TW201107385A

TW201107385A - Polarizer protective film, polarizing plate using same and method for production thereof

Info

Publication number: TW201107385A
Application number: TW99111283A
Authority: TW
Inventors: Yasushi Irie
Original assignee: Konica Minolta Opto Inc
Priority date: 2009-04-15
Filing date: 2010-04-12
Publication date: 2011-03-01
Also published as: TWI475059B; WO2010119732A1; JPWO2010119732A1

Abstract

Provided is a polarizer protective film which has high suitability for saponification without impairing the tight adhesion of a polarizer, particularly in the case of quickly performing the saponification, has a stable film roll shape and causes little image nonuniformity. Also provided are a polarizing plate using said polarizer protective film and a method for producing the same. The polarizer protective film, which comprises an acrylic resin (A) and a cellulose ester resin (B) at a ratio by mass of 85:15 to 30:70, is characterized in that, when saponified, the coefficient of friction thereof after the saponification is smaller than the coefficient of friction thereof before the saponification.

Description

201107385 六、發明說明：【發明所屬之技術領域】本發明係有關提高皂化處理適性的偏光鏡保護薄膜，更詳細係有關皂化後之捲筒之捲繞形狀良好，適合皂化處理步驟之迅速化’且可製造更耐久性優異的偏光板的偏光鏡保護薄膜。此外，本發明係有關使用該偏光鏡保護薄膜之偏光板及其製造方法。【先前技術】因近年技術進步，使液晶顯示裝置加速大型化，同時液晶顯示裝置之用途也多樣化。例如可作爲被設置在街頭或店舖之大型顯示器使用或被用於使用被稱爲電子看板之顯示機器之公共場所的廣告用顯示器等。這種用途係假設用於室外，因此，偏光鏡因高溫高濕而造成劣化的問題，偏光鏡保護薄膜需要更高的耐高溫高濕性。但是以往使用的纖維素三乙酸酯薄膜等之纖維素酯薄膜，很難得到充分的耐高溫高濕性。此外，丙烯酸樹脂所代表的聚甲基丙烯酸甲酯（以下簡稱爲「PMMA」）係除了低吸濕性外，也顯示優異的透明性及尺寸安定性，因此適用於偏光鏡保護薄膜。此外，PMMA薄膜相較於纖維素酯薄膜等時，有較容易破裂或易脆的特性，操作使用較困難，特別是很難穩定地製造大型液晶顯示裝置用之偏光鏡保護薄膜。對於上述問題，專利文獻1係提案藉由摻合丙烯酸樹 -5- 201107385 脂與纖維素衍生物之樹脂組成物所構成的光學薄膜。以此摻合後的樹脂組成物所構成之光學薄膜，透明性良好，具有在高溫高濕下之耐久性，且脆性優異的偏光鏡保護薄膜，但是僅單純混合並無皂化適性，與偏光鏡黏著時，需要與通常偏光鏡保護薄膜之纖維素酯薄膜所使用之聚乙烯醇系之水性黏著劑不同之特別的黏著劑，在偏光板之生產面而言，非常差。現在，考量偏光板之生產性時，藉由使用纖維素酯薄膜之皂化與偏光鏡黏著係非常有效的方法，今後爲了更提高生產性，對於皂化步驟期望迅速處理化。但是僅單純地縮短皂化處理時間時，與偏光鏡之密著性有劣化的傾向。特別是偏光板在高溫高濕下之耐久試驗可知完全破壞密著性。此外，也常發生皂化後之捲筒薄膜變形造成問題，熱切期待將皂化處理之迅速化發揮在偏光板之生產性的方法 0 〔先行技術文獻〕〔專利文獻〕〔專利文獻1〕特開2 0 0 8 - 8 8 4 1 7號公報【發明內容】〔發明槪要〕〔發明欲解決的課題〕本發明係有鑑於上述課題所完成者，本發明之解決課題係提供皂化處理適性優異，特別是在皂化迅速處理時， -6 - 201107385 也不會損及偏光鏡的密著性，薄膜之卷筒形狀安定，圖像斑優異的偏光鏡保護薄膜。此外，也提供使用該偏光鏡保護薄膜之偏光板及其製造方法。〔解決課題的手段〕本發明之上述課題可藉由以下手段來解決。 1. 一種偏光鏡保護薄膜，其係含有丙烯酸樹脂（A ) 與纖維素酯樹脂（B )的偏光鏡保護薄膜，其特徵係施加皂化處理時，該皂化處理後之摩擦係數小於該皂化處理前的摩擦係數。 2. 如前述第1項之偏光鏡保護薄膜，其係以8 5 : 15〜3 0 : 70之質量比含有前述丙烯酸樹脂（A )與前述纖維素酯樹脂（B)，且含有微粒子。 3- 如前述第2項之偏光鏡保護薄膜，其係含有無機微粒子作爲前述微粒子。 4- 如前述第2或3項之偏光鏡保護薄膜，其係含有無機微粒子與丙烯酸粒子作爲前述微粒子。 5 · —種偏光板，其係具備偏光鏡及挾著該偏光鏡之2 片偏光鏡保護薄膜的偏光板，其特徵係該偏光鏡保護薄膜中之至少1片爲前述第1〜4項中任一項之偏光鏡保護薄膜。 6- 一種偏光板之製造方法，其係製造前述第5項之偏光板之偏光板的製造方法，其特徵係具有將前述第1~4項中任一項之偏光鏡保護薄膜進行皂化處理的步驟。 7- 如前述第6項之偏光板之製造方法，其係在前述皂 201107385 化處理的步驟中，以1 8 0秒以內處理從皂洗爲止。〔發明效果〕藉由本發明之上述手段可提供皂化處別是在皂化迅速處理時，也不會損及偏光膜之卷筒形狀安定，圖像斑優異的偏光鏡，也提供使用該偏光鏡保護薄膜之偏光板〔實施發明之形態〕本發明之偏光鏡保護薄膜（以下適當」或僅稱爲「薄膜係含有丙烯酸樹月! 酯樹脂（Β )的偏光鏡保護薄膜，其特徵時，該皂化處理後之摩擦係數小於該皂化數。此特徵係申請專利範圍第1〜7項之發徵。本發明爲了達成藉由皂化所產生之黏之偏光鏡保護薄膜的表面狀態非常重要，增加面狀態之凹凸，例如有添加微粒子的延伸倍率或延伸速度，在表面形成微細龜面具有微細凹凸之輥緊壓，將凹凸轉印至。爲了形成適合與偏光鏡黏著之表面的分由具有親水性的化合物或較佳之可塑劑等。爲了抑制因皂化反應所生成之殘留物經化至乾燥前之水理適性優異，特鏡的密著性，薄保護薄膜。此外及其製造方法。稱爲「光學薄膜 ¥ ( A )與纖維素係實施皂化處理處理前的摩擦係明共通的技術特著性時，皂化後具體而言，需要方法、藉由調節裂的方法、將表薄膜上的方法等子狀態時，可藉的添加劑來達成過時間而阻礙黏 -8 - 201107385 著性時，也可藉由纖維素酯之適當的取代度或分子量、及與丙烯酸樹脂之較佳的比率來達成。本發明之實施態樣從展現本發明效果的觀點，較佳爲以85: 15~30: 70之質量比含有前述丙烯酸樹脂（A)與前述纖維素酯樹脂（B)，且含有微粒子較佳。前述微粒子較佳爲含有無機微粒子或無機微粒子與丙烯酸粒子的形態〇本發明之偏光鏡保護薄膜用於偏光板時，其係具備偏光鏡及挾著該偏光鏡之2片偏光鏡保護薄膜的偏光板，該偏光鏡保護薄膜中之至少1片較佳爲本發明之偏光鏡保護薄膜。製造該偏光板之偏光板的製造方法，較佳爲具有將本發明之偏光鏡保護薄膜進行皂化處理的步驟。此時’前述皂化處理的步驟中，從皂化至乾燥前之水洗爲止以1 8 0秒以內處理的形態較佳。以下詳細説明本發明與其構成要素、及實施本發明之形態·態樣。 <皂化處理> 本發明所謂的「皂化處理」係指爲了將薄膜之醋構造部分分解成原來之構成要素的酸與醇，因此添加驗分解成酸的鹽與醇的化學處理。本發明可採用以往公知之各種的皂化處理法，但是較佳爲下述方法。201107385 VI. Description of the Invention: [Technical Field] The present invention relates to a polarizer protective film for improving the saponification treatment, and more particularly relates to a winding shape of a saponified reel which is suitable for rapid saponification treatment step Further, it is possible to manufacture a polarizer protective film of a polarizing plate which is more durable. Further, the present invention relates to a polarizing plate using the polarizer protective film and a method of manufacturing the same. [Prior Art] Due to advances in technology in recent years, the liquid crystal display device has been accelerated and large-scale, and the use of the liquid crystal display device has also been diversified. For example, it can be used as a display for advertisements that is installed on a large display on a street or a store, or used in a public place where a display device called an electronic signboard is used. This use is assumed to be used outdoors, and therefore, the polarizer is deteriorated due to high temperature and high humidity, and the polarizer protective film requires higher resistance to high temperature and high humidity. However, it is difficult to obtain sufficient high temperature and high humidity resistance of a cellulose ester film such as a cellulose triacetate film which has been conventionally used. Further, polymethyl methacrylate (hereinafter abbreviated as "PMMA") represented by an acrylic resin exhibits excellent transparency and dimensional stability in addition to low hygroscopicity, and is therefore suitable for a polarizer protective film. Further, the PMMA film is more susceptible to cracking or brittleness than the cellulose ester film, etc., and is difficult to handle, and it is difficult to stably manufacture a polarizer protective film for a large liquid crystal display device. In order to solve the above problems, Patent Document 1 proposes an optical film comprising a resin composition of an acrylic tree-5-201107385 fat and a cellulose derivative. The optical film composed of the resin composition after the blending is excellent in transparency, has durability under high temperature and high humidity, and is excellent in fragility, but is only saponified and has a saponification property. When it is adhered, a special adhesive which is different from the polyvinyl alcohol-based aqueous adhesive used for the cellulose ester film of the usual polarizer protective film is very poor in the production surface of the polarizing plate. At the time of considering the productivity of a polarizing plate, it is very effective to use a saponification of a cellulose ester film and a polarizing film adhesion system, and in order to further improve productivity, it is desired to rapidly treat the saponification step. However, when the saponification treatment time is simply shortened, the adhesion to the polarizer tends to deteriorate. In particular, the durability test of the polarizing plate under high temperature and high humidity is known to completely destroy the adhesion. In addition, there is a problem that the deformation of the roll film after the saponification is often caused, and it is eagerly expected to accelerate the saponification treatment in the production of the polarizing plate. [Procedures] [Patent Document] [Patent Document 1] [Description of the Invention] [Problem to be Solved by the Invention] The present invention has been made in view of the above problems, and the object of the present invention is to provide an excellent saponification treatment. In particular, in the case of rapid saponification treatment, -6 - 201107385 does not impair the adhesion of the polarizer, the film has a stable roll shape, and the polarizer protective film is excellent in image spots. Further, a polarizing plate using the polarizer protective film and a method of manufacturing the same are also provided. [Means for Solving the Problems] The above problems of the present invention can be solved by the following means. A polarizer protective film comprising a polarizer protective film comprising an acrylic resin (A) and a cellulose ester resin (B), characterized in that, when saponification is applied, a friction coefficient after the saponification treatment is less than that before the saponification treatment The coefficient of friction. 2. The polarizer protective film according to the above item 1, which comprises the acrylic resin (A) and the cellulose ester resin (B) in a mass ratio of 8 5 : 15 to 3 0 : 70, and contains fine particles. 3-. The polarizer protective film according to the above item 2, which contains inorganic fine particles as the fine particles. The polarizer protective film according to the above item 2 or 3, which comprises inorganic fine particles and acrylic particles as the fine particles. A polarizing plate comprising a polarizing mirror and two polarizing mirror protective films sandwiching the polarizing mirror, wherein at least one of the polarizing protective films is in the first to fourth items. Any of the polarizer protective films. And a method of producing a polarizing plate according to the fifth aspect of the invention, wherein the polarizing plate protective film according to any one of the items 1 to 4 is subjected to saponification treatment. step. 7- The method for producing a polarizing plate according to the above item 6, wherein in the step of the above-mentioned soap 201107385 treatment, the treatment is carried out from soaping within 180 hours. [Effect of the Invention] According to the above-mentioned means of the present invention, it is possible to provide a polarizing mirror which is excellent in image shape and which does not damage the shape of the roll of the polarizing film when the saponification is rapidly processed, and also provides protection using the polarizer. Thin film polarizing plate (embodiment of the invention) The polarizer protective film of the present invention (hereinafter suitably referred to as "a film-based polarizing film protective film containing an acrylic resin ester resin (Β), which is characterized by saponification The friction coefficient after the treatment is less than the saponification number. This feature is the application of the first to seventh aspects of the patent application. The present invention is very important in order to achieve the surface state of the polarizing film protective film produced by saponification, and increase the surface state. The unevenness is, for example, a stretching ratio or an elongation speed at which fine particles are added, and a fine pressure surface is formed on the surface to form a fine concavo-convex roll, and the unevenness is transferred. The surface to be adhered to the polarizer is hydrophilic. a compound or a preferred plasticizer, etc., in order to suppress the residue formed by the saponification reaction to be excellent in water property before drying to dryness The adhesion of a special mirror, a thin protective film, and a method for producing the same. When the optical film ¥ (A) and the cellulose system are subjected to a technical characteristic common to the friction system before the saponification treatment, after saponification, Specifically, when a method, a method of adjusting a crack, or a method of adjusting a film on a surface film is used, an additive can be used to achieve an over time and hinder adhesion, and cellulose can also be used. A suitable degree of substitution or molecular weight of the ester and a preferred ratio to the acrylic resin are achieved. From the viewpoint of exhibiting the effects of the present invention, it is preferred to contain a mass ratio of 85: 15 to 30: 70. The acrylic resin (A) and the cellulose ester resin (B) are preferably fine particles. The fine particles preferably contain inorganic fine particles or inorganic fine particles and acrylic particles. The polarizing protective film of the present invention is used for a polarizing plate. A polarizing plate having a polarizing mirror and two polarizing mirror protective films next to the polarizing mirror, and at least one of the polarizing protective films is preferably a polarizing mirror of the present invention The method for producing a polarizing plate for producing the polarizing plate preferably has a step of saponifying the polarizer protective film of the present invention. In this step, the step of the saponification treatment is performed from saponification to washing before drying. The present invention will be described in detail below. The present invention and its constituent elements and the embodiment of the present invention will be described in detail. <Saponification treatment> The "saponification treatment" in the present invention means a film. Since the vinegar structure is partially decomposed into the acid and the alcohol of the original constituent elements, the chemical treatment of the salt and the alcohol which are decomposed into an acid is added. The present invention can be saponified by various conventionally known saponification methods, but the following method is preferred.

