200804211 九、發明說明： 【發明所屬之技術領域】 本舍明係關於藉由將玻璃基板浸潰於含有氟酸之化學 • 研磨液中，進行表面研磨至所需的基板厚度之研磨玻璃基 板之製造方法；尤其是關於適於製造液晶顯示器用玻璃基 板之製造方法。 【先前技術】 ⑩ 近年來’液晶顯示器用玻璃基板（以下簡稱為「玻璃基 板」）基於降低顯示器製品之能源消耗量的目的，玻璃基 板之厚度（以下簡稱為「玻璃厚度」）以儘量薄為佳。因此， 習知係採用藉由含有氟酸之化學研磨液，對玻璃基板之單 面或雙面進行化學研磨，以使玻璃厚度薄型化之研磨玻璃 基板之製造方法。 例如於專利文獻1中（日本專利特開2003-20255號公 報），揭示有藉由含有選自氟酸、鹽酸、硫酸、磷酸、硝 馨i文中之1種以上的無機酸之化學加工液進行研磨，例示之 實施例為使用含有氟酸5%、鹽酸1〇%、硝酸5%之化學加 工液進行研磨至所需的玻璃基板厚度。然而，此等習知技 術中，由於係以單一步驟研磨至所需之玻璃基板厚度，雖 可=磨加工至所需之玻璃厚度，惟，於玻璃基板表面（以 下簡稱為「玻璃表面」）之平滑性方面將產生問題。尤其， 原本存在於玻璃表面之微裂，於化學研磨過程中會成長為 j凹陷（以下稱為「凹痕（dimple)」），致引起製品不良之 嚴重問題，而以上述習知技術將難以抑制此等凹痕之發 312沿V發明說明書(補件)/96-08/96114959 6 200804211 生。200804211 IX. Description of the Invention: [Technical Field] The present invention relates to a ground glass substrate which is surface-polished to a desired substrate thickness by immersing a glass substrate in a chemical/grinding liquid containing fluoric acid. A manufacturing method; in particular, a manufacturing method suitable for manufacturing a glass substrate for a liquid crystal display. [Prior Art] 10 In recent years, the glass substrate for liquid crystal display (hereinafter referred to as "glass substrate") has been used to reduce the energy consumption of display products, and the thickness of the glass substrate (hereinafter referred to as "glass thickness") is as thin as possible. good. Therefore, a method of producing a ground glass substrate in which the thickness of the glass is thinned by chemically polishing one or both sides of the glass substrate by a chemical polishing liquid containing hydrofluoric acid is conventionally used. For example, Patent Document 1 (Japanese Laid-Open Patent Publication No. 2003-20255) discloses a chemical processing liquid containing one or more inorganic acids selected from the group consisting of hydrofluoric acid, hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid. Grinding, the illustrated embodiment is a grinding to a desired glass substrate thickness using a chemical processing fluid containing 5% of hydrofluoric acid, 1% by weight of hydrochloric acid, and 5% of nitric acid. However, in these prior art techniques, since the thickness of the glass substrate is polished in a single step, it can be ground to the desired glass thickness, but on the surface of the glass substrate (hereinafter referred to as "glass surface"). The smoothness aspect will cause problems. In particular, microcracks originally present on the surface of the glass may grow into j-pits (hereinafter referred to as "dimples") during the chemical polishing process, causing serious problems of defective products, and it is difficult to use the above-mentioned conventional techniques. The suppression of such dents is carried out along the V invention specification (supplement)/96-08/96114959 6 200804211.
作為用以解決此等問題點之手段，例如 2(:本專利特開_"麵號公報)中揭示J :含有齓酸10〜30重量%及硫酸20，重量%之表面研磨 2以1心秒以上的研磨速度研磨數秒鐘，進行用以抑 ^直徑4G㈣以上的損傷不致擴大為直徑1(){^以上的 爾段研磨之表面研磨，然後，浸潰於含有中〜低濃度之氟 酸的後段研磨液中，進行後段研磨至所f的玻璃基板厚 度。然而’依據此方法，於前段研磨之表面研磨中雖可抑 制凹痕之擴大，但由於與研磨液之接觸時間短，故難以控 制為對玻璃基板全體均一地進行研磨，於平滑部份會產^ 數私m之&差，將有其於後段研磨中會擴大的問題。As a means for solving such problems, for example, 2 (: JP-A- _" face number publication) discloses J: 10 to 30% by weight of citric acid and 20% by weight of surface grinding 2 Grinding at a polishing rate of at least a few seconds, the surface is ground to prevent the damage of 4G (four) or more from being reduced to a diameter of 1 () {^ or more, and then immersed in a medium-low concentration of fluorine. In the latter stage of the acid slurry, the latter stage is polished to the thickness of the glass substrate of f. However, according to this method, although the enlargement of the dent can be suppressed in the surface polishing of the front stage polishing, since the contact time with the polishing liquid is short, it is difficult to control the entire glass substrate to be uniformly polished, and the smooth portion is produced. ^ The number of private m & poor, there will be problems in the latter part of the grinding will be expanded.
又，於專利文獻3(日本專利特開2〇〇4—7764〇號公報） 中，曾提案之方法為：在玻璃基板之化學研磨中使用化學 研磨速度不同之複數的研磨液，依序由研磨速度快的研= 液至慢的研磨液進行數次研磨處理，藉此抑制凹痕之產 生。然而，依據此方法，即使可抑制凹痕之產生，卻須繁 多的步驟，由生產性、設備成本等方面考量，將有不符經 濟效益的問題。 二 又，於專利文獻4(日本專利特開2005-1 1894號公報） 中，曾提案之方法為：於對玻璃基板進行化學研磨時，先 浸潰於不與研磨液反應之液體（惰性液體）中，以惰性液體 填充存在玻璃表面之細孔’再進行化學研磨，藉此抑制細 孔成長為凹痕；惰性液體之例示為全氟烷基化合物等。然 312XP/發明說明書(補件)/96-08/96114959 7 200804211 而，依據此方法’即使可抑制凹痕之產生，由於將產生含 有有機化合物之廢水，故有必須對其進行廢水處理^Further, in Patent Document 3 (Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The polishing rate is fast, and the liquid is slowly polished to a plurality of times to suppress the generation of dents. However, according to this method, even if the generation of dents can be suppressed, a large number of steps are required, and in consideration of productivity, equipment cost, and the like, there will be problems that are not economically advantageous. Further, in the patent document 4 (Japanese Patent Laid-Open Publication No. 2005-1 1894), the method proposed is: when chemically grinding a glass substrate, first immersing in a liquid which does not react with the polishing liquid (inert liquid) In the case where the pores present on the surface of the glass are filled with an inert liquid, chemical polishing is performed to suppress the growth of the pores into pits; examples of the inert liquid are shown as perfluoroalkyl compounds and the like. However, according to the method 312XP/invention specification (supplement)/96-08/96114959 7 200804211, even if the generation of dents can be suppressed, since wastewater containing organic compounds is generated, it is necessary to carry out wastewater treatment.
