201107133 六、發明說明： 【發明所屬之技術領域】 本發明係關於改善薄膜之接著性及硬度的光學薄膜、 使用其之偏光板及液晶顯示裝置。 【先前技術】 液晶顯不裝置在液晶電視或電腦液晶顯不器等用途上 需要擴大。通常液晶顯示裝置爲將透明電極、液晶層、彩 色過濾器等以玻璃板挾持的晶胞、與設置於該兩側的二片 偏光板所構成，各偏光板爲將偏光子（偏光子亦稱爲偏光 薄膜）以二片光學薄膜（偏光板保護薄膜）成爲被挾持的 構成。作爲該偏光板保護薄膜，一般使用纖維素三乙酸酯 薄膜。 另一方面，因近年技術的進步，加速液晶顯示裝置的 大型化之同時，液晶顯示裝置之用途爲多樣化。例如，可 舉出作爲設置於街頭或店頭之大型顯示器的利用、使用稱 爲電子看板之顯示機器的公共場所中之廣告用顯示器的利 用等。 對於如此用途，因預設爲在屋外之利用，故藉由偏光 薄膜之吸濕的劣化成爲問題，對於偏光板保護薄膜要求更 高的耐濕性。然而，過去所使用的纖維素三乙酸酯薄膜等 纖維素酯薄膜中難得到充分耐濕性，欲得到耐濕性而使其 厚膜化時，有著光學性影響變大的問題。且，近年來因裝 置薄型化被要求，故偏光板本身的變厚亦成爲問題。 -5- 201107133 另一方面，作爲低吸濕性光學薄膜材料，作爲丙烯酸 樹脂代表之聚甲基甲基丙烯酸酯（以下簡稱爲「PMM A」 )除低吸濕性以外，亦寧示優良透明性或尺寸安定性，故 適合使用於光學薄膜。 然而，隨著如上述液晶顯示裝置大型化，對屋外之用 途擴大，欲在屋外亦可使映像充分辨識，必須增加背光之 光量的同時，變的於更嚴謹條件下使用，且在高溫下之耐 熱性或更長期的耐熱性被要求。 但，PMM A薄膜於缺乏耐熱性之高溫下的使用，且長 期使用等中，有著產生形狀變化的問題。 該問題不僅作爲在薄膜單體之物性，對於使用如此薄 膜的偏光板、顯示裝置亦爲重要課題。即，液晶顯示裝置 中，隨著薄膜之變形，因偏光板會彎曲，故會產生面板全 體變反的問題。 薄膜變形所引起的問題爲，在背光側亦成爲問題，但 在辨識側表面位置使用時，會因變形而使設計上之相位差 起變化，故會產生視野角之變動或色味變化的問題。 又，丙烯酸樹脂薄膜與纖維素酯薄膜等作比較時，有 著容易割裂之較脆性質，於切斷等上難以處理，特別爲難 以安定下製造大型液晶顯示裝置用之光學薄膜。 有鑑於上述問題•狀況等，例如專利文獻1中揭示作 爲改善耐濕性及耐熱性之技術，提出於丙烯酸樹脂組合耐 衝撃性丙烯酸橡膠-甲基甲基丙烯酸酯共聚物或丁基改性 乙醯基纖維素的樹脂。 -6- 201107133 又，專利文獻2中提出對於過去纖維素酯薄膜，作爲 可塑劑或欲控制光學性能，混合比較低分子量之丙烯酸樹 脂的技術。專利文獻3中揭示，將比較大分子量之丙烯酸 樹脂與纖維素酯樹脂經熔融混合的光學薄膜，該技術有丙 烯酸樹脂與纖維素酯樹脂之相溶性未充分的情況，其爲缺 乏廣泛使用性的技術，且爲硬度不足者。 且，專利文獻4及5中揭示，將丙烯酸樹脂薄膜與偏光 子接著時，必須要電暈處理、電漿處理、AGP處理等表面 處理，若需要接著性必須使用基底層等》 另一方面，藉由將光學薄膜作爲複層構成，可賦予新 穎特性、或兼具相反特性的技術被提案。例如，專利文獻 6中提出藉由使用無機微粒子之薄膜表層中的濃度比該無 機微粒子的薄膜中之平均濃度更大之2軸性光學補償薄膜 ，於廣範圍視野角中，可顯示較高對比的畫像，且移色器 (由斜方向見到時有顔色變化）被減輕的液晶顯示裝置， 特別爲VA模式液晶顯示裝置、賦予此的光學補償薄膜及 偏光板及光學補償薄膜之製造方法的技術。這些技術係關 於存在同一樹脂組成層的厚度方向之一部份層中的添加劑 之技術，有關藉由變更樹脂組成的特性改善之技術並無任 何記載。 專利文獻7中提出藉著由於有機溶劑或水爲可溶或可 分散之聚合物所成的芯層、於該芯層的至少單面上，具有 由0.1〜20μΐη膜厚的纖維素衍生物所成的表層爲特徵之偏 光板用保護薄膜，提供一種其爲低遲緩且較少光學性變形 201107133 ，亮點異物較少，高濕度下的尺寸安定性較佳，較少彎曲 ，與玻璃基板之接著性優良的偏光板用保護薄膜之技術。 該技術係爲設置芯層的技術，該芯層的特徵爲含有主要由 纖維素衍生物所成的表層、纖維素衍生物、具有乙烯性雙 鍵之化合物與光聚合啓始劑。該技術係關於將由樹脂組成 而變化的特性，因藉由設置樹脂組成相異的複數層，僅提 供較佳特性的光學薄膜的技術，除此以外並無其他記載。 又，特別使用丙烯酸樹脂與纖維素樹脂的情況，即使設置 具有複數層之光學薄膜，若設置樹脂比率相異的層，於層 間因相異樹脂組成而產生界面，對於作爲光學薄膜所得之 必要光學特性則完全無記載。 〔先行技術文獻〕 〔專利文獻〕 〔專利文獻1〕特開平5-1 192 17號公報 〔專利文獻2〕特開2003-12859號公報 〔專利文獻3〕特開2008-8 84 1 7號公報 〔專利文獻4〕特開2007-4 1 563號公報 〔專利文獻5〕特開2007-52404號公報 〔專利文獻6〕特開2008-262161號公報 〔專利文獻7〕特開200 1 -2 1 533號公報 【發明內容】 本發明係有鑑於上述問題•狀況所得者，該解決課題 爲提供改善薄膜的接著性及硬度之光學薄膜。又，提供使 -8 - 201107133 用該光學薄膜之偏光板及液晶顯示器° 有關本發明之上述課題，可由以下手段解決° 1. 一種光學薄膜，其爲具有至少二層以上的樹脂組 成爲相互相異的層之光學薄膜，其特徵爲（i)構成該光 學薄膜表面之層的至少一層爲含有50 : 5〇〜3Ό : 70之質量 比的丙烯酸樹脂（A)與纖維素酯樹脂（B) 、（ii)構成 該表面的層以外之層爲含有80: 20〜55: 45之質量比的丙 烯酸樹脂（A)與纖維素酯樹脂（B) 、（iii)前述丙烯 酸樹脂（A)之重量平均分子量爲8 000 0以上、（iv )前述 纖維素酯樹脂（B )的醯基之總取代度爲2.0〜3.0，碳數3 〜7的醯基之取代度爲1.2〜3.0，該纖維素酯樹脂（B)的 重量平均分子量爲75000以上。 2-如前述第1項所記載之光學薄膜，其中構成前述表 面之層的厚度爲前述光學薄膜全體厚度之5〜20%。 3.如前述第1項或第2項所記載之光學薄膜，其中於 構成前述表面之層，含有對於構成該表面之層的全質量而 言爲0.01〜1質量％，平均粒徑爲50〜300 μιη之範圍內的無 機化合物或有機化合物的微粒子。 4·如前述第1項至第3項中任一項所記載的光學薄膜 ，其爲含有防帶電劑。 5·如前述第1項至第4項中任一項所記載之光學薄膜 ，其爲在前述光學薄膜的寬方向之長度10〜90 %的範圍內 ，含有該薄膜寬方向之中心的部分爲含有至少二層以上的 前述樹脂組成之相異層。 -9- 201107133 6. 如前述第1項至第5項中任一項所記載的光學薄膜 ，其中前述樹脂組成爲相互相異的層係於薄膜製膜的同時 而形成。 7. —種偏光板，其特徵爲使用如前述第1項至第6項 中任一項所記載之光學薄膜者。 8. —種液晶顯示裝置，其特徵爲使用前述第1項至第 6項中任一項所記載之光學薄膜。 藉由本發明之上述手段，可提供改善薄膜之接著性及 硬度的光學薄膜。又，可提供使用該光學薄膜的偏光板及 液晶顯示器。 實施發明的形態 本發明的光學薄膜爲樹脂組成具有至少二層以上的相 互相異的層之光學薄膜，（i)構成該光學薄膜之表面的 層之至少一層爲丙烯酸樹脂（A)與纖維素酯樹脂（B)以 5〇:5〇〜30:7〇的質量比下含有，（ii)構成該表面之層 以外的層爲丙烯酸樹脂（A )與纖維素酯樹脂（B )以80 : 20〜55: 45的質量比下含有，（iii)前述丙烯酸樹脂（A )的重量平均分子量爲80000以上，（iv)前述纖維素酯 樹脂（B)的醯基之總取代度爲2.0〜3.0，碳數3〜7的醯基 取代度爲1.2〜3.0，該纖維素酯樹脂（B)的重量平均分子 量爲75000以上爲特徵。該特徵與請求項1至請求項8的請 求項之相關發明具有共通技術特徵。 本發明的光學薄膜可適用於偏光板。因此，亦可適用 -10- 201107133 於液晶顯示裝置上。 以下對於本發明與其構成要素、及實施本發明時的形 態·型態等做詳細說明。 〔光學薄膜之構成槪要〕 本發明的光學薄膜雖具有種種層構成型態，但其特徵 爲樹脂組成爲具有至少二層以上的相互相異的層之光學薄 膜。又，滿足下述要件（〇〜（iv)者爲特徵。 (i)構成該光學薄膜表面之層的至少一層爲丙烯酸 樹脂（A)與纖維素酯樹脂（B )以50 ·· 50〜30 ·· 70的質量 比下含有 (Π)構成該表面之層以外的層爲丙烯酸樹脂（A) 與纖維素酯樹脂（B)以80: 20〜55: 45的質量比下含有 (iii) 前述丙烯酸樹脂（A)之重量平均分子量爲 8 0 0 0 0以上 (iv) 前述纖維素酯樹脂（B)的醯基之總取代度爲 2.0〜3.0，碳數3〜7之醯基取代度爲1.2〜3.0，該纖維素 酯樹脂（B)之重量平均分子量爲75000以上。 作爲本發明之實施型態，由本發明之效果表現的觀點 來看，構成前述表面之層厚度係以前述光學薄膜全體之厚 度的5〜20%爲佳。又’於構成該表面之層，將平均粒徑爲 50〜300μιη的範圍內之無機化合物或有機化合物的微粒子 ，對於構成該表面之層的全質量而言以0.01〜1質量％含有 的型態爲佳。且，本發明之光學薄膜以含有防帶電劑者爲 -11 - 201107133 佳。 本發明中，該光學薄膜的寬方向長度的至少10〜90% 之範圍內，含有該薄膜寬方向之中心的部分，以含有至少 二層以上的前述樹脂組成相異的層之型態爲佳。又，該樹 脂組成爲相互相異的層係以薄膜製膜的同時所形成者爲佳 〇 以下對於各構成要素做詳細說明。 <丙烯酸樹脂（A) > 本發明所使用的丙烯酸樹脂中亦含有甲基丙烯酸樹脂 。作爲樹脂雖無特別限制，但以甲基甲基丙烯酸酯單位5 0 〜99質量％、及與此可共聚合之其他單體單位1〜50質量％ 所成者爲佳。 作爲可共聚合之其他單體，可舉出烷基數之碳數爲2 〜18之烷基甲基丙烯酸酯、烷基數的碳數爲1〜18之烷基 丙烯酸酯、丙烯酸、甲基丙烯酸等α，β -不飽和酸、馬來酸 、富馬酸、衣康酸等含有不飽和基二價羧酸、苯乙烯、 α -甲基苯乙烯等芳香族乙烯基化合物、丙烯腈、甲基丙 烯腈等α，β-不飽和腈、馬來酸酐、順丁烯二酸酐、Ν-取代 順丁烯二酸酐、戊二酸酐等，這些可單獨、或合併二種以 上之單體使用^ 彼等中由共聚物之耐熱分解性或流動性之觀點來看， 以甲基丙烯酸酯、乙基丙烯酸酯、η-丙基丙烯酸酯、η-丁 基丙烯酸酯、s-丁基丙烯酸酯、2-乙基己基丙烯酸酯等爲 -12- 201107133 佳，以甲基丙烯酸酯或η-丁基丙烯酸酯爲特佳》 使用於本發明的光學薄膜之丙烯酸樹脂（Α)，特別 作爲光學薄膜的脆性改善及與纖維素酯樹脂（Β)之相溶 時的透明性之改善觀點下，重量平均分子量（Mw)爲 8 0000以上。丙烯酸樹脂（A)的重量平均分子量（Mw) 若比80000小時，無法得到充分脆性改善，與纖維素酯樹 脂（B)之相溶性亦會劣化。丙烯酸樹脂（A)的重量平均 分子量 （Mw)以80000〜1000000範圍內爲更佳，以 1 00000〜600000範圍內爲特佳，以1 50000〜400000的範圍 爲最佳。丙烯酸樹脂（A)的重量平均分子量（Mw)之上 限値雖無特別限定，於製造上的觀點來看以1000000以下 爲較佳形態。 本發明的丙烯酸樹脂之重量平均分子量可由凝膠滲透 層析法測定。測定條件如以下所示。 溶劑：二氯甲烷 管柱：Shodex K806、K805、K803G (使用連接3根昭 和電工（股）製者） 管柱溫度：25°C 試料濃度：0.1質量％ 檢測器：RI Model 504 ( GL科學公司製） 幫浦：L60 00 (日立製作所（股）製） 流量：1 .Oml/min S ] 校對曲線：使用標準聚苯乙烯STK standard聚苯乙烯 (TOSOH (股）製）Mw = 2,800,000〜500的13個取樣所得 -13- 201107133 之校對曲線。13個取樣爲使用幾乎等間隔者爲佳。 作爲本發明中之丙烯酸樹脂（A)的製造方法，並無 特別限定，可使用懸浮聚合、乳化聚合、塊狀聚合、或溶 液聚合等公知方法之任一種爲佳。其中，作爲聚合啓始劑 ’可使用一般的過氧化物系及偶氮系者，又可作爲氧化還 原系。對於聚合溫度，在懸浮或乳化聚合實爲30〜100。(： ，塊狀或溶液聚合下爲在80〜160 °c中實施。欲控制所得 之共聚物的還原黏度，可將烷 用而實施聚合。下述表示本發 方法的一例。 A1 :單體質量比（MMA : A2 :單體質量比（MMA : A3 :單體質量比（MMA : A4 :單體質量比（MMA : A5 :單體質量比（MMA : A6 :單體質量比（MMA : A7 :單體質量比（MMA : MSI :單體質量比（MMA MS2 :單體質量比（MMA MMA :甲基甲基丙烯酸酯 MA :甲基丙烯酸酯 ST :苯乙烯 基硫醇等作爲連鎖移動劑使 明中之丙烯酸樹脂與其製造 MA = 98 : 2 )、 Mw70000 MA = 97 ： 3 ) ' Mwl 60000 MA = 97 : 3 ) ' Mw3 50000 MA = 97 ： 3 )、 Mw550000 MA = 97 ： 3 )、 Mw800000 MA = 97 ： 3 )、 Mw93 0000 MA = 94 ： 6 )、 Mwl 1 00000 ：ST=60 :40) 、MwlOOOOO ：ST=40 :60) ' Mwl 00000 (A 8之合成例） 201107133 首先，將甲基甲基丙烯酸酯/丙烯醯胺共聚物系懸浮 劑如以下所示調整。 甲基甲基丙烯酸酯 2〇質量份 丙烯醯胺 質量份 過硫酸鉀 0.3質量份 離子交換水 1 500質量份 將上述裝入反應器中，一邊以氮氣取代反應器中的氣 體下，一邊將單體完全轉化至聚合物，於保持7 0°C下進行 反應。將所得之水溶液作爲懸浮劑。在容量爲5公升下， 於具備擋板及犁田型攪拌翼之不鏽鋼製高壓釜中，提供將 上述懸浮劑〇.〇5質量份溶解於離子交換水165質量份之溶 液，系統內由氮氣取代下進行400rpm下之攪拌。 其次，將裝入下述之組成的混合物質，一邊攪拌反應 系統下一邊添加。 甲基丙烯酸 27質量份 甲基甲基丙烯酸酯 73質量份 t-十二院基硫醇 1.2質量份 2,2’-偶氮二異丁腈 〇_4質量份 添加後昇溫至7〇°C，將內溫到達7〇°C的時間點作爲聚 合啓始時間點，保持ISO分鐘而進行聚合。 其後，依據一般方法，進行反應系之冷卻、聚合物之 分離 '洗淨、乾燥，得到珠子狀共聚物。該共聚物之聚合 率爲97 %，重量平均分子量爲13萬。 於該共聚物添加〇·2質量％之添加劑（NaOCH3 )，使 -15- 201107133 用2軸押出機（TEX30 (日本製鋼公司製之l/D = 44.5 ))， 由料斗部將氮氣以10L/分鐘的清除下，以螺旋回轉數 lOOrpm、原料供給量5kg/小時、汽缸溫度290T：下進行分子 內環化反應，製作出顆粒，在80 t進行8小時真空乾燥後 得到丙烯酸樹脂A8。丙烯酸樹脂A8之重量平均分子量（ Mw)爲 1300〇〇，Tg爲 140°C。 作爲本發明之丙烯酸樹脂，可使用販賣品。例如可舉 出 Delpet6 0N、80N (旭化成化學（股）製）、DianalBR52 、BR80、BR83、BR85、BR88 ( Mitsubishi Rayon (股） 製）、KT75 (電氣化學工業（股）製）等。丙烯酸樹脂可 倂用二種以上· <纖維素酯樹脂（B ) > 本發明的纖維素酯樹脂（B )，特別由脆性之改善或 與丙烯酸樹脂（A)相溶時的透明性之觀點來看，醯基之 總取代度（T)爲2.0〜3.0，碳數3〜7之醯基取代度爲1.2 〜3.0，碳數3〜7之醯基的取代度以2.0〜3.0爲佳。即，本 發明的纖維素酯樹脂係以碳數爲3〜7的醯基所取代之纖維 素酯樹脂，具體以使用丙醯基、丁醯基等爲佳，以使用丙 醯基爲特佳。 纖維素酯樹脂（B)的醯基之總取代度若比2.0小時， 即纖維素酯分子的2,3,6位之羥基殘度比1.0高時，丙烯酸 樹脂（A)與丙烯酸樹脂（B)無法充分相溶，作爲光學薄 膜使用時會有霧化之問題。又，醯基的總取代度即使爲 -16- 201107133 2.0以上，碳數爲3〜7之醯基的取代度若比1.2小時，依舊 無法得到充分的相溶性，使得脆性降低。例如，醯基的總 取代度即使爲2.0以上時，碳數2的醯基，即乙醯基的取代 度高，碳數3〜7之醯基的取代度比1.2小時，相溶性會降 低而使霧化上昇。又，醯基的總取代度即使爲2.0以上時 ，碳數8以上的醯基之取代度高，碳數3〜7的醯基之取代 度比1.2低時，脆性會劣化，無法得到期待的特性。 本發明的纖維素酯樹脂（B)之醯基取代度爲，總取 代度（T)爲2.0〜3.0者，碳數爲3〜7之醯基的取代度若爲 1.2〜3.0即無問題，但碳數爲3〜7以外的醯基，即乙醯基 或碳數爲8以上之醯基的取代度總計以1.3以下爲佳。 又，纖維素酯樹脂（B )的醯基之總取代度（T )以 2.5〜3.0的範圍時爲更佳。 本發明中，前述醯基可爲脂肪族醯基、亦可爲芳香族 醯基。脂肪族醯基的情況時，可爲直鏈或支鏈，亦可進一 步具有取代基。本發明中之醯基的碳數亦包含醯基之取代 基。 上述纖維素酯樹脂（B)具有芳香族醯基作爲取代基 時，取代爲芳香族環之取代基X的數目以0〜5個爲佳。此 時，必須留意含有取代基之碳數爲3〜7之醯基的取代度必 須成爲1.2〜3.0。例如，欲將苯甲醯基的碳數成爲7，具有 含有碳之取代基時，作爲苯甲醯基的碳數成爲8以上，而 不含於碳數爲3〜7之醯基》 且，取代爲芳香族環之取代基的數爲2個以上時，彼 -17- 201107133 此可爲相同或相異，又亦可形成相互連結之縮合多環化合 物（例如萘、茚、茚滿、菲、喹咐、異喹啉、氧萘、色滿 、酞嗪、吖啶、吲哚、吲哚滿等）。 對於如上述之纖維素酯樹脂（B)，持有具有至少1種 的碳數3〜7之脂肪族醯基的結構時，可作爲使用於本發明 之纖維素樹脂的結構而使用。 有關本發明之纖維素酯樹脂（B)的取代度，醯基之 總取代度（T)爲2.0〜3.0，碳數爲3〜7之醯基的取代度爲 1.2〜3.0 。 又，碳數爲3〜7之醯基以外，即乙醯基與碳數爲8以 上之醯基的取代度之總和以1 .3以下爲佳。 作爲有關本發明之纖維素酯樹脂（B )，特別以選自 纖維素乙酸酯丙酸酯、纖維素乙酸酯丁酸酯、纖維素乙酸 酯苯甲酸酯、纖維素丙酸酯、纖維素丁酸酯之至少一種爲 佳，即，具有碳原子數3或4的醯基作爲取代基者爲佳。 彼等中特佳的纖維素酯樹脂爲纖維素乙酸酯丙酸酯或 纖維素丙酸酯。 未經醯基取代的部分，一般以羥基方式存在。這些可 由公知方法合成。 且，乙醯基之取代度或其他醯基之取代度可藉由 ASTM-D817-96所規定之方法求得。 有關本發明之纖維素酯樹脂的重量平均分子量（Mw )，特別由與丙烯酸樹脂（A)之相溶性、脆性改善的觀 點來看以75000以上爲佳，以750〇〇〜300000的範圍爲較佳 -18- 201107133 ，以100000〜240000的範圍內爲更佳，以1 60000〜240000 者爲特佳。纖維素酯樹脂的重要平均分子量（Mw)若低 於75 000時，耐熱性或脆性之改善效果會不充分，無法得 到本發明之效果。本發明中可混合二種以上之纖維素樹脂 使用。 本發明的光學薄膜爲具有至少二層以上的相互相異的 樹脂組成的光學薄膜，由有關本發明之前述課題解決的觀 點來看，必須爲（i)構成該光學薄膜之表面的層的至少 —層爲丙烯酸樹脂（A)與纖維素酯樹脂（B)以50: 50〜 30: 70的質量比下含有，（ii)構成該表面之層以外的層 爲丙烯酸樹脂（A)與纖維素酯樹脂（B)以80: 20〜55: 45的質量比下含有。且，丙烯酸樹脂（A)與纖維素酯樹 脂（B)以相溶狀態下含有爲佳。 本發明的光學薄膜中，丙烯酸樹脂（A)與纖維素酯 樹脂（B )必須以相溶狀態下含有。作爲光學薄膜而言爲 必要的物性或品質可藉由相溶相異樹脂而相互補助的方式 達成。 對於丙烯酸樹脂（A)與纖維素酯樹脂（B)是否成爲 相溶狀態，例如可藉由玻璃轉移溫度T g做判斷。 [S.] 例如，兩者樹脂的玻璃轉移溫度相異時，混合兩者樹 脂時，欲使各樹脂的玻璃轉移溫度存在時，混合物的玻璃 轉移溫度存在2個以上，但當兩者樹脂相溶時，各樹脂固 有的玻璃轉移溫度會消失，成爲1個玻璃轉移溫度，成爲 經相溶樹脂之玻璃轉移溫度。 -19- 201107133 且，於此所謂的玻璃轉移溫度，係使用差示掃描熱量 測定器（Perkin Elmer公司製DSC-7型），在昇溫速度 2〇°C/分鐘下進行測定，依據JIS K7 1 21 ( 1 987 )所求之中 間點玻璃轉移溫度（Tmg)。 丙烯酸樹脂（A )與纖維素酯樹脂（B )各爲非結晶性 樹脂時爲佳，任一方爲結晶性高分子、或部分具有結晶性 的高分子亦可，本發明中，因丙烯酸樹脂（A)與纖維素 酯樹脂（B )爲相溶，成爲非結晶性樹脂者爲佳。 本發明的光學薄膜中之丙烯酸樹脂（A)的重量平均 分子量（Mw)或纖維素酯樹脂（B)的重量平均分子量（ M w )或取代度，係利用對於兩者樹脂溶劑之溶解性的差 進行分離後，經各自測定而得到。分離樹脂時，可藉由添 加相溶於僅溶解任一方溶劑中的樹脂，萃取經溶解之樹脂 而分離，此時亦可進行加熱操作或迴流。亦可將這些溶劑 之組合，以2步驟以上方式組合後進行樹脂分離。將經溶 解之樹脂、與作爲不溶物而殘留的樹脂進行過瀘分離，對 於含有萃取物之溶液，藉由將溶劑經蒸發並經乾燥的操作 ，可分離樹脂。這些經分離的樹脂，可藉由高分子之一般 結構解析而特定。本發明的光學薄膜含有丙烯酸樹脂（Α )或纖維素酯樹脂（Β)以外之樹脂時亦可依據同樣方法 進行分離。 又，經相溶之樹脂的重量平均分子量（Mw )各相異 時，藉由凝膠滲透層析法（GPC )，高分子量物於早期被 溶離，越低分子量物則越經長時間而被溶離，故可容易地 -20- 201107133 分離之同時，亦可測定分子量。 又，將經相溶的樹脂藉由GPC進行分子量測定之同時 ，分取出每小時被溶離的樹脂溶液，餾去溶劑並經乾燥的 樹脂，進行定量性結構解析後，檢測相異分子量的各部分 之樹脂組成，可特定經相溶之各樹脂。將事前以對溶劑的 溶解性差異所分取的樹脂，各藉由GPC測定其分子量分佈 ，可檢測出經相溶之各樹脂。 又，本發明中，所謂「將丙烯酸樹脂（A)或纖維素 酯樹脂（B )以相溶狀態下含有」表示，藉由混合各樹脂 (聚合物），結果成爲被相溶之狀態的意思，不含將單體 、二聚物、或寡聚物等丙烯酸樹脂之前驅物混合於纖維素 酯樹脂（B )後，藉由進行聚合成爲混合樹脂之狀態。 例如將單體、二聚物、或寡聚物等丙烯酸樹脂之前驅 物混合於纖維素酯樹脂（B)後，進行聚合後得到混合樹 脂之步驟爲聚合反應複雑，該方法製作的樹脂爲反應控制 爲困難，分子量之調整亦成爲困難。又，如此方法下合成 樹脂時’大多產生接枝聚合、交聯反應或環化反應、溶解 於溶劑之容器、或經加熱無法熔融者爲多，將混合樹脂中 之丙烯酸樹脂進行溶離後測定重量平均分子量（Mw )亦 變的困難，故難以控制物性，無法作爲可安定下製造光學 薄膜之樹脂使用。 本發明的光學薄膜僅作爲光學薄膜時的功能不損害下 ’亦可由含有丙烯酸樹脂（A)、纖維素酯樹脂（B)以外 之樹脂或添加劑所構成。 -21 - 201107133 含有丙烯酸樹脂（A)、纖維素酯樹脂（B)以外之樹 脂時，即使所添加的樹脂爲相溶狀態，亦可無溶解下進行 混合。 本發明的光學薄膜中之丙嫌酸樹脂（A)與纖維素酯 樹脂（B )之總質量爲光學薄膜的55質量％以上者爲佳， 更佳爲60質量％以上，特佳爲70質量〇/。以上。 使用丙烯酸樹脂（A)與纖維素酯樹脂（B)以外之樹 脂或添加劑時，在不損害本發明之光學薄膜的功能範圍下 調整添加量爲佳。 <丙烯酸粒子（C ) > 本發明的光學薄膜係以含有丙烯酸粒子者爲佳》 所謂有關本發明之丙烯酸粒子（C)表示，將前述丙 烯酸樹脂（A)及纖維素酯樹脂（B)以相溶狀態下含有的 光學薄膜中以粒子狀態（亦稱爲非相溶狀態）存在的丙烯 酸成分。 上述丙烯酸粒子（C )，例如採取定量的經製作之光 學薄膜，溶解於溶劑中並攪拌，經充分溶解•分散後，使 用具有未達丙烯酸粒子（C)的平均粒子徑之孔徑的PTFE 製薄膜過濾器進行過濾，經過濾所收集的不溶物重量以添 加於光學薄膜的丙烯酸粒子（C)之90質量％以上時爲佳 本發明所使用的丙烯酸粒子（C )雖無特別限定，以 具有二層以上之層結構的丙烯酸粒子（C)者爲佳，特佳 -22- 201107133 爲下述多層結構丙烯酸系粒狀複合體。 所謂多層結構丙烯酸系粒狀複合體爲，具有自中心部 往外周部的最內硬質層聚合物、顯示橡膠彈性的交聯軟質 層聚合物、及最外硬質層聚合物爲具有重疊爲層狀而成的 結構之粒子狀丙烯酸系聚合物而言。 即，所謂多層結構丙烯酸系粒狀複合體爲，自中心部 往外周部的最內硬質層、交聯軟質層、及最外硬質層所成 之多層結構丙烯酸系粒狀複合體。使用該三層芯殻結構之 多層結構丙烯酸系粒狀複合體爲佳。 作爲有關本發明之丙烯酸系樹脂組成物所使用的多層 結構丙烯酸系粒狀複合體的較佳型態爲，可舉出以下者》 具有（a)將甲基甲基丙烯酸酯80〜98.9質量％、烷基之碳 數爲1〜8的烷基丙烯酸酯1〜20質量％、及多官能性接枝劑 0.0 1〜0.3質量％所成之單體的混合物經聚合所得之最內硬 質層聚合物、（b)將於上述最內硬質層聚合物的存在下 ，烷基之碳數爲4〜8之烷基丙烯酸酯75〜98.5質量％、多 官能性交聯劑〇.〇1〜5質量％及多官能性接枝劑0.5〜5質量 %所成之單體的混合物經聚合所得的交聯軟質層聚合物、 (c)於由上述最內硬質層及交聯軟質層所成之聚合物的 存在下，將甲基甲基丙烯酸酯80〜99質量％與烷基之碳數 爲1〜8的烷基丙烯酸酯1〜20質量。/。所成的單體之混合物進 行聚合所得之最外硬層聚合物所成的兰層結構，且所得之 三層結構聚合物係由最內硬質層聚合物（a) 5〜40質量％ 、軟質層聚合物（b) 30.〜60質量％、及最外硬質層聚合物 -23- 201107133 (C ) 2〇〜5 0質量％所成，經丙酮分離時有不溶部份，該不 溶部份的甲基乙酮膨潤度爲1.5〜4.0之丙烯酸系粒狀複合 體可舉出。 且，如特公昭60- 1 7406號或特公平3-39095號中所揭示 ，不僅藉由規定多層結構丙烯酸系粒狀複合體之各層組成 或粒子徑，亦藉由設定多層結構丙烯酸系粒狀複合體之拉 伸彈性率或丙酮不溶部份的甲基乙酮膨潤度至特定範圍內 ，可實現進一步充分之耐衝撃性與耐應力白化性的平衡。 其中，構成多層結構丙烯酸系粒狀複合體之最內硬質 層聚合物（a)爲，將由甲基甲基丙烯酸酯80〜98.9質量％ 、烷基的碳數爲1〜8之烷基丙烯酸酯1〜20質量％及多官能 性接枝劑〇.〇1〜0.3質量％所成之單體的混合物進行聚合而 得者爲佳。 其中作爲烷基之碳數爲1〜8的烷基丙烯酸酯，可舉出 甲基丙烯酸酯、乙基丙烯酸酯、η-丙基丙烯酸酯、η-丁基 丙烯酸酯、s-丁基丙烯酸酯、2-乙基己基丙烯酸酯等，以 使用甲基丙烯酸酯或η-丁基丙烯酸酯爲佳。 最內硬質層聚合物（a)中之烷基丙烯酸酯單位的比 率爲1〜20質量％，該單位未達1質量％時，聚合物的熱分 解性變大，另一方面，該單位超過20質量％時，最內硬質 層聚合物（c)的玻璃轉移溫度變低，三層結構丙烯酸系 粒狀複合體之耐衝撃性賦予效果會降低故皆不佳。 作爲多官能性接枝劑，具有相異可聚合的官能基之多 官能性單體，例如可舉出丙烯酸、甲基丙烯酸、馬來酸、 -24 - 201107133 富馬酸之烯丙基酯等，使用烯丙基甲基丙烯酸酯爲佳。多 官能性接枝劑爲使用於最內硬質層聚合物與軟質層聚合物 以化學方式鍵結時，使用於該最內硬質層聚合時之比率爲 0 · 0 1〜0.3質量％。 構成丙烯酸系粒狀複合體之交聯軟質層聚合物（b) 爲上述最內硬質層聚合物（a)的存在下，將由烷基的碳 數爲1〜8之烷基丙烯酸酯75〜98.5質量％、多官能性交聯 劑0·01〜5質量％及多官能性接枝劑0.5〜5質量％所成之單 體的混合物進行聚合所得者爲佳。 其中，作爲烷基之碳數爲4〜8的烷基丙烯酸酯，以使 用η-丁基丙烯酸酯或2-乙基己基丙烯酸酯爲佳。 又，與這些聚合性單體之同時，亦可共聚合25質量％ 以下之可共聚合之其他單官能性單體。 作爲可共聚合之其他單官能性單體，可舉出苯乙烯及 取代苯乙烯衍生物。烷基之碳數爲4〜8的烷基丙烯酸酯與 苯乙烯之比率，前者越多，聚合物（b)之玻璃轉移溫度 越降低，即可軟質化。 另一方面’由樹脂組生物之透明性的觀點來看，將在 軟質層聚合物（b)之常溫的折射率接近最內硬質層聚合 物（a)、最外硬質層聚合物（c)、及硬質熱可塑性丙烯 酸樹脂時較爲有利，可考慮此而選定兩者比率。 作爲多官能性接枝劑，可舉出前述最內層硬質聚合物 (a)'項者使用。其中所使用的多官能性接枝劑爲使用於 軟質層聚合物（b)與最外硬質層聚合物（c)以化學方式 -25- 201107133 鍵結時，使用於該最內硬質層聚合時的比率由耐衝撃性賦 予效果之觀點來看以0.5〜5質量％爲佳。 作爲多官能性交聯劑，可使用二乙烯基化合物、二烯 丙基化合物、二丙烯酸化合物、二甲基丙烯酸化合物等一 般已知的交聯_劑，但使用聚乙二醇二丙烯酸酯（分子量 200〜600)爲佳。 其中，所使用的多官能性交聯劑爲，在軟質層（b) 的聚合時生成交聯結構，使用於欲表現耐衝撃性賦予之效 果上。但，若將先前多官能性接枝劑使用於軟質層之聚合 時，某程度上可生成軟質層（b)之交聯結構，故多官能 性交聯劑並非必須成分，但將多官能性交聯劑使用於軟質 層聚合時的比率由耐衝撃性賦予效果之觀點來看以0.01〜 5質量％爲佳。 構成多層結構丙烯酸系粒狀複合體之最外硬質層聚合 物（c)爲，於上述最內硬質層聚合物（a)及軟質層聚合 物（b)的存在下，以聚合由甲基甲基丙烯酸酯80〜99質 量％及烷基的碳數爲1〜8之烷基丙烯酸酯1〜20質量％所成 的單體之混合物而得者爲佳。 其中，作爲丙烯酸烷基化物，雖使用前述者，但以使 用甲基丙烯酸酯或乙基丙烯酸酯爲佳。最外硬質層（c) 中之烷基丙烯酸酯單位的比率以1〜20質量％爲佳。 又，於最外硬質層（c)之聚合時，將提高與丙烯酸 樹脂（A)之相溶性作爲目的，將欲調整分子量的烷基硫 醇等作爲連鎖移動劑使用時亦可實施。 -26- 201107133 換言之，於最外硬質層設有分子量自內側往外側時依 序變小的梯度，因可改良延伸與耐衝撃性之平衡故較佳。 作爲具體方法，藉由將欲形成最外硬質層之單體的混合物 分割爲2個以上，各次所添加的連鎖移動劑量依順序增加 的方法，可將形成最外硬質層的聚合物之分子量自多層結 構丙烯酸系粒狀複合體的內側往外側逐漸變小。 此時所形成之分子量，將各次所使用的單體的混合物 在此單獨且同條件下進行聚合，可藉由測定所得之聚合物 的分子量而調査。 對於本發明所使用的較佳丙烯酸粒子（C)之粒子徑 ，雖無特別限定，但以10〜lOOOnm爲佳，較佳爲20〜 500nm，特別以50〜400nm爲最佳。 對於本發明所使用的較佳多層結構聚合物之丙烯酸系 粒狀複合體，芯與殻之質量比雖無特別限定，當多層結構 聚合物全體作爲100質量份時，芯層爲50質量份以上，90 質量份以下時較佳，更佳爲60質量份以上，80質量份以下 。且其中所謂芯層爲最內硬質層。 作爲如此多層結構丙烯酸系粒狀複合體之販賣品例子 ，例如可舉出Mitsubishi Rayon公司製“metablen”、鐘淵化 學工業公司製“Kaneace”、吳羽化學工業公司製“parai〇id，， 、Rohm and Haas公司製“Acryloid”、Ganz化成工業公司製 “Stafiloid”及 KURARAY公司製 “ParapetSA”等，這些可單 獨至使用二種以上。 又’作爲本發明所使用的較佳丙烯酸粒子（C)而適 -27- 201107133 用的接枝共聚物之丙烯酸粒子（c-l)的具體例，可舉出 在橡膠質聚合物之存在下，將不飽和羧酸酯系單體、不飽 和羧酸系單體、芳香族乙烯基系單體 '及視必要與彼等可 共聚合之其他乙烯基系單體所成的單體混合物進行共聚合 而得之接枝共聚物。 接枝共聚物之丙烯酸粒子（c-l)所使用的橡膠質聚 合物中，雖無特別限制，可使用二烯系橡膠、丙烯酸系橡 膠及乙烯系橡膠等。作爲具體例，可舉出聚丁二烯、苯乙 烯-丁二烯共聚物、苯乙烯-丁二烯的嵌段共聚物、丙烯腈_ 丁二烯共聚物、丙烯酸丁基-丁二烯共聚物、聚異戊二烯 、丁二烯-甲基甲基丙烯酸酯共聚物、丙烯酸丁基-甲基甲 基丙烯酸酯共聚物、丁二烯-丙烯酸乙基共聚物、乙烯-丙 烯共聚物、乙烯-丙烯-二烯系共聚物、乙烯-異戊二烯共聚 物、及乙烯-丙烯酸甲^共聚物等。這些橡膠質聚合物可 使用一種或二種以上之混合物。 又，於本發明之光學薄膜添加丙烯酸粒子（C)時， 丙烯酸樹脂（A)與纖維素酯樹脂（B)之混合物的折射率 與丙烯酸粒子（C )的折射率接近時，因可得到透明性較 高的薄膜故較佳。具體而言，丙烯酸粒子（C)與丙烯酸 樹脂（A )的折射率差爲〇.〇5以下時爲佳，更佳爲〇.〇2以 下，換言之0.01以下時爲佳。 欲滿足如此折射率條件時，可藉由調整丙烯酸樹脂（ A)之各單體單位組成比的方法、及/或調製使用於丙烯酸 粒子（C)之橡膠質聚合物或單體的組成比之方法等，可 -28- 201107133 使折射率差變小，得到透明性優良的光學薄膜。 且’其中所謂的折射率差爲，可溶解丙烯酸樹脂（A )之溶劑中，將本發明的光學薄膜在適當條件下充分溶解 後作爲白濁溶液，將此藉由離心分離等操作，分離出溶劑 可溶部分與不溶部分，將該可溶部分（丙烯酸樹脂（A) )與不溶部分（丙烯酸粒子（C ))各經純化後，所測定 之折射率（23°C、測定波長：5 50nm)之差。 於本發明中之丙烯酸樹脂（A)，添加丙烯酸粒子（C )的方法並無特別限制，使用預先將丙烯酸樹脂（A)與 其他任意成分進行摻合後，通常在200〜3 5 0t，一邊添加 丙烯酸粒子（C) 一邊藉由一軸或二軸押出機進行均勻熔 融混煉的方法爲佳。 又，可使用將預先分散丙烯酸粒子（C)之溶液，添 加於溶解丙烯酸樹脂（A)、及纖維素酯樹脂（B)的溶液 (摻合液）後進行混合的方法、或將丙烯酸粒子（C)及 其他任意添加劑經溶解、混合的溶液添加於聯機等方法》 下述舉出本發明中之丙烯酸粒子與其製造方法的一例 子。 <丙烯酸粒子（C1 )之調製例> 於內容積60公升的迴流冷卻器付反應器中’投入離子 交換水38.2公升、二辛基磺基琥珀酸鈉lll·6g’在250Γpm 之轉數下一邊進行攪拌，—邊在氮氣環境下昇溫至75 °C， 使氧影響在事實上並無存在的狀態。投入APS0.36g，於 -29- 201107133 分鐘攪拌後一次添加由MMA1 657g、BA21.6g、及 ALMA1.68g所成之單體混合物，經發熱波峰之檢測後再保 持2〇分鐘，完成最內磾質層之聚合。 其次，投入APS3.48g，於5分鐘攪拌後經120分鐘連續 添力口由 BA8105g、PEGDA( 200) 31.9g、及 ALMA264.0g所 成之單體的混合物，添加終了後再保持120分鐘，完成軟 質層之聚合。 其次，投入APS1.32g，於5分鐘攪拌後經20分鐘連續 添加由MMA2106g、BA201.6g所成之單體的混合物，添加 終了後再保持20分鐘，完成最外硬質層1之聚合。 其次，投入APS1.32g，經5分鐘後將由MMA3148g、 BA20 1.6g、及n-OMlO.lg所成之單體的混合物經20分鐘連 續添加，添加終了後再保持20分鐘。繼續昇溫至95 °C後保 持6 0分鐘，完成最外硬質層2之聚合。 將如此所得之聚合物乳液，投入於3質量％硫酸鈉溫水 溶液中，使其鹽析·凝固後，再重複進行脫水•洗淨後進 行乾燥，得到三層結構之丙烯酸粒子（C 1 )。經吸光度法 求得平均粒子徑爲100nm ^ 上述簡稱各爲下述材料。 MMA ;甲基甲基丙烯酸酯 MA ;甲基丙烯酸酯 BA ; η-丁基丙烯酸酯 ALMA ;烯丙基甲基丙烯酸酯 PEGDA;聚乙二醇二丙烯酸酯（分子量200) -30- 201107133 n-OM ; η-辛基硫醇 APS ;過硫酸銨 作爲有關本發明之丙烯酸粒子，可使用販賣品。例如 metablenW-341 ( C2) ( Mitsubishi Rayon (股）製）可舉 出 ChemisnowMR-2G ( C3) 、MS-300X ( C4)(綜硏化學 (股）製）等。 對於本發明的光學薄膜，對於構成該薄膜之樹脂的總 質量而言，含有〇· 5〜30質量％之丙烯酸粒子（C )爲佳， 以1.0〜15質量％之範圍下含有爲更佳。 〈防帶電劑> 本發明之光學薄膜爲含有防帶電劑者爲佳，對於構成 該薄膜之樹脂1〇〇質量份而言，含有防帶電劑0.001〜2.0質 量份爲佳。 作爲防帶電劑，並無特別限制，可使用公知防帶電劑 ，但其中亦以選自陰離子性防帶電劑、陽離子性防帶電劑 、非離子性防帶電劑、兩性離子性防帶電劑、高分子防帶 電劑及導電性微粒子的至少一種爲佳，更佳爲選自導電性 微粒子，特佳爲氧化铈、氧化銦、氧化錫、氧化銻及氧化 砂的至少一種。 作爲陰離子性防帶電劑，.例如可舉出脂肪酸鹽類、高 級醇硫酸酯鹽類、液體脂肪油硫酸酯鹽類、脂肪族胺及脂 肪屬醯胺之硫酸鹽類、脂肪屬醇磷酸酯鹽類、二鹼性脂肪 酸酯之磺酸鹽類、脂肪族醯胺磺酸鹽類、烷基烯丙基磺酸 -31 - 201107133 鹽類、甲醛縮合之萘磺酸鹽類等，作爲陽離子性防帶電劑 ’例如可舉出脂肪族胺鹽類、第4級銨鹽類、烷基吡啶鑰 鹽等。作爲非離子性防帶零劑，例如可舉出聚環氧乙烯烷 基醚類、聚環氧乙烯烷基酚醚類、聚環氧乙烯烷基酯類、 山梨醇酐烷基酯類 '聚環氧乙烯山梨醇酐烷基酯類等，作 爲兩性離子性防帶電劑，例如可舉出咪唑啉衍生物、甜菜 鹼型高級烷基胺基衍生物、硫酸酯衍生物、磷酸酯衍生物 等’具體化合物如九茂秀雄著「防帶電劑高分子之表面 改質」幸書房、增補「塑質及橡膠用添加劑實用便覽 p 3 3 3〜P45 5」化學工業公司刊、特開平1 1 -256 1 43號、特 公昭52-32572號、特開平1 0- 1 5 8484號等所記載。 作爲較佳防帶電劑，可舉出如陰離子性防帶電劑或陽 離子性防帶電劑之離子性高分子化合物。作爲離子性高分 子化合物，有如特公昭49-23 828號、同49-23827號、同47-2 8 937號所見到的陰離子性高分子化合物；如特公昭55-734號、特開昭50-54672號、特公昭59- 1 473 5號、同57-18175號、同57-18176號、同57-56059號等所見到的主鏈中 具有解離基之離子型聚合物：如特公昭5 3 - 1 3 22 3號、同57-15376 號、特公昭 53-45231 號、同 55-145783 號、同 55-65950號、同 55-67746號、同 57-11342號、同57-19735號、 特公昭58-56858號、特開昭6 1 -27853號、同62-9346號各公 報所見到的側鏈中具有陽離子性解離基的陽離子性側鏈型 聚合物、如特開平5 - 2 3 0 1 6 1號公報所見到的接枝共聚物等 -32- 201107133 又’對於本發明之光學薄膜，作爲可使用的特佳導電 性微粒子之金屬氧化物的例子，以ZnO、Ti02、Sn02、 Al2〇3、In2〇3、Si〇2、MgO ' BaO、Ce〇2、Sb203、Mo〇2、 V2〇5等、或彼等複合氧化物爲佳，特別以Ce〇2、In2〇3、 Sn02、Sb203 '及Si02爲佳。作爲含有異種原子之例子， 例如對於ZnO添加Al、In等爲有效，對於Ti〇2添加Nb、Ta 等爲有效，又對於Sn02添加Sb、Nb、鹵素元素等爲有效。 這些異種原子之添加量以0.01〜25mol%的範圍爲佳，以 0.1〜15mol%的範圍爲特佳。 該導電性微粒子的平均微粒子徑爲lOOnm以下時爲佳 ，更佳爲5〜100nm。導電性微粒子之平均微粒子徑若爲 lOOnm以下，含於樹脂材料時，可賦予充分帶電特性之同 時，不會損害樹脂材料之透明性故較佳》 特佳防帶電劑由防帶電性能與添加量之關係來看，表 面固有電阻値以1χ1〇1()Ω以下者爲佳。表面固有電阻値爲 經試料在23 °C、50%RH的環境下進行24小時調濕後，使用 超級絕緣計，依據A S T M D 2 5 7進行測定。 又，本發明中可使用的較佳防帶電劑爲特開平9-203 8 1 0號所記載之離子導電性聚合物或具有分子間交聯之 第4級銨陽離子導電性聚合物等。 交聯型陽離子性導電性聚合物之特徵在於所得之分散 性粒狀聚合物，其爲可使微粒子內之陽離子成分具有高濃 度' 高密度，故不僅具有優良導電性，與樹脂之相溶性良 好’選出高透明性，且在低相對濕度下亦不會見到導電性 -33- 201107133 劣化。 於防帶電所使用的交聯型陽離子性導電性聚合物之分 散性粒狀聚合物爲一般使用約0.01〜0.3μιη之微粒子尺寸 範圍，較佳爲0.〇5〜〇.15μιη之範圍的微粒子尺寸。 對於本發明，上述所說明之各防帶電劑對於本發明之 光學薄膜100質量份而言，以〇·〇〇1〜2.0質量份之範圍下添 加爲佳，防帶電劑之添加量爲0.001質量份以上，2.0質量 份以下時’可有效果地抑制對樹脂材料之塵埃的附著，可 .維持樹脂材料之光透過率的所望値。且，防帶電劑之添加 量對於具有脂環式結構之聚合物100質量份而言，以0.005 〜1.0質量份爲佳，以0.01〜0.5質量份爲更佳。 對於本發明，藉由將上述防帶電劑及一般使用於防止 污染的含有氟化合物之層設置於樹脂時可得到相同效果。 又’欲得到本發明之光學薄膜的性能，亦可將含有至 少1種防帶電劑的層（防帶電層）設置於薄膜表面。 防帶電層爲藉由將具有前述防帶電劑之混合物塗佈於 光學元件表面而設置，亦可藉由如蒸鍍之方法而設置。且 ，防帶電層之厚度以50〜3 ΟΟμπι爲佳。 <拋光劑> 本發明的光學薄膜中，欲賦予滑潤性或光學性、機械 性功能’可將無機化合物之微粒子或有機化合物之微粒子 作爲拋光劑而添加。 拋光劑的形狀以使用球狀、棒狀、針狀、層狀、平板 -34- 201107133 狀等形狀者爲佳。 作爲拋光劑，例如可舉出二氧化矽、二氧化鈦、氧化 鋁、氧化锆、碳酸鈣、陶瓷、滑石、燒成矽酸鈣、水和矽 酸鈣、矽酸鋁、矽酸鎂、磷酸鈣等金屬原子之氧化物、磷 酸鹽、矽酸鹽、碳酸鹽等無機微粒子。 作爲有機化合物之微粒子，可使用如美國專利第 2,3 22,03 7號說明書等所記載之澱粉、比利時專利第 625，451號說明書或英國專利第981，1 98號說明書等所記載 之澱粉衍生物、特公昭44-3 643號公報等所記載之聚乙烯 基醇、瑞士專利第3 3 0，1 58號公報等所記載之聚苯乙烯或 聚甲基丙烯酸酯、美國專利第3,079,2 5 7號說明書等所記載 之聚丙烯腈 '美國專利第3,022,1 69號說明書等所記載之聚 碳酸酯的有機微粒子。 即，作爲有機化合物之微粒子的例子中作爲水分散性 乙烯基聚合物之例子，可舉出聚甲基丙烯酸酯、聚甲基甲 基丙烯酸酯、聚丙烯腈、丙烯腈-α-甲基苯乙烯共聚物、 聚苯乙烯、苯乙烯-二乙烯基苯共聚物、聚乙烯基乙酸酯 、聚乙烯碳酸酯、聚四氟伸乙基等，作爲纖維素衍生物的 例子，可舉’出甲基纖維素、纖維素乙酸酯、纖維素乙酸酯 丙酸酯等，作爲澱粉衍生物之例子，可舉出羧基澱粉、羧 基硝基苯基澱粉、尿素-甲醛-澱粉反應物等，以公知硬化 劑進行硬化的明膠及進行凝聚硬化作爲微少膠囊中空粒體 之硬化明膠等爲佳。 [S] 以上無機化合物的微粒子或有機化合物之微粒子中， -35- 201107133 二氧化矽可使薄膜的霧化降低故較佳。這些微粒子可藉由 有機物進行表面處理，故對於降低薄膜之霧化而言爲佳。 表面處理爲以鹵代矽烷類、烷氧基矽烷類、矽氮烷、 矽氧烷等進行爲佳。微粒子的平均粒徑越大其滑潤性效果 越大，相反地平均粒徑越小時，透明性越優良。 又，微粒子的一次粒子之平均粒徑爲0.01〜1.0 μιη之 範圍。較佳微粒子的一次粒子之平均粒徑以5〜5 Onm爲佳 ，更佳爲7〜14nm。 這些微粒子使用於使光學薄膜表面上生成0.01〜 Ι.Ομιη的凹凸爲佳。 作爲二氧化矽之微粒子，可舉出日本AERO SIL (股） 製的 AEROSIL200、200V、300、R972、R972V、R974、 R202、R812、0X50、TT600、NAX50等、日本觸媒（股） 製的 KE-P10、KE-P30 ' KE-P 1 00、KE-P 1 50 等，較佳爲 AEROSIL200V、R972V、N A X 5 0、KE - P 3 0、KE - P 1 0 0。這 些微粒子亦可合倂二種以上使用。 合倂二種以上使用時，可以任意比率下混合使用。平 均粒徑或材質相異的微粒子，例如可將AEROSIL200V與 R972V以質量比爲0.1: 99.9〜99.9: 0.1之範圍使用。 這些拋光劑的添加方法藉由混煉等進行爲佳》又，作 爲另一形態，將預先於溶劑分散的拋光劑與樹脂及/或可 塑劑及/或抗氧化劑及/或紫外線吸收劑進行混合分散後， 揮發溶劑後得到經沈澱的固體物，將此使用於樹脂熔融物 之製造過程時，由拋光劑可在樹脂中均勻地分散之觀點來 -36- 201107133 看爲佳。 