TW201211575A

TW201211575A - Optical compensative sheet, polar plate and liquid crystal display device

Info

Publication number: TW201211575A
Application number: TW100118623A
Authority: TW
Inventors: Yoji Ito; Eiichi Kato
Original assignee: Fujifilm Corp
Priority date: 2003-06-25
Filing date: 2004-06-24
Publication date: 2012-03-16
Also published as: CN1576888A; CN100414320C; KR20050001402A; TWI352820B; TW200508644A

Abstract

The invention provides an optical compensative sheet for modifying display quality of a liquid crystal display device. An optical compensative sheet using a cellulose acylate, of which the in-plane retardation value (Re) is 0 nm ≤ Re < 20 nm, the thickness (d) is 10 μ m < d < 85 μ m, the average ((Vmin + Vmax)/2) of minimum value (Vmin) and maximum value (Vmax) of the sonic velocity measured in plane of film is 2.2 km/sec < (Vmin + Vmax)/2 < 2.5 km/sec, and the proportion (Vmin / Vmax) of minimum value of the sonic velocity measured in plane of film as compared to the maximum value is 1.01 < Vmin/Vmax/2 < 1.02. An optical compensative sheet made by laminating an aligned membrane and an optically anisotropic layer in this order onto a transparent support comprising at least a micro particle having an average primary particle diameter of less than 80 nm and thickness of more than 20 μ m but less than 80 μ m, wherein the arithmetic average roughness (Ra) of surface unevenness related to a surface at the aligned membrane side of transparent support is more than 0.0002 μ m but less than 0.1 μ m measured according to JIS B0601-1994, the ten-points average roughness (Rz) is more than 0.0002 μ m but less than 0.3 μ m, as well as the maximum height (Ry) is more than 0.002 μ m but less than 0.5 μ m, Re value of transparent support is more than 2 nm but less than 200 nm and the Rth value is more than 50 nm but less than 400nm. An optical compensative sheet using a cellulose acylate film comprising a cellulose acylate film having an acylation index of 59.0 to 61.5%, of which the surface is treated by soapnification and contact angle with water of the surface is more than 30 DEG but less than 70 DEG.

Description

201211575 六、發明說明：【發明所屬之技術領域】本發明係關於一種改良液晶顯示裝置之視野角度的光學補償片，及使用它的偏光板及液晶顯示裝置。【先前技術】通常，液晶顯示裝置係由液晶單元、偏光板與光學補償片（相位差板）構成的。透過型液晶顯示裝置係將二片偏光板裝設於液晶單元之兩側，一片或二片之光學補償片係配置於液晶單元與偏光板之間。反射型液晶顯示裝置係依序配置反射板、液晶單元、一片光學補償片，然後，一片偏光板》一般例之液晶單元係組合由棒狀液晶性分子、爲了封合此液晶性分子的二片基板以及爲了將電壓施加於棒狀液晶性分子的電極層所構成的。由於棒狀液晶性分子的配向狀態不同，針對液晶單元，已有人提出 TN ( Twisted Nematic) ' ISP( In-Plane Switching) ' FLC( Ferroelectric Liquid Crystal) ' OCB ( Optically Compensatory Bend) STN( Super Twisted Nematic) ' VA( Vertically Aligned)；針對反射型，也有人提出如HAN( Hybrid Aligned Nematic) 之各種顯示模式。一般而言，偏光板係由偏光膜與透明保護膜構成的，通常，此偏光膜係藉由使聚乙烯醇浸漬於碘或二色性染料之水溶液之中，進一步進行此薄膜之單軸拉伸而得到。將二片透明保護膜黏合於此偏光膜之兩側而構成。光學補償片係爲了解決影像著色、擴大視野角度而適用 -4- 201211575 於各種液晶顯示裝置。若使用光學補償片，雖然有液晶顯示裝置變厚的問題，已有人提出（例如，參照專利文獻1 )偏光板一側之透明保護膜藉由使用具機能性之偏光板（橢圓偏光板）作爲光學補償片（相位差薄膜），不會增厚液晶顯示裝置且改善顯示品質（例如，提高正面對比）。要求液晶顯示裝置之光學補償片（相位差薄膜）要有光學異方向性（高的遲滯値）。因而，光學補償片通常使用如聚碳酸酯薄膜或聚颯薄膜之遲滯値高的合成聚合物薄膜。不同於由合成聚合物薄膜構成的光學補償片，有人提出於透明載體上設置由碟狀液晶性分子形成光學異方向性的光學補償片（例如，參照專利文獻2〜1 1 )。所要求之高相位差値係利用光學異方向性而達成的。針對於此’由於要求透明載體要有高的光學等方向性（低的相位差値）’通常使用纖維素醋酸酯薄膜。如上所述之光學材料的技術領域上，一般性原則係若要求聚合物薄膜中要有光學異方向性（高的遲滯値）之情形，使用合成聚合物薄膜；若要求要有光學各向同性（低的遲滯値）之情形，使用纖維素醋酸酯薄膜。於專利文獻1 2中，推翻了習知一般性原則，揭示一種能夠用於要求要有光學異方向性之用途而具有高遲滞値之纖維素醋酸酯薄膜。並揭示藉由將此纖維素醋酸酯薄膜作爲偏光膜之保護膜而插入該偏光膜與液晶單元之間，可以得到顯示品質高的液晶顯示裝置。 201211575 光學補償片具有受熱歪斜、容易發生相位差與耐久性之問題。由於所發生的相位差，一旦液晶顯示裝置發生外圍格子狀之漏光（透過率之上升），液晶顯示裝置之顯示品質將降低。爲了解決因歪斜所造成的相位差發生之問題，有人提出將透明載體上塗設由碟狀化合物形成之光學異方向層的光學補償片作爲偏光板保護膜使用（例如，參照專利文獻12 與 13 )。通常，光學補償片係將配向膜設置於透明載體上，或是直接於其上進行平磨處理之後，進行含有液晶性化合物之塗布液的塗布而設置光學異方向層，作成液晶性化合物單一區域之後，經由光聚合等，將配向予以固定等複雜之冗長製程而製得。於經歷此等製程而以寬幅之長型尺狀輥輪形態進行製作時，透明載體本身之光學異方向性等的光學特性爲均勻的，塗布於載體上之塗布膜的面狀並無不均勻等，對於影像顯示之均勻性爲重要的。針對於此，有人提出可以作成寬幅的輥輪狀態，將其整面作成均句的光學特性，針對改良視野角度之偏異，抑制載體遲相軸與薄膜拉伸方向之軸偏移角度（專利文獻14等），或是規定遲相軸角度之標準偏差値（專利文獻15等）等方法。最近，液晶顯示裝置正急速朝大型化與高精細化發展。藉由液晶顯示裝置之大型化，習用技術應解決的問題再度明顯浮現。例如，將習知光學補償片用於保護膜的偏光板後，將其安裝於由17吋以上之大型面板構成的液晶顯示裝置，因熱歪斜所造成的漏光將再度被確認。因此，期望能 -6- 201211575 有一種光學補償片，即使增大畫面之尺寸，也無面內視野角度等顯示特性之偏異，具有更優異的辨識性。報告中指出（例如，參照專利文獻16)，漏光之問題可以藉由薄化光學補償片之透明載體的厚度而加以解決。強烈期望透明載體之薄膜化係爲了輕量化以及因應於因生產性提高而導致的廉價化之要求，但是因薄膜化反而降低了強度，用於大型液晶顯示裝置之情形等，尤其實用上便發生了問題。利用習知所提出之方法仍未能完全解決如此之問題，雖然強烈期望提高載體之強度，若單純提高載體之強度，則將產生光學特性變差，辨識性降低之問題。另外，對於由20吋以上之大型面板構成的液晶顯示裝置，確認問題在於習用技術完全未曾探討過。進一步再確認因熱歪斜所產生的光。爲了解決因熱歪斜所發生的問題，對於光學補償片不僅要求液晶單元發揮光學補償的機能，也要求對於使用環境之變化要有優異的耐久性。【專利文獻1】日本公開專利第平1 -6 8 940號公報【專利文獻2】日本公開專利第平3 _ 9 3 2 5號公報【專利文獻3】日本公開專利第平6-148429號公報【專利文獻4】日本公開專利第平8-505206號公報【專利文獻5】日本公開專利第平9-26572號公報【專利文獻6】日本專利申請說明書第264〇〇83號公報 (歐洲專利申請公開說明書第646820號）【專利文獻7】日本專利申請說明書第2587398號公報 (西德專利申請公開說明書第19519928號、美國專利申請 201211575 說明書第5583679號）【專利文獻6】日本專利申請說明書第3 1 1 8 1 9 7號公報 (美國專利申請說明書第5 8 0 5 2 5 3號、歐洲專利申請公開說明書第7 746 8 3號）【專利文獻8】國際專利公開第96/3 7 8 04號冊子（曰本公開專利第平8-327822號公報、歐洲專利申請公開說明書第 07833128號、美國專利申請說明書第6124913號）【專利文獻9】國際專利公開第96/3 1 793號冊子【專利文獻10】日本公開專利第平11-316378號公報 (美國專利申請說明書第6064457號）【專利文獻1 1】日本公開專利第平9-21914號公報【專利文獻 12】歐洲專利申請公開說明書第 0911656A2 號【專利文獻1 3】日本公開專利第平7 -1 9 1 2 1 7號公報【專利文獻14】日本公開專利第2003-66230號公報【專利文獻1 5】日本公開專利第2 0 0 3 - 2 2 9 4 3號公報【專利文獻16】日本公開專利第2002-169023號公報【發明內容】發明所欲解決之枝術問顆本發明之目的在於藉由使用光學補償片而進行液晶單元的光學性補償。本發明之另一目的在於藉由將光學補償片配置於偏光膜之單側，再將它用於液晶顯示裝置，不發生如漏光之問題，改善了液晶顯示裝置之顯示品質。再者’本發明之另一目的在於不增加偏光板構造要件的 201211575 數目，而對偏光板追加光學補償機能。本發明之另一目的在於提供一種光學補償片’即使作成大畫面尺寸，不僅層薄、量輕’薄膜之力學特性也足夠，辨識性優異，並且也無視野角度擴大特性偏異之優點。另外，本發明之另一目的在於提供一種光學補償片，即使製成寬幅之長型尺狀輥輪形態之情形’也爲無視野角度擴大特性偏異的良好生產性。再者，本發明之另一目的在於提供一種辨識性優異的偏光板與液晶顯示裝置，使用層薄、量輕，並且無視野角度擴大特性偏異的優質光學補償片。本發明之另一目的在於提供一種光學補償片，將纖維素醋酸酯薄膜作爲構造要件，能夠作爲偏光板之保護膜使用，並能夠不增加偏光板上之構造要件數目，而對偏光板追加光學補償機能。本發明之另一目的在於提供一種偏光板，該光學補償片作爲保護膜使用，於偏光板之加工步驟，生產性不會降低。本發明之另一目的在於提供一種液晶顯示裝置，設置該偏光板，進行液晶單元之光學性補償。解決問顆之技術手段本發明提供下列之光學補償片、偏光板、液晶顯示裝置以及纖維素醯化物薄膜的製造方法。 (1 ) 一種光學補償片（第1態樣），係由纖維素醯化物薄膜構成的光學補償片，其特徵爲：纖維素醯化物薄膜之 (Ο面內遲滯値（Re)爲〇nmSRe<2 Onm ; 201211575 (ii) 厚度（d)爲 l〇vm<d<85//m; (iii )薄膜面內所測定的音速之最小値（Vmin )與最大値（Vmax)之平均（（Vmin + Vmax) /2)爲 2.2km/sec<Vmin + Vmax) /2<2.5km/sec ;以及 (iv )薄膜面內所測定的音速之最大値與最小値之比値 (Vmax/ Vmin)爲 1.01<Vmax/ Vmin<1.12。面內遲滯値（Re )係以下式（I )予以定義》 (I) R e = ( η X — n y ) x d 式中，nx係纖維素醯化物薄膜面內之遲相軸方向的折射率；ny係纖維素醯化物薄膜面內之進相軸方向的折射率；而且，d係纖維素醯化物薄膜之厚度（單位：nm)。還有，無特別定義之情形，測定所用之光的波長爲5 5 Onm。另外，於本專利說明書中，「遲相軸（slow axis )」意指折射率爲最大之方向，「進相軸（fast axis)」意指折射率爲最小之方向。用於本發明第1態樣之纖維素醯化物薄膜面內遲滯値 (Re)滿足下式（i)。 (i ) 0nm<Re<2 Onm 用於本發明第1態樣之纖維素醯化物薄膜的厚度（d) 滿足下式（Π)。 (i i ) 10// m ( = 1000 Onm) <d<85/z m ( = 85000nm) 用於本發明第1態樣之纖維素醯化物薄膜之薄膜面內所測定的音速之最小値（Vmin )與最大値（Vmax )之平均 ((Vmin+Vmax) /2)滿足下式（iii)。 (iii) 2.2km/sec< ( Vmin+ Vmax) /2<2.5km/sec -10- 201211575 式中’ Vmin係於纖維素醯化物薄膜面內，音速爲最小之方向的音速；Vmax係於纖維素醯化物薄膜面內，音速爲最大之方向的音速。還有，無特別定義之情形，使用ΙΟΚΗζ 至100MHz範圍之數個頻率而進行測定。用於本發明之纖維素醯化物薄膜，於薄膜面內所測定的音速之最大値（Vmax)與最小値（Vmin)之比値（Vmax/ Vmin )滿足下式（iv )。 (iv ) 1.0 1 <Vmax/ Vmin< 1 . 1 2。式中，Vmin係於纖維素醯化物薄膜面內，音速爲最小之方向的音速；Vmax係於纖維素醯化物薄膜面內，音速爲最大之方向的音速。 (2 ) —種光學補償片（第2態樣），係由纖維素醯化物薄膜與光學異方向層所構成的光學補償片，而該光學異方向層係由液晶性化合物構成的，其特徵爲：纖維素醯化物薄膜之 (i) 面內遲滯値（Re)爲 0nm<Re<20nm; (ii) 厚度（d)爲 l〇//m<d<85//m; (Ui )薄膜面內所測定的音速之最小値（Vmin)與最大値（\^!11&乂）之平均（（\^0^11+¥1113\)/2)爲2.21(111/560<\^111111 + Vmax) /2<2.5km/sec;以及 (iv )薄膜面內所測定的音速之最大値與最小値之比値 (Vmax/ Vmin)爲 1.01<Vmax/ Vmin<1.12。 (3)揭示於該（1)或（2)之光學補償片，其中纖維素醯化物薄膜於70至400nm之範圍具有厚度方向之遲滯値。 -11 - 201211575 厚度方向之遲滯値（Rth )係以下式（II )予以定義。 (II) Rth = { ( nx + ny) /2 — nz}xd 式中，nx係纖維素醯化物薄膜面內之遲相軸方向的折射率；ny係纖維素醯化物薄膜面內之進相軸方向的折射率； nz係纖維素醯化物薄膜之厚度方向的折射率；而且，d係纖維素醯化物薄膜的厚度（單位：nm )。還有，無特別定義之情形，測定所用之光的波長爲5 5 Onrn。本發明之第1態樣或第2態樣所用之纖維素醯化物薄膜之厚度方向的遲滯値（Rth)最好滿足下式（ii)。 (ii ) 70<Rth<400nm (4) 揭示於該（1)或（2)之光學補償片，其中纖維素醯化物薄膜爲一種纖維素醋酸酯薄膜。 (5) 揭示於該（4)之光學補償片，其中纖維素醋酸酯薄膜係由具有59.0至61.5%範圍之醯化度構成的。 (6) 揭示於該（1)或（2)之光學補償片，其中纖維素醯化物薄膜含有具至少2個芳香族環之芳香族化合物。 (7 )揭示於該（6 )之光學補償片，其中相對於1 〇〇份質量之纖維素醯化物，含有0.01至20份質量之具有至少二個芳香族環的芳香族化合物》 (8)揭示於該（6)之光學補償片，其中芳香族化合物具有至少一個1，3,5-三畊環。 (9 ) 一種光學補償片（第3態樣），係於至少含有平均一次粒徑爲80nm以下微顆粒之膜厚爲20 μ m以上、80 从m以下的透明載體上，依序層疊配向膜與光學異方向層而成的，其特徵爲： •12- 201211575 根據JISB0 60 1-19 94，該透明載體之配向膜側表面的表面凹凸之算術平均粗糙度（Ra)爲0.0002#m以上、0.1 //m以下，十點平均粗糙度（Rz)爲0.0002/zm以上、0.3 //m以下，最大高度（Ry)爲0.002/zm以上、0.5#m以下；以及該透明載體之式（I) 、（ Π)所定義的Re値爲2nm以上、200nm以下，Rth之値爲50nm以上、400nm以下之範圍。 (I) R e = ( η X — n y) x d (II) Rth= { ( nx+ny) /2 — nz}xd [式中，nx係透明載體面內之遲相軸方向的折射率；ny 係透明載體面內之進相軸方向的折射率；nz係透明載體之厚度方向的折射率；而且，d係透明載體的厚度》] (10) 揭示於該（8)之光學補償片，其中根據jis B0601-1994，透明載體之配向膜側表面的表面凹凸之平均間隔（S m )爲0.0 0 1 /z m以上、5 /z m以下，該算術平均粗糙度（Ra)與該十點平均粗糙度（Rz)之比値（Ra/Rz)爲〇 . 1以上、1以下。 (11) 揭示於該（8)之光學補償片，其中該透明載體之長度爲l〇〇m以上、5000m以下，並且，寬度爲〇.'7m以上、2m以下之長型尺狀物，寬度方向之卷曲爲 -10/m〜+10/m，並且，根據 JIS K7128-2: 1998，撕裂強度爲2g以上。 (12) 揭示於該（8)之光學補償片，其中該透明載體之遲相軸角度之面內平均絕對値爲〇度以上、3度以下， 201211575 並且，遲相軸角度之標準偏差爲〇度以上、1.5度以τ (13)揭示於該（8)之光學補償片，其中該透明係由醯化度55.0至62.5%範圍之纖維素醯化物、分別至少一種該微顆粒與具有至少2個芳香族環之芳香族物的纖維素醯化物薄膜所構成的。 (Μ)揭示於該（I3)之光學補償片，其中該芳香合物具有至少一個1，3,5-三畊環。 (15) 揭示於該（8)之光學補償片，其中該透明係一種藉由具有流延步驟之溶液流延方法所製得的纖醯化物薄膜，其特徵爲：進行該流延步驟的摻雜液之流延的金屬載體，其表算術平均粗糙度（Ra)爲0.001 μ m以上、0.015 // m以其表面之十點平均粗糙度（Rz)爲 O.OOlym以上、 y m以下8 (16) 揭示於該（8)之光學補償片，其中該透明配向膜側之相反側的表面算術平均粗糙度（Ra )及最度（Ry )分別爲配向膜側的表面算術平均粗糙度（Ra 最大高度（Ry)的3倍以下。 (17) 揭示於該（8)之光學補償片，其中該透明爲一種纖維素醯化物薄膜，該纖維素醯化物薄膜係藉列步驟所製造的薄膜：溶液調製步驟，將纖維素醯化物溶於實質非氯系溶調製成纖維素醯化物溶液；製膜步驟，由纖維素醯化物溶液製得纖維素醯化膜；以及載體含有化合族化載體維素面之下， 0.05 載體大高 )與載體由下劑而物薄 -14- 201211575 拉伸步驟，將纖維素醯化物薄膜予以拉伸。 (18) 揭示於該（17)之光學補償片，其中該實質非氯系溶劑係由碳原子數3以上、12以下之醚類、酮類、醋類選出的至少一種有機溶劑與醇類之混合溶劑構成的，全部溶劑中之醇類的比例爲2~40質量％之範圍。 (19) 揭示於該（8)之光學補償片，其中該透明載體係藉由至少含有沸點爲60〜1 2 0°C之有水溶性機溶劑、界面活性劑與/或相溶化劑的鹼性溶液，進行表面處理。 (20)揭示於該（1) 、（2) 、（13) 、（15)及（17) 中任一項之光學補償片，其中該纖維素醯化物爲一種纖維素醋酸酯。 (21) 揭示於該（9)之光學補償片，其中該光學異方向層係由液晶性化合物構成的。 (22) —種光學補償片（第4態樣），係由醯化度爲59〇至61.5%之纖維素醋酸酯薄膜構成，並經進行表面皂化處理’並且，表面之水的接觸角爲30。以上、70。以上》 (23) —種光學補償片（第5態樣），係於醯化度爲59.0 至61·5%之纖維素醋酸酯薄膜載體的一側面上，具有由液晶性化合物構成的光學異方向層，載體之單側表面進行皂化處理’並且水的接觸角爲3 0。以上、70。以上。 (24) 揭示於該（22 )或（23 )之光學補償片，其中相對於100份質量之纖維素醋酸酯，纖維素醋酸酯薄膜含有〇·〇1至20份質量之具有至少2個芳香族環的芳香族化合物。 (25) 揭示於該（24)之光學補償片，其中芳香族化合 -15- 201211575 物具有至少一個1,3,5 -三阱環。 (26 )揭示於該（22 )之光學補償片，其中以纖維素醋酸酯薄膜之下列數學式（I)所定義的Re遲滯値爲5至 lOOnm，下列數學式（π )所定義的Rth遲滯値爲70至 4 0 Onm 〇數學式（I) Re= (nx— ny) xd 數學式（II) Rth={(nx+ny) /2 — nz}xd [式中，nx係薄膜面內之遲相軸方向的折射率；ny係薄膜面內之進相軸方向的折射率；nz係薄膜之厚度方向的折射率；而且，d係薄膜的厚度（nm)。] (27) 揭示於該（2) 、（21)及（23)中任一項之光學補償片，其中液晶性化合物爲一種碟狀液晶性化合物。 (28) —種偏光板係由偏光膜與配置於其兩側之二片透明保護膜構成的偏光板，其特徵爲：該透明保護膜之一側使用該（1 ) 、（ 2 )及（9 )中任一項之光學補償片。 (29) 揭示於該（28)之偏光板，其中偏光膜之透過軸與透明保護膜之遲相軸實際上爲垂直或平行的。 (30) —種偏光板係由偏光膜與配置於其兩側之二片透明保護膜構成的，其特徵爲：透明保護膜之一側爲揭示於該（22)或（23 )之光學補償片；以及使該光學補償片之載體的皂化處理面配置於偏光膜側。 (31) 揭示於該（30)之偏光板，其中偏光膜之透過軸與透明保護膜之遲相軸實際上爲垂直或平行的。 -16- 201211575 (3 2 ) —種液晶顯示裝置係由液晶單元與配置於其兩側之二片偏光板構成的，而偏光板係由偏光膜與配置於其兩側之二片透明保護膜構成的，其特徵爲：配置於液晶單元與偏光膜之間的二片透明保護膜之中的至少一片使用該（1) 、（2) 、（9) ' (22)及（23) 中任一項之光學補償片。 (3 3 ).揭示於該（3 2 )之液晶顯示裝置，其中液晶單元爲TN模式、VA模式、MVA模式、n-ASM模式與OCB模式中任一種模式的液晶單元。 (34) —種纖維素醯化物薄膜的製造方法係將纖維素醯化物溶液流延於金屬基板上，從金屬基板予以剝離之後，進行乾燥，其特徵爲：剝離後之纖維素醯化物薄膜的殘留揮發部分爲45至70 %之狀態，以1 〇 0至1 6 0 °C的熱風，進行1 0至1 0 0 0秒鐘的乾燥。 (35) —種如揭示於該（9)之光學補償片的製造方法，透明載體爲纖維素醯化物薄膜，藉由利用具有該纖維素n 化物薄膜之流延步驟的溶液流延方法進行製膜而製造該$ 明載體，其特徵爲：將該流延步驟之摻雜液予以流延的金屬載體，其表面$ 算術平均粗糙度（Ra)爲0.001;zm以上、0.15/zm以下，其十點平均粗糖度（Rz)爲O.OOljtzm以上、0.05/zm以下。【發明之實施態樣】於本專利說明書，「（數値1 )至（數値2 )」以及「（數値1 )〜（數値2 )」分別表示「（數値1 )以上、（數値2 ) -17- 201211575 以下」之意義。 (第1態樣、第2態樣）於本發明’將纖維素醯化物薄膜之Re遲滯値調節成 0nmSRe<20nm之範圍。較宜爲 0nmSRe<10nm，更佳爲 0nmSRe<5nm。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical compensation sheet for improving a viewing angle of a liquid crystal display device, and a polarizing plate and a liquid crystal display device using the same. [Prior Art] Generally, a liquid crystal display device is composed of a liquid crystal cell, a polarizing plate, and an optical compensation sheet (phase difference plate). In the transmissive liquid crystal display device, two polarizing plates are mounted on both sides of the liquid crystal cell, and one or two optical compensating sheets are disposed between the liquid crystal cell and the polarizing plate. In a reflective liquid crystal display device, a reflecting plate, a liquid crystal cell, and an optical compensation sheet are sequentially disposed, and then a polarizing plate. A liquid crystal cell of a general example is a combination of a rod-like liquid crystal molecule and two sheets for sealing the liquid crystal molecule. The substrate and the electrode layer for applying a voltage to the rod-like liquid crystal molecules. Due to the different alignment states of rod-like liquid crystal molecules, TN (Twisted Nematic) 'ISP(In-Plane Switching) 'FLC(Ferroelectric Liquid Crystal) ' OCB ( Optically Compensatory Bend) STN (Super Twisted Nematic) has been proposed for liquid crystal cells. ) VA ( Vertically Aligned); For the reflection type, various display modes such as HAN (Hybrid Aligned Nematic) have also been proposed. In general, the polarizing plate is composed of a polarizing film and a transparent protective film. Generally, the polarizing film is further uniaxially pulled by immersing polyvinyl alcohol in an aqueous solution of iodine or a dichroic dye. Stretch it out. Two transparent protective films are bonded to both sides of the polarizing film. The optical compensation sheet is applied to various liquid crystal display devices in order to solve the problem of image coloring and widening the viewing angle. When an optical compensation sheet is used, there is a problem that the liquid crystal display device becomes thick (for example, refer to Patent Document 1). The transparent protective film on the polarizing plate side is used as a functional polarizing plate (elliptical polarizing plate). The optical compensation sheet (phase difference film) does not thicken the liquid crystal display device and improves display quality (for example, improves front contrast). The optical compensation sheet (phase difference film) of the liquid crystal display device is required to have optical anisotropy (high hysteresis 値). Therefore, the optical compensation sheet usually uses a synthetic polymer film having a retardation such as a polycarbonate film or a polyimide film. Unlike an optical compensation sheet composed of a synthetic polymer film, an optical compensation sheet in which optical anisotropy is formed by a discotic liquid crystal molecule is provided on a transparent carrier (see, for example, Patent Documents 2 to 1 1). The high phase difference required is achieved by optical anisotropy. The needle is generally used as a cellulose acetate film because it requires a high optical isotropic property (low phase difference 値). In the technical field of optical materials as described above, the general principle is to use a synthetic polymer film if optical anisotropy (high hysteresis 要) is required in the polymer film; if optical isotropy is required In the case of (low hysteresis ,), a cellulose acetate film is used. In Patent Document 12, the conventional general principle is reversed, and a cellulose acetate film which can be used for applications requiring optical anisotropy and having high hysteresis is disclosed. Further, it is revealed that a cellulose acetate film as a protective film for a polarizing film is inserted between the polarizing film and the liquid crystal cell, whereby a liquid crystal display device having high display quality can be obtained. 201211575 Optical compensation sheets have the problem of being heated and skewed, prone to phase difference and durability. Due to the phase difference that occurs, once the liquid crystal display device has a peripheral grid-like light leakage (increased transmittance), the display quality of the liquid crystal display device will be lowered. In order to solve the problem of the phase difference caused by the skew, it has been proposed to use an optical compensation sheet on which an optically oriented layer formed of a disk-like compound is coated on a transparent carrier as a polarizing plate protective film (for example, refer to Patent Documents 12 and 13). . Usually, the optical compensation sheet is formed by disposing an alignment film on a transparent carrier or directly performing a flat grinding treatment thereon, and then applying a coating liquid containing a liquid crystal compound to form an optically oriented layer to form a single region of a liquid crystal compound. Thereafter, it is produced by a complicated and lengthy process such as photopolymerization or the like to fix the alignment. When subjected to such a process and produced in the form of a wide long-shaped roller, the optical characteristics such as the optical anisotropy of the transparent carrier itself are uniform, and the surface of the coating film applied to the carrier is not Uniformity, etc., is important for the uniformity of image display. In view of this, it has been proposed that a wide roll state can be made, and the entire surface is made into the optical characteristics of the uniform sentence, and the axis deviation angle of the carrier slow axis and the film stretching direction is suppressed for improving the deviation of the viewing angle. Patent Document 14 or the like) is a method of specifying a standard deviation 迟 (patent document 15 or the like) of the retardation axis angle. Recently, liquid crystal display devices are rapidly developing toward large-scale and high-definition. With the increase in the size of liquid crystal display devices, the problems that should be solved by conventional technologies have once again become apparent. For example, after a conventional optical compensation sheet is used for a polarizing plate of a protective film, it is mounted on a liquid crystal display device composed of a large panel of 17 inches or more, and light leakage due to thermal skew is confirmed again. Therefore, it is expected that -6-201211575 has an optical compensation sheet, and even if the size of the screen is increased, the display characteristics such as the in-plane viewing angle are not different, and the visibility is more excellent. As indicated in the report (for example, refer to Patent Document 16), the problem of light leakage can be solved by thinning the thickness of the transparent carrier of the optical compensation sheet. It is strongly desired that the thin film of the transparent carrier is required for the weight reduction and the cost reduction due to the improvement in productivity, but the strength is lowered by the thin film, and the case for a large liquid crystal display device is particularly practical. The problem. The problem has not been completely solved by the conventional method. Although it is strongly desired to increase the strength of the carrier, if the strength of the carrier is simply increased, the optical characteristics are deteriorated and the visibility is lowered. Further, in the case of a liquid crystal display device comprising a large panel of 20 inches or more, it has been confirmed that the conventional technique has not been discussed at all. Further confirm the light generated by the thermal skew. In order to solve the problem caused by thermal skew, the optical compensation sheet not only requires the liquid crystal cell to perform optical compensation, but also requires excellent durability against changes in the use environment. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 4] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 7] Japanese Patent Application Laid-Open No. 2587398 (Western Patent Application Publication No. 19519928, and U.S. Patent Application No. 201211575, No. 5,583,679) [Patent Document 6] Japanese Patent Application Specification No. 3 1 1 8 1 9 7 (U.S. Patent Application Serial No. 5 80 0 2 5 3, European Patent Application Publication No. 7 746 8 3) [Patent Document 8] International Patent Publication No. 96/3 7 8 04 A booklet (Japanese Patent Laid-Open No. Hei 8-327822, European Patent Application Publication No. 07833128, and U.S. Patent Application Specification No. 6124913) [Patent Document 9] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 12] European Patent Application Publication No. 0911656A2 [Patent Document 13] Japanese Laid-Open Patent Publication No. Hei 7 - 1 9 1 2 1 7 [Patent Document 14] Japanese Laid-Open Patent Publication No. 2003-66230 [Patent Document 15] Japanese Laid-Open Patent Publication No. 2000-A No. 2002-169023 [Patent Document 16] Japanese Patent Laid-Open Publication No. 2002-169023 The purpose is to perform optical compensation of the liquid crystal cell by using an optical compensation sheet. Another object of the present invention is to improve the display quality of a liquid crystal display device by disposing an optical compensation sheet on one side of a polarizing film and applying it to a liquid crystal display device without causing problems such as light leakage. Further, another object of the present invention is to add an optical compensation function to the polarizing plate without increasing the number of 201211575 of the polarizing plate structural requirements. Another object of the present invention is to provide an optical compensation sheet which is not only thin and lightweight, but also has a mechanical property of sufficient thickness, excellent visibility, and no advantage in that the viewing angle is widened. Further, another object of the present invention is to provide an optical compensation sheet which is excellent in productivity in which the shape of the long-length roller is wide. Further, another object of the present invention is to provide a polarizing plate and a liquid crystal display device which are excellent in visibility, and which are excellent optical compensation sheets which are thin in layer, light in weight, and have no difference in viewing angle and characteristic deviation. Another object of the present invention is to provide an optical compensation sheet which can be used as a protective film for a polarizing plate as a structural element and can add optical light to the polarizing plate without increasing the number of structural elements on the polarizing plate. Compensation function. Another object of the present invention is to provide a polarizing plate which is used as a protective film and which does not deteriorate in productivity in the processing step of the polarizing plate. Another object of the present invention is to provide a liquid crystal display device in which the polarizing plate is provided to perform optical compensation of a liquid crystal cell. Means for Solving the Problems The present invention provides the following optical compensation sheets, polarizing plates, liquid crystal display devices, and methods for producing cellulose halide films. (1) An optical compensation sheet (first aspect), which is an optical compensation sheet composed of a cellulose halide film, characterized in that the cellulose halide film (Re) is 〇nmSRe< 2 Onm ; 201211575 (ii) The thickness (d) is l〇vm<d<85//m; (iii) the average of the sound velocity (Vmin) and the maximum enthalpy (Vmax) measured in the plane of the film ((Vmin) + Vmax) /2) is 2.2km/sec<Vmin + Vmax) /2<2.5km/sec; and (iv) the ratio of the maximum 値 to the minimum 音 (Vmax/Vmin) of the speed of sound measured in the plane of the film is 1.01 < Vmax / Vmin < 1.12. The in-plane retardation Re(Re ) is defined by the following formula (I): (I) R e = ( η X — ny ) xd where the refractive index of the nx-based cellulose oxime film in the in-plane axis direction; The refractive index of the ny-based cellulose oxime film in the in-plane direction of the phase in the axial direction; and the thickness of the d-based cellulose oxime film (unit: nm). Further, in the case where there is no particular definition, the wavelength of light used for the measurement is 5 5 Onm. Further, in the present specification, "slow axis" means a direction in which the refractive index is maximum, and "fast axis" means a direction in which the refractive index is the smallest. The in-plane retardation Re (Re) of the cellulose oxime film used in the first aspect of the invention satisfies the following formula (i). (i) 0 nm < Re < 2 Onm The thickness (d) of the cellulose halide film used in the first aspect of the invention satisfies the following formula (Π). (ii) 10 / / m ( = 1000 Onm) < d < 85 / zm ( = 85000 nm) The minimum sound velocity measured in the plane of the film of the cellulose halide film of the first aspect of the invention (Vmin) The average value ((Vmin+Vmax) /2) with the maximum 値 (Vmax ) satisfies the following formula (iii). (iii) 2.2km/sec<(Vmin+ Vmax) /2<2.5km/sec -10- 201211575 where 'Vmin is in the plane of the cellulose oxime film, the speed of sound is the smallest in the direction of sound; Vmax is based on cellulose In the plane of the bismuth film, the speed of sound is the speed of sound in the direction of the maximum. Further, in the case where there is no particular definition, the measurement is performed using a plurality of frequencies ranging from ΙΟΚΗζ to 100 MHz. The cellulose oxime film of the present invention has a ratio 値 (Vmax / Vmin ) of the maximum enthalpy (Vmax) to the minimum enthalpy (Vmin) measured in the plane of the film satisfying the following formula (iv). (iv) 1.0 1 < Vmax / Vmin < 1. 2 2. In the formula, Vmin is in the plane of the cellulose oxime film, and the speed of sound is the speed of sound in the smallest direction; Vmax is in the plane of the cellulose oxime film, and the speed of sound is the speed of sound in the largest direction. (2) An optical compensation sheet (second aspect) which is an optical compensation sheet composed of a cellulose halide film and an optically different direction layer, and the optically different direction layer is composed of a liquid crystal compound, and is characterized by For the cellulose halide film, (i) in-plane retardation Re (Re) is 0 nm < Re < 20 nm; (ii) thickness (d) is l〇 / / m < d < 85 / / m; (Ui ) film The minimum 値(Vmin) and the maximum 値(\^!11&乂) measured in the plane are (2.2) (111/560<\^111111 + Vmax) /2 < 2.5 km / sec; and (iv) The ratio of the maximum 値 to the minimum 音 (Vmax / Vmin) of the speed of sound measured in the plane of the film is 1.01 < Vmax / Vmin < 1.12. (3) The optical compensation sheet of (1) or (2), wherein the cellulose halide film has a hysteresis in the thickness direction in the range of 70 to 400 nm. -11 - 201211575 The hysteresis (Rth) in the thickness direction is defined by the following formula (II). (II) Rth = { ( nx + ny) /2 — nz}xd where the refractive index of the nx-based cellulose oxime film in the in-plane axis direction; the phase advancement of the ny-type cellulose oxime film The refractive index in the axial direction; the refractive index in the thickness direction of the nz-based cellulose oxime film; and the thickness (unit: nm) of the d-based cellulose oxime film. Also, in the case where there is no particular definition, the wavelength of the light used for the measurement is 5 5 Onrn. The retardation 値(Rth) in the thickness direction of the cellulose oxime film used in the first aspect or the second aspect of the present invention preferably satisfies the following formula (ii). (ii) 70<Rth<400 nm (4) The optical compensation sheet of (1) or (2), wherein the cellulose halide film is a cellulose acetate film. (5) The optical compensation sheet of (4), wherein the cellulose acetate film is composed of a degree of deuteration in the range of 59.0 to 61.5%. (6) The optical compensation sheet of (1) or (2), wherein the cellulose halide film contains an aromatic compound having at least two aromatic rings. (7) The optical compensation sheet of (6), which contains 0.01 to 20 parts by mass of an aromatic compound having at least two aromatic rings with respect to 1 part by mass of the cellulose halide (8) The optical compensation sheet of (6), wherein the aromatic compound has at least one 1, 3, 5 - three tillage ring. (9) An optical compensation sheet (third aspect) which is obtained by sequentially laminating an alignment film on a transparent carrier having a film thickness of at least 20 μm and a thickness of 80 μm or less of microparticles having an average primary particle diameter of 80 nm or less And the optically oriented layer is characterized by: • 12-201211575 According to JIS B0 60 1-19 94, the arithmetic mean roughness (Ra) of the surface irregularities on the side surface of the alignment film of the transparent carrier is 0.0002 #m or more. 0.1 / m or less, the ten point average roughness (Rz) is 0.0002 / zm or more, 0.3 / / m or less, the maximum height (Ry) is 0.002 / zm or more, 0.5 # m or less; and the transparent carrier formula (I Further, Re 定义 defined by ( Π) is 2 nm or more and 200 nm or less, and R 値 is 50 nm or more and 400 nm or less. (I) R e = ( η X — ny) xd (II) Rth= { ( nx+ny) /2 — nz}xd [wherein the refractive index of the slow phase axis in the plane of the nx transparent carrier; ny The refractive index in the direction of the phase axis of the transparent carrier; the refractive index in the thickness direction of the nz-type transparent carrier; and the thickness of the d-type transparent carrier] (10) is disclosed in the optical compensation sheet of (8), wherein According to jis B0601-1994, the average interval (S m ) of surface irregularities on the side surface of the alignment film of the transparent carrier is 0.00 1 /zm or more and 5 /zm or less, and the arithmetic mean roughness (Ra) and the ten point average roughness are The ratio (Ra/Rz) of the degree (Rz) is 〇. 1 or more and 1 or less. (11) The optical compensation sheet according to (8), wherein the transparent carrier has a length of 10 μm or more and 5000 m or less, and a long ruler having a width of 〇. '7 m or more and 2 m or less, width The direction of curl is -10/m to +10/m, and according to JIS K7128-2: 1998, the tear strength is 2 g or more. (12) The optical compensation sheet according to (8), wherein the in-plane average absolute 値 of the retardation axis angle of the transparent carrier is not less than or equal to or less than 3 degrees, 201211575, and the standard deviation of the retardation axis angle is 〇 An optical compensation sheet of the above (8), wherein the transparent system is composed of cellulose halides having a degree of deuteration of 55.0 to 62.5%, at least one of the microparticles and having at least 2 A cellulose halide film of an aromatic ring aromatic. (A) The optical compensation sheet of (I3), wherein the aromatic compound has at least one 1, 3, 5 - three tillage ring. (15) The optical compensation sheet of (8), wherein the transparency is a fiber halide film obtained by a solution casting method having a casting step, characterized by: doping the casting step The metal carrier of the casting of the mixed liquid has an arithmetic mean roughness (Ra) of 0.001 μm or more and 0.015 // m, and the ten-point average roughness (Rz) of the surface is O.OOlym or more and ym or less 8 ( [16] The optical compensation sheet of (8), wherein an arithmetic mean roughness (Ra) and a maximum (Ry) of the surface on the opposite side of the transparent alignment film side are surface arithmetic mean roughness (Ra) of the alignment film side, respectively. (17) The optical compensation sheet of (8), wherein the transparent is a cellulose oxime film which is a film produced by the step: a solution preparation step of dissolving the cellulose halide in a substantially non-chlorinated solution to form a cellulose halide solution; a film forming step of preparing a cellulose vaporized film from the cellulose halide solution; and the carrier containing the compounded carrier vector Under plain surface, 0.05 load Large High) by the agent with the carrier was thin -14-201211575 stretching step, the stretching will be acylated cellulose film thereof. (18) The optical compensation sheet according to (17), wherein the substantially non-chlorinated solvent is at least one organic solvent selected from the group consisting of ethers, ketones, and vinegar having 3 or more and 12 or less carbon atoms, and an alcohol. The ratio of the alcohol in the total solvent is composed of a mixed solvent in the range of 2 to 40% by mass. (19) The optical compensation sheet of (8), wherein the transparent carrier is a base having at least a water-soluble solvent, a surfactant, and/or a compatibilizing agent having a boiling point of 60 to 120 °C. Sex solution, surface treatment. (20) The optical compensation sheet of any one of (1), (2), (13), (15), and (17), wherein the cellulose halide is a cellulose acetate. (21) The optical compensation sheet of (9), wherein the optically oriented layer is composed of a liquid crystalline compound. (22) An optical compensation sheet (fourth aspect) consisting of a cellulose acetate film having a degree of deuteration of 59 to 61.5% and subjected to surface saponification treatment, and the contact angle of water on the surface is 30. Above, 70. (23) An optical compensation sheet (5th aspect) on one side of a cellulose acetate film carrier having a degree of deuteration of 59.0 to 61.5%, having an optical difference composed of a liquid crystalline compound The directional layer, the unilateral surface of the carrier was subjected to saponification treatment' and the contact angle of water was 30. Above, 70. the above. (24) The optical compensation sheet of (22) or (23), wherein the cellulose acetate film contains 〇·〇1 to 20 parts by mass with at least 2 fragrances relative to 100 parts by mass of cellulose acetate. Acyclic aromatic compound. (25) The optical compensation sheet of (24), wherein the aromatic compound -15-201211575 has at least one 1,3,5-three well ring. (26) The optical compensation sheet of (22), wherein the Re hysteresis 定义 defined by the following formula (I) of the cellulose acetate film is 5 to 100 nm, and the Rth hysteresis defined by the following mathematical formula (π)値70 to 40 Onm 〇 Mathematical formula (I) Re= (nx— ny) xd Mathematical formula (II) Rth={(nx+ny) /2 — nz}xd [wherein, nx is in-plane The refractive index in the direction of the slow axis; the refractive index in the direction of the phase axis of the ny-type film; the refractive index in the thickness direction of the nz-based film; and the thickness (nm) of the d-type film. The optical compensation sheet of any one of (2), (21), and (23), wherein the liquid crystalline compound is a discotic liquid crystalline compound. (28) A polarizing plate comprising a polarizing film and two transparent protective films disposed on both sides thereof, wherein: (1), (2) and (1) of the transparent protective film are used. 9) An optical compensation sheet according to any one of the items. (29) The polarizing plate of (28), wherein a transmission axis of the polarizing film is substantially perpendicular or parallel to a slow axis of the transparent protective film. (30) A polarizing plate is composed of a polarizing film and two transparent protective films disposed on both sides thereof, and is characterized in that: one side of the transparent protective film is an optical compensation disclosed in the (22) or (23) And a saponified surface of the carrier of the optical compensation sheet is disposed on the polarizing film side. (31) The polarizing plate of (30), wherein a transmission axis of the polarizing film and a slow axis of the transparent protective film are substantially perpendicular or parallel. -16- 201211575 (3 2 ) A liquid crystal display device is composed of a liquid crystal cell and two polarizing plates disposed on both sides thereof, and the polarizing plate is composed of a polarizing film and two transparent protective films disposed on both sides thereof. The structure is characterized in that at least one of the two transparent protective films disposed between the liquid crystal cell and the polarizing film uses (1), (2), (9) ' (22) and (23) An optical compensation sheet. (3 3) The liquid crystal display device of (32), wherein the liquid crystal cell is a liquid crystal cell of any one of a TN mode, a VA mode, an MVA mode, an n-ASM mode, and an OCB mode. (34) A method for producing a cellulose oxime film by casting a cellulose ruthenium solution onto a metal substrate, peeling it off from the metal substrate, and drying it, characterized by: a cellulose oxime film after peeling The residual volatile portion is in a state of 45 to 70%, and is dried at a temperature of 1 〇0 to 160 °C for 10 to 100 seconds. (35) A method of producing an optical compensation sheet according to (9), wherein the transparent carrier is a cellulose vaporized film, which is produced by a solution casting method using a casting step of the cellulose n-ide film The present invention is characterized in that: the metal carrier cast by the doping solution in the casting step has a surface having an arithmetic mean roughness (Ra) of 0.001; zm or more and 0.15/zm or less; The ten-point average crude sugar (Rz) is O.OOljtzm or more and 0.05/zm or less. [Embodiment of the Invention] In this patent specification, "(number 値1) to (number 値2)" and "(number 値1) to (number 値2)" respectively mean "(number 値1) or more, ( Number 値 2) -17- 201211575 The meaning of the following. (First aspect, second aspect) In the present invention, the retardation Re of the cellulose halide film was adjusted to a range of 0 nm SRe < 20 nm. It is preferably 0 nmSRe < 10 nm, more preferably 0 nm SRe < 5 nm.

