201107395 六、發明說明： 【發明所屬之技術領域】 本發明係有關光學薄膜、製造該光學薄膜的方法、使 用該光學薄膜之液晶面板 '及使用該液晶面板的圖像顯示 裝置。 【先前技術】 以往之丙烯酸樹脂所代表的聚甲基丙烯酸甲酯（以下 簡稱爲「PMMA」），從其優異的透明性、尺寸安定性、 低吸濕性等的觀點，非常適用於光學薄膜。 但是PMMA薄膜有耐熱性的問題，因製造時之溫度 環境使可塑劑、添加劑等析出於薄膜表面而造成滑性不佳 已爲人知。特別是近年，光學薄膜因長條化、廣寬化，因 此滑性是重要的生產特性。而且，長條薄膜生產時，膠漿 之安定性是不可或缺的，但是有時膠漿長時間放置時，會 產生造成薄膜故障原因之析出物。 爲了改善耐熱性，而提案在丙烯酸樹脂中添加聚碳酸 酯（以下簡稱爲「PC」）的方法，但是可使用的溶劑受 限制，樹脂彼此之相溶性不佳，因此產生白濁，霧度上昇 ’很難作爲光學薄膜使用（參照例如專利文獻1 )。 此外’導入作爲丙烯酸樹脂之共聚合成分之脂環式烷 基的方法或使分子內環化反應，在分子主鏈形成環狀構造 的方法等（參照例如專利文獻2、3、4)。 但是此等方法雖可某程度改善耐熱性，但是生產時所 -5- 201107395 產生之可塑齊彳' 添加劑等析出於薄膜表面之滑性依然有問 題。 [先行技術文獻] [專利文獻] [專利文獻1]特開 [專利文獻2 ]特開 [專利文獻3 ]特開 [專利文獻4]特開 平5-306344號公報 2002-12728 號公報 2005-146084 號公報 2007-191706 號公報 【發明內容】 [發明槪要] [發明欲解決的課題] 因此，本發明之目的係提供滑性被改善，膠漿之安定 性佳之長條狀生產適性高的光學薄膜、製造該光學薄膜的 方法、使用該光學薄膜的液晶面板、及使用該液晶面板的 圖像顯示裝置。 [解決課題的手段] 本發明之上述課題係藉由以下構成來達成。 1·—種光學薄膜，其係含有醯化纖維素樹脂20〜80質 量％、丙烯酸樹脂20〜80質量％的光學薄膜’其特徵係含 有0.1質量％以上未達1.0質量％之選自酯系溶劑、酮系溶 劑 '及脂肪族系溶劑之至少1種的溶劑者。 -6- .201107395 2.—種製造光學薄膜的方法，其係製造前述第1項之 光學薄膜的方法’其特徵係將醯化纖維素樹脂與丙烯酸樹 脂溶解於二氯甲烷、醇與選自甲基丙烯酸甲酯、酯系溶劑 、酮系溶劑、及脂肪族系溶劑之至少1種溶劑的混合溶劑 中，製作膠漿者。 3 . —種液晶面板，其特徵係使用前述第1項之光學薄 膜所製作者。 4.一種圖像顯示裝置，其特徵係使用前述第3項之液 晶面板所製作者。 發明效果 依據本發明時，可提供滑性被改善，膠漿之安定性佳 之長條狀生產適性高的光學薄膜、製造該光學薄膜的方法 、使用該光學薄膜的液晶面板、及使用該液晶面板的圖像 顯示裝置。 [實施發明之形態] 以下詳細說明實施本發明的形態，但是本發明不限於 此等。 本發明係提供一種改善因耐熱性的問題，在製造時產 生可塑劑、添加劑等析出於薄膜表面導致滑性劣化或膠漿 中產生析出物導致安定性劣化之以往含有丙烯酸樹脂之光 學薄膜的缺點之新穎的光學薄膜、及製造該光學薄膜的方 法。 201107395 本發明人發現以特定比率摻合丙烯酸樹脂（A)與酶 化纖維素樹脂（B)，且使用特定溶劑製造，可提高耐熱 性，不會因可塑劑、添加劑等析出於薄膜表面導致滑性劣 化可得到膠漿之安定性良好之長條生產適性高的光學薄膜 ，遂完成本發明。 以下詳細說明本發明。 <本發明之溶劑> 本發明之光學薄膜係含有選自酯系溶劑、酮系溶劑、 脂肪族系溶劑之至少1種溶劑的光學薄膜。 以特定比率含有丙烯酸樹脂（A)與醯化纖維素樹月旨 (B )，且含有此等特定溶劑，可明顯降低因耐熱性問題 ’在製造時所產生之可塑劑、添加劑等析出於薄膜表面導 致滑性劣化或膠漿長時間放置時產生析出物。 本發明之酯系溶劑係指分子內具有酯基的溶劑，例如 有甲基丙烯酸及其酯衍生物（甲基丙烯酸甲酯、甲基丙烯 酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯、甲基丙烯酸 i-丁酯 '甲基丙烯酸t-丁酯、甲基丙烯酸辛酯、甲基丙烯 酸環己酯、甲基丙烯酸2-羥基乙酯、甲基丙烯酸2-羥基 丙酯、甲基丙烯酸四氫糠酯、甲基丙烯酸苄酯、甲基丙烯 酸二甲基胺基乙酯、甲基丙烯酸二乙基胺基乙酯等）、丙 烯酸及其酯衍生物（丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙 酯、丙烯酸丁酯、丙烯酸卜丁酯、丙烯酸t-丁酯、丙烯酸 辛酯、丙烯酸環己酯、丙烯酸2-羥基乙酯、丙烯酸2-羥 -8- 201107395 基丙酯、丙烯酸四氫糠酯、丙烯酸2-乙氧基乙酯、丙烯 酸二乙二醇乙醇酯、丙烯酸3-甲氧基丁酯、丙烯酸苄酯 、丙烯酸二甲基胺基乙酯、丙烯酸二乙基胺基乙酯等）、 乙酸甲酯、乙酸丁酯、乙酸乙酯、乙酸異丙酯、乙酸戊酯 、乙酸異戊酯、甲氧基乙酸乙酯、乙氧基乙酸乙酯、丙二 醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、乙二醇單丙醚乙 酸酯、乙二醇單丁醚乙酸酯、乙二醇單苯醚乙酸酯、二乙 二醇單甲醚乙酸酯、二乙二醇單丙醚乙酸酯、二乙二醇單 乙醚乙酸酯、二乙二醇單苯醚乙酸酯、二乙二醇單丁醚乙 酸酯、二乙二醇單乙醚乙酸酯、2-甲氧基丁基乙酸酯、3-甲氧基丁基乙酸酯、4-甲氧基丁基乙酸酯、3-甲基Ο-甲氧 基丁基乙酸酯、3-乙基-3-甲氧基丁基乙酸酯、丙二醇單 甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯 、2-乙氧基丁基乙酸酯、4-乙氧基丁基乙酸酯、4-丙氧基 丁基乙酸酯、2-甲氧基戊基乙酸酯、3-甲氧基戊基乙酸酯 、4-甲氧基戊基乙酸酯、2-甲基-3-甲氧基戊基乙酸酯、3-甲基-3-甲氧基戊基乙酸酯、3_甲基·4_甲氧基戊基乙酸酯 、4 -甲基-4-甲氧基戊基乙酸酯、丙二醇二乙酸酯、甲酸 甲酯、甲酸乙酯 '甲酸丁酯、甲酸丙酯、乳酸乙酯 '乳酸 丁酯、乳酸丙酯、碳酸乙酯、碳酸丙酯、碳酸丁酯、丙酮 酸甲醋、丙酮酸乙酯、丙酮酸丙酯.、丙酮酸丁酯、乙醯乙 酸甲酯、乙醯乙酸乙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯 、丙酸異丙酯、2·羥基丙酸甲酯、2_羥基丙酸乙酯、甲 基-3-甲氧基丙酸酯、乙基·3·甲氧基丙酸酯、乙基·3·乙氧 -9- 201107395 基丙酸酯、丙基-3-甲氧基丙酸酯等，本發明較佳爲使用 甲基丙烯酸甲酯。 本發明之酮系溶劑係指分子內具有酮基之溶劑，例如 有1-辛嗣、2-辛酮、1-壬酮、2-壬酮、丙酮、4-庚酮、1-己酮、2 -己酮、二異丁基酮、環己酮、甲基環己酮、苯基 丙酮、甲基乙基酮、甲基異丁基酮 '乙醯基丙酮、丙酮基 丙酮、紫羅酮（i〇none)、二丙酮基醇、乙醯基甲醇、苯 乙酮、甲基萘基酮、異爾佛酮、丙烯碳酸酯、丁內酯 等，本發明較佳爲使用甲基乙基酮。 本發明之脂肪族系溶劑例如有戊烷、己烷、辛烷、癸 烷' 2,2,4-三甲基戊烷、2,2,3-三甲基己烷、環己烷等，較 佳爲使用己烷。 本發明之選自酯系溶劑、酮系溶劑、及脂肪族系溶劑 之至少一種溶劑係於光學薄膜中各自含有0.1質量％以上 未達1.0質量％。含量爲未達0.1質量％時，提高滑性及膠 漿安定性的效果小，含量爲1.0質量％以上時，膠漿之安 定性差，析出物等變多。一般而言，使用丙烯酸樹脂之光 學薄膜中，含有丙烯酸樹脂之單體成分，但是含量爲1質 量％以上，不包含在本發明之範圍內。 上述溶劑之光學薄膜中之含量可以下述方法測定。 (溶劑含量之定量方法） 光學薄膜中之溶劑含量可藉由頂空氣相層析定量。 頂空氣相層析法（headspace gas chromatography)係 -10- 201107395 將試料封入容器中，加熱使容器中充滿揮發成分的狀態， 快速的將容器中之氣體注入氣相層析儀，進行質量分析， 鑑定化合物同時將揮發成分定量者。頂空法係藉由氣相層 析儀，可觀測揮發成分之全波峰，同時也可倂用藉由使用 利用電磁的相互作用之分析法，以高精度進行揮發性物質 或單體等的定量。以下裝置可作爲一例使用》 headspace 裝置：HP7694 Head Space Sampler ( Hewlett-Packard 公司製）BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical film, a method of manufacturing the optical film, a liquid crystal panel using the optical film, and an image display device using the liquid crystal panel. [Prior Art] Polymethyl methacrylate (hereinafter abbreviated as "PMMA") represented by a conventional acrylic resin is very suitable for an optical film from the viewpoints of excellent transparency, dimensional stability, and low hygroscopicity. . However, the PMMA film has a problem of heat resistance, and it is known that the plasticity, the additives, and the like are deposited on the surface of the film due to the temperature environment at the time of manufacture, resulting in poor slipperiness. In particular, in recent years, optical films have been elongated and widened, and therefore slipperiness is an important production property. Moreover, the stability of the glue is indispensable in the production of long strip films, but sometimes when the glue is left for a long time, precipitates which cause the failure of the film are generated. In order to improve heat resistance, a method of adding polycarbonate (hereinafter abbreviated as "PC") to an acrylic resin has been proposed, but the solvent that can be used is limited, and the compatibility between the resins is not good, so that white turbidity occurs and haze rises. It is difficult to use as an optical film (see, for example, Patent Document 1). In addition, a method of introducing an alicyclic alkyl group as a copolymerization component of an acrylic resin or a method of forming a cyclic structure in a molecular main chain by a method of intramolecular cyclization (see, for example, Patent Documents 2, 3, and 4). However, although these methods can improve the heat resistance to some extent, the slipperiness of the surface of the film which is produced by the plastic molds produced by the -5-201107395 is still problematic. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open Publication No. JP-A No. 5-306344 [Invention] [Invention Summary] [Problems to be Solved by the Invention] Therefore, an object of the present invention is to provide an optical fiber having improved smoothness and high stability of a long strip. A film, a method of producing the optical film, a liquid crystal panel using the optical film, and an image display device using the liquid crystal panel. [Means for Solving the Problem] The above problems of the present invention are achieved by the following constitution. An optical film comprising 20 to 80% by mass of a deuterated cellulose resin and 20 to 80% by mass of an acrylic resin, characterized in that it is contained in an ester system in an amount of 0.1% by mass or more and less than 1.0% by mass. A solvent of at least one of a solvent, a ketone solvent, and an aliphatic solvent. -6-.201107395 2. A method for producing an optical film, which is characterized in that the method for producing the optical film of the above item is characterized in that the deuterated cellulose resin and the acrylic resin are dissolved in dichloromethane, alcohol and selected from the group consisting of A glue is prepared in a mixed solvent of at least one solvent of methyl methacrylate, an ester solvent, a ketone solvent, and an aliphatic solvent. A liquid crystal panel characterized in that the optical film of the above first item is used. An image display device characterized by using the liquid crystal panel of the third aspect. Advantageous Effects of Invention According to the present invention, it is possible to provide an optical film having high smoothness and high flexibility in which the stability of the glue is excellent, a method of producing the optical film, a liquid crystal panel using the optical film, and a liquid crystal panel using the same Image display device. [Mode for Carrying Out the Invention] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited thereto. The present invention provides a problem of improving the heat resistance of the conventional optical film containing an acrylic resin when a plasticizer, an additive, or the like is precipitated on the surface of the film to cause deterioration of slippage or deterioration of stability due to occurrence of precipitates in the dope during production. A novel optical film and a method of making the same. 201107395 The present inventors have found that blending an acrylic resin (A) with an enzymatic cellulose resin (B) at a specific ratio and using a specific solvent can improve heat resistance without causing slippage due to plasticizers, additives, etc., which are deposited on the surface of the film. The present invention can be completed by obtaining an optical film having a high yield stability in which the stability of the paste is good. The invention is described in detail below. <Solvent of the Invention> The optical film of the present invention contains an optical film selected from at least one solvent selected from the group consisting of an ester solvent, a ketone solvent, and an aliphatic solvent. The acrylic resin (A) and the deuterated cellulose tree (B) are contained in a specific ratio, and the specific solvent is contained, and the problem of heat resistance can be remarkably reduced. The plasticizer, the additive, and the like which are produced during the production are deposited on the surface of the film. Leaching is caused when the slip property is deteriorated or the glue is left for a long time. The ester-based solvent of the present invention means a solvent having an ester group in the molecule, and examples thereof include methacrylic acid and an ester derivative thereof (methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate). , i-butyl methacrylate t-butyl methacrylate, octyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methyl Acetyl tetrahydrofurfuryl acrylate, benzyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc., acrylic acid and its ester derivatives (methyl acrylate, ethyl acrylate) , propyl acrylate, butyl acrylate, butyl acrylate, t-butyl acrylate, octyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxy-8-201107395 propyl acrylate, acrylic acid Hydroquinone ester, 2-ethoxyethyl acrylate, diethylene glycol acrylate, 3-methoxybutyl acrylate, benzyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate Ester, etc.), methyl acetate, acetic acid , ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate Ester, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl Acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methylindole-methoxybutyl acetate, 3-ethyl-3-methyl Oxybutyl butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl Acid ester, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl 3-methoxymethoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxy Amyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate 'butyl formate, propyl formate, ethyl lactate Ester, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl acetonate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetate, ethyl acetate , methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, Ethyl·3·methoxypropionate, ethyl·3·ethoxy-9-201107395, propionate, propyl-3-methoxypropionate, etc., preferably methacrylic acid is used in the present invention. Methyl ester. The ketone solvent of the present invention refers to a solvent having a ketone group in the molecule, and examples thereof include 1-octyl, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, and 1-hexanone. 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone 'ethenyl acetone, acetone acetone, ionone (i〇none), diacetone alcohol, acetonitrile methanol, acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate, butyrolactone, etc., preferably methylethyl is used in the present invention. ketone. The aliphatic solvent of the present invention may, for example, be pentane, hexane, octane, nonane 2,2,4-trimethylpentane, 2,2,3-trimethylhexane or cyclohexane. Preferably, hexane is used. At least one solvent selected from the group consisting of an ester solvent, a ketone solvent, and an aliphatic solvent is contained in the optical film in an amount of 0.1% by mass or more and not more than 1.0% by mass. When the content is less than 0.1% by mass, the effect of improving the slipperiness and the stability of the paste is small, and when the content is 1.0% by mass or more, the stability of the dope is poor, and precipitates and the like are increased. In general, an optical film using an acrylic resin contains a monomer component of an acrylic resin, but the content is 1% by mass or more, and is not included in the scope of the present invention. The content in the optical film of the above solvent can be measured by the following method. (Quantification method of solvent content) The solvent content in the optical film can be quantified by headspace gas chromatography. Headspace gas chromatography -10- 201107395 The sample is sealed in a container, heated to fill the container with volatile components, and the gas in the container is quickly injected into the gas chromatograph for mass analysis. The compound is identified while the volatile components are quantified. In the headspace method, the full peak of the volatile component can be observed by a gas chromatograph, and the quantification of volatile substances or monomers can be performed with high precision by using an analysis method using electromagnetic interaction. . The following devices can be used as an example: headspace device: HP7694 Head Space Sampler (manufactured by Hewlett-Packard)