上述拋光劑可欲改善薄膜之機械性、電氣性、光學性 特性而添加。 且，添加這些微粒子時，可提高所得之薄膜的滑潤性 ’因添加可提高霧化，較佳含有量對於樹脂而言以0.001 〜5質量％爲佳，更佳爲0.005〜1質量％，更佳爲0.01〜0.5 質量％ ^ 且，作爲本發明的光學薄膜，若霧化値超過1.0%時， 作爲光學用材料時會受到影響，故較佳爲霧化値未達1.0% ，更佳爲未達0.5%。霧化値可依據JIS-K7 13 6進行測定。 <其他添加劑> 對於本發明的光學薄膜，欲提高組成物之流動性或柔 軟性，可並用可塑劑。作爲可塑劑，可舉出苯二甲酸酯系 、脂肪酸酯系、偏苯三酸酯系、磷酸酯系、聚酯系、或環 氧系等。 其中，使用聚酯系與苯二甲酸酯系之可塑劑爲佳。聚 酯系可塑劑與苯二甲酸二辛基等苯二甲酸酯系之可塑劑相 比較，具有優良非移行性或耐萃取性，但可塑化效果或相 溶性則稍差。 因此，配合用途可選擇或並用這些可塑劑，可適用於 廣範圍用途。 聚酯系可塑劑雖爲一員至四員的羧酸與一員至六員的 醇之反應物，但主要係使用將二員羧酸與甘醇進行反應所Ε -37- 201107133 得者。作爲代表性二員羧酸，可舉出戊二酸、衣康酸、己 二酸、苯二甲酸、壬二酸、癸二酸等。 特別使用己二酸、苯二甲酸等時可得到可塑化特性優 良者。作爲甘醇可舉出伸乙基、伸丙基、1，3-伸丁基、 1，4-伸丁基、1，6-六伸甲基、新伸戊基、二伸乙基 '三伸 乙基、二伸丙基等甘醇。這些二員羧酸及甘醇各可單獨、 或亦可混合後使用。 該酯系之可塑劑爲酯、寡聚酯、聚酯的任何型皆可， 分子量以100〜10000之範圍爲佳，較佳爲600〜3000之範 圍時可塑化效果較大。 又，可塑劑之黏度與分子結構或分子量相關，但己二 酸系可塑劑的情況時，由相溶性、可塑化效率之關係來看 以200〜5000MPa · s ( 25°C )之範圍爲佳。且，亦可倂用 幾樣聚酯系可塑劑》 可塑劑對於本發明之光學薄膜100質量份而言，添加 〇·5〜3 0質量份爲佳。可塑劑的添加量超過30質量份時， 表面會有黏性於實用上並不佳。 本發明的光學薄膜亦可含有紫外線吸收劑爲佳，作爲 所使用的紫外線吸收劑，可舉出苯並三唑系、2 -羥基二苯 甲酮系或水楊酸苯基酯系者等。例如可舉例出2-(5-甲基-羥基苯基）苯並三唑、2-〔 2·羥基_3,5-雙（α，α_二甲基 苯甲基）苯基〕-2 Η-苯並三唑、2_ (3,5-二-t-丁基-2-羥基 苯基）苯並三唑等三唑類、2-羥基-4-甲氧基二苯甲酮、2-經基·4-辛氧基二苯甲酮、2，2，-二羥基-4-甲氧基二苯甲酮 -38- 201107133 等二苯甲酮類。 其中’紫外線吸收劑之中，亦以分子量爲400以上的 紫外線吸收劑因在高沸點下難以揮發，亦在高溫成形時難 以飛散，故比較少量的添加下可有效地改良耐候性。 作爲分子量爲400以上之紫外線吸收劑，可舉出2_〔2_ 羥基-3,5 -雙（α，α -二甲基苯甲基）苯基〕-2_苯並三唑、 2,2-伸甲基雙〔4-(1，1，3,3-四丁基）-6-(211-苯並三唑-2-基）酚〕等苯並三唑系、雙（2,2,6,6 -四甲基-4 -哌啶基） 癸二酸酯、雙（1,2,2,6,6-五甲基-4-哌啶基）癸二酸酯等 受阻胺系，進一步可舉出2- ( 3,5-二-t-丁基-4-羥基苯甲基 )-2-n-丁基丙二酸雙（1，2,2,6,6-五甲基-4-哌啶基）、1-ί 2 - 〔 3 - ( 3 ， 5 - 二 -1 - 丁基 - 4 - 經基 苯基） 丙醯 氧基〕 乙基〕-4-〔 3- ( 3,5-二-t-丁基-4-羥基苯基）丙醯氧基〕-2,2,6,6-四甲基哌啶等分子內同時具有受阻酚與受阻胺的結構之混 合系統者，這些可單獨、或可並用二種以上。彼等中，以 2-〔2-羥基-3,5-雙（α，α-二甲基苯甲基）苯基〕-2-苯並三 唑或2,2 -伸甲基雙〔4- ( 1,1,3,3 -四丁基）-6- ( 2Η -苯並三 唑-2-基）酚〕爲特佳。 且，於本發明的光學薄膜中，欲改善成形加工時的熱 分解性或熱著色性，亦可添加各種抗氧化劑。又，除防帶 電劑亦可對於光學薄膜賦予防帶電性能。 本發明的光學薄膜中亦可使用添加磷系難燃劑的難燃 丙烯酸系樹脂組成物。 作爲此所使用的磷系難燃劑，可舉出選自紅磷 '三芳 -39- 201107133 基磷酸酯、二芳基磷酸酯、單芳基磷酸酯、芳基膦酸化合 物、芳基膦氧化物化合物、縮合芳基磷酸酯、鹵化烷基磷 酸酯、含鹵素縮合磷酸酯、含鹵素縮合膦酸酯、含鹵素亞 磷酸酯等的一種、或二種以上混合物。 作爲具體例子，可舉出三苯基磷酸酯、9,10-二氫-9- 噁-10-膦菲-10-氧化物、苯基膦酸、參（β-氯乙基）磷酸 酯、參（二氯丙基）磷酸酯、參（三溴新戊基）磷酸酯等 〇 所謂本發明的光學薄膜，可同時達成過去樹脂薄膜中 無法達到的低吸濕性、透明性、高耐熱性及脆性改善。 對於本發明，作爲脆性指標，係以是否「不會引起延 性破壞之光學薄膜」作爲基準而判斷。藉由得到不會引起 延性破壞、脆性經改善的光學薄膜，於製作大型液晶顯示 裝置用偏光板時，不會產生製造時的破裂或割裂，可成爲 處理性優良的光學薄膜。其中，所謂延性破壞被定義爲， 比某材料所具有的強度，更大應力的作用所產生的破裂， 直到最終破裂而引起材料的顯著延伸或扭絞之破壞。有著 於該破壞面會形成稱爲dimple的無數窪孔之特徵。 本發明中，是否爲「不會引起延性破壞的光學薄膜」 ，可藉由即使施予可折曲2片薄膜的巨大應力作用亦未見 到破裂等破壞而進行評估。若爲施予如此巨大應力亦不會 引起延性破壞的光學薄膜，即使作爲經大型化之液晶顯示 裝置用的偏光板保護薄膜使用時，亦可充分減低製造時的 破裂等問題，且，即使使用於一次貼合後再次引起剝落之 -40- 201107133 光學薄膜時’不會產生破裂，可充分對應光學薄膜之薄型 化。 本發明中，作爲耐熱性的指標，使用張力軟化點。除 了液晶顯示裝置被大型化、背光光源之亮度漸漸提高，對 於電子看板等屋外用途之利用，要求更闻亮度，故光學薄 膜被要求可耐住在更高溫度的環境下使用，張力軟化點若 爲105°C〜145°C ’可判斷爲顯示充分耐熱性者。特別爲控 制於1 10°C〜13 0°C時爲較佳。 作爲顯示光學薄膜之張力軟化點的溫度之具體測定方 法，例如可使用Tensilon試驗機（ORIENTEC公司製之 RTC-1225A)，將光學薄膜切出12 0mm (縱）xlOmm (橫 )，在10N的張力下一邊拉伸，一邊以30°C/min的昇溫速 度繼續昇溫，測定3次成爲9N的時間點之溫度，求得該平 均値。 又，由耐熱性之觀點來看，光學薄膜的玻璃轉移溫度 (Tg)以110°C以上爲佳。更佳爲120°C以上。特佳爲150°C 以上。 且，其中所謂玻璃轉移溫度爲使用差示掃描熱量測定 器（Perkin Elmer公司製DSC-7型），在昇溫速度20°C/分 鐘下進行測定，依據JIS K7 1 2 1 ( 1 987 )所求得之中間點 玻璃轉移溫度（Tmg)。 作爲判斷本發明光學薄膜的透明性之指標，使用霧化 値（濁度）。特別對於在屋外所使用的液晶顯示裝置，欲 求得明亮場所亦可得到充分亮度或較高對比，必須使霧化 -41 - 201107133 値爲1.0%以下，0.5%以下爲更佳。 所謂含有丙烯酸系樹脂（A)與纖維素酯樹脂（B)之 本發明的光學薄膜，雖可得到較高透明性，在改善其他物 性之目的下使用丙烯酸粒子，因使樹脂（丙烯酸系樹脂（ A)與纖維素醋樹脂（B))與丙烯酸粒子（C)之折射率 差變小，可防止霧化値的上昇。 又，表面粗度亦因表面霧化而影響霧化値，故可有效 地使丙烯酸粒子（C )的粒子徑或添加量控制於前述範圍 內，亦對於使製膜時的薄膜接觸部之表面粗度變小有效。 又，對於本發明中之光學薄膜的吸濕性，係藉由對於 濕度變化的尺寸變化作評估者。 作爲對於濕度變化的尺寸變化之評估方法，可使用以 下方法。 於所製作的光學薄膜之流延方向，賦予2處十字印， 在60°C，90%RH進行1000小時處理，將處理前與處理後之 十字印的距離以光學顯微鏡進行測定，求得尺寸變化率（ % )。尺寸變化率（％ )係以下述式表示。 尺寸變化率（％) =〔 （al-a2) /al〕χΙΟΟ al:熱處理前之距離 a2 :熱處理後之距離 作爲液晶顯示裝置之偏光板用保護薄膜使用光學薄膜 時，會產生因吸濕的尺寸變化而於光學薄膜引起不均或相 位差値變化，產生對比降低或色不均的問題。特別若爲在 屋外所使用的液晶顯示裝置所使用的偏光板保護薄膜，上 -42- 201107133 述問題變的顯著。然而，上述條件中之尺寸變化率（％) 若未達0.5%，可評估爲顯示充分低吸濕性的光學薄膜。且 ，未達0.3 %者爲佳。 又，本發明的光學薄膜係以薄膜面內的直徑5μπι以上 之缺陷爲1個/l〇cm四方以下者爲佳。且較佳爲0.5個/10cm 四方以下，一層較佳爲0.1個/10cm四方以下。 其中所謂缺陷的直徑，缺陷爲圓形時係以其直徑表示 .，若不是圓形時，缺陷的範圍以下述方法在顯微鏡下觀察 而決定，作爲該最大徑（外接圓之直徑）。 缺陷的範圍於缺陷若爲氣泡或異物時，其爲將缺陷以 微分干涉顯微鏡的透過光下觀察時的影子的大小。缺陷爲 輥傷害的轉印或擦傷等表面形狀之變化時，缺陷在微分干 涉顯微鏡的反射光下進行觀察而確認大小。 · 且，以反射光進行觀察時，若缺陷的尺寸不明瞭時， 於表面以鋁或鉑蒸鍍後觀察β 欲以生產性良好下得到以該缺陷頻度表示的品質優良 的薄膜，可將聚合物溶液於流延直前進行高精度過濾、或 提高流延機周邊的清潔度，且階段性地設定流延後之乾燥 條件，有效率地抑制該發泡而進行乾燥爲有效。 缺陷個數若比1個/10cm四方多時，例如在後步驟之加 工時等對於薄膜施予張力時，有著將缺陷作爲基點之薄膜 破裂降低生產性的情況。又，缺陷直徑成爲5 μηι以上時， 可藉由偏光板觀察等以目視確認，作爲光學部材使用的有 時會產生亮點。 -43- 201107133 又，即使無法以目視進行確認時，於該薄膜上形成硬 塗佈層等時，塗劑無法均勻地形成而有成爲缺陷（塗佈脫 落）之情況。其中，所謂缺陷爲，對於溶液製膜的乾燥步 驟中，溶劑的急激蒸發爲起因所產生薄膜中之空洞（發泡 缺陷）、或製膜原液中之異物或於製膜中混入的異物爲起 因之薄膜中之異物（異物缺陷）。 又，本發明的光學薄膜以JIS-K7 1 27- 1 999爲基準進行 測定時，至少一方向的破裂伸度以10%以上爲佳，更佳爲 2 0 %以上。 破裂伸度的上限並無特別限定，但現實上爲250%程度 。若使破裂伸度變大時，可有效地抑制異物或發泡爲起因 之薄膜中缺陷。 本發明的光學薄膜之厚度以20 μιη以上爲佳。更佳爲 3 0 μ m以上。 厚度上限並無特別限定，以溶液製膜法進行薄膜化時 ，由塗佈性、發泡、溶劑乾燥等觀點來看，上限爲25 Ομηι 程度。且，薄膜厚度可依據用途作適宜選定。 本發明的光學薄膜以該全光線透過率爲90 %以上者爲 佳’更佳爲93 %以上。又，作爲現實之上限爲99%程度。 欲達到該全光線透過率所示之優良透明性，可不要導入吸 收可見光之添加劑或共聚合成分、或將聚合物中之異物藉 由高精度過濾除去’減低薄膜內部的光擴散或吸收爲有效 〇 又’使製膜時的薄膜接觸部（冷卻輥、滾壓機、滾筒 -44 - 201107133 '輸送帶、溶液製膜中之塗佈基材、搬送輥等）的表面粗 度變小，而使薄膜表面之表面粗度變小、或藉由使丙烯酸 樹脂的折射率變小，減低薄膜表面之光擴散或反射爲有效 〇 本發明的光學薄膜若滿足如上述物性，可作爲大型液 晶顯示裝置或屋外用途之液晶顯示裝置用偏光板保護薄膜 使用時特佳。 <光學薄膜之製膜> 說明光學薄膜之製膜方法例子，但本發明並未限定於 此。 作爲本發明之光學薄膜的製膜方法，可使用膨脹法、 T字模法、滾壓法、切削法、流延法、乳化法、熱壓法等 製造法，但由著色抑制、異物缺陷之抑制、刀模線（die line )等光學缺陷之抑制等觀點來看，藉由流延法進行溶 液製膜爲佳。 且，本發明的光學薄膜爲具有二層以上的樹脂組成相 異的層之光學薄膜，（i)構成該光學薄膜之表面層的至 少一層爲丙烯酸樹脂（A)與纖維素酯樹脂（B)以5〇: 50 〜30 : 70的質量比下含有，（ii)構成該表面之層以外的 層爲丙烯酸樹脂（A )與纖維素酯樹脂（B )以80 : 20〜55 :45的質量比下含有，（iii)前述丙烯酸樹脂（A)的重 量平均分子量爲80000以上，（iv)前述纖維素酯樹脂（B )的醯基之總取代度爲2.0〜3.0，碳數爲3〜7之醯基取代 -45- 201107133 度爲1.2〜3.0，該纖維素酯樹脂（B )的重量平均分子量爲 7 5 000以上者作爲特徵。然而，作爲欲實現如此特徵的方 法，採用將該樹脂組成相異的層，與以下詳述薄膜製膜步 驟同時形成的方法爲佳。 例如，對於本發明之光學薄膜的製造，將樹脂組成相 異的複數摻合液使用具有複數狹縫的塑模狹縫，直接於流 延輸送帶上如流延而進行共流延（濺鍍步驟），其次，經 加熱除去溶劑之一部（流延輸送帶上之乾燥步驟）後，由 流延輸送帶進行剝離，將經剝離的薄膜藉由乾燥（薄膜乾 燥步驟），得到本發明之具有樹脂組成相異的複數層之光 學薄膜。 所謂本發明之表面側表示自薄膜表面至薄膜厚度之5 % 以上20%以下的深度部分而言。 圖1爲舉出本發明中所使用的可同時流延、連續流延 之裝置的較佳例子。 la〜lc表示各摻合液桶，2a〜2c表示各幫浦，3表示 共流延用塑模。共流延用之塑模的擴大截面圖如圖2所示 ，具有10、1 la、1 lb、及12之4根塑模狹縫。 各流延用摻合爲在塑模狹縫10、11a、lib各供給的合 流點形成層流而自1 2塑模狹縫供給至流延用輸送帶上。5 表示流延用之支持體（輸送帶），4表示轉動的滾筒、7表 示流延後適度將溶劑蒸發後，經剝離的光學薄膜，6表示 搬運該光學薄膜之輥子。 例如，於摻合液桶1 a、1 b、1 c裝滿各樹脂組成相異的 -46- 201107133 摻合A、摻合B、摻合C，改爲幫浦2a〜2c之流量，由流延 用之3個狹縫進行供給而得到三層共流延薄膜。 此時，在該光學薄膜的寬方向長度至少10〜90%之範 圍內，成爲含有該薄膜寬方向之中心的部分爲含有至少二 層以上的前述樹脂組成相異的層之型態爲佳。 (有機溶劑） 將本發明的光學薄膜以溶液流延法製造時形成摻合時 有用的有機溶劑，可使用同時將丙烯酸樹脂（A)、纖維 素酯樹脂（B)、其他添加劑進行溶解者即可並無限定。 例如，作爲氯系有機溶劑中，作爲氯化伸甲基、非氯 系有機溶劑，可舉出乙酸甲酯、乙酸乙酯、乙酸戊基、丙 酮、四氫呋喃、1，3-雙四氫呋喃、1,4-二噁烷、環己酮、 甲酸乙基、2,2,2-三氟乙醇、2,2,3，·3-六氟-1-丙醇、1,3-二 氟-2-丙醇、1，1，1，3,3,3-六氟-2-甲基-2-丙醇、1，1，1，3,3,3-六氟-2-丙醇、2,2,3,3,3-五氟-1-丙醇、硝基乙烷等，以氯 化伸甲基、乙酸甲酯、乙酸乙酯、丙酮爲佳。 摻合中除上述有機溶劑以外，亦可含有1〜40質量％之. 碳原子數1〜4的直鏈或分支鏈狀脂肪族醇爲佳。若摻合中 之醇比率變高時，織物（web )會凝膠化，容易由金屬支 持體剝離，又醇比率較少時，可促進在非氯系有機溶劑系 之丙烯酸樹脂（A)、纖維素酯樹脂（B)的溶解。 特別於含有二氯甲烷、及碳數1〜4的直鏈或分支鏈狀 脂肪族醇之溶劑，溶解至少15〜45質量％的丙烯酸樹脂s] -47- 201107133 A)、纖維素酯樹脂（B)、與丙烯酸粒子（C)的3種之 摻合組成物爲佳。 作爲碳原子數1〜4的直鏈或分支鏈狀脂肪族醇，可舉 出甲醇 '乙醇' η-丙醇、iso-丙醇、η-丁醇、sec-丁醇、 tert-丁醇。由這些內摻合的安定性、沸點亦比較低，乾燥 性亦佳等觀點來看以乙醇爲佳。 以下對於本發明之光學薄膜的較佳製膜方法作說明。 1 )溶解步驟 於對於丙烯酸樹脂（A) 、纖維素酯樹脂（b)爲良溶 劑爲主的有機溶，在溶解釜中一邊攪拌該丙烯酸樹脂（A ) '纖維素酯樹脂（B)、依情況與丙嫌酸粒子（c)、其 他添加劑，一邊溶解而形成摻合物的步驟、或於該丙烯酸 樹脂（A)、纖維素醋樹脂（B)溶液，依據情況，混合丙 烯酸粒子（C )溶液、其他添加劑溶液形成主溶解液之摻 合物的步驟。 對於丙烯酸樹脂（A)、纖維素酯樹脂（B)之溶解， 可使用常壓下進行的方法、在主溶劑沸點以下進行之方法 、在主溶《!!沸點以上經加壓進行之方法 '特開平9 _ 9 5 5 4 4 號公報、特開平9-95557號公報、或特開平9_95538號公報 所s5載之冷卻溶解法而進行之方法、特開平號公 報所S5載之尚壓下進行的方法等種種溶解方法，特別在主 溶劑之沸點以上經加壓進行之方法爲佳。 摻合中之丙烯酸樹脂（A)、與纖維素酯樹脂（B)以 -48- 201107133 計15〜45質量％之範圍時爲佳。於溶解中或後的摻合中加 入添加劑，經溶解及分散後，以濾材進行過濾，經脫泡以 送液幫浦送至下步驟。 過濾爲使用捕集粒子徑〇. 5〜5 μιη，且濾水時間爲1 〇〜 25sec/100ml的濾材爲佳。 該方法中，將粒子分散時所殘存之凝集物或主摻合添 加時產生的凝集物，使用在捕集粒子徑0.5〜5μιη，且濾水 時間爲10〜25sec/100ml之濾材，僅除去凝集物。主摻合中 因粒子濃度比添加液更爲薄，故過濾時凝集物彼此會會黏 在一起而使濾壓急速上昇。 圖3表示本發明之較佳溶液流延製膜方法的摻合調製 步驟、流延步驟及乾燥步驟之一例子模式圖。 視必要，藉由丙烯酸粒子裝入釜41以過濾器44除去較 大凝集物，移送液體至擠壓釜42。其後，藉由擠壓釜42添 加丙烯酸粒子添加液至主摻合溶解釜lx。 其後主摻合液以主過濾器3x進行過濾，於此將蠢外線 吸收劑添加液16x以聯機（inline)方式添加。 大多情況爲，於主摻合含有返回材料10〜50質量％程 度。返回材料中含有丙烯酸粒子，此時配合返回材料之添 加量’控制丙烯酸粒子添加液之添加量爲佳。 於含有丙烯酸粒子之添加液中，含有丙烯酸粒子0.5 〜1 0質量％爲佳，含有1〜1 〇質量％爲更佳，含有1〜5質量 %爲最佳。 若爲上述範圍內，添加液爲低黏度而容易處理，容易 -49- 201107133 添加於主慘合故較佳。 所謂返回材料爲’將光學薄膜成粉碎的物質，進行光 學薄膜的製膜時所產生，使用薄膜兩側部分切落的物質、 或擦傷等不合規格的光學薄膜輥軋材料。 又，使用預先混煉丙烯酸樹脂、纖維素酯樹脂、依據 情況與丙烯酸粒子而成爲顆粒化者爲佳。 2) 流延步驟 將摻合物通過送液幫浦（例如，加壓型定量齒輪幫浦 )’送至加壓塑模30，以無限移送之無端金屬輸送帶31， 例如不鏽鋼輸送帶、或回轉之金屬滾筒等金屬支持體上的 流延位置上，自加壓塑模狹縫將摻合物流延的步驟。 可調整塑模的接頭部分之狹縫形狀，容易使膜厚均勻 的加壓塑模爲佳。於加壓塑模可使用衣架型模具或Τ塑模 等任一種亦佳。金屬支持體之表面成爲鏡面。欲提高製膜 速度，亦可於金屬支持體上設置2個以上的加壓塑模’分 割摻合量使其重疊。或藉由將複數摻合同時流延的共流延 法得到層合結構之薄膜亦佳。 3) 溶劑蒸發步驟 將織物（於流延用支持體上流延摻合物’將所形成之 摻合膜稱爲織物）在流延用支持體上進行加熱，使溶劑蒸 發的步驟。 使溶劑蒸發時，由織物側吹入風的方法及/或自支持 -50- 201107133 體的裏面藉由液體傳熱的方法、藉由輻射熱自表裏傳熱之 方法等’以裏面液體傳熱方法可得到良好乾燥效率故較佳 。又亦可使用組合彼等的方法。將流延後之支持體上的織 物在40〜100°C之環境下，以支持體上進行乾燥爲佳。欲 於40〜100 °C的環境下維持，將該溫度的溫風由織物上面 吹入、或藉由紅外線等手段進行加熱爲佳。 由面品質、透濕性、剝離性之觀點來看，在30〜120 秒以內將該織物自支持體進行剝離爲佳。 4 )剝離步驟 將在金屬支持體上蒸發溶劑的織物，在剝離位置進行 剝離之步驟。經剝離的織物被送至下步驟。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical film for improving the adhesion and hardness of a film, a polarizing plate using the same, and a liquid crystal display device. [Prior Art] The liquid crystal display device needs to be expanded in applications such as liquid crystal televisions or computer liquid crystal displays. Generally, a liquid crystal display device is a unit cell in which a transparent electrode, a liquid crystal layer, a color filter or the like is held by a glass plate, and two polarizing plates provided on the both sides, and each polarizing plate is a polarizer (also known as a polarizer). In the case of a polarizing film, two optical films (polarizing plate protective films) are sandwiched. As the polarizing plate protective film, a cellulose triacetate film is generally used. On the other hand, due to advances in technology in recent years, the use of liquid crystal display devices has been diversified while accelerating the enlargement of liquid crystal display devices. For example, the use of an advertisement display in a public place which is used as a display device for an electronic signboard, which is used for a large display installed on a street or a storefront, and the like. For such use, since it is premised for use outside the house, the deterioration of moisture absorption by the polarizing film becomes a problem, and the polarizing plate protective film is required to have higher moisture resistance. However, in the cellulose ester film such as the cellulose triacetate film used in the past, it is difficult to obtain sufficient moisture resistance, and when it is desired to obtain moisture resistance and to form a thick film, the optical effect is increased. Further, in recent years, since the thickness of the device is required to be reduced, the thickness of the polarizing plate itself has become a problem. -5- 201107133 On the other hand, as a low-hygroscopic optical film material, polymethyl methacrylate (hereinafter referred to as "PMM A"), which is an acrylic resin, is also excellent in transparency in addition to low hygroscopicity. It is suitable for use in optical films because of its stability or dimensional stability. However, as the liquid crystal display device is enlarged as described above, the use for the outside of the room is enlarged, and the image can be sufficiently recognized outside the house. It is necessary to increase the amount of backlight light and to use it under more stringent conditions, and at a high temperature. Heat resistance or longer-term heat resistance is required. However, the use of the PMM A film at a high temperature lacking heat resistance, and long-term use, etc., has a problem of shape change. This problem is not only a physical property of a film monomer but also an important problem for a polarizing plate or a display device using such a film. That is, in the liquid crystal display device, as the film is deformed, the polarizing plate is bent, so that the entire panel is reversed. The problem caused by the deformation of the film is that it is also a problem on the backlight side. However, when the position of the identification side surface is used, the phase difference of the design changes due to the deformation, so that the variation of the viewing angle or the change of the color odor occurs. . Further, when the acrylic resin film is compared with a cellulose ester film or the like, it has a brittle nature which is easily cleaved, and is difficult to handle in cutting or the like, and it is particularly difficult to manufacture an optical film for a large liquid crystal display device in a stable manner. In view of the above-mentioned problems, conditions, and the like, for example, as a technique for improving moisture resistance and heat resistance disclosed in Patent Document 1, it is proposed to use an acrylic resin-bonded acrylic rubber-methyl methacrylate copolymer or butyl modified B. A resin of sulfhydryl cellulose. -6- 201107133 Further, Patent Document 2 proposes a technique of mixing a relatively low molecular weight acrylic resin as a plasticizer or as a plasticizer in the past. Patent Document 3 discloses an optical film in which a relatively large molecular weight acrylic resin and a cellulose ester resin are melt-mixed, and this technique has a case where the compatibility between the acrylic resin and the cellulose ester resin is insufficient, which is a lack of wide-use property. Technology, and is insufficient hardness. Further, in Patent Documents 4 and 5, when the acrylic resin film and the polarizer are bonded, surface treatment such as corona treatment, plasma treatment, or AGP treatment is required, and if the adhesion is required, the base layer or the like must be used. A technique for imparting novel characteristics or having opposite characteristics is proposed by using an optical film as a multi-layer structure. For example, Patent Document 6 proposes that a biaxial optical compensation film having a concentration in a film surface layer of inorganic fine particles larger than that in the film of the inorganic fine particles can exhibit a high contrast in a wide range of viewing angles. A liquid crystal display device in which a color shifter (a color change occurs when seen obliquely) is particularly used for a VA mode liquid crystal display device, an optical compensation film, and a method for manufacturing a polarizing plate and an optical compensation film. technology. These techniques are related to the technique of adding an additive in one of the thickness directions of the same resin composition layer, and there is no description about the technique for improving the characteristics of the resin composition. Patent Document 7 proposes a core layer formed by a polymer which is soluble or dispersible due to an organic solvent or water, and a cellulose derivative having a film thickness of 0.1 to 20 μΐ on at least one side of the core layer. The surface layer is characterized by a protective film for a polarizing plate, which provides a low retardation and less optical distortion 201107133, less bright foreign matter, better dimensional stability under high humidity, less bending, and subsequent to the glass substrate A technique for protecting a thin film for a polarizing plate excellent in properties. This technique is a technique for providing a core layer characterized by containing a surface layer mainly composed of a cellulose derivative, a cellulose derivative, a compound having an ethylenic double bond, and a photopolymerization initiator. This technique relates to a property of changing the composition of a resin, and a technique of providing only an optical film having a preferable property by providing a plurality of layers having different resin compositions, and there is no other description. Further, in the case where an acrylic resin and a cellulose resin are particularly used, even if an optical film having a plurality of layers is provided, if a layer having a different resin ratio is provided, an interface is formed between the layers due to the composition of the dissimilar resin, and the necessary optical fiber is obtained as an optical film. The characteristics are completely undocumented. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. 2003-12859 (Patent Document 3) [Patent Document 4] Japanese Laid-Open Patent Publication No. 2007-52404 [Patent Document 6] JP-A-2008-262161 (Patent Document 7) JP-A-200 1 - 2 1 SUMMARY OF THE INVENTION The present invention has been made in view of the above problems and circumstances, and an object of the present invention is to provide an optical film which improves the adhesion and hardness of a film. Further, a polarizing plate and a liquid crystal display using the optical film of -8 to 201107133 are provided. The above problems of the present invention can be solved by the following means: 1. An optical film having at least two or more layers of resin as a mutual phase An optical film of a different layer characterized in that (i) at least one layer constituting the surface of the optical film is an acrylic resin (A) and a cellulose ester resin (B) having a mass ratio of 50:5 〇 to 3 Ό:70; And (ii) the layer other than the layer constituting the surface is an acrylic resin (A) and a cellulose ester resin (B) having a mass ratio of 80:20 to 55:45, and (iii) the weight of the aforementioned acrylic resin (A). The average molecular weight is 8,000 or more, (iv) the total substitution degree of the thiol group of the cellulose ester resin (B) is 2.0 to 3.0, and the degree of substitution of the fluorenyl group having 3 to 7 carbon atoms is 1.2 to 3.0. The weight average molecular weight of the ester resin (B) is 75,000 or more. The optical film according to the above item 1, wherein the thickness of the layer constituting the surface is 5 to 20% of the total thickness of the optical film. 3. The optical film according to the above item 1, wherein the layer constituting the surface contains 0.01 to 1% by mass and the average particle diameter is 50% for the total mass of the layer constituting the surface. A fine particle of an inorganic compound or an organic compound in the range of 300 μm. The optical film according to any one of the items 1 to 3, which contains an antistatic agent. The optical film according to any one of the items 1 to 4, wherein the optical film has a length in the width direction of 10 to 90%, and a portion including a center of the film width direction is A phase layer containing at least two or more layers of the foregoing resin. The optical film according to any one of the items 1 to 5, wherein the resin composition is formed by forming a film which is different from each other in the film formation. A polarizing plate characterized by using the optical film according to any one of the items 1 to 6 above. A liquid crystal display device using the optical film according to any one of the items 1 to 6 above. By the above means of the present invention, an optical film which improves the adhesion and hardness of the film can be provided. Further, a polarizing plate and a liquid crystal display using the optical film can be provided. MODE FOR CARRYING OUT THE INVENTION The optical film of the present invention is an optical film having a resin composition having at least two or more mutually different layers, and (i) at least one layer constituting the surface of the optical film is acrylic resin (A) and cellulose. The ester resin (B) is contained in a mass ratio of 5 〇:5 〇30:7 ,, and (ii) the layer other than the layer constituting the surface is an acrylic resin (A) and a cellulose ester resin (B) at 80: 20 to 55: 45 by mass ratio, (iii) the weight average molecular weight of the acrylic resin (A) is 80,000 or more, and (iv) the total substitution degree of the thiol group of the cellulose ester resin (B) is 2.0 to 3.0. The thiol substitution degree of carbon number 3 to 7 is 1.2 to 3.0, and the cellulose ester resin (B) has a weight average molecular weight of 75,000 or more. This feature has a common technical feature with the invention relating to the request items of claim 1 to claim 8. The optical film of the present invention can be applied to a polarizing plate. Therefore, it can also be applied to the liquid crystal display device -10- 201107133. Hereinafter, the present invention, its constituent elements, and the form and type when the present invention is implemented will be described in detail. [Configuration of Optical Film] The optical film of the present invention has various layer constitutional forms, but is characterized in that the resin composition is an optical film having at least two or more layers which are different from each other. Further, the following requirements (〇~(iv) are satisfied. (i) At least one layer constituting the surface of the optical film is an acrylic resin (A) and a cellulose ester resin (B) at 50 ·· 50 to 30 · 70 mass ratio of (Π) the layer other than the layer constituting the surface is acrylic resin (A) and cellulose ester resin (B) at a mass ratio of 80: 20 to 55: 45 (iii) The weight average molecular weight of the acrylic resin (A) is 8000 or more. (iv) The total substitution degree of the thiol group of the cellulose ester resin (B) is 2.0 to 3.0, and the thiol substitution degree of the carbon number of 3 to 7 is 1.2 to 3.0, the weight average molecular weight of the cellulose ester resin (B) is 75,000 or more. As an embodiment of the present invention, the thickness of the layer constituting the surface is the entire optical film from the viewpoint of the effect of the present invention. 