Application number: TW099145463A
Authority: TW
Inventors: Tetsuo Kimijima
Original assignee: Avanstrate Inc
Priority date: 2009-12-24
Filing date: 2010-12-23
Publication date: 2011-11-01
Also published as: CN102958855A; CN102574720A; JP5281634B2; KR20120060847A; JP2011148685A; JP5269870B2; KR20120086733A; TWI401219B; WO2011077756A1; JPWO2011077734A1; KR101276494B1; TW201139303A; KR101346930B1; CN102574720B; WO2011077734A1; KR101541631B1; TWI412499B; JP5186602B2; KR20130108463A; CN102958855B

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

201136847 六、發明說明：【發明所屬之技術領域】本發明係關於一種使用下拉法製造玻璃板之玻璃板製造方法及尤其適合用於該製造方法之玻璃板製造裝置。【先前技術】液晶顯示器或電漿顯示器等平板顯示器（以下稱為 FPD」）中’使用厚度例如薄至1 .〇 mm以下之玻璃板作為玻璃基板。近年來，FPD玻璃基板用之玻璃板之大型化正在推進，例如被稱作第8代之玻璃板之尺寸為22〇〇 mmx2500 mm 〇為了製造此種FPD玻璃基板用玻璃板，最常使用下拉法。例如溢流下拉法中，藉由使熔融玻璃自成形裝置之溝槽溢流而連續地成形出帶狀之玻璃帶。此時，玻璃帶向下方下拉，並根據該下拉速度進行厚度之調整。其後，玻璃帶被切斷成特定長度，從而製造玻璃板。例如，專利文獻1中揭示有如圖1〇所示之玻璃板製造裝置之一部分即成形單元。該成形單元具備成形裝置7與。圍成形裝置7之絕熱構造體8。絕熱構造體8係藉由於成形聚置7之周圍保持高溫之空氣來維持自成形裝置7溢流之炫融玻璃之溫度者，通常，除了使玻璃帶通過之繞口 (gate)81以外係為密閉構造。具體而言，專利文齡1由& 4 獻1中所揭示之成形單元中，絕構造體8由開口向下之容器狀主體8Α、及以阻塞主體, 之開口之方式而配置之心構成體8β所構成。洗口構成 201136847 8B之内部成為空腔，於該澆口構成體8B之内部通過冷卻管82而供給冷卻用空氣。藉此，專利文獻i所揭示之成形單元中，剛形成玻璃帶9後便可進行冷卻。進而，專利文獻1中所揭示之成形單元中，於澆口構成體8B s史置有將來自冷卻管82之冷卻用冷氣喷出至由主體8A覆蓋之空間内之喷出口 83,藉由自喷出口 83流入至洗口 81之冷卻用空氣來冷卻玻璃帶9。專利文獻1 :日本特表2009-519884號公報【發明内容】此處，FpD玻璃基板用之玻璃板或蓋玻璃用之玻璃板被要求較高之表面品質。因此，重要的是防止對玻璃板之表面造成損傷。然而’揮發成分會從熔融狀態之玻璃（熔融玻璃及剛形成後之玻璃帶）與空氣接觸之邊界面處揮發。本發明之發明人等考慮到，若將該現象有效用於下拉法中，則可於玻璃板之兩主面形成所期望之壓縮應力層，藉此可防止損傷玻璃板之表面。然而’如專利文獻1中所揭示之成形單元般，於將冷部用空氣導入絕熱構造體8内之情形時，沿著成形裝置7 之壁面上流下之熔融玻璃亦會冷卻，因此揮發成分自熔融玻璃表面揮發會被抑制。其結果，無法形成應力值較高之坚縮應力層’從而無法獲得表面不易受損之玻璃板（第1 課題）。又，即便如專利文獻1所揭示之成形單元般，於澆口 4 201136847 81附近產生強制對流，較其更上側之空氣，即由主體8八覆蓋之空間内之大部分空氣滯留於該場所，因此對於揮發成分自熔融玻璃揮發會被抑制這一點並無改變（第2課題）。本發明鑒於此種情況，其目的在於提供一種可獲得表面不易受損之玻璃板之玻璃板製造方法。又，本發明之目的在於提供一種尤其適合用於該製造方法之可促進揮發成分自成形裝置溢流之熔融玻璃揮發的玻璃板製造裝置。為了解決上述第1課題，本發明提供一種玻璃板製造方法，其包含下述步驟：熔融步驟，其使玻璃原料熔解而獲得熔融玻璃；成形步驟，其藉由下拉法由上述熔融玻璃形成玻璃帶；揮發促進步驟，其促進揮發成分自上述熔融玻璃及上述玻璃帶之至少一者之表面揮發；緩冷步驟，其將上述玻璃帶冷卻；及切斷步驟，其將上述玻璃帶切斷而獲得玻璃板。為了解決上述第2課題，本發明提供一種玻璃板製造裝置，其具備下述裝置：成形裝置，其使熔融玻璃自溝槽之兩側溢流，利用壁面誘導該溢流之熔融玻璃彼此而使其熔合，藉此形成玻璃帶；及絕熱構造體，其包圍上述成形裝置且具有使由上述成形裝置形成之上述玻璃帶通過之澆口；且於上述絕熱構造體中設置有排出口，該排出口為了促進揮發成分自上述熔融玻璃之表面揮發，將自上述絕熱構造體外導入至上述絕熱構造體内並沿著在上述成形裝置之壁面上流下之熔融玻璃而上升的氣體排出至上述絕熱構造體外。 201136847 根據本發明，可獲得於兩主面形成有應力值較高之壓縮應力層之表面不易受損之玻璃板。【實施方式】以下，一邊參照圖式一邊對用以實施本發明之形態進行說明。再者，以下說明係關於本發明之一例者，本^明並不限定於此。 <玻璃板製造方法> 本發明之一實施形態之玻璃板製造方法例如藉由如圖 1所示之玻璃板製造裝置100來實施，該玻璃板製造裝置 100具備：熔融槽51、澄清槽52、成形裝置！及包圍^形裝置i之絕熱構造體2。熔融槽51中進行使玻璃原料熔解而獲得熔融玻璃3之熔融步驟，澄清槽52中進行澄清熔融玻璃3之澄清步驟。成形裝置〖係進行成形步驟者=藉由溢流下拉法而由熔融玻璃3形成玻璃帶4。絕熱構造體2 t，進行促進輝發成分自熔融玻璃3之表面、有時熔二玻璃3及剛形成後之玻璃帶4之表面揮發之揮發促進步驟。又，玻璃板製造裝置100具備下述裝置：下拉裝置，其包含將藉由成形裝置1形成之玻璃帶4向下方下拉之滾輪對，冷部裝置（未圖示），其進行將玻璃帶4冷卻之冷卻步驟；及切斷裝置（未圖示）’其進行將破璃帶4以特定長度切斷而獲得玻璃板之切斷步驟。再者，雖未圖示，但亦可於d π槽52與成形裝置i之間g己置有藉由利用撥拌翼等搜拌熔融玻璃3而提高玻璃之均質度的攪拌裝置。投入至熔融槽51之玻璃原料可使用調配成寸獲得下述 6 201136847 玻璃者：硼矽酸鹽玻璃、鋁矽酸鹽玻璃、鋁硼矽酸鹽玻璃、鹼石灰玻璃、鹼矽酸鹽玻璃、鹼鋁矽酸鹽破璃、鹼鋁鍺酸 I玻璃荨再者，藉由本發明之製造方法而獲得之玻璃並不限定於上述者，只要為至少包含Si〇2與揮發成分之玻璃即可。此處，所謂「揮發成分」，係指比Si〇2更容易揮發之成分，換言之，係指玻璃熔融溫度（玻璃之黏性成為丨〇x〖〇5 Pa.s以下之玻璃之溫度）時之飽和蒸氣壓高於si〇2之成分。揮發成分，例如可列舉Al2〇3、B2〇3、Li2〇、Na20、K20、BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass sheet manufacturing method for manufacturing a glass sheet using a down-draw method, and a glass sheet manufacturing apparatus particularly suitable for use in the manufacturing method. [Prior Art] In a flat panel display (hereinafter referred to as FPD) such as a liquid crystal display or a plasma display, a glass plate having a thickness of, for example, 1 mm or less is used as a glass substrate. In recent years, the size of the glass plate for FPD glass substrates is advancing. For example, the size of the glass plate called the 8th generation is 22〇〇mmx2500 mm. In order to manufacture such a glass plate for FPD glass substrates, the most commonly used pull-down is used. law. For example, in the overflow down-draw method, a strip-shaped glass ribbon is continuously formed by overflowing molten glass from a groove of a forming apparatus. At this time, the glass ribbon is pulled down to the bottom, and the thickness is adjusted according to the pull-down speed. Thereafter, the glass ribbon is cut into a specific length to manufacture a glass plate. For example, Patent Document 1 discloses a forming unit which is a part of a glass sheet manufacturing apparatus as shown in Fig. 1A. The forming unit is provided with a forming device 7 and . The heat insulating structure 8 of the surrounding forming device 7. The heat insulating structure 8 is a temperature which maintains the temperature of the glazed glass overflowing from the forming device 7 by the air which is kept at a high temperature around the forming and collecting portion 7, and is usually a door other than the gate 81 through which the glass ribbon passes. Closed structure. Specifically, in the molding unit disclosed in Japanese Patent Application No. 1, the permanent structure 8 is constituted by a container-shaped main body 8 that is open downward, and a heart that is arranged to block the opening of the main body. The body 8β is composed of. The inside of the nozzle structure 201136847 8B is a cavity, and the inside of the gate structure 8B is supplied with cooling air through the cooling pipe 82. Thereby, in the forming unit disclosed in Patent Document i, the glass ribbon 9 can be cooled immediately after the glass ribbon 9 is formed. Further, in the molding unit disclosed in Patent Document 1, the gate structure 8B s is provided with a discharge port 83 for discharging the cooling cold air from the cooling pipe 82 into the space covered by the main body 8A. The discharge port 83 flows into the cooling air of the washing port 81 to cool the glass ribbon 9. Patent Document 1: Japanese Laid-Open Patent Publication No. 2009-519884. SUMMARY OF THE INVENTION Here, a glass plate for an FpD glass substrate or a glass plate for a cover glass is required to have a high surface quality. Therefore, it is important to prevent damage to the surface of the glass sheet. However, the volatile component volatilizes from the boundary surface of the glass in the molten state (the molten glass and the glass ribbon immediately after formation) in contact with the air. The inventors of the present invention have considered that if this phenomenon is effectively used in the down-draw method, a desired compressive stress layer can be formed on both main faces of the glass sheet, thereby preventing damage to the surface of the glass sheet. However, as in the case of the forming unit disclosed in Patent Document 1, when the cold portion air is introduced into the heat insulating structure 8, the molten glass flowing down along the wall surface of the forming device 7 is also cooled, so that the volatile component is self-generated. The volatilization of the molten glass surface is inhibited. As a result, a shrinkage stress layer having a high stress value cannot be formed, and a glass sheet having a surface which is not easily damaged can be obtained (first problem). Further, even in the case of the forming unit disclosed in Patent Document 1, forced convection is generated in the vicinity of the gate 4 201136847 81, and most of the air in the space covered by the main body 8 is retained in the place. Therefore, there is no change in the volatilization of the volatile component from the molten glass (second problem). The present invention has been made in view of such circumstances, and an object thereof is to provide a method for producing a glass sheet which can obtain a glass sheet whose surface is not easily damaged. Further, it is an object of the present invention to provide a glass sheet manufacturing apparatus which is particularly suitable for use in the production method and which can promote the volatilization of molten glass from which the volatile component overflows from the forming apparatus. In order to solve the above first problem, the present invention provides a glass sheet manufacturing method comprising the steps of: a melting step of melting a glass raw material to obtain molten glass; and a forming step of forming a glass ribbon from the molten glass by a down-draw method a volatilization promoting step of promoting volatilization of the volatile component from at least one of the molten glass and the glass ribbon; a slow cooling step of cooling the glass ribbon; and a cutting step of cutting the glass ribbon to obtain glass plate. In order to solve the above-described second problem, the present invention provides a glass sheet manufacturing apparatus including: a molding apparatus that causes molten glass to overflow from both sides of a groove, and induces the overflowed molten glass by a wall surface And fused to form a glass ribbon; and a heat insulating structure surrounding the molding apparatus and having a gate through which the glass ribbon formed by the molding apparatus passes; and the heat insulating structure is provided with a discharge port, the row In order to promote the volatilization of the volatile component from the surface of the molten glass, the outlet is introduced into the heat insulating structure outside the heat insulating structure, and the gas which rises along the molten glass flowing down the wall surface of the molding apparatus is discharged to the outside of the heat insulating structure. . According to the present invention, it is possible to obtain a glass sheet in which the surface of the compressive stress layer having a high stress value is not easily damaged on both main surfaces. [Embodiment] Hereinafter, embodiments for carrying out the invention will be described with reference to the drawings. Further, the following description is based on an example of the present invention, and the present invention is not limited thereto. <Method of Producing Glass Sheet> The method for producing a glass sheet according to an embodiment of the present invention is carried out, for example, by a glass sheet manufacturing apparatus 100 as shown in Fig. 1, which comprises a melting tank 51 and a clarification tank 52, forming device! And a heat insulating structure 2 surrounding the device i. In the melting tank 51, a melting step of melting the glass raw material to obtain the molten glass 3, and a clarification step of clarifying the molten glass 3 in the clarification tank 52 are performed. The forming apparatus is a forming step. The glass ribbon 4 is formed from the molten glass 3 by an overflow down-draw method. The heat insulating structure 2 t is subjected to a volatilization promoting step of promoting the volatilization of the surface of the molten glass 3 from the surface of the molten glass 3 and sometimes the surface of the glass ribbon 3 immediately after the formation. Further, the glass sheet manufacturing apparatus 100 includes a lowering apparatus including a pair of rollers that pull the glass ribbon 4 formed by the molding apparatus 1 downward, and a cold section apparatus (not shown) that performs the glass ribbon 4 Cooling step of cooling; and cutting device (not shown) 'cutting step of cutting the glass ribbon 4 by a specific length to obtain a glass plate. Further, although not shown, a stirring device for improving the homogeneity of the glass by mixing the molten glass 3 with the mixing blade or the like may be placed between the d π groove 52 and the forming device i. The glass raw material put into the melting tank 51 can be used to obtain the following 6 201136847 glass: borosilicate glass, aluminosilicate glass, aluminoborosilicate glass, soda lime glass, alkali silicate glass, Further, the glass obtained by the production method of the present invention is not limited to the above, and may be any glass containing at least Si 2 and a volatile component. Here, the term "volatile component" means a component which is more volatile than Si 〇 2, in other words, a glass melting temperature (when the viscosity of the glass becomes 丨〇 x 〇 5 Pa.s or less) The saturated vapor pressure is higher than the composition of si〇2. Examples of the volatile component include Al2〇3, B2〇3, Li2〇, Na20, and K20.