溫度條件：輸送管線200°C、迴路溫度200°C 試料量：〇.8g/20mlvial GC : HP5 890 ( Hewlett-Packar 公司製） MS : HP5971 ( Hewlett-Packard 公司製） 柱：HP-624 ( 30mx 內徑 0.25mm) 烘箱溫度：初期溫度40°C (保持時間3分鐘）、昇溫 速度10°c/分鐘、到達溫度200 °c (保持時間5分鐘） 測定模式：SIM( selective ion mass:選擇離子質譜 )模式 <含有丙烯酸樹脂之光學薄膜> 首先，說明本發明之含有丙烯酸樹脂之光學薄膜的物 性値。 本發明之光學薄膜係依據JIS K71 25- 1 999的方法測 定之薄膜的滑性較佳爲0.40以下，更佳爲0.30以下。滑 性爲上述範圍時，可明顯將低因析出物所造成之皺紋、鬆 -11 - 201107395 弛等之長條薄膜之操作故障。該滑性之測定係由乾燥後至 捲繞爲止進行採樣。測定機可使用動摩擦係數摩擦測定機 TR型（東洋精機製）、島津製作所製 UNIVERSAL TESTING MACHINE RH-30 等。 本發明之光學薄膜係含有丙烯酸樹脂（A)、醯化纖 維素樹脂（B)、本發明之特定溶劑，較佳爲含有不會產 生延性破壞之丙烯酸樹脂的光學薄膜。 上述延性破壞係定義爲以大於某材料所具有之強度更 大的應力作用所產生者，且最終破斷前伴隨著材料之明顯 的延伸或收縮的破壞。該斷面之特徵爲形成無數被稱爲窩 的凹洞。 因此，「不會產生延性破壞的光學薄膜」，其特徵係 藉由即使施加將薄膜折彎成2片之大應力作用，也未出現 破斷等之破壞。 從隨著今日液晶表示裝置之大型化之光學薄膜之大型 化、隨著薄膜化之加工性 '生產性的觀點，對於光學薄膜 之脆性要求越來越高，也要求不會產生上述延性破壞。 本發明之光學薄膜若考慮降低霧度，且在如投影機之 高溫的機器或汽車搭載用顯示機器之高溫環境下使用時， 其張力軟化點較佳爲控制在1 0 5 °C ~ 1 4 5 °C，更佳爲控制在 1 1 0 °C 〜1 3 0 °C。 光學薄膜之張力軟化點溫度的具體測定方法，例如使 用萬能拉力試驗機（ORIENTEC公司製RTC-1225A)，將 光學薄膜切成120mm (長）xlOmm (寬）後，以ion之 -12- 201107395 張力拉伸，同時以3(TC/min之升溫速度持續升溫’ 3次測 定到達9N時點的溫度，求其平均値而得。 又，本發明之光學薄膜的玻璃轉化溫度（Tg)較佳爲 ll〇°C以上。更佳爲120°C以上。特佳爲15〇°C以上。 玻璃轉化溫度係指使用差示、掃描熱量測定器（Perkin Elmer公司製DSC-7型），以升溫速度20°C/分鐘測定， 依據 JI S K 7 1 2 1 ( 1 9 8 7 )求得的中間點玻璃轉化溫度（ Tmg )。 又，本發明之光學薄膜係在薄膜面內之直徑5μιη以 上的缺點較佳爲1個/10cm四方以下。更佳爲0.5個/10cm 四方以下，更佳爲0.1個/10cm四方以下。 該缺點之直徑係指缺點爲圓形時表示其直徑，非圓形 時可藉由下述方法使用顯微鏡觀察缺點之範圍來決定，作 爲其最大徑（外接圓之直徑）。 缺點的範圍係當缺點爲氣泡或異物時，係指以微分干 擾顯微鏡之透過光觀察缺點時之影子的大小。缺點爲輥傷 之轉印或擦傷等表面形狀之變化時，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，缺點大小不明確時，可於表面 蒸鍍鋁或鉑來觀察。 爲了以較佳生產性得到以此種缺點頻度表示之品質優 異的薄膜時，可利用在流延前高精度過濾聚合物溶液，或 提高流延機周邊之潔淨度，或以階段性設定流延後之乾燥 條件’以高效率且抑制發泡進行乾燥。 -13- 201107395 缺點個數多於1個/ l〇cm四方時，例如於其後 加工時等對薄膜施加張力時，有時以缺點爲起點， 裂’生產性有明顯降低的情形。又，缺點的直徑 以上時’可以偏光板觀察等以目視確認，有時作爲 件使用時會產生亮點。 即使無法以目視確認時，有時於該薄膜上形成 等時’塗劑無法均一形成，成爲缺點（未被塗佈） 。缺點係指在溶液製膜之乾燥步驟中，因溶劑之急 所產生之薄膜中的空洞（發泡缺陷）或因製膜原液 物或製膜中混入之異物所產生之薄膜中的異物（異 又，本發明之光學薄膜依據 JIS-K7 1 27- 1 999 ’至少一方向之斷裂伸度較佳爲1 〇%以上，更佳爲 上。 斷裂伸度之上限並無特別限制，實際上爲約 欲斷裂伸度時，可藉由抑制因異物或發泡所造 膜中的缺點。 本發明之光學薄膜之光線透過率較佳爲90 %以 佳爲93 %以上。又實際的上限爲99%。爲了達成此 光線透過率表示之優異的透明性時，可藉由避免導 收可見光之添加劑或共聚合成份、或藉由高精度過 聚合物中的異物，或降低薄膜內部之光擴散或吸收 此外’可藉由降低製膜時之薄膜接觸部（冷卻 延輥、滾筒、輸送帶、溶液製膜之塗佈基材、搬運 :步驟之 薄膜斷 爲 5 μιτ 光學構 硬塗層 的情形 速蒸發 中之異 物缺點 測定時 2 0 %以 2 5 0% ° 成之薄 上，更 種以全 入會吸 據去除 〇 輥、壓 輥等） -14- 201107395 之表面粗糙度’以降低薄膜表面之表面粗糙度，或降低丙 燦酸樹脂之折射率’減少薄膜表面之光擴散或反射。 本發明之光學薄膜之表示透明性的指標之一的霧度値 (濁度）較佳爲未達0.5%，但是考慮組裝於液晶顯示裝 置時之亮度、對比的觀點，更佳爲〇 . 4 %以下。 上述光學薄膜之霧度値係依據JIS K7 361-1-1997及 JIS K7 1 3 6-2000所測定的値。 本發明之含有丙烯酸樹脂的薄膜只要滿足上述物性時 ，可作爲光學薄膜使用，但是藉由形成以下組成，可得到 加工性、耐熱性優異的薄膜。 換言之，從兼顧加工性及耐熱性的觀點，前述光學薄 膜爲以80: 20〜20: 80之質量比含有丙烯酸樹脂（A)與 醯化纖維素樹脂爲特徴的光學薄膜可得到本發明之優異的 效果。 本發明之光學薄膜中，以80 : 20〜20 : 80之質量比含 有丙烯酸樹脂（A)與醯化纖維素樹脂（B)，但是丙烯 酸樹脂（A )較佳爲5 0質量％以上。 丙烯酸樹脂成分變多時，例如可抑制在高溫·高濕下 之尺寸變化，明顯降低作爲偏光板使用時之偏光板之捲曲 或面板之變形。此外，丙烯酸樹脂成分爲50質量％以上 之組成時，可長時間維持上述物性。 本發明之光學薄膜也可爲含有丙烯酸樹脂（A)、醯 化纖維素樹脂（B )以外之樹脂的構成。 丙烯酸樹脂（A)與醯化纖維素樹脂（B)之総質量 -15- 201107395 係光學薄膜之55~100質量％，較佳爲60〜99質量％。 (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。 樹脂並無特別限制，但較佳爲由甲基丙烯酸甲酯單位 5 0〜99質量％，及可與此共聚合之其他單體單位1〜50質量 %所構成者。 可共聚之其他單體例如有烷基之碳數爲2〜18的烷基 甲基丙烯酸酯、烷基之碳數爲1〜18之烷基丙烯酸酯、丙 烯酸、甲基丙烯酸等之（X，β-不飽和酸、馬來酸、富馬酸 、衣康酸等之含有不飽和基的二元羧酸、苯乙烯、α-甲基 苯乙烯、核取代苯乙烯等之芳香族乙烯基化合物、丙烯腈 、甲基丙烯腈等之α，β -不飽和腈、馬來酸酐、馬來醯亞 胺、Ν-取代馬來醯亞胺、戊二酸酐等，此等可單獨使用或 倂用二種以上之單體使用。 其中從共聚合物之耐熱分解性及流動性的觀點，較佳 爲甲基丙烯酸酯、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， 特佳爲使用甲基丙烯酸酯或η-丁基丙烯酸酯。 本發明之光學薄膜所使用的丙烯酸樹脂（Α)特別是 從改善光學薄膜之機械強度、薄膜生產性的觀點，重量平 均分子量（Mw)爲80000〜1 000000。 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。測定條件如下述。 -16- 201107395 溶劑：二氯甲烷 柱：Shodex K806、K805、K803G (昭和電工（股） 製連接3支使用） 柱溫度：2 5 °C 試料濃度：〇. 1質量％ 檢測器：RI Model 504 ( GL Science 公司製） 泵：L6000(日立製作所（股）製） 流量：l.Oml/min 校正曲線：使用標準聚苯乙稀STK standard聚苯乙 烯（東曹（股）製）Mw = 2，800 ’ 000~500之 13個試樣 的校正曲線。1 3個試樣以大致等間隔使用較佳。 本發明之丙烯酸樹脂（A )的製造方法並無特別限制 ，可使用懸浮聚合、乳化聚合、塊狀聚合或溶液聚合等公 知的任何一種方法。其中聚合起始劑可使用一般的過氧化 物系及偶氮系的聚合起始劑，也可使用氧化還原系。聚合 溫度若爲懸浮或乳化聚合可以30〜100°C聚合，塊狀或溶液 聚合可以80~160°C聚合。爲了控制所得之共聚合物的還原 黏度，也可以烷基硫醇等作爲連鏈轉移劑使用，進行聚合 〇 設定爲此分子量，可兼顧耐熱性與脆性。 本發明之丙烯酸樹脂可使用市售品。例如有Delpet 6 ON、8 ON (旭化成化學（股）製）、Dianal BR52、BR80 、BR83、BR85、BR88 (三菱 Rayon (股）製）、KT75 ( 電化學工業（股）製）等。 -17- 201107395 (醯化纖維素樹脂（B )) 本發明之醯化纖維素樹脂（B)可被脂肪族之醢基、 芳香族之醯基中任一取代，較佳爲被乙醯基取代。 本發明之醯化纖維素樹脂爲與脂肪族醯基之酿時，脂 肪族醯基例如有碳原子數爲2 ~20，具體例有乙醯基、丙 醯基、丁醯基、異丁醯基、戊醯基、三甲基乙醯基、己醯 基、辛醯基、月桂醯基、硬酯醯基等。 本發明中，前述脂肪族醯基係指包含進一步具有取代 基者’取代基爲上述之芳香族醯基時，芳香族環爲苯環時 ，例如有以苯環之取代基例示者。 上述醯化纖維素樹脂爲與芳香族醯基之酯時，芳香族 環上取代之取代基X之數爲0或1~5個，較佳爲1~3個 ，特佳爲1或2個。 此外，在芳香族環上取代之取代基的數量爲2個以上 時’彼此可相同或相異，且可相互連結形成縮合多環化合 物（例如萘、茚、茚滿、菲、喹啉、異喹啉、色烯、色滿 、酞嗪、吖啶、吲哚、吲哚滿等）。 上述之醯化纖維素樹脂中，具有選自取代或無取代之 脂肪族醯基、取代或無取代之芳香族醯基之至少一種之構 造，可作爲用於本發明之纖維素樹脂的構造使用，此等可 爲纖維素或混合酸酯》 本發明之醯化纖維素樹脂的取代度係醯基之總取代度 (T)爲2.00〜3.00，醯基並不一定需要，醯基的取代度（ ac)爲〇〜1.89。更佳爲醯基以外之醯基之取代度（r)爲 -18- 201107395 2.00~2.89 ° 醯基以外之醯基較佳爲碳數3~7者。 本發明之醯化纖維素樹脂中，較佳爲選自具有碳原子 數2 ~7之醯基爲取代基者，即纖維素乙酸酯、纖維素丙酸 酯、纖維素丁酸酯、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及纖維素苯甲酸酯中之至 少一種。 此等中特佳的醯化纖維素樹脂爲纖維素乙酸酯、纖維 素丙酸酯、纖維素丁酸酯、纖維素乙酸酯丙酸酯、纖維素 乙酸酯丁酸酯。 混合脂肪酸較佳爲纖維素乙酸酯丙酸酯、纖維素乙酸 酯丁酸酯之低級脂肪酸酯，較佳爲具有碳原子數2〜4之醯 基爲取代基者。 未被醯基取代之部分通常以羥基的形態存在。這些可 以公知的方法合成。 又，乙醯基之取代度或其他之醯基的取代度可藉由 ASTM-D817-96所規定的方法得到。 本發明之醯化纖維素樹脂的重量平均分子量（Mw) 只要爲75000以上時，即使爲i〇0〇〇〇〇程度者，也可達成 本發明之目的’但是考慮生產性時，較佳爲 7 5000〜280000 者’更佳爲 looooo〜240000 者。 (丙烯酸粒子（C )) 本發明之光學薄膜可含有丙烯酸粒子。 -19- 201107395 本發明用之丙烯酸粒子（C)可與前述丙烯酸樹脂（ A )及醯化纖維素樹脂（B )在光學薄膜中，以粒子狀態 (也稱非相溶狀態）存在。 上述丙烯酸粒子（C)係例如將製作之光學薄膜採取 所定量後，溶解於溶劑後進行攪拌，使充分溶解分散後， 使用具有未達丙烯酸粒子（C)之平均粒徑之孔徑的PTFE 製薄膜過濾器過濾，過濾捕集之不溶物的重量較佳爲添加 於光學薄膜之丙烯酸粒子（C)的90質量％以上。 本發明所使用的丙烯酸粒子（C )並無特別限制，較 佳爲具有2層以上之層構造之丙烯酸粒子（C)，特佳爲 下述多層構造丙烯酸系粒狀複合物。 多層構造丙烯酸系粒狀複合物係指具有由中心部向外 周部’最內硬質層聚合物、顯示橡膠彈性之交聯軟質層聚 合物及最外硬質層聚合物以層狀重疊所成之構造的粒子狀 丙烯酸聚合物。 本發明之多層構造丙烯酸系粒狀複合物之較佳形態， 例如有下述者。例如由（a)由甲基丙烯酸甲酯8 0〜9 8.9 質量％、烷基之碳數爲1〜8的烷基丙烯酸酯1〜20質量％及 多官能性接枝劑0.01〜0·3質量％所構成之單體混合物進行 聚合而得的最內硬質層聚合物；（b)在上述最內硬質層聚 合物之存在下，由烷基之碳數爲4〜8的烷基丙烯酸酯 75〜98.5質量％、多官能性交聯劑0.01〜5質量％及多官能 性接枝劑0.5〜5質量％所構成之單體混合物進行聚合而得 的交聯軟質層聚合物；（c)在上述最內硬質層及交聯軟質 -20- 201107395 層所構成的聚合物存在下，由甲基丙烯酸甲酯8 0〜99質量 %與烷基之碳數爲之烷基丙烯酸酯1〜20質量％所構成 之單體混合物進行聚合而得的最外硬層聚合物；所構成之 具有3層構造，且所得的3層構造聚合物爲最內硬質層聚 合物（a) 5~40質量％、軟質層聚合物（b) 30〜60質量％ 及最外硬質層聚合物（c) 2 0〜5 0質量％所構成，以丙酮區 分時有不溶部分，該不溶部分之甲基乙基酮膨潤度爲 1.5〜4.0的丙烯酸系粒狀聚合物。 又如日本特公昭 60-17406號公報或特公平3-39095 號公報所揭示’不僅規定多層構造丙烯酸系粒狀複合物之 各層的組成及粒徑，也將多層構造丙烯酸系粒狀複合物之 拉伸彈性率及丙酮不溶部分之甲基乙基酮膨潤度設定在特 定範圍內’藉此可實現更充分之耐衝擊性與耐應力白化性 的平衡。 構成多層構造丙烯酸系粒狀複合物之最內硬質層聚合 物（a)較佳爲由甲基丙烯酸甲酯80〜98.9質量％、烷基之 碳數爲1~8的烷基丙烯酸酯1〜20質量。/。及多官能性接枝 劑0.0 1〜0.3質量％所構成之單體混合物進行聚合所得者。 烷基之碳數爲1〜8的烷基丙烯酸酯，例如有甲基丙烯 酸酯、乙基丙烯酸酯、η-丙基丙烯酸酯、n_ 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 甲基丙稀酸酯及η-丁基丙烯酸醋。 最內硬質層聚合物（a)中之烷基丙烯酸酯單位的比 例較佳爲1〜20質量％，該單位未達i質量％時，聚合物之 -21 - 201107395 熱分解性變大，該單位超過20質量％時，最 合物（c )之玻璃轉化溫度降低，3層構造丙 複合體之耐衝撃性賦予效果降低，故不佳。 多官能性接枝劑係具有不同之可聚合之官 能性單體，例如丙烯酸、甲基丙烯酸、馬來酸 烯丙酯等，較佳爲使用烯丙基甲基丙烯酸酯。 枝劑係用於使最內硬質層聚合物與軟質層聚合 性結合，因此，該最內硬質層聚合時所用 0.0 1 ~ 0.3 質量 ％。 構成丙烯酸系粒狀複合物之交聯軟質層靠 較佳爲在上述最內硬質層聚合物（a)之存在 之碳數爲1~8的烷基丙烯酸酯75〜98.5質量％ 交聯劑0.01~5質量％及多官能性接枝劑0.5〜5 成之單體混合物進行聚合而得者。 其中烷基之碳數爲4~8的烷基丙烯酸酯， η-丁基丙烯酸酯及2-乙基己基丙烯酸酯。 又，此等聚合性單體也可與25質量％以 合之其他單官能性單體共聚合。 可共聚合之其他單官能性單體，例如有苯 苯乙烯衍生物。烷基之碳數爲4〜8的烷基丙烯 烯之比例係當前者越多時’生成聚合物（b ) 溫度越低，即越能軟質化。 又從樹脂組成物之透明性的觀點，軟質層 )之常溫下的折射率越接近最內硬質層聚合杉 內硬質層聚 燏酸系粒狀 能基的多官 、富馬酸之 多官能性接 物進行化學 丨的比例爲 卜合物（b ) 下，由烷基 、多官能性 質量％所構 較佳爲使用 下的可共聚 乙烯及取代 酸酯與苯& 之玻璃轉化 ^聚合物（b J ( a )、最 -22- 201107395 外硬質層聚合物（C)及硬質熱塑性丙烯酸樹脂越佳，考 慮這些後選定兩者的比例。 例如被覆層厚度較低的用途時，不一定要將苯乙烯進 行共聚合。 多官能性接枝劑可使用如前述最內硬質層聚合物（a )之項所列舉者。在此所用之多官能性接枝劑係用於使軟 質層聚合物（b)與最外硬質層聚合物（c)進行化學性結 合，該最內硬質層聚合時所使用的比例，從耐衝擊性賦予 效果的觀點，較佳爲0.5〜5質量％。 多官能性交聯劑可使用二乙烯基化合物、二烯丙基化 合物、二丙烯酸化合物、二甲基丙烯酸化合物等一般已知 的交聯劑，較佳爲使用聚乙二醇二丙烯酸酯（分子量 200〜600) 〇 此處使用之多官能性交聯劑係用於軟質層（b)聚合 時生成交聯構造，使具有耐衝擊性賦予的效果。但是先前 多官能接枝劑用於軟質層之聚合時，某程度上會生成軟質 層（b )之交聯構造，因此多官能性交聯劑非必須成份， 但從耐衝擊性賦予效果的觀點，多官能性交聯劑用於軟質 層聚合時的比例，較佳爲〇 . 〇 1 ~5質量％。 構成多層構造丙烯酸系粒狀複合物之最外硬質層聚合 物（c)較佳爲在上述最內硬質層聚合物（a)及軟質層聚 合物（b)之存在下，由甲基丙烯酸甲酯80〜99質量％及 烷基之碳數爲的烷基丙烯酸酯1~20質量％所構成之 單體混合物進行聚合而得者。 -23- 201107395 其中烷基丙烯酸酯可使用前述者，較佳爲使用甲基丙 烯酸酯及乙基丙烯酸酯。最外硬質層（C)中之烷基丙烯 酸酯單位的比例較佳爲1〜2 0質量％。 又，最外硬質層（c)之聚合時’爲了提升與丙烯酸 樹脂（A)之相溶性，爲了調節分子量，可將烷基硫醇等 作爲鏈轉移劑使用進行聚合。 特別是最外硬質層上設置分子量由內側朝外側逐次減 少的斜度（斜率），可改良延伸與耐衝擊性之平衡性，故 較佳。具體的方法係將形成最外硬質層用之單體混合物分 割爲2個以上，依序增加每次添加之鏈轉移劑量的方法， 可使分子量由內側朝外側減少。 此時所形成的分子量可藉由測定將每次使用之單體混 合物各自單獨在相同條件聚合所得之聚合物的分子量而得 知。 本發明較適合使用之多層構造之丙烯酸系粒狀複合物 的粒徑並無特別限定，較佳爲l〇nm以上、1 〇〇〇nm以下 ，更佳爲20nm以上、500nm以下，最佳爲50nm以上、 400nm以下。 本發明較適合使用之多層構造聚合物的丙烯酸系粒狀 複合物中，芯與殼之質量比並無特別限定，但是多層構造 聚合物全體爲100質量份時，芯層較佳爲50質量份以上 ' 90質量份以下，更佳爲60質量份以上、80質量份以下 〇 這種多層構造丙烯酸系粒狀複合物之市售品，例如有 -24- 201107395 三菱 Rayon公司製“metablen”、鐘淵化學工業公司製 “kanes”、吳羽化學工業公司製“paraloid”、Rohm and Haas 公司製“Acryloid” 、 ganz 化成工業公司製 “staphiloid”及 kuraray 公司製 “parapet SA” 等，此等可單 獨使用或使用2種以上。 又，本發明較適合使用之丙烯酸粒子（C)，較適用 之接枝共聚合之丙烯酸粒子（c-1)的具體例有在橡膠質 聚合物之存在下，由不飽和羧酸酯系單體、不飽和羧酸系 單體、芳香族乙烯基系單體，及必要時可與此等共聚合之 其他乙稀基系單體所構成之單體混合物進行共聚而得的接 枝共聚物。 接枝共聚物之丙烯酸粒子（c-1)所使用的橡膠質聚 合物並無特別限制’可使用二烯系橡膠、丙烯酸系橡膠及 乙烯系橡膠等。具體例有聚丁二烯、苯乙烯·丁二嫌共聚 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 丙烯酸甲酯共聚物、丙烯酸丁酯-甲基丙烯酸甲酯共聚物 、丁二烯-丙烯酸乙酯共聚物、乙烯-丙烯共聚物、乙嫌_ 丙烯-二烯系共聚物、乙烯-異戊二烯共聚物、及乙稀-丙 烯酸甲酯共聚物等。此等橡膠質聚合物可使用1種或2種 以上的混合物。 丙烯酸樹脂（A)與丙烯酸粒子（C)之各自的折射 率近似時’可得到本發明之光學薄膜的透明性，故較佳。 具體而言’丙烯酸粒子（C)與丙烯酸樹脂（a)之折射 -25- 201107395 率差較佳爲0.05以下’更佳爲0.02以下’特佳爲0.01以 下。 爲了滿足這種折射率條件時，可藉由調整丙烯酸樹脂 (A)之各單體單位組成比的方法及/或調整丙烯酸粒子（ 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，可得到透明性優異的光學薄膜。 此處所謂的折射率差係指在丙烯酸樹脂（A )可溶的 溶劑中，以適當條件將本發明之光學薄膜充分溶解形成白 濁溶液後，藉由離心分離等操作，分離成溶劑可溶部分與 不溶部分，此可溶部分（丙烯酸樹脂（A))與不溶部分 (丙烯酸粒子（C ))分別純化後，顯示測得的折射率（ 2 3 °C、測定波長：5 5 Onm )之差。 本發明中，丙烯酸樹脂（A)中調配丙烯酸粒子（C )的方法並無特別限定，較佳爲使用預先摻合丙烯酸樹脂 (A)與其他任意成份後，一般於200〜3 50°C下添加丙烯 酸粒子（C)，同時藉由單軸或雙軸擠壓機進行均勻熔融 混練的方法。 此外，可使用將預先分散有丙烯酸粒子（C)的溶液 添加於溶解有丙烯酸樹脂（A)及醯化纖維素樹脂（B) 的溶液（膠漿液）進行混合的方法或將丙烯酸粒子（C) 及其他任意之添加劑溶解、混合後的溶液進行連線（ inline)添加等的方法》 本發明之丙烯酸粒子（C )可使用市售品。例如有 metablen W-341 ( C2 )(三菱 Rayon (股）製）、 -26- 201107395 chemisnow MR-2G ( C3 ) 、MS-3 00X ( C4 )(綜硏化學（ 股）製）等。 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0.5〜4 5質量％之丙烯酸粒子（C)。 <其他的添加劑> 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。可塑劑例如有酞酸酯系、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與酞酸酯系的可塑劑。聚酯系 可塑劑雖相較於酞酸二辛酯等酞酸酯系的可塑劑時，非遷 移性及耐萃取性更優異，但可塑化效果及相溶性稍微差。 因此，配合用途選擇或倂用此等可塑劑，可適用於廣 範圍的用途。 聚酯系可塑劑係一價至四價羧酸與一價至六價醇的反 應物，但主要係使用二價羧酸與甘醇反應而得者。代表性 之一價竣酸例如有戊二酸、衣康酸、己二酸、酞酸、壬二 酸、癸二酸等。 特別是使用己二酸、酞酸等時，可得可塑化特性優異 者。甘醇例如有乙烯、丙烯、1,3 -丁烯、1,4 -丁稀、1，6· 己靖、新戊條、二乙Μ、三乙燒、二丙燒等之甘醇。此等 二價羧酸及甘醇可各自單獨使用或混合使用。 此酯系之可塑劑可爲酯、低聚酯、聚酯等中任何一形 態，分子量可爲100~10000之範圍’較佳爲600-3000的 -27- 201107395 範圍時可塑化效果較大。 又，可塑劑之黏度雖與分子構造或分子量有關，但爲 己二酸系可塑劑時，從相溶性'可塑化效率的關係，較佳 爲2 00〜5 00011^34(2 5°(：)的範圍。另外，可倂用數個聚 酯系可塑劑。 可塑劑係相對於含有丙烯酸樹脂（A )之組成物1 〇〇 質量份，較佳爲添加0.5 ~30質量份。可塑劑之添加量超 過30質量份時，表面具黏性，實用上不佳。 本發明之光學薄膜可含有紫外線吸收劑，所使用的紫 外線吸收劑例如有苯并三唑系、2_羥基二苯甲酮系或水楊 酸苯酯系者等。例如有2- (5 -甲基-2 -羥基苯基）苯并三 哗、2-[2-羥基- 3,5-雙（α,α-二甲基苯甲基）苯基]-2H-苯 并三哩、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_甲氧基二苯甲酮等的二苯甲酮類。 此等紫外線吸收劑中，分子量爲400以上之紫外線吸 收劑於高沸點下不易揮發，且於高溫形成時也不易飛散， 因此可以較少量添加即可有效改良耐候性。 特別是由薄的被覆層往基板層之遷移性較小，不易析 出於層合板的表面，因此含有的紫外線吸收劑量可長時間 維持’耐候性改良效果之持續性優異等，因此較佳。 分子量爲400以上之紫外線吸收劑例如有2- ( 2-羥 基- 3,5-雙（α，α_二甲基苯甲基）苯基）-2_苯并三唑、2,2· 亞甲基雙^-^丄允:^四丁基广^^^苯并三唑-八基） -28- 201107395 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）癸二酸酯等之受 阻胺系，及2- (3,5 -二-t -丁基-4 -經基苯甲基）-2-η -丁基 丙二酸雙（1，2,2,6,6-五甲基-4-哌啶基酯）、1-[2-[3-( 3,5 -二-t-丁基-4 -經基苯基）丙釀氧基]乙基]-4-[3- ( 3,5_ 二-t -丁基-4-羥基苯基）丙醯氧基]-2,2,6,6 -四甲基哌啶等 之分子內同時具有受阻酚及受阻胺構造的混合系者’此等 可單獨使用或倂用2種以上。其中特佳爲2-[2-羥基-3，5-雙（α，α-二甲基苯甲基）苯基]-2-苯并三唑及2,2-亞甲基 雙[4-(1,1,3，3-四丁基）-6-( 2Η-苯并三唑-2-基）酚]。 此外，本發明之光學薄膜所使用的丙烯酸樹脂（A ) ，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。此外添加防靜電劑，對光學薄膜可賦予防靜 電性能。 本發明之光學薄膜也可使用添加有磷系難燃劑之難燃 丙烯酸系樹脂組成物。 此處使用的磷系難燃劑例如有選自紅磷、三芳基磷酸 酯、二芳基憐酸酯、單芳基磷酸酯、芳基膦酸化合物、芳 基膦氧化物化合物、縮合芳基磷酸酯、鹵化烷基磷酸酯、 含鹵素縮合磷酸酯、含鹵素縮合膦酸酯、含鹵素亞磷酸酯 等之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-9-噁-10-磷雜菲-10-氧化物、苯基膦酸、三（β-氯乙基）磷酸酯、三（二 氯丙基）磷酸酯、三（三溴新戊基）磷酸酯等。 -29- 201107395 <光學薄膜之製膜> 以下說明本發明之光學薄膜之製膜方法例，但本發明 不限定於此等。 製膜方法可使用例如吹塑法、T模法、壓延法、切削 法、流延法、乳化法、熱壓法等製造方法，但是從抑制著 色、抑制異物缺點、抑制模痕等之光學缺點等的觀點，藉 由流延法之溶液製膜較佳。 (有機溶劑） 以溶液流延法製造本發明之光學薄膜時，形成膠漿用 的有機溶劑’較佳爲可同時溶解丙烯酸樹脂（A)、醯化 纖維素樹脂（B )、其他的添加劑者。 較佳爲使用例如氯系有機溶劑之二氯甲烷、醇與選自 本發明之酯系溶劑、酮系溶劑、及脂肪族系溶劑之至少1 種溶劑的混合溶劑。 醇較佳爲碳原子數1〜4之直鏈或支鏈狀之脂肪族醇， 例如有甲醇、乙醇、η-丙醇、iso-丙醇、n_ 丁醇、 醇、tert-丁醇。 使丙燏酸樹脂（A)與醯化纖維素樹脂（b)與丙烯 酸粒子（C)之3種至少共計15〜45質量％溶解於上述溶 劑的膠漿組成物較佳。 以下說明本發明之光學薄膜之較佳的製膜方法。 -30- 201107395 1 )溶解步驟 在以對於丙烯酸樹脂（A)、醯化纖維素樹脂（b) 之良溶劑爲主的有機溶劑中，在溶解鍋中將該丙烯酸樹脂 (A)、醯化纖維素樹脂（B )、及必要時之丙烯酸粒子 (C )、其他的添加劑進行攪拌同時溶解，形成膠漿的步 驟、或將該丙烯酸樹脂（A) '醯化纖維素樹脂（B)溶 液中必要時混合丙烯酸粒子（C )溶液、其他的添加劑溶 液，形成主溶解液之膠漿的步驟。 丙烯酸樹脂（A )、醯化纖維素樹脂（B )之溶解可 使用常壓下溶解的方法、在主溶劑之沸點以下溶解的方法 、在主溶劑之沸點以上進行加壓溶解的方法、如特開平 9-95544號公報、特開平9-95 557號公報、或特開平9-95 5 3 8號公報所記載，以冷却溶解法溶解的方法、如特開 平1 1 -2 1 3 7 9號公報所記載，以高壓溶解的方法等各種的 溶解方法，特佳爲在主溶劑之沸點以上進行加壓溶解的方 法。 