200528548 九、發明說明： 【發明所屬之技術領域】 本發明是有關於一種用於研磨如硬碟或相似物之資料 錄製媒體（informat ion - record ing㈣心⑽）用玻璃基板之 研磨組成物。本發明亦關於一種應用此研磨組成物之研磨 方法。 【先前技術】 傳統上’用於研磨資料錄製媒體用玻璃基板研磨組成籲 物以為習知。於曰本早期公開之第2〇〇卜89748號專利申請 案中揭露了包括主要由如氧化鈽之稀土氧化物組成之研磨 料與水之一種研磨組成物（於下文中稱之為第一習知研磨 組成物）。於曰本早期公開之第2〇〇〇 —144112號專利申請案 則揭路了包括擇自由包括含鐵氧化物（ir〇n_c〇ntaining oxide)與含鐵基化合物（ir〇n —c〇ntaining basic c ⑽ p〇und) 所組成族群之至少一研磨料與水之一種研磨組成物（於下 文中稱之為第二習知研磨組成物）。上述第一與第二習知研 磨組成物可藉由研磨料的作用而機械地研磨一玻璃基板。 應用於研磨玻璃基底之研磨組成物所需條件，包括·· (1) 研磨後之玻璃基板之表面粗链度為小； (2) 研磨組成物需易於清除，亦即研磨組成物需可藉由 清洗而自玻璃基板上輕易移除； (3) 研磨粒於研磨組成物中需有良好之分散性；以及 (4) 研磨組成物需具有高物料移除率 砂陡手例如適用於快速 2188-6645-PF/Ahddub 5 200528548 地研磨破璃基板。 兩、而，上述第一與第二習知研磨組成物並不滿足上述 需求’因而便需針對其加以改善。 【發明内容】 有鑑於此，本發明的主要目的就是提供一種研磨組成 物，其適用於研磨玻璃基板。本發明之另一目的為提供一 種應用此研磨組成物之研磨方法。 為達上述目的，本發明提供了一種研磨組成物。此研籲 磨組成物適用於研磨一玻璃基板，其包括二氧化矽、酸與 水。 本發明一提供了一種研磨玻璃基底之方法，其包括下 列步驟： 提供上述研磨組成物，以及利用此研磨組成物研磨玻 璃基板表面。 為了讓本發明之上述和其他目的、特徵、和優點能更 明顯易懂，下文特舉一較佳實施例，並配合所附圖示，作馨 詳細說明如下： 【實施方式】 本發明之實施例將配合下文作一詳細描述。 應用於如磁碟之資料錄製媒體之玻璃基板，係由如鋁 石夕酸鹽玻璃（aluminosilicate glass)、納約玻璃（soda lime glass)、碳酸鈉鋁矽酸鹽玻璃（soda aluminosilicate 2188-6645-PF；Ahddub 6 200528548 glass)、蝴石夕酸紹玻璃（alumino boros i 1 i cat e glass)、 鄉石夕酸鋁玻璃（borosilicate glass)、石英玻璃（quartz glass)或結晶玻璃（crystallized glass)等材質所組成。 結晶玻璃之主要結晶相可能為裡輝石（spodumene)、模來石 (mullite)、銘硼酸鹽結晶（aluminum borate crystal)、 /3 -石英固態溶液、α-石英、堇青石（cordierite)、頑火 石（enstatite)、鋇長石（celsian)、矽灰石 (wollastonite)、鈣長石（anorthite)、鎂橄欖石 (forsterite)、石夕酸裡（lithium metasilicate)或二石夕酸 _ 鋰（1 i thium disi 1 icate)。玻璃基板通常藉由化學機械研 •磨程序之應用，藉以將其表面鏡面化處理。 一般而言’為了改善材料移除率與研磨後玻璃基版之 研磨品質等目的，研磨玻璃基板程序之施行可細分為以下 數個研磨步驟。舉例來說，此些研磨步驟包括：粗磨玻璃 基板表面之步驟以及細磨玻璃基板表面之步驟。換言之， 此些研磨步驟包括：預磨（preliminarily p〇lishing)玻璃0 基板表面之步驟以及搬光研磨（finished-polishing)之步 驟。舉例來說’依據本實施例之研磨組成物，可用於此些 研磨步驟中之最終研磨步驟（拋光研磨步驟）。接著置入研 磨後玻璃基板於化學強化程序，利用低溫離子交換方法或 類似方法’以改善其對於震動與搖晃之耐性。 依據本發明實施例之研磨組成物包括二氧化矽、酸以 及水。一氧化石夕可作為機械研磨玻璃基板用之研磨料。二 乳化石夕叮月&為膝態石夕（c〇U〇idai silica)、燻石夕（fumed 2188-6645-PF；Ahddub 7 200528548 S1 11 Ca)或沉澱型矽（Precipitated suica)。其中，較佳 地使用膠態石夕或燒矽’以得到較低表面粗糙度之研磨後2 璃基板，而膠態矽為最佳之選擇。於研磨組成物可包括— 或多種二氧化石夕。 當二氧化矽為膠態矽時，藉由比表面積法（BET法）所判 定出之此膠態矽之特定表面區域之平均粒徑，較佳地介 於5-30 0奈米，更佳地介於5 —2〇〇奈米，而最佳地介於5 —12〇 奈米。而藉由雷射繞射散射法所判定出此膠態矽之平均粒 徑1，較佳地介於5 —3〇〇奈米，更佳地介於5 —2〇〇奈米， 而最佳地介於5-150奈米。當二氧化矽為燻矽時，藉由βΕΤ 法所判定出之此膠態矽之特定表面區域之燻矽之平均粒徑 Dsa ’較佳地介於10 —3〇〇奈米，更佳地介於1〇 —2〇〇奈米， 且取佳地介於10-120奈米。而藉由雷射繞射散射法所判定 出此燻矽之平均粒徑，較佳地介於3 〇-5 〇 〇奈米，更佳 地；1於40-400奈米，而最佳地介於5〇 — 3〇〇奈米。當膠態 矽之平均粒徑Dsa或Dim或當燻矽之平均粒徑Dsa或Dn4過小 時，將可能得到不夠高之材料移除率。而當膠態矽之平均 粒徑Dsa或Dw或當燻矽之平均粒徑1)^或Dn4過大時，則將 可能使得研磨後玻璃基底之表面粗趟度過大，或於研磨後 玻璃基底表面產生到傷。 於研磨組成物中之二氧化矽含量較佳地介於 〇·卜50%(mass%)，更佳地介於卜4〇%(mass%)，而最佳地介 於3-3 0%(mass%)。當二氧化矽的含量低於〇. 1%(mass%)時， 將無法得到足夠高之材料移除率，或者於研磨玻璃基板將 2188-6645-PF;Ahddub 8 200528548 遭遇較高之研磨抵抗。當二氧化石夕含量高於50%( mass%) 時，研磨組成物之黏度將大幅地增加，使得研磨組成物傾 向於凝結，因而降低了研磨組成物中之掌控度。 另外，酸可作為研磨加速劑之用，並藉由二氧化矽的 應用而可加速機械研磨。酸可加速機械研磨之推論理由之 一為，酸可活化二氧化矽表面，進而增加了二氧化矽之機 械研磨力。此外，酸亦腐蝕或蝕刻了玻璃基板表面，以作 為化學研磨玻璃基板表面之其他作用。相較於二氧化矽之 機械研磨，酸化學機械研磨反應相對較弱。酸可能為無機 酸或有機酸。 無機酸例如包括鹽酸、填酸、硫酸、正構酸（phosphoni c acid)、硝酸、次磷酸與硼酸。有機酸例如為醋酸、衣康酸 (itaconic acid)、號 J白酸（succinic acid)、酒石酸 (tartaric acid)、檸檬酸（citric acid)、馬來酸（maleic acid)、甘醇酸（glycolic acid)、丙二酸（malonic acid)、 甲基績酸（methanesulfonic acid)、甲酸（formic acid)、 蘋果酸（malic acid)、葡萄糖酸（gluconic acid)、丙胺酸 (alanine)、對苯基甘氯酸（giycin)、乳酸（lactic acid)、 經基乙叉二填酸（hydroxyethylidene diphosphonic acid;縮寫為 HEDP)、甲叉二林酸（nitrilotris (methylene phosphonic acid);縮寫為 NTMP)以及膦醯基丁基三縮酸 (phosphonobutane tricarboxylic acid;縮寫為 PBTC)。 於上述酸中，較佳的為鹽酸、磷酸、硫酸、正磷酸、 硝酸、次磷酸、硼酸、醋酸、衣康酸、琥珀酸、酒石酸、 2188-6645-PF;Ahddub 9 200528548 檸樣酸、馬來酸、甘醇酸、丙二酸、甲基磺酸、甲酸、蘋 果酸、葡萄糖酸、乳酸、HEDP、NTMP或PBTC，其可有效地 加速二氧化矽之機械研磨效果。於上述較佳酸中，鹽酸、 碟酸、正磷酸、酒石酸、檸檬酸、馬來酸或丙二酸具有更 佳表現。於研磨組成物中可包含一或多種酸。 於研磨組成物中之酸含量介於（K〇5-10%(mass%)，較佳 地介於〇·1 —8%(mass%)，而最佳地介於0.3_5%(mass%)。當 酸含量低於0.05%(mass%)時，由於酸不足以加速二氧化石夕 之機械研磨效果，故有可能無法得到足夠之材料移除率。 當酸含量高於1 〇%(mass%)時，研磨組成物之黏度大幅地增 加’因而使得研磨組成物傾向凝結，進而使得後續研磨後 玻璃基板上之粗链度的增加。 於研磨組成物中，水作為溶解與分散原料其他之用。 水較佳地包含儘量少之雜質以避免抑制其他原料之作用。 特別地，較佳地使用藉由移除雜質離子利用離子交換樹脂 與接著經由過濾器過濾污染物過之純水或超純水，或蒸餾 水。 依據實際需要，研磨組成物可更包括蜇合劑 (chelating agent)、表面活性劑、防腐劑或類似物。 研磨組成物係藉由將水之外原料與水混合而成。於混 合過程中，可以使用刀片型之㈣器或超音波分散器。: 以外原料與水混合之順序則並不限定。 研磨組成物之PH值較佳地不高於 ^ 9 ’更佳地介於 0· 5-6，更佳地介於1-4，而最佳地介於]〇 c 於卜2· 5。當pH值高 2188-6645-PF;Ahddub 10 200528548 於9時，將無法得到足夠之材料移除率。當pH低於〇.5時， 將有損於對於研磨組成物性質之掌控度。當pH值設定介於 0.5 6 %，研磨組成物適用於研磨玻璃基板之用，因而改善 材料移除率。研磨組成物之PH值可藉由改變酸的含量而加 以調整。 依據本發明實施例之研磨組成物加水稀釋或沒有經過 加水稀釋。當研磨組成物經加水稀釋時，稀釋比（體積比） 較佳地不大於5 0倍，更佳地不大於2 〇倍，而最佳地不大 於10倍。當稀釋倍率超過50倍，於稀釋後研磨組成物中鲁 之二氧化石夕與酸之含量可能過低，因而造成不足之材料移 除率。 藉由包含粗磨步驟與細磨步驟之兩步驟研磨程序研磨 玻璃基板之情形如下所述。首先，於粗磨步驟中，玻璃基 底表面相對粗略地藉由包含氧化鈽之研磨漿研磨。