Rth遲滯値較宜調節成70nm<Rth<400nm之範圍。於液晶顯示裝置內，使用二片光學異方向性纖維素醯化物薄膜之情形，薄膜之Rth遲滯値較宜爲70nm<Rth<2 5 0nm 之範圍，更佳爲75nm<Rth<150nm之範圍。於液晶顯示裝置內，使用一片光學異方向性纖維素醯化物薄膜之情形，薄膜之 Rth 遲滯値較宜爲 150nm<Rth<400nm 之範圍，更佳爲 160nm<Rth<250nm 之範圍。還有，纖維素醯化物薄膜之複折射率（△ n : nx — ny ) 較宜爲0.00至0.002之範圍。另外，纖維素醯化物薄膜之厚度方向的複折射率{(nx+ny)/2-nZ}較宜爲0.001至 0.04之範圍。再者，纖維素醯化物薄膜之複折射率的波長依賴性A = Δ η ( 450 ) /Δ η ( 5 50 )以及 Β=Δη(650) / Δ η ( 5 5 0 )，較宜爲 0·20<Α<1.05 與 1·00<Β<1·55。 [防止漏光] 爲了防止液晶顯示裝置之熱歪斜，進行纖維素醯化物薄膜之厚度與彈性率的調節。纖維素醯化物薄膜之厚度（d)係設於l〇Am<d<85#m 之範圍。雖然纖維素醯化物薄膜之厚度（d)越薄越好，基 -18- 201211575 於製造上操作的觀點，較宜爲30 v m<d<80 # m。另外，一般爲了減小假想歪斜，較宜藉由將纖維素醯化物薄膜進行二軸拉伸而提高聚合物分子面配向，或是將吸濕膨脹係數設於3〇x 1(T 5/% RH以下。維素醯化物薄膜之吸濕膨脹係數更佳爲15x10— 5/% RH以下，最好爲1〇χ10_ 5/% RH。抑制吸濕膨脹係數的方法爲一種提高纖維素醯化物薄膜密度的方‘法。纖維素醯化物薄膜之彈性率較宜爲3 OOOMPa以下，更佳爲2500 MPa以下。爲了滿足該（iii)與（iv)而進行音速之調整，基於彈性率或密度之調節或製造上操作的觀點也爲有利的。纖維素醯化物薄膜之薄膜面內所測定的音速之最小値 (Vmin)與最大値（Vmax)之平均（（Vmin+Vmax) /2) 更佳爲 2.3<( (Vmin+Vmax) /2) <2.4km/sec。薄膜面內所測定的音速之最大値與最小値之比値（Vmax/ Vmin )更佳爲 1.03<Vmax/Vmin<1.10。 [纖維素醯化物] 纖維素醯化物係一種纖維素與酸之酯類。酸較宜爲羧酸，更佳爲脂肪酸，更理想爲碳原子數爲2至4之脂肪酸，最理想爲醋酸（纖維素醋酸酯）》醯化度爲5 9.0至6 1 . 5 %範圍之纖維素醋酸酯特別理想。所謂醯化度意指每纖維素單位質量之鍵結醋酸量。醯化度係遵循ASTM : D-817-91 (纖維素醋酸酯等之測試法）之醯化度的測定與計算。纖維素醯化物之黏度平均聚合度（DP )較宜爲250以 -19- 201211575 上，更佳爲2 9 0以上。另外，用於本發明之纖維素醯化物係利用凝膠滲透層析儀之Mm/Μη (Mm爲質量平均分子量、Μη爲數目平均分子量）的分子量分布狹窄者較佳。具體之Mm/Mn之値較宜爲 1.0至1.7之範圍，更佳爲1.3至1.65之範圍，最好爲1.4 至1.6之範圍。 [遲滞値提昇劑] 爲了調整纖維素醯化物薄膜之遲滯値，將具有至少二個芳香族環的芳香族化合物作爲遲滯値提昇劑使用。對於100份質垃之纖維素醯化物，芳香族化合物使用〇.〇1至20份質量之範圍。對於100份質量之纖維素醋酸酯，芳香族化合物較宜使用0.05至15份質量之範圍，更佳使用0.1至10份質量之範圍。也可以將二種以上之芳香族化合物予以合倂使用。於芳香族化合物之芳香族環中，除了芳香族碳氫環之外，含有芳香族性雜環。芳香族化合物尤以具有至少一個 1，3，5 -三嗪環爲特別理想。遲滯値提昇劑之具體例已揭示於日本公開專利第 2002-169023 號公報。藉由利用遲滯値提昇劑而導致遲滯値控制，能夠不伴隨如拉伸之變形，而將音速控制於適當之範圍。 (第3態樣）本發明之光學補償片係於含有特定粒徑之微顆粒的特定膜厚之透明載體上，依序層疊配向膜與光學異方向層而成的，其特徵爲：透明載體具有特定之表面形狀與光學特 -20- 201211575 性。 <透明載體> 本發明之透明載體較宜爲一種透明的聚合物薄膜。透明載體之光透過率較宜爲8 0%以上、霧度較宜爲3%以下。構成聚合物薄膜之聚合物例子，可列舉：纖維素酯（例如，纖維素之一、二或三醯化物等）、原菠烯系聚合物等。該原菠烯系聚合物可列舉ARTON與ZEONEX (均爲商品名）。另外，如習知之聚碳酸酯或聚颯之易發現複折射的聚合物，如揭示於國際公開第00/26705號冊子之內容，只要能藉由修飾分子而控制複折射之發現性的話，能夠用於本發明之透明載體。可以爲此等之摻合聚合物、接枝聚合物等，也能夠使用二種以上之聚合物。本發明之透明載體等該特定膜厚爲2 0〜8 0 μ m，較宜爲 30〜80// m，更佳爲40〜65以m。若該膜厚低於20y m，則無法發現足夠的強度，若超過80^m，重量或操作性方面便不足夠。另外，膜厚之變動幅度較宜爲±3%以內，更佳爲±2%以內，更理想爲±1.5%以內。於此變動內爲良好的，便不會對於載體厚度之光學異方向層造成實質上之影響。用於本發明之透明載體，由於將光學補償片、偏光板與液晶顯示裝置予以薄化、輕量化，或是提高透過率而將對比或顯示亮度予以改善等之可以穩定地得到良好的光學特性，並能夠操作性良好地處理長型尺狀且寬幅的載體。尤其，用於本發明之該透明載體，較宜使用由纖維素酯所形成的聚合物薄膜。 -21 - 201211575 作爲該纖維素酯原料的纖維素，有棉花纖維、洋麻、木材紙漿（闊葉樹紙漿、針葉樹紙漿）等，而於本發明，只要由任何之原料纖維所得到的纖維素酯均可以使用，也可以視情況而定，進行混合而使用》於本發明，較宜使用由纖維素經酯化而成的纖維素醯化物，尤其，較佳之該纖維素並非直接利用，而是將該棉花纖維、洋麻、紙漿予以精製後使用。於本發明，所謂纖維素醯化物係一種纖維素的脂肪酸酯，更佳爲纖維素之低級脂肪酸酯。所謂脂肪酸酯係指碳原子數爲6以下之脂肪酸。碳原子數較宜爲2(纖維素醋酸酯）、3(纖維素丙酸酯）或4(纖維素丁酸酯）。纖維素酯較宜爲纖維素醋酸酯，其例子可列舉二乙醯纖維素與三乙醯纖維素等。較宜使用如纖維素醋酸酯丙酸酯或纖維素醋酸丁酸酯之混合脂肪酸酯。 —般而言，纖維素醯化物2,3,6-位之羥基並非均等分配於整個取代率的各1 /3，而有6-位羥基取代率變小的傾向。相較於2,3-位，本發明之纖維素醯化物的6-位羥基取代率較宜爲相同水準或更多。相對於整體取代率，6-位羥基乙醯基較宜爲進行30%以上、40%以下之取代，更佳爲3 1%以上，尤以32%以上更爲理想》除了乙醯基之外，6-位羥基也可以利用碳數3以上之醯基的丙醯基、丁醯基、戊醯基、苯醯基、丙烯醯基等進行取代。各位置取代率之測定，可以利用NMR法等而求出。用於本發明之透明載體的聚合物薄膜，較宜使用醯化度 -22- 201211575 爲55.0~62.5%之纖維素醯化物的薄膜，更佳爲使用醯化度爲57·0~61·5%之纖維素醯化物的薄膜。此處所謂之醯化度係指每單位質量纖維素之鍵結醋酸量。醯化度係遵循 ASTM: D-817-91(纖維素醋酸酯等之測試法）之醯化度的測定與計算而求出的。另外，纖維素醯化物之黏度平均聚合度（DP)較宜爲 25〇以上，更佳爲290以上。另外，聚合物薄膜係利用凝膠滲透層析儀，所測出的多分散性指數Mm/Mn( Mm爲質量平均分子量、Μη爲數目平均分子量）宜小，分子量分布宜窄。具體之Mm/Mn之値較宜爲1.0至2.5，更佳爲1.0 至2.0，最好爲1.0至1.6。 [微顆粒] 於本發明，對於所用之透明載體，爲了使透明載體之強度增加，並保持良好的薄膜之卷曲抑制、搬送性、輥輪形態的抗黏著或耐刮傷性而添加微顆粒。該微顆粒之該特定粒徑的平均一次粒徑爲80nm以下，較宜爲5〜80nm，更佳爲5〜60nm，尤以8〜50nm爲最好。若平均一次粒徑超過80nm，透明載體之表面平滑性將受損。尤其，較宜使該微顆粒粒徑的分散度一致，更佳的話，不存在粒徑500nm以上之顆粒。藉由使用如此之超微顆粒，最好於分散物中之分散性安定，不損壞製得之薄膜的機械物性，也降低霧度，並且表面之凹凸形狀爲微細的且形成凹凸一致的狀態。微顆粒之莫氏硬度較宜爲2〜10。更佳爲2.5〜10。只要微顆粒爲呈現該機能的材料即可，並無特別之限 -23- 201211575 定’無論是無機化合物、有機化合物任一種均可，更佳之具體例’無機化合物較宜爲含矽之化合物、二氧化矽、氧化鈦、氧化鋅、氧化鋁、氧化鋇、氧化鉻、氧化緦、氧化銻、氧化錫•銻、碳酸鈣、滑石、黏土、煅燒陶土、煅燒矽酸鈣、水合矽酸鈣、矽酸鋁、矽酸鎂及磷酸鈣等，更佳爲含矽之無機化合物或氧化锆。另外’經表面處理的無機微顆粒較宜於纖維素醯化物中之分散性爲良好的。具體而言，較宜爲已進行表面加工成疏水性的無機顆粒。例如’可列舉揭示於柳田博明監修之「微顆顆粒工學體系第一卷之應用技術」第9章（Fuji Techno System股份公司，2002年發行）：加賀美敏郎、林瑛監修之「高純度二氧化矽之製造與應用」（CMC(股份公司），1999年發行）❶ 有機化合物，例如，較宜爲交聯聚苯乙烯、矽樹脂、氟樹脂與丙烯基樹脂等之聚合物，其中，更佳爲使用‘矽樹脂。於矽樹脂之中，尤以具有三次元網狀構造者特別理想。對於該聚合物薄膜之原料聚合物的該微顆粒添加量，相對於份質量之聚合物，微顆粒較宜爲〇.〇1~〇.3份質量，更佳爲〇.〇5〜0.2份質量。 [遲滯値調整劑] 基於光學異方向性的觀點，本發明作爲透明載體使用之聚合物薄膜較宜含有一種遲滯値調整劑，將吸收較溶液本身之紫外線吸收光譜之吸收極大波長（λ max ) 400nm更短波長紫外線的化合物作爲遲滯値調整劑。如此之化合物例子，可列舉：苯基水楊酸、2-羥基二苯甲酮類、苯并三唑 -24- 201211575 類、三苯基磷酸酯等之紫外線吸收劑。另外，可列舉：較宜具有至少二個芳香族環之芳香族化合物、三伸苯基化合物、碟狀化合物（分子中含有1,3,5 -三嗪骨幹、卟吩骨幹之化合物等）等。於本發明，用於該遲滯値調整劑之化合物較宜於可見光領域無實質吸收。 *具有至少二個芳香族環之芳香族化合物尤其較宜將具有至少二個芳香族環之芳香族化合物（以下，也稱爲「芳香族化合物A」）作爲該遲滯値調整劑使用特別理想。於芳香族化合物A之芳香族環中，除了芳香族碳氫環之外，也可以爲芳香族性雜環。芳香族碳氫環尤以6員環（亦即，苯環）特別理想。芳香族性雜環一般爲不飽和雜環。芳香族性雜環較宜爲5員環、6員環或7員環，但是以5 員環或6員環更佳。芳香族性雜環一般具有最多的雙鍵。雜原子較宜爲氮原子、氧原子與硫原子，尤以氮原子特別理想。具有芳香族化合物A之芳香族環的數目較宜爲2至20, 更佳爲2至12。具有三個以上芳香族環之情形，只要不會對至少二個芳香族環之立體構形造成立體障礙的話即可。二個芳香族環之鍵結關係可以分類爲：（a)形成稠環之情形；（b )以單鍵直接進行鍵結之情形；以及（c )隔著連結基進行鍵結之情形。（由於爲芳香族環，無法形成螺鍵結）。基於遲滯値改善機能之觀點，（a )〜（c )之中的任一種均可。具體而言，可列舉揭示於日本公開專利第 2 002 - 1 3 1 5 3號公報之段落編號[0016] ~[0023 ]的內容。再 -25- 201211575 者，該（b)或（c)之情形，較宜爲不會對至少二個芳香族環之立體構形造成立體障礙。作爲芳香族化合物A，可列舉：具有相同揭示於日本公開專利第2002-363343號公報之段落編號[0011]〜[0031]內容之線形分子構造的棒狀化合物；相同揭示於日本公開專利第2000-111914號公報之段落編號[〇〇11] ~[0085]內容之不會造成立體障礙之立體構形的含有二個芳香族環之化合物；含有至少一個芳香族環作爲取代基的1，3,5-三嗪化合物或是具有卟吩骨幹的化合物（揭示於日本公開專利第 2001-166144號公報之化合物）。尤以含有至少一個芳香族環作爲取代基的1，3,5-三嗪化合物較佳（該三嗪環已形成一個芳香族環）。具體而言，可列舉揭示於日本公開專利第200 1 - 1 66 1 44號公報之段落編號[0016]之一般式（I)所揭示的1，3,5-三嗪化合物。該芳香族化合物 A可以單獨使用或是也可以混合二種以上該化合物而使用。芳香族化合物A之含量係爲了調整所要之遲滯値，選擇遲滯値調整用化合物之種類與用量而使用。於製作透明載體之時，由於爲了不使透明載體成型物內之溶解性、製膜時之不溶化或分離等問題發生，相對於100份質量之該聚合物，較宜使用〇.〇1〜30份質量之範圍，更佳使用0.1 ~2 5 份質量之範圍。 [可塑劑] 對於該透明載體，爲了改良薄膜之機械物性，或是爲了提高乾燥速度，較宜添加習知之可塑劑。可塑劑，例如可 -26- 201211575 列舉：較宜爲磷酸酯類、羧酸酯類（羧酸可列舉：脂肪族羧酸、羥酸（檸檬酸、蘋果酸等）、芳香族羧酸（苯二酸等）等，已揭示於日本發明協會公開技法公技編號 2001-1745號（2001年3月15日發行，日本發明協會）Ρ·16 之化合物等）。另外，烷聚醇與羧酸之酯化化合物（於曰本公開專利第平11-124445、2001-247717號公報）所揭示之化合物）等。相對於1〇〇份質量之該聚合物，可塑劑之添加量較宜爲 0.05~25份質量，更佳爲1至20份質量。 [其他之添加劑] 於該透明載體中，進一步也可以添加抗紫外線劑（例如，羥基二苯甲酮系化合物、苯并三唑系化合物、水楊酸酯系化合物、氰基丙烯酸酯系化合物等）、抗劣化劑（例如，抗氧化劑、過氧化物分解劑、自由基抑制劑、金屬不活化劑、氧捕獲劑、光安定化劑（大取代基之胺基等）等）、剝離劑、防靜電劑等。此等之詳細說明，較宜使用已詳細揭示於該日本公技編號 2001-1745 號，p.17-22 的原料。 « 本發明之該透明載體較宜由含有各至少一種之該醯化度55.0至62.5%範圍的纖維素醯化物、該微顆粒以及該芳香族化合物A之纖維素醯化物薄膜而構成的。另外，此時對該纖維素醯化物薄膜添加該可塑劑以外的添加劑，並無特別之限制。該纖維素醯化物薄膜之纖維素醯化物、微顆粒及芳香族化合物A之摻合比例相同於該摻合比例。 -27- 201211575 [透明載體之特性（表面形狀）] #發明之光學補償片之特徵爲：透明載體具有特定之表 ©开$狀。以下，針對本發明之特徵部分的透明載體之表面形狀進行說明。該透明載體之配向膜側的表面係根據JISB0601-1994, 該膜表面凹凸的算術平均粗糙度（Ra)爲0.0002/im以上、 lym以下’十點平均粗糙度爲〇.〇〇〇2#m以上、ο」以下，以及最大高度（Ry)爲0.002"m以上、0.05 β m以下；較佳的話，算術平均粗糙度（Ra)爲0.0002 # m以上、0.08ym以下，十點平均粗糙度（Rz)爲〇〇〇〇2 以上、o.^m以下，以及最大高度（Ry)爲〇〇〇2#m 以上、0.5 /z m以下；更好的話，算術平均粗糙度（Ra )爲 0.0002/zm以上、〇〇15/zm以下，十點平均粗糙度（rz) 爲0.00 2//Π1以上、〇·〇5/Ζπι以下，並且最大高度（Ry)爲 0.002^ m以上、〇.5//m以下；特別理想的話，算術平均粗糖度（Ra)爲o.ooiym以上、〇.〇i〇ym以下，十點平均粗縫度（Rz)爲〇·〇〇2μιη以上、〇.〇25/zm以下，並且最大咼度（Ry)爲〇.〇〇2ym以上、〇.〇4/zm以下。於該範圍內，設置無塗布不均的均勻配向膜。再者’於微細表面凹凸形態，算術平均粗糙度（Ra )與十點平均粗糙度（RZ)之比値（Ra/Rz)較宜爲〇」以上' 1以下’並且根據JIS B0601-1994，該膜表面凹凸的平均間隔（Sm)較宜爲〇.〇〇iem以上、5#m以下。於此，Ra 與Rz之關係表示表面之凹凸均勻性。再者’ （Ra/Rz)比値更佳爲〇. 1 5以上、1以下；更理想的話，爲〇.丨7以上、 -28- 201211575 1以下’平均間(Sm)爲0.001 以上、lym以下。表面之凹與凸的形狀能夠利用透過型電子顯微鏡 (TEM )、原子力顯微鏡（AFM )等進行評估。 (其他之表面形狀）另外，本發明之透明載體配向膜側之相反側的表面算術平均粗糙度（Ra)與最大高度（Ry)，較宜爲配向膜側表面之算術平均粗糙度（Ra)與最大高度（Ry)的3倍以下。更佳的話爲1〜2倍’尤以1 ~ 1 · 5倍特別理想。於如此之範圍，薄膜之透明性、於輕輪形態之抗黏著性等均爲良好。 (長型尺狀物）透明載體較宜爲長型尺狀物。其長度較宜爲l〇〇m以上、5000m以下，更佳爲300m以上、4500m以下。其寬度較宜爲0.7m以上、2m以下，更佳爲l.〇m以上、ι 7ιη以下。 [薄膜之力學特性] (卷曲）用於本發明之透明載體之寬度方向的卷曲値較宜爲 -10/m〜+10/m，更佳爲- 8/ m〜+ 8/ m。針對本發明之透明載體，對於長型尺狀物且寬廣的透明載體進行後述之表面處理、平磨處理的實施，或是配向膜、光學異方向層的設置等之際，若透明載體之寬度方向的卷曲値爲該範圍內，薄膜之操作性將變得良好，不會導致薄膜之切斷。另外，於薄膜之邊緣或中央部分等，薄膜與搬送輥輪強烈接觸往往產生塵埃，薄膜上之污染物附著便不會發生’能夠將光學補償片之點缺陷或塗布線條之頻率設 •29- 201211575 於容許値之範圍內。另外，較宜藉由將卷曲設於該範圍內，於設置光學異方向層之時，除了能夠減低容易發生的色斑缺陷之外，也能夠於黏合偏光膜時防止氣泡之進入。卷曲値能夠遵循美國國家規格協會所規定的測定方法 (ANSI/ASCPH 1 .29- 1 985 )而進行測定。 (撕裂強度）如上所述，該透明載體之膜厚爲2 0〜8 0〆m，根據其JIS K7128-2: 1998之撕裂測試方法（Elmendorf撕裂法），撕裂強度爲2g以上，該膜厚能夠充分保持膜之強度者較佳。更佳爲5〜25g，更理想爲6~25g。另外，以60/zm換算，較宜爲8g以上，更佳爲8~15g。具體而言，於25°C、65% RH之條件下，能夠將試樣片 5 0mm X 6 4 mm予以2小時調濕之後，利用輕量載重撕裂強度測試機進行測定。尤其，該卷曲及該撕裂強度於結束既定之製造步驟後，所得到的該透明載體之長度l〇〇m以上、5000m以下，寬度 0.7 m以上、2m以下之長型尺狀物的情形下，較宜設爲該範圍內。 (刮傷強度）另外，刮傷強度較宜爲1 g以上，更佳爲5 g以上，尤以 5 g以上特別理想。藉由設爲此範圍，無問題地可保持薄膜表面之耐刮傷性、操作性。刮傷強度能夠利用圓錐頂角爲90°且尖端半徑爲〇.25m 之藍寶石針刮傷載體表面，具有能夠以目視確認刮傷痕跡的載重（g)而進行評估。 -30- 201211575 [薄膜之吸濕膨脹係數] 另外’該透明載體較宜將其吸濕膨脹係數設於3〇χ1〇-5/ % RH以下，更佳設爲15x1〇-5/!)6 RH以下，尤以設爲ι〇χ1〇 —5/% RH特別理想。另外，吸濕膨脹係數雖然越小越好，但是通常爲1.0x10 - 5/% RH以上之値。吸濕膨脹係數係於一定溫度下，顯示使相對濕度改變時之試料長度的變化量。藉由調節此吸濕膨脹係數，能夠原狀維持光學補償片之光學補償機能，防止因外圍格子狀之透過率上升，亦即，歪斜所造成的漏光。吸濕膨脹係數之測定方法係將製得的聚合物薄膜切成寬度5mm、長度20mm之試料，於25°C、20% RH(RO)之氣體環境中，將單側邊緣予以固定而懸掛。接著，於另一側邊緣懸掛0.5 g之砝碼，放置1 〇分鐘後進行長度（L0 ) 之測定。然後，溫度維持25°C，但是將濕度設爲80% RH (R 1 )後，進行長度（L 1 )之測定。將測定結果代入下式後算出吸濕膨脹係數。針對相同試料之1 0片試樣進行測定，採用平均値。吸濕膨脹係數[/% RH] = { ( LI - LO ) /LO}/ ( R1 — R0 ) [透明載體之光學異方向性] 用於本發明之透明載體，其特徵爲：顯示特定之光學異方向性。具體而言，以下式（I )與（II )予以定義，表示光學異方向性程度的Re遲滯値與Rth遲滯値，個別之Re 爲2〜200nm，較宜爲4〜200nm; Rth爲50~400nm，較宜爲 55~350nm 0 (I) Re = ( nx — ny ) x d -31 - 201211575 (II) Rth= { ( nx + ny) / 2 — n z } x d 於式（I)與（II)中，nx係薄膜面內之遲相軸方向（折射率爲最大之方向）的折射率。於式（I)與（II)中，ny係薄膜面內之進相軸方向（折射率爲最小之方向）的折射率。於式（II)中，nz係薄膜之厚度方向的折射率。於式（I)與（II)中，d係單位設爲nm之薄膜的厚度。還有，相對於波長5 50nm，透明載體之複折射率（△ n : nx-ny )較宜爲 0.0000 1 5-0.0088 > 更佳爲 0.00025〜0.005。另外，相對於波長5 5 0nm，厚度方向的複折射率{( nx+ ny) /2- nz}較宜爲 0.0006-0.02，更佳爲 0.001〜0.007。尤其用於TN模式之光學補償片的透明載體，Re遲滯値較宜爲4〜4〇nm，而且Rth遲滯値較宜爲50〜200nm之範圍，用於OCB、HAN、VAN、均勻配向模式等ECB模式之光學補償片的載體，Re遲滯値較宜爲10〜70nm，而且Rth遲滯値較宜爲7〇~400nm之範圍。 [薄膜之遲相軸角度] 透明載體之面內的遲相軸角度係定義爲以輥輪狀薄膜之寬度方向作爲基準線（〇 ° )，遲相軸與基準線所成的角度。順時鐘方向設爲+。遲相軸角度（軸偏移）之平均値的絕對値較宜爲〇度以上、3度以下，視野角度之偏異將被改善而成爲顯示影像之辨識性良好；更佳爲0度以上、2 度以下：最好爲〇度以上、1度以下。將遲相軸角度平均値之方向定義爲遲相軸之平均方向。另外，遲相軸角度之標準偏差較宜爲0度以上、1.5度 -32- 201211575 以下；更佳爲〇度以上、〇 · 8度以下；最好爲0度以上、ο . 4 度以下。藉由將標準偏差設爲〇度以上、1.5度以下，能夠進一步防止發生顯示器顔色改變的「色澤不均」。 (第4態樣、第5態樣） [光學補償片] 本發明之第4態樣的光學補償片係由醯化度爲5 9.0至 61.5%之光學異方向性的纖維素醋酸酯薄膜構成的，表面進行皂化處理，並且，表面之水的接觸角爲3 0°以上、70° 以上，更佳爲40°以上、70°以上之光學補償片。本發明之第5態樣的光學補償片係於醯化度爲5 9.0至 61.5%之纖維素醋酸酯薄膜載體之一側面上具有光學異方向層，載體之單側表面進行皂化處理，並且，水的接觸角爲30°以上、70°以上，更佳爲40°以上、70°以上之光學補償片。如此方式，本發明之特徵爲；將用於光學補償片的纖維素醋酸酯薄膜進行皂化處理，並且，水的接觸角爲30°以上、70°以上。將本發明之光學補償片適用於偏光板之情形，藉由此皂化處理，對於偏光板之接著性將提高，而且，若對水的接觸角爲30°以上，由於對水之濕潤性將降低，於偏光板加工步驟之水洗後，水滴將不會殘留，良率將提高。另外，若水的接觸角超過70°，由於變得容易將水彈開，所附著的污垢便難以脫落。第5態樣的光學補償片，較宜於纖維素醋酸酯薄膜上形成配向膜，再於其上設置碟狀化合物或含有棒狀化合物之 -33- 201211575 光學異方向層。光學異方向層係藉由於配向膜上使碟狀化合物或棒狀液晶化合物予以配向，將其配向狀態予以固定而形成。如此方式，於纖維素醋酸酯薄膜上設置光學異方向層之情形，習知爲了確保纖維素醋酸酯薄膜與配向膜之接著性，必須於二者之間設置明膠塗底層，但是進行後述之表面處理，例如，藉由進行具有該至少二個芳香族環之芳香族化合物的添加等，能夠使水的接觸角成爲該範圍而不需要明膠塗底層。光學異方向層之厚度較宜爲0.1〜10// m，更佳爲0.5〜50 μ m。該碟狀液晶化合物，由於一般具有大的複折射率而有多樣之配向形態，藉由使用碟狀化合物，能夠製得具有習知拉伸複折射薄膜所無法得到之光學性質的光學補償片。針對使用碟狀化合物之光學補償片，已揭示於日本公開專利第平6-214116號公報、美國專利第5583679、5646703號、西德專利公報第39 1 1 62 0A1號之各專利說明書。 [纖維素醋酸酯薄膜] 本發明所用之纖維素醋酸酯薄膜係使用醯化度爲59.0 至61.5%之纖維素醋酸酯。所謂醯化度意指每纖維素單位質量之鍵結醋酸量。醯化度係遵循ASTM: D-817-91(纖維素醋酸酯等之測試法）之醯化度的測定與計算》纖維素醋酸酯之黏度平均聚合度（DP)較宜爲2 5 0以上，更佳爲290以上。另外，用於本發明之纖維素醋酸酯係利用凝膠滲透層析 -34- 201211575 儀之Mm/Mn( Mm爲質量平均分子量、Μη爲數目平均分子量）所示的分子量分布要窄。具體之Mm/Mn之値較宜爲 1.0至5.0之範圍，更佳爲1.3至3.0之範圍，最好爲1.4 至2.0之範圍。 <纖維素醋酸酯薄膜之皂化處理> 於本發明，表面處理係進行皂化處理，必要的話，進行電漿處理、火焰處理與紫外線照射處理。於皂化處理含有酸的皂化處理與鹼的皂化處理。於電漿處理包括電暈放電處理與輝光放電處理。爲了確保薄膜之平面性，於此等之表面處理，將纖維素醋酸酯薄膜之溫度爲玻璃轉移溫度（Tg)以下，具體而言，較宜於150〇c以下。鹼的皂化處理較宜將纖維素醋酸酯薄膜浸漬於鹼性溶液之後，以酸性溶液進行中和、經水洗後，進行乾燥的循環。鹼性溶液之例子，可列舉：氫氧化鉀溶液與氫氧化鈉溶液。鹼性溶液中之氫氧化離子的標準濃度較宜爲0.1N至 3.0N’更佳爲0.5 N至2.0N。鹼性溶液之溫度較宜爲〇至 90°C之範圍，更佳爲40至70°C。電暈放電處理係藉由於連接高電壓產生裝置之電極與介電體之間外加高電壓’將纖維素醋酸酯薄膜置於電極與介電體輥輪之間所產生的電暈放電中，或是使其移動而進行。另外’於本專利說明書，揭示於電極與介電體輥輪之間外加的高電壓之頻率爲放電頻率》於空氣中進行電暈放電處理的話，雖然簡便，必要的 -35- 201211575 話，也可以將處理裝置予以作成密閉或半密閉狀態，也能夠於以其他氣體充滿的狀態下，或是於混合其他氣體與空氣之狀態下進行處理。氣體之例子，可列舉：氮氣、氬氣、氧氣等。於電暈放電處理，一般之放電頻率爲50Hz〜5000kHz，較宜爲5 kHz~數百kHz。於電暈處理，若放電頻率過低，由於放電將變得不穩定，並且於纖維素醋酸酯薄膜中將產生針孔，故並不適合。另外，若放電頻率過高，由於必需具有爲了配合電阻之追加裝置，因而裝置之價格變高，故也不適合。爲了改善通常之濕潤性，最好將纖維素醋酸酯薄膜之電暈放電處理較宜設爲 O.OOlkV ·Α ·分/m2~5kV ·Α .分/m2，更佳的話，設爲O.OlkV.A·分/m2〜lkV.A·分/m2。電極與介電體輥輪之間隔較宜爲0.5至2.5mm，更佳爲1.0至 2 · 〇 m m 〇電暈放電處理係於低壓氣體中，藉由將高電壓外加於一對以上之電極間，再將纖維素醋酸酯薄膜放置於電極間所產生的電暈放電中，或是使纖維素醋酸酯薄膜進行移動而進行。於電暈放電處理之氣壓，一般爲〇.〇〇5~20Torr之範圍，更佳爲0.02-2 Torr之範圍。若壓力過低，則表面處理效果將降低。若壓力過高，則過大電流將通過，容易造成火花而有危險，也有纖維素醋酸酯薄膜遭受破壞之虞。放電係藉由於真空槽中，設置一對以上空間而於金屬板或金屬棒之間外加高電壓所產生的。雖然此電壓係根據環境氣體之 -36- 201211575 組成、壓力而可以取得各種數値，通常於該於500〜5000V之間，產生穩定的電暈放電。爲了改善接著性，較宜將外加電壓 2000〜4000V。另外’一般之放電頻率係來自 MHz，較宜設爲50Hz〜22MHz。爲了得到所要較佳將被處理物之電暈放電處理設爲〇 /m2〜5kV.A·分/ m2’更佳的話，設爲〇.i5kV_ • A ·分 / m2 ° 紫外線照射處理係藉由將紫外線照射於薄膜所進行的。於紫外線照射處理，膜表面約1 50°C，若性能上無問題的話，可以使用主之高壓水銀燈作爲光源使用。若必須進行形，較宜使用主波長爲2 5 4nm之低壓水銀燈以使用無臭氧式之高壓水銀燈與低壓水銀燈量，雖然處理光量越多薄膜與被接著層之接是隨著光量之增加，將發生薄膜著色、或是題。因而，使用以365nm爲主波長之高壓水照射光量較宜爲20〜10000 ( 111〗/(^2)，更 (mJ/cm2)。使用以254nm爲主波長之低壓7』照射光量較宜爲10〇〜10000 ( 111〗/(；1112)，更-(mJ/cm2)。具體而言，本發明之光學補償片（纖維素表面之水的接觸角係將表面純水滴入纖維素於液滴表面與薄膜表面之交點，自液滴畫出表面形成的角度，將含液滴之角度定義爲接壓力範圍內，之範圍設爲於直流的數千 :之接著強度，丨.01 kV · A ·分 1 A ·分 /m2〜1kV 纖維素醋酸酯溫度將上升至波長爲365nm 低溫處理之情。另外，也可。關於處理光著力越高，但薄膜變脆之問銀燈的情形，佳爲 50〜2000 <銀燈的情形，隹爲300〜1500 ;醋酸酯薄膜）醋酸酯薄膜，的切線與薄膜觸角而進行測 -37- 201211575 定。即於纖維素醋酸酯薄膜實施該皂化處理，發生與偏光膜之接著性的問題（利用耐久性測試，發生與偏光膜之剝離等之問題）。將保護膜表面之水的接觸角設爲30°以上、70°以下，並且爲了改善與偏光膜之接著性，較宜將如下述之疏水性化合物（具有二個芳香族環之芳香族化合物）添加於纖維素醋酸酯薄膜。 <具有二個芳香族環的芳香族化合物> 爲了調整纖維素醋酸酯薄膜之接觸角與遲滯値，將具有至少二個芳香族環之芳香族化合物作爲添加劑使用。以下，將此化合物也稱爲遲滯値調整劑。相對於1〇〇份質量之纖維素醋酸酯，芳香族化合物係使用0.01至20份質跫之範圍。相對於100份質量之纖維素醋酸酯，芳香族化合物較宜使用0.05至15份質量之範圍，更佳使用0.1至10份質量之範圍。也可以合倂二種以上之芳香族化合物而使用。於芳香族化合物之芳香族環中，除了芳香族碳氫環之外，也含有芳香族性雜環。基於控制接觸角之觀點，芳香族化合物較宜爲疏水性高的化合物。於本發明所用之芳香族化合物之芳香族環（芳香族碳氫環、芳香族性雜環）已揭示於日本公開專利第2000- 1 1 1 91 4 號公報之段落[001 1]〜[008 5]。遲滯値提昇劑之分子量較宜爲300至800。 -38- 201211575 <纖維醋酸酯薄膜之遲滞値> 薄膜之Re遲滯値與Rth遲滯値，分別定義爲下式（I ) 與（Π )。數學式（I) Re= ( nx — ny ) xd 數學式（II) Rth={(nx+ny) /2 — nz}xd 於數學式（I)與（II)中，nx係薄膜面內之遲相軸方向（折射率爲最大之方向）的折射率。 ny係薄膜面內之進相軸方向（折射率爲最小之方向）的折射率。 nz係薄膜之厚度方向的折射率。 d係單位設爲nm之薄膜的厚度。於本發明，較宜將纖維醋酸酯薄膜之Re遲滯値調節至5 至100nm，而且，Rth遲滯値調節至70至400nm。於液晶顯示裝置內，使用二片光學異方向性纖維素醋酸酯薄膜（光學補償片）之情形，薄膜之Rth遲滯値較宜爲 70 至 250nmo 於液晶顯示裝置內，使用一片光學異方向性纖維素醋酸酯薄膜（光學補償片）之情形，薄膜之Rth遲滯値較宜爲 150 至 400nm° 還有，纖維素醋酸酯薄膜之複折射率（Δη: ηχ-ny)較宜爲0.00025至0.00088。另外，纖維素醋酸醋薄膜之厚度方向的複折射率{(nx+ny)/2— nz}較宜爲0.00088至 0_005 。 [透明載體、纖維素醯化物薄膜之製造方法] 針對較宜用於本發明之第1〜第5態樣之纖維素醯化物等 -39- 201211575 之透明載體的製造方法，進行說明。於本發明，該透明載體較宜利用溶液流延方法（溶延方法）進行製造，該溶液流延方法係使用將聚合物維素醯化物等）等溶於有機溶劑之溶液（摻雜液）而薄膜的製造。 (溶液調製步驟）於溶液流延方法，所用之有機溶劑，只要能用於通液流延方法之有機溶劑，並無特別之限制，例如，較溶解度參數爲17~22之範圍。具體而言，可列舉：低肪族碳氫化合物之氯化物、低級脂肪族醇、碳原子數之酮類、碳原子數3~12之酯類、碳原子數3〜12之酯碳原子數5~8之脂肪族碳氫類、碳原子數6〜12之芳香氫類等。醚、酮與酯也可以具有環狀構造。可以使用具有二上酸、嗣與醋之官能基（亦即，一 0—、— CO-與— —)之中的任一種化合物、有機溶劑。再者，有機溶可以具有如醇性羥基之其他官能基。該有機溶劑具有以上官能基之有機溶劑的情形，其碳原子數只要爲具一種官能基之化合物的該較佳碳數範圍內即可》碳原子數3~12之醚類的例子，包含：二異丙基醚甲氧基甲烷、二甲氧基乙烷、1,4 -二噁烷、1，3 -二氧雜Θ 四氫呋喃、苯甲醚與苯乙醚。碳原子數3~12之酮類的例子，包含：丙酮、甲基酮、二乙基酮、二異丁基酮、環己酮與甲基環己酮。碳原子數3〜12之酯類的例子，包含：甲酸乙酯' 劑流 (纖進行常溶宜爲級脂 3〜12 類、族碳個以 COO 劑也二種有任環、乙基甲酸 -40- 201211575 丙酯、甲酸苯酯、乙酸甲酯、乙酸乙酯與乙酸戊酯。具有二種以上官能基之有機溶劑例子，包含·· 2·乙氧基乙酸乙酯、2-甲氧基乙醇與2-丁氧基乙醇。鹵化碳氫化合物之碳原子數較宜爲1或2，而以1爲最好。鹵化碳氫化合物之鹵素較宜爲氯。鹵化碳氫化合物之氫原子，被鹵素取代的比例，較宜爲25至75莫耳％，更佳爲30至70莫耳％，更理想爲35至65莫耳％，最好爲 40至60莫耳％。二氯甲烷爲一種代表性之鹵化碳氫化合物。爲了製造遵循本發明之纖維素醯化物薄膜，較宜混合二種以上有機溶劑而予以使用。基於控制音速的觀點，具體而言，較宜使用二氯甲烷、甲醇與丁醇之三種溶劑，較宜於下列之範圍進行混合：二氯甲烷爲75份質量至85份質量；甲醇爲15份質量至25份質量；以及丁醇爲〇.〇5份質量至5份質量。本發明之該有機溶劑，尤以使用混合二種以上有機溶劑之混合溶劑較佳。特別以相互不同的三種以上混合溶劑更爲理想：第1溶劑較宜爲由碳原子數3〜4之酮類與碳原子數3〜4之酯類或其混合液；第2溶劑較宜爲由碳原子數5〜7 之酮類或乙醯乙酸乙酯所選出的；第3溶劑較宜爲由沸點 30~170°C之醇類或沸點30〜170°C之碳氫化合物所選出的。尤其，以2 0〜9 0質量％之醋酸酯、5〜60質量％之酮類、 5〜3 0質量％之醇類之混合比例予以混合而成。基於纖維素醯化物溶解性的觀點，較宜使用醋酸酯、酮類與醇類之混合溶劑。 -41 - 201211575 此混合溶劑中’醇類之摻合比例較宜爲全部溶劑中之 2vol%以上、40vol%以下’更佳爲3 vol%以上、30vol% 以下，更理想爲5 vol%以上' 20vol%以下。該醇類較宜爲碳原子數1以上、8以下之一醇或二醇，或者碳原子數2以上、1〇以下之氟醇’更佳可列舉：甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、tert-丁醇、1-戊醇、2 -甲基-2-丁醇、環己醇、乙二醇、2-氟乙醇、2，2,2-三氟乙醇、2,2,3,3 -四氟-1-丙醇。此等可以單獨添加，或是也可以混合二種以上而予以添加。尤其，可列舉：不含鹵化碳氫化合物之非鹵素系有機溶劑系，尤以不含氯原子之實質非氯系溶劑（以下，簡稱爲「非氯系溶劑」）的較佳態樣。技術性上，雖然可以無問題地使用如二氯甲烷之鹵化碳氫化合物，但是基於地球環境或作業環境之觀點，有機溶. 劑較宜實質上不含鹵化碳氫化合物。所謂「實質上不含」意指有機溶劑中之鹵化碳氫化合物的比例低於5質量％ (較宜爲低於2質量％ )。另外，從製得的纖維素醯化物薄膜，較宜完全檢測不出如二氯甲烷之鹵化碳氫化合物。用於本發明之非氯系溶劑，例如，可列舉：揭示於日本公開專利第 2002- 1 46043 號公報之段落編號 [0021]〜[0025]、日本公開專利第2002-146045號公報之段落編號[0016]〜[002 1 ]等溶劑系之例子。該非氯系溶劑，較宜爲由碳原子數3以上、12以下之醚、酮、酯選出的至少一種有機溶劑與醇之混合溶劑，該溶劑中之醇的含有比例爲2~40質量％之混合溶劑。 -42- 201211575 具體而言，如此之混合溶劑，例如，可列舉以下之混合溶劑。醋酸甲酯/環己酮/甲醇/乙醇（= 70/20/5/5、份質量）醋酸甲酯/甲基乙基酮/乙醯醋酸甲酯/甲醇/乙醇（= 50/20/20/5/5 、份質量）丙酮/乙醯醋酸甲酯/甲醇（=75/20/5、份質量）醋酸甲酯/丙酮/甲醇/乙醇/ 丁醇（=75/10/5/5/5、份質量）醋酸甲酯/1,4-二噁烷/環戊酮/甲醇/1- 丁醇（= 60/20/12/5/3 、份質量）丙酮/環戊酮/甲醇/乙醇（=60/3 0/5/5、份質量） 1，3-二噁烷/環己酮/甲基乙基酮/甲醇/乙醇（= 55/20/15/5/5、份質量）於該混合溶劑中，也可以添加Ovol%以上、lOvol%以下之碳原子數爲5以上、1〇以下之芳香族或脂肪族之碳氫化合物。碳氫化合物之例，可含有：環己酮、己烷、苯、甲苯、二甲苯。另外，於該摻雜液中，除了該有機溶劑之外，也可以含有全部有機溶劑量10質量％以下之氟醇，更佳爲含有5質量％以下，較宜改善薄膜之透明性、加速溶解性。該氟醇例如可列舉：揭示於日本公開專利第平8- 1 43 709號公報之段落編號[0020]、第平11-60807號公報之段落編號[0037] 等之化合物。此等之氟醇可以使用一種或二種以上。於本發明’調製該摻雜液之際，也可以使氮氣等之不活性氣體充滿於容器內。另外，於摻雜液即將製膜前之黏度，只要於製膜之際爲可流延的範圍即可，通常較宜調製成 -43- 201211575 10ps，s〜2000ps.s 之範圍，尤以 30ps.s〜400ps.s 更佳。針對該摻雜液之調製’其溶解方法並無特別之限定，可以爲室溫溶解法、冷卻溶解法或高溫溶解法，甚至組合此等方法而進行。關於此等溶解方法，例如，摻雜液之調製法，可列舉：揭示於日本公開專利第平5 - 1 6 3 3 0 1、昭 61-106628、昭 58-127737、平 9-95544、平 10-958454、平 1 0-45950 ' 2000-53 784、平 1 1 -3 22946 ' 平 1 1 -322947、平 2-276830 、 2000-273239 、平 11-71463 、平 4-259511 、 2000-273184、平 11-323017、平 11-302388 號公報等，揭示於此等公報之透明載體原料聚合物之對有機溶劑的溶解方法，本發明可以採用適合此等之技術。再者，將纖維素醯化物作爲聚合物使用之情形的纖維素醯化物摻雜液溶液，通常，實施溶液的濃縮與過濾，同樣已詳細揭示於該公技編號2001-1745號ρ·25。還有，於高溫下進行溶解之情形，幾乎爲所用之有機溶劑的沸點以上之情形，此情形也可用於加壓狀下。進一步敘述摻雜液之調製方法。利用一般之方法，可以調製纖維素醯化物溶液。所謂一般方法意指於〇 t以上之溫度（常溫或高溫）進行處理。溶液之調製能夠利用通常之溶劑流延法的摻雜液調整方法與裝置而進行。還有，一般方法之情形，也可以使用鹵化碳氫化合物（尤其是二氯甲烷）作爲有機溶劑使用。纖維素醯化物之量係調整至所得到的溶液中含有1 0至 40質量％。纖維素醯化物之量更佳爲10至30質量％。於有機溶劑（主溶劑）中，也可以添加後述之任意添加劑。 * -44- 201211575 溶液能夠藉由於常溫（0至40°c )下，進行纖維素醯化物與有機溶劑之攪拌而予以調製。高濃度之溶液也可以於加壓與加熱條件下進行攪拌。具體而言，將纖維素醯化物與有機溶劑倒入加壓容器中而予以密閉，於加壓下，於常溫溶劑之沸點以上、並且於溶劑未沸騰之範圍的溫度，一面加熱並一面進行攪拌。通常之加熱溫度爲40°C以上，較宜爲60至200°C，更佳爲80至110°C。各成分也可以預先進行初步混合之後倒入容器中。另外，也可以依序倒入容器中。容器必須要有能夠攪拌的構造。能夠將氮氣等之不活性氣體予以注入之後進行容器之加壓。另外，也可以利用因加熱而造成溶劑蒸氣壓之上升。或是也可以將容器密閉之後，於加壓下添加各成分。進行加熱之情形，較宜從容器之外部進行加熱》例如，可以利用套管式之加熱裝置。另外，也可以藉由於容器之外部設置加熱板，配管而使液體循環，進行整個容器之加熱。較宜於容器內部設置攪拌葉片，利用此攪拌葉片進行攪拌。攪拌葉片較宜達到容器壁附近之長度。於攪拌葉片之末端，爲了更換新的攪拌葉片，較宜設置刮取式葉片。於容器內，也可以設置壓力計、溫度計等之度量器具類。於容器內，將各成分溶於溶劑中。調製後之摻雜液經冷卻後而從容器中予以取出，或是於取出後再利用熱交換器進行冷卻。藉由冷卻溶解法，也可以進行溶液之調製。冷卻溶解法可以利用通常之溶解方法而使纖維素醯化物可溶於難溶的 -45- 201211575 有機溶劑中。還有，即使利用通常之溶解方法可以溶解纖維素醯化物之溶劑，若利用冷卻溶解法，則具有可以得到迅速而均勻之溶液的效果。冷卻溶解法方面，最初於室溫，一面攪拌有機溶劑中之纖維素醯化物，並一面慢慢地進行添加。纖維索醯化物之量較宜調整至此混合物中含有10至40 質量％。纖維素醯化物之量更佳爲10至30質量％。再者，也可以將後述之任意添加劑添加於混合物中。接著，將混合物冷卻至-100至-10 °C (較宜爲-80至-10 °C，更佳爲-5 0至-2 0 °c，最好爲-5 0至-3 0 °C )。例如，冷卻能夠於乾冰-甲醇浴（-75 °C )中或已冷卻的二甘醇溶液 (-3 0至-2 0°C )中進行。若以如此方式進行冷卻，纖維素醯化物與有機溶劑之混合物將固化。冷卻速度較宜爲4°C /分以上，更佳爲8 °C /分以上，最好爲12°c /分以上。雖然冷卻速度越快越好，l〇〇〇〇°C /秒爲理論之上限，l〇〇〇°C /秒爲技術之上限，而且l〇〇°C /秒馬實用之上限。還有，冷卻速度係將開始進行冷卻之時的溫度與最後之冷卻溫度的差値除以從開始進行冷卻直到最後冷卻溫度爲止之時間的數値。再者，一旦將溶液升溫至0至200°c (較宜爲0至150 °C，更佳爲0至12 0 °C，最好爲〇至5 0 °C ) ’纖維素醯化物將溶於有機溶劑中。升溫可以僅放置於室溫中’也可以於熱水浴中進行加熱。升溫速度較宜爲4°C /分以上，更佳爲8°C /分以上’最好爲12°C /分以上。雖然升溫速度越快越好，l〇〇〇〇°C /秒爲理 -46- 201211575 論之上限，1 000°c /秒爲技術之上限，而且100°c /秒爲實用之上限。還有，升溫速度係將開始進行升溫之時的溫度與最後之升溫溫度的差値除以從開始進行升溫直到最後升溫溫度爲止之時間的數値。進行如此方式，可以得到均勻的溶液。還有，溶解不完全的情形，也可以重複進行冷卻、升溫之操作。溶解是否完全，可以藉由目視，僅觀察溶液的外觀而進行判斷。冷卻溶解法係爲了避免因冷卻時之凝結而造成的水份混入，較宜使用密閉容器。另外，於冷卻升溫操作，若於冷卻時進行加壓，於升溫進行減壓，能夠縮短溶解時間。爲了實施加壓與減壓，較宜使用耐壓性容器。還有，藉由冷卻溶解法，將纖維素醯化物（醯化度：60.9 % ，黏度平均聚合度：299)溶於醋酸甲酯中而形成20質量％之溶液，若利用微分掃瞄式熱量計（DSC)之測定，於3 3 °C附近，存在溶膠狀態與凝膠狀態之虛擬相轉移點，於此溫度以下的話，成爲均勻的凝膠狀態。因而，此溶液必須保持於虛擬相轉移溫度之上，較宜爲凝膠相轉移溫度加上1 〇°C左右之溫度。但是，此虛擬相轉移溫度係依纖維素醋酸酯之醯化度、黏度平均聚合度、溶液濃度或所使用之有機溶劑而有所不同。於該摻雜液中，必要的話，也可以含有遲滞値調整劑、可塑劑、紫外線吸收劑等之其他添加劑。於本發明之第3 態樣的情形，進一步添加微顆粒。 (微顆粒之添加混合物方法）將微顆粒添加至纖維素醯化物溶液的情形，重要的是如 -47- 201211575 上所述之粗大顆粒不可存在，以及不可使其產生凝聚或沈澱等，必須分散而存在，若能夠滿足此等條件，方法上並無特別之限定，即使利用任一種方法，均可以得到所要之纖維素醯化物溶液。該微顆粒係不同於該摻雜液調整，較宜另外進行分散液之調製，之後，混合分散於摻雜液內之方法。例如，可列舉如下所示之方法。 (1)將溶劑（相同用於溶液流延方法的該有機溶劑）與微顆粒予以攪拌混合之後，利用分散機而形成微顆粒分散物，加入摻雜液後進行攪拌。 (2 )將該溶劑與微顆粒予以攪拌混合之後，利用分散機形成微顆粒分散物，再將少量纖維素醯化物加入溶劑中，進行攪拌溶解。添加該微顆粒分散物於此溶液中，利用連線攪拌機進行攪拌所得到的微顆粒添加液與摻雜液之充分混合。 (3 )將少量之膠黏劑加入該溶劑後進行攪拌溶解，再將微顆粒加入其中，利用分散機予以分散而形成微顆粒分散物。利用連線攪拌機進行微顆粒添加液與摻雜液之充分混合。膠黏劑可列舉纖維素醯化物等，較宜使用供應摻雜液之纖維素醯化物。分散能夠利用習知之濕式分散方法。媒介物濕式分散機可列舉：砂磨機（例如，附針狀之珠磨機）、沖模磨機、高速渦輪磨機、卵石磨機、輥輪磨機、磨耗機、膠體磨機、球磨機等習知之分散機。尤其將本發明之氧化物微顆粒分散爲超微顆粒，較宜爲砂磨機、沖模 -48- 201211575 磨機與高速渦輪磨機。分散不含該範圍之粗大顆粒的超微顆粒大小，較宜使用平均粒徑低於〇.8mm之媒介物的濕式分散方法。與該分散機一同使用之媒介物，其平均粒徑低於〇.8mm，平均粒徑能夠藉由利用此範圍之媒介物，得到該無機微顆粒直徑爲 lOOnm以下，並且微顆粒直徑一致之超微顆粒。媒介物之平均粒徑較宜爲0.5mm以下，更佳爲0.05〜0.3mm。另外，用於濕式分散之媒介物較宜爲珠粒。具體而言，可列舉：氧化锆珠、玻璃珠、陶瓷珠、鋼珠等，基於難以產生分散中之珠粒破壞等之耐久性與超微顆粒化之考量，尤以0.05〜0_2mm之氧化鉻珠特別理想。無媒介物分散機，可利用超音波型、離心型、高壓型等。例如，於1 -2000 /z m之細管中，高壓分散裝置內部之最大壓力條件較宜爲9.8MPa以上，更佳爲19.6 MPa以上。另外，此時最高速度達到l〇〇m/sec以上，傳熱速度較宜爲 420kJ/hr以上。局壓分散裝置可列舉：Micro fluidics Corporation公司製之超高壓均化器（商品名爲 Micro Fluidizer)或是 Nanomizer 公司製之 Nanomizer;其他之 Manton Galling型高壓分散裝置，例如，可列舉 :Izumi HoodRth hysteresis is preferably adjusted to 70nm <Rth <400nm range. In the case of using two optically anisotropic cellulose oxime films in a liquid crystal display device, the Rth hysteresis of the film is preferably 70 nm. <Rth < 2 5 0 nm range, more preferably 75 nm <Rth <150 nm range. In the case of using an optically anisotropic cellulite film in a liquid crystal display device, the Rth hysteresis of the film is preferably 150 nm. <Rth <400nm range, more preferably 160nm <Rth <250nm range. Further, the complex refractive index (?n: nx - ny ) of the cellulose halide film is preferably in the range of 0.00 to 0.002. Further, the complex refractive index {(nx + ny) / 2 - nZ} in the thickness direction of the cellulose halide film is preferably in the range of 0.001 to 0.04. Furthermore, the wavelength dependence of the complex refractive index of the cellulose halide film is A = Δ η (450 ) / Δ η ( 5 50 ) and Β = Δη (650) / Δ η ( 5 5 0 ), preferably 0. ·20 <Α <1.05 and 1·00 <Β <1·55. [Preventing Light Leakage] In order to prevent thermal skew of the liquid crystal display device, the thickness and the elastic modulus of the cellulose halide film are adjusted. The thickness (d) of the cellulose halide film is set at l〇Am <d <85#m range. Although the thickness (d) of the cellulose halide film is as thin as possible, the viewpoint of the operation of the substrate -18-201211575 is preferably 30 v m . <d <80 # m. In addition, in order to reduce the imaginary skew, it is preferable to increase the molecular orientation of the polymer by biaxially stretching the cellulose vapor film, or to set the hygroscopic expansion coefficient to 3 〇 x 1 (T 5 /%). Below RH, the hygroscopic expansion coefficient of the vitamin bismuth film is preferably 15x10-5/% RH or less, preferably 1〇χ10_5/% RH. The method for suppressing the coefficient of hygroscopic expansion is to improve the cellulose oxime film. The modulus of the cellulose phthalate film is preferably 3 OOOMPa or less, more preferably 2500 MPa or less. To adjust the speed of sound in order to satisfy the (iii) and (iv), based on the modulus of elasticity or density It is also advantageous to adjust or manufacture the operation. The minimum 音 (Vmin) and the maximum 値 (Vmax) of the measured sound velocity in the film of the cellulose oxime film are better ((Vmin+Vmax) /2). For 2.3 <( (Vmin+Vmax) /2) <2.4km/sec. The ratio of the maximum 値 to the minimum 音 (Vmax/Vmin ) of the speed of sound measured in the plane of the film is preferably 1.03. <Vmax/Vmin <1.10. [Cellulose Telluride] Cellulose Telluride is an ester of cellulose and acid. The acid is preferably a carboxylic acid, more preferably a fatty acid, more preferably a fatty acid having 2 to 4 carbon atoms, most preferably acetic acid (cellulose acetate). The degree of cleavage is from 59.0 to 6.1. Cellulose acetate is particularly desirable. The degree of deuteration means the amount of bonded acetic acid per unit mass of cellulose. The degree of hydration is measured and calculated according to ASTM: D-817-91 (test method for cellulose acetate, etc.). The viscosity average polymerization degree (DP) of the cellulose halide is preferably 250 to -19-201211575, more preferably 290 or more. Further, the cellulose halide used in the present invention is preferably a narrow molecular weight distribution of Mm/Μη (Mm is a mass average molecular weight and Μη is a number average molecular weight) by a gel permeation chromatography. The specific Mm/Mn is preferably in the range of 1.0 to 1.7, more preferably in the range of 1.3 to 1.65, and most preferably in the range of 1.4 to 1.6. [Hysteric retardation enhancer] In order to adjust the hysteresis of the cellulose halide film, an aromatic compound having at least two aromatic rings is used as a hysteresis enhancer. For 100 parts of the cellulose silicide, the aromatic compound is used in an amount of from 1 to 20 parts by mass. For 100 parts by mass of cellulose acetate, the aromatic compound is preferably used in the range of 0.05 to 15 parts by mass, more preferably in the range of 0.1 to 10 parts by mass. It is also possible to combine two or more aromatic compounds. The aromatic ring of the aromatic compound contains an aromatic heterocyclic ring in addition to the aromatic hydrocarbon ring. It is particularly preferred that the aromatic compound has at least one 1,3,5-triazine ring. A specific example of the hysteresis sputum enhancer is disclosed in Japanese Laid-Open Patent Publication No. 2002-169023. By using the hysteresis 値 lifter to cause hysteresis 値 control, the speed of sound can be controlled to an appropriate range without accompanying deformation such as stretching. (Third aspect) The optical compensation sheet of the present invention is obtained by sequentially laminating an alignment film and an optically different direction layer on a transparent carrier having a specific film thickness of microparticles having a specific particle diameter, and is characterized in that: a transparent carrier Has a specific surface shape with optical properties - 20-2111575. <Transparent Carrier> The transparent carrier of the present invention is preferably a transparent polymer film. The light transmittance of the transparent carrier is preferably 80% or more, and the haze is preferably 3% or less. Examples of the polymer constituting the polymer film include a cellulose ester (for example, one of cellulose, a di- or tri-telluride), a raw spintenyl polymer, and the like. Examples of the raw spinylene-based polymer include ARTON and ZEONEX (both are trade names). In addition, as the conventional polycarbonate or polypene is easy to find a birefringent polymer, as disclosed in International Publication No. 00/26705, as long as the discovery of the birefringence can be controlled by modifying the molecule, A transparent carrier for use in the present invention. A polymer, a graft polymer or the like may be blended for this purpose, and two or more polymers may be used. The specific thickness of the transparent carrier or the like of the present invention is from 20 to 80 μm, preferably from 30 to 80 / m, more preferably from 40 to 65 m. If the film thickness is less than 20 μm, sufficient strength cannot be found, and if it exceeds 80 μm, weight or workability is insufficient. Further, the variation of the film thickness is preferably within ±3%, more preferably within ±2%, and even more preferably within ±1.5%. It is good within this variation that it does not substantially affect the optically different directional layer of the carrier thickness. The transparent carrier used in the present invention can stably obtain good optical characteristics by thinning and lightening the optical compensation sheet, the polarizing plate, and the liquid crystal display device, or improving transmittance, improving contrast or display brightness, and the like. And can handle the long-shaped and wide-sized carrier with good operability. In particular, as the transparent carrier used in the present invention, a polymer film formed of a cellulose ester is preferably used. -21 - 201211575 As the cellulose ester raw material, there are cotton fiber, kenaf, wood pulp (broadwood pulp, conifer pulp), and the like, as long as the cellulose ester obtained from any raw fiber is It may be used or may be mixed and used as the case may be. In the present invention, it is preferred to use a cellulose oxime formed by esterification of cellulose. In particular, it is preferred that the cellulose is not directly used, but The cotton fiber, kenaf and pulp are refined and used. In the present invention, the cellulose halide is a cellulose fatty acid ester, more preferably a lower fatty acid ester of cellulose. The fatty acid ester refers to a fatty acid having 6 or less carbon atoms. The number of carbon atoms is preferably 2 (cellulose acetate), 3 (cellulose propionate) or 4 (cellulose butyrate). The cellulose ester is preferably cellulose acetate, and examples thereof include diethyl cellulose, triethylene cellulose, and the like. It is preferred to use a mixed fatty acid ester such as cellulose acetate propionate or cellulose acetate butyrate. In general, the hydroxyl groups at the 2, 3, and 6-positions of the cellulose halide are not uniformly distributed to 1 / 3 of the entire substitution ratio, and the 6-position hydroxyl substitution ratio tends to be small. The 6-position hydroxyl group substitution rate of the cellulose halide of the present invention is preferably the same level or more as compared with the 2, 3-position. The 6-position hydroxyethyl hydrazide group is preferably substituted with 30% or more and 40% or less, more preferably 31% or more, and more preferably 32% or more, more preferably than the ethyl hydrazide group. The 6-position hydroxyl group may be substituted with a fluorenyl group having a carbon number of 3 or more, a fluorenyl group, a butyl group, a pentamidine group, a benzoinyl group, an acrylonitrile group or the like. The measurement of the substitution rate of each position can be determined by an NMR method or the like. For the polymer film used in the transparent carrier of the present invention, it is preferred to use a film of cellulose halide of 55.0 to 62.5% with a degree of deuteration-22-201211575, and more preferably a degree of deuteration of 57·0 to 61.5. % of a film of cellulose halide. The degree of deuteration referred to herein means the amount of bonded acetic acid per unit mass of cellulose. The degree of deuteration is determined by measuring and calculating the degree of enthalpy of ASTM: D-817-91 (test method for cellulose acetate, etc.). Further, the average degree of polymerization (DP) of the cellulose halide is preferably 25 Å or more, more preferably 290 or more. Further, the polymer film is a gel permeation chromatograph, and the polydispersity index Mm/Mn (Mm is a mass average molecular weight, Μη is a number average molecular weight) is preferably small, and the molecular weight distribution is preferably narrow. The specific enthalpy of Mm/Mn is preferably from 1.0 to 2.5, more preferably from 1.0 to 2.0, most preferably from 1.0 to 1.6. [Microparticles] In the present invention, for the transparent carrier to be used, microparticles are added in order to increase the strength of the transparent carrier and maintain good film curl suppression, transportability, roll-to-roll adhesion resistance or scratch resistance. The specific primary particle diameter of the specific particle diameter of the fine particles is 80 nm or less, more preferably 5 to 80 nm, still more preferably 5 to 60 nm, and particularly preferably 8 to 50 nm. If the average primary particle diameter exceeds 80 nm, the surface smoothness of the transparent carrier will be impaired. In particular, it is preferred to make the dispersion of the particle diameter of the fine particles uniform, and more preferably, particles having a particle diameter of 500 nm or more are not present. By using such ultrafine particles, it is preferable that the dispersibility in the dispersion is stabilized, the mechanical properties of the obtained film are not impaired, the haze is also lowered, and the uneven shape of the surface is fine and the unevenness is formed. The Mohs hardness of the microparticles is preferably from 2 to 10. More preferably 2.5 to 10. As long as the microparticles are materials exhibiting the function, there is no particular limitation -23-201211575. 'Either an inorganic compound or an organic compound may be used. More preferably, the inorganic compound is preferably a compound containing ruthenium. Cerium oxide, titanium oxide, zinc oxide, aluminum oxide, cerium oxide, chromium oxide, cerium oxide, cerium oxide, tin oxide, antimony, calcium carbonate, talc, clay, calcined clay, calcined calcium citrate, calcium citrate hydrate, Aluminum citrate, magnesium citrate, calcium phosphate, etc., more preferably an inorganic compound containing cerium or zirconia. Further, the surface-treated inorganic fine particles are preferably in dispersibility in the cellulose halide. Specifically, it is preferably an inorganic particle which has been surface-processed to be hydrophobic. For example, it can be listed in Chapter 9 of the "Application Technology of the First Volume of the Microparticle Engineering System" (Fuji Techno System Co., Ltd., published in 2002): Kaga Minami, and Lin Biao, "High Purity II" "Manufacturing and Application of Cerium Oxide" (CMC (Joint Company), issued in 1999) ❶ Organic compounds, for example, polymers which are preferably crosslinked polystyrene, oxime resin, fluororesin and propylene-based resin, among others, Good for using '矽 resin. Among the enamel resins, those having a three-dimensional network structure are particularly preferred. The amount of the microparticles added to the base polymer of the polymer film is preferably 〇.〇1~〇.3 parts by mass, more preferably 〇.〇5~0.2 parts, relative to the mass of the polymer. quality. [Hysteresis 値 adjuster] The polymer film used as the transparent carrier of the present invention preferably contains a hysteresis oxime adjusting agent which absorbs the absorption maximum wavelength (λ max ) of the ultraviolet absorption spectrum of the solution itself, based on the optical anisotropy. A compound having a 400 nm shorter wavelength ultraviolet ray is used as a retardation oxime adjusting agent. Examples of such a compound include ultraviolet absorbers such as phenylsalicylic acid, 2-hydroxybenzophenone, benzotriazole-24-201211575, and triphenyl phosphate. Further, an aromatic compound having at least two aromatic rings, a triphenylene compound, a dish-like compound (a compound containing a 1,3,5-triazine backbone, a porphin backbone, etc.) is preferably used. . In the present invention, the compound for the hysteresis oxime adjusting agent is preferably not substantially absorbed in the visible light field. *Aromatic compound having at least two aromatic rings It is particularly preferred to use an aromatic compound having at least two aromatic rings (hereinafter, also referred to as "aromatic compound A") as the hysteresis oxime adjusting agent. The aromatic ring of the aromatic compound A may be an aromatic heterocyclic ring in addition to the aromatic hydrocarbon ring. The aromatic hydrocarbon ring is particularly preferably a 6-membered ring (i.e., a benzene ring). The aromatic heterocyclic ring is generally an unsaturated heterocyclic ring. The aromatic heterocyclic ring is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, but is preferably a 5-membered ring or a 6-membered ring. Aromatic heterocycles generally have the most double bonds. The hetero atom is preferably a nitrogen atom, an oxygen atom or a sulfur atom, and particularly a nitrogen atom is particularly preferred. The number of aromatic rings having the aromatic compound A is preferably from 2 to 20, more preferably from 2 to 12. In the case of having three or more aromatic rings, it is sufficient that steric hindrance is not caused to the three-dimensional configuration of at least two aromatic rings. The bonding relationship of the two aromatic rings can be classified into: (a) formation of a fused ring; (b) direct bonding by a single bond; and (c) bonding by a bonding group. (Because it is an aromatic ring, it is impossible to form a screw bond). Any of (a) to (c) can be used based on the viewpoint of the improvement of the function of the hysteresis. Specifically, the contents of paragraph numbers [0016] to [0023] disclosed in Japanese Laid-Open Patent Publication No. 2 002 - 1 3 1 5 3 can be cited. Further, in the case of (b) or (c), it is preferred not to cause steric hindrance to the three-dimensional configuration of at least two aromatic rings. The aromatic compound A is a rod-shaped compound having a linear molecular structure similar to that of the paragraphs [0011] to [0031] disclosed in Japanese Laid-Open Patent Publication No. 2002-363343; the same is disclosed in Japanese Laid-Open Patent No. 2000 a compound containing two aromatic rings which does not cause a steric hindrance in the paragraph number [111] to [0085]; and 1, 3 containing at least one aromatic ring as a substituent A 5-triazine compound or a compound having a porphin backbone (a compound disclosed in Japanese Laid-Open Patent Publication No. 2001-166144). More preferably, a 1,3,5-triazine compound containing at least one aromatic ring as a substituent (the triazine ring has formed an aromatic ring). Specifically, the 1,3,5-triazine compound disclosed in the general formula (I) disclosed in Paragraph No. [0016] of Japanese Laid-Open Patent Publication No. 2001-1661 44 can be cited. The aromatic compound A may be used singly or in combination of two or more kinds of the compounds. The content of the aromatic compound A is selected in order to adjust the desired hysteresis, and the type and amount of the compound for retardation adjustment are selected. When the transparent carrier is produced, it is preferable to use 〇.〇1~30 with respect to 100 parts by mass of the polymer in order not to cause problems such as solubility in the transparent carrier molded product or insolubilization or separation during film formation. The range of quality is better than 0.1 to 25 parts by mass. [Plastic Agent] For the transparent carrier, in order to improve the mechanical properties of the film or to increase the drying speed, a conventional plasticizer is preferably added. Plasticizers, for example, can be -26- 201211575. Listed: preferably phosphates, carboxylates (carboxylic acids, aliphatic carboxylic acids, hydroxy acids (citric acid, malic acid, etc.), aromatic carboxylic acids (benzene) Diacids, etc., etc., have been disclosed in Japanese Society of Inventions Public Technology No. 2001-1745 (issued on March 15, 2001, Japanese Invention Association) 化合物·16 compounds, etc.). Further, an esterified compound of an alkylalkol and a carboxylic acid (a compound disclosed in Japanese Laid-Open Patent Publication No. Hei 11-124445, No. 2001-247717) and the like. The amount of the plasticizer added is preferably from 0.05 to 25 parts by mass, more preferably from 1 to 20 parts by mass, based on 1 part by mass of the polymer. [Other Additives] Further, an ultraviolet ray-resistant agent (for example, a hydroxybenzophenone-based compound, a benzotriazole-based compound, a salicylate-based compound, a cyanoacrylate-based compound, etc.) may be added to the transparent carrier. An anti-deterioration agent (for example, an antioxidant, a peroxide decomposer, a radical inhibitor, a metal inactive agent, an oxygen scavenger, a photo-stabilizing agent (a large substituent such as an amine group), etc.), a release agent, Antistatic agent, etc. For the detailed description, it is preferable to use the raw materials which have been disclosed in detail in Japanese Utility Model No. 2001-1745, p.17-22. The transparent carrier of the present invention is preferably composed of a cellulose halide containing at least one of the degree of deuteration of 55.0 to 62.5%, the microparticles, and a cellulose halide film of the aromatic compound A. Further, at this time, the addition of the additive other than the plasticizer to the cellulose halide film is not particularly limited. The blend ratio of the cellulose halide, the fine particles and the aromatic compound A of the cellulose halide film is the same as the blend ratio. -27- 201211575 [Characteristics of Transparent Carrier (Surface Shape)] #The optical compensation sheet of the invention is characterized in that the transparent carrier has a specific surface. Hereinafter, the surface shape of the transparent carrier of the characteristic portion of the present invention will be described. The surface of the transparent carrier on the side of the alignment film is based on JIS B0601-1994, and the arithmetic mean roughness (Ra) of the surface unevenness of the film is 0.0002 / im or more, and the lym or less '10 points average roughness is 〇. 〇〇〇 2 #m The above, ο" and below, and the maximum height (Ry) are 0.002 "m or more, 0.05 β m or less; preferably, the arithmetic mean roughness (Ra) is 0.0002 # m or more, 0.08 μm or less, and ten-point average roughness. (Rz) is 〇〇〇〇2 or more, o.^m or less, and the maximum height (Ry) is 〇〇〇2#m or more and 0.5/zm or less; more preferably, the arithmetic mean roughness (Ra) is 0.0002. /zm or more, 〇〇15/zm or less, ten point average roughness (rz) is 0.00 2//Π1 or more, 〇·〇5/Ζπι or less, and the maximum height (Ry) is 0.002^m or more, 〇.5 //m or less; especially ideal, the arithmetic mean coarse sugar (Ra) is above o.ooiym, below 〇.〇i〇ym, and the ten-point average rough degree (Rz) is 〇·〇〇2μιη or more, 〇.〇 Below 25/zm, and the maximum twist (Ry) is 〇.〇〇2ym or more, 〇.〇4/zm or less. Within this range, a uniform alignment film having no coating unevenness was provided. Furthermore, in the fine surface unevenness form, the ratio 算术(Ra/Rz) of the arithmetic mean roughness (Ra) to the ten point average roughness (RZ) is preferably 〇" or more "1 or less" and according to JIS B0601-1994, The average interval (Sm) of the unevenness on the surface of the film is preferably 〇.〇〇iem or more and 5#m or less. Here, the relationship between Ra and Rz represents the unevenness of the surface. Further, '(Ra/Rz) is better than 値. 1 5 or more and 1 or less; more preferably, 〇.丨7 or more, -28-201211575 1 or less, 'average interval (Sm) is 0.001 or more, lym the following. The concave and convex shapes of the surface can be evaluated by a transmission electron microscope (TEM), an atomic force microscope (AFM), or the like. (Other surface shapes) Further, the arithmetic mean roughness (Ra) and the maximum height (Ry) of the surface on the opposite side of the transparent carrier alignment film side of the present invention are preferably the arithmetic mean roughness (Ra) of the side surface of the alignment film. It is 3 times or less with the maximum height (Ry). More preferably, it is 1 to 2 times, especially 1 to 1 · 5 times. In such a range, the transparency of the film and the anti-adhesion property in the form of a light wheel are good. (Long ruler) The transparent carrier is preferably a long ruler. The length thereof is preferably l〇〇m or more, 5000 m or less, more preferably 300 m or more and 4500 m or less. The width thereof is preferably 0.7 m or more and 2 m or less, more preferably l.〇m or more and ι 7ιη or less. [Mechanical properties of film] (Curling) The crimp entanglement in the width direction of the transparent carrier used in the present invention is preferably -10/m to +10/m, more preferably -8/m to +8/m. With respect to the transparent carrier of the present invention, the surface of the long-sized ruler and the wide transparent carrier is subjected to surface treatment, flat-grinding treatment, or alignment film, or optically oriented layer, and the like, and the width of the transparent carrier is When the crimping direction of the direction is within this range, the workability of the film will become good and the film will not be cut. In addition, at the edge or the central part of the film, the film is in strong contact with the conveying roller, which often produces dust, and the contaminant on the film does not adhere to 'the ability to set the point of the optical compensation sheet or the frequency of the coating line. 201211575 is within the scope of allowable defects. Further, it is preferable to set the curl in this range, and in addition to being able to reduce the occurrence of stain defects which are likely to occur, it is also possible to prevent the entry of the bubbles when the polarizing film is bonded. The crimped file can be measured in accordance with the measurement method specified by the National Institute of Standards (ANSI/ASCPH 1.29-1985). (Tear Strength) As described above, the transparent carrier has a film thickness of 20 to 80 μm, and the tear strength is 2 g or more according to the tear test method (Elmendorf tear method) of JIS K7128-2:1998. It is preferable that the film thickness can sufficiently maintain the strength of the film. More preferably 5 to 25 g, more preferably 6 to 25 g. Further, in terms of 60/zm, it is preferably 8 g or more, more preferably 8 to 15 g. Specifically, the sample piece 50 mm X 6 4 mm was conditioned for 2 hours under conditions of 25 ° C and 65% RH, and then measured by a lightweight load tear strength tester. In particular, in the case where the curl and the tear strength are completed after a predetermined manufacturing step, the length of the transparent carrier obtained is l〇〇m or more, 5000 m or less, and a length of 0.7 m or more and 2 m or less. It is better to be within this range. (Scratch strength) Further, the scratch strength is preferably 1 g or more, more preferably 5 g or more, and particularly preferably 5 g or more. By setting it as such a range, scratch resistance and workability of the film surface can be maintained without any problem. The scratch strength can be evaluated by scratching the surface of the carrier with a sapphire needle having a conical apex angle of 90 and a tip radius of 〇25 mm, and having a load (g) capable of visually confirming the scratch marks. -30- 201211575 [Coefficient of hygroscopic expansion of film] In addition, the transparent carrier should preferably have a hygroscopic expansion coefficient of 3〇χ1〇-5/% RH or less, more preferably 15x1〇-5/!)6 Below RH, it is particularly preferable to set it to ι〇χ1〇-5/% RH. Further, although the coefficient of hygroscopic expansion is as small as possible, it is usually 1.0x10 - 5/% RH or more. The coefficient of hygroscopic expansion is at a certain temperature and shows the amount of change in the length of the sample when the relative humidity is changed. By adjusting the coefficient of hygroscopic expansion, the optical compensation function of the optical compensation sheet can be maintained as it is, and the leakage due to the increase in the transmittance in the outer lattice shape, that is, the skew can be prevented. The hygroscopic expansion coefficient was measured by cutting the obtained polymer film into a sample having a width of 5 mm and a length of 20 mm, and fixing the one-side edge in a gas atmosphere of 25 ° C and 20% RH (RO). Next, a weight of 0.5 g was suspended from the other side edge, and the length (L0) was measured after being left for 1 minute. Then, the temperature was maintained at 25 ° C, but after the humidity was set to 80% RH (R 1 ), the length (L 1 ) was measured. The hygroscopic expansion coefficient was calculated by substituting the measurement results into the following formula. Ten samples of the same sample were measured, and the average enthalpy was used. Moisture absorption coefficient [/% RH] = { ( LI - LO ) /LO} / ( R1 - R0 ) [Optical anisotropy of transparent carrier] Transparent carrier for use in the present invention, characterized by: display specific optical Different direction. Specifically, the following formulas (I) and (II) are defined, and Re hysteresis R and Rth hysteresis 光学 of the degree of optical anisotropy are shown, and the individual Re is 2 to 200 nm, preferably 4 to 200 nm; Rth is 50~ 400nm, preferably 55~350nm 0 (I) Re = ( nx — ny ) xd -31 - 201211575 (II) Rth= { ( nx + ny) / 2 — nz } xd in formula (I) and (II) In the middle surface of the nx-based film, the refractive index in the direction of the slow axis (the direction in which the refractive index is maximum). In the formulae (I) and (II), the refractive index of the phase axis direction (the direction in which the refractive index is the smallest) in the plane of the ny-based film. In the formula (II), the refractive index of the nz-based film in the thickness direction. In the formulae (I) and (II), the thickness of the film in which the unit d is set to nm. Further, the complex refractive index (Δ n : nx - ny ) of the transparent carrier is preferably 0.0000 1 5-0.0088 > more preferably 0.00025 to 0.005 with respect to the wavelength of 50 nm. Further, the complex refractive index {(nx+ny) / 2-nz} in the thickness direction is preferably 0.0006-0.02, more preferably 0.001 to 0.007, with respect to the wavelength of 550 nm. Especially for the transparent carrier of the optical compensation sheet of the TN mode, the Re hysteresis is preferably 4 to 4 〇 nm, and the Rth hysteresis 値 is preferably in the range of 50 to 200 nm, and is used for OCB, HAN, VAN, uniform alignment mode, etc. For the carrier of the optical compensation sheet of the ECB mode, the Re hysteresis is preferably 10 to 70 nm, and the Rth hysteresis is preferably in the range of 7 〇 to 400 nm. [Laser phase angle of the film] The retardation axis angle in the plane of the transparent carrier is defined as the angle formed by the width direction of the roller-shaped film as the reference line (〇 ° ) and the retardation axis and the reference line. The clockwise direction is set to +. The absolute value of the average 値 of the retardation axis angle (axis offset) is preferably greater than or equal to 3 degrees, and the deviation of the viewing angle is improved to be good for display image recognition; more preferably 0 degrees or more. 2 degrees or less: It is preferably more than 1 degree below 1 degree. The direction of the average of the slow phase axes is defined as the average direction of the slow phase axes. In addition, the standard deviation of the retardation axis angle is preferably 0 degrees or more, 1.5 degrees -32 to 201211575 or less; more preferably more than the degree of enthalpy, 〇 · 8 degrees or less; preferably 0 degrees or more, ο. 4 degrees or less. By setting the standard deviation to be more than or equal to 1.5 degrees or less, it is possible to further prevent "color unevenness" in which the display color changes. (4th aspect, 5th aspect) [Optical compensation sheet] The optical compensation sheet of the fourth aspect of the invention is composed of an optically anisotropic cellulose acetate film having a degree of deuteration of 59.0 to 61.5%. The surface is subjected to a saponification treatment, and the contact angle of the water on the surface is 30° or more and 70° or more, and more preferably 40° or more and 70° or more. The optical compensation sheet according to the fifth aspect of the present invention has an optically different direction layer on one side of the cellulose acetate film carrier having a degree of deuteration of 59.0 to 61.5%, and the unilateral surface of the carrier is subjected to saponification treatment, and The optical compensation sheet having a contact angle of water of 30° or more and 70° or more, more preferably 40° or more and 70° or more. In this manner, the present invention is characterized in that the cellulose acetate film used for the optical compensation sheet is subjected to saponification treatment, and the contact angle of water is 30 or more and 70 or more. When the optical compensation sheet of the present invention is applied to a polarizing plate, the adhesion to the polarizing plate is improved by the saponification treatment, and if the contact angle with water is 30 or more, the wettability to water is lowered. After the water washing in the polarizing plate processing step, the water droplets will not remain and the yield will increase. Further, if the contact angle of water exceeds 70°, it becomes easy to bounce off the water, and the adhered dirt is hard to fall off. The optical compensation sheet of the fifth aspect is preferably formed on the cellulose acetate film to form an alignment film, and then a disc-like compound or a linear heterogeneous layer containing a rod-like compound is provided thereon. The optically oriented layer is formed by aligning the disc-like compound or the rod-like liquid crystal compound on the alignment film and fixing the alignment state. In this manner, in the case where an optically different layer is provided on the cellulose acetate film, it is conventionally necessary to provide a gelatin coating layer between the cellulose acetate film and the alignment film, but a surface to be described later is provided. In the treatment, for example, by adding an aromatic compound having the at least two aromatic rings, the contact angle of water can be made into the range without requiring a gelatin-coated underlayer. The thickness of the optically different direction layer is preferably from 0.1 to 10/m, more preferably from 0.5 to 50 m. The discotic liquid crystal compound has a large complex refractive index and a plurality of alignment forms. By using a disc-like compound, an optical compensation sheet having optical properties which are not obtained by a conventional stretch birefringent film can be obtained. An optical compensation sheet using a disk-like compound is disclosed in Japanese Patent Laid-Open Publication No. Hei. No. Hei. 6-214116, U.S. Patent No. 5,583,679, 5,564, 703, and No. 39 1 1 62 0 A1. [Cellulose Acetate Film] The cellulose acetate film used in the present invention is a cellulose acetate having a degree of enthalpy of 59.0 to 61.5%. The degree of deuteration means the amount of bonded acetic acid per unit mass of cellulose. The degree of hydration is measured and calculated according to ASTM: D-817-91 (test method for cellulose acetate, etc.). The average degree of polymerization (DP) of cellulose acetate is preferably 2 50 or more. More preferably 290 or more. Further, the cellulose acetate used in the present invention has a narrow molecular weight distribution as indicated by Mm/Mn (Mm is a mass average molecular weight and Μη is a number average molecular weight) of the gel permeation chromatography-34-201211575. The specific enthalpy of Mm/Mn is preferably in the range of 1.0 to 5.0, more preferably in the range of 1.3 to 3.0, and most preferably in the range of 1.4 to 2.0. <Saponification treatment of cellulose acetate film> In the present invention, the surface treatment is saponified, and if necessary, subjected to plasma treatment, flame treatment, and ultraviolet irradiation treatment. The saponification treatment with an acid and the saponification treatment with an alkali are carried out in a saponification treatment. The plasma treatment includes corona discharge treatment and glow discharge treatment. In order to ensure the planarity of the film, the surface temperature of the cellulose acetate film is less than or equal to the glass transition temperature (Tg), and specifically, it is preferably 150 Å or less. The saponification treatment of the alkali is preferably carried out by immersing the cellulose acetate film in an alkaline solution, neutralizing with an acidic solution, washing with water, and drying. Examples of the alkaline solution include potassium hydroxide solution and sodium hydroxide solution. The standard concentration of hydroxide ions in the alkaline solution is preferably from 0.1 N to 3.0 N', more preferably from 0.5 N to 2.0 N. The temperature of the alkaline solution is preferably in the range of 〇 to 90 ° C, more preferably 40 to 70 ° C. The corona discharge treatment is performed by applying a high voltage between the electrode connected to the high voltage generating device and the dielectric body to place the cellulose acetate film in a corona discharge generated between the electrode and the dielectric roller, or It is made to move it. In addition, in the patent specification, it is disclosed that the frequency of the high voltage applied between the electrode and the dielectric roller is the discharge frequency. If the corona discharge treatment is performed in the air, it is simple, and the necessary -35-201211575 The treatment device may be sealed or semi-sealed, or may be treated in a state of being filled with another gas or in a state of mixing other gases and air. Examples of the gas include nitrogen gas, argon gas, and oxygen gas. For corona discharge treatment, the general discharge frequency is 50 Hz to 5000 kHz, and is preferably 5 kHz to several hundreds kHz. In the corona treatment, if the discharge frequency is too low, the discharge becomes unstable, and pinholes are formed in the cellulose acetate film, which is not suitable. Further, if the discharge frequency is too high, it is necessary to have an additional device for matching the resistance, so that the price of the device becomes high, which is not suitable. In order to improve the usual wettability, it is preferable to set the corona discharge treatment of the cellulose acetate film to O. OOlkV · Α · min / m2 ~ 5kV · Α · min / m2, and more preferably, O. OlkV.A·min/m2~lkV.A·min/m2. The distance between the electrode and the dielectric roller is preferably 0.5 to 2.5 mm, more preferably 1.0 to 2 · 〇 mm. The corona discharge treatment is in a low pressure gas by applying a high voltage to between one or more electrodes. Then, the cellulose acetate film is placed in a corona discharge generated between the electrodes, or the cellulose acetate film is moved. The gas pressure for the corona discharge treatment is generally in the range of ~. 〇〇 5 to 20 Torr, more preferably in the range of 0.02 to 2 Torr. If the pressure is too low, the surface treatment effect will be reduced. If the pressure is too high, too much current will pass, which is likely to cause sparks and danger, and the cellulose acetate film is damaged. The discharge system is generated by applying a high voltage between the metal plates or the metal rods by providing one or more spaces in the vacuum chamber. Although this voltage is based on the composition of the ambient gas -36-201211575, the pressure can be obtained in various numbers, usually between 500 and 5000V, resulting in a stable corona discharge. In order to improve the adhesion, it is preferable to apply a voltage of 2000 to 4000V. In addition, the general discharge frequency is from MHz, and is preferably set to 50 Hz to 22 MHz. In order to obtain a corona discharge treatment of the object to be treated, preferably 〇/m2 to 5kV.A·min/m2', it is set to 〇.i5kV_ • A · min / m2 ° by ultraviolet irradiation treatment The ultraviolet light is irradiated onto the film. In the case of ultraviolet irradiation, the surface of the film is about 150 ° C. If there is no problem in performance, the main high-pressure mercury lamp can be used as the light source. If it is necessary to form, it is better to use a low-pressure mercury lamp with a dominant wavelength of 254 nm to use an ozone-free high-pressure mercury lamp and a low-pressure mercury lamp, although the amount of light to be treated is increased as the amount of light increases. Film coloring, or problem. Therefore, the amount of light to be irradiated with high-pressure water having a main wavelength of 365 nm is preferably 20 to 10000 (111 Å/(^2), more (mJ/cm 2 ). The amount of light used at a wavelength of 254 nm is preferably 7 □ 10〇~10000 (111)/(;1112), more-(mJ/cm2). Specifically, the optical compensation sheet of the present invention (the contact angle of the water of the cellulose surface is such that the surface is purely water-dropped into the cellulose The intersection of the surface of the droplet and the surface of the film, the angle formed by the surface of the droplet, defines the angle of the droplet as the range of the pressure, and the range is set to thousands of DC: the subsequent strength, 丨.01 kV · A · min 1 A · min / m2 ~ 1kV The cellulose acetate temperature will rise to a low temperature of 365nm. In addition, the higher the processing light power, but the film becomes brittle. , good for 50~2000 <In the case of a silver lamp, 隹 is 300 to 1500; acetate film) Acetate film, tangential line and film antennae are measured -37-201211575. That is, the cellulose acetate film is subjected to the saponification treatment to cause a problem of adhesion to the polarizing film (a problem such as peeling of the polarizing film by the durability test). The contact angle of the water on the surface of the protective film is 30° or more and 70° or less, and in order to improve the adhesion to the polarizing film, a hydrophobic compound (an aromatic compound having two aromatic rings) is preferably used. Add to cellulose acetate film. <Aromatic compound having two aromatic rings> In order to adjust the contact angle and hysteresis of the cellulose acetate film, an aromatic compound having at least two aromatic rings is used as an additive. Hereinafter, this compound is also referred to as a hysteresis oxime adjuster. The aromatic compound is used in an amount of from 0.01 to 20 parts by mass based on 1 part by mass of the cellulose acetate. The aromatic compound is preferably used in an amount of from 0.05 to 15 parts by mass, more preferably from 0.1 to 10 parts by mass, based on 100 parts by mass of the cellulose acetate. It is also possible to use two or more aromatic compounds in combination. The aromatic ring of the aromatic compound contains an aromatic heterocyclic ring in addition to the aromatic hydrocarbon ring. The aromatic compound is preferably a compound having high hydrophobicity from the viewpoint of controlling the contact angle. The aromatic ring (aromatic hydrocarbon ring, aromatic heterocyclic ring) of the aromatic compound used in the present invention is disclosed in paragraph [001 1] to [008] of Japanese Laid-Open Patent Publication No. 2000-1 1 1 91 4 5]. The molecular weight of the hysteresis enhancer is preferably from 300 to 800. -38- 201211575 <Hysterosis of fiber acetate film> Re retardation R and Rth hysteresis 薄膜 of the film are defined as the following formulas (I) and (Π), respectively. Mathematical formula (I) Re= ( nx — ny ) xd Mathematical formula (II) Rth={(nx+ny) /2 — nz}xd In the mathematical formulae (I) and (II), the nx film is in-plane The refractive index of the slow axis direction (the direction in which the refractive index is the largest). The refractive index of the in-phase axis direction (the direction in which the refractive index is the smallest) in the plane of the ny film. The refractive index of the nz-based film in the thickness direction. The thickness of the film in which the d system is set to nm. In the present invention, it is preferred to adjust the Re hysteresis of the cellulose acetate film to 5 to 100 nm, and the Rth hysteresis is adjusted to 70 to 400 nm. In the case of using two optically anisotropic cellulose acetate films (optical compensation sheets) in a liquid crystal display device, the Rth hysteresis of the film is preferably 70 to 250 nm in a liquid crystal display device, and an optical anisotropic fiber is used. In the case of a cellulose acetate film (optical compensation sheet), the Rth hysteresis of the film is preferably from 150 to 400 nm. Further, the complex refractive index (Δη: ηχ-ny) of the cellulose acetate film is preferably from 0.00025 to 0.00088. Further, the complex refractive index {(nx+ny)/2-nz} in the thickness direction of the cellulose acetate vinegar film is preferably from 0.00088 to 0_005. [Method for Producing Transparent Carrier and Cellulose Telluride Film] A method for producing a transparent carrier of -39 to 201211575, which is preferably used in the first to fifth aspects of the present invention, is described. In the present invention, the transparent carrier is preferably produced by a solution casting method (dissolution method) using a solution (doping liquid) which dissolves the polymer vitamins, etc. in an organic solvent. And the manufacture of thin films. (Solution preparation step) In the solution casting method, the organic solvent to be used is not particularly limited as long as it can be used in the organic solvent for the liquid casting method. For example, the solubility parameter is in the range of 17 to 22. Specific examples thereof include a chloride of a low aliphatic hydrocarbon, a lower aliphatic alcohol, a ketone having a carbon number, an ester having 3 to 12 carbon atoms, and an ester carbon number having 3 to 12 carbon atoms. 5 to 8 aliphatic hydrocarbons, aromatic hydrogens having 6 to 12 carbon atoms, and the like. The ether, ketone and ester may also have a cyclic structure. Any one of a functional group having a diacid, an anthracene and a vinegar (i.e., a 0-, -CO-, and -), an organic solvent can be used. Further, the organic solvent may have other functional groups such as an alcoholic hydroxyl group. In the case where the organic solvent has an organic solvent having the above functional group, the number of carbon atoms in the preferred carbon number range of the compound having a functional group may be an ether having 3 to 12 carbon atoms, and includes: Diisopropyl ether methoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxantetrahydrofuran, anisole and phenylethyl ether. Examples of the ketone having 3 to 12 carbon atoms include acetone, methyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexanone. Examples of esters having 3 to 12 carbon atoms include: ethyl formate' agent stream (fibers are usually dissolved in the class of 3 to 12 grades, group carbons are COO agents, and there are also two kinds of rings, ethyl formate. -40- 201211575 Propyl ester, phenyl formate, methyl acetate, ethyl acetate and amyl acetate. Examples of organic solvents with two or more functional groups, including · · Ethyl ethoxyacetate, 2-methoxy Ethyl alcohol and 2-butoxyethanol. The number of carbon atoms of the halogenated hydrocarbon is preferably 1 or 2, and most preferably 1. The halogen of the halogenated hydrocarbon is preferably chlorine. The hydrogen atom of the halogenated hydrocarbon The ratio substituted by halogen is preferably from 25 to 75 mol%, more preferably from 30 to 70 mol%, still more desirably from 35 to 65 mol%, most preferably from 40 to 60 mol%. It is a representative halogenated hydrocarbon. In order to manufacture a cellulose halide film according to the present invention, it is preferred to use two or more organic solvents in combination. Based on the viewpoint of controlling the speed of sound, specifically, dichloromethane is preferably used. , three solvents of methanol and butanol, suitable for the following range Mixing: methylene chloride is 75 parts by mass to 85 parts by mass; methanol is 15 parts by mass to 25 parts by mass; and butanol is 〇. 〇 5 parts by mass to 5 parts by mass. The organic solvent of the present invention is especially used It is preferred to mix a mixed solvent of two or more organic solvents, and it is more preferable to use three or more mixed solvents different from each other: the first solvent is preferably a ketone having 3 to 4 carbon atoms and an ester having 3 to 4 carbon atoms. Or a mixture thereof; the second solvent is preferably selected from a ketone having 5 to 7 carbon atoms or ethyl acetate; the third solvent is preferably an alcohol or boiling point having a boiling point of 30 to 170 ° C. It is selected by a hydrocarbon of 30 to 170 ° C. In particular, it is mixed with a mixing ratio of 20 to 90% by mass of acetate, 5 to 60% by mass of ketone, and 5 to 30% by mass of alcohol. In view of the solubility of cellulose oxime, it is preferred to use a mixed solvent of acetate, ketone and alcohol. -41 - 201211575 The blending ratio of 'alcohols' in this mixed solvent is preferably in all solvents. 2 vol% or more and 40 vol% or less 'more preferably 3 vol% or more, 30 vol% or less, more preferably 5 vol% The above is preferably 20 vol% or less. The alcohol is preferably an alcohol or a diol having 1 or more carbon atoms and 8 or less carbon atoms, or a fluoroalcohol having 2 or more carbon atoms and 1 or less carbon atoms. More preferably, methanol or ethanol is used. 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol, cyclohexanol, ethylene glycol, 2- Fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol. These may be added singly or in combination of two or more. In the non-halogen-based organic solvent system containing no halogenated hydrocarbon, a substantially non-chlorinated solvent containing no chlorine atom (hereinafter, simply referred to as "non-chlorinated solvent") is preferred. Technically, although a halogenated hydrocarbon such as dichloromethane can be used without problems, the organic solvent is preferably substantially free of halogenated hydrocarbons from the viewpoint of the global environment or the working environment. The term "substantially free" means that the proportion of the halogenated hydrocarbon in the organic solvent is less than 5% by mass (more preferably less than 2% by mass). Further, from the obtained cellulose halide film, it is preferable to completely detect a halogenated hydrocarbon such as dichloromethane. For the non-chlorinated solvent to be used in the present invention, for example, the paragraph number of the paragraph number [0021] to [0025] disclosed in Japanese Laid-Open Patent Publication No. 2002-146043, and the Japanese Patent Publication No. 2002-146045 [0016] Examples of solvent systems such as [0021]. The non-chlorinated solvent is preferably a mixed solvent of at least one organic solvent and an alcohol selected from ethers, ketones and esters having 3 or more and 12 or less carbon atoms, and the content of the alcohol in the solvent is 2 to 40% by mass. Mixed solvent. -42-201211575 Specifically, examples of such a mixed solvent include the following mixed solvents. Methyl acetate/cyclohexanone/methanol/ethanol (= 70/20/5/5, part by mass) Methyl acetate/methyl ethyl ketone/acetonitrile methyl acetate/methanol/ethanol (= 50/20/20 /5/5, part by mass) Acetone/acetonitrile methyl acetate/methanol (=75/20/5, part by mass) Methyl acetate/acetone/methanol/ethanol/butanol (=75/10/5/5/ 5, part by mass) methyl acetate / 1,4-dioxane / cyclopentanone / methanol / 1-butanol (= 60 / 20/12/5 / 3, part by mass) acetone / cyclopentanone / methanol / Ethanol (=60/3 0/5/5, part by mass) 1,3-dioxane/cyclohexanone/methyl ethyl ketone/methanol/ethanol (= 55/20/15/5/5, part by mass In the mixed solvent, an aromatic or aliphatic hydrocarbon having an Ovol% or more and 10 vol% or less of 5 or more and 1 or less carbon atoms may be added. Examples of the hydrocarbon may include cyclohexanone, hexane, benzene, toluene, and xylene. Further, the dope may contain, in addition to the organic solvent, a fluoroalcohol having a total organic solvent content of 10% by mass or less, more preferably 5% by mass or less, and it is preferable to improve transparency and accelerate dissolution of the film. Sex. The fluoroalcohol may, for example, be a compound disclosed in Paragraph No. [0020] of Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. These fluoroalcohols may be used alone or in combination of two or more. In the present invention, when the doping liquid is prepared, an inert gas such as nitrogen gas may be filled in the container. In addition, the viscosity of the doping liquid before the film formation is as long as it can be cast at the time of film formation, and is usually preferably adjusted to -43-201211575 10ps, s~2000ps.s, especially 30ps. .s ~400ps.s is better. The method of dissolving the preparation of the dope is not particularly limited, and may be carried out by a room temperature dissolution method, a cooling dissolution method or a high-temperature dissolution method, or even a combination thereof. For the dissolution method, for example, the preparation method of the doping liquid is disclosed in Japanese Laid-Open Patent Publication No. Hei 5 - 1 6 3 3 0 1 , Sho 61-106628, Sho 58-127737, Hei 9-95544, and flat. 10-958454, flat 1 0-45950 '2000-53 784, flat 1 1 -3 22946 ' flat 1 1 -322947, flat 2-276830, 2000-273239, flat 11-71463, flat 4-259511, 2000-273184 Japanese Laid-Open Patent Publication No. Hei 11-323017, No. Hei 11-302388, and the like, discloses a method of dissolving an organic solvent in a transparent carrier raw material polymer of the above publications, and the present invention can employ a technique suitable for the above. Further, a cellulose halide dope solution in the case where a cellulose halide is used as a polymer is usually subjected to concentration and filtration of a solution, and is also disclosed in detail in the art No. 2001-1745 ρ·25. Further, in the case where the dissolution is carried out at a high temperature, it is almost the boiling point of the organic solvent used, and this case can also be used under pressure. Further, a method of preparing a doping liquid will be described. The cellulose halide solution can be prepared by a general method. The so-called general method means that the temperature is above 常t (normal temperature or high temperature). The preparation of the solution can be carried out by a doping solution adjustment method and apparatus of a usual solvent casting method. Further, in the case of a general method, a halogenated hydrocarbon (especially dichloromethane) can also be used as the organic solvent. The amount of the cellulose halide is adjusted to be 10 to 40% by mass in the obtained solution. The amount of the cellulose halide is more preferably from 10 to 30% by mass. Any additive described later may be added to the organic solvent (main solvent). * -44- 201211575 The solution can be prepared by stirring the cellulose oxime with an organic solvent at normal temperature (0 to 40 ° C). The high concentration solution can also be stirred under pressure and heating. Specifically, the cellulose halide and the organic solvent are poured into a pressurized container, sealed, and heated under a pressure at a temperature equal to or higher than the boiling point of the solvent at a normal temperature and while the solvent is not boiling. . The heating temperature is usually 40 ° C or higher, preferably 60 to 200 ° C, more preferably 80 to 110 ° C. The ingredients may also be pre-mixed in advance and poured into a container. Alternatively, it can be poured into the container in sequence. The container must have a structure that can be agitated. The inert gas such as nitrogen gas can be injected and then pressurized. Further, it is also possible to use an increase in the vapor pressure of the solvent due to heating. Alternatively, after the container is sealed, the components are added under pressure. In the case of heating, it is preferred to heat from the outside of the container. For example, a cannulated heating device can be utilized. Further, the heating of the heating plate may be provided outside the container, and the liquid may be circulated to heat the entire container. It is preferable to provide a stirring blade inside the container, and stir the stirring blade. The agitating blades are preferably of a length near the wall of the vessel. At the end of the agitating blade, it is preferable to provide a scraping blade in order to replace the new agitating blade. A measuring instrument such as a pressure gauge or a thermometer may be provided in the container. The ingredients are dissolved in a solvent in a container. The prepared dope is cooled out of the container or cooled and then cooled by a heat exchanger. The solution can also be prepared by a cooling dissolution method. Cooling Dissolution Method The cellulose oxime can be dissolved in a poorly soluble -45-201211575 organic solvent by a usual dissolution method. Further, even if the solvent of the cellulose ruthenium compound can be dissolved by a usual dissolution method, a rapid and uniform solution can be obtained by the cooling dissolution method. In the case of the cooling dissolution method, the cellulose halide in the organic solvent is first stirred at room temperature and slowly added. The amount of the fiber cord is preferably adjusted to be 10 to 40% by mass in the mixture. The amount of the cellulose halide is more preferably from 10 to 30% by mass. Further, any of the additives described later may be added to the mixture. Next, the mixture is cooled to -100 to -10 ° C (more preferably -80 to -10 ° C, more preferably -5 0 to -2 0 ° C, most preferably -5 0 to -3 0 ° C) ). For example, the cooling can be carried out in a dry ice-methanol bath (-75 ° C) or in a cooled diethylene glycol solution (-3 0 to -200 ° C). If cooled in this manner, the mixture of the cellulose halide and the organic solvent will solidify. The cooling rate is preferably 4 ° C / min or more, more preferably 8 ° C / min or more, and most preferably 12 ° c / min or more. Although the cooling rate is as fast as possible, l〇〇〇〇°C / sec is the upper limit of the theory, l 〇〇〇 ° C / sec is the upper limit of the technology, and the upper limit of l 〇〇 ° C / sec. Further, the cooling rate is the number of times between the temperature at which the cooling is started and the last cooling temperature is divided by the time from the start of cooling to the final cooling temperature. Furthermore, once the solution is warmed to 0 to 200 ° C (more preferably 0 to 150 ° C, more preferably 0 to 12 0 ° C, preferably 〇 to 50 ° C) 'cellulose bismuth will dissolve In organic solvents. The temperature rise can be placed only at room temperature' or it can be heated in a hot water bath. The heating rate is preferably 4 ° C / min or more, more preferably 8 ° C / min or more 'preferably 12 ° C / min or more. Although the faster the temperature is, the better, l〇〇〇〇°C / sec is the upper limit of -46-201211575, 1 000 °c / sec is the upper limit of the technology, and 100 ° c / sec is the practical upper limit. Further, the rate of temperature rise is the number 时间 of the time when the temperature at which the temperature rise is started and the temperature of the last temperature is divided by the time from the start of the temperature rise to the temperature at which the temperature is finally increased. In this way, a homogeneous solution can be obtained. Further, in the case where the dissolution is not complete, the operation of cooling and warming may be repeated. Whether or not the dissolution is complete can be judged by visual observation of only the appearance of the solution. The cooling dissolution method is preferably a closed container in order to avoid moisture intrusion due to condensation during cooling. Further, in the cooling and temperature increasing operation, if the pressure is applied during cooling, the pressure is reduced at the temperature rise, and the dissolution time can be shortened. In order to carry out pressurization and depressurization, it is preferred to use a pressure resistant container. Further, by a cooling dissolution method, a cellulose halide (degree of deuteration: 60.9 %, viscosity average degree of polymerization: 299) is dissolved in methyl acetate to form a 20% by mass solution, if differential scanning heat is used. In the measurement (DSC), there is a virtual phase transition point between the sol state and the gel state at around 3 3 ° C, and if it is below this temperature, it becomes a uniform gel state. Therefore, the solution must be maintained above the virtual phase transition temperature, preferably at a gel phase transfer temperature plus a temperature of about 1 〇 °C. However, this virtual phase transfer temperature differs depending on the degree of deuteration of the cellulose acetate, the average degree of polymerization of the viscosity, the concentration of the solution, or the organic solvent used. In the dope, if necessary, other additives such as a hysteresis modifier, a plasticizer, and an ultraviolet absorber may be contained. In the case of the third aspect of the invention, microparticles are further added. (Method of Adding Mixture of Microparticles) In the case where microparticles are added to a cellulose halide solution, it is important that coarse particles as described in -47 to 201211575 are not present, and that aggregation or precipitation cannot be caused, and dispersion is necessary. However, if any of these conditions are satisfied, the method is not particularly limited, and even if any of the methods is used, the desired cellulose halide solution can be obtained. The microparticles are different from the dope adjustment, and it is preferred to separately prepare the dispersion, and then mix and disperse them in the dope. For example, the methods shown below can be listed. (1) A solvent (the same organic solvent used in the solution casting method) is stirred and mixed with the fine particles, and then a dispersion of the fine particles is formed by a disperser, and the dope is added and stirred. (2) After the solvent and the fine particles are stirred and mixed, a fine particle dispersion is formed by a disperser, and a small amount of cellulose halide is added to the solvent to be stirred and dissolved. The microparticle dispersion was added to the solution, and the microparticle addition liquid obtained by stirring with a line mixer was thoroughly mixed with the dopant liquid. (3) A small amount of an adhesive is added to the solvent, stirred and dissolved, and the fine particles are added thereto, and dispersed by a disperser to form a fine particle dispersion. The mixture of the microparticle addition liquid and the doping solution is sufficiently mixed by a line mixer. The adhesive may, for example, be a cellulose halide or the like, and a cellulose halide which supplies a doping liquid is preferably used. Dispersion can utilize conventional wet dispersion methods. The medium wet dispersing machine can be exemplified by a sand mill (for example, a needle-shaped bead mill), a die mill, a high-speed turbine mill, a pebble mill, a roller mill, an abrasion machine, a colloid mill, and a ball mill. Such as the known dispersion machine. In particular, the oxide microparticles of the present invention are dispersed into ultrafine particles, preferably a sand mill, a die-48-201211575 mill and a high-speed turbine mill. The size of the ultrafine particles which do not contain the coarse particles in the range is preferably a wet dispersion method using a medium having an average particle diameter of less than 〇8 mm. The medium used together with the dispersing machine has an average particle diameter of less than 〇8 mm, and the average particle diameter can be obtained by using a medium of this range to obtain a diameter of the inorganic microparticles of 100 nm or less and a uniform diameter of the microparticles. Microparticles. The average particle diameter of the medium is preferably 0.5 mm or less, more preferably 0.05 to 0.3 mm. Further, the medium for wet dispersion is preferably a bead. Specific examples include zirconia beads, glass beads, ceramic beads, steel balls, and the like, and oxidized chromium beads of 0.05 to 0-2 mm are particularly considered based on durability and ultrafine granulation which are less likely to cause bead breakage during dispersion. Especially ideal. The medium-free disperser can be used in an ultrasonic type, a centrifugal type, a high pressure type or the like. For example, in the thin tube of 1 - 2000 /z m, the maximum pressure inside the high-pressure dispersing device is preferably 9.8 MPa or more, more preferably 19.6 MPa or more. In addition, at this time, the maximum speed reaches l〇〇m/sec or more, and the heat transfer speed is preferably 420 kJ/hr or more. Examples of the pressure dispersion device include an ultrahigh pressure homogenizer (trade name: Micro Fluidizer) manufactured by Micro Fluidics Corporation or a Nanomizer manufactured by Nanomizer Co., Ltd.; and other Manton Galling type high pressure dispersion devices, for example, Izumi Hood