S -9 - 201107385 (1 )浸漬於鹼液的方法將薄膜以適當的條件浸漬於鹼液中，使薄膜全表面之具有與鹼反應性之全部的面進行皂化處理的手法，不需要特別的設備，因此從成本的觀點較佳。鹼液較佳爲氫氧化鉀水溶液、氫氧化鈉水溶液等。較佳的濃度爲0.5 ~3 mo 1/L ，特佳爲1〜2 · 5 m ο 1 / L。較佳之鹼液的液溫爲3 0 ~ 7 5 °C，特佳爲35〜60°C。較佳之浸漬時間爲20秒〜300秒，特佳爲 3 0〜1 0 0秒。前述皂化條件的組合係比較溫和條件彼此的組合較佳，可藉由光散射薄膜或反射防止薄膜之素材或構成、目標之接觸角來設定。浸漬於鹼液後，爲了避免薄膜中殘留鹼成分，以水充分水洗，或浸漬於稀酸中，中和鹼成分較佳。親水化後的表面可改良與以聚乙烯醇爲主成分之黏著層的黏著性。薄膜接受使用鹼之皂化程度的指標爲使用對水之接觸角時，本發明之薄膜從與偏光膜之黏著性、物理強度等的觀點，較佳爲10〜55度的範圍內。較佳爲30〜50度，特佳爲 40~50度的範圍內。 (2 )塗佈鹼液的方法上述浸漬法中避免鹼皂化影響薄膜之各功能層的手段，較佳爲以適當的條件僅在具有防眩層或低折射率層等之功能層之表面的相反側表面塗佈鹼液後，進行加熱、水洗 -10- 201107385 、乾燥的鹼液塗佈法。此時之塗佈係指僅對於進行皂化的面接觸鹼液等，除塗佈外也包括噴霧、接觸含有液體之輸送帶等進行塗佈者。採用此等方法另外需要塗佈鹼液的設備 '步驟，從成本的觀點’不如（1 )的浸漬法。此外，僅在實施皂化處理的面接觸鹼液，因此在相反側的面可具有對耐鹼液較弱的素材。例如蒸鍍膜或溶膠-凝膠膜會被鹼液腐食、溶解、剝離#產生各種影響’因此設置浸漬法較不理想，而此塗佈法不會與液體接觸，因此可安全使用。前述（1)及（2)中任一的皂化方法均可在捲筒狀之支持體捲出形成各層後進行皂化，因此薄膜製造步驟後，可進行一連串的操作。此外，同樣的，可配合與捲出的支持體所構成之偏光板之貼合步驟，以連續方式進行，相較於以單片進行同樣的操作，可更有效率製作偏光板。 <摩擦係數> 本發明之最重要的特徵係皂化後之摩擦係數小於皂化前的摩擦係數，爲了此目的可在表面形成凹凸，增加黏著面積。同樣的，可考慮在偏光鏡與薄膜之界面含有微粒子，以調整爲更佳的環境。如上述，可在皂化後之薄膜表面增加凹凸的設計。本發明係使用JIS-K-7 1 25 ( 1 987 )所規定的方法測定薄膜之接觸面彼此間的摩擦係數。 <丙烯酸樹脂（A) > -11 - 201107385 本發明所使用的丙烯酸樹脂也包括甲基丙烯樹脂並無特別限制，但較佳爲由甲基丙烯酸 5 0〜9 9質量％，及可與此共聚合之其他單體單位1. 所構成者。可共聚合之其他單體例如有烷基之碳數爲2〜甲基丙烯酸酯、烷基之碳數爲卜18之烷基丙烯酸酸、甲基丙烯酸等之α，β-不飽和酸、馬來酸、衣康酸等之含有不飽和基的二元羧酸、苯乙烯、乙烯等之芳香族乙烯基化合物、丙烯腈、甲基丙 α，β -不飽和腈、馬來酸酐、馬來醯亞胺、Ν -取亞胺、戊二酸酐等、丙烯醯基嗎啉等之丙烯醯胺，此等可1種或倂用二種以上之單體使用。其中從共聚合物之耐熱分解性及流動性的觀爲甲基丙烯酸酯、乙基丙烯酸酯、η-丙基丙烯酸基丙烯酸酯、s -丁基丙烯酸酯、2 -乙基己基丙烯特佳爲使用甲基丙烯酸酯或η-丁基丙烯酸酯。本發明之光學薄膜所使用的丙烯酸樹脂（Α 平均分子量（Mw)較佳爲1 1 0,000〜1，000,000的更佳爲140,000〜600,000的之範圍內， 200,0〇〇〜400,000的範圍。本發明之丙烯酸樹脂的重量平均分子量可藉透色譜法測定。測定條件如下述。溶劑：二氯甲烷柱：Shodex K8 06、K8 05、K803G (昭和電酸樹脂。甲酯單位 -50質量％ 1 8的烷基酯、丙烯富馬酸、 α -甲基苯烯腈等之代馬來醯衍生物等點，較佳酯、η-丁酸酯等， )的重量範圍內，特佳爲由凝膠滲工（股） -12- 201107385 製連接3支使用）柱溫度：2 5 °C 試料濃度：〇.1質量％檢測器：RI Model 504 ( GL Science公司製）栗· L6000 (日立製作所（股）製）流量：l.Oml/min 校正曲線：使用標準聚苯乙烯STK standard 聚苯乙烯（東曹（股）製）Mw = 2,800,000-500之13個試樣的校正曲線。1 3個試樣以大致等間隔使用較佳。本發明之丙烯酸樹脂（A )的製造方法並無特別限制，可使用懸浮聚合、乳化聚含、塊狀聚合或溶液聚合等公知的任何一種方法。其中聚合起始劑可使用一般的過氧化物系、偶氮系、氧化還原系的聚合起始劑。聚合溫度若爲懸浮或乳化聚合可以3 0〜1 00°C聚合，塊狀或溶液聚合可以 8 0〜160 °C聚合。爲了控制所得之共聚合物的還原黏度，也可以烷基硫醇等作爲鏈轉移劑使用，進行聚合。本發明之丙烯酸樹脂可使用市售品。例如有Delpet 6 0N、8 0N (旭化成化學（股）製）、Dianal BR52、BR80 、BR83、BR85、B R 8 8 (三菱 R a y 〇 n (股）製）、KT75 ( 電化學工業（股）製）等。丙烯酸樹脂也可倂用二種以上 (纖維素酯樹脂（Β )) 本發明之纖維素醋樹脂（Β )，特別是從改善脆性或 201107385 與丙烯酸樹脂（A )相溶時之透明性的觀點，醯基之總取代度（T)爲2.0〜3.0，碳數爲3〜7之醯基的取代度爲 1·2~3.0較佳，更佳爲醯基的總取代度爲2.5~3.0、碳數3〜7 之醯基的取代度爲2.0〜3.0。纖維素酯樹脂（Β )之醯基的總取代度爲低於2.0時，丙烯酸樹脂（Α)與纖維素酯樹脂（Β)無法充分相溶，作爲丙稀酸薄膜用時會有霧度（haze)的問題。此外，即使醯基之總取代度爲2.0以上，但碳數爲3〜7之醯基的取代度低於1.2時，仍無法得到充分的相溶性，或脆性降低。本發明中，前述醯基可爲脂肪族醯基或芳香族醯基。其爲脂肪族醯基時，可爲直鏈或支鏈，尙可具有取代基。未被醯基取代部分通常以羥基形態存在。此等可以公知的方法合成。本發明之纖維素酯樹脂（B )特佳爲選自纖維素乙酸酯丙酸酯、纖維素乙酸酯丁酸酯、纖維素乙酸酯苯甲酸酯、纖維素丙酸酯、纖維素丁酸酯中之至少一種。此等中特佳的纖維素酯樹脂爲纖維素乙酸酯丙酸酯、纖維素丙酸酯〇又，乙醯基之取代度或其他之醯基的取代度可藉由 ASTM-D817-96所規定的方法得到。本發明之纖維素酯樹脂的重量平均分子量（Mw )，特別是從與丙烯酸樹脂（A )之相溶性、改善脆性的觀點爲75000以上，較佳爲7 5,000~240,000之範圍，更佳爲 100,000〜240,000之範圍內，特佳爲160,000〜240,〇〇〇者。 201107385 本發明可混合使用二種以上的纖維素樹脂。本發明之丙烯酸薄膜中，從展現本發明之效果的觀點 ’丙烯酸樹脂（A )與纖維素酯樹脂（B )較佳爲以8 5 : 15〜3 0: 70之質量比使用，更佳爲8 0: 20〜40: 60，最佳爲 80 ： 20〜50 : 50 ° 本發明之薄膜係以相溶狀態含有丙烯酸樹脂（A )與纖維素酯樹脂（B )較佳。使不同的樹脂相溶、互補可達成作爲光學薄膜所必要之物性或品質。例如可藉由玻璃轉化溫度Tg來判斷丙烯酸樹脂（A ) 與纖維素酯樹脂（B )是否成爲相溶狀態。例如兩者之樹脂的玻璃轉化溫度不同時，混合兩者的樹脂時，因有各自樹脂之玻璃轉化溫度，因此混合物之玻璃轉化溫度也有2個以上，但兩者之樹脂相溶時，各自樹脂固有的玻璃轉化溫度消失，成爲1個玻璃轉化溫度，成爲相溶後之樹脂的玻璃轉化溫度。又，此處所謂的玻璃轉化溫度係指使用差示掃描熱量測定器（Perkin Elmer公司製DSC-7型），以升溫速度 2〇°C/分鐘測定後，依JIS K712l ( 1 9 8 7 )得到的中間點玻璃轉化溫度（Tmg)。本發明之薄膜在不損及本發明效果的範圍內，可含有丙烯酸樹脂（A)、纖維素酯樹脂（B )以外之樹脂或添加劑。本發明中，爲了改善偏光鏡與偏光鏡保護薄膜之黏著性，較佳爲使用微粒子。本發明可使用的微粒子例如有無 £ -15- 201107385 機微粒子或有機微粒子。有機微粒子較佳爲例如有聚矽氧樹脂、氟樹脂及丙烯酸系樹脂等之聚合物，其中較佳爲使用丙烯酸粒子。本發明中’較佳爲使用皂化後之捲筒形狀優異，可長條捲繞的無機微粒子，但是倂用無機微粒子與有機微粒子可使偏光板之黏著性更強固，故最佳。 <無機微粒子> 無機微粒子較佳爲例如有含矽的化合物、二氧化矽、氧化鋁、氧化鉻、碳酸鈣、滑石、黏土、燒成高嶺土、燒成矽酸鈣、水和矽酸鈣、矽酸鋁、矽酸鎂及磷酸鈣等，更佳爲含砂之無機微粒子或氧化結。其中較佳爲使用折射率與纖維素酯較近，因此透明性 (霧度：haze )優異的二氧化矽。二氧化矽之具體例較佳爲使用 AEROSIL200V、AEROSIL R972 V、AEROSIL R972 、 R974 、 R812 、 200 、 300 、 R202 、 0X50 ' TT600 ( 以上爲日本 AEROSIL (股）製）、SEAHOSTAR KEP-10、 SEAHOSTAR KEP-30 、 SEAHOSTAR KEP-50 、 SEAHOSTAR KE-P100 (以上爲（股）日本觸媒製）、 SylophobiclOO (富士 Silysia製）、Nipseal E220A (日本 Silica 工業製）、ADM AFINE SO ( Admatechs 製）等之商品名的市售品等。無機微粒子的形狀例如有不定形、針狀、扁平、球狀等無特別限定，均可使用’特別是使用球狀粒子時’可使 -16- 201107385 用所得之薄膜的透明性佳’故較佳。粒子之大小係當接近可見光之波長時，光產生散射，透明性變差，因此比可見光之波長小較佳’更佳爲在可見光之波長之1/2以下。粒子之大小係在〇.05Mm至3·〇μπι之範圍較佳。此等微粒子可單獨使用或倂用2種以上使用。藉由倂用粒徑或形狀（例如針狀與球狀等）不同的粒子，可同時兼具高度透明性與滑性。此等微粒子可含有光學薄膜全體之Ο. Ο 1〜5質量％。粒子之大小係指粒子爲1次粒子的凝集體時’凝集體之大小。粒子爲非球狀時，表示相當於該投影面積之圓的直徑。 <丙烯酸粒子> 本發明之丙烯酸粒子’其特徵係在前述丙烯酸樹脂（ A )及纖維素酯樹脂（Β )與含有丙烯酸樹脂之薄膜中，以粒子狀態（也稱非相溶狀態）存在。上述丙烯酸粒子係例如將製作後之含有丙烯酸樹脂之薄膜採取所定量，溶解於溶劑後進行攪拌，使充分溶解分散’使用具有未達丙烯酸粒子之平均粒徑之孔徑的P T F E製薄膜過濾器過濾，過濾捕集之不溶物的重量較佳爲添加於含有丙烯酸樹脂之薄膜之丙烯酸粒子的90質量％以上。本發明所使用的丙烯酸粒子並無特別限制，較佳爲具有2層以上之層構造之丙烯酸粒子，特佳爲下述多層構造丙烯酸系粒狀複合物。多層構造丙烯酸系粒狀複合物係指由中心部向外周部 -17- 201107385 ，具有最內硬質層聚合物 '顯示橡膠彈性之交聯軟質層聚合物及最外硬質層聚合物以層狀重疊所成之構造的粒子狀丙烯酸系聚合物。本發明之丙烯酸系樹脂組成物所使用的多層構造丙烯酸系粒狀複合物之較佳形態，例如有下述者。例如由（a )由甲基丙烯酸甲酯80〜98.9質量％、烷基之碳數爲1〜8的烷基丙烯酸酯1〜20質量％、及多官能性接枝劑〇.〇1〜〇.3質量％所構成之單體混合物進行聚合而得的最內硬質層聚合物；（b)在上述最內硬質層聚合物之存在下，由烷基之碳數爲4~8的烷基丙烯酸酯75~98.5質量％、多官能***聯劑0.0 1〜5質量％及多官能性接枝劑0.5〜5質量％所構成之單體混合物進行聚合而得的交聯軟質層聚合物；（c )在上述最內硬質層及交聯軟質層所構成的聚合物存在下，由甲基丙烯酸甲酯8 0〜99質量％與烷基之碳數爲1〜8之烷基丙烯酸酯卜20質量％所構成之單體混合物進行聚合而得的最外硬層聚合物；所構成之具有3層構造，且所得的3層構造聚合物爲最內硬質層聚合物（a) 5〜4〇質量％、軟質層聚合物 (b) 30~60質量％及最外硬質層聚合物（c) 20~50質量％所構成，以丙酮區分時有不溶部分’該不溶部分之甲基乙基酮膨潤度爲1 .5〜4.0的丙烯酸系粒狀聚合物。又如日本特公昭60-17406號公報或特公平3-39095號公報所揭示，不僅規定多層構造丙烯酸系粒狀複合物之各層的組成及粒徑，也將多層構造丙烯酸系粒狀複合物之拉伸彈性率及丙酮不溶部分之甲基乙基酮膨潤度設定在特定範 -18- 201107385 圍內，藉此可實現更充分之耐衝擊性與耐應力白化性的平衡。構成多層構造丙烯酸系粒狀複合物之最內硬質層聚合物（a)較佳爲由甲基丙烯酸甲酯80〜98.9質量％、烷基之碳數爲1~8的烷基丙烯酸酯1〜20質量％及多官能性接枝劑 0.0 1-0.3質量％所構成之單體混合物進行聚合所得者。烷基之碳數爲1〜8的烷基丙烯酸酯，例如有甲基丙烯酸酯、乙基丙烯酸酯、η-丙基丙烯酸酯、η-丁基丙烯酸酯、s-丁基丙烯酸酯、2-乙基己基丙烯酸酯等，較佳爲使用甲基丙烯酸酯及η-丁基丙烯酸酯。最內硬質層聚合物（a )中之烷基丙烯酸酯單位的比例較佳爲1 ~ 2 0質量％。該單位未達1質量％時，聚合物之熱分解性變大，而該卓位超過20質量％時，最內硬質層聚合物（c )之玻璃轉化溫度降低，3層層構造丙烯酸系粒狀複合物之耐衝撃性賦予效果降低，故兩者均不佳。多官能性接枝劑係具有不同之可聚合之官能基的多官能性單體’例如丙烯酸、甲基丙烯酸、馬來酸、富馬酸之烯丙酯等’較佳爲使用烯丙基甲基丙烯酸酯。多官能性接枝劑係用於使最內硬質層聚合物與軟質層聚合物進行化學性結合’因此，該最內硬質層聚合時所用的比例爲 0.0 1〜0 · 3質量％。構成丙烯酸系粒狀複合物之交聯軟質層聚合物（b) 較佳爲在上述最內硬質層聚合物（a)之存在下，由院基之碳數爲1〜8的烷基丙烯酸酯75〜98.5質量％、多官能*** -19- 201107385 聯劑Ο _ ΟΙ〜5質量％及多官能性接枝劑ο · 5〜5質量％所構成之單體混合物進行聚合而得者。其中烷基之碳數爲4-8的烷基丙烯酸酯，較佳爲使用 η-丁基丙烯酸酯或2-乙基己基丙烯酸酯。又，此等聚合性單體也可與25質量％以下的可共聚合之其他單官能性單體共聚合。可共聚合之其他單官能性單體，例如有苯乙烯及取代苯乙烯衍生物。烷基之碳數爲4〜8的烷基丙烯酸酯與苯乙稀之比例係當前者越多時，生成聚合物（b )之玻璃轉化溫度越低，即越能軟質化。又從樹脂組成物之透明性的觀點，軟質層聚合物（b )之常溫下的折射率越接近最內硬質層聚合物（a)、最外硬質層聚合物（c)及硬質熱塑性丙烯酸樹脂越佳，考慮這些後選定兩者的比例。例如在被覆層厚度較小的用途時，不一定要使苯乙烯共聚合。多官能性接枝劑可使用如前述最內硬質層聚合物（a )之項所列舉者。在此所用之多宫能性接枝劑係用於使軟質層聚合物（b )與最外硬質層聚合物（c )進行化學性結合，該最內硬質層聚合時所使用的比例，從耐衝擊性賦予效果的觀點，較佳爲0.5〜5質量％。多官能***聯劑可使用二乙烯基化合物、二烯丙基化合物、二丙烯酸化合物、二甲基丙烯酸化合物等一般已知的交聯劑，較佳爲使用聚乙二醇二丙烯酸酯（分子量 -20- 201107385 200〜600) 〇此處使用之多官能***聯劑係用於軟質層（b )聚合時生成交聯構造，使具有耐衝擊性賦予的效果。但是先前多官能接枝劑用於軟質層之聚合時，某程度上會生成軟質層（b )之交聯構造，因此多官能***聯劑非必須成份，但從耐衝擊性賦予效果的觀點，多官能***聯劑用於軟質層聚合時的比例，較佳爲0.01〜5質量％。構成多層構造丙烯酸系粒狀複合物之最外硬質層聚合物（c)較佳爲在上述最內硬質層聚合物（a)及軟質層聚合物（b )之存在下，由甲基丙烯酸甲酯80〜99質量％及烷基之碳數爲1~8的院基丙稀酸醋1~20質量％所構成之單體混合物進行聚合而得者。其中烷基丙烯酸酯可使用前述者，較佳爲使用甲基丙烯酸酯及乙基丙烯酸酯。最外硬質層（c)中之烷基丙烯酸酯單位的比例較佳爲1〜2 0質量％。又，最外硬質層（c)之聚合時，爲了提升與丙烯酸樹脂（A )之相溶性，爲了調節分子量，可將烷基硫醇等作爲鏈轉移劑使用進行聚合。特別是最外硬質層上設置分子量由內側往外側逐次減少的斜度（斜率），可改良延伸與耐衝擊性之平衡性，故較佳。具體的方法係將形成最外硬質層用之單體混合物分割爲2個以上，依序增加每次添加之鏈轉移劑量的方法，可使分子量由內側往外側減少。此時所形成的分子量可藉由測定將每次使用之單體混S -9 - 201107385 (1) Method of immersing in lye The film is immersed in an alkali solution under appropriate conditions, and the saponification treatment is performed on the entire surface of the film having the reactivity with all of the alkali, and no special method is required. Equipment is therefore preferred from a cost perspective. The alkali solution is preferably an aqueous potassium hydroxide solution or an aqueous sodium hydroxide solution. The preferred concentration is 0.5 to 3 mo 1 / L, particularly preferably 1 to 2 · 5 m ο 1 / L. The liquid temperature of the preferred lye is from 30 to 7.5 ° C, particularly preferably from 35 to 60 ° C. Preferably, the immersion time is from 20 seconds to 300 seconds, and particularly preferably from 30 to 100 seconds. The combination of the above saponification conditions is preferably a combination of mild conditions, and can be set by the material or composition of the light-scattering film or the reflection preventing film, and the contact angle of the target. After immersing in the alkali solution, in order to avoid residual alkali components in the film, it is preferably washed with water or immersed in a dilute acid to neutralize the alkali component. The hydrophilized surface improves the adhesion to the adhesive layer mainly composed of polyvinyl alcohol. When the film is subjected to a degree of saponification using a base, when the contact angle with water is used, the film of the present invention preferably has a range of from 10 to 55 degrees from the viewpoint of adhesion to a polarizing film, physical strength, and the like. It is preferably 30 to 50 degrees, and particularly preferably 40 to 50 degrees. (2) Method of Coating Alkali Solution The means for avoiding alkali saponification in the above impregnation method affecting each functional layer of the film is preferably only on the surface of a functional layer having an antiglare layer or a low refractive index layer under appropriate conditions. After the opposite side surface is coated with the alkali solution, it is heated, washed with water - -10-201107385, and dried by an alkali solution coating method. The coating at this time refers to a surface contact lye or the like which is subjected to saponification, and includes a spray, a contact with a liquid-containing conveyor belt, and the like, in addition to coating. The use of such a method additionally requires an apparatus for applying a lye "step, which is inferior to the impregnation method of (1) from the viewpoint of cost. Further, since only the surface to which the saponification treatment is applied is contacted with the alkali liquid, the material on the opposite side may have a material which is weak to the alkali-resistant liquid. For example, a vapor deposition film or a sol-gel film may be affected by alkali rot, dissolution, and peeling. Thus, it is less desirable to provide a dipping method, and this coating method does not come into contact with a liquid, so that it can be used safely. The saponification method according to any one of the above (1) and (2) can be saponified after the roll-shaped support is wound up to form each layer, so that after the film production step, a series of operations can be performed. Further, similarly, the bonding step with the polarizing plate composed of the rolled support can be carried out in a continuous manner, and the polarizing plate can be produced more efficiently than the same operation in a single film. <Coefficient of Friction> The most important feature of the present invention is that the coefficient of friction after saponification is smaller than the coefficient of friction before saponification, and for this purpose, irregularities can be formed on the surface to increase the adhesion area. Similarly, it is conceivable to contain fine particles at the interface between the polarizer and the film to adjust to a better environment. As described above, the design of the unevenness on the surface of the film after saponification can be increased. The present invention measures the coefficient of friction between the contact faces of the film using the method specified in JIS-K-7 1 25 (1 987). <Acrylic Resin (A) > -11 - 201107385 The acrylic resin used in the present invention also includes a methacrylic resin, which is not particularly limited, but is preferably from 5 to 99% by mass of methacrylic acid, and is compatible with The other monomer units of this copolymerization 1. The constituents. Other monomers which can be copolymerized include, for example, an alkyl group having a carbon number of 2 to methacrylate, an alkyl group having a carbon number of 18, an alkyl acrylate acid, a methacrylic acid or the like, an α, β-unsaturated acid, or a horse. An aromatic vinyl compound containing an unsaturated group such as an acid or itaconic acid, an styrene or an ethylene, an acrylonitrile, a methyl propylene α, a β-unsaturated nitrile, a maleic anhydride, and a Malay Yttrium imine, hydrazine - acrylamide, such as imine, glutaric anhydride, and the like, acryloyl morpholine, etc., may be used alone or in combination of two or more kinds of monomers. Among them, the viewpoint of thermal decomposition resistance and fluidity of the copolymer is methacrylate, ethyl acrylate, η-propyl acrylate, s-butyl acrylate, and 2-ethylhexyl propylene. Use methacrylate or η-butyl acrylate. The acrylic resin (the average molecular weight (Mw) used in the optical film of the present invention is preferably in the range of from 1,100,000 to 1,000,000, more preferably in the range of from 140,000 to 600,000, and in the range of from 200,0 to 400,000. The weight average molecular weight of the acrylic resin of the invention can be determined by chromatography. The measurement conditions are as follows. Solvent: dichloromethane column: Shodex K8 06, K8 05, K803G (Showa acid resin. Methyl ester unit - 50% by mass 1 8 Alkane ester, propylene fumaric acid, α-methylbenzonitrile, etc., such as a maleate derivative, preferably an ester, η-butyrate, etc., within the weight range, particularly preferably by coagulation Adhesive (share) -12- 201107385 3 connections for use) Column temperature: 2 5 °C Sample concentration: 〇.1 mass% Detector: RI Model 504 (made by GL Science) Chestnut L6000 (Hitachi, Ltd. ( Stock) Flow: l.Oml/min Calibration curve: Calibration curve of 13 samples of standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 2,800,000-500. It is preferred to use 13 samples at substantially equal intervals. The method for producing the acrylic resin (A) of the present invention is not particularly limited, and any of known methods such as suspension polymerization, emulsion polymerization, bulk polymerization or solution polymerization can be used. Among them, a general peroxide system, an azo-based or redox-based polymerization initiator can be used as the polymerization initiator. If the polymerization temperature is suspended or emulsion polymerization, it can be polymerized at 30 to 100 ° C, and the polymerization in bulk or solution can be carried out at 80 to 160 ° C. In order to control the reduction viscosity of the obtained copolymer, an alkylthiol or the like may be used as a chain transfer agent to carry out polymerization. A commercially available product can be used for the acrylic resin of the present invention. For example, there are Delpet 6 0N, 80 N (made by Asahi Kasei Chemicals Co., Ltd.), Dianal BR52, BR80, BR83, BR85, BR 8 8 (Mitsubishi R ay 〇n (share) system), KT75 (electrochemical industry) )Wait. The acrylic resin may also be used in two or more kinds (cellulose ester resin (Β)). The cellulose vinegar resin (Β) of the present invention, particularly from the viewpoint of improving the brittleness or the transparency when 201107385 is compatible with the acrylic resin (A) The total degree of substitution (T) of the fluorenyl group is 2.0 to 3.0, the degree of substitution of the fluorenyl group having a carbon number of 3 to 7 is preferably from 1. 2 to 3.0, and more preferably the total substitution degree of the fluorenyl group is from 2.5 to 3.0. The degree of substitution of the fluorenyl group having 3 to 7 carbon atoms is 2.0 to 3.0. When the total degree of substitution of the thiol group of the cellulose ester resin (Β) is less than 2.0, the acrylic resin (Α) and the cellulose ester resin (Β) are not sufficiently compatible, and when used as an acrylic film, there is haze ( Haze) problem. Further, even when the total degree of substitution of the fluorenyl group is 2.0 or more, when the degree of substitution of the fluorenyl group having 3 to 7 carbon atoms is less than 1.2, sufficient compatibility or brittleness is not obtained. In the present invention, the above mercapto group may be an aliphatic mercapto group or an aromatic mercapto group. When it is an aliphatic fluorenyl group, it may be a straight chain or a branched chain, and hydrazine may have a substituent. The moiety that is not substituted by a thiol group is usually present in the form of a hydroxyl group. These can be synthesized by a known method. The cellulose ester resin (B) of the present invention is particularly preferably selected from the group consisting of cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate benzoate, cellulose propionate, fiber At least one of the butyrate. These particularly preferred cellulose ester resins are cellulose acetate propionate, cellulose propionate, and the degree of substitution of ethyl thiol or other thiol groups can be achieved by ASTM-D817-96. The prescribed method is obtained. The weight average molecular weight (Mw) of the cellulose ester resin of the present invention is particularly preferably 75,000 or more, preferably 75,000 to 240,000, more preferably 100,000, from the viewpoint of compatibility with the acrylic resin (A) and improvement of brittleness. Within the range of ~240,000, the best is 160,000~240, the best. 201107385 Two or more types of cellulose resins can be used in combination in the present invention. In the acrylic film of the present invention, from the viewpoint of exhibiting the effects of the present invention, the acrylic resin (A) and the cellulose ester resin (B) are preferably used in a mass ratio of 8 5 : 15 to 3 0: 70, more preferably 8 0: 20 to 40: 60, preferably 80: 20 to 50: 50 ° The film of the present invention preferably contains an acrylic resin (A) and a cellulose ester resin (B) in a compatible state. The different resins are compatible and complementary to the physical properties or qualities necessary for the optical film. For example, whether or not the acrylic resin (A) and the cellulose ester resin (B) are in a compatible state can be determined by the glass transition temperature Tg. For example, when the glass transition temperatures of the resins of the two are different, when the resins of the two are mixed, the glass transition temperature of the respective resins is also present, so that the glass transition temperature of the mixture is also two or more. However, when the resins of the two are compatible, the respective resins are used. The intrinsic glass transition temperature disappears and becomes one glass transition temperature, which becomes the glass transition temperature of the resin after the compatibility. Here, the glass transition temperature referred to herein means a differential scanning calorimeter (DSC-7 type manufactured by Perkin Elmer Co., Ltd.), and is measured at a temperature increase rate of 2 〇 ° C/min, according to JIS K712l (1 9 8 7 ). The intermediate point glass transition temperature (Tmg) obtained. The film of the present invention may contain a resin other than the acrylic resin (A) or the cellulose ester resin (B) or an additive, within a range not impairing the effects of the present invention. In the present invention, in order to improve the adhesion between the polarizer and the polarizer protective film, it is preferred to use fine particles. The fine particles which can be used in the present invention are, for example, those having a particle size of -15 - 201107385 or organic fine particles. The organic fine particles are preferably polymers such as polyoxyxylene resins, fluororesins, and acrylic resins. Among them, acrylic particles are preferably used. In the present invention, it is preferable to use inorganic fine particles which are excellent in the shape of a roll after saponification and which can be elongated, but it is preferable to use inorganic fine particles and organic fine particles to make the polarizing plate more adhesive. <Inorganic Fine Particles> The inorganic fine particles are preferably, for example, a cerium-containing compound, cerium oxide, aluminum oxide, chromium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium citrate, water, and calcium citrate. , aluminum citrate, magnesium citrate and calcium phosphate, etc., more preferably inorganic fine particles or oxidized knots containing sand. Among them, it is preferable to use cerium oxide which is close to the cellulose ester and has excellent transparency (haze: haze). Specific examples of cerium oxide are preferably AEROSIL 200V, AEROSIL R972 V, AEROSIL R972, R974, R812, 200, 300, R202, 0X50 'TT600 (above is Japan AEROSIL), SEAHOSTAR KEP-10, SEAHOSTAR KEP -30, SEAHOSTAR KEP-50, SEAHOSTAR KE-P100 (above (Japan), Japan), SylophobiclOO (made by Fuji Silysia), Nipseal E220A (made by Japan Silica Industries), ADM AFINE SO (made by Admatechs), etc. Famous commercial items, etc. The shape of the inorganic fine particles is, for example, amorphous, needle-like, flat, spherical, or the like, and can be used, particularly when spherical particles are used, so that the transparency of the film obtained in the use of the film -16-201107385 is better. good. When the particle size is close to the wavelength of visible light, light is scattered and the transparency is deteriorated, so that it is preferably smaller than the wavelength of visible light, and more preferably 1/2 or less of the wavelength of visible light. The size of the particles is preferably in the range of 〇.05Mm to 3·〇μπι. These fine particles may be used singly or in combination of two or more. By using particles of different particle sizes or shapes (for example, needles and spheres), it is possible to simultaneously achieve high transparency and slipperiness. These fine particles may contain the entire optical film. Ο 1 to 5 mass%. The size of the particles refers to the size of the aggregate when the particles are aggregates of primary particles. When the particles are non-spherical, they indicate the diameter of a circle corresponding to the projected area. <Acrylic Particles> The acrylic particles of the present invention are characterized in that the acrylic resin (A), the cellulose ester resin (?) and the film containing the acrylic resin are present in a particle state (also referred to as an incompatible state). . For example, the acrylic particles are prepared by dissolving a film containing the acrylic resin after the preparation, dissolving in a solvent, stirring, and sufficiently dissolving and dispersing 'filtering using a PTFE membrane filter having a pore diameter of less than the average particle diameter of the acrylic particles. The weight of the insoluble matter collected by filtration is preferably 90% by mass or more based on the acrylic particles added to the film containing the acrylic resin. The acrylic particles to be used in the present invention are not particularly limited, and are preferably acrylic particles having a layer structure of two or more layers, and particularly preferably a multilayer structure of acrylic particles as described below. The multi-layered structure of the acrylic granular composite refers to a layered overlap of the crosslinked soft layer polymer and the outermost hard layer polymer having the innermost hard layer polymer 'having the innermost hard layer polymer' from the center portion to the outer peripheral portion -17-201107385 A particulate acrylic polymer of the resulting structure. A preferred embodiment of the multilayer structure acrylic-based particulate composite used in the acrylic resin composition of the present invention is, for example, the following. For example, (a) from 80 to 98.9 mass% of methyl methacrylate, from 1 to 20% by mass of the alkyl acrylate having an alkyl group of from 1 to 8, and a polyfunctional grafting agent 〇.〇1~〇 An internal hard layer polymer obtained by polymerizing a monomer mixture composed of 3 mass%; (b) an alkyl group having 4 to 8 carbon atoms from an alkyl group in the presence of the innermost hard layer polymer a crosslinked soft layer polymer obtained by polymerizing a monomer mixture composed of 75 to 98.5% by mass of acrylate, 0.01 to 5% by mass of a polyfunctional crosslinking agent, and 0.5 to 5% by mass of a polyfunctional grafting agent; c) an alkyl acrylate having a carbon number of 8 to 99% by mass of methyl methacrylate and 1 to 8 carbon atoms in the presence of a polymer composed of the innermost hard layer and the crosslinked soft layer The outermost hard layer polymer obtained by polymerizing a monomer mixture composed of % by mass; having a three-layer structure and the obtained three-layer structure polymer being the innermost hard layer polymer (a) 5 to 4 〇 % by mass, soft layer polymer (b) 30 to 60% by mass, and outermost hard layer polymer (c) 20 to 50% by mass The insoluble portion 'insoluble portion of the methyl ethyl ketone swelling degree of the acrylic polymer is a particulate .5~4.0 when one distinction. Further, as disclosed in Japanese Patent Publication No. Sho 60-17406 or Japanese Patent Publication No. Hei No. 3-39095, the composition and particle diameter of each layer of the multilayered acrylic particulate composite are specified, and the multilayered structural acrylic composite is also used. The tensile modulus and the methyl ethyl ketone swelling degree of the acetone insoluble portion are set within a specific range of -18 to 201107385, whereby a balance of more sufficient impact resistance and stress whitening resistance can be achieved. The innermost hard layer polymer (a) constituting the multilayer structure acrylic granulated composite is preferably an alkyl acrylate having a methyl methacrylate of 80 to 98.9 mass% and an alkyl group having a carbon number of 1 to 8. 20% by mass and a polyfunctional grafting agent 0.0 1-0.3% by mass of the monomer mixture obtained by polymerization. The alkyl acrylate having an alkyl group having 1 to 8 carbon atoms, for example, methacrylate, ethacrylate, η-propyl acrylate, η-butyl acrylate, s-butyl acrylate, 2- As the ethylhexyl acrylate or the like, methacrylate and η-butyl acrylate are preferably used. The ratio of the alkyl acrylate unit in the innermost hard layer polymer (a) is preferably from 1 to 20% by mass. When the unit is less than 1% by mass, the thermal decomposition property of the polymer becomes large, and when the position exceeds 20% by mass, the glass transition temperature of the innermost hard layer polymer (c) is lowered, and the 3-layer structure is composed of acrylic particles. The effect of the punching resistance of the composite is lowered, so both are not good. The polyfunctional grafting agent is a polyfunctional monomer having different polymerizable functional groups such as acrylic acid, methacrylic acid, maleic acid, allyl fumarate, etc. Preferably, allyl group is used. Acrylate. The polyfunctional grafting agent is used to chemically bond the innermost hard layer polymer to the soft layer polymer. Therefore, the ratio of the innermost hard layer to be polymerized is 0.0 1 to 0. 3 mass%. The crosslinked soft layer polymer (b) constituting the acrylic granular composite is preferably an alkyl acrylate having a carbon number of from 1 to 8 in the presence of the innermost hard layer polymer (a). 75 to 98.5 mass%, polyfunctionality -19-201107385 A combination of 单体 5 5 5 mass % and a polyfunctional grafting agent ο · 5 to 5 mass % of the monomer mixture is obtained by polymerization. The alkyl acrylate wherein the alkyl group has a carbon number of 4-8 is preferably η-butyl acrylate or 2-ethylhexyl acrylate. Further, these polymerizable monomers may be copolymerized with 25% by mass or less of other monofunctional monomers copolymerizable. Other monofunctional monomers which can be copolymerized are, for example, styrene and substituted styrene derivatives. When the ratio of the alkyl acrylate having an alkyl group of 4 to 8 to styrene is the same as the current one, the lower the glass transition temperature of the resulting polymer (b), the softer it is. Further, from the viewpoint of the transparency of the resin composition, the refractive index of the soft layer polymer (b) at normal temperature is closer to the innermost hard layer polymer (a), the outermost hard layer polymer (c), and the hard thermoplastic acrylic resin. The better, consider the ratio of the two after considering these. For example, in the case where the thickness of the coating layer is small, it is not necessary to copolymerize styrene. As the polyfunctional grafting agent, those enumerated as mentioned in the above-mentioned innermost hard layer polymer (a) can be used. The poly-energetic grafting agent used herein is for chemically bonding the soft layer polymer (b) to the outermost hard layer polymer (c), and the ratio of the innermost hard layer used for polymerization is The viewpoint of the impact resistance imparting effect is preferably 0.5 to 5% by mass. As the polyfunctional crosslinking agent, a generally known crosslinking agent such as a divinyl compound, a diallyl compound, a diacrylic compound or a dimethacrylic compound can be used, and polyethylene glycol diacrylate (molecular weight - 20-201107385 200 to 600) The polyfunctional crosslinking agent used herein is used to form a crosslinked structure during polymerization of the soft layer (b), and has an effect of imparting impact resistance. However, when the conventional polyfunctional grafting agent is used for the polymerization of the soft layer, the crosslinked structure of the soft layer (b) is formed to some extent, so that the polyfunctional crosslinking agent is not essential, but from the viewpoint of imparting impact resistance, The ratio of the polyfunctional crosslinking agent used in the polymerization of the soft layer is preferably 0.01 to 5% by mass. The outermost hard layer polymer (c) constituting the multilayer structure acrylic granular composite is preferably composed of methacrylic acid in the presence of the innermost hard layer polymer (a) and the soft layer polymer (b). A monomer mixture composed of 80 to 99% by mass of an ester and 1 to 20% by mass of a base acrylic vinegar having an alkyl group of 1 to 8 is polymerized. Among them, the alkyl acrylate may be used as described above, and it is preferred to use methacrylate and ethacrylate. The proportion of the alkyl acrylate unit in the outermost hard layer (c) is preferably from 1 to 20% by mass. Further, in the polymerization of the outermost hard layer (c), in order to improve the compatibility with the acrylic resin (A), in order to adjust the molecular weight, an alkyl mercaptan or the like may be used as a chain transfer agent for polymerization. In particular, it is preferable that the outermost hard layer has a slope (slope) in which the molecular weight is gradually decreased from the inside to the outside, and the balance between the elongation and the impact resistance can be improved. The specific method is to divide the monomer mixture for forming the outermost hard layer into two or more, and sequentially increase the chain transfer dose per addition, thereby reducing the molecular weight from the inner side to the outer side. The molecular weight formed at this time can be determined by mixing the monomers used each time.