接著， 於細磨步驟中’藉由依據本發明之研磨組成物研磨玻璃基 底表面。於細磨步驟中，玻璃基底係依附於一研磨頭，此 研磨頭持續施壓於位於一固定壓力下之轉盤上一研磨墊，_ 當研磨頭與轉盤旋轉時，研磨組成物則持續供應至研磨墊 表面。 值得注意的，玻璃基板採用依據本發明之研磨組成 物，於單一步驟研磨程序下研磨，進而取代一多重階段研 磨程序。 本發明具有以下優點。 依據本實施例之研磨組成物包含一氧化發之研磨料。 2188-6645-PF；Ahddub 11 200528548 相較於含氧化鈽之研磨物之研磨組成物，如此可降低研磨 後玻璃基板之表面粗糙度。據推論，如此之表現係由於氧 化錦之主要粒子具有不規則形狀’而二氧化碎之為一球狀 粒子。由於主要形狀為球狀，二氧化矽更較氧化鈽適用於 精細地研磨玻璃基板表面，以降低研磨後玻璃基板之表面 粗糙度。 此外，對於玻璃基板材料，二氧化矽具有相較於氧化 鈽為低之反應性。基於此原因，黏附於玻璃基板上之二氧 化矽可輕易地藉由清洗玻璃基板而移除，而不會與玻璃基 板之材料反應而黏附於玻璃基板表面。因此依據本實施例 之研磨組成物具有可輕易由研磨表面清除之特性。 此外，相較於氧化鈽，於研磨組成物中二氧化矽具有 對於較大之抗凝聚力與高分散性（請參照稍後之範例卜μ 與比較例4與5)。因此’依據本實施例之研磨組成物亦包 括具有良好分散性之黏著劑。 於研磨組成物中酸之化學研磨作用，可加速使用二氧 化石夕料玻璃基底表面之機械研磨。#由如此酸的作用， 可改善研磨組成物研磨玻璃基板表面之能力，纟改善材料 移除率。值得注意#，當酸藉由活化二氧化矽表面與蝕刻 玻璃基板表面等方式改善於材料移除#，其並非視作為氧 化玻璃基板表面並使之脆化。 接著，於下文中將詳細敘述本發明之範例與比較例。 範例卜37與比較例卜5之研磨組成物係藉由將研磨 料、研磨加速劑與水混合後所製備而《。研磨料與研磨加 2188-6645-PF；Ahddub 12 200528548 速劑之種類如表！所示。量測依據範例卜37與比較範例U 所製備之研磨組成物之pH值，並將量測值結顯示於表1中 採用依據範例卜37與比較例卜5之各研磨組成物於如 下所述研磨條件下研磨不同之玻璃基板表面。在此，於 磨前後量測各玻璃基板之質量，接著藉由下述公式計曾特 ㈣除率。基於所得到之材料移除率，各研磨組成物:評 定為四個等級：⑴極佳；⑵良好；（3)稍差；⑷不良。 特別地，當研磨組成物評定為極佳時，其材料移除率不低 於0.12微米/每分鐘；當材料移除率低於〇12微米/每分 鐘而不低於0. 08微米/每分鐘時，則評定為良好；當材料 =除率低於0.08微米/每分鐘而不低於〇〇5微米/每分鐘 犄，其將砰定為稍差；當材料移除率低於〇 · 〇 5微米/每分 鐘時則將評定為極差。上述評定結果請參照表一中標題 為”材料移除率，，之欄中所示。 研磨條件： 研磨裝置：單面研磨機15”妒（三片/每盤），由Engis 公司（日本）所製造。 欲研磨材料為：採用含氧化鈽之研磨漿所粗磨強化玻 璃表面所得到之2.5吋（外徑=63.5mm)之玻璃基板，其具有 Ra = 0. 8奈米之表面粗糙度。 研磨墊··絨面研磨墊” Belatix N0058 ” ，由佳麗寶 (kanebo)公司製造。 研磨壓力：100克/平方公分（ = 9.8KPa)。 轉檯旋轉速度：102rpm; 2188-6645-PF;Ahddub 13 200528548 研磨組成物供應速率：50毫升/每分鐘； 研磨時間：2 0分鐘。 計算公式： 材料移除率（奈米/每分鐘於研磨前後之玻璃基板質 量差（公克）/[30· 02625平方公分*2. 52(公克/每平方公 分）]*10000(；z m/公分）/研磨時間（分鐘）。 研磨後之玻璃基板接著刷洗3〇秒以及超音波清洗45 秒，並接著旋轉乾燥18〇秒。此後，接著利用由Digital Instruments lnc.製造之原子力顯微鏡” Nan〇Sc〇pe nia_ Dimension 3000” （掃描區域：1〇//m*1Mm，掃描速率： 1· 0Hz，取樣行數：256條）觀察玻璃基板之表面狀況。基於 觀察到之於玻璃基底表面上黏附物之數量，將各研磨組成 物評定為四個等級，（1)極佳、（2)良好；（3)稍差；與（4) 極差。特別地，當所觀察到之黏附物數量為零時，研磨組 成物將評定為極佳；當所觀察到之黏附物數量少於3時， 研磨組成物則評定為良好；當所觀察到之黏附物數量少於5 但不少於3時，研磨組成物則評定為稍差，·當所觀察到之參 黏附物數量不少於5時，研磨組成物將評定為極差。此些 評定結果如表一内標題為，，清洗容易度，，之欄位中所顯 示〇 玻璃基板之表面粗糙度Ra於旋轉乾燥後係藉由原子力 顯微鏡’’ NanoScope Ilia Dimension 3 0 0 0 ” （掃插區域· 1 0 A m*l 0 // m，掃描速率：1 · 0Hz，取樣行數：256條；離線 濾、鏡：flatten auto order-2)所量側。基於所量測到之玻 2188-6645-PF;Ahddub 14 200528548 璃基板之表面粗糙度，各研磨組成物將評定為以下四個 等級（1)極佳、（2)良好；（3)稍差；與（4)極差。特別地， 當表面粗糙度Ra少於〇·2奈求時，研磨組成物將評定為極 佳’ §表面粗糙度少於〇· 2 5奈米而不少於〇· 2奈米時\ 研磨組成物將評定為良好；當表面粗糙度少於0· 3奈米而 不少於0· 25奈米時，研磨組成物將評定為稍差；當表面粗 糙度不少於〇 · 3奈米時，研磨組成物將評定為極差。此^ 斤疋、果如表一内標題為”表面粗糙度”之攔位中所顯 示。 .、 、將範例丨―37與比較範例1-5之研磨組成物放置於内秤 為2· 5么分之比色試管（colorimetric tube)中，且將之靜 置一1小％。然後，量測各比色試管中之研磨組成物之沉幾 物同度。基於所量測之沉澱物高度，各研磨組成物將 為四個等級⑴極佳、⑴良好；⑶稍i ;與⑷極差。特 別地，當沉㈣之高度低於1公分時，研磨組成物將評定 為極佳；當沉殿物之高度低力2公分而不低於i公分時， 研磨組成物將評定為良好；當沉澱物之高度低⑨3公分而 不低2 2公分時，研磨組成物將評定為稍差；以及當沉凝 门度不低於3公分時，研磨組成物將評定為極差 些評定結果將如表-内標題為，，分散性，，之攔位中所顯 7f\ ° 基於前述評定四個項目 表面粗糙度、以及分散性， 極佳、（2 )良好；（3)稍差； :材料移除率、清洗容易度、 各研磨組成物分別地評定為（j) 以及（4)極差，並將分別地與以 2188-6645-PF；Ahddub 15 200528548 評分為5分、3分、1分與〇分，且計算 #合研磨組成物所得 總分。當總分為20分時，研磨組成物將評定為極佳；當總 分介於16-19分時，研磨組成物將評定為良好；當總分^ 於10 —15分時，研磨組成物將評定為稍差；而當：二： 於9分時，研磨組成物將評定為極差。此些評定結果將如 表一中之”綜合評定”之欄位所顯示。 表一 研磨料 (mass%) 研磨加速劑 (mass%) pH 材料 移除率 清除 容易度 表面 粗糙:廣 分散 性 綜合 評定 範例1 膠態矽20% 馬來酸3% 1.3 1 1 1 1 口1 1 範例2 膠態矽20% 馬來酸1% 1.6 1 1 1 1 上 1 範例3 膠態矽20% 馬來酸0.1% 2.2 1 1 1 1 1 範例4 膠態矽20% 馬來酸0.04% 5.0 2 1 1 1 2 範例5 膠態矽20% 馬來酸0· 01% 8.5 3 1 1 1 2 範例6 膠態矽10% 馬來酸1% 1.5 1〜 1 1 1 1 範例7 膠態矽1% 馬來酸1% 1.4 3 1 1 1 2 範例8 燻矽20% 馬來酸1% 1.7 1 1 3 1 2 範例9 膠態矽40% 馬來酸1% 2.6 1 1 1 1 1 範例10 膠態矽20% 鱗酸3% 1.6 1 1 1 1 1 範例11 2. 6膠態1.6 矽 20% 1.9 磷酸1% 1.9 1 1 1 1 X 1 範例12 膠態矽20% 磷酸0· 1% 2.6 1 1 1 1 1 範例13 膠態矽20% 鱗酸0. 01% 9.0 ~~—_ 1 1 1 2 範例14 膠態矽10% 磷酸1% 1.7 2」 1 1_ 1 2 範例15 膠態矽1% 磷酸1% 1.7 1 1 1 2 範例16 燻矽20% 磷酸1% 1.9 1 3 1 2 範例17 膠態矽40% 磷酸1% 2.8 1 ------ 1 1 1 1 範例18 膠態矽20% 甲基續酸 1.1 1 1 1 1 1 範例19 膠態矽20% HEDP1%__ 1.4 1 1 1 1 1 範例20 膠態矽20% NTMP1% 1. 4 1 ---—.^ 1 1 1 1 範例21 膠態矽20% 鹽酸亚一_· 1.4 1 1 1 1 1 範例22 膠態矽20% PBTC1% 1. 5 1 1 1 1 1 範例23 膠態矽20% 馬來酸1% 1. 5 1 1 1 1 1 範例24 膠態矽20% 次構酸1% 1. 