MgO、Ca〇、Sr0、Ba〇、Zr〇2、Sn〇2 等，但並不限定於該等。再者，因b2o3、鹼氧化物（Li2〇 v Na2〇、K2〇)、及鹼土金屬氧化物（MgO、CaO、SrO、BaO )揮發性較高，故而較佳為玻璃組成含有其中至少1種。該等揮發成分因玻璃熔融溫度時之飽和蒸氣壓高於 Si〇2，故於成形時或剛成形後（玻璃為熔融之狀態下）比 SiCh早揮發。即，由熔融玻璃形成玻璃帶之成形步驟中，於溶融玻璃冬表面Si〇2以外之成分揮發，因此其結果，Si 原子之含量多於玻璃内部之Si原子之含量的富含矽（siHca rich)之層被形成於成形後之玻璃板之表面。又，若富含矽之層被形成於玻璃板之表面’則藉由與玻璃板内部之熱膨脹率之差’壓縮應力層被形成於玻璃板之兩主面。再者，玻璃板之厚度方向之中心位置中之玻璃組成中的揮發成分之含量以質量。/。表示’較佳為1 〇%以上（或丨50/。以上）’更佳為30%以上，進而較佳為35%以上（或40%以 201136847 上）。若玻璃組成中之揮發成分之含量未達10%，則不能促進揮發成分揮發，富含矽之層或壓縮應力層難以被形成於玻璃板表面。相反，若較多地含有揮發成分’則揮發過於增加，玻璃之均質化變得困難。因此，較佳為50%以下（或 45%以下、42%以下）’進而較佳為40%以下。液晶用之矽酸鹽玻璃之一例，存在實質上由以下組成構成之鋁硼矽酸鹽玻璃。再者，本說明書中，以後含量全部以質量％表示，括號内表示進而較佳之含量。又，所謂「實質上」，係指允許自工業原料不可避免地混入之微量成分的存在於未達0.1質量％之範圍内。MgO, Ca〇, Sr0, Ba〇, Zr〇2, Sn〇2, etc., but are not limited thereto. Furthermore, since b2o3, alkali oxides (Li2〇v Na2〇, K2〇), and alkaline earth metal oxides (MgO, CaO, SrO, BaO) have high volatility, it is preferred that the glass composition contains at least one of them. . Since these volatile components have a saturated vapor pressure higher than Si〇2 at the glass melting temperature, they are volatilized earlier than SiCh at the time of molding or just after molding (the glass is in a molten state). That is, in the forming step of forming the glass ribbon from the molten glass, the components other than Si〇2 on the winter surface of the molten glass are volatilized, and as a result, the content of Si atoms is more than that of the Si atoms in the glass (siHca rich). The layer is formed on the surface of the formed glass sheet. Further, if the layer rich in ruthenium is formed on the surface of the glass sheet, the compressive stress layer is formed on both principal surfaces of the glass sheet by the difference between the thermal expansion ratio and the inside of the glass sheet. Further, the content of the volatile component in the glass composition in the center position in the thickness direction of the glass plate is in mass. /. Preferably, 'it is preferably 1% or more (or 50% or more)', more preferably 30% or more, and still more preferably 35% or more (or 40% on 201136847). If the content of the volatile component in the glass composition is less than 10%, the volatilization of the volatile component is not promoted, and the layer rich in ruthenium or the compressive stress layer is difficult to be formed on the surface of the glass plate. On the other hand, if a volatile component is contained in a large amount, volatilization is excessively increased, and homogenization of glass becomes difficult. Therefore, it is preferably 50% or less (or 45% or less, 42% or less) and further preferably 40% or less. As an example of the silicate glass for liquid crystal, there is an aluminoborosilicate glass which is substantially composed of the following composition. Further, in the present specification, all contents are expressed in mass% in the future, and further preferred contents are shown in parentheses. Further, the term "substantially" means that the trace component which is inevitably mixed in from the industrial raw material is present in the range of less than 0.1% by mass.

Si〇2 : 50 〜70% (55 〜65%、57 〜64 %、58 〜62%)Si〇2 : 50 to 70% (55 to 65%, 57 to 64%, 58 to 62%)

Al2〇3 : 5〜20% ( 10〜20%、12〜18%、15〜18〇/〇) B2O3 . 〇〜15A (5〜15%、6〜13%、7〜12%)Al2〇3: 5~20% (10~20%, 12~18%, 15~18〇/〇) B2O3 . 〇~15A (5~15%, 6~13%, 7~12%)

MgO : 〇〜10% ( 0.01 〜5%以上、〇 5〜4%、〇 5〜2%)MgO : 〇~10% (0.01~5% or more, 〇5~4%, 〇5~2%)

CaO : 0〜10% ( 1〜9%、3〜8%、4〜7%、4〜6%)CaO : 0 to 10% (1 to 9%, 3 to 8%, 4 to 7%, 4 to 6%)

SrO : 0〜1〇% ( 〇·5〜9%、3〜8%、3〜7%、3〜6%)SrO : 0~1〇% (〇·5~9%, 3~8%, 3~7%, 3~6%)

BaO : 〇〜1〇% ( 〇〜8%、〇〜3%、〇〜1%、〇〜〇 2%) Zr〇2 : 〇〜1 〇% ( 〇〜5%、〇〜4%、〇〜1 〇/〇、〇〜〇 1 % ) 液晶用之矽酸鹽玻璃之另一例，存在實質上由以下組成所構成之鋁硼矽酸鹽玻璃。BaO : 〇~1〇% (〇~8%, 〇~3%, 〇~1%, 〇~〇2%) Zr〇2 : 〇~1 〇% (〇~5%, 〇~4%, 〇 ~1 〇/〇, 〇~〇1 %) Another example of a silicate glass for liquid crystals, there is an aluminoborosilicate glass which is substantially composed of the following composition.

Si〇2 : 50〜7〇%(5 5 〜65%、58〜62〇/〇) AI2O3 · 〜254 ( 15 〜2.0%、15 〜18%) B2〇3 : 5〜18% ( 8〜14%、ι〇〜13〇/〇)Si〇2: 50~7〇% (5 5~65%, 58~62〇/〇) AI2O3 · ~254 (15~2.0%, 15~18%) B2〇3 : 5~18% (8~14 %, ι〇~13〇/〇)

MgO : 〇〜1 〇% ( 1 〜5%、1 〜204 ) 8 201136847MgO : 〇~1 〇% (1 ～5%, 1 ～204) 8 201136847

Ca〇 ’ 0〜20% ( 1〜7%、4〜7%) 〇〜20% ( 1〜1〇%、1〜3%)Ca〇 ’ 0~20% (1~7%, 4~7%) 〇~20% (1~1〇%, 1~3%)

Ba0 ’ 〇〜10% ( 〇〜2%、〇〜1〇/〇) 0〜2% ( 0·1 〜2%、0.1 〜0.5%) 將具有複數之價 .=2:〇〜i%(〇m〇.01〜0.3%) ^ ’上述組成中之Sn〇2之含有率係將具 ^ 成刀王。P作為Sn〇2而處理換算之值盘坡壤用之矽酸鹽玻璃例如包含以下成分作為必要成分。Ba0 ' 〇~10% (〇~2%, 〇~1〇/〇) 0~2% (0·1 ～2%, 0.1 ～0.5%) will have a complex price.=2:〇~i%( 〇m〇.01~0.3%) ^ 'The content of Sn〇2 in the above composition will be the result of the knife. P is used as the value of the conversion of Sn 〇 2 The silicate glass for the sloping soil contains, for example, the following components as a necessary component.

Sl〇2 ’ 50〜7〇。/0 ( 55 〜65%、57〜64〇/〇，57〜62%)、 A12〇3 : 5 〜2〇%(9〜18%、12〜17%)Sl〇2 ’ 50~7〇. /0 (55 to 65%, 57 to 64 〇 / 〇, 57 to 62%), A12 〇 3: 5 to 2 〇% (9 to 18%, 12 to 17%)

Na2〇 : 6〜3〇% ( 7〜20%、8〜18%、1〇〜15%) 2〇 . 〇〜8% ( 0〜6%、〇〜2%、〇〜〜0.2〇/〇) 〇, 6 %、〇〜 0.4% > 〇 B2〇3 : 〇〜5% ( 〇〜2%、。〜ι% 十 ^ 0.8% ) 2 G 〜(1 〜6%、.2 〜5%、2, ^ 4% ) Mg〇 : 0〜10°/。（ 1〜9%、2〜8%、3 〆7%、4〜 7%) Ca〇: 0〜20% (〇」〜_、！〜5%、 2 -~f 4 %、2 :〜3%) Zr〇2 : 〇〜10% (〇〜5%、.〇〜4%、〇, ^ 1%、0〜 0.1%) 盍破璃用之矽酸鹽玻璃之一例，存在貧質上由成所構成之鹼鋁矽酸鹽玻璃。 Sl〇2 : 50〜70% 以下組 AI2〇3 ·· 5〜20% 201136847Na2〇: 6~3〇% (7~20%, 8~18%, 1〇~15%) 2〇. 〇~8% (0~6%, 〇~2%, 〇~~0.2〇/〇 ) 〇, 6 %, 〇~ 0.4% > 〇B2〇3 : 〇~5% (〇~2%, .〜ι% 十^0.8%) 2 G ~(1 ～6%, .2 〜5% , 2, ^ 4% ) Mg〇: 0~10°/. (1 to 9%, 2 to 8%, 3 to 7%, 4 to 7%) Ca〇: 0 to 20% (〇)~_, !~5%, 2 -~f 4 %, 2:~3 %) Zr〇2 : 〇~10% (〇~5%, 〇~4%, 〇, ^1%, 0~0.1%) 之一之一用之一之一之一之一之一之一之一The alkali aluminosilicate glass formed by the composition. Sl〇2 : 50~70% The following groups AI2〇3 ·· 5~20% 201136847

Na2〇: 6〜20% K20 : 0〜10%Na2〇: 6~20% K20 : 0~10%

MgO : 0〜10%MgO : 0~10%

CaO :大於2%且〜20%CaO: greater than 2% and ~20%

Zr02 : 0〜4.8% 進而，較佳為滿足以下條件。 • ( Si02含量）-(Al2〇3 含量）/2= 46 5 〜59% • CaO/RO (其中，R係選自Mg、ca、Sr及Ba之中之至少1種）之含量比大於0.3 • SrO含量與BaO含量之和未達1〇〇/〇 • ( Zr02+ Ti02) /Si02之含量比為〇〜未達〇〇7 .B203/ri2〇 (其中，幻係選自u、Na及κ之中之至少1種）之含量比為〇〜未達蓋玻璃用之矽酸鹽玻璃之另外一例，存在實質上由以下組成所構成之鹼鋁矽酸鹽破瑪。Zr02 : 0 to 4.8% Further, it is preferred to satisfy the following conditions. • (SiO2 content) - (Al2〇3 content) / 2 = 46 5 to 59% • CaO/RO (wherein R is at least one selected from the group consisting of Mg, Ca, Sr and Ba) is greater than 0.3 • The sum of SrO content and BaO content is less than 1〇〇/〇• (Zr02+ Ti02) /Si02 content ratio is 〇~未达〇〇7.B203/ri2〇 (where the phantom is selected from u, Na and κ The content ratio of at least one of them is another example of bismuth silicate glass which is not used for capping glass, and there is an alkali aluminosilicate which is substantially composed of the following composition.

Si〇2 : 58〜68%Si〇2 : 58~68%

Al2〇3 : 8〜15%Al2〇3 : 8~15%

Na2〇 : 1 〇〜2〇〇/0 Li2〇 : 〇〜1 % K2〇 : 1 〜5〇/〇Na2〇 : 1 〇~2〇〇/0 Li2〇 : 〇~1 % K2〇 : 1 ～5〇/〇

Mg0 : 2〜ι〇〇/0 再者’熔融玻璃3同樣亦可實質上由上述各成分所構具有.提高玻璃之化學Mg0 : 2~ι〇〇/0 Further, the molten glass 3 can also be substantially composed of the above components.

Sl〇2係構成玻璃之骨架之成分 10 201136847 • 耐久性與耐熱性之效果。於含量過少之情形時無法充分獲得該效果，若含量過多則玻璃變得易於引起失透明，成= 變得困難，並且黏性上升玻璃之均質化變得困難。Sl〇2 is a component of the skeleton of glass. 10 201136847 • The effect of durability and heat resistance. When the content is too small, the effect cannot be sufficiently obtained. If the content is too large, the glass tends to cause loss of transparency, and the formation becomes difficult, and the homogenization of the viscous glass becomes difficult.