5 to 20% of the thickness is preferable. Further, in the layer constituting the surface, fine particles of an inorganic compound or an organic compound having an average particle diameter of 50 to 300 μm are used for the total mass of the layer constituting the surface. It is preferred to be in a form of 0.01 to 1% by mass. Further, the present invention The optical film preferably contains an antistatic agent in the range of -11 to 201107133. In the present invention, the optical film has at least 10 to 90% of the width in the width direction, and contains a portion of the center of the film in the width direction to contain at least two. It is preferable that the layer having the above-described resin composition differs from each other in a layer or more. Further, the resin composition is a layer which is different from each other, and it is preferable to form a film by a film. Hereinafter, each component will be described in detail. <Acrylic resin (A) > The acrylic resin used in the present invention also contains a methacrylic resin. The resin is not particularly limited, but is preferably 50 to 99% by mass of the methyl methacrylate unit and 1 to 50% by mass of the other monomer unit copolymerizable therewith. Examples of the other monomer which can be copolymerized include an alkyl methacrylate having an alkyl group number of 2 to 18, an alkyl acrylate having an alkyl number of 1 to 18, acrylic acid, methacrylic acid, or the like. α,β-unsaturated acid, maleic acid, fumaric acid, itaconic acid, etc., aromatic vinyl compound containing unsaturated divalent carboxylic acid, styrene, α-methylstyrene, acrylonitrile, methyl α,β-unsaturated nitrile such as acrylonitrile, maleic anhydride, maleic anhydride, hydrazine-substituted maleic anhydride, glutaric anhydride, etc., which may be used alone or in combination of two or more monomers. From the viewpoint of thermal decomposition resistance or fluidity of the copolymer, etc., methacrylate, ethacrylate, η-propyl acrylate, η-butyl acrylate, s-butyl acrylate, 2 -ethylhexyl acrylate or the like is preferably -12-201107133, particularly preferably methacrylate or η-butyl acrylate. The acrylic resin (Α) used in the optical film of the present invention, particularly as the brittleness of the optical film Improvement in transparency when it is compatible with cellulose ester resin (Β) From the good point of view, the weight average molecular weight (Mw) is more than 80,000. When the weight average molecular weight (Mw) of the acrylic resin (A) is less than 80,000, sufficient brittleness cannot be obtained, and the compatibility with the cellulose ester resin (B) is also deteriorated. The weight average molecular weight (Mw) of the acrylic resin (A) is more preferably in the range of 80000 to 1,000,000, particularly preferably in the range of 1,000 to 600,000, and most preferably in the range of 150,000 to 400,000. The weight average molecular weight (Mw) of the acrylic resin (A) is not particularly limited, and is preferably 1,000,000 or less from the viewpoint of production. The weight average molecular weight of the acrylic resin of the present invention can be determined by gel permeation chromatography. The measurement conditions are as follows. Solvent: Dichloromethane column: Shodex K806, K805, K803G (using 3 joints of Showa Denko (stock)) Column temperature: 25 °C Sample concentration: 0.1% by mass Detector: RI Model 504 ( GL Scientific )): L60 00 (Hitachi, Ltd.) Flow: 1. Oml / min S ] Proofreading curve: Standard polystyrene STK standard polystyrene (TOSOH) Mw = 2,800,000~500 The calibration curve of 13 samples obtained from -13 to 201107133. 13 samples are preferred for use with almost equal intervals. The method for producing the acrylic resin (A) in the present invention is not particularly limited, and any of known methods such as suspension polymerization, emulsion polymerization, bulk polymerization, or solution polymerization can be preferably used. Among them, as the polymerization initiator, a general peroxide system or an azo system can be used, and it can be used as an oxidation reduction system. For the polymerization temperature, the suspension or emulsion polymerization is 30 to 100. (: It is carried out in a block or solution polymerization at 80 to 160 ° C. To control the reduction viscosity of the obtained copolymer, an alkane can be used for polymerization. An example of the method of the present invention is shown below. A1 : Monomer Mass ratio (MMA: A2: monomer mass ratio (MMA: A3: monomer mass ratio (MMA: A4: monomer mass ratio (MMA: A5: monomer mass ratio (MMA: A6: monomer mass ratio (MMA: A7: monomer mass ratio (MMA: MSI: monomer mass ratio (MMA MS2: monomer mass ratio (MMA MMA: methyl methacrylate MA: methacrylate ST: styryl mercaptan, etc. as a chain move) The agent makes the acrylic resin of Mingzhong and its manufacture MA = 98 : 2 ), Mw70000 MA = 97 : 3 ) ' Mwl 60000 MA = 97 : 3 ) ' Mw3 50000 MA = 97 : 3 ) , Mw550000 MA = 97 : 3 ), Mw800000 MA = 97 : 3 ), Mw93 0000 MA = 94 : 6 ), Mwl 1 00000 :ST=60 :40) , MwlOOOOOO :ST=40 :60) ' Mwl 00000 (composite example of A 8) 201107133 First, The methyl methacrylate/acrylamide copolymer suspending agent was adjusted as shown below. Methyl methacrylate 2 parts by mass of propylene oxime Parts by mass of potassium persulfate 0.3 parts by mass of ion-exchanged water: 500 parts by mass. The above was charged into the reactor, and the monomer was completely converted to the polymer while replacing the gas in the reactor with nitrogen gas, and maintained at 70 ° C. The reaction was carried out as follows. The obtained aqueous solution was used as a suspending agent. In a stainless steel autoclave equipped with a baffle plate and a plowing type stirring blade, 5 parts by mass of the above suspending agent was dissolved in the ion at a capacity of 5 liters. A solution of 165 parts by mass of water was exchanged, and the system was stirred at 400 rpm under nitrogen substitution. Next, a mixture of the following composition was charged and added while stirring the reaction system. 27 parts by mass of methyl methacrylate 73 parts by mass of acrylate, 1.2 parts by mass of t-thirty base thiol, 2 parts by weight of 2,2'-azobisisobutyronitrile, 4 parts by mass, and then heated to 7 ° C, and the internal temperature reached 7 ° C. The time point is polymerized at the polymerization initiation time point and maintained for ISO minutes. Thereafter, the reaction system is cooled, the polymer is separated, washed, and dried according to a general method to obtain a bead copolymer. The polymerization rate of the material was 97%, and the weight average molecular weight was 130,000. The additive (NaOCH3) of 〇·2 mass% was added to the copolymer, and the 2-axis extruder was used for -15-201107133 (TEX30 (manufactured by Nippon Steel Co., Ltd.) /D = 44.5 )), the hopper part removes nitrogen gas at 10 L/min, performs intramolecular cyclization at a screw rotation number of 100 rpm, a raw material supply amount of 5 kg/hr, and a cylinder temperature of 290 T: Acrylic resin A8 was obtained after vacuum drying for 8 hours at 80 t. The acrylic resin A8 had a weight average molecular weight (Mw) of 1,300 Å and a Tg of 140 °C. As the acrylic resin of the present invention, a vending product can be used. For example, Delpet 6 0N, 80N (made by Asahi Kasei Chemicals Co., Ltd.), Dianal BR52, BR80, BR83, BR85, BR88 (manufactured by Mitsubishi Rayon Co., Ltd.), KT75 (manufactured by Electric Chemical Industry Co., Ltd.), and the like can be given. Acrylic resin can be used in two or more types. <Cellulose Ester Resin (B) > The cellulose ester resin (B) of the present invention, in particular, from the viewpoint of improvement in brittleness or transparency in compatibility with the acrylic resin (A), total substitution of mercapto groups The degree of substitution (T) is 2.0 to 3.0, the degree of substitution of the thiol group having a carbon number of 3 to 7 is 1.2 to 3.0, and the degree of substitution of the fluorenyl group having 3 to 7 carbon atoms is preferably 2.0 to 3.0. In other words, the cellulose ester resin of the present invention is preferably a cellulose ester resin substituted with a fluorenyl group having 3 to 7 carbon atoms, particularly preferably a propyl sulfonyl group or a butyl sulfonyl group, and particularly preferably a fluorenyl group. When the total degree of substitution of the thiol group of the cellulose ester resin (B) is more than 2.0 hours, that is, the hydroxyl residue at the 2, 3, and 6 positions of the cellulose ester molecule is higher than 1.0, the acrylic resin (A) and the acrylic resin (B) ) It is not fully compatible, and there is a problem of fogging when used as an optical film. Further, even if the total degree of substitution of the fluorenyl group is -16 to 201107133 2.0 or more, and the degree of substitution of the fluorenyl group having a carbon number of 3 to 7 is more than 1.2 hours, sufficient compatibility is still not obtained, and the brittleness is lowered. For example, when the total degree of substitution of the fluorenyl group is 2.0 or more, the degree of substitution of the fluorenyl group having 2 carbon atoms, that is, the thiol group is high, and the degree of substitution of the fluorenyl group having 3 to 7 carbon atoms is 1.2 hours, and the compatibility is lowered. Raise the atomization. Further, when the total degree of substitution of the fluorenyl group is 2.0 or more, the substitution degree of the fluorenyl group having 8 or more carbon atoms is high, and when the degree of substitution of the fluorenyl group having 3 to 7 carbon atoms is lower than 1.2, the brittleness is deteriorated, and the desired property cannot be obtained. characteristic. The degree of substitution of the thiol group of the cellulose ester resin (B) of the present invention is such that the total degree of substitution (T) is from 2.0 to 3.0, and the degree of substitution of the fluorenyl group having a carbon number of from 3 to 7 is as low as 1.2 to 3.0. However, the degree of substitution of the fluorenyl group having a carbon number of 3 to 7 or more, that is, an oxime group or a fluorenyl group having a carbon number of 8 or more is preferably 1.3 or less. Further, the total degree of substitution (T) of the thiol group of the cellulose ester resin (B) is more preferably in the range of 2.5 to 3.0. In the present invention, the thiol group may be an aliphatic fluorenyl group or an aromatic fluorenyl group. In the case of an aliphatic thiol group, it may be a straight chain or a branched chain, and may further have a substituent. The carbon number of the fluorenyl group in the present invention also includes a substituent of a fluorenyl group. When the cellulose ester resin (B) has an aromatic fluorenyl group as a substituent, the number of substituents X substituted with an aromatic ring is preferably 0 to 5. At this time, it must be noted that the degree of substitution of the fluorenyl group having a carbon number of 3 to 7 having a substituent must be 1.2 to 3.0. For example, when the number of carbon atoms of the benzamidine group is 7 and the substituent containing carbon is used, the carbon number of the benzamidine group is 8 or more, and is not contained in the fluorenyl group having 3 to 7 carbon atoms. When the number of substituents substituted with an aromatic ring is two or more, -17-201107133 may be the same or different, or may form a condensed polycyclic compound (for example, naphthalene, anthracene, anthracene, phenanthrene). , quinoxaline, isoquinoline, oxynaphthalene, chroman, pyridazine, acridine, anthracene, anthracene, etc.). When the cellulose ester resin (B) as described above has a structure having at least one aliphatic fluorenyl group having 3 to 7 carbon atoms, it can be used as a structure of the cellulose resin used in the present invention. Regarding the degree of substitution of the cellulose ester resin (B) of the present invention, the total degree of substitution (T) of the mercapto group is from 2.0 to 3.0, and the degree of substitution of the mercapto group having a carbon number of from 3 to 7 is from 1.2 to 3.0. Further, in addition to the fluorenyl group having a carbon number of 3 to 7, the sum of the substitution degrees of the fluorenyl group and the fluorenyl group having a carbon number of 8 or more is preferably 1.3 or less. As the cellulose ester resin (B) according to the present invention, particularly selected from the group consisting of cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate benzoate, cellulose propionate At least one of cellulose butyrate is preferred, that is, a fluorenyl group having 3 or 4 carbon atoms is preferred as the substituent. Among them, a particularly preferred cellulose ester resin is cellulose acetate propionate or cellulose propionate. The moiety which is not substituted by a thiol group is generally present as a hydroxy group. These can be synthesized by a known method. Moreover, the degree of substitution of the thiol group or the degree of substitution of other thiol groups can be determined by the method specified in ASTM-D817-96. The weight average molecular weight (Mw) of the cellulose ester resin of the present invention is preferably 75,000 or more from the viewpoint of improving compatibility with the acrylic resin (A) and brittleness, and is preferably in the range of 750 Å to 300,000. Good -18- 201107133, with a range of 100000~240000 is better, and 1 60000~240000 is especially good. When the important average molecular weight (Mw) of the cellulose ester resin is less than 75,000, the effect of improving heat resistance or brittleness may be insufficient, and the effects of the present invention may not be obtained. In the present invention, two or more kinds of cellulose resins may be used in combination. The optical film of the present invention is an optical film having at least two or more mutually different resin compositions, and from the viewpoint of solving the above problems of the present invention, it is necessary to (i) at least a layer constituting the surface of the optical film. - the layer is composed of an acrylic resin (A) and a cellulose ester resin (B) in a mass ratio of 50:50 to 30:70, and (ii) a layer other than the layer constituting the surface is an acrylic resin (A) and cellulose. The ester resin (B) is contained in a mass ratio of 80:20 to 55:45. Further, it is preferred that the acrylic resin (A) and the cellulose ester resin (B) are contained in a compatible state. In the optical film of the present invention, the acrylic resin (A) and the cellulose ester resin (B) must be contained in a compatible state. The physical properties or qualities necessary for the optical film can be achieved by mutually compensating the dissimilar resins. Whether or not the acrylic resin (A) and the cellulose ester resin (B) are in a compatible state can be judged, for example, by the glass transition temperature T g . [S.] For example, when the glass transition temperatures of the two resins are different, when the two resins are mixed, if the glass transition temperature of each resin is to be present, the glass transition temperature of the mixture may be two or more, but when the two phases are resin phase At the time of dissolution, the glass transition temperature inherent to each resin disappears, and becomes one glass transition temperature, and becomes the glass transition temperature of the compatible resin. -19- 201107133 The glass transition temperature is measured by a differential scanning calorimeter (DSC-7 model manufactured by Perkin Elmer Co., Ltd.) at a temperature increase rate of 2 ° C/min, in accordance with JIS K7 1 21 ( 1 987 ) The intermediate point glass transition temperature (Tmg). When the acrylic resin (A) and the cellulose ester resin (B) are each a non-crystalline resin, either one of a crystalline polymer or a partially crystalline polymer may be used. In the present invention, an acrylic resin (in the present invention) A) It is preferable that it is compatible with the cellulose ester resin (B) and becomes a non-crystalline resin. The weight average molecular weight (Mw) of the acrylic resin (A) or the weight average molecular weight (M w ) or degree of substitution of the cellulose ester resin (B) in the optical film of the present invention is based on the solubility of the resin solvent for both. After the difference was separated, it was obtained by measurement. When the resin is separated, it may be separated by extracting the dissolved resin by adding a resin dissolved in only one of the solvents, and heating or reflux may be performed at this time. The combination of these solvents may be combined in two or more steps to carry out resin separation. The