TW201033274A - Optical film, process for producing the optical film, and polarizing plate and liquid crystal display device using the optical film - Google Patents

Optical film, process for producing the optical film, and polarizing plate and liquid crystal display device using the optical film Download PDF

Info

Publication number
TW201033274A
TW201033274A TW098135944A TW98135944A TW201033274A TW 201033274 A TW201033274 A TW 201033274A TW 098135944 A TW098135944 A TW 098135944A TW 98135944 A TW98135944 A TW 98135944A TW 201033274 A TW201033274 A TW 201033274A
Authority
TW
Taiwan
Prior art keywords
optical film
film
resin
acrylic
mass
Prior art date
Application number
TW098135944A
Other languages
Chinese (zh)
Inventor
Rumiko Yamada
Original Assignee
Konica Minolta Opto Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Opto Inc filed Critical Konica Minolta Opto Inc
Publication of TW201033274A publication Critical patent/TW201033274A/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • G02B1/105—
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/16—Esters of inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/20—Esters of both organic acids and inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polarising Elements (AREA)

Abstract

Disclosed is an optical film composed mainly of an acrylic resin and a cellulose ester resin. Also disclosed are a process for producing the optical film and a polarizing plate and a liquid crystal display device using the optical film. The optical film has high heat resistance and is free from dropouts flight leakages that affect images when the optical film is formed into a polarizing plate that is then disposed in a liquid crystal display device followed by display of black. Further, the optical film is free from frame shaped unevenness upon exposure thereof under hot moist condition of high temperature and humidity. The optical film is characterized in that the optical film comprises an acrylic resin (A) and a cellulose ester resin (B) at a mass ratio in the range of 50: 50 to 95: 5 and acrylic particles (C) in an amount of 0.5 to 30% by mass of the total mass of the resin constituting the optical film and has a residual solvent content of not more than 0.01% by mass.