題0 J •[專利文獻1]日本專利特開2003-20255號公報 [專利文獻2]日本專利特開2〇〇5 —343742號公報 [專利文獻3]日本專利特開2〇〇4—7764〇號公報 [專利文獻4]日本專利特開2〇〇5 —1 1894號公報 【發明内容】 ·(發明所欲解決之問題） 本發明之課題在於解決此等習知技術之問題，提供： 制凹痕之成長並對玻璃基板進行表面研磨，以得到無凹痕 與段差之具有平滑玻璃表面的玻璃基板之製造方法；及藉 此方法所製造之研磨玻璃基板，以及表面研磨液。曰 (解決問題之手段） 本發明為下述之研磨玻璃基板之製造方法、研磨玻璃基 板及表面研磨液。 ⑴-種研磨玻璃基板之製造方&，㈣玻璃基板浸潰 於含有氟酸之研磨液中’對表面進行化學研磨以製造研磨 玻璃基板者；其特徵在於， ^含表面平滑化步驟，係將玻璃基板浸潰於含有40〜9〇 重酸及〇·4〜4重量·酸之表面研磨液中並進行表 面研磨’抑制凹痕成長而形成平滑的玻璃表面。 (2) —種研磨玻璃基板之製造方法，係將玻璃基板浸潰 於含有氟酸之研磨液中，對表面進行化學研磨以製造研磨 8 312ΧΡ/發明說明書(補件)/96-〇8/96114959 200804211 玻璃基板者；其特徵在於，包含下述步驟： 表面平滑化步驟，係將玻璃基板浸潰於含有4〇〜9〇重量 乂石瓜k及〇 · 4〜4重量％氟酸之表面研磨液中並進行表面研 磨’抑制凹痕成長而形成平滑的玻璃表面； 後段研磨步驟，係將經表面平滑化之玻璃基板浸潰於含 有2〜30重量％氟酸之後段研磨液，進行後段研磨至所需 基板厚度。 @ ' (3)如上述（1)或（2)之方法，其中，表面研磨液為含有 50〜85重量％硫酸及〇· 5〜4重量％氟酸之研磨液。 ⑷如上述⑴〜⑻中任一方法，其中，玻璃基板為液 晶顯示器用玻璃基板。 (5) —種研磨玻璃基板，係藉由上述（1)至（4)中任一項 之方法所製造之研磨玻璃基板，其係凹痕之成長得到抑 制’並具有平滑的玻璃表面。 (6) —種表面研磨液，係用以將玻璃基板浸潰並進行表 面研磨，抑制凹痕之成長而形成平滑的玻璃表面者；其係 含有40〜90重量％硫酸及〇·4〜4重量％氟酸之表面研磨液。 作為本發明所製造之玻璃基板可舉出：液晶顯示器、有 機電致發光顯示器、電漿面板顯示器等之平面顯示器用玻 璃基板，尤其適於液晶顯示器用玻璃基板。玻璃基板之材 質，有如鋁硼矽酸玻璃基板等上述玻璃基板所通常使用 者’皆為研磨之對象。 *=發明之研磨玻璃基板之製造方法中，藉由將玻璃基板 次潰於表面研磨液中，以化學研磨進行表面研磨之表面平 312ΧΡ/胃 明書(補件)/96·〇8/96ΐ 14959 9 200804211 滑=步驟，將可抑制凹痕之成長而形成有平滑 此4表面千滑化步驟中可使用之表面研磨 液，可牛出含有40〜90重量％硫酸及〇.4〜4 =纽’尤以含有5。™硫酸及。 二：研磨=為佳。表面研磨液之其餘部份主要為水，亦 1其他溶劑、界面活性劑、安定劑等添加劑。於 研磨液中’硫酸漠度或氟酸濃度若低於上述下限，則㈣ ^成長之仙變弱，而硫酸濃度或氟酸濃度若高於上述 艮，則玻璃表面容易產生段差，故不佳。 定表::二化步驟中之表面研磨液的溫度並無特別限 ;吊，皿，惟，溫度愈高、凹痕之抑制效果愈大。因 此，可加溫至3 0〜s i) 、在—士 眚睥mn 平滑化步驟。研磨液之 =厂：為卜90分鐘’以5,分鐘為佳。若未滿i分鐘， 凹痕之成長抑制效果不佳，而在9()分鐘以上 守 潰的情況下，玻璃美柘夕m府上 、守間/文 声面单〜以 的生產性會降低。於此 表面平滑化步驟雖可推乂 、& 進仃表面研磨至所需的基板厚度， 惟,，於組合後段研磨步驟之情況下，於表面平滑化步ς =研=:::=厚度’只要可得到平滑的玻璃表面 文了 •又為上述之浸潰時間。 藉由表面平滑化步驟中之表面研 磨，可於抑制凹痕之成長 仃之表面研 基板。抑制凹痕之成長而开=成具有平滑破璃表面之玻璃 尚未閣明，但推1下而=有/滑的破璃表面的機制 (一·學研磨過==速璃上之微裂 狂Τ將之快連成長、擴大，而 312ΧΡ/發明說明書(補件)/96-08/96114959 10 200804211 2㈣此之機制為’其與含有適當濃度之氟酸的高 黏性研磨液接觸，使氟化物析出至微裂中並將其封塞住， 使平坦部先進行研磨而消除裂痕。 專利文獻2中，f揭示之方法為：使用含有氟酸10~30 里％及硫酸20〜50重量％之表面研磨液，以l#m/秒以上 、研磨速度進仃研磨數秒鐘，以進行用以抑制直徑爪 二上的損傷擴大為直徑1〇〇"以上的前段研磨之表面研 I ’但€載有：依據此方法，於前段研磨之表面研磨中雖 可抑制知傷之擴大，但由於與研磨液接觸時間短，故難以 控制為對玻璃基板全體均—地進行研磨，於平滑部份中容 易產生數"的段差，此段差將於後段研磨中擴大。 私ί利文獻2中之此等問題點，可認為原因在於氟酸濃度 乂回。對玻璃之溶解具有效果者為氟酸 度愈高、峨度愈快’控制變得困難。硫酸等其二： 對玻璃之〉谷出狀離$ ^岡敕從| 則無直接絲。。雖有絲’但對_之溶解本身 本發明中’於表面平滑化步驟中，藉由使用低 =玻璃之溶出均一化。此時，藉由含有高濃度的硫酸 二士為：钻性之研磨液’藉此，將析出於微裂内之氟化物 :^平坦部的研磨以消除裂痕，而可形成無凹痕 、、、又之平滑的玻璃表面。於表面平滑化步驟中，於形成 ^月的玻璃表面後’即使以高氟酸濃度之後段研磨液進行 後段研磨至所需厚度，亦可維持平滑的玻璃表面。 於表面平滑化步驟中藉由浸潰於表面研磨液中，抑制凹 312ΧΡ/發明說明書(補件)/96-08/96114959 n 200804211 =3 =滑玻，面之基板，將可在後段研磨 後段研磨至所需的:其板:，後段研磨液中’進行 之研麻#苴基厚度，猎製造具有目標基板厚度 %(以5〜30^=。、此後段研磨液，為含有氟酸2〜30重量 二 ,、垔％為佳）之研磨液，亦可含有鹽酸、硫酸、 并-夂Ί酸等之氟m卜之無機酸’無錢之合計量 二4主0要重爲量Γ以10〜20重量%為佳。後段研磨液之其餘部 ;加劑^ ’亦可含有其他溶劑、界面活性劑、安定劑等 ，後段研磨㈣為胃知所進行的研磨進行研磨至所 而的基板厚度以製造研磨玻璃基板的方法。因而，於後段 =磨步驟中’可採用f知所施行之研磨至所需的玻璃基板 厚度之方法中之條件、操作等。後段研磨步驟中之後段研 磨液之溫度並無特別限定，可為常溫’通常係於15~50。。 左=進行後&研磨步驟。後段研磨液之浸潰時間為 分f的程度，為研磨至目標玻璃基板厚度所須之時間。 藉由在後段研磨步财研磨至所需的玻璃基板厚度，可 製造目標玻璃基板厚度之研磨玻璃基板。此情況下，於本 發明中’以表面平滑化步驟抑制凹痕之成長而進行表面研 磨’藉此可得到平滑的玻璃表面，故於此狀態下，即使於 後段研磨步驟中研磨至所需的玻璃基板厚度，玻璃表面亦 不會產生凹痕與段差，可得到具有平滑玻璃表面之研磨玻 璃基板。因此’藉由以上述方法進行液晶顯示器用玻璃基 板之化學研磨’可提供抑制凹痕產生且維持良好表面狀態 312XP/發明說明書(補件)/96-08/96114959 12 200804211 之高品質製品。 (發明效果） 於人右m错由在表面平滑化步驟中將玻璃基板浸潰 中：重量%硫酸及0.4〜4重量%氟酸之表面研磨液 Γ進仃表面研磨，將抑制凹痕成長而進行表面研磨，可 仔到热凹痕與段差之具有平滑麵表面之玻璃基板。 \表面平π化步驟中，將經表面研磨之表面研磨玻[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 〇 公报 公报 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ( ( A method of manufacturing a glass substrate having a smooth glass surface without dents and steps, and a surface of the glass substrate, and a surface polishing liquid produced by the method.曰 (Means for Solving the Problem) The present invention relates to a method for producing a ground glass substrate, a polished glass substrate, and a surface polishing liquid. (1) a manufacturer of a ground glass substrate & (4) a glass substrate impregnated in a polishing liquid containing fluoric acid, 'chemically polishing the surface to produce a polished glass substrate; characterized by, ^ containing a surface smoothing step, The glass substrate was immersed in a surface polishing liquid containing 40 to 9 Torr of heavy acid and 4 to 4 weights of acid and subjected to surface polishing to suppress the growth of dents to form a smooth glass surface. (2) A method for producing a ground glass substrate by immersing a glass substrate in a polishing liquid containing hydrofluoric acid, and chemically grinding the surface to produce a polishing 8 312 ΧΡ / invention specification (supplement) / 96-〇 8 / 96114959 200804211 Glass