膠漿中之丙烯酸樹脂（A)與醯化纖維素樹脂（B) 合計爲15~45質量％的範圍較佳。溶解中或溶解後之膠漿 中加入添加劑，經溶解及分散後，以過濾材過濾、脫泡， 並以送液泵送至下一步驟。 本發明使用的膠漿係藉由過濾除去異物較佳，過濾用 的過濾器可使用紙、金屬等，可以並列、直列進行複數次 過濾。 過濾係使用捕集粒徑 〇.5〜5μιη，且濾水時間 -31 - 201107395 10〜25sec/100ml的爐材較佳。 此方法係將粒子分散時殘留之凝集物或主膠漿添加時 所發生之凝集物，使用捕集粒徑0.5〜5 μηι、且濾水時間 10〜25sec/100ml的濾材可僅除去凝集物。主膠漿中，粒子 之濃度相較於添加液爲非常低，因此過濾時不會產生因凝 集物彼此黏結，造成急速的濾壓上昇。 可將本發明使用的丙烯酸樹脂（A)、醯化纖維素樹 脂（B)、丙烯酸粒子（C) 1種或複數種的粉體投入容器 中，然後添加溶劑溶解，或將粉體投入溶劑中，也可同時 添加，或各自溶解後進行混合。此外，也可僅將1部份另 外溶解後添加。添加順序無特別限定，溶解溫度、攪拌數 也無特別限定，但是以均勻混合的條件較佳。 將本發明用的丙烯酸樹脂（A )、醯化纖維素樹脂（ B )、丙烯酸粒子（C)投入容器的方法，例如可由容器 上部直接投入，但是以空氣運送投入的方法較佳。 圖1係表示本發明較佳之溶液流延製膜方法之膠漿調 製步驟、流延步驟及乾燥步驟之一例的模式圖。 必要時，由丙烯酸粒子投入鍋41以過濾器44除去較 大的凝集物，然後送液至儲存槽42。其後，由儲存槽42 將丙烯酸粒子添加液加入主膠漿溶解鍋1中。 其後，主膠漿液係主過濾器3過濾，然後藉由16連 線（inline)添加紫外線吸收劑添加液。 較多的情形是主膠漿中含有回料10~50質量％。回料 中有時含有丙烯酸粒子，此時配合回料之添加量控制丙烯 -32- 201107395 酸粒子添加液之添加量較佳。 含有丙烯酸粒子之添加液中，較佳爲含有丙烯酸粒子 0.5〜10質量％，更佳爲含有1〜1〇質量％，最佳爲含有i〜5 質量％。 丙烯酸粒子含量較少時，可以低黏度使用，丙烯酸粒 子含量較多時，添加量較少，也容易添加至主膠漿中，故 上述範圍較佳。 回料係指將光學薄膜經過微細粉碎之物品，製膜光學 薄膜時所發生之將薄膜之兩端部分切掉後的物品或因擦傷 等當作規格外之光學薄膜原料使用者。 預先將丙烯酸樹脂、醯化纖維素樹脂及必要時之丙烯 酸粒子混練形成顆粒化者，較適用》 2 )流延步驟 將膠漿通過送液栗（例如加壓型定量齒輪栗）送液至 加壓模3 0，再由加壓模縫將膠漿流延至無限移送之無終 端的金屬支持體31 ’例如有不銹鋼帶、或旋轉之金屬滾 筒等的金屬支持體上之流延位置的流延步驟。 本發明之製造步驟可將複數種的膠漿進行送液，或將 單獨的膠漿進行送液。複數的膠漿進行送液時，在切換膠 漿時’可設置膠漿之置換時間。可進行置換直到沒有先前 膠漿的影響爲止，但是時間較短較佳。 本發明使用的模係可調整模之模頭部分的細縫形狀， 且容易使膜厚均一之加壓模較佳。加壓模有衣架型模（ -33- 201107395 coat hanger die)或T模等均可使用。金屬支 成爲鏡面。爲了提高製膜速度，可在金屬支持 座加壓模，將膠獎量分割進行層合。或可藉由 漿同時流延的共流延法，可得到層合構造的薄 3)溶劑蒸發步驟 將纖維網（使膠漿流延至流延用支持體上 漿膜稱爲「纖維網」）在流延用支持體上加熱 發的步驟。 欲使溶劑蒸發時，有由纖維網側吹風的2 支持體之內面藉由液體傳熱的方法、藉由輻射 熱的方法等，但是內面液體傳熱方法乾燥效率 。也可使用組合彼等的方法。使流延後之支持 網在40〜l〇〇°c之氣氛下，在支持體上乾燥較 40〜10(TC之氣氛下時，將此溫度之熱風吹纖維 藉由紅外線等的手段加熱較佳。 從面品質、透濕性、剝離性的觀點， 3 0〜120秒以內，將該纖維網由支持體上剝離。 4 )剝離步驟 將在金屬支持體上使溶劑蒸發後的纖維網 剝離的步驟。剝離後的纖維網係被送至下一步 金屬支持體上之剝離位置的溫度較佳爲1 佳爲 11~30°C。 持體之表面 體上設置2 將複數之膠 膜。 所形成的膠 ，使溶劑蒸 Ϊ法及/或由 熱由表裏傳 局·故較佳 體上的纖維 佳。欲維持 網上面，或 較佳爲在 在剝離位置 0〜4 0〇C，更 •34- 201107395 剝離之時點之金屬支持體上之纖維網的剝離時殘留溶 劑量係依乾燥條件之強弱、金屬支持體之長度等，在 5 0〜120質量％之範圍進行剝離較佳，但是殘留溶劑量更多 的時點進行剝離時，若纖維網太柔軟時，會損害剝離時平 面性，或因剝離張力容易產生鬆弛或直線條，因此以兼顧 經濟速度與品質，來決定剝離時的殘留溶劑量。 纖維網之殘留溶劑量係下述式定義。 殘留溶劑量（％ )=(纖維網之加熱處理前質量-纖維 網之加熱處理後質量）/(纖維網之加熱處理後質量）x 100 此外，測定殘留溶劑量時之加熱處理係表示以1 1 5。(： 加熱處理1小時。 剝離金屬支持體與薄膜時之剝離張力通常爲 196〜245N/m，但是剝離時易產生皺紋時，以i9〇N/m以下 的張力剝離較佳，更佳爲以可剝離之最低張力〜166.6N/m 、接著以最低張力〜137_2N/m剝離，特佳爲以最低張力 ~1 ΟΟΝ/m 剝離 ° 本發明中’該金屬支持體上之剝離位置的溫度較佳 爲-50〜40°C，更佳爲10〜40°C，最佳爲15〜30。(：。 5 )乾燥及延伸步驟 ί S1 剝離後’使用將纖維網交互通過在乾燥裝置內複數配 -35- 201107395 置之輕’進行搬送之乾燥裝置35及/或以夾具夾住纖維網 之兩端進行搬送之拉幅延伸裝置34，使纖維網乾燥。 乾燥手段一般係將熱風吹纖維網之兩面，也可使用微 波爐靠近加熱取代熱風，進行加熱的手段。太過急速的乾 燥容易損及完成之薄膜的平面性。藉由高溫之乾燥使殘留 溶劑成爲約8質量％以下即可。整體乾燥大槪是以 40〜250°C乾燥。特佳爲以40〜160°C乾燥。 使用拉幅延伸裝置時，較佳爲使用藉由拉幅器之左右 把持手段可以左右獨立控制薄膜之把持長度（把持開始至 把持終了的距離）的裝置。拉幅步驟中，爲了改善平面性 ，也可刻意製作具有不同溫度之區間。 爲了在不同溫度之區間，各自之區間之間不會產生干 擾可設置中性區域。 延伸操作可分割成多階段實施，也可在流延方向、寬 度方向實施二軸延伸。進行二軸延伸時，可同時進行二軸 延伸或分階段實施》 此時，分階段係例如可依順序進行延伸方向不同之延 伸，或將同一方向之延伸分割成多階段，且不同方向之延 伸可加諸於其中任一階段。換言之，例如可有以下的延伸 步驟。 •流延方向延伸-寬度方向延伸-流延方向延伸-流延方向延 伸 .寬度方向延伸-寬度方向延伸-流延方向延伸-流延方向延 伸 -36- 201107395 此外，同時2軸延伸時，也包括一方向延伸後，另一 方則張力緩和產生收縮的情形。同時2軸延伸之較佳之延 伸倍率係寬度方向、長度方向均可爲xl 〇1倍〜χ1 5倍的 範圍。 進行拉幅時之纖維網的殘留溶劑量，在拉幅開始時， 較佳爲20〜100質量％ ’且纖維網之殘留溶劑量成爲1〇質 量％以下爲止使用拉幅器同時乾燥較佳，更佳爲5質量％ 以下。 進行拉幅時之乾燥溫度較佳爲30〜150 °C，更佳爲 50〜120°C，最佳爲 70〜100°C。 拉幅步驟中，氣氛之寬度方向的溫度分布較少，從提 高薄膜之均一性的觀點較佳，拉幅步驟之寬度方向之溫度 分布較佳爲±5°C以內，更佳爲±2°C以內，最佳爲±l°c以內 6 )捲繞步驟 纖維網中之殘留溶劑量成爲2質量％以下後，以光學 薄膜的形態藉由捲繞機3 7捲繞的步驟’使殘留溶劑量在 0.4質量％以下，可得到尺寸安定性良好的薄膜。 捲繞方法使用一般使用的方法即可’例如有定轉距法 、定張力法、錐度張力法（taper tension)、內部應力固 定之程式張力控制法等，將此等分開使用即可。 本發明之光學薄膜較佳爲長條薄膜’具體而言爲 100m〜5000m程度者，通常以捲筒提供的形態者。此外， -37- 201107395 薄膜的寬度較佳爲1.3〜4m，更佳爲1.4〜2m。 本發明之光學薄膜之膜厚無特別限定，但是用於後述 偏光板保護薄膜時，較佳爲20〜200μπι，更佳爲25~100μιη ，特佳爲30〜80μιη。 [偏光板] 可使用一般方法製作偏光板。較佳爲在本發明之光學 薄膜之內面側設置黏著層，再貼合於浸漬於碘溶液中延伸 所製作之偏光子之至少一面上。 另一面可使用本發明之光學薄膜，或其他的偏光板保 護薄膜。例如較佳爲使用市售的纖維素酯薄膜（例如， KonicaMinolta TAC KC8UX、KC4UX、KC5UX、KC8UY、 KC4UY、KC12UR、KC8UCR-3、KC8UCR-4、KC8UCR-5 、KV8UY-HA、KV8UX-RHA，以上爲 KonicaMinolta Opto (股）製）等。 偏光板之主要構成要素的偏光子係指僅能通過一定方 向之偏波面之光的元件，目前已知的代表性偏光膜爲聚乙 烯醇系偏光薄膜，此偏光薄膜有將碘使聚乙烯醇系薄膜染 色者與雙色性染料染色者。 偏光子可使用將聚乙烯醇水溶液製膜後，將其單軸延 伸再染色，或染色後單軸延伸，較佳爲以硼化合物進行耐 久性處理者。 上述黏著層所使用的黏著劑較佳爲使用黏著層之至少 一部分使用在25 °C之儲存彈性模數（storage modulus )爲 -38- 201107395 1.0xl04Pa〜1.0xl09Pa之範圍的黏著劑，而塗佈黏著劑， 貼合後藉由各種化學反應形成高分子量物或交聯構造之硬 化型黏著劑較適用。 具體例如有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 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、丙烯酸酯與過氧化物系之二液型瞬間黏著劑等。 上述黏著劑可爲一液型、或使用前混合二液以上再使 用的二液型。 上述黏著劑可以有機溶劑爲介質的溶劑系、或以水爲 主成份之介質的乳液型、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依據黏著後之膜 厚、塗佈方法、塗佈條件等適當決定，一般爲0.1〜50質 量％。 [液晶顯示裝置] 將貼合本發明之光學薄膜的偏光板組裝於液晶面板後 ’可製作各種辨識性優之液晶顯示裝置。上述偏光板係介 於前述黏著層等貼合於液晶胞上。 本發明之偏光板適用於反射型、透過型、半透過型 LCD 或 TN 型、STN 型、OCB 型、HAN 型、VA 型（PVA 型、MVA型）、IPS型等各種驅動方式的[CD。特別是畫 -39- 201107395 面爲30吋以上，更佳爲30吋~5 4吋之大畫面的顯示裝置 ，在畫面周邊部無泛白等，可長時間維持該效果。 而且色斑、眩光或狀斑紋較少，具有即使長時間觀賞 ，眼睛也不會疲倦的效果。 【實施方式】 實施例 以下舉實施例具體說明本發明，但本發明非限定於此 等。Temperature conditions: transfer line 200 ° C, circuit temperature 200 ° C Sample amount: 〇.8g / 20mlvial GC : HP5 890 (made by Hewlett-Packar) MS : HP5971 (made by Hewlett-Packard Company) Column: HP-624 ( 30mx Inner diameter 0.25mm) Oven temperature: initial temperature 40 ° C (holding time 3 minutes), heating rate 10 ° c / min, reaching temperature 200 ° c (holding time 5 minutes) Measurement mode: SIM (select ion mass: selective ion Mass spectrometry mode <Optical film containing acrylic resin> First, the physical properties of the optical film containing an acrylic resin of the present invention will be described. The optical film of the present invention is preferably a film having a slipperiness of 0.40 or less, more preferably 0.30 or less, as measured according to the method of JIS K71 25-1999. When the slipperiness is in the above range, the operation of the long film which is caused by the wrinkles caused by the precipitates, looseness, and the like can be remarkably broken. The measurement of the slip property was carried out from drying to winding. The measuring machine can use a dynamic friction coefficient friction measuring machine TR type (Toyo Seiki mechanism), and UNIVERSAL TESTING MACHINE RH-30 manufactured by Shimadzu Corporation. The optical film of the present invention contains an acrylic resin (A), a cellulose fiber (B), and a specific solvent of the present invention, and preferably an optical film containing an acrylic resin which does not cause ductile damage. The ductile failure described above is defined as the occurrence of a stress greater than the strength of a material, and is accompanied by significant elongation or contraction of the material prior to the final fracture. The section is characterized by the formation of a myriad of recesses called pockets. Therefore, "an optical film which does not cause ductile damage" is characterized in that no damage such as breakage occurs even if a large stress is applied to bend the film into two sheets. From the viewpoint of the increase in the size of the optical film of the liquid crystal display device and the processability of the film formation, the brittleness of the optical film is becoming more and more demanding, and the above-described ductile damage is also required. When the optical film of the present invention is used in consideration of reducing the haze and is used in a high-temperature environment such as a high-temperature projector or a display device for a vehicle, the tension softening point is preferably controlled at 105 ° C to 1 4 . 5 ° C, more preferably controlled at 1 1 0 °C ~ 1 3 0 °C. For the specific measurement method of the tension softening point temperature of the optical film, for example, using a universal tensile tester (RTC-1225A manufactured by ORIENTEC Co., Ltd.), the optical film is cut into 120 mm (length) x 10 mm (width), and the tension is -12-201107395. While stretching, at the same time, the temperature is increased by 3 (the temperature rise rate of TC/min is continued '3 times, and the temperature at the point of reaching 9 N is measured, and the average enthalpy is obtained. Further, the glass transition temperature (Tg) of the optical film of the present invention is preferably ll. 〇 ° C or more, more preferably 120 ° C or more. Particularly preferably 15 ° ° C or more. Glass transition temperature means using a differential and scanning calorimeter (DSC-7 type manufactured by Perkin Elmer Co., Ltd.) at a temperature increase rate of 20 The average glass transition temperature (Tmg) determined according to JI SK 7 1 2 1 (1 9 8 7 ) was measured at ° C/min. Moreover, the optical film of the present invention has a disadvantage of a diameter of 5 μm or more in the plane of the film. Preferably, it is 1/10 cm square or less, more preferably 0.5/10 cm square or less, more preferably 0.1/10 cm square. The diameter of the defect means that the diameter is a circle, indicating a diameter, and when it is non-circular, it can be borrowed. The scope of the defect is observed using a microscope by the following method Decide, as its maximum diameter (diameter of the circumscribed circle). The shortcoming is the size of the shadow when the shortcoming is the interference of the microscope to observe the shortcomings of the microscope. The disadvantage is the transfer of the roller injury or When the surface shape changes such as scratches, the size of the reflected light of the interference microscope can be differentially observed to confirm the size. Further, when the size of the defect is not clear when the reflected light is observed, aluminum or platinum can be vapor-deposited on the surface for observation. When a film having excellent quality represented by such a defect frequency is obtained, it is possible to use a high-precision filtration of the polymer solution before casting, or to improve the cleanliness of the periphery of the casting machine, or to set the drying conditions after casting in stages. Drying with high efficiency and suppression of foaming. -13- 201107395 When the number of defects is more than one / l〇cm square, for example, when tension is applied to the film during the subsequent processing, sometimes the defect is used as a starting point, and cracking' In the case where the diameter of the defect is significantly lower, it can be visually confirmed by observation of a polarizing plate or the like, and sometimes a bright spot is generated when used as a member. When the method is visually confirmed, the coating may not be uniformly formed on the film, and the coating agent may not be uniformly formed, which may be a disadvantage (not applied). The disadvantage is a film which is generated by the solvent in the drying step of the solution film formation. a void in a film (foaming defect) or a foreign matter in a film produced by a film-forming raw material or a foreign matter mixed in a film (the optical film of the present invention is at least one direction according to JIS-K7 1 27- 1 999 ' The elongation at break is preferably at least 1% by weight, more preferably at least. The upper limit of the elongation at break is not particularly limited, and may actually be caused by inhibiting foreign matter or foaming. Shortcomings. The optical film of the present invention preferably has a light transmittance of 90% or more and preferably 93% or more. The actual upper limit is 99%. In order to achieve excellent transparency as indicated by the light transmittance, it is possible to avoid the absorption of visible light additives or copolymerization components, or to pass high-precision foreign matter in the polymer, or to reduce light diffusion or absorption inside the film. 