S 21 - 201107385 合物各自單獨在相同條件聚合所得之聚合物的分子量而得知。、本發明較適合使用之多層構造聚合物的丙烯酸粒子之粒徑並無特別限定，較佳爲1 〇 n m以上、1 〇〇〇 n m以下，更佳爲20nm以上、500nm以下，最佳爲50nm以上、400nm以下。本發明較適合使用之多層構造聚合物的丙烯酸系粒狀複合物中，芯與殼之質量比並無特別限定，但是多層構造聚合物全體爲1 〇〇質量份時，芯層較佳爲5 0質量份以上、 90質量份以下，更佳爲60質量份以上' 80質量份以下。這種多層構造丙烯酸系粒狀複合物之市售品，例如有三菱Rayon公司製“metablen”、鐘淵化學工業公司製 “kanes”、吳羽化學工業公司製 “Paraloid”、Rohm and Haas 公司製“Acryloid”、ganz化成工業公司製“staphiloid，，及 kuraray公司製“parapet SA”等，此等可單獨使用或使用2種以上。又，本發明較適合使用之丙烯酸粒子，較適用之接枝共聚合之丙烯酸粒子的具體例有在橡膠質聚合物之存在下，由不飽和羧酸酯系單體、不飽和羧酸系單體、芳香族乙烯基系單體，及必要時可與此等共聚合之其他乙烯基系單體所構成之單體混合物進行共聚而得的接枝共聚物。接枝共聚物之丙烯酸粒子所使用的橡膠質聚合物並無特別限制，可使用二烯系橡膠、丙烯酸系橡膠及乙烯系橡膠等。具體例有聚丁二烯、苯乙烯-丁二烯共聚物 '苯乙 -22- 201107385 烯-丁二烯之嵌段共聚物、丙烯腈-丁二烯共聚物、丙烯酸丁酯-丁一烯共聚物、聚異戊二烯、丁二烯-甲基丙烯酸甲酯共聚物、丙烯酸丁酯-甲基丙烯酸甲酯共聚物、丁二烯_ 丙烯酸乙酯共聚物、乙烯·丙.稀共聚物、乙烯—丙烯-二烯系共聚物、乙稀-異戊二烯共聚物、及乙烯-丙烯酸甲酯共聚物等。此等橡膠質聚合物可使用1種或2種以上的混合物。丙烯酸樹脂（A )及丙烯酸粒子之各自的折射率近似時’可得到本發明之含有丙烯酸樹脂薄膜的透明性，故較佳。具體而言，丙烯酸粒子與丙烯酸樹脂（A )之折射率差較佳爲〇.〇5以下’更佳爲〇·〇2以下，特佳爲0 01以下。爲了滿足這種折射率條件時，可藉由調整丙烯酸樹脂 (A )之各單體單位組成比的方法，及/或調整丙烯酸粒子所使用的橡膠質聚合物或單體之組成比的方法等，縮小折射率差’可得到透明性優異之含有丙烯酸樹脂的薄膜。此處所謂的折射率差係指在丙烯酸樹脂（A )可溶的溶劑中，以適當條件將本發明之含有丙烯酸樹脂之薄膜充分溶解形成白濁溶液後，藉由離心分離等操作，分離成溶劑可溶部分與不溶部分，此可溶部分（丙烯酸樹脂（A ) )與不溶部分（丙烯酸粒子）分別純化後，顯示測得的折射率（2 3 °C、測定波長：5 5 0 n m )之差。本發明中，丙烯酸樹脂（A )中調配丙烯酸粒子的方法並無特別限定，較佳爲使用預先摻合丙烯酸樹脂（A ) 與其他任意成份後，一般於200〜35(TC下添加丙烯酸粒子 ’同時藉由單軸或雙軸擠壓機進行均勻熔融混練的方法。 -23- 201107385 此外，可使用將預先分散有丙烯酸粒子的溶液添加於溶解有丙烯酸樹脂（A)及纖維素酯樹脂（B )的溶液（膠漿液）進行混合的方法或將丙烯酸粒子及其他任意之添加劑溶解、混合後的溶液進行連線（inline )添加等的方法〇本發明之丙稀酸粒子可使用市售品。例如有metablen W-341 (三菱 Rayon (股）製）、chemisnow MR-2G、 MS-3 00X (綜硏化學（股）製）等。本發明之含有丙烯酸樹脂之薄膜中，相對於構成該薄膜之樹脂總質量’較佳爲含有0.5〜45質量％之丙烯酸粒子 <可塑劑> 本發明之薄膜製造時，在薄膜形成材料中可含有可塑劑。可使用的可塑劑無特別限定，例如有多元醇酯系可塑劑、聚酯系可塑劑、3價以上之芳香族多元羧酸酯系可塑劑、乙醇酸酯系可塑劑、磷酸酯系可塑劑、苯二甲酸酯系可塑劑、脂肪酸酯系可塑劑 '糖酯系化合物 '丙烯酸系可塑劑等。特佳爲多元醇系可塑劑。磷酸酯系可塑劑之添加量’從偏光度之耐久性的觀點，較佳爲6質量％以下。可塑劑之1%減量溫度（Tdl )較佳爲250°C以上，更佳爲2 8 0 °C以上，特佳爲300°C以上。多元醇酯係由2價以上之脂肪族多元醇與單羧酸酯所 -24- 201107385 構成’在分子內具有芳香環或環烷基環者較佳。所用的多元醇係下述一般式（1 )表示。一般式（1) : 式中’ R !係表示η價有機基，n係表示2以上 ’〇 Η基係表示醇性羥基或酚性羥基。較佳之多元醇例如有以下所列舉者，但是本於此等。例如有核糖醇、***糖醇、乙二醇、二乙乙二醇 '四乙二醇、1，2 -丙二醇、1，3 -丙二醇、、三丙二醇、1，2-丁二醇、1,3-丁二醇、1,4-丁二二醇、1，2,4-丁三醇、1，5-戊二醇 ' 1,6_己二醇 ' 三醇、1,2，6 -己三醇、甘油、二甘油、半乳糖醇甘露糖醇、3-甲基戊烷-1，3,5-三醇 '四甲基乙二糖醇、三羥甲基丙烷、三羥甲基乙烷、季戊四醇四醇、木糖醇等。其中較佳爲甘油、三羥甲基乙甲基丙院、季戊四醇。本發明之多元醇酯所使用之單羧酸，並無特可使用習知之脂肪族單羧酸、脂環族單羧酸、芳酸等。可提升透濕性、保留性的觀點，較佳爲使單羧酸 '芳香族單羧酸。較佳單羧酸例如有下者，但是本發明不限定於此等。脂肪族單羧酸較佳爲使用具有碳数1〜3 2之直多元醇酯之正整數發明不限二醇、三二丙二醇醇、二丁 1，2,3-己、肌醇、醇 '山梨、二季戊烷、三羥別限制，香族單羧用脂環族述所例示鏈或側鏈 -25- 201107385 之脂肪酸。碳數1~20者更佳，碳數卜10者特佳。使用乙酸時，由於可增加與纖維素酯之相溶性’故較佳’此外也可將乙酸與其他之單羧酸混合使用。較佳之脂肪族單羧酸例如有乙酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、壬酸、癸酸、2 -乙基-庚酸（ h e X a n e c a r b ο X y 1 i c a c i d )、十一·酸、月桂酸、十二酸、肉宣蔻酸、十五酸、棕櫚酸、十七酸、硬脂酸、十九酸、花生酸、二十二烷酸、二十四烷酸、二十六烷酸、二十七烷酸、二十八碳酸、三十碳烷酸、三十二烷酸等之飽和脂肪酸、十一碳烯酸、油酸、山梨酸、亞油酸、亞麻酸、花生浸烯酸等之不飽和脂肪酸等。較佳脂環族單羧酸例如較佳爲碳數3〜8之環烷基，具體例有環戊烷羧酸、環己烷羧酸 '環辛烷羧酸等。較佳芳香族單羧酸例如有苯甲酸、甲苯酸等之苯甲酸之苯環上導入烷基者 '聯苯基羧酸、萘酸 '四氫萘甲酸等具有2個以上之本環的芳香族單殘酸。特佳爲苯甲酸。此等之脂環族單羧酸及芳香族單羧酸可被取代，較佳取代基例如有鹵素原子，例如氯原子、溴原子、氣原子等、經基、垸基、院氧S、環院氧基、芳院基（此苯基可再被烷基或鹵素原子等取代）、乙烯基、烯丙基等之輝基、原子等取代）、苯氧基（取代）、乙醯基、丙醯基丙藤氧基等之碳數爲2〜8 苯基（此苯基可再被烷基或鹵素此苯基可再被烷基或鹵素原子等等之碳數2〜8之醯基、乙醯氧基、之無取代羰氧基等。 -26- 201107385 多元醇酯之分子量並無特別限制，從揮發性、相溶的觀點，較佳爲3 00〜1 500的範圍，更佳爲400〜1 000的範〇多元醇酯所使用之單羧酸可爲1種類或2種以上之混。多元醇中之OH基可全部酯化或一部份直接以〇H基保〇多元醇酯可藉由習知的方法合成。將前述單羧酸與述多元醇例如在酸的存在進行縮合酯化的方法，預先將機酸形成酸氯化物或酸酐後，與多元醇反應的方法，或有機酸的苯基酯與多元醇反應的方法等，可依據目的之化合物適當選擇、產率較佳的方法。可塑劑之多元醇酯可兼前述多元醇脂肪酸酯。聚酯系可塑劑較佳爲使用分子內具有芳香環或環烷環的聚酯系可塑劑。較佳之聚酯系可塑劑無特別限定，如下述一般式（i )表示。The molecular weights of the polymers obtained by polymerizing the S 21 - 201107385 compounds under the same conditions are known. The particle size of the acrylic particles of the multilayer structure polymer which is suitably used in the present invention is not particularly limited, but is preferably 1 〇 nm or more and 1 〇〇〇 nm or less, more preferably 20 nm or more and 500 nm or less, and most preferably 50 nm. Above, below 400nm. In the acrylic granular composite in which the multilayer structure polymer is suitably used in the present invention, the mass ratio of the core to the shell is not particularly limited, but when the multilayer structure polymer is 1 part by mass, the core layer is preferably 5 0 parts by mass or more and 90 parts by mass or less, more preferably 60 parts by mass or more and 80 parts by mass or less. Commercial products of such a multilayer structure of the acrylic granular composite are, for example, "metablen" manufactured by Mitsubishi Rayon Co., Ltd., "kanes" manufactured by Kaneka Chemical Industry Co., Ltd., "Paraloid" manufactured by Kureha Chemical Industry Co., Ltd., and manufactured by Rohm and Haas Co., Ltd. "Acryloid", "staphiloid" manufactured by ganz Chemical Industry Co., Ltd., and "parapet SA" manufactured by Kuraray Co., Ltd., etc., may be used alone or in combination of two or more. Further, the acrylic particles which are more suitable for use in the present invention are more suitable for grafting. Specific examples of the copolymerized acrylic particles include an unsaturated carboxylic acid ester monomer, an unsaturated carboxylic acid monomer, an aromatic vinyl monomer in the presence of a rubbery polymer, and if necessary, A graft copolymer obtained by copolymerizing a monomer mixture composed of another vinyl monomer which is copolymerized. The rubber polymer used for the acrylic particles of the graft copolymer is not particularly limited, and a diene system can be used. Rubber, acrylic rubber, vinyl rubber, etc. Specific examples are polybutadiene, styrene-butadiene copolymer 'phenylethyl-22- 201107385 olefin-butadiene block copolymer Acrylonitrile-butadiene copolymer, butyl acrylate-butene copolymer, polyisoprene, butadiene-methyl methacrylate copolymer, butyl acrylate-methyl methacrylate copolymer, butyl Diene-ethyl acrylate copolymer, ethylene-propylene dilute copolymer, ethylene-propylene-diene copolymer, ethylene-isoprene copolymer, ethylene-methyl acrylate copolymer, etc. It is preferable to use one or a mixture of two or more kinds of the polymer. When the refractive index of each of the acrylic resin (A) and the acrylic particles is approximated, the transparency of the acrylic resin-containing film of the present invention can be obtained, which is preferable. The refractive index difference between the acrylic particles and the acrylic resin (A) is preferably 〇.〇5 or less, more preferably 〇·〇2 or less, particularly preferably 0.001 or less. In order to satisfy the refractive index condition, A method of adjusting the monomer unit composition ratio of the acrylic resin (A), and/or a method of adjusting the composition ratio of the rubber polymer or the monomer used for the acrylic particles, and the like, and reducing the refractive index difference can be excellent in transparency. Acrylic resin The refractive index difference herein means that the acrylic resin-containing film of the present invention is sufficiently dissolved in a solvent soluble in the acrylic resin (A) to form a white turbid solution under appropriate conditions, and then separated by centrifugation or the like. Solvent-soluble and insoluble fractions, the soluble fraction (acrylic resin (A)) and the insoluble fraction (acrylic acid particles) were separately purified to show the measured refractive index (23 ° C, measurement wavelength: 550 nm) In the present invention, the method of formulating the acrylic particles in the acrylic resin (A) is not particularly limited, and it is preferred to use the acrylic resin (A) and other optional components in advance, usually at 200 to 35 (TC). A method of uniformly adding melt-kneading by adding a acryl particle to a uniaxial or biaxial extruder. -23- 201107385 Further, a method in which a solution in which acrylic particles are dispersed in advance is added to a solution (slurry) in which an acrylic resin (A) and a cellulose ester resin (B) are dissolved may be used, or an acrylic particle and any other particles may be used. A method in which the additive is dissolved and mixed, and the solution is added inline or the like. A commercially available product can be used as the acrylic acid particles of the present invention. For example, there are metablen W-341 (Mitsubishi Rayon (share) system), chemisnow MR-2G, MS-3 00X (complex chemical system). In the acrylic resin-containing film of the present invention, the acrylic resin particles are preferably contained in an amount of from 0.5 to 45% by mass based on the total mass of the resin constituting the film. <Plasticizer> In the film-forming material, the film of the present invention is produced. It may contain a plasticizer. The plasticizer which can be used is not particularly limited, and examples thereof include a polyol ester-based plasticizer, a polyester-based plasticizer, a trivalent or higher aromatic polycarboxylate-based plasticizer, a glycolate-based plasticizer, and a phosphate-based plasticizer. A phthalate-based plasticizer, a fatty acid ester-based plasticizer, a 'sugar ester-based compound', an acrylic plasticizer, and the like. Particularly preferred is a polyol-based plasticizer. The amount of addition of the phosphate-based plasticizer is preferably 6% by mass or less from the viewpoint of durability of the degree of polarization. The 1% reduction temperature (Tdl) of the plasticizer is preferably 250 ° C or higher, more preferably 280 ° C or higher, and particularly preferably 300 ° C or higher. The polyol ester is composed of a divalent or higher aliphatic polyol and a monocarboxylic acid ester -24 to 201107385. It is preferred to have an aromatic ring or a cycloalkyl ring in the molecule. The polyol used is represented by the following general formula (1). In the formula (R), 'R? represents an η-valent organic group, and n represents 2 or more. 〇 Η Η represents an alcoholic hydroxyl group or a phenolic hydroxyl group. Preferred polyols are, for example, those listed below, but are herein. For example, ribitol, arabitol, ethylene glycol, diethylene glycol 'tetraethylene glycol, 1,2-propylene glycol, 1,3-propanediol, tripropylene glycol, 1,2-butanediol, 1, 3-butanediol, 1,4-butanediol, 1,2,4-butanetriol, 1,5-pentanediol '1,6-hexanediol' triol, 1,2,6 - Hexatriol, glycerin, diglycerin, galactitol mannitol, 3-methylpentane-1,3,5-triol 'tetramethylethylene glycolitol, trimethylolpropane, trimethylol Ethane, pentaerythritol, xylitol, and the like. Among them, glycerin, trimethylolmethicone, and pentaerythritol are preferred. The monocarboxylic acid used in the polyol ester of the present invention is not particularly limited to a conventional aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic acid or the like. From the viewpoint of improving moisture permeability and retention, it is preferred to use a monocarboxylic acid 'aromatic monocarboxylic acid. The preferred monocarboxylic acid is, for example, the following, but the invention is not limited thereto. The aliphatic monocarboxylic acid is preferably a positive integer using a straight polyol ester having a carbon number of 1 to 32. The invention is not limited to diol, triethylene glycol alcohol, dibutyl 1,2,3-hexyl, inositol, alcohol Yamanashi, diquapentane, tri-hydroxyl restriction, fragrant monocarboxylates are exemplified by the alicyclic family of fatty acids of the chain or side chain -25- 201107385. The carbon number is 1 to 20, and the carbon number is 10. When acetic acid is used, it is preferable because it can increase the compatibility with the cellulose ester. Further, acetic acid can be used in combination with other monocarboxylic acids. Preferred aliphatic monocarboxylic acids are, for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, 2-ethyl-heptanoic acid (he X anecarb ο X y 1 icacid ), eleven acid, lauric acid, dodecanoic acid, meat, acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nineteen acid, arachidic acid, behenic acid, twenty-four Alkanoic acid, hexadecanoic acid, heptacosanoic acid, octadecanoic acid, tridecanoic acid, tridecanoic acid, etc., saturated fatty acid, undecylenic acid, oleic acid, sorbic acid, linoleic acid An unsaturated fatty acid such as acid, linolenic acid or arachidonic acid. The alicyclic monocarboxylic acid is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include cyclopentanecarboxylic acid and cyclohexanecarboxylic acid 'cyclooctanecarboxylic acid. A preferred aromatic monocarboxylic acid is a phenol having a benzene ring such as benzoic acid or toluic acid, and an aromatic group having two or more rings, such as a biphenyl carboxylic acid or a naphthoic acid, tetrahydronaphthoic acid. The family is single acid. Particularly preferred is benzoic acid. These alicyclic monocarboxylic acids and aromatic monocarboxylic acids may be substituted, and preferred substituents are, for example, a halogen atom such as a chlorine atom, a bromine atom, a gas atom, etc., a thiol group, a sulfhydryl group, a house oxygen S, a ring. a oxy group, a aryl group (this phenyl group may be further substituted by an alkyl group or a halogen atom, etc.), a vinyl group, an allyl group or the like, a fluorenyl group, an atom or the like), a phenoxy group (substituted), an ethyl group, The carbon number of the propyl ketone ketone or the like is 2 to 8 phenyl groups (this phenyl group may be further alkyl or halogen), and the phenyl group may be further substituted with an alkyl group or a halogen atom or the like having a carbon number of 2 to 8 , ethoxycarbonyl, unsubstituted carbonyloxy, etc. -26- 201107385 The molecular weight of the polyol ester is not particularly limited, and from the viewpoint of volatility and compatibility, it is preferably in the range of 300 to 1,500, more preferably The monocarboxylic acid to be used in the range of 400 to 1 000 of the hydrazine polyol ester may be one type or a mixture of two or more types. The OH groups in the polyol may be all esterified or partially protected by hydrazine H group. The polyol ester can be synthesized by a conventional method. The above-mentioned monocarboxylic acid and the polyol are condensed and esterified, for example, in the presence of an acid, and the acid is preliminarily A method of reacting with a polyhydric alcohol after forming an acid chloride or an acid anhydride, or a method of reacting a phenyl ester of an organic acid with a polyhydric alcohol, etc., may be appropriately selected depending on the intended compound, and a yield is preferred. The polyester-based plasticizer is preferably a polyester-based plasticizer having an aromatic ring or a cycloalkane ring in the molecule. The preferred polyester-based plasticizer is not particularly limited, as in the following general formula. (i) indicated.