substrate; characterized in that it comprises the following steps: a surface smoothing step of immersing a glass substrate on a surface containing 4 〇 to 9 〇 weight 乂 k k and 〇 4 to 4% by weight of fluoric acid Surface grinding is performed in the polishing liquid to suppress the growth of the dents to form a smooth glass surface. In the subsequent polishing step, the surface-smoothed glass substrate is immersed in a slurry containing 2 to 30% by weight of hydrofluoric acid for the subsequent stage. Grind to the desired substrate thickness. The method of the above (1) or (2), wherein the surface polishing liquid is a polishing liquid containing 50 to 85% by weight of sulfuric acid and 5% to 4% by weight of hydrofluoric acid. (4) The method according to any one of the above (1) to (8) wherein the glass substrate is a glass substrate for a liquid crystal display. (5) A ground glass substrate produced by the method according to any one of the above (1) to (4), wherein the growth of the dent is suppressed and has a smooth glass surface. (6) A surface polishing liquid for impregnating a glass substrate and performing surface polishing to suppress the growth of dents to form a smooth glass surface; it contains 40 to 90% by weight of sulfuric acid and 〇·4 to 4 Surface grinding solution of wt% fluoric acid. The glass substrate to be produced by the present invention may be a liquid crystal display, a glass substrate for a flat panel display such as an electroluminescence display or a plasma panel display, and is particularly suitable for a glass substrate for a liquid crystal display. The material of the glass substrate, such as a glass substrate such as an aluminoborosilicate glass substrate, is generally used for polishing. *=In the manufacturing method of the ground glass substrate of the invention, the surface of the surface of the glass substrate is crushed by the surface polishing liquid by chemical polishing, and the surface is flat 312 ΧΡ / stomach Ming (supplement) / 96 · 〇 8 / 96 ΐ 14959 9 200804211 Slip = step, which can suppress the growth of dents and form a surface polishing liquid which can be used in the smoothing step of the four surfaces. It can contain 40~90% by weight of sulfuric acid and 〇.4~4 = New's especially contains 5. TM sulfuric acid and. Two: Grinding = is better. The rest of the surface polishing liquid is mainly water, and also other additives such as solvents, surfactants, stabilizers. If the concentration of sulfuric acid influent or the concentration of hydrofluoric acid in the polishing liquid is lower than the above lower limit, then (4) ^the growth of the fairy is weak, and if the concentration of sulfuric acid or the concentration of the hydrofluoric acid is higher than the above, the surface of the glass is prone to a step difference, so it is not good. . Table setting: The temperature of the surface polishing liquid in the second step is not particularly limited; hanging, dish, but the higher the temperature, the greater the suppression effect of the dent. Therefore, it can be warmed up to 3 0~s i) in the smoothing step of the - 眚睥 mn. The slurry = factory: for 90 minutes '5 minutes, preferably 5 minutes. If it is less than i minutes, the growth inhibition effect of the dent is not good, and in the case of a collapse of 9 () minutes or more, the productivity of the glass 柘 m 府 、 、 守 守 守 文 文 文 文 文 文 文 文 文 文 文 文. In this surface smoothing step, the surface of the substrate can be pushed and polished to the desired substrate thickness. However, in the case of combining the subsequent polishing steps, the surface smoothing step = grinding =:::=thickness 'As long as a smooth glass surface is available, it is the above-mentioned impregnation time. By surface grinding in the surface smoothing step, the substrate can be grown on the surface of the growth of the dent. Suppresses the growth of the dents and opens = the glass with a smooth glass surface is not yet clear, but the mechanism of pushing the glass surface with 1 or = slip/sliding (1) grinding over == micro-cracking on the glass Τ 成长 成长 成长 成长 ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ ΧΡ 96 96 96 96 96 96 96 96 96 96 96 96 96 96 96 96 96 96 96 96 96 96 96 96 96 96 The compound is precipitated into the microcrack and is sealed, and the flat portion is first ground to eliminate the crack. In