'By reducing the film contact portion during film formation (cooling rolls, rollers, conveyor belts, coated substrates for solution film formation, handling: the film of the step is broken into 5 μιτ optical hard coating) When the foreign matter defect is measured, 20% is thinned at 250%, and the surface roughness of the film is removed by the full-loading method to remove the surface roughness of -14-201107395 to reduce the surface of the film surface. Roughness, or reducing the refractive index of the acrylic acid resin' reduces the light diffusion or reflection on the surface of the film. The haze 浊 (turbidity) of one of the indexes indicating the transparency of the optical film of the present invention is preferably less than 0.5%, but it is more preferable to consider the brightness and contrast when assembled in a liquid crystal display device. %the following. The haze of the above optical film is ruthenium measured in accordance with JIS K7 361-1-1997 and JIS K7 1 3 6-2000. When the acrylic resin-containing film of the present invention satisfies the above physical properties, it can be used as an optical film. However, by forming the following composition, a film excellent in workability and heat resistance can be obtained. In other words, the optical film is an optical film containing an acrylic resin (A) and a deuterated cellulose resin in a mass ratio of 80:20 to 20:80 from the viewpoint of both workability and heat resistance, and the present invention is excellent. Effect. In the optical film of the present invention, the acrylic resin (A) and the deuterated cellulose resin (B) are contained in a mass ratio of 80:20 to 20:80, but the acrylic resin (A) is preferably 50% by mass or more. When the amount of the acrylic resin component is increased, for example, dimensional change under high temperature and high humidity can be suppressed, and the curl of the polarizing plate or the deformation of the panel when used as a polarizing plate can be remarkably reduced. Further, when the acrylic resin component has a composition of 50% by mass or more, the above physical properties can be maintained for a long period of time. The optical film of the present invention may have a structure containing a resin other than the acrylic resin (A) or the cellulose-modified resin (B). The quality of the acrylic resin (A) and the deuterated cellulose resin (B) is -15-201107395, which is 55 to 100% by mass, preferably 60 to 99% by mass. (Acrylic Resin (A)) The acrylic resin used in the present invention also includes a methacrylic resin. The resin is not particularly limited, but is preferably composed of 50 to 99% by mass of methyl methacrylate unit and 1 to 50% by mass of other monomer units copolymerizable therewith. Other monomers copolymerizable include, for example, an alkyl methacrylate having an alkyl group having 2 to 18 carbon atoms, an alkyl acrylate having an alkyl group having 1 to 18 carbon atoms, acrylic acid, methacrylic acid or the like (X, An aromatic vinyl compound containing an unsaturated group-containing dicarboxylic acid such as β-unsaturated acid, maleic acid, fumaric acid or itaconic acid, styrene, α-methylstyrene or nuclear-substituted styrene , α,β-unsaturated nitrile such as acrylonitrile or methacrylonitrile, maleic anhydride, maleimide, fluorene-substituted maleimide, glutaric anhydride, etc., which may be used alone or in combination. Two or more kinds of monomers are used. Among them, from the viewpoint of heat decomposition resistance and fluidity of the copolymer, methacrylate, ethyl acrylate, η-propyl acrylate, η-butyl acrylate, and the like are preferable. S-butyl acrylate, 2-ethylhexyl acrylate, etc., particularly preferably methacrylate or η-butyl acrylate. The acrylic resin used in the optical film of the present invention is particularly improved from optics. Mechanical strength of film, viewpoint of film productivity, weight average molecular weight (Mw) The weight average molecular weight of the acrylic resin of the present invention can be measured by gel permeation chromatography. The measurement conditions are as follows. -16- 201107395 Solvent: dichloromethane column: Shodex K806, K805, K803G (Showa Denko (Unit) 3 connections are used) Column temperature: 2 5 °C Sample concentration: 〇. 1 mass% Detector: RI Model 504 (manufactured by GL Science) Pump: L6000 (manufactured by Hitachi, Ltd.) Flow rate: l .Oml/min calibration curve: Calibration curve of 13 samples of standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 2,800 ' 000-500. 13 samples were The method for producing the acrylic resin (A) of the present invention is not particularly limited, and any known method such as suspension polymerization, emulsion polymerization, bulk polymerization or solution polymerization can be used. A redox system can also be used by using a general peroxide-based or azo-based polymerization initiator. The polymerization temperature can be 30 to 100 ° C for suspension or emulsion polymerization, and the block or solution polymerization can be 80 to 160. In order to control the reduction viscosity of the obtained copolymer, an alkyl mercaptan or the like may be used as a chain transfer agent, and the polymerization enthalpy may be used to set the molecular weight to achieve both heat resistance and brittleness. The acrylic resin of the present invention can be used. For example, Delpet 6 ON, 8 ON (Asahi Kasei Chemical Co., Ltd.), Dianal BR52, BR80, BR83, BR85, BR88 (Mitsubishi Rayon), KT75 (Electrochemical Industry Co., Ltd.) -17- 201107395 (deuterated cellulose resin (B)) The deuterated cellulose resin (B) of the present invention may be substituted by any of an aliphatic sulfhydryl group or an aromatic fluorenyl group, preferably B Substituted by thiol. When the deuterated cellulose resin of the present invention is blended with an aliphatic sulfhydryl group, the aliphatic fluorenyl group has, for example, a carbon number of 2 to 20, and specific examples thereof include an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, an isobutyl fluorenyl group, and a pentylene group. A group, a trimethylethyl group, a hexyl group, a octyl group, a lauryl group, a stearyl group, and the like. In the present invention, the aliphatic fluorenyl group is a group having a substituent which is further a substituent. When the substituent is the above-mentioned aromatic fluorenyl group, when the aromatic ring is a benzene ring, for example, a substituent of a benzene ring is exemplified. When the above deuterated cellulose resin is an ester with an aromatic fluorenyl group, the number of substituents X substituted on the aromatic ring is 0 or 1 to 5, preferably 1 to 3, particularly preferably 1 or 2 . Further, when the number of the substituents substituted on the aromatic ring is two or more, 'they may be the same or different from each other, and may be bonded to each other to form a condensed polycyclic compound (for example, naphthalene, anthracene, indane, phenanthrene, quinoline, or different). Quinoline, chromene, chroman, pyridazine, acridine, anthracene, anthracene, etc.). The above-mentioned deuterated cellulose resin has a structure selected from at least one of a substituted or unsubstituted aliphatic mercapto group, a substituted or unsubstituted aromatic mercapto group, and can be used as a structure for the cellulose resin of the present invention. , such may be cellulose or mixed acid esters. The degree of substitution (T) of the degree of substitution of the fluorenyl cellulose of the present invention is 2.00 to 3.00, and the sulfhydryl group is not necessarily required, and the degree of substitution of the fluorenyl group (ac) is 〇~1.89. More preferably, the degree of substitution (r) of the sulfhydryl group other than the fluorenyl group is -18-201107395 2.00~2.89 ° The sulfhydryl group other than the fluorenyl group is preferably a carbon number of 3 to 7. In the deuterated cellulose resin of the present invention, it is preferably selected from those having a fluorenyl group having 2 to 7 carbon atoms as a substituent, that is, cellulose acetate, cellulose propionate, cellulose butyrate, fiber. At least one of a cellulose acetate propionate, a cellulose acetate butyrate, a cellulose acetate benzoate, and a cellulose benzoate. Particularly preferred deuterated cellulose resins are cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate. The mixed fatty acid is preferably a lower fatty acid ester of cellulose acetate propionate or cellulose acetate butyrate, and preferably a fluorenyl group having 2 to 4 carbon atoms is a substituent. The moiety that is not substituted by a thiol group usually exists in the form of a hydroxyl group. These can be synthesized by a known method. Further, the degree of substitution of the thiol group or the degree of substitution of other thiol groups can be obtained by the method specified in ASTM-D817-96. When the weight average molecular weight (Mw) of the deuterated cellulose resin of the present invention is 75,000 or more, even if it is at a level of i〇0, it can achieve the object of the invention', but when productivity is considered, it is preferably 7 5000~280000 Those are better for looooo ~240000. (Acrylic Particle (C)) The optical film of the present invention may contain acrylic particles. -19-201107395 The acrylic particles (C) used in the present invention may be present in the optical film together with the aforementioned acrylic resin (A) and deuterated cellulose resin (B) in a particulate state (also referred to as an incompatible state). The acrylic particles (C) are prepared by dissolving the produced optical film in a predetermined amount, dissolving in a solvent, stirring, and sufficiently dissolving and dispersing, and then using a PTFE film having a pore diameter which does not reach the average particle diameter of the acrylic particles (C). The weight of the insoluble matter collected by the filter filtration and filtration is preferably 90% by mass or more of the acrylic particles (C) added to the optical film. The acrylic particles (C) used in the present invention are not particularly limited, and are preferably acrylic 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 multilayered acrylic granulated composite refers to a structure in which the innermost portion of the central portion is the innermost hard layer polymer, the crosslinked soft layer polymer exhibiting rubber elasticity, and the outermost hard layer polymer are layered. A particulate acrylic polymer. Preferred embodiments of the multilayer structure acrylic particulate composite of the present invention include, for example, the following. For example, (a) an alkyl acrylate having a methyl methacrylate of 80 to 98.9 % by mass, an alkyl group having a carbon number of 1 to 8 of 1 to 20% by mass, and a polyfunctional grafting agent of 0.01 to 0·3 The innermost hard layer polymer obtained by polymerizing a monomer mixture composed of % by mass; (b) an alkyl acrylate having a carbon number of 4 to 8 from an alkyl group in the presence of the innermost hard layer polymer a crosslinked soft layer polymer obtained by polymerizing a monomer mixture composed of 75 to 98.5% by mass, a polyfunctional crosslinking agent of 0.01 to 5% by mass, and a polyfunctional grafting agent of 0.5 to 5% by mass; (c) In the presence of the polymer composed of the innermost hard layer and the crosslinked soft -20-201107395 layer, the alkyl acrylate is 1 to 20 by mass of methyl methacrylate 80 to 99% by mass and the carbon number of the alkyl group. The outermost hard layer polymer obtained by polymerizing a monomer mixture composed of %; has a three-layer structure, and the obtained three-layer structure polymer is the innermost hard layer polymer (a) 5 to 40% by mass , the soft layer polymer (b) 30 to 60% by mass and the outermost hard layer polymer (c) 20 to 50% by mass An insoluble portion having an acetone portion and an insoluble portion having an methyl ethyl ketone swelling degree of 1.5 to 4.0 is an acrylic granular polymer. Further, as disclosed in Japanese Patent Publication No. Sho 60-17406 or Japanese Patent Publication No. Hei No. 3-39095, the composition and particle diameter of each layer of the multi-layer structure acrylic particulate composite are not limited, and the multilayer structure acrylic granular composite is also used. The tensile modulus and the methyl ethyl ketone swelling degree of the acetone-insoluble portion are set within a specific range, whereby a balance of more sufficient impact resistance and stress whitening resistance can be achieved. The innermost hard layer polymer (a) constituting the multilayer structure acrylic granulated composite is preferably an alkyl acrylate having a methyl methacrylate of 80 to 98.9 mass% and an alkyl group having a carbon number of 1 to 8. 