Bz〇3係使玻璃之黏性下降、促進玻璃之熔解及澄清之成分。若含量過多，則玻璃之耐酸性降低、破璃之均質化變得困難。 Α1ζ〇3係構成玻璃之骨架之成分，具有提高玻璃之化學耐久性與耐熱性之效果。又，具有提高離子交換性能或蝕刻速度之效果。於含量過少之情形時無法充分獲得該效果。另一方面，若含量過多，則玻璃之黏性上升、熔解變得困難，並且耐酸性降低。Bz〇3 is a component that lowers the viscosity of the glass and promotes the melting and clarification of the glass. If the content is too large, the acid resistance of the glass is lowered and the homogenization of the glass is difficult. Α1ζ〇3 is a component of the skeleton of the glass and has an effect of improving the chemical durability and heat resistance of the glass. Further, it has an effect of improving ion exchange performance or etching speed. This effect cannot be fully obtained in the case where the content is too small. On the other hand, if the content is too large, the viscosity of the glass rises, the melting becomes difficult, and the acid resistance decreases.

MgO及CaO係使玻璃之黏性下降、促進玻璃之熔解及澄清之成分。又，Mg& Ca0於鹼土金屬中使玻璃之密度上升之比例較小，故而於為使所獲得之玻璃輕量化且提高溶解性方面為有利之成分。然而若其等含量過多，則玻璃之化學耐久性降低。MgO and CaO are components which lower the viscosity of the glass and promote the melting and clarification of the glass. Further, since Mg& Ca0 has a small ratio of increasing the density of the glass in the alkaline earth metal, it is an advantageous component for reducing the weight of the obtained glass and improving the solubility. However, if the content is too large, the chemical durability of the glass is lowered.

SrO及BaO係使玻璃之黏性降低、促進玻璃之熔解及澄清之成分。又’亦為提高玻璃原料之氧化性而提高澄清性之成分。然而若其含量變得過多，則玻璃之密度上升，無法實現玻璃板之輕量化，並且玻璃之化學耐久性降低。SrO and BaO are components which lower the viscosity of the glass and promote the melting and clarification of the glass. Further, it is also a component which improves the oxidizing property of the glass raw material and improves the clarity. However, if the content is too large, the density of the glass increases, the weight of the glass sheet cannot be reduced, and the chemical durability of the glass is lowered.

Ll2〇係離子交換成分之一，係使玻璃之黏度下降、提面玻璃之熔融性或成形性之成分。又，Li20係提高玻璃之揚氏模數之成分。進而，Li20於鹼金屬氧化物中提高壓縮應力值之效果較高。然而，若Li20之含量變得過多，則液 11 201136847 相黏度降低，玻璃變得容易失透明，因此大量生產利用下拉法之廉價之玻璃變得困難。又，破璃之熱膨脹率變得過高，玻璃之耐熱衝擊性降低，熱膨脹率變得難以與金屬或有機系接著劑等周邊材料整合。進而，存在進行玻璃基板之強化之步驟即離子交換處理中之離子交換鹽的劣化變快之不良清形。又，由於低溫黏度過於降低，於化學強化後之加熱步驟中產生應力緩和，且壓縮應力值降低，因此無法獲得充分之強度。One of the L12 lanthanide ion exchange components is a component which lowers the viscosity of the glass and improves the meltability or formability of the glass. Further, Li20 is a component that increases the Young's modulus of the glass. Further, Li20 has a high effect of increasing the compressive stress value in the alkali metal oxide. However, if the content of Li20 becomes too large, the viscosity of the liquid 11 201136847 is lowered, and the glass tends to lose transparency, so that it is difficult to mass-produce an inexpensive glass using the pull-down method. Further, the thermal expansion coefficient of the glass is excessively high, and the thermal shock resistance of the glass is lowered, and the thermal expansion coefficient becomes difficult to integrate with a peripheral material such as a metal or an organic binder. Further, there is a poor clearing in which the deterioration of the ion exchange salt in the ion exchange treatment, which is a step of strengthening the glass substrate, is accelerated. Further, since the low-temperature viscosity is excessively lowered, stress relaxation occurs in the heating step after chemical strengthening, and the compressive stress value is lowered, so that sufficient strength cannot be obtained.

NaaO係離子交換成分，係使玻璃之高溫黏度降低、提高玻璃之熔融性或成形性之必要成分。又，係改善玻璃之抗失透明性之成分。若其含量未達6%則玻璃之熔融性降低，導致用以熔融之成本變高。又，離子交換性能亦降低，因此無法獲得充分之強度。又，熱膨脹率過於降低，熱膨脹率變得難以與金屬或有機系接著劑等周邊材料整合。進而’因玻璃變得易於引起失透明，抗失透明性亦降低，故而憂得無法應用於溢流下拉法，因此大量生產變得，另一方面’若含量大於2。%，則低==璃熱膨脹率變得過剩，耐衝擊性降低，熱膨脹率變得難以與金屬或有機系接著劑等周邊材料整合。又，因亦產生玻璃平衡惡化所致之抗失透明性降低，故而大量生產利用下拉法之廉價之玻璃變得困難〇 K2〇係離子交換成分，係藉由含有其而可提高玻璃之離子交換性能之成分。又，ΙΟ亦為使玻璃之高溫黏度降低、提高玻璃之熔融性或成形性，與此同時改善抗失透明性之 12 201136847 成刀、';而右K2〇之含量變得過多，則低溫黏度降低，熱膨脹率變得過剩，耐衝擊性降低，因此不宜用作蓋玻璃之情形。X ’熱膨脹率變得難以與金屬或有機系接著劑等周邊材料整合。又’目亦產生玻璃平衡惡化所致之抗失透月f降低故而大置生產利用下拉法之廉價之玻璃變得困難。The NaaO-based ion exchange component is a component which lowers the high-temperature viscosity of the glass and improves the meltability or formability of the glass. Further, it is a component which improves the anti-missing property of glass. If the content is less than 6%, the meltability of the glass is lowered, resulting in a high cost for melting. Further, the ion exchange performance is also lowered, so that sufficient strength cannot be obtained. Further, the coefficient of thermal expansion is too low, and the rate of thermal expansion becomes difficult to integrate with peripheral materials such as metal or an organic binder. Further, since the glass becomes liable to cause loss of transparency and the anti-missing transparency is also lowered, it is unfortunate that it cannot be applied to the overflow down-draw method, so mass production becomes, and on the other hand, the content is greater than 2. %, the lower == glass The thermal expansion coefficient becomes excessive, the impact resistance is lowered, and the thermal expansion coefficient becomes difficult to integrate with a peripheral material such as a metal or an organic adhesive. In addition, since the loss of transparency due to deterioration of the glass balance is also reduced, it is difficult to mass-produce a cheap glass using a down-draw method. The K2 lanthanide ion exchange component can improve the ion exchange of the glass by containing it. The composition of performance. In addition, ΙΟ also reduces the high-temperature viscosity of the glass, improves the meltability or formability of the glass, and at the same time improves the resistance to loss of transparency 12 201136847 into a knife, '; while the content of the right K2 变得 becomes too much, the low temperature viscosity When the temperature is lowered, the coefficient of thermal expansion becomes excessive, and the impact resistance is lowered, so that it is not suitable for use as a cover glass. The X' thermal expansion rate becomes difficult to integrate with peripheral materials such as metal or an organic binder. In addition, the anti-devitrification of the glass balance caused by the deterioration of the glass balance is reduced, and it is difficult to produce an inexpensive glass using the down-draw method.

Na20及κ2〇係自玻璃溶析而使tft特性劣化或者使玻璃之熱膨脹率變大而於熱處理時使基板破損之成分因此於應用於顯示裝置用玻璃基板之情形時，$宜大量含有。然而，強行於玻璃中含有特定量上述成分，藉此亦可將TFT特f生之劣化或玻璃之熱膨脹抑制在一定範圍内，並且提高玻璃之鹼性度或熔融性，使價數變動之金屬之氧化變得容易，從而發揮澄清性。汾〇2係使離子交換性能顯著提高，並使玻璃之去玻化溫度附近之黏性或應變點變高之成分。又，心〇2亦為提高玻璃之耐熱性之成分 '然而，若Zr〇2之含量變得過多，則去玻化溫度上升，抗失透明性降低。When Na20 and κ2 are eluted from the glass to deteriorate the tft characteristics or to increase the thermal expansion coefficient of the glass, and the component which breaks the substrate during the heat treatment is applied to a glass substrate for a display device, it is preferable to contain it in a large amount. However, it is forcibly contained in the glass to contain a specific amount of the above-mentioned components, whereby the deterioration of the TFT or the thermal expansion of the glass can be suppressed within a certain range, and the alkalinity or meltability of the glass can be improved, and the metal having a valence change can be obtained. Oxidation becomes easy and clarification is exhibited.汾〇2 is a component which significantly improves the ion exchange performance and makes the viscosity or strain point near the devitrification temperature of the glass high. Further, the palpitations 2 are also a component for improving the heat resistance of the glass. However, when the content of Zr 〇 2 is too large, the devitrification temperature is increased and the anti-missing transparency is lowered.

Ti〇2係|離子交換性能提高之成分，幻系使玻璃之高溫黏度降低之成分。然而若Τι〇2之含量變得過多，則導致抗失透明性降低。進而導致玻璃著色，對蓋玻璃等不宜。又，由於玻璃著色，紫外線透射率亦降低，因此於進行使用紫外線硬化樹脂之處理之情形時，會產生無法使紫外線硬化樹脂充分硬化之類的不良情形。可添加澄清劑作為使玻璃中之氣泡消泡之成分。澄清 13 201136847 劑只要為環境負擔較小、玻璃之澄清性優異者並無特別限制，例如可列舉選自氧化錫、氧化鐵、氧化鈽'氧化試、氧化翻及氧化鎢之類的金屬氧化物之至少1種。再者，As2〇3、Sb2〇3及PbO係具有於熔融玻璃中產生伴隨價數變動之反應、澄清玻璃之效果之物質，但由於其等為環境負擔較大之物質，故而於本實施形態之玻璃板，玻璃中實質上不含有As2〇3、Sb>2〇3及Pb〇。再者，本說明書中，所謂實質上不含有AS2〇3、Sb2〇3及pb〇 ,係指未達 0.01%且除了雜質刻意地不含有。其次，關於液晶用之矽酸鹽玻璃，說明尤佳之態樣。如後述般，就提高壓縮應力層之應力值之觀點而言，較佳為熔融玻璃3含有較多之揮發成分。以Si〇2為主成分之矽酸鹽玻璃之情形時，si〇2以外之各成分與Si〇2相比於熔融中相對而言易於揮發，因此為廣義上之揮發成分。上述所例示之玻璃組成中之揮發性較高之揮發成分，可列舉 Βζ〇3、Sn〇2 (揮發作為Sn〇)、K2〇。因此，該等成分之含有率較佳為較高H若揮發變得過度則成形時產生不良情形，因此1〇3之含有率之上限更佳為14質量％，尤佳為13質里％。又，若Sn〇2之含有率較高，則玻璃會產生失透明。因此，就防止玻璃之失透明之觀點而言，Sn〇2之含有率之上限更佳為〇.5質量％，尤佳為〇 3質量％。進而，被用作玻璃之炼解促進劑之Κ2◦若大量添加，則會自玻璃板/合析而產生問題，因此K2〇之含有率之上限更佳為〇 5 質量％。 14 201136847 本實施形態之玻璃板製造方法中，於絕熱構造體2中進行揮發促進步驟。因此，所製造之玻璃板中，於表面形成富含矽之層。以下，對該玻璃板進行說明。 (1 )富含矽之層所謂「富含矽之層」’係指下述區域：以玻璃板厚度方向之中心之玻璃組成中的Si原子含量為基準值，自相對於該基準值之玻璃組成中之Si原子含量的比成為ι 〇5以上之位置起至玻璃板之主面為止。Ti〇2 series | A component that improves ion exchange performance, and a component that reduces the high temperature viscosity of glass. However, if the content of Τι〇2 becomes excessive, the loss of transparency is lowered. Further, the glass is colored, which is not suitable for a cover glass or the like. Further, since the glass is colored, the ultraviolet transmittance is also lowered. Therefore, when the ultraviolet curable resin is used for the treatment, there is a problem that the ultraviolet curable resin cannot be sufficiently cured. A clarifying agent may be added as a component for defoaming bubbles in the glass. Clarification 13 201136847 The agent is not particularly limited as long as it has a small environmental burden and excellent clarification of the glass. For example, a metal oxide selected from the group consisting of tin oxide, iron oxide, cerium oxide 'oxidation test, oxidized turn, and tungsten oxide can be cited. At least one of them. In addition, As2〇3, Sb2〇3, and PbO have a substance which causes a reaction with a change in the number of valences in the molten glass, and clarifies the effect of the glass. However, since the environment is a large burden, the present embodiment is In the glass plate, the glass does not substantially contain As2〇3, Sb>2〇3 and Pb〇. Further, in the present specification, the term "substantially does not contain AS2〇3, Sb2〇3, and pb〇 means that it is less than 0.01% and is intentionally not contained except for impurities. Secondly, the bismuth silicate glass for liquid crystals shows a particularly good aspect. As described later, from the viewpoint of increasing the stress value of the compressive stress layer, it is preferred that the molten glass 3 contains a large amount of volatile components. In the case of a bismuth phosphate glass containing Si 〇 2 as a main component, each component other than si 〇 2 is relatively volatile in comparison with Si 〇 2 in fusion, and therefore is a volatile component in a broad sense. Examples of the volatile component having a high volatility in the glass composition exemplified above include Βζ〇3, Sn〇2 (evaporation as Sn〇), and K2〇. Therefore, the content of the components is preferably high. If the volatilization becomes excessive, the formation is unfavorable. Therefore, the upper limit of the content of 1〇3 is more preferably 14% by mass, and particularly preferably 13% by mass. Further, if the content of Sn 〇 2 is high, the glass will be opaque. Therefore, from the viewpoint of preventing the glass from being lost in transparency, the upper limit of the content of Sn 〇 2 is more preferably 5% by mass, and particularly preferably 3% by mass. Further, when a large amount of ruthenium is used as a glass refining accelerator, a problem arises from the glass plate/separation. Therefore, the upper limit of the content of K2 更 is more preferably 〇 5 mass%. 14 201136847 In the method for producing a glass sheet of the present embodiment, a volatilization promoting step is performed in the heat insulating structure 2. Therefore, in the glass plate to be produced, a layer rich in ruthenium is formed on the surface. Hereinafter, the glass plate will be described. (1) A layer rich in bismuth The term "layer rich in bismuth" means a region in which the content of Si atoms in the glass composition at the center of the thickness direction of the glass plate is a reference value from the glass relative to the reference value. The ratio of the Si atom content in the composition is from the position of ι 〇 5 or more to the main surface of the glass plate.