Machinery製均化器、日本三和機械（股份）公司製之 UHM-01 等。再者，分散物中之分散顆粒的平均粒徑以及粒徑之單分散性’除了滿足該範圍之外，爲了去除分散物中之粗大凝聚物’與珠粒之分離處理上’較宜配置可進行精密過濾之濾材。爲了進行精密過濾之濾材的過濾顆粒大小較宜爲2 5 -49- 201211575 //m以下。爲了進行精密過濾之濾材型式只要具有該性能的話’並無特別之限定，例如，可列舉：纖維型、氈型、網眼型。爲了進行分散物之精密過濾的濾材材質具有該性能’並且只要不對塗布液造成不良影響的話，並無特別之限定’例如’可列舉：不銹鋼、聚乙稀、聚丙稀、耐隆等。該微顆粒以外之添加劑，例如，也可以於進行纖維素醯化物與溶劑混合之階段含有，也可以利用溶劑與纖維素醯化物製得混合溶液之後，進行添加物之添加。再者，也可以於即將進行摻雜液的流延之前，進行添加混合，亦即所謂即將添加之前的方法，其混合係以線上方式設置螺旋式混攪而予以使用。此等添加劑之混合可以添加添加物本身’較佳的態樣也可以預先使用溶劑或黏合劑（較宜爲纖維素醯化物）進行溶解，並視狀況而定，形成經分散而安定化之溶液使用。 (製膜步驟）接著’於本發明，針對使用摻雜液的薄膜製造方法進行說明。製造聚合物薄膜之方法與設備，稱爲供應聚合物薄膜製造之轉筒方法或帶狀物方法，可以使用習知之溶液流延製膜方法與溶液流延製膜裝置。若進行製膜步驟之說明，將由溶解機（鍋）製得的摻雜液（纖維素醯化物溶液）暫時貯藏於貯藏鍋，將含於摻雜液的氣泡予以脫氣泡後進行最後調製。重要的是，調製後之摻雜液係藉由精密過濾於將凝聚物、污染物予以去除》具體而言，過濾的濾膜較宜使用盡可能不去除摻雜液中之成分的範圍之孔徑小的濾膜。爲了過濾，較宜使用絕對過 -50- 201211575 據精度爲0.1〜100/zrn的濾膜，更佳使用絕對過濾精度爲 0.1〜2 5" m的濾膜。濾膜之厚度較宜爲〇.卜1〇mm，更佳爲 0.2~2mm。此情形下，過濾壓力爲15kgf/cm2以下，更佳爲 1 0 kgf/cm2以下，最好爲2 kgf/cm2以下進行過濾。另外’爲了精密過濾，較宜依序減小濾膜之孔徑而進行數次過濾。爲了進行精密過濾之濾材型式，只要具有該性能的話，並無特別之限定，例如，可列舉：纖維型、氈型 '網眼型。爲了進行分散物之精密過濾的濾材材質具有該性能，並且只要不對塗布液造成不良影響的話，並無特別之限定，例如’可列舉：不銹鋼、聚乙稀、聚丙稀、耐隆等。例如，藉由旋轉數而將製得的摻雜液，從摻雜液排出口 ’通過能高精度定量送液的加壓型定量齒輪幫浦而送至加壓型模頭，從加壓型模頭的噴嘴（狹縫），將摻雜液均勻地流延於環形移動中之流延部金屬載體之上，金屬載體於約旋轉一周之剝離點，從金屬載體而將未完全乾燥之摻雜液膜（也稱爲纖維網）予以剝離。利用夾子夾住所得到的纖維網之兩端，一面保持寬度，並一面利用定幅器經搬送而進行乾燥，接著，利用乾燥裝置之輥輪群，經搬送而完成乾燥，再利用捲取機捲取成既定之長度。定幅器與輥輪群之乾燥裝置的組合，係根據其目的而有所改變。本發明第3態樣之情形，於流延步驟所用之金屬載體，其表面之算術平均粗糙度（Ra)較宜爲O.OOlym以上、〇.〇15以111 以下’十點平均粗糙度（Rz)較宜爲0.001/zm以上、0.05 //m以下。更佳的話，算術平均粗糙度（Ra)爲Ο.ΟΟΙμπι -51 - 201211575 以上、0.01 # m以下，十點平均粗糙度（Rz)爲0_001 v m 以上、〇. 〇 2 A m以下。最好的話，（Ra ) / ( Rz )比値爲0.1 5 以上。如此方式，藉由將金屬載體之表面粗糙度設於既定之範圍，能夠將製膜後之薄膜表面形狀控制於第3態樣的範圍內。針對此等之各製造步驟（分爲：流延（含共流延）、乾燥、剝離、拉伸等），較笪爲已詳細揭示於該公技編號 2001-1745號ρ·25-30之步驟。流延步驟可以將一種摻雜液予以單層流延，也可以分別將溶解不同的聚合物而成的二種以上之摻雜液，同時與/或逐次予以進行共流延。尤其，由如該組成物而成的摻雜液製成薄膜的步驟，爲了實施上不使添加的化合物造成凝聚或不均，乾燥步驟爲重要的。於載體上之摻雜液的乾燥方法，可列舉：通常將熱風吹向載體（轉筒或帶狀物）之表面側，亦即，載體上之纖維網表面的方法；將熱風吹向轉筒或帶狀物之背面的方法；使已進行溫度控制的液體與帶狀物或轉筒之摻雜液流延面之相反側背面相接觸，藉由傳熱而進行轉筒或帶狀物之加熱’控制表面溫度的液體傳熱方法等。較宜爲背面液體傳熱方式。進行流延前之載體表面溫度只要爲用於摻雜液之溶劑的沸點以下，任何溫度均可以。然而，爲了加速乾燥，或是爲了使載體上之流動性失去，較宜設爲較所使用的溶劑中之沸點最低的溶劑沸點再低1〜1 Ot之溫度。於載體上，使流延之摻雜液予以乾燥而得到聚合物薄膜之聚合物薄膜乾燥步驟之乾燥溫度較宜爲3 〇〜2 5 〇〇c，尤以 -52- 201211575 4 0〜180 °C更佳。再者，爲了去除殘留溶劑，較宜採用於 5 0〜160 °C進行乾燥’此情形下’以逐次改變溫度的高溫熱風進行乾燥而使殘留溶劑蒸發。以上之方法係揭示於曰本公開專利第平5-17844號公報。若藉由此方法，便可能縮短從流延起直到剝離爲止之時間。因所使用之溶劑種類，乾燥溫度、乾燥.風量及乾燥時間將有所不同，也可以因應於使用溶劑之種類、組合而進行適當選擇。最終加工薄膜之殘留溶劑量較宜爲2質量％以下、更佳爲〇.4質量％以下’便得到尺寸安定性良好之薄膜。還有，於本發明，因爲利用剝離劑能夠進一步縮短剝離時間，並且剝離時之電阻將變低’可以得到面狀（歸因於剝離時橫向之異常、凝膠狀殘渣之剝離殘留的殘渣等）無惡化的聚合物薄膜。具體而言，將從摻雜液之流延直到剝取爲止之平均乾燥速度較宜設爲超過300質量°/。/分，並且1〇〇〇質量％ /分以下，更佳設爲超過400質量％ /分，並且900質量％ /分以下，最好設爲超過5 00質量％ /分，並且8 00質量％ /分以下。因爲平均乾燥速度若爲3 00質量％ /分以下，將無法高速剝取薄膜，其結果，生產性往往變差，另外，若超過1 〇〇〇質量％ /分，因乾燥風而導致風異常之發生，往往薄膜之平面性及表面形狀將產生異常，所以設爲該範圍內較佳。所謂平均乾燥速度，係將流延摻雜液之溶劑含量的變化量除以時間的數値。爲了調整平均乾燥速度，能夠藉由適宜調整乾燥風之溫度、風量、溶劑氣體之濃度、流延載體之表面溫度、進行 201211575 流延之摻雜液的溫度、進行流延之摻雜進行流延之摻雜液的溶劑組成等而進行再者，距離摻雜液之流延點1 5m以內速度超過300質量％ /分，並且爲1〇〇〇宜爲超過400質量？ϋ /分，並且爲900: 佳爲超過500質量％ /分，並且爲800, 外，超過距離流延點15m之位置，平均之限定，較宜以同樣的範圍進行。開始流延後的3秒至流延後20秒之超過300質量％ /分，並且爲1〇〇〇質量| 超過400質量％ /分，並且爲900質量％超過500質量％ /分，並且爲800質量％超過流延後2 0秒之範圍，平均乾燥速度從載體剝離之後的乾燥步驟，因溶劑於寬度方向產生收縮。高溫下，越進行大。此收縮較宜盡可能地予以抑制而進薄膜之平面性變佳。基於此點，例如，利第昭6246 62 5號公報所揭示的乾燥全驟，於寬度方向上，利用夾子一面保持纖 —面進行乾燥的方法（定幅器方式）。雖然因製造聚合物薄膜之速度係依帶方法、摻雜液溶劑組成等而有所改變，予以剝離的時間點之殘留溶劑量幾乎爲摻雜液薄膜厚度方向之帶狀物表面附近情形，剝離時，摻雜液殘留於帶狀物中液的纖維網厚度、〇之範圍的平均乾燥 I量％ /分以下，較霞量％ /分以下，更 Ϊ量％ /分以下。另乾燥速度並無特別間的平均乾燥速度 ;/分以下，較宜爲 /分以下，更佳爲 /分以下》另外，並無特別之限定。之蒸發而使得薄膜乾燥，收縮變得越行乾燥，使完成的較宜如日本公開專部步驟或一部分步 ,維網之寬度兩端，狀物之長度、乾燥從帶狀物將纖維網固定的。亦即，於的溶劑濃度過高的，由於將造成下一 -54- 201211575 次流延時之阻礙’因此絕不宜有剝離殘留現象，再者，必須要有經得起進行剝離之力量的纖維網強度。於剝離時間點之殘留溶劑量將因帶狀物或轉筒上之乾燥方法而有所不同，相較於將風吹向摻雜液表面而進行乾燥的方法，從帶狀物或轉筒背面進行傳熱的方法，能夠有效減低殘留溶劑量。具體而言，聚合物薄膜中的殘留溶劑量較宜爲0.01〜1.5 質量％範圍的條件下進行乾燥。更佳爲0.01〜1.0質量％。於流延步驟較宜僅進行流延方向（縱向）等之一方向的單軸拉伸，或是進行流延方向及其他方向（橫向）之二軸拉伸等。再者，摻雜液也可以同時進行其他機能層（例如，接著層、染料層、防靜電層、抗光暈層、UV吸收層、偏光層等）之流延。. 本發明採用之光學補償片的製造方法係一種製造該透明載體之光學補償片的製造方法，第3態樣之情形下，該透明載體爲一種纖維素醯化物薄膜，利用具有流延步驟之溶液流延方法而進行該纖維素醯化物薄膜之製膜，其特徵爲：進行該流延步驟之摻雜液的流延之金屬載體，其表面之算術平均粗糙度（Ra)爲0.001/zm以上、0.015ym以下，其表面之十點平均粗糙度（Rz)爲0.001//m以上、〇.〇5 以下。但是，本發明之光學補償片並非受此製造方法所限制，可以利用各種方法進行製造。 (拉伸處理步驟）製得的聚合物薄膜能夠進一步藉由拉伸處理而進行遲 -55- 201211575 滯値之調整。拉伸倍率較宜爲3至100% 。採用該（1 )與/或（2 )之拉伸方法的情形，能夠將軸偏移（遲相軸角度）調整至既定之範圍內。 (1)以3至40% ，較宜爲7至37% 、更佳爲15至35% 之拉伸倍率進行寬度方向之拉伸。接著，一面使其於長軸方向膨脹0.4%以上、5%以下，較宜爲0.7%以上、4%以下，更佳爲1%以上、3.5%以下，並一面於60〜160 °C進行熱處理。 (2 )於拉伸時，表面與背面賦予溫差。於流延時，將接觸於基板（帶狀物或轉筒）之表面的溫度較其相反面的溫度，設爲更高2 °C以上、2 0 °C以下，較宜爲3 °C以上、1 5 °C以下，更佳爲4 °C以上、1 2 °C以下。利用如此之方法，藉以消除拉伸步驟之添加於薄膜內之添加劑（可塑劑、遲滞値調整劑、超微顆粒等）之不均化，便控制「軸偏移」。另外，藉由調整此拉伸處理之條件，能夠縮小光學補償片之遲相軸角度的標準偏差。雖然拉伸處理之方法，並無特別之限定，其例子可列舉：利用定幅器的拉伸方法。對於利用該溶劑流延法所製作的薄膜，能夠利用定幅器而進行拉伸之際，藉由控制拉伸後的薄膜狀態，縮小遲相軸角度之標準偏差。具體而言，利用定幅器而進行調整遲滯値之拉伸處理，然後，藉由維持拉伸後瞬間的聚合物薄膜狀態，保持薄膜之玻璃轉移溫度以下，能夠縮小遲相軸.角度之標準偏差。若將此保持時之薄膜溫度設爲玻璃轉移溫度以上進行的話，標準偏差將變大。 -56- 201211575 如上所述，於本發明第3態樣之該透明載體爲一種纖維素醯化物薄膜，該纖維素醯化物薄膜較宜爲藉由下列之步驟所製得的薄膜：溶液調製步驟，將纖維素醯化物溶於實質之非氯系溶劑中而調製纖維素醯化物溶液；製膜步驟，由纖維素醯化物溶液製作纖維素醯化物薄·膜；以及拉伸步驟利用進行纖維素醯化物薄膜之拉伸所製造的薄膜。另外，第4及第5態樣之纖維素醋酸酯薄膜，能夠進一步藉由拉伸處理而進行遲滯値之調整，作成光學異方向性薄膜。本發明第4態樣必須將纖維素醋酸酯薄膜作成具有光學異方向性。拉伸倍率較宜爲3至1 0 0 % 。纖維素醋酸酯薄膜之厚度，此等態樣之情形較宜爲2 0 至120"m，更佳爲30至ΙΟΟμηι。最好爲40至80//m。再者，若針對製膜方法進行說明，較宜將該遲滯値提昇劑加入摻雜液中。摻雜液係於轉筒或帶狀物上進行流延，使溶劑蒸發而形成薄膜。流延前之摻雜液的固形成分含量較宜調整爲18至 3 5%的濃度。轉筒或帶狀物之表面較宜預先加工成鏡面狀態。針對溶劑流延法之流延與乾燥方法，已揭示於美國專利第 2336310 ' 2367603、 2492078、 2492977、 2492978、 2607704'2739069'2739070 號；英國專利第 640731、736892 號之各專利說明書；日本專利第昭45-4 5 54、昭49-5614 號公報；日本公開專利第昭60-176834、昭60-203430、昭 62-115035號之各公報。摻雜液較宜於表面溫度爲10 °C以下之轉筒或帶狀物上進行流延。從流延開始起進行2秒鐘以上之吹風後予以乾 -57- 201211575 燥。從轉筒或帶狀物剝取所得到的薄膜，進一步發物爲45〜70%狀態下，以逐次改變溫度的熱而使殘留溶劑蒸發。剝取後之揮發部分較宜爲更佳爲50~65% 。若揮發部分低於45%的話，大至20〜30nm，若超過70% ，隨著蒸發而往往薄膜之變形，任一種情形均將成爲問題。熱風爲100〜160°C，更佳爲110〜140°C。若溫度低於滯値將變大。若溫度超過160 °C，隨著蒸發而造成薄膜之變形，任一種情形均將成爲問題。從轉筒或帶狀物剝取所得到的薄膜，進一步至1 6(TC，以逐次改變溫度的高溫熱風進行乾溶劑蒸發。以上之方法已揭示於日本公開專利第號公報。若根據此方法，便可能縮短從流延直的時間。爲了實施此方法，流延時之轉筒或帶溫度，必須要能使摻雜液予以凝膠化。也能夠使用已調整的纖維素醯化物溶液（摻行二層以上之流延而予以薄膜化。此情形下，劑流延法，製作纖維素醯化物薄膜》摻雜液係狀物上進行流延，使溶劑蒸發而形成薄膜。流液濃度較宜使固形成分含量調整至10至40% 筒或帶狀物之表面，較宜預先加工成鏡面狀態進行二層以上之數種纖維素醯化物溶液白形’可以進行數種纖維素醯化物溶液之流延，之行進方向，從隔著間隔所設置的數個流延口可以於可揮風進行乾燥 4 5 ~ 7 0 % ，相位差將變起泡，造成之溫度較宜 ‘ 100。。，遲往往起泡，可以從1 0 0 燥而使殘留 i 平 5- 1 7844 到剝取爲止狀物的表面雜液），進較宜利用溶於轉筒或帶延前之摻雜之範圍。轉〇 i勺流延之情能夠於載體 ’分別一面 -58 - 201211575 使含有纖維素醯化物之溶液予以流延而層疊，並一面製作薄膜（例如，揭示於日本公開專利第昭 6 1 - 1 584 1 4、平 1-122419與平11-198285號之各公報）。另外，也可以從二個流延口進行纖維素醯化物溶液之流延而進行薄膜化 (例如，揭示於日本專利第昭6 0 - 2 7 5 6 2號公報；日本公開專利第昭 61-94724、昭 61-947245、昭 61-104813、昭 61-158413與平6-134933號之各公報）。另外，也可以使用一種纖維素醯化物薄膜的流延方法，以低黏度之纖維素醯化物溶液包圍高黏度之纖維素醯化物溶液的流動，再同時將其高、低黏度之纖維素醯化物溶液予以同時擠出（例如，揭示於日本公開專利第昭5 6- 1 62 6 1 7號公報）。另外，也可以採用藉由使用二個流延口，經由第一流延口，剝取成型於載體之薄膜，於接觸載體面之側，進行第二流延而製作薄膜·的方法（例如，揭示於日本公開專利第昭44-2023 5號公報）。進行流延之纖維素醯化物溶液，可以使用相同的溶液，也可以使用不同的纖維素醯化物溶液。爲了於數個纖維素醯化物層中具有機能，可以從個別的流延口擠出對應於其機能之纖維素醯化物溶液。再者，本發明之纖維素醯化物溶液，也可以同時流延其他之機能層（例如，接著層、染料層、防靜電層、抗光暈層、紫外線吸收層、偏光膜）。習知之單層液，爲了形成必要之薄膜的厚度，必須要高濃度擠出高黏度之纖維素醯化物溶液。此情形下，纖維素醯化物溶液之安定性變差而產生固態物，成爲殘渣阻礙， -59- 201211575 大多造成平面性不佳之問題。此問題之解決方法，可以藉由從流延口而進行數種纖維素醯化物溶液的流延，能夠將高黏度之溶液同時於載體上進行擠出，不僅平面性良好，能夠製得優異的面狀薄膜，藉由使用濃度高的纖維素醯化物溶液，能夠達成降低乾燥負荷，提高薄膜之生產速度。較宜於纖維素醯化物薄膜中，爲了改善機械物性而添加聚尿酯。另外，聚尿酯較宜爲下列一般式（1)所示之聚酯與二異氰酸酯之反應物，更佳爲可溶於二氯甲烷。 (1) H-(0-(CH2),-00C-(CH2)m-C0)n-0-(CH2) , -OH 式中，1表示2至4之整數；m表示2至4之整數；η 表示1至1 00之整數。更詳ΙΪ之，此構造聚酯之二醇成分爲乙二醇、1，3-丙二醇或I，4-丁二醇；二鹽基性酸成分爲具有由琥珀酸、戊二酸或己二酸構成的具有低於二羥基的聚酯，其聚合度η係於1~100的範圍，只要聚合度η爲1〜100的範圍即可，其最適聚合度將視所用之二醇與二鹽基酸的種類而有些許之差異，聚酯之分子量尤以1000至4500之範圍爲特別理想。二氯甲院可溶之聚尿酯樹脂係藉由（1)式之聚醋與二異氰酸酯之反應而得到，一般式爲以（2 )式所示之重複單位的化合物。 (2) C0NH-R-NHC0-(0-(CH2),-00C-(CH2)m-C0)n-0-(CH2) , 式中’ 1表示2至4之整數；m表示2至4之整數；η 表示1至100之整數；R表示2價之原子團殘基。 2價之原子團殘基之例子，例如，可列舉：如下式之原子團殘基。 -60- 201211575 :Lli :SU:. 6:1 ,之：【..化..Π::)' 對於聚尿酯化合物所用之二異氰酸酯成分.的以伸乙基二異氰酸酯、三亞甲基二異氰酸酯、異氰酸酯、六耍甲基二異氰酸酯所代表的聚亞酸酯（一般式：OCN-(CH2)p-NCO( ρ 表示 2〜8 5 芳香族二異氰酸酯（例如，含有p_伸苯基二異苯基二異氰酸酯、ρ,ρ’-二苯基甲烷二異氰酸酯二異氰酸酯）與m-苯二甲基二異氰酸酯。甲苯酯' m-苯二甲基二異氰酸酯與四亞甲基二異氰取得’較穩定且容易操作，而且，聚尿酯化之. 與纖維素醯化物之相溶性優異。聚尿酯樹脂之分子量較宜爲2000至50000 子量可以藉由成分聚酯類或此等連結群之二異之種類或分子量而予以適度調節。基於纖維素之機械物性的提高與對於纖維素醯化物之相溶聚尿酯樹脂之分子量更佳於5000至1 5000之範二氯甲烷可溶性聚尿酯之合成能夠藉由將（之聚酯二醇類與二異氰酸酯予以混合，於攪拌例子，含有四亞甲基二甲基二異氰 :整數））；氰酸酯、甲 ' 1,5-萘基基二異氰酸酸酯較容易情形，較宜之範圍。分氰酸酯成分醯化物薄膜性的觀點，圍。 1 )式所示下進行加熱 -61 - 201211575 而容易得到。 (1)式所示之聚酯類係藉由利用適合的二鹽基其烷基酯類與二醇類之酯化反應或酯類交換反應之縮合法，或是此等酸之酸氯化物與二醇類之界面縮中的任一種方法，若末端基適度調整成羥基的話，容易合成。二氯甲烷可溶性聚尿酯樹脂與醯化度58%以上素醯化物之相溶性極佳。雖然因樹脂之構造而確認之相異，聚尿酯之分子量爲10000以下之情形，對份質量之醋酸纖維素，即使200份質量之聚尿酯也溶。因而，欲將聚尿酯樹脂混入纖維素醯化物而改善之機械物性的情形，聚尿酯樹脂之含量可以根據尿之種類、分子量、所要之機械物性而予以適當決定欲保持纖維素醯化物之特性原狀而改善機械物形下，對於纖維素醯化物，較宜含有10至50質量尿酯樹脂。另外，此聚尿酯樹脂至少達180 °C仍爲安定且不解。此二氯甲烷可溶性之聚尿酯類，尤其對於醯化; 以上之纖維素醯化物之相溶性極佳。因而，若混合進行製膜，可以得到透明度極高的薄膜。而且，由聚尿酯類之平均分子量高，與習知之低分子可塑劑即使於高溫下也幾乎無揮發性。因而，藉由此等混行製膜而得到的皮膜，於隨後之加工，減少習知可見到的因可塑劑之揮發或轉移而造成的不當。性酸或熱熔融合法之便能夠之纖維有些許於1〇〇可以相其皮膜酯樹脂〇性的情 %之聚會熱分荽58% 二者而於此等不同，合物進塑劑所 -62- 201211575 藉由將聚尿酯加入纖維素膜，高溫與低溫下之耐折強度以及撕裂強度將變大’而且’如薄膜破裂之不當現象將被消除。習知，爲了提高皮膜之耐折強度或撕裂強度而使用低分子可塑劑。雖然此方法於常溫、高濕狀態下具有某種程度的效果，但是於常溫、高濕狀態下之皮膜柔軟性將失去，不一定可以得到滿意之結果。再者，若藉由低分子可塑劑而試著機械性質之改善，通常隨著可塑劑添加量之增加，如拉伸強度之機械性質將明顯降低。將二氯甲烷可溶性聚尿酯樹脂加入纖維素醯化物之情形，雖然確認隨著樹脂添加量之增加而降低些許之拉伸強度，相較於低分子可塑劑添加之情形，強度之降低明顯減少，可以得到幾乎相同於無添加之情形的耐折強度大之強韌薄膜。再者，藉由混合此聚尿酯，可以防止低溫、高濕下之可塑劑的轉移。因此，薄膜相互間不會黏著，並且具有極佳的柔軟性，可以.得到無皺摺之透明且具有光澤之薄膜。爲了對於纖維素醯化物薄膜進行機械物性之改良，較宜添加該聚尿酯，也可以取代聚尿酯，或是與聚尿酯合倂使用，使用以下之可塑劑。可塑劑可以使用磷酸酯或羧酸酯。磷酸酯代表性例子，包括：三苯基磷酸酯（TPP )與三甲酚磷酸酯（TCP )。羧酸酯代表性例子爲：苯二酸酯與檸檬酸酯。苯二酸酯例子，包括：苯二酸二甲酯（DMP )、苯二酸二乙酯（DEP)、苯二酸二丁酯（DBP)、苯二酸二辛酯（DOP)、苯二酸二苯酯（DPP)與己基苯二酸二乙酯 (DEHP )。檸檬酸酯代表性例子，包括：檸檬酸三乙基 -63 - 201211575 0 -乙醯（OACTE)與檸檬酸三丁基〇 -乙醯（〇ACTB)。其他羧酸酯例子爲：油酸丁酯、蓖麻醇酸甲基乙醯酯、癸二酸二丁酯、各種之三苯六甲酸酯。較宜使用苯二酸酯系可塑齊！1 (DMP、DEP、DBP、DOP、DPP、DEHP)。尤以 DEP 與D P P更佳。可塑劑添加量之纖維素酯的量較宜爲〇.1至25質量 % ，更佳爲1至20質量％，尤以3至15質量％最好，於纖維素醯化物薄膜中，也可以添加抗劣化劑（例如，抗氧化劑、過氧化物分解劑、自由基抑制劑、金屬不活化劑、氧捕獲劑、胺）。針對抗劣化劑，已揭示於日本公開專利第平 3-199201、平 5-1907073、平 5-194789、平 5 - 2 7 1 4 7 1、平6 - 1 0 7 8 5 4號之各公報。抗劣化劑之添加量，較宜爲進行調製之溶液（摻雜液）的〇.〇1至1質量％，更佳爲〇.〇1至〇·2質量％。若添加量低於0.01質量％，抗劣化劑之效果幾乎無法確認。若添加量超過1質量％，往往確認向表面之抗劣化劑的滲出。抗劣化劑特別理想之例子，可列舉：丁基化羥基甲苯（ΒΗΤ )、三苯甲基胺（ΤΒΑ ) » [二軸拉伸] 爲了使假想歪斜得以減低，纖維素醋酸酯薄膜較宜進行適度之拉伸處理。因爲藉由進行拉伸，可以減低拉伸方向之假想歪斜，爲了減低面內所有方向的歪斜，較宜進行二軸拉伸。但是’基於製造上操作性之觀點，最好進行成爲該音速範圍的二軸拉伸。二軸拉伸有同時二軸拉伸法與逐次二軸拉伸法，基於連續製造的觀點，較宜爲逐次二軸拉伸法，進行摻雜液流延 -64- 201211575 之後，剝取帶狀物或輥輪上之薄膜，向寬度方向（長軸方向）進行拉伸之後，向長軸方向（寬度方向）進行拉伸。於寬度方向進行拉伸的方法，例如，已揭示於日本公開專利第昭 62-115035、平 4-152125、平 4-284211、平 4-2983 1 0、平1148217號之各公報。於常溫或加熱條件下進行薄膜之拉伸。加熱溫度較宜爲薄膜之玻璃轉移溫度以下。薄膜可以於乾燥中處理而進行拉伸，尤其殘存溶劑之情形特別有效。長軸方向拉伸之情形，例如，調節薄膜搬送輥輪之速度，若進行相較於薄膜剝取速度更快的薄膜卷取速度的話，薄膜將進行拉伸。寬度方向拉伸之情形，能夠一面利用定幅器維持薄膜之寬度，並一面進行搬送，藉由慢慢擴大定幅器之寬度而進行薄膜之拉伸。也可以於薄膜乾燥之後，使用拉伸機進行拉伸（較宜爲使用長拉伸機之單軸拉伸）。薄膜之拉伸倍率（相對於原來長度，因拉伸造成增加部分的比例）較宜爲〇至5 0%的範圍，更佳爲 10至40%的範圍，最好爲15至35%的範圍。從流延直到乾燥爲止之步驟，可以於空氣環境中進行，也可以於氮氣等不活性氣體環境中進行。用於纖維素醯化物薄膜製造之卷取機可以使用一般所用之卷取機。可以利用定張力法、定轉矩法、錐形張力法、如內部應力一定之程式張力控制法之卷取方法而進行卷取。 [吸濕膨脹係數] 吸濕膨脹係數係顯示於定溫下，使相對濕度改變時之試料長度的變化量。爲了防止外圍格子狀透過率的上升，纖維素醯化物薄膜 -65- 201211575 之吸濕膨脹係數較宜設爲30x1 Ο-5/% RH以γ xl(T 5/% RH以下，最好爲10xl0- 5/% RH以下然吸濕膨脹係數越小越好，通常爲1 . 〇 x 1 〇、5/% 値。以下’針對吸濕膨脹係數的測定方法進行說的聚合物薄膜（相位差板）切成寬度5mm、長試料’於25°C ' 20% RH(RO)之氣體環境中，予以固定而懸掛。於另一側則懸掛0 · 5 g之联石分鐘後進行長度（L0 )之測定。接著，溫度依但是將濕度設爲80% RH(R1)後進行長度（L 吸濕膨脹係數係利用下式而算出的。測定係針之1 〇片試樣進行測定，採用平均値。吸濕膨脹係數[/% RH] = { ( LI - LO) /LO}/ ( 因該吸濕而造成的尺寸變化，發現較宜縮小中之自由體積。影響自由體積之主要原因爲製溶劑量，其量越少，尺寸變化也越小。爲了減少殘留溶劑的一般手法係高溫且長乾燥，但是時間若太長，生產性當然將降低。維素醯化物薄膜之殘留溶劑量，較宜爲0.01至範圍，更佳爲0.02至0.07質量％之範圍，最女 0·05質量％之範圍。藉由抑制該殘留溶劑量’能夠便宜且高生產有光學補償能力的偏光板。殘留溶劑量係意指相對於固形成分含量ΰ 量，以下式定義，更佳爲1 5 。另外，雖 RH以上之明。將製得度2 0 m m之將單側邊緣馬，放置10 然爲2 5 °c， 1 )之測定。對相同試料 :R1 — RO) 聚合物薄膜膜時之殘留時間下進行因而對於纖 1質量％之 ?爲0.03至性地製造具勺揮發物之 -66- 201211575 殘留溶劑量（質量％ ) = ( (w—wo) /wo) χίοο W :試料軟膜質量 WO :於110°C，進行試料軟膜2小時之乾燥後的試料質量殘留溶劑量係將定量之試料溶於氯仿中，再利用氣體層析儀（GC1 8 A ’日本島津製作所（股份公司）製）進行測定。溶液流延法係使用將聚合物材料溶於有機溶劑的溶液 (摻雜液）而進行薄膜的製造。如後所述，利用溶液流延法之乾燥大致分爲於轉筒（或帶狀物）面之乾燥與薄膜搬送時之乾燥。於轉筒（或帶狀物）面之乾燥時，於不超過所使用之溶劑沸點的溫度（若超過沸點將成爲氣泡），較宜慢慢進行乾燥。爲了實現本發明之纖維素醯化物薄膜，重要的是從轉筒 (或帶狀物）剝離之後立即進行加熱。加熱之溫度較宜爲 1 10 至 160°C，更佳爲 120 至 15〇。(：。另外，薄膜搬送時之乾燥，較宜爲聚合物材料之玻璃轉移點±30t ，更佳爲±2(TC進行。另外’減小因該吸濕而造成的尺寸戀彳αMachinery homogenizer, UHM-01 manufactured by Japan Sanhe Machinery Co., Ltd., etc. Further, the average particle diameter of the dispersed particles in the dispersion and the monodispersity of the particle diameter 'in addition to satisfying the range, in order to remove the coarse aggregates in the dispersion and the separation treatment of the beads are preferably disposed. Filter material for precision filtration. The filter particle size of the filter material for precision filtration is preferably 2 5 -49-201211575 //m or less. The filter medium type to be subjected to the fine filtration is not particularly limited as long as it has such a property, and examples thereof include a fiber type, a felt type, and a mesh type. The material of the filter material for the precise filtration of the dispersion has such a property' and is not particularly limited as long as it does not adversely affect the coating liquid. For example, stainless steel, polyethylene, polypropylene, and london may be mentioned. The additive other than the fine particles may be contained, for example, at the stage of mixing the cellulose oxime with the solvent, or may be added after the mixed solution is prepared by using a solvent and a cellulose hydride. Further, it is also possible to carry out the addition and mixing immediately before the casting of the doping liquid, that is, the method immediately before the addition, and the mixing is performed by providing the spiral mixing in an on-line manner. The mixing of these additives may be added to the additive itself. The preferred aspect may also be dissolved by using a solvent or a binder (preferably cellulose mash), and depending on the conditions, a dispersed and stabilized solution may be formed. use. (Film Forming Step) Next, the present invention will be described with respect to a method for producing a film using a dope. A method and apparatus for producing a polymer film, which is referred to as a drum method or a belt method for supplying a polymer film, can be carried out by a conventional solution casting film forming method and a solution casting film forming apparatus. When the film forming step is described, the doping liquid (cellulose mash solution) prepared by the dissolving machine (pot) is temporarily stored in a storage pot, and the bubbles contained in the doping liquid are deaerated and finally prepared. It is important that the prepared doping liquid is used to remove the agglomerates and contaminants by precise filtration. Specifically, the filtered filter membrane is preferably used with a pore size that does not remove the components in the doping liquid as much as possible. Small filter. For filtration, it is better to use an absolute filter of -50-201211575 according to the accuracy of 0.1~100/zrn, and it is better to use a filter with an absolute filtration accuracy of 0.1~2 5" m. The thickness of the filter membrane is preferably 〇. Bu 1 〇 mm, more preferably 0.2 to 2 mm. In this case, the filtration pressure is 15 kgf/cm2 or less, more preferably 10 kgf/cm2 or less, and most preferably 2 kgf/cm2 or less. In addition, for precision filtration, it is preferable to perform filtration several times in order to reduce the pore size of the membrane. The filter medium type to be subjected to the fine filtration is not particularly limited as long as it has such a property, and examples thereof include a fiber type and a felt type 'mesh type. The filter material for the precise filtration of the dispersion has such a property, and is not particularly limited as long as it does not adversely affect the coating liquid. For example, stainless steel, polyethylene, polypropylene, and nylon can be mentioned. For example, the doping liquid obtained by the number of rotations is sent from the doping liquid discharge port to the pressurizing die by a pressurized type quantitative gear pump capable of accurately feeding the liquid, from the pressurized type. a nozzle (slit) of the die, which uniformly flows the doping liquid on the metal carrier of the casting portion in the circular movement, the metal carrier is at a peeling point of about one rotation, and the aluminum carrier is not completely dried. The liquid film (also known as the fiber web) is peeled off. The both ends of the obtained fiber web are sandwiched by a clip, and the width is maintained, and the film is dried by being conveyed by a stopper, and then dried by the roller group of the drying device, and then the coiler is used for drying. Take the established length. The combination of the limiter and the drying unit of the roller group varies depending on the purpose. In the case of the third aspect of the present invention, in the metal carrier used in the casting step, the arithmetic mean roughness (Ra) of the surface is preferably more than O. OOlym, and 〇. 〇 15 is less than 111 '10 points average roughness ( Rz) is preferably 0.001/zm or more and 0.05 //m or less. More preferably, the arithmetic mean roughness (Ra) is Ο.ΟΟΙμπι -51 - 201211575 or more, 0.01 #m or less, and the ten-point average roughness (Rz) is 0_001 v m or more, 〇. 〇 2 A m or less. In the best case, the ratio of (Ra ) / ( Rz ) is 0.1 5 or more. In this manner, by setting the surface roughness of the metal carrier to a predetermined range, the surface shape of the film after film formation can be controlled within the range of the third aspect. For each of the manufacturing steps (divided into: casting (including co-casting), drying, peeling, stretching, etc.), it has been disclosed in detail in the technical number 2001-1745 ρ·25-30 step. In the casting step, one type of doping liquid may be cast in a single layer, or two or more kinds of doping liquids obtained by dissolving different polymers may be co-cast simultaneously and/or sequentially. In particular, the step of forming a film from a doping liquid such as the composition is important in that the addition step does not cause aggregation or unevenness of the added compound, and the drying step is important. The drying method of the doping liquid on the carrier may, for example, be a method of blowing hot air to the surface side of the carrier (drum or ribbon), that is, the surface of the fiber web on the carrier; blowing the hot air toward the rotating drum Or a method of the back side of the ribbon; contacting the temperature-controlled liquid with the opposite side of the casting surface of the ribbon or the rotating dope of the drum, and performing the transfer or the belt by heat transfer Heating 'liquid heat transfer method to control surface temperature, etc. It is more suitable for the liquid heat transfer on the back side. The surface temperature of the carrier before casting may be any temperature as long as it is below the boiling point of the solvent for the doping liquid. However, in order to accelerate the drying, or to lose the fluidity on the carrier, it is preferably set to a temperature lower by 1 to 1 Ot than the boiling point of the solvent having the lowest boiling point in the solvent to be used. On the carrier, the drying temperature of the polymerized film obtained by drying the doped liquid to obtain a polymer film is preferably 3 〇~2 5 〇〇c, especially -52- 201211575 4 0~180 ° C is better. Further, in order to remove the residual solvent, it is preferred to carry out drying at 50 to 160 ° C. In this case, drying is carried out by high-temperature hot air which is successively changed in temperature to evaporate the residual solvent. The above method is disclosed in Japanese Laid-Open Patent Publication No. Hei 5-17844. By this method, it is possible to shorten the time from the flow until the peeling. The drying temperature, drying, air volume, and drying time vary depending on the type of solvent to be used, and may be appropriately selected depending on the type and combination of the solvent to be used. The amount of the residual solvent of the final processed film is preferably 2% by mass or less, more preferably 〇.4% by mass or less, to obtain a film having good dimensional stability. Further, in the present invention, since the peeling time can be further shortened by the release agent, and the electric resistance at the time of peeling is lowered, a planar shape can be obtained (due to the abnormality in the lateral direction at the time of peeling, the residue remaining in the peeling of the gel-like residue, etc.) A non-degraded polymer film. Specifically, the average drying speed from the casting of the dope to the stripping is preferably set to more than 300 mass%. /min, and 1% by mass/min or less, more preferably more than 400% by mass/min, and 900% by mass/min or less, preferably set to more than 500% by mass/min, and 800% by mass / points below. When the average drying rate is 300% by mass/min or less, the film cannot be peeled off at a high speed, and as a result, the productivity tends to be deteriorated, and if it exceeds 1% by mass/min, the wind is abnormal due to the dry wind. This occurs because the planarity and surface shape of the film tend to be abnormal, so it is preferable to set it within this range. The average drying speed is obtained by dividing the amount of change in the solvent content of the casting dope by the number of times. In order to adjust the average drying speed, it is possible to perform casting by appropriately adjusting the temperature of the drying wind, the amount of the air, the concentration of the solvent gas, the surface temperature of the casting carrier, the temperature of the doping liquid of 201211575 casting, and doping of the casting. Further, the solvent composition of the doping liquid or the like is further increased, and the rate of the doping solution is more than 300% by mass/min in a casting point of 15 m or less, and is preferably more than 400 mass in 1? ϋ / min, and 900: preferably more than 500% by mass / min, and 800, in addition, beyond the distance of 15m from the casting point, the average limit, preferably in the same range. More than 300% by mass/minute from 3 seconds after the start of casting to 20 seconds after the casting, and 1 〇〇〇 mass | over 400% by mass/min, and 900% by mass exceeding 500% by mass/min, and 800% by mass exceeds the range of 20 seconds after casting, and the average drying speed is from the drying step after the carrier is peeled off, and the solvent shrinks in the width direction. At high temperatures, the larger the size. This shrinkage is preferably suppressed as much as possible to improve the planarity of the film. In this regard, for example, the drying step disclosed in Japanese Patent Publication No. 6246 62 5 discloses a method of drying the fiber surface by a clip in the width direction (a tenter method). Although the speed at which the polymer film is produced is changed depending on the tape method, the solvent composition of the dope, and the like, the amount of residual solvent at the time of peeling is almost in the vicinity of the surface of the ribbon in the thickness direction of the doped film, and peeling off In the case where the dope remains in the thickness of the web of the liquid in the ribbon, the average dry I amount %/min or less of the range of the crucible is less than or equal to %/min, and more than %/min. Further, the drying speed is not particularly limited to an average drying speed; /min or less, preferably less than /minor, more preferably /minor or less.) Further, there is no particular limitation. Evaporation causes the film to dry, shrinking becomes more and more dry, so that it is better to complete the special steps or part of the steps as disclosed in Japan, the width of the ends of the mesh, the length of the material, and the drying of the fiber from the ribbon of. That is to say, if the solvent concentration is too high, it will cause the next-54-201211575 flow delay to be hindered. Therefore, it is absolutely not suitable to have the peeling residue. In addition, there must be a fiber web that can withstand the force of peeling. strength. The amount of residual solvent at the stripping time point will vary depending on the drying method on the ribbon or the drum, and the method of drying the wind from the surface of the doping liquid is carried out from the back of the belt or the drum. The heat transfer method can effectively reduce the amount of residual solvent. Specifically, the amount of the residual solvent in the polymer film is preferably from 0.01 to 1.5% by mass. More preferably 0.01 to 1.0% by mass. In the casting step, it is preferred to carry out uniaxial stretching in only one direction such as casting direction (longitudinal direction), or biaxial stretching in the casting direction and other directions (lateral direction). Further, the doping liquid may simultaneously perform casting of other functional layers (for example, an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, a UV absorbing layer, a polarizing layer, etc.). The manufacturing method of the optical compensation sheet used in the present invention is a method for manufacturing an optical compensation sheet for manufacturing the transparent carrier. In the third aspect, the transparent carrier is a cellulose halide film, which has a casting step. The film formation of the cellulose vapor film is carried out by a solution casting method, characterized in that the metal carrier on which the doping liquid of the casting step is cast has an arithmetic mean roughness (Ra) of 0.001/zm on the surface thereof. Above the 0.015 ym or less, the ten-point average roughness (Rz) of the surface is 0.001/m or more and 〇.〇5 or less. However, the optical compensation sheet of the present invention is not limited by this production method, and can be manufactured by various methods. (Stretching treatment step) The obtained polymer film can be further adjusted by the stretching treatment to be delayed from -55 to 201211575. The draw ratio is preferably from 3 to 100%. In the case of the stretching method of (1) and/or (2), the shaft offset (latient phase axis angle) can be adjusted to a predetermined range. (1) The stretching in the width direction is carried out at a stretching ratio of 3 to 40%, preferably 7 to 37%, more preferably 15 to 35%. Then, it is expanded by 0.4% or more and 5% or less in the long axis direction, preferably 0.7% or more and 4% or less, more preferably 1% or more and 3.5% or less, and is heat-treated at 60 to 160 °C. . (2) When stretching, the surface and the back surface are given a temperature difference. In the flow delay, the temperature of the surface contacting the substrate (belt or drum) is set to be higher than 2 ° C and above 20 ° C, preferably above 3 ° C. 1 5 ° C or less, more preferably 4 ° C or more, 1 2 ° C or less. By such a method, the "axis shift" is controlled by eliminating the unevenness of the additives (plasticizer, hysteresis modifier, ultrafine particles, etc.) added to the film in the stretching step. Further, by adjusting the conditions of the stretching process, the standard deviation of the retardation axis angle of the optical compensation sheet can be reduced. Although the method of the stretching treatment is not particularly limited, examples thereof include a stretching method using a stopper. With respect to the film produced by the solvent casting method, when the film is stretched by the stopper, the standard deviation of the retardation axis angle is reduced by controlling the state of the film after stretching. Specifically, the stretching process for adjusting the hysteresis is performed by the stopper, and then the state of the polymer film is instantaneously maintained, and the glass transition temperature of the film is maintained below the glass transition temperature. deviation. When the film temperature at the time of holding is set to be higher than the glass transition temperature, the standard deviation will become large. -56- 201211575 As described above, the transparent carrier of the third aspect of the present invention is a cellulose oxime film which is preferably a film obtained by the following steps: solution modulating step a cellulose halide solution prepared by dissolving a cellulose halide in a substantially non-chlorinated solvent; a film forming step, a cellulose halide thin film formed from a cellulose halide solution; and a stretching step utilizing the cellulose A film produced by stretching a bismuth film. Further, the cellulose acetate film of the fourth and fifth aspects can be further adjusted by the stretching treatment to form an optically anisotropic film. In the fourth aspect of the invention, the cellulose acetate film must be made to have optical anisotropy. The draw ratio is preferably from 3 to 100%. The thickness of the cellulose acetate film is preferably from 20 to 120 " m, more preferably from 30 to ΙΟΟμηι. It is preferably 40 to 80//m. Further, if the film forming method is described, it is preferable to add the hysteresis sputum enhancer to the doping liquid. The doping liquid is cast on a drum or ribbon to evaporate the solvent to form a film. The solid content of the dope before casting is preferably adjusted to a concentration of 18 to 3 5%. The surface of the drum or ribbon is preferably pre-machined into a mirrored state. The method of casting and drying for the solvent casting method is disclosed in U.S. Patent Nos. 2,336,310, 2,367,603, 2, 492, 078, 2, 492, 977, 2, 492, 978, 2, 607, 704, 2, 739, 069, 2, 739, 070; Japanese Laid-Open Patent Publication No. Sho. No. Sho 60-176834, No. Sho 60-203430, Sho 62-115035. The doping solution is preferably cast on a drum or ribbon having a surface temperature of 10 ° C or less. Drying is carried out for 2 seconds or more from the start of casting. -57- 201211575 Dry. The obtained film was peeled off from the drum or the belt, and the residual solvent was evaporated by sequentially changing the heat of the temperature in a state of 45 to 70%. The volatile portion after stripping is preferably 50 to 65%. If the volatile portion is less than 45%, it is as large as 20 to 30 nm. If it exceeds 70%, the film is often deformed by evaporation, and any of the cases will become a problem. The hot air is 100 to 160 ° C, more preferably 110 to 140 ° C. If the temperature is lower than the hysteresis, it will become larger. If the temperature exceeds 160 °C, the film is deformed by evaporation, and any situation will become a problem. The obtained film is peeled off from the drum or the belt, and further dried to dry solvent at a high temperature hot air which is successively changed in temperature by 16 ° C. The above method has been disclosed in Japanese Laid-Open Patent Publication No. Hei. It is possible to shorten the time from casting straight. In order to carry out this method, the flow drum or belt temperature must be able to gel the dope. It is also possible to use the adjusted cellulose halide solution (doped Thinning is carried out by casting two or more layers. In this case, the solution casting method is used to form a cellulose halide film, and the doping liquid is cast to form a film by evaporation of the solvent. It is advisable to adjust the solid content to 10 to 40% of the surface of the cylinder or ribbon, and it is better to pre-process into a mirror-like state to carry out several kinds of cellulose oxime solutions in two or more layers. The casting direction, the plurality of casting openings provided at intervals may be dried by 4 5 to 70%, and the phase difference will be foamed, resulting in a temperature of '100. , It is often foamed, and it can be dried from 100 to make the residual i flat 5 - 1 7844 to the surface of the stripped material.) It is better to use the doping range dissolved in the drum or strip. The 流i spoon casting can be carried out by laminating a solution containing a cellulose sulphate on the side of the carrier, respectively, and forming a film on the one side (for example, as disclosed in Japanese Laid-Open Patent Publication No. 61-1 - 584 1 4, pp. 1-122419 and pp. 11-198285.) Alternatively, the cellulose mash solution may be cast from two casting openings to be thinned (for example, disclosed in Japanese Patent No. 6 0 - 2 7 5 6 2; Japanese Laid-Open Patent Publication No. Sho 61-94724, Sho 61-947245, Sho 61-104813, Sho 61-158413, and JP-A-6-134933. A casting method of a cellulose oxime film, which surrounds a flow of a high-viscosity cellulose mash solution with a low-viscosity cellulose oxime solution, and simultaneously simultaneously extrudes the high-viscosity cellulose mash solution (for example, disclosed in Japanese public patents Japanese Patent Publication No. Sho. No. 5-6-62 6 1 7). Alternatively, a film formed on a carrier may be stripped through a first casting opening by using two casting openings on the side contacting the carrier surface. A method of producing a film by the second casting (for example, disclosed in Japanese Laid-Open Patent Publication No. SHO 44-2023 No. 5). For casting a cellulose mash solution, the same solution may be used, or different fibers may be used. A bismuth telluride solution. In order to function in several cellulose mash layers, a cellulose mash solution corresponding to its function can be extruded from individual casting openings. Further, the cellulose halide solution of the present invention may simultaneously cast other functional layers (e.g., an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, an ultraviolet absorbing layer, a polarizing film). In the conventional single layer liquid, in order to form the thickness of the necessary film, it is necessary to extrude a high viscosity cellulose mash solution at a high concentration. In this case, the stability of the cellulose bismuth solution is deteriorated to cause solid matter, which is a hindrance to the residue, and the problem of poor planarity is often caused by -59-201211575. The solution to this problem is that by casting a plurality of cellulose halide solutions from the casting opening, the high viscosity solution can be extruded on the carrier at the same time, which is excellent in planarity and can be produced excellently. In the planar film, by using a cellulose mash solution having a high concentration, it is possible to reduce the drying load and increase the production speed of the film. It is preferred to add a polyurethane in order to improve mechanical properties in a cellulose halide film. Further, the polyurea ester is preferably a reaction product of a polyester represented by the following general formula (1) with a diisocyanate, more preferably soluble in dichloromethane. (1) H-(0-(CH2), -00C-(CH2)m-C0)n-0-(CH2), -OH wherein 1 represents an integer from 2 to 4; m represents an integer from 2 to 4. ;η represents an integer from 1 to 100. More specifically, the diol component of the polyester is ethylene glycol, 1,3-propanediol or I,4-butanediol; the dibasic acid component has succinic acid, glutaric acid or hexamethylene The polyester having a lower hydroxyl group than the dihydroxy group has a polymerization degree η in the range of 1 to 100, and the polymerization degree η is in the range of 1 to 100, and the optimum polymerization degree depends on the diol and the di-salt used. There are some differences in the type of base acid, and the molecular weight of the polyester is particularly preferably in the range of 1,000 to 4,500. The diurethane-soluble polyurethane resin is obtained by the reaction of the polyacetate of the formula (1) with a diisocyanate, and the general formula is a compound of the repeating unit represented by the formula (2). (2) C0NH-R-NHC0-(0-(CH2), -00C-(CH2)m-C0)n-0-(CH2), where '1 represents an integer from 2 to 4; m represents 2 to 4 An integer; η represents an integer from 1 to 100; and R represents a divalent atomic residue. Examples of the divalent radical residue include, for example, an atomic group residue of the following formula. -60- 201211575 :Lli :SU:. 6:1 ,: [..化..Π::)' For the diisocyanate component used in polyurethane compounds, ethylidene diisocyanate, trimethylene di Polyorthoester represented by isocyanate, isocyanate, and hexamethyl diisocyanate (general formula: OCN-(CH2)p-NCO (ρ represents 2 to 8 5 aromatic diisocyanate (for example, contains p_phenylene) Isophenyl diisocyanate, ρ, ρ'-diphenylmethane diisocyanate diisocyanate) and m- benzene dimethyl diisocyanate. Toluene ester 'm- phenyl dimethyl diisocyanate and tetramethylene diisocyanate 'Stable and easy to handle, and polyurethane esterified. Excellent compatibility with cellulose oxime. Polyurethane resin preferably has a molecular weight of 2,000 to 50,000. It can be linked by component polyester or these. Moderately adjusted according to the species or molecular weight of the group. The improvement of mechanical properties based on cellulose and the molecular weight of the colloidal polyurethane resin for cellulose halides are better than 5000 to 1 5000. The synthesis of urethane esters Mix with diisocyanate, in the case of stirring, containing tetramethylene dimethyl diisocyanide: integer)); cyanate ester, methyl 1,5-naphthyl diisocyanate is easier, The range is suitable. The viewpoint of the filminess of the cyanate component is as follows: 1) The heating is carried out under the formula -61 - 201211575 and is easily obtained. The polyester represented by the formula (1) is a condensation method using an esterification reaction or an ester exchange reaction of an alkyl ester of a suitable dibasic group with a glycol, or an acid chloride of such an acid. Any of the methods of shrinking the interface with a diol is easy to synthesize if the terminal group is appropriately adjusted to a hydroxyl group. The methylene chloride-soluble polyurethane resin is excellent in compatibility with a bismuth chelate of 58% or more. Although the molecular weight of the polyurethane is 10,000 or less depending on the structure of the resin, the cellulose acetate of a part by mass is dissolved even in 200 parts by mass of the polyurethane. Therefore, in order to improve the mechanical properties of the polyurethane resin by mixing the polyurethane resin, the content of the polyurethane resin can be appropriately determined depending on the type of urine, the molecular weight, and the desired mechanical properties. It is preferable to contain 10 to 50 mass of urethane resin for the cellulose oxime in the original shape to improve the mechanical shape. In addition, the polyurethane resin is still stable and insoluble at at least 180 °C. The methylene chloride-soluble polyurethane ester is especially suitable for deuteration; the above cellulose halide is excellent in compatibility. Therefore, if the film is formed by mixing, a film having an extremely high transparency can be obtained. Moreover, the average molecular weight of the polyurethane esters is high, and the conventional low molecular plasticizers have almost no volatility even at high temperatures. Therefore, the film obtained by the above-mentioned mixed film formation can be processed in the subsequent process to reduce the improperness which is conventionally observed due to volatilization or transfer of the plasticizer. If the acid or hot melt is legal, the fiber can be slightly different from that of the film ester resin. The heat of the party is 58%. The difference is that the compound is plasticizer. 62- 201211575 By adding polyurethane to the cellulose film, the folding strength and tear strength at high and low temperatures will become larger and the improper phenomenon such as film rupture will be eliminated. It is known to use a low molecular plasticizer in order to increase the folding strength or tear strength of the film. Although this method has a certain degree of effect at normal temperature and high humidity, the softness of the film under normal temperature and high humidity will be lost, and satisfactory results may not be obtained. Further, if the improvement of the mechanical properties is attempted by a low molecular plasticizer, generally, as the amount of the plasticizer added increases, the mechanical properties such as tensile strength are remarkably lowered. In the case where a dichloromethane-soluble polyurethane resin is added to a cellulose halide, it is confirmed that the tensile strength is lowered as the amount of the resin is increased, and the decrease in strength is remarkably reduced as compared with the case of adding a low-molecular plasticizer. It is possible to obtain a tough film having a folding strength which is almost the same as that in the case of no addition. Further, by mixing the polyurethane, the transfer of the plasticizer under low temperature and high humidity can be prevented. Therefore, the films do not adhere to each other and have excellent flexibility, so that a wrinkle-free transparent and glossy film can be obtained. In order to improve the mechanical properties of the cellulose oxime film, it is preferred to add the urethane, or to replace the urethane or to use the urethane, and to use the following plasticizer. A phosphate or a carboxylate can be used as the plasticizer. Representative examples of phosphates include: triphenyl phosphate (TPP) and tricresol phosphate (TCP). Representative examples of carboxylates are: phthalates and citrates. Examples of phthalic acid esters include: dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), benzene Diphenyl diester (DPP) and diethyl hexyl phthalate (DEHP). Representative examples of citrate include: triethyl citrate-63 - 201211575 0 - acetamidine (OACTE) and tributyl hydrazine citrate - hydrazine (ACTB). Examples of other carboxylic acid esters are: butyl oleate, methyl decyl ricinoleate, dibutyl sebacate, and various trimellitates. It is better to use the benzoate to make it fit! 1 (DMP, DEP, DBP, DOP, DPP, DEHP). Especially DEP and D P P are better. The amount of the cellulose ester added in an amount of the plasticizer is preferably from 1 to 25% by mass, more preferably from 1 to 20% by mass, particularly preferably from 3 to 15% by mass, preferably in the cellulose halide film. An anti-deterioration agent (for example, an antioxidant, a peroxide decomposing agent, a radical inhibitor, a metal inactivating agent, an oxygen scavenger, an amine) is added. The anti-deterioration agent has been disclosed in Japanese Laid-Open Patent Publication No. Hei 3-199201, Hei 5-1907073, Hei 5-194789, Hei 5 - 2 7 1 4 7 1 , Ping 6 - 1 0 7 8 5 4 . The amount of the anti-deterioration agent to be added is preferably 〇1 to 1% by mass, more preferably 〇.〇1 to 〇·2% by mass, of the solution (dopant) to be prepared. If the amount added is less than 0.01% by mass, the effect of the anti-deterioration agent can hardly be confirmed. When the amount added exceeds 1% by mass, it is often confirmed that the anti-deterioration agent on the surface is oozing out. Particularly preferred examples of the anti-deterioration agent include butylated hydroxytoluene (oxime) and tritylamine (ΤΒΑ). [Biaxial stretching] In order to reduce the imaginary skew, the cellulose acetate film is preferably carried out. Moderate stretching treatment. Since stretching is performed, the imaginary skew of the stretching direction can be reduced, and in order to reduce the skew in all directions in the plane, it is preferable to perform the biaxial stretching. However, it is preferable to perform biaxial stretching in the range of the sound velocity based on the viewpoint of manufacturing operability. Biaxial stretching has simultaneous biaxial stretching method and successive biaxial stretching method. Based on the viewpoint of continuous manufacturing, it is more suitable for successive biaxial stretching method, after doping liquid casting -64-201211575, stripping tape The film on the roll or the roll is stretched in the width direction (long axis direction) and then stretched in the long axis direction (width direction). The method of stretching in the width direction is disclosed, for example, in Japanese Laid-Open Patent Publication No. Sho 62-115035, No. 4-152125, No. 4-284211, No. Hei 4-2983, No. Hei 1148217. The film is stretched at room temperature or under heating. The heating temperature is preferably below the glass transition temperature of the film. The film can be stretched by treatment in a dry state, and particularly in the case of a residual solvent. In the case of stretching in the long axis direction, for example, adjusting the speed of the film transport roller, the film is stretched if a film take-up speed is made faster than the film peeling speed. In the case of stretching in the width direction, the width of the film can be maintained by the stopper to be carried, and the film can be stretched by gradually expanding the width of the stopper. It is also possible to use a stretching machine for stretching after the film is dried (preferably, uniaxial stretching using a long stretching machine). The stretching ratio of the film (relative to the original length, the proportion of the increased portion due to stretching) is preferably in the range of 〇 to 50%, more preferably in the range of 10 to 40%, and most preferably in the range of 15 to 35%. . The step from casting to drying may be carried out in an air atmosphere or in an inert gas atmosphere such as nitrogen. A coiler for use in the manufacture of a cellulose-based film can be used in a conventionally used coiler. The winding method can be performed by a constant tension method, a constant torque method, a conical tension method, or a winding method such as a program tension control method in which internal stress is constant. [Moisture absorption coefficient] The coefficient of hygroscopic expansion is the amount of change in the length of the sample when the relative humidity is changed at a constant temperature. In order to prevent the increase of the outer lattice-like transmittance, the hygroscopic expansion coefficient of the cellulose vapor film-65-201211575 is preferably set to 30x1 Ο-5/% RH to γ xl (T 5/% RH or less, preferably 10x10). - 5/% RH or less The hygroscopic expansion coefficient is as small as possible, usually 1. 〇x 1 〇, 5/% 値. The following is a polymer film (phase difference plate) for measuring the coefficient of hygroscopic expansion coefficient. Cut into a width of 5mm, long sample 'in 25 ° C ' 20% RH (RO) in a gas environment, fixed and suspended. On the other side, suspend 0 · 5 g of the joint stone minutes and then length (L0) Then, the temperature was determined by setting the humidity to 80% RH (R1) and then calculating the length (L hygroscopic expansion coefficient was calculated by the following formula. The measurement was performed on the cymbal sample of the tying needle, and the average 値 was used. Moisture absorption coefficient [/% RH] = { ( LI - LO) /LO} / ( Due to the dimensional change caused by the moisture absorption, it is found that the free volume is better to be reduced. The main reason for affecting the free volume is the solvent. The smaller the amount, the smaller the dimensional change. The general method for reducing the residual solvent is high temperature and long drying. However, if the time is too long, the productivity will of course be lowered. The residual solvent amount of the vitamin bismuth film is preferably in the range of 0.01 to 1,500, more preferably in the range of 0.02 to 0.07% by mass, and most preferably in the range of 0.55% by mass. The polarizing plate having optical compensation ability can be produced inexpensively and high by suppressing the amount of residual solvent. The amount of residual solvent means the amount of 固 relative to the solid content, which is defined by the following formula, more preferably 1 5 . The determination will be made to obtain a degree of 20 mm from the one-sided edge of the horse, placing 10 as 2 5 °c, 1). For the same sample: R1 - RO) the polymer film film is carried out at the residual time and thus 1% by mass of fiber is 0.03 to produce volatiles with spoon -66-201211575 Residual solvent amount (% by mass) = ( (w-wo) /wo) χίοο W : Sample soft film quality WO: at 110 ° C The amount of the residual mass of the sample after the sample film was dried for 2 hours was measured by dissolving the sample in a quantitative amount in chloroform, and measuring it by a gas chromatograph (GC1 8 A 'made by Shimadzu Corporation, Ltd.). Extended law system The polymer material is dissolved in a solution (doping solution) of an organic solvent to perform film production. As will be described later, the drying by the solution casting method is roughly classified into drying of the drum (or ribbon) surface and film transfer. Drying at the time. When drying on the surface of the drum (or ribbon), it is preferably dried at a temperature not exceeding the boiling point of the solvent to be used (if it exceeds the boiling point), in order to achieve the fiber of the present invention. It is important to heat the film immediately after peeling off the drum (or ribbon). The heating temperature is preferably from 1 10 to 160 ° C, more preferably from 120 to 15 Torr. (:. In addition, the drying of the film during transport is preferably a glass transition point of the polymer material of ± 30 t, more preferably ± 2 (TC is carried out. In addition, the size of the moisture caused by the moisture absorption is reduced by α.