Description

201033274 六、發明說明： 【發明所屬之技術領域】 本發明係有關光學薄膜、其製造方法、使用其之偏光 板及液晶顯示裝置。 【先前技術】 •就液晶電視及電腦之液晶顯示器等用途，擴大需求液 Φ 晶顯示裝置，而一般的液晶顯示裝置係由，玻璃板挾持透 明電極、液晶層、彩色濾光片等而得之液晶單元，及設置 於其兩側之2枚偏光板所構成，又偏光板各自係由，以2枚 光學薄膜（偏光板保護薄膜）挾持起偏鏡（亦稱爲偏光膜 、偏光薄膜）所構成。該偏光板保護薄膜一般係使用纖維 素三乙酸酯薄膜。 另外隨著近年來的技術進步，使液晶顯示裝置加速大 型化’及使液晶顯示裝置之用途多樣化。例如被使用於設 ❹ 置在街頭或店舖之大型顯示器、或被使用於稱爲電子看板 之顯示機器的公共場所廣告用顯示器等。 但隨著上述液晶顯示裝置大型化，及擴大其屋外用途 等而要求，既使屋外也能充分認識映像需增加背光之光量 ’且使用於嚴苛條件下時具有更高之耐濕性及耐熱性。 爲了改善耐濕性及耐熱性曾提案之技術如，丙烯酸樹 脂組合耐衝擊性丙烯酸橡膠-甲基甲基丙烯酸酯共聚物或 丁基改性乙醯纖維素之樹脂（例如參考專利文獻1及2 )。 但既使該方法也無法充分改善脆性，因此製造大型液 -5- 201033274 晶顯示裝置用之光學薄膜時無法得到充分處理性。又會因 混合之成份而產生混濁，因此使用於要求更高對比之屋外 等時，會發生降低畫像對比之問題。 又，相對於先前之纖維素酯薄膜曾提案，混合可塑劑 及控制光學特性用丙烯酸樹脂之技術（例如參考專利文獻 3 ) ° 但此等目的中未添加可充分改善耐濕性之丙烯酸樹脂 ，因此無法得到充分耐濕性，會發生高濕環境下偏光板惡 化及光學薄膜之光學値改變等問題。又，先前爲了提升纖 維素酯樹脂之耐濕性而添加大量其他樹脂時，推斷會降低 透明性，而無法得到高濕環境下光學値不會改變可改善耐 濕性之纖維素酯薄膜。 有鑑於上述狀況，伴隨著最近液晶顯示裝置用途的擴 大而要求改善日益顯著的低吸濕性、透明性、高耐熱性、 脆性等課題。 丙烯酸樹脂爲持有低雙折射性，而纖維素酯樹脂爲持 有優良耐熱性之樹脂，但以二氯甲烷等溶劑使該二種樹脂 溶液製膜後，將製膜後之該相溶物乾燥時，去除溶劑會發 生相溶物收縮而產生大量皺紋之問題。 又不混合該二種樹脂下以纖維素酯樹脂之熔融溫度（ 240°C )熔融流延時雖可改良皺紋，但因二種樹脂之相溶 不足，因此會形成雙折射率較高、表面紋路較多之薄膜。 爲了消除相溶不足問題，而以高溫（270°C )進行熔融流 延時雖可達成改良雙折射性及表面性，但使用該類以高溫 -6- 201033274 製膜而得之薄膜製作偏光板後，貼合於面板的結果會降低 對比。 因此需爲低溫條件下具有良好相溶性之組成物。一般 已知的使樹脂相溶化之方法爲添加低分子量型之添加劑， 但添加大量該類低分子量型之添加劑時，將使用製膜而得 之薄膜的液晶面板曝露於高溫高濕條件下，會有大量發生 框斑（液晶顯示裝置於黑顯示時畫面周邊脫白）之問題（ φ 例如參考專利文獻4 )。 因此本發明者們開始探索既使於殘留溶劑較少之狀態 下製造光學薄膜時，也可得框斑較少之光學薄膜。 先前技術文獻 專利文獻 專利文獻1 :特開平5-1 192 17號公報 專利文獻2:特開2008-8841 7號公報 φ 專利文獻3:特開2〇〇3_12859號公報 專利文獻4:特開2007-1 785 1 4號公報 【發明內容】 發明槪要 發明所欲解決之課題 有鑑於上述問題及狀況，本發明所欲解決課題爲，提 供主要構成成份爲丙烯酸樹脂及纖維素酯樹脂之光學薄膜 中’持有優良耐熱性，又使用該光學薄膜加工偏光板後， -7- 201033274 將相同偏光板配置於液晶顯示裝置進行黑顯示時不會出現 影響畫像般脫白（漏光）’且曝露於高濕及高溫之濕熱條 件下時不會產生框斑的光學薄膜及其製造方法。另外係提 供使用其之偏光板及液晶顯示裝置。 解決課題之方法 本發明之上述課題係以下述方法解決。 1. —種光學薄膜，其特徵爲’含有丙烯酸樹脂（A _ )、纖維素酯樹脂（B)及丙烯酸基粒子（c)之光學薄 膜中’係以50: 50至95: 5之範圍內之質量比含有前述丙 烯酸樹脂（A)及纖維素酯樹脂（B)，且相對於構成該 光學薄膜之樹脂總質量，前述丙烯酸基粒子（C)之含有 率爲0.5至30質量％，殘留溶劑量之含有率爲0.01質量％ 以下。 2. 如前述1·所記載之光學薄膜，其中前述丙烯酸樹 脂（A)之重量平均分子量（Mw)爲110000至1000000之 ❹ 範圍內。 3. —種光學薄膜之製造方法，其特徵爲，如前述1. 或前述2.所記載之光學薄膜的製造方法爲，使用接觸輥之 熔融流延製膜法。 4. 一種偏光板，其特徵爲，使用如前述1.或前述2. 所記載之光學薄膜。 5. —種液晶顯示裝置，其特徵爲，使用如前述4·所 記載之偏光板。 -8 - 201033274 發明之效果 本發明之上述方法可提供，主要構成成份爲丙烯酸樹 脂及纖維素酯樹脂之光學薄膜中，持有優良耐熱性，又使 用該光學薄膜加工偏光板後，將相同偏光板配置於液晶顯 示裝置進行黑顯示時不會出現影響畫像般脫白（以下稱爲 「漏光」）’且曝露於高濕及高溫之濕熱條件下時不會產 0 生框斑的光學薄膜及其製造方法。另外可提供使用其之偏 光板及液晶顯示裝置。 實施發明之形態 本發明之光學薄膜的特徵爲，含有丙烯酸樹脂（A) 、纖維素酯樹脂（B)及丙烯酸基粒子（C)之光學薄膜 中，係以50: 50至95: 5之質量比含有前述丙烯酸樹脂（ A)及纖維素酯樹脂（B)，且相對於構成該光學薄膜之 參 樹脂總質量’前述丙稀酸基粒子（C)之含有率爲〇.5至30 質量％ ’殘留溶劑量之含有率爲0.01質量％以下。該特徵 爲，有關申請專利範圍第1至第5項之發明的共通性技術上 之特徵。 本發明之實施形態較佳爲，前述丙烯酸樹脂（A)之 重量平均分子量（Mw)爲1 1 0000至loooooo。 本發明之光學薄膜的製造方法較佳爲，使用接觸輥之 熔融流延製膜法。 本發明之光學薄膜適用於偏光板，及使用其之液晶顯 -9- 201033274 示裝置。 施發明 樹脂。 單位50 50質量 的烷基 酯、丙 富馬酸 'α -甲 丙烯腈 取代馬 種以上 爲甲基 基丙烯 特佳爲 下面將詳細說明本發明及其構成要素，以及實 之形態及態樣等。 (丙烯酸樹脂（A )) 本發明所使用的丙烯酸樹脂也包括甲基丙烯酸 樹脂並無特別限制，但較佳爲由甲基甲基丙烯酸酯 至99質量％，及能與其共聚合之其他單體單位1至 %所形成之物。 能共聚合之其他單體如，烷基之碳數爲2至18 甲基丙烯酸酯、烷基之碳數爲1至18之烷基丙烯酸 烯酸、甲基丙烯酸等之〇：，A -不飽和酸、馬來酸、 、衣康酸等之含有不飽和基的二價羧酸、苯乙烯 基苯乙烯等之芳香族乙烯基化合物、丙烯腈、甲基 等之α，/3-不飽和腈、馬來酸酐、馬來醯亞胺、N-來醯亞胺、戊二酸酐等，此等可單獨使用或倂用二 之單體。 其中就共聚物之耐熱分解性及流動性觀點較佳 丙烯酸酯、乙基丙烯酸酯、η-丙烯丙烯酸酯、η-丁 酸酯、s-丁基丙烯酸酯、2-乙基己基丙烯酸酯等， 使用甲基丙烯酸酯及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)，特別 是就改善光學薄膜用之脆性及改善與纖維素酯樹脂（Β) 相溶時之透明性觀點，其重量平均分子量（Mw)爲80000 201033274 以上。 丙烯酸樹脂（A)之重量平均分子量（Mw)更佳爲 1 1 0000至1000000之範圍內，特佳爲100000至600000之範 圍內。丙烯酸樹脂（A)之重量平均分子量（MW)的上限 値並無特別限制，但就製造性觀點又以1 000000以下之形 態爲佳。 本發明之丙烯酸樹脂的重量平均分子量可藉由凝膠滲 • 透色譜法測定。測定條件如下所述。 溶劑：二氯甲烷 柱：Shodex K806、K8 05、K8 03 G (接連使用 3根，昭 和電工（股）製） 柱溫度：2 5 °C 試料濃度：0.1質量％ 檢驗器：RI Model 504 ( GL賽恩斯公司製） 唧筒：L6000 (日立製作所（股）製） ^ 流量：l.Oml/min 校正曲線：使用由標準聚苯乙烯STK standard聚苯 乙烯（東索（股）製）Mw = 2,800,000至500之13個樣品而 得的校正曲線。所使用的13個樣品較佳爲幾乎等間隔。 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、乳化聚合、塊狀聚合或溶液聚合等已 知任何一種方法。其中所使用的聚合引發劑可爲一般的過 氧化物系及偶氮系之物，又可使用氧化還原系。就聚合溫 度而θ ’懸浮或乳化聚合可以30至+ 100C ’塊狀或溶液聚 -11 - 201033274 合可以80至160 °C實施。爲了控制所得共聚物之還原黏度 ，可以烷基硫醇等作爲鏈移動劑用實施聚合。 本發明之丙烯酸樹脂也可使用市售物，例如德佩特 60N、80N (旭化成化學（股）製）、戴亞那BR52、BR80 、BR8 5、BR8 8(三菱人造絲（股）製）、KT75 (電化學 工業（股）製）等。丙烯酸樹脂可併用二種以上。 (纖維素酯樹脂（B )) 本發明所使用的纖維素酯樹脂（B )，特別是就改善 脆性及與丙烯酸樹脂（A)相溶時之透明性觀點較佳爲， 醯基之總取代度（T)爲2.0至3_0，碳數3至7之醯基的取 代度爲1.2至3.0，碳數3至7之醯基的取代度爲2.0至3.0。 即，本發明之纖維素酯樹脂爲，被碳數3至7之醯基取代的 纖維素酯樹脂，具體上較佳爲使用丙醯基、丁醯基等，特 佳爲使用丙醯基。 纖維素酯樹脂（B)之醯基的總取代度低於2.0時，即 ，纖維素酯分子之2，3，6位的羥基殘度高於1.0時，丙烯 酸樹脂（A)與纖維素酯樹脂（B)將無法充分相溶，因 此作爲光學薄膜用時會有混濁問題。又，既使醯基之總取 代度爲2.0以上，但碳數3至7之醯基的取代度低於1.2時’ 仍無法得到充分相溶性，或降低脆性。例如既使醯基之總 取代度爲2.0以上，但碳數2之醯基，即乙醯基之取代度較 高，而碳數3至7之醯基的取代度低於1.2時，仍會降低相 溶性而提升混濁度。又，既使醯基之總取代度爲2.0以上 201033274 ’但碳數8以上之醯基的取代度較高，而碳數3至7之醯基 的取代度低於I.2時，仍會使脆性變差而無法得到所希望 之特性。 本發明之纖維素酯樹脂（B)的醯基取代度可爲，總 取代度（T )爲2.0至3.0，且碳數3至7之醯基的取代度爲 12至3.0，但碳數3至7以外之醯基，即乙醯基及碳數8以 上之醯基的取代度總計較佳爲1 .3以下。 • 又，纖維素酯樹脂（B)之醯基的總取代度（T)更 佳爲2.5至3.0之範圍。 本發明之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狀或支鏈狀，另外可具有取代基 。本發明之醯基的碳數係包含醯基之取代基。 上述纖維素酯樹脂（B)爲具有取代基用之芳香族醯 基時，芳香族環中取代用之取代基X數量較佳爲〇至5個。 此時仍需留意使包含取代基的碳數3至7之醯基的取代度爲 β U至3·0。例如爲了使苯醯基之碳數爲7，而具有含碳之 取代基時，會使苯醯基用之碳數爲8以上，而不含有碳數3 至7之醯基。 另外芳香族環中取代用之取代基數量爲2個以上時， 可相同或相異’又可相互連結形成縮合多環化合物（例如 萘、茚、茚滿、菲、喹啉、異唾啉、色烯、色滿、酞嗪、 吖啶、吲哚、吲哚滿等）。 上述般纖維素醋樹脂（Β)中，因具有含至少1種碳數 3至7之脂肪族酿基的構造’故適用爲本發明之纖維素樹脂 -13- 201033274 所使用的構造。 本發明之纖維素酯樹脂（B)的取代度爲，醯基之總 取代度（T)爲2.0至3.0’碳數3至7之醯基的取代度爲12 至 3 · 0 〇 又以碳數3至7之醯基以外，即乙醯基及碳數8以上之 醯基的取代度總和爲1 .3以下之構造爲佳。 本發明之纖維素酯樹脂（B)特佳爲纖維素乙酸酯丙 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、纖維素丁酸酯中所選出的至少一種，即較佳 爲具有取代基用之碳原子數3或4的醯基之物。 此等中特佳之纖維素醋樹脂爲纖維素乙酸酯丙酸醋及 纖維素丙酸酯。 一般未被醯基取代之部分係以羥基形態存在。其可由 已知之方法合成。 又乙醯基之取代度及其他醯基之取代度可由AS TM-D817-96所規定之方法求取。 本發明之纖維素酯樹脂的重量平均分子量（Mw)， 特別是就與丙烯酸樹脂（A )之相溶性、改善脆性觀點爲 75000以上，較佳爲75000至300000之範圍，更佳爲100000 至240000之範圍內，特佳爲1 60000至240000。纖維素酯樹 脂之重量平均分子量（Mw)低於75000時，耐熱性及脆性 之改善效果將不足，而無法得到本發明的效果。本發明可 混合使用二種以上之纖維素樹脂。 本發明之光學薄膜中，爲了發現本發明之效果、耐濕 -14- 201033274 性等觀點，係以50 : 50至95: 5之質量比含有丙烯酸樹脂 (A)及纖維素酯樹脂（B)，較佳爲90: 10至60: 40。 丙烯酸樹脂（A)及纖維素酯樹脂（B)之質量比中 ’丙烯酸樹脂（A)多於95: 5時，將無法充分得到來自 纖維素酯樹脂（B)之效果，又丙烯酸樹脂少於同質量比 50 : 50時，耐濕性將不足。 本發明之光學薄膜中，丙烯酸樹脂（A)及纖維素醋 φ 樹脂（B )較佳以相溶狀態含有。光學薄膜所必需的物性 及品質，可藉由不同之樹脂相溶互補而達成。 丙烯酸樹脂（A)及纖維素酯樹脂（B)是否爲相溶 狀態，例如可由玻璃化溫度Tg判斷。 例如兩者之樹脂的玻璃化溫度不同時，混合兩者之樹 脂時會因存在各自樹脂之玻璃化溫度而使混合物存在2個 以上之玻璃化溫度，但兩者之樹脂相溶時會使各自樹脂之 固有的玻璃化溫度消失，而使相溶樹脂之玻璃化溫度爲1 〇 個玻璃化溫度。 又，該玻璃化溫度係指，使用差示掃描熱量測定器（ Perkin Elmer公司製DSC-7型），以升溫速度20 °C/分測定 後，依JIS K7 1 2 1 ( 1 987 )求取之中間點玻璃化溫度（Tmg )° 丙烯酸樹脂（A)及纖維素酯樹脂（B)各自較佳爲 非結晶性樹脂，又可爲任何一方爲結晶性高分子，或部分 具有結晶性之高分子，但本發明之丙烯酸樹脂（A)及纖 維素酯樹脂（B )相溶，因此以非結晶性樹脂爲佳。 -15- 201033274 本發明之光學薄膜中，丙烯酸樹脂（A)之重量平均 分子量（Mw)及纖維素酯樹脂（B)之重量平均分子量（ Mw )及取代度可藉由兩樹脂對溶劑之溶解性差進行區分 後各自測定而得。區分樹脂之方法可爲，將相溶之樹脂加 入僅能溶解任何一方之溶劑中，再萃取溶解之樹脂而區分 ，又此時可進行加熱處理及環流。又可爲，以2個步驟以 上組合此等溶劑之組合物，再區分樹脂。另外可濾分溶解 之樹脂及殘存之不溶物樹脂，再對含有萃取物之溶液實施 溶劑蒸發、乾燥之步驟以區分樹脂。此等區分後之樹脂可 藉由一般高分子之構造解析而特定化。本發明之光學薄膜 含有丙烯酸樹脂（A)及纖維素酯樹脂（B)以外之樹脂 時也可以相同方法區分。 又，相溶之樹脂的重量平均分子量（Mw)各自不同 時，可藉由凝膠滲透色譜法（GPC)早期溶離高分子量物 ，因低分子量物需較長時間溶融，故易區分且可測定分子 量。 又，藉由GPC測定相溶後樹脂之分子量的同時，可分 取每段時間溶離之樹脂溶液，餾去溶劑後乾燥再定量進行 樹脂之構造解析，以檢驗不同分子量之每分區的樹脂組成 ，而使相溶之樹脂各自特定化。又事前以藉由對溶劑之溶 解性差分取的樹脂，可各自以GPC測定分子量分布，而各 自驗出相溶之樹脂。 又，本發明中「丙烯酸樹脂（A)及纖維素酯樹脂（ B )係以相溶狀態含有」係指，混合各樹脂（聚合物）後 -16- 201033274 爲相溶之狀態，並不包含纖維素酯樹脂（B)混合單體、 二聚物或低聚物等之丙烯酸樹脂先驅物後聚合而得的混合 樹脂狀態。 例如使用纖維素酯樹脂（B)混合單體、二聚物或低 聚物等之丙烯酸樹脂先驅物後聚合而得混合樹脂之步驟時 ，會因聚合反應煩雜，而使該方法所製作之樹脂因難控制 反應而難調整分子量。又以該方法合成樹脂時多半會產生 $ 接枝聚合、交聯反應或環化反應，而多半成爲溶解於溶劑 之情況、或無法加熱熔融，因此難溶離混合樹脂中之丙烯 酸樹脂以測定重量平均分子量（Mw )，故難控制物性而 不適用爲可安定製造光學薄膜之樹脂。 本發明之光學薄膜於無損光學薄膜用之機能下，可含 有丙烯酸樹脂（A)、纖維素酯樹脂（B)以外之樹脂及 添加劑而構成。 含有丙烯酸樹脂（A)、纖維素酯樹脂（B)以外之 φ 樹脂時，所添加之樹脂可爲相溶狀態，或不溶解而爲混合 狀。 本發明之光學薄膜中丙烯酸樹脂（A)及纖維素酯樹 月旨（B)之總質量較佳爲’光學薄膜之55質量％以上，更 佳爲60質量％以上’特佳爲70質量％以上。 使用丙烯酸樹脂（A)及纖維素酯樹脂（B)以外之 樹脂及添加劑時’又以無損本發明之光學薄膜機能的範圍 調整添加量爲佳。 -17- 201033274 (丙烯酸基粒子（c )) 本發明之光學薄膜較佳爲含有丙烯酸基粒子。本申請 書中「丙烯酸基粒子（C)」係指，於含有前述丙烯酸樹 脂（A)及纖維素酯樹脂（B)之光學薄膜中以粒子狀態 (亦稱爲非相溶狀態）存在的丙烯酸基成分。 上述丙烯酸基粒子（C)較佳爲，例如採取定量製作 而得之光學薄膜後，將其攪拌溶解於溶劑中，充分溶解分 散後以具有未達丙烯酸基粒子（C)之平均粒徑的孔徑之 PTFE製膜滤器過滅，結果過滤捕集之不溶物的重量爲加 入光學薄膜之丙烯酸基粒子（C)的9 0質量％以上。 本發明所使用的丙烯酸基粒子（C )並無特別限制， 較佳爲具有2層以上層構造之丙烯酸基粒子（C)，特佳爲 下述多層構造丙烯酸基系粒狀複合物。 多層構造丙烯酸基系粒狀複合物係指，中心部朝向外 周部具有層狀重合最內硬質層聚合物，持有橡膠彈性之交 聯軟質層聚合物及最外硬質層聚合物而得之構造的粒子狀 丙烯酸基聚合物。 即，多層構造丙烯酸基系粒狀複合物係指，由中心部 朝向外周部之最內硬質層、交聯軟質層及最外硬質層所構 成的多層構造丙烯酸基系粒狀複合物。又以使用該3層芯 殼構造之多層構造丙烯酸基系粒狀複合物爲佳。 本發明之丙烯酸基系樹脂組成物所使用的多層構造丙 烯酸基系粒狀複合物之較佳態樣如下述。例如具有（a) 由甲基甲基丙烯酸酯80至98.9質量％、烷基之碳數爲1至8 201033274 的烷基丙烯酸酯1至20質量％、及多官能性接枝劑o.oi至 0.3質量％所形成的單體混合物聚合而得之最內硬質層聚 合物’ （b)存在上述最內硬質層聚合物下，由烷基之碳 數爲4至8的烷基丙烯酸酯75至98.5質量％、多官能性交聯 劑0.01至5質量％及多官能性接枝劑〇.5至5質量％所形成 的單體混合物聚合而得之交聯軟質層聚合物、（c)存在 上述最內硬質層及交聯軟質層所形成的聚合物下，由甲基 φ 甲基丙烯酸酯80至99質量％及烷基之碳數爲1至8的烷基丙 烯酸酯1至20質量％所形成之單體混合物聚合而得的最外 硬層聚合物所構成的3層構造，且所得的3層構造聚合物中 最內硬質層聚合物（a)爲5至40質量％，軟質層聚合物（ b)爲30至60質量％，及最外硬質層聚合物（c)爲20至50 質量％，又，以丙酮區分時具有不溶部分，且該不溶部分 之甲基乙基酮膨潤度爲1.5至4.0的丙烯酸基系粒狀複合物 〇 φ 又如特公昭60-17406號公報或特公平3-39095號公報 所揭示，除了規定多層構造丙烯酸基系粒狀複合物之各層 組成及粒徑外，也將多層構造丙烯酸基系粒狀複合物之拉 伸彈性率及丙酮不溶部分的甲基乙基酮膨潤度設定爲特定 範圍內時，另可實現充分耐衝擊性及耐應力白化性之均衡 性。 其中構成多層構造丙烯酸基系粒狀複合物之最內硬質 層聚合物（a)較佳由甲基甲基丙烯酸酯80至98.9質量％ 、烷基之碳數爲1至8的烷基丙烯酸酯1至20質量％及多官 -19- 201033274 能性接枝劑0.01至〇·3質量％所形成的單體混合物聚合而 該烷基之碳數爲1至8的烷基丙烯酸酯如’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)中烷基丙烯酸酯單位之比率 爲1至20質量％，該單位未達1質量％時，會增加聚合物之 _ 熱分解性，又該單位超過20質量％時，會降低最內硬質層 聚合物（c)之玻璃化溫度，而降低3層構造丙烯酸基系粒 狀複合物之耐衝擊性賦予效果，故均不宜。 多官能性接枝劑如，具有不同的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 之烯丙基酯等，較佳爲使用烯丙基甲基丙烯酸酯。使用多 官能性接枝劑之目的爲，使最內硬質層聚合物及軟質層聚 合物化學性鍵結，因此其使用於最內硬質層聚合時之比率 © 爲0.01至0.3質量％。 構成丙烯酸基系粒狀複合物之交聯軟質層聚合物（b )較佳爲，存在上述最內硬質層聚合物（a)下，由烷基 之碳數爲1至8的烷基丙烯酸酯75至98.5質量％、多官能性 交聯劑0.01至5質量％及多官能性接枝劑0.5至5質量％所 形成的單體混合物聚合而得。 其中烷基之碳數爲4至8的烷基丙烯酸酯較佳爲使用n-丁基丙烯酸酯及2-乙基己基丙烯酸酯。 -20- 201033274 又，此等聚合性單體可與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如，苯乙烯及取代苯乙 烯衍生物。烷基之碳數爲4至8的烷基丙烯酸酯與苯乙烯之 比率係前者較多時，可降低聚合物（b )之玻璃化溫度， 即軟質化。 又就樹脂組成物之透明性觀點，軟質層聚合物（b ) φ 之常溫下的折射率較佳爲近似最內硬質層聚合物（a)、 最外硬質層聚合物（c)及硬質熱塑性丙烯酸樹脂，因此 可勘定此等後選定兩者之比率。 所使用之多官能性接枝劑可如前述最內硬質層聚合物 (a)項。使用該多官能性接枝劑之目的爲，使軟質層聚 合物（b)與最外硬質層聚合物（c)化學性鍵結，因此其 使用於最內硬質層聚合時之比率，就耐衝擊性賦予效果的 觀點較佳爲0.5至5質量％。 φ 所使用之多官能性交聯劑可爲二乙烯基化合物、二烯 丙基化合物、二丙烯酸基化合物、二甲基丙烯酸基化合物 等一般已知之交聯劑，較佳爲使用聚乙二醇二丙烯酸酯（ 分子量200至600 )。 使用該多官能性交聯劑之目的爲，聚合軟質層（b) 時生成交聯構造而發現耐衝擊性賦予效果。但聚合軟質層 時先使用多官能性接枝劑令某程度生成軟質層（b)之交 聯構造，因此多官能性交聯劑非必須成份，但就耐衝擊性 賦予效果之觀點，軟質層聚合時之多官能性交聯劑使用比 -21 - 201033274 率較佳爲0.01至5質量％。 構成多層構造丙烯酸基系粒狀複合物之最外硬質層聚 合物（c)較佳爲，存在上述最內硬質層聚合物（a)及軟 質層聚合物（b)下，由甲基甲基丙烯酸酯8 0至99質量％ 及烷基之碳數爲1至8的烷基丙烯酸酯1至20質量％所形成 之單體混合物聚合而得。 其中烷基丙烯酸酯可使用前述之物，較佳爲使用甲基 丙烯酸酯及乙基丙烯酸酯。最外硬質層（c)中烷基丙烯 酸酯單位之比率較佳爲1至20質量％。 又，聚合最外硬質層（c)時爲了提升對丙烯酸樹脂 (A)之相溶性，實施時可以烷基硫醇等作爲鏈移動劑調 整分子量。 特別是最外硬質層係以由內側朝外側逐次減少分子量 之梯狀方向設置時，可改良延伸與耐衝擊性之均衡性而爲 佳。具體方法如，將形成最外硬質層之單體混合物分割爲 2批以上，依序增加每回加入之鏈移動劑量的方法，可使 多層構造丙烯酸基系粒狀複合物由內側朝外側減少形成最 外硬質層用之聚合物的分子量。 此時所形成之分子量可由，以相同條件單獨聚合每回 使用之單體混合物後，測定所得聚合物之分子量而得。 本發明所使用的丙烯酸基粒子（C)之較佳粒徑並無 特別限定，但以10至l〇〇〇nm爲佳，更佳爲20至500nm，最 佳爲50至400nm。 本發明較佳使用之多層構造聚合物的丙烯酸基系粒狀 201033274 複合物中’芯與殼之質量比並無特別限定，但以多層構造 聚合物全體爲100質量份時，芯層較佳爲50至90質量份， 更佳爲60至80質量份。該芯層係指最內硬質層。 該類多層構造丙烯酸基系粒狀複合物之市售品如，三 菱人造絲公司製“美達布”、鐘淵化學工業公司製“卡內 耶”、吳羽化學工業公司製“帕拉洛”、洛姆安公司製“ 艾克里”、剛滋化成工業公司製“斯達芬”及庫拉雷公司 φ 製“帕拉佩SA”等，此等可單獨或2種以上混合使用。 又，適用爲本發明較佳之丙烯酸基粒子（C)的接枝 共聚物之丙烯酸基粒子（c-1)的具體例如，存在橡膠質 聚合物下，共聚合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，及必要時使用的能與此等共聚 合之其他乙烯基系單體所形成的單體混合物共聚合而得之 接枝共聚物。 接枝共聚物之丙烯酸基粒子（c-Ι)所使用的橡膠質 φ 聚合物並無特別限制，可使用二烯系橡膠、丙烯酸基系橡 膠及乙烯系橡膠等。具體例如’聚丁二烯、苯乙烯-丁二 烯共聚物、苯乙烯-丁二烯之嵌段共聚物、丙烯腈-丁二烯 共聚物、丙烯酸丁酯-丁二烯共聚物、聚異戊二烯、丁二 烯-甲基甲基丙烯酸酯共聚物、丙烯酸丁酯-甲基甲基丙烯 酸醋共聚物、丁二嫌-丙燒酸乙酯共聚物、乙嫌-丙嫌共聚 物、乙烯-丙烯-二烯系共聚物、乙烯-異戊二烯共聚物、 及乙烯-丙烯酸甲酯共聚物等。此等橡膠質聚合物可使用1 種或2種以上之混合物。 -23- 201033274 又’本發明之光學薄膜添加丙烯酸基粒子（c)時較 佳爲’丙烯酸樹脂（A)及纖維素酯樹脂（B)之混合物 的折射率近似丙烯酸基粒子（C)之折射率，如此可得透 明性較高之薄膜。具體上丙烯酸基粒子（C)與丙烯酸樹 脂（A)之折射率差較佳爲〇.〇5以下，更佳爲0.02以下， 特佳爲0.01以下。 爲了符合該折射率條件，可藉由調整丙烯酸樹脂（A )之各單體單位組成比的方法，及/或調整丙烯酸基粒子 (C)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，而得透明性優良之光學薄膜。 上述之折射率差係指，以適當條件將本發明之光學薄 膜充分溶解於丙烯酸樹脂（A)可溶之溶劑中，形成白濁 溶液後藉由離心分離等操作，分離溶劑可溶部分及不溶部 分，各自精製該可溶部分（丙烯酸樹脂（A))及不溶部 分（丙烯酸基粒子（C ))後測得的折射率（23 °C，測定 波長：5 5 Onm )。 本發明之丙烯酸樹脂（A)添加丙烯酸基粒子（C) 的方法並無特別限定，較佳爲使用預先摻混丙烯酸樹脂（ A)及其他任意成份後，一般於200至350 °C下加入丙烯酸 基粒子（C)的同時藉由單軸或雙軸擠壓機均勻熔融混練 的方法。 本發明之丙烯酸基粒子可使用市售品。例如美達布 W-341 ( C2 )(三菱人造絲（股）製）、肯密斯MR-2G( C3) 、MS-300X(C4)(綜硏化學（股）製）等。 201033274 本發明之光學薄膜中，相對於構成該薄膜之樹脂總質 量較佳爲，含有0.5至30質量％之丙烯酸基粒子（C)，更 佳爲含有1.0至15質量％之範圍。 丙烯酸基粒子（C)之含量相對於薄膜全體質量少於 0.5質量％時，抑制因溫度及環境的變化而發生之框斑的 效果將不足，又丙烯酸基粒子（C)多於30質量％時，將 偏光板本身或偏光板貼合於液晶顯示裝置之狀態下曝露於 φ 高溫時會發生熱變形。因此會影響原有設計之液晶顯示裝 置的畫像。 (防氧化劑） 本發明之丙烯酸樹脂等樹脂混合物較佳爲含有防氧化 劑。 本發明之防氧化劑較佳爲磷系或酚系氧化劑，更佳爲 同時組合磷系及酚系防氧化劑。 φ 下面將說明本發明適用之防氧化劑。 <酚系防氧化劑> 本發明可使用下述一般式（AOl)所表示之酚系防氧 化劑。 -25- 201033274 [化1] -難式(A01)[Technical Field] The present invention relates to an optical film, a method for producing the same, a polarizing plate using the same, and a liquid crystal display device. [Prior Art] • Expanding the demand liquid Φ crystal display device for LCD TVs and computer LCD monitors, etc., and the general liquid crystal display device is obtained by holding a transparent electrode, a liquid crystal layer, a color filter, etc. on a glass plate. The liquid crystal cell is composed of two polarizing plates disposed on both sides thereof, and the polarizing plates are respectively supported by two polarizing films (also referred to as polarizing films and polarizing films) by two optical films (polarizing plate protective films). Composition. The polarizing plate protective film is generally a cellulose triacetate film. Further, with the advancement of technology in recent years, the liquid crystal display device has been accelerated in size and the use of the liquid crystal display device has been diversified. For example, it is used for a large display that is installed on a street or a store, or a public place advertisement display that is used for a display device called an electronic signage. However, as the liquid crystal display device is enlarged and expanded for outdoor use, it is required to increase the amount of backlight light when the image is externally recognized, and it has higher moisture resistance and heat resistance when used under severe conditions. Sex. A technique which has been proposed to improve moisture resistance and heat resistance, for example, an acrylic resin combined with an impact-resistant acrylic rubber-methyl methacrylate copolymer or a butyl-modified acetonitrile cellulose resin (for example, refer to Patent Documents 1 and 2) ). However, even if the method does not sufficiently improve the brittleness, sufficient processing properties cannot be obtained when manufacturing an optical film for a large liquid liquid crystal display device. In addition, turbidity is caused by the mixed components, so when used in a room where higher contrast is required, the problem of reducing the contrast of the image may occur. Further, a technique of mixing a plasticizer and an acrylic resin for controlling optical properties has been proposed in comparison with the prior cellulose ester film (for example, refer to Patent Document 3). However, an acrylic resin which can sufficiently improve moisture resistance is not added to such an object. Therefore, sufficient moisture resistance cannot be obtained, and problems such as deterioration of the polarizing plate and change of optical enthalpy of the optical film in a high-humidity environment occur. Further, when a large amount of other resin is added in order to improve the moisture resistance of the cellulose ester resin, it is presumed that the transparency is lowered, and the cellulose ester film which does not change the moisture resistance in a high-humidity environment cannot be obtained. In view of the above-mentioned situation, with the recent expansion of the use of liquid crystal display devices, there has been a demand for improvement of problems such as low hygroscopicity, transparency, high heat resistance, and brittleness. The acrylic resin has a low birefringence, and the cellulose ester resin is a resin having excellent heat resistance. However, after the two resin solutions are formed into a film by a solvent such as dichloromethane, the solvent is formed after the film formation. When drying, removal of the solvent causes a problem that the consumable shrinks to cause a large amount of wrinkles. Without mixing the two resins, the melting temperature of the cellulose ester resin (240 ° C) melt flow delay can improve wrinkles, but because of the lack of compatibility of the two resins, it will form a high birefringence, surface texture More film. In order to eliminate the problem of insufficient compatibility, the melt flow delay at a high temperature (270 ° C) can achieve improved birefringence and surface properties, but after using the film obtained by filming at a high temperature of -6-201033274, a polarizing plate is produced. The result of fitting to the panel will reduce the contrast. Therefore, it is necessary to have a composition which is excellent in compatibility under low temperature conditions. A generally known method for dissolving a resin is to add a low molecular weight type additive. However, when a large amount of such a low molecular weight type additive is added, the liquid crystal panel of the film obtained by using the film is exposed to high temperature and high humidity conditions. There is a problem that a large number of frame spots occur (the liquid crystal display device is whitened at the periphery of the screen when the black display is displayed) (φ, for example, refer to Patent Document 4). Therefore, the inventors of the present invention have begun to explore an optical film having a small number of frame spots even when an optical film is produced in a state where the residual solvent is small. CITATION LIST Patent Literature Patent Literature 1: Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION In view of the above problems and circumstances, the object of the present invention is to provide an optical film whose main constituent components are acrylic resin and cellulose ester resin. Medium's excellent heat resistance, and after processing the polarizing plate with the optical film, -7-201033274, when the same polarizing plate is disposed on the liquid crystal display device for black display, there is no effect on the image-like whitening (light leakage)' and exposure to An optical film which does not cause a frame spot under high-humidity and high-temperature wet heat conditions and a method for producing the same. Further, a polarizing plate and a liquid crystal display device using the same are provided. Solution to Problem The above problems of the present invention are solved by the following methods. 1. An optical film characterized in that the 'optical film containing acrylic resin (A _ ), cellulose ester resin (B) and acrylic-based particles (c) is in the range of 50:50 to 95:5 The mass ratio is contained in the acrylic resin (A) and the cellulose ester resin (B), and the content of the acrylic-based particles (C) is 0.5 to 30% by mass based on the total mass of the resin constituting the optical film, and the residual solvent The content of the amount is 0.01% by mass or less. 2. The optical film according to the above 1, wherein the acrylic resin (A) has a weight average molecular weight (Mw) of from 110,000 to 1,000,000. 3. A method of producing an optical film according to the above 1. or 2. wherein the method for producing an optical film is a melt casting film forming method using a contact roll. A polarizing plate characterized by using the optical film as described in the above 1. or 2. A liquid crystal display device using the polarizing plate described in the above 4th. -8 - 201033274 Effect of the Invention The above method of the present invention can provide an optical film having a main constituent component of an acrylic resin and a cellulose ester resin, which has excellent heat resistance, and after the polarizing plate is processed using the optical film, the same polarized light is used. When the liquid crystal display device is black-displayed, the optical film which does not affect the image-like whitening (hereinafter referred to as "light leakage") and does not produce a frame-like spot when exposed to high humidity and high temperature humidity and heat is not present. Its manufacturing method. Further, a polarizing plate and a liquid crystal display device using the same can be provided. MODE FOR CARRYING OUT THE INVENTION The optical film of the present invention is characterized in that the optical film containing the acrylic resin (A), the cellulose ester resin (B) and the acrylic-based particles (C) has a quality of 50:50 to 95:5. The content ratio of the aforementioned acrylic acid-based particles (C) to the total mass of the reference resin constituting the optical film is 〇. 5 to 30% by mass, based on the ratio of the acrylic resin (A) and the cellulose ester resin (B). The content of the residual solvent amount is 0.01% by mass or less. This feature is a common technical feature of the inventions of claims 1 to 5 of the patent application. In an embodiment of the present invention, the acrylic resin (A) preferably has a weight average molecular weight (Mw) of from 1,000,000 to loooooo. The method for producing an optical film of the present invention is preferably a melt casting film forming method using a contact roll. The optical film of the present invention is suitable for use in a polarizing plate, and a liquid crystal display device using the same. The invention was applied to a resin. 50 50 mass alkyl esters, propyl fumarate 'α-methacrylonitrile substituted horses or more are methyl propylene. The following is a detailed description of the present invention and its constituent elements, as well as the actual form and aspect, etc. . (Acrylic Resin (A)) The acrylic resin to be used in the invention also includes a methacrylic resin, which is not particularly limited, but preferably is 99% by mass from methyl methacrylate, and other monomers copolymerizable therewith The unit formed by 1 to %. Other monomers capable of copolymerization, such as an alkyl group having a carbon number of 2 to 18 methacrylate, an alkyl group having a carbon number of 1 to 18, an alkyl acrylate, a methacrylic acid, etc.: A - no An aromatic vinyl compound such as a saturated acid, maleic acid, or itaconic acid containing an unsaturated group such as a divalent carboxylic acid or a styryl styrene, an acrylonitrile or a methyl group, or a 3-unsaturated Nitrile, maleic anhydride, maleimide, N-decimine, glutaric anhydride, etc., which may be used alone or in combination with two monomers. Among them, acrylate, ethyl acrylate, η-propylene acrylate, η-butyric acid ester, s-butyl acrylate, 2-ethylhexyl acrylate, etc. are preferable from the viewpoints of thermal decomposition resistance and fluidity of the copolymer. Methacrylate and η-butyl acrylate were used. The acrylic resin used in the optical film of the present invention has a weight average molecular weight (Mw) of 80000 in view of improving the brittleness of the optical film and improving the transparency when it is compatible with the cellulose ester resin. 201033274 and above. The weight average molecular weight (Mw) of the acrylic resin (A) is more preferably in the range of from 1 1 0000 to 1,000,000, particularly preferably in the range of from 100,000 to 600,000. The upper limit of the weight average molecular weight (MW) of the acrylic resin (A) is not particularly limited, but it is preferably in the form of 1,000,000 or less in terms of manufacturability. The weight average molecular weight of the acrylic resin of the present invention can be determined by gel permeation chromatography. The measurement conditions are as follows. Solvent: Dichloromethane column: Shodex K806, K8 05, K8 03 G (3 in succession, manufactured by Showa Denko Co., Ltd.) Column temperature: 2 5 °C Sample concentration: 0.1% by mass Verifier: RI Model 504 (GL赛 : :: L6000 (Hitachi, Ltd.) ^ Flow: l.Oml / min Calibration curve: using standard polystyrene STK standard polystyrene (made by Dongsuo Co., Ltd.) Mw = 2,800,000 Calibration curve up to 13 samples of 500. The 13 samples used are preferably almost equally spaced. 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. The polymerization initiator to be used may be a general peroxide type or an azo type, or a redox system. For the polymerization temperature, θ 'suspension or emulsion polymerization can be carried out in a 30 to + 100 C 'block or solution polymerization -11 - 201033274 and can be carried out at 80 to 160 ° C. In order to control the reduction viscosity of the obtained copolymer, polymerization may be carried out by using an alkylthiol or the like as a chain shifting agent. Commercially available materials can also be used as the acrylic resin of the present invention, for example, Deppert 60N, 80N (made by Asahi Kasei Chemicals Co., Ltd.), Daiana BR52, BR80, BR8 5, BR8 8 (manufactured by Mitsubishi Rayon). KT75 (electrochemical industry (stock) system) and so on. Acrylic resins may be used in combination of two or more kinds. (Cellulose ester resin (B)) The cellulose ester resin (B) used in the present invention is particularly preferred in terms of improving the brittleness and transparency when it is compatible with the acrylic resin (A), and the total substitution of the mercapto group. The degree of substitution (T) is 2.0 to 3_0, the degree of substitution of the fluorenyl group having 3 to 7 carbon atoms is 1.2 to 3.0, and the degree of substitution of the fluorenyl group having 3 to 7 carbon atoms is 2.0 to 3.0. That is, the cellulose ester resin of the present invention is a cellulose ester resin substituted with a fluorenyl group having 3 to 7 carbon atoms, and specifically, a propyl fluorenyl group, a butyl fluorenyl group or the like is preferably used, and a propyl fluorenyl group is particularly preferably used. When the total degree of substitution of the thiol group of the cellulose ester resin (B) is less than 2.0, that is, when the hydroxyl residue at the 2, 3, and 6 positions of the cellulose ester molecule is higher than 1.0, the acrylic resin (A) and the cellulose ester Since the resin (B) is not sufficiently compatible, there is a problem of turbidity when used as an optical film. Further, even if the total degree of substitution of the fluorenyl group is 2.0 or more, the degree of substitution of the fluorenyl group having 3 to 7 carbon atoms is less than 1.2 Å, the sufficient compatibility is not obtained, or the brittleness is lowered. For example, even if the total degree of substitution of the fluorenyl group is 2.0 or more, the thiol group having a carbon number of 2, that is, the degree of substitution of the fluorenyl group is higher, and when the degree of substitution of the fluorenyl group having 3 to 7 carbon atoms is less than 1.2, Reduces compatibility and increases turbidity. Further, even if the total substitution degree of the fluorenyl group is 2.0 or more 201033274', the degree of substitution of the fluorenyl group having a carbon number of 8 or more is higher, and when the degree of substitution of the fluorenyl group having 3 to 7 carbon atoms is lower than I.2, The brittleness is deteriorated and the desired characteristics are not obtained. The cellulose ester resin (B) of the present invention may have a thiol substitution degree of 2.0 to 3.0 in total degree of substitution (T), and a degree of substitution of a fluorenyl group having 3 to 7 carbon atoms of 12 to 3.0, but a carbon number of 3 The degree of substitution of the fluorenyl group other than 7 to the fluorenyl group and the fluorenyl group having 8 or more carbon atoms is preferably 1.3 or less. Further, the total degree of substitution (T) of the thiol group of the cellulose ester resin (B) is more preferably in the range of 2.5 to 3.0. The aforementioned mercapto group of the present invention may be an aliphatic mercapto group or an aromatic mercapto group. When it is an aliphatic fluorenyl group, it may be linear or branched, and may have a substituent. The carbon number of the fluorenyl group of the present invention is a substituent containing a fluorenyl group. When the cellulose ester resin (B) is an aromatic fluorenyl group having a substituent, the number of substituents X for substitution in the aromatic ring is preferably from 〇 to 5. At this time, it is still necessary to note that the degree of substitution of the fluorenyl group having 3 to 7 carbon atoms which has a substituent is β U to 3.0. For example, in order to make the phenylhydrazine group have a carbon number of 7 and a carbon-containing substituent, the phenylhydrazine group has a carbon number of 8 or more and does not contain a carbon number of 3 to 7 fluorenyl group. When the number of substituents for substitution in the aromatic ring is two or more, they may be the same or different and may be linked to each other to form a condensed polycyclic compound (for example, naphthalene, anthracene, indane, phenanthrene, quinoline, iso-isoline, Chalylene, chroman, pyridazine, acridine, anthracene, anthracene, etc.). The above-mentioned cellulose vinegar resin (Β) has a structure of the cellulose resin -13-201033274 of the present invention because it has a structure containing at least one aliphatic alcohol group having 3 to 7 carbon atoms. The degree of substitution of the cellulose ester resin (B) of the present invention is that the total degree of substitution (T) of the fluorenyl group is from 2.0 to 3.0. The degree of substitution of the fluorenyl group having from 3 to 7 carbon atoms is from 12 to 3·0 〇 and carbon It is preferable that the sum of the substitution ratios of the thiol group having 3 to 7 or more, that is, the thiol group and the fluorenyl group having 8 or more carbon atoms, is 1.3 or less. The cellulose ester resin (B) of the present invention is particularly preferably cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate benzoate, cellulose propionate, cellulose butyl At least one selected from the acid esters is preferably a fluorenyl group having 3 or 4 carbon atoms for the substituent. Among these preferred cellulose vinegar resins are cellulose acetate propionic acid vinegar and cellulose propionate. Generally, the moiety not substituted by a thiol group exists in the form of a hydroxyl group. It can be synthesized by a known method. Further, the degree of substitution of the thiol group and the degree of substitution of other thiol groups can be determined by the method specified in ASTM-D817-96. The weight average molecular weight (Mw) of the cellulose ester resin of the present invention is particularly preferably 75,000 or more, preferably 75,000 to 300,000, more preferably 100,000 to 240,000, in view of compatibility with the acrylic resin (A) and improvement of brittleness. Within the range, it is particularly good for 1 60000 to 240,000. When the weight average molecular weight (Mw) of the cellulose ester resin is less than 75,000, the effect of improving heat resistance and brittleness will be insufficient, and the effects of the present invention will not be obtained. In the present invention, two or more kinds of cellulose resins may be used in combination. The optical film of the present invention contains an acrylic resin (A) and a cellulose ester resin (B) in a mass ratio of 50:50 to 95:5 in order to find the effect of the present invention and the resistance to moisture-14-201033274. Preferably, it is 90: 10 to 60: 40. When the mass ratio of the acrylic resin (A) and the cellulose ester resin (B) is more than 95: 5 in the 'acrylic resin (A), the effect from the cellulose ester resin (B) is not sufficiently obtained, and the acrylic resin is less than When the mass ratio is 50:50, the moisture resistance will be insufficient. In the optical film of the present invention, the acrylic resin (A) and the cellulose vinegar φ resin (B) are preferably contained in a compatible state. The physical properties and qualities necessary for the optical film can be achieved by the compatibility of different resins. Whether or not the acrylic resin (A) and the cellulose ester resin (B) are in a compatible state can be judged, for example, by the glass transition temperature Tg. For example, when the glass transition temperatures of the resins are different, when the resins of the two are mixed, the glass transition temperature of the respective resins may be present, and the mixture may have two or more glass transition temperatures, but when the resins are compatible, the respective resins may cause The intrinsic glass transition temperature of the resin disappears, and the glass transition temperature of the compatible resin is 1 玻璃 glass transition temperature. In addition, the glass transition temperature is measured by a differential scanning calorimeter (DSC-7 model manufactured by Perkin Elmer Co., Ltd.) at a temperature increase rate of 20 ° C / min, and then obtained according to JIS K7 1 2 1 (1 987). The intermediate point glass transition temperature (Tmg) ° The acrylic resin (A) and the cellulose ester resin (B) are each preferably a non-crystalline resin, and either one of them is a crystalline polymer or partially has high crystallinity. Although the molecule is soluble in the acrylic resin (A) and the cellulose ester resin (B) of the present invention, it is preferred to use a non-crystalline resin. -15- 201033274 In the optical film of the present invention, the weight average molecular weight (Mw) of the acrylic resin (A) and the weight average molecular weight (Mw) and the degree of substitution of the cellulose ester resin (B) can be dissolved by the two resins. The difference was determined by each of the differences. The method of distinguishing the resins may be such that the compatible resin is added to a solvent which can dissolve only one of the solvents, and the dissolved resin is extracted to distinguish them, and at this time, heat treatment and circulation can be performed. Further, the composition of the solvents may be combined in two steps to distinguish the resins. Further, the dissolved resin and the remaining insoluble resin may be filtered, and the solution containing the extract may be subjected to a solvent evaporation and drying step to distinguish the resin. These differentiated resins can be specified by structural analysis of general polymers. When the optical film of the present invention contains a resin other than the acrylic resin (A) and the cellulose ester resin (B), it can be distinguished in the same manner. Moreover, when the weight average molecular weight (Mw) of the compatible resin is different, the high molecular weight substance can be dissolved early by gel permeation chromatography (GPC), and the low molecular weight substance needs to be melted for a long time, so it is easy to distinguish and can be determined. Molecular weight. Further, by measuring the molecular weight of the resin after the dissolution by GPC, the resin solution dissolved in each period can be separated, the solvent is distilled off, dried, and the structural analysis of the resin is quantitatively determined to examine the resin composition of each partition of different molecular weights. The compatible resins are each specified. Further, the resin which was obtained by the difference in solubility of the solvent was used to measure the molecular weight distribution by GPC, and each of the resins was found to be compatible. Further, in the present invention, "the acrylic resin (A) and the cellulose ester resin (B) are contained in a compatible state", and the respective resins (polymers) are mixed, and the period of -16-201033274 is compatible, and does not include The cellulose ester resin (B) is a mixed resin state obtained by polymerizing an acrylic resin precursor such as a monomer, a dimer or an oligomer. For example, when a cellulose resin (B) is mixed with an acrylic resin precursor such as a monomer, a dimer or an oligomer to obtain a mixed resin, the resin produced by the method may be complicated by a polymerization reaction. It is difficult to adjust the molecular weight because it is difficult to control the reaction. Further, when the resin is synthesized by this method, a graft polymerization, a crosslinking reaction or a cyclization reaction is likely to occur, and most of them are dissolved in a solvent or cannot be heated and melted, so that the acrylic resin in the mixed resin is hardly dissolved to measure the weight average. Since the molecular weight (Mw) is difficult to control the physical properties, it is not suitable as a resin which can stably produce an optical film. The optical film of the present invention may be composed of a resin other than the acrylic resin (A) or the cellulose ester resin (B) and an additive under the function of the non-destructive optical film. When the φ resin other than the acrylic resin (A) or the cellulose ester resin (B) is contained, the added resin may be in a compatible state or may be in a mixed state without being dissolved. The total mass of the acrylic resin (A) and the cellulose ester tree (B) in the optical film of the present invention is preferably 55 mass% or more of the 'optical film, more preferably 60% by mass or more', and particularly preferably 70% by mass. the above. When a resin other than the acrylic resin (A) and the cellulose ester resin (B) and an additive are used, it is preferable to adjust the amount of addition without departing from the range of the optical film function of the present invention. -17- 201033274 (Acrylic-based particles (c)) The optical film of the present invention preferably contains acrylic-based particles. In the present application, the "acrylic-based particles (C)" means acrylic acid present in a particle state (also referred to as an incompatible state) in an optical film containing the acrylic resin (A) and the cellulose ester resin (B). Base ingredients. It is preferable that the acrylic-based particles (C) are, for example, an optical film obtained by quantitative production, and then dissolved and dissolved in a solvent to sufficiently dissolve and disperse to have an pore diameter which does not reach the average particle diameter of the acrylic-based particles (C). When the PTFE membrane filter was excessively destroyed, the weight of the insoluble matter collected by filtration was 90% by mass or more based on the acrylic-based particles (C) added to the optical film. The acrylic-based particles (C) used in the present invention are not particularly limited, and are preferably acrylic-based particles (C) having a layer structure of two or more layers, and particularly preferably an acrylic-based particulate composite having a multilayer structure as described below. The multilayer structure of the acrylic-based granular composite refers to a structure in which the center portion has a layered overlapping innermost hard layer polymer toward the outer peripheral portion, and a rubber-elastic crosslinked soft layer polymer and an outermost hard layer polymer are obtained. A particulate acrylic based polymer. In other words, the multilayer structure acrylic-based particulate composite refers to a multilayer structure acrylic-based particulate composite composed of an innermost hard layer, a crosslinked soft layer, and an outermost hard layer having a central portion toward the outer peripheral portion. Further, it is preferable to use a multilayer structure of the three-layered core structure to form an acrylic-based particulate composite. Preferred embodiments of the multilayer structure acrylic-based particulate composite used in the acrylic-based resin composition of the present invention are as follows. For example, having (a) from 80 to 98.9% by mass of methyl methacrylate, from 1 to 20% by mass of the alkyl acrylate having a carbon number of from 1 to 8 201033274, and a polyfunctional grafting agent o.oi to 0.3% by mass of the monomer mixture formed by polymerization of the innermost hard layer polymer' (b) in the presence of the innermost hard layer polymer, alkyl acrylate 75 having an alkyl group having a carbon number of 4 to 8 98.5 mass%, a polyfunctional crosslinking agent 0.01 to 5% by mass, and a polyfunctional grafting agent 〇5 to 5% by mass of the monomer mixture formed by polymerization to obtain a crosslinked soft layer polymer, (c) the above The polymer formed by the innermost hard layer and the crosslinked soft layer is from 1 to 20% by mass of the alkyl acrylate of 80 to 99% by mass of the methyl φ methacrylate and from 1 to 8 of the alkyl group. a three-layer structure composed of the outermost hard layer polymer obtained by polymerizing the formed monomer mixture, and the innermost hard layer polymer (a) of the obtained three-layer structure polymer is 5 to 40% by mass, and the soft layer is polymerized. The substance (b) is 30 to 60% by mass, and the outermost hard layer polymer (c) is 20 to 50% by mass, and further, acetone is used. An acryl-based granular composite 〇φ having an insoluble portion at a time division and having a methyl ethyl ketone swelling degree of 1.5 to 4.0 in the insoluble portion is also disclosed in Japanese Patent Publication No. Sho 60-17406 or Japanese Patent Publication No. Hei 3-39095 It is disclosed that in addition to the composition and particle size of each layer of the multi-layered acrylic-based granular composite, the tensile modulus of the multilayered acrylic-based granular composite and the methyl ethyl ketone swelling of the acetone-insoluble portion are also set. When it is within a specific range, the balance between sufficient impact resistance and stress whitening resistance can be achieved. The innermost hard layer polymer (a) constituting the multilayer structure acrylic-based particulate composite preferably has an alkyl acrylate of 80 to 98.9% by mass of methyl methacrylate and 1 to 8 carbon atoms of the alkyl group. 1 to 20% by mass and more than -19-201033274 energy grafting agent 0.01 to 〇·3 mass% of the monomer mixture formed by polymerization and the alkyl group having a carbon number of 1 to 8 alkyl acrylate such as 'A Base acrylate, ethyl acrylate, η-propyl acrylate, η-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, etc., preferably using methacrylate and η- Butyl acrylate. The ratio of the alkyl acrylate unit in the innermost hard layer polymer (a) is from 1 to 20% by mass, and when the unit is less than 1% by mass, the thermal decomposition property of the polymer is increased, and the unit exceeds 20% by mass. In this case, the glass transition temperature of the innermost hard layer polymer (c) is lowered, and the impact resistance imparting effect of the three-layer structure acrylic-based granular composite is lowered, which is not preferable. Polyfunctional grafting agents such as polyfunctional monomers having different polymerizable functional groups, such as acrylic acid, methacrylic acid, maleic acid, allyl fumarate, etc., preferably using allylic monomers Methyl methacrylate. The purpose of using the polyfunctional grafting agent is to chemically bond the innermost hard layer polymer and the soft layer polymer, so that the ratio of the use of the innermost hard layer polymerization is 0.01 to 0.3% by mass. The crosslinked soft layer polymer (b) constituting the acrylic-based particulate composite is preferably an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms in the innermost hard layer polymer (a). A monomer mixture of 75 to 98.5% by mass, a polyfunctional crosslinking agent of 0.01 to 5% by mass, and a polyfunctional grafting agent of 0.5 to 5% by mass is obtained by polymerization. The alkyl acrylate wherein the alkyl group has a carbon number of 4 to 8 is preferably n-butyl acrylate and 2-ethylhexyl acrylate. -20- 201033274 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 large, the glass transition temperature of the polymer (b) can be lowered, i.e., softened. Further, from the viewpoint of the transparency of the resin composition, the refractive index at room temperature of the soft layer polymer (b) φ is preferably approximately the innermost hard layer polymer (a), the outermost hard layer polymer (c), and the hard thermoplastic. Acrylic resin, so the ratio of the two can be determined after this. The polyfunctional grafting agent used may be as described above for the innermost hard layer polymer (a). The purpose of using the polyfunctional grafting agent is to chemically bond the soft layer polymer (b) to the outermost hard layer polymer (c), so that it is resistant to the ratio of the innermost hard layer polymerization. The viewpoint of the impact imparting effect is preferably from 0.5 to 5% by mass. The polyfunctional crosslinking agent used for φ may be a generally known crosslinking agent such as a divinyl compound, a diallyl compound, a diacrylic compound, or a dimethacrylic compound, and preferably polyethylene glycol is used. Acrylate (molecular weight 200 to 600). The purpose of using the polyfunctional crosslinking agent is to form a crosslinked structure when the soft layer (b) is polymerized, and an impact resistance imparting effect is found. However, when a soft layer is polymerized, a polyfunctional grafting agent is used to form a crosslinked structure of a soft layer (b) to some extent. Therefore, a polyfunctional crosslinking agent is not an essential component, but a soft layer polymerization is obtained from the viewpoint of imparting impact resistance. The polyfunctional crosslinking agent preferably has a ratio of from 0.01 to 5% by mass based on the ratio of from 21 to 201033274. The outermost hard layer polymer (c) constituting the multilayer structure acryl-based granulated composite is preferably composed of the methyl group as the innermost hard layer polymer (a) and the soft layer polymer (b). A monomer mixture of 80 to 99% by mass of an acrylate and 1 to 20% by mass of an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms is obtained by polymerization. Among them, the above-mentioned ones can be used for the alkyl acrylate, and methacrylate and ethyl acrylate are preferably used. The ratio of the alkyl acrylate units in the outermost hard layer (c) is preferably from 1 to 20% by mass. Further, in order to improve the compatibility with the acrylic resin (A) when the outermost hard layer (c) is polymerized, an alkylthiol or the like may be used as a chain shifting agent to adjust the molecular weight. In particular, when the outermost hard layer is provided in a stepwise direction in which the molecular weight is gradually decreased from the inner side to the outer side, the balance between the elongation and the impact resistance can be improved. Specifically, for example, the monomer mixture forming the outermost hard layer is divided into two or more batches, and the method of increasing the movement amount of the chain added every time is sequentially added, so that the multilayer structure acrylic-based granular composite can be reduced from the inner side to the outer side. The molecular weight of the polymer used in the outermost hard layer. The molecular weight formed at this time can be obtained by separately polymerizing the monomer mixture used each time under the same conditions and measuring the molecular weight of the obtained polymer. The preferred particle diameter of the acrylic-based particles (C) used in the present invention is not particularly limited, but is preferably 10 to 10 nm, more preferably 20 to 500 nm, still more preferably 50 to 400 nm. The mass ratio of the core to the shell in the acrylic-based granular 201033274 composite of the multilayer structure polymer preferably used in the present invention is not particularly limited, but when the total amount of the multilayer structure polymer is 100 parts by mass, the core layer is preferably 50 to 90 parts by mass, more preferably 60 to 80 parts by mass. The core layer refers to the innermost hard layer. Such a commercially available product of the multi-layered structure of the acrylic-based granular composite is, for example, "Midab" manufactured by Mitsubishi Rayon Co., Ltd., "Kaneye" manufactured by Zhongyuan Chemical Industry Co., Ltd., and "Palalo" manufactured by Wu Yu Chemical Industry Co., Ltd. "Aikeli" manufactured by Lomian Co., "Starfine" manufactured by Kosei Chemicals Co., Ltd., and "Palape SA" manufactured by Kuraray Co., Ltd., etc., may be used alone or in combination of two or more. Further, specific examples of the acrylic-based particles (c-1) which are preferably used as the graft copolymer of the acrylic-based particles (C) which are preferred in the present invention include copolymerization of unsaturated carboxylic acid ester-based monomers in the presence of a rubbery polymer. A graft copolymer obtained by copolymerizing an unsaturated carboxylic acid monomer, an aromatic vinyl monomer, and a monomer mixture which can be used in combination with other vinyl monomers copolymerized therewith. The rubbery φ polymer used for the acrylic-based particles (c-Ι) of the graft copolymer is not particularly limited, and a diene rubber, an acrylic-based rubber, a vinyl rubber or the like can be used. Specifically, for example, 'polybutadiene, styrene-butadiene copolymer, styrene-butadiene block copolymer, acrylonitrile-butadiene copolymer, butyl acrylate-butadiene copolymer, polyiso Pentadiene, butadiene-methyl methacrylate copolymer, butyl acrylate-methyl methacrylate copolymer, butyl succinyl-propionate copolymer, B-propylene copolymer An ethylene-propylene-diene copolymer, an ethylene-isoprene copolymer, and an ethylene-methyl acrylate copolymer. These rubbery polymers may be used alone or in combination of two or more. -23- 201033274 Further, when the acrylic film of the present invention is added with the acrylic-based particles (c), the refractive index of the mixture of the 'acrylic resin (A) and the cellulose ester resin (B) is approximately the refractive index of the acrylic-based particles (C). Rate, so that a film with higher transparency can be obtained. Specifically, the difference in refractive index between the acrylic-based particles (C) and the acrylic resin (A) is preferably 〇. 5 or less, more preferably 0.02 or less, and particularly preferably 0.01 or less. In order to satisfy the refractive index condition, the composition ratio of each monomer unit of the acrylic resin (A) may be adjusted, and/or the composition ratio of the rubbery polymer or monomer used for the acrylic-based particle (C) may be adjusted. The method or the like reduces the refractive index difference to obtain an optical film excellent in transparency. The above-mentioned refractive index difference means that the optical film of the present invention is sufficiently dissolved in a solvent soluble in the acrylic resin (A) under appropriate conditions to form a white turbid solution, and then the solvent-soluble portion and the insoluble portion are separated by centrifugation or the like. The refractive index (23 ° C, measurement wavelength: 5 5 Onm) measured after the soluble portion (acrylic resin (A)) and the insoluble portion (acrylic particles (C)) were respectively purified. The method of adding the acrylic-based particles (C) to the acrylic resin (A) of the present invention is not particularly limited, and it is preferred to add acrylic acid at 200 to 350 ° C after premixing the acrylic resin (A) and other optional components. The method in which the base particles (C) are uniformly melt-kneaded by a uniaxial or biaxial extruder. A commercially available product can be used for the acrylic-based particles of the present invention. For example, Medabu W-341 (C2) (Mitsubishi Rayon (manufactured by Mitsubishi Rayon)), Kensie MR-2G (C3), MS-300X (C4) (manufactured by Chemicals Co., Ltd.). In the optical film of the present invention, the acrylic resin particles (C) are preferably contained in an amount of from 0.5 to 30% by mass, more preferably from 1.0 to 15% by mass, based on the total mass of the resin constituting the film. When the content of the acrylic-based particles (C) is less than 0.5% by mass based on the total mass of the film, the effect of suppressing the frame spots caused by changes in temperature and environment will be insufficient, and when the acrylic-based particles (C) are more than 30% by mass When the polarizing plate itself or the polarizing plate is attached to the liquid crystal display device, it is thermally deformed when exposed to a high temperature of φ. Therefore, it will affect the image of the original design of the liquid crystal display device. (Antioxidant) The resin mixture such as the acrylic resin of the present invention preferably contains an antioxidant. The antioxidant of the present invention is preferably a phosphorus-based or phenol-based oxidizing agent, and more preferably a phosphorus-based or phenol-based antioxidant. φ The antioxidants to which the present invention is applied will be described below. <Phenolic antioxidant> The phenol-based antioxidant represented by the following general formula (AO1) can be used in the present invention. -25- 201033274 [Chemical 1] - Difficult (A01)