Si〇2之含有率多於玻璃板厚度方向之中心之Si〇2含有率的富含矽之層被形成於玻璃板表面。該富含矽之層之深度較佳為大於0且〜2G nm，更佳為大於q且〜15 nm (進而較佳為1〜12麵、2〜11 _、3〜U·)。藉此，可獲得 =刀之冰度之㈣應力層。另—方面，富含石夕之層之深度 1促進自剛形成後之玻璃帶表面之揮發而可變深’但藉 1 匕會產生成形精·確條件之脫離或者生產率之降低。因此，虽含矽之層之深度較佳為30 nm以下。A cerium-rich layer having a Si 〇 2 content ratio of Si 〇 2 in the thickness direction of the glass plate is formed on the surface of the glass plate. The depth of the cerium-rich layer is preferably greater than 0 and 〜2 G nm, more preferably greater than q and 〜15 nm (more preferably 1 to 12 faces, 2 to 11 _, 3 to U·). Thereby, the (four) stress layer of the ice of the knife can be obtained. On the other hand, the depth of the layer rich in the stone eve 1 promotes the volatilization of the surface of the glass ribbon immediately after the formation, and becomes deeper, but the detachment of the forming precision or the decrease in productivity is caused by the 1. Therefore, although the depth of the layer containing germanium is preferably 30 nm or less.