—般式（i) : B-(G-A) ni-G-B (式中，B爲苯單羧酸殘基，G爲碳數2〜12之伸烷基二殘基或碳數6〜12之芳基乙二醇殘基或碳數爲4〜12之氧基烷基二醇殘基，A爲碳數2~12之伸烷基二羧酸殘基或碳 6〜12之芳基二羧酸殘基，nl爲1以上之整數） —般式（i)中，由B表示之苯單羧酸殘基與G表示伸烷二醇殘基或氧基伸烷基二醇殘基或芳基乙二醇殘基性圍合留前有使酯基例醇伸數之General formula (i): B-(GA) ni-GB (wherein B is a benzene monocarboxylic acid residue, G is an alkyl 2 residue having a carbon number of 2 to 12 or a carbon number of 6 to 12 a glycol residue or an oxyalkyl glycol residue having a carbon number of 4 to 12, and A is an alkyl dicarboxylic acid residue having 2 to 12 carbon atoms or an aryl dicarboxylic acid having 6 to 12 carbon atoms. Residue, nl is an integer of 1 or more.) In the general formula (i), the benzene monocarboxylic acid residue represented by B and G represent an alkylene glycol residue or an alkylene glycol residue or an aryl group B. The residue of the diol residue is retained before the retention of the ester base

S -27- 201107385 A表示之伸烷基二羧酸殘基或芳基二羧酸殘基所構成者，可藉由與通常之聚酯系可塑劑同樣之反應而得到。本發明所使用之聚酯系可塑劑之苯單錢酸成分’例如有苯甲酸、對第三丁基苯甲酸、鄰甲苯酸、間甲苯酸、對甲苯酸、二甲基苯甲酸、乙基苯甲酸、正丙基苯甲酸、胺基苯甲酸、乙醯氧基苯甲酸等，此等可爲各自使用1種或使用2種以上之混合物。聚酯系可塑劑之碳數2〜1 2之伸烷基二醇成分’例如有乙二醇、1，2-丙二醇、1，3-丙二醇、1,2-丁二醇、1，3-丁二醇、2-甲基1，3-丙二醇、1，4-丁二醇、1，5-戊二醇、2,2-二甲基-1，3-丙二醇（新戊基二醇）、2，2-二乙基-1,3-丙二醇 (3,3-二羥甲基戊烷）、2-11-丁基-2-乙基-1，3-丙二醇（ 3,3-二羥甲基庚烷）、3-甲基-1,5-戊二醇、1,6-己二醇、 2,2,4·三甲基-1，3-戊二醇、2-乙基-1，3-己二醇、2-甲基· 1，8-辛二醇、1,9 -壬二醇、1，1〇_癸二醇、1,12 -十八烷二醇等，此等之二醇可使用1種或使用2種以上之混合物。芳香族末端酯之碳數4〜12之氧基伸烷基二醇成分，例如有二乙二醇、三乙二醇、四乙二醇、二丙二醇、三丙二醇等，此等之二醇可使用1種或使用2種以上之混合物。芳香族末端酯之碳數4〜1 2之伸烷基二羧酸成分，例如有琥珀酸、馬來酸、富馬酸、戊二酸、己二酸、壬二酸、癸二酸、十二烷二羧酸等，此等可使用各1種或使用2種以上之混合物。碳數6~ 1 2之伸芳基二羧酸成分，例如有苯二甲酸、間苯二甲酸、對苯二甲酸、1,5-萘二羧酸、1,4-萘 -28- 201107385 二羧酸等。本發明所使用之聚酯系可塑劑之數平均分子量較佳爲 40 0〜2000 ’更佳爲500〜150〇之範圍。其酸價爲 0.5mgKOH/g以下’且羥基價爲25mgKOH/g以下較佳，更佳爲酸價〇.3mg KOH/g以下，且羥基價爲l5mgKOH/g以下者。 3價以上之芳香族多元羧酸酯系可塑劑較佳爲均苯三酸酯、偏苯三酸酯或均苯四甲酸酯。與芳香族多元羧酸形成酯的醇較佳爲碳數1〜8的醇。特佳的3價以上之芳香族多元羧酸酯系可塑劑，例如有均苯三酸三丁酯、均苯三酸三己酯、均苯三酸三2 -乙基-己酯、均苯三酸三環己酯、偏苯三酸三丁酯、偏苯三酸三己酯、偏苯三酸三2-乙基-己酯、偏苯三酸三環己酯、均苯四甲酸四丁酯、均苯四甲酸四己酯、均苯四甲酸四2 -乙基-己酯、均苯四甲酸四環己酯等，但是本發明不受此限定。乙醇酸酯系可塑劑可使用例如乙基鄰苯二醯基乙基乙醇酸酯、丁基鄰苯二醯基丁基乙醇酸酯，磷酸酯系可塑劑可使用例如三苯基磷酸酯、三甲苯基磷酸脂、甲苯基二苯基磷酸脂、辛基二苯基磷酸脂、二苯基聯苯基磷酸脂、三辛基磷酸脂、三丁基磷酸脂、1，3_伸苯基雙（二磷酸二甲苯脂）、：l，3 -伸苯基雙（二苯基磷酸脂）等，酞酸酯系可塑劑可使用例如二乙基酞酸酯、二甲氧基乙基酞酸酯、二甲基酞酸酯、二辛基酞酸酯、二丁基酞酸酯、丁基苄基酞酸酯、二-2-乙基己基酞酸酯。其他可使用乙醯基三丁基檸 -29- 201107385 檬酸酯等之檸檬酸酯系可塑劑、環氧化油系可塑劑等。《抗氧化劑、熱劣化防止劑》本發明中，抗氧化劑、熱劣化防止劑可使用通常所知的劣化防止劑（抗氧化劑、過氧化物分解劑、自由基抑制劑、金屬惰性化劑、酸捕捉劑、胺等）。特佳爲使用內酯系、硫系、酚系、雙鍵系、受阻胺系、磷系化合物。劣化防止劑例如記載於日本特開平3· 1 99201號公報、特開平5-1 94789號公報、特開平5-27 1 47 1號公報、特開平6- 1 07854 號公報等。上述酚系化合物較佳爲具有2,6-二烷基酚之結構者，例如有 Ciba Japan (股）以 IrganoxI076、IrganoxlOlO之商品名所市售者。上述磷系化合物較佳爲例如有住友化學（股）之商品名 Sumilizer-GP、ADEKA (股）之商品名八01<：3丁八8?£?-24G、ADK STAB PEP-3 6 及 ADK STAB 30 1 0、Ciba Japan ( 股）之商品名I R G A F O S P - E P Q、堺化學（股）之商品名 GSY-P101所市售者。上述受阻胺系化合物較佳爲例如C i b a J a p a η (股）之商品名 Tinuvinl44 及 Tinuvin770、ADEKA (股）之商品名 ADK STAB LA-52 所市售者。上述硫系化合物較佳爲例如有住友化學（股）之商品名 Sumilizer TPL-R及 Sumilizer TP-D所巾售者。上述雙鍵系化合物較佳爲例如有住友化學（股）之商 -30- 201107385 品名 Sumilizer-GM及 Sumilizer-GS所市售者。此外’可含有作爲酸捕捉劑之如美國專利第4,1 3 7,20 1 號說明書所記載之具有環氧基的化合物。這些抗氧化劑等可配合再生使用時之步驟決定適當的添加量’但是一般相對於薄膜之主原料的樹脂添加0.05〜5 質量％。這些抗氧化劑、熱劣化防止劑相較於使用單獨一種，不如倂用數種不同體系的化合物，可得到相乘效果。例如較佳爲倂用內酯系、磷系、酚系及雙鍵系化合物。 <著色劑> 本發明可使用著色劑。通常著色劑係指染料或顏料，但是本發明係指具有使液晶畫面之色調形成藍色調的效果或調整黃色指數（黃色度）、降低霧度者。著色劑可使用各種染料、顏料，較佳爲蒽醌染料、偶氮染料、酞青顏料等。 <紫外線吸收劑> 本發明所使用之紫外線吸收劑並無特別限制，例如有氧基二苯甲酮系化合物、苯并***系化合物、水楊酸酯系化合物、二苯甲酮系化合物、氰基丙烯酸酯系化合物、三曉系化合物、鎳錯鹽系化合物、無機粉體等。也可爲高分子型紫外線吸收劑。本發明較適合使用的紫外線吸收劑係透明性高、防止偏光板或液晶元件之劣化的效果優異的苯S -27-201107385 A, which is represented by an alkyl dicarboxylic acid residue or an aryl dicarboxylic acid residue, can be obtained by the same reaction as a usual polyester plasticizer. The benzoic acid component of the polyester-based plasticizer used in the present invention is, for example, benzoic acid, p-tert-butylbenzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, dimethylbenzoic acid, ethyl Benzoic acid, n-propyl benzoic acid, aminobenzoic acid, ethoxylated benzoic acid, etc. may be used alone or in combination of two or more. The polyester-based plasticizer has a carbon number of 2 to 1 2 of an alkylene glycol component, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, and 1,3- Butanediol, 2-methyl1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol) 2,2-Diethyl-1,3-propanediol (3,3-dihydroxymethylpentane), 2-11-butyl-2-ethyl-1,3-propanediol (3,3-di Hydroxymethylheptane), 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4·trimethyl-1,3-pentanediol, 2-ethyl -1,3-hexanediol, 2-methyl·1,8-octanediol, 1,9-nonanediol, 1,1〇-nonanediol, 1,12-octadecanediol, etc. These diols may be used alone or in combination of two or more. The aromatic terminal ester has an alkyl group having a carbon number of 4 to 12, and examples thereof include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol. These diols can be used. One type or a mixture of two or more types is used. The aromatic terminal ester has a carbon number of 4 to 1 2 alkyl dicarboxylic acid component, for example, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, sebacic acid, sebacic acid, ten As the dialkyldicarboxylic acid or the like, one type of these may be used or a mixture of two or more types may be used. a aryl aryl dicarboxylic acid component having 6 to 12 carbon atoms, such as phthalic acid, isophthalic acid, terephthalic acid, 1,5-naphthalene dicarboxylic acid, 1,4-naphthalene-28-201107385 Carboxylic acid, etc. The number average molecular weight of the polyester-based plasticizer used in the present invention is preferably from 40 to 2,000 Å, more preferably from 500 to 150 Å. The acid value is preferably 0.5 mgKOH/g or less and the hydroxyl group value is 25 mgKOH/g or less, more preferably the acid value is 〇3 mg KOH/g or less, and the hydroxyl group value is 15 mgKOH/g or less. The aromatic polyvalent carboxylate plasticizer having a trivalent or higher content is preferably a trimesic acid ester, a trimellitic acid ester or a pyromellitic acid ester. The alcohol which forms an ester with the aromatic polycarboxylic acid is preferably an alcohol having 1 to 8 carbon atoms. Particularly preferred trivalent or higher aromatic polycarboxylate plasticizers, such as tributyl trimellitate, trihexyl trimellitate, tris-ethylhexyl trimellitate, and benzene Tricyclohexyl triacetate, tributyl trimellitate, trihexyl trimellitate, tri-2-ethylhexyl trimellitate, tricyclohexyl trimellitate, pyromellitic acid tetra Butyl ester, tetrahexyl pyromelliate, tetrakis-ethyl-hexyl pyromelliate, tetracyclohexyl pyromelliate, etc., but the invention is not limited thereto. As the glycolate-based plasticizer, for example, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, and a phosphate plasticizer such as triphenyl phosphate can be used. Tolyl phosphate, tolyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, 1,3_phenylene (xylylene diphosphate), :1,3-phenylphenylbis(diphenyl phosphate), etc., and phthalate plasticizers such as diethyl phthalate, dimethoxyethyl decanoic acid can be used. Ester, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate, di-2-ethylhexyl phthalate. Other citrate-based plasticizers such as ethyltributylsulfon -29-201107385 citrate and epoxidized oil-based plasticizers can be used. <<Antioxidant and Thermal Deterioration Agent>> In the present invention, as the antioxidant or the thermal deterioration preventing agent, a commonly known deterioration preventing agent (antioxidant, peroxide decomposing agent, radical inhibitor, metal inerting agent, acid) can be used. Capture agent, amine, etc.). Particularly preferred is a lactone-based, sulfur-based, phenol-based, double-bonded, hindered amine-based or phosphorus-based compound. For example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The phenolic compound is preferably a structure having a 2,6-dialkylphenol. For example, Ciba Japan is commercially available under the trade names of Irganox I076 and IrganoxlO10. The phosphorus-based compound is preferably, for example, Sumitomo Chemical Co., Ltd. under the trade name Sumilizer-GP, ADEKA (trade name), trade name 八01<3, 八八八?£?-24G, ADK STAB PEP-3 6 and ADK. STAB 30 1 0, Ciba Japan (share) trade name IRGAFOSP - EPQ, 堺Chemical (share) trade name GSY-P101 is commercially available. The hindered amine-based compound is preferably sold, for example, under the trade names of Tinbinl44 and Tinuvin 770, and ADEKA (trade name) ADK STAB LA-52, under the trade names of C i b a J a p a η (shares). The above-mentioned sulfur-based compound is preferably sold, for example, by Sumitomo Chemical Co., Ltd. under the trade names of Sumilizer TPL-R and Sumilizer TP-D. The above double bond compound is preferably, for example, commercially available from Sumitomo Chemical Co., Ltd. -30-201107385 under the names Sumilizer-GM and Sumilizer-GS. Further, it may contain a compound having an epoxy group as described in the specification of U.S. Patent No. 4,1,7,201, which is an acid scavenger. These antioxidants and the like can be used in combination with the step of recycling, and the appropriate amount of addition is determined, but the amount of the resin added to the main raw material of the film is generally 0.05 to 5% by mass. These antioxidants and thermal deterioration preventive agents are comparable to those of a single system, and a multiplication effect can be obtained by using a compound of several different systems. For example, a lactone-based, phosphorus-based, phenol-based or double-bonded compound is preferred. <Colorant> A colorant can be used in the present invention. Usually, the coloring agent means a dye or a pigment, but the present invention means an effect of causing a hue of a liquid crystal picture to form a blue hue or adjusting a yellow index (yellowness) to lower the haze. As the colorant, various dyes and pigments can be used, and an anthraquinone dye, an azo dye, an indigo pigment or the like is preferable. <Ultraviolet absorber> The ultraviolet absorber used in the present invention is not particularly limited, and examples thereof include an oxybenzophenone-based compound, a benzotriazole-based compound, a salicylate-based compound, and a benzophenone-based compound. A compound, a cyanoacrylate compound, a tricholine compound, a nickel salt fault compound, an inorganic powder, or the like. It can also be a high molecular ultraviolet absorber. The ultraviolet absorber which is suitably used in the present invention is a benzene having high transparency and excellent effect of preventing deterioration of a polarizing plate or a liquid crystal element.