dissolved resin is separated from the resin remaining as an insoluble matter, and the solution containing the extract is subjected to an operation of evaporating and drying the solvent to separate the resin. These separated resins can be specified by the general structural analysis of the polymer. When the optical film of the present invention contains a resin other than an acrylic resin or a cellulose ester resin, it can be isolated in the same manner. Further, when the weight average molecular weight (Mw) of the compatible resin is different, the high molecular weight substance is dissolved in the early stage by gel permeation chromatography (GPC), and the lower the molecular weight, the longer the molecular weight is Dissolved, it can be easily separated from -20- 201107133, and the molecular weight can also be determined. Further, the molecular weight of the compatible resin is measured by GPC, and the resin solution which is dissolved every hour is taken out, and the solvent is distilled off, and the dried resin is subjected to quantitative structural analysis to detect the respective portions of the molecular weight difference. The resin composition can specify the respective resins that are compatible. Each of the resins which were obtained by the difference in the solubility of the solvent in advance and each of which was measured by GPC was used to detect the respective resins which were compatible. In the present invention, "the acrylic resin (A) or the cellulose ester resin (B) is contained in a state of being compatible", and the resin (polymer) is mixed to form a state of being dissolved. It does not contain a state in which the acrylic resin resin (B) is mixed with an acrylic resin precursor such as a monomer, a dimer, or an oligomer, and then polymerized to form a mixed resin. For example, after mixing an acrylic resin precursor such as a monomer, a dimer, or an oligomer with the cellulose ester resin (B), the step of obtaining a mixed resin after polymerization is a polymerization reaction, and the resin produced by the method is a reaction. Control is difficult and molecular weight adjustment becomes difficult. Further, in the case of synthesizing a resin in such a method, a graft polymerization, a crosslinking reaction, a cyclization reaction, a solvent dissolved in a solvent, or a melting without melting are often carried out, and the acrylic resin in the mixed resin is dissolved and the weight is measured. Since the average molecular weight (Mw) also becomes difficult, it is difficult to control the physical properties, and it cannot be used as a resin capable of producing an optical film in a stable manner. The optical film of the present invention may be composed of a resin or an additive other than the acrylic resin (A) or the cellulose ester resin (B), without impairing the function as an optical film. -21 - 201107133 When a resin other than the acrylic resin (A) or the cellulose ester resin (B) is contained, even if the added resin is in a compatible state, it may be mixed without dissolution. In the optical film of the present invention, the total mass of the acrylic acid resin (A) and the cellulose ester resin (B) is preferably 55 mass% or more, more preferably 60 mass% or more, and particularly preferably 70 mass% of the optical film. 〇/. the above. When a resin or an additive other than the acrylic resin (A) and the cellulose ester resin (B) is used, it is preferred to adjust the amount of addition without impairing the functional range of the optical film of the present invention. <Acrylic Particles (C) > The optical film of the present invention is preferably one containing acrylic particles. The acrylic particles (C) according to the present invention are represented by the acrylic resin (A) and the cellulose ester resin (B). An acrylic component which exists in a particulate state (also referred to as an incompatible state) in an optical film contained in a compatible state. The acrylic particles (C) are, for example, a quantitatively produced optical film, dissolved in a solvent and stirred, and after being sufficiently dissolved and dispersed, a PTFE film having a pore diameter of an average particle diameter of the acrylic particles (C) is used. The filter is filtered, and the weight of the insoluble matter collected by the filtration is preferably 90% by mass or more of the acrylic particles (C) added to the optical film. The acrylic particles (C) used in the present invention are not particularly limited, and have two. Acrylic particles (C) having a layer structure of more than one layer are preferred, and Tejia-22-201107133 is a multilayered acrylic granular composite as described below. The multilayered acrylic granulated composite has an innermost hard layer polymer from the center portion to the outer peripheral portion, a crosslinked soft layer polymer exhibiting rubber elasticity, and an outermost hard layer polymer having overlapping layers. The particulate acrylic polymer of the structure is obtained. In other words, the multi-layered acrylic granulated composite is a multi-layered acrylic granulated composite formed of an innermost hard layer, a crosslinked soft layer, and an outermost hard layer from the center portion to the outer peripheral portion. It is preferred to use the multilayered acrylic granular composite of the three-layer core-shell structure. A preferred embodiment of the multilayered acrylic particulate composite used in the acrylic resin composition of the present invention is as follows: (a) methyl methacrylate 80 to 98.9 mass% The innermost hard layer polymerization obtained by polymerization of a mixture of monomers having an alkyl group having 1 to 8 carbon atoms of alkyl groups and 1 to 20% by mass of the polyfunctional grafting agent and 0.01 to 0.3% by mass of the polyfunctional grafting agent And (b) an alkyl acrylate having an alkyl group having a carbon number of 4 to 8 in an amount of from 75 to 98.5% by mass in the presence of the innermost hard layer polymer, and a polyfunctional crosslinking agent 〇.〇1 to 5 mass % and a polyfunctional grafting agent 0.5 to 5 mass% of a mixture of monomers obtained by polymerization of a crosslinked soft layer polymer, (c) polymerization by the innermost hard layer and a crosslinked soft layer In the presence of the substance, the alkyl acrylate having a methyl methacrylate content of 80 to 99% by mass and the alkyl group having a carbon number of 1 to 8 is 1 to 20 mass. /. a blue layer structure formed by the outermost hard layer polymer obtained by polymerization of the obtained monomer mixture, and the obtained three-layer structure polymer is composed of the innermost hard layer polymer (a) 5 to 40% by mass, soft Layer polymer (b) 30. to 60% by mass, and outermost hard layer polymer-23-201107133 (C) 2〇~5 0% by mass, insoluble fraction when separated by acetone, the insoluble portion The acrylic granular composite having a methyl ethyl ketone swelling degree of 1.5 to 4.0 is exemplified. Further, as disclosed in Japanese Patent Publication No. Sho 60-11760 or Japanese Patent No. 3-39095, not only by specifying the composition or particle diameter of each layer of the multi-layered acrylic granular composite, but also by setting the multilayer structure of acrylic granular The tensile modulus of the composite or the methyl ethyl ketone swelling of the acetone-insoluble portion is within a specific range, and a balance of further sufficient blister resistance and stress whitening resistance can be achieved. The innermost hard layer polymer (a) constituting the multilayered acrylic granulated composite is an alkyl acrylate having a methyl group of 80 to 98.9 mass% and an alkyl group having a carbon number of 1 to 8. It is preferred that the mixture of monomers of 1 to 20% by mass and the polyfunctional grafting agent 〇.〇1 to 0.3% by mass be polymerized. Examples of the alkyl acrylate having an alkyl group having 1 to 8 carbon atoms include methacrylate, ethyl acrylate, η-propyl acrylate, η-butyl acrylate, and s-butyl acrylate. Or 2-ethylhexyl acrylate or the like, preferably methacrylate or η-butyl acrylate. The ratio of the alkyl acrylate unit in the innermost hard layer polymer (a) is 1 to 20% by mass, and when the unit is less than 1% by mass, the thermal decomposition property of the polymer becomes large, and on the other hand, the unit exceeds When the amount is 20% by mass, the glass transition temperature of the innermost hard layer polymer (c) becomes low, and the effect of imparting the punching resistance of the three-layer structure acrylic granular composite is lowered, which is not preferable. Examples of the polyfunctional monomer having a functional polymerizable functional group as a polyfunctional grafting agent include acrylic acid, methacrylic acid, maleic acid, and allyl fumarate of -24 - 201107133. It is preferred to use allyl methacrylate. When the polyfunctional grafting agent is used for chemically bonding the innermost hard layer polymer and the soft layer polymer, the ratio of the innermost hard layer polymerization is 0·0 1 to 0.3 mass%. The crosslinked soft layer polymer (b) constituting the acrylic granular composite is in the presence of the innermost hard layer polymer (a), and the alkyl acrylate having an alkyl group having a carbon number of 1 to 8 is 75 to 98.5. It is preferred that the mixture of the monomers of the mass %, the polyfunctional crosslinking agent 0·01 to 5 mass%, and the polyfunctional grafting agent 0.5 to 5 mass% is polymerized. Among them, as the alkyl acrylate having an alkyl group having 4 to 8 carbon atoms, η-butyl acrylate or 2-ethylhexyl acrylate is preferably used. Further, in addition to these polymerizable monomers, a copolymerizable other monofunctional monomer of 25% by mass or less may be copolymerized. As the other monofunctional monomer which can be copolymerized, styrene and a substituted styrene derivative are mentioned. The ratio of the alkyl acrylate having an alkyl group of 4 to 8 to styrene, the more the former, the lower the glass transition temperature of the polymer (b), and the softening can be achieved. On the other hand, from the viewpoint of the transparency of the resin group, the refractive index at room temperature of the soft layer polymer (b) is close to that of the innermost hard layer polymer (a) and the outermost hard layer polymer (c). It is advantageous in the case of a hard thermoplastic acrylic resin, and the ratio of the two can be selected in consideration of this. The polyfunctional grafting agent may be used as described above for the innermost layer of the hard polymer (a). The polyfunctional grafting agent used therein is used when the soft layer polymer (b) and the outermost hard layer polymer (c) are chemically bonded to -25107 07133 for use in the polymerization of the innermost hard layer. The ratio is preferably 0.5 to 5% by mass from the viewpoint of imparting impact resistance. As the polyfunctional crosslinking agent, a generally known crosslinking agent such as a divinyl compound, a diallyl compound, a diacrylic compound or a dimethacrylic compound can be used, but polyethylene glycol diacrylate (molecular weight) is used. 200~600) is better. Among them, the polyfunctional crosslinking agent to be used is a crosslinked structure formed during polymerization of the soft layer (b), and is used for the effect of imparting impact resistance. However, if a previously used polyfunctional grafting agent is used for the polymerization of the soft layer, the crosslinked structure of the soft layer (b) can be formed to some extent, so that the polyfunctional crosslinking agent is not an essential component, but the polyfunctional crosslinking is carried out. The ratio of the agent used in the polymerization of the soft layer is preferably from 0.01 to 5% by mass from the viewpoint of the effect of imparting impact resistance. The outermost hard layer polymer (c) constituting the multilayered acrylic granulated composite is obtained by polymerization in the presence of the innermost hard layer polymer (a) and the soft layer polymer (b) A mixture of 80 to 99% by mass of the acrylate and 1 to 20% by mass of the alkyl acrylate having 1 to 8 carbon atoms in the alkyl group is preferred. Among them, as the alkyl acrylate, the above is used, but methacrylate or ethyl acrylate is preferred. The ratio of the alkyl acrylate units in the outermost hard layer (c) is preferably from 1 to 20% by mass. Further, in the polymerization of the outermost hard layer (c), it is also possible to improve the compatibility with the acrylic resin (A), and it is also possible to use an alkylthiol or the like having a molecular weight to be adjusted as a chain shifting agent. -26- 201107133 In other words, in the outermost hard layer, a gradient in which the molecular weight is gradually decreased from the inner side to the outer side is preferable, and it is preferable because the balance between the extension and the punching resistance can be improved. As a specific method, by dividing the mixture of the monomers to be formed into the outermost hard layer into two or more, the molecular weight of the polymer forming the outermost hard layer can be increased by sequentially increasing the amount of the linkage movement amount added each time. The inner side of the multilayered acrylic granulated composite body gradually becomes smaller toward the outer side. The molecular weight formed at this time was polymerized separately and under the same conditions as the mixture of the monomers used in the respective times, and the molecular weight of the obtained polymer was measured. The particle diameter of the preferred acrylic particles (C) used in the present invention is not particularly limited, but is preferably 10 to 100 nm, more preferably 20 to 500 nm, and particularly preferably 50 to 400 nm. In the acrylic granular composite of the preferred multilayer structure polymer used in the present invention, the mass ratio of the core to the shell is not particularly limited, and when the entire multilayer polymer is 100 parts by mass, the core layer is 50 parts by mass or more. It is preferably 90 parts by mass or less, more preferably 60 parts by mass or more and 80 parts by mass or less. And wherein the core layer is the innermost hard layer. Examples of the multi-layered acrylic-based granular composites include "metablen" manufactured by Mitsubishi Rayon Co., Ltd., "Kaneace" manufactured by Kaneka Chemical Industry Co., Ltd., and "parai〇id," manufactured by Kureha Chemical Industry Co., Ltd. "Acryloid" manufactured by Rohm and Haas Co., "Stafiloid" manufactured by Ganz Chemical Industries Co., Ltd., and "ParapetSA" manufactured by Kuraray Co., Ltd., etc., which can be used alone or in combination of two or more. Further preferred acrylic particles (C) used as the present invention Specific examples of the acrylic particles (cl) of the graft copolymer used in -27-201107133 include unsaturated carboxylic acid ester monomers and unsaturated carboxylic acid monomers in the presence of a rubbery polymer. a graft copolymer obtained by copolymerizing a monomer, an aromatic vinyl monomer, and a monomer mixture which may be copolymerized with other vinyl monomers which are copolymerizable with each other. (a) The rubbery polymer to be used is not particularly limited, and a diene rubber, an acrylic rubber, a vinyl rubber, or the like can be used. Specific examples include polybutylene. , styrene-butadiene copolymer, block copolymer of styrene-butadiene, acrylonitrile-butadiene copolymer, butyl-butadiene copolymer, polyisoprene, butadiene -Methyl methacrylate copolymer, butyl-methyl methacrylate copolymer, butadiene-ethyl acrylate copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene - an isoprene copolymer, an ethylene-acrylic acid copolymer, etc. These rubbery polymers may be used alone or in combination of two or more. Further, when the acrylic film (C) is added to the optical film of the present invention, acrylic acid When the refractive index of the mixture of the resin (A) and the cellulose ester resin (B) is close to the refractive index of the acrylic particles (C), it is preferred because a film having a high transparency can be obtained. Specifically, acrylic particles (C) The refractive index difference with the acrylic resin (A) is preferably 〇. 5 or less, more preferably 〇. 