Patent Document 2, the method disclosed in the method is as follows: using 10 to 30% of hydrofluoric acid and 20 to 50% by weight of sulfuric acid The surface polishing liquid is polished for a few seconds at a polishing rate of l#m/sec or more to suppress the damage on the diameter of the claw 2 to be expanded to a diameter of 1 〇〇" According to this method, although the surface grinding in the front stage grinding can suppress the expansion of the damage, the contact time with the polishing liquid is short, so it is difficult to control the grinding of the entire glass substrate in the smooth portion. It is easy to generate the number difference of the number, this step will be In the latter stage of grinding, it is considered that the reason is that the concentration of the hydrofluoric acid is roundabout. The effect on the dissolution of the glass is that the higher the degree of hydrofluoric acid and the faster the degree of twisting, the control becomes difficult. Sulfuric acid, etc. 2: For the glass, the grain is separated from the $ ^ 敕 敕 from | then there is no direct silk. Although there is silk 'but the dissolution of _ itself is in the invention in the surface smoothing step, by using low = The dissolution of the glass is uniform. At this time, by containing a high concentration of sulfuric acid, the slurry is: a drilling slurry, whereby the fluoride in the microcrack is polished: the flat portion is polished to eliminate cracks. A glass surface having no dents and smoothness can be formed. In the surface smoothing step, after forming the surface of the glass of the moon, the slurry is polished to the desired thickness even after the high-fluoric acid concentration. It can maintain a smooth glass surface. In the surface smoothing step, it is immersed in the surface polishing liquid to suppress the concave 312ΧΡ/invention specification (supplement)/96-08/96114959 n 200804211 =3 = slid glass, surface substrate Will be able to grind the back section to the back section Required: its plate:, in the latter section of the grinding liquid, the thickness of the base is calculated, and the thickness of the target substrate is made to have a thickness of the target substrate (to 5 to 30^=., the slurry in the latter stage is 2 to 30% by weight of the hydrofluoric acid). Second, 垔% is better) of the slurry, can also contain hydrochloric acid, sulfuric acid, and citric acid, such as fluoride, m, the inorganic acid 'no money, the total amount of 2, the main 0, the weight is Γ to 10~ 20% by weight is preferred. The remainder of the latter stage of the slurry; the addition agent ' can also contain other solvents, surfactants, stabilizers, etc., after the grinding (4) for the grinding of the stomach to grind to the thickness of the substrate A method of manufacturing a ground glass substrate. Therefore, in the latter stage = the grinding step, conditions, operations, and the like in the method of polishing to the desired thickness of the glass substrate can be employed. The temperature of the polishing liquid in the subsequent stage in the subsequent polishing step is not particularly limited, and may be from room temperature 'normally from 15 to 50. . Left = post- & grinding step. The impregnation time of the latter slurry is the extent of f, which is the time required to grind to the thickness of the target glass substrate. The ground glass substrate having the thickness of the target glass substrate can be produced by grinding in the subsequent stage to the desired thickness of the glass substrate. In this case, in the present invention, "the surface smoothing step is performed to suppress the growth of the dents and the surface is polished", whereby a smooth glass surface can be obtained, so in this state, even in the subsequent polishing step, the polishing is performed to a desired level. The thickness of the glass substrate does not cause dents and step on the surface of the glass, and a ground glass substrate having a smooth glass surface can be obtained. Therefore, the "chemical polishing of the glass substrate for liquid crystal display by the above method" can provide a high-quality article which suppresses generation of dents and maintains a good surface condition 312XP/invention specification (supplement)/96-08/96114959 12 200804211. (Effect of the Invention) In the case where the glass substrate is immersed in the surface smoothing step: the surface polishing liquid of the weight% sulfuric acid and the 0.4 to 4% by weight of the fluoric acid is rubbed into the surface of the crucible to suppress the growth of the dent Surface grinding is performed to obtain a glass substrate having a smooth surface with hot dents and steps. \ Surface flat π step, the surface of the surface is ground glass