S -31 - 201107385 並***系紫外線吸收劑或二苯甲酮系紫外線吸收劑爲佳，特佳爲不必要之著色更少的苯並***系紫外線吸收劑。本發明使用之紫外線吸收劑的具體例，較佳爲使用例如Ciba Japan (股）製之 TINUVIN 109、TINUVIN 171 、 TINUVIN3 26、TINUVIN 3 27、TINUVIN 3 28、TINUVIN 900、TINUVIN928、ADEKA (股）之 LA-31等，但是本發明不受此限。紫外線吸收劑較佳爲使用高分子紫外線吸收劑’特佳爲使用特開平6- 1 48430號記載之聚合物型的紫外線吸收劑。紫外線吸收劑可單獨使用或使用2種以上之混合物。紫外線吸收劑之使用量係依化合物之種類、使用條件等而不同’纖維素酯薄膜之乾燥膜厚爲30~200μηι時，相對於纖維素酯薄膜’較佳爲〇 · 5〜4 · 0質量％，更佳爲〇 · 6〜3 . 5質量％〇 <本發明之薄膜的製膜方法> 本發明之薄膜可藉由溶液流延方法、熔融流延來製作，以下首先敘述熔融製膜方法。 <熔融流延製膜方法> 藉由溶融製膜法之薄膜的成形法可分類爲熔融擠出成形法、加壓成形法、吹袋成型（Inflation )、射出成形法、吹塑成形法、延伸成形法等。其中爲了可得到機械強度及表面精度等優異的薄膜時，熔融擠出成形法較優異。 -32- 201107385 以下舉熔融擠出成形法爲例，針對本發明之薄膜的製造方法來説明。薄膜之製造方法中，熔融擠出之條件可與一般熱可塑性樹脂所用的條件同樣進行熔融擠出。《顆粒製造步驟》使用於熔融擠出之複數的原材料，一般預先經混煉成顆粒（p e 11 e t )化較佳。顆粒化可藉由公知方法，例如將乾燥的丙烯酸樹脂、纖維素酯樹脂或添加劑由供應器供給擠出機，並使用1軸或2軸之擠出機進行混煉，由塑模擠出成單紗狀，經水冷卻或空氣冷卻後進行切割。紫外線吸收劑或消光劑等係製作高濃度之主（master )顆粒後，也可在薄膜製膜時，在擠出機中與主要的顆粒混合。原材料於擠出前先行乾燥，對於防止原材料分解是非常重要的。特別是纖維素酯較容易吸濕，故可使用除濕熱風乾燥機或真空乾燥機，以7 0〜1 4 0。(：下乾燥3小時以上，使水分率成爲200ppm以下’更佳爲i〇〇ppm以下。添加劑可於供給於擠出機前先混合 '或各自以個別供應器供給。抗氧化劑等少量之添加劑爲了均勻混合時，事前先混合較佳。真空圓錐螺旋混合機等可同時乾燥與混合，故較佳。又’與由供應器部或塑模之出口等與空氣接觸之處，較佳爲除濕空氣或經除濕之氮氣體等環境下。 S- -33- 201107385 又，對擠出機之供給料斗等在保溫狀態時，可防止吸濕，故較佳。擠出機係抑制剪切力，避免樹脂劣化（分子量降低、著色、凝膠生成等），以低溫加工較佳，例如2軸擠出機的情況時，使用深溝型螺旋以同方向轉動較佳。由混煉均勻性的觀點，以咬合型爲佳。捏和圓盤雖可提高混煉性，但是必須注意剪切發熱。由吸孔之吸引必要時可實施。只要是低溫時，幾乎不會產生揮發成分，故也可爲無吸孔。顆粒的顏色係黃味指標之b ’値爲-5〜1 0之範圍較佳，-1〜8之範圍更佳’ -1〜5之範圍更佳。b *値可以分光測色計 CM-3 700d ( KONICA MINOLTA SENSING (股）製），光源使用D65 (色溫度65 04K)，以視角1〇。測定。較佳爲使用如上所得之顆粒進行薄膜製膜，但是可不進行顆粒化，而直接將原材料粉末以供應器供給擠出機，進行薄膜製膜。《溶融物擠出步驟》顆粒等之材料係預先經乾燥爲佳。以真空或減壓乾燥機或除濕熱風乾燥機使水分乾燥至2 00ppm以下，較佳爲 1 0 0 p p m 以下。除濕熱風或真空或減壓下乾燥後的聚合物使用1軸或2 軸型的擠出機，熔融後，以葉片式（leaf disk filter)過濾器等過濾除去異物後’從流延模流延成薄膜狀，在冷卻 -34- 201107385 輥上固化。擠出機可使用市售的擠出機，但以熔融混煉擠出機爲佳，可爲單軸擠出機或2軸擠出機。由供給斗導入擠出機的部位及擠出機內係以氮氣體等惰性氣體取代，或減壓時，藉由降低氧的濃度可抑制氧化分解，故較佳。使擠出機內之薄膜構成材料熔融的溫度係因薄膜構成材料之黏度或吐出量、製造之薄片的厚度等，造成較佳條件不同，但是通常爲150〜300°C，較佳爲180〜270°C，更佳爲2 00〜260°C。溫度太低時，會發生溶解不良或熔融黏度上昇，而溫度太高時，材料會產生熱劣化。擠出時之熔融黏度係l~l〇〇〇〇Pa · s，較佳爲 10〜lOOOPa· s。熔融黏度太高時，因壓力上昇使得擠出機內之滯留時間延長。擠出機內之薄膜構成材料的滯留時間較短爲佳，5分鐘以內，較佳爲3分鐘以內，更佳爲2分鐘以內。滯留時間雖因擠出機之種類、擠出條件而異，但可藉由調整材料之供給量或L/D、螺旋轉數、螺旋之溝深等縮短滯留時間。擠出機之螺旋形狀或轉數等係依據薄膜構成材料之黏度或吐出量等來適當選擇。本發明中，擠出機之剪切速度爲1/秒〜1 0000/秒，較佳爲5/秒〜1 000/秒，更佳爲10/秒 ~ 1 0 0 / 秒。由擠出機所擠出之熔融樹脂係被送至流延模，由流延模之細縫擠出成薄膜狀。流延模只要是製造薄片或薄膜所 -35- 201107385 用者即可，並無特別限定。流延模之材質例如將硬鉻、碳化鉻、氮化鉻、碳化鈦、碳氮化鈦、氮化鈦、超鋼、陶瓷（碳化鎢、氧化鋁、氧化鉻）等經溶射或電鍍，施予表面加工之拋光、使用 # 1 000號以下之磨石硏磨、使用#1 000號以上之鑽石磨石之平面切削（切削方向係與樹脂流向垂直的方向）、電解硏磨、電解複合硏磨等之加工者。流延模之唇部之較佳材質係與流延模相同。又，唇部之表面精度較佳爲0.5 S以下，較佳爲0.2 S以下。此流延模之狹縫之間隙可調整》形成流延模之狹縫之一對之唇中，其一係剛性較低易變形之撓性的唇，另一係固定的唇，間隙容易調整，故較佳。爲了調整間隙，因此，將多數加熱螺栓於流延模之寬方向，以一定間距排列。各加熱螺栓上設置具有埋入電熱器與冷卻介質通路的區塊，各加熱螺栓爲縱向貫穿各區塊〇加熱螺栓之基部固定於模本體上，前端銜接於撓性唇之外面。而區塊時常空氣冷卻，同時增減埋入電熱器之輸入，使區塊之溫度升降，藉此使加熱螺栓熱伸縮，使撓性唇之位置改變，以調整薄膜的厚度。模後流之所要處所設置厚度計，藉此檢測出之纖維網 (web )厚度資訊回饋給控制裝置，將此厚度資訊與以控制裝置設定厚度資訊比較，藉由來自同裝置之修正控制量 -36- 201107385 的信號，可控制加熱螺栓的發熱體電力或接通率（on rate )° 加熱螺栓較佳爲具有長度20〜4〇cm，直徑7〜14mm，複數（例如數十支）的加熱螺栓爲以間距20〜40mm排列爲佳〇可設置以手動於軸方向進行前後移動來調整狹縫之間隙之螺栓爲主體的間隙調節構件來取代加熱螺栓。藉由間隙調節構件所調節之狹縫間隙，一般爲 200~2000μηι，較佳爲 300 〜ΙΟΟΟμίΏ，更佳爲 400 〜800μηι。擠出流量係藉由導入齒輪泵等使流量安定較佳。此外，除去異物用之過濾器較佳爲使用不鏽鋼纖維燒結過濾器〇不鏽鋼纖維燒結過濾器係將不鏽鋼纖維體製成複雜纏合狀態’再經壓縮，將接觸處燒結一體化者，藉由該纖維之粗細與壓縮量，改變密度，可調整過濾精度。組合過濾精度不同之過濾材料，使過濾器成爲多層體較佳。採用漸漸提高過濾精度的構成，或重複過濾精度之粗、密的方法，延長過濾器之過濾壽命，可提高異物或凝膠等之補充精度，因此較佳。模上有損傷或有異物附著時，有時會產生條紋狀的缺陷。這種缺陷也稱爲模線，爲了降低模線等之表面缺陷時 ’盡可能使用模之內部或模唇上無損傷等者，由擠壓機至模的配管中，形成盡可能減少樹脂之滯留部的構造較佳。擠壓機或模等與熔融樹脂接觸的內面，較佳爲降低表 -37- 201107385 面粗度或使用表面能較低的材質等，或實施不易附著熔融樹脂的表面加工。具體而言，例如將硬鍍鉻或陶瓷溶射者進行硏磨使其表面粗度成爲0.2 S以下者。可塑劑等之添加劑可預先與樹脂混合，或在擠出機之途中混鍊。爲了均勻添加時，較佳爲使用靜態混合機等的混合裝置。《冷卻輥》冷卻輥並無特別限制，可爲高剛性金屬輥，內部具備流通可控制溫度之熱介質或冷介質之構造的輥，大小不受限’只要是能充分冷卻被熔融擠出之薄膜的大小即可，通常冷卻輕之直徑爲100mm~lm。冷卻輥之表面材質例如有碳鋼、不鏽鋼、鋁、鈦等。又爲了提升表面硬度’或改良與樹脂之剝離性，較佳爲實施鍍硬鉻、鍍鎳、鍍非晶質鉻等，或陶瓷溶射等的表面處理。冷卻$昆係厚度爲約20~30mm之無縫鋼管製，表面加工成鏡面。冷卻輕表面之表面粗糙度Ra較佳爲〇丨μιη以下，更佳爲0.0 5 μιτι以下。輥表面越平滑時，所得薄膜之表面也越平滑。冷卻輥係具有至少一個，具有二個以上較佳。只有1 個時，冷卻輥之表面溫度Tr係設定爲Tg_50各Tr各Tg。二個以上時’第1冷卻輥之表面溫度Trl與第2冷卻輥之表面溫 -38 - 201107385 度 Tr2 係設定爲 Tg-50^TrlSTg、Tg-50 客 Tr2STg。較佳爲 Tr2>Trl，0<Tr2-Trl<50。藉此，添加劑在冷卻輥上的凝結量被控制，再熔融於纖維素薄膜中。藉由纖維素酯薄膜與第1及第2冷卻輥之接觸時間也可促進再溶解，但是本發明中，較佳爲1.0秒以上、3.0秒以下。接觸時間係以由薄膜與滾筒開始接觸的接觸點與開始剝離之接觸點之圓周的距離與薄膜之搬送速度算出的秒數表不。第2冷卻輥之周速度R2大於第1冷卻輥之周速度R1較佳。換言之，對於此2個輥間之薄膜施加張力，薄膜與第1輥之密著性提高。此周速度之比較佳爲1.00〜1.05之範圍，超過1 .05時，薄膜有斷裂的危險性。同樣的，第3以後的輥周速度大於其前面之冷卻輥的周速度較佳。《彈性接觸輥》與冷卻輥接觸的接觸輥，其表面具有彈性，藉由對冷卻輥之擠壓力而沿著冷卻輥表面變形，與冷卻輥之間可形成狹縮（nip)之彈性接觸輥。本發明之彈性接觸輥可使用例如專利第3 1 949〇4號、專利第3422798號、特開平03-124425號、特開平08-224772 號、特開平07-100960號、特開平10-272676號公報、 WO97/028950號說明書、特開平11-235747號、特開2002- -39- 201107385 3 63 3 2號、特開2002-3 6 3 3 3號 '特開2005- 1 72940號或特開 2 0 0 5 - 2 8 0 2 1 7號公報所記載之彈性接觸輥。本發明用的彈性接觸輥係金屬製外筒與內筒之2重構造，其間具有可流通冷卻流體的空間者。金屬製外筒具有彈性，因此可精確控制接觸輥表面的溫度，且適度利用彈性變形的性質，在長度方向具有可取得按壓薄膜之距離的效果，以液晶顯示裝置顯示圖像時，可得到無明暗之線條或斑點不均之本發明的效果。金屬製外筒之壁厚的範圍只要是0.003 $ (金屬製外筒之壁厚）/(接觸輥半徑）$〇.03時，可成爲適度的彈性，故較佳。接觸輥之半徑較大時，金屬外筒之壁厚即使較厚，也可有適度的撓性。金屬製外筒之壁厚太薄時，強度不足，有破損的疑慮。另一方面，太厚時，輥質量會變得過重，有轉動不均的疑慮。因此，金屬外筒之壁厚以 0.1〜5mm爲佳。彈性接觸輥之直徑爲100mm〜600mm，輥有效寬 L= 5 00〜1 6 00mm，且r/L< 1，橫長的形狀較佳。金屬外筒表面之表面粗糙度係以算術平均粗糙度Ra表示’較佳爲Ο.ίμηι以下’更佳爲〇·〇5μηι以下。輥表面越平滑，所得之薄膜表面也越平滑。金屬外筒之材質係需要平滑且具有適度的彈性，具有耐久性。因此，較佳爲使用碳鋼、不鏽鋼、鈦、電鑄法所製造之鎳等。欲進一步提高其表面的硬度，或改良與樹脂之剝離性’較佳爲施予鍍硬鉻、鍍鎳、鍍非晶質鉻 '或陶 -40- 201107385 瓷溶射等表面處理較佳。經表面加工的表面可再硏磨成爲上述表面粗糙度較佳。內筒係碳鋼、不鏽鋼、鋁、鈦等輕質且具有剛性之金屬製內筒爲佳。內筒因具有剛性，故可抑制輥之轉動晃動。內筒之壁厚爲外筒之2〜1 0倍，可得到充分的剛性。內筒上可進一步被覆聚矽氧、氟橡膠等樹脂製彈性材料。冷卻流體流通之空間的構造只要是可均勻地控制輥表面的溫度者即可，例如向寬度方向往返可互相流動，形成螺旋狀流動，即可控制輥表面之溫度分佈之微小溫度。冷卻流體並無特別限制，配合使用之溫度範圍可使用水或油。接觸輥之表面溫度（TrO )比薄膜之玻璃轉化溫度（ Tg )低較佳。比Tg高時，薄膜與輥之剝離性有較差的情況〇 Tg-50。。〜Tg更佳。本發明使用的彈性接觸輥係設定成寬度方向之中央部爲外徑大於兩端部的太鼓型輥的形狀較佳。接觸輥一般係將其兩端部以加壓手段按壓於薄膜，此時因接觸輥可撓性，因此有越靠端部，越強力按壓的現象。輥設定成太鼓型，可得到高度均一的按壓。本發明使用的彈性接觸輥之寬比薄膜寬度更寬時，可使薄膜全體與冷卻輥密著，故較佳。又，牽伸比（draw ratio)變大時，薄膜之兩端部會因頸縮（neck-in)現象，端部變高（端部的膜厚變厚）的情況，此時，欲避免端高 -41 - 201107385 部，可將金屬製外筒之寬度設定爲比薄膜寬更狹窄。或將金屬製外筒的外徑變小避免端高部》欲防止接觸輥之撓性，相對於冷卻輥，可在接觸輥之相反側上配置支持輥。也可配置清除彈性接觸輥之污垢的裝置。清掃裝置較佳爲使用例如輥表面必要時將浸透溶劑之不織布等構件緊壓於輥的方法、液體中接觸輥的方法、藉由電暈放電或輝光放電等電漿放電，使輥表面之污垢揮發的方法等。 ^ 欲使彈性接觸輥之表面溫度均勻，因此使接觸輥與溫度調整輥接觸、或吹入溫度被控制的空氣、或接觸液體等的熱介質。本發明中，彈性接觸輥按壓時的接觸輥線壓較佳爲 9.8N/cm以上，147N/cm以下。線壓小於此範圍時，無法充分消除模線。線壓係指彈性接觸輥按壓薄膜的力量除以按壓時之薄膜寬度所得的値。使線壓於上述範圍的方法，並無特別限定，例如可使用汽缸或油壓汽缸等按壓輥兩端。也可藉由支持輥按壓彈性接觸輥，間接地按壓薄膜。爲了藉由接觸輥有效的消除模線時，接觸輥在挾壓丙烯酸薄膜時之丙烯酸薄膜的黏度在適當的範圍是很重要的〇此外’纖維素酯因溫度所產生黏度變化較大已爲人知〇薄膜之玻璃轉化化溫度爲Tg時，被擠出之薄膜被接觸 -42- 201107385 輥挾壓前之接觸輥側薄膜表面溫度Tt設定爲 Tg<Tt<Tg+l 1 O〇c 較佳 ° 換言之，被接觸輥挾壓前之薄膜的溫度Tt在上述範圍時，可將挾壓薄膜時之薄膜的黏度在適當的範圍，可矯正模線’此外’薄膜表面與輥均勻地接著，可矯正模線。較佳爲 Tg+10°C<Tt<Tg + 90°C，更佳爲丁吕 + 20°(：<1^<丁§ + 70。(：。使按壓時之薄膜溫度在上述範圍的方法並無特別限定，例如使模與冷卻輥間之距離縮小，抑制模與冷卻輥間之冷卻的方法、或模與冷卻輥間以隔熱材包圍保溫或藉由熱風或紅外線加熱器或微波加熱等加溫的方法。薄膜表面溫度及輥表面溫度可由非接觸式之紅外線溫度計測定。具體可使用非接觸攜帶型溫度計（IT2-80、（股）KEYENCE製）於薄膜之寬方向，由距離被測定物 0.5 m測定1 0處。彈性接觸輥側薄膜表面溫度Tt係指將被搬送之薄膜於與接觸輥分離的狀態，由接觸輥側以非接觸式紅外線溫度計所測定的薄膜表面溫度。《流延步驟》本發明中，由流延模之開口部（唇部）至冷卻輥之部分減壓至7〇kP a以下’發現上述之模線的矯正效果更大。較佳爲減壓係50-7OkPa。由流延模之開口部（唇部）至冷卻輥之部分的壓力保持在7 OkP a以下的方法無特別限 -43- 201107385 定’例如有由流延模至輥周邊以耐壓構件覆蓋，進行減壓的方法等》此時，吸引裝置係爲了避免裝置本身成爲昇華物之附著場所，而實施以加熱器加熱等的措施較佳。本發明係當吸引壓太小時，無法有效的吸引昇華物，因此必須有適當的吸引壓。本發明係將含有纖維素酯之熔融物由模擠出成薄膜狀 ’形成牽伸比5以上3 0以下所得之薄膜，以彈性接觸輥按壓冷卻輥，同時搬送。牽伸比係指將模之唇間隙（ clearance)除以在冷卻輥上固化之薄膜之平均膜厚所得的値。牽伸比在此範圍’以液晶顯示裝置顯示圖像時，可得到無明暗之線條或斑點狀不均，生產性良好的偏光鏡保護薄膜。牽伸比可藉由模唇間隙與冷卻輥之拉引速度來調整。模唇間隙較佳爲9 0 0 μ m以上，更佳爲1 m m以上2 m m以下。太大或太小，有時無法改善斑點狀不均^ 使用冷卻輥與彈性接觸輥將薄膜挾壓時之接觸輥側的薄膜溫度設定爲薄膜之Tg以上Tg+110 °C以下，可調整薄膜表面之顯像性，故較佳。具有這種目的使用之彈性體表面的輥可使用公知的輥。薄膜從冷卻輥上剝離時，控制張力防止薄膜變形較佳《輥清掃設備》 -44- 201107385 本發明之製造裝置中，較佳爲附加清掃轉筒及輥的裝置。清掃裝置無特別限定，例如有夾持刷•輥、吸水輥、黏著輕、擦拭輥等的方式'吹送清淨空氣之空氣吹拂方式、以雷射燒毀裝置、或此等之組合等》夾持清掃用輥的方式時，改變皮帶線速度與轉筒線速度時’清掃效果較大。《延伸步驟》本發明中，如上述所得之薄膜係通過與冷卻輥接觸的步驟後’長（薄膜搬送方向）、寬（寬方向）之至少一方向進行1 . 1 ( 1 0 % )〜2.5 ( 1 5 0 % )倍延伸。通常光學薄膜爲了改善平面性，而調整延遲而進行延伸處理’但是本發明之薄膜係藉由延伸可使皂化適性更強固。其理由可能是藉由延伸處理，薄膜之活性能量較高的部分從表面露出，而該部分提高巷化適性。延伸方法較佳爲使用已知的輥延伸機或拉幅器等。延伸溫度通常在構成薄膜之樹脂的Tg〜Tg + 50°c ,較佳爲 Tg〜Tg + 40°C的溫度範圍內進行延伸。延伸係在寬度方向，且被控制之均勻溫度分布下進行延伸較佳。較佳爲±2 t以內’更佳爲± 1。<：以內，特佳爲以內。延伸步驟可在公知的熱固定條件下，進行冷卻、緩和處理’可適度調整以具有目的之薄膜所要求的特性。 -45- 201107385 欲在長度方向產生收縮時，例如有使寬度延伸暫時夾具鬆開，於長度方向上鬆弛或橫延伸機之相鄰之夾具之間隔慢慢縮小，使薄膜收縮的方法。後者的方法可使用一般之同時二軸延伸機，使縱向之相鄰之夾具的間隔，例如以縮放（P a n t 〇 g r a p h )方式或線性驅動方式驅動夾具部分，平滑且徐徐縮小的方法來進行〇必要時，也可與任意方向（斜方向）之延伸組合。長度方向、寬度手方向皆收縮0.5 10%，可降低薄膜之尺寸變化率。可藉由延伸提高薄膜之彈性率，因此延伸可作爲補充熔融製膜後之薄膜之彈性率降低的手段。延伸係對於例如薄膜之長度方向及在薄膜面內正交的方向、即寬度方向，可逐次或同時進行。藉由相互正交之2軸方向進行延伸，可減少所得之薄膜的膜厚變動。薄膜的膜厚變動過大時’會產生相位差不均，使用於液晶顯示器時會有著色等不均的問題。薄膜的膜厚變動較佳爲±3 %，更佳爲± 1 %的範圍。延伸後，將薄膜之端部藉由切割機切割成製品之寬度進行剪裁後，藉由浮雕環（emboss ring)及背輥所構成之凸邊加工裝置，對薄膜兩端部施行凸邊加工（embossing 加工），然後，藉由捲繞機捲繞，防止薄膜（原捲）中之黏貼或擦傷。凸邊加工的方法可藉由對於側面上具有凸凹圖型之金屬環加熱或加壓來加工。 -46 - 201107385 藉由切割機切除後之薄膜的兩端部可作爲原料再利用〇其次，偏光鏡保護薄膜的捲繞步驟係圓筒形卷之外周面與此前的移動式搬送輥之外周面間的最短距離保持一定，同時將薄膜捲繞於捲繞輥者。且捲繞輥之前可設置除去或減低薄膜之表面電位的除靜電吹風機等的手段。本發明之薄膜製造的捲繞機可爲一般使用者，可以定張力法 '定轉距法、錐度張力法 '內部應力固定之程式張力控制法等之捲繞方法進行捲繞。丙烯酸薄膜之捲繞時之初期捲繞張力爲90.2〜3 00.8N/m爲佳。本發明方法之薄膜捲繞步驟，較佳爲在溫度20〜30 °C ’濕度20〜6 0%RH的環境條件下，捲繞薄膜。捲繞步驟之溫度爲20~30°C的範圍時，不會產生皺紋，丙烯酸薄膜卷之品質不會劣化。捲繞步驟之濕度2 0〜6 0 % R Η時，可降低因吸濕造成薄膜卷品質劣化，卷品質優異，不會有黏貼故障，也無搬送性劣化。將薄膜捲繞成滚同狀時之捲芯’只要是圓筒狀的芯時，任何的材質者皆可，較佳爲中空塑膠芯。塑膠材料只要是能耐加熱處理溫度之耐熱性塑膠皆可，例如有酚樹脂、二甲苯樹脂、三聚氰胺樹脂、聚酯樹脂、環氧樹脂等樹脂〇又’藉由玻璃纖維等塡充材強化後的熱硬化性樹脂較佳。例如可使用中空塑膠芯：FRP製之外徑6英吋（以下， 1英吋表示2.54 cm)、內徑5英吋之捲芯。 -47- 201107385 製造本發明之偏光鏡保護薄膜時，考慮生產性與運搬性時，輥長度較佳爲10〜7 5 00m，更佳爲50〜5 5 00m。此時之偏光鏡保護薄膜的寬可選擇適合偏光鏡之寬或製造生產線的寬，以0.5〜4.0m，較佳爲1.0〜3.0m的寬製造薄膜，捲繞成輥狀爲佳。判斷本發明之薄膜之透明性的指標係使用霧度値（濁度）。特別是於屋外使用之液晶顯示裝置，即使於明亮場所也要求可得到充分的亮度及高對比，因此霧度値必須在 0 · 5 %以下，更佳爲〇 . 3 5 %以下。本發明之薄膜之全光線透過率較佳爲90%以上，更佳爲92%以上。爲了達成此種以全光線透過率表示之優異的透明性時，可藉由避免導入會吸收可見光之添加劑或共聚合成份、或藉由高精度過濾去除聚合物中的異物，降低薄膜內部之光擴散或吸收。此外，可藉由降低製膜時之薄膜接觸部（冷卻輥、壓延輥、滾筒、輸送帶、溶液製膜之塗佈基材、搬運輥等）之表面粗糙度，以降低薄膜表面之表面粗糙度，或降低丙烯酸樹脂之折射率，以減少薄膜表面之光擴散或反射^ 本發明之偏光鏡保護薄膜之膜厚無特別限定，但是用於後述的偏光鏡保護薄膜時，較佳爲20〜200μηι，更佳爲 25~1〇〇μιη，特佳爲 30〜65μηι。本發明之偏光鏡保護薄膜係藉由熔融流延製膜方法製作，因此以輥狀薄膜捲繞的時點’含有的溶劑量爲0.01質量％以下。含有溶劑量可藉由下述方法測定。 -48- 201107385 將各試料置入20ml之密閉玻璃容器內，間加熱條件處理後，以下述氣體色譜對於S 製作檢量線來測定。含有溶劑量係以相對左整體質量之質量份表示。S -31 - 201107385 It is preferable to use a triazole-based ultraviolet absorber or a benzophenone-based ultraviolet absorber, and it is particularly preferable to use a benzotriazole-based ultraviolet absorber which is less colored. Specific examples of the ultraviolet absorber used in the present invention are preferably, for example, TINUVIN 109, TINUVIN 171, TINUVIN 3 26, TINUVIN 3 27, TINUVIN 3 28, TINUVIN 900, TINUVIN 928, ADEKA (manufactured by Ciba Japan Co., Ltd.). LA-31, etc., but the invention is not limited thereto. The ultraviolet absorber is preferably a polymer type ultraviolet absorber, which is preferably a polymer type ultraviolet absorber described in JP-A-6-148430. The ultraviolet absorber may be used singly or in combination of two or more. The amount of the ultraviolet absorber to be used varies depending on the type of the compound, the conditions of use, etc., and when the dry film thickness of the cellulose ester film is 30 to 200 μm, it is preferably 〇·5 to 4 · 0 with respect to the cellulose ester film. %, more preferably 6·6~3. 5 mass% 〇<Method of film formation of the film of the present invention> The film of the present invention can be produced by a solution casting method or melt casting, and the melting first will be described first. Membrane method. <Melt Casting Film Forming Method> The film forming method by the melt film forming method can be classified into a melt extrusion molding method, a pressure molding method, a blow molding method (Inflation), an injection molding method, and a blow molding method. , extension forming method, etc. Among them, in order to obtain a film excellent in mechanical strength and surface precision, the melt extrusion molding method is excellent. -32-201107385 The following is a description of a method for producing a film of the present invention by taking a melt extrusion molding method as an example. In the method for producing a film, the conditions of melt extrusion can be melt extruded in the same manner as in the case of a general thermoplastic resin. <<Pellet Manufacturing Step>> A plurality of raw materials used for melt extrusion are generally preliminarily kneaded into pellets (p e 11 e t ). The granulation can be carried out by a known method, for example, by supplying a dried acrylic resin, a cellulose ester resin or an additive from a supply to an extruder, and kneading using a 1-axis or 2-axis extruder, and extruding the mold into a mold. Single yarn-like, cut after water cooling or air cooling. After the ultraviolet absorber or the matting agent is used to prepare a high-concentration master particle, it may be mixed with the main particles in the extruder at the time of film formation. Raw materials are dried prior to extrusion and are important to prevent decomposition of raw materials. In particular, cellulose esters are relatively easy to absorb moisture, so a dehumidifying hot air dryer or a vacuum dryer can be used, with a temperature of 70 to 140. (: drying for 3 hours or more, and setting the water content to 200 ppm or less) more preferably i 〇〇 ppm or less. The additives may be mixed before being supplied to the extruder or supplied separately by individual suppliers. A small amount of additives such as antioxidants In order to uniformly mix, it is preferred to mix beforehand. Vacuum conical spiral mixer or the like can be dried and mixed at the same time, so it is preferable. Further, it is preferably dehumidified from the point of contact with air by the outlet of the supplier portion or the mold or the like. In the environment of air or dehumidified nitrogen gas, etc. S--33-201107385 Further, it is preferable to prevent moisture absorption when the supply hopper of the extruder is kept in a warm state. The extruder suppresses shearing force. It is preferable to avoid deterioration of the resin (molecular weight reduction, coloring, gel formation, etc.) at a low temperature, for example, in the case of a 2-axis extruder, it is preferable to use a deep groove type spiral to rotate in the same direction. From the viewpoint of kneading uniformity, The bite type is preferred. Although the kneading disc can improve the kneading property, it is necessary to pay attention to the shear heat. The suction by the suction hole can be carried out as necessary. As long as it is at a low temperature, almost no volatile component is generated, so It is a non-suction hole. The color of the particles is yellow, and the b'値 is -5 to 1 0. The range is better, the range of -1 to 8 is better. - The range of -1 to 5 is better. b *値 can be split. Color measuring instrument CM-3 700d (manufactured by KONICA MINOLTA SENSING Co., Ltd.), the light source is D65 (color temperature 65 04K), and the viewing angle is 1 〇. It is preferable to use the granules obtained above for film formation, but not The granulation is carried out, and the raw material powder is directly supplied to the extruder as a film to form a film. "Slurry extrusion step" The material such as granules is preferably dried in advance, and dried by a vacuum or a vacuum dryer or dehumidified hot air. The machine dries the water to below 200 ppm, preferably below 100 ppm. The polymer after drying in a hot air or under vacuum or under reduced pressure uses a 1-axis or 2-axis extruder, and after melting, it is blade-shaped ( Leaf disk filter) After filtering and removing foreign matter, the filter is cast into a film shape from a casting die and solidified on a roll of -34-201107385. The extruder can be used as a commercially available extruder, but melt-kneaded. The machine is preferably a single-axis extruder or a 2-axis extruder. It is preferable to replace the oxidative decomposition by reducing the concentration of oxygen in the portion where the supply hopper is introduced into the extruder and the inside of the extruder, or to reduce the oxygen concentration during the pressure reduction. The temperature at which the material is melted differs depending on the viscosity or discharge amount of the film constituent material, the thickness of the sheet to be produced, and the like, but is usually 150 to 300 ° C, preferably 180 to 270 ° C, more preferably 2 00~260°C. When the temperature is too low, poor dissolution or increased melt viscosity will occur, and when the temperature is too high, the material will be thermally degraded. The melt viscosity during extrusion is l~l〇〇〇〇Pa·s, It is preferably 10 to lOOOPa·s. When the melt viscosity is too high, the residence time in the extruder is prolonged due to an increase in pressure. The residence time of the film constituent material in the extruder is preferably shorter, within 5 minutes, preferably within 3 minutes, more preferably within 2 minutes. Although the residence time varies depending on the type of extruder and the extrusion conditions, the residence time can be shortened by adjusting the supply amount of the material or the L/D, the number of spiral revolutions, and the depth of the spiral groove. The spiral shape or the number of revolutions of the extruder is appropriately selected depending on the viscosity or discharge amount of the film constituent material. In the present invention, the shearing speed of the extruder is from 1/sec to 1 0000/sec, preferably from 5/sec to 1 000/sec, more preferably from 10/sec to 1 0 0 /sec. The molten resin extruded from the extruder is sent to a casting die and extruded into a film shape by a slit of a casting die. The casting die is not particularly limited as long as it is used for the production of a sheet or a film - 35 - 201107385. The material of the casting die is, for example, hard-dissolved or electroplated, such as hard chrome, chromium carbide, chromium nitride, titanium carbide, titanium carbonitride, titanium nitride, ultra-steel, ceramics (tungsten carbide, aluminum oxide, chromium oxide). Polishing for surface processing, grinding with #1 000 or less, cutting with diamond grindstone #1 000 or above (cutting direction is perpendicular to the direction of resin flow), electrolytic honing, electrolytic composite 硏The processor of grinding and so on. The preferred material of the lip of the casting die is the same as that of the casting die. Further, the surface accuracy of the lip portion is preferably 0.5 S or less, preferably 0.2 S or less. The gap of the slit of the casting die can be adjusted to form a pair of slits of the casting die, one of which is a flexible lip with a low rigidity and a deformable shape, and the other is a fixed lip, and the gap is easily adjusted. Therefore, it is better. In order to adjust the gap, a plurality of heating bolts are arranged at a certain pitch in the width direction of the casting die. Each heating bolt is provided with a block having a buried electric heater and a cooling medium passage, and each heating bolt is longitudinally penetrated through each block. The base of the heating bolt is fixed to the die body, and the front end is connected to the outside of the flexible lip. The block is often air cooled, and the input of the embedded electric heater is increased or decreased to raise and lower the temperature of the block, thereby thermally expanding and contracting the heating bolt, and changing the position of the flexible lip to adjust the thickness of the film. A thickness gauge is set at a desired location of the mold flow, whereby the web thickness information detected is fed back to the control device, and the thickness information is compared with the thickness information set by the control device, and the correction control amount from the same device is The signal of 36-201107385 can control the heating power or on rate of the heating bolt. The heating bolt preferably has a length of 20~4〇cm, a diameter of 7~14mm, and a plurality of (for example, dozens of) heating. It is preferable that the bolts are arranged at a pitch of 20 to 40 mm, and a gap adjusting member mainly composed of a bolt which is manually moved forward and backward in the axial direction to adjust the gap of the slit can be provided instead of the heating bolt. The slit gap adjusted by the gap adjusting member is generally 200 to 2000 μm, preferably 300 to ΙΟΟΟμίΏ, more preferably 400 to 800 μm. The extrusion flow rate is preferably stabilized by introducing a gear pump or the like. In addition, the filter for removing foreign matter is preferably a stainless steel fiber sintered filter, a stainless steel fiber sintered filter is formed into a complicated entangled state of the stainless steel fiber body, and then compressed, and the contact is sintered and integrated, by the The thickness and compression of the fiber change the density and adjust the filtration accuracy. It is preferable to combine the filter materials having different filtration precisions to make the filter into a multilayer body. It is preferable to adopt a configuration in which the filtration accuracy is gradually increased, or a method of repeating the coarseness and density of the filtration precision to extend the filtration life of the filter, and it is possible to improve the replenishing precision of foreign matter or gel. When there is damage on the mold or foreign matter adheres, streaky defects sometimes occur. Such a defect is also called a mold line. In order to reduce the surface defects of the mold line or the like, as much as possible, the inside of the mold or the lip on the lip is used as much as possible, and the resin is formed as much as possible from the extruder to the mold. The structure of the retention portion is preferred. The inner surface of the extruder or the mold which is in contact with the molten resin preferably has a surface roughness of a surface of -37 to 201107385 or a material having a low surface energy, or a surface processing which is less likely to adhere to the molten resin. Specifically, for example, hard chrome plating or ceramic spray is honed to have a surface roughness of 0.2 S or less. Additives such as plasticizers may be mixed with the resin in advance or mixed in the middle of the extruder. In order to uniformly add, it is preferred to use a mixing device such as a static mixer. <<Cooling Roller>> The chill roll is not particularly limited, and may be a high-rigidity metal roll having a structure in which a heat medium or a cold medium having a temperature controllable is disposed, and the size is not limited 'as long as it is sufficiently cooled and melted and extruded. The size of the film is sufficient, and the diameter of the light is usually 100 mm to lm. The surface material of the cooling roll is, for example, carbon steel, stainless steel, aluminum, titanium or the like. Further, in order to improve the surface hardness or to improve the releasability to the resin, it is preferred to carry out surface treatment such as hard chrome plating, nickel plating, amorphous chromium plating, or ceramic spraying. It is cooled by a seamless steel tube with a thickness of about 20~30mm, and the surface is processed into a mirror surface. The surface roughness Ra of the cooling light surface is preferably 〇丨μηη or less, more preferably 0.05 μmτι or less. The smoother the surface of the roll, the smoother the surface of the resulting film. The chill roll system has at least one, preferably two or more. When there is only one, the surface temperature Tr of the cooling roll is set to Tg_50 Tr of each Tr. When two or more times, the surface temperature Tr1 of the first cooling roll and the surface temperature of the second cooling roll are -38 - 201107385 degrees Tr2 are set to Tg-50^TrlSTg and Tg-50 passenger Tr2STg. It is preferably Tr2 > Trrl, 0 < Tr2 - Tr1 < 50. Thereby, the amount of condensation of the additive on the chill roll is controlled and remelted in the cellulose film. The redissolution can be promoted by the contact time between the cellulose ester film and the first and second cooling rolls. However, in the present invention, it is preferably 1.0 second or longer and 3.0 seconds or shorter. The contact time is expressed by the number of seconds calculated from the distance between the contact point at which the film is brought into contact with the roll and the circumference of the contact point at which the peeling starts, and the transport speed of the film. The peripheral speed R2 of the second cooling roll is preferably larger than the peripheral speed R1 of the first cooling roll. In other words, when the tension is applied to the film between the two rolls, the adhesion between the film and the first roll is improved. The speed of this week is preferably in the range of 1.00 to 1.05. When the temperature exceeds 1.05, the film may be broken. Similarly, the circumferential speed of the third and subsequent rolls is preferably greater than the circumferential speed of the front side of the cooling rolls. "Elastic contact roller" The contact roller that is in contact with the cooling roller has a surface that is elastic, deforms along the surface of the cooling roller by the pressing force of the cooling roller, and forms a nip elastic contact with the cooling roller. Roller. The elastic contact roller of the present invention can be used, for example, in the patents No. 3,949,4, Patent No. 3,422,798, Japanese Patent Application No. Hei 03-124425, No. Hei 08-224772, No. Hei 07-100960, and No. Hei 10-272676. Bulletin, WO97/028950, special edition No. 11-235747, special opening 2002--39-201107385 3 63 3 No. 2, special opening 2002-3 6 3 3 No. 3 'Special opening 2005- 1 72940 or special opening 2 0 0 5 - 2 8 0 2 1 The elastic contact roller described in the 7th bulletin. The elastic contact roller used in the present invention is a metal outer cylinder and an inner cylinder 2 which are reconfigured with a space through which a cooling fluid can flow. The metal outer cylinder has elasticity, so that the temperature of the surface of the contact roller can be precisely controlled, and the property of elastic deformation is moderately utilized, and the effect of obtaining the distance of pressing the film in the longitudinal direction can be obtained, and when the image is displayed by the liquid crystal display device, no The effect of the present invention is that the lines or spots of light and dark are uneven. The range of the wall thickness of the metal outer cylinder is preferably 0.003 $ (the thickness of the metal outer cylinder) / (the contact roller radius) $ 〇.03, which is preferable because it can be moderately elastic. When the radius of the contact roller is large, the thickness of the metal outer cylinder can be moderately flexible even if it is thick. When the wall thickness of the metal outer cylinder is too thin, the strength is insufficient and there is a fear of breakage. On the other hand, when it is too thick, the quality of the roll becomes too heavy and there is a concern that the rotation is uneven. Therefore, the wall thickness of the metal outer cylinder is preferably 0.1 to 5 mm. The elastic contact roller has a diameter of 100 mm to 600 mm, a roller effective width L = 5 00 to 1 600 mm, and r/L < 1, and a transversely long shape is preferred. The surface roughness of the surface of the metal outer cylinder is expressed by the arithmetic mean roughness Ra, preferably Ο.ίμηι or less, more preferably 〇·〇5μηι or less. The smoother the surface of the roll, the smoother the surface of the resulting film. The material of the metal outer cylinder needs to be smooth and has moderate elasticity and durability. Therefore, it is preferable to use carbon steel, stainless steel, titanium, nickel produced by electroforming, or the like. It is preferable to further improve the hardness of the surface or to improve the releasability to the resin, preferably by applying a surface treatment such as hard chrome plating, nickel plating, amorphous chromium plating, or ceramic-40-201107385 porcelain spraying. The surface-finished surface can be honed to a better surface roughness as described above. It is preferable that the inner cylinder is a lightweight and rigid metal inner cylinder such as carbon steel, stainless steel, aluminum or titanium. Since the inner cylinder has rigidity, the rotation of the roller can be suppressed. The inner cylinder has a wall thickness of 2 to 10 times that of the outer cylinder, and sufficient rigidity can be obtained. The inner cylinder can be further coated with a resin elastic material such as fluorene or fluororubber. The structure of the space through which the cooling fluid flows may be any one that can uniformly control the temperature of the surface of the roll. For example, it is possible to flow back and forth in the width direction to form a spiral flow, thereby controlling the minute temperature of the temperature distribution on the surface of the roll. The cooling fluid is not particularly limited, and water or oil can be used in the temperature range in which it is used. The surface temperature (TrO) of the touch roll is preferably lower than the glass transition temperature (Tg) of the film. When the film is higher than Tg, the peeling property of the film and the roll is poor. 〇 Tg-50. . ~Tg is better. The elastic contact roller used in the present invention is preferably formed such that the central portion in the width direction is a shape of a Taiko-type roll having an outer diameter larger than both end portions. The contact roller is generally pressed against the film by pressurizing means at both ends thereof. In this case, since the contact roller is flexible, it is more strongly pressed against the end portion. The roller is set to the Taiko type, and a highly uniform press can be obtained. When the width of the elastic contact roller used in the present invention is wider than the width of the film, the entire film can be adhered to the cooling roll, which is preferable. Further, when the draw ratio becomes large, the both ends of the film may be neck-in and the ends become high (the thickness of the end portion is thick). End height -41 - 201107385, the width of the metal outer tube can be set to be narrower than the film width. Or, the outer diameter of the metal outer cylinder is made smaller to avoid the end height. To prevent the flexibility of the contact roller, a support roller may be disposed on the opposite side of the contact roller with respect to the cooling roller. It is also possible to configure a device for removing dirt from the elastic contact roller. The cleaning device preferably uses, for example, a method in which a member such as a non-woven fabric impregnated with a solvent is pressed against a roller, a method of contacting a roller in a liquid, a plasma discharge by a corona discharge or a glow discharge, and the like, and a dirt on the surface of the roller is preferably used. Volatilization method, etc. ^ To make the surface temperature of the elastic contact roller uniform, the contact roller is brought into contact with the temperature adjustment roller, or blown into a temperature-controlled air or a heat medium that contacts a liquid or the like. In the present invention, the contact roller linear pressure at the time of pressing the elastic contact roller is preferably 9.8 N/cm or more and 147 N/cm or less. When the line pressure is less than this range, the mold line cannot be fully removed. The line pressure is the enthalpy obtained by dividing the force of the elastic contact roller against the film by the width of the film when pressed. The method of pressing the wire in the above range is not particularly limited, and for example, both ends of the pressing roller such as a cylinder or a hydraulic cylinder can be used. It is also possible to indirectly press the film by pressing the elastic contact roller by the support roller. In order to effectively eliminate the mold line by the contact roller, it is important that the viscosity of the acrylic film when the contact roll is pressed against the acrylic film is in an appropriate range. In addition, it is known that the cellulose ester has a large viscosity change due to temperature. When the glass transition temperature of the tantalum film is Tg, the extruded film is contacted. -42-201107385 The contact roll side film surface temperature Tt before the roll rolling is set to Tg<Tt<Tg+l 1 O〇c is preferably ° In other words, when the temperature Tt of the film before being pressed by the contact roll is in the above range, the viscosity of the film when the film is pressed can be in an appropriate range, and the surface of the film can be corrected, and the surface of the film can be uniformly followed by the roller to be corrected. Mold line. It is preferably Tg + 10 ° C < Tt < Tg + 90 ° C, more preferably Ding Lu + 20 ° (: < 1 ^ < Ding § + 70. (:: The film temperature at the time of pressing is in the above range The method is not particularly limited, for example, a method of reducing the distance between the mold and the cooling roll, suppressing the cooling between the mold and the cooling roll, or enclosing the heat between the mold and the cooling roll with a heat insulating material or by a hot air or infrared heater or Heating method such as microwave heating. The surface temperature of the film and the surface temperature of the roll can be measured by a non-contact infrared thermometer. Specifically, a non-contact portable type thermometer (IT2-80, manufactured by KEYENCE) can be used in the width direction of the film. The measurement object is measured at a distance of 0.5 m. The elastic contact roller side film surface temperature Tt is a state in which the film to be conveyed is separated from the contact roller, and the surface temperature of the film is measured by a contact roller side by a non-contact infrared thermometer. <<Casting Step>> In the present invention, the pressure reduction from the opening portion (lip portion) of the casting die to the portion of the cooling roller to 7 〇 kP a or less is found to be more effective in correcting the above-mentioned mold line. Pressure system 50-7OkPa. Casting die The method of maintaining the pressure at the portion of the opening portion (lip portion) to the portion of the cooling roller at 7 OkPa or less is not limited to -43 to 201107385. For example, there is a method in which the casting die is covered with a pressure-resistant member from the casting die to the periphery of the roller, and the pressure is reduced. At this time, in order to prevent the apparatus itself from becoming a place where the sublimate is attached, it is preferable to carry out heating by a heater, etc. The present invention is effective in attracting sublimate when the suction pressure is too small, so it is necessary to have In the present invention, the melt containing the cellulose ester is extruded into a film form by a mold to form a film having a draw ratio of 5 or more and 30 or less, and the elastic roll is pressed against the cooling roll while being conveyed. The ratio refers to the 値 obtained by dividing the clearance of the mold by the average film thickness of the film cured on the chill roll. The draw ratio is in this range. When the image is displayed on the liquid crystal display device, no dark lines are obtained. Or a speckle-shaped protective film with uneven spots and good productivity. The draft ratio can be adjusted by the lip gap and the pulling speed of the cooling roller. The lip gap is preferably more than 9000 μm. It is preferably 1 mm or more and 2 mm or less. Too large or too small, sometimes it is impossible to improve spot unevenness. ^ Use a cooling roll and an elastic contact roll to set the film temperature on the contact roll side when the film is pressed to Tg or more of the film. It is preferable to adjust the surface development of the film surface at +110 ° C or lower. A roller having a surface for the elastomer used for such a purpose can be a known roller. When the film is peeled off from the cooling roller, the tension is controlled to prevent the film from being deformed. Optimum "Roll Cleaning Apparatus" - 44- 201107385 In the manufacturing apparatus of the present invention, it is preferable to add a device for cleaning the drum and the roller. The cleaning device is not particularly limited, and for example, a holding brush, a roller, a suction roller, a light bonding, and a wiping In the case of a roller or the like, the air blowing method of blowing clean air, the laser burning device, or the combination of these, etc., when the cleaning roller is held, the cleaning effect is large when the belt linear speed and the linear speed of the drum are changed. . <<Extension Step>> In the present invention, the film obtained as described above is subjected to at least one direction of 'long (film transport direction) and width (width direction) after the step of contacting with the cooling roll, and is made to be 1. 1 (10%) to 2.5. (1 50%) times extended. In general, an optical film is subjected to an elongation treatment by adjusting the retardation in order to improve planarity. However, the film of the present invention is more stable in saponification by stretching. The reason may be that the portion of the active energy of the film is exposed from the surface by the stretching treatment, and the portion improves the suitability of the lane. The stretching method is preferably a known roll stretcher or tenter or the like. The stretching temperature is usually extended in a temperature range of Tg to Tg + 50 ° C, preferably Tg to Tg + 40 ° C, of the resin constituting the film. The extension is preferably in the width direction and is extended under a controlled uniform temperature distribution. It is preferably within ±2 t', more preferably ±1. <: Within, especially good. The stretching step can be carried out under known heat-fixing conditions, and can be appropriately adjusted to have the characteristics required for the intended film. -45- 201107385 When it is desired to cause shrinkage in the longitudinal direction, for example, there is a method in which the width extension temporary holder is loosened, the lengthwise direction is relaxed, or the adjacent jigs of the lateral stretching machine are gradually narrowed to shrink the film. The latter method can use a general simultaneous two-axis stretching machine to make the interval of the adjacent jigs in the longitudinal direction, for example, driving the clamp portion by a pan 〇 graph method or a linear driving method, and smoothing and gradually reducing the method. If necessary, it can also be combined with the extension of any direction (oblique direction). Both the length direction and the width of the hand contract by 0.5 10%, which reduces the dimensional change rate of the film. The elongation of the film can be increased by extension, so that the extension can be used as a means for reducing the elastic modulus of the film after the melt film formation. The stretching may be performed successively or simultaneously for, for example, the longitudinal direction of the film and the direction orthogonal to the film surface, i.e., the width direction. By extending in the two-axis directions orthogonal to each other, the film thickness variation of the obtained film can be reduced. When the film thickness of the film is excessively changed, the phase difference is uneven, and there is a problem that unevenness in coloring or the like occurs when used in a liquid crystal display. The film thickness variation of the film is preferably ± 3%, more preferably ± 1%. After the extension, the end of the film is cut by the cutter to cut the width of the product, and then the hem processing of the emboss ring and the back roller is used to perform the hem processing on both ends of the film ( Embossing processing), and then, by winding up the winder, preventing sticking or scratching in the film (original roll). The method of burring can be processed by heating or pressurizing a metal ring having a convex and concave pattern on the side. -46 - 201107385 Both ends of the film cut by the cutter can be reused as raw materials. Next, the winding step of the polarizer protective film is the outer peripheral surface of the cylindrical roll and the outer peripheral surface of the previous movable transfer roll. The shortest distance between them is kept constant while the film is wound around the winding roller. Further, means for removing the electrostatic discharge blower or the like to remove or reduce the surface potential of the film may be provided before the winding roller. The winder manufactured by the film of the present invention can be a general user, and can be wound by a winding method such as a tension method, a constant torque method, a taper tension method, and an internal stress-fixed program tension control method. The initial winding tension at the time of winding the acrylic film is preferably from 90.2 to 3 00.8 N/m. In the film winding step of the method of the present invention, it is preferred to wind the film under ambient conditions at a temperature of 20 to 30 ° C 'humidity of 20 to 60% RH. When the temperature in the winding step is in the range of 20 to 30 ° C, wrinkles are not generated, and the quality of the acrylic film roll is not deteriorated. When the humidity in the winding step is 2 0 to 6 0 % R Η, the film roll quality deterioration due to moisture absorption can be reduced, the roll quality is excellent, adhesion failure is not caused, and transportability is not deteriorated. When the film is wound into a roll shape, the core ’ can be any material as long as it is a cylindrical core, and is preferably a hollow plastic core. As long as the plastic material is a heat-resistant plastic that can withstand the heat treatment temperature, for example, a resin such as a phenol resin, a xylene resin, a melamine resin, a polyester resin, or an epoxy resin can be reinforced by a ruthenium material such as glass fiber. A thermosetting resin is preferred. For example, a hollow plastic core can be used: a FRP made of an outer diameter of 6 inches (hereinafter, 1 inch indicates 2.54 cm) and an inner diameter of 5 inches. -47- 201107385 When manufacturing the polarizer protective film of the present invention, the roll length is preferably from 10 to 7 500 m, more preferably from 50 to 5 500 m, in consideration of productivity and transportability. In this case, the width of the polarizer protective film can be selected to be suitable for the width of the polarizer or the width of the manufacturing line, and the film is formed to have a width of 0.5 to 4.0 m, preferably 1.0 to 3.0 m, preferably wound into a roll. The index for judging the transparency of the film of the present invention is haze (turbidity). In particular, a liquid crystal display device used outside the house requires sufficient brightness and high contrast even in a bright field, so the haze must be 0. 5 % or less, more preferably 〇 3 5 % or less. The total light transmittance of the film of the present invention is preferably 90% or more, more preferably 92% or more. In order to achieve such excellent transparency as the total light transmittance, it is possible to reduce the light inside the film by avoiding introduction of an additive or a copolymer component which absorbs visible light, or removing foreign matter in the polymer by high-precision filtration. Diffusion or absorption. In addition, the surface roughness of the film surface can be reduced by reducing the surface roughness of the film contact portion (cooling roll, calender roll, roller, conveyor belt, coated substrate, transfer roll, etc.) at the time of film formation. The film thickness of the polarizer protective film of the present invention is not particularly limited, but is preferably 20~ when used in a polarizer protective film to be described later. 200μηι, more preferably 25~1〇〇μιη, especially preferably 30~65μηι. Since the polarizer protective film of the present invention is produced by a melt casting film forming method, the amount of the solvent contained at the time of winding the roll film is 0.01% by mass or less. The amount of solvent contained can be determined by the following method. -48- 201107385 Each sample was placed in a sealed glass container of 20 ml, and the measurement was performed under the heating conditions, and then the calibration curve was prepared for S by the following gas chromatography. The amount of solvent contained is expressed in parts by mass relative to the left overall mass.