〇 2 or less, in other words, 0.01 or less. To satisfy such a refractive index condition, the acrylic acid can be adjusted. Resin (A) monomer unit composition ratio The method and/or the method of modulating the composition ratio of the rubbery polymer or the monomer used for the acrylic particles (C), etc., can reduce the refractive index difference from 28 to 201107133, and obtain an optical film excellent in transparency. In the solvent in which the acrylic resin (A) is soluble, the optical film of the present invention is sufficiently dissolved under appropriate conditions to be a white turbid solution, and the solvent is dissolved by centrifugation or the like. The difference between the refractive index (23 ° C, measurement wavelength: 5 50 nm) of the soluble fraction (acrylic resin (A)) and the insoluble fraction (acrylic acid particle (C)) after partial purification and partial insoluble fraction . In the acrylic resin (A) of the present invention, the method of adding the acrylic particles (C) is not particularly limited, and the acrylic resin (A) is blended with other optional components in advance, usually at 200 to 3 50 tex. It is preferred to add the acrylic particles (C) while uniformly melting and kneading by means of a one-axis or two-axis extruder. Further, a method of mixing a solution in which acrylic particles (C) are dispersed in advance, a solution (blending liquid) in which the acrylic resin (A) and the cellulose ester resin (B) are dissolved, or a method of mixing or using acrylic particles ( C) and other optional additives are added to the solution by mixing and mixing, etc. An example of the acrylic particles of the present invention and a method for producing the same will be described below. <Preparation Example of Acrylic Particles (C1)> In the reflux reactor of the 60 liter internal volume reactor, 'injection of 38.2 liters of ion-exchanged water, sodium dioctylsulfosuccinate ll·6g' at 250 rpm The lower side was stirred, and the temperature was raised to 75 ° C in a nitrogen atmosphere, so that the oxygen effect did not exist in fact. APS 0.36g was charged, and the monomer mixture formed by MMA1 657g, BA21.6g, and ALMA1.68g was added once after mixing for -29-201107133 minutes. After the detection of the hot peak, it was kept for 2 minutes to complete the innermost enthalpy. Polymerization of the layer. Next, APS 3.48g was charged, and after stirring for 5 minutes, a mixture of monomers of BA8105g, PEGDA (200) 31.9g, and ALMA 264.0g was continuously added for 120 minutes, and the addition was completed for 120 minutes. Polymerization of soft layers. Next, 1.32 g of APS was charged, and after stirring for 5 minutes, a mixture of monomers obtained by MMA 2106 g and BA 201.6 g was continuously added over 20 minutes, and after completion of the addition, the polymerization of the outermost hard layer 1 was completed for 20 minutes. Next, APS 1.32 g was charged, and after 5 minutes, a mixture of monomers made of MMA 3148g, BA20 1.6g, and n-OMlO.g was continuously added over 20 minutes, and the addition was continued for 20 minutes. After continuing to raise the temperature to 95 °C for 60 minutes, the polymerization of the outermost hard layer 2 was completed. The polymer emulsion thus obtained was placed in a 3 mass% sodium sulfate warm water solution, salted out and solidified, and then dehydrated, washed, and dried to obtain a three-layer acrylic particle (C 1 ). The average particle diameter was found to be 100 nm by the absorbance method. The above abbreviations are each as follows. MMA; methyl methacrylate MA; methacrylate BA; η-butyl acrylate ALMA; allyl methacrylate PEGDA; polyethylene glycol diacrylate (molecular weight 200) -30- 201107133 n- OM; η-octyl mercaptan APS; ammonium persulfate As the acrylic particles relating to the present invention, a vending product can be used. For example, the metablenW-341 (C2) (manufactured by Mitsubishi Rayon Co., Ltd.) may be Chemisnow MR-2G (C3) or MS-300X (C4) (manufactured by Suga Chemical Co., Ltd.). In the optical film of the present invention, the acrylic resin particles (C) containing 5 to 30% by mass of the total mass of the resin constituting the film are more preferable, and more preferably contained in the range of 1.0 to 15% by mass. <Antistatic agent> The optical film of the present invention is preferably an antistatic agent, and it is preferable to contain an antistatic agent in an amount of 0.001 to 2.0 parts by mass based on 1 part by mass of the resin constituting the film. The antistatic agent is not particularly limited, and a known antistatic agent can be used, but it is also selected from the group consisting of an anionic antistatic agent, a cationic antistatic agent, a nonionic antistatic agent, a zwitterionic antistatic agent, and a high At least one of a molecular antistatic agent and conductive fine particles is preferred, and more preferably selected from the group consisting of conductive fine particles, particularly preferably at least one of cerium oxide, indium oxide, tin oxide, cerium oxide and oxidized sand. Examples of the anionic antistatic agent include fatty acid salts, higher alcohol sulfate salts, liquid fatty oil sulfate salts, aliphatic amines and fatty acid sulfonates, and aliphatic alcohol phosphate salts. Sulfonic acid salts, aliphatic decyl sulfonates, alkyl allylic sulfonic acids - 31 - 201107133 salts, formaldehyde condensed naphthalene sulfonates, etc., as cationic Examples of the antistatic agent include aliphatic amine salts, fourth ammonium salts, and alkyl pyridyl salts. Examples of the nonionic anti-zeroing agent include polyepoxyalkyl ethers, polyepoxyalkylphenol ethers, polyepoxyalkyl esters, and sorbitan alkyl esters. Examples of the zwitterionic antistatic agent include, for example, an imidazoline derivative, a betaine-based higher alkylamino derivative, a sulfate derivative, a phosphate derivative, and the like. 'Specific compounds such as Jiu Mao Xiu Xiong's "Anti-charged polymer surface modification" fortunately, add "Plastics and rubber additives practical notes p 3 3 3 ~ P45 5" Chemical Industry Company, special Kaiping 1 1 - 256 1 43, special public Zhao 52-32572, and special Kaiping 1 0- 1 5 8484, etc. As the preferable antistatic agent, an ionic polymer compound such as an anionic antistatic agent or a cationic antistatic agent may be mentioned. Examples of the ionic polymer compound include an anionic polymer compound as disclosed in Japanese Patent Publication No. Sho 49-23 828, No. 49-23827, and No. 47-2 8 937; for example, Japanese Patent Publication No. 55-734, JP-A-2004 An ionic polymer having a dissociation group in the main chain as seen in No. 54672, Japanese Patent No. 59- 1 473 5, No. 57-18175, No. 57-18176, and No. 57-56059: 3 - 1 3 22 No. 3, the same as 57-15376, special public Zhao 53-45231, the same 55-145783, the same 55-65950, the same 55-67746, the same 57-11342, the same 57-19735 a cationic side chain type polymer having a cationic dissociative group in a side chain as seen in each of the publications of JP-A-58-56858, JP-A-61- -27853, and JP-A-62-9346, such as JP-A-5-2 Graft copolymer, etc., as seen in the publication No. 3, and the like, in the optical film of the present invention, as an example of a metal oxide which can be used as a particularly preferable conductive fine particle, ZnO, TiO 2 and Sn02 are used. , Al2〇3, In2〇3, Si〇2, MgO 'BaO, Ce〇2, Sb203, Mo〇2, V2〇5, etc., or their composite oxides, especially CeC2 In2〇3, Sn02, Sb203 'and Si02 is preferred. As an example of containing a hetero atom, for example, it is effective to add Al or In to ZnO, to add Nb, Ta, etc. to Ti〇2, and to add Sb, Nb, a halogen element or the like to Sn02. The amount of these hetero atoms to be added is preferably in the range of 0.01 to 25 mol%, particularly preferably in the range of 0.1 to 15 mol%. The average particle diameter of the conductive fine particles is preferably 100 nm or less, more preferably 5 to 100 nm. When the average particle diameter of the conductive fine particles is 100 nm or less, when it is contained in a resin material, it can impart sufficient charging characteristics without impairing the transparency of the resin material. Therefore, the antistatic property and the added amount of the antistatic agent are better. In terms of the relationship, the surface specific resistance 値 is preferably 1χ1〇1()Ω or less. The surface specific resistance 値 was measured for 24 hours in an environment of 23 ° C and 50% RH, and then measured using a super insulation meter according to A S T M D 2 5 7 . Further, a preferred antistatic agent which can be used in the present invention is an ion conductive polymer described in JP-A-9-203810 or a fourth-order ammonium cation conductive polymer having intermolecular crosslinking. The crosslinked cationic conductive polymer is characterized in that the obtained dispersible particulate polymer has a high concentration of high density in the cationic component in the fine particles, so that it has excellent electrical conductivity and good compatibility with the resin. 'Select high transparency, and will not see conductivity at low relative humidity -33- 201107133 Deterioration. The dispersible granulated polymer of the cross-linking type cationic conductive polymer used for the anti-static charging is generally used in the range of fine particle size of about 0.01 to 0.3 μm, preferably in the range of 0.1 to 5.15 μm. size. In the present invention, each of the antistatic agents described above is preferably added in an amount of from 1 to 2.0 parts by mass per 100 parts by mass of the optical film of the present invention, and the amount of the antistatic agent added is 0.001 by mass. When the amount is 2.0 parts by mass or less, the adhesion to the dust of the resin material can be effectively suppressed, and the light transmittance of the resin material can be maintained. Further, the amount of the antistatic agent to be added is preferably from 0.005 to 1.0 part by mass, more preferably from 0.01 to 0.5 part by mass, per 100 parts by mass of the polymer having an alicyclic structure. In the present invention, the same effect can be obtained by providing the above antistatic agent and a layer containing a fluorine compound which is generally used for preventing contamination. Further, in order to obtain the performance of the optical film of the present invention, a layer containing at least one antistatic agent (antistatic layer) may be provided on the surface of the film. The antistatic layer is provided by applying a mixture having the antistatic agent to the surface of the optical element, or by a method such as evaporation. Moreover, the thickness of the antistatic layer is preferably 50 to 3 ΟΟμπι. <Polishing agent> In the optical film of the present invention, it is desired to impart a lubricity, an optical property, or a mechanical function. The fine particles of an inorganic compound or fine particles of an organic compound may be added as a polishing agent. The shape of the polishing agent is preferably a shape such as a sphere, a rod, a needle, a layer, or a flat plate - 34 - 201107133. Examples of the polishing agent include ceria, titania, alumina, zirconia, calcium carbonate, ceramics, talc, calcined calcium citrate, water and calcium citrate, aluminum citrate, magnesium citrate, calcium phosphate, and the like. Inorganic fine particles such as oxides of metal atoms, phosphates, citrates, carbonates, and the like. As the fine particles of the organic compound, starch as described in the specification of the U.S. Patent No. 2,323,037, etc., the specification of Belgian Patent No. 625,451, or the specification of British Patent No. 981,1 98, etc., can be used. The polystyrene or polymethacrylate described in the above-mentioned publications, such as the polyvinyl alcohol described in Japanese Patent Publication No. Sho 44-3643, and the like, and the like. The organic fine particles of the polycarbonate described in the specification of the polyacrylonitrile described in the specification of the Japanese Patent No. 3,022,1,69, and the like. In the example of the fine particles of the organic compound, examples of the water-dispersible vinyl polymer include polymethacrylate, polymethyl methacrylate, polyacrylonitrile, and acrylonitrile-α-methylbenzene. Ethylene copolymer, polystyrene, styrene-divinylbenzene copolymer, polyvinyl acetate, polyvinyl carbonate, polytetrafluoroethylene, etc., as an example of a cellulose derivative, Examples of the starch derivative include methyl cellulose, cellulose acetate, cellulose acetate propionate, and the like, and examples thereof include carboxyl starch, carboxyl nitrophenyl starch, and urea-formaldehyde-starch reactant. Gelatin which is hardened by a known hardening agent and hardened gelatin which is agglomerated and hardened as a hollow capsule of a microcapsule is preferable. [S] Among the fine particles of the above inorganic compound or fine particles of the organic compound, -35-201107133 cerium oxide can reduce the atomization of the film, which is preferable. These fine particles can be surface-treated by an organic substance, so that it is preferable to reduce the atomization of the film. The surface treatment is preferably carried out using a halogenated decane, an alkoxy decane, a decazane, a decane or the like. The larger the average particle diameter of the fine particles, the greater the smoothness effect, and conversely, the smaller the average particle diameter, the more excellent the transparency. Further, the average particle diameter of the primary particles of the fine particles is in the range of 0.01 to 1.0 μm. The average particle diameter of the primary particles of the preferred fine particles is preferably 5 to 5 Onm, more preferably 7 to 14 nm. These fine particles are preferably used to form irregularities of 0.01 to Ο.Ομηη on the surface of the optical film. Examples of the fine particles of cerium oxide include AEROSIL 200 manufactured by Japan AERO SIL Co., Ltd., 200V, 300, R972, R972V, R974, R202, R812, 0X50, TT600, NAX50, etc., and KE manufactured by Nippon Shokubai Co., Ltd. - P10, KE-P30 'KE-P 1 00, KE-P 1 50, etc., preferably AEROSIL 200V, R972V, NAX 5 0, KE - P 3 0, KE - P 1 0 0. These fine particles may be used in combination of two or more kinds. When used in combination of two or more types, it can be mixed at any ratio. The fine particles having an average particle diameter or a different material can be used, for example, in a range of a mass ratio of AEROSIL 200V and R972V of 0.1: 99.9 to 99.9: 0.1. The method of adding these polishing agents is preferably carried out by kneading or the like. In another aspect, the polishing agent previously dispersed in a solvent is mixed with a resin and/or a plasticizer and/or an antioxidant and/or an ultraviolet absorber. After the dispersion, the precipitated solid is obtained by volatilizing the solvent, and this is preferably used in the production process of the resin melt, from the viewpoint that the polishing agent can be uniformly dispersed in the resin, from -36 to 201107133. The above polishing agent may be added to improve the mechanical, electrical and optical properties of the film. Further, when these fine particles are added, the smoothness of the obtained film can be improved. The atomization can be increased by the addition. The content of the resin is preferably 0.001 to 5% by mass, more preferably 0.005 to 1% by mass, even more preferably 0.005 to 1% by mass. In the optical film of the present invention, when the atomization enthalpy exceeds 1.0%, it is affected as an optical material. Therefore, it is preferred that the atomization enthalpy is less than 1.0%, more preferably Less than 0.5%. The atomization crucible can be measured in accordance with JIS-K7 13 6. <Other Additives> For the optical film of the present invention, in order to improve the fluidity or flexibility of the composition, a plasticizer may be used in combination. Examples of the plasticizer include a phthalate type, a fatty acid ester type, a trimellitic acid ester type, a phosphate type, a polyester type, or an epoxy type. Among them, a polyester-based and phthalate-based plasticizer is preferred. The polyester-based plasticizer has excellent non-migration or extraction resistance as compared with a phthalate-based plasticizer such as dioctyl phthalate, but has a slightly poorer plasticizing effect or compatibility. Therefore, these plasticizers can be selected or used in combination for a wide range of applications. The polyester-based plasticizer is a reactant of a carboxylic acid of one to four members and an alcohol of one to six members, but mainly uses a reaction of a two-membered carboxylic acid with a glycol. -37-201107133. Examples of the representative two-membered carboxylic acid include glutaric acid, itaconic acid, adipic acid, phthalic acid, sebacic acid, and sebacic acid. Particularly excellent use of adipic acid, phthalic acid or the like can be obtained. Examples of the glycol include an exoethyl group, a stretching propyl group, a 1,3-butylene group, a 1,4-butylene group, a 1,6-hexamethyl group, a neopentyl group, and a di-ethyl group. Ethyl alcohol, di-propyl and other glycols are extended. These two members of the carboxylic acid and the glycol may each be used singly or in combination. The ester-based plasticizer may be any of ester, oligoester, and polyester. The molecular weight is preferably in the range of 100 to 10,000, and preferably in the range of 600 to 3,000. Moreover, the viscosity of the plasticizer is related to the molecular structure or molecular weight, but in the case of the adipic acid plasticizer, it is preferably in the range of 200 to 5000 MPa · s (25 ° C) from the relationship of compatibility and plasticizing efficiency. . Further, a plurality of polyester-based plasticizers may be used. A plasticizer is preferably added in an amount of 〇 5 to 30 parts by mass based on 100 parts by mass of the optical film of the present invention. When the amount of the plasticizer added exceeds 30 parts by mass, the surface is sticky and practically not preferable. The optical film of the present invention may preferably contain an ultraviolet absorber, and examples of the ultraviolet absorber to be used include a benzotriazole-based, a 2-hydroxybenzophenone-based or a phenyl salicylate. For example, 2-(5-methyl-hydroxyphenyl)benzotriazole, 2-[2.hydroxy-3,5-bis(?,?-dimethylbenzyl)phenyl]-2 can be exemplified. Triazoles such as hydrazine-benzotriazole, 2_(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-hydroxy-4-methoxybenzophenone, 2 - Benzophenone such as 4-octyloxybenzophenone, 2,2,-dihydroxy-4-methoxybenzophenone-38-201107133. Among the ultraviolet ray absorbing agents, the ultraviolet ray absorbing agent having a molecular weight of 400 or more is hardly volatilized at a high boiling point, and is difficult to scatter at the time of high temperature molding. Therefore, the weather resistance can be effectively improved with a small amount of addition. Examples of the ultraviolet absorber having a molecular weight of 400 or more include 2_[2_hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2_benzotriazole, 2,2- a benzotriazole system such as methyl bis[4-(1,1,3,3-tetrabutyl)-6-(211-benzotriazol-2-yl)phenol], double (2, 2, a hindered amine such as 6,6-tetramethyl-4-piperidinyl) sebacate or bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, Further, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis(1,2,2,6,6-pentamethyl) -4-piperidinyl), 1-ί 2 -[ 3 - ( 3 , 5 - bis - 1 - butyl - 4 - phenylphenyl ) propenyloxy ) ethyl ] -4- [ 3- ( a mixture of a hindered phenol and a hindered amine in a molecule such as 3,5-di-t-butyl-4-hydroxyphenyl)propanoxy]-2,2,6,6-tetramethylpiperidine For the system, these may be used alone or in combination of two or more. Among them, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2-benzotriazole or 2,2-extension methyl bis[4 - (1,3,3,4-tetrabutyl)-6-( 2Η-benzotriazol-2-yl)phenol is particularly preferred. Further, in the optical film of the present invention, various antioxidants may be added in order to improve thermal decomposition property or thermal coloring property during molding. Further, in addition to the antistatic agent, the antistatic property can be imparted to the optical film. A flame-retardant acrylic resin composition to which a phosphorus-based flame retardant is added may be used in the optical film of the present invention. Examples of the phosphorus-based flame retardant used herein include red phosphorus 'triaryl-39-201107133-based phosphate, diaryl phosphate, monoaryl phosphate, arylphosphonic acid compound, and arylphosphine oxide. One or a mixture of two or more of a compound, a condensed aryl phosphate, a halogenated alkyl phosphate, a halogen-containing condensed phosphate, a halogen-containing condensed phosphonate, a halogen-containing phosphite, or the like. Specific examples thereof include triphenyl phosphate, 9,10-dihydro-9-ox-10-phosphinophen-10-oxide, phenylphosphonic acid, and stilbene (β-chloroethyl) phosphate. The optical film of the present invention, such as ginseng (dichloropropyl) phosphate or ginseng (tribromoneopentyl) phosphate, can simultaneously achieve low hygroscopicity, transparency, and high heat resistance which