20 quality. /. And a monomer mixture composed of a polyfunctional grafting agent of 0.01 to 0.3% by mass, which is obtained by polymerization. The alkyl acrylate having an alkyl group having a carbon number of 1 to 8, such as methacrylate, ethyl acrylate, η-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-B As the hexyl acrylate or the like, it is preferred to use methyl acrylate and η-butyl acrylate. The ratio of the alkyl acrylate unit in the innermost hard layer polymer (a) is preferably from 1 to 20% by mass, and when the unit is less than i% by mass, the thermal decomposition property of the polymer is increased from 21 to 201107395. When the unit content is more than 20% by mass, the glass transition temperature of the most preferred compound (c) is lowered, and the effect of imparting the punching resistance of the three-layer structure propylene composite is lowered, which is not preferable. The polyfunctional grafting agent has a different polymerizable functional monomer such as acrylic acid, methacrylic acid, allyl maleate or the like, and allyl methacrylate is preferably used. The branching agent is used to polymerize the innermost hard layer polymer and the soft layer. Therefore, 0.01 to 0.3% by mass of the innermost hard layer is used for polymerization. The crosslinked soft layer constituting the acrylic granular composite is preferably 75 to 98.5% by mass of the alkyl acrylate having a carbon number of 1 to 8 in the presence of the innermost hard layer polymer (a). ~5 mass% and a polyfunctional grafting agent of 0.5 to 5 of a monomer mixture are polymerized. The alkyl acrylate having an alkyl group having 4 to 8 carbon atoms, η-butyl acrylate and 2-ethylhexyl acrylate. Further, these polymerizable monomers may be copolymerized with 25% by mass of other monofunctional monomers. Other monofunctional monomers which can be copolymerized, such as styrene derivatives. When the ratio of the alkyl propylene group having a carbon number of 4 to 8 is more than the current one, the lower the temperature of the resulting polymer (b), the softer it is. From the viewpoint of the transparency of the resin composition, the refractive index at room temperature of the soft layer is closer to the polyfunctionality of the poly- and fumaric acid of the hard layer of the hard layer of the innermost hard layer. The ratio of the chemical enthalpy of the substrate to the compound (b) is preferably composed of an alkyl group and a polyfunctional mass%, preferably a copolymerizable polyethylene and a substituted acid ester, and a glass conversion polymer of benzene & (b J ( a ), most -22- 201107395 The outer hard layer polymer (C) and the hard thermoplastic acrylic resin are better, considering the ratio of the latter selected. For example, when the thickness of the coating layer is low, it is not necessary The styrene is copolymerized. The polyfunctional grafting agent can be used as described in the above-mentioned innermost hard layer polymer (a). The polyfunctional grafting agent used herein is used for the soft layer polymer. (b) chemically bonding to the outermost hard layer polymer (c), and the ratio used in the polymerization of the innermost hard layer is preferably from 0.5 to 5% by mass from the viewpoint of the impact resistance imparting effect. a cross-linking agent can use a divinyl compound A commonly known crosslinking agent such as a diallyl compound, a diacrylic compound, or a dimethacrylic compound is preferably a polyethylene glycol diacrylate (molecular weight: 200 to 600). Polyfunctional crosslinking is used herein. The agent is used to form a crosslinked structure when the soft layer (b) is polymerized, so as to have an effect of imparting impact resistance. However, when a polyfunctional grafting agent is used for the polymerization of a soft layer, a soft layer is formed to some extent (b). Since the cross-linking structure is a non-essential component of the polyfunctional cross-linking agent, the ratio of the polyfunctional cross-linking agent used in the soft layer polymerization is preferably 〇1 to 5 mass% from the viewpoint of the impact-imparting effect. The outermost hard layer polymer (c) constituting the multilayer structure acrylic granular composite is preferably methacrylic acid in the presence of the innermost hard layer polymer (a) and the soft layer polymer (b). A monomer mixture composed of 80 to 99% by mass of a methyl ester and 1 to 20% by mass of an alkyl acrylate having an alkyl group is polymerized. -23- 201107395 wherein the alkyl acrylate can be used as described above, Preferably use a Acrylate and ethyl acrylate. The ratio of the alkyl acrylate unit in the outermost hard layer (C) is preferably from 1 to 20% by mass. Further, in the polymerization of the outermost hard layer (c), The compatibility of the acrylic resin (A), in order to adjust the molecular weight, can be carried out by using an alkyl mercaptan or the like as a chain transfer agent. In particular, the slope of the outermost hard layer is gradually decreased from the inner side to the outer side (slope). It is preferable to improve the balance between elongation and impact resistance. The specific method is to divide the monomer mixture for forming the outermost hard layer into two or more, and sequentially increase the chain transfer dose for each addition. The molecular weight is decreased from the inside to the outside. The molecular weight formed at this time can be known by measuring the molecular weight of the polymer obtained by separately polymerizing the monomer mixture used each time under the same conditions. The particle size of the acrylic particulate composite having a multilayer structure which is suitable for use in the present invention is not particularly limited, but is preferably 1 nm or more and 1 〇〇〇 nm or less, more preferably 20 nm or more and 500 nm or less, and most preferably 50 nm or more and 400 nm or less. In the acrylic granular composite in which the multilayer structure polymer is suitably used in the present invention, the mass ratio of the core to the shell is not particularly limited, but when the entire multilayer structure polymer is 100 parts by mass, the core layer is preferably 50 parts by mass. The commercially available product of the above-mentioned '90 parts by mass or less, more preferably 60 parts by mass or more and 80 parts by mass or less of the multilayer structure acrylic granular composite, for example, -24-201107395 Mitsubishi Rayon Co., Ltd. "metablen", clock "Kanes" manufactured by Yuan Chemical Industry Co., Ltd., "paraloid" manufactured by Wu Yu Chemical Industry Co., Ltd., "Acryloid" manufactured by Rohm and Haas Co., "staphiloid" manufactured by ganz Chemical Industry Co., Ltd., and "parapet SA" manufactured by Kuraray Co., Ltd., etc. Use or use 2 or more types. Further, in the acrylic particle (C) which is more suitably used in the present invention, a specific example of the graft copolymerized acrylic particle (c-1) which is more suitable is an unsaturated carboxylic acid ester in the presence of a rubbery polymer. A graft copolymer obtained by copolymerizing a monomer, an unsaturated carboxylic acid monomer, an aromatic vinyl monomer, and, if necessary, a monomer mixture of other ethylene-based monomers copolymerized therewith . The rubbery polymer used for the acrylic particles (c-1) of the graft copolymer is not particularly limited. A diene rubber, an acrylic rubber, a vinyl rubber or the like can be used. Specific examples are 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, butadiene-ethyl acrylate copolymer, ethylene-propylene copolymer, susceptibility _ propylene-two An olefin copolymer, an ethylene-isoprene copolymer, and a ethylene-methyl acrylate copolymer. These rubbery polymers may be used alone or in combination of two or more. When the refractive index of each of the acrylic resin (A) and the acrylic particles (C) is approximated, the transparency of the optical film of the present invention can be obtained, which is preferable. Specifically, the refractive index of the acryl particle (C) and the acrylic resin (a) -25-201107395 is preferably 0.05 or less, more preferably 0.02 or less, and particularly preferably 0.01 or less. In order to satisfy such a 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 particle (C) may be adjusted. By reducing the refractive index difference by the method or the like, an optical film excellent in transparency can be obtained. Here, the refractive index difference means that the optical film of the present invention is sufficiently dissolved in a solvent soluble in the acrylic resin (A) to form a white turbid solution under appropriate conditions, and then separated into a solvent-soluble portion by centrifugation or the like. And the insoluble portion, the soluble portion (acrylic resin (A)) and the insoluble portion (acrylic acid particles (C)) were separately purified to show the difference between the measured refractive index (23 ° C, measurement wavelength: 5 5 Onm ) . In the present invention, the method of formulating the acrylic particles (C) in the acrylic resin (A) is not particularly limited, and it is preferred to use the acrylic resin (A) and other optional components in advance, usually at 200 to 3 50 ° C. A method in which acrylic particles (C) are added while performing uniform melt kneading by a uniaxial or biaxial extruder. Further, a method of adding a solution in which acrylic particles (C) are dispersed in advance to a solution (slurry) in which an acrylic resin (A) and a cellulose-deposited resin (B) are dissolved may be used or a method of mixing acrylic acid particles (C) may be used. A method in which a solution obtained by dissolving or mixing any of the other additives is added in an inline or the like. A commercially available product can be used for the acrylic particles (C) of the present invention. For example, there are metablen W-341 (C2) (Mitsubishi Rayon), -26-201107395 chemisnow MR-2G (C3), MS-3 00X (C4) (complex chemical system). In the optical film of the present invention, it is preferred to contain 0.5 to 45 mass% of the acrylic particles (C) based on the total mass of the resin constituting the film. <Other Additives> The optical film of the present invention can be used in order to enhance the fluidity and flexibility of the composition. The plasticizer may, for example, be a phthalate type, a fatty acid ester type, a trimellitic acid ester type, a phosphate type, a polyester type or an epoxy type. Among them, a polyester-based and phthalate-based plasticizer is preferably used. Although the polyester-based plasticizer is superior to the phthalate-based plasticizer such as dioctyl phthalate, it has excellent non-migration property and extraction resistance, but has a slightly poor plasticizing effect and compatibility. Therefore, the selection or use of these plasticizers in combination with the application can be applied to a wide range of applications. The polyester-based plasticizer is a reactant of a monovalent to tetravalent carboxylic acid and a monovalent to hexavalent alcohol, but mainly obtained by reacting a divalent carboxylic acid with a glycol. Representative one-price tannins are, for example, glutaric acid, itaconic acid, adipic acid, decanoic acid, azelaic acid, sebacic acid and the like. In particular, when adipic acid, citric acid or the like is used, it is excellent in plasticizing properties. The glycol may, for example, be a glycol such as ethylene, propylene, 1,3-butene, 1,4-butadiene, 1,6·hexan, neopentyl, diacetamidine, triethylidene or dipropylene. These divalent carboxylic acids and glycols may each be used singly or in combination. The ester-based plasticizer may be in any one of ester, oligoester, polyester, etc., and may have a molecular weight of from 100 to 10,000, preferably from 600 to 3,000, in the range of -27 to 201107395. Further, although the viscosity of the plasticizer is related to the molecular structure or molecular weight, when it is an adipic acid plasticizer, the relationship of the compatibility 'plasticizing efficiency is preferably 200 to 5 000 11 ^ 34 (2 5 ° (: In addition, a plurality of polyester-based plasticizers may be used. The plasticizer is preferably added in an amount of from 0.5 to 30 parts by mass based on 1 part by mass of the composition containing the acrylic resin (A). When the amount is more than 30 parts by mass, the surface is sticky and practically poor. The optical film of the present invention may contain an ultraviolet absorber, and the ultraviolet absorber used is, for example, a benzotriazole system or a 2-hydroxybenzophenone. Or phenyl salicylate, etc., for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazine, 2-[2-hydroxy-3,5-bis(α,α-di Triazoles such as methylbenzyl)phenyl]-2H-benzotriazine, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-hydroxy- a benzophenone such as 4-methoxybenzophenone or 2-hydroxy-4-octyloxybenzophenone 2,2'-dihydroxy-4-methoxybenzophenone. UV absorption with a molecular weight of 400 or more in the ultraviolet absorber The agent is not volatile at a high boiling point, and is not easily scattered when formed at a high temperature, so that the weather resistance can be effectively improved by adding a small amount. In particular, the migration from the thin coating layer to