機器：HP公司 5 890SERIES II 柱：J&W公司 DB-WAX (內徑 0.32mm 檢出：FIDMachine: HP 5 890SERIES II Column: J&W Company DB-WAX (inside diameter 0.32mm detected: FID

GC昇溫條件：以4(rc保持5分鐘後，以至 1 0 0 °C 頂部空間加熱條件：12〇°C、20min (溶液流延製膜方法）接著說明溶液流延製膜法。 (有機溶劑）以溶液流延法製造本發明之光學薄膜病的有機溶劑，只要是可同時溶解丙烯酸樹f 素醋樹脂（B )、必要時之丙烯酸粒子及其時’無k別限制均可使用。例如氯系有機溶劑有二氯甲烷，非氯男有乙酸甲酯、乙酸乙酯、乙酸戊酯、丙酮 1,3-二氧雜環戊烷、丨，4_二噁烷、環己酮 2,2,2-二藤（乙酉f、2,2,3,3 -六氟-1-丙醇、1，3 1，1，1，3,3,3-六氟 _2 -甲基-2-丙醇' 以下述頂部空先使用的溶劑丙烯酸薄膜之、長度3 0m ) 8〇°C/分鐘昇溫幸，形成膠漿用 i旨（A )、纖維 ;他的添加劑者 ^有機溶劑例如、四氫肤喃、、甲酸乙酯、 -二氟-2-丙醇、，3 _六氟_ 2 -丙醇 -49 - 201107385 、1 2 3,2,3,3,3-五氟-1-丙醇、硝基乙烷等，較佳爲使用二氯甲烷、乙酸甲酯、乙酸乙酯、丙酮。膠漿中除了上述有機溶劑外，較佳爲含有1〜40質量％之碳原子數1〜4之直鏈或支鏈狀之脂肪族醇。膠漿中之醇的比率升高時，纖維網（web )產生凝膠化，容易由金屬支持體上剝離，而醇的比例較少時，非氯素系有機溶劑系也有促進溶解丙烯酸樹脂（A )、纖維素酯樹脂（B )的功用。特別是使丙烯酸樹脂（A )與纖維素酯樹脂（B )及必要時之丙烯酸粒子之3種至少共計1 5〜45質量％溶解於含有二氯甲烷及碳數1〜4之直鏈或支鏈狀之脂肪族醇的溶劑中的膠漿組成物較佳。碳原子數1〜4之直鏈或支鏈狀之脂肪族醇，例如有甲醇、乙醇、η-丙醇' iso-丙醇、η-丁醇、sec-丁醇、tert-丁醇。此等當中，膠漿之安定性、沸點較低、乾燥性佳等，因此較佳爲甲醇。 -50- 1 )溶解步驟 2GC heating conditions: 4 (rc hold for 5 minutes, up to 1000 ° C. Headspace heating conditions: 12 ° C, 20 min (solution casting film forming method) Next, the solution casting film forming method will be described. (Organic solvent The organic solvent for the optical film disease of the present invention is produced by a solution casting method, and can be used as long as it can simultaneously dissolve the acrylic acid vinegar resin (B) and, if necessary, the acrylic particles. The chlorine-based organic solvent is dichloromethane, and the non-chlorine male has methyl acetate, ethyl acetate, amyl acetate, acetone 1,3-dioxolane, anthracene, 4-dioxane, cyclohexanone 2, 2,2-two vines (acetamidine f, 2,2,3,3-hexafluoro-1-propanol, 1,3 1,1,1,3,3,3-hexafluoro-2-methyl-2 -propanol' is heated at a temperature of 30 m) 8 〇 ° C / min in the solvent-based acrylic film used at the top of the following space, forming a paste for the purpose of (A), fiber; his additive ^ organic solvent, for example, Tetrahydrofuran, ethyl formate, difluoro-2-propanol, 3 _ hexafluoro-2-propanol-49 - 201107385 , 1 2 3,2,3,3,3-pentafluoro-1 -propanol, nitroethane, etc., preferably using dichloro Methane, methyl acetate, ethyl acetate, acetone. In addition to the above organic solvent, the dope preferably contains 1 to 40% by mass of a linear or branched aliphatic alcohol having 1 to 4 carbon atoms. When the ratio of the alcohol in the slurry is increased, the web is gelated and easily peeled off from the metal support, and when the proportion of the alcohol is small, the non-chlorine organic solvent also promotes dissolution of the acrylic resin (A) And the function of the cellulose ester resin (B). In particular, at least a total of 15 to 45 mass% of the acrylic resin (A), the cellulose ester resin (B) and, if necessary, the acrylic particles are dissolved in the dichlorinated product. A mortar composition in a solvent of methane and a linear or branched aliphatic alcohol having 1 to 4 carbon atoms is preferred. A linear or branched aliphatic alcohol having 1 to 4 carbon atoms, for example, methanol. , ethanol, η-propanol 'iso-propanol, η-butanol, sec-butanol, tert-butanol. Among these, the stability of the glue, the lower boiling point, good drying properties, etc., are preferred. For methanol. -50- 1 ) Dissolution step 2