1 土板藉由在後段研磨步财研磨輯需之玻璃基板厚 =’可製造於玻璃表面不產生凹痕與段差之具有平滑玻璃 表面之研磨玻璃基板。 本毛月中得到之研磨玻璃基板，係於玻璃表面不產生凹 痕與段差，具有平滑的玻璃表面，並有所需的基板厚度。 f發明之表面平滑化步驟中所用之表面研磨液，由於含 有前述濃度之硫酸及氟酸，故藉由將玻璃基板浸潰於其中 並進行表面研磨，將可於抑制凹痕成長而形成平滑的玻璃 •表面。 【實施方式】 以下，針對本發明之實施形態之液晶顯示器用玻璃基板 的製造方法之一例，藉圖1進行說明，惟，本發明並非限 疋於貝Μ形態中所用之玻璃基板的種類、研磨液槽之型 態、玻璃基板之保持具等各種器具、裝置類之運用方法。 、圖1中，1為表面研磨液槽、2為第1水洗槽、3為後 段研磨槽、4為第2水洗槽、5為最終水洗槽。 液晶顯示器用玻璃基板20有各種尺寸。如圖1之順序 3ΠΧΡ/發明說明書(補件)/96-08/96114959 13 200804211 依序配置：裝滿表面研磨液6之表面平滑化槽丨、裝滿洗 萍水7之第1水洗槽2、與裝滿後段研磨液8之後段研磨 槽3、1滿洗淨水9之第2 洗槽4 H滿洗淨水！ 〇之 最終水洗槽5;將容納玻璃基板20之卡座容器21依序進 出表面平滑化槽1、第1水洗槽2、後段研磨槽3、第2 水洗槽4及最終水洗槽5而進行化學研磨。 首先，作為表面平滑化步驟，係將卡座21浸潰於裝滿 ，面研磨液6之表面平滑化槽”，由送氣裝置^以氮 氣或空氣之吹氣(gas bubbi ing)等之手段攪拌表面研磨 液6而進行表面研磨。表面平滑化槽i之浸潰時間宜為 1〜90分鐘，以5〜30分鐘為佳。若為1分鐘以下，凹痕成 長之抑制效果不佳，9〇分鐘以上之長時間浸潰，則會造 成玻璃基板20之研磨加工之生產性降低，故不佳。又， =表面平滑化步射之表面研磨液6之溫度並無特別限 疋’已知溫度愈局’凹痕之抑制效果愈佳。液溫方面，可 將表面研磨液6加溫至30〜5〇°c而進行。 接著，自表面平滑化槽1取出卡二後立即浸潰於第 1水洗槽2中，由送氣裝置12 p壮 /於弟 # 衣置12以吹氣等之手段攪拌，將 附者於表面20之表面研磨液以夺> 、 洗乎水7洗淨除去。接著 自弟1水洗槽2取出卡座21，浸涪&丨狀 之德妒讲府描q ^ 喂$衣滿後4又研磨液8 之後&研磨槽3，進行後段研磨步驟之後段研磨。 段研磨液8較佳係藉由送氣裝置13之吹氣等之手段或用 以循環研磨液等之手段，保持 次用 於破璁其柘9n主人+ 的机動。流動若不足， ㈤基板2〇表面會畜積析出物，致使研磨速度發生不 312XP/發明說明書(補件)/%傭961卿 14 200804211 均而導致研磨厚衫均―，使得表面加工度Μ。由後段 研磨液8所進行之處理，可依預先訂定之玻璃 研磨時間。 疋 於後段研磨槽3中完成後段研磨後立即取出卡座2卜 浸潰到裝滿洗淨水9之第2水洗槽4巾，對基板2〇進行 水洗。洗淨水可由自送氣裝置14之吹氣機進行攪掉，或 使洗淨水循環以提高水洗效果。最後，將卡座21移至最 終水洗槽5中’進行與第卜第2水洗槽2、4之同樣的 操作，完成化學研磨。 [實施例] (實施例1〜9) 鋪設適當粗度的砂紙，在其上水平放置將鋁硼矽酸玻璃 裁切成10cm方塊者，再於其上施加特定的荷重，賦予玻 璃表面人造刮痕作為試樣，驗證凹痕抑制效果。 試驗裝置係作成為模擬圖i之小型基板收納卡座21、 _表面平滑化槽1、後段研磨槽3、第i水洗槽2、第2水 洗槽4及最終水洗槽5，對前述試樣以圖i之方法進行研 磨。表面平滑化步驟中之表面平滑化槽1之表面研磨液6 之、’且成/jm·度及改潰時間示於表1。後段研磨步驟中之由 後段研磨槽3之後段研磨液8所進行之研磨，係藉由含有 乱酸10重量％及硫酸5重量％之研磨液，於常溫下加工約 50分鐘。研磨後，對試樣表面以顯微鏡觀察以人造刮痕 為起點所成長之凹痕之大小，i計算其數目。&，對破璃 基板之表面狀態以目視觀察。結果示於表j。 312xp/發明說明書(補件)/96-08/96114959 15 200804211 (比較例1〜4) 以與實施例卜9同樣之做法，，准，表面平滑化步驟中之 表面平滑化槽1之表面研磨液6之組成、溫度及浸潰時間 係如表1所示般改變而進行加工。結果示於表i。、 (比較例5 ) 於實施例1〜9及比較例丨〜4中，未進行由表面平滑化槽 1之表面研磨液6所進行之處理表面平滑化步驟，及第j 水洗槽2之水洗，只進行後段研磨槽3中之後段研磨液8 之處理、與第2及最終水洗槽4、5中之水洗，進行比較。 結果示於表1。 評估方法： 表1中之評估方法，係將分別滿足直徑5〇#m以上之凹 痕數較比較例5減少、及無前述段差存在者，判定為抑制 效果。 由表1之結果可判讀出··首先，凹痕之減少傾向與段差 籲之產生傾向係由硫酸濃度與氟酸濃度及於表面研磨液中 之浸潰時間的均衡而決定。亦即，由實施例1、2、6、8 及9之結果，於硫酸濃度6〇〜85重量％、氟酸濃度h l〜3 9 重虽％之條件下，未確認到徑為15 〇 # m以上之凹痕，且凹 痕合計數亦減少至比較例5之大约/7以下，亦未產 生段差。 又，於硫酸為70%、氟酸濃度低（〇· 9重量％)之實施例3 中’藉由延長浸潰時間，凹痕數減少至比較例5之ι/1〇， 藉由設定為較長的浸潰時間，可提高凹痕抑制效果。 ^^^^^Μ^9(Μ{ψ)/96-08/96114959 16 200804211 再者，於氟酸濃度低（0· 5重量％)之實施例4，與硫酸濃 度低（50重量％)之實施例5，及實施例7中，則無徑為150 ‘ # m以上之凹痕，合計數可降低至比較例5之4/5之程度。 . 另一方面，硫酸濃度超過90重量％之比較例3，氟酸濃 度超過4重量％之比較例1、2，以及硫酸濃度低至30重 量％、氟酸濃度高達5· 5重量％之比較例4中，任一者雖皆 確認到有凹痕產生之抑制效果，卻容易產生段差，故不佳。 由上述結果可知·為了不產生段差並抑制凹痕之產生， •必須於硫酸40〜90重量％(以50〜85重量％為佳）及敗酸 0.4〜4重倾以〇·5~4重量%為佳)的濃度範圍内進行研 磨01 The earth plate is made of a polished glass substrate with a smooth glass surface that does not cause dents and steps on the glass surface by grinding the glass substrate thickness required in the latter stage. The ground glass substrate obtained in this month has no unevenness and step on the surface of the glass, has a smooth glass surface, and has a desired substrate thickness. In the surface polishing liquid used in the surface smoothing step of the invention, since the sulfuric acid and the hydrofluoric acid having the above concentrations are contained, by dipping the glass substrate therein and performing surface polishing, it is possible to suppress the growth of the dents and form a smooth Glass • Surface. [Embodiment] Hereinafter, an example of a method for producing a glass substrate for a liquid crystal display according to an embodiment of the present invention will be described with reference to Fig. 1. However, the present invention is not limited to the type and polishing of the glass substrate used in the Bellows form. The use of various instruments and devices such as the type of liquid tank and the holder of the glass substrate. In Fig. 1, 1 is a surface polishing liquid tank, 2 is a first water washing tank, 3 is a rear grinding tank, 4 is a second water washing tank, and 5 is a final water washing tank. The glass substrate 20 for liquid crystal