曰夕之層中，相對於上述基準值之玻璃組成中之S 量之比的最大值較佳為1 以上，更佳為以J： :而較佳為i.io以上、⑴以上、i 14以上、i i5以上 I.16以上、1.18以上）。信f切之層之玻璃組成中之Si原子含量之最> ::以上厚度方向之中心之81原子含量相比，較佳為多更佳為多U0〆。以上（進而較佳為2%以上、2,5? 以上、3%以上）。 15 201136847 或者，富含矽之層之Si〇2含有率之最大值與玻璃板厚度方向之中心之Si〇2含有率相比，較佳為高〇 5%以上更佳為高1%以上（進而較佳為15%以上、2%以上、2 5%以上、3 %以上）。富含矽之層滿足上述條件，藉此可於玻璃板表面與玻璃板内部之間獲得充分之熱膨脹率之差，從而可於玻璃板之兩主面形成壓縮應力層。又，亦可提高玻璃板表面之維氏硬度或耐久性’從而可防止玻.璃板龜裂。此處，：¾被形成於玻璃板表面之富含石夕之層之si原子含量或Si〇2含有率未達上述範圍，則無法於玻璃板表面與玻璃板内部之間獲得充分之熱膨脹率之差，從而無法充分形成較大之應力值之壓縮應力層。或者，無法獲得充分之維氏硬度或财久性。另一方面，若富含矽之層之Si原子含量或si〇2含有率超過上述上限，則存在導致玻璃板之品質、物理特性、熱特性、化學特性）發生變化，從而無法用於先前之用途之 If形》例如，玻璃板之切斷或钮刻處理變得困難。又’會有下述情形：被形成於藉由本實施形態製造之玻璃板之富含矽之層中，Si原子含量或Si02含有率變得最大之位置並非為玻璃板表面上，而係存在於自玻璃板表面起大於0且〜5 nm之範圍。若富含矽之層被形成於玻璃板表面，則藉由玻璃板表面與玻璃板内部之熱膨脹率之差，壓縮應力層被形成於涪著玻璃板之兩主面之部分，並拉伸應力層被形成於該等壓 16 201136847 縮應力層之間。根據本實施形態之玻璃板製造方法，藉由將壓縮應力值及拉伸應力值作圖而繪製之應力分佈成為特異者。亦可藉由緩冷步驟中將玻璃帶急冷卻而於玻璃板之兩主面形成壓縮應力層，以此種方式所獲得之玻璃板之應力分佈為綠製成抛物線般之形狀（此情形之壓縮應力層係因於玻璃中由固定之導熱率所引起之玻璃板表面與玻璃板内部之導熱量之差而產生者）。對此，由本實施形態之玻璃板製造方法所獲得之玻璃板中，藉由揮發促進步驟形成壓縮應力層’即富含矽之層所引起之熱膨脹率之差有助於壓縮應力層之形成。因此，壓縮應力層被形成於距玻璃板之主面較近之區域（即壓縮應力層之深度較淺）。而且，該壓縮應力層與藉由急冷卻而形成之壓縮應力層之情形時所獲得者相比具有更大之應力值（因壓縮應力層與拉伸應力層取得均衡，故而壓縮應力層變薄時壓縮應力值變高）。即，於由本實施形態之玻璃板製造方法所獲得之玻璃板之表面附近，與藉由急冷卻而形成壓縮應力層之情形相比具有更大之應力值之壓縮應力層被形成，因此更不易受損玻璃板之表面。進而，拉伸應力層係於玻璃板厚度方向之兩側以外具有大致固定之應力值。即，藉由本實施形態之玻璃板製造方法所獲得之玻璃板之應力分佈成為底部寬度較寬且扁平之u字狀。 (2 )壓縮應力層壓縮應力層之深度較佳為50 em以下。其原因在於壓 17 201136847 縮應力層之深度可藉由促進自剛形成後之玻璃帶之表面之揮發而1冰’藉此會產生成形精確條件之脫離或者生產率之降低。壓縮應力層之深度更佳為45 ^以下，進而較佳為40 // m以下’尤佳為38 ^讯以下。再者所謂本說明書中之辽縮應力層深度，係表示被形成於沿著玻璃板之一主面之部分之壓縮應力層的深度。即，上述深度之壓縮應力層被形成於玻璃板之兩主面之各面。又，壓縮應力層之深度較佳為大於1〇以爪。若壓縮應力層之深度為某程度，則可防止操作所引起之細微傷痕所致之使玻璃板.變得易於龜裂。為了即便劃有更深之傷痕亦防止玻璃板之破損，壓縮應力層之深度更佳為15以爪以上進而較佳為20 以上（尤佳為25 "m以上、30以 m以上'35 以上）。或者’壓縮應力層之深度較佳為未達玻璃板之板厚之 1/13，更佳為未達ι/15 (進而較佳為未達1/u、未達1/2〇、未達1/22 '未達1/24 )。麼縮應力層之最大壓縮應力值較佳為4 MPa以下。其原因在於若大於4 MPa，則玻璃板之加工性變差。最大壓縮應力值更佳為3·7 MPa以下，進而較佳為3.5 MPa以下（尤佳為3.0 MPa以下、2.8 MPa以下）。又’壓縮應力層之最大壓縮應力值就提高玻璃板之機械強度之觀點而言，較佳為0.4 MPa以上，更佳為1 MPa 以上（進而較佳為1.5 MPa以上、2 MPa以上）。再者’所謂本說明書中之「應力值」，係指自玻璃板之 18 201136847 主面起於厚度方向每丨〇私m範圍測定時之值。因此，局部上亦會有存在超過上述壓縮應力值之範圍般之壓縮應力值之情形（關於後述之拉伸應力值亦相同）。 (3 )拉伸應力層如上所述，被形成於玻璃板内部之拉伸應力層係，玻 7板厚度方向之兩側以外具有大致固定之應力值。玻璃板厚度方向中之兩側各除去1/1〇之拉伸應力層之中心部分 4/5 (以下僅稱為「拉伸中心區域」）中之拉伸應力值的最大值與最小值之差（拉伸應力值偏差）較佳為〇 2 以下，更佳為0.15 MPa以下（進而較佳為〇 1〇Mpa以下、〇〇5 Mpa 以下、0.02 MPa以下）。若拉伸應力層之拉伸應力值變大，則會有下述情形：於切斷玻璃板之情形時，為了切斷而劃出之特定深度之切割線超出預計地伸長，將玻璃板分割為所期望之尺寸變得困難。根據本實施形態’即便使表層之最大壓縮應力增大，亦可將拉伸應力維持在較小之值。例如可設為（表層之最大麼縮應力之絕對值）/(拉伸應力層之最大拉伸應力之絕對值）=6以上。例如’拉伸應力層之最大拉伸應力值較佳為.0.4 MPa以下。其原因在於若拉伸應力層之最大拉伸應力值大於0.4 MPa，則會有下述情形：於切斷玻璃板之情形時’為了切斷而劃出之特定深度之切割線超出預計地伸長，將玻璃板分割為所期望之尺寸變得困難。拉伸應力層之最大拉伸應力值更佳為〇·3 Mpa以下，進而較佳為紙以下（尤佳為〇.15MPa、〇1〇Mpa以下）。 · 19 201136847 再者，被形成於玻璃板内部之拉伸應力層之應力值於玻璃板之厚度方向大致固定，因此與拉伸應力層之應力值於玻璃板之厚度方向繪製拋物線之情形相比，可獲得玻璃板難以龜裂之效果。更詳細而言，藉由本實施形態之玻璃板製造方法所獲得之玻璃板之拉伸應力值於玻璃板之厚度方向大致固定，該拉伸應力值之最大值小於緩冷步驟中僅藉由將玻璃帶急冷卻而形成之拉伸應力層的最大拉伸應力值。若拉伸應力. 值變得極大，則亦會有於加工時等玻璃板龜裂之虞，因此拉伸應力值較佳為較小者。再者，緩冷步驟中僅藉由將玻璃帶急冷而形成之壓縮應力層之深度通常為玻璃板之板厚之1/10以上之厚度，但藉由本實施形態之玻璃板製造方法所形成之愿縮應力層之深度例如未達板厚之1 / 1 3。即，若板厚變薄’則用以抵銷玻璃板表面之壓縮應力層之壓縮應力的拉伸應力層之厚度亦變薄’因此緩冷步驟中僅藉由將破璃帶急冷卻而形成之拉伸應力層之應力值變大，其結果為’玻璃板之加工精度降低。然而，藉由本實施形態之玻填板製造方法所獲得之玻璃板之拉伸應力層之應力值於玻璃板之厚度方向大致固定’因此拉伸應力值之最大值亦變小’亦可精度較佳地進行玻璃板之加工。 (4)維氏硬度由本實施形態之玻璃板製造方法所獲得之玻璃板之表面之維氏硬度大於玻璃板内部之維氏硬度。即，由本實施形態之玻璃板製造方法所製锋之玻璃板其表面之維氏硬度 20 201136847 提高’因此可獲得裂痕產生率降低，更不易受損、難以破才貝之效果。由本實施形態所形成之玻璃板表面之維氏硬度較佳為 4 GPa以上，更佳為5 GPa以上’進而較佳為5 35 GPa以上°或者’相對於玻璃板内部之維氏硬度之玻璃板表面之維氏硬度的比較佳為1 .〇 1以上，更佳為1 〇2以上（進而較佳為1.05以上、1.1〇以上）。 (5 )板厚由本實施形態之玻璃板製造方法所獲得之玻璃板之厚度較佳為1.5 mm以下。其原因在於，若厚度為3 mm以上，玻璃板本身之強度變大，被形成於表面附近之壓縮應力層無法發揮充分之效果。玻璃板之厚度更佳為1〇mm以下（進而較佳為0.7 mm以下' 0.5 mm以下、〇.3 mm以下）。玻螭板之厚度越薄，本發明之效果越顯著。 (6)玻璃板之尺寸本實㈣態之玻璃板製《方㈣合於肖大之玻璃板。其原因在於’玻璃板越大撓曲量越多，因操作所引起之細微傷痕之玻璃板變得容易龜裂，但藉由麼縮應力層被形成於玻璃板表面，可減少上述問題之產生。因此，本實施形態之玻璃板製造方法適合於例如寬度方向為1〇〇〇咖以上、2000 mm以上之玻璃板之製造。本實施形態中，進行促進揮發成分自溶融玻璃3之表面、有時溶融玻璃3及剛形成後之玻璃帶*之表面揮發的揮發促進步驟’本發明之揮發促進步驟中，只要促進揮發 21 201136847 成分自溶融玻璃及玻璃帶之至少一者之表面揮發即可。為了實現上述.内只要使面向熔融玻璃及玻璃帶之至少一者之表面之環境中的揮發成分的分壓（自該環境中去除揮發成分以外之氣體時之揮發成分的壓力）與揮發成分之飽和蒸氣壓之差變大即可。作為叫列，只要使面向炫融玻璃及玻璃帶之至少-者之表面之環境之揮發成分的濃度降低即可。尤其於如本實施形態般成形步驟於絕熱構造體2内使用成形裝置1來進行之情形時，亦可使自絕熱構造體2 外導入至絕熱構造體2内之氣體接觸於流下之熔融玻璃3 及/或下拉之玻璃帶4之表面後，排出至絕熱構造體2外。其次’對由成形裝置1及絕熱構造體2所構成之成形單元之具體例進行詳細說明。 <第1實施形態> 圖2及圖3表示第1實施形態之玻璃板製造裝置之一部分即成形單元10A。該成形單元1 〇A係用以藉由將自絕熱構造體2外導入至絕熱構造體2内之氣體排出至絕熱構造體2外而進行揮發促進步驟者。如此，藉由將新鮮空氣導入至絕熱構造體2内，可降低絕熱構造體2内之經氣化之揮發成分之濃度’藉此可促進揮發成分自熔融玻璃3之表面揮發。其原因在於在絕熱構造體2内揮發成分變為飽和狀態時，更多之揮發成分之揮發變得難以進行。尤其於本實施形態中，沿著流下之熔融玻璃3之表面使氣體上升。成形裝置1成為朝下之尖五角形楔狀（寬度較窄之本壘狀）之剖面形狀，且具有：上表面，其設置有直線延伸 22 201136847In the layer of the layer, the maximum value of the ratio of the amount of S in the glass composition with respect to the above reference value is preferably 1 or more, more preferably J: : and more preferably i. io or more, (1) or more, i 14 Above, i i5 or more I.16 or more, 1.18 or more). It is preferable that the content of the Si atom in the glass composition of the letter f-cut layer is more than the number of 81 atoms in the center of the thickness direction, more preferably more than U0. The above (further, it is preferably 2% or more, 2, 5 or more, or 3% or more). 15 201136847 Alternatively, the maximum content of Si〇2 in the layer rich in antimony is preferably more than 5% or more preferably more than 1% higher than the Si〇2 content in the center of the thickness direction of the glass sheet. Further, it is preferably 15% or more, 2% or more, 25% or more, or 3% or more. The ruthenium-rich layer satisfies the above conditions, whereby a sufficient difference in thermal expansion ratio between the surface of the glass plate and the inside of the glass plate can be obtained, so that a compressive stress layer can be formed on both main faces of the glass plate. Further, the Vickers hardness or durability of the surface of the glass plate can be increased to prevent the glass plate from cracking. Here, it is not possible to obtain a sufficient thermal expansion rate between the surface of the glass plate and the inside of the glass plate, the Si atom content or the Si〇2 content of the layer rich in the stone layer formed on the surface of the glass plate is not within the above range. The difference is such that a compressive stress layer having a large stress value cannot be sufficiently formed. Or, it is not possible to obtain sufficient Vickers hardness or longevity. On the other hand, if the Si atom content or the si〇2 content of the cerium-rich layer exceeds the above upper limit, the quality, physical properties, thermal properties, and chemical properties of the glass sheet are changed, and thus cannot be used in the prior art. For the shape of the use, for example, the cutting or button processing of the glass sheet becomes difficult. Further, there is a case where the Si atom content or the SiO 2 content is formed in the ruthenium-rich layer of the glass plate produced by the present embodiment, which is not on the surface of the glass plate but is present in It is greater than 0 and ~5 nm from the surface of the glass plate. If the layer rich in ruthenium is formed on the surface of the glass plate, the compressive stress layer is formed on the two main faces of the glass plate by the difference in thermal expansion between the surface of the glass plate and the inside of the glass plate, and tensile stress A layer is formed between the equal pressure 16 201136847 shrinkage stress layers. According to the method for producing a glass sheet of the present embodiment, the stress distribution drawn by plotting the compressive stress value and the tensile stress value is a special one. The compressive stress layer may be formed on both main faces of the glass plate by the rapid cooling of the glass ribbon in the slow cooling step, and the stress distribution of the glass plate obtained in this manner is a parabolic shape of green (in this case) The compressive stress layer is caused by the difference in the amount of heat conduction between the surface of the glass sheet and the inside of the glass sheet caused by the fixed thermal conductivity in the glass. On the other hand, in the glass plate obtained by the method for producing a glass sheet of the present embodiment, the difference in the coefficient of thermal expansion caused by the formation of the compressive stress layer ** by the volatilization promoting step, i.e., the layer rich in ruthenium, contributes to the formation of the compressive stress layer. Therefore, the compressive stress layer is formed in a region closer to the main surface of the glass sheet (i.e., the depth of the compressive stress layer is shallow). Moreover, the compressive stress layer has a larger stress value than that obtained in the case of a compressive stress layer formed by rapid cooling (since the compressive stress layer and the tensile stress layer are balanced, so the compressive stress layer becomes thinner) The compressive stress value becomes higher). In other words, in the vicinity of the surface of the glass sheet obtained by the method for producing a glass sheet of the present embodiment, a compressive stress layer having a larger stress value is formed than in the case where a compressive stress layer is formed by rapid cooling, and thus it is more difficult. The surface of the damaged glass plate. Further, the tensile stress layer has a substantially constant stress value other than the both sides in the thickness direction of the glass sheet. In other words, the stress distribution of the glass sheet obtained by the glass sheet manufacturing method of the present embodiment has a U-shaped width which is wide and flat. (2) Compressive stress layer The depth of the compressive stress layer is preferably 50 em or less. The reason for this is that the depth of the stress-reducing layer can be promoted by the volatilization of the surface of the glass ribbon immediately after formation, thereby causing a detachment of the precise forming conditions or a decrease in productivity. The depth of the compressive stress layer is more preferably 45 ^ or less, and further preferably 40 // m or less, and particularly preferably 38 μm or less. Further, the depth of the stress relief layer in the present specification means the depth of the compressive stress layer formed in a portion along one main surface of the glass sheet. That is, the compression stress layer of the above depth is formed on each of the two main faces of the glass sheet. Further, the depth of the compressive stress layer is preferably greater than 1 〇 to the claw. If the depth of the compression stress layer is to some extent, it is possible to prevent the glass sheet from being easily cracked by the slight flaw caused by the operation. In order to prevent breakage of the glass sheet even if a deeper flaw is formed, the depth of the compressive stress layer is preferably 15 or more, more preferably 20 or more (particularly 25 "m or more, 30 or more or more '35 or more) . Or the depth of the 'compression stress layer is preferably less than 1/13 of the thickness of the glass plate, more preferably less than ι/15 (and further preferably less than 1/u, less than 1/2 〇, not reached) 1/22 'not up to 1/24). The maximum compressive stress value of the stress reducing layer is preferably 4 MPa or less. The reason is that if it is more than 4 MPa, the workability of the glass sheet is deteriorated. The maximum compressive stress value is more preferably 3·7 MPa or less, further preferably 3.5 MPa or less (especially preferably 3.0 MPa or less and 2.8 MPa or less). Further, from the viewpoint of increasing the mechanical strength of the glass sheet, the maximum compressive stress value of the compressive stress layer is preferably 0.4 MPa or more, more preferably 1 MPa or more (more preferably 1.5 MPa or more and 2 MPa or more). Further, the term "stress value" in the present specification means a value measured from the main surface of the glass sheet 18 201136847 in the thickness direction. Therefore, there is a case where there is a local compressive stress value exceeding the range of the above-described compressive stress value (the same applies to the tensile stress value described later). (3) Tensile stress layer As described above, the tensile stress layer formed inside the glass sheet has a substantially constant stress value other than the both sides in the thickness direction of the glass plate. The maximum value and the minimum value of the tensile stress values in the central portion 4/5 (hereinafter simply referred to as "tensile center region") of the tensile stress layer of each of the two sides in the thickness direction of the glass plate are removed. The difference (the tensile stress value deviation) is preferably 〇2 or less, more preferably 0.15 MPa or less (more preferably 〇1〇Mpa or less, 〇〇5 Mpa or less, or 0.02 MPa or less). When the tensile stress value of the tensile stress layer becomes large, there is a case where, when the glass plate is cut, the cutting line of a specific depth which is drawn for cutting is extended beyond the expected degree, and the glass plate is divided. It becomes difficult to achieve the desired size. According to this embodiment, even if the maximum compressive stress of the surface layer is increased, the tensile stress can be maintained at a small value. For example, it can be set to (the absolute value of the maximum stress of the surface layer) / (the absolute value of the maximum tensile stress of the tensile stress layer) = 6 or more. For example, the maximum tensile stress value of the tensile stress layer is preferably 0.40.4 MPa or less. The reason is that if the maximum tensile stress value of the tensile stress layer is more than 0.4 MPa, there is a case where the cutting line at a specific depth which is cut for cutting is out of the expected elongation when the glass sheet is cut. It is difficult to divide the glass sheet into a desired size. The maximum tensile stress value of the tensile stress layer is more preferably 〇3 Mpa or less, and further preferably less than paper (particularly 〇15 MPa, 〇1 〇Mpa or less). · 19 201136847 Furthermore, the stress value of the tensile stress layer formed inside the glass sheet is substantially constant in the thickness direction of the glass sheet, and therefore compared with the case where the stress value of the tensile stress layer is plotted in the thickness direction of the glass sheet. The effect that the glass plate is difficult to crack can be obtained. More specifically, the tensile stress value of the glass sheet obtained by the method for producing a glass sheet of the present embodiment is substantially constant in the thickness direction of the glass sheet, and the maximum value of the tensile stress value is smaller than that in the slow cooling step only The maximum tensile stress value of the tensile stress layer formed by the glass ribbon being rapidly cooled. If the value of the tensile stress becomes extremely large, there is a possibility that the glass sheet is cracked during processing, and therefore the tensile stress value is preferably smaller. Further, in the slow cooling step, the depth of the compressive stress layer formed only by quenching the glass ribbon is usually 1/10 or more of the thickness of the glass sheet, but is formed by the method for producing a glass sheet of the present embodiment. The depth of the stress-reducing layer is, for example, less than 1 / 13 of the thickness of the plate. That is, if the thickness of the sheet is thinned, the thickness of the tensile stress layer for offsetting the compressive stress of the compressive stress layer on the surface of the glass sheet is also reduced. Therefore, the slow cooling step is formed only by rapidly cooling the glass ribbon. The stress value of the tensile stress layer becomes large, and as a result, the processing precision of the glass plate is lowered. However, the stress value of the tensile stress layer of the glass plate obtained by the method for producing a glass-filled plate of the present embodiment is substantially fixed in the thickness direction of the glass plate, so that the maximum value of the tensile stress value is also small. Good processing of glass plates. (4) Vickers hardness The Vickers hardness of the surface of the glass plate obtained by the method for producing a glass plate of the present embodiment is larger than the Vickers hardness of the inside of the glass plate. In other words, the glass plate of the front plate made by the method for producing a glass sheet of the present embodiment has a Vickers hardness of 20 201136847, which is improved by the fact that the crack generation rate is lowered, and it is less likely to be damaged and hard to break. The Vickers hardness of the surface of the glass plate formed by the present embodiment is preferably 4 GPa or more, more preferably 5 GPa or more, and further preferably 5 35 GPa or more or a glass plate with respect to Vickers hardness inside the glass plate. The Vickers hardness of the surface is preferably 1. 〇1 or more, more preferably 1 〇 2 or more (more preferably 1.05 or more and 1.1 〇 or more). (5) Thickness of the sheet The thickness of the glass sheet obtained by the method for producing a glass sheet of the present embodiment is preferably 1.5 mm or less. The reason for this is that if the thickness is 3 mm or more, the strength of the glass plate itself becomes large, and the compressive stress layer formed near the surface cannot exhibit sufficient effects. The thickness of the glass plate is preferably 1 mm or less (more preferably 0.7 mm or less '0.5 mm or less, 〇.3 mm or less). The thinner the thickness of the glass plate, the more remarkable the effect of the present invention. (6) Dimensions of the glass plate The glass plate of the real (four) state is made up of the glass plate of Xiao Dazhi. The reason is that the larger the amount of deflection of the glass plate, the more easily the glass plate of the fine scratch caused by the operation is cracked, but the stress reduction layer is formed on the surface of the glass plate, thereby reducing the above problem. . Therefore, the glass sheet manufacturing method of the present embodiment is suitable for, for example, the production of a glass sheet having a width direction of 1 〇〇〇 or more and 2000 mm or more. In the present embodiment, the volatilization promoting step of promoting the volatilization of the volatilized component from the surface of the molten glass 3, and sometimes the surface of the molten glass 3 and the glass ribbon* immediately after the formation is promoted, in the volatilization promoting step of the present invention, as long as the volatilization is promoted 21 201136847 The component may be volatilized from the surface of at least one of the molten glass and the glass ribbon. In order to achieve the above, the partial pressure of the volatile component in the environment facing the surface of at least one of the molten glass and the glass ribbon (the pressure of the volatile component when the gas other than the volatile component is removed from the environment) and the volatile component are used. The difference in saturated vapor pressure becomes large. As the column, the concentration of the volatile component in the environment facing at least the surface of the glass and the glass ribbon may be lowered. In particular, when the molding step is performed in the heat insulating structure 2 using the molding apparatus 1 as in the present embodiment, the gas introduced into the heat insulating structure 2 from the outside of the heat insulating structure 2 may be brought into contact with the molten glass 3 flowing down. And/or the surface of the glass ribbon 4 that has been pulled down is discharged to the outside of the heat insulating structure 2. Next, a specific example of a molding unit composed of the molding device 1 and the heat insulating structure 2 will be described in detail. <First Embodiment> Fig. 2 and Fig. 3 show a molding unit 10A which is a part of the glass sheet manufacturing apparatus of the first embodiment. The forming unit 1A is used to discharge a gas introduced into the heat insulating structure 2 from the outside of the heat insulating structure 2 to the outside of the heat insulating structure 2 to perform a volatilization promoting step. By introducing fresh air into the heat insulating structure 2, the concentration of the vaporized volatile component in the heat insulating structure 2 can be lowered, whereby the volatile component can be volatilized from the surface of the molten glass 3. This is because when the volatile component becomes saturated in the heat insulating structure 2, volatilization of more volatile components becomes difficult. In particular, in the present embodiment, the gas is raised along the surface of the molten glass 3 that flows down. The forming apparatus 1 has a cross-sectional shape of a downwardly pointed pentagonal wedge shape (a narrow width of the base shape), and has an upper surface provided with a linear extension 22 201136847