the substrate layer is small, and it is difficult to precipitate the layer. The surface of the plywood is preferably a UV absorber having a molecular weight of 400 or more, such as 2-(2-hydroxy-3,5-, which is excellent in the durability of the weather-resistant improvement effect. Bis(α,α-dimethylbenzyl)phenyl)-2_benzotriazole, 2,2·methylenebis^-^丄: ^tetrabutyl guang^^^ benzotriazole -八基) -28- 201107395 benzotriazole, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis (1,2,2) , a hindered amine system such as 6,6-pentamethyl-4 -piperidinyl) sebacate, and 2-(3,5-di-t-butyl-4-carbylmethyl)-2 -η-butylmalonic acid bis(1,2,2,6,6-pentamethyl-4-piperidyl ester), 1-[2-[3-( 3,5 -di-t-butyl) 4--4-Phenylphenyl)propanyloxy]ethyl]-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoxy]-2,2, 6,6-tetramethylpiperidine, etc. In the case of a mixture of a hindered phenol and a hindered amine structure, the above may be used alone or in combination of two or more. Among them, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2-benzotriazole and 2,2-methylenebis[4- (1,1,3,3-tetrabutyl)-6-( 2Η-benzotriazol-2-yl)phenol]. Further, the acrylic resin (A) used in the optical film of the present invention may be added with various antioxidants in order to improve thermal decomposition properties and thermal coloring properties during molding. In addition, an antistatic agent is added to impart antistatic properties to the optical film. As the optical film of the present invention, a flame-retardant acrylic resin composition to which a phosphorus-based flame retardant is added can also be used. The phosphorus-based flame retardant used herein is, for example, selected from the group consisting of red phosphorus, triaryl phosphate, diaryl rich acid ester, monoaryl phosphate, arylphosphonic acid compound, arylphosphine oxide compound, condensed aryl group. One or a mixture of two or more of a phosphate ester, a halogenated alkyl phosphate, a halogen-containing condensed phosphate, a halogen-containing condensed phosphonate, and a halogen-containing phosphite. Specifically, for example, triphenyl phosphate, 9,10-dihydro-9-ox-10-phosphaphenanthrene-10-oxide, phenylphosphonic acid, tris(β-chloroethyl)phosphate, tris(dichloro Propyl) phosphate, tris(tribromoneopentyl) phosphate, and the like. -29- 201107395 <Film film formation of optical film> An example of a film formation method of the optical film of the present invention will be described below, but the present invention is not limited thereto. As the film forming method, for example, a production 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 can be used, but optical defects such as suppression of coloring, suppression of foreign matter defects, and suppression of mold marks are suppressed. From the viewpoint of the above, it is preferred to form a film by a solution of a casting method. (Organic solvent) When the optical film of the present invention is produced by a solution casting method, the organic solvent for forming a dope is preferably one in which the acrylic resin (A), the deuterated cellulose resin (B), and other additives are simultaneously dissolved. . Preferably, a mixed solvent of, for example, a chlorine-based organic solvent, methylene chloride, an alcohol, and at least one solvent selected from the group consisting of the ester solvent, the ketone solvent, and the aliphatic solvent of the present invention is used. The alcohol is preferably a linear or branched aliphatic alcohol having 1 to 4 carbon atoms, and examples thereof include methanol, ethanol, η-propanol, iso-propanol, n-butanol, alcohol, and tert-butanol. It is preferable to dissolve the propionate resin (A), the deuterated cellulose resin (b) and the acrylic acid particles (C) in at least 15 to 45 mass% in total to the above-mentioned solvent. A preferred film forming method of the optical film of the present invention will be described below. -30- 201107395 1 ) Dissolution step In an organic solvent mainly composed of a good solvent for acrylic resin (A) and cellulose halide resin (b), the acrylic resin (A) and bismuth fiber are dissolved in a dissolution pot. The resin (B), and, if necessary, the acrylic particles (C) and other additives are stirred and dissolved to form a dope, or the acrylic resin (A) is dehydrated in a cellulose (B) solution. The step of mixing the acrylic particle (C) solution and the other additive solution to form a dope of the main solution. The dissolution of the acrylic resin (A) or the deuterated cellulose resin (B) can be carried out by a method of dissolving under normal pressure, a method of dissolving below the boiling point of the main solvent, or a method of performing pressure dissolution at a boiling point or higher of the main solvent. A method of dissolving in a cooling and dissolving method, such as JP-A No. Hei 9-95 554, JP-A-H09-95 557, or JP-A-H09-95-53, As described in the publication, various dissolution methods such as a method of dissolving at a high pressure are particularly preferably a method of performing pressure dissolution at a boiling point or higher of a main solvent. The acrylic resin (A) and the deuterated cellulose resin (B) in the dope preferably have a total range of 15 to 45% by mass. Adding an additive to the dope after dissolution or dissolution, dissolving and dispersing, filtering, defoaming with a filter material, and pumping to the next step by liquid feeding. The paste used in the present invention is preferably a filter for removing foreign matter, and the filter for filtration may be paper or metal, and may be subjected to a plurality of filtrations in parallel or in series. The filtration system is preferably a crucible having a particle diameter of 〇.5 to 5 μm, and a filtration time of -31 to 201107395 10 to 25 sec/100 ml. This method is a method of removing agglomerates by using a filter material having a particle diameter of 0.5 to 5 μm and a filtration time of 10 to 25 sec/100 ml when agglomerates which are left when the particles are dispersed or agglomerates which are generated when the main gel is added. In the main dope, the concentration of the particles is extremely low compared to the additive liquid, so that the aggregates do not stick to each other during filtration, resulting in a rapid increase in filtration pressure. The acrylic resin (A), the deuterated cellulose resin (B), the acrylic particles (C), or a plurality of powders used in the present invention may be put into a container, and then dissolved in a solvent or charged into a solvent. They can also be added at the same time or mixed separately after dissolution. Alternatively, only one part may be separately dissolved and added. The order of addition is not particularly limited, and the dissolution temperature and the number of stirring are not particularly limited, but conditions for uniform mixing are preferred. The method of putting the acrylic resin (A), the deuterated cellulose resin (B), and the acrylic particles (C) used in the present invention into a container can be directly carried out, for example, by directly feeding the upper portion of the container, but it is preferably carried out by air transportation. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing an example of a dosing step, a casting step and a drying step of a preferred solution casting film forming method of the present invention. If necessary, the acrylic particles are introduced into the pot 41 to remove the larger aggregates by the filter 44, and then supplied to the storage tank 42. Thereafter, the acrylic particle addition liquid is added to the main dope dissolving pot 1 from the storage tank 42. Thereafter, the main dope was filtered by the main filter 3, and then the ultraviolet absorbent addition liquid was added by 16 inline. In many cases, the main glue contains 10 to 50% by mass of the recycled material. The acrylic material may be contained in the recycled material. In this case, the addition amount of the propylene-32-201107395 acid particle addition liquid is preferably controlled in accordance with the amount of the recycled material. The additive liquid containing acrylic particles preferably contains 0.5 to 10% by mass of the acrylic particles, more preferably 1 to 1% by mass, and most preferably 1 to 5% by mass. When the content of the acrylic particles is small, it can be used at a low viscosity. When the content of the acrylic particles is large, the amount of addition is small, and it is easy to be added to the main dope, so the above range is preferable. The term "returning material" refers to an article in which an optical film is finely pulverized, and an article which cuts off both end portions of the film which occurs when the film is formed into an optical film or a material which is an optical film material which is used as a specification due to abrasion or the like. The acrylic resin, the deuterated cellulose resin and, if necessary, the acrylic particles are mixed and formed into granules, which is more suitable for use. 2) The casting step is to feed the glue through the liquid supply pump (for example, a pressurized quantitative gear pump) to the addition. The die 30 is further cast by the press die to the infinitely transferred endless metal support 31', for example, a casting of a casting position on a metal support such as a stainless steel belt or a rotating metal drum step. The manufacturing steps of the present invention may be carried out by feeding a plurality of types of dopes or by feeding a separate dope. When a plurality of glues are supplied for liquid supply, the replacement time of the glue can be set when the glue is switched. The displacement can be carried out until there is no influence of the previous glue, but the time is shorter. The mold system used in the present invention can adjust the shape of the slit of the die portion of the mold, and it is easy to make the press mold uniform in film thickness. The press mold can be used with a hanger mold (-33-201107395 coat hanger die) or a T die. The metal branch becomes a mirror surface. In order to increase the film forming speed, the stamping amount can be divided and laminated in the metal support press mold. Alternatively, the laminated structure can be obtained by a co-casting method in which the slurry is simultaneously cast. 3) Solvent evaporation step. The fiber web (the slurry is cast to the support film of the casting support is referred to as "web") The step of heating the hair on the support for casting. When the solvent is to be evaporated, there is a method of transferring heat to the inner surface of the support body by the side of the fiber web by means of liquid heat, a method of radiating heat, etc., but the inner surface liquid heat transfer method is effective in drying. It is also possible to use a combination of these methods. After the cast support web is dried in a 40 to 10 ° C atmosphere, the hot air blown fiber of this temperature is heated by means of infrared rays or the like when the support is dried in an atmosphere of 40 to 10 (TC atmosphere). From the viewpoint of surface quality, moisture permeability, and peelability, the fiber web is peeled off from the support within 30 to 120 seconds. 