displays has various sizes. In the order of Fig. 1 3ΠΧΡ/Invention manual (supplement)/96-08/96114959 13 200804211 Sequential configuration: surface smoothing tank filled with surface grinding liquid 6, first washing tank 2 filled with washing water 7 And after filling the rear stage polishing liquid 8, the grinding tank 3, 1 is full of washing water 9 and the second washing tank 4 H is full of washing water! The final washing tank 5 of the crucible; the cassette container 21 containing the glass substrate 20 is sequentially introduced into and out of the surface smoothing tank 1, the first washing tank 2, the subsequent grinding tank 3, the second washing tank 4, and the final washing tank 5 to carry out chemistry Grinding. First, as a surface smoothing step, the card holder 21 is immersed in the surface smoothing tank of the surface polishing liquid 6 and is stirred by a gas supply device by means of gas or gas bubbi ing. The surface polishing liquid 6 is surface-polished. The surface smoothing groove i preferably has a dipping time of 1 to 90 minutes, preferably 5 to 30 minutes. If it is 1 minute or less, the suppression of the dent growth is not good, 9〇 If the immersion for a long period of time or longer, the productivity of the polishing process of the glass substrate 20 is lowered, which is not preferable. Further, the temperature of the surface polishing liquid 6 of the surface smoothing step is not particularly limited to the known temperature. The effect of suppressing the dent is better. In terms of liquid temperature, the surface polishing liquid 6 can be heated to 30 to 5 〇 ° C. Then, after the card is removed from the surface smoothing tank 1 , it is immediately immersed in the first In the water washing tank 2, the air supply device 12 p-strong/Yu-Yi clothing 12 is stirred by means of blowing or the like, and the surface polishing liquid attached to the surface 20 is washed and removed by washing water. Then take out the deck 21 from the brother 1 washing tank 2, dip & 之 之 妒 妒 妒 描 ^ q ^ $ $ After the cloth is filled, the slurry 8 is then polished and the polishing bath 3 is subjected to the subsequent polishing step. The segment slurry 8 is preferably a means for blowing the gas by the gas supply device 13 or a means for circulating the slurry or the like. , keep the second used to break the 机动 9n master + maneuver. If the flow is insufficient, (5) the substrate 2 〇 surface will accumulate precipitates, resulting in the grinding speed does not occur 312XP / invention manual (supplement) /% commission 961 Qing 14 200804211 Both of them result in the grinding of the thick shirts, which makes the surface processing degree Μ. The processing by the latter grinding liquid 8 can be carried out according to the predetermined glass grinding time. 疋 After the finishing of the rear grinding in the rear grinding groove 3, the cartridge 2 is taken out immediately. The cloth is immersed in a second washing tank 4 filled with the washing water 9, and the substrate 2 is washed with water. The washing water can be stirred by the air blower from the air supply device 14, or the washing water can be circulated to improve the washing effect. Finally, the cartridge 21 is moved to the final washing tank 5 to perform the same operation as the second water washing tanks 2, 4 to complete the chemical polishing. [Examples] (Examples 1 to 9) Laying the appropriate thickness Sandpaper, placed on top of it will be aluminum borax The acid glass is cut into 10cm squares, and a specific load is applied thereto, and the artificial scratch on the glass surface is applied as a sample to verify the dent suppression effect. The test device is used as a small substrate storage card holder 21 of the simulation diagram i. _ Surface smoothing tank 1, rear grinding tank 3, i-th washing tank 2, second washing tank 4, and final washing tank 5, the sample is polished by the method of Fig. i. Surface smoothing in the surface smoothing step The surface polishing liquid 6 of the tank 1 is shown in Table 1. The polishing time by the polishing liquid 8 in the subsequent stage grinding step 3 is caused by the chaos. The slurry of 10% by weight of acid and 5% by weight of sulfuric acid was processed at room temperature for about 50 minutes. After the grinding, the surface of the sample was observed by microscopic