塑劑或抗劣化劑之中所添加的原料。g + ’可列舉：三薄膜中的可可列舉：三苯基磷酸酯（TPP )與三苯甲基胺（τΒΑ)。A raw material added to a plasticizer or an anti-deterioration agent. Examples of g + ' can be exemplified by the three types of cocoa in the film: triphenyl phosphate (TPP) and tritylamine (τΒΑ).

-67- 201211575 溶液（摻雜液），較宜爲0.01至10質量％之範圍，更佳爲0.1至5質量％之範圍，最好爲1至3質量％之範圍。 [透明載體、纖維素醯化物薄膜之表面處理] 對於纖維素醯化物薄膜等之透明載體，較宜進行表面處理。尤其於光學異方向層與透明載體之間設置配向膜之情形，發現進行配向膜形成用組成物之均句塗布，並且藉由塗布所塗上之配向膜與透明載體之足夠密著性，進行載體之表面處理，較宜進行表面改質成親水性的親水化表面處理。對纖維素醯化物薄膜等透明載體之親水化處理的態樣，物理性處理可列舉：電暈放電處理、輝光放電處理、火焰處理、紫外線照射處理、火焰電漿處理。濕式處理，可列舉：臭氧處理、氧化處理、鹼處理等。具體而言，可列舉：揭示於日本發明協會公開技法公技編號200 1 - 1 745 號（2001年3月15日發行）ρ·30-31之內容，曰本公開專利第200 1 -9973號公報等。另外，最好設置塗底層（例如，揭示於日本公開專利第平7 -3 3 3 43 3號公報）》基於維持薄膜平面性之觀點，於此等處理下，較宜將纖維素醯化物薄膜之溫度設爲Tg (玻璃轉移溫度）以下，具體而言設爲150°C以下。基於與偏光板之接著性的觀點’作爲偏光板透明保護膜使用之情形，尤其較宜進行酸處理或鹼處理，亦即，實施對纖維素醯化物之皂化處理。以下’尤其針對較佳之鹼的皂化處理，進行具體說明。 -68- 201211575 纖維素醯化物薄膜之鹼的皂化處理較宜將薄膜表漬於鹼性溶液之後，利用酸性溶液進行中和、水洗後之循環。基於親水化處理的簡便性、裝置之維護性（難以腐倉較宜利用鹼性溶液進行鹼的皂化處理。鹼的皂化處理，能夠利用將透明載體浸漬於鹼性中，於透明載體表面噴塗鹼性溶液或是進行塗布等之任一種方法。更佳的話，僅將透明載體之單面，利用無偏異且均句之皂化處理的塗布方式，進行驗的皂化虔皂化處理較宜於不超過不產生處理中之薄膜變形、液變質等之溫度l2〇°C範圍的處理溫度下進行。更佳度10°c以上、100°c以下之範圍。尤以溫度20〜60-C爲聋另外，皂化處理的時間係依鹼性溶液、處理溫度，宜調整而予以決定，但是最好於1~60秒鐘之範圍下進 [鹼性溶液] 本發明之鹼性溶液較宜爲pH 1 1以上之鹼性溶液。爲 ρ Η 1 2 ~ 1 4。用於鹼性溶液之鹼性劑的例子，可以使用氫氧化鈉氧化鉀、氫氧化鋰等無機鹼性劑，另外，二乙醇胺、醇胺、DBU( 1，8-二吖雙環[5,4,0]-7-十一烯）、DBN( 二吖雙環[4,3，0]-5-壬烯）、四甲基銨氫氧化物、四乙氫氧化物、四丙基銨氫氧化物、四丁基銨氫氧化物、基丁基銨氫氧化物等有機鹼性劑。此等之鹼性劑可以使用或組合二種以上而合倂使用，也可以例如以鹵化的鹽形式而添加一部分。面浸乾燥虫等）溶液中的能夠 i理。處理爲溫 !好。經適 ;行。更佳、氫三乙：1,5- 基銨三乙 •單獨之類 -69- 201211575 於此等鹼性劑之中，由於氫氧化鈉或氫氧化鉀較宜藉由此等之量的調整，便可能於更廣的pH領域進行pH調整。鹼性溶液之鹼性劑的濃度係因應於所用之鹼性劑種類、反應溫度與反應時間而予以決定，鹼性劑之含量較宜爲鹼性溶液中的0.1〜3mol/Kg，更佳爲0.5〜2mol/Kg。該鹼性溶液之溶劑較宜爲水與水溶性有機溶劑的混合溶液。水溶性有機溶劑可以使用只要與水能混合的有機溶劑的話均可’但是基於處理液隨時間改變之濃縮抑制與從處理後薄膜的去除性（乾燥性）之觀點，沸點較宜爲120 °C以下，更佳爲60~120°C，最好爲l〇〇°C以下。其中’有機溶劑的無機性/有機性基（I/O値）較宜爲0.5 以上’並且，溶解度參數較宜爲16〜40[mJ/m3]l/2; I/O値更佳爲〇.6~1〇,並且，溶解度參數更佳爲i8~31[mJ/m3]1/2。若I/O値相較於此範圍爲無機性強的，或是溶解參數低的，則鹼的皂化速度將降低，或是皂化度的整面均勻性將變得不足。另一方面，若I/O値相較於該範圍爲有機性側，或是溶解參數爲高溶解性側，則皂化速度將加速，容易產生模糊，因而整面均勻性之方面同樣變得不足。另外，有機溶劑，尤其一旦將該有機性、溶解性之各範圍的有機溶劑，與後述之界面活性劑與/或相溶化劑等相組合而使用，將維持高的皂化速度，並且遍及整面之皂化度的均勻性將提高。具有較佳特性値之水溶性有機溶劑，例如，可列舉：揭示於日本有機合成化學協會編之「新版溶劑口袋書」（曰本Ohm (股份）公司，1994年發行）等。（另外，針對有 -70- 201211575 機溶劑之無機性/有機性値（I/O値），例如，田中善生著之「有機槪念圖」（日本三共出版1983年發行）P.1-31所解說的）。具體而言’可列舉：一價脂肪族醇類（例如，甲醇、乙醇、丙醇、丁醇、戊醇 '己醇等）：脂環式烷醇（例，環己醇、甲基環己醇、甲氧基環己醇、環己基甲醇、環己基乙醇、環己基丙醇等）：苯基烷醇（例如，苯甲醇、苯乙醇、苯丙醇.、苯氧基乙醇、甲氧基苯甲醇、苯甲氧基乙醇等）；雜環式烷醇類（糠醇、四氫糠醇等）：二醇化合物之一醚類（甲基纖維素、乙基纖維素、丙基纖維素、甲氧基甲氧基乙醇、丁基纖維素、己基纖維素、甲基二甘醇一乙醚、乙基二甘醇一乙醚、丙基二甘醇一乙醚、丁基二甘醇一乙醚、乙氧基三甘醇、丙二醇一甲基醚、丙二醇一乙基醚、丙二醇一丙基醚等）：酮類（例如，N，N -二甲基甲醯胺、二甲基甲醯胺、N-甲基-2-吡咯烷酮、1，3-二甲基咪唑烷二酮等）；亞颯類（例如，二甲基亞楓）：以及醚類 (例如，四氫呋喃、吡喃、二噁烷、三噁烷、二甲基纖維素、二丙基纖維素、甲基乙基纖維素、二甲基二甘醇一乙醚、二乙基二甘醇一乙醚、甲基乙基二甘醇一乙醚等）等。所用之有機溶劑可以單獨使用或混合二種以上而使用。單獨一種或混合二種以上之有機溶劑之情形的至少一種有機溶劑，較宜對水的溶解性大。有機溶劑之水的溶解度較宜爲50質量％以上，更佳爲自由與水進行混合的有機溶劑。藉此，能夠調製一種鹼性溶液，其吸收對於鹼性劑、皂化處理所副產的脂肪酸的鹽、空氣中的二氧化碳而生成 -71 - 201211575 的碳酸鹽等之溶解性便足夠。有機溶劑之溶劑中的使用比例係因應於溶劑的種類、與水的混合性（溶解性）、反應溫度以及反應時間而予以決定。水與有機溶劑的混合比例較宜爲 3/97〜85/15之質量比，更佳爲5/95~60/4 0之質量比，最好爲15/85〜40/60之質量比。於此範圍內，不會破壞纖維素醯化物薄膜的光學特性，整面薄膜容易進行均勻的皂化處理。用於本發明之鹼性溶液所含之有機溶劑，也可以將具有不同於該較佳之I/O値的有機溶劑（例如，氟化醇等）與後述之界面活性劑、相溶化劑之溶解助劑合倂使用。對於鹼性溶液之總質量而言，其含量較宜爲0.1~5質量％。用於本發明之鹼性溶液較宜含有界面活性劑。藉由添加界面活性劑，降低表面張力而使塗布變得容易，提高塗膜之均勻性且防止彈跳之不良現象，並且，若存在有機溶劑，將抑制容易發生的霧度，進一步均勻進行皂化反應。藉由後述之相溶化劑的共存，其效果變得特別顯著。所用之界面活性劑並無特別之限制，可以爲陰離子性界面活性劑、陽離子性界面活性劑、兩性界面活性劑、非離子性界面活性劑、氟系界面活性劑等之中的任一種。具體而言，例如，可列舉：吉田時行著之「界面活性劑手冊（新版）」（·日本工學圖書，1987年發行）、「界面活性劑之機能創製•素材開發•應用技術」第1編（日本技術教育出版，2000年發行）等揭示之習知化合物。於此等界面活性劑之中，較宜爲陽離子性界面活性劑之 -72- 201211575 4級銨鹽類；非離子性界面活性劑之各種聚亞烷生物類；各種聚環氧乙烷附加物類等之聚環氧乙類；以及兩性界面活性劑之甜菜鹼型化合物類。於鹼性溶液中，較宜使非離子性界面活性劑與界面活性劑，或是非離子性界面活性劑與陽離子性劑共存而予以使用，可以提高本發明之效果。對於此等界面活性劑之鹼性溶液的添加量，可宜爲0.001~10質量％，更佳爲0.01~5質量％之| 用於本發明之鹼性溶液，較宜含有相溶化劑明，所謂「相溶化劑」係指於溫度2 5 °C，相對於相溶化劑，水的溶解度爲5 0 g以上之親水性化合化劑之水的溶解度係相對於1 0 0 g之相溶化劑，鞍以上’更佳爲1 〇〇 g以上。另外，相溶化劑爲液之情形，沸點較宜爲1 〇〇 °c以上，更佳爲12 〇 r ϋ 相溶化劑係防止附著於貯藏鹼性溶液之浴槽鹼性溶液的乾燥，並抑制黏著，具有穩定維持鹼作用。另外，於透明載體之表面，塗布鹼性溶液定時間之後，直到停止皂化處理爲止的期間，所性溶液的薄膜將進行乾燥，產生固態物析出，具水洗步驟之難以進行固態物的洗去。再者，防止之水與有機溶劑之相分離。尤其，藉由界面活性溶劑與該相溶化劑之共存，已處理之載體，即使並且爲長型尺狀連續巷化處理之情形，仍穩定而均勻的皂化度。相溶化劑只要能滿足該條件的材料，並無特屈基二醇衍烷衍生物陰離子性性界面活列舉：較 β圍。。於本發 l〇〇g 之物。相溶 :宜爲80g 狀化合物 (上。等壁面之性溶液之並保持一塗布之鹼有防止於作爲溶劑劑、有機霧度少，成爲整面 j之限定， -73- 201211575 例如，可列舉較宜爲：聚醇化合物、含有具醣類等之羥基與/或醯胺基之重複單位的水溶性聚合物。聚醇化合物可以使用低分子化合物、寡聚物與高分子化合物之中的任一種。脂肪族聚醇類，例如，可列舉：碳數2 ~ 8之烷二醇（例如，乙二醇、丙二醇、丁二醇、戊二醇、己二醇、甘油一甲基醚、甘油一乙基醚、環己烷二醇、環己烷二甲醇、二乙二醇、二丙二醇等）、含有三個以上羥基之碳數3〜18 的烷類（例如，甘油、三羥甲基乙烷、三羥甲基丙烷、三羥甲基丁烷、環己烷三醇、季戊四醇、雙甘油酯、雙季戊四醇、肌醇等）。聚環氧烷聚醇類’可列舉：可以如該相同的亞烷基二醇之間進行鍵結，也可以不同的亞烷基二醇之間進行鍵結；較佳爲相同的亞烷基二醇之間進行鍵結的聚亞烷基聚醇。任一種情形之鍵結數較宜爲3〜100，更佳爲3~50。具體而言’例如，可列舉：聚乙二醇、聚丙二醇、聚（環氧乙烷-環氧丙烷）。例如，醣類可列舉揭示於日本高分子學會高分子實驗學編集委員會編之「天然高分子」第二章（日本共立出版（股份），1 984年發行）；以及小田良平等編之「近代工業化 22、天然物工業化學II」（日本朝倉書店（股份），1967 年發行）等之水溶性化合物。其中，較宜爲不具有游離的醛基與酮基、不顯示還原性之醣類。一般而言，醣類分類成葡萄糖、蔗糖、還原官能基之間鍵結的海藻糖型少醣類、對於醣類之還原基與非醣類鍵結 -74- 201211575 的配糖物以及於醣類添加氫而還原的糖醇，任一種均適用於本發明。例如，可列舉：蔗糖、海藻糖、烷基配糖物、酚配糖物、芥子油配糖物、D，L-阿拉伯糖、核糖醇、木糖醇、D,L-山梨糖醇、D，L-甘露糖醇、D，L-伊地醇、D，L-塔羅糖醇、甜醇、阿洛糖醇、還原麥芽糖。此等之醣類可以單獨使用或組合二種以上而使用。具有羥基與/或胺基的重複單位之水溶性聚合物，例如，可列舉：天然膠類（例如，阿拉伯膠、膠樹膠、西黃蓍膠等）、聚乙烯吡咯烷酮、二羥基丙基丙烯酸酯聚合物、纖維素類或甲殻素類與環氧化物（環氧乙烷或環氧丙烷）之加成反應物。其中，較宜爲烯化聚醇、聚環氧聚醇、糖醇等之聚醇化合物》相對於鹼性溶液，相溶化劑之含量較宜爲0.5〜2 5質量 % ，更佳爲1〜20質量％。用於本發明之鹼性溶液，可以含有其他之添加劑。其他之添加劑’例如，可列舉：消泡劑、鹼性溶液安定化劑、 pH緩衝劑、防腐劑、防菌劑等之習知添加劑。如上所述’於本發明’該透明載體較宜爲藉由至少含有沸點爲6 0〜1 2 (TC之水溶性有機溶劑以及界面活性劑與/或相溶化劑之鹼性溶液（當然含有鹼性劑）進行表面處理。 [鹼性溶液之塗布皂化方法] 使用該鹼性溶液之聚合物薄膜（以下，此方法之說明係以「纖維素醯化物薄膜」爲例進行說明）之表面處理方法， -75- 201211575 較宜爲能夠僅處理薄膜單面的塗布方式。塗布方法可列舉：浸漬塗布法、淋幕塗布法、擠壓塗布法、桿式塗布法以及E型塗布法。再者，較宜藉由以下之步驟進行鹼的皂化處理：表面於至少1 〇 °C以上之溫度，利用鹼性溶液進行纖維素醯化物薄膜之皂化處理的步驟；將纖維素醯化物薄膜的溫度至少維持10°c以上之步驟；然後，從纖維素醯化物薄膜將鹼性溶液予以洗去的步驟。於既定之溫度，利用鹼性溶液，進行表面纖維素醯化物的皂化處理，可列舉：於進行塗布之前，預先調整爲既定溫度的步驟；將鹼性溶液預先調整爲既定溫度的步驟；或是組合此等之步驟等。較宜與於進行塗布之前已預先調整爲既定溫度的步驟相組合。皂化反應之後，較宜進行水洗、中和等，利用水洗等，從薄膜表面進行鹼性溶液以及皂化處理反應物之洗淨去除。具體而言，例如，可列舉：揭示於國際公開第02/468 09 號手冊等之內容。 [親水化處理過的透明載體之特性] 進行該處理的透明載體表面的親水性，較宜爲以下之物性範圍。 (1) 與薄膜表面上之水的接觸角，較宜爲2〇~55°之範圍。與水的接觸角更佳爲2 5 ~50°之範圍，更理想爲30〜4 5° 之範圍。 (2) 薄膜表面上之表面能量較宜爲55~75mN/m之範 -76- 201211575 圍。更佳爲60〜75mN/m之範圍。表面能量（評估項目（2 ))之評估方法，能夠藉由揭示於「濕潤之基礎與應用」（Realize公司，1989年發行）的接觸角法、濕潤熱法以及吸附法而求出。使用纖維素醯化物薄膜作爲透明載體使用之情形，較宜使用接觸角法。具體而言，將表面能量已知之二種溶劑滴下纖維素醯化物薄膜，於液滴表面與薄膜表面之交點，自液滴畫出的切線與薄膜表面所形成的角度，且包含液滴的角度定義爲接觸角，能夠藉由計算而算出薄膜之表面能量。用於本發明第3態樣之具有特定之表面形狀及光學特性之透明載體，能夠參考上述方法而進行調製，爲了將該表面形狀及光學特性設爲該範圍，藉由下列方式，達成辨識性良好的光學補償片。 (1 )如於該微顆粒之添加混合方法欄所揭示的，利用根據溶液流延方法的製膜方法，將單分散性微顆粒予以混合分散於摻雜液之前，預先進行濕式分散處理而形成已去除粗大顆粒的分散物，亦即，如上所述，不存在超過500 # m之粒徑的顆粒而使微顆粒之粒徑一致；（2 )如上所述，摻雜液係於流延步驟之前，進行精密過濾；（3 )如上所述，使用於流延步驟之金屬載體表面的凹凸成爲一定之大小； (4 )如上所述，控制於摻雜液之乾燥步驟的乾燥條件：（5 ) 如上所述，將流延步驟之流延條件予以精密化等；可以適度調整。其結果，也抑制遲相軸角度之偏異。再者，（6) 如上所述，藉由進行迅速皂化之鹼性溶液處理的親水化處理，配向膜與光學異方向層將無不均地塗布於塗布面內。 -77- 201211575 光學補償片能夠於製作的纖維素醯化物薄膜之上，設置由液晶性化合物所形成的光學異方向層。較宜於纖維素醯化物薄膜與於其上設置的光學異方向層之間設置配向膜》配向膜係進行使本發明所用之液晶性化合物達成配向於一定方向。因而，配向膜於進行本發明之光學補償片的製造上爲必須的。但是，於配向後，將液晶性化合物之配向狀態予以固定，配向膜爲了達到其目的，光學補償片之構造要件並非必要的。亦即，可以僅將已固定配向狀態之配向膜上的光學異方向層轉印至纖維素醯化物薄膜上而製作光學補償片。 [配向膜] 配向膜係具有規定液晶性化合物之配向方向的機能。配向膜能夠利用如下列之方法而予以設置、有機化合物（較宜爲聚合物）之平磨處理、無機化合物之斜方蒸鍍、具有，微群之層的形成、或是因Langmuir-Blodgett法（LB膜）而製成的有機化合物（例如，ω-二十二酸、雙十八甲基銨氯化物、硬脂酸甲酯）之累積。再者，習知藉由外加電場、外加磁場或光照射，產生配向機能的配向膜。配向膜較宜藉由聚合物的平磨處理而予以形成。提供本發明之配向膜，可以因應於液晶單元之顯示模式的種類。液晶單元內之多數棒狀液晶性分子，實質進行垂直配向的顯示模式（例如，VA、0CB、ΗΑΝ )方面，具有使光學異方向層之大多液晶性分子予以水平配向的機能。液晶單元內之大多棒狀液晶性分子，實質進行水平配向的顯示模 -78- 201211575 式（例如，STN )方面，具有使光學異方向層之大多液晶性分子予以垂直配向的機能。液晶單元內之大多棒狀液晶性分子，實質進行傾斜配向的顯示模式（例如，TN )方面，具有使光學異方向層之大多液晶性分子予以實質傾斜配向的機能。配向膜較宜藉由聚合物之平磨處理而予以形成。聚乙烯 •醇爲較佳之聚合物。尤以鍵結疏水性基的變性聚乙烯醇特別理想。雖然配向膜能夠由一種聚合物而予以形成，但是更佳爲藉由將由交聯後之二種聚合物而成的薄層，經平磨處理而予以形成。至少一種聚合物較宜使用本身可交聯的聚合物，或是藉由交聯劑進行交聯的聚合物之中的任一種》配向膜係使具有官能基之聚合物或是將官能基導入聚合物者，藉由光、熱、pH變化等，於聚合物間進行反應而形成；或是能夠藉由使用反應活性高的化合物之交聯劑而於聚合物之間導入歸因於交聯劑之鍵結官能基，將聚合物之間予以交聯而形成。如此交聯係將該聚合物或含有聚合物與交聯劑之混合物的配向膜塗布液，塗布於纖維素醯化物薄膜之後，藉由進行加熱等而實施的。因爲最好能夠確保最終商品（光學補償片）之耐久性，也可以將配向膜塗布於纖維素膜薄膜上之後，直到得到光學補償片爲止之任一階段，進行交聯之處理。若考慮由形成於配向膜之液晶性化合物而成的薄層（光學異方向層）之配向性，較宜於使液晶性化合物予以配向 -79- 201211575 之後，再進行充分之交聯。 —般配向膜之交聯係將配向膜塗布液塗布於纖維素醯化物薄膜上，藉由加熱乾燥而進行的。將此塗布液之加熱溫度設爲低値，較宜於形成後述之光學異方向層時的加熱處理階段，進行配向膜之充分交聯。用於配向膜之聚合物，能夠使用本身可交聯之聚合物或是利用交聯劑交聯的聚合物之中的任一種。當然也可以具有二者之聚合物。聚合物之例子，可列舉：聚甲基丙烯酸甲酯、丙烯酸/甲基丙烯酸共聚物、苯乙烯/馬來酸酐縮亞胺共聚物、聚乙烯醇及變性聚乙烯醇、聚（N-羥甲基丙烯醯胺）、苯乙烯/乙烯甲苯共聚物、氯磺化聚乙稀、硝基纖維素、聚氯乙烯、氯化聚烯烴、聚酯、聚醯亞胺、醋酸乙烯/氯乙烯共聚物、乙烯/醋酸乙烯共聚物、羧甲基纖維素、聚乙稀、聚丙稀與聚碳酸酯。可以使用有機矽烷偶合劑。較佳之聚合物爲水溶性聚合物（例如，聚（N-羥甲基丙烯醯胺）、羧甲基纖維素、明膠、聚乙烯醇與變性聚乙烯醇）。較宜使用明膠、聚乙烯醇與變性聚乙烯醇，更佳使用聚乙烯醇與變性聚乙烯醇代替聚合物。另外，最好合倂使用二種聚合度不同的聚乙烯醇或變性聚乙烯醇。聚乙烯醇之皂化度較宜爲70至100%之範圍。皂化度更佳爲80至100%之範圍，最好爲85至95%之範圍。另外，聚乙烯醇之聚合度較宜爲100至3000之範圍。變性聚乙烯醇之例，可列舉：形成共聚合變性、因鏈轉移形成的變性、或是因塊狀聚合形成的變性之聚乙烯醇 -80 - 201211575 等。進行共聚合變性之情形的變性基的例子，可 COONa、Si(OX) 3、N(CH3) 3.C1、C9H19COO、S C12H25。形成因鏈轉移形成的變性之情形的變性基可歹IJ 舉：COOH、C〇NH2、COOR、C6H5。皂化度較宜爲80至100%範圍的未變性或變性醇。皂化度更佳爲85至95%之範圍的未變性聚乙變性聚乙烯醇。變性聚乙烯醇尤以使用下列一般式所示之化合的聚乙烯醇變性物特別理想。以下，將此變性聚乙示爲特定之變性聚乙烯醇。 :(.谭女稿:第§ 〇貪之【化:2】. 式中，R1係表示烷基、丙烯醯烷基、甲基丙烯醯是環氧烷基；W係齒素原子、烷基或是烷氧基；X 爲了形成活性酯、酸酐或是酸鹵化物所必需之原^ 表不0或1;並且，η表示0至4之整數。該特定之變性聚乙烯醇更佳爲下列一般式所示物形成的聚乙烯醇變性物。 ........ .......二.： · ν ... ....... .. · · .... (原文稿第81頁之【化3】）； • " ............. . · ’一. ...... 式中，X1係表示爲了形成活性酯、酸酐或是酸鹵必需之原子群，並且，m表示2至24之整數。爲了與此等一般式所示之化合物進行反應而所列舉： Ο 3 N a、例子，聚乙烯烯醇與物形成烯醇揭烷基或係表示 1群；P 之化合化物所用之聚 -81 - 201211575 乙烯醇，可列舉：該未變性之聚乙烯醇與共聚合變性之聚乙烯醇，亦即，藉由鏈轉移而變性之聚乙烯醇，進行依塊狀聚合而造成變性等之聚乙烯醇變性物。特定之變性聚乙烯醇的較佳例，已揭示於日本公開專利第平9- 1 52 5 09號公報。此等聚合物之合成方法、可見光吸收光譜測定以及變性基導入率之決定方法等，已揭示於曰本公開專利第平 8 - 3 3 8 9 1 3號公報。交聯劑之例子’可列舉：醛類、N-羥甲基化合物 '二噁烷衍生物、藉由活化羧基而產生作用的化合物、活化乙烯化合物、活性鹵化物、異噁唑類以及二醛澱粉。醛類之例子’可列舉：甲醛、乙二醛以及戊二醛。N_羥甲基化合物之例子，可列舉：二羥甲基尿素以及羥甲基二甲基乙內醯脲。二噁烷衍生物之例子，可列舉：2，3 -二羥基二噁烷。藉由活化羧基而產生作用的化合物之例子，可列舉：碳陰離子、2-萘磺酸鹽、1，卜雙吡咯烷基-1-氯吡咯烷鑰以及1-嗎啉代羰基-3-(磺酸鹽胺甲基）。活化乙烯化合物之例子，可列舉：1，3,5-三丙烯醯基-六氫-s-三嗪、雙（乙烯基颯基）甲烷以及N，N’-亞甲基雙-[沒-(乙烯磺醯）丙醯胺]。而且活性鹵化物之例子，可列舉：2,4-二氯-6-羥基-S-三嗪。此等交聯劑能夠組合而使用。此等交聯劑較宜與該水溶性聚合物、尤其與聚乙烯醇以及變性聚乙烯醇（也包含該特定之變性物）合倂使用之情形。考慮生產性之情形，較宜使用反應性高的醛類，尤以戊二醛之使用爲更佳。 -82- 201211575 添加多量之交聯劑，則耐濕性傾向於變佳。但是，相對於聚合物，添加5 0質量％以上交聯劑之情形’作爲配向膜之配向能力將降低。因而，相對於聚合物之交聯劑的添加量，較宜爲0.1至20質量％之範圍，更佳爲0.5至15質量 %之範圍。即使於交聯反應結束之後’某種程度上’配向膜中仍含有未反應之交聯劑，其交聯劑之量’於配向膜中較宜爲1.0質量％以下，更佳爲〇.5質量％以下。若配向膜中含有超過1 . 〇質量!之量的未反應交聯劑，無法得到足夠的耐久性。亦即，用於液晶顯示裝置之情形’長期使用或於高溫高濕之氣體環境中長期間放置之情形’可能生成網狀物。變性聚乙烯醇之變性基的例子，可列舉：親水性基（羧酸基、磺酸基、磷酸基、胺基、銨基、醯胺基、硫醇基等）、碳數10〜100個之烴基、氟原子取代之烴基、硫醚基、聚合性基（不飽和聚合性基、環氧基、氮雜環丙基等）、烷氧矽烷基（三烷氧基、二烷氧基、一烷氧基）等。此等變性聚乙烯醇化合物之具體例，例如，揭示於日本公開專利第 2000-563 10號公報之段落編號[0074]、日本公開專利第 2000- 1 552 1 6號公報之段落編號[0022]〜[0145]、日本公開專利第2002-62426號公報之段落編號[0018]〜[0022]等。另外，利用光照射進行配向之情形，於分子內具有發現光配向機能的光配向基。此等光配向基，例如，可列舉：長谷川雅樹著書之「液晶、第3卷（I) 3〜16頁（1 999 ). 所揭示之光配向基、藉由具有C=C鍵結之光二量化反應而發現光配向機能的光配向基（例如，多烯基、1,2-二苯 -83 - 201211575 乙烯基、苯乙基哌啶基、苯乙基哌啶鑰基、肉桂醯基、半硫靛基、苯丙烯醯苯基等）、藉由具有c=o鍵結之光二量化反應而發現光配向機能的光配向基（例如，具有二苯甲酮基、香豆素基等之構造的官能基等）。具體而言，例如，可列舉：揭示於日本公開專利第2000-122069號公報、日本公開專利第2002-317013號公報之段落編號[0021]等。 [配向膜中所含之羧酸化合物] 本發明之配向膜形成用組成物較宜含有特定之羧酸化合物。藉此，發現利用配向裝置，對所得到的配向膜予以配向之後，塗設光學異方向層而得到的光學補償片之塗布面狀爲良好的，減輕或解決去除白色等之光學缺陷的改善效果。據推測理由之一要因，認爲於配向膜中所含之特定羧酸化合物，穩定配向膜之膜表面氫離子濃度等，於光學異方向層塗設之時，減小對液晶分子配向狀態的影響。另外，認爲利用鹼的皂化處理而將透明載體表面予以親水化之情形，即使於該薄膜表面僅殘存少量的處理液，仍穩定而形成良好光學性能的配向膜。當然，由於依照添加量，效果將有所不同，必須進行適宜量之調整。特定之羧酸化合物，可列舉：至少含有一種具有氫鍵性質之含氫原子極性基的羧酸。此等羧酸也可以爲脂肪族化合物、芳香族化合物或是雜環化合物之中的任一種。特定之極性基，可列舉：—OH、— SH、— NHR、— CONHR ' -S02NHR、-NHCONHR、-NHS02NHR、-NHCOR1、— NH S02R1。但是，R係表示氫原子、J|旨肪族基、 -84 - 201211575 芳基或是雜環基。R1係表示脂肪族基、芳基或是雜環基。該羧酸含有數個該極性基之情形，該極性基可以相同，也可以不同。本發明之較佳特定的極性基，可列舉：—OH、— SH、 -NHR 、一 CONH2 、 - SO2NH2 、 - NHCONHR 、- NHSO2NHR ' - NH SOzR1。此處，R係表示氫原子、脂肪族基、芳基或是雜環基。 R1係表示脂肪族基、芳基或是雜環基。 R表示脂肪族基之情形，可列舉：脂肪族基爲碳數1〜2 2 之直鏈狀或分歧狀之烷基（例如，甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一碳基、十二碳基、十三碳基、十四碳基、十五碳基、十六碳基、十七碳基、十八碳基、十九碳基、二十碳基、二十一碳基、二十二碳基等）、碳數2〜2 2之直鏈狀或分歧狀之烯基（例如，乙烯基、丙烯基、丁烯基、戊烯基、己烯基、辛烯基、十二碳稀基、十三碳稀基、十四碳稀基、十六碳稀基、十八碳烯基、二十碳烯基、二十一碳烯基、丁二烯基、戊二烯基、己二烯基、辛二烯基等）、碳數2〜22之直鏈狀或分歧狀之炔基（例如，乙快基、丙炔基、丁炔基、己炔基、辛炔基、十炔基、十二炔基）、碳數5〜22之脂環式烴基（例如，環戊烷、環戊烯、環戊二烯、環己烷、環己烯、環己二烯、環庚烷、環庚烯、環庚二烯、環辛烷、環辛烯、環辛二烯、萘烷等）。脂肪族基，此等之中，更佳爲碳數1〜18之直鏈狀、碳數3〜18之分歧狀脂肪族基。 -85- 201211575 芳基表示碳數6〜18之芳基（芳基環爲苯、萘、二氫化萘、聯苯等）。雜環基可列舉：含有至少一個氧原子、硫原子、氮原子之中的任一種具單環式或多環式之環構造的雜環基（雜環基，例如爲吡喃基、吡喃酮基、吡啶基、吡嗪基、嗎啉基、噻嗯基、苯并噻嗯基）等。該脂肪族基、芳基、雜環基也可以具有個別之取代基，使用除了氫之外的一價非金屬原子團作爲其可導入之取代基。非金屬原子團之具體例，表示鹵素原子（氟原子、氯原子、溴原子、碘原子）、氰基、硝基、—OR11、— SR11、 -COR1 1 、 - COOR" 、 - OCOR1 1 、 - S02R"、- NHCONHR1 1 ' - N ( R12 ) COR1 1、- N ( R 12 ) S O 2 R1 1、— N (R13) ( R14 ) 、- CON(R13) ( R14 ) 、-S02N(R13) (R14)、- P(=0) ( R1 5 ) (R16)、- 0P(=0) ( R15 ) (R16) 、— Si(R17) (R18) (R19) ' 碳數 1 〜22 之脂肪族基、碳數2~ 18之烯基、碳數6~18之芳基或雜環基。此等脂肪族基、芳基、雜環基係與該R爲同義的。該R11表示碳數1〜22之脂肪族基、碳數6〜18之芳基或雜環基。R11之脂肪族基係與該R所示之脂肪族基爲相同的。R11之芳基可列舉與該R所示之芳基相同。Ru之雜環基可列舉與該R所示之雜環基相同。如此之芳基也可以進一步具有取代基，作爲其取代基，可列舉：與可導入該R 所示之脂肪族基、芳基、雜環基之取代基相同於所例示者。 R12表示氫原子或與R11基相同的。 -86 - 201211575 該R13與R14係表示各自獨立的氣原子、或與R11基相同的。R13與R14相互鍵結，也可以形成含有N原子之5 員或6員環。該R15與R16係表示各自獨立的碳數1〜22之脂肪族基、碳數6-14之芳基或是- OR11。R15與R16之脂肪族基係相同於該R所示之脂肪族基° Rl5與Rl0的芳基可列舉：與該 R所示之芳基相同。如此之芳基也可以更具有取代基’作爲其取代基，可列舉：與可導入該R所示之脂肪族基、芳基、雜環基之取代基係相同於所例示者。該Ri7、R18與R19表示各自獨立的碳數1〜22之烴基或一 OR2()，此等取代基內至少一個表示烴基。烴基表示該R 所示之與該脂肪族基與芳基相同者，- 〇r2()表示相同於該 —OR11同樣的內容。 R1之脂肪族基、芳基與雜環基係表示與R相同。本發明之特定羧酸化合物爲碳數1〜2 2(除了羧酸碳原子之外）之脂肪族羧酸、碳數6~ 14之芳香族羧酸、雜環羧酸之羧酸化合物，尤以pKa爲6_5以下較爲理想。羧酸之PKa 更佳爲3.0〜6.5之化合物。此等特定之羧酸化合物，具體而言，例如，可列舉：羥酸（例如’乙醇酸、乳酸、甘油酸、α 羥基烷酸（烷爲碳數3〜1 8之烷）等）、胺基酸、α -羥基-冷-胺基酸、α -羥基-r-胺基酸、/S-羥基胺基酸 '此等羥酸或羥基胺基酸之羥基衍生爲烷氧基之化合物、羥基環己烷羧酸類、羥基苯羧酸類、利用環狀羧酸酐（琥珀酸、馬來酸、己二酸、環己二羧酸、苯二酸等之酸酐等）而將聚醇（例如，烷二 -87- 201211575 醇、甘油、三羥甲基丙烷、季戊四醇、二季戊四醇、環己一醇等）之至少一個羥基予以酯化的化合物、由聚胺化合物（例如’亞烷基二胺、二伸乙基三胺、三伸乙基四胺、環己院二胺、伸苯基二胺等）與環狀羧酸酐經醯胺化之化合物所衍生的化合物，但是本發明並非受此等化合物所限定。更佳的話’可列舉：含有至少一個羥基的羧酸，其至少一個羧基係經酯化而成的羧酸化合物。含有至少一個羥基之聚羧酸，可列舉：羥基丙二酸、蘋果酸、酒石酸、檸檬酸、羥基谷胺酸（體、γ-體）、利用環狀羧酸酐而將該聚醇之至少二個羥基予以酯化的化合物等。較宜利用碳數1~22之烴基，進行此等聚羧酸化合物之至少一個羧酸的酯取代。進行醋取代之碳數1〜1 8之烴基的具體態樣係與該R所揭示的脂肪族基、芳香族基、雜環基相同。另外，此等烴基也可以被取代’取代基可列舉相同於與被該R所取代的內容。本發明之特定羧酸化合物較宜以0.01〜1()質量％之比例添加於配向膜形成用組成物中。更佳爲〇〇2~〇5質量％。於此範圍內’可以得到維持足夠薄膜強度之去除白色等之無光學缺陷的光學補償片。再者，即使連續製造長型尺狀薄膜’也可以極爲穩定性能地進行製造。基本上’配向膜係—種硬化膜，其能夠將含有配向膜形成用組成物的該聚合物、交聯劑與特定之羧酸的塗布液塗 -88- 201211575 布於透明載體上，之後，藉由進行加熱乾燥（使其交聯）、配向處理而形成。交聯反應也可以於透明載體上進行塗布後之任意時期進行。將聚乙烯醇之類的水溶性聚合物作爲配向膜形成用組成物使用之情形，塗布液較宜作成具有消泡作用的有機溶劑（例如，甲醇）與水之混合溶劑。其水：甲醇之質量比較宜爲0: 10 0~ 99: 1，更佳爲〇: 1〇〇〜91: 9。藉此’可以抑制氣泡之發生，明顯減少配向膜，甚至光學異方向層之層表面的缺陷。配向膜之塗布方法較宜爲浸漬塗布法、淋幕塗布法、擠壓塗布法、桿式塗布法或輥輪塗布法。尤以桿式塗布法較佳。另外，乾燥後之膜厚較宜爲0.1至10；am。加熱乾燥能夠於20°C〜100°C進行。爲了形成足夠之交聯，較宜爲60 °C〜100°C，尤以80°C〜10 0°C特別理想。乾燥時間可以於1 分鐘至36小時進行，較宜爲1分鐘至30分鐘。更佳爲5 分鐘至30分鐘。再者，將含有本發明之配向膜形成用組成物的塗布液塗布於載體，經乾燥，利用配向裝置予以配向之後，塗布光學異方向層用塗布液時，該配向膜表面較宜維持pH2.0〜6.9 之範圍。更佳爲ρΗ2· 5〜5.0之範圍。使用戊二醛之情形，較宜爲ΡΗ4.5〜5.5。尤以ΡΗ5更佳。另外’於進行該光學異方向層用塗布液之塗布時，於塗布寬度方向之配向膜表面的pH之變動幅度ΔρΗ較宜於 ±0.30之範圍。ΔρΗ更佳於±0.15之範圍。較宜於此範圍內，已塗設光學異方向層之光學補償片之光學缺陷將明顯減少。 -89- 201211575 配向膜表面之pH値的測定方法係於溫度2 5 °C /濕度6 5 % RH之環境下，將已塗設配向膜之試料靜置一日之後，於氮氣環境中’將10ml純水淋於其上，立即以pH計讀取pH 値。爲了將本發明配向膜表面的pH値予以特定，並且控制於塗布寬度方向之△ pH，藉由該桿式塗布方式之塗布而達成。進一步調節膜表面之乾燥溫度、使用乾燥風之情形的風量、風向等，也爲有效的。如上所述，配向膜能夠藉由將聚合物層予以交聯之後，進行表面之平磨處理而得到。該平磨處理能夠應用已被LCD液晶配向處理步驟所廣泛採用之處理方法。亦即，能夠採用藉由使用紙或棉布、氈、橡膠或耐隆、聚酯纖維等，順著一定方向，進行配向膜表面的磨擦而得到配向的方法。一般而言，藉由使用將長度與粗細均勻的纖維而予以平均値毛的布等，進行數次左右之平磨所實施的。另外，藉由光照射而進行光配向之情形，作爲光照射裝置之光源，可以使用超高壓水銀燈、氙燈、螢火燈、雷射等，爲了進行光二Μ化化合物之光配向，組合該光源與偏光子（通過偏光子）而將紫外線形成直線偏光，照射於光配向膜。主要作爲偏光子使用者爲拉伸染色PVA。例如，此直線偏光照射裝置能夠使用揭示於日本公開專利第平 10-90684號公報的。配向膜之厚度較宜爲〇·〇1至l〇#m，更佳爲0.〇1至5 /zm，最好爲 0.05 至 1/zm。 -90- 201211575 [光學異方向性] 能夠將由液晶性化合物所形成的光學異方向層，形成於已塗設於纖維素醯化物薄膜的配向膜之上。用於光學異方向層之液晶性化合物中，含有棒狀液晶性化合物與碟狀液晶化合物。棒狀液晶性化合物與碟狀液晶化合物可以爲高分子液晶，也可以爲低分子液晶’，再者，也含有交聯低分子液晶而不顯示液晶性。光學異方向層能夠藉由將液晶性化合物以及必須含有聚合性起始劑或任意成分之塗布液，塗布於配向膜之上。使用於塗布液調整之溶劑，較宜使用有機溶劑。有機溶劑之例子，包含：醯胺（例如，N，N-二甲基甲醛）、亞颯 (例如，二甲基亞楓）、雜環化合物（例如，吡啶）、碳· 氫化合物（例如，苯、己烷）、烷基鹵化物（例如，氯仿、四氯甲烷）、酯（例如，醋酸甲酯、醋酸丁 +醋）、酮（例如’丙酮、甲基乙基酮）、醚（例如，四氫呋喃、1,2-二甲氧基乙烷）。較宜爲烷基鹵化物與酮。也可以合倂二種以上之有機溶劑而使用。塗布液之塗布，可以藉由習知之方法（例如，線棒式塗布法、擠出塗布法、直接照相凹版塗布法、反照相凹版塗布法、模頭塗布法）而實施。棒狀液晶性化合物，較宜使用甲亞胺類、氧化偶氮類、氰基聯苯類、氰基苯基酯類、安息香酸酯類；環己烷羧酸苯基酯類、氰基苯基環己烷類、氰基取代苯基嘧啶類、烷氧基取代苯基嘧啶類、二苯乙炔類與烯基環己烷基苯甲腈類。 -91 - 201211575 還有，於棒狀液晶性化合物中，也含有金屬錯體。另外，也可以將重複單位中含有棒狀液晶性化合物之液晶聚合物作爲棒狀液晶性化合物使用。換言之，棒狀液晶性化合物也可以與（液晶）聚合物進行鍵結。針對棒狀液晶性化合物，已揭示於日本季刊化學總說第 22卷液晶化學（1 994 )，日本化學會編之第4、7、11章；以及液晶元件手冊，日本學術振興會第142委員會編之第 3章。棒狀液晶性化合物之複折射率較宜於0.001至0.7之範圍內。爲了固定其配向狀態，棒狀液晶性化合物較宜具有聚合性基。以下，表示聚合性基（Q )之例子。-67- 201211575 Solution (doping solution), preferably 0. 01 to 10% by mass, more preferably 0. It is in the range of 1 to 5 mass%, preferably in the range of 1 to 3 mass%. [Surface Treatment of Transparent Carrier and Cellulose Telluride Film] For the transparent carrier such as a cellulose halide film, surface treatment is preferably carried out. In particular, in the case where an alignment film is provided between the optically oriented layer and the transparent carrier, it is found that the composition for forming the alignment film is applied uniformly, and by applying sufficient adhesion of the applied alignment film and the transparent carrier, The surface treatment of the carrier is preferably carried out by surface modification to a hydrophilic hydrophilized surface treatment. For the hydrophilization treatment of a transparent carrier such as a cellulose oxime film, physical treatments include corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, and flame plasma treatment. Examples of the wet treatment include ozone treatment, oxidation treatment, and alkali treatment. Specifically, it can be cited as disclosed in Japanese Society of Inventions Public Technology No. 200 1 - 1 745 (issued on March 15, 2001) ρ·30-31, 曰Patent Patent No. 2001-9973 Bulletin and so on. In addition, it is preferable to provide a primer layer (for example, disclosed in Japanese Laid-Open Patent Publication No. Hei 7-3 3 3 43 3). Based on the viewpoint of maintaining the planarity of the film, it is preferred to use a cellulose halide film under such treatment. The temperature is set to be equal to or less than Tg (glass transition temperature), and specifically to be 150 ° C or lower. In view of the use of the polarizing plate as a transparent protective film, it is particularly preferable to carry out an acid treatment or an alkali treatment, i.e., a saponification treatment of the cellulose halide. Hereinafter, the saponification treatment of a preferred base will be specifically described. -68- 201211575 The saponification treatment of the alkali of the cellulose oxime film is preferably carried out after the film is applied to the alkaline solution, and then neutralized by an acidic solution and then washed with water. The simplicity of the hydrophilization treatment and the maintainability of the device (it is more difficult to use the alkaline solution for the saponification treatment of the alkali by the alkali solution. The saponification treatment of the alkali can be carried out by immersing the transparent carrier in the alkaline to spray the alkali on the surface of the transparent carrier. a solution of either the solution or the like, and more preferably, the saponification treatment of the saponification of the single side of the transparent carrier by the saponification treatment without eccentricity and uniformity is preferably not exceeded. It is carried out at a treatment temperature in the range of temperature l2 〇 ° C which does not cause deformation of the film during processing, liquid deterioration, etc., and preferably ranges from 10 ° C to 100 ° C. Especially at a temperature of 20 to 60 ° C. The saponification treatment time is determined according to the alkaline solution and the treatment temperature, and is preferably adjusted, but it is preferably carried out in the range of 1 to 60 seconds [alkaline solution] The alkaline solution of the present invention is preferably pH 1 1 The above basic solution is ρ Η 1 2 ~ 1 4. For the alkaline agent used in the alkaline solution, an inorganic alkaline agent such as potassium hydroxide or lithium hydroxide may be used, and diethanolamine or alcohol may be used. Amine, DBU ( 1,8- Bicyclo[5,4,0]-7-undecene), DBN (dioxacyclo[4,3,0]-5-pinene), tetramethylammonium hydroxide, tetraethyl hydroxide, An organic alkaline agent such as tetrapropylammonium hydroxide, tetrabutylammonium hydroxide or butylammonium hydroxide. These alkaline agents may be used singly or in combination of two or more, or may be used, for example. Add a part in the form of a halogenated salt. The surface is soaked in dry insects, etc.) The solution can be used. Processing is warm! Good. Appropriate; More preferably, hydrogen triethyl: 1,5-ammonium triethyl, alone, etc. -69- 201211575 Among these alkaline agents, sodium hydroxide or potassium hydroxide is preferably adjusted by this amount. It is possible to adjust the pH in a wider pH range. The concentration of the alkaline agent in the alkaline solution is determined according to the type of the alkaline agent used, the reaction temperature and the reaction time, and the content of the alkaline agent is preferably 0. 1 to 3 mol / Kg, more preferably 0. 5~2mol/Kg. The solvent of the alkaline solution is preferably a mixed solution of water and a water-soluble organic solvent. The water-soluble organic solvent can be used as long as it can be mixed with water. However, the boiling point is preferably 120 ° C from the viewpoint of concentration inhibition of the treatment liquid over time and the removal property (dryness) of the film after treatment. Hereinafter, it is more preferably 60 to 120 ° C, and most preferably 10 ° C or less. Wherein the inorganic/organic group (I/O値) of the organic solvent is preferably 0. 5 or more 'and, the solubility parameter is preferably 16~40 [mJ/m3]l/2; I/O値 is more preferably 〇. 6~1〇, and the solubility parameter is more preferably i8~31[mJ/m3]1/2. If the I/O 较 is inorganic in nature or the solubility parameter is low, the saponification rate of the alkali will decrease, or the uniformity of the saponification degree will become insufficient. On the other hand, if the I/O 値 is on the organic side compared to the range, or the dissolution parameter is on the highly soluble side, the saponification rate will be accelerated, and blurring will easily occur, so that the uniformity of the entire surface also becomes insufficient. . In addition, the organic solvent is used in combination with an organic solvent in various ranges of organic properties and solubility, in combination with a surfactant and/or a compatibilizing agent to be described later, and maintains a high saponification rate and spreads over the entire surface. The uniformity of the degree of saponification will increase. A water-soluble organic solvent having a preferred property is, for example, a "new solvent pocket book" (published by Ohm (share) company, issued in 1994), which is published by the Japan Society of Organic Synthetic Chemistry. (In addition, for the inorganic/organic enthalpy (I/O値) of the solvent of -70-201211575, for example, the "organic commemorative map" of Tanaka Satoshi (issued by the Japanese Communist Party in 1983). 1-31 explained). Specifically, 'monovalent aliphatic alcohols (for example, methanol, ethanol, propanol, butanol, pentanol 'hexanol, etc.): alicyclic alkanols (for example, cyclohexanol, methylcyclohexane) Alcohol, methoxycyclohexanol, cyclohexylmethanol, cyclohexylethanol, cyclohexylpropanol, etc.): phenylalkanol (for example, benzyl alcohol, phenylethyl alcohol, phenylpropanol. , phenoxyethanol, methoxybenzyl alcohol, benzyloxyethanol, etc.); heterocyclic alkanols (sterols, tetrahydrofurfuryl alcohols, etc.): one of the diol compounds (methyl cellulose, ethyl Cellulose, propyl cellulose, methoxymethoxyethanol, butyl cellulose, hexyl cellulose, methyl diglycol monoethyl ether, ethyl diglycol monoethyl ether, propyl diglycol monoethyl ether, butyl Diethylene glycol monoethyl ether, ethoxy triethylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, etc.): ketones (for example, N,N-dimethylformamide, Dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, etc.; anthraquinones (eg, dimethyl sulfoxide): and ethers (eg, tetrahydrofuran) , pyran, dioxane, trioxane, dimethyl cellulose, dipropyl cellulose, methyl ethyl cellulose, dimethyl diglycol monoethyl ether, diethyl diglycol monoethyl ether, A Base ethyl diglycol monoethyl ether, etc.). The organic solvent to be used may be used singly or in combination of two or more. At least one organic solvent in the case of a single one or a mixture of two or more organic solvents is preferably more soluble in water. The solubility of the organic solvent water is preferably 50% by mass or more, and more preferably an organic solvent which is freely mixed with water. Thereby, it is possible to prepare an alkaline solution which absorbs the solubility of the alkaline agent, the salt of the fatty acid produced by the saponification treatment, and the carbon dioxide in the air to form a carbonate such as -71 - 201211575. The ratio of use in the solvent of the organic solvent is determined depending on the kind of the solvent, the miscibility with water (solubility), the reaction temperature, and the reaction time. The mixing ratio of water to the organic solvent is preferably a mass ratio of 3/97 to 85/15, more preferably a mass ratio of 5/95 to 60/40, and most preferably a mass ratio of 15/85 to 40/60. Within this range, the optical properties of the cellulose halide film are not damaged, and the entire film is easily subjected to uniform saponification treatment. The organic solvent contained in the alkaline solution of the present invention may also dissolve an organic solvent (for example, a fluorinated alcohol or the like) different from the preferred I/O oxime with a surfactant and a compatibilizing agent described later. The additives are used together. For the total mass of the alkaline solution, the content is preferably 0. 1~5 mass%. The alkaline solution used in the present invention preferably contains a surfactant. By adding a surfactant, the surface tension is lowered to facilitate coating, the uniformity of the coating film is improved, and the phenomenon of bounce is prevented, and if an organic solvent is present, the haze which is likely to occur is suppressed, and the saponification reaction is further uniformly performed. . The effect is particularly remarkable by the coexistence of the compatibilizing agent described later. The surfactant to be used is not particularly limited, and may be any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, and a fluorine-based surfactant. Specifically, for example, "The surfactant manual (new edition)" (Japan Engineering Books, issued in 1987), "Creativity of surfactants, material development, and application technology" A well-known compound disclosed in 1 (Japanese Technical Education Publishing, issued in 2000). Among these surfactants, it is preferably a cationic surfactant-72-201211575 grade 4 ammonium salt; a non-ionic surfactant of various polyalkylene organisms; various polyethylene oxide additions Polyepoxides of the class; and betaine-type compounds of amphoteric surfactants. In the alkaline solution, it is preferred to use a nonionic surfactant together with a surfactant or a nonionic surfactant and a cationic agent to enhance the effect of the present invention. The amount of the alkaline solution added to the surfactant may be preferably 0. 001~10% by mass, more preferably 0. 01 to 5 mass% | The alkaline solution used in the present invention preferably contains a compatibilizing agent, and the term "combustion agent" means that the solubility of water is 5 at 25 ° C relative to the compatibilizing agent. The solubility of water of the hydrophilic compounding agent of 0 g or more is relative to 100 g of the compatibilizing agent, and the above saddle is more preferably 1 〇〇 g or more. Further, in the case where the compatibilizing agent is a liquid, the boiling point is preferably 1 〇〇 ° C or more, more preferably 12 〇 ϋ ϋ the solvating agent prevents drying of the alkaline solution in the bath which is attached to the storage alkaline solution, and inhibits adhesion. It has a stable alkali function. Further, after applying the alkaline solution to the surface of the transparent carrier for a predetermined period of time, until the saponification treatment is stopped, the film of the solution is dried to cause precipitation of the solid matter, and it is difficult to wash off the solid matter with the water washing step. Furthermore, the separation of the water from the organic solvent is prevented. In particular, by the coexistence of the interfacially active solvent and the compatibilizing agent, the treated carrier has a stable and uniform degree of saponification even in the case of a long-sized continuous roadway treatment. As long as the compatibilizing agent can satisfy the above conditions, there is no alkyl diol derivative derivative anionic interface activity: . In the hair of the l〇〇g. Equilibrium: It is preferably 80g-like compound (upper. It is a solution of a wall-like solution and keeps a coating base to prevent it from being used as a solvent, and the organic haze is small, which is a limitation of the whole surface j. -73- 201211575 For example, It is preferably a polyhydric alcohol compound, a water-soluble polymer containing a repeating unit having a hydroxyl group and/or a mercaptoamine group such as a saccharide, etc. The polyol compound may be any of a low molecular compound, an oligomer, and a polymer compound. An aliphatic polyalcohol, for example, an alkanediol having 2 to 8 carbon atoms (for example, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, glycerin monomethyl ether, glycerin) Monoethyl ether, cyclohexanediol, cyclohexanedimethanol, diethylene glycol, dipropylene glycol, etc.), alkane having 3 to 18 carbon atoms containing three or more hydroxyl groups (for example, glycerin, trimethylol) Ethane, trimethylolpropane, trimethylolbutane, cyclohexanetriol, pentaerythritol, diglyceride, dipentaerythritol, inositol, etc.) Polyalkylene oxide polyols can be enumerated: Bonding between the same alkylene glycol, or not Bonding between the alkylene glycols; preferably a polyalkylene polyol to be bonded between the same alkylene glycols. In any case, the number of bonds is preferably from 3 to 100, more Preferably, it is 3 to 50. Specifically, for example, polyethylene glycol, polypropylene glycol, and poly(ethylene oxide-propylene oxide) can be cited. For example, the sugars can be exemplified by the Polymer Society of Japan Polymer Society. Chapter 2 of "Natural Polymers" edited by the Editorial Committee (Japan Kyoritsu Publishing Co., Ltd., issued in 1984); and "Modern Industrialization 22, Natural Industrial Chemicals II" edited by Oda Era (Japan Asakura Bookstore (shares) ), a water-soluble compound, etc., issued in 1967. Among them, it is preferably a sugar which does not have a free aldehyde group and a ketone group and does not exhibit reducing properties. Generally, sugars are classified into glucose, sucrose, and a reducing functional group. Any of the trehalose-type saccharides bonded to the saccharide, the saccharide-reducing group and the non-sugar-bonding-------------- For example, sucrose, seaweed Sugar, alkyl glycoside, phenol glycoside, mustard oil glycoside, D, L-arabinose, ribitol, xylitol, D, L-sorbitol, D, L-mannitol, D , L-Ideol, D, L-talitol, sweet alcohol, alditol, and reduced maltose. These saccharides may be used singly or in combination of two or more. The water-soluble polymer of the repeating unit, for example, may be exemplified by natural gums (for example, gum arabic, gum, tragacanth, etc.), polyvinylpyrrolidone, dihydroxypropyl acrylate polymer, cellulose or An addition reaction of a chitin with an epoxide (ethylene oxide or propylene oxide), wherein a polyalcohol compound such as an alkylene polyol, a polyepoxypolyol or a sugar alcohol is preferred. The content of the solution and the compatibilizing agent is preferably 0. 5 to 2 5 mass%, more preferably 1 to 20 mass%. The alkaline solution used in the present invention may contain other additives. Other additives' include, for example, conventional additives such as an antifoaming agent, an alkaline solution stabilizer, a pH buffer, a preservative, and a fungicide. As described above, in the present invention, the transparent carrier is preferably an alkaline solution containing at least a boiling point of 60 to 12 (TC of a water-soluble organic solvent and a surfactant and/or a compatibilizing agent (of course, a base) Surface treatment. [Method for coating saponification of alkaline solution] Surface treatment method using a polymer film of the alkaline solution (hereinafter, this method is described by taking "cellulose oxime film" as an example) -75- 201211575 It is preferable to apply only the coating method of the single side of a film. The coating method is a dip coating method, a curtain coating method, an extrusion coating method, a rod coating method, and an E type coating method. Preferably, the saponification treatment of the alkali is carried out by the following steps: a step of saponifying the cellulose oxime film with an alkaline solution at a temperature of at least 1 〇 ° C or higher; maintaining the temperature of the cellulose oxime film at least a step of 10 ° C or more; then, the alkaline solution is washed away from the cellulose halide film. At a predetermined temperature, the surface cellulose is deuterated using an alkaline solution. The saponification treatment may be a step of previously adjusting to a predetermined temperature before coating, a step of preliminarily adjusting the alkaline solution to a predetermined temperature, or a combination of such steps, etc., preferably before the coating is performed. After the saponification reaction, it is preferred to carry out washing, neutralization, etc., and washing with an alkaline solution and a saponification reaction from the surface of the film by water washing or the like. Specifically, for example, For example, it is disclosed in the International Publication No. 02/468 09, etc. [Characteristics of Hydrophilized Transparent Carrier] The hydrophilicity of the surface of the transparent carrier subjected to the treatment is preferably in the following physical properties. The contact angle with water on the surface of the film is preferably in the range of 2 〇 to 55 °. The contact angle with water is preferably in the range of 25 to 50 °, more preferably in the range of 30 to 4 5 ° (2) The surface energy on the surface of the film is preferably between 55 and 75 mN/m - 76 - 201211575. More preferably, it is in the range of 60 to 75 mN/m. The evaluation method of surface energy (evaluation item (2)) can be Revealed in "wet The basis and application (Realize, issued in 1989) are determined by the contact angle method, the wet heat method, and the adsorption method. When a cellulose halide film is used as a transparent carrier, the contact angle method is preferably used. The two kinds of solvents with known surface energies are dropped into the cellulose oxime film at the intersection of the surface of the droplet and the surface of the film, the angle formed by the tangent drawn from the droplet and the surface of the film, and the angle of the droplet is defined as The contact angle can be calculated by calculating the surface energy of the film. The transparent carrier having the specific surface shape and optical characteristics used in the third aspect of the present invention can be modulated by referring to the above method, in order to shape the surface and the optical The characteristic is set to this range, and an optical compensation sheet having good visibility is obtained by the following means. (1) As disclosed in the column of the method of adding and mixing the microparticles, the monodisperse microparticles are mixed and dispersed in the dope before the doping solution by the film forming method according to the solution casting method, and the wet dispersion treatment is performed in advance. Forming a dispersion in which coarse particles have been removed, that is, as described above, particles having a particle diameter exceeding 500 # m are not present to make the particle diameters of the micro particles uniform; (2) as described above, the doping liquid is casted Before the step, precision filtration is performed; (3) as described above, the unevenness of the surface of the metal carrier used in the casting step becomes a certain size; (4) as described above, the drying condition for controlling the drying step of the doping liquid: 5) As described above, the casting conditions of the casting step are refined, etc.; it can be appropriately adjusted. As a result, the deviation of the retardation axis angle is also suppressed. Further, (6) as described above, by the hydrophilization treatment by the rapid saponification alkaline solution treatment, the alignment film and the optically oriented layer are applied unevenly in the coated surface. -77- 201211575 The optical compensation sheet can be provided with an optically oriented layer formed of a liquid crystalline compound on the produced cellulose halide film. It is preferred to provide an alignment film between the cellulose oxide film and the optically different direction layer provided thereon. The alignment film system is used to align the liquid crystal compound used in the present invention in a certain direction. Therefore, the alignment film is necessary for the production of the optical compensation sheet of the present invention. However, after the alignment, the alignment state of the liquid crystal compound is fixed, and the alignment film is not necessary for the purpose of achieving the purpose. That is, the optically exclusive layer on the alignment film in the fixed alignment state can be transferred onto the cellulose halide film to form an optical compensation sheet. [Alignment film] The alignment film has a function of defining the alignment direction of the liquid crystal compound. The alignment film can be provided by a method as follows, a flat grinding treatment of an organic compound (preferably a polymer), an oblique vapor deposition of an inorganic compound, a formation of a layer of a micro-group, or a Langmuir-Blodgett method. (LB film) The accumulation of an organic compound (for example, ω-docosic acid, bis-octadecyl ammonium chloride, methyl stearate). Furthermore, it is conventional to generate an alignment film of an alignment function by applying an electric field, an applied magnetic field or light. The alignment film is preferably formed by a flat grinding treatment of the polymer. The alignment film of the present invention can be provided depending on the type of display mode of the liquid crystal cell. Many of the rod-like liquid crystal molecules in the liquid crystal cell have a function of substantially aligning a plurality of liquid crystal molecules in the optically different layer in a display mode (for example, VA, 0CB, ΗΑΝ) which substantially aligns vertically. Many of the rod-like liquid crystal molecules in the liquid crystal cell have a function of vertically aligning a plurality of liquid crystal molecules in the optically different layer in the form of a horizontally aligned display mode (for example, STN). Many of the rod-like liquid crystal molecules in the liquid crystal cell have a function of substantially tilting the liquid crystal molecules of the optically different layer in a display mode (for example, TN) which is substantially obliquely aligned. The alignment film is preferably formed by a flat grinding treatment of the polymer. Polyethylene • Alcohol is a preferred polymer. Particularly, a denatured polyvinyl alcohol having a hydrophobic group bonded thereto is particularly preferable. Although the alignment film can be formed of a single polymer, it is more preferably formed by subjecting a thin layer of the two polymers after crosslinking to a flat grinding treatment. Preferably, at least one polymer is a polymer which is crosslinkable by itself or a polymer which is crosslinked by a crosslinking agent. Alignment film system allows a polymer having a functional group or introduces a functional group a polymer which is formed by reacting between polymers by light, heat, pH change, etc.; or can be introduced between polymers by crosslinking agent using a highly reactive compound due to crosslinking The bonding function of the agent is formed by crosslinking the polymers. The alignment film coating liquid containing the polymer or the mixture of the polymer and the crosslinking agent is applied to the cellulose vaporized film, followed by heating or the like. Since it is preferable to ensure the durability of the final product (optical compensation sheet), the alignment film may be applied to the cellulose film film, and then the crosslinking treatment may be performed at any stage until the optical compensation sheet is obtained. When the alignment of the thin layer (optical anisotropic layer) formed of the liquid crystalline compound formed on the alignment film is considered, it is preferred to carry out the crosslinking after the liquid crystal compound is aligned from -79 to 201211575. In the case of the general alignment film, the alignment film coating liquid is applied onto the cellulose varnish film by heating and drying. When the heating temperature of the coating liquid is low, it is preferable to carry out sufficient crosslinking of the alignment film in a heat treatment stage in the case where an optically different direction layer to be described later is formed. The polymer used for the alignment film can be either a polymer which is crosslinkable by itself or a polymer which is crosslinked by a crosslinking agent. It is of course also possible to have a polymer of both. Examples of the polymer include polymethyl methacrylate, acrylic acid/methacrylic acid copolymer, styrene/maleic acid imide copolymer, polyvinyl alcohol and denatured polyvinyl alcohol, and poly(N-hydroxyl). Acrylamide, styrene/vinyl toluene copolymer, chlorosulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimine, vinyl acetate/vinyl chloride copolymer , ethylene/vinyl acetate copolymer, carboxymethyl cellulose, polyethylene, polypropylene and polycarbonate. An organic decane coupling agent can be used. Preferred polymers are water soluble polymers (e.g., poly(N-hydroxymethyl propyl decylamine), carboxymethyl cellulose, gelatin, polyvinyl alcohol, and denatured polyvinyl alcohol). It is preferred to use gelatin, polyvinyl alcohol and denatured polyvinyl alcohol, and it is preferred to use polyvinyl alcohol and denatured polyvinyl alcohol instead of the polymer. Further, it is preferred to use two kinds of polyvinyl alcohol or denatured polyvinyl alcohol having different degrees of polymerization. The degree of saponification of the polyvinyl alcohol is preferably in the range of 70 to 100%. The degree of saponification is more preferably in the range of 80 to 100%, more preferably in the range of 85 to 95%. Further, the degree of polymerization of the polyvinyl alcohol is preferably in the range of from 100 to 3,000. Examples of the denatured polyvinyl alcohol include polyvinyl alcohol-80-201211575 which forms copolymerization denaturation, denaturation due to chain transfer, or denaturation formed by bulk polymerization. Examples of denatured groups in the case of copolymerization denaturation may be COONa, Si(OX) 3, N(CH3) 3. C1, C9H19COO, S C12H25. A denatured group which forms a case of denaturation due to chain transfer can be exemplified by COOH, C〇NH2, COOR, and C6H5. The degree of saponification is preferably an undenatured or denatured alcohol in the range of 80 to 100%. The degree of saponification is more preferably an undenatured polyethylene-modified polyvinyl alcohol in the range of 85 to 95%. It is particularly preferable to use a modified polyvinyl alcohol denatured product which is modified by the following general formula. Hereinafter, this denatured polyethylene is shown as a specific denatured polyvinyl alcohol. :(. Tan female draft: the first § 〇之之 [化: 2]. Wherein R1 represents an alkyl group, an acryl alkyl group, a methacrylium oxime is an epoxyalkyl group; a W-based dentate atom, an alkyl group or an alkoxy group; and X is used to form an active ester, an acid anhydride or an acid halide. The necessary original table is not 0 or 1; and η represents an integer of 0 to 4. The specific denatured polyvinyl alcohol is more preferably a polyvinyl alcohol denature formed from the following general formula. . . . . . . . . . . . . . . . two. : · ν . . . . . . . . . . . . · · · . . . . (Original document on page 81); • " . . . . . . . . . . . . . . · 'One. . . . . . . In the formula, X1 represents an atomic group necessary for forming an active ester, an acid anhydride or an acid halide, and m represents an integer of 2 to 24. For the reaction with the compounds of the general formula, exemplified by: Ο 3 N a, an example, a polyvinyl enol and a compound forming an enol group or a group representing a group; a poly-81 used for a compound of P - 201211575 The vinyl alcohol is exemplified by the undenatured polyvinyl alcohol and the copolymerized denatured polyvinyl alcohol, that is, the polyvinyl alcohol denatured by chain transfer, and the polyethylene which is denatured by bulk polymerization. Alcohol denatured matter. A preferred example of a specific denatured polyvinyl alcohol is disclosed in Japanese Laid-Open Patent Publication No. Hei 9-152589. The synthesis method of these polymers, the measurement of the visible light absorption spectrum, and the method of determining the rate of introduction of the denatured base are disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei. Examples of the crosslinking agent are exemplified by an aldehyde, an N-methylol compound 'dioxane derivative, a compound which acts by activating a carboxyl group, an activated vinyl compound, an active halide, an isoxazole, and a dialdehyde. starch. Examples of the aldehydes include formaldehyde, glyoxal, and glutaraldehyde. Examples of the N-hydroxymethyl compound include dimethylol urea and hydroxymethyldimethylhydantoin. Examples of the dioxane derivative include 2,3-dihydroxydioxane. Examples of the compound which acts by activating a carboxyl group include a carbon anion, a 2-naphthalenesulfonate, 1, a bispyrrolidinyl-1-chloropyrrolidine key, and a 1-morpholinocarbonyl-3-( Sulfonate amine methyl). Examples of the activated vinyl compound include 1,3,5-tripropenyl-hexahydro-s-triazine, bis(vinylindenyl)methane, and N,N'-methylenebis-[no- (Vinyl sulfonium) propionamide]. Further, examples of the active halides include 2,4-dichloro-6-hydroxy-S-triazine. These crosslinking agents can be used in combination. These crosslinkers are preferably used in combination with the water soluble polymer, especially with polyvinyl alcohol and modified polyvinyl alcohol (which also includes the particular denature). In view of productivity, it is preferred to use a highly reactive aldehyde, especially glutaraldehyde. -82- 201211575 When a large amount of cross-linking agent is added, the moisture resistance tends to be better. However, in the case where 50% by mass or more of the crosslinking agent is added with respect to the polymer, the alignment ability as the alignment film is lowered. Therefore, the amount of the crosslinking agent relative to the polymer is preferably 0. 1 to 20% by mass, more preferably 0. 5 to 15% by mass. Even if the unreacted crosslinking agent is contained in the "some extent" of the alignment film after the end of the crosslinking reaction, the amount of the crosslinking agent is preferably 1. in the alignment film. 0% by mass or less, more preferably 〇. 5 mass% or less. If the alignment film contains more than 1 . 未Quality! The amount of unreacted cross-linking agent does not provide sufficient durability. That is, in the case of a liquid crystal display device, the case of 'long-term use or long period of time in a high-humidity high-humidity gas environment' may generate a mesh. Examples of the denatured group of the denatured polyvinyl alcohol include a hydrophilic group (a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, an amine group, an ammonium group, a guanamine group, a thiol group, etc.), and a carbon number of 10 to 100 a hydrocarbon group, a fluorine atom-substituted hydrocarbon group, a thioether group, a polymerizable group (unsaturated polymerizable group, an epoxy group, an azacyclopropyl group, etc.), an alkoxyalkyl group (trialkoxy group, a dialkoxy group, Monoalkoxy) and the like. Specific examples of such denatured polyvinyl alcohol compounds are disclosed, for example, in paragraph number [0074] of Japanese Laid-Open Patent Publication No. 2000-56310, and paragraph number [0022] of Japanese Laid-Open Patent Publication No. 2000-1552. ~ [0145], paragraphs [0018] to [0022] of Japanese Laid-Open Patent Publication No. 2002-62426. Further, in the case where alignment is performed by light irradiation, a light alignment group having a photo-alignment function is found in the molecule. Such light-aligning bases can be exemplified by: "The LCD, Volume 3 (I) 3~16 (1 999) by Hasegawa Yashu. The disclosed photoalignment group, the photoalignment group of the photo-alignment function is found by photo-quantization reaction with C=C bond (for example, polyalkenyl, 1,2-diphenyl-83 - 201211575 vinyl, phenylethyl) Photo-alignment reaction of photo-alignment function by photodimerization reaction with c=o bond A group (for example, a functional group having a structure such as a benzophenone group or a coumarin group, etc.). Specifically, for example, the paragraph number [0021] disclosed in Japanese Laid-Open Patent Publication No. 2000-122069, Japanese Laid-Open Patent Publication No. 2002-317013, and the like. [The carboxylic acid compound contained in the alignment film] The composition for forming an alignment film of the present invention preferably contains a specific carboxylic acid compound. In this way, it has been found that the alignment surface of the obtained alignment film is aligned by the alignment device, and the optical compensation sheet obtained by coating the optically oriented layer has a good coating surface shape, thereby reducing or solving the improvement effect of removing optical defects such as white. . It is presumed that one of the reasons is that the specific carboxylic acid compound contained in the alignment film stabilizes the hydrogen ion concentration on the surface of the film of the alignment film, and when the optically oriented layer is coated, the alignment state of the liquid crystal molecules is reduced. influences. Further, it is considered that the surface of the transparent support is hydrophilized by the saponification treatment of the alkali, and even if only a small amount of the treatment liquid remains on the surface of the film, it is stable and forms an alignment film having good optical properties. Of course, since the effect will vary depending on the amount added, an appropriate amount of adjustment must be made. Specific examples of the carboxylic acid compound include a carboxylic acid having at least one hydrogen atom-containing polar group having a hydrogen bond property. These carboxylic acids may be any of an aliphatic compound, an aromatic compound or a heterocyclic compound. Specific polar groups include: -OH, - SH, - NHR, - CONHR ' -S02NHR, -NHCONHR, -NHS02NHR, -NHCOR1, - NH S02R1. However, R represents a hydrogen atom, a J|aliphatic group, an -84 - 201211575 aryl group or a heterocyclic group. R1 represents an aliphatic group, an aryl group or a heterocyclic group. The carboxylic acid may contain a plurality of such polar groups, and the polar groups may be the same or different. Preferred specific polar groups of the present invention include -OH, -SH, -NHR, a CONH2, -SO2NH2, -NHCONHR, -NHSO2NHR'-NH SOzR1. Here, R means a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group. R1 represents an aliphatic group, an aryl group or a heterocyclic group. R represents an aliphatic group, and examples thereof include a linear or divalent alkyl group having an aliphatic group of 1 to 2 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group). , heptyl, octyl, decyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecanyl, heptadecyl, octadecyl a linear or divalent alkenyl group having a carbon number, a nineteen carbon group, a twenty carbon group, a twenty carbon group, a twenty carbon group, or the like, and a carbon number of 2 to 2 2 (for example, a vinyl group or a propylene group) Base, butenyl, pentenyl, hexenyl, octenyl, dodecyl, thirteen, tetradecyl, hexadecyl, octadecenyl, twenty a linear or divalent alkynyl group having a carbon number of 2 to 22, such as a hexenyl group, a hexenylalkenyl group, a butadienyl group, a pentadienyl group, a hexadienyl group, an octadienyl group or the like. , Ethyl, propynyl, butynyl, hexynyl, octynyl, decynyl, dodecynyl, alicyclic hydrocarbon groups having 5 to 22 carbon atoms (for example, cyclopentane, cyclopentane) Alkene, cyclopentadiene, cyclohexane, cyclohexene, cyclohexadiene , cycloheptane, cycloheptene, cycloheptadiene, cyclooctane, cyclooctene, cyclooctadiene, decalin, etc.). The aliphatic group, among these, is preferably a linear aliphatic group having a carbon number of 1 to 18 and a divalent aliphatic group having a carbon number of 3 to 18. -85- 201211575 An aryl group means an aryl group having 6 to 18 carbon atoms (the aryl ring is benzene, naphthalene, dihydronaphthalene, biphenyl, etc.). The heterocyclic group may, for example, be a heterocyclic group having a monocyclic or polycyclic ring structure of any one of at least one of an oxygen atom, a sulfur atom and a nitrogen atom (heterocyclic group, for example, pyranyl group, pyran group) Keto group, pyridyl group, pyrazinyl group, morpholinyl group, thiol group, benzothiophene group and the like. The aliphatic group, the aryl group, and the heterocyclic group may have an individual substituent, and a monovalent non-metal atomic group other than hydrogen is used as the substituent which can be introduced. Specific examples of the non-metal atomic group indicate a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a nitro group, -OR11, -SR11, -COR1 1 , - COOR", - OCOR1 1 , - S02R&quot ;,- NHCONHR1 1 ' - N ( R12 ) COR1 1 , - N ( R 12 ) SO 2 R1 1 , — N (R13) ( R14 ) , - CON(R13) ( R14 ) , -S02N(R13) (R14 ), - P(=0) ( R1 5 ) (R16), - 0P(=0) ( R15 ) (R16) , — Si(R17) (R18) (R19) 'Aromatic group with carbon number 1 to 22 An alkenyl group having 2 to 18 carbon atoms or an aryl group or a heterocyclic group having 6 to 18 carbon atoms. These aliphatic, aryl, and heterocyclic groups are synonymous with R. R11 represents an aliphatic group having 1 to 22 carbon atoms, an aryl group having 6 to 18 carbon atoms or a heterocyclic group. The aliphatic group of R11 is the same as the aliphatic group represented by R. The aryl group of R11 may be the same as the aryl group represented by R. The heterocyclic group of Ru may be the same as the heterocyclic group represented by R. Such an aryl group may further have a substituent, and examples of the substituent include the same substituents as those in which an aliphatic group, an aryl group or a heterocyclic group represented by R is introduced. R12 represents a hydrogen atom or the same as the R11 group. -86 - 201211575 The R13 and R14 series represent the same independent gas atom or the same as the R11 group. R13 and R14 are bonded to each other, and a 5-member or 6-membered ring containing an N atom can also be formed. R15 and R16 represent an independently aliphatic group having 1 to 22 carbon atoms, an aryl group having 6 to 14 carbon atoms or -OR11. The aliphatic group of R15 and R16 is the same as the aliphatic group represented by R, and the aryl group of Rl5 and R10 is the same as the aryl group represented by R. The aryl group may have a substituent as a substituent, and examples thereof include the substituents which may be introduced into the aliphatic group, the aryl group or the heterocyclic group represented by R. The Ri7, R18 and R19 represent independently a hydrocarbon group having 1 to 22 carbon atoms or an OR2 (), and at least one of the substituents represents a hydrocarbon group. The hydrocarbon group means that the R is the same as the aliphatic group and the aryl group, and - 〇r2() means the same content as the -OR11. The aliphatic group, the aryl group and the heterocyclic group of R1 are the same as R. The specific carboxylic acid compound of the present invention is an aliphatic carboxylic acid having 1 to 2 carbon atoms (other than a carbon atom of a carboxylic acid), an aromatic carboxylic acid having 6 to 14 carbon atoms, or a carboxylic acid compound of a heterocyclic carboxylic acid. It is preferable that the pKa is 6_5 or less. The PKa of the carboxylic acid is more preferably 3. 0~6. 5 compounds. Specific examples of such specific carboxylic acid compounds include hydroxy acids (for example, 'glycolic acid, lactic acid, glyceric acid, α-hydroxyalkanoic acid (alkane is a carbon number of 3 to 18 carbon atoms), etc.), and an amine. a base acid, an α-hydroxy-col-amino acid, an α-hydroxy-r-amino acid, a /S-hydroxyamino acid, a compound of which a hydroxyl group of a hydroxy acid or a hydroxylamino acid is derived as an alkoxy group, a hydroxycyclohexanecarboxylic acid, a hydroxybenzenecarboxylic acid, or a polyalcohol by using a cyclic carboxylic anhydride (an acid anhydride such as succinic acid, maleic acid, adipic acid, cyclohexanedicarboxylic acid or phthalic acid) (for example, a compound which is esterified with at least one hydroxyl group of alkane-87-201211575 alcohol, glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, cyclohexanol, etc., from a polyamine compound (for example, 'alkylenediamine, a compound derived from a compound which is oxime-formed with a cyclic carboxylic anhydride, such as diethyltriamine, tri-extension ethyltetramine, cycloheximide diamine, phenyldiamine, etc., but the present invention is not subject to such The compound is defined. More preferably, a carboxylic acid compound containing at least one hydroxyl group and having at least one carboxyl group esterified is exemplified. The polycarboxylic acid containing at least one hydroxyl group may, for example, be hydroxymalonic acid, malic acid, tartaric acid, citric acid, hydroxyglutamic acid (body, γ-body), or at least two of the polyalcohol using a cyclic carboxylic anhydride. A compound in which a hydroxyl group is esterified or the like. It is preferred to use an alkyl group having 1 to 22 carbon atoms for ester substitution of at least one carboxylic acid of the polycarboxylic acid compound. The specific aspect of the hydrocarbon group having 1 to 18 carbon atoms substituted by vinegar is the same as the aliphatic group, aromatic group or heterocyclic group disclosed in the above R. Further, these hydrocarbon groups may be substituted. The substituents may be the same as those substituted by the R. The specific carboxylic acid compound of the present invention is preferably 0. The ratio of 01 to 1 (% by mass) is added to the composition for forming an alignment film. More preferably 〇〇2~〇5 mass%. Within this range, an optical compensation sheet having no optical defects such as white which can maintain sufficient film strength can be obtained. Further, even if the elongated ruled film ‘ is continuously produced, it can be manufactured with extremely stable performance. Basically, an 'alignment film system-type hardening film which can coat the polymer containing the composition for forming an alignment film, a crosslinking agent and a specific carboxylic acid coating solution on a transparent carrier, after that, It is formed by heat drying (crosslinking) and alignment treatment. The crosslinking reaction can also be carried out at any time after coating on a transparent support. When a water-soluble polymer such as polyvinyl alcohol is used as the composition for forming an alignment film, the coating liquid is preferably used as a mixed solvent of an organic solvent (for example, methanol) having a defoaming action and water. Its water: The quality of methanol should be 0: 10 0~ 99: 1, more preferably: 1〇〇~91: 9. Thereby, the occurrence of bubbles can be suppressed, and the defects of the alignment film and even the surface of the layer of the optically different layer can be remarkably reduced. The coating method of the alignment film is preferably a dip coating method, a curtain coating method, an extrusion coating method, a rod coating method or a roll coating method. Especially the rod coating method is preferred. In addition, the film thickness after drying is preferably 0. 1 to 10; am. Heating and drying can be carried out at 20 ° C to 100 ° C. In order to form a sufficient crosslink, it is preferably from 60 ° C to 100 ° C, especially from 80 ° C to 10 0 ° C. The drying time can be from 1 minute to 36 hours, preferably from 1 minute to 30 minutes. More preferably 5 minutes to 30 minutes. Further, the coating liquid containing the composition for forming an alignment film of the present invention is applied to a carrier, dried, and aligned by an alignment device, and then coated with a coating liquid for an optically oriented layer, the surface of the alignment film is preferably maintained at pH 2. 0~6. The scope of 9. More preferably ρΗ2· 5~5. The range of 0. In the case of using glutaraldehyde, it is preferably ΡΗ4. 5~5. 5. Especially ΡΗ 5 is better. Further, when the coating liquid for the optically different direction layer is applied, the fluctuation range Δρ of the pH of the surface of the alignment film in the width direction of the coating is preferably ±0. 30 range. ΔρΗ is better than ±0. The scope of 15. Preferably, the optical defects of the optical compensation sheet to which the optically oriented layer is applied are significantly reduced in this range. -89- 201211575 The pH of the alignment film surface is measured at a temperature of 25 ° C / humidity of 6 5 % RH. After the sample coated with the alignment film is allowed to stand for one day, it will be in a nitrogen atmosphere. 10 ml of pure water was poured thereon, and the pH was immediately read by a pH meter. In order to specify the pH of the surface of the alignment film of the present invention, and to control the pH of the coating width direction, it is achieved by coating by the bar coating method. It is also effective to further adjust the drying temperature of the film surface, the air volume in the case of using a dry wind, the wind direction, and the like. As described above, the alignment film can be obtained by subjecting the polymer layer to cross-linking and then subjecting the surface to a flat grinding treatment. The flat grinding process can apply a processing method that has been widely adopted by the LCD liquid crystal alignment processing step. That is, a method of obtaining the alignment by rubbing the surface of the alignment film in a predetermined direction by using paper, cotton cloth, felt, rubber, nylon or polyester fiber or the like can be employed. In general, it is carried out by using a cloth which is averaged by pulverizing fibers having a uniform length and a thickness, and performing flat grinding for several times. Further, in the case of performing light alignment by light irradiation, an ultrahigh pressure mercury lamp, a xenon lamp, a fluorescent lamp, a laser or the like can be used as a light source of the light irradiation device, and the light source and the light source are combined for light alignment of the photodiodizing compound. The polarizer (by a polarizer) forms a linearly polarized light beam and is irradiated to the light alignment film. Mainly as a polarizer user, the dyed PVA is stretched. For example, the linear polarized light irradiation device can be used as disclosed in Japanese Laid-Open Patent Publication No. Hei 10-90684. The thickness of the alignment film is preferably 〇·〇1 to l〇#m, more preferably 0. 〇1 to 5 /zm, preferably 0. 05 to 1/zm. -90-201211575 [Optical anisotropy] An optically oriented layer formed of a liquid crystal compound can be formed on an alignment film which is coated on a cellulose halide film. The liquid crystalline compound used for the optically oriented layer contains a rod-like liquid crystal compound and a discotic liquid crystal compound. The rod-like liquid crystal compound and the discotic liquid crystal compound may be a polymer liquid crystal or a low molecular liquid crystal ', and may also contain a crosslinked low molecular liquid crystal without exhibiting liquid crystallinity. The optically oriented layer can be applied onto the alignment film by using a liquid crystal compound and a coating liquid which must contain a polymerizable initiator or an optional component. For the solvent to be used for the coating liquid adjustment, it is preferred to use an organic solvent. Examples of the organic solvent include: decylamine (for example, N,N-dimethylformaldehyde), anthracene (for example, dimethyl sulfoxide), a heterocyclic compound (for example, pyridine), a carbon·hydrogen compound (for example, Benzene, hexane), alkyl halides (eg, chloroform, tetrachloromethane), esters (eg, methyl acetate, butyl acetate + vinegar), ketones (eg, 'acetone, methyl ethyl ketone), ether (eg, , tetrahydrofuran, 1,2-dimethoxyethane). More preferred are alkyl halides and ketones. It is also possible to use a combination of two or more organic solvents. The application of the coating liquid can be carried out by a conventional method (for example, a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, or a die coating method). For rod-like liquid crystal compounds, it is preferred to use methylimine, azo, cyanobiphenyl, cyanophenyl ester, benzoic acid ester; phenyl cyclohexane carboxylate, cyanobenzene A cyclohexane, a cyano substituted phenyl pyrimidine, an alkoxy substituted phenyl pyrimidine, a diphenylacetylene, and an alkenylcyclohexane benzonitrile. -91 - 201211575 Further, the rod-like liquid crystalline compound also contains a metal complex. Further, a liquid crystal polymer containing a rod-like liquid crystal compound in a repeating unit may be used as a rod-like liquid crystal compound. In other words, the rod-like liquid crystalline compound may also be bonded to the (liquid crystal) polymer. For rod-like liquid crystal compounds, it has been disclosed in the Japanese Quarterly Chemicals, Vol. 22, Liquid Crystal Chemistry (1 994), Chapters 4, 7 and 11 of the Japanese Chemical Society; and the Handbook of Liquid Crystal Components, Committee 142 of the Japan Society for the Promotion of Science Chapter 3 of the series. The complex refractive index of the rod-like liquid crystalline compound is preferably 0. 001 to 0. Within the scope of 7. In order to fix the alignment state thereof, the rod-like liquid crystalline compound preferably has a polymerizable group. Hereinafter, an example of the polymerizable group (Q) will be described.