cannot be achieved in the past resin film. And the improvement of brittleness. In the present invention, the brittleness index is judged based on whether or not "an optical film which does not cause ductile damage" is used as a reference. By producing an optical film which does not cause ductile damage and is improved in brittleness, when a polarizing plate for a large-sized liquid crystal display device is produced, cracking or cracking during production is not caused, and an optical film excellent in handleability can be obtained. Among them, the ductile failure is defined as the rupture caused by the action of a larger stress than the strength of a material, until the final rupture causes a significant extension of the material or the destruction of the twist. The destruction surface will form a feature of countless pupils called dimple. In the present invention, whether or not it is "an optical film which does not cause ductile damage" can be evaluated by causing no damage such as cracking even if a large stress of the two films which can be bent is applied. When an optical film which does not cause ductile damage is applied to such a large-scale stress, even when it is used as a polarizing plate protective film for a liquid crystal display device which is enlarged, it is possible to sufficiently reduce problems such as cracking during production, and even if it is used. When it is peeled off again after a lamination, the -40-201107133 optical film does not cause cracking, and can sufficiently correspond to the thinning of the optical film. In the present invention, a tension softening point is used as an index of heat resistance. In addition to the increase in the size of the liquid crystal display device and the increasing brightness of the backlight source, the use of outdoor applications such as electronic signage requires more brightness, so the optical film is required to be used in a higher temperature environment, and the tension softening point is It is judged to be sufficient heat resistance from 105 ° C to 145 ° C '. It is preferably controlled at a temperature of from 10 ° C to 130 ° C. As a specific measurement method of the temperature at which the tension softening point of the optical film is displayed, for example, a Tensilon tester (RTC-1225A manufactured by ORIENTEC Co., Ltd.) can be used to cut the optical film by 120 mm (vertical) x 10 mm (horizontal) at a tension of 10 N. While the lower side was stretched, the temperature was further raised at a temperature increase rate of 30 ° C / min, and the temperature at the time point of 9 N was measured three times to obtain the average enthalpy. Further, from the viewpoint of heat resistance, the glass transition temperature (Tg) of the optical film is preferably 110 ° C or higher. More preferably, it is 120 ° C or more. Very good is above 150 °C. In addition, the glass transition temperature was measured using a differential scanning calorimeter (DSC-7 model manufactured by Perkin Elmer Co., Ltd.) at a temperature increase rate of 20 ° C / min, and was determined in accordance with JIS K7 1 2 1 (1 987). The intermediate point glass transition temperature (Tmg) is obtained. As an index for judging the transparency of the optical film of the present invention, atomization enthalpy (turbidity) was used. Especially for liquid crystal display devices used outside the house, it is necessary to obtain sufficient brightness or high contrast in a bright place, and it is necessary to make the atomization -41 - 201107133 1.0 1.0% or less, and 0.5% or less. The optical film of the present invention containing the acrylic resin (A) and the cellulose ester resin (B) has high transparency, and acrylic particles are used for the purpose of improving other physical properties, because the resin (acrylic resin) A) The difference in refractive index between the cellulose vinegar resin (B) and the acrylic particles (C) is small, and the increase in the atomization enthalpy can be prevented. Further, since the surface roughness also affects the atomization enthalpy due to surface atomization, the particle diameter or the addition amount of the acrylic particles (C) can be effectively controlled within the above range, and also the surface of the film contact portion at the time of film formation. The thickness becomes smaller and effective. Further, the hygroscopicity of the optical film of the present invention is evaluated by dimensional change with respect to humidity change. As a method of evaluating the dimensional change of the humidity change, the following method can be used. In the casting direction of the produced optical film, two cross marks were applied, and the treatment was performed at 60 ° C, 90% RH for 1000 hours, and the distance between the pre-treatment and the processed cross-print was measured by an optical microscope to obtain a size. Rate of change (%). The dimensional change rate (%) is expressed by the following formula. Dimensional change rate (%) = [(al-a2) / al] χΙΟΟ al: distance before heat treatment a2: distance after heat treatment When an optical film is used as a protective film for a polarizing plate of a liquid crystal display device, moisture absorption occurs. The change in size causes unevenness in the optical film or a change in phase difference, resulting in a problem of contrast reduction or color unevenness. In particular, if it is a polarizing plate protective film used for a liquid crystal display device used outside the house, the problem described in the above-mentioned -42-201107133 becomes remarkable. However, if the dimensional change rate (%) in the above conditions is less than 0.5%, it can be evaluated as an optical film exhibiting sufficiently low hygroscopicity. Moreover, it is better if it is less than 0.3%. Further, in the optical film of the present invention, it is preferable that the defect having a diameter of 5 μm or more in the film surface is one/l〇cm square or less. It is preferably 0.5/10 cm square or less, and one layer is preferably 0.1/10 cm square. The diameter of the defect is represented by the diameter of the defect. If it is not a circle, the extent of the defect is determined by observation under a microscope as follows, as the maximum diameter (diameter of the circumscribed circle). The range of the defect is the size of the shadow when the defect is a bubble or a foreign matter, and the defect is observed under the transmitted light of the differential interference microscope. When the defect is a change in the surface shape such as transfer or scratch of the roller damage, the defect is observed under the reflected light of the differential interference microscope to confirm the size. In addition, when the size of the defect is unknown, the surface is observed by vapor deposition of aluminum or platinum, and β is obtained. The film having excellent quality indicated by the frequency of the defect is obtained with good productivity, and the polymerization can be carried out. The material solution is subjected to high-precision filtration before casting, or the cleanliness of the periphery of the casting machine is increased, and the drying conditions after the casting are set in stages, and it is effective to effectively suppress the foaming and drying. When the number of defects is more than one /10 cm square, for example, when a tension is applied to the film at the time of processing in the subsequent step, the film is broken at the base point, and the productivity is lowered. Further, when the defect diameter is 5 μη or more, it can be visually confirmed by observation of a polarizing plate or the like, and sometimes a bright spot is generated as an optical member. -43-201107133 When the hard coating layer or the like is formed on the film, the coating agent cannot be uniformly formed and may become defective (coating and detachment). In the drying step of the solution film formation, the rapid evaporation of the solvent causes a void (foaming defect) in the film, or a foreign matter in the film forming solution or a foreign matter mixed in the film formation as a cause. Foreign matter in the film (foreign matter defect). Further, when the optical film of the present invention is measured in accordance with JIS-K7 1 27- 1 999, the elongation at least in one direction is preferably 10% or more, more preferably 20% or more. The upper limit of the rupture elongation is not particularly limited, but is actually about 250%. When the elongation at break is made large, defects in the film caused by foreign matter or foaming can be effectively suppressed. The thickness of the optical film of the present invention is preferably 20 μm or more. More preferably, it is more than 30 μm. The upper limit of the thickness is not particularly limited, and when the film is formed by a solution film forming method, the upper limit is about 25 Ομηι from the viewpoints of coatability, foaming, solvent drying, and the like. Further, the film thickness can be appropriately selected depending on the use. The optical film of the present invention preferably has a total light transmittance of 90% or more, more preferably 93% or more. Moreover, the upper limit as a reality is about 99%. In order to achieve excellent transparency as shown by the total light transmittance, it is possible to introduce an additive or a copolymerized component that absorbs visible light, or to remove foreign matter in the polymer by high-precision filtration to reduce the light diffusion or absorption inside the film. In addition, the surface roughness of the film contact portion (cooling roll, roller press, roller-44 - 201107133 'conveyor belt, coating substrate in solution film, transfer roller, etc.) at the time of film formation is reduced, and It is effective to reduce the surface roughness of the surface of the film or to reduce the light diffusion or reflection on the surface of the film by making the refractive index of the acrylic resin small. The optical film of the present invention can be used as a large liquid crystal display device if it satisfies the above physical properties. Or a polarizing plate for a liquid crystal display device for outdoor use is particularly useful when used. <Film film formation of optical film> An example of a film formation method of an optical film will be described, but the present invention is not limited thereto. As a film forming method of the optical film of the present invention, a production method such as an expansion method, a T-die method, a rolling method, a cutting method, a casting method, an emulsification method, or a hot pressing method can be used, but the coloring suppression and the suppression of foreign matter defects are suppressed. It is preferable to carry out solution film formation by a casting method from the viewpoints of suppression of optical defects such as a die line. Further, the optical film of the present invention is an optical film having two or more layers having different resin compositions, and (i) at least one layer constituting the surface layer of the optical film is an acrylic resin (A) and a cellulose ester resin (B). The mass ratio of 5:50 to 30:70 is contained, and (ii) the layer other than the layer constituting the surface is acrylic resin (A) and cellulose ester resin (B) at a mass of 80:20 to 55:45. The ratio of the weight average molecular weight of the acrylic resin (A) is 80,000 or more, and (iv) the total substitution degree of the thiol group of the cellulose ester resin (B) is 2.0 to 3.0, and the carbon number is 3 to 7. The thiol group-substituted -45-201107133 degree is 1.2 to 3.0, and the cellulose ester resin (B) has a weight average molecular weight of 75,000 or more. However, as a method for realizing such a feature, it is preferred to use a layer having a different resin composition, which is formed simultaneously with the film forming step described in detail below. For example, for the manufacture of the optical film of the present invention, a plurality of blending liquids having different resin compositions are used, and a casting slit having a plurality of slits is used, and co-casting (sputtering) is performed directly on the casting conveyor such as casting. Step), secondly, one part of the solvent is removed by heating (drying step on the casting conveyor belt), then peeled off by a casting belt, and the peeled film is dried (film drying step) to obtain the present invention. An optical film having a plurality of layers having different resin compositions. The surface side of the present invention means a depth portion from the surface of the film to the thickness of the film of 5% or more and 20% or less. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a preferred example of a device capable of simultaneous casting and continuous casting used in the present invention. La to lc denotes each of the mixing liquid tanks, 2a to 2c denote pumps, and 3 denotes a mold for co-casting. An enlarged cross-sectional view of the mold for co-casting is shown in Fig. 2, and has four mold slits of 10, 1 la, 1 lb, and 12. Each of the castings is formed into a laminar flow at the junctions supplied from the respective mold slits 10, 11a, and lib, and is supplied from the mold slit to the casting conveyor. 5 denotes a support for transfer (conveyor belt), 4 denotes a rotating drum, 7 denotes an optical film which is peeled off after moderately evaporating the solvent, and 6 denotes a roller for transporting the optical film. For example, in the mixing liquid tanks 1 a, 1 b, 1 c filled with different resin compositions -46-201107133 blending A, blending B, blending C, changing to the flow of the pump 2a~2c, by Three slits were supplied for the casting to obtain a three-layer co-cast film. In this case, in the range of at least 10 to 90% in the width direction of the optical film, it is preferred that the portion including the center of the film in the width direction is a layer containing at least two or more layers having different resin compositions. (Organic solvent) When the optical film of the present invention is produced by a solution casting method, an organic solvent which is useful for blending can be used, and the acrylic resin (A), the cellulose ester resin (B), and other additives can be used for dissolution. There is no limit. For example, examples of the chlorinated organic solvent include methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, and 1,3-bistetrahydrofuran. 4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-trifluoro-1-propanol, 1,3-difluoro-2- Propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2, 2,3,3,3-pentafluoro-1-propanol, nitroethane, etc., preferably methyl chloride, methyl acetate, ethyl acetate or acetone. In addition to the above organic solvent, the blend may contain 1 to 40% by mass of a linear or branched aliphatic alcohol having 1 to 4 carbon atoms. When the ratio of the alcohol in the blending becomes high, the web (web) gels and is easily peeled off from the metal support, and when the alcohol ratio is small, the acrylic resin (A) in the non-chlorinated organic solvent system can be promoted. Dissolution of the cellulose ester resin (B). Particularly, a solvent containing a dichloromethane or a linear or branched aliphatic alcohol having 1 to 4 carbon atoms is dissolved in at least 15 to 45 mass% of an acrylic resin s] -47 - 201107133 A), a cellulose ester resin ( B) It is preferable to mix the composition with three kinds of acrylic particles (C). Examples of the linear or branched aliphatic alcohol having 1 to 4 carbon atoms include methanol 'ethanol' η-propanol, iso-propanol, η-butanol, sec-butanol, and tert-butanol. Ethanol is preferred from the viewpoints of stability of such blending, low boiling point, and good drying property. Hereinafter, a preferred film forming method of the optical film of the present invention will be described. 1) The dissolution step is an organic solvent mainly composed of the acrylic resin (A) and the cellulose ester resin (b), and the acrylic resin (A) 'cellulose ester resin (B) is stirred in the dissolution vessel. a case in which a mixture of the acrylic acid particles (c) and other additives is dissolved to form a blend, or a solution of the acrylic resin (A) or the cellulose acetate resin (B), and the acrylic particles (C) are mixed as the case may be. The step of forming a blend of the main solution by the solution, other additive solution. The dissolution of the acrylic resin (A) or the cellulose ester resin (B) can be carried out by a method carried out under normal pressure, a method carried out below the boiling point of the main solvent, or a method in which the main solution is "!! The method of performing the cooling and dissolving method in the s5 of the Japanese Patent Laid-Open No. Hei 9-95557, or the s5 of the Japanese Patent Laid-Open No. Hei 9-95538, and the method of the S5 The method of dissolving various methods, such as a method of pressurizing at least above the boiling point of the main solvent is preferred. The blending of the acrylic resin (A) and the cellulose ester resin (B) in the range of from 15 to 45% by mass based on -48 to 201107133 is preferred. An additive is added to the blending during or after the dissolution, and after dissolving and dispersing, it is filtered with a filter medium, and defoamed to be sent to the next step. Filtration is preferably carried out using a filter medium having a diameter of 5 to 5 μιη, and a filtration time of 1 〇 to 25 sec/100 ml. In this method, the agglomerates remaining when the particles are dispersed or the aggregates generated during the main blending are used, and the filter medium having a diameter of 0.5 to 5 μm and a filtration time of 10 to 25 sec/100 ml is used to remove only agglomeration. Things. In the main blending, since the concentration of the particles is thinner than the additive liquid, the aggregates will stick to each other during filtration, and the filtration pressure will rise rapidly. Fig. 3 is a view showing an example of a blending preparation step, a casting step and a drying step of the preferred solution casting film forming method of the present invention. If necessary, the larger agglomerates are removed by the filter 44 by charging the acrylic particles into the kettle 41, and the liquid is transferred to the extruder 42. Thereafter, the acrylic particle addition liquid was added to the main blending dissolution vessel 1x by the extrusion pot 42. Thereafter, the main blending liquid was filtered by the main filter 3x, and the stray external absorbent addition liquid 16x was added thereto in an inline manner. In most cases, the main blend contains 10 to 50% by mass of the return material. The returning material contains acrylic particles, and in this case, it is preferable to adjust the amount of addition of the acrylic particles to the amount of the added material. The additive liquid containing acrylic particles preferably contains 0.5 to 10% by mass of the acrylic particles, more preferably 1 to 1% by mass, more preferably 1 to 5% by mass. If it is within the above range, the added liquid is low in viscosity and easy to handle, and it is easy to add -49-201107133 to the main cause. The return material is a material obtained by pulverizing an optical film, and is formed when a film of an optical film is formed, and a material which is cut off on both sides of the film or an optical film rolled material which is out of specification such as scratches is used. Further, it is preferred to use a pre-kneaded acrylic resin, a cellulose ester resin, and granules depending on the case and the acrylic particles. 