7 1 1 1 1 16 2188-6645-PF;Ahddub 200528548200528548 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a polishing composition for polishing a glass substrate for recording media (informat ion-recording), such as a hard disk or the like. The present invention also relates to a grinding method using the grinding composition. [Prior art] Conventionally, it has been conventionally known that a glass substrate for polishing a recording medium is polished to form an object. An abrasive composition comprising an abrasive and water mainly composed of a rare earth oxide such as thorium oxide was disclosed in an earlier-published patent application No. 200b 89748 (hereinafter referred to as the first practice (Known grinding composition). The earlier patent application No. 2000-144112 published in the early days of this year revealed the possibility of including iron oxides (iron-containing oxide) and iron-based compounds (iron-conontaining). basic c ⑽ pund) a polishing composition of at least one abrasive and water of the group (hereinafter referred to as the second conventional polishing composition). The above-mentioned first and second conventional grinding compositions can mechanically grind a glass substrate by the action of an abrasive. The conditions required for the abrasive composition used for grinding glass substrates include: (1) The coarse chain degree of the surface of the polished glass substrate is small; (2) The abrasive composition needs to be easy to remove, that is, the abrasive composition needs to be borrowed. Easily removed from the glass substrate by cleaning; (3) The abrasive particles must have good dispersibility in the abrasive composition; and (4) The abrasive composition must have a high material removal rate. -6645-PF / Ahddub 5 200528548 Grind the broken glass substrate. Secondly, the above-mentioned first and second conventional grinding compositions do not meet the above-mentioned needs' and therefore need to be improved. SUMMARY OF THE INVENTION In view of this, a main object of the present invention is to provide a polishing composition which is suitable for polishing a glass substrate. Another object of the present invention is to provide a polishing method using the polishing composition. To achieve the above object, the present invention provides a polishing composition. The grinding composition is suitable for grinding a glass substrate, which includes silicon dioxide, acid and water. The first aspect of the present invention provides a method for polishing a glass substrate, which includes the following steps: providing the above-mentioned polishing composition, and polishing the surface of a glass substrate using the polishing composition. In order to make the above and other objects, features, and advantages of the present invention more comprehensible, a preferred embodiment is given below in conjunction with the accompanying drawings to make a detailed description as follows: [Embodiment] Implementation of the present invention Examples will be described in detail below. The glass substrates used in data recording media such as magnetic disks are made of materials such as aluminosilicate glass, soda lime glass, and soda aluminosilicate 2188-6645- PF; Ahddub 6 200528548 glass), alumino boros i 1 i cat e glass, borosilicate glass, quartz glass or crystallized glass, etc. Made of materials. The main crystal phases of crystallized glass may be spodumene, mullite, aluminum borate crystal, / 3-quartz solid solution, α-quartz, cordierite, and refractory stone (Enstatite), barium feldspar (celsian), wollastonite (wollastonite), anorthite, forsterite, lithium metasilicate, or lithium dilithium (1 i thium disi 1 icate). Glass substrates are usually mirror-finished by the application of CMP procedures. Generally speaking, in order to improve the material removal rate and the polishing quality of the glass substrate after grinding, the execution of the grinding glass substrate procedure can be subdivided into the following several grinding steps. For example, these grinding steps include a step of rough grinding the surface of the glass substrate and a step of fine grinding the surface of the glass substrate. In other words, these polishing steps include a step of preliminarily polishing the surface of the glass substrate and a step of finishing-polishing. For example, the polishing composition according to this embodiment can be used in the final polishing step (polishing polishing step) of these polishing steps. Next, the ground glass substrate is placed in a chemical strengthening process, and a low temperature ion exchange method or the like is used to improve its resistance to vibration and shaking. The polishing composition according to the embodiment of the present invention includes silicon dioxide, acid, and water. Oxide oxide can be used as an abrasive for mechanically grinding glass substrates. 