一般式（AOl)中，Rl、R2及R3爲可另被取 v代或未 取代之烷基取代基。阻胺苯酚化合物之具體例如含有，n-十八烷基3-(3,5-二-t-丁基-4-羥基苯基）-丙酸酯、η-十 八烷基3- ( 3,5-二-t-丁基_4_羥基苯基）-乙酸酯、η-十八 烷基3,5-二-t-丁基-4-羥基苯甲酸酯、n-己基3,5-二-t-丁 基-4-羥基苯基苯甲酸酯、η-十二烷基3,5-二-t-丁基-4-羥 基苯基苯甲酸酯、新-十二烷基3- (3,5-二-t-丁基-4-羥基 苯基）丙酸酯、十二烷基Θ (3,5-二-t-丁基-4-羥基苯基） 丙酸醋、乙基經基- 3,5 - __-t -丁基苯基）異丁酸酯 、十八烷基α-(4-羥基-3,5-二-t-丁基苯基）異丁酸酯、 十八烷基α - ( 4 -羥基- 3,5 -二-t-丁基-4-羥基苯基）丙酸酯 、2- (η-辛基硫基）乙基3,5-二-t-丁基-4-羥基-苯甲酸酯 、2- (η-辛基硫基）乙基3,5-二-t-丁基-4-羥基-苯基乙酸 酯、2- (η-十八烷基硫基）乙基3,5-二-t-丁基-4-羥基苯基 乙酸酯、2- ( η-十八烷基硫基）乙基3,5-二-t-丁基-4-羥 基-苯甲酸酯、2- (2-羥基乙基硫基）乙基3,5-二-t-丁基-4-羥基苯甲酸酯、二乙基乙二醇雙-(3,5-二-t-丁基-4-羥 基·苯基）丙酸酯、2· (η -十八烷基硫基）乙基3- ( 3，5_ 二_t_ 丁基-4-羥基苯基）丙酸酯、硬脂醯胺Ν，Ν-雙[伸乙基 201033274 3- (3,5-二-t-丁基-4-羥基苯基）丙酸酯]、η-丁基亞胺基 Ν，Ν-雙-[伸乙基3- ( 3,5-二小丁基·4·羥基苯基）丙酸酯] 、2- (2-硬脂醯氧基乙基硫基）乙基3,5-二-t-丁基-4-羥基 苯甲酸酯、2-(2-硬脂醯氧基乙基硫基）乙基7-(3-甲基-5-t-丁基-4-羥基苯基）庚酸酯、1,2-丙二醇雙-[3- ( 3,5-二-t-丁基-4-羥基苯基）丙酸酯]、乙二醇雙-[3-(3,5-二-t-丁基-4-羥基苯基）丙酸酯]、新戊二醇雙-[3- (3,5-二-t-φ 丁基-4-羥基苯基）丙酸酯]、乙二醇雙-(3，5-二-t-丁基- 4- 羥基苯基乙酸酯）、甘油-1-n-十八烷酸酯-2,3-雙-( 3，5-二-t-丁基-4-羥基苯基乙酸酯）、季戊四醇-四-[3-( 3’，5’-二-t-丁基-4’-羥基苯基）丙酸酯]、1，1，1-三羥甲基 乙烷-三-[3- (3,5-二-t-丁基-4-羥基苯基）丙酸酯]、山梨 糖醇六- [3- (3,5-二-t-丁基-4-羥基苯基）丙酸酯]、2-羥基 乙基7- ( 3-甲基-5-t-丁基-4-羥基苯基）丙酸酯、2-硬脂醯 氧基乙基7-(3-甲基- 5-t-丁基-4-羥基苯基）庚酸酯、1，6- φ n-己二醇·雙[(3，，5’-二-t-丁基-4-羥基苯基）丙酸酯]、季 戊四醇-四（3,5-二-t-丁基-4-羥基氫化肉桂酸酯）。上述 型之阻胺苯酚化合物如，市售的來自Ciba Japan之商品名 Irganoxl〇76” 及 “IrganoxlOlO” 。 <磷系防氧化劑> 本發明可使用之磷系防氧化劑如，亞磷酸酯（ phosphite)、鱗酸醋化合物（phosphonite)或次憐酸酯 (phosphinite)等隣系化合物。 -27- 201033274 磷系防氧化劑可使用先前已知之化合物。較佳如’特 開2002- 1 38 1 88號、特開2005-344044號段落編號0022〜 0027、特開2004- 1 82979號段落編號0023〜0039、特開平 1 0-306 1 75 號' 特開平 1-254744 號、特開平 2-270892 號、 特開平5-202〇78號、特開平5- 1 78870號、特表 2004-504435號、特表 2004-530759 號、及特願 2〇〇5_353229號公報之說明書中所記載之物。 較佳之磷系化合物如下述一般式所表示之化合物，但 非限於此等。 [化2]In the general formula (AO1), R1, R2 and R3 are alkyl substituents which may be additionally substituted or unsubstituted. Specific examples of the hindered phenol compound include, for example, n-octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, η-octadecyl 3-(3) ,5-di-t-butyl-4-hydroxyphenyl)-acetate, η-octadecyl 3,5-di-t-butyl-4-hydroxybenzoate, n-hexyl 3 , 5-di-t-butyl-4-hydroxyphenyl benzoate, η-dodecyl 3,5-di-t-butyl-4-hydroxyphenyl benzoate, new-ten Dialkyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, dodecylphosphonium (3,5-di-t-butyl-4-hydroxyphenyl) Propionic acid vinegar, ethyl peroxy-3,5- __-t-butylphenyl) isobutyrate, octadecyl α-(4-hydroxy-3,5-di-t-butylphenyl Isobutyrate, octadecyl α-(4-hydroxy-3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2-(η-octylthio)ethyl 3,5-di-t-butyl-4-hydroxy-benzoate, 2-(η-octylthio)ethyl 3,5-di-t-butyl-4-hydroxy-phenyl Acid ester, 2-(η-octadecylthio)ethyl 3,5-di-t-butyl-4-hydroxyphenyl acetate, 2-( η-octadecylthio)B 3,5-di-t-butyl-4-hydroxy-benzoate, 2-(2-hydroxyethylsulfide Ethyl 3,5-di-t-butyl-4-hydroxybenzoate, diethylethylene glycol bis-(3,5-di-t-butyl-4-hydroxyphenyl) Propionate, 2·(η-octadecylthio)ethyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, stearylamine oxime, Ν-double [ Ethylethyl 201033274 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], η-butylimidopyrene, Ν-bis-[stretch ethyl 3-( 3 ,5-di-butylbutyl-4-hydroxyphenyl)propionate], 2-(2-stearyloxyethylthio)ethyl 3,5-di-t-butyl-4-hydroxyl Benzoate, 2-(2-stearyloxyethylthio)ethyl 7-(3-methyl-5-t-butyl-4-hydroxyphenyl)heptanoate, 1,2 -propanediol bis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], ethylene glycol bis-[3-(3,5-di-t-butyl- 4-hydroxyphenyl)propionate], neopentyl glycol bis-[3-(3,5-di-t-φ butyl-4-hydroxyphenyl)propionate], ethylene glycol bis-( 3,5-di-t-butyl-4-hydroxyphenyl acetate), glycerol-1-n-octadecanoate-2,3-bis-(3,5-di-t-butyl -4-hydroxyphenyl acetate), pentaerythritol-tetraki-[3-( 3',5'-di-t-butyl-4'-hydroxyphenyl Propionate], 1,1,1-trishydroxymethylethane-tris-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], sorbitol Hexa-6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2-hydroxyethyl 7-(3-methyl-5-t-butyl-4- Hydroxyphenyl)propionate, 2-stearyloxyethyl 7-(3-methyl-5-t-butyl-4-hydroxyphenyl)heptanoate, 1,6-φ n-hexyl Glycol·bis[(3,5'-di-t-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis(3,5-di-t-butyl-4-hydroxy hydrogenated cinnamyl Acid ester). The hindered amine phenol compound of the above type is, for example, commercially available from Ciba Japan under the trade name Irganoxl(R) 76" and "IrganoxlOlO". <Phosphorus-based antioxidant> Phosphorus-based antioxidants such as phosphites which can be used in the present invention An phthalate compound such as a phosphite, a phosphonite or a phosphinite. -27- 201033274 A phosphorus-based antioxidant can be a previously known compound, preferably as described in 'Special Open 2002- 1 38 1 88 No. 2005-344044 Paragraph No. 0022~0027, Special Opening 2004- 1 82979 Paragraph No. 0023~0039, Special Kaiping 1 0-306 1 75 'Special Kaiping 1-245844, Special Kaiping 2-270892 And the contents described in the specification of Japanese Patent Application Laid-Open No. Hei No. Hei 5- No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. The preferred phosphorus compound is a compound represented by the following general formula, but is not limited thereto. [Chemical 2]