2) The casting step sends the blend to the pressurizing mold 30 through a liquid feeding pump (for example, a pressurized metering gear pump) to transfer the endless metal conveyor belt 31 infinitely, such as a stainless steel conveyor belt, or The step of casting the blend from the pressurizing mold slit at a casting position on a metal support such as a rotating metal drum. The slit shape of the joint portion of the mold can be adjusted, and it is easy to make a press mold having a uniform film thickness. It is also preferable to use a coat type mold or a squeegee mold for the press mold. The surface of the metal support becomes a mirror surface. In order to increase the film forming speed, two or more press molds may be provided on the metal support to divide the blending amount to overlap. It is also preferable to obtain a film of a laminated structure by a co-casting method in which a plurality of contracts are cast. 3) Solvent evaporation step The step of heating the fabric on the casting support by elongating the fabric (the formed blended film on the casting support is referred to as a woven fabric) is heated to evaporate the solvent. When the solvent is evaporated, the method of blowing air from the fabric side and/or the method of heat transfer by means of liquid heat transfer from the inside of the support -50-201107133 body, the method of heat transfer from the surface by radiant heat, etc. It is preferred to obtain good drying efficiency. It is also possible to use a combination of these methods. It is preferred that the fabric on the cast support is dried on a support at 40 to 100 ° C. In order to maintain it in an environment of 40 to 100 ° C, it is preferred that the warm air of this temperature is blown from the top of the fabric or heated by means of infrared rays or the like. From the viewpoint of surface quality, moisture permeability, and peelability, it is preferred to peel the fabric from the support within 30 to 120 seconds. 4) Peeling step A step of ejecting the solvent of the fabric on the metal support and peeling off at the peeling position. The peeled fabric is sent to the next step.
I 金屬支持體上的剝離位置中之溫度較佳爲1 0〜40。(：， 更佳爲1 1〜3 0 °C。 且，在剝離時點之金屬支持體上的織物之剝離時殘留 溶劑量，依據乾燥條件之強弱、金屬支持體之長度等，在 50〜120質量％之範圍下進行剝離爲佳，在殘留溶劑量較多 時點進行剝離時，若織物過於柔軟時，會損害剝離時平面 性’因剝離張力容易產生皺折或縱條紋，故兼具經濟速度 與品質下決定剝離時的殘留溶劑量。 織物的殘留溶劑量如下述式所定義。 殘留溶劑量（％)=(織物之加熱處理前質量-織物之 加熱處理後質量）/(織物之加熱處理後質量）XI 00 且，測定殘留溶劑量時的加熱處理表示在1 1 5 °c進行1 -51 - 201107133 小時之加熱處理。 剝離金屬支持體與薄膜時的剝離張力，一般爲196〜 245N/m，剝離時容易產生皺折時，在l90N/m以下之張力 進行剝離爲佳，且可剝離的最低張力〜166.6N/m，其次在 最低張力〜137.2Ν/Π1進行剝離爲佳，特佳爲在最低張力〜 lOON/m進行剝離。 本發明中，將該金屬支持體上之剝離位置的溫度設定 爲-50〜40°C時爲佳，以10〜40°C爲較佳，以15〜30°C爲最 佳。 5)乾燥及延伸步驟 剝離後，使用將織物於乾燥裝置內於複數配置的輥以 交互方式搬送的乾燥裝置35、及/或以夾子夾住織物兩端 進行搬送之拉幅器延伸裝置34來乾燥織物。 乾燥手段爲於織物兩面以熱風吹爲一般方法，但亦有 取代風使用微波的加熱手段。若過渡急激的乾燥所得之薄 膜平面性容易有損害。藉由高溫之乾燥爲，自殘留溶劑爲 8質量％以下時進行爲佳。對於全體而言，乾燥大槪於4〇〜 250 °C下進行。特佳爲40〜160 °C下進行乾燥。 使用拉幅器延伸裝置時，使用藉由拉幅器的左右把持 手段，控制薄膜之把持長（自把持開始至把持終了的距離 )可獨立地控制的裝置爲佳。又，對於拉幅器步驟，欲改 善平面性，製作具有相異溫度的區域亦佳。 又，欲於相異溫度區域間不會引起各區域的干涉，設 -52- 201107133 置中性區亦佳。 且，亦可將延伸操作分割爲多段階而實施，亦可於流 延方向、寬方向實施二軸延伸。又，進行二軸延伸時，亦 可同時進行二軸延伸、或亦可段階性地實施。 此時，所謂段階方視爲，例如可將延伸方向相異的延 伸依序進行、或將同一方向的延伸分爲多段階、且亦可將 相異方向的延伸加入於該任意段階中。即，例如亦可爲以 下延伸階段。 •於流延方向延伸-於寬方向延伸-於流延方向延伸-於 流延方向延伸 •於寬方向延伸-於寬方向延伸-於流延方向延伸·於流 延方向延伸 又，亦包含於同時2軸延伸時，於一方向延伸，將另 —方緩和張力而使收縮的情況含。同時2軸延伸的較佳延 伸倍率爲寬方向、長手方向皆可爲Xl.01倍〜xl.5倍之範圍 〇 進行拉幅器時的織物殘留溶劑量於拉幅器開始時以2〇 〜100質量％爲佳，該織物的殘留溶劑量成爲10質量％以下 時，一邊施予拉幅器一邊施予乾燥爲佳，更佳爲5質量％以 下。 進行拉幅器時的乾燥溫度較佳爲30〜160°C，50〜 15 0°C爲更佳，70〜140°C爲最佳。 對於拉幅器步驟，若環境寬方向的溫度分佈較少時’ 由提高薄膜均句性之觀點來看爲佳，在拉幅器步驟的寬方[ -53- 201107133 向之溫度分佈以±5°C以內爲佳，以±2°C以內爲較佳，以土 1 °C以內爲Μ佳。 6)捲取步驟 使織物中的殘留溶劑量成爲2質量％以下後，作爲光學 薄膜藉由捲取機37進行捲取的步驟，藉由將殘留溶劑量成 爲0.4質量％以下，可得到尺寸安定性良好之薄膜。特別以 0.00〜0.10質量％進行捲取爲佳。 捲取的方法使用一般使用者即可，可使用定轉矩法、 定張力法、錐度張力法 '內部應力一定之程序張力控制法 等。 本發明的光學薄膜以長形薄膜爲佳，具體爲顯示100m 〜5000m程度者，一般爲以輥狀方式提供的形態者。又， 薄膜的寬度以1.3〜4m爲佳，以1.4〜2m爲較佳。 本發明的光學薄膜之膜厚雖無特別限制，使用後述偏 光板保護薄膜時以20〜200μϊη爲佳，以25〜ΙΟΟμπι爲較佳 ，以30〜80μιη爲特佳。 〔偏光板〕 將本發明的光學薄膜作爲偏光板用保護薄膜使用時， 偏光板可由一般方法製作。於本發明的光學薄膜之裏面側 設置黏著層，貼合於碘溶液中進行浸漬延伸所製作的偏光 子的至少一面上爲佳。 於另一面上亦使用本發明的光學薄膜，亦可使用其他 -54- 201107133 偏光板保護薄膜。例如販賣的纖維素酯薄膜（例如， KONICA MINOLTA TAC KC8UX 、 KC4UX 、 KC5UX 、 KC8UY、KC4UY ' KC12UR、KC8UCR-3、KC8UCR-4、 KC8UCR-5、KC8UE、KC4UE、KC4FR-3、KC4FR-4、 KC4HR-1 、 KC8UY-HA 、 KC8UX-RHA 、以上 Konica Minolta Opto (股）製）等爲佳。 所謂偏光板之主要構成要素的偏光子爲，僅通過一定 方向之偏波面的光之元件，現在已知的代表性偏光膜爲聚 乙烯基醇系偏光薄膜，此爲於聚乙烯基醇系薄膜上以碘染 色所得者與經二色性染料染色所得者。 偏光子爲，使用將聚乙烯基醇水溶液進行製膜，將此 經一軸延伸後進行染色、或經染色後經一軸延伸後，較佳 爲以硼化合物進行耐久性處理者。 作爲使用於上述黏著層之黏著劑，使用對於黏著層的 至少一部分，在WC的貯藏彈性率爲l.〇xl〇4Pa〜 1·0 XI 09Pa之範圍的黏著劑爲佳，使用塗佈黏著劑經貼合後 藉由種種化學反應形成高分子量體或交聯結構之硬化型黏 著劑爲佳。 作爲具體例，例如可舉出胺基甲酸酯系黏著劑、環氧 系黏著劑、水性高分子-異氰酸酯系黏著劑、熱硬化型丙 烯酸黏著劑等硬化型黏著劑 '濕氣硬化胺基甲酸酯黏著劑 、聚醚甲基丙烯酸酯型、酯系甲基丙烯酸酯型、氧化型聚 醚甲基丙烯酸酯等厭氣性黏著劑、氰基丙烯酸酯系之瞬間 黏著劑、丙烯酸酯與過氧化物系之2液型瞬間黏著劑等。 -55- 201107133 作爲上述黏著劑可爲1劑型、或使用前混合2劑以上後 使用的類型亦可。 又，上述黏著劑可爲將有機溶劑作爲媒體之溶劑系' 亦可爲將水作爲主成分之媒體的乳化型、膠體分散液型、 水溶液型等水系、或無溶劑型亦可。上述黏著劑液之濃度 可依據黏著後的膜厚、塗佈方法、塗佈條件等而作適宜決 定，一般爲〇· 1〜50質量％。 〔液晶顯示裝置〕 將貼合本發明之光學薄膜的偏光板組裝於液晶顯示裝 置時，可製做出轉種辨識性優良的液晶顯示裝置，特別爲 使用於大型液晶顯示裝置或電子看板等室外用途的液晶顯 示裝置爲佳。有關本發明之偏光板爲介著前述黏著層等而 貼合於晶胞。 有關本發明之偏光板可適用於反射型、透過型、半透 過型LCD或TN型、STN型、OCB型、HAN型、VA型（PVA 型、MVA型）、IPS型（亦含有FFS方式）等各種驅動方式 之LCD。特別爲畫面爲30吋以上，特別30吋〜54吋的大畫 面的顯示裝置中，見不到畫面周圍部分的脫白等，其效果 可長期間維持。 又，具有色不均、閃爍或波狀不均較少，即使長時間 鑑賞下眼睛也不會疲勞之效果" 【實施方式】 -56- 201107133 〔實施例〕 以下舉出實施例對本發明作具體說明，但本發明並未 限定於此。 實施例1 〔光學薄膜的製作〕 <光學薄膜1的製作> (摻合液1組成） D i an al B R 8 5 ( Mi t sub i shi Ray on (股）製） 65 質量份 丙烯酸粒子（Cl) 5質量份 纖維素酯（纖維素乙酸酯丙酸酯醯基總取代度2.75、乙 醯基取代度0.19、丙醯基取代度2.56、Mw = 200000 ) 30質量份 二氯甲烷 300質量份 乙醇 40質量份 將上述組成物一邊加熱一邊充分溶解，製作出摻合液 〇 同樣地，將樹脂組成如下述變更以外以同樣方式製作 摻合液2。 (摻合液2組成）The temperature in the peeling position on the metal support is preferably from 10 to 40. (:, more preferably 1 1 to 3 0 ° C. Moreover, the amount of residual solvent at the time of peeling off the fabric on the metal support at the time of peeling, depending on the strength of the drying condition, the length of the metal support, etc., 50 to 120 It is preferable to carry out the peeling in the range of the mass %, and when the amount of the residual solvent is large, if the fabric is too soft, the flatness at the time of peeling is impaired. Wrinkles or vertical streaks are easily caused by the peeling tension, so that the fabric is economical. The amount of residual solvent at the time of peeling is determined by the quality. The residual solvent amount of the fabric is defined by the following formula: The amount of residual solvent (%) = (mass before heat treatment of the fabric - the quality of the heat treatment of the fabric) / (heat treatment of the fabric) After the mass) XI 00, the heat treatment at the time of measuring the residual solvent amount indicates that the heat treatment is performed at 1 to 15 ° C for 1 - 51 - 201107133 hours. The peeling tension when peeling the metal support and the film is generally 196 to 245 N / m, when wrinkles are likely to occur at the time of peeling, it is preferable to perform peeling at a tension of not more than 90 N/m, and the minimum tension that can be peeled is ～166.6 N/m, and secondly, peeling at a minimum tension of 137.2 Ν/Π1 is preferable. In the present invention, it is preferable to set the peeling position on the metal support to a temperature of -50 to 40 ° C, preferably 10 to 40 ° C. Preferably, the temperature is 15 to 30 ° C. 5) After the peeling of the drying and stretching steps, the drying device 35 that carries the fabric in a plurality of rollers arranged in the drying device in an interactive manner, and/or the ends of the fabric are clamped by the clips. The tenter extender 34 is transported to dry the fabric. The drying method is a general method of blowing hot air on both sides of the fabric, but there is also a heating means for replacing the wind using microwaves. The flatness of the film obtained by the rapid drying of the transition is liable to be damaged. The drying at a high temperature is preferably carried out when the residual solvent is 8 mass% or less. For the whole, dry simmering is carried out at 4 〇 to 250 °C. It is particularly preferably dried at 40 to 160 °C. When the tenter extension device is used, it is preferable to control the length of the holding of the film (the distance from the start of gripping to the end of gripping) independently controlled by the left and right gripping means of the tenter. Further, in the tenter step, it is preferable to produce a region having a different temperature in order to improve planarity. Also, if you want to interfere with each other in different temperature zones, set -52- 201107133 Neutral zone is also good. Further, the extension operation may be carried out by dividing the extension operation into a plurality of stages, and the two-axis extension may be performed in the casting direction and the width direction. Further, when the two-axis extension is performed, the two-axis extension may be simultaneously performed or may be performed stepwise. In this case, the so-called step is considered to be, for example, the extension of the different extension directions may be sequentially performed, or the extension of the same direction may be divided into a plurality of stages, and an extension of the different direction may be added to the arbitrary step. That is, for example, it may be a lower extension stage. • extending in the casting direction - extending in the width direction - extending in the casting direction - extending in the casting direction, extending in the width direction - extending in the width direction - extending in the casting direction, extending in the casting direction, and also included in At the same time, when the two-axis is extended, it is extended in one direction, and the other side is moderated to make the contraction. At the same time, the preferred stretching ratio of the 2-axis extension is the width direction and the long-hand direction can be Xl.01 times to xl.5 times. The amount of residual solvent of the fabric when the tenter is performed is 2 〇 at the beginning of the tenter. When the amount of the residual solvent of the woven fabric is 10% by mass or less, it is preferably applied to the tenter while applying the tenter, and more preferably 5% by mass or less. The drying temperature at which the tenter is carried out is preferably from 30 to 160 ° C, more preferably from 50 to 150 ° C, and most preferably from 70 to 140 ° C. For the tenter step, if the temperature distribution in the width direction of the environment is small, it is better from the viewpoint of improving the uniformity of the film, and the width of the tenter step is [-53- 201107133] It is preferably within ±C, preferably within ±2 °C, preferably within 1 °C of soil. 6) The winding step is such that when the amount of the residual solvent in the woven fabric is 2% by mass or less, the optical film is wound by the winder 37, and the amount of the residual solvent is 0.4% by mass or less, whereby dimensional stability can be obtained. Good film. In particular, it is preferred to carry out the winding at 0.00 to 0.10% by mass. The winding method can be used by a general user, and a constant torque method, a constant tension method, a taper tension method, a program tension control method with a constant internal stress, and the like can be used. The optical film of the present invention is preferably an elongated film, specifically, a film having a thickness of from 100 m to 5,000 m, and is generally provided in a roll form. Further, the width of the film is preferably 1.3 to 4 m, preferably 1.4 to 2 m. The film thickness of the optical film of the present invention is not particularly limited, and is preferably 20 to 200 μϊη, preferably 25 to ΙΟΟμπι, and particularly preferably 30 to 80 μm, in the case of using a polarizing plate protective film to be described later. [Polarizing Plate] When the optical film of the present invention is used as a protective film for a polarizing plate, the polarizing plate can be produced by a general method. It is preferable to provide an adhesive layer on the back side of the optical film of the present invention, and to adhere it to at least one surface of the polarizer produced by immersion stretching in an iodine solution. The optical film of the present invention is also used on the other side, and other -54-201107133 polarizing plate protective film can also be used. For example, cellulose ester films sold (eg, KONICA MINOLTA TAC KC8UX, KC4UX, KC5UX, KC8UY, KC4UY 'KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC8UE, KC4UE, KC4FR-3, KC4FR-4, KC4HR -1, KC8UY-HA, KC8UX-RHA, and above Konica Minolta Opto (share)) are preferred. The polarizer of the main component of the polarizing plate is a light element that passes only a polarizing surface in a certain direction, and a representative polarizing film which is known now is a polyvinyl alcohol-based polarizing film, which is a polyvinyl alcohol-based film. Those obtained by dyeing with iodine and those dyed with dichroic dyes. The polarizer is formed by forming a film of a polyvinyl alcohol aqueous solution, stretching it by one axis, dyeing it, or dyeing it and then stretching it through one axis, preferably by durability treatment with a boron compound. As the adhesive used for the above-mentioned adhesive layer, it is preferable to use an adhesive for a coating elastic modulus of at least a part of the adhesive layer in a range of a storage elastic modulus of WC of 〇xl〇4Pa to 1·0 XI 09Pa, and a coating adhesive is used. It is preferred to form a hardening type adhesive having a high molecular weight body or a crosslinked structure by various chemical reactions after lamination. Specific examples thereof include a urethane-based pressure-sensitive adhesive, an epoxy-based pressure-sensitive adhesive, a water-based polymer-isocyanate-based pressure-sensitive adhesive, and a thermosetting acrylic adhesive such as a thermosetting amine-based adhesive. An anaerobic adhesive such as an acid ester adhesive, a polyether methacrylate type, an ester type methacrylate type, an oxidized polyether methacrylate, a cyanoacrylate type instant adhesive, an acrylate and an acrylate Oxide type 2-liquid type instant adhesive. -55- 201107133 The above-mentioned adhesive may be one dosage form or a type which is used after mixing two or more agents before use. Further, the above-mentioned adhesive may be a solvent type in which an organic solvent is used as a medium, or may be an emulsified type, a colloidal dispersion type, an aqueous solution type, or the like, or a solventless type, which is a medium containing water as a main component. The concentration of the above-mentioned adhesive liquid can be appropriately determined depending on the film thickness after the adhesion, the coating method, the coating conditions, and the like, and is generally from 1 to 50% by mass. [Liquid crystal display device] When a polarizing plate to which the optical film of the present invention is bonded is incorporated in a liquid crystal display device, a liquid crystal display device having excellent seed identification can be manufactured, and is particularly used for outdoor use such as a large liquid crystal display device or an electronic signboard. A liquid crystal display device for use is preferred. The polarizing plate of the present invention is bonded to a unit cell via the above-mentioned adhesive layer or the like. The polarizing plate according to the present invention can be applied to a reflective type, a transmissive type, a transflective type LCD or a TN type, an STN type, an OCB type, a HAN type, a VA type (PVA type, MVA type), an IPS type (also including an FFS method). LCDs of various driving methods. In particular, in a display device having a large screen of 30 吋 or more, particularly 30 吋 to 54 吋, no whitening or the like around the screen is observed, and the effect can be maintained for a long period of time. Further, there is a color unevenness, flicker, or wavy unevenness, and the effect of not swearing even if the eyes are recognized for a long time" [Embodiment] - 56 - 201107133 [Embodiment] The following examples are given for the present invention. Specifically, the present invention is not limited to this. Example 1 [Production of Optical Film] <Production of Optical Film 1> (Composition of Blending Liquid 1) D i an al BR 8 5 (manufactured by Mi t sub i shi Ray on) 65 parts by mass of acrylic particles (Cl) 5 parts by mass of cellulose ester (cellulose acetate propionate thiol group total degree of substitution 2.75, acetyl group substitution degree 0.19, propyl thiol group substitution degree 2.56, Mw = 200000) 30 parts by mass of dichloromethane 300 40 parts by mass of ethanol The above-mentioned composition was sufficiently dissolved while being heated to prepare a blending liquid. Similarly, the blending liquid 2 was produced in the same manner except that the resin composition was changed as described below. (combination liquid 2 composition)