2. Emulsified stone Xi Dingyue & is knee oxidized silica (cooidaida silica), fumed stone (fumed 2188-6645-PF; Ahddub 7 200528548 S1 11 Ca) or Precipitated suica. Among them, colloidal silica or sintered silicon is preferably used to obtain a polished glass substrate with a lower surface roughness, and colloidal silicon is the best choice. The abrasive composition may include—or a plurality of dioxides. When the silicon dioxide is colloidal silicon, the average particle diameter of the specific surface area of the colloidal silicon determined by the specific surface area method (BET method) is preferably between 5 and 30 nm, more preferably Between 5 and 200 nanometers, and most preferably between 5 and 120 nanometers. The average particle diameter of the colloidal silicon determined by laser diffraction scattering method is 1, preferably between 5 and 300 nm, and more preferably between 5 and 200 nm. A good place is between 5-150 nm. When the silicon dioxide is fumigated silicon, the average particle diameter Dsa 'of the fumigated silicon in the specific surface area of the colloidal silicon determined by the βET method is preferably between 10 and 300 nm, more preferably It is between 10 and 200 nanometers, and preferably between 10 and 120 nanometers. The average particle diameter of the fumigated silicon determined by laser diffraction and scattering method is preferably between 30 and 500 nm, more preferably; between 1 and 40 and 400 nm, and most preferably Between 50 and 300 nanometers. When the average particle diameter Dsa or Dim of colloidal silicon or when the average particle diameter Dsa or Dn4 of fumed silicon is too small, a material removal rate that is not sufficiently high may be obtained. When the average particle diameter of colloidal silicon Dsa or Dw or when the average particle diameter of fumed silicon 1) ^ or Dn4 is too large, it may make the surface roughness of the glass substrate after grinding too large, or the surface of the glass substrate after grinding. Injured. The silicon dioxide content in the abrasive composition is preferably between 50% (mass%), more preferably between 40% (mass%), and most preferably between 3 and 30%. (mass%). When the content of silicon dioxide is less than 0.1% (mass%), a sufficiently high material removal rate cannot be obtained, or 2188-6645-PF; Ahddub 8 200528548 encounters a higher resistance to grinding when grinding glass substrates . When the content of the dioxide is higher than 50% (mass%), the viscosity of the abrasive composition will be greatly increased, so that the abrasive composition tends to coagulate, thereby reducing the control of the abrasive composition. In addition, acids can be used as grinding accelerators and can accelerate mechanical grinding through the application of silicon dioxide. One reason for the inference that acid can accelerate mechanical grinding is that acid can activate the surface of silicon dioxide, which in turn increases the mechanical grinding force of silicon dioxide. In addition, the acid also corrodes or etches the surface of the glass substrate for other functions of chemically polishing the surface of the glass substrate. Compared with the mechanical grinding of silicon dioxide, the acid chemical mechanical grinding reaction is relatively weak. The acid may be an inorganic or organic acid. Inorganic acids include, for example, hydrochloric acid, filling acid, sulfuric acid, phosphoric acid, nitric acid, hypophosphorous acid, and boric acid. Organic acids are, for example, acetic acid, itaconic acid, succinic acid, tartaric acid, citric acid, maleic acid, and glycolic acid. ), Malonic acid, methanesulfonic acid, formic acid, malic acid, gluconic acid, alanine, p-phenylglycine Acid (giycin), lactic acid, hydroxyethylidene diphosphonic acid (abbreviated as HEDP), nitrilotris (methylene phosphonic acid; abbreviated as NTMP), and phosphinobutylene Phosphonobutane tricarboxylic acid (abbreviated as PBTC). Among the above acids, preferred are hydrochloric acid, phosphoric acid, sulfuric acid, orthophosphoric acid, nitric acid, hypophosphorous acid, boric acid, acetic acid, itaconic acid, succinic acid, tartaric acid, 2188-6645-PF; Ahddub 9 200528548 citrate, horse Maleic acid, glycolic acid, malonic acid, methanesulfonic acid, formic acid, malic acid, gluconic acid, lactic acid, HEDP, NTMP or PBTC can effectively