之溝槽11;及一對壁面12,其自與該上表面中之溝槽n 平打之兩端部起朝向下方。再者，本說明書中，為了方便說明’亦將於水平面上溝槽u之延伸之方向稱為X 於水平面上與X方向正交之方向稱為γ方向，垂直方為Ζ方向（參照圖3)。溝槽11係以使自省略圖示之供給管供給至—端之溶融玻璃3遍及全長均勾地溢流之方式，隨著自—端起朝向另一端深度逐漸變淺。一對壁面12之各者由自上表面之Υ方向之端部起垂直垂下之垂直面與自該垂直面之下端部起以相互接近之方式向内傾斜之傾斜面所構成，傾斜面之下端部彼此相交而形成於X方向延伸之陵線。接下來，成形裝置1使熔融玻璃3自溝槽丨丨之兩側溢 /瓜，由壁面12誘導該溢流之熔融玻璃彼此而使其炫合萨此連續地形成帶狀之玻璃帶4。絕熱構造體2形成容納成形裝置丨之成形腔室。具體而言，絕熱構造體2由絕熱性優異之材料構成，且具有：底壁21及頂壁23,其於上下方向夾著成形裝置7而相互相對；及矩形筒狀之周壁22，其將底壁21與頂壁23之周緣彼此連接。於底壁21之中央設置有使藉由成形裝置1形成之玻璃帶4通過之澆口 25。再者，絕熱構造體2成為中空構造’亦可形成為將加熱用或冷卻用之空氣供給至内部。本實施形態中，於與周壁22中之成形裝置1之壁面12 相對之Υ方向側之長壁部之上部，設置有貫通該周壁22之複數之排出口 26，並且於周壁22之Υ方向側之長壁部之下 23 201136847 部，設置有貫通該周壁22之複數之導入口 27。因此，藉由自然對流，形成有如圖2中由箭頭a、b、c所示之空氣：产動。即’絕熱構造體2外之空氣通過導入σ27被導入至: 熱構造體2内’該空氣沿著在成形裝置】之壁面12上流下之炫融玻璃3上升，其後通過排出σ 26排出至絕熱構造體 2外。如此，藉由於絕熱構造體2内使自外部取入之新鮮命氣上升，可防止使面向熔融玻璃3之表面之環境中的揮發成分之濃度降低而揮發成分變為飽和狀態，因此可促進揮發成分“列如B2〇3、Sn0、Κ2〇 )自炫融玻璃3揮發。換士之，因可使面向熔融玻璃3之表面之環境中的揮發成分: 分廢與揮發成分之飽和蒸氣壓的差變大，故而可促進揮發成分自熔融玻璃3之表面揮發。該揮發成分揮發之部分，即=上升之空氣接觸之熔融玻璃3之表面於玻璃帶4被冷部時成為壓縮應力層。為了使I缩應力層之應力值變高，較佳為熔融玻璃3含有較多之揮發成分。The groove 11 and the pair of wall faces 12 face downward from both end portions of the groove n in the upper surface. In addition, in the present specification, for convenience of explanation, the direction in which the groove u extends in the horizontal plane is also referred to as X. The direction orthogonal to the X direction on the horizontal plane is referred to as the γ direction, and the vertical direction is the Ζ direction (refer to FIG. 3). . The groove 11 is such that the molten glass 3 supplied from the supply pipe (not shown) to the end is overflowed over the entire length, and gradually becomes shallower toward the other end from the end. Each of the pair of wall faces 12 is formed by a vertically perpendicular vertical surface from an end portion of the upper surface in a meandering direction and an inclined surface which is inclined inwardly from the lower end portion of the vertical surface so as to approach each other, and the lower end of the inclined surface The sections intersect each other to form a mausoleum extending in the X direction. Next, the molding apparatus 1 causes the molten glass 3 to overflow from the both sides of the groove /, and the molten glass which is overflowed by the wall surface 12 is caused to converge to each other to form a strip-shaped glass ribbon 4 continuously. The heat insulating structure 2 forms a forming chamber that houses the forming device. Specifically, the heat insulating structure 2 is made of a material having excellent heat insulating properties, and has a bottom wall 21 and a top wall 23 which face each other with the molding device 7 interposed therebetween in the vertical direction, and a rectangular tubular peripheral wall 22 which will The peripheral edges of the bottom wall 21 and the top wall 23 are connected to each other. A gate 25 through which the glass ribbon 4 formed by the forming device 1 passes is disposed at the center of the bottom wall 21. Further, the heat insulating structure 2 has a hollow structure, and may be formed to supply air for heating or cooling to the inside. In the present embodiment, a plurality of discharge ports 26 penetrating the peripheral wall 22 are provided on the upper portion of the long wall portion on the side in the radial direction with respect to the wall surface 12 of the molding apparatus 1 in the peripheral wall 22, and are disposed on the side of the circumferential wall 22 A portion 23 201136847 below the long wall portion is provided with a plurality of introduction ports 27 penetrating the peripheral wall 22 . Therefore, by natural convection, air as shown by arrows a, b, and c in Fig. 2 is formed: production. That is, the air outside the 'insulation structure 2 is introduced into the heat structure 2 by the introduction of the σ 27, and the air rises along the glazed glass 3 flowing down the wall surface 12 of the forming device, and is then discharged to the σ 26 through the discharge σ 26 . Outside the heat insulating structure 2. By raising the fresh air from the outside in the heat insulating structure 2, it is possible to prevent the concentration of the volatile component in the environment facing the surface of the molten glass 3 from being lowered and the volatile component to be saturated, thereby promoting the volatilization. The components "column such as B2〇3, Sn0, Κ2〇) are volatilized from the fused glass 3. For the change of the volatile components in the environment facing the surface of the molten glass 3: the saturated vapor pressure of the waste and volatile components Since the difference is large, the volatile component is promoted to volatilize from the surface of the molten glass 3. The volatilized component is volatilized, that is, the surface of the molten glass 3 which is in contact with the rising air becomes a compressive stress layer when the glass ribbon 4 is cooled. The stress value of the I-shrinkage layer is increased, and it is preferred that the molten glass 3 contains a large amount of volatile components.