(Q1) —ch=ch2 (Q2) —ch=ch-ch3 (Q3) —CH=CH-C2H5 (Q4) —CH ^zCH—n-CgHy (Q5) ' —C=CH〇 6h3 (Q6) —ch=c-ch3 iH3 (Q7) —C=CH (Q8) 0 —ClH-CHa (Q9) H N —c1h-ch2 (Ql〇) —SH (Qli) —CHO (Q12) —OH (Q13) —co2h (Q14) ‘~N=C=〇 (Q15.) ~^H2 (Q16) —503H .(Q17) —N=C=S -92- 201211575 聚合性基（Q)較宜爲不飽和聚合性基（Q1〜Q7)、環氧基（Q8)或雜氮環丙烷基（Q9)，更佳爲不飽和聚合性基，最好爲乙烯性不飽和聚合性基（Q 1〜Q6 )。棒狀液晶性化合物較宜具有對於短軸方向幾乎成爲對稱的分子構造。因此，於棒狀分子構造之兩端，較宜具有聚合性基。 &下’顯示棒狀液晶性化合物之例子。 (N1)(Q1) —ch=ch2 (Q2) —ch=ch-ch3 (Q3) —CH=CH—C2H5 (Q4) —CH ^zCH—n—CgHy (Q5) ' —C=CH〇6h3 (Q6) — Ch=c-ch3 iH3 (Q7) —C=CH (Q8) 0 —ClH-CHa (Q9) HN —c1h-ch2 (Ql〇) —SH (Qli) —CHO (Q12) —OH (Q13) —co2h (Q14) '~N=C=〇(Q15.) ~^H2 (Q16) —503H .(Q17) —N=C=S -92- 201211575 The polymerizable group (Q) is preferably an unsaturated polymerizable group. (Q1 to Q7), epoxy group (Q8) or azacyclocyclopropane group (Q9), more preferably an unsaturated polymerizable group, and more preferably an ethylenically unsaturated polymerizable group (Q 1 to Q6 ). The rod-like liquid crystalline compound preferably has a molecular structure which is almost symmetrical with respect to the short axis direction. Therefore, it is preferred to have a polymerizable group at both ends of the rod-like molecular structure. & Below shows an example of a rod-like liquid crystalline compound. (N1)

CH2 =CH -CO -〇-C7Hi4 (Ν2) Ρ, H2C -c Η -CO -〇 -C7H14 (N3) ch2=ch~c〇-〇-c7h14CH2 =CH -CO -〇-C7Hi4 (Ν2) Ρ, H2C -c Η -CO -〇 -C7H14 (N3) ch2=ch~c〇-〇-c7h14

-93- 201211575 (N4) ρχ h2c~ch~c〇hd-c7h14 (Ν5) ch2=ch~co-o-c7h14 (N6) CH2=CH-C〇-〇-C7H14 (N7) ch2=ch -co -o-c7h14 -94- 201211575 (N8)-93- 201211575 (N4) ρχ h2c~ch~c〇hd-c7h14 (Ν5) ch2=ch~co-o-c7h14 (N6) CH2=CH-C〇-〇-C7H14 (N7) ch2=ch -co -o-c7h14 -94- 201211575 (N8)

CH2=CH-€〇-〇-C5H10—CN (N9)CH2=CH-€〇-〇-C5H10—CN (N9)

(N10)(N10)

NN

ch2=ch-co-o-c3h5—< H (Nil)Ch2=ch-co-o-c3h5—< H (Nil)

ch2=ch-co~o-c7h14*—^ 7—COλ)~05Η^Ch2=ch-co~o-c7h14*—^ 7—COλ)~05Η^

NC -95- 201211575 (N12)NC -95- 201211575 (N12)

P, h2c-ch-co-o-c7h14P, h2c-ch-co-o-c7h14

NC CN (N13) CH2=CH-C〇-〇-C7H14〇NC CN (N13) CH2=CH-C〇-〇-C7H14〇

5^11 (N14)5^11 (N14)

(N15>(N15>

-96- 201211575 (N16) ch2=ch -co-ok:7h14 (N17) GHg ^OH. ~CO- —〇-C7H··) 40· (N18) CH2 =CH -CO -〇-CSH10 (N19) P、 H2C-CH-C〇-〇~C7H14 -97 201211575 (N20) CH2=CH'-C0~0-C3He-96- 201211575 (N16) ch2=ch -co-ok:7h14 (N17) GHg ^OH. ~CO- —〇-C7H··) 40· (N18) CH2 =CH -CO -〇-CSH10 (N19) P, H2C-CH-C〇-〇~C7H14 -97 201211575 (N20) CH2=CH'-C0~0-C3He

(N21) (N22) ch2=ch-co -o-c7h14(N21) (N22) ch2=ch-co -o-c7h14

N η2Λη^ο-ο-ο7η14N η2Λη^ο-ο-ο7η14

(N23) CH -CO -0-C7H14O -<^y-N=CH —(N23) CH -CO -0-C7H14O -<^y-N=CH —

ch2 \=/ N=N -98- 201211575 (N24) HgC^H -€0 -〇-C7H14Ch2 \=/ N=N -98- 201211575 (N24) HgC^H -€0 -〇-C7H14

0-0 ~0 N F F (N25) CH2=CH-C〇-〇-C7H14 —^jV-CH =CH-C〇-〇—^~^V-〇cs.Hn r (N26)0-0 ~0 N F F (N25) CH2=CH-C〇-〇-C7H14 —^jV-CH=CH-C〇-〇—^~^V-〇cs.Hn r (N26)

?·Η2 C4H3?·Η2 C4H3

-99- 201211575 (N28)9H CJO · o-c4h8o-99- 201211575 (N28)9H CJO · o-c4h8o

N H~<^^~OC4H8 (N29)N H~<^^~OC4H8 (N29)

(N31) CH2=CH-00-0-07^4(N31) CH2=CH-00-0-07^4

c8h16-o-co-ch=ch2 100- 201211575 (N32)C8h16-o-co-ch=ch2 100- 201211575 (N32)

Q c3h6—o-hc-ch2 P, h2c ~ch -co -〇 *-c7h14 (N33)Q c3h6—o-hc-ch2 P, h2c ~ch -co -〇 *-c7h14 (N33)

c3h6-o-hc-ch2 ch2=ch -co -o-c7hu (N34) CH2 =CH -CO-〇-C7H,4\Tiy-〇C8H16-〇-€〇-CH=CH2 2c Η Η 〇 T .cn9cioC3h6-o-hc-ch2 ch2=ch -co -o-c7hu (N34) CH2 =CH -CO-〇-C7H,4\Tiy-〇C8H16-〇-〇〇-CH=CH2 2c Η Η 〇T . Cn9cio

2 ΗΪΗ o CICIC!^ 8 H c4 -101 - 201211575 (N36)2 ΗΪΗ o CICIC!^ 8 H c4 -101 - 201211575 (N36)

CH〇=CH~C〇-〇-C C5Hi〇-〇-C〇-CH=CHj (N37)CH〇=CH~C〇-〇-C C5Hi〇-〇-C〇-CH=CHj (N37)

C5H10-〇-C〇-HCr-CH 2 p4 h2c；-ch -CO -〇-C7H14 (N38) 9·η2 9-ch3S〇_c7Hl4_f\^C5H10-〇-C〇-HCr-CH 2 p4 h2c;-ch -CO -〇-C7H14 (N38) 9·η2 9-ch3S〇_c7Hl4_f\^

?丨士 Cf-〇H39° c5H10-o (N39)? gentleman Cf-〇H39° c5H10-o (N39)

-102- 201211575 (N40)-102- 201211575 (N40)

(N41)(N41)

(N42) CH2=CH.-C〇-〇-C7Hi4(N42) CH2=CH.-C〇-〇-C7Hi4

-CO CH2=CH-C〇-〇-C7H14-CO CH2=CH-C〇-〇-C7H14

-co-co

FeFe

-103 201211575 (N43)-103 201211575 (N43)

(N44)(N44)

-104- 201211575 (N45)-104- 201211575 (N45)

(N46)(N46)

ch2=ch-co -o-c7h14o -105- 201211575 (N47)Ch2=ch-co -o-c7h14o -105- 201211575 (N47)

光學異方向層能夠藉由將含有棒狀液晶性化合物或後述之聚合性起始劑或任意之添加劑（例如，可塑劑、單體、界面活性劑、纖維素酯、1,3,5-三嗪化合物、光學活性劑）之液晶組成物（塗布液），塗布於配向膜之上而形成。碟狀液晶性化合物之例子，可列舉：揭示於C . D e s t r a d e 等人之硏究報告、Mol.Cry st. 71卷，111頁（1981年）之苯衍生物；揭示於C. Destrade等人之硏究報告、Mol. Cryst. 122 卷，141 頁（1 98 5 年）、Physics lett. A 78 卷，82 頁 (1990)之二亞蘊衍生物；揭示於B.Kohne等人之硏究報告、Angew. Chem. 96卷，70頁（1 984年）之環己烷衍生物；以及揭示於 J. M. Lehn等人之硏究報告、J. Chem. Commun.，1974頁（1985年）、J. Zhang等人之硏究報告、 J.Am.Chem.Soc. 116 卷，2655 頁（1994 年）的吖冠狀酸 -106- 201211575 系或本基乙炔系巨環。再者，碟狀液晶性化合物，通常含有將此等化合物作爲分子中心的母核，直鏈烷基或烷氧基、取代苯甲酸基等作爲其直鏈而取代成放射線狀之構造，顯示液晶性。另外’於本發明，由碟狀液晶性化合物所形成的光學異方向層’最終製得的物質不一定爲該化合物’例如’低分子之碟狀液晶性化合物具有利用熱或光進行反應的官能基’其結果’含有藉由利用熱、光等反應進行聚合或交聯，經高分子量化而失去液晶的物質。碟狀液晶性化合物之較佳例’已揭示於日本公開專利第平8-50206 號公報。另外’針對碟狀液晶性化合物之聚合，也已揭示於日本公開專利第平8 - 2 7 2 8 4號公報。爲了藉由聚合而將碟狀液晶性化合物予以固定，於碟狀液晶性化合物之碟狀核上’必須使作爲取代基之聚合性基得以鍵結。但是，一旦使聚合性基直接鍵結於碟狀核，便難以保持聚合反應之配向狀態。因此，於碟狀核與聚合性基之間，導入連結基。因而，具有聚合性基之碟狀化合物，較宜爲下式（III )所示之化合物。 (III) D(— L— Q) n 式中’D爲碟狀核；L爲二價之連結基，q爲聚合性基；而且，η爲4至12之整數。The optically oriented layer can be composed of a rod-like liquid crystalline compound or a polymerizable initiator described later or an optional additive (for example, a plasticizer, a monomer, a surfactant, a cellulose ester, 1, 3, 5 - 3 A liquid crystal composition (coating liquid) of a azine compound or an optically active agent is formed by being applied onto an alignment film. Examples of the discotic liquid crystalline compound include those disclosed in C. Destrade et al., Mol. Cry st., Vol. 71, p. 111 (1981); disclosed in C. Destrade et al. The research report, Mol. Cryst. 122, 141 (1 98 5), Physics lett. A 78, 82 (1990) dioxin derivatives; revealed in B. Kohne et al. Report, Angew. Chem. Vol. 96, p. 70 (1 984) cyclohexane derivatives; and published in JM Lehn et al., J. Chem. Commun., 1974 (1985), J Zhang et al., Research Report, J. Am. Chem. Soc. 116, pp. 2655 (1994), 吖Corona acid-106-201211575 or the acetylene macrocycle. In addition, the dish-like liquid crystal compound usually contains such a compound as a core of a molecular center, and a linear alkyl group, an alkoxy group, a substituted benzoic acid group or the like is linearly substituted for its linear structure, and liquid crystal is displayed. Sex. Further, in the present invention, the material which is finally produced by the optically anisotropic layer formed of the discotic liquid crystalline compound is not necessarily the compound. For example, the low molecular discotic liquid crystalline compound has a function of reacting with heat or light. The base 'the result' contains a substance which is polymerized or crosslinked by a reaction such as heat or light, and which loses liquid crystal by high molecular weight. A preferred example of the dish-like liquid crystal compound is disclosed in Japanese Laid-Open Patent Publication No. Hei 8-50206. Further, the polymerization of a discotic liquid crystalline compound is also disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei 8- 2 2 2 8 . In order to fix the discotic liquid crystalline compound by polymerization, it is necessary to bond the polymerizable group as a substituent to the discotic core of the discotic liquid crystalline compound. However, once the polymerizable group is directly bonded to the discotic core, it is difficult to maintain the alignment state of the polymerization reaction. Therefore, a linking group is introduced between the discotic core and the polymerizable group. Therefore, the discotic compound having a polymerizable group is preferably a compound represented by the following formula (III). (III) D(— L—Q) n wherein 'D is a discotic core; L is a divalent linking group, and q is a polymerizable group; and η is an integer of 4 to 12.

以下，顯示碟狀核（D )之例子。於以下之各例子，LQ (或是QL)意指二價之連結基（L)與聚合性基（Q)之組合。 -107- 201211575 (Dl) (D2)Hereinafter, an example of the disc core (D) will be described. In each of the following examples, LQ (or QL) means a combination of a divalent linking group (L) and a polymerizable group (Q). -107- 201211575 (Dl) (D2)

-108 201211575 (D5) (D6) QL lq-108 201211575 (D5) (D6) QL lq

QL LQQL LQ

(D7) (DB)(D7) (DB)

QL LQQL LQ

QLv LQ LQQLv LQ LQ

109 201211575 (D9)109 201211575 (D9)