accelerate the mechanical grinding effect of silicon dioxide. Among the above-mentioned preferred acids, hydrochloric acid, dishic acid, orthophosphoric acid, tartaric acid, citric acid, maleic acid, or malonic acid have better performance. One or more acids may be included in the abrasive composition. The acid content in the abrasive composition is between (K0-5-10% (mass%), preferably between 0.1-8% (mass%), and most preferably between 0.3_5% (mass%) ). When the acid content is less than 0.05% (mass%), because the acid is not enough to accelerate the mechanical grinding effect of the dioxide, it may not be possible to obtain a sufficient material removal rate. When the acid content is higher than 10% ( mass%), the viscosity of the grinding composition is greatly increased, thus causing the grinding composition to tend to condense, which in turn increases the coarse chain degree on the glass substrate after subsequent grinding. In the grinding composition, water is used as a dissolution and dispersion raw material. Water preferably contains as few impurities as possible to avoid inhibiting the effects of other raw materials. In particular, it is preferable to use pure water that uses ion exchange resin by removing impurity ions and then filters the pollutants through a filter or Ultrapure water, or distilled water. According to actual needs, the grinding composition may further include a chelating agent, a surfactant, a preservative or the like. The grinding composition is obtained by mixing raw materials other than water with water. During the mixing process, you can use Tablet-type device or ultrasonic disperser .: The order of mixing raw materials with water is not limited. The PH value of the grinding composition is preferably not higher than ^ 9 ', more preferably between 0 · 5-6, More preferably between 1-4, and most preferably between 〇c and 2.5. When the pH is higher than 2188-6645-PF; Ahddub 10 200528548 at 9, sufficient material removal rate cannot be obtained When the pH is lower than 0.5, it will damage the control of the properties of the polishing composition. When the pH value is set between 0.56%, the polishing composition is suitable for polishing glass substrates, thus improving the material removal rate The pH value of the grinding composition can be adjusted by changing the acid content. The grinding composition according to the embodiment of the present invention is diluted with or without water. When the grinding composition is diluted with water, the dilution ratio (volume ratio) It is preferably not more than 50 times, more preferably not more than 20 times, and most preferably not more than 10 times. When the dilution ratio exceeds 50 times, the lubricating dioxide and acid in the grinding composition after dilution are diluted. The content may be too low, resulting in insufficient material removal rate. By including a rough grinding step The two-step grinding process of the fine grinding step is as follows. First, in the rough grinding step, the surface of the glass substrate is relatively coarsely polished with a grinding slurry containing hafnium oxide. Then, in the fine grinding step, The surface of the glass substrate is polished by the polishing composition according to the present invention. In the fine grinding step, the glass substrate is attached to a polishing head, and the polishing head is continuously pressed against a polishing pad on a turntable under a fixed pressure. When the head and the turntable rotate, the polishing composition is continuously supplied to the surface of the polishing pad. It is worth noting that the glass substrate adopts the polishing composition according to the present invention and is polished under a single-step polishing process, thereby replacing a multi-stage polishing process. The present invention has the following advantages. The polishing composition according to the present embodiment includes an abrasive that is oxidized. 