DianalBR85 (Mitsubishi Rayon (股）製） 37質量份 丙烯酸粒子（C1) 3質量份 纖維素酯（纖維素乙酸酯丙酸酯醯基總取代度2.75、乙[s；j -57- 201107133 醯基取代度0.19、丙醯基取代度2.56、Mw = 200000 ) 6〇質量份 二氯甲烷 300質量份 乙醇 40質量份 (丙烯酸樹脂薄膜的製膜） 將上述製作之摻合液1、2，使用輸送帶流延裝置（參 照圖1 )，在溫度22°C、2m寬下，於不鏽鋼帶支持體上均 勻地流延。在不鏽鋼帶支持體上蒸發溶劑至殘留溶劑量至 100%，以剝離張力160N/m由不鏽鋼帶支持體上剝離。其 次，將摻合液1及2的流延量作適宜控制下，得到成爲所望 層厚之薄膜。將經剝離的薄膜之織物以3 5 °C蒸發溶劑，以 拉幅器於寬方向延伸至1.5倍下，在140 °C的乾燥溫度下進 行乾燥。此時以拉幅器開始延伸時的殘留溶劑量爲1 〇%。 以拉幅器延伸後，在130°C進行5分鐘緩和後，將i〇(TC、 120 °C的乾燥區以多數輥一邊搬送一邊結束乾燥，以 寬度的狹縫，於薄膜兩端施予寬度10mm高度5μπι之壓邊加 工，在初期張力220N/m、終張力ΙΙΟΝ/m下於內徑15.24cm 芯進行捲取，得到本發明之光學薄膜1。 <本發明的光學薄膜2〜13及比較例之光學薄膜丨〜7的製作 > 對於上述光學薄膜1之製作，將丙烯酸樹脂（A)、纖 維素酯樹脂（B )的種類與組成比取代爲表1所記載者以外 -58- 201107133 ，同樣地製作出本發明的光學薄膜2〜13及比較例之光學 薄膜1〜7。丙烯酸樹脂的DianalBR85與丙烯酸粒子（C1) 的比率爲一定。 且，對於本發明的光學薄膜1之製作，將丙烯酸樹脂 改爲旭化成化學（股）製之Delpet80N，將丙烯酸樹脂（A )、纖維素樹脂（B )的組成比取代爲表2所記載以外，同 樣地至做出本發明的光學薄膜14〜20。丙烯酸樹脂的 Delpet80N與丙烯酸粒子（C1)的比率爲一定* 《評估方法》 對於所得之光學薄膜，實施以下評估。 (與偏光子之接著性） 在下述1)〜5)的步驟，貼合偏光子與樹脂薄膜後製 作出偏光薄膜。 1) 將18 cm x5 cm的光學用薄膜的二片b面朝下，配置於玻 璃板上。 2) 將由與樹脂薄膜同尺寸的1軸延伸之聚乙烯基醇染色薄 膜所成之偏光子於固體成分2質量％的聚乙烯基醇接著劑槽 浸漬1〜2秒（偏光子之兩面）。 3 )將附著於上述2 )的偏光子之過剩接著劑輕輕除去，載 持於上述1)之保護薄膜試料上，層合另一片試料1)。 4)以手動輥由以上述3)層合的偏光子與樹脂薄膜之層合 物取出過剩接著劑及氣泡後貼合。手動輥的壓力爲0.2〜[s 3 -59- 201107133 0.3Mpa，速度約2m/min。 5 )將於80°C的乾燥器中以4 )貼合的試料放置2分鐘後使 其乾燥。 <接著性：初期接著> 貼合樹脂薄膜與偏光子後，以手測定剝離性，產生材 料破壞之程度以下述3段階進行評估。 〇：引起材料破壞 △:引起一部份試料破壞，但光學用薄膜與偏光薄膜 間所剝落的面積大 X :光學用薄膜與偏光子之間被剝落 (鉛筆硬度） 對於上述我製作之實施例1〜20及比較例1〜7的各光 學薄膜，使用JIS S 6006所規定的試驗用鉛筆，依據JIS K 5400所規定之鉛筆硬度評估法，使用lkg荷重以各硬度鉛 筆刮傷實施例1〜2 0及比較例1〜7之各光學薄膜表面，測 定鉛筆硬度。本發明的光學薄膜爲，刮傷層2側表面而評 估。所得之結果歸納於下述表1及表2所示。 -60- 201107133 π谳〕 錯震疆度 03 W cs cs ffi <N cs cs OJ K cs K CN κ CN K 03 m CO CO PQ PQ K PQ PQ cs 黏著性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 <] < 〇 X < 〇 〇 〇 〇 _ <N 濉 S -LA ΛΙΠ Π33 m 40% 40% 40% 40% 30% 50% 40% 40% 40% 40% 40% 40% 40% 1 1 1 1 15% 40% 40% PQ 60% 60% 60% 60% 70% 50% 1 60% i 60% 60% 60% 60% 60% 1 60% 1 1 1 1 85% 60% 60% 層厚比率 g cn cn CO cn CO cn iT) cs 1 1 1 1 m cn m 層厚 I CNj uo OO V〇 i〇 i—H CO 寸 o 1 1 1 1 褂 -U dm £H3 m 70% 70% 70% 70% 70% ! 70% 80% 50% 50% 50% 50% 70% 70% Ο 100% 70% 45% 70% 45% 20% 30% 30% 30% 30% 30% 30% 20% 50% 50% 50% 50% 30% 30% 100% o 30% i 55% 30% 55% 80% 1 ii 層厚比率 g ON oo oo OO oo OO oo OO oo OO oo OO oo VO 〇\ wn in ο ο o o 〇 o 〇 o OO oo OO OO OO oo 層厚 1—^ I 〇〇 cn cs cn ν〇 CO m cn vn cn V) cn m cn ON VO ο o o o ΙΟ CO VO CO CO 全層厚 _ o o o o o 〇 o o § o Ο ο o o o 〇 〇 o 丨本發明1丨 CM 餾 •14 本發明3 1本發明4 1 本發明5 1本發明6 本錢明7 本發明8 本發明9 〇 s 餾 锊 本發明11 本發明12 本發明13 t < 鎰 Jjj a_\ 比較例2 比較例3 比較例4 鎰 SJ 比較例6 丨比較例7 1 (v)ss癍氍联E: (V) siii . s -61 - 201107133 mm Ητΐΐ ffirrl ϊργ διπτ CS) cs <N m <N K CN κ CO ffi cn a W 〇 〇 〇 〇 〇 〇 〇 跞 Μ <fg o o Ο Ο ο 〇 JJ XJDI Dm m 〇=a m _ 8赇岜 s s o S § s s C<J 濉 M m 層厚 比率 [%] un CO ν〇 VO 14百 ，彐 m s m ggg o o o 褂 AJ IE m trc3 m em 繫 搬 _ 層厚 比率 [%] § § oo oo V〇 ON v〇 ON 層厚 _ oo cn OS E〇 VO tt ^ 幽i o o ο o S § v〇 r-j oo On £ s £ s s 餾 鹩 鹩 鹬 饀 鹬 餾 恃 柃 柃 柃 -62- 201107133 如表1及表2所記載，得知本發明的光學薄膜爲可得到 硬度高、與偏光子之接著性優良、厚度方向之樹脂組成均 勻下無法實現的特性 實施例2 對於實施例1之摻合液2的調整，如表3所示，添加追 加化合物以外，同樣地製作出光學薄膜21〜28。表3中之 P-1、P-2爲如特開平9-203 8 1 0號公報的實施例所記載之防 帶電劑。將製作之光學薄膜除進行實施例1的彎曲評估、 鉛筆硬度評估以外，亦實施下述垃圾附著測試。將所得之 結果歸納如下述表3所示。 (垃圾附著測試） 於香菸灰上將薄膜a面側以高度lcm接近10秒後觀察垃 圾之附著。 〇：完全未見到垃圾附著 △:確認稍有垃圾附著 x :確認有顯著的垃圾附著 -63- 201107133 〔e撇〕 垃圾 附著 〇 〇 〇 〇 〇 〇 〇 〇 鉛筆硬 度單體 w cs <N CO K CO CN 黏著 性 〇 〇 〇 〇 〇 〇 〇 〇 第2層 追加化合物 iW v〇 o r H CN) * H OJ 1 i o CO o 種類 2 *—H ώ cs AEROSIL200V AEROSIL 200V AEROSIL 972V AEROSIL 972Y 褂 JJ3 I 40% I | 40% | | 40% 1 | 40% 1 | 40% | I 40% I | 40% | | 40% 1 am DXJ g 60% i 60% | 60% | 60% | 60% 60% | 60% | 60% 1 層厚 比率 [%] uo ί〇 i〇 V〇 VO 層厚 _ 03 CS CO CO CNJ CNJ CM CvJ 欄旨比率 70% | | 70% 1 | 70% 1 70% | 70% | 70% | 70% | 70% g 30% | | 30% 1 | 30% 1 | 30% | 30% | 30% | 30% | | 30% | m 層厚 比率 [%] v〇 ON ON v〇 ON a\ ON a\ a\ 層厚 [μπι] 〇〇 CO OO cn OO cn OO CO OO m OO cn OO cn OO CO 全層厚 [μιη] o o 〇 o 〇 〇 o o 本發明21 本發明22 本發明23 本發明24 本發明25 本發明26 本發明27 本發明28 1 φ_»:¥ III - -64- 201107133 如表3所記載得知，使用防帶電劑或拋光劑之本發明 的光學薄膜爲除具有硬度高，與偏光子之接著性優良的特 性以外，亦具有垃圾附著性優良的特徵之光學薄膜。 實施例3 對於實施例1的光學薄膜1之製作，僅薄膜的兩端部部 分之比較例1的摻合以單一層進行流延，變更拉幅器部分 之薄膜的把持方法以外，同樣地製作出光學薄膜。本發明 的光學薄膜30爲藉由金屬嵌段將薄膜端部自上下夾持下把 持的夾子方式、光學薄膜31爲於薄膜端部刺上針，藉由貫 通的針把持薄膜而以拉幅器進行延伸。這些薄膜之搬送性 如以下表4所示。 (搬送性測試） 將拉幅器內部溫度各設定爲100°C、130°C、150°c，以 延伸率1.5倍搬運薄膜，觀察薄膜。 〇：無薄膜破裂、變形而可搬送 △:雖無薄膜的破裂，但產生變形 X:有薄膜的破裂、變形故無法搬送 〔表4〕 薄膜寬方向的構成 拉幅器 保持方法 薄膜搬送 0 〜100[mm] 100-1400[nun] 1400〜1500[mm] 本發明30 比較例1之構成 實施例1之構成 比較例1之構成 夾子 〇 本發明31 比較例1之構成 實施例1之構成 比較例1之構成 針 〇 -65- 201107133 如表4所記載之本發明的光學薄膜，以拉幅器之把持 手段藉由夾子、針雙方而顯示安定搬送性。 實施例4 (作爲液晶顯不裝置之特性評估） <偏光板之製作> 將各光學薄膜作爲偏光板保護薄膜的偏光板如以下而 製作。 將厚度120μηι的長形輥聚乙烯基醇薄膜，浸漬於含有 碘沃素1質量份、硼酸4質量份之水溶液100質量份中，在 5 〇°C於搬送方向延伸5倍，製作出偏光膜。 其次，於該偏光膜之單面上使用丙烯酸接著劑，於實 施例1所製作之光學薄膜1施予電暈處理後貼合。 進一步於偏光膜的另一面上貼合經驗音化處理的相位 差薄膜之Konica Minolta Opto公司製KC8UX，經乾燥後製 做出偏光板。同樣地，使用本發明的光學薄膜2〜13、比 較例之光學薄膜1〜7製作出偏光板^ 使用本發明的光學薄膜之偏光板具有優良薄膜切斷性 ，亦容易加工。 <液晶顯示裝置之製作> 使用上述製作之各偏光板，進行光學薄膜的顯示特性 評估。 -66 - 201107133 剝開東芝股份有限公司製之32吋電視32H2000的預先 貼合的兩面偏光板，各KC 8 UX不會成爲晶胞之玻璃面側下 ，將上述製作之偏光板，且於與預先貼合的偏光板爲同一 方向下，面向吸收軸而貼合，製作出各液晶顯示裝置。 (顯示品質評估） 有關上述製作之液晶顯示裝置，顯示各種畫像，評估 在2 3 °C，5 5 % RH的環境下的顯示影像品質。 〇：顯示良好 △:顯示的影像欠缺均勻性，見到不均 X : —部份產生極端顏色變化 (移色器：作爲偏光板之耐熱•耐濕性之評估） 有關上述製作之液晶顯示裝置，在23 °C且5 5%RH之環 境下將顯示器顯示黑影像，由斜度45°之角度進行觀察。 繼續將上述偏光板在60°C且90%RH下進行1 000小時處理者 進行相同觀察，將色變化以下述基準進行評估。 〇：完全無顏色變化 △:稍確認到顏色變化 X :顏色變化大 -67- 201107133Dianal BR85 (manufactured by Mitsubishi Rayon Co., Ltd.) 37 parts by mass of acrylic particles (C1) 3 parts by mass of cellulose ester (cellulose acetate propionate thiol group total substitution degree 2.75, B [s; j -57- 201107133 fluorenyl group) The degree of substitution is 0.19, the degree of substitution of propyl thiol is 2.56, Mw = 200000) 6 parts by mass of dichloromethane, 300 parts by mass of ethanol, 40 parts by mass (film formation of acrylic resin film), and the blending liquids 1 and 2 prepared above are used for transport. The tape casting apparatus (refer to Fig. 1) was uniformly cast on the stainless steel belt support at a temperature of 22 ° C and a width of 2 m. The solvent was evaporated on a stainless steel belt support to a residual solvent amount of 100%, and peeled off from the stainless steel belt support at a peeling tension of 160 N/m. Next, the casting amount of the blending liquids 1 and 2 was appropriately controlled to obtain a film having a desired layer thickness. The woven fabric of the peeled film was evaporated at 35 ° C, extended to 1.5 times in the width direction with a tenter, and dried at a drying temperature of 140 °C. At this time, the amount of residual solvent when the tenter starts to extend is 1% by weight. After stretching with a tenter and then relaxing at 130 ° C for 5 minutes, the drying zone of TC and 120 ° C was dried while being conveyed by a plurality of rolls, and the slit was applied at both ends of the film by a slit having a width. The film was wound at a height of 10 mm and a height of 5 μm, and was wound up at a core tension of 15.24 cm at an initial tension of 220 N/m and a final tension of ΙΙΟΝ/m to obtain an optical film 1 of the present invention. <Optical film 2 to 13 of the present invention. And the production of the optical film 丨7 of the comparative example. For the production of the optical film 1, the type and composition ratio of the acrylic resin (A) and the cellulose ester resin (B) were replaced by those other than those described in Table 1. - 201107133, the optical films 2 to 13 of the present invention and the optical films 1 to 7 of the comparative examples were produced in the same manner. The ratio of the Dianal BR85 of the acrylic resin to the acrylic particles (C1) was constant. Moreover, the optical film 1 of the present invention was used. In the production, the acrylic resin was changed to Delpet 80N manufactured by Asahi Kasei Chemical Co., Ltd., and the composition ratio of the acrylic resin (A) and the cellulose resin (B) was replaced by the composition of Table 2, and the optical film of the present invention was similarly prepared. 14~20. The ratio of Delpet 80N to acrylic acid particles (C1) of the enoic acid resin is constant* [Evaluation method] The following evaluations were carried out on the obtained optical film. (Adhesion to polarizers) In the following steps 1) to 5), lamination After the polarizer and the resin film, a polarizing film is produced. 1) Place the 18 cm x 5 cm optical film with the b side facing down on the glass plate. 2) A polarizer made of a polyvinyl alcohol-dyed film extending in the same direction as the resin film was immersed in a polyvinyl alcohol adhesive bath having a solid content of 2% by mass for 1 to 2 seconds (both sides of the polarizer). 3) The excess adhesive attached to the polarizer of the above 2) was lightly removed, and it was carried on the protective film sample of the above 1), and another sample 1) was laminated. 4) The excess adhesive and air bubbles were taken out from the laminate of the polarizer and the resin film laminated in the above 3) by a hand roll, and then bonded. The pressure of the manual roll is 0.2~[s 3 -59- 201107133 0.3Mpa, and the speed is about 2m/min. 5) The sample to which 4) was attached in a desiccator at 80 ° C was allowed to stand for 2 minutes and then dried. <Adhesiveness: Initially followed by > After the resin film and the polarizer were bonded, the peeling property was measured by hand, and the degree of material damage was evaluated in the following three steps. 〇: causing material damage △: causing a part of the sample to be broken, but the area between the optical film and the polarizing film is large. X: peeling between the optical film and the polarizer (pencil hardness) For the above-described example In each of the optical films of 1 to 20 and Comparative Examples 1 to 7, the test pencil specified in JIS S 6006 was used, and according to the pencil hardness evaluation method prescribed in JIS K 5400, the pencil was scratched with each hardness using the lkg load. The surface hardness of each optical film of 20 and Comparative Examples 1 to 7 was measured. The optical film of the present invention was evaluated by scratching the side surface of the layer 2. The results obtained are summarized in Tables 1 and 2 below. -60- 201107133 π谳] Error Earthquake 03 W cs cs ffi <N cs cs OJ K cs K CN κ CN K 03 m CO CO PQ PQ K PQ PQ cs Adhesive 〇〇〇〇〇〇〇〇〇 〇〇<] < 〇X < 〇〇〇〇_ <N 濉S -LA ΛΙΠ Π33 m 40% 40% 40% 40% 30% 50% 40% 40% 40% 40% 40% 40% 40% 1 1 1 1 15% 40% 40% PQ 60% 60% 60% 60% 70% 50% 1 60% i 60% 60% 60% 60% 60% 1 60% 1 1 1 1 85% 60% 60% layer thickness ratio g cn cn CO cn CO cn iT) cs 1 1 1 1 m cn m layer thickness I CNj uo OO V〇i〇i—H CO inch o 1 1 1 1 褂-U dm £H3 m 70 % 70% 70% 70% 70% ! 70% 80% 50% 50% 50% 50% 70% 70% Ο 100% 70% 45% 70% 45% 20% 30% 30% 30% 30% 30% 30 % 20% 50% 50% 50% 50% 30% 30% 100% o 30% i 55% 30% 55% 80% 1 ii Layer thickness ratio g ON oo oo OO oo OO oo OO oo OO oo OO oo VO 〇 \ wn in ο ο oo oo 〇o 〇o OO oo OO OO OO oo layer thickness 1—^ I 〇〇cn cs cn ν〇CO m cn vn cn V) cn m cn ON VO ο ooo ΙΟ CO VO CO CO full layer Thick _ ooooo 〇oo § o Ο ο ooo 〇〇o 丨 the invention 1丨CM Distillation•14 Invention 3 1 Invention 4 1 Invention 5 1 invention 6 Ben Qian Ming 7 invention 8 invention 9 〇s distillate invention 11 invention 12 invention 13 t < 镒Jjj a_\ comparative example 2 Comparative Example 3 Comparative Example 4 镒SJ Comparative Example 6 丨Comparative Example 7 1 (v) ss E E: (V) siii . s -61 - 201107133 mm Ητΐΐ ffirrl ϊργ διπτ CS) cs <N m < NK CN κ CO ffi cn a W 〇〇〇〇〇〇〇跞Μ <fg oo Ο Ο ο 〇JJ XJDI Dm m 〇=am _ 8赇岜sso S § ss C<J 濉M m layer thickness ratio [ %] un CO ν〇VO 14 hundred, 彐msm ggg ooo 褂AJ IE m trc3 m em system _ layer thickness ratio [%] § § oo oo V〇ON v〇ON layer thickness _ oo cn OS E〇VO tt ^ ioioo ο o S § v〇rj oo On £ s £ ss Distillate 恃柃柃柃-62- 201107133 As shown in Table 1 and Table 2, the present invention is known The optical film has high hardness, excellent adhesion to a polarizer, and a resin composition in a thickness direction is not uniform. Example 2 The adjustment of the blending liquid 2 of Example 1 is as shown in Table 3, Optical films 21 to 28 were produced in the same manner as the additional compounds. P-1 and P-2 in Table 3 are antistatic agents described in the examples of JP-A-9-203810. The following optical adhesion test was carried out in addition to the bending evaluation and pencil hardness evaluation of Example 1 of the produced optical film. The results obtained are summarized in Table 3 below. (Garbage adhesion test) The adhesion of the garbage was observed by placing the side of the film a on the cigarette ash at a height of lcm for 10 seconds. 〇: No rubbish adhesion was observed at all △: Confirm that there is a little rubbish adhesion x: Confirm that there is significant rubbish adhesion -63- 201107133 〔e撇〕 Garbage attachment 〇〇〇〇〇〇〇〇 pencil hardness monomer w cs <N CO K CO CN Adhesive 〇〇〇〇〇〇〇〇 Layer 2 additional compound iW v〇or H CN) * H OJ 1 io CO o Species 2 *—H ώ cs AEROSIL200V AEROSIL 200V AEROSIL 972V AEROSIL 972Y 褂JJ3 I 40% I | 40% | | 40% 1 | 40% 1 | 40% | I 40% I | 40% | | 40% 1 am DXJ g 60% i 60% | 60% | 60% | 60% 60% 60% | 60% 1 layer thickness ratio [%] uo ί〇i〇V〇VO layer thickness _ 03 CS CO CO CNJ CNJ CM CvJ column ratio 70% | | 70% 1 | 70% 1 70% | 70 % | 70% | 70% | 70% g 30% | | 30% 1 | 30% 1 | 30% | 30% | 30% | 30% | | 30% | m Layer thickness ratio [%] v〇ON ON v〇ON a\ ON a\ a\ layer thickness [μπι] 〇〇CO OO cn OO cn OO CO OO m OO cn OO cn OO CO full layer thickness [μιη] oo 〇o 〇〇oo invention 21 invention 22 Invention 23 invention 24 invention 25 invention 26 invention 27 invention 28 1 φ_»: ¥ III - -64- 201107133 As shown in Table 3, the optical film of the present invention using an antistatic agent or a polishing agent has a property of high hardness and excellent adhesion to a polarizer, and also has garbage adhesion. An excellent optical film. [Example 3] In the production of the optical film 1 of Example 1, only the blending of Comparative Example 1 of the both end portions of the film was carried out by casting in a single layer, and the method of changing the film of the tenter portion was changed, and the same was carried out. An optical film is produced. The optical film 30 of the present invention is a clip method in which the end portion of the film is gripped by the metal block by the upper and lower sides, and the optical film 31 is used to puncture the needle at the end of the film, and the tenter is held by the penetrating needle. Extend. The transportability of these films is shown in Table 4 below. (Transportability test) The internal temperature of the tenter was set to 100 ° C, 130 ° C, and 150 ° C, and the film was conveyed at an elongation of 1.5 times to observe the film. 〇: No film rupture, deformation, and transportable △: Although there is no film rupture, deformation occurs. X: The film is broken and deformed, so it cannot be transported. [Table 4] The film width maintaining direction of the film holder is maintained. 100 [mm] 100-1400 [nun] 1400 to 1500 [mm] The present invention 30 Comparative Example 1 Configuration Example 1 Configuration Example 1 Comparative Example 1 Comparative Example 1 Comparative Example 1 Configuration Example 1 Comparison In the optical film of the present invention as described in Table 4, the image holding means of the tenter shows the stable conveyance by both the clip and the needle. Example 4 (Evaluation of characteristics of liquid crystal display device) <Production of polarizing plate> A polarizing plate in which each optical film was used as a polarizing plate protective film was produced as follows. The film of the long-form roll polyvinyl alcohol having a thickness of 120 μm was immersed in 100 parts by mass of an aqueous solution containing 1 part by mass of iodoporin and 4 parts by mass of boric acid, and was extended 5 times in the transport direction at 5 ° C to prepare a polarizing film. Next, an acrylic adhesive was applied to one surface of the polarizing film, and the optical film 1 produced in Example 1 was subjected to corona treatment and then bonded. Further, KC8UX, manufactured by Konica Minolta Opto Co., Ltd., which was subjected to an empirically processed phase difference film, was attached to the other side of the polarizing film, and dried to prepare a polarizing plate. Similarly, the polarizing plates are produced using the optical films 2 to 13 of the present invention and the optical films 1 to 7 of the comparative examples. The polarizing plate using the optical film of the present invention has excellent film cutting properties and is easy to process. <Production of Liquid Crystal Display Device> The display characteristics of the optical film were evaluated using the polarizing plates produced as described above. -66 - 201107133 Stripped the pre-bonded two-sided polarizing plate of 32-inch TV 32H2000 made by Toshiba Co., Ltd., each KC 8 UX will not become the glass surface side of the unit cell, and the polarizing plate produced above will be The polarizing plates which are bonded in advance are bonded to the absorption axis in the same direction, and each liquid crystal display device is produced. (Display quality evaluation) The liquid crystal display device produced as described above displays various images and evaluates the image quality in an environment of 23 ° C and 5 5 % RH. 〇: Good display △: The displayed image lacks uniformity, and unevenness is seen X: - Partially produces extreme color change (Color shifter: Evaluation of heat resistance and moisture resistance as a polarizing plate) Related to the above-mentioned liquid crystal display device The black image is displayed on the display at 23 ° C and 5 5% RH, and is observed at an angle of 45°. The same observation was continued for the above-mentioned polarizing plate to be treated at 60 ° C and 90% RH for 1 000 hours, and the color change was evaluated on the basis of the following criteria. 〇: No color change at all △: A slight color change is confirmed X: The color change is large -67- 201107133
〔表5〕 表不品質 移色 本發明1 〇 〇 本發明2 〇 〇 本發明3 〇 〇 本發明4 〇 〇 本發明5 〇 〇 本發明6 〇 〇 本發明7 〇 〇 本發明8 〇 〇 本發明9 〇 〇 本發明10 〇 〇 本發明11 〇 〇 本發明12 〇 〇 本發明13 〇 〇 比較例1 Δ X 比較例2 〇 X 比較例3 〇 X 比較例4 Δ Δ 比較例5 X Δ 比較例6 Δ Δ 比較例7 Δ X 使用本發明的光學薄膜所製作之偏光板、液晶顯示裝 置爲顯示優良顯示品質及移色之特性者。 【圖式簡單說明】 〔圖1〕表示可將複數摻合於同時進行流延之樹脂薄 膜製造裝置的槪略圖 〔圖2〕共流延用塑模之截面圖 -68- 201107133 〔圖3〕溶液流延製膜方法之摻合調製步驟、流延步 驟及乾燥步驟的一例以模型方式表示的圖 【主要元件符號說明】 1 a〜1 d :摻合液桶 2a〜2c :幫浦 3 :流延用塑模 4 :滾筒 5 :流延輸送帶 6 :輥子 7 :樹脂薄膜 10、11a、lib、12:塑模狹縫 lx :溶解釜 3 X ' 6x ' 12 X ' 15 X ：過濃器 4 X、1 3 X :擠壓桶 5x、14x :送液幫浦 8x、16x :導管 1 〇χ :紫外線吸收劑裝入釜 2 0 :合流管 2 1 :混合機 3 0 :塑模 31 :金屬支持體 3 2 :織物 3 3 :剝離位置 [S ] -69- 201107133 3 4 :拉幅器裝置 3 5 :輥乾燥裝置 4 1 :粒子裝入釜 42 :擠壓桶 43 :幫浦 44 :過濾器[Table 5] Table of quality shifting The present invention 1 〇〇 The present invention 2 〇〇 The present invention 3 〇〇 The present invention 4 〇〇 The present invention 5 〇〇 The present invention 6 〇〇 The present invention 7 〇〇 The present invention 8 〇〇 Invention 9 〇〇 the present invention 10 〇〇 the present invention 11 〇〇 the present invention 12 〇〇 the present invention 13 〇〇 comparative example 1 Δ X Comparative Example 2 〇 X Comparative Example 3 〇 X Comparative Example 4 Δ Δ Comparative Example 5 X Δ Comparison Example 6 Δ Δ Comparative Example 7 Δ X The polarizing plate and the liquid crystal display device produced by using the optical film of the present invention are those which exhibit excellent display quality and color shift characteristics. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] shows a schematic view of a resin film manufacturing apparatus capable of blending plural numbers in a simultaneous casting process (Fig. 2) a cross-sectional view of a mold for co-casting-68-201107133 [Fig. 3] An example of a blending preparation step, a casting step, and a drying step of the solution casting film forming method is shown in a model manner. [Main component symbol description] 1 a to 1 d: blending liquid tank 2a to 2c: pump 3: Casting mold 4: Roller 5: Casting conveyor belt 6: Roller 7: Resin film 10, 11a, lib, 12: Mold slit lx: Dissolving kettle 3 X ' 6x ' 12 X ' 15 X : Too thick 4 X, 1 3 X : Extrusion barrel 5x, 14x: liquid supply pump 8x, 16x: conduit 1 〇χ : UV absorber is charged into the kettle 2 0 : Confluence tube 2 1 : Mixer 3 0 : Mold 31 : metal support 3 2 : fabric 3 3 : peeling position [S ] -69 - 201107133 3 4 : tenter device 3 5 : roll drying device 4 1 : particle charging kettle 42 : squeeze barrel 43 : pump 44 :filter