QLQL

QL (Dll) (»12}201211575QL (Dll) (»12}201211575

LQLQ

111 - 201211575111 - 201211575

(D15) QL LQ(D15) QL LQ

於式（III)，二價之連結基（L)較宜爲由亞烷基、亞烧基、伸芳基、—CO—、— NH—、一〇_ ' _s —與由此等之組合而成的群中所選出的二價之連結基。二價之連結基（L)更佳爲組合由亞垸基、伸芳基、_c〇-、一 NH—、 —〇_與一 S—而成的群中所選出的至少二個二價官能基之二價連結基。二價之連結基（L)最好爲組合由亞烷基、伸芳基、一 CO—與一 0—而成的群中所選出的至少二個二價官能基之二價連結基。亞烯基之碳原子數較宜爲2至 12。芳基之碳原子數較宜爲6至10。以下，顯示二價之連結基（L )之例子。左側鍵結於碟狀核（D )，右側鍵結於聚合性基（Q ) 。AL係意指亞烷基或亞烯基、AR係意指芳基。還有，亞烷基、亞烯基與伸芳基也可以具有取代基（例如，烷基）。 LI： -AL-C0-0-AL-L2 ： - AL - CO - 0 - AL - 0- -112- 201211575 L3 ： -AL- CO - 0 - AL - 0 - AL - L4 ：一 AL- CO - 0 — AL - o - CO - L5 ： —C 0 — AR - 0 - A L — L6 ： -CO _ AR - 0 - AL - 0 - L7 ： -CO — AR - 0 - AL - 0 - CO - L8 : -CO - NH - AL — L9 ： -NH - AL - 0 — L 1 0 ：-NH -AL -0 -CO — L1 1 :-0 - AL - L 1 2 ：-0 - AL - 0 — L 1 3 ：-0 - AL - 0 - CO - L1 4 :—0 - AL - 0 - CO - NH -AL L 1 5 ：-0 - AL - s - AL - L 1 6 ：-0 — CO - AR —0 — AL -CO L1 7 :-0 - CO - AR —〇 — AL -0- CO L 1 8 ：-0 - CO - AR —0 — AL -0 - AL - -0 - -CO L1 9 : - 0 - CO - AR —0 — AL - -0 - AL - o - AL - 0 - CO L20 :-S - AL - L2 1 : - S — AL - 0 一 L22 :—S - AL - 0 - CO L2 3 : - S - AL s - AL - L24 ：-S - AR - AL - 一式（III )之聚合性基（Q )係相同於以棒狀液晶性化合物說明的聚合性基（Q )。於式（III) ，11爲4至12之整數。具體之數字係因應 -113- 201211575 於碟狀核（D)之種類而決定的。還有，數個L與Q之組合可以不同，但是較宜爲相同的。使用碟狀液晶性化合物之情形，光學異方向層具有負的複折射之薄層，而且，碟狀構造單位之面，對纖維素醯化物薄膜表面傾斜，並且碟狀構造單位之面與纖維素醯化物薄膜表面所形成的角度較宜於光學異方向層之深度方向進行改變。一般而言，碟狀構造單位之面的角度（傾斜角）係於光學異方向層之深度方向，並且從光學異方向層底面起，隨著距離的增加而增加或減少。傾斜角較宜隨著距離的增加而增加。再者，傾斜角之變化可列舉：連續性增加、連續性減少、間歇性增加、間歇性減少 '包含連續性增加與連續性減少之變化、以及包含增加與減少之間歇性變化等。間歇性變化包含於厚度方向之中途，傾斜角無變化之區域。傾斜角即使包含傾斜角無變化之區域，整體較宜增加或減少。再者，傾斜角整體較宜增加，尤以連續性進行變化較爲理想。 —般而言’載體側之碟狀單位的傾斜角係藉由選擇碟狀液晶性化合物或是配向膜材料，或是藉由選擇平磨處理而能夠予以調整。另外，一般表面側（空氣側）之碟狀單位的傾斜角能夠藉由選擇碟狀液晶性化合物或是與碟狀液晶性化合物一起使用的其他化合物而予以調整。與碟狀液晶性化合物一起使用的化合物之例子，可列舉：可塑劑、界面活性劑、聚合性單體與聚合物等。再者，傾斜角之變化程度也可以藉由與上述同樣的選擇而進行調整。 -114- 201211575 與碟狀液晶性化合物一起使用的可塑劑、界面活性劑、聚合性單體與聚合物，具有與碟狀液晶性化合物之相溶性，只要不導致碟狀液晶性化合物之傾斜角的變化，或是妨礙配向，可以使用任何一種化合物。於此等化合物之中，較宜爲聚合性單體（例如，具有乙烯基、乙烯羥基、丙烯醯基與甲基丙烯基之化合物）。例如，可列舉揭示於日本公開專利第2002-296423號公報之段落編號[0018]〜[0020]。相對於碟狀液晶性化合物，一般該化合物之添加量較宜爲1至50質量％之範圍，更佳爲5至30質量％之範圍。與碟狀液晶性化合物一起使用的界面活性劑，可列舉習知之化合物，尤以氟系化合物特別理想。具體而言，例如，可列舉揭示於日本公開專利第2 0 0 1 - 3 3 0 7 2 5號公報之段落編號[0028]〜[0056]的化合物》與碟狀液晶性化合物一起使用的聚合物，只要與碟狀液晶性化合物具有相溶性，且對於碟狀液晶性化合物不造成傾斜角的變化，可以使用任一種聚合物。聚合物之例子，可列舉纖維素酯。纖維素酯之較佳例子，可列舉：纖維素醋酸酯、纖維素醋酸酯丙酸酯、羥丙基纖維素與纖維素醋酸丁酯。欲不妨礙碟狀液晶性化合物之配向，相對於碟狀液晶性化合物，該聚合物之添加量一般爲0.1至10質量％之範圍，較宜爲0.1至8質量％之範圍，更佳爲〇.1至5 質量％之範圍。一般而言，光學異方向層係將碟狀液晶性化合物與其他化合物溶於溶劑的溶液塗布於配向膜上，經乾燥，接著， -115- 201211575 直到形成碟狀向列相之溫度爲止進行加熱，其後，藉由維持配向狀態（碟狀向列相），進行冷卻而得到。或是，該光學異方向層可以藉由將碟狀液晶性化合物與其他化合物 (再者，例如聚合性單體、光聚合起始劑）溶於溶劑的溶液塗布於配向膜上，經乾燥，接著，直到形成碟狀向列相之溫度爲止進行加熱之後，使其聚合（藉由UV光之照射等），進一步冷卻而得到。碟狀液晶性化合物之碟狀向列液晶相-固相移轉溫度較宜爲70至300 °c，更佳爲70至170 〇C。 [液晶性化合物之配向狀態的固定] 能夠將已配向之液晶性化合物維持配向狀態而予以固定。固定化較宜藉由聚合反應進行。聚合反應包含使用熱聚合起始劑與使用光熱聚合起始劑之光聚合反應。較宜爲光聚合反應。光聚合起始劑之例子，包括：α -羰基化合物（揭示於美國專利第2367661、2367670號之各專利說明書）、偶姻醚（揭示於美國專利第2448 8Η號之專利說明書）、α -烴取代芳香族偶姻化合物（揭示於美國專利第2 7 2 2 5 1 2號之專利說明書）、多核醌化合物（揭示於美國專利第 3046127、2951758號之各專利說明書）、三芳基咪唑二聚物與Ρ-胺苯基酮之組合（揭示於美國專利第3 5493 67號之專利說明書）、吖啶與吩嗪化合物（揭示於日本公開專利第昭60-105667號公報、美國專利第4239850號之專利說明書）與噁二唑化合物（揭示於美國專利第42 1 2970號之專利說明書）。 -116- 201211575 光聚合起始劑之用量較宜於塗布液固形成分之0.01至 20質量％之範圍，更佳爲0.5至5質量！*6之範圍》爲了液晶性化合物之聚合的光照射，較宜使用紫外線。照射能量較宜爲20 mJ/cm2至50J/cm2之範圍，更佳爲 20至5000 mJ/cm2之範圍，最好爲1〇〇至800 mJ/cm2之範圍。另外，爲了加速光聚合反應，也可以於加熱條件下實施光照射。也可以於光學異方向層之上設置保護層。本發明之光學補償片係藉由與偏光板貼合，或是作爲偏光板之保護膜使用而顯著發揮其機能。接著，針對本發明之偏光板及其製造，進行詳細之說明。 <偏光板> 本發明之偏光板係一種由偏光膜及配置於其兩側之二片透明保護膜構成的偏光板，其特徵爲：於該透明保護膜之一側’使用該本發明之光學補償片。此處，所謂「一側」意指一側必須使用本發明之光學補償片，兩側也可以利用本發明之光學補償片而構成。 [偏光板的透明保護膜] 於本發明，透明保護膜，亦即，保護膜爲透明的，意指光透過率爲80%以上。該本發明光學補償片以外之透明保護膜，一般使用纖維素酯膜，較宜使用醋酸纖維素膜。醋酸纖維素膜較宜藉由揭示於該透明載體之說明欄的溶劑流延法而予以形成。透明保護膜之厚度較宜爲20〜2 00 μ m，更佳爲30〜1 00 // m。尤以30〜80 y m特別理想。如本發明，藉由於偏光板之一側，使用該本發明光學補償片，於偏光膜與光學異方向層之間，不使用透明保護膜， -117- 201211575 作成隨偏光板尺寸變化而產生的應力（歪斜χ截面積χ彈性率）小且薄的偏光板。若將本發明製得的偏光板裝設於大型液晶顯示裝置中，並不會發生漏光等之問題，呈現高顯示品質之影像。 [光學補償片的表面處理] 爲了改善光學補償片與偏光板之接著性，較宜進行光學補償片之偏光膜側面的表面處理。表面處理係實施電暈放電處理、輝光放電處理、火焰處理、紫外線照射處理、臭氧處理、酸處理或鹼處理。電暈放電處理、輝光放電處理、火焰處理、紫外線照射處理、臭氧處理、酸處理、鹼處理等之處理方法，例如，可列舉：揭示於該公技編號2001-1745號ρ·30-31的內容。本發明較宜爲鹼處理，可列舉與揭示於利用本發明塗布方式之鹼性溶液皂化處理相同的內容。 [偏光膜] 通常’用於本發明之偏光膜較宜爲Opt iv a Inc.製代表性之塗布型偏光膜’或是由黏合劑與碘或二色性染料而成的偏光膜。於偏光膜中之碘與二色性染料，藉由於黏合劑中進行配向而發現偏向性能。碘與二色性染料較宜順著黏合劑分子進行配向’或是二色性染料藉由如液晶之自我組織化而進行單方向之配向。現在’ 一般之市售之偏光子（偏光膜）係將已拉伸之聚合物浸漬於浴槽中之碘或二色性染料的溶液中，藉由使碘或二色性染料滲入黏合劑而予以製作。 -118- 201211575 市售的偏光子係自聚合物表面起約4 v m(兩値 μιη)進行碘或二色性染料之分布，爲了得到足性能，必須至少要有1 〇 β m的厚度。滲透度能夠二色性染料之溶液濃度、相同浴槽溫度、相同浸進行控制。如上所述，黏合劑厚度之下限，較宜爲10/zrr 晶顯示裝置之漏光的觀點，厚度之上限越薄越好現在市售之偏光板（約3 0 // m )以下，更佳爲2 5 a 最好爲20#m以下，漏光現象於17吋之液晶顯觀察不到。偏光膜之黏合劑可以使用可本身交聯的聚合用交聯劑進行交聯的聚合物之中的任一種。聚子’可列舉：相同於利用該配向膜所揭示之聚合聚乙烯醇與變性聚乙烯醇最好。針對變性聚乙烯醇，揭示於日本公開| 8-3 3 8 9 1 3、平 9- 1 52509 與平 9-316127 號之各公 i 聚乙烯醇與變性聚乙烯醇也可以合倂二種以上偏光膜之黏合劑也可以進行交聯。進行交聯_之黏合劑’可以使用本身可交聯之聚夠使具有官能基的聚合物或是已將官能基導入聚到的黏合劑’藉由光、熱或pH變化，於黏合劑反應而形成偏光膜。另外’也可以利用交聯劑而將交聯構造導入赛一般而言’交聯係將聚合物或是將含有聚合物之混合物的塗布液塗布於透明載體上之後，再進合計約8 夠的偏光藉由碘或漬時間而。基於液。較宜爲 m以下，示裝置便物或是利合物之例物。 Ϊ利第平瑕。 .使用。合物。能合物而得之間進行丨合物。與交聯劑行加熱而 •119- 201211575 實施的。於最終商品之階段，爲了能夠盡量確保耐久性，進行交聯之處理，可以於直到製得最終偏光板爲止之任一階段進行。相對於黏合劑，黏合劑之交聯劑較宜爲0.1至20質量 % 。偏光元件之配向性、偏光膜之耐濕熱性將變佳。即使交聯反應結束之後，偏光膜仍含有某種程度上之未反應的交聯劑。但是，所殘存之交聯劑的量，於偏光膜中較宜爲1.0質量％以下，更佳爲0.5質量％以下。藉此，將偏光膜裝入液晶顯示裝置內，即使長期使用或是長期間放置於高溫高濕之氣體環境中，也不會發生偏光度之降低。針對交聯劑。可列舉：揭示於美國再發行專利第23297 號之專利說明書》另外，也可以使用硼化合物（例如，硼酸、硼砂）作爲交聯劑使用。二色性染料可以使用偶氮系染料、二苯乙烯系染料、吡唑啉系染料、三苯基甲烷系染料、喹啉系染料、噁嗪系染料、噻嗪系染料或蒽醌系染料。二色性染料較宜爲水溶性。二色性染料較宜具有親水性取代基（例如，磺基、胺基、羥基）。二色性染料之例子，例如，可列舉揭示於日本發明協會公開技法’公技編號2001-1745號，58頁（發行日2001 年3月15日）之化合物。爲了提高液晶顯示裝置之對比比値，偏光板之透過率高者較佳’偏光度闻者也較佳。對於波長550nm之光，偏光板之透過率較宜爲30至50%之範圍，更佳爲35至50%之範圍，最好爲40至50%之範圍。對於波長550nm之光， -120- 201211575 偏光度較宜爲90至10 0%之範圍，更佳爲95至10 0%之範圍，最好爲99至100%之範圍。也可以藉由接者劑’進行偏光膜與光學異方向層或是偏光膜與配向膜之配置。接著劑可以使用聚乙烯醇系樹脂（含有由乙醯乙炔基、擴酸基、殘基、經院基衍生的變性聚乙烯醇）或硼化合物水溶液。較宜爲聚乙烯醇系樹脂。於乾燥後’接著劑層之厚度較宜爲0.01至lo^m之範圍，尤以 0.05至5 v m之範圍特別理想。 [偏光板的製造] 基於良率的觀點，對於偏光膜之長軸方向（MD方向），偏光膜較宜將黏合劑予以10至80度傾斜而進行拉伸（拉伸法），或是於平磨之後（平磨法），利用碘、二色性染料進行染色。傾斜角度較宜與於貼合於構成LCD之液晶單元兩側的二片偏光板透過軸與液晶單元之縱向或橫向所成的角度相一致而進行拉伸。通常之傾斜角度爲45°。然而，對於透過型、反射型與半透過型LCD，最近已開發出傾斜角未必爲45°之裝置，拉伸方向較宜配合LCD之設計而進行任意之調整。拉伸法之情形，拉伸倍率較宜爲1 · 1至3 0 · 0倍，更佳爲 1.5至10.0倍。拉伸能夠藉由於空氣中進行乾式拉伸。另外，也可以進行浸漬於水的狀態下之濕式拉伸。乾式拉伸之拉伸倍率較宜爲1 · 2至5.0倍。濕式拉伸之拉伸倍率較宜爲3 · 0至1 0 . 〇倍。拉伸步驟也可以包含傾斜拉伸而分成數次進行。藉由分成數次，即使高倍率拉伸，也可以進行均勻的拉伸。於傾斜拉伸前’也可以進行橫向或縱向些許 -121 - 201211575 之拉伸（防止寬度方向收縮的程度）。拉伸能夠藉由以左右不同的步驟進行二軸拉器拉伸而予以實施。該二軸拉伸係相同於一般製的拉伸方法。二軸拉伸方面，由於藉由左右不同行拉伸’拉伸前之黏合劑薄膜之厚度必須作成左流延製膜方面，能夠藉由將錐形物裝設於模頭，差異賦予黏合劑溶液的流量。如上所述，對於偏光膜之MD方向，製造10] 斜拉伸的黏合劑薄膜。磨平方法的話，能夠應用已被LCD液晶配向所廣泛採用的平磨處理方法。亦即，使用紙或棉橡膠或耐隆、聚酯纖維等，順著一定方向，進行的磨擦而得到配向。一般而言，藉由使用將長度勻的纖維予以平均値毛的布，進行數次左右之平實施的。較宜使用輥輪本身之正圓度、圓筒度、振動（爲30;zm以下之平磨輥輪而予以實施。朝平磨輥的平磨角度較宜爲0.1至90°。但是，如日本公開 8- 1 6043 〇號公報中所揭示的，藉由進行360°以上可以得到穩定之平磨處理。進行長型尺狀薄膜之平磨處理的情形，較宜利置，於一定張力之狀態下，以1〜100m/min之速度膜之搬送。由於設定任意之平磨角度，平磨輥輪行進方向之水平方向較宜作成自由旋轉。較宜於I 圍，選擇適宜的平磨角度。用於液晶顯示裝置之伸的定幅膜所進行的速度進右不同。將左右之 5 8 0度傾處理步驟布、賣毛、薄膜表面與粗細均磨而予以離心）均輪之薄膜專利第平之捲繞，用搬送裝，進行薄對於薄膜 1〜60°之範情形，較 -122- 201211575 宜爲40至5 0°。尤以45°特別理想。然後，於偏光膜之兩面側，配置該透明保護膜（本發明之光學補償片/偏光膜/其他之保護膜，或是本發明之光學補償片/偏光膜/本發明之光學補償片）。透明保護膜也可以於其最外側表面設置具有防污性及耐磨擦刮傷性之抗反射膜。可以使用習知任意一種之抗反射膜。進行該方式，製造本發明之偏光板》利用本發明光學補償片之本發明的偏光板，有利於用於液晶顯示裝置，尤其是透過型液晶顯示裝置。透明保護膜係爲了提高與偏光膜之接著性而進行表面處理。偏光膜爲聚乙烯醇之情形，保護膜較宜進行親水化處理。保護膜與偏光膜進行接著之前，較宜利用水洗步驟進行除塵，基於水滴殘留之觀點，對於保護膜表面之水的接觸角較宜爲30°以上。若低於30°，整個保護膜表面仍將被水沾濕，除去水份變得非常困難。尤其，偏光板之光學特性上，較宜控制保護膜之偏光膜側表面的接觸角。於本發明之第4及第5態樣，於偏光板之二片保護膜之一片係本發明使用纖維素醋酸酯薄膜而成的光學補償片。另一片保護膜也可以使用通常的纖維素醋酸酯薄膜。使透明保護膜之遲相軸與偏光膜之透過軸，進行實質上成垂直或平行的配置。另外，對於偏光板之生產性，得知保護膜之透濕性爲重要的。偏光膜與保護膜係利用水系接著劑進行貼合，此接著劑溶劑係藉由進行保護膜中之擴散而予以乾燥。保護膜 -123- 201211575 之透濕性越高，乾燥越快，雖然提高生產性，但是，若透濕性過高，藉由因液晶顯示裝置之使用環境（高濕下），水份將滲入偏光膜中而使偏光能降低。' 光學補償片之透濕性係根據聚合物薄膜（與聚合性液晶化合物）之厚度、自由體積或是親疏水性等所決定的。將光學補償片作爲偏光板之保護膜使用之情形，光學補償片之透濕性較宜爲1〇〇至1 000 (g/cm2)/24hrs之範圍，更佳爲300至700 (g/cm2) /24hrs之範圍。光學補償片之厚度能夠藉由製造纖維素醯化物薄膜之情形的切口流量與生產線速度、或是拉伸、壓縮而進行調整。因爲依照所使用之主材料而導致透濕性產生差異，便可能藉由厚度調整而成爲更佳之範圍。光學補償片之自由體積可以藉由製膜情形之乾燥溫度與時間進行調整。於此情形下，另外也因爲因所使用之主材料而導致透濕性的差異，便可能藉由自由體積調整而成爲更佳之範圍。光學補償片之親疏水性能夠藉由添加劑進行調整。藉由於自由體積中添加親水的添加劑，透濕性將變高，相反地，能夠藉由添加疏水性添加劑，透濕性將降低。藉由調整光學補償片之透濕性，便可能廉價而高生產性地進行具有光學補償能力之偏光板的製造。如上所述，對於偏光膜之MD方向，製造10至80度傾斜拉伸的黏合劑薄膜。磨平方法的話，能夠應用已被LCD液晶配向處理步驟所廣泛採用的平磨處理方法。亦即，使用紙或棉布、氈、 -124- 201211575 橡膠或耐隆、聚酯纖維等，順著一定方向，進行薄膜表面的磨擦而得到配向。一般而言，藉由使用將長度與粗細均句的纖維予以平均値毛的布，進行數次左右之平磨而予以實施。較宜使用輥輪本身之正圓度、圓筒度、振動（離心）均爲30μιη以下之平磨輥輪而予以實施。朝平磨輥輪之薄膜的平磨角度較宜爲0.1至90°。但是，如日本公開專利第平 8- 1 60430號公報中所揭示的，藉由進行3 60°以上之捲繞，可以得到穩定之平磨處理。進行長型尺狀薄膜之平磨處理的情形，較宜利用搬送裝置，於一定張力之狀態下，以l~l〇〇m/min之速度，進行薄膜之搬送。由於設定任意之平磨角度，平磨輥輪對於薄膜行進方向之水平方向較宜作成自由旋轉。較宜於〇~60°之範圍，選擇適宜的平磨角度。用於液晶顯示裝置之情形，較宜爲40至5 0° »尤以45°特別理想。然後，於偏光膜之兩面側，配置該透明保護膜（本發明之光學補償片/偏光膜/其他之保護膜，或是本發明之光學補償片/偏光膜/本發明之光學補償片）。透明保護膜也可以於其最外側表面設置具有防污性及耐磨擦刮傷性之抗反射膜。可以使用習知任意一種之抗反射膜。 . 進行該方式，製造本發明之偏光板。利用本發明光學補償片之本發明的偏光板，有利於用於液晶顯示裝置，尤其是透過型液晶顯示裝置。接著，針對本發明之液晶顯示裝置，尤其針對透過型液 -125- 201211575 晶顯示裝置及其製造進行詳細之說明。 <液晶顯示裝置> 本發明之液晶顯示裝置係由液晶單元與配置於其兩側之二片偏光板構成的，而偏光板係由偏光膜與配置於其兩側之二片透明保護膜構成的，其特徵爲：配置於液晶單元與偏光膜之間的二片透明保護膜之中的至少一片使用該本發明之光學補償片。亦即，本發明之液晶顯示裝置係將該本發明之偏光板作爲偏光板使用。以下，針對各液晶模式之光學異方向層的較佳態樣進行說明。於各液晶模式之光學異方向層的較佳態樣，本發明之光學補償片偏光板能夠有利進行光學補償。 (TN模式液晶顯示裝置） TN模式之液晶單元最多被利用於彩色TFT液晶顯示裝置’可列舉許多已揭示之文獻。TN模式之顯示黑色的液晶單元中的配向狀態係於液晶單元中央部分之棒狀液晶性分子成爲直立的，於液晶單元基板附近之棒狀液晶性分子則成爲橫躺之配向狀態。 (OCB模式液晶顯示裝置） OCB模式之液晶單元係一種使棒狀液晶性分子，於液晶單元之上部與下部實質上顛倒方向（對稱性）使其配向之彎曲配向模式的液晶單元。使用彎曲配向模式的液晶單元之液晶顯示裝置，可列舉：揭示於美國專利第4 5 8 3 8 2 5、 541 0422號之各專利說明書的裝置。爲了將棒狀液晶性分子於液晶單元之上部與下部予以對稱配向，彎曲配向模式 -126- 201211575 的液晶單元具有自我光學補償機能。爲此，此液晶模式也稱爲 OCB ( Optically Compensatory Bend)液晶模式》 OCB模式之液晶單元也相同於TN模式，對於顯示黑色，液晶單元中的配向狀態係於液晶單元中央部分之棒狀液晶性分子成爲直立的，於液晶單元基板附近之棒狀液晶性分子則成爲橫躺之配向狀態》 (VA模式液晶顯示裝置） V A模式之液晶單元方面，於無外加電壓時，棒狀液晶性分子實質上進行垂直配向。對於VA模式之液晶單元，可列舉··（ 1 )除了於無外加電壓時，使棒狀液晶性分子實質上進行垂直配向之外，於外加電壓時，使其實質進行水平配向的狹義VA模式之液晶單元（揭示於日本公開專利第平2-176625號公報）；（2) 爲了擴大視野角度，將VA模式予以多重領域化（MVA模式）之液晶單兀（SID97，Digest of tech. Papers (揭示於預稿集）28(1997) p.845) ; (3)於無外加電壓時，使棒狀液晶性分子實質進行垂直配向，於外加電壓時，予以扭曲多重領域配向之模式（n-ASM模式）的液晶單元（揭示於日本液晶討論會之預稿集，p.58~59( 1998));以及 (4 ) SURVAIVAL模式之液晶單元（發表於 LCD International 9 8) 〇 (其他液晶顯示裝置）對於ECB模式與STN模式之液晶顯示裝置，能夠利用該相同之想法而能夠進行光學補償。於本發明之液晶顯示裝置，雖然該液晶單元爲TN模 -127- 201211575 式、VA模式、MVA模式、n-ASM模式或OCB模式之液晶單元’較宜爲使本發明之光學補償片之效果發揮至最大限度的特點。 TN模式之液晶方面，於無外加電壓時，棒狀液晶性分子實質上進行水平配向，進一步進行60至120。扭曲配向。 TN模式之液晶最多被利用於彩色TFT液晶顯示裝置，已揭示於許多之文獻中。本發明人等改良揭示於歐洲專利第〇 9 1 1 6 5 6 A 2號專利說明書中的纖維素醋酸酯薄膜，維持習知之膜厚原狀，或是即使進一步使厚度薄化，完成能夠無副作用地進行液晶單元之光學性補償的光學補償片（第4及第5態樣）。藉由調節對纖維素醋酸酯薄膜之添加劑（具體而言，具有二個芳香族環的芳香族化合物）的種類與量或是製造條件（例如，薄膜之拉伸條件），可以得到Re相位差値爲5 至lOOnm，Rth相位差値爲70至40〇nm之纖維素醋酸酯薄膜。此纖維素醋酸酯薄膜具有爲了進行液晶單元之充分光學性補償的光學異方向性。再者，藉由進行該纖維素醋酸酯薄膜之表面處理，可以得到一種由纖維素醋酸酯薄膜構成的光學補償片，其對水之接觸角爲30°以上、70°以下且最適合於偏光板加工。另外，偏光板係由偏光膜及配置於其兩側的保護膜構成的。而且，偏光膜係使碘或二色性染料吸附於已進行拉伸配向的聚乙烯醇上，一般而言，保護膜係由纖維素醋酸酯薄膜構成的。若將該纖維素醋酸酯薄膜作爲偏光板一側之保護膜使用，不會增加偏光板構造要件的數目，能夠將光 -128- 201211575 學補償機能追加於偏光板。此時，本發明由於對纖維素醋酸酯薄膜表面之水的接觸角爲30°以上，能夠兼具偏光板加工步驟之良率以及與偏光膜之接著性。還有’若使用醯化度低於59.0之纖維素醋酸酯，雖然容易達成該光學異方向性，但是，作爲纖維素醋酸酯薄膜之物性將降低。本發明使用醯化度爲59.0至61.5%之纖維素醋酸酯，藉由利用其他之方法（該添加劑或製造條件之調節）而達成該相位差値，可以得到光學異方向性與物性二者均爲優異的，進而與偏光膜之接著性爲優異的一種纖維素醋酸酯薄膜。將由該纖維素醋酸酯薄膜構成的光學補償片以及該纖維素醋酸酯薄膜作爲保護膜使用之偏光板能夠特別有利於用於 OCB( Optically Compensatory Bend)型、VA( Vertically Alignment)型或 TN( Twisted Nematic)型之液晶顯示裝置。本發明之第1及第2態樣之光學補償片，特別有利於TN 型或ISP型之液晶顯示裝置。本發明之第4及第5態樣之光學補償片，特別有利於VA型（包含MVA型或n-ASP型）或OCB型之液晶顯示裝置。【實施例】 (第1態樣、第2態樣） [實施例1] (纖維素醯化物薄膜之製作）將下列組成物倒入攪拌槽中，一面加熱並一面攪拌，溶解各成分而調製纖維素醋酸酯溶液。 -129- 201211575 纖維素醯化物溶液組成 1 0 0份質量 7.8份質量 3.9份質量 2 9 5份質量 6 8份質量 2份質量醯化度60.9%之纖維素醯化物三苯基磷酸酯（可塑劑）聯苯二苯基磷酸酯（可塑劑）二氯甲烷（第1溶劑）甲醇（第2溶劑） 1·丁醇（第3溶劑）於另一個攪拌槽中，倒入1 6份質量之下列相位差改善劑、80份質量之二氯甲烷以及20份質量之甲醇，一面加熱並一面攪拌，調製相位差改善劑溶液。遲滯値提昇劑In formula (III), the divalent linking group (L) is preferably a combination of an alkylene group, a pyridyl group, an exoaryl group, —CO—, —NH—, a 〇 ′′ _s — and the like. The divalent linkage selected in the group. The divalent linking group (L) is preferably a combination of at least two divalent functional groups selected from the group consisting of an anthracene group, an exoaryl group, a _c〇-, an NH-, a 〇_ and an S- group. The base of the divalent linkage. The divalent linking group (L) is preferably a divalent linking group of at least two divalent functional groups selected from the group consisting of an alkylene group, an aryl group, a CO- and a group. The alkenylene group preferably has 2 to 12 carbon atoms. The number of carbon atoms of the aryl group is preferably from 6 to 10. Hereinafter, an example of a divalent linking group (L) is shown. The left side is bonded to the disc core (D) and the right side is bonded to the polymerizable group (Q). The AL system means an alkylene group or an alkenylene group, and the AR system means an aryl group. Further, the alkylene group, the alkenylene group and the aryl group may have a substituent (e.g., an alkyl group). LI: -AL-C0-0-AL-L2 : - AL - CO - 0 - AL - 0- -112- 201211575 L3 : -AL- CO - 0 - AL - 0 - AL - L4 : One AL- CO - 0 — AL - o - CO - L5 : —C 0 — AR - 0 - AL — L6 : -CO _ AR - 0 - AL - 0 - L7 : -CO — AR - 0 - AL - 0 - CO - L8 : -CO - NH - AL - L9 : -NH - AL - 0 - L 1 0 : -NH -AL -0 -CO - L1 1 :-0 - AL - L 1 2 :-0 - AL - 0 — L 1 3 :-0 - AL - 0 - CO - L1 4 : -0 - AL - 0 - CO - NH -AL L 1 5 :-0 - AL - s - AL - L 1 6 :-0 — CO - AR — 0 — AL -CO L1 7 :-0 - CO - AR —〇 — AL -0- CO L 1 8 :-0 - CO - AR —0 — AL -0 - AL - -0 - -CO L1 9 : - 0 - CO - AR —0 — AL - -0 - AL - o - AL - 0 - CO L20 :-S - AL - L2 1 : - S - AL - 0 - L22 : -S - AL - 0 - CO L2 3 : - S - AL s - AL - L24 : -S - AR - AL - The polymerizable group (Q) of the formula (III) is the same as the polymerizable group (Q) described by the rod-like liquid crystal compound. In the formula (III), 11 is an integer of 4 to 12. The specific figures are determined by the type of disc-shaped core (D) -113- 201211575. Also, the combination of several L and Q may be different, but it is preferably the same. In the case of a dish-like liquid crystalline compound, the optically anisotropic layer has a thin layer of negative birefringence, and the surface of the dish-like structural unit is inclined to the surface of the cellulose halide film, and the surface of the dish-like structural unit is cellulose. The angle formed by the surface of the bismuth film is preferably changed in the depth direction of the optically different direction layer. In general, the angle (inclination angle) of the face of the dish-shaped structural unit is in the depth direction of the optically different direction layer, and increases or decreases with increasing distance from the bottom surface of the optically different direction layer. The tilt angle is preferably increased as the distance increases. Further, the change in the inclination angle may be, for example, an increase in continuity, a decrease in continuity, an increase in intermittentness, and an intermittent decrease, "including a change in continuity and decrease in continuity, and an intermittent change including increase and decrease." The intermittent change is included in the middle of the thickness direction, and the area where the inclination angle does not change. Even if the tilt angle contains an area where the tilt angle does not change, the overall ratio is preferably increased or decreased. Further, the inclination angle is preferably increased as a whole, and it is preferable to change in continuity. In general, the inclination angle of the dish-shaped unit on the carrier side can be adjusted by selecting a discotic liquid crystal compound or an alignment film material, or by selecting a flat grinding treatment. Further, the inclination angle of the dish unit on the general surface side (air side) can be adjusted by selecting a discotic liquid crystal compound or other compound used together with the discotic liquid crystal compound. Examples of the compound to be used together with the discotic liquid crystalline compound include a plasticizer, a surfactant, a polymerizable monomer, and a polymer. Further, the degree of change in the tilt angle can be adjusted by the same selection as described above. -114- 201211575 A plasticizer, a surfactant, a polymerizable monomer, and a polymer used together with a discotic liquid crystalline compound have compatibility with a discotic liquid crystalline compound as long as it does not cause a tilt angle of a discotic liquid crystalline compound Any kind of compound can be used to change or interfere with the alignment. Among these compounds, a polymerizable monomer (for example, a compound having a vinyl group, a vinyl hydroxy group, a propylene group and a methacryl group) is preferred. For example, paragraph numbers [0018] to [0020] disclosed in Japanese Laid-Open Patent Publication No. 2002-296423 can be cited. The compound is usually added in an amount of from 1 to 50% by mass, more preferably from 5 to 30% by mass, based on the liquid crystalline compound. The surfactant to be used together with the discotic liquid crystalline compound may, for example, be a conventional compound, and particularly preferably a fluorine-based compound. Specifically, for example, a compound disclosed in Paragraph Nos. [0028] to [0056] disclosed in Japanese Laid-Open Patent Publication No. WO01-303075, and the use of a liquid crystal compound can be used. Any one may be used as long as it has compatibility with the discotic liquid crystalline compound and does not cause a change in the tilt angle with respect to the discotic liquid crystalline compound. Examples of the polymer include cellulose esters. Preferable examples of the cellulose ester include cellulose acetate, cellulose acetate propionate, hydroxypropyl cellulose and cellulose butyl acetate. The amount of the polymer to be added is generally in the range of 0.1 to 10% by mass, more preferably in the range of 0.1 to 8% by mass, more preferably 〇, relative to the alignment of the liquid crystalline compound. .1 to 5 mass% range. In general, the optically oriented layer coats a solution in which a discotic liquid crystalline compound and other compounds are dissolved in a solvent onto an alignment film, and is dried, and then -115-201211575 is heated until a temperature of a dish-like nematic phase is formed. Then, it is obtained by maintaining the alignment state (disc nematic phase) and cooling. Alternatively, the optically oriented layer may be applied to the alignment film by a solution in which a discotic liquid crystalline compound and another compound (further, for example, a polymerizable monomer or a photopolymerization initiator) are dissolved in a solvent, and dried. Next, heating is performed until the temperature of the dish-like nematic phase is formed, and then it is polymerized (by irradiation with UV light or the like) and further cooled. The dish-like liquid crystal phase-solid phase shift temperature of the disc-like liquid crystal compound is preferably from 70 to 300 ° C, more preferably from 70 to 170 〇C. [Fixing of the alignment state of the liquid crystal compound] The aligned liquid crystal compound can be fixed by maintaining the alignment state. The immobilization is preferably carried out by a polymerization reaction. The polymerization involves photopolymerization using a thermal polymerization initiator and a photothermal polymerization initiator. It is preferably a photopolymerization reaction. Examples of the photopolymerization initiator include: an α-carbonyl compound (disclosed in each of the patent specifications of U.S. Patent No. 2,376,661, 2,367, 670), an affixed ether (a patent specification disclosed in U.S. Patent No. 2,448, Η), α-hydrocarbon Substituted aromatic auxin compounds (disclosed in U.S. Patent No. 2,722,152), polynuclear ruthenium compounds (disclosed in U.S. Patent Nos. 3,046,127, 2,951,758), triaryl imidazole dimers Combination with hydrazine-amine phenyl ketone (disclosed in the specification of U.S. Patent No. 3, 493, 473), acridine and phenazine compounds (disclosed in Japanese Patent Laid-Open Publication No. SHO 60-105667, U.S. Patent No. 4,239,850 The patent specification) and the oxadiazole compound (disclosed in the specification of U.S. Patent No. 4,221,970). -116- 201211575 The amount of the photopolymerization initiator is preferably in the range of 0.01 to 20% by mass, more preferably 0.5 to 5% by mass of the coating liquid solid content! *6 Range" For the light irradiation of the polymerization of a liquid crystal compound, it is preferred to use ultraviolet rays. The irradiation energy is preferably in the range of 20 mJ/cm 2 to 50 J/cm 2 , more preferably in the range of 20 to 5000 mJ/cm 2 , and most preferably in the range of 1 〇〇 to 800 mJ/cm 2 . Further, in order to accelerate the photopolymerization reaction, light irradiation may be carried out under heating. It is also possible to provide a protective layer on top of the optically different direction layer. The optical compensation sheet of the present invention exhibits its function significantly by being bonded to a polarizing plate or as a protective film for a polarizing plate. Next, the polarizing plate of the present invention and its manufacture will be described in detail. <Polarizing Plate> The polarizing plate of the present invention is a polarizing plate comprising a polarizing film and two transparent protective films disposed on both sides thereof, and is characterized in that the present invention is used on one side of the transparent protective film Optical compensation sheet. Here, "one side" means that the optical compensation sheet of the present invention must be used on one side, and both sides can also be constructed by using the optical compensation sheet of the present invention. [Transparent Protective Film of Polarizing Plate] In the present invention, the transparent protective film, that is, the protective film is transparent, means that the light transmittance is 80% or more. As the transparent protective film other than the optical compensation sheet of the present invention, a cellulose ester film is generally used, and a cellulose acetate film is preferably used. The cellulose acetate film is preferably formed by a solvent casting method disclosed in the description column of the transparent carrier. The thickness of the transparent protective film is preferably 20 to 200 μm, more preferably 30 to 1 000 // m. Especially ideal for 30~80 y m. According to the present invention, by using one side of the polarizing plate, the optical compensation sheet of the present invention is used, and a transparent protective film is not used between the polarizing film and the optically different direction layer, and -117-201211575 is formed as a function of the size change of the polarizing plate. A small and thin polarizing plate with stress (cross-sectional area, elastic modulus). When the polarizing plate produced by the present invention is mounted in a large-sized liquid crystal display device, there is no problem such as light leakage, and an image of high display quality is exhibited. [Surface Treatment of Optical Compensation Sheet] In order to improve the adhesion between the optical compensation sheet and the polarizing plate, it is preferable to perform surface treatment on the side surface of the polarizing film of the optical compensation sheet. The surface treatment is carried out by corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, ozone treatment, acid treatment or alkali treatment. For the treatment methods such as corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, ozone treatment, acid treatment, alkali treatment, etc., for example, it is disclosed in the technical model No. 2001-1745 ρ·30-31. content. The present invention is preferably an alkali treatment, and the same contents as those disclosed in the alkaline solution saponification treatment using the coating method of the present invention are exemplified. [Polarizing film] Generally, the polarizing film used in the present invention is preferably a coating type polarizing film made by Opt iv a Inc. or a polarizing film made of a binder and iodine or a dichroic dye. The iodine and dichroic dyes in the polarizing film are found to have a biasing property by alignment in the binder. The iodine and the dichroic dye are preferably aligned along the binder molecule or the dichroic dye is aligned in a single direction by self-organization such as liquid crystal. Now, the general commercially available polarizer (polarizing film) is obtained by immersing the stretched polymer in a solution of iodine or a dichroic dye in a bath by infiltrating the iodine or dichroic dye into the binder. Production. -118- 201211575 The commercially available polarizer system has a distribution of iodine or a dichroic dye from the polymer surface of about 4 v m (two 値 μηη). In order to obtain sufficient performance, it must have a thickness of at least 1 〇 β m. The permeability can be controlled by the solution concentration of the dichroic dye, the same bath temperature, and the same dip. As described above, the lower limit of the thickness of the adhesive is preferably from the viewpoint of light leakage of the 10/zrr crystal display device, and the thinner the upper limit of the thickness, the better the commercially available polarizing plate (about 30 // m) or less, more preferably 2 5 a is preferably 20#m or less, and the light leakage phenomenon is not observed in the liquid crystal of 17吋. As the binder of the polarizing film, any of the polymers crosslinked by the crosslinking agent for polymerization which can be crosslinked by itself can be used. The poly' can be exemplified by the same as the polymerized polyvinyl alcohol and the denatured polyvinyl alcohol disclosed by the alignment film. For denatured polyvinyl alcohol, it is disclosed in Japanese Laid-Open | 8-3 3 8 9 1 3, Ping 9- 1 52509 and Ping 9-316127, each of which can be combined with two or more kinds of polyvinyl alcohol and denatured polyvinyl alcohol. The adhesive of the polarizing film can also be crosslinked. The crosslinking agent can be crosslinked by using a crosslinkable polymer such that the polymer having a functional group or the binder to which the functional group has been introduced is changed by light, heat or pH to react with the binder. A polarizing film is formed. In addition, it is also possible to introduce a crosslinked structure into a race by using a crosslinking agent. In general, a polymer or a coating liquid containing a mixture of polymers is applied to a transparent carrier, and then about 8 polarized lights are further integrated. By iodine or staining time. Based on liquid. Preferably, it is less than m, and the device is a matter of convenience or a compound. Ϊ利第平瑕. .use. Compound. The compound is obtained between the compounds. And the cross-linking agent is heated and implemented by 119-201211575. In the final stage of the product, in order to ensure durability as much as possible, the crosslinking treatment can be carried out at any stage until the final polarizing plate is produced. The binder of the binder is preferably from 0.1 to 20% by mass based on the binder. The alignment of the polarizing element and the moist heat resistance of the polarizing film will be improved. Even after the end of the crosslinking reaction, the polarizing film contains a somewhat unreacted crosslinking agent. However, the amount of the crosslinking agent remaining in the polarizing film is preferably 1.0% by mass or less, more preferably 0.5% by mass or less. Thereby, the polarizing film is incorporated in the liquid crystal display device, and the polarization degree is not lowered even if it is used for a long period of time or in a high-temperature and high-humidity gas environment for a long period of time. For crosslinkers. For example, a patent document disclosed in U.S. Patent No. 23,297 may be used. Further, a boron compound (e.g., boric acid, borax) may be used as a crosslinking agent. As the dichroic dye, an azo dye, a stilbene dye, a pyrazoline dye, a triphenylmethane dye, a quinoline dye, an oxazine dye, a thiazine dye or an anthraquinone dye can be used. The dichroic dye is preferably water soluble. The dichroic dye preferably has a hydrophilic substituent (e.g., a sulfo group, an amine group, a hydroxyl group). Examples of the dichroic dyes include, for example, compounds disclosed in Japanese Invention Association Open Technology No. 2001-1745, page 58 (issued on March 15, 2001). In order to improve the contrast ratio of the liquid crystal display device, it is preferable that the transmittance of the polarizing plate is high. For light having a wavelength of 550 nm, the transmittance of the polarizing plate is preferably in the range of 30 to 50%, more preferably in the range of 35 to 50%, and most preferably in the range of 40 to 50%. For light having a wavelength of 550 nm, the -120-201211575 polarization is preferably in the range of 90 to 100%, more preferably in the range of 95 to 100%, and most preferably in the range of 99 to 100%. It is also possible to carry out the arrangement of the polarizing film and the optically oriented layer or the polarizing film and the alignment film by the carrier. As the subsequent agent, a polyvinyl alcohol-based resin (containing a denatured polyvinyl alcohol derived from an ethynyl group, an acid-expanding group, a residue, or a trans-group) or an aqueous solution of a boron compound can be used. More preferably, it is a polyvinyl alcohol type resin. The thickness of the adhesive layer after drying is preferably in the range of 0.01 to lo m, particularly preferably in the range of 0.05 to 5 v m. [Manufacturing of Polarizing Plate] From the viewpoint of yield, in the long-axis direction (MD direction) of the polarizing film, the polarizing film is preferably subjected to stretching (stretching) by bending the adhesive at 10 to 80 degrees, or After flat grinding (flat grinding method), dyeing is carried out using iodine or a dichroic dye. The angle of inclination is preferably stretched in conformity with the angle formed by the transmission axis of the two polarizing plates attached to both sides of the liquid crystal cell constituting the LCD in the longitudinal or lateral direction of the liquid crystal cell. The usual tilt angle is 45°. However, for transmissive, reflective, and transflective LCDs, devices having a tilt angle of not necessarily 45° have recently been developed, and the stretching direction is preferably adjusted to match the design of the LCD. In the case of the stretching method, the stretching ratio is preferably from 1 · 1 to 3 0 · 0 times, more preferably from 1.5 to 10.0 times. Stretching can be performed by dry stretching in air. Further, wet stretching in a state of being immersed in water may be carried out. The stretching ratio of the dry stretching is preferably from 1.2 to 5.0 times. The stretching ratio of the wet stretching is preferably from 3 · 0 to 10 . The stretching step may also be carried out by oblique stretching and being divided into several times. By dividing it several times, even stretching at a high magnification can be performed uniformly. It is also possible to perform a stretching in the transverse direction or in the longitudinal direction before the oblique stretching (the degree of shrinkage in the width direction is prevented). Stretching can be carried out by stretching the two-axis puller in different steps. This biaxial stretching system is the same as the general stretching method. In terms of biaxial stretching, since the thickness of the adhesive film before stretching can be made into a left casting film by stretching the left and right rows, the adhesive can be imparted by the difference in the die. The flow rate of the solution. As described above, for the MD direction of the polarizing film, a 10* obliquely stretched adhesive film was produced. In the case of the flattening method, it is possible to apply a flat grinding treatment method which has been widely used by LCD liquid crystal alignment. That is, paper or cotton rubber, nylon or polyester fiber, and the like are rubbed in a certain direction to obtain alignment. In general, it is carried out several times by using a cloth which averages the fibers with a uniform length of fibers. It is more suitable to use the roundness, the cylinder degree and the vibration of the roller itself (for a flat grinding roller of 30; zm or less). The flat grinding angle of the flat grinding roller is preferably 0.1 to 90°. However, As disclosed in Japanese Laid-Open Patent Publication No. Hei 8- 1 6043, a stable flat grinding process can be obtained by performing 360° or more. In the case of performing a flat grinding process of a long-shaped film, it is preferable to use it at a certain tension. In the state, the film is transported at a speed of 1 to 100 m/min. Since the arbitrary flat grinding angle is set, the horizontal direction of the flat grinding roller is preferably free to rotate. It is preferable to select the appropriate flat grinding angle. The speed of the fixed-width film used for the extension of the liquid crystal display device is different to the right. The left and right 580 degrees of the processing step, the selling of the wool, the surface of the film and the thickness of the film are ground and centrifuged. For the winding of the flat, use the transport to carry out the thin film 1~60° for the film, which is preferably 40 to 50° for -122-201211575. Especially ideal for 45°. Then, the transparent protective film (the optical compensation sheet / polarizing film / other protective film of the present invention, or the optical compensation sheet / polarizing film of the present invention / optical compensation sheet of the present invention) is disposed on both sides of the polarizing film. The transparent protective film may also be provided with an anti-reflection film having antifouling property and abrasion resistance on the outermost surface thereof. Any of the conventional anti-reflection films can be used. In this manner, the polarizing plate of the present invention is produced. The polarizing plate of the present invention using the optical compensation sheet of the present invention is advantageously used for a liquid crystal display device, particularly a transmissive liquid crystal display device. The transparent protective film is subjected to surface treatment in order to improve adhesion to the polarizing film. In the case where the polarizing film is polyvinyl alcohol, the protective film is preferably subjected to hydrophilization treatment. Before the protective film and the polarizing film are subsequently passed, it is preferable to perform dust removal by a water washing step, and the contact angle of water to the surface of the protective film is preferably 30 or more from the viewpoint of water droplet retention. If it is lower than 30°, the entire surface of the protective film will still be wetted by water, and it becomes very difficult to remove water. In particular, in terms of optical characteristics of the polarizing plate, it is preferable to control the contact angle of the side surface of the polarizing film of the protective film. In the fourth and fifth aspects of the present invention, one of the two protective films on the polarizing plate is an optical compensation sheet obtained by using the cellulose acetate film of the present invention. A conventional cellulose acetate film can also be used as the other protective film. The slow axis of the transparent protective film and the transmission axis of the polarizing film are arranged substantially perpendicularly or in parallel. Further, for the productivity of the polarizing plate, it is important to know the moisture permeability of the protective film. The polarizing film and the protective film are bonded together by a water-based adhesive, and the carrier solvent is dried by diffusion in a protective film. Protective film-123- 201211575 The higher the moisture permeability, the faster the drying, although the productivity is improved, but if the moisture permeability is too high, the water will penetrate due to the environment (high humidity) of the liquid crystal display device. The polarizing energy is lowered in the polarizing film. The moisture permeability of the optical compensation sheet is determined by the thickness, free volume or hydrophilicity of the polymer film (and the polymerizable liquid crystal compound). When the optical compensation sheet is used as a protective film for a polarizing plate, the optical compensation sheet preferably has a moisture permeability of from 1 Torr to 1 000 (g/cm 2 ) / 24 hrs, more preferably from 300 to 700 (g/cm 2 ). ) /24hrs range. The thickness of the optical compensation sheet can be adjusted by the slit flow rate and the production line speed in the case of producing the cellulose halide film, or by stretching and compression. Since the moisture permeability is different depending on the main material used, it is possible to achieve a better range by thickness adjustment. The free volume of the optical compensation sheet can be adjusted by the drying temperature and time of the film formation. In this case, it is also possible to make a better range by free volume adjustment because of the difference in moisture permeability due to the main material used. The hydrophilicity of the optical compensation sheet can be adjusted by additives. By adding a hydrophilic additive to the free volume, the moisture permeability becomes higher, and conversely, the moisture permeability can be lowered by the addition of the hydrophobic additive. By adjusting the moisture permeability of the optical compensation sheet, it is possible to manufacture the polarizing plate having optical compensation ability inexpensively and with high productivity. As described above, for the MD direction of the polarizing film, a 10 to 80 degree obliquely stretched adhesive film is produced. In the flattening method, it is possible to apply a flat grinding treatment method which has been widely used in the LCD liquid crystal alignment processing step. That is, using paper or cotton cloth, felt, -124-201211575 rubber or nylon, polyester fiber, etc., the surface of the film is rubbed in a certain direction to obtain alignment. In general, it is carried out by using a cloth which averages the fibers of the length and the thickness of the sentence, and performs flat grinding for several times. It is preferable to use a flat grinding roller in which the roundness, the cylinder degree, and the vibration (centrifugation) of the roller itself are 30 μm or less. The flat grinding angle of the film of the flat grinding roller is preferably 0.1 to 90°. However, as disclosed in Japanese Laid-Open Patent Publication No. Hei 8-160430, a stable flat grinding process can be obtained by performing winding of 3 60° or more. In the case of performing the flat grinding treatment of the long-shaped film, it is preferable to carry out the film transfer at a speed of l~l〇〇m/min under a certain tension by the transfer device. Since the arbitrary flat grinding angle is set, the flat grinding roller is preferably free to rotate in the horizontal direction of the film traveling direction. It is better to choose a suitable flat grinding angle in the range of 〇~60°. In the case of a liquid crystal display device, it is preferably 40 to 50°, particularly 45°. Then, the transparent protective film (the optical compensation sheet / polarizing film / other protective film of the present invention, or the optical compensation sheet / polarizing film of the present invention / optical compensation sheet of the present invention) is disposed on both sides of the polarizing film. The transparent protective film may also be provided with an anti-reflection film having antifouling property and abrasion resistance on the outermost surface thereof. Any of the conventional anti-reflection films can be used. In this manner, the polarizing plate of the present invention is produced. The polarizing plate of the present invention using the optical compensation sheet of the present invention is advantageously used for a liquid crystal display device, particularly a transmissive liquid crystal display device. Next, the liquid crystal display device of the present invention will be described in detail with respect to the transmissive liquid-125-201211575 crystal display device and its manufacture. <Liquid Crystal Display Device> The liquid crystal display device of the present invention comprises a liquid crystal cell and two polarizing plates disposed on both sides thereof, and the polarizing plate is composed of a polarizing film and two transparent protective films disposed on both sides thereof. The present invention is characterized in that at least one of the two transparent protective films disposed between the liquid crystal cell and the polarizing film uses the optical compensation sheet of the present invention. That is, the liquid crystal display device of the present invention uses the polarizing plate of the present invention as a polarizing plate. Hereinafter, preferred embodiments of the optically oriented layer of each liquid crystal mode will be described. The optical compensation sheet polarizing plate of the present invention can advantageously perform optical compensation in a preferred aspect of the optically different direction layer of each liquid crystal mode. (TN mode liquid crystal display device) The liquid crystal cell of the TN mode is used at most for a color TFT liquid crystal display device. A number of published documents can be cited. In the TN mode, the alignment state in the black liquid crystal cell is such that the rod-like liquid crystal molecules in the central portion of the liquid crystal cell are erected, and the rod-like liquid crystal molecules in the vicinity of the liquid crystal cell substrate are aligned. (OCB mode liquid crystal display device) The liquid crystal cell of the OCB mode is a liquid crystal cell in which a rod-like liquid crystal molecule is aligned in a direction in which the upper portion and the lower portion of the liquid crystal cell are substantially reversed (symmetric) to be aligned. The liquid crystal display device using the liquid crystal cell of the curved alignment mode is exemplified by the device disclosed in each of the patent specifications of U.S. Patent Nos. 4, 5, 3, 8 2, 5, 5, 4, 4,022. In order to symmetrically align the rod-like liquid crystal molecules on the upper and lower portions of the liquid crystal cell, the liquid crystal cell of the curved alignment mode -126-201211575 has a self-optical compensation function. Therefore, this liquid crystal mode is also called OCB (Optically Compensatory Bend) liquid crystal mode. The liquid crystal cell of the OCB mode is also the same as the TN mode. For displaying black, the alignment state in the liquid crystal cell is the rod-like liquid crystal property in the central portion of the liquid crystal cell. The molecules become erect, and the rod-like liquid crystal molecules in the vicinity of the liquid crystal cell substrate become the alignment state of the lie ("VA mode liquid crystal display device". In the VA mode liquid crystal cell, when there is no applied voltage, the rod-like liquid crystal molecules are substantially Vertical alignment is performed on the top. In the VA mode liquid crystal cell, (1) a narrow VA mode in which the rod-like liquid crystal molecules are substantially vertically aligned, and the voltage is substantially horizontally aligned when a voltage is applied without an applied voltage. Liquid crystal cell (disclosed in Japanese Laid-Open Patent Publication No. Hei-2-176625); (2) In order to expand the viewing angle, the VA mode is multi-domain (MVA mode) liquid crystal unit (SID97, Digest of tech. Papers ( Revealed in the pre-collection) 28 (1997) p. 845); (3) In the absence of applied voltage, the rod-like liquid crystalline molecules are substantially vertically aligned, and when the voltage is applied, the multi-domain alignment mode is distorted (n- ASM mode) liquid crystal cell (disclosed in the Japanese liquid crystal seminar pre-collection, p.58~59 (1998)); and (4) SURVAIVAL mode liquid crystal cell (published in LCD International 9 8) 〇 (other liquid crystal display Apparatus) For the liquid crystal display devices of the ECB mode and the STN mode, optical compensation can be performed using the same idea. In the liquid crystal display device of the present invention, although the liquid crystal cell is a liquid crystal cell of TN mode-127-201211575 type, VA mode, MVA mode, n-ASM mode or OCB mode, it is preferable to make the effect of the optical compensation sheet of the present invention. Play to the maximum extent. In the liquid crystal of the TN mode, when no voltage is applied, the rod-like liquid crystalline molecules are substantially horizontally aligned, and further 60 to 120 are used. Distorted alignment. Liquid crystals of the TN mode are most widely used in color TFT liquid crystal display devices, and have been disclosed in many documents. The present inventors have improved the cellulose acetate film disclosed in the specification of the European Patent No. 9 1 1 6 5 6 A 2 to maintain the conventional film thickness, or to complete the thickness without further reducing the thickness. An optical compensation sheet (fourth and fifth aspects) for optically compensating the liquid crystal cell. The Re phase difference can be obtained by adjusting the kind and amount of the additive to the cellulose acetate film (specifically, the aromatic compound having two aromatic rings) or the manufacturing conditions (for example, the stretching conditions of the film). A cellulose acetate film having a rhodium phase difference of from 70 to 40 nm and having a Rth phase difference of from 5 to 100 nm. This cellulose acetate film has optical anisotropy for performing sufficient optical compensation of the liquid crystal cell. Further, by performing surface treatment of the cellulose acetate film, an optical compensation sheet composed of a cellulose acetate film having a contact angle with water of 30° or more and 70° or less is most suitable for polarized light. Board processing. Further, the polarizing plate is composed of a polarizing film and a protective film disposed on both sides thereof. Further, the polarizing film adsorbs iodine or a dichroic dye on the polyvinyl alcohol which has been subjected to stretching and orientation. Generally, the protective film is composed of a cellulose acetate film. When the cellulose acetate film is used as a protective film on the polarizing plate side, the number of polarizing plate structural components is not increased, and the light compensation function can be added to the polarizing plate. In this case, in the present invention, since the contact angle with water on the surface of the cellulose acetate film is 30 or more, both the yield of the polarizing plate processing step and the adhesion to the polarizing film can be achieved. Further, if cellulose acetate having a degree of deuteration of less than 59.0 is used, the optical anisotropy is easily achieved, but the physical properties of the cellulose acetate film are lowered. The present invention uses cellulose acetate having a degree of enthalpy of 59.0 to 61.5%, and by using other methods (adjustment of the additive or manufacturing conditions) to achieve the phase difference 値, both optical anisotropy and physical properties can be obtained. It is a cellulose acetate film which is excellent and further excellent in adhesion to a polarizing film. The optical compensation sheet composed of the cellulose acetate film and the polarizing plate used as the protective film of the cellulose acetate film can be particularly advantageously used for OCB (Optically Compensatory Bend) type, VA (Vertically Alignment) type or TN (Twisted). Nematic type liquid crystal display device. The optical compensation sheet according to the first and second aspects of the present invention is particularly advantageous for a liquid crystal display device of the TN type or the ISP type. The optical compensation sheet according to the fourth and fifth aspects of the present invention is particularly advantageous for a VA type (including an MVA type or n-ASP type) or an OCB type liquid crystal display device. EXAMPLES (First Aspect, Second Aspect) [Example 1] (Production of Cellulose Telluride Film) The following composition was poured into a stirring tank, and heated while stirring, and the components were dissolved to prepare Cellulose acetate solution. -129- 201211575 Cellulose telluride solution composition 100 parts mass 7.8 parts mass 3.9 parts mass 2 9 5 parts mass 6 8 parts mass 2 parts mass cellulose 60.9% cellulose telluride triphenyl phosphate (plastic Benzene diphenyl phosphate (plasticizer) dichloromethane (first solvent) methanol (second solvent) 1 · butanol (third solvent) in another stirred tank, pour 16 parts by mass The following retardation improver, 80 parts by mass of methylene chloride, and 20 parts by mass of methanol were stirred while heating to prepare a phase difference improver solution. Hysteresis 値 enhancer

混合474份質量之纖維素醯化物溶液與25份質量之相位差改善劑溶液，進行充分攪拌而調製出摻雜液。相對於 100份質量之纖維素醋酸酯，相位差改善劑之添加量爲3.5 份質量。 -130- 201211575 利用轉筒流延機，進行得到的摻雜液之流延。轉筒上之膜表面溫度從40°C起，以70°C之熱風進行1分鐘乾燥，於揮發成分爲5 5 %之狀態下，將薄膜自轉筒予以剝取，之後立即以140 °C之乾燥風進行1分鐘乾燥，進一步以130°C之乾燥風進行15分鐘乾燥，製造殘留溶劑量爲0.3質量％之纖維素醯化物薄膜（厚度：80ym)。針對製得的纖維素醯化物薄膜（CAF-01)，測定光學特性。將結果顯示於表1。還有，光學特性係利用橢圓偏光計（M-150，日本分光 (股份公司）製），測定波長550nm的Re相位差値與Rth 相位差値。將製得的纖維素醯化物薄膜浸漬於2.0N之氫氧化鉀溶液（2 5 °C ) 2分鐘後，以硫酸進行中和，利用純水予以洗淨’並進行乾燥。利用接觸角法，求出此纖維素醯化物薄膜之表面能量爲63mN/m。 (配向膜之形成）於製得的纖維素醯化物薄膜上，利用# 1 6線棒式塗布機，進行下列組成塗布液之塗布，塗布量爲28ml/m2。以 6〇 °C之熱風進行60秒鐘乾燥，進一步以90 °C之熱風進行 1 5 0秒鐘乾燥。接著’與纖維素醯化物薄膜之長軸方向成平行的方向上，對形成的薄膜進行平磨處理。配向膜塗布液組成 -131 - 201211575 1 0份質量 3 7 1份質量 1 1 9份質量 0.5份質量該變性聚乙烯醇水甲醇戊二醛（交聯劑）變性聚乙烯醇一(CH2~CH)87.8— 一(CH2-CH)12.〇— OH O-CO-CH3A mixture of 474 parts by mass of the cellulose oxime solution and 25 parts by mass of the phase difference improver solution was sufficiently stirred to prepare a dope. The phase difference improver was added in an amount of 3.5 parts by mass based on 100 parts by mass of the cellulose acetate. -130- 201211575 The casting of the obtained dope was carried out using a tumble casting machine. The surface temperature of the film on the drum is from 40 ° C, dried by hot air at 70 ° C for 1 minute, and the film is stripped from the drum under the condition that the volatile component is 5 5 %, and then immediately at 140 ° C. The dry air was dried for 1 minute, and further dried in a dry air at 130 ° C for 15 minutes to produce a cellulose halide film (thickness: 80 μm) having a residual solvent amount of 0.3% by mass. The optical properties were measured for the obtained cellulose vapor film (CAF-01). The results are shown in Table 1. In addition, the optical characteristics were measured by an ellipsometer (M-150, manufactured by JASCO Corporation), and the Re phase difference 値 and Rth phase difference 波长 at a wavelength of 550 nm were measured. The obtained cellulose halide film was immersed in a 2.0 N potassium hydroxide solution (25 ° C) for 2 minutes, neutralized with sulfuric acid, washed with pure water' and dried. The surface energy of the cellulose halide film was found to be 63 mN/m by the contact angle method. (Formation of alignment film) On the obtained cellulose halide film, the following composition coating liquid was applied by a #1 6-bar bar coater at a coating amount of 28 ml/m2. It was dried by hot air at 6 ° C for 60 seconds, and further dried at 150 ° C for 150 seconds. Next, the formed film was subjected to a flat grinding treatment in a direction parallel to the long axis direction of the cellulose halide film. Orientation film coating liquid composition -131 - 201211575 1 0 parts mass 3 7 1 part mass 1 1 9 parts mass 0.5 parts mass the denatured polyvinyl alcohol water methanol glutaraldehyde (crosslinking agent) denatured polyvinyl alcohol one (CH2~CH )87.8—一(CH2-CH)12.〇—OH O-CO-CH3

一(CH2-CH)〇.2 0-COOne (CH2-CH)〇.2 0-CO

〇一(CHgh—0—CO - CH 二 CHg (光學異方向層之形成）於配向膜上，將4 1 . 0 1 g之下列碟狀液晶性化合物、4.0 6 g 之環氧乙烷變性三羥甲基丙烷三丙烯酸酯（V# 3 60，曰本大阪有機化學（股份公司）製）、〇.9〇g之纖維素醋酸丁酸醋（CAB551-0.2，Eastman Chemical 公司製）、0.23g 之纖維素醋酸丁酸酯（CAB53卜1’ EastmanChemical公司製）、 1.35g 光聚合起始劑（Irgacure-907，Ciba Geigy 公司製）、〇.45g之增感劑（KayacureDETX，日本化藥（股份公司）製）溶於l〇2g之甲基乙基酮的塗布液，利用# 3.6線棒進行塗布。於130°C之恒溫區中進行塗布液之2分鐘加熱，使碟狀液晶性化合物予以配向。接著，於60°C之氣體環境中，利用120W/cm高壓水銀燈，進行1分鐘之UV照射，使碟狀液晶性化合物得以聚合。之後，直到室溫進行冷卻。進行如此方式，形成光學異方向層而製得光學補償片 (ΚΗ-0 1 )。碟狀液晶性化合物 -132- 201211575〇一(CHgh—0—CO—CH, two CHg (formation of optically oriented layer) on the alignment film, densifying 4 1 0 1 g of the following discotic liquid crystalline compound, 4.0 6 g of ethylene oxide Hydroxymethylpropane triacrylate (V# 3 60, manufactured by Sakamoto Osaka Organic Chemical Co., Ltd.), 〇.9〇g cellulose acetate butyric acid vinegar (CAB551-0.2, manufactured by Eastman Chemical Co., Ltd.), 0.23g Cellulose acetate butyrate (CAB53 Bu 1' Eastman Chemical Co., Ltd.), 1.35 g photopolymerization initiator (Irgacure-907, manufactured by Ciba Geigy Co., Ltd.), 45.45 g sensitizer (Kayacure DETX, Nippon Chemical Co., Ltd. Company)) A coating solution of methyl ethyl ketone dissolved in 1 g 2 g was applied by a # 3.6 wire rod. The coating liquid was heated in a constant temperature zone at 130 ° C for 2 minutes to impart a discotic liquid crystalline compound. Then, in a gas atmosphere of 60 ° C, a 120 W/cm high-pressure mercury lamp was used for 1 minute of UV irradiation to polymerize the discotic liquid crystalline compound, and then cooled at room temperature. An optical compensation sheet is produced by a different direction layer (Κ Η-0 1 ). Discotic liquid crystalline compound -132- 201211575