-般式(W —ίέ式㈣ >"Rr >一妒 \ 0- General (W - ίέ (4) >"Rr > a 妒 \ 0

\ β Ο\ β Ο

-般式(ivy- general (ivy

RiRi

-0,汽 A • «?· 1» L-0, steam A • «?· 1» L

-28- 201033274 [化3] —般式(Pp-28- 201033274 [Chemical 3] - General (Pp

-缺式⑻ (R\·^- missing (8) (R\·^

•R1•R1

His^mHis^m

^般式{Sip^式式{Sip

例如一般式（I)至（V)之亞磷酸酯、一般式（VI) 至（XII)之膦酸酯、及一般式（XIII)至（XV)之次磷 酸酯。各自之基相互獨立爲，R1爲C1至C24之烷基（直鏈 或支鏈，可含有雜原子、N、0、P'S) 、C5至C30之環烷 基（可含有雜原子、N、0、P、S) 、（：1至C30之烷芳基' C6至C24之芳基或雜芳基、C6至C24之芳基或雜芳基（可 被C1至C18之烷基（直鏈或支鏈）、C5至C12之環院基或 C1至C18之烷氧基取代）。 -29- 201033274 R2爲H、Cl至C2 4之烷基（直鏈或支鏈，可含有雜原 子、N、0、P、S) 、C5至C30之環烷基（可含有雜原子、 N、0、P、S) 、C1至C30之烷芳基、C6至C24之芳基或雜 芳基、C6至C24之芳基或雜芳基（可被C1至C18之烷基（ 直鏈或支鏈）、C5至C12之環烷基或C1至C18之烷氧基取 代）。 R3爲，C1至C30之伸烷基型的η價之基（直鏈或支鏈 ，可含有雜原子、N、0、P'S) 、C1至C30之亞烷基（可 含有雜原子、N、0、P、S) 、C5至C12之環伸烷基或C6 至C24之伸芳基（可被C1至C18之烷基（直鏈或支鏈）、 C5至C12之環烷基或C1至C18之烷氧基取代）。 R4爲，C1至C24之烷基（直鏈或支鏈，可含有雜原子 、N、0、P、S) 、C5至C30之環烷基（可含有雜原子、N 、P、0、S) ' C1至C30之烷芳基、C6至C24之芳基或雜 芳基、C6至C2 4之芳基或雜芳基（可被C1至C18之烷基（ 直鏈或支鏈）、C5至C12之環烷基或C1至C18之烷氧基取 代）。 R5爲，C1至C24之烷基（直鏈或支鏈，可含有雜原子 、Ν、Ο、p、S) 、C5至C30之環烷基（可含有雜原子、N 、0、P、S) 、C1至C30之烷芳基、C6至C24之芳基或雜 芳基、C6至C24之芳基或雜芳基（可被C1至C18之烷基（ 直鏈或支鏈）、C5至C12之環烷基或C1至C18之烷氧基取 代）。 R6爲，C1至C24之烷基（直鏈或支鏈，可含有雜原子 201033274For example, the phosphites of the general formulae (I) to (V), the phosphonates of the general formulae (VI) to (XII), and the hypophosphites of the general formulae (XIII) to (XV). The respective groups are independent of each other, and R1 is an alkyl group of C1 to C24 (straight or branched, may contain a hetero atom, N, 0, P'S), a C5 to C30 cycloalkyl group (may contain a hetero atom, N, 0) , P, S), (: 1 to C30 alkaryl) 'C6 to C24 aryl or heteroaryl, C6 to C24 aryl or heteroaryl (can be C1 to C18 alkyl (straight chain or Branched), C5 to C12 ring-based or C1 to C18 alkoxy substituted) -29- 201033274 R2 is H, Cl to C2 4 alkyl (straight or branched, may contain heteroatoms, N , 0, P, S), C5 to C30 cycloalkyl (may contain heteroatoms, N, 0, P, S), C1 to C30 alkaryl, C6 to C24 aryl or heteroaryl, C6 An aryl or heteroaryl group to C24 (may be substituted by an alkyl group (linear or branched) of C1 to C18, a cycloalkyl group of C5 to C12 or an alkoxy group of C1 to C18). R3 is, C1 to C30 The η-valent group of an alkyl group (straight or branched, may contain a hetero atom, N, 0, P'S), an alkylene group of C1 to C30 (may contain a hetero atom, N, 0, P, S) a C5 to C12 cycloalkyl group or a C6 to C24 exoaryl group (a C1 to C18 alkyl group (straight or branched), C5 to C a cycloalkyl group of 12 or an alkoxy group of C1 to C18). R4 is an alkyl group of C1 to C24 (straight or branched, may contain a hetero atom, N, 0, P, S), C5 to C30 Cycloalkyl (which may contain a hetero atom, N, P, 0, S) 'C1 to C30 alkaryl, C6 to C24 aryl or heteroaryl, C6 to C2 4 aryl or heteroaryl (may Substituted by an alkyl group (linear or branched) of C1 to C18, a cycloalkyl group of C5 to C12 or an alkoxy group of C1 to C18). R5 is an alkyl group of C1 to C24 (straight or branched) a cycloalkyl group containing a hetero atom, ruthenium, rhodium, p, S), C5 to C30 (which may contain a hetero atom, N, 0, P, S), an alkylaryl group of C1 to C30, an aryl group of C6 to C24 or Heteroaryl, C6 to C24 aryl or heteroaryl (may be substituted by C1 to C18 alkyl (straight or branched), C5 to C12 cycloalkyl or C1 to C18 alkoxy). Is an alkyl group of C1 to C24 (straight or branched, may contain a hetero atom 201033274

、N、0、P、S) 、C5至C30之環烷基（可含有雜原子、N 、0、P、S) 、C1至C3 0之烷芳基、C6至C24之芳基或雜 芳基、C6至C24之芳基或雜芳基（可被C1至C18之烷基（ 直鏈或支鏈）、C5至C12之環烷基或C1至C18之烷氧基取 代）。 A爲直接鍵結、C1至C30之亞烷基（可含有雜原子、N 、0、P、S) 、>NH、> NR1、-S-、> S(O)、> S(〇h、 Φ 或-〇-。 D爲Cl至C30之伸烷基型的q價之基（直鏈或支鏈，可 含有雜原子、N、0、P、S) 、C1至C30之亞烷基（可含有 雜原子、N、0、P、S) 、C5至C12之環伸烷基（可含有雜 原子、N、〇、P、S)或C6至C24之伸芳基（可被C1至C18 之烷基（直鏈或支鏈）、C5至C12之環烷基或C1至C18之 烷氧基取代）、-Ο-或-S-。 X爲Cl、Br、F或OH (包含結果生成互變異構形〉P ( ❹ Ο) H)。 k爲0至4之整數，η爲1至4之整數，m爲0至5之整數， P爲〇或1。 該類化合物中特佳之化合物如下述化合物。又此等化 合物可2種以上倂用。磷系化合物之添加量相對於纖維素 酯100質量份一般爲〇.〇1至10質量份，較佳爲0.05至5質量 份，更佳爲0.1至3質量份。 -31 - 201033274 [化4], N, 0, P, S), C5 to C30 cycloalkyl (which may contain a hetero atom, N, 0, P, S), a C1 to C3 alkaryl group, a C6 to C24 aryl group or a heteroaryl group An aryl or heteroaryl group of C6 to C24 (which may be substituted by an alkyl group (linear or branched) of C1 to C18, a cycloalkyl group of C5 to C12 or an alkoxy group of C1 to C18). A is a direct bond, an alkylene group of C1 to C30 (may contain a hetero atom, N, 0, P, S), >NH, > NR1, -S-, > S(O), > S (〇h, Φ or -〇-. D is the base of the q-valent alkyl group of Cl to C30 (straight or branched, may contain heteroatoms, N, 0, P, S), C1 to C30 An alkylene group (which may contain a hetero atom, N, 0, P, S), a C5 to C12 cycloalkyl group (which may contain a hetero atom, N, fluorene, P, S) or a C6 to C24 exoaryl group (may Substituted by an alkyl group (straight or branched) of C1 to C18, a cycloalkyl group of C5 to C12 or an alkoxy group of C1 to C18), -Ο- or -S-. X is Cl, Br, F or OH (Including results to produce tautomeric forms > P ( ❹ Ο) H). k is an integer from 0 to 4, η is an integer from 1 to 4, m is an integer from 0 to 5, and P is 〇 or 1. The compound of the above-mentioned compound is preferably the following compound, and these compounds may be used in combination of two or more kinds. The amount of the phosphorus compound added is generally from 1 to 10 parts by mass, preferably from 0.05 to 5, based on 100 parts by mass of the cellulose ester. The mass part is more preferably 0.1 to 3 parts by mass. -31 - 201033274 [Chemical 4]

-CHi CHa-CHi CHa

-32- 201033274 [化5]-32- 201033274 [化5]

(CH2|2COOC2Hs Λ—(CH2)2COOC2H6(CH2|2COOC2Hs Λ—(CH2)2COOC2H6

33- 201033274 [化6]33- 201033274 [Chem. 6]

HON-9 {n)C8H17-〇 Ο-ΡβΗ^ (n)C,H,7-a 〇-〇·Ηιτ(η) HON-10HON-9 {n)C8H17-〇 Ο-ΡβΗ^ (n)C,H,7-a 〇-〇·Ηιτ(η) HON-10

34- 201033274 [化7]34- 201033274 [化7]

ch3 -35- 201033274 [化8]Ch3 -35- 201033274 [化8]

-36- 201033274-36- 201033274

[化9][Chemistry 9]

HIT-4 HIT-5 _Hs^〇-0-O<c>〇O-e— -37- 201033274 [化 ίο]HIT-4 HIT-5 _Hs^〇-0-O<c>〇O-e- -37- 201033274 [化 ίο]

HIT-8 <n)C„H27-〇 p—o-c8h17 P-HIT-8 <n)C„H27-〇 p—o-c8h17 P-

H*CH*C

〇—p P«r V CHs c H^C HIT-9〇—p P«r V CHs c H^C HIT-9

ch3 h3c, # CaHy ϋ13Η27《η) -C«Hz7(n) I-CiaH27(n)； -C^H27(n) -38- 201033274 [化11] HIT-10 (n)C1sHn9- (n)C19H19 -^〇-° >_〇~Ch3 h3c, # CaHy ϋ13Η27“η) -C«Hz7(n) I-CiaH27(n); -C^H27(n) -38- 201033274 [11] HIT-10 (n)C1sHn9- (n)C19H19 -^〇-° >_〇~

HIT-11HIT-11

(nJC^Has-O(nJC^Has-O

P—O (nJCiaHae-O HIT-12P-O (nJCiaHae-O HIT-12

Or 〇- -o-c,h17 O-C^H^n) HIT-13 Hlt-14 V- I —O-C10H2i (nJCioHzi- p一〇-Ci«HmOr 〇- -o-c,h17 O-C^H^n) HIT-13 Hlt-14 V- I —O-C10H2i (nJCioHzi- p一〇-Ci«Hm

-39- 201033274 [化 12]-39- 201033274 [Chem. 12]

HIT-19HIT-19

HaP HIT-20HaP HIT-20

H,CH, C

-40- 201033274 [化 13]-40- 201033274 [Chem. 13]

-41 - 201033274 [化 14] HlN-9 h3c- •ο-41 - 201033274 [Chem. 14] HlN-9 h3c- •ο

-42- 201033274 [化 15] HAN-1 HAN-2-42- 201033274 [Chem. 15] HAN-1 HAN-2

43- 201033274 [化 16]43- 201033274 [Chem. 16]

除了上述之例如外’本發明可使用的磷系化合物之具 體例如’三苯基亞磷酸酯、二苯基異癸基亞磷酸酯、苯基 二異癸基亞磷酸酯、三（壬基苯基）亞磷酸酯、三（二壬 基苯基）亞磷酸酯、三（2,4-二-t-丁基苯基）亞磷酸醋、 10-(3,5-二-卜丁基-4-羥基苄基）_9，10_二氫基-9_噁_1〇_ 磷雜菲-10-氧化物、6-[3- ( 3-t-丁基·_4-羥基-5-甲基苯基） 丙氧基]-2，4,8,10-四-t-丁基二苯并[d，f] [1.3.2]二噁亞磷酸 衍生物（phosphepine )、十三烷基亞磷酸酯等單亞磷酸 酯系化合物；4,4’-亞丁基-雙（3_甲基_6小丁基苯基_二_ 十三烷基亞磷酸酯）、4，4，-異亞丙基-雙（苯基-二-院基 (C12至C15)亞磷酸酯）等二亞磷酸酯系化合物；三苯 基膦酸酯、四（2,4-二-tert-丁基苯基）[1，〗·聯苯]_4,4，_二 基雙膦酸酯、四（2,4-二-tert-丁基-5-甲基苯基）[^^聯 苯]-4,4’-二基雙膦酸酯等膦酸酯系化合物；三苯基次碟酸 醋、2,6-二甲基苯基二苯基次磷酸醋等次磷酸酯系化合物 :三苯基膦 '三（2,6 -二甲氧基苯基）膦等膦系化合物等 -44- 201033274 上述型之磷系化合物如，市售的住友化學股份公司製 商品名 “ SumilizerGP ” 、ADEKA股份公司製商品名“In addition to the above, for example, specific examples of the phosphorus-based compound which can be used in the present invention are, for example, 'triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, tris(nonylbenzene) Phosphite, tris(didecylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, 10-(3,5-di-b-butyl-4- Hydroxybenzyl)_9,10-dihydro-9-ox_1〇_phosphonium-10-oxide, 6-[3-( 3-t-butyl·_4-hydroxy-5-methylbenzene Propyl]-2,4,8,10-tetra-t-butyldibenzo[d,f] [1.3.2] bisphosphonate derivative, tridecylphosphite Monophosphite-based compound such as ester; 4,4'-butylidene-bis(3-methyl-6-butylbutylphenyl-ditridecylphosphite), 4,4,-isopropylene a bisphosphite compound such as a bis-bis(phenyl-di-hoc (C12 to C15) phosphite); triphenylphosphonate, tetrakis(2,4-di-tert-butylphenyl) [1,〗·Biphenyl]_4,4,_Diylbisphosphonate, tetrakis(2,4-di-tert-butyl-5-methylphenyl)[^^biphenyl]-4,4 a phosphonate compound such as '-diyl bisphosphonate; three Phosphine-based compounds such as phenyl-disc vinegar and 2,6-dimethylphenyldiphenylphosphoric acid vinegar: phosphines such as triphenylphosphine 'tris(2,6-dimethoxyphenyl)phosphine Compounds such as -44-201033274 Phosphorus compounds of the above type are commercially available under the trade name "SumilizerGP" from Sumitomo Chemical Co., Ltd., and under the trade name of ADEKA AG.