2188-6645-PF; Ahddub 11 200528548 Compared with the abrasive composition of abrasives containing hafnium oxide, this can reduce the surface roughness of the polished glass substrate. It is inferred that such a performance is due to the fact that the main particles of the oxidized brocade have an irregular shape ' Because the main shape is spherical, silicon dioxide is more suitable than rubidium oxide for finely polishing the surface of glass substrates to reduce the surface roughness of the ground glass substrates. In addition, for glass substrate materials, silicon dioxide has a lower reactivity compared to hafnium oxide. For this reason, the silicon dioxide adhered to the glass substrate can be easily removed by cleaning the glass substrate, and does not react with the material of the glass substrate and adhere to the surface of the glass substrate. Therefore, the polishing composition according to this embodiment has a characteristic that it can be easily removed from the polishing surface. In addition, compared with hafnium oxide, silicon dioxide in the polishing composition has greater resistance to cohesion and high dispersibility (please refer to the later examples, μ and Comparative Examples 4 and 5). Therefore, the abrasive composition according to this embodiment also includes an adhesive having good dispersibility. The chemical grinding effect of the acid in the grinding composition can accelerate the mechanical grinding of the surface of the glass substrate using the silica. #As a result of this acid, the ability of the polishing composition to polish the surface of the glass substrate can be improved, and the material removal rate can be improved. It is worthwhile to note that when the acid improves the material removal by activating the surface of the silicon dioxide and etching the surface of the glass substrate, it is not regarded as oxidizing the glass substrate surface and making it brittle. Next, examples and comparative examples of the present invention will be described in detail below. The polishing compositions of Example 37 and Comparative Example 5 were prepared by mixing an abrasive, a grinding accelerator and water. Abrasives and grinding plus 2188-6645-PF; Ahddub 12 200528548 The types of speeding agents are shown in the table! As shown. Measure the pH value of the abrasive composition prepared according to Example 37 and Comparative Example U, and display the measured value results in Table 1. The abrasive compositions according to Example 37 and Comparative Example 5 are described below. Polish different glass substrate surfaces under polishing conditions. Here, the mass of each glass substrate was measured before and after the grinding, and then the Zengte removal rate was calculated by the following formula. Based on the obtained material removal rate, each abrasive composition was evaluated as four grades: ⑴excellent; ⑵good; (3) slightly worse; ⑷bad. In particular, when the abrasive composition is evaluated as excellent, its material removal rate is not less than 0.12 micrometers per minute; when the material removal rate is less than 012 micrometers per minute and not less than 0.08 micrometers per At the minute, it is rated as good; when the material = removal rate is less than 0.08 micron / minute but not less than 0.05 micron / minute 犄, it will be rated as slightly worse; when the material removal rate is less than 0 · It was rated as very poor at 0 micrometers per minute. For the above evaluation results, please refer to the table titled “Material Removal Rate” in Table 1. Grinding conditions: Grinding device: single-sided grinder 15 ”(three pieces per plate), by Engis Corporation (Japan) Made by. The material to be ground is: a 2.5-inch (outer diameter = 63.5mm) glass substrate obtained by rough grinding the strengthened glass surface with a grinding slurry containing hafnium oxide, which has a surface roughness of Ra = 0.8 nm. Abrasive pads · Suede abrasive pads "Belatix N0058", manufactured by Kanebo. Grinding pressure: 100 g / cm2 (= 9.8KPa). Turntable rotation speed: 102 rpm; 2188-6645-PF; Ahddub 13 200528548 Milling composition supply rate: 50 ml / minute; Milling time: 20 minutes. Calculation formula: Material removal rate (nano / minute difference between glass substrate before and after grinding (g) / [30 · 02625 cm² * 2. 52 (g / cm²)] * 10000 (; zm / cm ) / Grinding time (minutes). The polished glass substrate is then brushed for 30 seconds and ultrasonically cleaned for 45 seconds, and then spin-dried for 180 seconds. Thereafter, an atomic force microscope manufactured by Digital Instruments lnc. 