4) The peeling step peels off the fiber web after evaporating the solvent on the metal support. A step of. The temperature at which the peeled fiber web is fed to the peeling position on the next metal support is preferably 1 to 10 °C. Set the surface of the body to 2 sets of multiple films. The formed glue is preferred for the evaporation of the solvent and/or the transfer of heat from the surface to the fibers of the preferred body. It is desirable to maintain the surface of the net, or preferably the amount of residual solvent in the peeling of the web on the metal support at the time of stripping at 0 to 40 ° C, and more than 34 to 201107395. It is preferable to carry out the peeling in the range of 50 to 120% by mass in the length of the support, etc., but when the amount of residual solvent is more, when the web is too soft, the flatness at the time of peeling may be impaired, or the peeling tension may be caused. Since it is easy to produce slack or a straight line, the amount of residual solvent at the time of peeling is determined by taking into consideration the economic speed and quality. The residual solvent amount of the fiber web is defined by the following formula. The amount of residual solvent (%) = (mass before heat treatment of the fiber web - mass after heat treatment of the fiber web) / (mass after heat treatment of the fiber web) x 100 Further, the heat treatment at the time of measuring the amount of residual solvent is indicated by 1 1 5. (: Heat treatment for 1 hour. The peeling tension when peeling the metal support and the film is usually 196 to 245 N/m, but when wrinkles are likely to occur during peeling, it is preferable to peel at a tension of i9 〇 N/m or less, more preferably The peelable minimum tension is ~166.6 N/m, and then peeled off at a minimum tension of ~137_2 N/m, particularly preferably at a minimum tension of ~1 ΟΟΝ/m. In the present invention, the temperature at the peeling position on the metal support is preferably It is -50 to 40 ° C, more preferably 10 to 40 ° C, and most preferably 15 to 30. (: 5) Drying and stretching steps ί S1 After peeling off, the fiber web is interactively passed through the drying device. -35- 201107395 Light-drying 'drying device 35 and/or tenter stretching device 34 for gripping both ends of the fiber web by the clamp to dry the fiber web. Drying means generally blowing hot air to the fiber web On both sides, it is also possible to use a microwave oven to heat the hot air instead of heating, and the drying is too fast, and the flatness of the completed film is easily damaged. The residual solvent is dried at a high temperature to be about 8 mass% or less. Daxie is 40 It is dried at 250 ° C. It is particularly preferably dried at 40 to 160 ° C. When using a tenter stretching device, it is preferable to use the left and right holding means of the tenter to independently control the holding length of the film (the holding start to the end of the holding) In the tentering step, in order to improve the planarity, it is also possible to intentionally create intervals having different temperatures. In order to prevent interference between the respective intervals in different temperature ranges, a neutral region can be set. It can be divided into multiple stages, and the two-axis extension can be carried out in the casting direction and the width direction. When the two-axis extension is performed, the two-axis extension or the phase-by-stage implementation can be performed simultaneously. At this time, the staged system can be extended, for example, in sequence. The extension of the direction is different, or the extension of the same direction is divided into multiple stages, and the extension of the different directions may be applied to any of the stages. In other words, for example, the following extension steps may be performed: • Casting direction extension - width direction extension - Casting direction extension - casting direction extension. width direction extension - width direction extension - casting direction extension - casting direction extension -36- 201107395 In addition, at the same time, when extending in two directions, the tension is relaxed in one direction and the other side is relaxed. At the same time, the preferred stretching ratio of the two-axis extension is x1 〇1 times to 长度1 5 . The amount of the solvent remaining in the web at the time of the tentering is preferably 20 to 100% by mass at the start of the tentering, and the tenter is used at the same time as the residual solvent amount of the fiber web is 1% by mass or less. The drying is preferably carried out, more preferably 5% by mass or less. The drying temperature at the time of tentering is preferably from 30 to 150 ° C, more preferably from 50 to 120 ° C, most preferably from 70 to 100 ° C. The temperature distribution in the width direction of the atmosphere is small, and from the viewpoint of improving the uniformity of the film, the temperature distribution in the width direction of the tentering step is preferably within ±5 ° C, more preferably within ± 2 ° C, most Preferably, the amount of residual solvent in the fiber web is 2% by mass or less, and the step of winding in the form of an optical film by the winding machine 37 is to make the residual solvent amount 0.4 mass. Below %, a film having good dimensional stability can be obtained. The winding method can be carried out by using a method generally used, for example, a fixed torque method, a constant tension method, a taper tension method, a program tension control method for internal stress fixation, and the like. The optical film of the present invention is preferably a long film ‘specifically, it is in the range of 100 m to 5000 m, and is usually provided in the form of a roll. Further, the width of the film of -37 to 201107395 is preferably from 1.3 to 4 m, more preferably from 1.4 to 2 m. The film thickness of the optical film of the present invention is not particularly limited, but is preferably 20 to 200 μm, more preferably 25 to 100 μm, and particularly preferably 30 to 80 μm, for use in a polarizing plate protective film to be described later. [Polarizing Plate] A polarizing plate can be produced by a general method. Preferably, an adhesive layer is provided on the inner surface side of the optical film of the present invention, and is bonded to at least one surface of the polarizer formed by stretching in the iodine solution. On the other hand, the optical film of the present invention, or other polarizing plate protective film can be used. For example, it is preferred to use a commercially available cellulose ester film (for example, Konica Minolta TAC KC8UX, KC4UX, KC5UX, KC8UY, KC4UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KV8UY-HA, KV8UX-RHA, etc. For Konica Minolta Opto (shares) and so on. The polarizer of the main constituent elements of the polarizing plate refers to an element which can pass only the light of the deflecting surface in a certain direction. The representative polarizing film which is known at present is a polyvinyl alcohol-based polarizing film which has iodine to make polyvinyl alcohol. Film dyes and dichroic dyes. The polarizer can be obtained by forming a film of a polyvinyl alcohol aqueous solution, stretching it by uniaxial stretching, or uniaxially stretching after dyeing, and it is preferred to carry out durability treatment with a boron compound. The adhesive used in the above adhesive layer is preferably coated with at least a part of the adhesive layer using an adhesive having a storage modulus of -38 to 201107395 1.0xl04Pa to 1.0xl09Pa at 25 °C. Adhesives, which are suitable for forming a high molecular weight or crosslinked structure by various chemical reactions after bonding. Specific examples thereof include a urethane-based pressure-sensitive adhesive, an epoxy-based pressure-sensitive adhesive, a water-based polymer-isocyanate-based pressure-sensitive adhesive, a thermosetting acrylic adhesive, and the like, and a moisture-curing urethane adhesive. , polyether methacrylate type, ester type methacrylate type, oxidized polyether methacrylate and other anaerobic adhesives, cyanoacrylate type instant adhesives, acrylates and peroxides The second liquid type instant adhesive and the like. The above-mentioned adhesive may be a one-liquid type or a two-liquid type which is used in combination of two or more liquids before use. The above-mentioned adhesive may be a solvent based on an organic solvent or an emulsion type, a colloidal dispersion type, an aqueous solution type or the like which is a medium containing water as a main component, or a solventless type. The concentration of the above adhesive liquid can be appropriately determined depending on the film thickness after the adhesion, the coating method, the coating conditions, etc., and is usually 0.1 to 50% by mass. [Liquid crystal display device] After the polarizing plate to which the optical film of the present invention is bonded is assembled to a liquid crystal panel, various liquid crystal display devices having excellent visibility can be produced. The polarizing plate is bonded to the liquid crystal cell via the adhesive layer or the like. The polarizing plate of the present invention is suitable for a variety of driving modes such as 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), and an IPS type. In particular, the painting is -39-201107395. The display device with a size of 30 inches or more, more preferably 30 inches to 5 inches, has no whitening at the periphery of the screen, and can maintain this effect for a long time. Moreover, there are fewer spots, glare or streaks, and the eyes are not tired even if they are watched 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.
實施例AExample A
[光學薄膜比較例1之製作] (膠漿液組成） 丙烯酸樹脂 DIANAL BR85 ( Mitsubishi Rayon (股）製） 70質量份 醯化纖維素樹脂CAP482-20C醯基總置換度2.75、乙醯基 取代度 0.19、丙醯基取代度 2.56、Mw = 200000 Eastman Chemical (股）製） 30質量份 二氯甲院 300質量份 乙醇 40質量份 將上述組成物加熱充分溶解’製作膠漿液。 (光學薄膜比較例1之製膜） -40- .201107395 使用帶狀流延裝置，以溫度22 °C、2m寬度，將上述 製作的膠漿液均勻地流延於不銹鋼帶支持體上。在不銹鋼 帶支持體上使溶劑蒸發直到殘留溶劑量變成1 〇〇%爲止， 自不銹鋼帶支持體上以剝離張力16 ON/m剝離。 使剝離後之薄膜的纖維網以3 5 °C使溶劑蒸發，裁切成 1.6m寬，然後使用拉幅器在寬度方向延伸1 · 1倍，同時以 1 3 5 °C之乾燥溫度乾燥。 使用拉幅器延伸後，以13 0°C緩和5分鐘後，以多數 輥搬送通過120°C、130°C之乾燥區域（zone)，同時乾燥 結束，裁切成1.5m寬，對薄膜兩端施加寬10mm、高度 5μιη之壓花加工，以初期張力220N/m '最終張力1 ΙΌΝ/m 捲繞於內徑6吋的芯上，得到膜厚爲 60 μιη、卷長爲 4000m的光學薄膜比較例1。 由不銹鋼帶支持體之旋轉速度與拉幅器之運轉速度計 算之M D方向的延伸倍率爲1 . 1倍。 <光學薄膜比較例2之製作> 除了將甲基丙烯酸甲酯0.0008質量份作爲上述膠漿 液組成的溶劑，混合使用與比較例1同量之二氯甲烷、乙 醇外，與光學薄膜比較例1同樣製作光學薄膜比較例2。 <光學薄膜實施例1之製作> 除了將甲基丙烯酸甲酯0.2000質量份作爲上述膠漿 液組成之溶劑，混合使用與比較例1同量之二氯甲烷、乙 201107395 醇外’與光學薄膜比較例1製作光學薄膜實施例1。 <光學薄膜比較例3~31之製作> 除了將丙烯酸樹脂（A)、醯化纖維素樹脂（B)之 混合比率、作爲溶劑之甲基丙烯酸甲酯、乙酸甲酯、甲基 乙基酮、己烷之添加量改爲如表1外，與光學薄膜比較例 2製作同樣製作光學薄膜比較例3 ~3 1。 <光學薄膜實施例2~12之製作> 除了將丙烯酸樹脂（A)、醯化纖維素樹脂（b)之 混合比率、作爲溶劑之甲基丙烯酸甲酯、乙酸甲酯、甲基 乙基酮、己烷之添加量改爲如表1外，與光學薄膜實施例 1製作同樣製作光學薄膜實施例2~12。 《評價》 使用上述製作之光學薄膜實施例1〜12、比較例卜31 進行以下評價。 <溶劑含量之定量> 光學薄膜中之本發明的酯系溶劑、酮系溶劑、及脂肪 族系溶劑之含量係藉由前述頂空氣相層析進行定量。 <延性破壞> 將在23°C、55%RH之空調室進行24小時調濕後的光 -42- 201107395 學薄膜在同條件下，切成100 mm (長）xl〇mm (寬），於 長度方向之中央部以曲率半徑〇mm、折彎角爲180°，使 薄膜完全重疊的狀態分別外折、內折各折1次，此評價測 定3次，以下述基準評價。此處之評價之折斷係表示破裂 分離成2片以上的片段。 〇：3次均未折斷 X : 3次中，至少1次折斷 實施例1〜12之試料在上述評價均爲〇的評價，且無 延性破壞的光學薄膜。而僅以丙烯酸樹脂所構成的比較例 13、14的光學薄膜爲x的評價。 <滑性> 將上述製作之各薄膜試料在23 °C、55 % RH之空調室 中調濕24小時後，同條件下，將薄膜試料1片依據JIS K7 1 25 - 1 999使用動摩擦係數摩擦測定機tr型（東洋精機 製）測定。 <膠漿狀態> 將製作後的各膠漿採樣’在室溫下放置1日進行觀察 〇 〇：與放置前相同無變化 X :有析出物發生 -43- 201107395[Production of Optical Film Comparative Example 1] (Mixed liquid composition) Acrylic resin DIANAL BR85 (manufactured by Mitsubishi Rayon Co., Ltd.) 70 parts by mass of deuterated cellulose resin CAP482-20C 醯 base total substitution degree 2.75, acetyl group substitution degree 0.19 , propylene group substitution degree 2.56, Mw = 200000 Eastman Chemical Co., Ltd.) 30 parts by mass of dichlorocarbyl 300 parts by mass of ethanol 40 parts by mass. The above composition was sufficiently dissolved by heating to prepare a dope. (Film film comparative example 1 film formation) -40-.201107395 The above-prepared cement slurry was uniformly cast on a stainless steel belt support at a temperature of 22 ° C and a width of 2 m using a belt-shaped casting device. The solvent was evaporated on the stainless steel belt support until the amount of residual solvent became 1 〇〇%, and peeled off from the stainless steel belt support at a peeling tension of 16 ON/m. The web of the peeled film was allowed to evaporate at 35 ° C, cut into 1.6 m width, and then stretched by 1.1 times in the width direction using a tenter while being dried at a drying temperature of 135 °C. After stretching with a tenter, it was allowed to relax at 130 ° C for 5 minutes, and then conveyed through a plurality of rolls through a drying zone of 120 ° C and 130 ° C, while drying was completed, and cut into 1.5 m width, two films on the film. An embossing process with a width of 10 mm and a height of 5 μm was applied to the end and wound on a core having an inner diameter of 6 以 at an initial tension of 220 N/m 'final tension of 1 ΙΌΝ/m to obtain an optical film having a film thickness of 60 μm and a roll length of 4000 m. Comparative Example 1. The stretching ratio in the M D direction calculated by the rotation speed of the stainless steel belt support and the running speed of the tenter is 1.1 times. <Production of Optical Film Comparative Example 2> In addition to using 0.0008 parts by mass of methyl methacrylate as a solvent for the above-mentioned dope solution, the same amount of dichloromethane and ethanol as in Comparative Example 1 were used in combination, and an optical film was used. 1 Comparative Example 2 of optical film was produced in the same manner. <Production of Optical Film Example 1> Except that 0.2000 parts by mass of methyl methacrylate was used as a solvent for the above-mentioned dope solution, the same amount of methylene