ADK STAB PEP-24G” 、 ** ADK STAB PEP-36” 及 “ADK STAB 3010” 、 “ADK STAB 2112” 、吉巴加股份公司製 商品名 “ IRGAFOS P-EPQ” 、 “IRGAFOS 168” 、堺化學 工業股份公司製商品名“GSY-P101” 。 《其他防氧化劑》 又如，二月桂基-3,3’-硫二丙酸酯、二肉豆蔻基-3，3’-硫二丙酸酯、二硬脂醯-3，3’-硫二丙酸酯、季戊四醇基四 (3-月桂基硫丙酸酯）等硫系防氧化劑、2-tert-丁基-6-( 3-tert-丁基-2-羥基-5-甲基苄基）-4-甲基苯基丙烯酸酯、 2-[1- ( 2 -經基- 3,5 - 一 -tert-戊基苯基）乙基]-4,6-二- tert· 戊基苯基丙烯酸酯等耐熱加工安定劑、特公平08-27508號 參 記載之3,4-二氫基-211-1-苯并吼喃系化合物、3,3，-螺二色 滿系化合物、1，1 -螺印滿系化合物、嗎啉、硫嗎啉、硫嗎 啉氧化物、硫嗎啉二氧化物、部分構造具有哌嗪骨架之化 合物、特開平03- 1 74 1 50號公報所記載之二烷氧基苯系化 合物等氧消除劑等。此等防氧化劑之部分構造可垂掛於部 分聚合物，或規則垂掛於聚合物，又可導入可塑劑、酸捕 捉劑、紫外線吸收劑等添加劑之部分分子構造中。 (其他添加劑） -45- 201033274 《可塑劑》 本發明之光學薄膜爲了提升組成物的流動性及柔軟性 ，可倂用可塑劑。可塑劑如，酞酸酯系、脂肪酸酯系、偏 苯三甲酸酯系、磷酸酯系、聚酯系或環氧系等。 其中較佳爲使用聚酯系及酞酸酯系之可塑劑。聚酯系 可塑劑雖具有比酞酸二辛酯等酞酸酯系之可塑劑更優良的 非移行性及耐萃取性，但可塑化效果及相溶性較差。 因此可因應用途選擇此等可塑劑，或倂用而適用於廣 範圍之用途。 聚酯系可塑劑可爲一價至四價之羧酸與一價至六價之 乙醇的反應物，但主要係使用二價羧酸與乙二醇反應而得 之物。代表性之二價羧酸如，戊二酸、衣康酸、己二酸、 酞酸、壬二酸、癸二酸等。 特別是使用己二酸、酞酸等可得優良可塑化特性。乙 二醇如，乙烯、丙烯、1，3-丁烯、1，4-丁烯、1，6-六甲烯 、新戊烯、二乙烯、三乙烯、二丙烯等之乙二醇。此等二 價羧酸及乙二醇可各自單獨，或混合使用。 該酯系之可塑劑可爲酯、低聚酯、聚酯型中任何一種 ，分子量可爲100至10000之範圍，又以600至3000之範圍 時可塑化效果較大。 又，可塑劑之黏度雖與分子構造、分子量有關，但爲 己二酸系可塑劑時，就相溶性、可塑化效率之關係可爲 200至5000MPa.s(25°C )之範圍。另外可倂用數個聚酯系 可塑劑。 -46- 201033274 可塑劑相對於本發明之光學薄膜100質量份的添加量 較佳爲0.5至30質量份。可塑劑之添加量超過30質量份時 表面具黏性，因此實用上不宜。 《紫外線吸收劑》 本發明之光學薄膜較佳爲含有紫外線吸收劑，所使用 的紫外線吸收劑如，苯并三唑系、2 -羥基二苯甲酮系或水 φ 楊酸苯基酯系之物等。例如，2- (5-甲基-2-羥基苯基）苯 并三唑、2-[2·羥基-3,5-雙（α，α-二甲基苄基）苯基]_ 2Η-苯并三唑、2- ( 3,5-二-t-丁基-2-羥基苯基）苯并三唑 等三唑類、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-辛氧基 二苯甲酮、2，2’-二羥基-4-甲氧基二苯甲酮等二苯甲酮類 〇 此等紫外線吸收劑中，又以分子量400以上之紫外線 吸收劑於高沸點下較難揮發，且於高溫形成時難飛散，因 Φ 此既使較少添加量也能有效改良耐候性而爲佳。 分子量400以上之紫外線吸收劑如，2- ( 2-羥基-3,5-雙（α,α-二甲基苄基）苯基]-2-苯并三唑、2,2-伸甲基雙 [4- ( 1，1，3,3-四丁基）-6- ( 2Η-苯并三唑-2-基）苯酚]等之 苯并三唑系、雙（2,2,6,6-四甲基-4-哌啶基）癸二酸酯、 雙（1,2,2,6,6-五甲基-4-哌啶基）癸二酸酯等之阻胺胺系 ，又如2- ( 3,5-二-t-丁基-4-羥基苄基）-2-n-丁基丙二酸 雙（1，2,2,6,6-五甲基-4-哌啶酯）、l-[2-[3- ( 3,5-二-t-丁 基-4-羥基苯基）丙醯氧基]乙基]-4-[3- ( 3,5-二-t-丁基-4- -47- 201033274 羥基苯基）丙醯氧基]-2,2,6,6-四甲基哌啶等之分子內同 時具有阻胺酚及阻胺胺構造的混合系之物，此等可單獨使 用或2種以上倂用。其中特佳爲2-[2-羥基-3,5-雙（α，α-二甲基苄基）苯基]-2-苯并三唑及2,2-伸甲基雙( 1，1，3,3-四丁基）-6-(2Η-苯并三唑-2-基）苯酚]。 另外本發明之光學薄膜爲了改良成形加工時之熱分解 性及熱著色性，可添加各種防氧化劑。又加入防靜電劑可· 賦予光學薄膜之防靜電性能。 本發明之光學薄膜可使用添加磷系難燃劑之難燃丙烯 酸系樹脂組成物。 所使用的磷系難燃劑可爲紅磷、三芳基磷酸酯、二芳 基磷酸酯、一芳基磷酸酯、芳基膦酸化合物、芳基膦氧化 物化合物、縮合芳基磷酸酯、鹵化烷基磷酸酯、含鹵素縮 合磷酸酯、含鹵素縮合膦酸酯、含鹵素亞磷酸酯等中所選 出之1種或2種以上的混合物。 具體例如，三苯基磷酸酯、9，10-二氫基-9-噁-10-磷 雜菲-10-氧化物、苯基鱗酸、三（氯乙基）磷酸酯、 三（二氯丙基）磷酸酯、三（三溴新戊基）磷酸酯等。 本發明之光學薄膜同時可達成先前樹脂薄膜無法得到 的低吸濕性、透明性、優良之耐熱性及脆性之改善。 本發明判斷脆性之指標係以是否爲「不造成延性破壞 之光學薄膜」爲基準。所得的不造成延性破壞可改善脆性 之光學薄膜既使使用於製作大型液晶顯示裝置用之偏光板 ，製造時也不會發生破斷及裂開，可爲處理性優良之光學 -48- 201033274 薄膜。該延性破壞係以，作用大於材料原 時會造成破斷，且最終破斷會明顯破壞材 縮率定義。該斷面之特徵爲，形成無數稱 本發明中是否爲「不造成延性破壞之 ，既使將薄膜折彎成2片般之較大應力作 斷等破壞方式評估。將既使施加該類較大 延性破壞之光學薄膜，作爲大型化液晶顯 φ 板保護薄膜用，也可充分減少製造時破斷 使使用一度貼合後再剝取之光學薄膜，也 可充分對應光學薄膜之薄型化。 本發明所使用的耐熱性指標爲張力軟 顯示裝置大型化及日益提高背光光源亮度 等運用於屋外用途時要求更高亮度，而需 耐更高溫環境之使用之特性，但張力軟化 時就可判斷爲具有充分耐熱性。特佳爲控 參 具體上測定表示光學薄膜之張力軟化 如，使用電子論試驗機（ORIENTEC公司 ，將光學薄膜切成120mm (長）xl0mm( 之張力拉伸，同時以30°C /min之升溫速虔 次測定到達9N時之溫度後求其平均値而得 又，就耐熱性觀點光學薄膜之玻璃化 爲110t以上，更佳爲120°C以上，特佳爲 該玻璃化溫度係指，使用差示掃fi 有之強度的應力 料之延伸性及收 爲窩之凹洞。 光學薄膜」係以 用，也未出現破 應力也不會造成 示裝置用之偏光 等問題，另外既 不會發生破斷， 化點。隨著液晶 ，以及電子看板 求光學薄膜具有 點爲1 〇 5至1 4 5 °c 制於1 1 〇至1 3 0 °C 點的溫度之方法 製 RTC- 1 225A ) 寬）後，以10N :持續升溫，經3 〇 溫度（Tg)較佳 1 5 0 °C以上。 吉熱量測定器（ -49- 201033274ADK STAB PEP-24G", ** ADK STAB PEP-36" and "ADK STAB 3010", "ADK STAB 2112", trade name "IRGAFOS P-EPQ", "IRGAFOS 168", 堺Chem Industrial Co., Ltd. made the trade name "GSY-P101". "Other antioxidants" Another example is dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-sulfur Sulfur-based antioxidants such as dipropionate, pentaerythritol tetrakis(3-lauryl thiopropionate), 2-tert-butyl-6-( 3-tert-butyl-2-hydroxy-5-methylbenzyl 4-methylphenyl acrylate, 2-[1-(2-amino- 3,5-mono-tert-pentylphenyl)ethyl]-4,6-di-tert·pentyl a heat-resistant processing stabilizer such as phenyl acrylate, a 3,4-dihydro-211-1-benzopyranyl compound described in JP-A 08-27508, a 3,3,-spirochromic compound, 1,1 - siro-printed full compound, morpholine, thiomorpholine, thiomorpholine oxide, thiomorpholine dioxide, a compound having a piperazine skeleton in part, and JP-A 03- 1 74 1 50 An oxygen scavenger such as a dialkoxybenzene compound described above. Some of these antioxidants may be suspended from a part of the polymer, or may be suspended from the polymer, or may be introduced into a part of the molecular structure of an additive such as a plasticizer, an acid trapping agent, or an ultraviolet absorber. (Other Additives) -45- 201033274 <<Plasticizer>> The optical film of the present invention can be used in order to enhance the fluidity and flexibility of the composition. The plasticizer is, for example, a phthalate ester, a fatty acid ester, a trimellitate, a phosphate, a polyester or an epoxy. Among them, polyester-based and phthalate-based plasticizers are preferably used. Although the polyester-based plasticizer has better non-migration property and extraction resistance than a phthalate-based plasticizer such as dioctyl phthalate, it has a poor plasticizing effect and compatibility. It is therefore possible to select these plasticizers for their intended use or to use them for a wide range of applications. The polyester-based plasticizer may be a reactant of a monovalent to tetravalent carboxylic acid and a monovalent to hexavalent ethanol, but mainly obtained by reacting a divalent carboxylic acid with ethylene glycol. Representative divalent carboxylic acids such as glutaric acid, itaconic acid, adipic acid, citric acid, azelaic acid, sebacic acid and the like. In particular, the use of adipic acid, citric acid or the like can provide excellent plasticizing properties. Ethylene glycol such as ethylene glycol, propylene, 1,3-butene, 1,4-butene, 1,6-hexamethylene, neopentene, diethylene, triethylene, dipropylene or the like. These divalent carboxylic acids and ethylene glycols may be used singly or in combination. The ester-based plasticizer may be any of ester, oligoester, and polyester types, and may have a molecular weight of from 100 to 10,000, and a plasticizing effect in the range of from 600 to 3,000. Further, although the viscosity of the plasticizer is related to the molecular structure and molecular weight, when it is an adipic acid plasticizer, the relationship between the compatibility and the plasticizing efficiency may be in the range of 200 to 5000 MPa.s (25 ° C). In addition, several polyester-based plasticizers can be used. The amount of the plasticizer added to 100 parts by mass of the optical film of the present invention is preferably from 0.5 to 30 parts by mass. When the amount of the plasticizer added exceeds 30 parts by mass, the surface is sticky, so it is not practical. "Ultraviolet absorber" The optical film of the present invention preferably contains an ultraviolet absorber, and the ultraviolet absorber used is, for example, benzotriazole, 2-hydroxybenzophenone or water phenyl salicylate. Things and so on. For example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2.hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]_ 2Η- Triazoles such as benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-hydroxy-4-methoxybenzophenone, 2- a benzophenone such as hydroxy-4-octyloxybenzophenone or 2,2'-dihydroxy-4-methoxybenzophenone; and ultraviolet rays having a molecular weight of 400 or more in such ultraviolet absorbers The absorbent is less volatile at high boiling points and is less likely to scatter when formed at a high temperature, and Φ is preferable because it can effectively improve weather resistance even with a small addition amount. Ultraviolet absorbers having a molecular weight of 400 or more, such as 2-(2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2-benzotriazole, 2,2-methyl Benzotriazole, bis(2,2,6, bis[4-(1,1,3,3-tetrabutyl)-6-( 2Η-benzotriazol-2-yl)phenol] a hindered amine amine such as 6-tetramethyl-4-piperidinyl sebacate or bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Another example is 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis(1,2,2,6,6-pentamethyl-4- Piperidine), 1-[2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoxy]ethyl]-4-[3-(3,5- Di-t-butyl-4-47-201033274 hydroxyphenyl)propanoxy]-2,2,6,6-tetramethylpiperidine and the like have both hindered phenol and hindered amine structures For the mixed system, these may be used alone or in combination of two or more. Among them, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2 is particularly preferred. -benzotriazole and 2,2-extended methylbis(1,1,3,3-tetrabutyl)-6-(2Η-benzotriazol-2-yl)phenol]. Further optical of the invention Film to improve thermal decomposition and heat during forming Coloring property, various anti-oxidants can be added, and an antistatic agent can be added to impart antistatic properties to the optical film. The optical film of the present invention can be a flame-retardant acrylic resin composition to which a phosphorus-based flame retardant is added. The flame retardant may be red phosphorus, triaryl phosphate, diaryl phosphate, monoaryl phosphate, arylphosphonic acid compound, aryl phosphine oxide compound, condensed aryl phosphate, halogenated alkyl phosphate One or a mixture of two or more selected from the group consisting of halogen-containing condensed phosphates, halogen-containing condensed phosphonates, halogen-containing phosphites, etc. Specifically, for example, triphenyl phosphate, 9,10-dihydro group- 9-oxo-10-phosphaphenanthrene-10-oxide, phenyl chromic acid, tris(chloroethyl)phosphate, tris(dichloropropyl)phosphate, tris(tribromoneopentyl)phosphate, etc. The optical film of the present invention can simultaneously achieve the improvement of low hygroscopicity, transparency, excellent heat resistance and brittleness which are not obtained by the prior resin film. The index for judging the brittleness of the present invention is whether or not the optical film does not cause ductile damage. Based on the benchmark. The optical film which is capable of improving the brittleness is used for producing a polarizing plate for a large-sized liquid crystal display device, and is not broken or cracked during manufacture, and can be an optical film of excellent optical properties - 48-201033274. If the damage is greater than the original material, it will cause breakage, and the final break will obviously destroy the definition of the material shrinkage. The feature of the cross section is that it forms a myriad that the invention is "not causing ductile damage, even if The film was bent into two pieces and the stress was evaluated by breaking the damage. Even if an optical film which is subjected to such a large ductile damage is used as a protective film for a large-sized liquid crystal display, it is also possible to sufficiently reduce the optical film which is broken during production and which is peeled off after being used for one time, and can be sufficiently matched. The optical film is thinned. The heat resistance index used in the present invention is characterized in that the tension soft display device is enlarged and the brightness of the backlight source is increased, and the brightness is required for outdoor use, and the use of a higher temperature environment is required, but the tension is softened. To have sufficient heat resistance. The specific control for the control refers to the softening of the optical film. For example, using an electronic theory tester (ORIENTEC, the optical film is cut into 120 mm (length) x 10 mm (tension tension, while heating at 30 ° C / min) When the temperature is reached at a temperature of 9 N, the average temperature is determined, and the glass film of the heat-resistant optical film is 110 t or more, more preferably 120° C. or more, and particularly preferably the glass transition temperature is used. The differential sweep has the strength of the elongation of the stress material and the recess of the nest. The optical film is used, and there is no problem of stress or damage caused by the device, and neither occurs. Breaking, turning point. With liquid crystal, and electronic kanban, the optical film has a point of 1 〇5 to 1 4 5 °c and is made at a temperature of 1 1 1 to 130 °C. RTC-1 225A ) After the width is 10 N: the temperature is continuously increased, and the temperature (Tg) of 3 Torr is preferably 150 ° C or more. Ji heat measuring device ( -49- 201033274

Perkin Elmer公司製DSC-7型），以升溫速度20°C /分測定 後，依據JIS K712l ( 1 987 )求得的中間點玻璃化溫度（Perkin Elmer's DSC-7 type), measured at a heating rate of 20 ° C / min, the intermediate point glass transition temperature determined according to JIS K712l (1 987)