RR

R:—O-CO—《y—〇_(QH2)4 ~ -CH=CH2 利用波長5 4 6 n m測得的光學異方向層之R e相位差値爲 43nm。另外，碟面與透明載體（纖維素醯化物薄膜）面之間的角度（傾斜角）平均爲42° ° [實施例2] (纖維素醯化物薄膜之製作）將下列組成物倒入攪拌槽中’ 一面加熱並一面攪拌，溶解各成分而調製纖維素醋酸酯溶液。纖維素醯化物溶液組成醯化度60.7%之纖維素醋酸酯 100份質量聚醚尿酯 16份質量 (B-326，日本住友Bayer尿醋（股份公司），Desmocol 176) 二氯甲烷（第1溶劑） 290份質量甲醇（第2溶劑） 7 3份質量 1-丁醇（第3溶劑） 2份質量 -133- 201211575 於另一個攪拌槽中，倒入16份質量之實施例所用之相位差改善劑、80份質量之二氯甲烷以及20份質量之甲醇， —面加熱並一面攪拌，調製相位差改善劑溶液。混合484份質量之纖維素醯化物溶液與1 5份質量之相位差改善劑溶液，進行充分攪拌而調製出摻雜液。相對於 100份質量之纖維素醋酸酯，相位差改善劑之添加量爲2.0 份質量。利用轉筒流延機，進行所得到的摻雜液之流延。轉筒上之膜表面溫度從40°C起，以65 °C之熱風進行乾燥，將殘留溶劑爲60%之薄膜自轉筒予以剝取。接著，利用定幅器，於此狀態下，一面於寬度方向進行薄膜20%之拉伸，一面利用1 3 0°C之乾燥風進行5分鐘乾燥，製得殘留溶劑量爲5 質量％。進一步於此狀態下，於長軸方向進行18%之拉伸，再於140 °C乾燥10分鐘，製得殘留溶劑量爲0.3質量％之纖維素醯化物薄膜（厚度：40 #m)。針對製得的纖維素醯化物薄膜（CAF-02 )，測定光學特性。結果顯示於表1。還有，光學特性係利用橢Μ偏光計（Μ-1 50，日本分光 (股份公司）製），測定波長5 5 0nm的Re相位差値與Rth 相位差値。相同於實施例1，於纖維素醯化物薄膜進行表面處理，形成配向膜與光學異方向層，製得光學補償片（KH-02)。 [比較例1 ] (纖維素醯化物薄膜之製作）將下列組成物倒入攪拌槽中，一面加熱並一面攪拌，溶 -134- 201211575 解各成分而調製纖維素醯化物溶液。纖維素醯化物溶液組成 1 0 0份質量 7.8份質量 3.9份質量 3 0 0份質量 5 4份質量 1 1份質量醯化度60.9%之纖維素醋酸酯三苯基磷酸酯（可塑劑）聯苯二苯基磷酸酯（可塑劑）二氯甲烷（第1溶劑）甲醇（第2溶劑） 1-丁醇（第3溶劑）直接將此纖維素醯化物溶液作成摻雜液，利用帶狀流延機進行流延。帶狀上之膜表面溫度從40°c起，以4(TC之熱風進行1分鐘乾燥，於揮發成分爲30%之狀態下，將薄膜自轉筒予以剝取。接著，利用1 00t之乾燥風進行薄膜30 分鐘之乾燥，製得殘留溶劑量爲0.9質量％之纖維素醯化物薄膜（厚度：80/zm)。針對製得的纖維素醯化物薄膜（CAF-H1 )，測定光學特性。結果顯示於表1。【表1】薄膜改善劑之量 Re Rth V m a x V m i n 實施例1 C AF-0 1 3 .5份 8 n m 8 0 n m 2.33 2.28 實施例2 CAF-02 2.5份 4 n m 9 0 n m 2.35 2.29 比較例1 CAF-H1 無 4 η m 4 8 n m 2.12 2.14 註：音速係利用日本野村商事（股份公司）製之SST-2500 -135- 201211575 型進行測定的。 [實施例4] 使碘吸附於已拉伸的聚乙烯醇薄膜而製作偏光膜，使用聚乙烯醇系接著劑，使纖維素醯化物薄膜（CAF_01)成爲偏光膜側’而將實施例1製得的光學補償片（ΚΗ-0 1 )貼付於偏光膜之單側。使偏光膜之透過軸與光學補償片（KH-01) 之遲相軸成平行而予以配置。對市售之纖維素醋酸酯薄膜（Fuji tec TD80UF，日本富士寫真Film (股份公司）製）進行者化處理，使用聚乙稀醇系接著劑而貼付於偏光膜之相反側。進行如此方式而製得偏光板。 [實施例5] 使碘吸附於已拉伸的聚乙烯醇薄膜而製作偏光膜，使用聚乙烯醇系接著劑，纖維素醯化物薄膜（CAF-02 )成爲偏光膜側，將實施例2製得的光學補償片（KH-02 )貼付於偏光膜之單側。使偏光膜之透過軸與光學補償片（KH-02 )之遲相軸成平行而予以配置。對市售之纖維素醋酸酯薄膜（Fujitec TD8 0UF，日本富士寫真Film (股份公司）製）進行皂化處理，使用聚乙烯醇系接著劑而貼付於偏光膜之相反側。進行如此方式而製得偏光板。 [比較例2 ] 使碘吸附於已拉伸的聚乙烯醇薄膜而製作偏光膜，使用聚乙烯醇系接著劑，將比較例1製得的纖維素醯化物薄膜貼付於偏光膜之單側。使偏光膜之透過軸與纖維素醯化物 -136- 201211575 薄膜（CAF-H1)之遲相軸成平行而予以配置。對市售之纖維素醋酸酯薄膜（Fujitec TD80UF，.日本富士寫真Film (股份公司）製）進行皂化處理，使用聚乙烯醇系接著劑而貼付於偏光膜之相反側。進行如此方式而製得偏光板。 [實施例7] 將裝設於使用TN型液晶單元之液晶顯示裝置（6E-A3， Sharp (股份公司）製）的一對偏光板予以剝離，替代方式係藉由黏著劑而使光學補償片（KH - 0 1 )成爲液晶單元側面，而將實施例4製得的偏光板各一片貼付於觀察者側與背光源側。使觀察者側之偏光板的透過軸與背光源側之偏光板的透過軸成爲垂直而予以配置。針對製得的液晶顯示裝置，利用測定機（EZ-Contrast 160D，ELDIM公司製），根據從顯示黑色（L1)直到顯示白色（L 8 )之8階段，測定視野角度。將結果顯示於表2。 [實施例8] 將裝設於使用TN型液晶單元之液晶顯示裝置（6E-A3， Sharp (股份公司）製）的一對偏光板予以剝離，替代方式係藉由黏著劑而使光學補償片（KH-02 )成爲液晶單元側面，而將實施例5製得的偏光板各一片貼付於觀察者側與背光源側。使觀察者側之偏光板的透過軸與背光源側之偏光板的透過軸成爲垂直而予以配置。針對製得的液晶顯示裝置，利用測定機（EZ-Contrast 160D，ELDIM公司製），根據從顯示黑色（L1)直到顯示白色（L8 )之8階段，測定視野角度。將結果顯示於表2。 -137- 201211575 [比較例3 ] 針對使用TN型液晶單兀之液晶顯示裝置（6E-A3、Sharp (股份公司）製），利用測定機（E Z - C ο n t r a s t 1 6 0 D，E L D IΜ 公司製）’根據從顯示黑色（LI)直到顯示白色（L8)之 8階段’測定視野角度。將結果顯示於表2。【表2】液晶視野角度 (對比比値爲1 0 以上且無黑色側深淡反轉的範圍）顯示裝置上上左右實施例7 70° 45° 1 60° 實施例8 75° 45° 160° 比較例3 15° 25° 37° (註）黑色側深淡反轉：L 1與L2之間的反轉。 [實施例1〇] 將裝設於使用TN型液晶單元之20吋液晶顯示裝置 (LC-20V1，Sharp (股份公司）製）的一對偏光板予以剝離，替代方式係藉由黏著劑而使光學補償片（KH-01 )成爲液晶單元側面，而將實施例4製得的偏光板各一片貼付於觀察者側與背光源側。使觀察者側之偏光板的透過軸與背光源側之偏光板的透過軸成爲垂直而予以配置。於溫度25 °C、相對濕度60%之環境條件下，進行背光源連續5小時之點亮，於暗室中，目視觀察整面黑色狀態而進行漏光之評估。其結果，於液晶顯示裝置之顯示畫面，漏光現象並未觀察到。 [實施例1 1 ] -138- 201211575 除了使用於實施例5製作的偏光板之外，進行相同於實施例10之方式而將偏光板構裝於液晶顯示裝置內。進行相同於實施例1 0之方式而進行漏光之評估。其結果’於液晶顯示裝置之顯示畫面，漏光現象並未觀察到。 [比較例4 ] 除了使用於比較例2製作的偏光板之外，進行相同於實施例10之方式而將偏光板構裝於液晶顯示裝置內》進行相同於實施例10之方式而評估漏光。其結果，於液晶顯示裝置之顯示畫面，外圍格子狀之漏光並未觀察到。 (第3態樣） [實施例12] <透明載體之製作> (微顆粒分散物（RL-1 )之調整）調製由下列組成而成的溶液，利用硏磨機，使體積平均粒徑成爲8 Onrn而進行分散，得到微顆粒分散。測定所得到的微顆粒分散物之粒度分布，粒徑5 00nm以上之顆粒爲0 % 0 於此，體積平均粒徑係利用『粒度分布測定裝置LA9 20 (曰本堀場製作所製）』而進行測定。 ♦微顆粒分散物（RL-1 )組成疏水性二氧化矽 2.0 0份質量 (商品名「AEROSIL R8 12」（甲基變性物、一次粒徑7nm : 日本AEROSIL (股份公司）））纖維素醋酸酯 2.00份質量醯化度60.7% (6 -位之取代率0.90) -139- 201211575 三苯基磷酸酯 0.1 6份質量聯苯二苯基磷酸酯 0.0 8份質量二氯甲烷 7 8.7 0份質量甲醇 1 4.2 0份質量 1-丁醇（第3溶劑） 2.8 6份質量 (纖維素醯化物溶液（A-l)之調整）將由下列組成而成的混合物予以攪拌溶解，調整纖維素醯化物溶液（A-1 )。 *纖維素醯化物溶液（A-1)組成纖維素醋酸酯 8 9.3份質量醯化度60.7% ( 6-位之取代率 0.90) 三苯基磷酸酯 7.1份質量聯苯二苯基磷酸酯 3.6份質量二氯甲烷 3 0 0份質量甲醇 54份質量 1-丁醇 1 1份質量進行下列組成之相位差調整劑溶液組成物之加熱攪拌，調製相位差調整劑溶液（RE-1 )。 *遲滯値調整劑溶液（RE-1 )組成物 2-羥基-4-苄氧基二苯甲酮 1 2份質量 2,4-苄氧基二苯甲酮 4份質量二氯甲烷 8 2.2份質量甲醇 1 4.8份質量 1-丁醇 3.0份質量 (摻雜液之調製） -140- 201211575 將15.3份質量之微顆粒分散物添加於474份質量之纖維素醯化物溶液（A-1)中，進行充分攪拌之後’再添加22 份質量之相位差調整劑溶液（RE- 1 ) ’經充分攪拌而進一步於室溫（25°C )放置3小時’然後於-70°C ’將所得到的不均勻凝膠狀溶液予以6小時冷卻之後’攪拌並加熱至5 0 °C，得到完全溶解之摻雜液。接著，於50°C，利用絕對過濾精度0.01mm之濾膜（曰本東洋濾紙（股份公司）製，# 63 )’進行所得到的摻雜液之過濾，進一步利用絕對過濾精度〇.〇〇25mm之濾膜 (Pole公司製，FH025)，進行瀘膜過濾與脫氣泡而調製摻雜液。 (溶液流延方法）如上所述，進行調製纖維素醯化物溶液之步驟，利用帶狀流延機，將所得到的摻雜液予以流延，進行從纖維素醯化物溶液製造纖維素醯化物薄膜之步驟。金屬載體（流延帶狀物）係由不銹鋼構成的，使用由寬度2m、長度5 6m (面積112m2)而成的載體。該金屬載體之算術平均粗糙度（Ra)爲0.006/zm，最大高度（Ry)爲 0.06/zm，另外，十點平均粗糙度（Rz)爲0.009ym»算術平均粗糙度（Ra)、最大高度（Ry)、十點平均粗糙度 (Rz)之各測定係遵循JIS B 060 1所規定的。被流延的摻雜液係於流延後之1秒鐘，立即以風速 0.5m/s以下進行乾燥，之後，以風速15m/s進行乾燥。乾燥風之溫度爲50°C。從流延帶狀物剝取時之薄膜的殘留溶劑量爲230質量 -141 - 201211575 % ，薄膜的溫度爲-6°C。從流延直到剝取爲止之期間的平均乾燥速度爲744質量％ /分。另外，於剝取時間點之摻雜液的凝膠化溫度約爲1 0 °C。金屬載體上之膜表面溫度從40°C起，進行1分鐘乾燥、剝取之後，將乾燥風之溫度設爲120 °C。此時之薄膜寬度方向的溫度分布爲5 °C以下，乾燥之平均風速爲5 m/s，熱傳係數爲25kcal/m2*Hr«°C，薄膜之寬度方向分布均爲5 %以內。另外，乾燥區中之針式定幅器載持部分係利用遮風裝置，使乾燥熱風不直接吹送。接著，進行將纖維素醯化物薄膜予以拉伸的步驟。亦即，殘留溶劑量爲15質量!!(；之薄膜的狀態下，於1 3 (TC之條件，利用定幅器而以25%之拉伸倍率予以橫向拉伸，於 50 °C，維持拉伸後之寬度30秒鐘之後，卸下夾子而進行卷取。從剝取直到卷取爲止之期間，已蒸發之溶劑爲初期溶劑量之97質量％。乾燥後之薄膜，進一步藉由輥輪進行搬送並予以乾燥的乾燥步驟，藉由以145 °C之乾燥熱風予以乾燥之後，進行濕度、溫度之調整而於卷取時之殘留溶劑量0.35質量％、水份量〇·8質量％下進行卷取，得到透明載體之纖維素醢化物薄膜（CA-1)(厚度65/zm)。針對所得到的纖維素醯化物薄膜（CA-1 )，測定相位差時，厚度方向之相位差Rth爲61 nm，面內之相位差Re爲 6nm ° [比較例12-1〜12-3] (比較例12-1 ) 於實施例12，對於微顆粒分散物（RL-1 )之分散，變 -142- 201211575 更分散條件而將分散物中之分散顆粒的平均粒徑調整爲 200nm之分散物。此時之分散物500nm以上之顆粒爲20 體積％。除了使用此分散物之外，進行相同於實施例12之方式，製作膜厚65//m之纖維素醯化物薄膜（CAR1-1)。 (比較例12-2 ) 於實施例12,除了設定拉伸製膜時之乾燥熱風的平均風速爲25m/分、溫度爲60°C之外，進行相同於實施例12之方式，製作膜厚65#m之纖維素醯化物薄膜（CAR1-2)。 (薄膜表面之凹凸形狀）測定所得到的纖維素醯化物薄膜 C A-1以及比較例 1 2-1~1 2-2的各試料帶狀側面的表面形狀。將其結果顯示於表1。另外，針對以下之光學特性或力學特性進行評估，將其結果合併而顯不於表3。 (光學特性之評估方法） •遲滯値利用橢圓偏光計（M-150，日本分光（股份公司）製），測定波長5 5 0nm的Re相位差値（Re55〇 )與Rth相位差値 (Rth550)。 •遲相軸偏移及標準偏差利用自動複折射計（KOBRA-21ADH，日本王子計測機器（股份公司））測定軸偏移角度。各測定係於寬度方向 1 〇點進行的，求得平均値。也針對遲相軸角度，求得標準偏差。 *霧度霧度係利用霧度計（1001DP型，日本電色工業（股份 -143- 201211575 公司）製）進行測定。每一片薄膜試料，測定5點而取其平均値。 (力學特性之評估方法） «卷曲卷曲値能夠遵循美國國家規格協會所規定的測定方法 (ANSI/ASCPH1.29-1985’方法-A)而進行測定。將聚合物薄膜切成寬度方向35mm、長軸方向2mm大小之後，放置於卷曲板上。將其於溫度25t、相對濕度65%之環境下，進行1小時之調濕後，讀取卷曲値。然後，同樣地將聚合物薄膜切成寬度方向2mm、長軸方向35mm大小之後，放置於卷曲板上。將其於溫度2 5 °C、相對濕度65%之環境下，進行1小時之調濕後，讀取卷曲値。於寬度方向之長軸方向的二方向進行測定，將二者之中的較大値設爲卷曲値。卷曲値表示曲率半徑（m )之倒數。 *撕裂強度將薄膜切成寬度65mmx長度50 mm而製成試料。將此試料於溫度3 0 °C、相對濕度85 %之室內’進行2小時以上之調濕，遵循IS06383/2-1983之規格’利用日本東洋精機製造所製之輕載重撕裂強度測試器，求得撕裂所需之載重 (g ) 0 -144- 201211575 【表3】纖維素面狀 Ra( β Rz( β Ra/Rz RyC β Sm( β Re/Rth 遲相軸偏標準霧卷曲/m 撕裂醯化物 m) m) 比 m) m) (nm) 移角度偏差度強度薄膜 (°) (。） (g) 實施例12 CA-1 〇 0.005 0.014 0.367 0.022 0.150 6/61 0.5 0.3 0.2 -2 12 比較例12-1 CAR1-1 〇 0.008 0.085 0.094 0.555 0.300 7/63 0.6 1.8 1.3 -1 10 比較例12-2 CAR1-2 X ( 平面性不佳） 6/61 偏異大 0.3 平面性 4-11 不佳如該表3所示，實施例12之纖維素醯化物薄膜（CA-1) 係面狀良好的，表面形狀係表3所示之値，凹凸形狀一致。另外，相位差値、遲相軸角度偏移、標準偏差、霧度値之光學特性以及卷曲、撕裂強度之力學特性均爲良好。另一方面，比較例12-1顯示表面凹凸形狀之偏異，霧度値變大。比較例12-2之面狀與平面性顯著降低》如上所述，於膜厚65 /zm之薄膜中，含有不具5 0 Onm 以上之顆粒的超微顆粒分散物，可以得到不僅抑制霧度變大，並且保持力學特性之光學補償片用的透明載體。 (比較例1 2 - 3 ) 於實施例1 2，使用定幅器之拉伸維持條件，將殘留溶劑量爲1 5質量％之薄膜，於1 3 0°C之條件下，利用定幅器而以2 5%之拉伸倍率進行橫向拉伸，除了於130°C、維持拉伸後之寬度1 5秒鐘之外，進行相同於實施例1 2之方式，製得膜厚65 v m之纖維素醯化物薄膜（CAR1-3 )。相同於實施例12與比較例12-1 ~ 12-2之方式，測定所得到的薄膜表面之凹凸形狀、光學特性與力學特性》比較例 -145- 201211575 12-3之遲相軸角度偏移增大至3.5。另外’表面形狀、遲相軸角度偏移、標準偏差、霧度均降低。 (鹼的皂化處理）於該表3之各薄膜與比較例12-3之薄膜試料的單面，進行以下之鹼的皂化處理。亦即，於薄膜之上，使溫度60°C之介電式加熱輥輪通過，薄膜表面升溫至40t之後，利用桿式塗布機，以塗布量12ml/m2進行下列所示之組成的鹼性溶液（S-1 )的塗布，於加熱至 U〇°C之NORITAKE (股份）有限公司製之蒸氣式遠紅外線加熱器之下，停留1 0秒鐘。接著，同樣利用桿式塗布機，以4m 1/m2之塗布量進行純水之塗布。此時之薄膜溫度爲40 °C。接著，重複三次進行利用水源塗布機之水洗與利用氣動刮塗機之去除水，之後，於70 °C之乾燥區內停留5秒鐘後使其乾燥。 *鹼性溶液（S-1 )組成氫氧化鉀 8.6份質量水 24.1份質量異丙醇 5 6.3份質量界面活性劑 1 . 0份質量 (K-1 ： c14h29o ( CH2CH2〇) 20h) 甘油 1 0 · 0份質量消泡劑 SURFYNOL DF110D 0.010 份質量 (商品名，日本日信化學工業（股份公司）製） (親水化表面處理後之薄膜特性）針對作成的各薄膜’進行以下之測試，確認鹼性處理之 -146 - 201211575 效果。將其結果顯示於表4。 (與水之接觸角）利用接觸角計（日本協和界面科學（股份公司製），CA_x 型接觸角計）’於乾燥狀態下（201 /65% RH)，液體使用純水’於針尖作成直徑1.0mm之液滴，使其接觸於薄膜表面而作成液滴。對於固體-液體接觸點之液體表面的切線與固體表面所形成的角度’將包含液體之角度定義爲接觸角。針對各薄膜，每一平方公尺之面內，測定兩側與中央之 9處接觸角，記錄上限値與下限値。但是，± Γ之範圍係測定上的誤差範圍，顯示其中央値。 (表面之面狀；污染物、濁度）由皂化處理之薄膜，於長軸方向以全部寬度切成lm之長度，置於？投射板？上，一面使光透過此試料，並一面目視，同時利用放大鏡觀察污染物與濁度之有無，根據以下之基準進行評估。〇：確認完全無污染物與濁度之發生（10人進行評估，無一人察覺之水準） A :確認稍有污染物與濁度之發生（1〇人進行評估，2~5 人察覺之水準） X :確認強烈污染物與濁度之發生（1 〇人進行評估，6 人以上察覺之水準） -147- 201211575R: -O-CO - "y-〇_(QH2)4 ~ -CH=CH2 The R e phase difference 値 of the optically different direction layer measured by the wavelength of 5 4 6 n m is 43 nm. Further, the angle (inclination angle) between the dish surface and the surface of the transparent carrier (cellulose oxime film) was 42 ° on average [Example 2] (Production of cellulose oxime film) The following composition was poured into a stirring tank. Medium's one side heated and stirred while stirring to dissolve the ingredients to prepare a cellulose acetate solution. Cellulose Telluride Solution Composition 60.7% Cellulose Acetate 100 Parts Quality Polyether Urethane 16 Parts Quality (B-326, Sumitomo Bayer Uric Vinegar (Join Company), Desmocol 176) Dichloromethane (1st) Solvent) 290 parts by mass of methanol (second solvent) 7 3 parts by mass of 1-butanol (third solvent) 2 parts by mass - 133 - 201211575 In another stirred tank, pour 16 parts by mass for the phase difference used in the examples A improver, 80 parts by mass of methylene chloride, and 20 parts by mass of methanol were mixed while stirring to prepare a phase difference improver solution. A solution of 484 parts by mass of the cellulose oxime solution and 15 parts by mass of the phase difference improver solution were mixed and sufficiently stirred to prepare a dope solution. The phase difference improving agent was added in an amount of 2.0 parts by mass based on 100 parts by mass of the cellulose acetate. The casting of the obtained dope was carried out using a tumble casting machine. The surface temperature of the film on the drum was from 40 ° C, dried by hot air at 65 ° C, and the film with a residual solvent of 60% was stripped from the drum. Then, in the state in which the film was stretched by 20% in the width direction, the film was dried by drying air at 130 ° C for 5 minutes to obtain a residual solvent amount of 5% by mass. Further, in this state, 18% of the film was stretched in the long axis direction, and further dried at 140 °C for 10 minutes to obtain a cellulose halide film (thickness: 40 #m) having a residual solvent amount of 0.3% by mass. The optical properties were measured for the obtained cellulose halide film (CAF-02). The results are shown in Table 1. In addition, the optical characteristics were measured by an ellipsometer (Μ-1 50, manufactured by JASCO Corporation), and the Re phase difference 値 and Rth phase difference 波长 at a wavelength of 550 nm were measured. In the same manner as in Example 1, the cellulose halide film was surface-treated to form an alignment film and an optically different direction layer to prepare an optical compensation sheet (KH-02). [Comparative Example 1] (Production of Cellulose Telluride Film) The following composition was poured into a stirring tank, and while heating and stirring, the components were dissolved to prepare a cellulose halide solution. Cellulose telluride solution composition 100 parts mass 7.8 parts mass 3.9 parts mass 300 parts mass 5 4 parts mass 1 1 part cellulose acetate triphenyl phosphate (plasticizer) Phenyl diphenyl phosphate (plasticizer) Dichloromethane (first solvent) Methanol (second solvent) 1-butanol (third solvent) Directly use this cellulose halide solution as a doping solution, using a ribbon flow Extend the machine for casting. The surface temperature of the film on the strip was from 40 ° C, and dried by hot air for 4 minutes in TC. The film was stripped from the drum with a volatile component of 30%. Then, a dry wind of 100 t was used. The film was dried for 30 minutes to obtain a cellulose oxime film (thickness: 80/zm) having a residual solvent amount of 0.9% by mass. Optical properties were measured for the obtained cellulose oxime film (CAF-H1). Shown in Table 1. [Table 1] Amount of film improving agent Re Rth V max V min Example 1 C AF-0 1 3 .5 parts 8 nm 8 0 nm 2.33 2.28 Example 2 CAF-02 2.5 parts 4 nm 9 0 nm 2.35 2.29 Comparative Example 1 CAF-H1 No 4 η m 4 8 nm 2.12 2.14 Note: The sonic speed is measured by SST-2500-135-201211575 type manufactured by Nomura Corporation of Japan. [Example 4] An optical compensation sheet obtained in Example 1 was prepared by adsorbing iodine on a stretched polyvinyl alcohol film to prepare a polarizing film, and using a polyvinyl alcohol-based adhesive to form a cellulose vapor film (CAF_01) on the polarizing film side. (ΚΗ-0 1 ) is attached to one side of the polarizing film to make the transmission axis of the polarizing film The retardation axis of the optical compensation sheet (KH-01) is arranged in parallel. The commercially available cellulose acetate film (Fuji tec TD80UF, manufactured by Fujifilm Japan Film Co., Ltd.) is used for the treatment. A polarizing-based adhesive was attached to the opposite side of the polarizing film. A polarizing plate was obtained in this manner. [Example 5] A iodine was adsorbed on a stretched polyvinyl alcohol film to prepare a polarizing film, and a polyvinyl alcohol-based film was used. Then, the cellulose oxime film (CAF-02) became the polarizing film side, and the optical compensation sheet (KH-02) obtained in Example 2 was attached to one side of the polarizing film. The transmission axis of the polarizing film was optically compensated. The late phase axes of the sheets (KH-02) are arranged in parallel. The commercially available cellulose acetate film (Fujitec TD8 0UF, manufactured by Fujifilm Japan Film Co., Ltd.) is saponified, and polyvinyl alcohol is used. The agent was attached to the opposite side of the polarizing film. A polarizing plate was obtained in this manner. [Comparative Example 2] A iodine was adsorbed on the stretched polyvinyl alcohol film to prepare a polarizing film, and a polyvinyl alcohol-based adhesive was used. Comparative example 1 The obtained cellulose halide film is attached to one side of the polarizing film, and the transmission axis of the polarizing film is arranged in parallel with the late phase axis of the cellulose halide-136-201211575 film (CAF-H1). A cellulose acetate film (Fujitec TD80UF, manufactured by Fujifilm Japan Film Co., Ltd.) was subjected to a saponification treatment, and was attached to the opposite side of the polarizing film using a polyvinyl alcohol-based adhesive. The polarizing plate was produced in this manner. [Example 7] A pair of polarizing plates mounted on a liquid crystal display device (6E-A3, manufactured by Sharp Co., Ltd.) using a TN liquid crystal cell was peeled off, and an optical compensation sheet was replaced by an adhesive. (KH - 0 1 ) became the side surface of the liquid crystal cell, and each of the polarizing plates prepared in Example 4 was attached to the viewer side and the backlight side. The transmission axis of the polarizing plate on the observer side is arranged perpendicular to the transmission axis of the polarizing plate on the backlight side. With respect to the obtained liquid crystal display device, the viewing angle was measured in accordance with eight stages from the display of black (L1) to the display of white (L8) by a measuring machine (EZ-Contrast 160D, manufactured by ELDIM Co., Ltd.). The results are shown in Table 2. [Example 8] A pair of polarizing plates mounted on a liquid crystal display device (6E-A3, manufactured by Sharp Co., Ltd.) using a TN liquid crystal cell were peeled off, and an optical compensation sheet was replaced by an adhesive. (KH-02) became the side surface of the liquid crystal cell, and each of the polarizing plates prepared in Example 5 was attached to the viewer side and the backlight side. The transmission axis of the polarizing plate on the observer side is arranged perpendicular to the transmission axis of the polarizing plate on the backlight side. With respect to the obtained liquid crystal display device, the viewing angle was measured in accordance with eight stages from the display of black (L1) to the display of white (L8) by a measuring machine (EZ-Contrast 160D, manufactured by ELDIM Co., Ltd.). The results are shown in Table 2. -137-201211575 [Comparative Example 3] A liquid crystal display device (6E-A3, manufactured by Sharp Co., Ltd.) using a TN liquid crystal cell, using a measuring machine (EZ-C ο ntrast 1 6 0 D, ELD IΜ The system view 'measures the viewing angle according to the 8 stages from the display of black (LI) until the display of white (L8). The results are shown in Table 2. [Table 2] LCD viewing angle (comparison ratio 値 is 10 or more and no black side darkening inversion range) Display device upper and lower embodiment 7 70° 45° 1 60° Example 8 75° 45° 160° Comparative Example 3 15° 25° 37° (Note) Black side dark reversal: Inversion between L 1 and L2. [Example 1] A pair of polarizing plates mounted on a 20-inch liquid crystal display device (LC-20V1, manufactured by Sharp Co., Ltd.) using a TN liquid crystal cell were peeled off, and an alternative was made by an adhesive. The optical compensation sheet (KH-01) was placed on the side of the liquid crystal cell, and each of the polarizing plates obtained in Example 4 was attached to the viewer side and the backlight side. The transmission axis of the polarizer on the observer side is arranged perpendicular to the transmission axis of the polarizing plate on the back light source side. The backlight was lit for 5 hours under ambient conditions of a temperature of 25 ° C and a relative humidity of 60%. In the dark room, the black state of the entire surface was visually observed to evaluate the light leakage. As a result, the light leakage phenomenon was not observed on the display screen of the liquid crystal display device. [Example 1 1] -138 - 201211575 A polarizing plate was incorporated in a liquid crystal display device in the same manner as in Example 10 except that the polarizing plate produced in Example 5 was used. Evaluation of light leakage was performed in the same manner as in Example 10. As a result, the light leakage phenomenon was not observed on the display screen of the liquid crystal display device. [Comparative Example 4] Except that the polarizing plate produced in Comparative Example 2 was used, the polarizing plate was incorporated in the liquid crystal display device in the same manner as in Example 10, and the light leakage was evaluated in the same manner as in Example 10. As a result, in the display screen of the liquid crystal display device, the leakage light in the outer grid shape was not observed. (Third aspect) [Example 12] <Preparation of transparent carrier> (Adjustment of fine particle dispersion (RL-1)) A solution composed of the following composition was prepared, and a volume average particle was obtained by a honing machine. The diameter became 8 Onrn and dispersion was carried out to obtain dispersion of fine particles. The particle size distribution of the obtained fine particle dispersion was measured, and the particle diameter of 500 nm or more was 0%. Here, the volume average particle diameter was measured by "particle size distribution measuring apparatus LA9 20 (manufactured by Sakamoto Seisakusho Co., Ltd.)" . ♦ Microparticle dispersion (RL-1) consists of hydrophobic cerium oxide 2.00 parts by mass (trade name “AEROSIL R8 12” (methyl denature, primary particle size 7nm: Japan AEROSIL (stock company))) Cellulose acetate Ester 2.00 parts mass degree of chemical conversion 60.7% (6-position substitution rate 0.90) -139- 201211575 Triphenyl phosphate 0.16 parts by mass of biphenyl diphenyl phosphate 0.0 8 parts by mass of dichloromethane 7 8.7 0 parts by mass Methanol 1 4.2 parts by mass 1-butanol (third solvent) 2.8 6 parts by mass (adjustment of cellulose oxime solution (Al)) The mixture of the following composition was stirred and dissolved to adjust the cellulose oxime solution (A -1 ). * Cellulose oxime solution (A-1) consists of cellulose acetate 8 9.3 parts mass degree 60.7% (6-position substitution rate 0.90) triphenyl phosphate 7.1 parts mass biphenyl diphenyl phosphate 3.6 Part by mass of dichloromethane, 300 parts by mass of methanol, 54 parts by mass of 1-butanol, 1 part by mass, and the phase difference adjuster solution composition of the following composition was heated and stirred to prepare a phase difference adjuster solution (RE-1). * Hysteresis 値 adjuster solution (RE-1) composition 2-hydroxy-4-benzyloxybenzophenone 1 2 parts mass 2,4-benzyloxybenzophenone 4 parts mass dichloromethane 8 2.2 parts Mass methanol 1 4.8 parts by mass 1-butanol 3.0 parts by mass (modulation of doping solution) -140- 201211575 Adding 15.3 parts by mass of the fine particle dispersion to 474 parts by mass of cellulose oxime solution (A-1) After thorough stirring, 'addition of 22 parts of phase difference adjuster solution (RE-1)' is further stirred at room temperature (25 ° C for 3 hours) and then at -70 ° C. The uneven gelatinous solution was allowed to cool for 6 hours, 'stirred and heated to 50 ° C to obtain a completely dissolved dope. Then, at 50 ° C, the obtained dope was filtered using a filter having an absolute filtration accuracy of 0.01 mm (manufactured by Sakamoto Toyo Filter Paper Co., Ltd., #63 ), and the absolute filtration accuracy was further utilized. A 25 mm filter (FH025, manufactured by Pole Co., Ltd.) was subjected to membrane filtration and degassing to prepare a doping solution. (Solution Casting Method) As described above, a step of preparing a cellulose halide solution is carried out, and the obtained dope is cast by a ribbon casting machine to produce a cellulose telluride from a cellulose telluride solution. The step of the film. The metal carrier (casting ribbon) was made of stainless steel, and a carrier having a width of 2 m and a length of 6 6 m (area of 112 m2) was used. The metal carrier has an arithmetic mean roughness (Ra) of 0.006/zm, a maximum height (Ry) of 0.06/zm, and a ten point average roughness (Rz) of 0.009 ym»arithmetic mean roughness (Ra), maximum height. Each measurement of (Ry) and ten-point average roughness (Rz) is as specified in JIS B 060 1. The cast dope was dried for 1 second after the casting, and immediately dried at a wind speed of 0.5 m/s or less, and then dried at a wind speed of 15 m/s. The temperature of the dry wind is 50 °C. The residual solvent amount of the film when peeled from the cast ribbon was 230 mass -141 - 201211575 %, and the film temperature was -6 °C. The average drying speed during the period from casting to stripping was 744 mass% /min. Further, the gelation temperature of the dope at the stripping time is about 10 °C. The surface temperature of the film on the metal carrier was dried from 40 ° C, and after drying for 1 minute, the temperature of the dry air was set to 120 ° C. At this time, the temperature distribution in the film width direction is 5 ° C or less, the average wind speed in drying is 5 m / s, the heat transfer coefficient is 25 kcal / m 2 * Hr « ° C, and the width distribution of the film is within 5%. In addition, the needle-type stylus carrying portion in the drying zone utilizes a windshield device so that dry hot air is not directly blown. Next, a step of stretching the cellulose halide film is carried out. That is, the amount of residual solvent is 15 mass%!! (In the state of the film, in the condition of TC, it is transversely stretched at a stretching ratio of 25% by a fixer at a stretching ratio of 25%, and maintained at 50 °C. After the width after stretching for 30 seconds, the clip was removed and wound up. The solvent evaporated from the stripping until the coiling was 97% by mass of the initial solvent amount. The dried film was further passed through a roll. The drying step of carrying and drying the wheel is dried by drying hot air at 145 ° C, and then the humidity and temperature are adjusted, and the amount of residual solvent at the time of coiling is 0.35 mass %, and the amount of water is 〇 8 mass %. The film was taken up to obtain a cellulose halide film (CA-1) (thickness: 65/zm) of a transparent carrier. For the obtained cellulose vapor film (CA-1), the phase difference in the thickness direction was measured when the phase difference was measured. Rth was 61 nm, and the in-plane phase difference Re was 6 nm [Comparative Example 12-1 to 12-3] (Comparative Example 12-1) In Example 12, for dispersion of the fine particle dispersion (RL-1), Change-142- 201211575 to adjust the average particle size of the dispersed particles in the dispersion under more dispersed conditions A dispersion of 200 nm. At this time, the particles having a dispersion of 500 nm or more were 20% by volume. A cellulose oxime film having a film thickness of 65/m was produced in the same manner as in Example 12 except that this dispersion was used. CAR1-1) (Comparative Example 12-2) In Example 12, except that the average wind speed of the dry hot air at the time of setting the stretch film formation was 25 m/min, and the temperature was 60 ° C, the same procedure as in Example 12 was carried out. In the manner, a cellulose oxime film (CAR1-2) having a film thickness of 65 #m was produced. (Concavo-convex shape on the surface of the film) The obtained cellulose oxime film C A-1 and Comparative Example 1 2-1 to 1 2 were measured. The surface shape of the strip side surface of each sample of -2 is shown in Table 1. The following optical characteristics or mechanical properties were evaluated, and the results were combined and shown in Table 3. (Evaluation method of optical characteristics) • Hysteresis 値 An ellipsometer (M-150, manufactured by JASCO Corporation) was used to measure the Re phase difference Re (Re55〇) and the Rth phase difference R (Rth 550) at a wavelength of 550 nm. • Delayed phase deviation Shift and standard deviation using automatic birefringence meter (KOBRA-21ADH, Prince of Japan The measuring machine (share company) measures the axis shift angle. Each measurement is performed at 1 宽度 in the width direction, and the average 値 is obtained. The standard deviation is also obtained for the slow phase axis angle. * Haze haze is fog. The meter (Model 1001DP, manufactured by Nippon Denshoku Industries Co., Ltd., pp. 143-201211575) was used for each film sample. The average enthalpy was measured at 5 points. (Evaluation method for mechanical properties) «Curled 値 can follow The measurement was performed by the measurement method specified by the National Institute of Standards (ANSI/ASCPH 1.29-1985 'Method-A). The polymer film was cut into a width of 35 mm and a length of 2 mm in the longitudinal direction, and then placed on a crimping plate. This was immersed in an environment of a temperature of 25 t and a relative humidity of 65% for 1 hour, and then the crimp enthalpy was read. Then, the polymer film was cut into a width direction of 2 mm and a long axis direction of 35 mm in the same manner, and then placed on a crimping plate. The mixture was conditioned at a temperature of 25 ° C and a relative humidity of 65% for 1 hour, and then the crimp enthalpy was read. The measurement was performed in two directions in the longitudinal direction of the width direction, and the larger of the two was set as the curl 値. Curl 値 represents the reciprocal of the radius of curvature (m). *Tear strength The film was cut into a width of 65 mm x a length of 50 mm to prepare a sample. The sample was conditioned at a temperature of 30 ° C and a relative humidity of 85% for 2 hours or more, and the light weight heavy tear strength tester manufactured by Toyo Seiki Co., Ltd. was used in accordance with the specifications of IS06383/2-1983. Load required to obtain tear (g) 0 -144- 201211575 [Table 3] Cellulose surface Ra (β Rz ( β Ra / Rz RyC β Sm ( β Re / Rth retardation axis deviation standard fog curl / m tear Splitting m) m) ratio m) m) (nm) shifting angular deviation intensity film (°) (.) (g) Example 12 CA-1 〇0.005 0.014 0.367 0.022 0.150 6/61 0.5 0.3 0.2 -2 12 Comparative Example 12-1 CAR1-1 〇0.008 0.085 0.094 0.555 0.300 7/63 0.6 1.8 1.3 -1 10 Comparative Example 12-2 CAR1-2 X (poor planarity) 6/61 Large deviation 0.3 Flatness 4- 11 is not preferable. As shown in Table 3, the cellulose halide film (CA-1) of Example 12 has a good surface shape, and the surface shape is as shown in Table 3, and the uneven shape is uniform. In addition, the phase difference 値, the retardation of the retardation axis, the standard deviation, the optical characteristics of the haze, and the mechanical properties of the crimp and tear strength were good. On the other hand, Comparative Example 12-1 showed a deviation in the surface unevenness shape, and the haze was large. Comparative Example 12-2, the planarity and planarity were significantly lowered. As described above, in the film having a film thickness of 65 /zm, the ultrafine particle dispersion containing no particles of 50 Onm or more can be obtained not only to suppress haze change. A transparent carrier for optical compensation sheets that is large and maintains mechanical properties. (Comparative Example 1 2 - 3 ) In Example 12, using a stretching condition of a stopperer, a film having a residual solvent amount of 15% by mass was used, and at a temperature of 130 ° C, a stopper was used. The transverse stretching was carried out at a draw ratio of 25%, and the film was 65 mm in the same manner as in Example 12 except that the width after stretching was maintained at 130 ° C for 15 seconds. Cellulose halide film (CAR1-3). The uneven shape, optical characteristics and mechanical properties of the obtained film surface were measured in the same manner as in Example 12 and Comparative Examples 12-1 to 12-2. The retardation axis angular shift of Comparative Example -145-201211575 12-3 Increase to 3.5. In addition, the surface shape, the retardation angle shift, the standard deviation, and the haze are all lowered. (Saponification of alkali) The saponification treatment of the following base was carried out on each of the film of Table 3 and the film sample of Comparative Example 12-3. That is, on the film, a dielectric heating roller having a temperature of 60 ° C was passed, and the surface of the film was heated to 40 t, and then an alkalinity of the composition shown below was carried out by a bar coater at a coating amount of 12 ml/m 2 . The solution (S-1) was applied to a vapor-type far-infrared heater manufactured by NORITAKE Co., Ltd. heated to U 〇 ° C for 10 seconds. Next, the coating of pure water was carried out in the same manner using a bar coater at a coating amount of 4 m 1 /m 2 . The film temperature at this time was 40 °C. Next, water washing by a water source coater and water removal by a pneumatic blade coater were repeated three times, and then left in a drying zone of 70 ° C for 5 seconds and then dried. *Alkaline solution (S-1) Composition Potassium hydroxide 8.6 parts by mass Water 24.1 parts by mass of isopropanol 5 6.3 parts by mass of surfactant 1. 0 parts by mass (K-1: c14h29o (CH2CH2〇) 20h) Glycerin 1 0 · 0 parts of quality defoamer SURFYNOL DF110D 0.010 parts by mass (product name, manufactured by Nippon Shine Chemical Co., Ltd.) (film properties after hydrophilization surface treatment) The following tests were performed on each of the prepared films to confirm the alkali Sexual treatment -146 - 201211575 effect. The results are shown in Table 4. (contact angle with water) Using a contact angle meter (Japan Concord Interface Science Co., Ltd., CA_x contact angle meter) 'In a dry state (201 /65% RH), the liquid is made of pure water' at the tip of the needle. A droplet of 1.0 mm was brought into contact with the surface of the film to form droplets. The angle formed by the tangent to the solid surface of the liquid surface of the solid-liquid contact point is defined as the contact angle. For each film, the contact angle between the two sides and the center was measured in the plane of each square meter, and the upper limit 値 and the lower limit 记录 were recorded. However, the range of ± Γ is the error range on the measurement, showing the center 値. (Surface of the surface; contaminant, turbidity) The saponified film is cut into a length of lm in the long axis direction and placed at a length of lm. Projection board? On the other hand, light was transmitted through the sample and visually observed while using a magnifying glass to observe the presence or absence of contaminants and turbidity, and the evaluation was performed based on the following criteria. 〇: Confirm that there is no pollution and turbidity at all (10 people are assessed, no one is aware of the level) A: Confirm the occurrence of slight pollutants and turbidity (1 person evaluates, 2 to 5 people detect the level) X: Confirm the occurrence of strong pollutants and turbidity (1 〇 person to assess, the level of detection of more than 6 people) -147- 201211575

【表4】試料No. 纖維素醯化物薄膜與水之接觸角η 處理後之面狀性實施例12 FS-1 CA-1 34 〇比較例：12-1 FSR1-1 CAR1-1 33 〜45 Δ 比較例12-2 FSR1-2 CAR1-2 33 〜44 X 比較例12-3 FSR1-3 CAR1-3 33-43 X 如表4所示，於實施例1之光學補償片（F S -1 )與每平方公尺表面之水的接觸角爲34°，並無面內之偏異而爲均勻的處理。確認面狀與薄膜整面完全無污染物與濁度之發生。表面凹凸爲大的形狀之比較例l(FSRl-l)，與每平方公尺表面內之水的接觸角之偏異增大，成爲35至43 °。另外，面狀也惡化，尤其見到許多污染物。另外，比較例 (FSR1-2、FSR1-3)之皂化處理並非均勻的，與水的接觸角之偏異明顯。如上所述，證明實施例1 2之本發明光學補償片的透明載體係均勻地將面內予以親水化而成的。 (配向膜之形成）於進行此親水化表面處理而得到的各透明載體上，利用桿式塗布機，以28ml/m2之塗布量，進行下列組成之配向膜塗布液（0-1 )之塗布。以60°C之熱風進行60秒鐘乾燥，進一步以90°C之熱風進行150秒鐘乾燥。測定乾燥後之塗布面的pH値，其値爲4.0。另外，於塗布寬度方向之中央與左右兩側位置之pH値爲3.95~·4.10之範圍。接著，於已進行親水化表面處理之各薄膜長軸方向，進 -148- 201211575 行平磨處理。 *配向膜塗布液（0-1 )組成以下式69所示之變性聚乙烯醇檸檬酸戊二醛水甲醇變性聚乙烯醇 20份質量 0 · 0 6份質量 0.5份質量 3 6 0份質量 1 2 0份質量 Ί2.0[Table 4] Sample No. Cellular oxime film contact angle with water η Surface property after treatment Example 12 FS-1 CA-1 34 〇 Comparative Example: 12-1 FSR1-1 CAR1-1 33 ～45 Δ Comparative Example 12-2 FSR1-2 CAR1-2 33 to 44 X Comparative Example 12-3 FSR1-3 CAR1-3 33-43 X As shown in Table 4, the optical compensation sheet (FS-1) of Example 1 The contact angle with the water per square meter of surface is 34°, and there is no in-plane deviation and uniform treatment. Confirm that the surface and the entire surface of the film are completely free of contaminants and turbidity. In Comparative Example 1 (FSRl-1) in which the surface unevenness is large, the deviation from the contact angle with water in the surface of each square meter is increased to 35 to 43 °. In addition, the surface is also deteriorated, especially in the case of many pollutants. Further, the saponification treatment of the comparative examples (FSR1-2, FSR1-3) was not uniform, and the difference in contact angle with water was remarkable. As described above, it was confirmed that the transparent carrier of the optical compensation sheet of the present invention of Example 12 was uniformly hydrophilized in-plane. (Formation of alignment film) On each of the transparent supports obtained by the hydrophilization treatment, the coating film of the alignment film (0-1) having the following composition was applied by a bar coater at a coating amount of 28 ml/m2. . It was dried by hot air at 60 ° C for 60 seconds, and further dried by hot air at 90 ° C for 150 seconds. The pH of the coated surface after drying was measured, and the enthalpy was 4.0. Further, the pH 位置 at the center and the left and right sides in the width direction of the coating is in the range of 3.95 to 4.10. Next, in the long-axis direction of each film which has been subjected to the hydrophilization surface treatment, the flat grinding treatment was carried out in -148 - 201211575. *Orientation film coating liquid (0-1) consists of denatured polyvinyl alcohol citrate glutaraldehyde water methanol modified methanol as shown in the following formula 69 20 parts mass 0 · 0 6 parts mass 0.5 parts mass 3 60 parts mass 1 20 copies of quality Ί 2.0

OHOH

0=C 〇c〇ch3 〇(CH2)4OCOCH=CH2 (平均聚合度：4000 ) 然後，針對所得到的配向膜之已形成的透明載體，進行如下之配向膜的密著性測試。將其結果顯示於表3。 (配向膜之密著性的評估法）遵照JIS K-5400之棋盤格膠布法，利用製式之切刀、切刀導桿，於配向膜層表面，置入100個lmmxlmm之方格，於溫度25 °C、相對濕度60%之條件下放置2小時後，貼上製式之玻璃紙膠帶，再用橡皮擦磨擦而附著於塗膜上。附著膠帶2分鐘之後，垂直於塗布面之垂直方向將剝離膠帶予以剝離，藉由計算配向膜從透明載體所剝落的格子數目而進行評估。 ◎:確認全部1 00格完全無剝落〇：確認100格中，2格以內已剝落 -149- 201211575 △:確認100格中，1〇~3格已剝落 X :確認1 0 0格中，超過1 0格已剝落 (光學異方向層之形成）接著，針對已形成配向膜之透明載體，進行以下之方式，形成光學異方向層而得到光學補償片。亦即，利用# 4之線棒式塗布機，於配向膜上進行下列組成之碟狀液晶塗布液（DA-1 )之塗布，再於125°C之高溫槽中進行3分鐘加熱，使碟狀液晶配向之後，使用高壓水銀燈，進行U V之5 0 0 m J / c m 2之照射，直到室溫進行冷卻，作成表3所示之各光學補償片。 *碟狀液晶塗布液（DA-1 ) 以下式2所示之碟狀液晶DLC-A 9.1份質量環氧乙烷變性三羥甲基丙烷丙烯酸脂 0.9份質量 (商品名：V # 3 60，日本大阪有機化學（股份公司））纖維素醋酸丁酯 0.2份質量 (商品名：CAB551-0.2，Eastman Chemical 公司製）纖維素醋酸酯丁酸酯〇.〇5份質量 (商品名：CAB531-1，Eastman Chemical 公司製）下式2所示之氟化物（F-1 ) 1.3份質量0 = C 〇 c 〇 ch 3 〇 (CH 2 ) 4 OCOCH = CH 2 (average degree of polymerization: 4000) Then, with respect to the formed transparent carrier of the obtained alignment film, the adhesion test of the following alignment film was carried out. The results are shown in Table 3. (Evaluation method for adhesion of alignment film) According to the checkerboard method of JIS K-5400, using a cutter and a cutter guide, 100 squares of lmmxlmm are placed on the surface of the alignment film. After standing at a temperature of 25 ° C and a relative humidity of 60% for 2 hours, the cellophane tape of the standard type was attached, and then rubbed with an eraser to adhere to the coating film. After the tape was attached for 2 minutes, the release tape was peeled off perpendicularly to the vertical direction of the coated surface, and evaluated by counting the number of lattices in which the alignment film was peeled off from the transparent carrier. ◎: Confirm that all 100 squares are completely free of flaking 〇: Confirm 100 squares, 2 squares have been peeled off -149- 201211575 △: Confirm 100 grids, 1〇~3 grids have been peeled off X: Confirm 1 0 0 grid, exceed 10 Å have been peeled off (formation of optically oriented layer) Next, the optically complementary layer is formed on the transparent carrier on which the alignment film has been formed, and an optical compensation sheet is obtained. That is, the coating of the disc-shaped liquid crystal coating liquid (DA-1) having the following composition was applied to the alignment film by a #4 bar coater, and then heated in a high temperature bath at 125 ° C for 3 minutes to make the dish After the alignment of the liquid crystals, a high-pressure mercury lamp was used, and UV irradiation of 510 mJ / cm 2 was performed, and the mixture was cooled at room temperature to prepare optical compensation sheets shown in Table 3. *Disc liquid crystal coating liquid (DA-1) The disc-shaped liquid crystal DLC-A shown in the following formula 2 9.1 parts by mass of ethylene oxide-denatured trimethylolpropane acrylate 0.9 parts by mass (trade name: V # 3 60, Osaka Organic Chemicals Co., Ltd. (Japan) Organic cellulose butyl acetate 0.2 parts by mass (trade name: CAB551-0.2, manufactured by Eastman Chemical Co., Ltd.) Cellulose acetate butyrate 〇. 〇 5 parts by mass (trade name: CAB531-1 , manufactured by Eastman Chemical Co., Ltd.) Fluoride (F-1) of the following formula 2: 1.3 parts by mass

Irgacure-907 3.0 份質量 (商品名，Ciba Geigy公司製）Irgacure-907 3.0 parts (product name, manufactured by Ciba Geigy)

Kayacure DETX 〇·1 份質量 (商品名，日本化藥（股份公司）製）甲基乙基酮 29.6份質量Kayacure DETX 〇·1 part (product name, manufactured by Nippon Kayaku Co., Ltd.) methyl ethyl ketone 29.6 parts by mass

碟狀液晶DLC-A -150- 201211575Dish liquid crystal DLC-A -150- 201211575

RR

R R R： ~OCO—^^—〇(CH2)4°c〇CH:=CH2 氟化物（F-l) C3H7R R R: ~OCO—^^—〇(CH2)4°c〇CH:=CH2 Fluoride (F-l) C3H7

CBFi7S〇2N(CH2)2O(CH2CH2O)10H 各薄膜之光學異方向層的厚度均爲另外，針對所得到的各光學補償片，進行以下之性能評估測試。將其結果顯示於表5。 (光學補償片之性能評估測試） (密著性）利用丙烯基系接著劑而將表 5所示之光學補償片 KS-1' KSR1-1〜KSR1-3貼付於玻璃板，於90°C保存20小時。同樣地，丙烯基系接著劑係用於液晶顯示裝置之組裝，玻璃板用於液晶單元。藉由於垂直方向，將光學補償片從玻璃板予以剝離，探討發生剝離殘留的部分，進行密著性之評估。 ◎:完全未發生（10人進行評估，無一人察覺）〇：極少部分發生（1 〇人進行評估，1〜3人察覺的水準） △:稍微發生（10人進行評估，3〜5人察覺的水準） X :強烈發生（1 〇人進行評估，6人以上察覺的水準） (透過光不均勻） -151 - 201211575 於交錯放置的二片偏光板之間，將各光學補償片予以夾住，目視觀察透過光之不均現象而進行評估。〇：完全未發生（10人進行評估，無一人察覺） △:稍微發生（10人進行評估，1〜5人察覺的水準） X:強烈發生（10人進行評估，6人以上察覺的水準）由下表5所示之結果，可明確得知，本發明之光學補償片KS-1爲極佳的，其密著性爲足夠的，並且無透過光之不均現象。 (偏光膜之製作）將平均聚合度4000、皂化度99.8mol%之PVA溶於水中，得到4.0%之水溶液。利用裝有圓錐物之模頭，進行此溶液之帶狀流延而予以乾燥，拉伸前之寬度爲110mm，使其左端厚度成爲l2〇/z m、右端厚度成爲1 3 5 // m，經製膜而得到薄膜。從帶狀物將此薄膜予以剝離，於乾燥狀態下，傾斜45 度方向進行拉伸，維持此狀態並浸漬於30°C之碘〇.5g/L、碘化鉀50 g/L的水溶液中1分鐘，接著，浸漬於70°C之硼酸100 g/L、碘化鉀60 g/L的水溶液中5分鐘，再於水洗槽中，以20 °C之水洗淨1〇秒鐘之後，於80 °C，乾燥5分鐘後，得到碘系偏光膜（HF-01 )。偏光膜之寬度660mm、厚度左右皆爲20/zm。 (偏光板之製作）使用聚乙烯醇系接著劑，將該方形光學補償片（KS-1、尺3尺-1〜3)，以纖維素醯化物薄膜（〇八-1)表面貼付於偏光膜（HF-01)的單面。另外，於厚度8〇νιη之纖維素醋 -152- 201211575 酸酯薄膜（TD-80UF，日本富士寫真Film(股份公司）製），相同於實施例1 2之利用鹼性溶液的皂化處理而進行單面之皂化處理，再使用聚乙烯醇系接著劑，貼付於偏光膜之相反側。偏光膜之透過軸與纖維素醯化物薄膜（CA_1)之遲相軸成平行配置。偏光膜之透過軸與該纖維素醋酸酯薄膜之遲相軸成垂直配置。進行如此方式，製得偏光板（HB-1 )與 (HBR- 1 )〜（HBR-3 )。 (液晶顯示裝置）將設置於使用TN型液晶單元之液晶顯示裝置（6E-A3， Sharp (股份公司）製）之一對偏光板予以剝離，替代方式係使實施例1所製作的光學補償片成爲液晶單元側，藉由黏著劑，將該製得的各偏光板各一片貼付於觀察者側與背光源側。觀察者側之偏光板的透過軸與背光源側之偏光板的透過軸，成爲〇模式而予以配置。針對所得到的液晶顯示裝置，進行以下之評估測試。將其結，果顯示於表5。 (描繪影像之不均勻評估）針對進行如此方式而製得的液晶顯示裝置，利用測定機 (EZ-Contrast 160D，ELDIM公司製），目視觀察顯示黑色（L1)時之描繪不均。〇：完全未發生（10人進行評估，無一人察覺） △:稍微發生（10人進行評估’ 1〜5人察覺的水準） X :強烈發生（1 〇人進行評估，6人以上察覺的水準） (描繪影像之對比及視野角度） -153- 201211575 將顯示白色之電壓2V、顯示黑色之電壓6V外加於液晶顯示裝置之液晶單元，利用測定機（EZ-Contrast 160D， ELDIM公司製），測定正面對比値。進一步調査左右方向 (液晶單元之平磨方向與垂直方向）之視野角度（對比比値成爲10以上之角度範圍）。【表5】光雜償片載體薄膜配向膜密著性光學補償片液晶顯示裝置密著性透過光不均影像視野角度對比不均 (左/右）實施例12 KS-1 FS-1 ◎ ◎ 〇〇 160 120 比較例12-1 KSR1-1 FSR1-1 X Δ Δ Δ 一一比較例12-2 KSR1-2 FSR1-2 X Δ X 〜X _ 一比較例12-3 KSR1-3 FSR1-3 Δ Δ X 〜X — — 由表5所示之結果可明確得知，將纖維素醯化物薄膜 K S -1作爲透明載體使用’使用所形成的本發明光學補償片之液晶顯示裝置’可以得到所有整個畫面鮮明不模糊而爲高亮度之影像’並且’對比及視野角度優異的描繪影像。亦即’辨識性良好。另一方面’使用比較用薄膜KSR-1與 KSR-3之液晶顯示裝置，整個畫面整面均看得到不均現象，成爲供應於實用上之問題。由以上之目視觀察結果，得知使用本發明之光學補償片的液晶顯不裝置具有良好的光學特性，並且裝設此光學補償片的液晶顯示裝置具有極佳的描繪性。 [實施例1 3 ] (透明載體之製作） -154- 201211575 (微顆粒分散物（RL-2)之調整）利用壓模之磨削機，將由下列組成而成的混合物及顆粒直徑0.3mm之銷珠粒予以倒入，經濕式分散而進行體積平均粒徑爲65nm之分散。利用200網眼之耐隆布，將所得到的分散物進行珠粒分離，調製微顆粒分散物（RL-2 )。利用掃瞄型電子顯微鏡測定所得到的分散物之分散顆粒直徑。另外，測定分散物之顆粒分布（雷射解析與散亂粒徑測定裝置LA-920，日本堀場製作所製）的結果，粒徑 300nm以上之顆粒爲0% 。 *微顆粒分散物（RL-2 )組成疏水性二氧化矽 2.2 0份質量 (商品名「AEROSIL972」甲基變性物，一次粒徑 16nm，日本AEROSIL (股份公司））醯化度59.9%之纖維素三醋酸酯 2.00份質量 (6-位取代率0.90 ) 0.22份質量〇 . 〇 8份質量 7 1 . 〇份質量 6.2份質量 6. 1份質量 6.1份質量 6.1份質量單月桂基磷酸酯 (微顆粒化分散助劑）聯苯二苯基磷酸酯醋酸甲酯甲醇丙酮乙醇 1-丁醇 (纖維素醯化物溶液（A - 2 )之調整）將下列組成之各成分倒入攪拌槽中，經加熱攪拌而調製 -155- 201211575 纖維素醯化物溶液 *纖維素醯化物溶液 (A-2 )組成醯化度59.9%之纖維素三醋酸酯 1 0 0份質量 (6-位取代率0.90 ) 三苯基磷酸酯 7.9份質量聯苯二苯基磷酸酯 3.9份質量下列化學式7 1所示之 UV 劑：UV-1 1 . 0份質量下列化學式7 1所示之 UV 劑：UV-2 1 . 0份質量醋酸甲酯 2 9 0份質量甲醇 2 5份質量丙酮 2 5份質量乙醇 2 5份質量 1-丁醇 2 5份質量 UV劑The thickness of the optically different direction layer of each film of CBFi7S〇2N(CH2)2O(CH2CH2O)10H was also the same, and the following performance evaluation tests were performed for each of the obtained optical compensation sheets. The results are shown in Table 5. (Performance evaluation test of optical compensation sheet) (Adhesion) The optical compensation sheets KS-1' KSR1-1 to KSR1-3 shown in Table 5 were attached to a glass plate by a propylene-based adhesive at 90 ° C. Save for 20 hours. Similarly, a propylene-based adhesive is used for assembly of a liquid crystal display device, and a glass plate is used for a liquid crystal cell. The optical compensation sheet was peeled off from the glass plate by the vertical direction, and the portion where the peeling occurred was examined, and the adhesion was evaluated. ◎: Nothing happened at all (10 people evaluated, no one noticed) 〇: Very few cases occurred (1 〇 person evaluated, 1 to 3 people perceived level) △: Slightly occurred (10 people evaluated, 3 to 5 people noticed) Level X: Strong occurrence (1 〇 person's assessment, level of 6 or more) (inhomogeneous light transmission) -151 - 201211575 Clamp the optical compensation sheets between two interdigitated polarizing plates Visually observed through the unevenness of light. 〇: Nothing happened at all (10 people evaluated, no one noticed) △: Slightly occurred (10 people evaluated, 1 to 5 people perceived level) X: Strong occurrence (10 people assessed, 6 people or more perceived level) From the results shown in Table 5 below, it is clear that the optical compensation sheet KS-1 of the present invention is excellent, the adhesion is sufficient, and there is no unevenness of transmitted light. (Preparation of polarizing film) PVA having an average degree of polymerization of 4000 and a degree of saponification of 99.8 mol% was dissolved in water to obtain an aqueous solution of 4.0%. Using a die equipped with a cone, the strip was cast and dried, and the width before stretching was 110 mm, so that the thickness of the left end became l2 〇 / zm, and the thickness of the right end became 1 3 5 / m. Film formation to obtain a film. The film was peeled off from the ribbon, and stretched in a state of 45 degrees in a dry state, maintained in this state, and immersed in an aqueous solution of iodine. 5 g/L and potassium iodide 50 g/L at 30 ° C for 1 minute. Then, it was immersed in an aqueous solution of 100 g/L of boric acid and 60 g/L of potassium iodide at 70 ° C for 5 minutes, and then washed in a water washing tank at 20 ° C for 1 〇 and then at 80 ° C. After drying for 5 minutes, an iodine-based polarizing film (HF-01) was obtained. The width of the polarizing film is 660 mm, and the thickness is about 20/zm. (Production of Polarizing Plate) Using a polyvinyl alcohol-based adhesive, the square optical compensation sheet (KS-1, ruler 3 to 1 to 3) was attached to the surface of the cellulose halide film (〇8-1) by polarized light. One side of the membrane (HF-01). In addition, the cellulose vinegar-152-201211575 acid ester film (TD-80UF, manufactured by Fujifilm Japan Film Co., Ltd.) having a thickness of 8 〇νιη was subjected to the saponification treatment using the alkaline solution in the same manner as in Example 12. The saponification treatment on one side is carried out by using a polyvinyl alcohol-based adhesive and attached to the opposite side of the polarizing film. The transmission axis of the polarizing film is arranged in parallel with the late phase of the cellulose halide film (CA_1). The transmission axis of the polarizing film is arranged perpendicular to the retardation axis of the cellulose acetate film. In this manner, a polarizing plate (HB-1) and (HBR-1)~(HBR-3) were obtained. (Liquid Crystal Display Device) The polarizing plate was peeled off from one of liquid crystal display devices (6E-A3, manufactured by Sharp Co., Ltd.) using a TN liquid crystal cell. Alternatively, the optical compensation sheet produced in Example 1 was used. On the side of the liquid crystal cell, each of the obtained polarizing plates was attached to the viewer side and the backlight side by an adhesive. The transmission axis of the polarizing plate on the observer side and the transmission axis of the polarizing plate on the backlight side are arranged in a meandering mode. The following evaluation test was performed for the obtained liquid crystal display device. The results are shown in Table 5. (Evaluation of unevenness in image) The liquid crystal display device manufactured in this manner was visually observed for unevenness in drawing when black (L1) was displayed by a measuring machine (EZ-Contrast 160D, manufactured by ELDIM Co., Ltd.). 〇: Nothing happened at all (10 people evaluated, no one noticed) △: Slightly occurred (10 people evaluated '1 to 5 people perceived level) X: Strongly occurred (1 〇 person evaluated, 6 people or more perceived level (Drawing image contrast and viewing angle) -153- 201211575 A liquid crystal cell with a white voltage of 2V and a black voltage of 6V is applied to a liquid crystal display device, and is measured by a measuring machine (EZ-Contrast 160D, manufactured by ELDIM). Positive contrast. Further investigate the viewing angle of the left and right direction (the flat grinding direction and the vertical direction of the liquid crystal cell) (the contrast ratio becomes an angular range of 10 or more). [Table 5] Optical hybrid film carrier film alignment film adhesion optical compensation sheet liquid crystal display device Adhesive transmission unevenness image viewing angle contrast unevenness (left/right) Example 12 KS-1 FS-1 ◎ ◎ 〇〇160 120 Comparative Example 12-1 KSR1-1 FSR1-1 X Δ Δ Δ One-to-one comparison example 12-2 KSR1-2 FSR1-2 X Δ X ～ X _ A comparative example 12-3 KSR1-3 FSR1-3 Δ Δ X 〜 X — — From the results shown in Table 5, it is clear that the cellulose halide film KS-1 can be used as a transparent carrier by using the liquid crystal display device of the optical compensation sheet of the present invention. The entire image is sharp and unblurred, and is a high-brightness image 'and' contrasting image with excellent viewing angle. That is, 'the identification is good. On the other hand, the liquid crystal display device using the comparative films KSR-1 and KSR-3 has a problem in that the entire screen is unevenly displayed, which is a practical problem. From the above visual observation results, it was found that the liquid crystal display device using the optical compensation sheet of the present invention has good optical characteristics, and the liquid crystal display device equipped with the optical compensation sheet has excellent descriptive properties. [Example 1 3] (Production of transparent carrier) -154 - 201211575 (Adjustment of fine particle dispersion (RL-2)) A mixture of the following composition and a particle diameter of 0.3 mm were used by a stamper. The pin beads were poured and dispersed by a wet dispersion to have a volume average particle diameter of 65 nm. The obtained dispersion was subjected to bead separation using a 200-mesh lonlon cloth to prepare a fine particle dispersion (RL-2). The dispersed particle diameter of the obtained dispersion was measured by a scanning electron microscope. Further, as a result of measuring the particle distribution of the dispersion (laser analysis and scattering particle diameter measuring device LA-920, manufactured by Horiba, Japan), the particles having a particle diameter of 300 nm or more were 0%. *Microparticle dispersion (RL-2) constitutes 2.20 parts of hydrophobic cerium oxide (trade name "AEROSIL972" methyl denature, primary particle size 16nm, Japan AEROSIL (stock company)) 醯化度59.9% of fiber Triacetate 2.00 parts by mass (6-position substitution rate 0.90) 0.22 parts by mass 〇. 8 parts by mass 7 1 〇 part by mass 6.2 parts by mass 6. 1 part by mass 6.1 parts by mass 6.1 parts by mass of monolauryl phosphate ( Microgranular dispersing aid) Biphenyl diphenyl phosphate methyl acetate methanol acetone ethanol 1-butanol (adjustment of cellulose oxime solution (A - 2 )) Pour the ingredients of the following composition into a stirred tank, Prepared by heating and stirring -155- 201211575 Cellulose Telluride Solution* Cellulose Telluride Solution (A-2) Composition of cellulose triacetate having a degree of deuteration of 59.9%, 100 parts by mass (6-position substitution rate 0.90) Triphenyl phosphate 7.9 parts by mass of biphenyl diphenyl phosphate 3.9 parts by mass The UV agent shown in the following Chemical Formula 71: UV-1 1.0 parts by mass The UV agent shown in the following Chemical Formula 71: UV-2 1 0 parts by mass of methyl acetate 2 90 parts by mass of methanol 2 5 parts by mass 25 parts by weight Ethanol 25 parts by mass 1-Butanol 25 parts by mass UV agent

R -C4H9(t) ： UV-1 -C5Hn(t) ： UV-2 將4份質量之該纖維素三醋酸酯、1 6份質量之下列化學式72所示之相位差調整劑、74.4份質量之醋酸甲酯、6.4 份質量之甲醇、6.4份質量之丙酮、6.4份質量之乙醇以及 6.4份質量之i-丁醇，一面加熱並一面攪拌，調製相位差調整劑溶液（RE-2 )。 -156- 201211575 遲滯値調整劑R - C4H9(t) : UV-1 - C5Hn(t) : UV-2 4 parts by mass of the cellulose triacetate, 16 parts by mass of the phase difference adjuster shown by the following chemical formula 72, 74.4 parts by mass Methyl acetate, 6.4 parts by mass of methanol, 6.4 parts by mass of acetone, 6.4 parts by mass of ethanol, and 6.4 parts by mass of i-butanol were heated while stirring, and a phase difference adjuster solution (RE-2) was prepared. -156- 201211575 Hysteresis 値 adjuster

將10.5份質量之微顆粒分散物加入464份質量之纖醯化物溶液，進行充分之攪拌，接著’混合36份質量滞値調整劑溶液，經充分攪拌之後’於室溫（2 5 °C ) 3小時，將所得到的不均勻凝膠狀溶液，於-7〇°C進行時冷卻之後，於50°C進行加熱與攪拌而得到完全溶解雜液。接著，於50°C，利用絕對過濾精度0.01mm之濾膜本東洋濾膜（股份公司）製，# 63 )，進行所得到的液之過濾，進一步利用絕對過濾精度〇.〇〇25mm之 (Pole公司製，FH025 )，進行濾膜過濾與脫氣泡而接雜液。然後，利用旋轉轉筒流延機而進行摻雜液之流延。轉筒係使用已進行硬質鉻鑛金，其表面之算術平均度（Ra )、十點平均粗糙度（Rz )分別作成001 0 # m、（ em，直徑200mm、寬度2500mm之轉筒。流延方法係利用相同於實施例1 2所示之帶狀物流條件所進行的。於轉筒表面上之膜表面溫度從40°C起行1分鐘乾燥，剝取殘留溶劑量爲5 0質量％之薄膜後以1 40 °C之乾燥熱風，並利用定幅器進行殘留溶劑量】維素之遲放置 6小的摻 (曰摻雜濾膜調製粗糙 1.016 延的，進，再善4 0 -157- 201211575 質量％之薄膜的寬度方向之1 7%之拉伸，維持拉伸後之寬度而於130 °C維持30秒鐘。其後，以130 °C之乾燥熱風進行20分鐘之乾燥，於厚度6〇Aim、長度l〇〇〇m、寬度1.34m 之卷取輥輪形態，製得殘留溶劑量爲0.25質量％之纖維素醯化物薄膜（CA-2 )。所得到的纖維素醯化物薄膜（CA-2 )之波長5 90nm的相位差値（Re )爲29nm，波長5 90nm的相位差値（Rth )爲 1 0 1 n m。針對所得到的長型尺狀輥輪之纖維素醯化物薄膜 (CA-2 )的表面凹凸形狀，進行薄膜轉筒之表面側（外面）與轉筒表面相反側（內面）之兩面的測定。將其結果顯示於表6。【表6】Add 10.5 parts by mass of the microparticle dispersion to 464 parts by mass of the fibril compound solution, and stir well, then 'mix 36 parts of the mass hysteresis modifier solution, after thorough stirring' at room temperature (25 ° C) After 3 hours, the obtained uneven gel-like solution was cooled at -7 ° C, and then heated and stirred at 50 ° C to obtain a completely dissolved liquid. Then, at 50 ° C, the filter was filtered using a filter having an absolute filtration accuracy of 0.01 mm, manufactured by Toyo Seisakusho Co., Ltd., # 63 ), and the filtration of the obtained liquid was further carried out, and the absolute filtration accuracy was further used. Pole company, FH025), filter filtration and deaeration to pick up the liquid. Then, casting of the dope is performed using a rotary drum casting machine. The drum is made of hard chrome ore, and the arithmetic mean (Ra) and ten-point average roughness (Rz) of the surface are made into 001 0 # m, (em, diameter 200mm, width 2500mm drum. The method was carried out under the same conditions as the strip stream shown in Example 12. The surface temperature of the film on the surface of the drum was dried from 40 ° C for 1 minute, and the residual solvent amount was 50% by mass. After the film, the hot air is dried at 1 40 °C, and the amount of residual solvent is made by the stirrer. The late addition of the vitamins is 6 small doping (曰 doped filter modulation rough 1.016 extension, advance, re-good 4 0 -157 - 201211575% by mass of the film in the width direction of the tensile layer, maintaining the width after stretching and maintaining at 130 ° C for 30 seconds. Thereafter, drying at 130 ° C for 20 minutes in dry hot air. A roll of a roll having a thickness of 6 〇 Aim, a length of 10 μm, and a width of 1.34 m was prepared to obtain a cellulose oxime film (CA-2) having a residual solvent amount of 0.25 mass%. The phase difference Re(Re ) of the film (CA-2) at a wavelength of 5 90 nm is 29 nm, and the wavelength is 5 90 nm. The positional 値(Rth) is 1 0 1 nm. The surface side (outer side) and the film of the film roll are subjected to the surface unevenness of the obtained long-sized roll of the cellulose hydride film (CA-2). The measurement was performed on both sides of the opposite side (inner surface) of the cylinder surface. The results are shown in Table 6. [Table 6]

Ra ( μ m) Rz ( β m) Ry ( ^ m ) S m ( β m ) 內面 0.002 0.065 0.085 0.220 外面 0.003 0.074 0.092 0.250 由表6所示之結果明確得知，所得到的薄膜表面之形狀係兩面形狀皆爲一致的。另外，外面與內面之（Ra)與（Ry) 的各比値均低於1 . 5，其差値小，爲良好的。 (鹼的皂化處理）接著’通過溫度6 0 °C之介電式加熱輥輪，膜表面溫度升溫至30C之後’利用桿式塗布機’.以塗布量l〇ml/m2，將下列內容之鹼性溶液（S-2)塗布於薄膜內面側表面，並於加熱至1 l〇°C之NORITAKE (股份）有限公司製之蒸氣式遠紅外線加熱器之下，停留8秒鐘。接著，同樣利用桿式 -158- 201211575 塗布機，以3ml/m2之塗布量進行純水之塗布。此時之薄膜溫度爲40°C。接著，重複三次進行利用水源塗布機之水洗與利用氣動刮塗機之去除水分，之後，於7 0 °C之乾燥區停留5秒鐘而使其乾燥。與所得到的薄膜表面之水的接觸角爲34°，表面之面狀無不均現象，爲良好的。 * 鹼性溶液（S-2 )組成氫氧化鉀水異丙醇乙二醇消泡劑 PLURONIC TR70 5.0份質量 2 1 . 8份質量 6 5.2份質量 8.0份質量 0.0 1份質量 (曰本旭電化工業（股份公司）製） (配向膜之形成）接著，除了使用下列配向膜塗布液（0-2)之外，其他則進行相同於實施例1 2的配向膜形成的方式，進行配向膜塗布液之塗布與乾燥之後，實施平磨處理。 «配向膜塗布液（0-2) 下列化學式73所示之變性聚乙烯醇 20份質量下列化學式73所示之羧酸（A) 0.06份質量水 3 6 0份質量甲醇 120份質量戊二醛 0.5份質量變性聚乙烯醇 -159- 201211575Ra ( μ m ) Rz ( β m) Ry ( ^ m ) S m ( β m ) inner surface 0.002 0.065 0.085 0.220 outer 0.003 0.074 0.092 0.250 It is clear from the results shown in Table 6 that the shape of the obtained film surface Both sides are identical in shape. In addition, the ratios of the outer and inner faces (Ra) and (Ry) are both lower than 1.5, and the difference is small and good. (Saponification treatment of alkali) Next, 'through a dielectric heating roller at a temperature of 60 ° C, the surface temperature of the film is raised to 30 C. 'Using a bar coater'. The coating amount is l〇ml/m2, and the following contents are The alkaline solution (S-2) was applied to the inner surface of the inner surface of the film, and was allowed to stand under a vapor-type far-infrared heater manufactured by NORITAKE Co., Ltd., which was heated to 1 l ° C, for 8 seconds. Next, the coating of pure water was carried out at a coating amount of 3 ml/m 2 by using a bar-158-201211575 coater. The film temperature at this time was 40 °C. Subsequently, the water was washed by a water source coater and the water was removed by a pneumatic coater three times, and then left in a drying zone at 70 ° C for 5 seconds to be dried. The contact angle with the water of the surface of the obtained film was 34°, and the surface of the surface had no unevenness and was good. * Alkaline solution (S-2) composition Potassium hydroxide water Isopropyl alcohol glycol defoamer PLURONIC TR70 5.0 parts 2 1. 8 parts mass 6 5.2 parts mass 8.0 parts mass 0.0 1 part mass (曰本旭化Industrial Co., Ltd. (Formation of alignment film) Next, an alignment film formation method similar to that of Example 12 was carried out except that the following alignment film coating liquid (0-2) was used, and alignment film coating was performed. After the coating and drying of the liquid, a flat grinding treatment is carried out. «Orientation film coating liquid (0-2) 20 parts by mass of the modified polyvinyl alcohol shown in the following chemical formula 73. The carboxylic acid represented by the following chemical formula 73 (A) 0.06 parts by mass of water 360 parts by mass of methanol 120 parts by mass of glutaraldehyde 0.5 parts by mass denatured polyvinyl alcohol-159- 201211575

(平均聚合度：3500 ) 羧酸（A)(Average polymerization degree: 3500) Carboxylic acid (A)

(光學異方向層之形成）實施例1所用之碟狀液晶塗布液（DA-1 )中’取代液晶 DLC-A與氟系化合物（F-1)而使用下列化學式74所示之 9.2份質量之液晶D L C - B，與下列化學式7 4所示之1 · 4份質量之氟系化合物（F-2)之外，其他使用相同於塗布液 DA-1之內容的塗布液DA-2,利用# 4之線棒式塗布機進行塗布，再於125 °C之高溫槽中進行3分鐘加熱，使碟狀液晶予以配向之後，使用高壓水銀燈，進行UV之500mJ/cm2 之照射，直到室溫進行冷卻，作成光學補償片KS -2。(Formation of an optically oriented layer) The liquid crystal DLC-A and the fluorine-based compound (F-1) were used in the disc-like liquid crystal coating liquid (DA-1) used in Example 1, and 9.2 parts by mass shown in the following chemical formula 74 was used. The liquid crystal DLC-B is used in the same manner as the coating liquid DA-2 which is the same as the content of the coating liquid DA-1, except for the fluorine compound (F-2) of the above-mentioned chemical formula 7.4. The coating was applied by a #4 bar coater, and then heated in a high temperature bath at 125 °C for 3 minutes to align the disc-shaped liquid crystal, and then irradiated with UV of 500 mJ/cm2 using a high-pressure mercury lamp until room temperature. After cooling, an optical compensation sheet KS-2 was formed.