再者，排出口 26及導入D 汉等入口 27亦可設置於周壁。 X方向側之短壁部。或者，亦可僅於周壁22之又短壁部設置排出口 26及導入口 27。妙，向側之 :3 :全寬均勻地使揮發成分揮發，較SC排：^ 入口 27僅於周壁2kY方向側 26及導置。 < 仅芏沖以固定之間距設又’排出口 26及導入口 27之形狀及數 22保持必要之強度即 ”要對周壁 w田選疋。例如，排出口口 27之形狀可為如圖3 26及導入國所不之圓形，亦可設為於χ方向延 24 201136847 伸之狹縫狀而減少個數。例如，使排出口 26及導入口 27 為圓形之情形時’其直徑較佳為1〜20 mm。其原因在於若直徑大於20 mm，則會有絕熱構造體2之強度不充分之虞。再者’為了均勻且有效地自絕熱構造體2將氣體排出，排出口 26為遍及玻璃帶之寬度方向整體延伸之狹縫更有效。 d而開面積越大，氣流量越過於增加，會產生玻璃板之表面缺陷之增加，或玻璃板之表面凹凸之惡化，成形溫度之確保良得困難之問題。然而，此點如以下所示般，可藉由以下述方式調整流量來解決：使自導入口 27導入至絕熱構1^體2内之空氣或者惰性氣體之溫度為絕熱構造體2 内之目標溫度，且絕熱構造體2内之壓力可維持在特定壓力0 進而，通過導入口 27導入至絕熱構造體2内之空氣較佳為例如不使熔融玻璃3或玻璃“之溫度降低之程度的溫度。此處，若所導入之空氣之量為少量，即便導入常溫之空氣熔融玻璃3或玻璃帶4之溫度亦不會降低至上述程度，因此亦可導入常溫之空氣。另一方面，若所導入之空氣之量為大量，則導入常溫之空氣時，熔融玻^ 3或玻璃帶4之溫度大幅降低。於此情形時’較佳為於絕轨構造體2 之外側或内側設置將通過導人口 27導人之空氣加熱至特定之溫度之加熱機構。於使用加熱機構之情形時，較佳為於絕熱構造體2夕卜’加熱空氣以使空氣之溫度與熔融玻璃3 之溫度大致相等（例如為熔融玻璃之溫度之±⑽之範圍内）或高於其之溫度，並將該經加熱之空氣導入至絕轨構造體2 25 201136847 内0 若使用以上所說明之本實施形態之成形單元1〇A，一邊從由絕熱構造體2所包圍之成形裝置丨之溝槽u之兩側使熔融玻璃3溢流，一邊執行下述步驟：使自絕熱構造體2 外導入至絕熱構造體2内之空氣沿著在成形裝置丨之壁面 1 2上流下之熔融玻璃3上升後將其排出至絕熱構造體2 外。如此，藉由使通過絕熱構造體2之氣體沿著在成形裝置1之壁面12上流下之熔融玻璃上升而可有效促進揮發成分自熔融玻璃3之揮發。藉此，可獲得應力值較高之壓縮應力層被形成於兩主面之玻璃板。再者，上述實施形態中，排出口 26設置於周壁22之. 上部，但對排出口 26之位置並無特別限制。例如，如圖5 所不之變形例之成形單元丨〇c般，亦可將排出口％設置於頂壁23中之成形裝置k正上方之部分。如此，亦可藉由自然對流，使自絕熱構造體2外導入至絕熱構造體2内之空氣沿著在成形裝置1之壁面12上流下之熔融玻璃3上升後通過排出口 26將其排出至絕熱構造體2外。又，於此情形時，溶融玻璃3亦於成形裝置i之上方與通過絕熱構造體2之空氣接觸，因此與將排出口％設置於周壁22之上部之情形相比，更能促進揮發成分揮發。然而，於將排出口 26設置於周壁22之頂壁23之情形時，會有來自絕熱構造體2之上方之落下物通過排出口 26 洛下至熔融玻璃3之虞。就此觀點而言，較佳為如上述實施形態般將排出口 26設置於周壁22之上部。 26 201136847 又，上述實施形態中，導入口 27設置於周壁22之下部，但對導入口 27之位置並無特別限制。例如如圖斗所示之變形例之成形單元10B般，亦可將導入口 27設置於底壁21。於此情形時，若導入口 27存在於成形裝置【之二下方之區域R内’則會有來自導入口 27之空氣之流動對玻璃帶4之形狀穩定性帶來影響之虞，因.此導入口 ”較佳為設置於區域R之外側。又，如圖5所示，可省略導入口 27。如此，絕熱構造體2外之空氣亦通料p 25而導人至絕熱構造體2内。藉此’可促進揮發成分自剛形成後之玻璃帶4之表面之揮發。然而，於此情形時氣體以與玻璃帶4相反方向通過澆口 25, :有玻璃I 4之形狀穩定性受損之虞，因此較佳為設置盘洗口 25不同之導入口 27。八構、^ 述實施形態中，#由自然對流進行導入朝絕熱空氣及排出朝絕熱構造體2外之空氣，但亦 ^制對流進行該等處理。例如，於絕熱構造體2之且對：=給管並於絕熱構造體2之上部貫通排出管，並造體2内^;^連接風扇即可。於此情形時，於絕熱構入口及排出口之供給管及排出管之端部分別構成導内之空：’使用強制對流之情形，即導入至絕熱構造體2 溫度之情2度與炫融玻璃3之溫度大致相等或高於其之 10D般，導日，例如亦可如圖6所示之變形例之成形單元入口 27設置於絕熱構造體2之上部，被導入至 27 201136847 :熱構造體2内之空氣沿著熔融玻璃3下降，自漁口 25排出至絕熱構造體2外。 ^ ^ . 右/〇者机下之熔融玻璃3使氧升’可利用藉由該等而形成之料a、+ ^ ^ Λ寻_办成之對向流更顯著地促進揮發成分揮發β —通過導入口 27或者洗口 25而被導至絕熱構造體2 之氣體未必必需為空氣’亦可為惰性氣體…隋性氣體， ::止成形⑴或絕熱構造體2之腐姓之觀點而言，尤為使用氮0或者，被導人j猫轨播导入至絕熱構造體2内之氣體亦可為二氣與惰性氣體之混合物。 <第2實施形態> "人參’’、、圖7’對第2實施形態之玻璃板製造裝置之 Γ部分即成形單元1GE進行說明。再者，對㈣i實施形態相同之構成部分賦予相同符號，並省略其說明。本實施形態之成形單元i 0E係用以藉由將絕熱構造體2 内減塵而於形成步驟中進行揮發促進步驟者。具體而言，於絕熱構造體2設置有抽氣口 28，於該抽氣口料接有真 I 6再者冑抽氣σ 28及真空系6之個數並無特別限制’只要為1個以上即可。若對絕熱構造體2内減壓過量，則導致自澆口 25大量導入低於絕熱構造體2内之溫度之氣體，玻璃無法均勻化，玻璃之厚度產生不均，進而亦會產生應變。因此，較佳為對絕熱構造體2内以絕熱構造體2之周圍之壓力之十分之一以下之範圍内進行減壓。即，於絕熱構造體2内之氣壓為1氣屋之It形時車交佳為以上限為〇 9氣壓而減壓。根據 28 201136847 本實施形態，可降低面向熔融玻璃掙柃rbk· 久敬喝命4之表面之中的揮發成分的濃度。換菸诂枯魅 '便面向炼融玻璃3 及玻璃帶4.之表面之環境中的揮發成分的㈣與揮發成分之飽和蒸氣壓之差變大。又，藉由將絕熱構造體2内減壓，因為降低揮發成分揮發所需之能量，故更加促進揮發成分揮發。 <其他實施形態> 本發明不僅可應用溢流下拉法，亦可應用例如流孔下拉法（Slot dowiuiraw)。於此情形時，進行促進揮發成分自剛形成後之玻璃帶4之表面揮發的揮發促進步驟。又，用以實現本發明之方法並不限定於上述實施形態，例如亦可藉由使將玻璃帶4保持在高溫之時間變長而於形成步驟後進行揮發促進步驟。實施例以下，列舉實施例對本發明進行詳細說明，但本發明並不限定於該等實施例。如圖2及圖3所示，使用具備設置有排出口 26及導入口 27之絕熱.構造體2之成形單元i〇A，製造5片尺寸11〇〇 mmx 13 00 mm、厚度0.7 mm之玻璃板（實施例1〜5 )。溶融玻璃之各成分之含有率如下所述。Further, the discharge port 26 and the inlet 27 into which the D Han is introduced may be provided on the peripheral wall. The short wall portion on the X direction side. Alternatively, the discharge port 26 and the introduction port 27 may be provided only in the short wall portion of the peripheral wall 22. Wonderful, to the side: 3: The full width evenly volatilizes the volatile components, compared to the SC row: ^ The inlet 27 is only on the 2kY direction side 26 of the peripheral wall and the guide. < Only the gap between the fixed distance and the shape and number 22 of the discharge port 26 and the inlet port 27 is maintained, that is, the wall wall is selected. For example, the shape of the discharge port 27 may be as shown in the figure. 3 26 and the circle that is not in the country of introduction, it can also be set to reduce the number of slits in the direction of the χ 24 24 24 24 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 36 The reason is preferably 1 to 20 mm. The reason is that if the diameter is larger than 20 mm, the strength of the heat insulating structure 2 is insufficient. Further, in order to uniformly and efficiently discharge the gas from the heat insulating structure 2, the discharge port 26 is discharged. It is more effective for the slit extending integrally in the width direction of the glass ribbon. The larger the opening area is, the more the gas flow rate is increased, and the surface defects of the glass sheet are increased, or the surface unevenness of the glass sheet is deteriorated, and the forming temperature is increased. This ensures that the problem is difficult. However, as shown below, it can be solved by adjusting the flow rate in such a manner that the temperature of the air or the inert gas introduced into the heat insulating structure 2 from the introduction port 27 is Thermal insulation structure 2 The target temperature and the pressure in the heat insulating structure 2 can be maintained at a specific pressure 0. Further, the air introduced into the heat insulating structure 2 through the introduction port 27 is preferably such that the temperature of the molten glass 3 or the glass is not lowered. temperature. Here, if the amount of the introduced air is small, the temperature of the air-melted glass 3 or the glass ribbon 4 introduced at a normal temperature is not lowered to the above-described degree, so that air at a normal temperature can be introduced. On the other hand, if the amount of air to be introduced is large, the temperature of the molten glass 3 or the glass ribbon 4 is largely lowered when air of normal temperature is introduced. In this case, it is preferable to provide a heating mechanism for heating the air guided by the guide person 27 to a specific temperature on the outer side or the inner side of the track structure 2 . In the case of using a heating mechanism, it is preferable to heat the air in the heat insulating structure 2 so that the temperature of the air is substantially equal to the temperature of the molten glass 3 (for example, within a range of ± (10) of the temperature of the molten glass) or high. At the temperature of this, the heated air is introduced into the rail structure 2 25 201136847. 0 When the forming unit 1A of the present embodiment described above is used, the molding is surrounded by the heat insulating structure 2 The both sides of the groove u of the apparatus 溢 overflow the molten glass 3, and the following steps are performed: the air introduced into the heat insulating structure 2 from the outside of the heat insulating structure 2 flows down the wall surface 12 of the forming apparatus After the molten glass 3 rises, it is discharged to the outside of the heat insulating structure 2. By raising the gas flowing through the heat insulating structure 2 along the molten glass flowing down the wall surface 12 of the molding apparatus 1, the volatilization of the volatile component from the molten glass 3 can be effectively promoted. Thereby, a compressive stress layer having a high stress value can be obtained on the glass sheets of the two main faces. Further, in the above embodiment, the discharge port 26 is provided in the upper portion of the peripheral wall 22, but the position of the discharge port 26 is not particularly limited. For example, as in the forming unit 丨〇c of the modification example shown in Fig. 5, the discharge port % may be provided in a portion directly above the forming device k in the top wall 23. In this manner, the air introduced into the heat insulating structure 2 from the outside of the heat insulating structure 2 can be lifted along the molten glass 3 flowing down the wall surface 12 of the molding apparatus 1 by natural convection, and then discharged to the through the discharge port 26 through the discharge port 26. Outside the heat insulating structure 2. Further, in this case, the molten glass 3 is also in contact with the air passing through the heat insulating structure 2 above the forming apparatus i, so that the volatilization of the volatile component is more promoted than when the discharge port % is provided on the upper portion of the peripheral wall 22. . However, when the discharge port 26 is provided in the top wall 23 of the peripheral wall 22, the fallen object from above the heat insulating structure 2 passes through the discharge port 26 to the top of the molten glass 3. From this point of view, it is preferable to provide the discharge port 26 to the upper portion of the peripheral wall 22 as in the above embodiment. Further, in the above embodiment, the introduction port 27 is provided below the peripheral wall 22, but the position of the introduction port 27 is not particularly limited. For example, the introduction port 27 may be provided to the bottom wall 21 as in the molding unit 10B of the modification shown in the figure. In this case, if the inlet port 27 exists in the region R below the forming device, the flow of air from the inlet port 27 may affect the shape stability of the glass ribbon 4, because of this. The inlet port is preferably provided on the outer side of the region R. Further, as shown in Fig. 5, the inlet port 27 can be omitted. Thus, the air outside the heat insulating structure 2 is also introduced into the heat insulating structure 2 by the p 25 This can promote the volatilization of the volatile component from the surface of the glass ribbon 4 immediately after formation. However, in this case, the gas passes through the gate 25 in the opposite direction to the glass ribbon 4: the shape stability of the glass I 4 is affected by In the case of the damage, it is preferable to provide the inlet port 27 which is different from the disk washing port 25. In the embodiment, the natural air convection is introduced into the heat insulating air and the air which is discharged outside the heat insulating structure 2, but The convection is performed in such a manner. For example, in the heat insulating structure 2, the pair of pipes is connected to the upper portion of the heat insulating structure 2, and the discharge pipe is connected to the upper portion of the heat insulating structure 2. Supply pipe and discharge at the inlet and outlet of the adiabatic structure The ends of the ends constitute the space in the guide: 'In the case of forced convection, that is, the temperature introduced into the adiabatic structure 2 is 2 degrees equal to or higher than the temperature of the glazed glass 3, for example, Alternatively, the molding unit inlet 27 of the modification shown in FIG. 6 is provided on the upper portion of the heat insulating structure 2, and is introduced into 27 201136847: the air in the thermal structure 2 descends along the molten glass 3, and is discharged from the fishing port 25 to Outside the adiabatic structure 2 ^ ^ . The molten glass 3 under the right / the lower part makes the oxygen rise 'can be used to form the material a, + ^ ^ Λ _ _ _ _ _ _ _ _ _ _ _ Promoting Volatilization of Volatile Components β—The gas introduced into the adiabatic structure 2 through the inlet port 27 or the washing port 25 does not necessarily have to be air 'may be an inert gas... an inert gas, :: a stop forming (1) or a heat insulating structure 2 From the viewpoint of the rot, it is preferable to use nitrogen 0 or a gas introduced into the heat insulating structure 2 by the guide j cat orbit. The gas may be a mixture of two gases and an inert gas. [2nd embodiment] " Ginseng'', Fig. 7', glass plate manufacturing apparatus of the second embodiment The forming unit 1GE will be described with the same reference numerals, and the description thereof will be omitted. The forming unit i 0E of the present embodiment is used for reducing the heat insulating structure 2 The dust is introduced into the volatilization promoting step in the forming step. Specifically, the heat insulating structure 2 is provided with an air suction port 28, and the air suction port is connected with the true I 6 and the air suction σ 28 and the vacuum system 6 The number is not particularly limited as long as it is one or more. If the pressure is excessively reduced in the heat insulating structure 2, a large amount of gas which is lower than the temperature in the heat insulating structure 2 is introduced from the gate 25, and the glass cannot be uniformized. The thickness of the glass is uneven, which in turn causes strain. Therefore, it is preferable to decompress the inside of the heat insulating structure 2 within a range of one tenth or less of the pressure around the heat insulating structure 2. That is, when the air pressure in the heat insulating structure 2 is in the It shape of the gas house, the car is preferably decompressed at an upper limit of 〇 9 atmosphere. According to the present embodiment, it is possible to reduce the concentration of volatile components in the surface of the surface of the molten glass. The difference between the (four) volatile components in the environment of the surface of the tempered glass 3 and the glass ribbon 4. and the saturated vapor pressure of the volatile component becomes large. Further, by decompressing the inside of the heat insulating structure 2, the energy required for volatilization of the volatile component is reduced, so that the volatile component is more volatilized. <Other Embodiments> The present invention can be applied not only to the overflow down-draw method but also to, for example, a Slot Dowiuiraw method. In this case, a volatilization promoting step of promoting volatilization of the volatile component from the surface of the glass ribbon 4 immediately after formation is carried out. Further, the method for carrying out the present invention is not limited to the above-described embodiment, and for example, the volatilization promoting step may be carried out after the forming step by lengthening the glass ribbon 4 at a high temperature for a long period of time. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. As shown in FIG. 2 and FIG. 3, five glass sheets having a size of 11 mm × 13 00 mm and a thickness of 0.7 mm were produced by using a molding unit i 〇 A having a heat insulating structure 2 provided with a discharge port 26 and an introduction port 27 . Plate (Examples 1 to 5). The content ratio of each component of the molten glass is as follows.