在以對於丙烯酸樹脂（A)、纖維素酯樹脂（B )之良溶劑爲主的有機溶劑中’在溶解鍋中將該丙烯酸樹脂（A 3 ) '纖維素酯樹脂（B )、及必要時之丙烯酸粒子、其他 4 的添加劑進行攪拌同時溶解，形成膠漿的步驟、或將該丙條酸樹脂（A )、纖維素酯樹脂（B )溶液中混合必要時之丙烧酸粒子溶液、其他的添加劑溶液，形成主溶解液之膠 201107385 漿的步驟。丙烯酸樹脂（A)、纖維素酯樹脂（B)之溶解可使用常壓下溶解的方法、在主溶劑之沸點以下溶解的方法、在主溶劑之沸點以上進行加壓溶解的方法、如特開平9-95544號公報、特開平9-95557號公報、或特開平9-95538號公報所記載，以冷卻溶解法溶解的方法、如特開平11-2 1 3 7 9號公報所記載，以高壓溶解的方法等各種的溶解方法，特佳爲在主溶劑之沸點以上進行加壓溶解的方法。膠漿中之丙烯酸樹脂（A )與纖維素酯樹脂（B )合計爲15〜45質量％的範圍較佳。溶解中或溶解後之膠漿中加入添加劑，經溶解及分散後，以過濾材過濾、脫泡，並以送液泵送至下一步驟。過濾係使用捕集粒徑〇_5〜5μηι，且濾水時間 10~25sec/100ml的濾材較佳。此方法係將粒子分散時殘留之凝集物或主膠漿添加時所發生之凝集物，使用捕集粒徑0.5〜5 μ m '且濾水時間 10~25sec/100ml的爐材可僅除去凝集物。主膠漿中，粒子之濃度相較於添加液爲非常低，因此過濾時不會產生因凝集物彼此黏結，造成急速的濾壓上昇。較多的情形是主膠漿中含有回料10〜50質量％。回料中有時含有丙烯酸粒子，此時配合回料之添加量控制丙稀酸粒子添加液之添加量較佳。含有丙烯酸粒子之添加液中，較佳爲含有丙燒酸粒子 0.5〜10質量％，更佳爲含有1~1〇質量％，最佳爲含有1〜5質 £ -51 - 201107385 量％。上述範圍內時，添加液係低黏度，且操作使用較容易，也容易添加至主膠漿中，故較佳。回料係指將薄膜經過微細粉碎之物品，製造薄膜時所發生之將薄膜之兩端部分切掉後的物品或因擦傷等’當作規格外之薄膜原料使用者。預先將丙烯酸樹脂、纖維素酯樹脂及必要時之丙烯酸粒子混練形成顆粒化者，較適用。 2)流延步驟將膠漿通過送液泵（例如加壓型定量齒輪泵）送液至加壓模，再由加壓模縫將膠漿流延至無限移送之無終端的金屬帶、例如有不鏽鋼帶或旋轉之金屬滾筒等的金屬支持體上之流延位置的流延步驟。可調整模之模頭部分的細縫形狀，且容易使膜厚均一之加壓模較佳。加壓模有衣架型模（coat hanger die)或T 模等均可使用。金屬支持體之表面成爲鏡面。爲了提高製膜速度，可在金屬支持體上設置2座以上之加壓模，將膠漿量分割進行層合。或可藉由將複數之膠漿同時流延的共流延法，可得到層合構造的薄膜。 3 )溶劑蒸發步驟將纖維網（使膠漿流延至流延用支持體上所形成的膠漿膜稱爲「纖維網」）在流延用支持體上加熱，使溶劑蒸 -52- 201107385 發的步驟。欲使溶劑蒸發時’有由纖維網側吹風的方法及/或由支持體之內面藉由液體傳熱的方法、藉由輻射熱由表裏傳熱的方法等，但是內面液體傳熱方法乾燥效率高，故較佳。也可使用組合彼等的方法。使流延後之支持體上的纖維網在40~100°C之氣氛下，在支持體上乾燥較佳。欲維持 40〜100 °C之氣氛下時，將此溫度之熱風接觸纖維網上面，或藉由紅外線等的手段加熱較佳。從面品質、透濕性、剝離性的觀點，較佳爲在3 〇〜〗2 〇秒以內，將該纖維網由支持體上剝離。 4 )剝離步驟將在金屬支持體上使溶劑蒸發後的纖維網在剝離位置剝離的步驟。剝離後的纖維網係被送至下一步驟。金屬支持體上之剝離位置的溫度較佳爲1 0〜40 °C，更佳爲1 1〜3 0 °c。剝離之時點之金屬支持體上之纖維網的剝離時殘留溶劑量係依乾燥條件之強弱、金屬支持體之長度等，在 50〜120質量％之範圍進行剝離較佳，但是殘留溶劑量更多的時點進行剝離時，若纖維網太柔軟時，會損害剝離時平面性，因剝離張力容易產生鬆弛或直線條，因此以兼顧經濟速度與品質，來決定剝離時的殘留溶劑量。纖維網之殘留溶劑量係以下述式定義。 •53- 201107385 殘留溶劑量（％)=(纖維網之加熱處理前質量-纖維網之加熱處理後質量）/(纖維網之加熱處理後質量） X 100 此外，測定殘留溶劑量時之加熱處理係表示以1 1 5 °C 加熱處理1小時。剝離金屬支持體與薄膜時之剝離張力通常爲 1 9 6 ~ 2 4 5 N / m，但是剝離時易產生皺紋時’以1 9 0 N /m以下的張力剝離較佳，更佳爲以可剝離之最低張力~166_6N/m 、接著以最低張力~ 1 3 7 · 2 N / m剝離’特佳爲以最低張力 ~1 ΟΟΝ/m彔丨J離。本發明中，該金屬支持體上之剝離位置的溫度較佳爲-5 0〜40°C，更佳爲1 0〜40°C，最佳爲15〜30°C。 5)乾燥及延伸步驟剝離後，使用將纖維網交互通過在乾燥裝置內複數配置之輥，進行搬送之乾燥裝置或以夾具夾住纖維網之兩端進行搬送之拉幅延伸裝置，使纖維網乾燥。乾燥手段一般係將熱風吹纖維網之兩面，也可使用微波爐照射加熱的手段取代熱風。太過急速的乾燥容易損及完成之薄膜的平面性。藉由高溫之乾燥使殘留溶劑成爲約 8質量％以下即可。整體乾燥大槪是以4〇〜25〇χ：乾燥。特佳爲以40〜160°C乾燥。使用拉幅延伸裝置時，較佳爲使用藉由拉幅器之左右 -54- 201107385 把持手段可以左右獨立控制薄膜之把持長度（把持開始至把持終了的距離）的裝置。拉幅步驟中’爲了改善平面性，也可刻意製作具有不同溫度之區間。爲了在不同溫度之區間，各自之區間之間不會產生干擾可設置中性區域。延伸處理較佳爲與前述熔融流延製膜方法相同的延伸處理。進行拉幅時之纖維網的殘留溶劑量，在拉幅開始時，較佳爲2 0〜1 〇〇質量％，且纖維網之殘留溶劑量成爲1 0質量％以下爲止進行拉幅同時乾燥較佳’更佳爲5質量％以下〇進行拉幅時之乾燥溫度較佳爲30〜16 0°C，更佳爲 50〜150°C，最佳爲 7〇〜140°C。拉幅步驟中，氣氛之寬度方向的溫度分布較少，從提高薄膜之均一性的觀點較佳，拉幅步驟之寬度方向之溫度分布較佳爲±5°C以內’更佳爲±2°C以內，最佳爲±i°c以內 201107385 定之程式張力控制法等，將此等分開使用即可。本發明之薄膜滿足上述物性時，特別適合作爲大型之液晶顯示裝置或屋外用途之液晶顯示裝置用的偏光鏡保護薄膜使用。 <偏光板之製造方法> 本發明之薄膜作爲偏光鏡保護薄膜使用時，可以將一般的纖維素酯作成偏光鏡保護薄膜的方法製作偏光板。換言之’將本發明之偏光鏡保護薄膜進行皂化處理後，偏光鏡之貼合可使用水性黏著劑。皂化處理係以近似以下條件的條件作爲基準條件進行皂化處理較佳。皂化步驟 2.0M-NaOH 4 5〇C 9 0秒水洗步驟水 3 0°C 45秒中和步驟 10質量份HC1 3〇t 45秒水洗步驟水 3 0°C 45秒皂化處理後’依水洗、中和、水洗的順序進行，接著以8 0 °C乾燥。但是本發明爲了巷化處理之迅速化，較佳爲使用近似下述條件的條件進行巷化處理。皂化步驟 1 .5M-NaOH 5 5〇C 4 0秒水洗步驟水 40°C 2 0秒中和步驟 1〇質量份HC1 40°C 2 0秒水洗步驟水 4 0°C 2 0秒 -56- 201107385 皂化處理後，依水洗、中和、水洗的順序進行，接著以90°C乾燥。皂化處理係在延伸後3 6 0小時以內較佳。此皂化處理後’藉由水性黏著劑黏貼偏光鏡。水性黏著劑係指溶劑之5 0質量％以上爲水的黏著劑，例如有聚乙烯醇系水性黏著劑、明膠黏著劑、乙烯基系乳膠黏著劑、水系聚酯等，其中較佳爲聚乙烯醇系水性黏著劑。通常將此等調製成0.5〜30質量％的固形分來使用較佳。特佳爲與纖維素酯作爲偏光鏡保護薄膜使用時相同的黏著劑。另一面可使用本發明之偏光鏡保護薄膜，或其他的偏光鏡保護薄膜。較佳爲使用例如市售的纖維素酯薄膜（例如 KonicaMinolta TAC KC8UX、KC4UX、KC5UX、KC8UY 、KC4UY、KC 12UR ' KC8UCR-3、KC8UCR-4、KC8UCR-5 、KC8UE、KC4UE、KC4FR-3、KC4FR-4、KC4HR-1、 KC8UY-HA、K C 8 UX - R Η A、以上爲 Ko n i c a M i η ο 11 a Opto ( 股）製）等。偏光板之主要構成要素的偏光鏡係指僅通過一定方向之偏波面之光的元件，現在已知之代表性偏光鏡係聚乙烯醇系偏光薄膜，例如有將聚乙烯醇系薄膜以碘染色者與經二色性染料染色者。偏光鏡係使用將聚乙烯醇水溶液製膜，將此一軸延伸後染色或染色後進行一軸延伸，較佳爲以硼化合物進行耐 -57- 201107385 久性處理者。〔液晶顯示裝置〕將貼合本發明之薄膜的偏光板組裝於液晶面板後，可製作各種辨識性優之液晶顯示裝置，特別適用於大型液晶顯示裝置或電子看板等屋外用途之液晶顯示裝置。本發明之偏光板係介於前述黏著層等貼合於液晶胞上。本發明之偏光板適用於反射型、透過型、半透過型 LCD 或 TN 型、STN 型、OCB 型、HAN 型、VA 型（PVA 型、 MVA型）、IPS型（包含FFS型）等各種驅動方式的LCD。特別是畫面爲吋以上，特別是3〇吋吋之大畫面的顯示裝置，在畫面周邊部無泛白等，可長時間維持該效果。【實施方式】〔實施例〕以下舉實施例具體說明本發明，但是本發明不受此限定。實施例1 <丙燃酸fit子AC1之調製〉在內容積60L之附有回流冷卻器的反應器中投入離子交換水38.2L、二辛基擴基琥珀酸鈉111.6g，以250rpm之轉數攪拌’同時在氮氣氛下升溫至75 ，形成事實上無氧影響的狀態。添加A p S 0 _ 3 6 g，攪拌5分鐘後，一次添加由 -58- 201107385 MMA 1 6 5 7 g、BA 2 1_6g及ALMA l_68g所構成之單體混合物 ’檢測出發熱波峰後再保持2 0分鐘完成最內硬質層之聚合〇其次添加APS 3.48g’攪拌5分鐘後以12〇分鐘連續添加由 BA 8105g、PEGDA( 200) 31.9g及 ALMA 264_0g所構成的單體混合物，添加結束後再保持1 2 〇分鐘完成軟質層之聚合。接著添加APS 1.32g，攪拌5分鐘後以20分鐘連續添加由Μ M A 2 1 0 6 g、B A 2 0 1 . 6 g所構成的單體混合物，添加結束後再保持20分鐘完成最外硬質層1之聚合。其次添加APS 1.32g，5分鐘後以20分鐘連續添加由 MMA 3148g、BA 201.6g及n-OM l〇.lg所構成的單體混合物’添加結束後再保持2 0分鐘。接著升溫至9 5。(：後保持6 0 分鐘，完成最外硬質層2之聚合。上述所得之聚合物乳膠採取少量，藉由吸光度法得到平均粒徑爲0.1 Ομπι。剩餘之乳膠投入3質量。/。硫酸鈉溫水溶液中’重覆鹽析、凝固，接著脫水' 洗淨後，進行乾燥得到3層構造之丙烯酸粒子AC 1。上述簡稱係各自爲下述材料。 ΜΜΑ :甲基丙烯酸甲酯 ΜΑ :甲基丙烯酸酯 BA : η-丁基丙烯酸酯 ALMA :烯丙基甲基丙烯酸酯 PEGDA:聚乙二醇二丙烯酸酯（分子量200) -59- 201107385 η - Ο Μ : η -辛基硫醇 APS :過硫酸銨 <偏光鏡保護薄膜試料1 〇 1之製作> (膠漿液1組成） DIANAL BR85 ( Mitsubishi Rayon (股）製） 65質量份纖維素乙酸酯丙酸酯（醯基總取代度2.75、乙醯基取代度0.20、丙醯基取代度2.55、Mw = 2 00000 ) 3 5質量份丙烯酸粒子（AC1) 1.1質量份無機微粒子（Aerosil R972V ) 0·27質量份二氯甲院 300質量份乙醇 4 0質量份將上述組成物加熱充分溶解，製作膠漿液1。使用帶狀流延裝置以溫度22°C、2m寬度，將上述製作的膠漿液均勻地流延於不銹鋼帶支持體上。在不銹鋼帶支持體上使溶劑蒸發直到殘留溶劑量變成1 〇〇%爲止，自不銹鋼帶支持體上以剝離張力1 62N/m剝離。使剝離後之樹脂組成物的纖維網以35°C使溶劑蒸發，切割成1·5τη寬後，使用拉幅器在寬度方向延伸1.30倍（30%)，同時以l4〇°C之乾燥溫度乾燥。此時，使用拉幅器延伸開始時的殘留溶劑量爲 1 0 %。使用拉幅器延伸後，以1 3 0°C緩和3 0秒鐘後，以多數輥搬送通過120°c、14(TC之乾燥區域（zone )，同時乾燥結束，裁切成1.5m寬，對薄膜兩端施加寬l〇mm、高度5μιη -60- 201107385 之壓花加工，以初期張力22〇N/m、最終張力11〇N/m捲繞於內徑15_24cm的芯上，得到厚度4〇μπι、卷長度12〇〇111之偏光鏡保護薄膜的捲筒試料I 〇 1。以下如表1所g3載變更材料及條件，與試料丨〇〗同樣製作試料1 0 2〜試料1 3 4。使用的原材料素材如下述。 <<丙烯酸樹脂>> A1 :單體質量比（MMA: MA = 98: 2) 、Mw75000 A2:單體質量比（MMA: MA = 97: 3) ' Mw 1 40000 A3:單體質量比（MMA: MA = 97: 3) 、Mw550000 A4:單體質量比（MMA: MA = 97: 3) ' Mw 1 1 00000 MMA :甲基丙烯酸甲酯 ΜΑ :甲基丙烯酸酯 BR85 ： DIANAL BR85 (三菱 Ray〇n (股）製）In the organic solvent mainly for the acrylic resin (A) and the cellulose ester resin (B), the acrylic resin (A 3 ) 'cellulose ester resin (B) is dissolved in a dissolving pot, and if necessary The acrylic acid particles and the other four additives are stirred and dissolved to form a dope, or the propionic acid resin (A) or the cellulose ester resin (B) solution is mixed with a propidyl acid particle solution if necessary, and the like. The additive solution forms the main solution of the glue 201107385 slurry. The dissolution of the acrylic resin (A) or the cellulose ester resin (B) can be carried out by a method of dissolving under normal pressure, a method of dissolving below the boiling point of the main solvent, or a method of performing pressure dissolution at a boiling point or higher of the main solvent, such as a special opening. A method of dissolving in a cooling and dissolving method, as described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 9-95. Various methods of dissolving such as a method of dissolving are particularly preferably a method of pressurizing and dissolving at a boiling point or higher of the main solvent. The acrylic resin (A) and the cellulose ester resin (B) in the dope preferably have a total range of 15 to 45 mass%. Additives are added to the dissolved or dissolved cement, dissolved and dispersed, filtered through a filter material, defoamed, and pumped to the next step. The filtration system is preferably a filter material having a particle size of 〇5 to 5 μm and a filtration time of 10 to 25 sec/100 ml. This method is a method in which agglomerates which are left when the particles are dispersed or agglomerates which are generated when the main dope is added, and only agglomerates having a particle diameter of 0.5 to 5 μm ' and a drainage time of 10 to 25 sec/100 ml can be used to remove only agglomeration. Things. In the main dope, the concentration of the particles is extremely low compared to the additive liquid, so that the aggregates do not stick to each other during filtration, resulting in a rapid increase in filtration pressure. In many cases, the main glue contains 10 to 50% by mass of the recycled material. In the returning material, acrylic acid particles are sometimes contained, and in this case, the addition amount of the acrylic acid particle-adding liquid is preferably controlled in accordance with the addition amount of the recycled material. The additive liquid containing acrylic acid particles preferably contains 0.5 to 10% by mass of the acrylic acid particles, more preferably 1 to 1% by mass, most preferably 1 to 5 by mass of -51 to 201107385. In the above range, it is preferred to add a liquid system with a low viscosity, which is easy to handle and easy to add to the main dope. The return material refers to an article obtained by finely pulverizing a film, and an article which is formed by cutting both ends of the film when the film is produced, or a film material user which is a specification other than the scratch. It is preferred to previously knead the acrylic resin, the cellulose ester resin and, if necessary, the acrylic particles to form granules. 2) Casting step The glue is fed to the pressurizing mold through a liquid feeding pump (for example, a pressurized quantitative gear pump), and then the rubber is cast by a pressurizing die slit to an endlessly transferred metal strip, for example, A casting step of a casting position on a metal support such as a stainless steel belt or a rotating metal drum. It is possible to adjust the shape of the slit of the die portion of the mold, and it is easy to make the pressurizing die having a uniform film thickness. The press mold can be used with a coat hanger die or a T die. The surface of the metal support becomes a mirror surface. In order to increase the film forming speed, two or more press dies may be provided on the metal support, and the amount of the sizing may be divided and laminated. Alternatively, a film of a laminated structure can be obtained by a co-casting method in which a plurality of cements are simultaneously cast. 3) The solvent evaporation step heats the fiber web (the film formed by casting the glue onto the support for casting) as a "web"), and heats the solvent on the casting support to evaporate the solvent -52-201107385 step. When the solvent is to be evaporated, there is a method of blowing from the side of the fiber web and/or a method of transferring heat from the inner surface of the support by liquid, a method of transferring heat from the surface by radiant heat, etc., but the inner liquid heat transfer method is dried. It is more efficient and therefore better. It is also possible to use a combination of these methods. It is preferred that the web on the cast support is dried on a support in an atmosphere of 40 to 100 °C. When it is desired to maintain an atmosphere of 40 to 100 ° C, it is preferred to contact the hot air of this temperature on the surface of the fiber web or by means of infrared rays or the like. From the viewpoint of surface quality, moisture permeability, and peelability, it is preferred that the fiber web is peeled off from the support within 3 〇 to 2 〇 seconds. 4) Peeling step The step of peeling the web after evaporating the solvent on the metal support at the peeling position. The stripped web is sent to the next step. The temperature at the peeling position on the metal support is preferably from 10 to 40 ° C, more preferably from 1 to 30 ° C. The amount of residual solvent at the time of peeling of the web on the metal support at the time of peeling is preferably in the range of 50 to 120% by mass, depending on the strength of the drying conditions, the length of the metal support, etc., but the amount of residual solvent is more When the web is too soft, the flatness at the time of peeling is impaired, and the peeling tension tends to cause slack or straight strips. Therefore, the amount of residual solvent at the time of peeling is determined in consideration of economic speed and quality. The residual solvent amount of the fiber web is defined by the following formula. •53- 201107385 Residual solvent amount (%)=(mass before heat treatment of fiber web-mass after heat treatment of fiber web)/(mass after heat treatment of fiber web) X 100 In addition, heat treatment when measuring residual solvent amount It means heat treatment at 1 1 5 °C for 1 hour. When the metal support and the film are peeled off, the peeling tension is usually from 1 6 6 to 2 4 5 N / m, but when wrinkles are likely to occur during peeling, it is preferable to peel at a tension of less than 190 N / m, more preferably The minimum tension of the peeling is ~166_6N/m, and then the minimum tension is ~1 3 7 · 2 N / m. The best is the lowest tension ~1 ΟΟΝ/m彔丨J. In the present invention, the temperature at the peeling position on the metal support is preferably -5 0 to 40 ° C, more preferably 10 to 40 ° C, most preferably 15 to 30 ° C. 5) After the drying and stretching steps are stripped, the web is transported through a plurality of rolls arranged in a drying device, and a stretching device for carrying the transfer or a tenter stretching device for holding the both ends of the fiber web by a jig is used to make the fiber web dry. The drying method generally uses hot air blowing on both sides of the fiber web, and the microwave oven can also be used to replace the hot air by means of irradiation heating. Too fast drying tends to damage the planarity of the finished film. The residual solvent may be about 8 mass% or less by drying at a high temperature. The overall dry sputum is 4 〇 ~ 25 〇χ: dry. It is particularly preferred to dry at 40 to 160 °C. When the tenter extension device is used, it is preferable to use a device for controlling the holding length of the film (the distance from the start to the end of the holding) by the left and right sides of the tenter -54-201107385. In the tentering step, in order to improve the planarity, it is also possible to intentionally make intervals having different temperatures. Neutral regions can be set so that there is no interference between the respective intervals in different temperature ranges. The stretching treatment is preferably the same stretching treatment as the above-described melt casting film forming method. The amount of residual solvent of the fiber web at the time of tentering is preferably 20 to 1% by mass at the start of tentering, and the amount of residual solvent of the fiber web is 10% by mass or less. Preferably, the drying temperature is preferably 30 to 16 0 ° C, more preferably 50 to 150 ° C, and most preferably 7 to 140 ° C. In the tentering step, the temperature distribution in the width direction of the atmosphere is small, and from the viewpoint of improving the uniformity of the film, the temperature distribution in the width direction of the tentering step is preferably within ±5 ° C, preferably ± 2 °. Within C, the best is the program tension control method of the 201107385 within ±i°c, etc., and these can be used separately. When the film of the present invention satisfies the above physical properties, it is particularly suitably used as a polarizer protective film for a large-sized liquid crystal display device or a liquid crystal display device for outdoor use. <Manufacturing Method of Polarizing Plate> When the film of the present invention is used as a polarizing film protective film, a polarizing plate can be produced by a method in which a general cellulose ester is used as a polarizer protective film. In other words, after the saponification treatment of the polarizer protective film of the present invention, an aqueous adhesive can be used for bonding the polarizer. The saponification treatment is preferably carried out by saponification treatment under conditions similar to the following conditions. Saponification step 2.0M-NaOH 4 5〇C 9 0 second water washing step water 3 0 ° C 45 seconds neutralization step 10 parts by mass HC1 3〇t 45 seconds water washing step water 3 0 ° C 45 seconds after saponification treatment 'by washing, The order of neutralization and washing was carried out, followed by drying at 80 °C. However, in order to speed up the lane-changing treatment, it is preferable to carry out the lane-forming treatment using conditions similar to the following conditions. Saponification step 1. 5M-NaOH 5 5〇C 4 0 second water washing step water 40 ° C 2 0 seconds neutralization step 1 〇 mass parts HC1 40 ° C 2 0 second water washing step water 4 0 ° C 2 0 seconds - 56- 201107385 After saponification, it is carried out in the order of washing, neutralization, and washing, followed by drying at 90 °C. The saponification treatment is preferably within 3 to 60 hours after the extension. After this saponification treatment, the polarizer is adhered by an aqueous adhesive. The water-based adhesive refers to an adhesive in which 50% by mass or more of the solvent is water, and examples thereof include a polyvinyl alcohol-based aqueous adhesive, a gelatin adhesive, a vinyl-based latex adhesive, and an aqueous polyester. Among them, polyethylene is preferred. Alcohol-based water-based adhesive. It is usually preferred to use these to be adjusted to a solid content of 0.5 to 30% by mass. Particularly preferred is the same adhesive as the cellulose ester used as a polarizer protective film. On the other hand, the polarizer protective film of the present invention or other polarizer protective film can be used. It is preferred to use, for example, a commercially available cellulose ester film (for example, Konica Minolta TAC KC8UX, KC4UX, KC5UX, KC8UY, KC4UY, KC 12UR 'KC8UCR-3, KC8UCR-4, KC8UCR-5, KC8UE, KC4UE, KC4FR-3, KC4FR -4, KC4HR-1, KC8UY-HA, KC 8 UX - R Η A, the above is Ko nica M i η ο 11 a Opto (system), and the like. The polarizer of the main constituent elements of the polarizing plate refers to an element that passes only the light of the deflecting surface in a certain direction. A representative polarizing lens is a polyvinyl alcohol-based polarizing film, and for example, a polyvinyl alcohol-based film is dyed with iodine. Dyeing with dichroic dyes. In the polarizer, a film of a polyvinyl alcohol aqueous solution is used, and the one axis is stretched, dyed or dyed, and then subjected to one-axis stretching. Preferably, the boron compound is subjected to a long-term treatment of -57-201107385. [Liquid crystal display device] When a polarizing plate to which the film of the present invention is bonded is assembled to a liquid crystal panel, various liquid crystal display devices having excellent visibility can be produced, and are particularly suitable for liquid crystal display devices for outdoor use such as large liquid crystal display devices or electronic signboards. The polarizing plate of the present invention is bonded to the liquid crystal cell by the adhesion layer or the like. The polarizing plate of the present invention is suitable for various types of driving such as reflective, transmissive, transflective LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type (including FFS type). The way the LCD. In particular, the display device has a screen size of 吋 or more, and in particular, a display device having a large screen size of 3 inches does not have whitening at the periphery of the screen, and the effect can be maintained for a long period of time. [Embodiment] [Examples] Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited thereto. Example 1 <Preparation of a propionic acid-fitted AC1> Into a reactor having a reflux condenser with an internal volume of 60 L, 38.2 L of ion-exchanged water and 111.6 g of dioctyl-based sodium succinate were introduced, and the mixture was rotated at 250 rpm. The number of stirrings was simultaneously raised to 75 in a nitrogen atmosphere to form a state of virtually no oxygen. Add A p S 0 _ 3 6 g, stir for 5 minutes, add a monomer mixture consisting of -58- 201107385 MMA 1 6 5 7 g, BA 2 1_6g and ALMA l_68g at one time to detect the starting heat peak and then keep 2 The polymerization of the innermost hard layer was completed in 0 minutes, followed by the addition of APS 3.48 g. After stirring for 5 minutes, the monomer mixture consisting of BA 8105g, PEGDA (200) 31.9g and ALMA 264_0g was continuously added for 12 minutes, and the addition was completed. The polymerization of the soft layer was completed in 1 2 minutes. Then, 1.32 g of APS was added, and after stirring for 5 minutes, a monomer mixture composed of Μ MA 2 1 0 6 g and BA 2 0 1.6 g was continuously added for 20 minutes, and the outermost hard layer was completed after 20 minutes of completion. 1 polymerization. Next, 1.32 g of APS was added, and after 5 minutes, the monomer mixture consisting of MMA 3148g, BA 201.6g, and n-OM l〇.lg was continuously added for 20 minutes, and the addition was continued for 20 minutes. Then the temperature is raised to 95. (: After 60 minutes, the polymerization of the outermost hard layer 2 is completed. The polymer latex obtained above is taken in a small amount, and the average particle diameter is 0.1 Ομπι by the absorbance method. The remaining latex is put into 3 masses. In the aqueous solution, 'repeating salting out, solidifying, followed by dehydration', washing, and drying to obtain acrylic particles AC 1 having a three-layer structure. The above abbreviations are each of the following materials: ΜΜΑ : methyl methacrylate ΜΑ : methacrylic acid Ester BA: η-butyl acrylate ALMA: allyl methacrylate PEGDA: polyethylene glycol diacrylate (molecular weight 200) -59- 201107385 η - Ο Μ : η-octyl thiol APS: persulfate Ammonium <Preparation of polarizer protective film sample 1 〇1> (Melting composition 1) DIANAL BR85 (manufactured by Mitsubishi Rayon Co., Ltd.) 65 parts by mass of cellulose acetate propionate (the total substitution degree of thiol group is 2.75, Acetyl group substitution degree 0.20, propyl ketone group substitution degree 2.55, Mw = 2 00000 ) 3 5 parts by mass of acrylic particles (AC1) 1.1 parts by mass of inorganic fine particles (Aerosil R972V) 0·27 parts by mass of dichlorocarbyl 300 parts by mass of ethanol 40 mass parts will be on The composition was sufficiently dissolved by heating to prepare a dope 1. The above-prepared cement slurry was uniformly cast on a stainless steel belt support using a belt casting apparatus at a temperature of 22 ° C and a width of 2 m. The solvent was evaporated until the amount of residual solvent became 1%, and the stripping force was peeled off from the stainless steel belt support at a shearing force of 1 62 N/m. The web of the resin composition after peeling was allowed to evaporate at 35 ° C, and cut into 1·. After 5 τη is wide, it is extended by 1.30 times (30%) in the width direction using a tenter, and dried at a drying temperature of l4 〇 ° C. At this time, the amount of residual solvent at the start of stretching using a tenter is 10%. After the tenter is extended, it is relaxed at 130 ° C for 30 seconds, and then conveyed by 120 ° C, 14 (the dry zone of TC) with a plurality of rolls, and the drying is finished, and the cut is 1.5 m wide. An embossing process of a width of l〇mm and a height of 5 μm -60 to 201107385 was applied to both ends of the film, and the core was wound on a core having an inner diameter of 15 to 24 cm at an initial tension of 22 〇N/m and a final tension of 11 〇N/m to obtain a thickness of 4 〇. Reel sample I of polarizer protective film of μπι and roll length 12〇〇111 〇1. The material and conditions of the change are shown in Table 3 below, and the sample 1 0 2 to the sample 1 3 4 are prepared in the same manner as the sample 。. The raw material used is as follows. <<Acrylic resin>> A1 : monomer mass ratio (MMA: MA = 98: 2), Mw75000 A2: monomer mass ratio (MMA: MA = 97: 3) ' Mw 1 40000 A3: monomer mass ratio (MMA: MA = 97: 3) , Mw550000 A4: monomer mass ratio (MMA: MA = 97: 3) ' Mw 1 1 00000 MMA : methyl methacrylate ΜΑ : methacrylate BR85 : DIANAL BR85 (Mitsubishi Ray〇n (stock) system)