〇pe nia_ Dimension 3000 ”(scanning area: 10 // m * 1Mm, scanning rate: 1.0 Hz, number of sampling lines: 256 lines) observe the surface condition of the glass substrate. Based on the observation of adhesion on the surface of the glass substrate The amount of each abrasive composition was rated as four grades, (1) excellent, (2) good; (3) slightly worse; and (4) very poor. In particular, when the number of adherents observed was At zero, the abrasive composition will be rated as excellent; when the number of adhered substances observed is less than 3, the abrasive composition will be evaluated as good; when the number of observed adherents is less than 5 but not less than 3 , Grinding composition is slightly worse, when When the observed amount of ginseng adherence is not less than 5, the grinding composition will be evaluated as extremely poor. The results of these evaluations are shown in the table in the title, “Easy to clean,” and the surface of the glass substrate is shown. The roughness Ra was rotated and dried by an atomic force microscope "NanoScope Ilia Dimension 3 0 0 0" (scanning area · 1 0 A m * l 0 // m, scanning rate: 1 · 0 Hz, number of sampling lines: 256 Strips; offline filters and mirrors: flatten auto order-2) Measured side. Based on the measured surface roughness of glass substrates 2188-6645-PF; Ahddub 14 200528548, each abrasive composition will be evaluated as the following four Grades (1) are excellent, (2) are good; (3) are slightly worse; and (4) are very poor. In particular, when the surface roughness Ra is less than 0.2, the polishing composition is evaluated as excellent '§ When the surface roughness is less than 2.5 nm but not less than 0.2 nm \ The abrasive composition will be evaluated as good; when the surface roughness is less than 0.3 nm and not less than 0.25 In the case of nanometers, the grinding composition will be evaluated as slightly worse; when the surface roughness is not less than 0.3 nanometers, the grinding composition will be evaluated. It was rated as extremely poor. This ^ catties and results are shown in the block titled "Surface Roughness" in Table 1.... Place the abrasive composition of Example 丨 37 and Comparative Example 1-5 in The scale is in a 2.5i colorimetric tube, and it is left to stand at 1%. Then, the same degree of the abrasive composition in each colorimetric tube is measured. Based on the measured sediment height, each grinding composition will be of four grades: excellent, good; (3) slightly different; and very poor. In particular, when the height of the sinker is less than 1 cm, the abrasive composition will be evaluated as excellent; when the height of the sinker is 2 cm and not lower than i cm, the abrasive composition will be evaluated as good; When the height of the precipitate is as low as 3 cm and not as low as 22 cm, the abrasive composition will be evaluated as slightly worse; and when the degree of sedimentation is not less than 3 cm, the abrasive composition will be evaluated as extremely poor. In the table, the title is ,, dispersibility, 7f \ ° shown in the block, based on the surface roughness and dispersibility of the four items evaluated above, excellent, (2) good; (3) slightly worse;: Material Removal rate, ease of cleaning, and each polishing composition were evaluated as (j) and (4) extremely poor, respectively, and 2188-6645-PF; Ahddub 15 200528548 scored 5 points, 3 points, 1 Divide by 0 points, and calculate the total score obtained from # 合 磨 组合 物. When the total score is 20 points, the abrasive composition will be evaluated as excellent; when the total score is between 16 and 19 points, the abrasive composition will be evaluated as good; when the total score is ^ 10 to 15 points, the abrasive composition will be evaluated as excellent The rating was slightly worse; and when: 2: At 9 points, the abrasive composition was rated as extremely poor. The results of these assessments will be shown in the “Comprehensive Assessment” column in Table 1. Table 1 Abrasive (mass%) Grinding accelerator (mass%) pH Material removal rate Ease of removal Rough surface: Comprehensive evaluation of wide dispersibility Example 1 Colloidal silicon 20% Maleic acid 3% 1.3 1 1 1 1 Mouth 1 1 Example 2 Colloidal silicon 20% maleic acid 1% 1.6 1 1 1 1 Up 1 Example 3 Colloidal silicon 20% maleic acid 0.1% 2.2 1 1 1 1 1 Example 4 Colloidal silicon 20% maleic acid 0.04% 5.0 2 1 1 1 2 Example 5 Colloidal silicon 20% maleic acid 0.01% 8.5 3 1 1 1 2 Example 6 Colloidal silicon 10% maleic acid 1% 1.5 1 ~ 1 1 1 1 Example 7 Colloidal silicon 1% maleic acid 1% 1.4 3 1 1 1 2 Example 8 Silicon fume 20% maleic acid 1% 1.7 1 1 3 1 2 Example 9 Colloidal silicon 40% maleic acid 1% 2.6 1 1 1 1 1 Example 10 Colloidal silicon 20% phosphonic acid 3% 1.6 1 1 1 1 1 Example 11 2. 