Tmg )。 判斷本發明之光學薄膜的透明性之指標爲混濁度。特 別是使用於屋外之液晶顯示裝置，爲了既使於明亮場所也 能得到充分亮度及高對比’其混濁度需爲1 · 〇 %以下，更 佳爲0.5%以下。 含有丙烯酸系樹脂（A)及纖維素酯樹脂（B)的本 @ 發明之光學薄膜可得高透明性，但爲了改善其他物性之目 的而使用丙烯酸基粒子時，減少樹脂（丙烯酸系樹脂（A )及纖維素酯樹脂（B))與丙烯酸基粒子（C)之折射 率差，可防止混濁値上升。 又，表面粗糙度也會影響表面混濁度之混濁値，因此 利用將丙烯酸基粒子（C)之粒徑及添加量抑制於前述範 圍內，可有效減少製膜時薄膜接觸部之表面粗糙度。 又，本發明之光學薄膜的吸濕性可以，相對於濕度變 @ 化之尺寸變化評估。 相對於濕度變化之尺寸變化的評估方法可使用下述方 法。 於所得光學薄膜之流延方向的2處所作記號（十字） 後，6(TC、90% RH下處理1 000小時，使用光學顯微鏡測 定處理前及處理後記號（十字）之距離，再求取尺寸變化 率（％)。尺寸變化率（％)如下述式所示。 -50- 201033274 尺寸變化率（％) = [(al-a2)/al ]xl 00 al:熱處理前之距離 a2:熱處理後之距離 以光學薄膜作爲液晶顯示裝置之偏光板用保護薄膜時 ，會因吸濕而改變尺寸，而使光學薄膜發生斑點及相位差 値改變，故會有降低對比及發生色斑之問題。特別是作爲 φ 使用於屋外之液晶顯示裝置的偏光板保護薄膜用，會使上 述問題更明顯。但上述條件下尺寸變化率（％ )未達0.5 %時，可評估爲具有充分低吸濕性之光學薄膜。更佳爲未 達 0.3%。 又，本發明之光學薄膜較佳爲，薄膜面內之直徑5 /2 m以上的缺點爲1個/10 cm四方以下，更佳爲0.5個/10 cm 四方以下，特佳爲0.1個/10cm四方以下。 該缺點之直徑係指，缺點爲圓形時爲其直徑，不爲圓 φ 形時可利用下述方法使用顯微鏡觀察缺點之範圍後再決定 其最大徑（外接圓之直徑）。 缺點範圍內之缺點爲氣泡及異物時係指，以微分干擾 顯微鏡之透過光線觀察缺點時的影子大小。缺點爲輥上之 刮傷轉印或擦傷等表面形狀改變時，可以微分干擾顯微鏡 之反射光觀察缺點確認大小。 又，以反射光觀察時缺點大小不明確之情況下，可於 表面蒸鍍鋁或鈾再觀察。 爲了可以良好生產性得到該缺點頻度所代表之單位優 -51 - 201033274 良的薄膜，可有效利用流延前高精度過濾聚合物溶液、提 高流延機周邊之乾淨度，或階段性設定流延後之乾燥條件 而更有效率抑制發泡而乾燥的方法。 缺點個數多於1個/l〇cm四方時，例如於後步驟之加工 時等會因薄膜施加張力，而由缺點爲基點使薄膜破斷故會 降低生產性。又，缺點直徑爲5 μ m以上時，可藉偏光板 觀察等以目視確認會出現作爲光學構件用時之亮點。 又，依據JIS-K7 1 27- 1 999測定本發明之光學薄膜時較 佳爲，至少一方向之破斷伸度爲10%以上，更佳爲20%以 上。 破斷伸度之上限並無特別限制，現實上可爲250%。 增加破斷伸度時可有效抑制起因於異物及發泡之薄膜中的 缺點。 本發明之光學薄膜的厚度較佳爲20 μ m以上，更佳爲 3 Ο μ m以上。 厚度上限並無特別限定，但就塗佈性等觀點，上限爲 250/zm。又薄膜厚度可因應用途適當選定。 本發明之光學薄膜較佳爲，其全光線透過率爲90%以 上，更佳爲93%以上。又現實性之上限爲99%。爲了達成 該全光線透過率所代表之優良透明性。可有效利用不導入 會吸收可視光之添加劑及共聚合成份、高精度過濾去除聚 合物中之異物，或降低薄膜內部光的擴散及吸收的方法。 又，可有效利用減少製膜時薄膜接觸部（冷卻輥、壓 延輥、轉鼓、傳送帶、搬運輥等）之表面粗糙度而減少薄 -52- 201033274 膜表面之表面粗糙度，或減少丙烯酸樹脂之折射率而降低 薄膜表面光的擴散及反射之方法。 本發明之光學薄膜符合上述物性時，特別適合作爲大 型液晶顯示裝置及屋外用途之液晶顯示裝置用的偏光板保 護薄膜用。 該類物性可由，光學薄膜之特徵爲以95 : 5至30 : 70 之質量比含有丙烯酸樹脂（A)及纖維素酯樹脂（B)， φ 又前述丙烯酸樹脂（A)之重量平均分子量Mw爲80000以 上，該纖維素酯樹脂（B)之醯基的總取代度（T)爲2.00 至3.00，碳數3至7之醯基的取代度爲1.2至3.0，且重量平 均分子量（Mw)爲75 000以上的光學薄膜而得。 〈光學薄膜之製膜〉 下面將舉例說明光學薄膜之製膜方法，但本發明非限 定於此。 本發明可使用的光學薄膜之製膜方法如，吹塑法、T 模法、壓延法、切削法、流延法、乳化法、熱壓法等製造 法，但就抑制著色、抑制異物缺點、抑制模痕等光學缺點 等之觀點’又以使用流延法熔融製膜爲佳。本發明特佳爲 使用接觸輥之熔融流延製膜法。 本申請書中「熔融製膜」係以，將含有丙烯酸樹脂、 纖維素酯樹脂及可塑劑等添加劑之組成物，加熱熔融至具 有流動性之溫度後，使流動性之含有纖維素酯樹脂、丙烯 酸樹脂等的熔融物流延而熔融製膜定義。 -53- 201033274 更詳細而言，加熱熔融之成形法可分類爲熔融擠壓成 形法、加壓成形法、吹塑法、射出成形法、吹煉成形法、 延伸成形法等。其中就得到具有優良機械強度及表面精度 等之光學薄膜，又以熔融擠壓法最佳。 使用熔融流延製膜法製膜爲本發明之光學薄膜時，實 質上製膜步驟係不使用溶劑，因此製膜後捲取之光學薄膜 所含的殘留有機溶劑量可爲安定狀未達0.01質量％，故可 提供持有比先前更安定的平面性及光學特性之光學薄膜。 特別是既使捲物長100m以上也可提供持有安定的平面性 及光學特性之光學薄膜。 又，以溶液流延法製作之光學薄膜的殘留有機溶劑量 (%)難達到〇.〇1質量％以下，因此需備有較長的乾燥步 驟，故成本較高。 本申請案中殘留溶劑量（質量％ )之値爲，以乾燥前 一定大小之捲筒（薄膜）的質量爲A，及110 °C下乾燥前 述A 3小時後之捲筒（薄膜）的質量爲B時，由（（A-B ) /B ) xl 00 =殘留溶劑量（質量％ )求取之値。 《製膜步驟》 下面將說明薄膜之製膜步驟。 〈丙烯酸樹脂及纖維素酯樹脂及添加劑之熔融顆粒製造步 驟〉 熔融擠壓時所使用的複數原材料一般較佳爲，預先混 201033274 練顆粒化。 顆粒化可使用已知之方法，例如利用進料器將丙烯酸 樹脂、纖維素酯樹脂、丙烯酸樹脂、可塑劑、其他添加劑 供給擠壓機，利用單軸或雙軸擠壓機混練後，由擠出板擠 壓爲單絲狀再水冷或空冷，其後切取。 爲了防止原材料分解，於擠壓前使原材料乾燥係重點 。特別是纖維素酯易吸濕，因此較佳爲使用除濕熱風乾燥 φ 機或真空乾燥機，以70至14(TC乾燥3小時以上，使水分率 爲200ppm以下，更佳爲lOOppm以下。 添加劑可於供給擠壓機之前先行混合，或以各自之進 料器供給。爲了使防氧化劑等之少量添加劑均勻混合，較 佳於事前混合。 混合防氧化劑時可爲固體同士相混合，又必要時可將 防氧化劑溶解於溶劑，再含浸於丙烯酸樹脂等樹脂而混合 ，或噴霧混合。 φ 較佳爲使用真空諾塔混合機等同時乾燥及混合。又， 進料器及模頭之出口等接觸空氣時，較佳於除濕空氣或除 濕後之N2氣體等環境下實施。 又’對擠壓機之供給料斗等保溫時可防止吸濕而爲佳 。另外可將所得顆粒塗滿消光劑或UV吸收劑等，於薄膜 製膜時再加入擠壓機中。 擠壓機較佳爲，以可抑制剪斷力，不使樹脂惡化（降 低分子量、著色、生成凝膠等）而顆粒化之低溫進行加工 。例如使用雙軸擠壓機時較佳爲，利用深溝型螺杆以同方 -55- 201033274 向回轉。就混練均勻性較佳爲咬合型。 揑合盤雖可提升混練性，但需注意剪斷發熱。又既使 不使用捏合盤也可得充分混合性。必要時可因應排氣孔進 行吸引處理。但低溫下幾乎不會發生揮發，因此可無需孔 〇 顆粒之顏色較佳爲，黃色指標之b*値爲-5至10，更佳 爲-1至8，特佳爲-1至5。b*値係使用分光測色計CM-3 700d (可尼佳（股）製，以D65(色溫度65 04K)爲光源，以 Λ 視野角10°測定。 使用以上所得的顆粒進行薄膜製膜。又當然可於未顆 粒化下，經由進料器直接將原材料粉末供給擠壓機，直接 進行薄膜製膜。 〈由擠出板擠出丙烯酸樹脂等樹脂混合物之熔融物的步驟 &gt; 使用單軸或雙軸型擠壓機，以擠出時熔融溫度Tm爲 © 200至300°C，及利用活動盤型濾器等過濾去除異物之後， 由T字模將經除濕熱風及真空或減壓下乾燥之聚合物流延 爲薄膜狀。 又由供給料斗導入擠壓機時較佳於真空下，減壓下或 不活性氣體環境下進行以防止氧化分解等。此外，Tm爲 擠壓機之模頭出口部分的溫度。 擠出流量又以導入齒輪泵等安定進行爲佳。又去除異 物用之濾器較佳爲，使用不銹鋼纖維燒結濾器。 -56- 201033274 不銹鋼纖維燒結濾器爲’不銹鋼纖維體複雜絡合之狀 態下壓縮燒結接觸處而一體化之物’因此可藉由該纖維之 粗細及壓縮量改變密度，而調整過濾精度。 較佳爲連續重覆複數粗、細之過濾精度的多層體。又 依序提升過濾精度之構造，及重覆過濾精度之粗、細的方 法，也可延長濾器之過濾壽命’及提升異物及凝膠等之補 足精度而爲佳。 Φ 模頭附著刮傷或異物時，會發生條紋狀之缺陷。該類 缺陷也稱爲模紋，爲了減少模紋等表面缺陷，擠壓機至模 頭之配管較佳爲，能極力減少樹脂之滯留部的構造。盡可 能使用模頭內部及唇部無刮傷之物爲佳。 擠壓機及模頭等接觸熔融樹脂之內面係減少表面粗糙 、或使用表面能量較低之材質等，施加溶融樹脂難以附著 之表面加工而爲佳。具體例如，將電鍍硬鉻或陶瓷熔射之 物硏磨爲表面粗糙度爲0.2S以下之物。 φ 可塑劑等添加劑可預先混合樹脂、或擠壓機途中混練 。爲了均与添加較佳爲使用靜態混合機等混合裝置。 〈於冷卻輥及彈性接觸輥之間擠壓由模頭擠出之熔融物的 同時流延形成薄膜之步驟〉 該步驟係藉由冷卻輥及彈性接觸輥挾合由模頭擠出之 薄膜狀熔融物，而形成一定薄膜形狀及膜厚。 [冷卻輥] -57- 201033274 本發明之冷卻輥並無特別限制，可爲高剛性金屬輥備 有內部流動可控制溫度之熱媒體或冷媒體般構造之輥，但 大小不受限，可爲能充分冷卻熔融擠出之薄膜的大小，又 一般冷卻輥之直徑爲100mm至lm。 冷卻輥之表面材質可爲碳鋼、不銹鋼：鋁、鈦等。又 爲了提升表面硬度，及改良對樹脂之剝離性較佳爲，實施 電鍍硬鉻、電鎪鎳、電鍍非晶質鉻等，或溶射陶瓷等表面 處理。 冷卻輥表面之表面粗糙度Ra較佳爲O.lym以下，更佳 爲0.05 /zm以下。輥表面平滑時，所得薄膜之表面也平滑 。當然又以表面加工後將表面再硏磨而得上述表面粗糙度 爲佳。 本發明之冷卻輥爲至少1個，較佳爲具有2個以上。僅 1個時冷卻輥之表面溫度Tr設定爲Tg-50S TrS Tg。2個以 上時第1冷卻輥及第2冷卻輥之表面溫度設定爲，Tg-50彡 TrlSTg、Tg-50STr2STg。 該Tg係指，丙烯酸樹脂及纖維素酯樹脂之混合物的玻 璃化溫度（°c )。 玻璃化溫度Tg之測定方法爲，依據Jis K 7121使用精 工電子工業（股）製差示掃描熱量計DSC 220進行。 設置樣品l〇mg後，於氮流量50ml/min之條件下，以20 °C /min將室溫升至250 °C並保持10分鐘（1st掃描），其次 以20°C /min之速度降溫至30°C並保持10分鐘（2nd掃描） ，再以20 °C /min升溫至250 °C( 3rd掃描），得DSC曲線。 201033274 其後由所得3rd掃描之DSC曲線求取玻璃化溫度。 [彈性接觸輥] 本發明所使用的彈性接觸輥可爲特開03- 1 24425號、 特開平08-224772號、特開平07-100960號、特開平 10-272676 號、WO97-028950、特開平 1 1 -235747 號、特開 2002-36332號、特開2005-172940號及特開2005-280217號 φ 公報所記載的表面被覆薄膜金屬套管之矽橡膠輥，但以下 述彈性接觸輥爲佳。 比較其他熱塑性樹脂，含有纖維素酯之熔融物的熔融 黏度較高，且不易延伸。 因此含有拉伸比較大時搬運方向易造成膜厚變動，又 拉幅步驟中延伸時易破斷之問題。雖然盡可能以拉伸比7 至8實施，但本發明較佳爲，由模頭以薄膜狀擠出含有纖 維素酯之熔融物後，利用彈性接觸輥將拉伸比1 〇以上30以 φ 下所得的薄膜擠壓於冷卻輥的同時進行搬運。 拉伸比係指，模頭之唇部間隙除以冷卻輥上固化之薄 膜平均膜厚而得的値。拉伸比爲該範圍時可得，以液晶顯 示裝置顯示畫像時不會有明暗紋路及斑點狀不均勻，生產 性良好之偏光板保護薄膜。 拉伸比可藉由模頭唇部間隙及冷卻輥之拉取速度調整 。模頭唇部間隙較佳爲900 # m以上，更佳爲1至2mm。太 大或太小均無法改善斑點狀不均勻。 本發明所使用的彈性接觸輥爲，由金屬製外筒及內筒 -59- 201033274 之2重構造形成，其間具有可流動冷卻流體般空間之物。 另外可藉由金屬製外筒具有彈性，更精準控制接觸輥 表面的溫度，且具有可利用適度的彈性變形性質得到爭取 長度方向上擠壓薄膜之距離的效果，而使液晶顯示裝置顯 示畫像時可得到無明暗紋路及斑點狀不均勻之效果。 金屬製外筒之厚度又以0.003 $ (金屬製外筒之厚度 )/(接觸輥半徑）S 〇.〇3時可得適度彈性而爲佳。又接 觸輥之半徑過大時既使金屬外筒厚度較厚也可造成適度彎 ❿ 曲。 彈性接觸輥之直徑較佳爲100至600mm。金屬製外筒 之厚度太薄時強度將不足，恐破損。又太厚時會使輥質量 過重，恐有回轉斑。因此金屬製外筒之厚度較佳爲0.1至 5mm ° 金屬外筒表面之表面粗糙度較佳爲，算術平均粗糙度 Ra爲0.1；zm以下，更佳爲0.05/zm以下。輥表面平滑時， 所得薄膜之表面也平滑。 @ 金屬製外筒之材質要求平滑、具有適度彈性及耐久性 。較佳爲使用碳鋼、不銹鋼、鈦，以電鍍法製造之鎳等。 另外爲了提升其表面之硬度，及改良對樹脂之剝離性較佳 爲，實施電鍍硬鉻、電鍍鎳、電鍍非晶質鉻等，或熔射陶 瓷等表面處理。又以表面加工後將表面再度硏磨而得上述 表面粗糙度爲佳。 內筒較佳爲碳鋼、不銹鋼、鋁、鈦等輕量且具剛性之 金屬製內筒。內筒具有剛性時，可抑制輥之回轉偏轉。內 -60- 201033274 筒之厚度爲外筒之2至1 0倍時可得充分剛性。 內筒可另被覆矽、氟橡膠等樹脂製彈性材料。 流動冷卻流體用之空間構造可爲，可均勻控制輥表面 溫度之物，例如可往返交互流動於幅寬方向、及以螺旋狀 流動時，可將輥表面之溫度分布控制於較小溫度內。 冷卻流體並無特別限制，可配合所使用的溫度域使用 水或油。 彈性接觸輥之表面溫度TrO較佳爲，低於薄膜之玻璃 化溫度（Tg )。其高於Tg時，會使薄膜與輥之剝離性變 差。更佳爲Tg-5(TC至Tg。 本發明所使用的彈性接觸輥較佳爲，幅寬方向之中央 部的徑大於端部，即冕輥之形狀。 接觸輥一般係以加壓手段將其兩端部擠壓於薄膜上， 但此時接觸輥會彎曲，故會有愈往端部押壓力愈強之現象 。因此輥爲冕形狀時可高度均勻擠壓。 本發明所使用的彈性接觸輥之幅寬較佳爲，大於薄膜 幅寬時可使薄膜全體密合於冷卻輥。又，拉伸比較大時， 會因薄膜之兩端部出現縮幅現象而形成邊緣凸起（端部之 厚度較厚）。 此時爲了逃避邊緣凸起，可使金屬製外筒之幅寬窄於 薄膜幅寬。換言之即，縮小金屬製外筒之外徑可逃避邊緣 凸起部。 金屬製彈性接觸輥之具體例如，專利第3194904號、 專利第3422798號、特開2002-36332號及特開2002-3 6333 -61 - 201033274 號各公報所記載之成形用輥。 爲了防止彈性接觸輥彎曲，可於相對於冷卻輥之接觸 輥的反對側配置支撐輥。 又可配置清掃接觸輥之污垢用的裝置。所使用的清胃 裝置較佳如，利用輥將必要時浸透溶劑之不織布等構件擠 壓於輥表面之方法，或於液體中接觸輥之方法，或藉由電 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。 爲了使彈性接觸輥之表面溫度TrO更均勻，可使接觸 輥接觸調溫輥，或吹附控制溫度之空氣，或接觸液體等熱 媒體。 本發明又以彈性接觸輥擠壓時之接觸輥線壓爲lkg/cm 以上，15kg/cm以下，接觸輥側薄膜表面溫度Tt爲Tg&lt;Tt &lt; Tg+1 10°C 更佳。 彈性接觸輥線壓爲該範圍時，可得以液晶顯示裝置顯 示畫像時無明暗紋路及斑點狀不均勻之偏光板保護薄膜。 線壓係指，彈性接觸輥擠壓薄膜之力除以擠壓時薄膜 幅寬之値。使線壓爲上述範圍之方法並無特別限制，例如 可以氣缸或油壓缸等擠壓輥兩端。 又可藉由支撐輥擠壓彈性接觸輥而間接擠壓薄膜。 以彈性接觸輥擠壓薄膜時提高薄膜溫度可改良起因於 模頭紋之明暗紋路，但太高時會使斑點狀不均勻惡化。推 斷其因爲，使薄膜中之揮發成份揮發，而造成接觸輥擠壓 時無法均勻擠壓。太低時將無法改良起因於模頭紋之明暗 -62- 201033274 紋路。 使擠壓時之薄膜溫度爲上述範圍的方法並無特別限制 ，例如可爲’縮短模頭與冷卻輥之間的距離，以抑制模頭 與冷卻輥之間冷卻的方法，或以隔熱材包圍模頭與冷卻輥 之間進行保溫’或藉由熱風、紅外線加熱器或微波加熱器 等加溫之方法。 薄膜表面溫度及輥表面溫度可以非接觸式紅外溫度計 φ 測定。具體上可使用非接觸手提溫度計（ΙΤ2-80，吉恩斯 (股）製），由被測定物距離〇.5m處測定薄膜幅寬方向上 1 0處所。 彈性接觸輥側薄膜表面溫度Tt係指，搬運之薄膜離開 接觸輥之狀態下，由接觸輥側以非接觸式紅外溫度計測定 的薄膜表面溫度。 〈以Tg + 30°c以上Tg + 60°c以下之範圍加熱及延伸冷卻後 φ 之薄膜的步驟〉 一般製膜過程中形成熔融流延薄膜後，又以使用冷卻 輥盡快冷卻爲佳。 但本發明之特徵爲，使用冷卻輥冷卻後再度進行加熱 處理。即，冷卻步驟後設有以Tg + 30°C以上Tg + 60°C以下 之範圍再度加熱冷卻後之薄膜的步驟。加熱時間較佳爲5 至60秒，更佳爲10至30秒。 該再度加熱步驟較佳爲延伸步驟。又以延伸的同時再 度加熱之步驟爲佳。該延伸步驟較佳爲橫延伸步驟（薄膜 -63- 201033274 幅寬方向）。 本發明較佳爲，至少延伸1.01至5.0倍。更佳爲縱、 橫（幅寬方向）兩方向各自延伸1.1至3.0倍。 又可設有複數的以Tg + 30°C以上Tg + 60°C以下之範圍 加熱冷卻薄膜的步驟。此時各加熱步驟之間較佳爲，使用 保持於Tg以下之溫度的冷卻輥冷卻。 延伸方法較佳爲，使用已知的輥延伸機及拉幅器等。 本發明之光學薄膜可選用能得到所希望之相位延遲性 般的溫度及倍率。 延伸時較佳爲，於均勻控制幅寬方向之溫度分布下進 行。又以± 2 °C以內爲佳，更佳爲± 1 °C以內，特佳爲± 0.5 °C 以內。 〈延伸步驟之後步驟（包含捲取步驟）〉 將上述方法所得之光學薄膜中可塑劑等凝結物減少至 無混濁障礙般程度後，爲了調整相位延遲性及尺寸變化率 ，可收縮薄膜之長度方向及幅寬方向。 收縮長度方向之方法如，幅寬延伸時一時鬆夾使其往 長度方向弛緩、或緩緩縮減橫延伸機之相鄰夾子的間隔使 薄膜收縮的方法。 後者之方法一般係使用同時雙軸延伸機，縮減縱方向 之相鄰夾子的間隔時，例如可以縮放儀方式或線驅動方式 驅動夾子部分緩緩滑動縮減之方法進行。必要時可組合延 伸任意方向（斜方向）。同時將長度方向、幅寬方向收縮 -64- 201033274 0.5%至10%時可減少光學薄膜之尺寸變化率。 捲取前縱切裁斷製品幅寬之端部，爲了防止捲取時貼 附刮傷，可於兩端實施壓花加工（壓紋加工）。壓花加工 之方法可爲，藉由側面具有凹凸圖型之金屬環加熱及加壓 進行加工。 又，薄膜兩端部被夾子把持之部分一般爲，薄膜會變 形而無法作爲製品用需切除，再利用爲原材料。 φ 本發明可藉由減少薄膜之自由體積，減少相位延遲性 (R〇、Rt)之溫度變化率、尺寸變化率而爲佳。 爲了減少自由體積可有效利用，延伸步驟後設有以近 似薄膜之Tg的溫度進行熱處理之步驟。熱處理時間1秒以 上可得效果，且時間愈長效果愈佳，但1〇〇〇小時會達飽和 ，因此較佳爲Tg-20°C至Tg下1秒至1 000小時。 更佳爲Tg-15°c至Tg下1分鐘至1小時。又以將Tg以上 緩緩冷卻至Tg-20°c範圍的同時進行熱處理，可以比一定 φ 溫度下熱處理更短的時間得到效果而爲佳。 冷卻速度較佳爲-〇.l°C/秒至-20°c/秒，更佳爲-l°c/秒 至-l〇°C /秒。熱處理方法並無特別限定，可使用調溫後之 烤箱或輥群、熱風、紅外加熱器、微波加熱裝置等處理。 薄膜可於搬運的同時以枚葉或輥狀進行熱處理。搬運 的同時可使用輥群或拉幅器進行熱處理同時搬運。又以輥 狀熱處理時，可以近Tg之溫度將薄膜捲成輥狀後直接冷卻 使其徐冷。 圖1爲，本發明之光學薄膜的製造裝置全體構造之槪 -65- 201033274 略流程圖。圖1中光學薄膜之製造方法爲’混合丙烯酸樹 脂等之薄膜材料後，使用擠壓機1’由流延模頭4熔融擠壓 於第1冷卻輥5上，再藉由第1冷卻輥5及其依序外接之第2 冷卻輥7、第3冷卻輥8之合計3座冷卻輥冷卻固化，得薄膜 10。其次將利用剝離輥9剝離之薄膜10，再藉由延伸裝置 12把持薄膜10之兩端部延伸幅寬方向，其後藉由捲取裝置 16捲取。又爲了矯正平面性可設置將熔融薄膜挾壓於第1 冷卻輥5表面之接觸輥6。該接觸輥6爲表面具有彈性，因 此與第1冷卻輥5之間會形成夾持。 〈製造後光學薄膜之特性〉 本發明之光學薄膜適用爲，保護主成份爲聚乙烯醇之 起偏鏡用的偏光板保護薄膜，又藉由調整相位延遲性，亦 適用爲液晶顯示裝置之光學補償薄膜。 [偏光板] φ 以本發明之光學薄膜作爲偏光板用保護薄膜時，可以 一般方法製作偏光板。較佳爲本發明之光學薄膜的背面側 設有黏著層，再貼合於浸漬於碘溶液中延伸而得的起偏鏡 之至少一表面上。 另一表面也可使用本發明之光學薄膜，或另一偏光板 保護薄膜。例如較佳爲使用市售的纖維素酯薄膜（例如， 可尼卡 KC8UX 、 KC4UX 、 KC5UX 、 KC8UY 、 KC4UY 、 KC12UR、KC8UCR-3、KC8UCR-4、KC8UCR-5、KC8UE、 -66- 201033274 KC4UE、KC4FR-3、KC4FR-4 ' KC4HR-1、KC8UY-HA、 KC8UX-RHA，以上爲可尼卡（股）製）等。 偏光板之主要構成要素的起偏鏡係指，僅能通過一定 方向之偏波面的光線之元件，目前已知的代表性偏光膜爲 聚乙烯醇系偏光膜，其爲聚乙烯醇系薄膜被碘染色之物及 被雙色性染料染色之物。 所使用的起偏鏡較佳爲，由聚乙烯醇水溶液製膜後， φ 將其單軸延伸再染色，或染色後單軸延伸後，以硼化合物 進行耐久性處理後之物。 上述黏著層所使用的黏著劑較佳爲，黏著層之至少一 部分使用25 °C下之貯藏彈性率爲1.0x1 〇4至1.0x1 09Pa之範 圍的黏著劑，又適用塗佈黏著劑，貼合後可藉由各種化學 反應形成高分子量物或交聯構造之硬化型黏著劑。 具體例如，胺基甲酸乙酯系黏著劑、環氧系黏著劑、 水性高分子-異氰酸酯系黏著劑、熱硬化型丙烯酸黏著劑 φ 等之硬化型黏著劑、濕氣硬化胺基甲酸乙酯黏著劑、聚醚 甲基丙烯酸酯型、酯系甲基丙烯酸酯型、氧化型聚醚甲基 丙烯酸酯等之厭氣性黏著劑、氰基丙烯酸酯系之瞬間黏著 劑、丙烯酸酯及過氧化物系之雙液型瞬間黏著劑等。 上述黏著劑可爲單液型、或使用前混合雙液以上再使 用之型。 又上述黏著劑可爲以有機溶劑爲媒體之溶劑系、或媒 體主成份爲水之乳液型、膠體分散液型、水溶液型等之水 系、或無溶劑型。上述黏著劑液之濃度可由黏著後之膜厚 -67- 201033274 、塗佈方法、塗佈條件等適當決定，一般爲0.1至50質量 %。 [液晶顯示裝置] 將貼合本發明之光學薄膜的偏光板組裝於液晶顯示裝 置後，可得各種視認性優良之液晶顯示裝置，特佳爲大型 液晶顯示裝置或電子看板等屋外用途之液晶顯示裝置。本 發明之偏光板係介有前述黏著層等貼合於液晶單元上。 本發明之偏光板較佳爲反射型、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方式）等各種驅動方式之LCD 。特別是畫面爲30型以上，更佳爲30型至54型之大畫面的 顯示裝置中，畫面周邊部無脫白等，可長時間維持其效果 〇 又可得減少色斑、內光及凹凸不勻，既使長時間鑑賞 眼睛也不疲倦之效果。 【實施方式】 實施例 下面將舉實施例具體說明本發明，但本發明非限定於 此等。 實施例1 [製造丙烯酸樹脂] -68- 201033274 本發明所使用的丙烯酸樹脂爲下述市售之丙烯酸樹脂 〇 戴亞那BR83 (三菱人造絲（股）製） Mw 40000 戴亞那BR85(三菱人造絲（股）製） Mw 2800 00 亞克力粒VH-4 (三菱人造絲（股）製）Mw 140000 亞克力粒V (三菱人造絲（股）製） MW105000 φ 本發明所使用的丙烯酸樹脂之分子中MMA單位的比 率均爲90質量％以上99質量％以上。 [調製丙烯酸基粒子] 〈調製丙烯酸基粒子（C1) &gt; 將離子交換水38.2升、二辛基磺基琥珀酸鈉111.6 g投 入內容積60升之附回流冷卻器的反應器中，以25 Orpm回轉 數攪拌的同時，氮環境下升溫至75 t而形成事實上不受氧 φ 影響之狀態。投入APS 0.36g後攪拌5分鐘，再一起加入 MMA 1 657g、BA 21.6g及ALMA l_68g所形成的單體混合 物’驗出發熱峰後另保持2 0分鐘完成最內硬質層聚合。 其次投入APS 3.48g，攪拌5分鐘後以120分鐘連續加 A BA 8 1 05g &gt; PEGDA ( 200 ) 31.9g及 ALMA 264.Og所形成 的單體混合物，添加結束後保持12 0分鐘完成軟質層聚合 〇 接著投入APS 1.32g，攪拌5分鐘後以20分鐘連續加入 MMA 2106g、BA 201.6g所形成的單體混合物，添加結束 -69- 201033274 後保持2 0分鐘完成最外硬質層1聚合。 其後投入APS 1.32g，5分鐘後以20分鐘連續加入ΜΜΑ 3148g、BA 201_6g及n-OM lO.lg所形成的單體混合物，添 加結束後保持20分鐘。升溫至95 °C後保持60分鐘，完成最 外硬質層2聚合。 將所得的聚合物膠乳投入3質量％硫酸鈉溫水溶液中 ，鹽析、凝固後重覆脫水洗淨再乾燥，得3層構造之丙烯 酸基粒子（C1 )。藉由吸光度法求取之平均粒徑爲i〇〇nm 上述代號各自爲下述材料。 MMA :甲基甲基丙烯酸酯 MA :甲基丙烯酸酯 BA : η-丁基丙烯酸酯 ALMA:烯丙基甲基丙烯酸酯 PEGDA:聚乙二醇二丙烯酸酯（分子量200 ) n-OM : η -辛基硫醇 APS :過硫酸銨 [製作光學薄膜] 〈製作光學薄膜1 &gt; (熔融樹脂組成η 戴亞那BR85 (三菱人造絲（股）製） 94質量份 纖維素酯（纖維素乙酸酯丙酸酯醯基總取代度2.75 ’乙醯基取代度0.19’丙醯基取代度2.56，Mw = 200000 ) -70- 201033274 5質量份 1質量份 0.5質量份 0.075質量份 0.075質量份 上述調製之丙烯酸基粒子（Cl) Irganox 1010 (日本吉巴（股）製） GSY-P101 (堺化學工業（股）製） ADKSTAB 2112 ( ADEKA (股）製） 斯密來GS (住友化學（股）製） 0.2質量份Tmg). The index for judging the transparency of the optical film of the present invention is turbidity. In particular, it is used in a liquid crystal display device outside the house, and in order to obtain sufficient brightness and high contrast in a bright place, the turbidity needs to be 1 · 〇 % or less, more preferably 0.5% or less. The optical film of the present invention containing the acrylic resin (A) and the cellulose ester resin (B) can have high transparency, but when acrylic-based particles are used for the purpose of improving other physical properties, the resin (acrylic resin) is reduced. And the difference in refractive index between the cellulose ester resin (B) and the acrylic-based particles (C) prevents the turbidity from rising. Further, since the surface roughness also affects the turbidity of the surface turbidity, the surface roughness of the film contact portion at the time of film formation can be effectively reduced by suppressing the particle diameter and the addition amount of the acrylic-based particles (C) within the above range. Further, the hygroscopicity of the optical film of the present invention can be evaluated with respect to the dimensional change of the humidity. The following method can be used to evaluate the dimensional change with respect to the change in humidity. After marking (cross) at two places in the casting direction of the obtained optical film, 6 (TC, 90% RH was treated for 1 000 hours, and the distance between the pre-treatment and the post-treatment mark (cross) was measured using an optical microscope, and then obtained. Dimensional change rate (%). Dimensional change rate (%) is as shown in the following formula: -50- 201033274 Dimensional change rate (%) = [(al-a2)/al ]xl 00 al: Distance before heat treatment a2: Heat treatment When the optical film is used as a protective film for a polarizing plate of a liquid crystal display device, the size of the optical film changes due to moisture absorption, and the optical film is changed in speckle and phase difference, so that the problem of contrast and occurrence of color unevenness is caused. In particular, the above problem is more pronounced as a polarizing plate protective film for φ outdoor liquid crystal display devices. However, when the dimensional change ratio (%) under the above conditions is less than 0.5%, it can be evaluated as having sufficiently low hygroscopicity. Further, the optical film is preferably less than 0.3%. Further, the optical film of the present invention preferably has a defect of a diameter of 5 /2 m or more in the in-plane of the film of 1/10 cm square or less, more preferably 0.5 / 10 cm below the square, especially good for 0.1 /10cm square. The diameter of the defect means that the diameter is the diameter of the circle. When it is not round φ, the maximum diameter (the diameter of the circumscribed circle) can be determined by using the microscope to observe the range of defects. The shortcomings in the range of shortcomings are bubbles and foreign matter, which refers to the shadow size when the differential light interferes with the transmitted light of the microscope. The disadvantage is that when the surface shape of the scratch or the scratch on the roller changes, the microscope can be differentially interfered. The size of the reflected light is confirmed by the shortcomings. In addition, when the size of the defect is not clear when the reflected light is observed, aluminum or uranium may be vapor-deposited on the surface and observed. In order to obtain good productivity, the unit represented by the frequency of the defect is excellent. 201033274 Good film can effectively use the high-precision filtration polymer solution before casting, improve the cleanliness around the casting machine, or set the drying conditions after casting to more effectively suppress the foaming and drying method. When the number is more than one/l〇cm square, for example, when the processing is performed in the subsequent step, tension is applied to the film, and the film is broken by the defect. In addition, when the diameter of the defect is 5 μm or more, the brightness of the optical member can be visually confirmed by observation by a polarizing plate, etc. Further, the present invention is measured in accordance with JIS-K7 1 27-1999. Preferably, the optical film has a breaking elongation of at least one direction of 10% or more, more preferably 20% or more. The upper limit of the breaking elongation is not particularly limited, and may be 250% in reality. The thickness of the optical film of the present invention is preferably 20 μm or more, more preferably 3 Ο μ m or more. The upper limit of the thickness is not particularly limited, but From the viewpoints of coatability and the like, the upper limit is 250/zm. Further, the film thickness can be appropriately selected depending on the application. The optical film of the present invention preferably has a total light transmittance of 90% or more, more preferably 93% or more. The upper limit of reality is 99%. In order to achieve the excellent transparency represented by the total light transmittance. It is effective to use a method that does not introduce an additive or a copolymerized component that absorbs visible light, and removes foreign matter in the polymer with high precision, or reduces the diffusion and absorption of light inside the film. Moreover, the surface roughness of the film contact portion (cooling roll, calender roll, drum, conveyor belt, conveyance roll, etc.) at the time of film formation can be effectively reduced to reduce the surface roughness of the film surface, or the acrylic resin can be reduced. The refractive index reduces the diffusion and reflection of light on the surface of the film. When the optical film of the present invention satisfies the above physical properties, it is particularly suitable for use as a polarizing plate protective film for a liquid crystal display device of a large liquid crystal display device and an outdoor use. The physical properties may be such that the optical film is characterized by containing the acrylic resin (A) and the cellulose ester resin (B) in a mass ratio of 95:5 to 30:70, and the weight average molecular weight Mw of the acrylic resin (A) is Above 80,000, the total degree of substitution (T) of the thiol group of the cellulose ester resin (B) is 2.00 to 3.00, the degree of substitution of the fluorenyl group having 3 to 7 carbon atoms is 1.2 to 3.0, and the weight average molecular weight (Mw) is More than 75,000 optical films. <Film Formation of Optical Film> Next, a film formation method of an optical film will be exemplified, but the present invention is not limited thereto. The film forming method of the optical film which can be used in the present invention is a manufacturing method such as a blow molding method, a T-die method, a calendering method, a cutting method, a casting method, an emulsification method, or a hot pressing method, but suppresses coloring and suppresses foreign matter defects. The viewpoint of suppressing optical defects such as mold marks and the like is preferably performed by melt casting using a casting method. The present invention is particularly preferably a melt casting film forming method using a contact roll. In the present invention, the "melt film formation" is a method in which a composition containing an additive such as an acrylic resin, a cellulose ester resin, and a plasticizer is heated and melted to have a fluidity temperature, and the fluidity contains a cellulose ester resin. The molten stream of an acrylic resin or the like is extended to form a film definition. -53- 201033274 In more detail, the heating and melting forming method can be classified into a melt extrusion molding method, a pressure molding method, a blow molding method, an injection molding method, a blow molding method, an extension molding method, and the like. Among them, an optical film having excellent mechanical strength and surface precision is obtained, and the melt extrusion method is optimal. When the optical film of the present invention is formed by the melt casting film forming method, the solvent is not substantially used in the film forming step. Therefore, the amount of residual organic solvent contained in the optical film taken up after film formation can be as stable as 0.01% by mass. Therefore, it is possible to provide an optical film which has a more stable planarity and optical characteristics than before. In particular, an optical film having stable planarity and optical characteristics can be provided even when the roll length is 100 m or more. Further, since the amount of residual organic solvent (%) of the optical film produced by the solution casting method is difficult to reach 〇1% by mass or less, a long drying step is required, so that the cost is high. The amount of residual solvent (% by mass) in the present application is the mass of the reel (film) of a certain size before drying, and the quality of the reel (film) after drying the aforementioned A for 3 hours at 110 °C. When it is B, it is determined by ((AB ) /B ) xl 00 = residual solvent amount (% by mass). <<Film Making Step>> The film forming step of the film will be described below. <Step of Producing Molten Particles of Acrylic Resin and Cellulose Ester Resin and Additives> The plurality of raw materials used in melt extrusion are generally preferably preliminarily mixed with 201033274. The granulation may be carried out by a known method, for example, using an feeder to supply an acrylic resin, a cellulose ester resin, an acrylic resin, a plasticizer, and other additives to an extruder, and kneading by a uniaxial or biaxial extruder, followed by extrusion. The plate is extruded into a monofilament and then water cooled or air cooled, and then cut. In order to prevent the decomposition of raw materials, the drying of raw materials is emphasized before extrusion. In particular, since the cellulose ester is hygroscopic, it is preferably used in a desiccant hot air drying φ machine or a vacuum dryer at 70 to 14 (TC drying for 3 hours or more, so that the water content is 200 ppm or less, more preferably 100 ppm or less. Mixing before feeding to the extruder, or feeding with the respective feeders. In order to uniformly mix a small amount of additives such as antioxidants, it is preferable to mix them beforehand. When mixing the antioxidants, they may be mixed with the solid phase and, if necessary, The antioxidant is dissolved in a solvent, and further mixed with a resin such as an acrylic resin, or mixed by spraying. φ is preferably dried and mixed at the same time using a vacuum Nota mixer, etc. Further, the contact of the feeder and the die is in contact with air. In the case of dehumidifying air or N2 gas after dehumidification, it is preferably carried out to prevent moisture absorption when the hopper of the extruder is kept warm. Further, the obtained particles may be coated with a matting agent or UV absorption. The agent is added to the extruder at the time of film formation. The extruder is preferably used to suppress the shearing force without deteriorating the resin (reducing molecular weight, coloring, gel formation, etc.) The granulation is processed at a low temperature. For example, when a biaxial extruder is used, it is preferable to use a deep groove type screw to rotate in the same direction as -55-201033274. The kneading uniformity is preferably a bite type. Sexuality, but it is necessary to pay attention to cutting off the heat. Even if the kneading disc is not used, it can be fully mixed. If necessary, it can be suctioned according to the vent hole. However, it does not volatilize at low temperature, so it is not necessary to use the pores. The color is preferably such that the b* 黄色 of the yellow indicator is -5 to 10, more preferably -1 to 8, and particularly preferably -1 to 5. The b* 値 is a spectrophotometer CM-3 700d (Kenica) The system is made of D65 (color temperature 65 04K) and measured at a viewing angle of 10°. The film obtained by the above-mentioned particles is used for film formation. Of course, the raw material can be directly fed through the feeder without granulation. The powder is supplied to the extruder to directly form a film of the film. <Step of extruding a melt of a resin mixture such as an acrylic resin from an extrusion plate> Using a uniaxial or biaxial extruder, the melting temperature Tm at the time of extrusion is © 200 to 300 ° C, and using a movable disc filter After removing the foreign matter, the polymer dried by dehumidifying hot air and vacuum or under reduced pressure is cast into a film shape by a T-shaped mold. When it is introduced into the extruder by the supply hopper, it is preferably under vacuum, under reduced pressure or in an inert gas atmosphere. It is carried out to prevent oxidative decomposition, etc. Further, Tm is the temperature at the exit portion of the die of the extruder. The extrusion flow rate is preferably carried out by introducing a gear pump or the like. The filter for removing foreign matter is preferably a stainless steel fiber sintered. -56- 201033274 The stainless steel fiber sintered filter is an integrated material that compresses the sintered contact in a state where the stainless steel fiber body is complexly complexed. Therefore, the density can be changed by the thickness and compression amount of the fiber to adjust the filtration precision. It is preferably a multilayer body in which a plurality of coarse and fine filtration precisions are continuously repeated. It is also preferable to increase the structure of the filtration precision in order, and to repeat the coarse and fine method of the filtration precision, and to extend the filtration life of the filter and to improve the accuracy of the foreign matter and the gel. Φ When the die is attached to scratches or foreign matter, streaky defects may occur. Such defects are also called pattern lines. In order to reduce surface defects such as mold lines, the piping from the extruder to the die is preferably such that the structure of the resin retention portion can be minimized. It is better to use the inside of the die and the scratch-free parts of the lips as much as possible. It is preferable that the inner surface of the melted resin such as the extruder and the die is used to reduce surface roughness or a material having a low surface energy, and it is preferable to apply a surface on which the molten resin is hard to adhere. Specifically, for example, electroplated hard chrome or ceramic spray is honed to a surface roughness of 0.2 S or less. Additives such as φ plasticizer can be pre-mixed with resin or kneaded on the extruder. It is preferred to use a mixing device such as a static mixer for the purpose of adding and adding. <Step of casting a film while extruding a melt extruded from a die between a cooling roll and an elastic contact roll> This step is a film form extruded by a die by a cooling roll and an elastic contact roll The melt is formed to form a certain film shape and film thickness. [Cooling Roller] -57- 201033274 The chill roll of the present invention is not particularly limited, and the high-rigidity metal roll may be provided with a heat medium or a cold medium-like roll having an internal flow controllable temperature, but the size is not limited and may be The size of the melt-extruded film can be sufficiently cooled, and the diameter of the cooling roll is generally 100 mm to lm. The surface of the cooling roll can be made of carbon steel or stainless steel: aluminum or titanium. Further, in order to improve the surface hardness and to improve the releasability to the resin, it is preferably subjected to surface treatment such as plating of hard chrome, electro-rhenium nickel, electroplating of amorphous chromium, or spray ceramic. The surface roughness Ra of the surface of the chill roll is preferably O.lym or less, more preferably 0.05 / zm or less. When the surface of the roll was smooth, the surface of the resulting film was also smooth. Of course, it is preferable to resurface the surface after surface processing to obtain the above surface roughness. The chill roll of the present invention has at least one, and preferably has two or more. The surface temperature Tr of the cooling roll was set to Tg-50S TrS Tg only for one time. The surface temperatures of the first cooling roll and the second cooling roll when two or more are set are Tg-50彡 TrlSTg and Tg-50STr2STg. The Tg means a glass transition temperature (°c) of a mixture of an acrylic resin and a cellulose ester resin. The glass transition temperature Tg was measured by using a differential scanning calorimeter DSC 220 manufactured by Seiko Instruments Inc. in accordance with Jis K 7121. After setting the sample l〇mg, raise the room temperature to 250 °C at 20 °C / min for 10 minutes (1st scan) at a flow rate of 50ml/min, and then cool down at 20 °C /min. The temperature was maintained at 30 ° C for 10 minutes (2nd scan), and then increased to 250 ° C (3 rd scan) at 20 ° C / min to obtain a DSC curve. 201033274 The glass transition temperature was then determined from the resulting 3rd scan DSC curve. [elastic contact roller] The elastic contact roller used in the present invention may be an open contact type: JP-A-2003-22424, JP-A-08-224772, JP-A- 07-100960, JP-A No. 10-272676, WO97-028950, and JP-A The rubber roller of the surface-coated thin film metal sleeve described in the publication of the specification of JP-A-2005-172940, JP-A-2005-172940, and JP-A-2005-280217, which is preferably the following elastic contact roller. . Compared with other thermoplastic resins, the melt containing cellulose ester has a high melt viscosity and is not easily stretched. Therefore, when the stretching is relatively large, the conveying direction is liable to cause a variation in the film thickness, and the film is easily broken when stretched in the stretching step. Although the stretching ratio is 7 to 8 as much as possible, in the present invention, after the melt containing the cellulose ester is extruded from the die in the form of a film, the stretching ratio is 1 〇 or more and 30 φ by the elastic contact roller. The film obtained below was carried while being pressed against a cooling roll. The draw ratio is the enthalpy of the lip gap of the die divided by the average film thickness of the film cured on the chill roll. When the stretching ratio is in this range, the polarizing plate protective film having good printability without unevenness of light and dark lines and speckles when the image is displayed by the liquid crystal display device can be obtained. The draw ratio can be adjusted by the lip gap of the die and the pull speed of the chill roll. The lip gap of the die is preferably 900 # m or more, more preferably 1 to 2 mm. Too large or too small can not improve speckle unevenness. The elastic contact roller used in the present invention is formed of a double structure of a metal outer cylinder and an inner cylinder -59-201033274, and has a space in which a cooling fluid can flow. In addition, the outer cylinder of the metal can be elasticized to more precisely control the temperature of the surface of the contact roller, and the effect of obtaining the distance of the extruded film in the longitudinal direction can be obtained by using the moderate elastic deformation property, so that the liquid crystal display device displays the image. The effect of unclear dark lines and uneven spots can be obtained. The thickness of the metal outer cylinder is preferably 0.003 $ (thickness of the metal outer cylinder) / (contact roller radius) S 〇. 〇 3 to obtain moderate elasticity. When the radius of the contact roller is too large, even if the thickness of the metal outer cylinder is thick, it can cause moderate bending. The diameter of the elastic contact roller is preferably from 100 to 600 mm. When the thickness of the metal outer cylinder is too thin, the strength will be insufficient and damage may occur. If it is too thick, the quality of the roll will be too heavy, and there will be a turning spot. Therefore, the thickness of the metal outer cylinder is preferably 0.1 to 5 mm. The surface roughness of the metal outer cylinder surface is preferably such that the arithmetic mean roughness Ra is 0.1; zm or less, more preferably 0.05/zm or less. When the surface of the roll is smooth, the surface of the resulting film is also smooth. @ The material of the metal outer tube is required to be smooth, moderately elastic and durable. Carbon steel, stainless steel, titanium, nickel produced by electroplating, or the like is preferably used. Further, in order to improve the hardness of the surface and to improve the releasability to the resin, it is preferred to perform surface treatment such as plating hard chrome, electroplating nickel, plating amorphous chromium, or molten ceramic. Further, the surface roughness is preferably obtained by honing the surface after surface processing. The inner cylinder is preferably a lightweight and rigid metal inner cylinder such as carbon steel, stainless steel, aluminum or titanium. When the inner cylinder is rigid, the rotational deflection of the roller can be suppressed. -60- 201033274 The thickness of the cylinder is 2 to 10 times the outer cylinder and sufficient rigidity is obtained. The inner cylinder may be additionally coated with a resin elastic material such as enamel or fluororubber. The space structure for the flow cooling fluid may be such that the temperature of the surface of the roll can be uniformly controlled, for example, the flow rate of the roll surface can be controlled to a small temperature by alternately flowing in the width direction and in a spiral flow. The cooling fluid is not particularly limited, and water or oil can be used in conjunction with the temperature range used. The surface temperature TrO of the elastic contact roller is preferably lower than the glass transition temperature (Tg) of the film. When it is higher than Tg, the peeling property of the film and the roll is deteriorated. More preferably, it is Tg-5 (TC to Tg. The elastic contact roller used in the present invention preferably has a diameter in the central portion in the width direction which is larger than the end portion, that is, the shape of the roll. The contact roller is generally pressurized. The two ends are pressed against the film, but at this time, the contact roller is bent, so that the pressure is increased toward the end portion. Therefore, the roller can be highly uniformly extruded when it is in the shape of a crucible. The elasticity used in the present invention. Preferably, the width of the contact roller is larger than the width of the film, so that the entire film can be closely adhered to the cooling roller. Further, when the stretching is relatively large, the edge protrusion is formed due to the shrinkage of the both ends of the film. The thickness of the portion is thicker. At this time, in order to escape the edge protrusion, the width of the metal outer cylinder can be narrowed to the width of the film. In other words, the outer diameter of the metal outer cylinder can be reduced to escape the edge protrusion. The roll for forming described in each of the publications of Japanese Patent No. 3,194, 904, No. 3,422, 798, JP-A-2002-36332, and JP-A-2002-3 6333-61-201033274, in order to prevent the elastic contact roller from being bent, Available in contact rolls with respect to the chill roll The supporting roller is disposed on the opposite side. The device for cleaning the dirt of the contact roller may be disposed. The gastrointestinal device to be used is preferably a method in which a member such as a non-woven fabric impregnated with a solvent by a roller is pressed against the surface of the roller by a roller, or a liquid. a method of contacting a roll in the middle, or a method of volatilizing a scale on a surface of a roll by plasma discharge such as corona discharge or glow discharge, etc. In order to make the surface temperature TrO of the elastic contact roll more uniform, the contact roll can be brought into contact with the temperature control roll, Or blowing the air to control the temperature, or contacting the heat medium such as a liquid. The contact roller has a linear pressure of lkg/cm or more and 15kg/cm or less, and the surface temperature Tt of the contact roller side is Tg&lt; Tt &lt; Tg+1 10 ° C. When the linear contact pressure of the elastic contact roller is within this range, the liquid crystal display device can display a portrait without a bright and dark pattern and a speckled uneven polarizing plate protective film. The force of the elastic contact roller for squeezing the film is divided by the width of the film during extrusion. The method for setting the line pressure to the above range is not particularly limited, and for example, the pressure roller or the hydraulic cylinder may be used to press both ends of the roller. support The roller presses the elastic contact roller to indirectly press the film. Increasing the film temperature when the film is pressed by the elastic contact roller can improve the bright and dark texture caused by the die pattern, but when it is too high, the speckle unevenness is deteriorated. The volatilization component in the film is volatilized, so that the contact roller cannot be uniformly extruded when pressed. When it is too low, the film will be unable to be improved due to the darkness of the die pattern-62-201033274. The film temperature during extrusion is in the above range. The method is not particularly limited, and may be, for example, 'shortening the distance between the die and the cooling roll to suppress the cooling between the die and the cooling roll, or by insulating the heat between the die and the cooling roll' Or heating by hot air, infrared heater or microwave heater. The surface temperature of the film and the surface temperature of the roll can be measured by a non-contact infrared thermometer φ. Specifically, a non-contact portable thermometer (ΙΤ2-80, manufactured by Gines) can be used, and 10 points in the width direction of the film are measured from the object to be measured at a distance of 55 m. The surface temperature Tt of the elastic contact roller side film refers to the surface temperature of the film measured by a non-contact infrared thermometer on the side of the contact roller in a state where the conveyed film leaves the contact roller. <Step of heating and extending the film of φ after cooling in a range of Tg + 30 ° C or more and Tg + 60 ° C or less > After forming a molten cast film in a general film forming process, it is preferred to use a cooling roll to cool it as quickly as possible. However, the present invention is characterized in that heat treatment is performed after cooling using a cooling roll. That is, after the cooling step, a step of heating and cooling the cooled film in a range of Tg + 30 ° C or more and Tg + 60 ° C or less is provided. The heating time is preferably from 5 to 60 seconds, more preferably from 10 to 30 seconds. This reheating step is preferably an extension step. It is preferable to carry out the step of heating again while extending. The stretching step is preferably a lateral stretching step (film -63 - 201033274 width direction). Preferably, the invention extends at least 1.01 to 5.0 times. More preferably, the longitudinal and transverse directions (width direction) extend 1.1 to 3.0 times each. Further, a plurality of steps of heating and cooling the film in a range of Tg + 30 ° C or more and Tg + 60 ° C or less may be provided. At this time, it is preferred to cool each of the heating steps by using a cooling roll maintained at a temperature lower than Tg. The stretching method is preferably a known roll stretching machine, a tenter, or the like. The optical film of the present invention can be selected to have a desired temperature and magnification of phase retardation. Preferably, the stretching is carried out under uniform temperature distribution in the width direction. It is preferably within ± 2 ° C, more preferably within ± 1 ° C, and particularly preferably within ± 0.5 ° C. <Step after the stretching step (including the winding step)> After reducing the coagulum such as the plasticizer in the optical film obtained by the above method to the extent that there is no turbidity, the length direction of the film can be contracted in order to adjust the phase retardation and the dimensional change rate. And the width direction. The method of contracting the length direction is, for example, a method in which the width is extended to loosen the lengthwise direction, or the interval between adjacent clips of the transverse stretching machine is gradually reduced to shrink the film. The latter method generally uses a simultaneous biaxial stretching machine to reduce the interval between adjacent clips in the longitudinal direction, for example, by a scaler method or a line driving method to drive the clip portion to gradually slide and reduce. If necessary, you can combine and extend in any direction (oblique direction). At the same time, shrinking the length direction and the width direction -64-201033274 0.5% to 10% can reduce the dimensional change rate of the optical film. The end of the width of the product is cut longitudinally before winding, and embossing (embossing) can be performed at both ends in order to prevent scratching during winding. The embossing process may be carried out by heating and pressurizing a metal ring having a concave-convex pattern on the side. Further, the portion where the both end portions of the film are held by the clip is generally such that the film is deformed and cannot be cut off as a product, and reused as a raw material. φ In the present invention, it is preferable to reduce the free volume of the film and to reduce the temperature change rate and the dimensional change rate of the phase retardation (R〇, Rt). In order to reduce the free volume, it is effective to use, and after the extending step, a step of heat-treating at a temperature similar to the Tg of the film is provided. The heat treatment time is more than 1 second, and the longer the time is, the better the effect is, but the saturation is 1 hour, so it is preferably 1 second to 1 000 hours from Tg-20 ° C to Tg. More preferably, it is 1 minute to 1 hour under Tg-15 °c to Tg. Further, heat treatment is carried out while gradually cooling the Tg or more to a temperature of Tg - 20 ° C, and it is preferable to obtain an effect in a shorter period of time than a heat treatment at a constant φ temperature. The cooling rate is preferably -1 ° C / sec to -20 ° c / sec, more preferably - l ° c / sec to - l 〇 ° C / sec. The heat treatment method is not particularly limited, and treatment with a temperature-controlled oven or a roll group, hot air, an infrared heater, a microwave heating device, or the like can be used. The film can be heat-treated in the form of a leaf or a roll while being conveyed. At the same time of handling, the roller group or the tenter can be used for heat treatment and simultaneous handling. Further, in the case of a roll heat treatment, the film can be wound into a roll at a temperature close to Tg, and then directly cooled to be quenched. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing the overall construction of an apparatus for producing an optical film of the present invention - 65 - 201033274. The method for producing an optical film in Fig. 1 is 'mixing a film material such as an acrylic resin, and then extruding it onto the first cooling roll 5 by a casting die 4 using an extruder 1', and then passing it through the first cooling roll 5 A total of three cooling rolls of the second cooling roll 7 and the third cooling roll 8 which are externally connected to each other are cooled and solidified to obtain a film 10. Next, the film 10 peeled off by the peeling roller 9 is used, and both ends of the film 10 are stretched in the width direction by the stretching device 12, and then taken up by the winding device 16. Further, in order to correct the planarity, a contact roll 6 for pressing the molten film on the surface of the first cooling roll 5 may be provided. Since the contact roller 6 has elasticity on the surface, a sandwich is formed between the contact roller 6 and the first cooling roller 5. <Characteristics of Optical Film After Manufacturing> The optical film of the present invention is suitable for protecting a polarizing plate protective film for a polarizer having a main component of polyvinyl alcohol, and is also suitable for optical of a liquid crystal display device by adjusting phase retardation. Compensation film. [Polarizing Plate] φ When the optical film of the present invention is used as a protective film for a polarizing plate, a polarizing plate can be produced by a general method. Preferably, the optical film of the present invention is provided with an adhesive layer on the back side thereof, and is attached to at least one surface of a polarizer which is immersed in an iodine solution. The other surface may also use the optical film of the present invention or another polarizing plate to protect the film. For example, it is preferred to use a commercially available cellulose ester film (for example, Konica KC8UX, KC4UX, KC5UX, KC8UY, KC4UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC8UE, -66-201033274 KC4UE, KC4FR-3, KC4FR-4 'KC4HR-1, KC8UY-HA, KC8UX-RHA, the above is the Nika (share) system, etc.). The polarizer of the main constituent elements of the polarizing plate refers to a component that can pass only the light of the deflecting surface in a certain direction. The currently known representative polarizing film is a polyvinyl alcohol-based polarizing film, which is a polyvinyl alcohol-based film. Iodine-dyed material and dyed by a dichroic dye. The polarizer to be used is preferably a film obtained by laminating a polyvinyl alcohol aqueous solution, and then uniaxially stretching and dyeing it, or uniaxially stretching after dyeing, and then performing durability treatment with a boron compound. Preferably, the adhesive used in the adhesive layer is such that at least a part of the adhesive layer uses an adhesive having a storage modulus at a temperature of from 1.0 x 1 〇 4 to 1.0 x 1 09 Pa at 25 ° C, and is also suitable for applying an adhesive. A hardening type adhesive having a high molecular weight substance or a crosslinked structure can be formed by various chemical reactions. Specifically, for example, a urethane-based adhesive, an epoxy-based adhesive, a water-based polymer-isocyanate-based adhesive, a thermosetting acrylic adhesive φ, a hardening type adhesive, and a moisture-curing urethane adhesive Anionic adhesive such as polyether methacrylate type, ester type methacrylate type, oxidized polyether methacrylate, cyanoacrylate type instant adhesive, acrylate and peroxide It is a two-liquid type instant adhesive. The above adhesive may be of a single liquid type or a mixture of two or more liquids before use. Further, the above-mentioned adhesive may be a solvent system using an organic solvent as a medium, or a water-based emulsion type, a colloidal dispersion type, an aqueous solution type or the like, or a solventless type in which the main component of the medium is water. The concentration of the above-mentioned adhesive liquid can be appropriately determined by the film thickness after adhesion -67 to 201033274, the coating method, the coating conditions, etc., and is usually 0.1 to 50% by mass. [Liquid crystal display device] When a polarizing plate to which the optical film of the present invention is bonded is assembled in a liquid crystal display device, various liquid crystal display devices having excellent visibility can be obtained, and liquid crystal displays for outdoor use such as a large liquid crystal display device or an electronic signboard are particularly preferable. Device. The polarizing plate of the present invention is bonded to the liquid crystal cell via the adhesive layer or the like. The polarizing plate of the present invention is preferably a reflective type, a transmissive type, a transflective LCD or a TN type, an STN type, an OCB type, a HAN type, a VA type (PVA type, MVA type), or an IPS type (including an FFS method). Drive mode LCD. In particular, in a display device with a screen size of 30 or more, and more preferably a model of 30 to 54 type, there is no whitening in the peripheral portion of the screen, and the effect can be maintained for a long time, and the stain, the internal light, and the unevenness can be reduced. Uneven, not only tired of appreciating the eyes for a long time. [Embodiment] Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited thereto. Example 1 [Production of acrylic resin] -68- 201033274 The acrylic resin used in the present invention is the following commercially available acrylic resin 〇Diana BR83 (manufactured by Mitsubishi Rayon Co., Ltd.) Mw 40000 Diana BR85 (Mitsubishi artificial) Mw 2800 00 Acrylic Particles VH-4 (Mitsubishi Rayon) Mw 140000 Acrylic Particles V (Mitsubishi Rayon) MW105000 φ MMA in the molecule of acrylic resin used in the present invention The ratio of the units is 90% by mass or more and 99% by mass or more. [Preparation of acrylic-based particles] <Preparation of acrylic-based particles (C1) &gt; 38.2 liters of ion-exchanged water and 111.6 g of sodium dioctylsulfosuccinate were placed in a reactor of a reflux condenser equipped with an internal volume of 60 liters, to 25 While the Orpm revolution is stirred, the temperature is raised to 75 t in a nitrogen atmosphere to form a state which is virtually unaffected by the oxygen φ. After the APS was charged at 0.36 g, the mixture was stirred for 5 minutes, and a monomer mixture of MMA 1 657 g, BA 21.6 g and ALMA l_68 g was added together. After the hot peak was examined, the innermost hard layer polymerization was completed for another 20 minutes. Next, APS 3.48g was charged, and after stirring for 5 minutes, the monomer mixture formed by A BA 8 1 05g &gt; PEGDA (200) 31.9g and ALMA 264.Og was continuously added for 120 minutes, and the soft layer was completed after 12 minutes of completion. The polymerized ruthenium was then charged with 1.32 g of APS, and after stirring for 5 minutes, a monomer mixture of 2106 g of MMA and 201.6 g of BA was continuously added over 20 minutes, and the outermost hard layer 1 was polymerized after completion of -69-201033274 and kept for 20 minutes. Thereafter, 1.32 g of APS was charged, and after 5 minutes, a monomer mixture of 148 3148 g, BA 201_6 g and n-OM 10·g was continuously added over 20 minutes, and the addition was continued for 20 minutes. After heating to 95 ° C for 60 minutes, the polymerization of the outer hard layer 2 was completed. The obtained polymer latex was poured into a 3 mass% sodium sulfate warm aqueous solution, salted out, solidified, and then repeatedly subjected to dehydration washing and drying to obtain a three-layer structure of acrylic acid-based particles (C1). The average particle diameter determined by the absorbance method is i 〇〇 nm. Each of the above codes is the following material. MMA: methyl methacrylate MA: methacrylate BA: η-butyl acrylate ALMA: allyl methacrylate PEGDA: polyethylene glycol diacrylate (molecular weight 200) n-OM : η - Octyl mercaptan APS: ammonium persulfate [production of optical film] <production of optical film 1 &gt; (molten resin composition η Diana BR85 (manufactured by Mitsubishi Rayon)) 94 parts by mass of cellulose ester (cellulose acetate Ester propionate thiol group total degree of substitution 2.75 'Ethyl thiol substitution degree 0.19' propyl hydrazyl substitution degree 2.56, Mw = 200000) -70-201033274 5 parts by mass 1 part by mass 0.5 parts by mass 0.075 parts by mass 0.075 parts by mass of the above preparation Acrylic-based particles (Cl) Irganox 1010 (manufactured by Jiba, Japan) GSY-P101 (manufactured by Daisei Chemical Co., Ltd.) ADKSTAB 2112 (made by ADEKA Co., Ltd.) Smithias GS (Sumitomo Chemical Co., Ltd.) 0.2 parts by mass