碟狀液晶DLC-BDish liquid crystal DLC-B

OCOCH^CH-f 'V-OCCH^zOOtCW^^ -160- 201211575 氟化物（F - 2 )OCOCH^CH-f 'V-OCCH^zOOtCW^^ -160- 201211575 Fluoride (F - 2 )

C8F17O(CH2CH2O)l0H 光學異方向層之厚度爲1.7^m。相同於實施例12之方式，進行以長型尺狀形態所製造的光學補償片KS-2之密著性與面狀性的評估，相同於實施例1，爲良好的光學補償片。 (偏光板之製作）使用聚乙烯醇系接著劑，於纖維素醯化物薄膜（CA-2 ) 面，將光學補償片KS-2貼付於偏光膜（HF-01 :揭示於實施例1)的單側。另外，對於厚度80/zm之纖維素三醋酸酯薄膜（TD-8 0UF，日本富士寫真Film (股份公司）製），進行相同於實施例1 2之鹼性溶液皂化處理的方式而進行單面之皂化處理，使用聚乙烯醇系接著劑而貼付於偏光膜之相反側。使偏光膜之透過軸與纖維素醯化物薄膜（CA-2 )之遲相軸成平行而予以配置。使偏光膜之透過軸與該纖維素三醋酸酯薄膜之遲相軸成垂直而予以配置。進行如此方式而製得偏光板（HB-2 )。 (彎曲配向液晶單元之製作）附有ITO電極之玻璃基板上，將聚醯亞胺薄膜作爲配向膜而予以設置，並對配向膜進行平磨處理。使所得到的二片玻璃基板於平行於平磨方向而相向配置，設定液晶單元間隙爲6 # m。注入△ η (折射率ne與n〇之差）爲0.1396 之液晶性化合物（ZLI1 1 32，MERK公司製），製得彎曲配向液晶單元。液晶單元之大小爲2 0吋。 -161 - 201211575 欲夾住製得的彎曲配向液晶單元，而將該製得的二片偏光板（HB-2 )予以貼付。偏光板之光學異方向層面向液晶單元基板，液晶單元之平磨方向與面向於此之光學異方向層的平磨方向成爲相反平行而予以配置。將5 5 Hz之矩形波電壓外加於液晶單元。設定顯示白色爲2V、顯示黑色爲5V之常態白色模式。將透過率之比値 (顯示白色/顯示黑色）設爲對比比値，並利用測定機 (EZ-Contrast 160D，ELDIM公司製），根據從顯示黑色 (L 1 )直到顯示白色（L8 )之8階段，測定視野角度。視野角度之評估尺度係使用維持視野影像之對比比値 1 〇以上，並且，不會發生黑色側之深淡反轉（亦即，顯示黑色（L 1 )與下一個位準（L2 )之間不會發生深淡反轉）之範圍的角度値。其結果爲160°，爲良好的。 (液晶顯示裝置面板上之不均評估）將實施例13之液晶顯示裝置的顯示面板調整至整面中間水準，進行不均現象之評估。無論從任何方向看去，實施例1 3均未觀察到不均現象。 (利用TN液晶單元之評估）將設SI於使用TN型液晶單元之液晶顯示裝置（AQU0S LC2 0C1S ’ Sharp (股份公司）製）的一對偏光板予以剝離，替代方式係使光學補償片（KS-2 )成爲液晶單元側而藉由黏著劑’將該偏光板（HB-2 )各一片貼付於觀察者側與背光源側。使觀察者側之偏光板的透過軸與背光源側之偏光板的透過軸，成爲0模式而予以配置。 -162- 201211575 針對所製作的液晶顯示裝置，利用測定機（EZ-Contrast 1 6 0D，ELD IΜ公司製），根據從顯示黑色（L1)直到顯示白色（L8 )之8階段，測定影像面內之成爲最小的視野角度。其結果，成爲80°以上，爲良好的。 [實施例14] (纖維素醯化物薄膜之製作） (纖維素醋酸酯原液溶液之調製）調製表7所示之組成的纖維素醋酸酯原液溶液（原摻雜液）。溶解係將原料倒入攪拌槽中，一面加熱並一面攪拌，進行各成分之溶解。【表7】纖維素醯化物原液溶液組成原摻雜液I 原摻雜液II 醯化度6 0.7 % ( 6 -位取代率0.9 0 ) 1 00份質量 1 0 0份質量之纖維素三醋酸.醋三苯基磷酸酯（可塑劑） 7.8份質量 2份質量聯苯二苯基磷酸酯（可塑劑） 3.9份質量 1份質量 UV 劑：UV-1 1份質量 1份質量 UV 劑：UV-2 1份質量 1份質量醋酸甲酯 290份質量 320份質量甲醇 2 5份質量 3 〇份質量丙酮 2 5份質量 30份質量乙醇 25份質量 3 〇份質量 1-丁醇 1 2份質量 1 2份質量 -163 - 201211575 (遲滯値調整劑溶液（RE-3 )的調製）將下列化學式7 5所示之1 1 · 6份質量之相位差調整劑、 82.4份質量之醋酸甲酯、7.1份質量之甲醇、7.1份質量之丙酮、3.4份質量之η-丁醇，倒入另一個攪拌槽中，一面加熱並一面攪拌，調製相位差調整劑溶液（RE-3 )。遲滞値調整劑The thickness of the C8F17O(CH2CH2O)10H optically oriented layer is 1.7^m. In the same manner as in Example 12, the evaluation of the adhesion and the planarity of the optical compensation sheet KS-2 produced in the form of a long ruler was carried out, which was the same as that of Example 1, and was a good optical compensation sheet. (Production of polarizing plate) The optical compensation sheet KS-2 was attached to a polarizing film (HF-01: disclosed in Example 1) on a cellulose halide film (CA-2) surface using a polyvinyl alcohol-based adhesive. One side. In addition, a cellulose triacetate film (TD-8 0UF, manufactured by Fujifilm Japan Film Co., Ltd.) having a thickness of 80/zm was subjected to the same method as the saponification treatment of the alkaline solution of Example 12 for one-sided operation. The saponification treatment was applied to the opposite side of the polarizing film using a polyvinyl alcohol-based adhesive. The transmission axis of the polarizing film was placed in parallel with the late phase axis of the cellulose halide film (CA-2). The transmission axis of the polarizing film is placed perpendicular to the retardation axis of the cellulose triacetate film. In this manner, a polarizing plate (HB-2) was produced. (Production of Bending alignment liquid crystal cell) On the glass substrate with the ITO electrode, a polyimide film was provided as an alignment film, and the alignment film was subjected to a flat grinding treatment. The obtained two glass substrates were arranged to face each other in parallel with the flat grinding direction, and the liquid crystal cell gap was set to 6 #m. A liquid crystal compound (ZLI1 1 32, manufactured by MERK Corporation) of Δ Δ (the difference between the refractive index ne and n )) of 0.1396 was injected to obtain a bent alignment liquid crystal cell. The size of the liquid crystal cell is 20 吋. -161 - 201211575 To obtain the bent alignment liquid crystal cell, the two polarizing plates (HB-2) obtained were attached. The optically oriented layer of the polarizing plate faces the liquid crystal cell substrate, and the flattening direction of the liquid crystal cell is arranged in parallel with the flat grinding direction of the optically oriented layer facing the substrate. A rectangular wave voltage of 5 5 Hz is applied to the liquid crystal cell. Set the normal white mode in which the display white is 2V and the black color is 5V. The transmittance ratio 显示 (display white/display black) is set as the contrast ratio, and the measurement machine (EZ-Contrast 160D, manufactured by ELDIM Co., Ltd.) is used, and 8 from the display black (L 1 ) to the display white (L8). At the stage, the angle of view is measured. The evaluation angle of the viewing angle is based on the contrast ratio of 维持1 〇 or more, and the dark side reversal of the black side does not occur (that is, between the display of black (L 1 ) and the next level (L2 ). The angle of the range of the dark reversal does not occur. The result was 160°, which was good. (Evaluation of unevenness on the panel of the liquid crystal display device) The display panel of the liquid crystal display device of Example 13 was adjusted to the intermediate level of the entire surface to evaluate the unevenness. No unevenness was observed in Example 13 regardless of the direction. (Evaluation by TN Liquid Crystal Cell) A pair of polarizing plates of a liquid crystal display device (AQU0S LC2 0C1S 'Sharp Corporation) using a TN liquid crystal cell are stripped, and an optical compensation sheet (KS) is used instead. -2) The liquid crystal cell side is attached, and each of the polarizing plates (HB-2) is attached to the viewer side and the backlight side by an adhesive. The transmission axis of the polarizing plate on the observer side and the transmission axis of the polarizing plate on the backlight side are arranged in the 0 mode. -162-201211575 For the liquid crystal display device to be produced, the measurement machine (EZ-Contrast 160D, manufactured by ELD I) was used to measure the in-plane of the image based on eight stages from black (L1) to white (L8). It becomes the smallest angle of view. As a result, it was 80 or more, and it was good. [Example 14] (Production of cellulose oxime film) (Preparation of cellulose acetate stock solution) A cellulose acetate stock solution (original dope) having the composition shown in Table 7 was prepared. In the dissolution system, the raw material is poured into a stirring tank, and while being heated, the mixture is stirred and the components are dissolved. [Table 7] Cellulose telluride solution solution consists of original doping solution I original doping solution II Degree of deuteration 6 0.7 % (6-position substitution rate 0.9 0 ) 1 00 parts by mass of 100 parts by mass of cellulose triacetate . vinegar triphenyl phosphate (plasticizer) 7.8 parts by mass 2 parts by mass of biphenyl diphenyl phosphate (plasticizer) 3.9 parts by mass 1 part by mass UV agent: UV-1 1 part by mass 1 part by mass UV agent: UV -2 1 part by mass 1 part by mass of methyl acetate 290 parts by mass 320 parts by mass methanol 2 5 parts by mass 3 parts by mass of acetone 2 5 parts by mass 30 parts by mass ethanol 25 parts by mass 3 parts by mass 1-butanol 1 2 parts by mass 1 2 parts by mass - 163 - 201211575 (Preparation of retardation 値 adjuster solution (RE-3)) 1 1 · 6 parts by mass of phase difference adjuster, 82.4 parts by mass of methyl acetate represented by the following chemical formula 75 7.1 parts by mass of methanol, 7.1 parts by mass of acetone, and 3.4 parts by mass of η-butanol were poured into another stirring tank, and while heating and stirring while stirring, a phase difference adjusting agent solution (RE-3) was prepared. Hysteresis

(內層用及外層用纖維素醋酸酯摻雜液溶液之調製）將表8所示之組成物，於原摻雜液中，於攪拌下，依照相位差調整劑溶液（RE-3 )、進而微顆粒分散物（RL-2) 的順序倒入攪拌槽中，經攪拌、混合而調製內層用、外層用纖維素醋酸酯摻雜液。相對於100份質量之纖維素醋酸酯，相位差調整劑與微顆粒分散物之各添加量係如表6所示。於5 0°C，利用絕對過濾精度0.01mm之濾膜（曰本東洋濾膜（股份公司）製，#63)與絕對過濾精度0.0 02 5 mm 之濾膜（Pole公司製，FH02 5 )，進行所得到的摻雜液之過濾。 -164- 201211575 【表8】各層用摻雜液配方內層用摻雜液A 外層用摻雜液A 原摻雜液I 4 8 2份質量 — 原摻雜液II — 4 7 3份質量相位差調整劑溶液 72份質量 26份質量微顆粒分散液（RL-2) 9份質量 1 0.2份質量將利用3層共流延模頭已過濾之摻雜液，再利用帶狀物流延機而使內層用摻雜液配置於內測、外層用摻雜液配置於兩外側，進行多層流延。使用相同於實施例1的帶狀物流延機。欲作成內層厚度48/zm、兩外層厚度6#m，調整摻雜液噴出量，流延與乾燥之條件相同於實施例1 2，利用定幅器，進行拉伸倍率1 6%之橫向拉伸，維持拉伸後之寬度’於130°C保持30秒鐘，製得長度3 000m、寬度1.2Π1 卷取輥輪形態之纖維素醯化物薄膜（CA-3) »Re爲14nm、 Rth 爲 80nm。 (纖維素醯化物薄膜之特性）進行所得到的透明載體之獲得性的評估，將結果顯示於表9。【表9】纖維面 Ra ( βΐη) Rz ( βχη) Ry ( /zm) Sm ( ^m) Re/ 遲相標準霧度卷曲撕裂素醯狀 Rth 軸角偏差強度化物內面外面內面外面內面外面內面外面 (nm) 度偏薄膜移實施例14 CA-3 〇 0.004 0.0055 0.028 0.038 0.047 0.058 0.155 0.160 15/85 0.4 0.5 0.2 -2 12 -165- 201211575 (纖維素三醋酸酯薄膜之皂化處理）於該纖維素三醯化物薄膜（CA-3 )之內面側表面上，利用# 6桿，進行1 · 0莫耳/升之氫氧化鉀溶液（溶劑：異丙醇/丙二醇/水= 75/13/12質量％ )之塗布，於40 °C、加熱' 1 〇秒鐘之後，於維持濕潤的塗布面，連續三次進行利用# 6桿，進行水之塗布之後，立即從噴嘴而將2 5 °C之洗淨水以5 00ml/m2進行噴淋，並利用氣動刮塗機，進行吹去薄膜表面之洗淨水之處理，再以1 〇〇°C之熱風予以乾燥，製得表面經皂化後之纖維素三醯化物薄膜（FS-3)。與所得到的薄膜表面之水的接觸角33°，表面之面狀無不均現象，爲良好的》 (配向膜之形成）利用# 1 4之線棒式塗布機，於所得到的透明載體之單面，進行下列配方之配向膜塗布液（0-3 )之塗布，先以 60 °C之熱風乾燥60秒鐘，再以90°C之熱風乾燥160秒鐘之乾燥，製得設置配向膜之長型尺輥輪狀之透明載體。接著，與設置於該配向膜之長型尺輥輪狀纖維素醋酸酯薄膜之遲相軸方向成爲45°之方向，進行平磨處理。 *配向膜塗布液（0-3 )配方下列化學式76所示之變性聚乙烯醇 1 9份質量下列化學式76所示之羧酸化合物A-2 0.07 5份質量水 3 60份質量甲醇 1 2 0份質量(Preparation of the inner layer and the outer layer with the cellulose acetate dope solution) The composition shown in Table 8 is mixed with the phase difference adjusting agent solution (RE-3) in the original doping solution under stirring. Further, the order of the fine particle dispersion (RL-2) was poured into a stirring tank, and the cellulose acetate doping liquid for the inner layer and the outer layer was prepared by stirring and mixing. The respective addition amounts of the phase difference adjusting agent and the fine particle dispersion are shown in Table 6 with respect to 100 parts by mass of cellulose acetate. At 50 ° C, a filter with an absolute filtration accuracy of 0.01 mm (manufactured by Sakamoto Toyo Filter Co., Ltd., #63) and a filter with an absolute filtration accuracy of 0.0 02 5 mm (manufactured by Pole Co., Ltd., FH02 5 ), Filtration of the resulting dope is performed. -164- 201211575 [Table 8] Doping solution for inner layer doping solution for each layer Doping solution for outer layer A Original doping solution I 4 8 2 parts mass - original doping solution II - 4 7 3 mass phase Poor adjuster solution 72 parts by mass 26 parts by mass microparticle dispersion (RL-2) 9 parts mass 1 0.2 part mass will be filtered using a 3-layer co-casting die-doped dope, and then using a strip-shaped logistics extension The inner layer doping liquid was placed in the inner measurement, and the outer layer doping liquid was placed on both outer sides to carry out multilayer casting. The tape casting machine similar to that of Example 1 was used. The thickness of the inner layer is 48/zm, the thickness of the two outer layers is 6#m, and the discharge amount of the doping liquid is adjusted. The conditions of casting and drying are the same as in the case of the embodiment 12, and the stretching ratio of the stretching ratio is 6%. Stretching, maintaining the width after stretching was maintained at 130 ° C for 30 seconds to obtain a cellulose oxime film (CA-3) having a length of 3 000 m and a width of 1.2 Π in the form of a reel roll » Re of 14 nm, Rth It is 80 nm. (Characteristics of Cellulose Telluride Film) The evaluation of the availability of the obtained transparent carrier was carried out, and the results are shown in Table 9. [Table 9] Fiber surface Ra (βΐη) Rz (βχη) Ry ( /zm) Sm ( ^m) Re / late phase standard haze curl tearing 醯 Rth axis angle deviation strength inside the outer surface of the inner surface of the inner surface The outer surface of the outer surface of the outer surface (nm) is deflected by the film. Example 14 CA-3 〇0.004 0.0055 0.028 0.038 0.047 0.058 0.155 0.160 15/85 0.4 0.5 0.2 -2 12 -165- 201211575 (Saponification of cellulose triacetate film) On the inner surface side of the cellulose triterpene film (CA-3), a potassium hydroxide solution of 1.0 mole/liter was carried out using a #6 rod (solvent: isopropanol / propylene glycol / water = The coating of 75/13/12 mass%) was heated at 40 °C for 1 〇 second, and the wet coated surface was applied three times in succession for three times. After the application of water, the nozzle was immediately applied. The washing water of 2 5 °C is sprayed at 500 ml/m2, and the washing water of the film surface is blown off by a pneumatic blade coating machine, and then dried by a hot air of 1 〇〇 ° C to obtain a water. A saponified cellulose triterpenoid film (FS-3). The contact angle with the water on the surface of the obtained film was 33°, and the surface of the surface had no unevenness, which was good (formation of the alignment film). The obtained transparent carrier was obtained by a #1 4 bar coater. On one side, the coating of the alignment film coating solution (0-3) of the following formulation was first dried by hot air at 60 ° C for 60 seconds, and then dried by hot air at 90 ° C for 160 seconds to obtain a set orientation. The long-shaped roller of the film is a wheel-shaped transparent carrier. Then, the flat grinding treatment was carried out in a direction in which the retardation axis direction of the long-type roller-shaped cellulose acetate film provided on the alignment film was 45°. *Orientation film coating liquid (0-3) Formulation Denatured polyvinyl alcohol represented by the following Chemical Formula 76 1 9 parts of carboxylic acid compound A-2 as shown in the following Chemical Formula 76 0.07 5 parts by mass of water 3 60 parts by mass of methanol 1 2 0 Quality

1份質量 -166- 201211575 變性聚乙烯醇1 part quality -166- 201211575 denatured polyvinyl alcohol

-(CH2-CH-^2 4CH2-CH-^ OH -fcH2-CH^_〇 I !T\ OCOCH3 OCOCH^CHH^ V〇(CH2)2OCOCH=CH2 (平均聚合度：3500-4000 ) 羧酸化合物A-2 COOC2H5-(CH2-CH-^2 4CH2-CH-^ OH -fcH2-CH^_〇I !T\ OCOCH3 OCOCH^CHH^ V〇(CH2)2OCOCH=CH2 (average degree of polymerization: 3500-4000) carboxylic acid compound A-2 COOC2H5

ch2〇hCh2〇h

COOH (光學異方向層之形成）於SUS製之槽中，調製下列配方之碟狀液晶塗布液 (DA-3 )。 *光學異方向層塗布液（DA-3)組成下列化學式7 7所示之碟狀液晶性分子 42份質量 (DLC-C) 環氧乙烷變性三羥甲基丙烷三丙烯酸酯 4份質量 (V# 3 60 -日本大阪有機化學（股份公司）製）纖維素醋酸酯丁酯 0.92份質量 (CAB551-0.2，Eastman Chemical 公司製）纖維素醋酸酯丁酯 0.23份質量 (CAB531-1，Eastman Chemical 公司製）下列化學式77所示之含氟化物（F-3 ) 4.2份質量光聚合起始劑 1.40份質量 (Irgacure-907，Ciba Geigy 公司製）增感劑 0.4 5份質量 -167- 201211575 (KayacureDETX，日本化藥（股份公司）製）甲基乙基酮 111份質量COOH (Formation of an optically oriented layer) A dish-form liquid crystal coating liquid (DA-3) of the following formulation was prepared in a bath made of SUS. *The optically oriented layer coating liquid (DA-3) is composed of the disc-like liquid crystalline molecules represented by the following Chemical Formula 77, 42 parts by mass (DLC-C), ethylene oxide-denatured trimethylolpropane triacrylate, 4 parts by mass ( V# 3 60 - Osaka Organic Chemistry Co., Ltd.) Cellulose Acetate Butyrate 0.92 parts by mass (CAB551-0.2, manufactured by Eastman Chemical Co., Ltd.) Cellulose Acetate Butyrate 0.23 parts by mass (CAB531-1, Eastman Chemical) Company-made) Fluoride (F-3) represented by the following Chemical Formula 77, 4.2 parts by mass of photopolymerization initiator, 1.40 parts by mass (Irgacure-907, manufactured by Ciba Geigy Co., Ltd.) sensitizer 0.4 5 parts by mass -167-201211575 ( Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) Methyl ethyl ketone 111 parts by mass

碟狀液晶DLC-CDish liquid crystal DLC-C

氟化物（F-3) 〒2.H:Fluoride (F-3) 〒2.H:

C8F17SO2N(CH2)2O(CH2CH2O)10H 於該透明載體上所形成的配向膜上，利用#3線棒式塗布機進行該塗布液之塗布。將其於130 °c之完成區進行2 分鐘之加熱，使碟狀液晶性分子得以配向。接著，於130 °C，利用120W/cm高壓水銀燈，進行1分鐘UV照射，使碟狀液晶性分子得以聚合。之後，冷卻至室溫。進行如此方式，製得具有光學異方向層之光學補償片（KS-3 )。進行相同於實施例1 3之方式，探討所得到的光學補償片之性能，得到相同於實施例1 3之光學補償片的良好性能。 (偏光膜（HF-02 )的製作）於25°C，將PVA薄膜浸漬於碘2.0g/L、碘化鉀4.0g/L 的水溶液中240秒鐘，進一步於25°C，浸漬於硼酸l〇g/L 的水溶液中60秒鐘之後，引入繃架拉伸機，拉伸至5·3倍之後，保持固定寬度，一面進行收縮並一面於8 〇°C之氣體 -168 - 201211575 環境中使其乾燥之後’從定幅器予以卸下而進行卷取。拉伸開始前之PVA薄膜的含水率爲31%，乾燥後之含水率爲 15% ° 左右之定幅器夾子的搬送速度差低於〇.〇5% ，於定幅器出口之皺摺、薄膜變形並未觀察到。所得到的偏光膜之550nm的透過率爲43.7%、偏光度爲 99.97% 〇 (抗反射薄膜之製作）進行下列配方之低折射率層塗布液的攪拌、調製，利用孔徑1// m之聚丙烯製薄膜進行過濾之後，並利用桿式塗布機，於Fujitec(TD80UF，日本富士寫真Fum (股份公司）製）上進行塗布，於8 0 °C經5分鐘乾燥後，於1 2 0 °C進行 10分鐘加熱而使聚合物得以交聯，形成厚度0.1#m之低折射率層，製得抗反射薄膜。 ♦低折射率層塗布液組成熱交聯性含氟聚合物 210份質量 (JN-7228，固形成分濃度6% ，JSR (股份公司）製）二氧化矽溶膠（MEK-ST) 18份質量 (平均粒徑10〜20"m，固形成分濃度30wt% ，日本日產化學（股份公司）製）甲基乙基酮 200份質量將此抗反射膜與具有該製得之光學異方向層的光學補償片，1分鐘浸漬於液溫5 5 °C之1 . 5莫耳/升的氫氧化鈉水溶液中而將兩面予以皂化之後，以稀硫酸與水進行充分洗淨，於乾燥後之各個纖維素三醋酸酯側，將聚乙嫌醇系黏 -169- 201211575 著材塗布成約30ym之厚度，貼合於該偏光膜（HF-02) 之兩側，進一步於80°C進行乾燥而製得偏光板》 (彎曲配向液晶單元之製作）附有ITO電極之玻璃基板上，將聚醯亞胺薄膜作爲配向膜而予以設置，並對配向膜進行平磨處理。使所得到的二片玻璃基板於平行平磨方向而相向配置，設定液晶單元間隙爲6ym。注入液晶單元間隙Δη(波長550nm)爲0.1396 之液晶性化合物（ZLI1 132，MERK公司製），製得彎曲配向液晶單元。 (彎曲配向模式之透過型液晶顯示裝置的製作）欲夾住製得的彎曲配向液晶單元，於製得的偏光板（由抗反射薄膜、偏光膜、光學補償片而成的）之光學補償片的光學異方向層上塗上丙烯基系黏著劑，使液晶單元之平磨方向與光學補償片之平磨方向成爲相反平行而予以貼付，製得彎曲配向模式之透過型液晶顯示裝置。將顯示白色之電壓2V、顯示黑色之電壓6V外加於此液晶顯示裝置之液晶單元，利用測定機（E Z - C ο n t r a s t 1 6 0 D， ELD IM公司製），測定正面對比比値。進一步調查左右方向（液晶單元之平磨方向與垂直方向）之視野角度（對比比値成爲10以上之角度範圍）。本發明之液晶顯示裝置顯示極佳的正面對比比値200與視野角度160°，具有良好的對比與廣的視野角度。除此之外，確認爲一種表面無霧狀或污染物之優異顯示品質的液晶顯示裝置。 (第4態樣、第5態樣） -170- 201211575 [實施例15] 將下列組成物倒入攪拌槽中，一面加熱並一面攪拌’溶解各成分而調製纖維素醋酸酯溶液。纖維素醋酸酯溶液組成 1 0 0份質量 1 1 . 7份質量 5.8 5份質量 3 0 0份質量 5 4份質量 1 1份質量醯化度60.8%之纖維素醋酸酯三苯基磷酸酯（可塑劑）聯苯二苯基磷酸酯（可塑劑）二氯甲烷（第1溶劑）甲醇（第2溶劑） 1 - 丁醇（第3溶劑）於另一個攪拌槽中，倒入1 6份質量之下列相位差改善劑、80份質量之二氯甲烷與20份質量之甲醇，一面加熱並一面攪拌，調製相位差改善劑溶液。於混合4 74份質量之纖維素醋酸酯溶液中，混合2 5份質量之相位差改善劑溶液，進行充分攪拌而調製出摻雜液。相對於1 00份質量之纖維素醋酸酯，相位差改善劑之添加量爲3 . 5份質量。 Η ΗC8F17SO2N(CH2)2O(CH2CH2O)10H was applied onto the alignment film formed on the transparent support, and the coating liquid was applied by a #3 wire bar coater. This was heated in a completion zone of 130 ° C for 2 minutes to align the discotic liquid crystalline molecules. Subsequently, UV irradiation was performed for 1 minute at 130 °C using a 120 W/cm high-pressure mercury lamp to polymerize the discotic liquid crystalline molecules. After that, it was cooled to room temperature. In this manner, an optical compensation sheet (KS-3) having an optically different direction layer was obtained. The same performance as in Example 13 was carried out, and the properties of the obtained optical compensation sheet were examined to obtain the same performance as the optical compensation sheet of Example 13. (Preparation of polarizing film (HF-02)) The PVA film was immersed in an aqueous solution of 2.0 g/L of iodine and 4.0 g/L of potassium iodide at 25 ° C for 240 seconds, and further immersed in boronic acid at 25 ° C. After 60 seconds in an aqueous solution of g/L, it was introduced into a stretcher stretching machine, and after stretching to 5.3 times, it was kept at a fixed width, and was shrunk while being in a gas atmosphere of - 8 ° C -168 - 201211575 After drying, it is taken off from the stopper and taken up. The moisture content of the PVA film before the start of stretching is 31%, and the difference in the conveying speed of the stopper clip after the drying is about 15% ° is less than 〇.〇5%, wrinkles at the exit of the stopper, Film deformation was not observed. The obtained polarizing film had a transmittance of 550 nm of 43.7% and a degree of polarization of 99.97%. 〇 (Production of an antireflection film) The following formula was used to stir and modulate the low refractive index layer coating liquid, and the pore size was 1//m. After the acryl film was filtered, it was coated on a Fujitec (TD80UF, manufactured by Fuji Photo Fum Co., Ltd.) using a bar coater, dried at 80 ° C for 5 minutes, and then dried at 120 ° C. The polymer was crosslinked by heating for 10 minutes to form a low refractive index layer having a thickness of 0.1 m, and an antireflection film was obtained. ♦ Low refractive index layer coating liquid composition Heat-crosslinkable fluoropolymer 210 parts by mass (JN-7228, solid component concentration 6%, manufactured by JSR) The cerium oxide sol (MEK-ST) 18 parts by mass ( The average particle diameter is 10 to 20 "m, the solid component concentration is 30% by weight, manufactured by Nissan Chemical Co., Ltd.) 200 parts by mass of methyl ethyl ketone, and the optical antireflection film and the optically different direction layer having the optically distorted layer are optically compensated. The sheet was immersed in a 5 m / liter aqueous solution of sodium hydroxide at a liquid temperature of 5 5 ° C for 1 minute, and then both sides were saponified, and then thoroughly washed with dilute sulfuric acid and water to separate the cellulose after drying. On the triacetate side, the polyethyl alcohol-based adhesive-169-201211575 was coated to a thickness of about 30 μm, bonded to both sides of the polarizing film (HF-02), and further dried at 80 ° C to obtain polarized light. Plate (Production of Bending alignment liquid crystal cell) On a glass substrate with an ITO electrode, a polyimide film was provided as an alignment film, and the alignment film was subjected to flat grinding treatment. The obtained two glass substrates were placed in the direction parallel to the rubbing direction, and the liquid crystal cell gap was set to 6 μm. A liquid crystal compound (ZLI1 132, manufactured by MERK Corporation) having a liquid crystal cell gap Δη (wavelength: 550 nm) of 0.1396 was injected to obtain a bent alignment liquid crystal cell. (Production of a transmissive liquid crystal display device in a curved alignment mode) An optical compensation sheet for a polarized plate (an antireflection film, a polarizing film, or an optical compensation sheet) to be obtained by sandwiching the obtained curved alignment liquid crystal cell The acryl-based adhesive is coated on the optically oriented layer, and the flattening direction of the liquid crystal cell and the flattening direction of the optical compensation sheet are applied in parallel to each other to obtain a transmissive liquid crystal display device in a curved alignment mode. A white voltage of 2 V and a black voltage of 6 V were applied to the liquid crystal cell of the liquid crystal display device, and the front contrast ratio 値 was measured by a measuring machine (E Z - C ο n t r a s t 1 60 0 D, manufactured by ELD IM Co., Ltd.). Further, the viewing angles of the right and left directions (the flat grinding direction and the vertical direction of the liquid crystal cell) are further investigated (the contrast ratio becomes an angular range of 10 or more). The liquid crystal display device of the present invention exhibits an excellent front contrast ratio 値200 and a viewing angle of 160°, and has a good contrast and a wide viewing angle. In addition, it was confirmed to be a liquid crystal display device having an excellent display quality of no fogging or contaminants. (4th aspect, 5th aspect) -170-201211575 [Example 15] The following composition was poured into a stirring tank, and the cellulose acetate solution was prepared by heating and stirring to dissolve each component. Cellulose acetate solution composition 100 parts mass 1 1. 7 parts mass 5.8 5 parts mass 300 parts mass 5 4 parts mass 1 1 part cellulose acetate triphenyl phosphate having a degree of deuteration of 60.8% ( Plasticizer) Biphenyl diphenyl phosphate (plasticizer) Dichloromethane (1st solvent) Methanol (2nd solvent) 1 - Butanol (3rd solvent) In another stirred tank, pour 16 parts of mass The following retardation improver, 80 parts by mass of methylene chloride and 20 parts by mass of methanol were stirred while heating to prepare a phase difference improver solution. A mixture of 25 parts by mass of the cellulose acetate solution was mixed with 25 parts of a mass phase difference improver solution, and the mixture was thoroughly stirred to prepare a dope. The amount of the phase difference improving agent added is 3.5 parts by mass based on 100 parts by mass of the cellulose acetate. Η Η

201211575 利用帶狀流延機’進行所得到的摻雜液之流延。將殘留溶劑量爲1 5質量％之薄膜，於1 3 〇之條件下，利用定幅器而以25%之拉伸倍率進行橫向拉伸，製得纖維素醋酸酯薄膜（厚度：80// m)。進一步將製得的纖維素醋酸酯薄膜，浸漬於1.5N氫氧化鉀溶液（5 0 °C ) 2分鐘之後，以硫酸進行中和。然後，從溶液中將纖維素醋酸酯薄膜予以取出，以純水洗淨之後’進行乾燥。如此方式，求出對於經皂化處理後之纖維素醋酸酯薄膜表面之水的接觸角40°。針對製得的纖維素醋酸酯薄膜（光學補償片），利用橢圓偏光計（M-150，日本分光（股份公司）製），測定波長 5 5 Onm的Re相位差値與Rth相位差値。結果係顯示於表 1 0 〇 [實施例16] 除了於474份質量之纖維素醋酸酯溶液中，混合56份質量之相位差改善劑溶液而進行摻雜液之調製（相對於1 00 份質量之纖維素醋酸酯，使用7.8份質量之相位差改善劑）、並將拉伸倍率變更爲1 4%以外，進行相同於實施例 15之方式，製得纖維素醋酸酯薄膜（光學補償片）。進一步將製得的纖維素醋酸酯薄膜，浸漬於1.5N氫氧化鉀溶液（4〇°C ) 5分鐘之後，以硫酸進行中和》然後，從溶液中將纖維素醋酸酯薄膜予以取出，以純水洗淨之後，進行乾燥。如此方式，求出對於經皂化處理後之纖維素醋酸酯薄膜表面之水的接觸角55°。針對製得的纖維素醋酸酯薄膜（光學補償片），進行相 -172- 201211575 同於實施例1 5之方式’測定Re相位差値與Rth相位差値。結果係顯示於表1 〇。 [實施例I7] 除了於474份質量之纖維素醋酸酯溶液中，混合35份質量之相位差改善劑溶液而進行摻雜液之調製（相對於1 〇〇份質量之纖維素醋酸酯，使用4.8份質量之相位差改善劑）、並將拉伸倍率變更爲28%以外，進行相同於實施例 16之方式，製得纖維素醋酸酯薄膜。進一步於製得的纖維素醋酸酯薄膜上，進行1.0N氫氧化鉀溶液（溶劑：水/異丙醇/丙二醇）的塗布，塗布量爲 1 8ml/m2，於使其不完全乾燥下，加熱至40°C，約20秒鐘後，利用純水去除鹼性溶液。如此方式，求出對於經皂化處理後之纖維素醋酸酯薄膜表面之水的接觸角58°。於此纖維素醋酸酯薄膜之經皂化處理後之表面上，利用 #16之線棒式塗布機，進行下列組成塗布液的塗布，塗布量爲28ml/m2。以60°C之熱風乾燥60秒鐘，進一步以90 °C之熱風乾燥150秒鐘。接著，與纖維素醋酸酯薄膜之遲相軸（於波長63 2.8nm 進行測定）成45°之方向，對於形成的薄膜進行平磨處理。配向膜塗布液組成下列之變性聚乙烯醇 1 〇. 〇份質量水 3 7 1.0份質量甲醇 1 1 9.0份質量戊二醛〇. 5份質量 -173 - 201211575201211575 The casting of the obtained doping liquid was carried out using a belt casting machine'. A film having a residual solvent amount of 15% by mass was subjected to transverse stretching at a draw ratio of 25% under a condition of 13 Torr by a stopper to obtain a cellulose acetate film (thickness: 80//). m). Further, the obtained cellulose acetate film was immersed in a 1.5 N potassium hydroxide solution (50 ° C) for 2 minutes, and then neutralized with sulfuric acid. Then, the cellulose acetate film was taken out from the solution, washed with pure water, and dried. In this manner, the contact angle of water to the surface of the cellulose acetate film after the saponification treatment was determined to be 40°. With respect to the obtained cellulose acetate film (optical compensation sheet), the Re phase difference 値 and the Rth phase difference 波长 of the wavelength of 5 5 Onm were measured by an ellipsometer (M-150, manufactured by JASCO Corporation). The results are shown in Table 10 〇 [Example 16] In addition to mixing 564 parts by mass of the phase difference modifier solution in 474 parts by mass of cellulose acetate solution, the doping solution was prepared (relative to 100 parts by mass). A cellulose acetate film (optical compensation sheet) was obtained in the same manner as in Example 15 except that the cellulose acetate was used in a weight difference of 7.8 parts by mass and the stretching ratio was changed to 14%. . Further, the obtained cellulose acetate film was immersed in a 1.5 N potassium hydroxide solution (4 ° C) for 5 minutes, and then neutralized with sulfuric acid. Then, the cellulose acetate film was taken out from the solution to remove After washing with pure water, it is dried. In this manner, the contact angle of water to the surface of the cellulose acetate film after the saponification treatment was determined to be 55°. With respect to the obtained cellulose acetate film (optical compensation sheet), the phase-172-201211575 was compared with the method of Example 15 to measure the Re phase difference 値 and the Rth phase difference 値. The results are shown in Table 1. [Example I7] The preparation of the doping solution was carried out by mixing 35 parts by mass of the phase difference improver solution in 474 parts by mass of the cellulose acetate solution (relative to 1 part by mass of cellulose acetate, used). A cellulose acetate film was obtained in the same manner as in Example 16 except that 4.8 parts by mass of the phase difference improving agent was used and the stretching ratio was changed to 28%. Further, on the obtained cellulose acetate film, a 1.0 N potassium hydroxide solution (solvent: water/isopropyl alcohol/propylene glycol) was applied, and the coating amount was 18 ml/m 2 , and the mixture was heated under incomplete drying. After about 20 seconds at 40 ° C, the alkaline solution was removed with pure water. In this manner, the contact angle of water to the surface of the cellulose acetate film after the saponification treatment was determined to be 58°. On the saponified surface of the cellulose acetate film, the following composition coating liquid was applied by a #16 bar coater at a coating amount of 28 ml/m2. It was dried by hot air at 60 ° C for 60 seconds, and further dried by hot air at 90 ° C for 150 seconds. Next, the formed film was subjected to a flat grinding treatment in a direction of 45° with respect to the retardation axis of the cellulose acetate film (measured at a wavelength of 63 2.8 nm). Orientation film coating liquid composition The following denatured polyvinyl alcohol 1 〇. 〇 part mass water 3 7 1.0 part mass methanol 1 1 9.0 parts mass glutaraldehyde 〇. 5 parts mass -173 - 201211575

(光學異方向層之形成）於配向膜上，將4 1.0 1 g之下列碟狀（液晶性）化合物、 4.06g之環氧乙烷變性三羥甲基丙烷三丙烯酸酯（V#360, 曰本大阪有機化學（股份公司）製）、0.90g之纖維素醋酸丁酸酯（CAB551-0.2，Eastman Chemical 公司製）、0.23g 之纖維素醋酸丁酸酯（CAB53卜1，Eastman Chemical公司製）、1.35g 光聚合起始劑（Irgacure-907，Ciba Geigy 公司製）、〇.45g之增感劑（Kayacure DETX，日本化藥（股份公司）製）〇.45g之檸檬酸酯（檸檬酸、檸檬酸一乙基酯、檸檬酸二乙基酯、檸檬酸三乙基酯之混合物）溶於102 g之甲基乙基酮的塗布液，利用# 3.6線棒進行塗布。將此薄膜貼付於金屬框上，於1 3 0°C之恒溫槽中進行2分鐘加熱，使碟狀液晶性化合物予以配向。接著，於1 0 0 °C ，利用 120W/cm高壓水銀燈，進行1分鐘之UV照射而使碟狀液晶性化合物得以聚合。之後，直到室溫進行冷卻。進行如此方式，形成光學異方向層。針對製得的纖維素醋酸酯薄膜（光學補償片），進行相同於實施例1之方式，測定Re相位差値與Rth相位差値。結果係顯示於表1。碟狀液晶性化合物 -174- 201211575(Formation of optically oriented layer) On the alignment film, 4 1.0 1 g of the following dish-like (liquid crystalline) compound, 4.06 g of ethylene oxide-denatured trimethylolpropane triacrylate (V#360, 曰The Osaka Organic Chemistry Co., Ltd., 0.90 g of cellulose acetate butyrate (CAB551-0.2, manufactured by Eastman Chemical Co., Ltd.), and 0.23 g of cellulose acetate butyrate (CAB53, manufactured by Eastman Chemical Co., Ltd.) 1.35 g of photopolymerization initiator (Irgacure-907, manufactured by Ciba Geigy Co., Ltd.), 45.45 g of sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.), 45 g of citric acid ester (citric acid, A coating solution of 100 g of methyl ethyl ketone in a mixture of monoethyl citrate, diethyl citrate and triethyl citrate was coated with a #3.6 wire bar. The film was applied to a metal frame and heated in a thermostat at 130 ° C for 2 minutes to align the liquid crystalline compound. Next, at 120 ° C, a 120 W/cm high-pressure mercury lamp was used to carry out UV irradiation for 1 minute to polymerize the disc-like liquid crystal compound. Thereafter, cooling is continued until room temperature. In this manner, an optically oriented layer is formed. With respect to the obtained cellulose acetate film (optical compensation sheet), the Re phase difference 値 and the Rth phase difference 値 were measured in the same manner as in Example 1. The results are shown in Table 1. Dish liquid crystalline compound -174- 201211575

[比較例5 ] 除了將纖維素醋酸酯溶液直接作爲摻雜液使用’不進行拉伸處理與皂化處理之外，進行相同於實施例15之方式，製作纖維素醋酸酯薄膜（光學補償片）後，測定Re相位差値與Rth相位差値。結果係顯示於表1 0。【表10】相位差改善劑 (份質量）接觸角 (.) 拉伸倍率 (%) Re (腿） Rth (nm) 實施例15 3.5 40 25 40 130 實施例16 7.8 40 14 50 240 實施例17 4.8 58 28 35 175 比較例5 無 20 未拉伸 4 48 [實施例1 8 ] 使碘吸附於已拉伸的聚乙烯醇薄膜而製作偏光膜，利用聚乙烯系接著劑，將實施例1 5所作成的纖維素醋酸酯薄膜貼付於偏光膜之單側。然後，對市售之纖維素醋酸酯薄膜 (Fujitec TD8.0UF，日本富士寫真Film (股份公司）製）進行皂化處理’使用聚乙烯醇系接著劑而貼付於偏光膜之相反側。對於市售之纖維素醋酸酯薄膜之皂化後表面之水的接 -175- 201211575 觸角爲18°。使偏光膜之透過軸與實施例1 5所作成的纖維素醋酸酯薄膜之遲相軸成平行而予以配置。進行如此方式而製得偏光板。 [實施例1 9 ] 除了使用實施例1 6所作成的纖維素醋酸酯薄膜之外，進行相同於實施例1 8之方式而製得偏光板。 [實施例2 0 ] 將實施例1 7所製得的光學補償片，浸漬於1 . 5N氫氧化鈉溶液（5 0 °C ) 2分鐘後，以硫酸進行中和，然後，從溶液中將纖維素醋酸酯薄膜予以取出，利用純水洗淨後，進行乾燥。如此方式，求出對於經皂化處理後之纖維素醋酸酯薄膜表面（無碟狀化合物層側的表面）之水的接觸角爲 40° 〇除此之外，進行相同於實施例1 8之方式而製得偏光板。 [實施例2 1 ] 將設置於使用垂直配向型液晶單元之液晶顯示裝置 (VL- 1530S，日本富士通（股份公司）製）的一對偏光板與一對光學補償片予以剝離，替代方式係使實施例1 5所製作的纖維素醋酸酯薄膜成爲液晶單元側，藉由黏著劑而將實施例4所製作的偏光板各一片貼付於觀察者側與背光源側。於觀察者側之偏光板的透過軸之上下方向，而且，背光源側之偏光板的透過軸成爲左右方向，作成交錯配置。針對製得的液晶顯示裝置，利用測定機（EZ-Contrast 160D，ELDIM公司製），根據從顯示黑色（L1)直到顯示 -176- 201211575 白色（L 8 )之8階段，測定視野角度。將結果顯示於表丨1。 [實施例22] 將設置於使用垂直配向型液晶單元之液晶顯示裝置 (VL- 1530S’日本富士通（股份公司）製）的一對偏光板與一對光學補償片予以剝離，替代方式係使實施例1 6所製作的纖維素醋酸酯薄膜成爲液晶單元側，藉由黏著劑而將實施例1 9所製作的偏光板一片貼付於觀察者側。另外，將市售之偏光板（HLC2-5618HCS，SanRitz (股份公司）製）一片貼付於背光源側。於觀察者側之偏光板的透過軸之上下方向，而且，使背光源側之偏光板的透過軸成爲左右方向，作成交錯配置。針對製得的液晶顯示裝置，利用測定機（EZ-Contrast 160D ’ ELDIM公司製），根據從顯示黑色（L1 )直到顯示白色（L8 )之8階段，測定視野角度。將.結果顯示於表【】。 [比較例6 ] 針對使用垂直配向型液晶單元之液晶顯示裝置 (VL- 1 5 30S，日本富士通（股份公司）製），利用測定機 (EZ-Contrast 160D，ELDIM公司製），根據從顯示黑色 (L1 )直到顯示白色（L8 )之8階段，測定視野角度。將結果顯不於表11。 -177- 201211575 【表11】液晶顯示裝置視野角度 (對比比値爲1 0以上，無黑色側深淡反鏈夕箣囿、透過軸方向離透過軸45°之方向實施例2 1 80° 80° 實施例22 80° 80° 比較例6 80° 44° (註）黑色側之深淡反轉：Ll與L2之間的反轉 [實施例23] (彎曲配向液晶單元之製作）附有IT Ο電極之玻璃基板上，將聚醯亞胺薄膜作爲配向膜而予以設置，並對配向膜進行平磨處理》使所得到的二片玻璃基板於平行平磨方向而相向配置，設定液晶單元間隙爲6/zm。注入Δη爲0.1396之液晶性化合物（ZLI1132, MERK公司製），製得彎曲配向液晶單元。欲夾住製得的彎曲配向液晶單元，而將實施例20所製得的二片偏光板予以貼付。偏光板之光學異方向層面向液晶單元基板，液晶單元之平磨方向與面向於此之光學異方向層的平磨方向成爲相反平行而予以配置。將55Hz之矩形波電壓外加於液晶單元。設定顯示白色爲2V、顯示黑色爲 5V之常態白色模式。將透過率之比値（顯示白色/顯示黑色）設爲對比比値’並利用測定機（EZ-C〇ntrast 160D ’ ELDIM公司製），根據從顯示黑色（L1)直到顯示白色（L8) 之8階段，測定視野角度。將測定之結果顯示於表1 2。 -178- 201211575 【表12】液晶顯示裝置視野角度 (對比比値爲10以上，無黑色側深淡反轉之範圍）上下左右實施例23 80° 80° 80° (註）黑色側之深淡反轉：L1與L2之間的反轉 [實施例24] 將裝設於使用TN型液晶單元之液晶顯示裝置（6E-A3 , Sharp (股份公司）製）的一對偏光板予以剝離，替代方式係藉由黏著劑而使實施例1 5所製作之纖維素醋酸酯.薄膜成爲液晶單元側面，而將實施例1 8製得的偏光板各一片貼付於觀察者側與背光源側。使觀察者側之偏光板的透過軸與背光源側之偏光板的透過軸成爲垂直而予以配置。針對製得的液晶顯示裝置，利用測定機（EZ-Contrast 160D，ELDIM公司製），根據從顯示黑色（L1 )直到顯示白色（L8 )之8階段，測定視野角度。將結果顯示於表1 3。 [比較例7 ] 針對使用TN型液晶單元之液晶顯示裝置（6E-A3, Sharp (股份公司）製），利用測定機（EZ-Contrast 1 60D，ELDIM 公司製），根據從顯示黑色（L1)直到顯示白色（L 8)之 8階段’測定視野角度。將結果顯示於表1 3。 -179- 201211575 [表1 3】液晶顯示裝置視野角度 (對比比値爲1 0以上，無黑色側深淡反轉之範圍）上下左右實施例24 18° 23° 77° 比較例7 15° 25° 3 7° (註）黑色側之深淡反轉：L1與L2之間的反轉【發明之效果】爲了進行液晶單元之光學性補償，能夠將由纖維素醯化物薄膜而成的光學補償片、或是由纖維素醯化物薄膜等之透明載體而成的光學補償片用於液晶顯示裝置。將光學補償片用於液晶顯示裝置之情形，通常，光學補償片係利用黏著劑而固定於液晶單元。因而，用於光學補償片之聚合物薄膜一旦進行膨脹或收縮，所產生的歪斜將抑制整個光學補償片，聚合物薄膜之光學特性將改變。經由本發明人之硏究，得知光學特性之變化係起因於二個原因所造成的。一個原因係由於液晶顯示裝置之使用環境上之濕熱條件變化，聚合物薄膜中產生膨脹或收縮，光學補償片之光學特性將改變。另一個原因係由於液晶顯示裝置內之熱源（例如，背光源），於光學補償片面內發生溫度分布，由於其熱歪斜而導致光學特性之改變。纖維素醯化物通常難以完全醯化，具有些許之羥基。而且，得知由於羥基而容易受到環境條件之影響。爲了消除漏光，也可以抑制因環境條件所造成的光學補償片之光學特性的變動。 -180- 201211575 光學特性的變動與光學補償片之光彈性係數'厚度、因環境造成的假想歪斜以及彈性率有關。因而，藉由降低光學補償片之光彈性係數、薄化厚度、進而縮小因環境造成的歪斜、減小彈性率，明顯減低漏光。本發明人進一步深入硏究的結果，爲了兼具發揮光學補償片的機能（Re，最好再加上Rth之控制）與工業製造容易性，再者，爲了防止該漏光，得知只要調整使纖維素醯化物薄膜面內之音速滿足該（iii)與（iv)即可。薄膜內之音速能夠利用市售之裝置（例如，Sonic Test Tester S ST-2500 型，Nomura Shoji )進行簡易測定。如上所述，若根據本發明，能夠使用習知厚度以下之光學補償片，無問題地進行液晶單元之光學性補償。再者，能夠藉由將遵循本發明之光學補償片用於液晶顯示裝置，抑制外圍格子狀透過率之上升。於本發明之第1與第2態樣，爲了抑制外圍格子狀透過率的上升，將用於光學補償片之纖維素醯化物薄膜的厚度 (d)調節至10"m<d<85vm之範圍。然後，使纖維素醯化物薄膜面內的音速調整至滿足該（iii)與（iv)。藉由將纖維素醯化物薄膜之厚度與音速設爲該範圍，不會造成光學補償片之生產或是使其黏合於偏光板之生產步驟的光學補償片的操作性變差’能夠解決該問題。再者，藉由使光學補償片之厚度變薄，也能夠薄化液晶顯示裝置的厚度，並能夠滿足液晶顯示裝置薄型化的要求。通常，偏光板之保護膜係由纖維素醯化物薄膜構成的。若將該光學補償片作爲一個偏光板之保護膜使用，不會增 -181 - 201211575 加偏光板構造要件的數目，能夠將光學補償機能追加於偏光板。將該光學補償片與該光學補償片作爲保護膜使用的偏光板，能夠有利於用於TN ( Twisted Nematic :扭轉向列）型之液晶顯示裝置。另外，本發明人等爲了解決該課題，鑽硏探討的結果，爲了提高強度而於構成載體之薄膜中，進行高強度顆粒之添加混合的情形，發現往往損及該載體表面之平滑性，因此而降低液晶之辨識性。然後，進一步針對載體表面之平滑性與辨識性之關係進行探討的結果，發現不僅使進行顆粒之添加混合而使載體之強度提高，載體表面滿足特定條件之情形，辨識性將變佳，於是完成了本發明。本發明之第3態樣的光學補償片，即使作成大畫面尺寸，不僅仍爲層薄、量輕，同時薄膜之力學特性足夠，辨識性優異。另外，本發明之光學補償片，並無視野角度特性之偏異，即使製成寬幅之長型尺狀輥輪形態之情形，也爲無視野角度擴大特性偏異的良好生產性。另外，本發明之偏光板與液晶顯示裝置也爲層薄且量輕，無視野角度特性之偏異，辨識性優異。使用本發明纖維素醋酸酯薄膜之光學補償片，無論任一態樣之情形，均能夠作爲偏光板之保護膜使用，而且，能夠於偏光板上增加構造要件的數目，而對偏光板追加光學補償機能。另外，若將第4與第5態樣之光學補償片作爲作爲偏光板之保護膜使用，因爲纖維素醋酸酯薄膜進行皂化處理，並且對水的接觸角大，與偏光膜之密著性佳，同 -182- 201211575 時，於包含偏光膜水洗之加工步驟，水份去除性佳，於加工步驟之良率將提高。設置本發明偏光板之液晶單元具有光學性補償、優異的辨識性、廣的視野角度。 183 -[Comparative Example 5] A cellulose acetate film (optical compensation sheet) was produced in the same manner as in Example 15 except that the cellulose acetate solution was directly used as a doping solution without performing a stretching treatment and a saponification treatment. Thereafter, the Re phase difference 値 and the Rth phase difference 测定 were measured. The results are shown in Table 10. [Table 10] Phase difference improver (parts by mass) Contact angle (.) Stretching ratio (%) Re (leg) Rth (nm) Example 15 3.5 40 25 40 130 Example 16 7.8 40 14 50 240 Example 17 4.8 58 28 35 175 Comparative Example 5 No 20 Unstretched 4 48 [Example 1 8] A iodine was adsorbed on a stretched polyvinyl alcohol film to prepare a polarizing film, and a polyethylene-based adhesive was used. The prepared cellulose acetate film was applied to one side of the polarizing film. Then, a commercially available cellulose acetate film (Fujitec TD8.0UF, manufactured by Fujifilm Japan Film Co., Ltd.) was subjected to saponification treatment, and was applied to the opposite side of the polarizing film using a polyvinyl alcohol-based adhesive. For the water of the saponified surface of a commercially available cellulose acetate film, the contact angle of -175-201211575 is 18°. The transmission axis of the polarizing film was placed in parallel with the slow axis of the cellulose acetate film of Example 15. A polarizing plate was produced in this manner. [Example 1 9] A polarizing plate was obtained in the same manner as in Example 18 except that the cellulose acetate film prepared in Example 16 was used. [Example 2 0] The optical compensation sheet prepared in Example 17 was immersed in a 1.5 N sodium hydroxide solution (50 ° C) for 2 minutes, neutralized with sulfuric acid, and then, from the solution. The cellulose acetate film was taken out, washed with pure water, and dried. In this manner, the contact angle of water to the surface of the cellulose acetate film after the saponification treatment (the surface on the side of the disk-free compound layer) was determined to be 40°, and the same manner as in Example 18 was carried out. A polarizing plate is produced. [Example 2 1] A pair of polarizing plates provided in a liquid crystal display device (VL-1530S, manufactured by Fujitec Co., Ltd.) using a vertical alignment type liquid crystal cell and a pair of optical compensation sheets were peeled off, and an alternative method was used. The cellulose acetate film produced in Example 1 was placed on the liquid crystal cell side, and each of the polarizing plates produced in Example 4 was attached to the viewer side and the backlight side by an adhesive. The transmission axis of the polarizing plate on the observer side is in the up-down direction, and the transmission axis of the polarizing plate on the backlight side is in the left-right direction, and is arranged in a staggered manner. With respect to the obtained liquid crystal display device, the viewing angle was measured in accordance with eight stages from the display of black (L1) to the display of -176 to 201211575 white (L 8 ) by a measuring machine (EZ-Contrast 160D, manufactured by ELDIM Co., Ltd.). The results are shown in Table 1. [Example 22] A pair of polarizing plates provided in a liquid crystal display device (VL-1530S' Japan Fujitsu Co., Ltd.) using a vertical alignment type liquid crystal cell and a pair of optical compensation sheets were peeled off, and an alternative method was implemented. The cellulose acetate film produced in Example 1 was placed on the liquid crystal cell side, and a polarizing plate produced in Example 19 was attached to the viewer side by an adhesive. Further, a commercially available polarizing plate (HLC2-5618HCS, manufactured by SanRitz Co., Ltd.) was attached to the backlight side. The transmission axis of the polarizing plate on the observer side is oriented in the vertical direction, and the transmission axis of the polarizing plate on the backlight side is arranged in the left-right direction. With respect to the obtained liquid crystal display device, the viewing angle was measured in accordance with eight stages from the display of black (L1) to the display of white (L8) by a measuring machine (EZ-Contrast 160D' ELDIM). The results are shown in the table []. [Comparative Example 6] A liquid crystal display device (VL-1 5 30S, manufactured by Fujitsu Co., Ltd., Japan) using a vertical alignment type liquid crystal cell, using a measuring machine (EZ-Contrast 160D, manufactured by ELDIM Co., Ltd.) (L1) The viewing angle is measured until eight stages of white (L8) are displayed. The results are not shown in Table 11. -177- 201211575 [Table 11] The viewing angle of the liquid crystal display device (the contrast ratio 1 is 10 or more, the black side is dark and the reverse chain is delayed, and the direction of the transmission axis is 45° from the transmission axis. Example 2 1 80° 80 ° Example 22 80° 80° Comparative Example 6 80° 44° (Note) Darkening of the black side: Inversion between L1 and L2 [Example 23] (Production of curved alignment liquid crystal cell) With IT On the glass substrate of the ruthenium electrode, a polyimide film is provided as an alignment film, and the alignment film is subjected to a flat grinding treatment. The obtained two glass substrates are arranged in a direction parallel to the rubbing direction to set a liquid crystal cell gap. 6 × zm, a liquid crystal compound (ZLI1132, manufactured by MERK Co., Ltd.) having a Δη of 0.1396 was injected to obtain a curved alignment liquid crystal cell. To obtain the bent alignment liquid crystal cell, the two films obtained in Example 20 were obtained. The polarizing plate is attached. The optically oriented layer of the polarizing plate faces the liquid crystal cell substrate, and the flat grinding direction of the liquid crystal cell is arranged in parallel with the flat grinding direction of the optically different direction layer facing the polarizing plate. The rectangular wave voltage of 55 Hz is applied. In the liquid crystal cell, set the normal white mode with white display of 2V and black of 5V. Set the transmittance ratio 显示 (display white/display black) to the contrast ratio 并' and use the measuring machine (EZ-C〇ntrast 160D ' The angle of view is measured in eight stages from the display of black (L1) to the display of white (L8). The results of the measurement are shown in Table 12. 2.178-201211575 [Table 12] Viewing angle of the liquid crystal display device ( The contrast ratio 値 is 10 or more, and there is no black side dark reversal range.) Up and down and left and right embodiments 23 80° 80° 80° (Note) Dark side reversal of black side: reversal between L1 and L2 [Example 24] A pair of polarizing plates mounted on a liquid crystal display device (6E-A3, manufactured by Sharp Co., Ltd.) using a TN type liquid crystal cell were peeled off, and an alternative method was produced by the embodiment 15 by an adhesive. The cellulose acetate. The film becomes the side of the liquid crystal cell, and each of the polarizing plates obtained in Example 18 is attached to the viewer side and the backlight side. The transmission axis of the polarizer on the observer side and the backlight side are The transmission axis of the polarizing plate becomes In the liquid crystal display device produced by the measurement system (EZ-Contrast 160D, manufactured by ELDIM Co., Ltd.), the viewing angle is measured in accordance with eight stages from the display of black (L1) to the display of white (L8). [Table 7] [Comparative Example 7] A liquid crystal display device (6E-A3, manufactured by Sharp Co., Ltd.) using a TN liquid crystal cell was used, and a measuring machine (EZ-Contrast 1 60D, manufactured by ELDIM Co., Ltd.) was used. The viewing angle is measured from 8 stages of displaying black (L1) until white (L 8) is displayed. The results are shown in Table 13. -179- 201211575 [Table 1 3] Viewing angle of liquid crystal display device (comparison ratio 値 is 10 or more, no black side darkening inversion range) Up and down and left and right embodiment 24 18° 23° 77° Comparative example 7 15° 25 ° 3 7° (Note) Inversion of black side: Inversion between L1 and L2 [Effect of the invention] In order to perform optical compensation of the liquid crystal cell, an optical compensation sheet made of a cellulose vapor film can be used. Or an optical compensation sheet made of a transparent carrier such as a cellulose halide film is used for a liquid crystal display device. In the case where an optical compensation sheet is used for a liquid crystal display device, generally, the optical compensation sheet is fixed to the liquid crystal cell by an adhesive. Therefore, once the polymer film for the optical compensation sheet is expanded or shrunk, the resulting skew will suppress the entire optical compensation sheet, and the optical characteristics of the polymer film will change. It has been found by the inventors of the present invention that the change in optical characteristics is caused by two reasons. One reason is that the optical properties of the optical compensation sheet will change due to the expansion or contraction in the polymer film due to changes in the moist heat conditions in the environment in which the liquid crystal display device is used. Another reason is that due to the heat source (e.g., backlight) in the liquid crystal display device, temperature distribution occurs in the plane of the optical compensation sheet, and the optical characteristics are changed due to thermal skew. Cellulose tellurides are generally difficult to completely deuterate and have some hydroxyl groups. Moreover, it is known that it is easily affected by environmental conditions due to the hydroxyl group. In order to eliminate light leakage, variations in the optical characteristics of the optical compensation sheet due to environmental conditions can also be suppressed. -180- 201211575 The variation in optical characteristics is related to the photoelastic coefficient 'thickness of the optical compensation sheet, the imaginary skew caused by the environment, and the elastic modulus. Therefore, by reducing the photoelastic coefficient of the optical compensation sheet, thinning the thickness, and thereby reducing the skew caused by the environment and reducing the elastic modulus, the light leakage is remarkably reduced. As a result of further intensive research, the present inventors have both the function of the optical compensation sheet (Re, preferably with the control of Rth) and the ease of industrial manufacture, and in order to prevent the light leakage, it is known that the adjustment is made. The speed of sound in the plane of the cellulose halide film satisfies the above (iii) and (iv). The speed of sound in the film can be easily measured using a commercially available device (for example, Sonic Test Tester S ST-2500, Nomura Shoji). As described above, according to the present invention, the optical compensation sheet of the conventional thickness or less can be used, and the optical compensation of the liquid crystal cell can be performed without any problem. Further, by using the optical compensation sheet according to the present invention for a liquid crystal display device, it is possible to suppress an increase in the peripheral lattice-like transmittance. In the first and second aspects of the present invention, the thickness (d) of the cellulose halide film for the optical compensation sheet is adjusted to a range of 10 "m<d<85 vm in order to suppress an increase in the outer lattice-like transmittance; . Then, the speed of sound in the plane of the cellulose halide film is adjusted to satisfy the above (iii) and (iv). By setting the thickness of the cellulose halide film to the range of the sound velocity, the operability of the optical compensation sheet which does not cause the production of the optical compensation sheet or the production step of the polarizing plate is deteriorated can solve the problem. . Further, by making the thickness of the optical compensation sheet thin, the thickness of the liquid crystal display device can be made thinner, and the liquid crystal display device can be made thinner. Generally, the protective film of the polarizing plate is composed of a cellulose halide film. When the optical compensation sheet is used as a protective film for a polarizing plate, the number of polarizing plate structural components is not increased, and an optical compensation function can be added to the polarizing plate. The polarizing plate used as the protective film by the optical compensation sheet and the optical compensation sheet can be advantageously used for a TN (Twisted Nematic) type liquid crystal display device. In order to solve this problem, the present inventors have found that in order to increase the strength, in the film constituting the carrier, when the high-strength particles are added and mixed, it is found that the smoothness of the surface of the carrier is often impaired. And reduce the visibility of the liquid crystal. Then, as a result of further investigation of the relationship between the smoothness of the surface of the carrier and the visibility, it was found that not only the addition of the particles but also the strength of the carrier is improved, and the surface of the carrier satisfies the specific conditions, the visibility is improved, and the completion is completed. The invention has been made. The optical compensation sheet according to the third aspect of the present invention is not only thin and lightweight, but also has sufficient mechanical properties and excellent visibility even when formed into a large screen size. Further, the optical compensation sheet of the present invention does not have a difference in viewing angle characteristics, and even in the case of a wide-length long-shaped roller form, it is excellent in productivity without a widening of the viewing angle. Further, the polarizing plate and the liquid crystal display device of the present invention are also thin and light in thickness, have no difference in viewing angle characteristics, and are excellent in visibility. The optical compensation sheet using the cellulose acetate film of the present invention can be used as a protective film for a polarizing plate in any case, and can increase the number of structural elements on the polarizing plate and add optical to the polarizing plate. Compensation function. Further, when the optical compensation sheets of the fourth and fifth aspects are used as a protective film for a polarizing plate, the cellulose acetate film is saponified, and the contact angle with water is large, and the adhesion to the polarizing film is good. At the same time as -182-201211575, in the processing step including water washing of the polarizing film, the moisture removal property is good, and the yield in the processing step is improved. The liquid crystal cell in which the polarizing plate of the present invention is provided has optical compensation, excellent visibility, and a wide viewing angle. 183 -

Claims

201211575 VII. Patent application scope: 1. An optical compensation sheet consisting of a cellulose acetate film with a degree of deuteration of 59.0 to 61.5%, and subjected to surface saponification treatment, and the contact angle of water on the surface is 30°. Above, 70° or more. 2. An optical compensation sheet having an optically different layer composed of a liquid crystalline compound on one side of a cellulose acetate film carrier having a degree of deuteration of 59.0 to 61.5%, and the unilateral surface of the carrier is saponified The treatment has a contact angle of water of 30° or more and 70° or more. 3 _ The optical compensation sheet of claim 1 or 2, wherein the cellulose acetate film contains 〇. 〇 1 to 20 parts by mass with at least two of cellulose acetate based on 1 part by mass Aromatic aromatic compounds. 4. The optical compensation sheet of claim 3, wherein the aromatic compound has at least one 1,3,5-trianthene ring. 5. The optical compensation sheet according to claim 1, wherein the retardation Re defined by the following formula (I) of the cellulose acetate film is 5 to 100 nm, and the Rth hysteresis defined by the following formula (II)値70 to 400 nm > Mathematical formula (I) Re= (nx- ny) xd Mathematical formula (II) Rth={(nx+ny) /2 — nz}xd [wherein, nx film surface The refractive index in the direction of the retardation axis in the inner surface; the refractive index in the direction of the phase axis of the ny-based film; the refractive index in the thickness direction of the nz-based film; and the thickness (nm) of the d-type film]. 6. The optical compensation sheet according to claim 2, wherein the liquid crystal compound is 184-201211575, which is a dish-like liquid crystalline compound. 7. A polarizing plate comprising a polarizing film and two transparent protective films disposed on both sides thereof, wherein: one side of the transparent protective film is an optical body as described in claim 1 or 2 of the patent application. a compensation sheet; and a saponified surface of the carrier of the optical compensation sheet is disposed on the polarizing film side. 8. The polarizing plate of claim 7, wherein the transmission axis of the polarizing film and the late phase axis of the transparent protective film are substantially perpendicular or parallel. 9. A liquid crystal display device comprising a liquid crystal cell and two polarizing plates disposed on both sides thereof, and the polarizing plate is composed of a polarizing film and two transparent protective films disposed on both sides thereof, wherein : At least one of the two transparent protective films disposed between the liquid crystal cell and the polarizing film uses the optical compensation sheet according to claim 1 or 2. A liquid crystal display device according to claim 9, wherein the liquid crystal cell is a liquid crystal cell of any one of a TN mode, a VA mode, an MVA mode, an n-ASM mode, and an OCB mode. -185- 201211575 IV. Designation of Representative Representatives (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: and. y \ \\ V. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: and. y\\\ 201211575 [erO(l^t?>y (Rl) ——(CH2)p—— (p = 2-8)

Revision page

(R6) CHg— 例子 For the example of the diisocyanate component used for the polyurethane compound, the poly(ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethyl diisocyanate) Methylene diisocyanate (general formula: 〇〇> 1-((:112)13^(:0(|) represents an integer of 2-8)); aromatic diisocyanate (for example, containing p_phenylene) Diisocyanate, tolyl diisocyanate, hydrazine, Ρ'-diphenylmethane diisocyanate, 1,5-naphthyl diisocyanate) and in- dimethyl dimethyl diisocyanate. Tolyl diisocyanate, m-benzene dimethyl Diisocyanate and tetramethylene diisocyanate are relatively easy to obtain Q, stable and easy to handle, and in the case of polyurethane esterification, it is more preferable to be compatible with cellulose oxime. The molecular weight of polyurethane resin is preferably The range of 2,000 to 50,000. The molecular weight can be appropriately adjusted by the kind or molecular weight of the component polyester or the diisocyanate component of the linking group. The mechanical properties of the cellulose oxime film are improved and From the viewpoint of the compatibility of the cellulose halide, the noon amount of the polyurethane resin is more preferably in the range of 5,000 to 15,000. The synthesis of the methylene chloride-soluble polyurethane can be achieved by the polyester of the formula (1) The alcohol and the diisocyanate are mixed and heated under stirring -61- Amendment page 201211575, etc. Examples of the denatured group in the case of performing copolymerization denaturation include COONa, Si(OX)3, and N(CH3)3. CJ, c9Hi9COO, S03Na, C ! 2 H 2 5. Examples of denatured groups in the case of denaturation due to chain transfer include COOH, C〇NH2, COOR, and C6H5. The degree of roadway is preferably 80 to H. 〇% of undenatured or denatured polyethyl alcohol storage. The degree of saponification is more preferably an undenatured polyvinyl alcohol and a denatured polyvinyl alcohol in the range of 85 to 953⁄4. It is particularly preferred that the denatured polyvinyl alcohol is a polyvinyl alcohol denatured product which is formed by using a compound represented by the following general formula. Hereinafter, this denatured polyvinyl alcohol is disclosed as a specific denatured polyvinyl alcohol.

In the formula, R1 represents an alkyl group, an acryloalkylene group, a methacrylium alkyl group or an epoxy fluorenyl group, a W-based aryl group, a hospital group or an alkoxy group; and an X system means that an active ester is formed, An acid anhydride or an atomic group necessary for an acid halide; PQ represents 〇 or 1; and η represents an integer of 0 to 4. The specific denatured polyvinyl alcohol is more preferably a polyvinyl alcohol denature formed from a compound represented by the following general formula.

Wherein 'X1' denotes an atomic group necessary for forming an active ester, an acid anhydride or an acid halide, and m represents an integer of 2 to 24. Poly-81 used for the reaction with the compounds of the general formula