Si02 ： 60.9%Si02 : 60.9%

Al2〇3 ： 16.9% B2〇3 ： 11.6%Al2〇3 : 16.9% B2〇3 : 11.6%

MgO ： 1.7% 29 201136847MgO : 1.7% 29 201136847

CaO : 5.1%CaO : 5.1%

SrO : 2.6%SrO : 2.6%

BaO : 0.7% K20 ： 0.25%BaO : 0.7% K20 : 0.25%

Sn02 : 0.13% 又’排出口 26設為直徑10 mm之圓形，於周壁22之 X方向側之各短壁部之上部各設置2個。導入口 27設為直徑10 mm之圓形，於周壁22之X方向側之各短壁部之下部各設置2個。 (試驗）對於實施例之玻璃板’使用X射線光電子光譜裝置 (ULVAC-PHI公司製造之Quantera SXM )，測定表面附近之原子濃度。具體而言，藉由濺鍍對玻璃板之表面向下挖至不同深度，並測定各深度中之原子濃度。作為測定元素，指定Si、以及含有率相對較高之揮發成分即Ai、b、Ca、 Sr、Ba，並求出測定元素中所占之Si之比率。之後實施例. 1、2之結果正如圖8所示。再者，揮發成分之中κ及Sn 之含有率較小，可認為該等之量對S i之比率所造成之影響較小，因此該等不包含於測定元素中。由圖8可明白’實施例中距表面極近之區域中si比率咼於玻璃板内部。這表示表面附近之揮發成分變少，可明白只要使用氣體自下而上通過之絕熱構造體，即可使揮發成分較多地揮發而可形成應力值較高之壓縮應力層。又’對實施例之玻璃板測定内部應力。内部應力係使 30 201136847 用微小面積雙折射計（王子計測機器公司製造之 KOBRA-CCD/X)，對於將玻璃板於厚度方向切斷之剖面自表面起母特定深度測定每丨cm之光程差率（光程差/光程長度）’由光彈性常數除以其而算出。之後實施例【之結果如圖9所示。· 由圖9可明白，應力值較高之壓縮應力層被形成於玻璃板之兩主面。又，被形成於玻璃板之拉伸應力之應力值於玻璃板厚度方向變得大致固定。其原因在於玻璃板之兩主面附近揮發成分變少。表1表示關於實施例1〜5之玻璃板之規格值。 31 201136847 [表1] 實施例 1 2 3 4 5 壓縮應力層深度（ym) 50 40 45 30 47 最大壓縮應力值'~~ 2.2 1.6 2.1 1.5 2 最大拉伸應力值（MPa) 0.11 0.11 0.16 0.12 0.13 _拉伸中心區域之拉伸應力值偏差（MPa〉 0.08 0.06 0.08 0.05 0.07 虽3吵之層深度（11111) 10 8 9 7 9 相對於基準值之富含矽之層之Si原子最尖含量的比 1.177 1.164 1.168 1.162 1.173 再者，所§胃表中之「基準值」，係如上所述，指「玻璃板厚度方向之中心之玻璃組成中的以原子含量其次，對實施例1〜5之玻璃板進行劃痕試驗。具體而 a，使用於前端具有直徑〇 7 5 mm之碳化物性球形尖梢 (carbid ball tip)之儀力信公司製造之劃痕硬度計型號 3 1 8S以劃痕負載2 N、劃痕長度3〇 mm進行劃痕試驗。利用雷射顯微鏡觀察該玻璃板表面之結果，實施例1〜5 中，於玻璃板之表面未產生裂痕。對此，若於研磨實施例^ 之玻璃板之表面後進行相同之劃痕試驗，則於研磨面產生有裂痕。 [產業上之可利用性] 本發明尤其適合於FPD玻璃基板用之板玻璃之製造。又’將藉由本發明所獲得之玻璃板進行化學強化之強化玻璃適合應用於行動電話、數位相機' pda (行動終端）、太陽能電池、FPD之蓋玻璃，又，除此以外，可期待於例如觸控面板顯示器之基板、窗玻璃、磁碟用基板、固體攝像 32 201136847 m 疋件用蓋玻璃、餐具等之應用。【圖式簡單說明】圖1係表示本發明之—實施形態之實施玻璃板製造方法之玻璃板製造裝置的概略構成圖。圖2係第1實施形態之玻璃板製造裝置之一部分即成形單元之剖面圖。圖3係圖2所示之成形單元之立體圖。圖4係變形例之成形單元之剖面圖。圖5係另一變形例之成形單元之咅彳面圖。圖6係再另一成形單元之剖面圖。圖7係第2實施形態之玻璃板製造裝置之一部分即成形單元之剖面圖。圖8係表示實施例卜2之玻璃板中之深度與Si比率之關係的圖表。圖9係表示實施例1之玻璃板之内部應力與深度之關係的圖表。圖1 〇係.先前之玻璃板製造裝置之一部分即成形單元之剖面圖。【主要元件符號說明】 100 玻璃板製造裝置 10Α〜10F成形單元 I ' 7 成形裝置 II 溝槽 12 壁面 33 201136847 2 ' 8 絕熱構造體 21 底壁 22 周壁 23 頂壁 25 > 81 澆口 26 排出口 27 導入口 3 熔融玻璃 4、9 玻璃帶 51 熔融槽 52 澄清槽 82 冷卻管 83 喷出口 8A 絕熱構造體之主體 8B 澆口構成體 a、b、c 箭頭 R 成形裝置之正下方之區域 34Sn02: 0.13% The discharge port 26 is a circular shape having a diameter of 10 mm, and two are provided on each of the upper portions of the short wall portions on the X-direction side of the peripheral wall 22. The guide port 27 is formed in a circular shape having a diameter of 10 mm, and two of the lower portions of the short wall portions on the X-direction side of the peripheral wall 22 are provided. (Test) For the glass plate of the example, the atomic concentration in the vicinity of the surface was measured using an X-ray photoelectron spectroscopy apparatus (Quantera SXM manufactured by ULVAC-PHI Co., Ltd.). Specifically, the surface of the glass plate was dug down to different depths by sputtering, and the atomic concentration in each depth was measured. As the measurement element, Si, and a volatile component having a relatively high content ratio, Ai, b, Ca, Sr, and Ba, are specified, and the ratio of Si in the measurement element is determined. The results of the examples 1. and 2 are as shown in Fig. 8. Further, among the volatile components, the content ratio of κ and Sn is small, and it is considered that the influence of the amounts on the ratio of S i is small, and therefore these are not included in the measurement elements. As can be understood from Fig. 8, the ratio of si in the region very close to the surface in the embodiment is in the interior of the glass plate. This means that the amount of volatile components in the vicinity of the surface is reduced, and it is possible to form a compressive stress layer having a high stress value by volatilizing a large amount of volatile components by using a heat insulating structure through which the gas passes from the bottom to the top. Further, the internal stress of the glass plate of the example was measured. The internal stress system makes 30 201136847 a micro-area birefringence meter (KOBRA-CCD/X manufactured by Oji Scientific Instruments Co., Ltd.), and measures the optical path per cm from the surface of the profile in which the glass plate is cut in the thickness direction. The difference (optical path difference / optical path length) is calculated by dividing the photoelastic constant by it. The results of the subsequent examples are shown in Fig. 9. It can be understood from Fig. 9 that a compressive stress layer having a high stress value is formed on both main faces of the glass plate. Further, the stress value of the tensile stress formed on the glass sheet is substantially constant in the thickness direction of the glass sheet. The reason for this is that the volatile components in the vicinity of the two main faces of the glass plate become less. Table 1 shows the specification values of the glass plates of Examples 1 to 5. 31 201136847 [Table 1] Example 1 2 3 4 5 Compressive stress layer depth (ym) 50 40 45 30 47 Maximum compressive stress value '~~ 2.2 1.6 2.1 1.5 2 Maximum tensile stress value (MPa) 0.11 0.11 0.16 0.12 0.13 _ tensile stress value deviation in the center of stretching (MPa> 0.08 0.06 0.08 0.05 0.07 although the depth of the layer of 3 noisy (11111) 10 8 9 7 9 The maximum content of Si atoms in the layer rich in yttrium relative to the reference value Ratio 1.177 1.164 1.168 1.162 1.173 In addition, the "reference value" in the stomach table is as described above, which means "the atomic content in the glass composition at the center of the thickness direction of the glass plate is second, and the examples 1 to 5" The glass plate was subjected to a scratch test. Specifically, a was used for a scratch hardness tester model 3 1 8S manufactured by Yilixin Co., Ltd. having a carbide ball tip having a diameter of 〇75 mm. 2 N, scratch length 3 〇 mm scratch test. The results of observing the surface of the glass plate by a laser microscope, in Examples 1 to 5, no cracks were formed on the surface of the glass plate. ^ The surface of the glass plate is the same after In the scratch test, cracks are formed on the polished surface. [Industrial Applicability] The present invention is particularly suitable for the production of sheet glass for FPD glass substrates. Further, the glass sheets obtained by the present invention are chemically strengthened. The tempered glass is suitable for use in a mobile phone, a digital camera 'pda (mobile terminal), a solar cell, a cover glass of an FPD, and, in addition, can be expected to be, for example, a substrate for a touch panel display, a window glass, a substrate for a magnetic disk, Solid-state imaging 32 201136847 m Application of cover glass, tableware, etc. [Brief Description of the Drawings] Fig. 1 is a schematic configuration diagram of a glass sheet manufacturing apparatus for carrying out a glass sheet manufacturing method according to an embodiment of the present invention. Fig. 3 is a perspective view of a molding unit shown in Fig. 2. Fig. 4 is a cross-sectional view of a molding unit according to a modification. Fig. 5 is another modification. Fig. 6 is a cross-sectional view showing still another molding unit. Fig. 7 is a view showing a part of the glass sheet manufacturing apparatus of the second embodiment. Fig. 8 is a graph showing the relationship between the depth and the Si ratio in the glass plate of Example 2. Fig. 9 is a graph showing the relationship between the internal stress and the depth of the glass plate of Example 1. Fig. 1 A cross-sectional view of a part of the prior glass plate manufacturing apparatus, that is, a forming unit. [Description of main components] 100 Glass plate manufacturing apparatus 10Α10F forming unit I' 7 Forming apparatus II Groove 12 Wall 33 201136847 2 ' 8 Insulation structure Body 21 bottom wall 22 peripheral wall 23 top wall 25 > 81 gate 26 discharge port 27 inlet 3 molten glass 4, 9 glass ribbon 51 melting tank 52 clarification tank 82 cooling tube 83 discharge port 8A main body of insulated structure 8B gate Structures a, b, c arrow R The area directly below the forming device 34

Claims

201136847 七、申請專利範圍：種玻璃板製造方法，其係包含下述步驟： .熔融步驟，其使玻璃原料熔解而獲得炼融玻璃；成形步驟，其藉由下拉法，由該溶融玻璃形成玻璃帶；揮發促進步驟，其促進揮發成分自該熔融玻璃及該玻璃帶之至少一者之表面揮發；缓冷步驟，其將該玻璃帶冷卻；及切斷步驟，其將該玻璃帶切斷而獲得玻璃板。 .2‘如申請專利範圍第1項之玻璃板製造方法，其中，該揮發促進步驟中，係使面向該熔融玻璃及該玻璃帶之至少一者2表面之環境令的該揮發成分之分壓與該揮發成分之矛“、、氣壓之差增大，藉此來促進揮發成分自該熔融玻璃及該玻璃帶之至少一者之表面揮發。 3.如申請專利範圍第2項之玻璃板製造方法，其中，該揮發促進步驟中，係使面向該熔融玻璃及該玻璃帶之至少「者之表面之環境中的該揮發成分之濃度降低，藉此來促進揮發成分自該熔融玻璃及該玻璃帶之至少一者之表面揮發。 4.如申請專利範圍第丨至3項中任一項之玻璃板製造方去’其中’該成形步驟係於絕熱構造體内使用成形裝置而進行； S亥揮發促進步驟中，使自該絕熱構造體外導入至該絕熱構造體内之氣體與流下之該熔融玻璃及/或下拉之該玻璃帶之表面接觸後，排出至該絕熱構造體外，藉此促進揮發 35 201136847 成分自該熔融玻璃及該玻璃帶之至少一者之表面揮發。 5. 如申請專利範圍第4項之玻璃板製造方法.，其中，使該氣體沿著流下之該熔融玻璃及/或下拉之該玻璃帶之表面上升。 6. 如申請專利範圍第4項之玻璃板製造方法，其中，該氣體為空氣及/或惰性氣體。 7 · 士申明專利範圍第1至3項中任一項之玻璃板製造方法，其中，該成形步驟係於絕熱構造體内使用成形裝置而進行；該揮發促進步驟中，藉由將該絕熱構造體内減壓來促進揮發成分自該熔融玻璃及該玻璃帶之至少一者之表面揮發。 8.—種玻璃板製造裝置，其具備成形裝置與絕熱構造體： s亥成形裝置’係使熔融玻璃自溝槽之兩側溢流，利用壁面誘導該溢流之熔融玻璃彼此而使其熔合，藉此形成玻璃帶；及該絕熱構造體，係包圍該成形裝置且具有使由該成形裝置形成之該玻璃帶通過之洗口；且於該絕熱構造體設置有排出口，該排出口為了促進揮發成分自該熔融玻璃之表面揮發，將自該絕熱構造體外導入至該絕熱構造體内並沿著在該成形裝置之壁面上流下之溶融玻璃而上升的氣體排出至該絕熱構造體外β 9.如申請專利範圍第8項之玻璃板製造裝置，其中，該 36 201136847 * 絕熱構造體具有：底壁’其設置有該繞口；頂壁’其隔著該成形裝置而與該底壁相對；及周壁’其將該底壁與該頂壁之周緣彼此連接；且該排出口設置於該周壁之上部。 10·如申請專利範圍第9項之玻璃板製造裝置，其中，於忒周壁之下部設置有將該氣體導入於該絕熱構造體内之導入口。 u.如申請專利範圍第8至10項中任一項之玻璃板製造裝置’其中，該氣體為空氣及/或惰性氣體。 37201136847 VII. Patent application scope: A method for manufacturing a glass plate, comprising the steps of: a melting step of melting a glass raw material to obtain a molten glass; and a forming step of forming a glass from the molten glass by a down-draw method a volatilization promoting step of promoting volatilization of volatilization from a surface of at least one of the molten glass and the glass ribbon; a slow cooling step of cooling the glass ribbon; and a cutting step of cutting the glass ribbon Get a glass plate. [2] The glass sheet manufacturing method of claim 1, wherein the volatilization promoting step is a partial pressure of the volatile component facing the surface of the molten glass and the at least one of the glass ribbons. The difference between the pressure of the spoiler and the volatilization component is increased, thereby promoting the volatilization of the volatile component from the surface of at least one of the molten glass and the glass ribbon. 3. Glass sheet manufacturing according to claim 2 In the volatilization promoting step, the concentration of the volatile component in the environment facing at least the surface of the molten glass and the glass ribbon is lowered, thereby promoting the volatile component from the molten glass and the glass. The surface of at least one of the belts is volatilized. 4. The glass sheet manufacturer according to any one of claims 1-3 to 'where' is formed by using a forming device in the heat insulating structure; In the volatilization promoting step, the gas introduced into the heat insulating structure from the outside of the heat insulating structure is brought into contact with the molten glass and/or the surface of the glass ribbon which is pulled down, and then discharged to the surface. Insulating the structure in vitro, thereby promoting volatilization 35 201136847 The composition is volatilized from the surface of at least one of the molten glass and the glass ribbon. 5. The method for producing a glass sheet according to claim 4, wherein the gas is caused to follow The molten glass and/or the surface of the glass ribbon which is drawn down is raised. 6. The method for producing a glass sheet according to claim 4, wherein the gas is air and/or an inert gas. The method for producing a glass sheet according to any one of the items 1 to 3, wherein the forming step is performed by using a forming device in the heat insulating structure; and the volatilizing promoting step is promoted by decompressing the heat insulating structure in the body The volatile component is volatilized from the surface of at least one of the molten glass and the glass ribbon. 8. A glass plate manufacturing apparatus comprising a molding device and a heat insulating structure: the shai forming device is configured to melt the glass from the groove a side overflow, which is formed by inducing the overflow molten glass to be fused by a wall surface, thereby forming a glass ribbon; and the heat insulating structure surrounding the forming device And having a washing port for passing the glass ribbon formed by the forming device; and the heat insulating structure is provided with a discharge port for promoting volatilization from the surface of the molten glass to be external to the insulating structure a gas that is introduced into the heat insulating structure and rises along the molten glass flowing down the wall of the forming device, and is discharged to the outer surface of the heat insulating structure. The glass plate manufacturing device according to claim 8 of the patent application, wherein 36 201136847 * The heat insulating structure has: a bottom wall 'which is provided with the winding; a top wall 'opposite the bottom wall across the forming device; and a peripheral wall 'which connects the bottom wall and the periphery of the top wall to each other The glass plate manufacturing apparatus according to claim 9, wherein the introduction port for introducing the gas into the heat insulating structure is provided at a lower portion of the peripheral wall of the crucible. The glass sheet manufacturing apparatus of any one of claims 8 to 10 wherein the gas is air and/or inert gas. 37