紫外線吸收劑Ti 928 (日本吉巴（股）製）1.5質量份 消光劑西候斯KEP-30日本觸媒（股）製）（平均 粒徑0.3 /z m二氧化矽微粒子） 0.1質量份 (光學薄膜之熔融製膜） 70 °C，3小時減壓下乾燥上述纖維素醋及丙烯酸樹脂 後冷卻至室溫’再混合消光劑以外之各添加劑。 使用圖1所示具有彈性接觸輥的製造裝置將上述混合 物製膜。氮環境下以240°C熔融後，由流延模頭擠壓於第1 φ 冷卻輥上’再利用第1冷卻輥與接觸輥之間挾壓薄膜而成 形。又由擠壓機1中間部之料斗開口部加入0.1質量份之滑 動劑用的消光劑。 調整熱螺栓使流延模頭之間隙幅寬爲，薄膜幅寬方向 端部起30mm以內爲0.5mm，其他場所爲lmm。所使用之接 觸輥爲，接觸輥內部流動80°C之冷卻用水。 將由流延模頭所擠出之樹脂接觸第1冷卻輥之位置起 ’至第1冷卻輥與接觸輥挾持之第1冷卻輥回轉方向上流端 的位置，沿著第1冷卻輥圓周之長度L設定爲20mm。其後 -71 - 201033274 由第1冷卻輥離間接觸輥’測定第1冷卻輥與接觸輥之挾持 挾壓前的溶融部之溫度T。第1冷卻輥與接觸輥之挾持挾壓 前的熔融部之溫度τ爲，使用溫度計（安立計器股份公司 製ΗA-200E )測定較挾持上流端更往1mm之上流側位置而 得。結果測得之溫度T爲1 4 1 °C。接觸輥對第1冷卻輥之線 壓爲 1 4.7N/cm。 其次導入拉幅器，160°C下將幅寬方向延伸爲1·3倍後 ，緩和幅寬方向3%的同時冷卻至30 °C，再放開夾子，裁 落夾子把持部分後，對薄膜兩端實施寬、高5 // m之 壓紋加工，再以捲取張力22 ON/m、斜度40%之條件藉由 捲芯捲取。捲芯大小爲內徑152mm、外徑165至180mm、 長度155 0mm。該捲芯母材爲，玻璃纖維、碳纖維含浸環 氧樹脂之預浸樹脂。捲芯表面塗覆環氧導電性樹脂後硏磨 表面，使表面粗縫度Ra爲0·3μιη。製作膜厚80/zm、捲長 3 500m之光學薄膜1〇1。 〈製作光學薄膜2至17〉 除了製作上述光學薄膜1時，丙烯酸樹脂（A)、纖 維素酯樹脂（B )之組成比及添加劑之種類、添加率如表1 所記載’丙烯酸樹脂（A)之種類如表2所記載，丙烯酸 基粒子（C )如表3所記載外，同樣製作光學薄膜2至1 7。 〈製作偏光板〉 使延伸後之聚乙烯醇薄膜吸附碘製作偏光膜，再使用 -72- 201033274 聚乙烯醇系接著劑將實施鹼化處理後之前述光學薄膜1貼 附於偏光膜單側上。對市售之纖維素乙酸酯薄膜（可尼卡 KC 8 UX)進行鹼化處理後，使用聚乙烯醇系接著劑貼附於 偏光膜之相反側上。此時偏光膜之透過軸與樣品之遲相軸 係以平行方式配置。偏光膜之透過軸與市售之纖維素乙酸 酯薄膜的遲相軸係以直行方式配置。其後對各光學薄膜各 自製作偏光板。 0 剝離設置於使用垂直配向型液晶單元之液晶顯示裝置 (VL- 1 53 0S，富士通（股）製）上的一對偏光板及相位 差板後，介由黏著劑將取代用的前述製作之偏光板的試料 薄膜貼附於液晶單元側。其次以觀察者側之偏光板的透過 軸方向爲上下方向，及以背光側之偏光板的透過軸爲左右 方向之方式配置正交尼科爾稜鏡。 《評估方法》 φ 對所得的光學薄膜1至17實施下述評估。評估對象之 該光學薄膜殘留溶劑量的含有率全部爲0.01質量％以下。 《評估》 (框斑） 將使用前述各光學薄膜製作之各液晶顯示裝置點燈 1000小時後’以目視確認黑顯示下有無畫面周邊脫白（框 斑）進行下述評估，以作爲框斑之評估指標。 ◎:完全未有周邊漏光情形 -73- 201033274 〇：周邊出現少許漏光情形 X :周邊明顯出現漏光情形。 (耐漏光性） 藉由偏光板於正交尼科爾稜鏡下，即以直交狀態（正 交尼科爾稜鏡狀態）配置之2板起偏鏡挾持所得光學薄膜 後，由一方偏光板之外側射入光線，及由另一方偏光板之 外側以目視觀察，再以下述基準設定漏光等級。 ◎:無透光情形，全體爲均勻暗視領域 〇：出現部分較弱的條紋狀明暗 X :出現部分較強的條紋狀明暗。 (薄膜之耐熱性評估） 以80°c下加熱評估用薄膜3 0分鐘後之狀態評估外觀形 狀有無變化。 〇：外觀形狀無變化 X:外觀形狀有變化（薄膜出現凹凸狀態，長寬尺寸 變化） 上述之評估結果等如表1至3所示。 201033274 參 【1® m S m ^ 〇 〇 ◎ ◎ ◎ ◎ 〇 〇 〇 ◎ 〇 〇 〇 X X 〇 〇 耐熱性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 X 〇 〇 〇 〇 耐框斑性 ◎ ◎ ◎ 〇 〇 ◎ ◎ ◎ ◎ ◎ X X 〇 〇 X X X 丙烯酸基粒子添 加比率(％) 1-^ »—Η 1-H ο ο ο ο m 丙烯酸基粒子 (C) U 1—^ 1-Η rj G 寸 U 摧 壊 ι—Η 摧 m 纖維素酯樹脂 (B)之比率 iTi 沄 Ο Ο ο σ\ 〇\ 沄 v-i 丙烯酸樹脂(A)之比率 % $ $ $ 5S ΟΝ Ον ο ο s 實施例 1_ 1 比較例 〇 Z r~H (N CO 寸 卜 〇〇 σ\ ο CN m 2 ν〇 o -75- 201033274 [表2] 光學薄膜Να 丙烯酸樹脂(Α) 重量平均分子量:Mw 1〜3、7〜14、15、17 戴亞那BR85* 280000 4 戴亞那BR83* 40000 5、16 亞克力粒V* 105000 6 亞克力粒VHM* 140000 *三菱人造絲（股）製 [表3] 光學薄，0. 丙烯酸基粒子No. 丙烯酸基粒子種 1〜6、10、13、14、17 Cl 本文中記載 7 C2 美塔布速W-341:三菱人造絲(股)製 8 C3 肯米斯諾MR-2G:綜硏化學(股)製 9 C4 肯米斯諾MS-300X:綜硏化學(股)製 由表1所表示之結果得知，相對於比較例，本發明之 光學薄膜的實施例之各評估性能較優良。 【圖式簡單說明】 圖1爲，使用彈性接觸輥之光學薄膜製造裝置。 【主要元件符號說明】 1 :擠壓機 2 :濾器 3 :靜態混合機 4 :流延模頭 5:回轉支持器（第1冷卻輥） -76- 201033274 6:夾壓回轉器（接觸輥） 7:回轉支持器（第2冷卻輥） 8:回轉支持器（第3冷卻輥） 9、 11、 13、 14、 15:搬運輥 10 :薄膜 1 2 :延伸機 16 :捲取裝置UV absorber Ti 928 (manufactured by JIB, Japan) 1.5 parts by mass of matting agent Xihousi KEP-30 Japan catalyst (manufactured by the company) (average particle size 0.3 / zm cerium oxide microparticles) 0.1 parts by mass (optical Melt film formation of the film) The cellulose vinegar and the acrylic resin were dried at 70 ° C for 3 hours under reduced pressure, and then cooled to room temperature to remix each additive other than the matting agent. The above mixture was formed into a film using a manufacturing apparatus having an elastic contact roll as shown in Fig. 1. After melting at 240 ° C in a nitrogen atmosphere, it was extruded from a casting die onto a first φ cooling roll. The film was formed by rolling a film between the first cooling roll and the contact roll. Further, 0.1 part by mass of a matting agent for a lubricant was added to the hopper opening of the intermediate portion of the extruder 1. The thermal bolt is adjusted so that the gap width of the casting die is 0.5 mm within 30 mm from the end in the width direction of the film, and 1 mm in other places. The contact roller used was a cooling water flowing inside the contact roller at 80 °C. The position at which the resin extruded from the casting die contacts the first cooling roller is set to the upper end of the first cooling roller in the rotation direction of the first cooling roller and the contact roller, and is set along the length L of the circumference of the first cooling roller. It is 20mm. Thereafter, -71 - 201033274, the temperature T of the molten portion before the rolling of the first cooling roller and the contact roller is measured by the first cooling roller separation roller '. The temperature τ of the molten portion before the rolling of the first cooling roll and the contact roll was measured by using a thermometer (A-200E manufactured by Anritsu Co., Ltd.) to measure the flow side position from the upper end to the upper end by 1 mm. As a result, the measured temperature T was 1 4 1 °C. The line pressure of the contact roller to the first cooling roller was 1 4.7 N/cm. Next, the tenter is introduced, and the width direction is extended to 1.3 times at 160 ° C, and then cooled to 30 ° C while relaxing the width direction of 3%, and then the clip is released, and the grip portion is cut off, and the film is pressed. The embossing processing of width and height of 5 // m is carried out at both ends, and the winding core is taken up by the winding tension 22 ON/m and the inclination of 40%. The core size is 152 mm in inner diameter, 165 to 180 mm in outer diameter, and 155 0 mm in length. The core material is a prepreg resin of glass fiber or carbon fiber impregnated epoxy resin. The surface of the core is coated with an epoxy conductive resin, and the surface is honed to have a surface roughness Ra of 0·3 μm. An optical film 1〇1 having a film thickness of 80/zm and a roll length of 3,500 m was produced. <Production of Optical Films 2 to 17> In addition to the production of the above-mentioned optical film 1, the composition ratio of the acrylic resin (A) and the cellulose ester resin (B), and the types and addition ratios of the additives are as described in Table 1 'Acrylic resin (A) The types of the optical films 2 to 17 were prepared in the same manner as described in Table 2, except that the acrylic-based particles (C) were as described in Table 3. <Preparation of Polarizing Plate> The polarizing film was prepared by adsorbing iodine on the stretched polyvinyl alcohol film, and the optical film 1 subjected to the alkalization treatment was attached to one side of the polarizing film by using a polyvinyl alcohol-based adhesive of -72 to 201033274. . The commercially available cellulose acetate film (Conica KC 8 UX) was alkalized and then attached to the opposite side of the polarizing film using a polyvinyl alcohol-based adhesive. At this time, the transmission axis of the polarizing film and the late phase of the sample are arranged in parallel. The transmission axis of the polarizing film and the late phase axis of the commercially available cellulose acetate film are arranged in a straight line. Thereafter, a polarizing plate was produced for each of the optical films. 0. The pair of polarizing plates and phase difference plates provided in a liquid crystal display device (VL-1500S, manufactured by Fujitsu Co., Ltd.) using a vertical alignment type liquid crystal cell are removed, and the above-mentioned fabrication is replaced by an adhesive. The sample film of the polarizing plate is attached to the liquid crystal cell side. Next, the crossed Nicols are arranged such that the transmission axis direction of the polarizer on the observer side is the up-and-down direction and the transmission axis of the polarizing plate on the backlight side is the left-right direction. <<Evaluation Method>> φ The obtained optical films 1 to 17 were subjected to the following evaluations. The content of the residual amount of the optical film of the evaluation target was 0.01% by mass or less. "Evaluation" (frame spot) After each liquid crystal display device produced using each of the above optical films was turned on for 1000 hours, the following evaluation was performed by visually confirming whether or not the screen periphery was whitened (frame spot) under black display, and the following evaluation was performed as a frame spot. Evaluation indicators. ◎: There is no leakage at the periphery -73- 201033274 〇: There is a little light leakage around the X. X: There is obvious light leakage around the perimeter. (Light leakage resistance) A polarizing plate is held by a polarizing plate under a crossed Nicols, that is, a two-plate polarizer disposed in an orthogonal state (orthogonal Nicols state). Light is incident on the outside and visually observed from the outside of the other polarizer, and the light leakage level is set based on the following criteria. ◎: No light transmission, the whole is the area of uniform sacred vision 〇: Partially weak stripe-like light and darkness appears X: Partially strong striped light and dark appear. (Evaluation of heat resistance of film) The appearance of the film for evaluation was heated at 80 ° C for 30 minutes to evaluate whether or not the appearance was changed. 〇: No change in appearance shape X: Appearance shape changes (concave and convex appearance of film, change in length and width) The evaluation results described above are shown in Tables 1 to 3. 201033274 参 [1® m S m ^ 〇〇 ◎ ◎ ◎ ◎ 〇〇〇 ◎ 〇〇〇 〇〇〇 〇〇〇 〇〇 heat resistance 〇〇〇〇〇〇〇〇〇〇〇〇 X 〇〇〇〇 frame resistance ◎ ◎ ◎ 〇〇 ◎ ◎ ◎ ◎ ◎ XX 〇〇 XXX Acrylic-based particle addition ratio (%) 1-^ »—Η 1-H ο ο ο ο m Acrylic-based particles (C) U 1—^ 1-Η rj G inch U 壊 壊 Η 摧 m m cellulose ester resin (B) ratio iTi 沄Ο Ο ο σ \ 〇 \ 沄vi Acrylic resin (A) ratio% $ $ $ 5S ΟΝ Ον ο ο s Example 1_ 1 Comparison Example rZ r~H (N CO 〇〇 〇〇 \ \ m CN m 2 ν〇o -75- 201033274 [Table 2] Optical film Να Acrylic resin (Α) Weight average molecular weight: Mw 1~3, 7~14 , 15, 17 Diana BR85* 280000 4 Diana BR83* 40000 5, 16 Acrylic V* 105000 6 Acrylic VHM* 140000 *Mitsubishi Rayon (Table 3) Optical thin, 0. Acrylic Particle No. Acrylic-based particle species 1 to 6, 10, 13, 14, 17 Cl This document describes 7 C2 Metalab speed W-3 41: Mitsubishi Rayon (stock) 8 C3 Kensino MR-2G: Comprehensive chemical (share) system 9 C4 Kensino MS-300X: comprehensive chemical (share) system results shown in Table 1. It is understood that the evaluation performance of the embodiment of the optical film of the present invention is superior with respect to the comparative example. [Schematic Description of the Drawing] Fig. 1 is an optical film manufacturing apparatus using an elastic contact roller. [Description of Main Components] 1 : Extruder 2 : Filter 3 : Static mixer 4 : Casting die 5 : Rotary holder (1st cooling roll) -76- 201033274 6: Crimp rotator (contact roller) 7: Slewing holder (No. 2 cooling roller) 8: rotary support (third cooling roller) 9, 11, 13, 14, 15: conveying roller 10: film 1 2: stretching machine 16: winding device