6 Colloidal 1.6 Silicon 20% 1.9 Phosphoric acid 1% 1.9 1 1 1 1 X 1 Example 12 Colloidal silicon 20% Phosphoric acid 0.1% 2.6 1 1 1 1 1 Example 13 Colloidal Silicon 20% Phosphoric Acid 0.01% 9.0 ~~ —_ 1 1 1 2 Example 14 Colloidal Silicon 10% Phosphoric Acid 1% 1.7 2 ″ 1 1_ 1 2 Example 15 Colloidal Silicon 1 % Phosphoric acid 1% 1.7 1 1 1 2 Example 16 Fumed silica 20% Phosphoric acid 1% 1.9 1 3 1 2 Example 17 Colloidal silicon 40% Phosphoric acid 1% 2.8 1 ------ 1 1 1 1 Example 18 Colloidal silicon 2 0% Methyl continued acid 1.1 1 1 1 1 1 1 Example 19 Colloidal silicon 20% HEDP1% __ 1.4 1 1 1 1 1 Example 20 Colloidal silicon 20% NTMP1% 1. 4 1 -----. ^ 1 1 1 1 Example 21 Colloidal Silicon 20% Hydrochloride 1.4 · 1 1 1 1 1 Example 22 Colloidal Silicon 20% PBTC1% 1. 5 1 1 1 1 1 Example 23 Colloidal Silicon 20% Maleic Acid 1% 1. 5 1 1 1 1 1 Example 24 Colloidal Silicon 20% Hypostructural Acid 1% 1. 7 1 1 1 1 16 2188-6645-PF; Ahddub 200528548
表一欄位中之縮寫代表： “膠態石夕”為罝右单始々_ /、有十均粒徑1為80奈米與平均粒徑 D n 4為8 0奈米之膠態石夕； 燦碎 為具右单π » 有十均粒徑Dsa為30奈米與平均粒徑DN4 為9 0奈米之燦石夕； 一鈽為具有平均粒徑Dso為450奈米之氧化鈽 (C e 2 0 3 );以及 為具有平均粒徑Dm為450奈米之氧化鐵 “氧化鐵 (d -Fe2〇3) 〇 氧化鈽與氣τ 化鐵之平均粒徑D5。係經藉由Beckman coulter Inc·所製谇夕 p , 衣 w 之 Coulter counter “LS-230” 所量 2188-6645-PF；Ahddub 17 200528548 測得到。 如表一所示，依據範例1 —37之各研磨組成物於任何項 目中並不至於評定為極差，且於綜合評定中皆評定為極佳 與良好。如此之結果建議了依據範例1 —37之研磨組成物適 用於研磨玻璃基板之應用。依據範例2、6、7與9研磨組 成物之評定結果，可發現到當酸（研磨加速劑）為馬來酸之 有機酸時可改善材料移除率，且特別於當二氧化矽含量（研 磨料）不少於10%(mass%)，且較佳地介於1〇 時。依據範例丨卜…㈣心研磨组成物之結二 可發現到當酸為磷酸之無機酸時可改善材料移除率改善， 且特別於當二氧化梦含量不少於2G%(mass%)，且較佳地介 於，順_s%)時。依據範例卜5與1(M3之研磨組成物 且Si::疋結果’藉由設定酸含量不低於〇.1%(mass%)， 車乂佳地；丨於〇.l-3%(mass%)時，可改盖挪府 丁 J改善研磨移除率。 雖然本發明已以較佳實施例揭露如上，鈇 限定本發明，任何熟習此技藝者，在不脫離太二”非用以 和範圍内，當可作夂鍤夕#* 本备明之精神 μ问山 種更動與潤飾，31此本發明之伴鳟 祝圍s視後附之申請專利範圍所界定者為準。 /… 圖式簡單說明 〇The abbreviations in the column of Table 1 represent: "Coloidal stone eve" is 罝 right single beginning 々 / /, colloidal stone with ten average particle diameters of 1 80 nm and average particle diameter D n 4 of 8 0 nm Evening; can be broken with right single π »Canshixi with ten average particle diameters Dsa of 30 nanometers and an average particle diameter of DN4 of 90 nanometers. (C e 2 0 3); and an iron oxide having an average particle diameter Dm of 450 nm "iron oxide (d-Fe2 03) 〇 average particle diameter D5 of hafnium oxide and gas iron oxide. Coulter counter “LS-230” by Beckman Coulter Inc., measured by 2188-6645-PF; Ahddub 17 200528548. As shown in Table 1, according to each grinding composition of Examples 1-37 In any project, it is not rated as very bad, and it is rated as excellent and good in the comprehensive evaluation. Such results suggest that the polishing composition according to Examples 1 to 37 is suitable for the application of polishing glass substrates. According to Example 2 The results of the evaluation of the abrasive composition of 6, 6, 7 and 9 showed that the material can be improved when the acid (grinding accelerator) is an organic acid of maleic acid. The removal rate, and especially when the content of silicon dioxide (abrasive) is not less than 10% (mass%), and preferably between 10. According to the example 丨 Bu ... When the acid is an inorganic acid of phosphoric acid, the material removal rate can be improved, and especially when the content of dream dioxide is not less than 2G% (mass%), and preferably between, cis_s%). Example 5 and 1 (Grinding composition of M3 and Si :: 疋 Result 'By setting the acid content not less than 0.1% (mass%), the car is good; 丨 at 0.1-3% (mass %), You can change the cover to improve the removal rate. Although the present invention has been disclosed in the preferred embodiment as described above, the present invention is limited. Anyone skilled in this art will not depart from Tai Er. Within the scope, when you can make 夂 锸 夕 # * The spirit of this preparation Ming asks the mountain species to change and retouch, 31 The companion trout Zhuwei of the present invention is subject to the definition of the scope of the attached patent. / ... Brief explanation
4WS 【主要元件符號說明】 益 〇 2188-6645-PP；Ahddub 184WS [Description of main component symbols] 〇 2188-6645-PP; Ahddub 18