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I 200000 ! I 200000 1 I 200000 I I 200000 ! 1 200000 : 1 200000 1 250000 1 250000 ； 250000 & Total 1 I 2.75 I <n I 2.83 I LO <N 1 2.70 I I 2.75 I LO <N LO <N 2.75 LO LC LO in <N LO CM 1 2.75」 2.75 cq LO <N in LO <M LO LO CM LO 〇i LO LO Oi Ln in 1 2.75 I LO <N LO 1 2.75 I 1 2.86 I | 2,86 I 2.86 爾 m 卜 I 1.00 I r in in <N CO •-H in | 0.85 I I 2.55 I in in CO in in in LO ιη LO (Ν in in C^l ΙΛ LO Oi in ΙΩ ΙΛ in ca 1 2.55 1 in LO ιο in CS) in in CSJ in tn C<J LO in CS3 ir> to <N in in LO in cs in iT> in in (N in lo <N in tn C^i in in CSl ID in in in C^3 in in CQ ϋ Ν3 〇 in f-H 00 CO r*H g I-H o »-H I 0.20 I | 0.20 I I 0.20 I I 0.20 I 0.20 | 0.20 I I 0.20 I 1 0.20 I 1 0.20 I 1 0.20 1 | 0.20 I 1 0.20 I I 0.20 I I 0.20 I 1 0.20 I I 0.20 I 0.20 I | 0.20 I I 0.20 I I 0.20 I 1 0.20 1 0.20 I | 0.20 I ! 0.20 0.20 I 0.20 I ! 2.86 to 00 CQ 2.86 sg B m 夔 IE MW I 280000] 1 2800001 280000 I 2800001 I 2800001 1 2800001 1 280000] I 280000] 1 2800001 1 2800001 1 2800001 I 750001 1 1400001 I 5500001 111000001 1 2800001 1 2800001 | 2800001 I 2800001 I 280000! I 2800001 I 2800001 I 2800001 I 2800001 ! 2800001 280000 280000 I 280000 I 280000 280000 I 280000 I 蓮 1 1 m BR85 [BR85 I I BR85 I 1 BR85 BR85 1 BR85 I I BR85| I BR85 | IBR85 1 BR85 I I BR85 | ·-H < La 2 CO < 1 A4 | BR85 I BR85| I BR85 I I BR85 I I BR85 I BR85 1 BR85 I BR85I BR85I BR85 I BR85 I BR85I BR85I BR85 I BR85 I BR85 I 播 1 試料 r-j 〇 g s o s f-H U〇6 叫 o o ΙποΙ Iml CV3 «-H CO liiii U15j to U17 00 r-1 s 120 122 1 123 TT (N in 2 126 127 128 129 § •-η CO 132 CO CO ΟΙ—dga HV1SOHV3S ·- ο_Icsltslfssav .· q_Λζιν :lca -62- 201107385 <鹼皂化處理> 101〜試料134各1500m，進行下述 (2 } ’各自以捲筒狀捲繞於相同將表1之捲同狀試米斗兩種的皂化處理（1 )、的芯上。 (鹼皂化處理（1 )...基淮@ 化條件）音化步驟 4 5V 9 0秒水洗步驟水 3 0°C 45秒中和步驟 1 〇質量份H C 1 3 0°C 45秒水洗步驟水 3 0°C 45秒乾燥 8 0°C 3 6 0秒 (驗皂化處理（2) · ·.迅速巷化條件）皂化步驟 1.5M-NaOH 5 5〇C 4 0秒水洗步驟水 4 0°C 2 0秒中和步驟 1 〇質量份H C1 4 0°C 2 0秒水洗步驟水 4 0°C 2 0秒乾燥 9 5〇C 1 8 0秒 <滑性評價、摩擦係數之測定> 將上述製作之各試料在23 °C、55 %RH之環境下，將薄膜調濕5小時後，依據JIS-K-7 1 25 ( 1 987 )所規定的方法測定薄膜彼此之摩擦係數。皂化後之摩擦係數係以皂化處理（1 )、皂化處理（2 -63- 201107385 )之平均値表示。 <捲形狀•凹凸率> 對於進行皂化處理後之捲筒狀之薄膜，測定捲筒寬之中央之表面凹凸。即，由測定捲筒之外周轉1圈份，得到凹凸之差成爲最大的値Xm。再由轉1圈的平均値計算得到由相同處之捲筒最表面至捲筒芯的厚度Rm，以 Xm/Rmx 100 ( % )作爲凹凸率。表1係以皂化條件（丨）、皂化條件（2 )之平均値表示。 <偏光板之製作> 厚度120μιη之長條卷聚乙烯醇薄膜浸漬於含有碘1質量份、硼酸4質量份之水溶液1 〇〇質量份，以5 0 t：在製膜方向延伸6倍製作偏光鏡。其次，使用聚乙烯醇系之水性黏著劑（2 · 5質量％溶、液 )，使偏光鏡之透過軸與先行皂化處理之試料之面內遲相軸平行的狀態，在偏光鏡之兩面貼合皂化後之試料〗〇 i〜試料1 3 4 ’製作偏光板1 〇 1〜1 3 4。如此，對於各薄膜製作巷化條件不同之2種類的偏光板。 <偏光鏡密著性> 以下述基準評價所製作之偏光板的密著性。將各偏光板切成各5cm><7cm之尺寸。使用丙烯酸系黏著劑將所得之切斷片分別暫時黏著於6cm X 8cm之玻璃板的 -64- 201107385 中央部，接著按壓此等，完全除去各片與玻璃丰反，然後將各切斷片黏著於玻璃板。將上述製作的試驗片以互相不重疊的狀態，於設定爲80°C、90%RH之恆溫恆濕烘箱內，於支定5 0 0小時後，對於各片測定偏光鏡與試料〗〇〗薄膜的密著性。僅偏光鏡與丙烯酸薄膜之密著性評價：高溫後，目視觀察評價偏光鏡與保護薄膜間的剝離狀述基準表示。〇：完全未發現膜之浮起的部分 △:膜之浮起的部分爲周邊l〜5mm的範圍 X :膜之浮起的部分爲周邊5mm以上 <偏光鏡透過率> 與偏光鏡密著性同樣，進行80°C、90%RH ' 之偏光板的劣化試驗，求劣化試驗前後之偏光鏡差，且以下述評價基準表示。〇：劣化試驗之透過率差未達〇 . 5 % △:劣化試驗之透過率差未達5 % x :劣化試驗之透過率差爲5%以下 <液晶顯示裝置之製作> 使用由上述製作之由皂化條件（2 )所構成，評價本發明之薄膜的顯示特性。使用橫電場模間的氣泡垂直配置持框上固文料1 3 4之高濕處理態，以下 5 0 0小時的透過率之偏光板式液晶顯 -65- 201107385 示裝置之日立製液晶電視Wo 00 W3 2-L7 000，將預先貼合之兩面的偏光板剝離，將上述製作之偏光板分別貼於貼於液晶胞之玻璃面。使吸收軸朝向與預先貼合之偏光板相同方向的狀態，貼合上述製作的偏光板，分別製作液晶顯示裝置。 (圖像不均）使用如上述製作的液晶顯示裝置，目視評價灰色之均一圖像，以下述基準表示。〇：完全無圖像不均 △:非常注意時，稍微發現有圖像不均 X :看見三角形、橢圓形的圖像不均 -66 - 201107385Mw280000 The ratio of the MM A unit in the molecule of the commercially available acrylic resin is 90% by mass or more and 99% by mass or less. -61 - 1 201107385 [L撇] Remarks m 癖恃mm Resignation *Τ=Γ m μ T=rr JJ 馁辞綮饀* Resignation 44 Resignation* 辞 hammer special s -LA m Special m 丨丨丨 J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J 1 1 5200 1 1 5200 1 5200 1 5200 1 5200 1 5200 1 5200 1 5200 1 5200 I 5200 I 5200 1 4000 I 7000 1 4000 1 3000 I 3000 1 3000 13000 Film thickness % § o § § ο § § § ο § § ο § § § § § § § § % co § o § § S § Magnification (%) in <N s ιο in Another 8 in in in LO ΙΛ μ 2 to ΙΛ 8 LO in oo 义 m 裴 Quality % ο 0.27 | 0.27 | os ο 0.27" 0.27 | ο 1 0.27 I 0.27 I 0.27 I 〇1 0.27 1 1 0.27 1 1 0.27 1 in ο 1 0.45 1 1 0.65 1 1 0.27 1 1 0.27 1 0.55 ο ο 1 0.45 c5 ο 裴o 1 0.27 I 0.27 t 0.27 I 0.27 I 0.30 | 0.45 I 0.80 Type n3 c〇<a (3⁄4 Λ ca ¢0 ¢0 03 c〇<0 c〇c〇c〇ca e〇C3 CO X » υ C0 m 1 1 CO CO «3 (0 a Π3 CC c〇Nenoic acid particle mass% fH rH rH 1-^ «-Η rH •"H tH fH »-H •Η fH tH *-H rH rH rH fH fH divination CO 揉rH 二壊r-^ ι-Μ r—4 rH TH Shoe Lujun SS Μ m : composition ratio in CO \ in C£5 LO CO \ to in CO \ in to Lfi cn \ Lrt in 00 \ ir> in CO \ mo \ g \ gs \ s ΙΓ3 to \ ιη CQ to \ in <N LO CO \ in in CO \ ΙΛ LO CO \ ΙΛ m CO \ in in 00 \ in in CO \ in in CO \ in in CO \ ΙΛ ΙΟ CO \ in in CO \ ΙΟ in CO \ in ΙΛ CO \ LO \ S ΙΛ CO \ s in CO \ in in CO \ LO in CO \ tn m CO \ in <X) in CO \ to ΙΛ CO \ LO 〇o \ ooo \ ooo \ o MW 200000 1 ! 200000 1 I 200000 II 200000 I | 200000" | 80000 II 200000 I 1 200000 II 200000 I 1 200000 1 I 200000 II 200000 I 1 200000 I 1 200000 I 1200000 II 200000 I 1 200000 I | 200000 I 1 200000 1 I 200000 : I 200000 1 200000 I 200000 I 1 200000 j I 200000 ! I 200000 ! I 200000 1 I 200000 II 200000 ! 1 200000 : 1 200000 1 250000 1 250000 ; 250000 & Total 1 I 2.75 I <n I 2.83 I LO <N 1 2.70 II 2.75 I LO <N LO <N 2.75 LO LC LO in <N LO CM 1 2.75" 2.75 cq LO <N in LO <M LO LO CM LO 〇i LO LO Oi Ln in 1 2.75 I LO <N LO 1 2.75 I 1 2.86 I | 2,86 I 2.86 尔 m 卜 I 1.00 I r in in <N CO •-H in | 0.85 II 2.55 I In in CO in in LO ιη LO (Ν in in C^l ΙΛ LO Oi in ΙΩ ΙΛ in ca 1 2.55 1 in LO ιο in CS) in in CSJ in tn C<J LO in CS3 ir> to <N In in LO in cs in iT> in in (N in lo <N in tn C^i in in CSl ID in in C^3 in in CQ ϋ Ν3 〇in fH 00 CO r*H g IH o »- HI 0.20 I | 0.20 II 0.20 II 0.20 I 0.20 | 0.20 II 0.20 I 1 0.20 I 1 0.20 I 1 0.20 1 | 0.20 I 1 0.20 II 0.20 II 0.20 I 1 0.20 II 0.20 I 0.20 I | 0.20 II 0.20 II 0.20 I 1 0.20 1 0.20 I | 0.20 I ! 0.20 0.20 I 0.20 I ! 2.86 to 00 CQ 2.86 sg B m 夔IE MW I 280000] 1 2800001 280000 I 2800001 I 2800001 1 2800001 1 280000] I 280000] 1 2800001 1 2800001 1 2800001 I 750001 1 1400001 I 5500001 111000 001 1 2800001 1 2800001 | 2800001 I 2800001 I 280000! I 2800001 I 2800001 I 2800001 I 2800001 ! 2800001 280000 280000 I 280000 I 280000 280000 I 280000 I Lotus 1 1 m BR85 [BR85 II BR85 I 1 BR85 BR85 1 BR85 II BR85| I BR85 | IBR85 1 BR85 II BR85 | ·-H < La 2 CO < 1 A4 | BR85 I BR85| I BR85 II BR85 II BR85 I BR85 1 BR85 I BR85I BR85I BR85 I BR85 I BR85I BR85I BR85 I BR85 I BR85 I broadcast 1 sample rj 〇gsos fH U〇6 called oo ΙποΙ Iml CV3 «-H CO liiii U15j to U17 00 r-1 s 120 122 1 123 TT (N in 2 126 127 128 129 § •-η CO 132 CO CO ΟΙ—dga HV1SOHV3S ·- ο_Icsltslfssav .· q_Λζιν :lca -62- 201107385 <alkali saponification treatment> 101 to sample 134 each 1500 m, and the following (2 } ' are each wound in a roll shape and the same as Table 1 The core is saponified (1) on both sides of the test tube. (Alkaline saponification treatment (1)... jihuai @化condition) Sounding step 4 5V 9 0 second water washing step water 3 0 ° C 45 seconds neutralization step 1 〇 mass part HC 1 3 0 ° C 45 second water washing step Water 3 0 ° C 45 seconds dry 8 0 ° C 3 6 0 seconds (saponification treatment (2) · ·. rapid road conditions) saponification step 1.5M-NaOH 5 5〇C 4 0 seconds water washing step water 4 0 ° C 2 0 second neutralization step 1 〇 mass part H C1 4 0 ° C 2 0 second water washing step water 40 ° C 2 0 second drying 9 5 〇 C 1 8 0 sec <slip evaluation, measurement of friction coefficient gt The film prepared above was subjected to humidity conditioning at 23 ° C and 55% RH for 5 hours, and then the coefficient of friction of the films was measured in accordance with the method specified in JIS-K-7 1 25 (1 987). The coefficient of friction after saponification is represented by the average enthalpy of saponification treatment (1) and saponification treatment (2 - 63 - 201107385). <Roll shape • Concavity and convexity rate> The film of the roll shape after the saponification treatment was measured for the surface unevenness at the center of the roll width. In other words, one turn of the circumference of the measurement reel was obtained, and 値Xm having the largest difference in unevenness was obtained. Then, from the average enthalpy of one revolution, the thickness Rm from the outermost surface of the reel to the core of the reel is obtained, and Xm/Rmx 100 (%) is used as the concavity and convexity ratio. Table 1 is represented by the average enthalpy of saponification conditions (丨) and saponification conditions (2). <Preparation of polarizing plate> A long-rolling polyvinyl alcohol film having a thickness of 120 μm was immersed in an aqueous solution containing 1 part by mass of iodine and 4 parts by mass of boric acid, and a mass fraction of 5 ton: 6 times in the film forming direction. Make a polarizer. Next, a polyvinyl alcohol-based aqueous adhesive (2.5 mass% solution) was used, and the transmission axis of the polarizer was parallel to the in-plane slow axis of the sample which was previously saponified, and was attached to both sides of the polarizer. Sample after saponification 〇i~ sample 1 3 4 'Preparation of polarizing plate 1 〇1~1 3 4. In this manner, two types of polarizing plates having different laneping conditions were produced for each film. <Polarizer adhesion> The adhesion of the produced polarizing plate was evaluated by the following criteria. Each of the polarizing plates was cut into a size of 5 cm each < 7 cm. The obtained cut pieces were temporarily adhered to the center of -64-201107385 of a 6 cm X 8 cm glass plate by using an acrylic adhesive, and then pressed, and the pieces were completely removed from the glass, and then the cut pieces were adhered to the glass. board. The test pieces prepared above were placed in a constant temperature and humidity oven set to 80 ° C and 90% RH in a state of not overlapping each other, and after 500 hours of setting, the polarizer and the sample were measured for each piece. The adhesion of the film. Only the adhesion between the polarizer and the acrylic film was evaluated. After the high temperature, the peeling between the polarizer and the protective film was visually observed and evaluated. 〇: The portion where the film floats is not found at all △: the floating portion of the film is in the range of 1 to 5 mm in the periphery X: the portion in which the film floats is 5 mm or more in the periphery <polarizing lens transmittance> In the same manner, the deterioration test of the polarizing plate of 80 ° C and 90% RH ' was performed, and the polarizer difference before and after the deterioration test was obtained, and it was shown by the following evaluation criteria. 〇: The transmittance difference of the deterioration test is less than 〇. 5 % Δ: the transmittance difference of the deterioration test is less than 5% x: the transmittance difference of the deterioration test is 5% or less <Production of liquid crystal display device> The production was carried out by saponification conditions (2), and the display characteristics of the film of the present invention were evaluated. Using the horizontal electric field mode, the vertical arrangement of the air bubbles on the frame is fixed in the high-humidity state of the solid material, and the following 500-hour transmittance of the polarizing plate type liquid crystal display-65-201107385 device Hitachi LCD TV Wo 00 W3 2-L7 000, the polarizing plates on both sides of the front surface are peeled off, and the polarizing plates produced above are attached to the glass surface of the liquid crystal cell. The polarizing plate produced above was bonded to the state in which the absorption axis was oriented in the same direction as the polarizing plate to be bonded in advance, and a liquid crystal display device was produced. (Image unevenness) Using the liquid crystal display device produced as described above, a uniform image of gray was visually evaluated and expressed by the following reference. 〇: There is no image unevenness at all △: When you pay attention, you may find that there is uneven image X: Seeing triangles and ovals are uneven -66 - 201107385

【CVJS 備註墩 Μ m m m 5：燄柃 m 特 1比較例丨粼丨本發明丨 m 饀 m 鎞饀鹬 -Η- 1本發明1 镞鹬 1本發明1 燉 1本發明1 jj 辭 m 辭镞 m 1比較例1 1比較例1 1比較例1 ίΓ 1ν 鏜鶴1 μ 邮〇〇〇 <] 〇 X <1 〇 <3 X 〇〇〇〇〇〇〇〇〇〇〇〇〇 <] X 〇〇〇〇 <3 X X X 褂 m 龌擊 CN 缕卹〇 0 <] 〇〈〇〇〇〇 0 ο 〇〇〇〇〇〇〇〇〇〇〇〇〇〇 <] 〇 < 〇〇 X X X /—S 1—^ 逄 ffip 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 ψ 齡 m 進 ip 〇〇 <] 〇 <] 〇 X <] 〇 <] X <] 〇〇 <] 〇〇 <] 〇〇〇〇 <] <3 〈 X 〇〇〇〇 <] X X X #: 邮〇〇〇〇 <3 〇 X <3 〇〇 < 〇〇〇 <3 〇〇〇〇〇〇〇〇〇 0 <] 〇〇〇〇〇〇〇〇捲形狀凹凸率 {%) σ> 〇 »-Η ο Cvj m ι-Η CS3 寸 <N 寸 00 Ο in CO 1—( Ο eg in i-H •-H Ο in ο 寸 <Ji ο σ> ο 00 ο 寸 CV3 ο 卜寸〇) 〇 CS CM f-H 00 00 un 12.5 1 σ> U 避镊丨皂化後 I 0.46 1 0.52 1 0.58 I 0.53 1 0.50 I 0.49 1 0.69 I 0.52 I 0.56 1 0.56 J 1 0.70 1 1 0.49 1 1 0.49 1 I 0.54 | I 0.59 | 1 0.57 | 1 0.42 1 〇·42 1 1 0.51 1 1 0.46 1 0.47 1 0.45 1 0.49 1 0.56 1 0.59 | 0.70 」 0.46 I 0.46 1 0.46 I 0.50 | 0.51 | Ο CD ο in 00 o 丨皂化前 [0.56 1 0.56 1 0.60 I 0.62 1 0.61 1 0.56 1 0.58 I 0.58 I 0.58 1 0.58 1 0.60 1 0.55 1 in in o I 0.60 | | 0.67 | 1 0.65 | 0,52 1 0.49 1 0-59 1 0.54 1 0.57 J CO in o 0.55 1 0.58 」 0.62 | 0.67 | 0.56 | 0.56_1 0.56 1 0.58 | 0.60 I 0.73 1 in to o 0.46 試料 »Ή Ο s s o ir> o o rH 00 o O ο hu 1 1 U2 1 〇〇 1 ii41 1 n? 1 2 σ> r*W 112Q1 rH 1 122 1 CQ eg r-i 〇24_ in 2 CQ p-H 127 § 04 g r-^ CO CQ CO CO CO i-H 134 | 由表2可知，本發明之試料即使進行迅速的皂化處理也可確保充分的密著性與圖像安定性。 S- 67-[CVJS Remarks Μm mm 5: 柃柃 m special 1 comparative example 丨粼丨m 饀m 鎞饀鹬-Η- 1 invention 1 镞鹬 1 invention 1 stew 1 invention 1 jj speech m remarks m 1 Comparative Example 1 1 Comparative Example 1 1 Comparative Example 1 ίΓ 1ν 镗 Crane 1 μ 〇〇〇<] 〇X <1 〇<3 X 〇〇〇〇〇〇〇〇〇〇〇〇〇&lt ;] X 〇〇〇〇<3 XXX 褂m sniper CN 〇〇 0 <] 〇 < 〇〇〇〇0 ο 〇〇〇〇〇〇〇〇〇〇〇〇〇〇<] 〇&lt ; 〇〇XXX /—S 1—^ 逄ffip 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇ψ Age m Ip 〇〇<] 〇<] 〇X <] 〇<] X <] 〇〇<] 〇〇<] 〇〇〇〇<] <3 〈 X 〇〇〇〇&lt ;] XXX #: 邮<3 〇X <3 〇〇<〇〇〇<3 〇〇〇〇〇〇〇〇〇0 <] 〇〇〇〇〇〇〇〇卷shape Concavity rate {%) σ> 〇»-Η ο Cvj m ι-Η CS3 inch<N inch 00 Ο in CO 1—( Ο eg in iH •-H Ο in ο inch<Ji ο σ> ο 00 ο寸CV3 ο 卜〇〇〇 CS CM fH 00 00 un 12.5 1 σ> U After saponification I 0.46 1 0.52 1 0.58 I 0.53 1 0.50 I 0.49 1 0.69 I 0.52 I 0.56 1 0.56 J 1 0.70 1 1 0.49 1 1 0.49 1 I 0.54 | I 0.59 | 1 0.57 | 1 0.42 1 〇·42 1 1 0.51 1 1 0.46 1 0.47 1 0.45 1 0.49 1 0.56 1 0.59 | 0.70 ” 0.46 I 0.46 1 0.46 I 0.50 | 0.51 | Ο CD ο in 00 o 前 before saponification [0.56 1 0.56 1 0.60 I 0.62 1 0.61 1 0.56 1 0.58 I 0.58 I 0.58 1 0.58 1 0.60 1 0.55 1 in in o I 0.60 | | 0.67 | 1 0.65 | 0,52 1 0.49 1 0-59 1 0.54 1 0.57 J CO in o 0.55 1 0.58 ” 0.62 | 0.67 | 0.56 | 0.56_1 0.56 1 0.58 | 0.60 I 0.73 1 in to o 0.46 Sample »Ή s sso ir> oo rH 00 o O ο hu 1 1 U2 1 〇〇1 ii41 1 n? 1 2 σ> r*W 112Q1 rH 1 122 1 CQ eg ri 〇24_ in 2 CQ pH 127 § 04 g r-^ CO CQ CO CO CO iH 134 | The sample of the present invention is subjected to rapid saponification treatment. Ensuring sufficient adhesion between the image stability. S- 67-

Claims

201107385 七、申請專利範圍： 1·—種偏光鏡保護薄膜，其係以85 : 15~30 : 70之質量比含有丙烯酸樹脂（A)與纖維素酯樹脂（B)的偏光鏡保護薄膜’其特徵係施予皂化處理時，該皂化處理後之摩擦係數小於該皂化處理前的摩擦係數。 2 ·如申請專利範圍第1項之偏光鏡保護薄膜，其係含有微粒子。 3 .如申請專利範圍第2項之偏光鏡保護薄膜，其係含有無機微粒子作爲前述微粒子。 4.如申請專利範圍第2或3項之偏光鏡保護薄膜，其係含有無機微粒子與丙烯酸粒子作爲前述微粒子。 5 . —種偏光板’其係具備偏光鏡及挾著該偏光鏡之2 片偏光鏡保護薄膜的偏光板，其特徵係該偏光鏡保護薄膜中之至少1片爲申請專利範圍第1〜4項中任一項之偏光鏡保護薄膜。 6 · —種偏光板之製造方法，其係製造申請專利範圍第5項之偏光板之偏光板的製造方法，其特徵係具有將申請專利範圍第1〜4項中任一項之偏光鏡保護薄膜進行皂化處理的步驟。 7.如申請專利範圍第6項之偏光板之製造方法，其係在前述皂化處理的步驟中，以1 80秒以內處理從皂化至乾燥前之水洗爲止。 -68- 201107385 四指定代表圖： (一）本案指定代表圖為：無。 (二）本代表圖之元件符號簡單說明：無 201107385 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：無201107385 VII. Patent application scope: 1. A kind of polarizer protective film, which is a polarizer protective film containing acrylic resin (A) and cellulose ester resin (B) with a mass ratio of 85:15~30:70. When the characteristic is applied to the saponification treatment, the friction coefficient after the saponification treatment is smaller than the friction coefficient before the saponification treatment. 2 • A polarizer protective film as claimed in claim 1 contains microparticles. 3. A polarizer protective film according to claim 2, which contains inorganic fine particles as the fine particles. 4. The polarizer protective film according to claim 2 or 3, which comprises inorganic fine particles and acrylic particles as the fine particles. 5. A polarizing plate comprising a polarizing plate and a polarizing plate of two polarizing film protective films next to the polarizing lens, wherein at least one of the polarizing film protective films is in the patent application range 1 to 4 A polarizer protective film according to any one of the items. (6) A method for producing a polarizing plate, which is a method for producing a polarizing plate of a polarizing plate of claim 5, which is characterized by having a polarizer protection according to any one of claims 1 to 4. The film is subjected to a saponification step. 7. The method for producing a polarizing plate according to claim 6, wherein in the step of the saponification treatment, the water washing from saponification to drying is performed within 180 seconds. -68- 201107385 IV Designated representative map: (1) The representative representative of the case is: None. (II) Simple description of the symbol of the representative figure: None 201107385 V. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: none