-77--77-

Claims (1)

201033274 七、申請專利範圍： 1·—種光學薄膜’其特徵爲’含有丙烯酸樹脂（A )、纖維素酯樹脂（B)及丙烯酸基粒子（c)之光學薄 膜中’係以5〇 : 5〇至95 : 5之範圍內之質量比含有前述 丙嫌酸樹脂（A)及纖維素酯樹脂（B)，且相對於構成 該光學薄膜之樹脂總質量，前述丙烯酸基粒子（C)之含 有率爲0.5至30質量％，殘留溶劑量之含有率爲〇〇1質 量％以下。 2-如申請專利範圍第1項之光學薄膜，其中前述丙 烯酸樹脂（A)之重量平均分子量（Mw)爲110000至 1 000000之範圍內。 3· —種光學薄膜之製造方法，其特徵爲，如申請專 利範圍第1或2項之光學薄膜的製造方法爲，使用接觸輥 之熔融流延製膜法。 4.—種偏光板，其特徵爲，使用如申請專利範圍第 1或2項之光學薄膜。 5 · —種液晶顯示裝置’其特徵爲，使用如申請專利 範圍第4項之偏光板。 -78-201033274 VII. Patent application scope: 1. An optical film characterized by 'an optical film containing an acrylic resin (A), a cellulose ester resin (B) and an acrylic-based particle (c) '5 〇: 5 The mass ratio in the range of 95:5 is contained in the above-mentioned acrylic acid (A) and cellulose ester resin (B), and the content of the acrylic particles (C) is relative to the total mass of the resin constituting the optical film. The ratio is 0.5 to 30% by mass, and the content of the residual solvent amount is 〇〇1% by mass or less. The optical film of claim 1, wherein the acrylic resin (A) has a weight average molecular weight (Mw) in the range of from 110,000 to 1,000,000. A method for producing an optical film, which is characterized in that the method for producing an optical film according to claim 1 or 2 is a melt casting film forming method using a contact roll. 4. A polarizing plate characterized by using an optical film as claimed in claim 1 or 2. A liquid crystal display device is characterized in that a polarizing plate as in item 4 of the patent application is used. -78-
TW098135944A 2008-10-27 2009-10-23 Optical film, process for producing the optical film, and polarizing plate and liquid crystal display device using the optical film TW201033274A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2008275451 2008-10-27

Publications (1)

Publication Number Publication Date
TW201033274A true TW201033274A (en) 2010-09-16

Family

ID=42128655

Family Applications (1)

Application Number Title Priority Date Filing Date
TW098135944A TW201033274A (en) 2008-10-27 2009-10-23 Optical film, process for producing the optical film, and polarizing plate and liquid crystal display device using the optical film

Country Status (2)

Country Link
TW (1) TW201033274A (en)
WO (1) WO2010050287A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6204789B2 (en) * 2013-10-21 2017-09-27 旭化成株式会社 Resin base for ball game machines

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3322406B2 (en) * 1991-10-23 2002-09-09 鐘淵化学工業株式会社 Polarizing film protective film
JP2002356658A (en) * 2001-05-31 2002-12-13 Nippon Carbide Ind Co Inc Acrylic overlay film
JP2008055890A (en) * 2006-06-06 2008-03-13 Fujifilm Corp Thermoplastic resin film, its production method, polarizing plate, optical compensation film, antireflection film, and liquid crystal display device
JP4895290B2 (en) * 2006-12-25 2012-03-14 日東電工株式会社 Optical film manufacturing method, optical film, polarizing plate, and image display device
JP5170083B2 (en) * 2007-03-12 2013-03-27 コニカミノルタアドバンストレイヤー株式会社 Method for producing antiglare antireflection film, antiglare antireflection film, polarizing plate and display device

Also Published As

Publication number Publication date
WO2010050287A1 (en) 2010-05-06

Similar Documents

Publication Publication Date Title
JP5447374B2 (en) Acrylic film manufacturing method and acrylic film produced by the manufacturing method
JP5505302B2 (en) Optical film manufacturing method, optical film, polarizing plate, and liquid crystal display device
US8470448B2 (en) Acryl resin containing film, polarizing plate by use thereof and liquid crystal display
JP5521552B2 (en) Acrylic resin-containing film, polarizing plate and liquid crystal display device using the same
JP5333447B2 (en) Acrylic film manufacturing method and acrylic film manufactured by the manufacturing method
JP5402925B2 (en) Polarizing plate and liquid crystal display device
JPWO2013080847A1 (en) Method for producing acrylic resin-containing film
KR101606228B1 (en) Optical film
JP5533858B2 (en) Optical film, polarizing plate and liquid crystal display device using the same
WO2010041513A1 (en) Optical film, method for producing optical film, polarizing plate and liquid crystal display device
JP5640743B2 (en) Optical film for polarizing plate, production method thereof, polarizing plate and liquid crystal display device using the same
JP5533857B2 (en) Optical film, polarizing plate and liquid crystal display device using the same
TWI544014B (en) Optical film
WO2011055590A1 (en) Protective film roll for liquid crystal polarization plate and manufacturing method thereof
TW201033274A (en) Optical film, process for producing the optical film, and polarizing plate and liquid crystal display device using the optical film
WO2011138913A1 (en) Polarizing plate, method for producing same, and liquid crystal display device
WO2010116822A1 (en) Optical film, process for producing optical film, liquid crystal panel, and image display device
TW201107395A (en) Optical film, method for producing optical film, liquid crystal panel and image display device
JP5263299B2 (en) Optical film, polarizing plate, liquid crystal display device, and method of manufacturing optical film
JP2012025871A (en) Optical film