chloride as that of Comparative Example 1 and B. 201107395 Alcohol and 'Optical film were used in combination. Comparative Example 1 An optical film Example 1 was produced. <Production of Optical Film Comparative Examples 3 to 31> In addition to mixing ratio of acrylic resin (A) and deuterated cellulose resin (B), methyl methacrylate, methyl acetate, methyl ethyl group as a solvent The addition amount of the ketone and the hexane was changed to the same as in Table 1, and the optical film Comparative Example 3 to 3 1 was produced in the same manner as in the optical film Comparative Example 2. <Production of Optical Film Examples 2 to 12> In addition to the mixing ratio of the acrylic resin (A) and the cellulose halide resin (b), methyl methacrylate, methyl acetate, methyl ethyl group as a solvent The amounts of the ketone and the hexane were changed as shown in Table 1, and the optical film Examples 2 to 12 were produced in the same manner as in the optical film Example 1. <<Evaluation>> The following evaluations were carried out using the optical film Examples 1 to 12 and Comparative Example 31 produced as described above. <Quantification of Solvent Content> The content of the ester solvent, the ketone solvent, and the aliphatic solvent of the present invention in the optical film is quantified by the above-described headspace phase chromatography. <ductile destruction> The light-42-201107395 film after conditioning for 24 hours in an air-conditioned room at 23 ° C and 55% RH was cut into 100 mm (length) x l 〇 mm (width) under the same conditions. In the center portion in the longitudinal direction, the radius of curvature 〇mm and the bending angle were 180°, and the film was completely folded and folded in one state in the state in which the films were completely overlapped. This evaluation was measured three times and evaluated according to the following criteria. The fracture of the evaluation herein indicates that the fragment is separated into two or more pieces by rupture. 〇: No breakage in 3 times X: At least 1 break in 3 times The samples of Examples 1 to 12 were evaluated as 〇, and there was no ductile-destroyed optical film. On the other hand, the optical films of Comparative Examples 13 and 14 composed only of an acrylic resin were evaluated for x. <Slip property> After the film samples prepared above were conditioned in an air-conditioned room at 23 ° C and 55% RH for 24 hours, the film samples were subjected to dynamic friction in accordance with JIS K7 1 25 - 1 999 under the same conditions. Coefficient friction measuring machine tr type (Toyo Seiki mechanism) measurement. <Mastic state> Each of the prepared cement samples was placed at room temperature for one day for observation. 〇 〇: same as before the placement. X: Precipitates occurred -43- 201107395
光學薄膜 No. ※質量比 溶劑 溶劑添加量 (質量份） 溶劑含有量 (質量％) 滑性 mm 狀態 比較例1 30/70 一 一 一. 0.49; 〇 比較例2 30/70 甲基丙烯酸甲酯 0.0008 0,0004 0.49 ο 實施例1 30/70 甲基丙#酸甲SI 0,2000 0.1035 0.30 ο 實施例2 30/70 甲基丙烯酸甲酯 ι.θοαο 0.9107： 0,07 ο , 比較例3 .30/70 甲基丙烯酸甲酯 2.3000 1.1146 0,15 X 比較例4 30/70 甲基丙烯酸甲酯 3.0000 1.5388 0,17 X 比較例5 20/80 — — 一 0：.52 ο. 比較例6 20/80 甲基丙烯酸甲酯 0.0008 0.0004 0?54 ο 實施例3 20/8.0 甲基丙烯酸甲酯 0.2000 0.1048 0..3:4 〇 實施例4 20/80 甲基丙烯酸甲酯 i獅 0.9207 Q.10 〇 比較例7 20/80.: 甲基丙烯酸甲酯 2.3000 1.1138 0.22 X 比較例8 20/80 甲基丙烯酸甲酯 3.0000 1.5074 0,24 乂 比較例9 80/20： — 0,54 〇 比較例10 80/20 甲基丙烧酸甲酯 0.0008 0.0004 0.55 ο 實施例5 80/20' 甲基丙陆酸甲酯 0,2000 0.1039 0.34 〇 實施例6 80/20 申基丙烯酸甲酯 1.8000 0.9176 Q-14 ο ,比較例11 80/20 甲基丙烯酸申酯 2.3000 1.1184 0.2Ί2 X 比較例12 80/20 甲基丙稀酸甲酯 3.0000 1.5746 0,24 X 比較例13 0/100 — — - 0.57 ό 比較例14 0/100 甲基丙烯酸甲酯 1.8000 0.9013 0.59 〇 比較例15 100/0 一 — 0.56 比較例16 1.0:0/0 甲基丙稀酸甲酯 1.8000 0.9337 D.57 〇 比較例17 30/70 乙酸甲酯 0.0008 0.0004 0.52 〇 實施例7 20/10 乙酸甲酯 0.2000 0.1034 0.28. ο 實施例8 30>^70, 乙酸甲酯 1.8000 0.9025 0.09 〇 比較例18 30/70 乙酸甲酯 2.3000 1.1079 0,16 Η 比較例19 30./70 乙酸甲酯 3.00i3d T.5326 0；18 X 比較例20 0/100 乙酸甲酯 i.8b〇d Q.9350 0,56 〇 比較例21 100X0 乙酸甲酯 1.8000 0.9167 0.56 〇 比較例22 30/70 甲基乙基酮 0,0008. 0.0004 0.52 〇 實施例9 30/70 甲基乙基酮 0.2000 :0.1006 :0·31 ο 實施例10 30/^70 甲基乙基酮 1.8000 0.9084 0；Ό8 Ο 比較例23 30/7(3 甲基乙基酮 2,3000 1.1237 0:1¾ X 比較例24 30/70 甲基乙基酮 3.0000 1.5306 0.21 X 比較例25 0/100 甲基乙基酮 1.8000 0,9114 0,58 ο 比較例26 iOQ/Ό 甲基乙基酮 1,βόοο 0.9146 0.56 〇 比較例27 30/70 環己酿 0.0008 0.0004 0.48 ο 實施例11 30/70 環己酮 0.2000 0.1039 0.29 ο 實施例12 30/70 環己酿 1.8000 0.9072 .0.08. Ο 比較例28 30/70 環己酮 2.3000 1.1)17: 0.18 父 比較例29 30/70 環己嗣 3.0000 1.5727 0.20 X 比較例30 0/100 環己酿 1.8000 Ό.9110 0.56 ο 比較例31 ιόο/ρ 環己酿 r.eocfo 0.9221 0.5S 〇 绛質量比:醯化纖維素樹脂俩烯酸樹脂之質量比 基 有 丙 1 由比較例1 ~ 4 烯酸甲酯含有 .〇質量％以上時 由比較例1 ~ 1 6 、實施例1、2得知在光學薄膜中 〇 · 1質量％以上可改善滑性。此外 ，膠漿中有析出物發生。 與實施例1〜6的結果可知，纖維 ，甲 ，含 素與 -44- 201107395 丙烯酸之比在20/80〜80/20的範圍可得到上述的效果，但 是僅由纖維素或丙燃酸所構成的光學薄膜，即使添加甲基 丙烯酸甲酯也無法得到同樣的結果。 因此’僅在纖維素與丙稀酸之比爲20/80~80/20時， 可得到上述效果。 由比較例17〜31、實施例7〜12可知，對於乙酸甲酯 、甲基乙基酮’己院也可得到同樣的效果。 由上述可知，含有醯化纖維素樹脂20〜80質量％、丙 嫌酸樹脂20〜80質量％的光學薄膜中，含有〇1質量％以 上未達1 ·〇質量％之選自酯系溶劑、酮系溶劑、脂肪族系 溶劑之至少1種的溶劑’可製造改良滑性，膠漿之保存安 定性佳的光學薄膜。Optical film No. * Mass ratio Solvent solvent addition amount (mass part) Solvent content (% by mass) Slip property mm Comparative Example 1 30/70 One-to-one. 0.49; 〇Comparative Example 2 30/70 Methyl methacrylate 0.0008 0,0004 0.49 ο Example 1 30/70 Methyl propyl #酸甲SI 0,2000 0.1035 0.30 ο Example 2 30/70 Methyl methacrylate ι.θοαο 0.9107: 0,07 ο , Comparative Example 3 . 30/70 Methyl methacrylate 2.3000 1.1146 0,15 X Comparative Example 4 30/70 Methyl methacrylate 3.000 1.5388 0, 17 X Comparative Example 5 20/80 — — A 0:.52 ο. Comparative Example 6 20 /80 Methyl methacrylate 0.0008 0.0004 0?54 ο Example 3 20/8.0 Methyl methacrylate 0.2000 0.1048 0..3:4 〇 Example 4 20/80 Methyl methacrylate i Lion 0.9207 Q.10 〇Comparative Example 7 20/80.: Methyl methacrylate 2.3000 1.1138 0.22 X Comparative Example 8 20/80 Methyl methacrylate 3.000 1.5074 0,24 乂Comparative Example 9 80/20: — 0,54 〇Comparative Example 10 80/20 methyl propyl acetonate 0.0008 0.0004 0.55 ο Example 5 80/20' methyl methacrylate 0, 2000 0.1039 0.34 〇 Example 6 80/20 methyl methacrylate 1.8000 0.9176 Q-14 ο , Comparative Example 11 80/20 dimethyl methacrylate 2.3000 1.1184 0.2 Ί 2 X Comparative Example 12 80/20 Methyl methacrylate 3.000 1.5746 0,24 X Comparative Example 13 0/100 — — — 0.57 ό Comparative Example 14 0/100 Methyl methacrylate 1.8000 0.9013 0.59 〇Comparative Example 15 100/0 I—0.56 Comparative Example 16 1.0:0/0 Methyl methacrylate 1.8000 0.9337 D.57 〇Comparative Example 17 30/70 Methyl acetate 0.0008 0.0004 0.52 〇Example 7 20/10 Methyl acetate 0.2000 0.1034 0.28. ο Example 8 30>^70, methyl acetate 1.8000 0.9025 0.09 〇Comparative Example 18 30/70 Methyl acetate 2.3000 1.1079 0,16 Η Comparative Example 19 30./70 Methyl acetate 3.00i3d T.5326 0; 18 X Comparative Example 20 0/100 Methyl acetate i.8b〇d Q.9350 0 , 56 〇 Comparative Example 21 100X0 Methyl acetate 1.8000 0.9167 0.56 〇Comparative Example 22 30/70 Methyl ethyl ketone 0,0008. 0.0004 0.52 〇Example 9 30/70 Methyl ethyl ketone 0.2000 :0.1006 :0·31 ο Example 10 30/^70 methyl ethyl ketone 1.8000 0.9084 0; Ό 8 Ο Comparative Example 23 30/7 (3 methyl ethyl ketone 2, 3000 1.1237 0 :13⁄4 X Comparative Example 24 30/70 methyl ethyl ketone 3.000 1.5306 0.21 X Comparative Example 25 0/100 methyl ethyl ketone 1.8000 0, 9114 0, 58 ο Comparative Example 26 iOQ/Ό methyl ethyl ketone 1, ό οοο 0.9146 0.56 〇Comparative Example 27 30/70 Cyclohexanol 0.0008 0.0004 0.48 ο Example 11 30/70 Cyclohexanone 0.2000 0.1039 0.29 ο Example 12 30/70 Cyclohexamethylene 1.8000 0.9072 .0.08. Ο Comparative Example 28 30/ 70 cyclohexanone 2.3000 1.1) 17: 0.18 parent comparative example 30 30/70 cyclohexanthene 3.000 1.5727 0.20 X Comparative Example 30 0/100 ring brewed 1.8000 Ό.9110 0.56 ο Comparative Example 31 ιόο/ρ 环己酿. Eocfo 0.9221 0.5S 〇绛 mass ratio: the mass ratio of bismuth cellulose resin bisenoic acid resin has C 1 from Comparative Example 1 ~ 4 olefinic acid methyl ester. 〇 mass% or more by Comparative Example 1 ~ 16 In Examples 1 and 2, it was found that s·1 mass% or more in the optical film can improve the slipperiness. In addition, precipitates occur in the cement. As can be seen from the results of Examples 1 to 6, the ratio of fiber, nail, and cellulose to -44 to 201107395 acrylic acid was in the range of 20/80 to 80/20, but the cellulose or acrylic acid was used only. The optical film formed was not able to obtain the same result even if methyl methacrylate was added. Therefore, the above effects can be obtained only when the ratio of cellulose to acrylic acid is 20/80 to 80/20. From Comparative Examples 17 to 31 and Examples 7 to 12, the same effects were obtained for methyl acetate and methyl ethyl ketone. According to the above, the optical film containing 20 to 80% by mass of the deuterated cellulose resin and 20 to 80% by mass of the acrylic acid resin is selected from the group consisting of an ester solvent and not more than 1% by mass. The solvent of at least one of a ketone solvent and an aliphatic solvent can produce an optical film having improved smoothness and good storage stability of the paste.
實施例B 與實施例7〜1 2同樣，即使使用乙酸乙酯、環己酮、 環己烷等的添加劑取代乙酸甲酯、甲基乙基酮，己烷，也 可得到同樣的效果。 實施例C <偏光板之製作> 如下述製作將實施例1〜12之光學薄膜作爲偏光板保 護薄膜的偏光板。Example B In the same manner as in Examples 7 to 12, the same effects can be obtained by using an additive such as ethyl acetate, cyclohexanone or cyclohexane instead of methyl acetate, methyl ethyl ketone or hexane. Example C <Production of Polarizing Plate> A polarizing plate using the optical films of Examples 1 to 12 as a polarizing plate protective film was prepared as follows.
將厚度120μιη之長條筒狀聚乙烯醇薄膜浸漬於含有 碘1質量份、硼酸4質量份的水溶液100質量份中，50°C -45- 201107395 下在搬送方向延伸5倍製作偏光膜。 其次，使用丙烯酸接著劑’對實施例A製作的實施 例1的光學薄膜施加電暈處理後’貼合於上述偏光膜之單 面。 在偏光膜之另一面貼合以鹼皂化處理之相位差薄膜之 KonicaMinolta Opto公司製KC8UCR-5，經乾燥製作偏光 板P1。同樣的，使用本發明之實施例2-12的光學薄膜製 作偏光板P2~P12。 使用本發明之光學薄膜的偏光板係滑性優異，容易加 工。 <液晶顯示裝置之製作> 使用上述製作的偏光板評價本發明之光學薄膜的顯示 特性。 將股份公司東芝製32吋電視32H2000之預先貼合於 兩面的偏光板剝離，將上述製作的偏光板使各自 KC8UCR-5在液晶胞之玻璃面側，且使吸收軸朝向於與預 先貼合之偏光板相同方向來貼合，分別製作液晶顯示裝置 〇 上述製作的液晶表示裝置係色彩偏移降低，正面對比 優異之辨識性佳的液晶顯示裝置。 【圖式簡單說明】 [圖1]係表示本發明使用之溶液流延製膜方法之膠漿 -46 - 201107395 調製步驟、流延步驟及乾燥步驟之模式圖。 【主要元件符號說明】 1 :溶解鍋： 3、 6、 12、 15:過濾器 4、 13 :儲存槽 5、 14 :送液泵 8、1 6 :導管 1 0 :紫外線吸收劑投入鍋 2 0 :合流管 2 1 :混合機 30 :模 31 :金屬支持體 3 2 :纖維網 3 3 :剝離位置 3 4 :拉幅延伸裝置 3 5 :乾燥裝置 4 1 :粒子投入鍋 42 :儲存槽 43 :泵 44 :過濾器 -47-The strip-shaped polyvinyl alcohol film having a thickness of 120 μm was immersed in 100 parts by mass of an aqueous solution containing 1 part by mass of iodine and 4 parts by mass of boric acid, and a polarizing film was formed by stretching five times in the transport direction at 50 ° C -45 - 201107395. Then, the optical film of Example 1 produced in Example A was subjected to corona treatment using an acrylic adhesive ‘after bonding to the single surface of the above polarizing film. On the other surface of the polarizing film, KC8UCR-5 manufactured by Konica Minolta Opto Co., Ltd., which was subjected to alkali saponification, was dried, and a polarizing plate P1 was produced by drying. Similarly, polarizing plates P2 to P12 were produced using the optical films of Examples 2 to 12 of the present invention. The polarizing plate using the optical film of the present invention is excellent in slipperiness and is easy to process. <Production of Liquid Crystal Display Device> The display characteristics of the optical film of the present invention were evaluated using the polarizing plate produced as described above. The polarizing plate prepared by the company's 32-inch TV 32H2000, which is bonded to the two sides, was peeled off, and the polarizing plate produced above was placed on the glass surface side of the liquid crystal cell, and the absorption axis was oriented in advance. The polarizing plates were bonded in the same direction, and a liquid crystal display device was produced, and the liquid crystal display device produced as described above was provided with a liquid crystal display device having a reduced color shift and excellent front view contrast. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] is a schematic view showing a preparation step, a casting step, and a drying step of a solution casting film forming method used in the present invention -46 - 201107395. [Explanation of main component symbols] 1 : Dissolving pot: 3, 6, 12, 15: Filter 4, 13: Storage tank 5, 14: Liquid feeding pump 8, 1 6 : Catheter 1 0: UV absorber is put into the pot 2 0 : Confluence pipe 2 1 : Mixer 30 : Mold 31 : Metal support 3 2 : Web 3 3 : Peeling position 3 4 : Stretching extension device 3 5 : Drying device 4 1 : Particles into the pan 42 : Storage tank 43 : Pump 44: Filter-47-