observation of the size of the dent which was grown starting from the artificial scratch, and the number was calculated. &, the surface state of the glass substrate was visually observed. The results are shown in Table j. 312xp/Invention Manual (Supplement)/96-08/96114959 15 200804211 (Comparative Examples 1 to 4) In the same manner as in Example 9, the surface smoothing of the surface smoothing tank 1 in the surface smoothing step The composition, temperature and impregnation time of the liquid 6 were changed as shown in Table 1 and processed. The results are shown in Table i. (Comparative Example 5) In Examples 1 to 9 and Comparative Examples 丨 to 4, the surface smoothing step by the surface polishing liquid 6 of the surface smoothing tank 1 and the water washing of the j-th washing tank 2 were not performed. Only the treatment of the subsequent polishing liquid 8 in the subsequent grinding tank 3 and the water washing in the second and final water washing tanks 4, 5 are performed. The results are shown in Table 1. Evaluation method: The evaluation method in Table 1 is that the number of pits satisfying the diameter of 5 〇 #m or more is reduced as compared with Comparative Example 5, and the absence of the above-described step difference is judged as the suppression effect. It can be judged from the results of Table 1. First, the tendency of the reduction of the dents and the tendency of the step are determined by the balance between the concentration of sulfuric acid and the concentration of the fluoric acid and the immersion time in the surface polishing liquid. That is, as a result of Examples 1, 2, 6, 8, and 9, under the conditions of a sulfuric acid concentration of 6 Torr to 85% by weight and a hydrofluoric acid concentration of hl to 3 9%, the diameter was not confirmed to be 15 〇 # m. The above dents, and the total number of dents were also reduced to about /7 or less of Comparative Example 5, and no step difference was produced. Further, in Example 3 in which sulfuric acid was 70% and the concentration of hydrofluoric acid was low (〇·9 wt%), by increasing the impregnation time, the number of dimples was reduced to ι/1 比较 of Comparative Example 5, by setting A longer dipping time can improve the dent suppression effect. ^^^^^Μ^9(Μ{ψ)/96-08/96114959 16 200804211 Furthermore, in Example 4 with a low concentration of hydrofluoric acid (0.5% by weight), the concentration of sulfuric acid was low (50% by weight). In Example 5 and Example 7, the dents having a diameter of 150 Å or more were not obtained, and the total count was reduced to the extent of 4/5 of Comparative Example 5. On the other hand, Comparative Example 3 in which the sulfuric acid concentration exceeds 90% by weight, Comparative Examples 1 and 2 in which the concentration of the hydrofluoric acid exceeds 4% by weight, and the sulfuric acid concentration as low as 30% by weight and the concentration of the hydrofluoric acid as high as 5.9 % by weight In Example 4, although it was confirmed that the effect of suppressing the occurrence of the dent was generated, the step was liable to occur, which was not preferable. From the above results, it is known that in order not to cause a step and suppress the generation of dents, it is necessary to have a weight of 40 to 90% by weight of sulfuric acid (preferably 50 to 85% by weight) and a weight of 0.4 to 4 with a weight of 败·5 to 4 by weight. Grinding is performed within the concentration range of %)
312ΧΡ/發明說明書(補件)/96-08/96114959 17 200804211 [表i ]312ΧΡ/Invention Manual (supplement)/96-08/96114959 17 200804211 [Table i]
表面研J (重: 液組成 t%) 溫度 (°C ) 時間 (分） 各凹痕直徑（μ m)之個數 有無 段差 判定 硫酸 氟酸 50 〜99 100 〜149 150〜 合計 實 施 例 1 70 1.3 20 15 41 0 0 41 無 Ο 2 60 1.8 20 15 63 0 0 63 無 Ο 3 70 0.9 25 50 16 0 0 16 無 Ο 4 60 0.5 25 15 122 11 0 133 益 Ο 5 50 1.7 25 15 110 18 0 128 無 Ο 6 60 3. 9 25 15 22 0 0 22 無 Ο 7 50 3. 6 25 15 95 7 0 102 無 Ο 8 85 1.1 25 15 66 0 0 66 無 Ο 9 85 3. 7 25 15 78 8 0 85 無 Ο 比 較 例 1 70 4. 3 20 10 29 0 0 29 有 X 2 50 4. 8 25 5 41 0 0 41 有 X 3 95 1. 1 25 10 38 0 0 38 有 X 4 30 5. 5 25 5 90 0 0 90 有 X 5 — — 一 — 144 19 5 168 無 XSurface grinding J (heavy: liquid composition t%) Temperature (°C) Time (minutes) Number of each dimple diameter (μm) Whether there is a step difference judgment sulfuric acid fluoride 50 to 99 100 to 149 150~ Total Example 1 70 1.3 20 15 41 0 0 41 无Ο 2 60 1.8 20 15 63 0 0 63 无Ο 3 70 0.9 25 50 16 0 0 16 无Ο 4 60 0.5 25 15 122 11 0 133 益Ο 5 50 1.7 25 15 110 18 0 128 无 无 6 60 3. 9 25 15 22 0 0 22 无Ο 7 50 3. 6 25 15 95 7 0 102 无Ο 8 85 1.1 25 15 66 0 0 66 无Ο 9 85 3. 7 25 15 78 8 0 85 无Ο Comparative example 1 70 4. 3 20 10 29 0 0 29 With X 2 50 4. 8 25 5 41 0 0 41 With X 3 95 1. 1 25 10 38 0 0 38 With X 4 30 5. 5 25 5 90 0 0 90 with X 5 — — one — 144 19 5 168 None X
312XP/發明說明書(補件)/96-08/96114959 18 200804211 (實施例ίο)〈實基板之試驗結果> 使用鋁硼矽酸玻璃基板（第4代尺寸）進行試驗。表面研 .磨液6使用硫酸70重量％、氟酸1 · 3重量％之水溶液，_ ^由將玻璃基板浸潰於表面研磨液中，進行玻璃表面之研 磨。此時，表面研磨液之溫度設定為15〇c，玻璃基板浸 潰於研磨液中之時間為約15分，以吹氣方式攪拌表面S 磨液。於表面研磨完成後，對玻璃基板進行水洗。然後， 藉由含有氟酸10重量％及硫酸5重量％之表面研磨液，加 ⑩工至所需的基板厚度。其結果，於實用評估基準中之不合 格率減少至1/3。 (實施例11)〈實基板之試驗結果〉 使用鋁硼矽酸玻璃基板（第4代尺寸）進行試驗。表面研 磨液6使用硫酸60重量％、氟酸1 · 4重量％之水溶液，藉 由將玻璃基板浸潰於表面研磨液中，進行玻璃表面之研 磨。此時，表面研磨液之溫度設定為15t：，玻璃基板浸 籲潰於研磨液中之時間為約70分，以吹氣方式攪拌表面研 磨液。於表面研磨完成後，對玻璃基板進行水洗。然後， 藉由含有氟酸10重量％及硫酸5重量％之表面研磨液，加 工至所需的基板厚度。其結果，於實用評估基準中之不合 格率減少至1/20。 (產業上之可利用性） • 本發明之製造方法可利用於作為藉含氟酸之化學研磨 .液浸潰玻璃基板，進行表面研磨至所需玻璃基板厚度之研 磨玻璃基板，尤其是液晶顯示器用玻璃基板之製造方法。 3 UXP/發明說明書(補件)/96_08/96114959 19 200804211 【圖式簡單說明】 圖1為顯示液晶顯示器用玻璃基板之製造方法的實施 .形態之流程圖。 : 【主要元件符號說明】 »： 1 表面平滑化槽 2 第1水洗槽 3 後段研磨槽 4 第2水洗槽 馨5 最終水洗槽 6 表面研磨液 7 洗淨水 8 後段研磨液 9 洗淨水 10 洗淨水 11 送氣裝置 _ 12 送氣裝置 13 送氣裝置 14 送氣裝置 15 送氣裝置 20 玻璃基板 21 小型之基板收納卡座 312XP/發明說明書(補件)/96-08/96114959 20312XP/Invention Manual (Supplement)/96-08/96114959 18 200804211 (Example ίο) <Test Results of Real Substrate> The test was carried out using an aluminoborosilicate glass substrate (fourth generation size). Surface grinding. The grinding liquid 6 was made by using an aqueous solution of 70% by weight of sulfuric acid and 1.3% by weight of hydrofluoric acid, and immersing the glass substrate in a surface polishing liquid to grind the surface of the glass. At this time, the temperature of the surface polishing liquid was set to 15 ° C, and the time during which the glass substrate was immersed in the polishing liquid was about 15 minutes, and the surface S grinding liquid was agitated by blowing. After the surface polishing is completed, the glass substrate is washed with water. Then, by adding a surface polishing liquid containing 10% by weight of hydrofluoric acid and 5% by weight of sulfuric acid, it is added to the desired substrate thickness. As a result, the rate of disqualification in the practical evaluation benchmark was reduced to 1/3. (Example 11) <Test results of solid substrate> The test was carried out using an aluminoborosilicate glass substrate (fourth generation size). The surface grinding liquid 6 was an aqueous solution of 60% by weight of sulfuric acid and 1.4% by weight of hydrofluoric acid, and the glass substrate was ground by dipping the glass substrate into the surface polishing liquid. At this time, the temperature of the surface polishing liquid was set to 15 t: the time for the glass substrate to be immersed in the polishing liquid was about 70 minutes, and the surface grinding liquid was agitated by blowing. After the surface polishing is completed, the glass substrate is washed with water. Then, it is processed to a desired substrate thickness by a surface polishing liquid containing 10% by weight of hydrofluoric acid and 5% by weight of sulfuric acid. As a result, the rate of disqualification in the practical evaluation benchmark was reduced to 1/20. (Industrial Applicability) The manufacturing method of the present invention can be utilized as a ground glass substrate, which is subjected to surface polishing to a desired glass substrate thickness, as a liquid crystal display, as a chemical polishing by a fluorine-containing acid. A method of manufacturing a glass substrate. 3 UXP/Invention Manual (Supplement)/96_08/96114959 19 200804211 [Simplified Schematic Description] Fig. 1 is a flowchart showing the implementation of a method for manufacturing a glass substrate for a liquid crystal display. : [Main component symbol description] »: 1 Surface smoothing tank 2 First washing tank 3 Rear grinding tank 4 Second washing tank Xin 5 Final washing tank 6 Surface polishing liquid 7 Washing water 8 After-stage grinding liquid 9 Washing water 10 Washing water 11 air supply device _ 12 air supply device 13 air supply device 14 air supply device 15 air supply device 20 glass substrate 21 small substrate storage card holder 312XP / invention manual (supplement) / 96-08/96114959 20