TW201107801A - Optical film, polarizing plate using same, and liquid crystal display device - Google Patents

Optical film, polarizing plate using same, and liquid crystal display device Download PDF

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Publication number
TW201107801A
TW201107801A TW099110370A TW99110370A TW201107801A TW 201107801 A TW201107801 A TW 201107801A TW 099110370 A TW099110370 A TW 099110370A TW 99110370 A TW99110370 A TW 99110370A TW 201107801 A TW201107801 A TW 201107801A
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Taiwan
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optical film
resin
film
mass
cellulose ester
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TW099110370A
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Chinese (zh)
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TWI468749B (en
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Tsuyoshi Ikeda
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Konica Minolta Opto Inc
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/14—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose characterised by containing special compounding ingredients
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/20—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02—Synthetic macromolecular particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/202—LCD, i.e. liquid crystal displays
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
    • G02F2201/50—Protective arrangements

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Disclosed are: an optical film which has improved film hardness and handling properties; a polarizing plate using the optical film; and a liquid crystal display device. Specifically disclosed is an optical film which has at least two layers that are different from each other in resin compositions. The optical film is characterized in that (i) at least one layer constituting the surface of the optical film contains an acrylic resin (A) and a cellulose ester resin (B) at a mass ratio of from 95:5 to 85:15, (ii) the layers other than the layer constituting the surface contain the acrylic resin (A) and the cellulose ester resin (B) at a mass ratio of from 80:20 to 50:50, (iii) the acrylic resin (A) has a weight average molecular weight of not less than 80,000, and (iv) the cellulose ester resin (B) has a total degree of substitution of acyl groups of 2.0-3.0, a degree of substitution of acyl groups having 3-7 carbon atoms of 1.2-3.0, and a weight average molecular weight of not less than 75,000.

Description

201107801 六、發明說明： 【發明所屬之技術領域】 本發明係有關改善硬度及使用性的光學薄膜、使用該 光學薄膜之偏光板及液晶顯示裝置。 【先前技術】 液晶顯示裝置係在液晶電視及個人電腦之液晶顯示器 等的用途方面，需求越來越大。通常，液晶顯示裝置係以 玻璃板挾著透明電極、液晶層、彩色濾光片等的液晶胞與 設置於其兩側之2片偏光板所構成，各自的偏光板係以2片 光學薄膜（偏光板保護薄膜）挾著偏光子（也稱爲偏光子 、偏光膜）所構成。此偏光板保護薄膜通常使用纖維素三 乙酸酯薄膜。 此外，因近年技術進步，使液晶顯示裝置加速大型化 ’同時液晶顯示裝置之用途也多樣化。例如可作爲被設置 在街頭或店舖之大型顯示器使用或被用於使用被稱爲數字 標示板之顯示機器之公共場所的廣告用顯示器等。 這種用途係假設用於室外，因此，因偏光薄膜之吸濕 而有造成劣化的問題，偏光板保護薄膜需要更高的耐濕性 。但是以往使用的纖維素三乙酸酯薄膜等之纖維素酯薄膜 ’很難得到充分的耐濕性。爲了得到耐濕性而厚膜化時， 而有光學上的影響變大的問題。近年，因要求裝置之薄型 化，因此偏光板本身厚度增加也會有問題。 此外，作爲低吸濕性之光學薄膜材料之丙烯酸樹脂所 -5- 201107801 代表的聚甲基丙烯酸甲酯（以下簡稱爲「PMMA」）係除 了低濕性外，也顯示優異的透明性及尺寸安定性，因此適 用於光學薄膜。 但如上述，隨著液晶顯示裝置大型化，及屋外用途之 擴大，即使在屋外也要能充分辨識影像，因此必須增加背 光的光量，同時使用於更嚴苛條件下時，要求具有高溫下 之耐熱性及長期的耐熱性。 但是PMMA薄膜係因缺乏耐熱性，且高溫下使用、長 期的使用等時，會產生形狀改變的問題。 此問題不僅是薄膜單體的物性，而且使用這種薄膜的 偏光板、顯示裝置也是重要的課題。換言之，液晶顯示裝 置中，隨著薄膜的變形，偏光板會捲曲，因此產生面板整 體變形的問題。 薄膜變形所造成的問題，在背光側有會有問題，在辨 識側表面位置使用時因變形而在設計上之相位差會改變， 因此會產生視角變動或色調變化的問題。 此外，丙烯酸樹脂薄膜相較於纖維素酯薄膜等時，有 較容易破裂或易脆的特性，在切割（切斷）等操作較困難 ，特別是很難穩定地製造大型液晶顯示裝置用的光學薄膜 〇 有鑑於上述問題.狀況等，例如在專利文獻1中提案 改善耐濕性及耐熱性的技術爲丙烯酸樹脂組合耐衝擊性丙 烯酸橡膠-甲基丙烯酸甲酯共聚物或丁基改性乙醯基纖維 素的樹脂。 -6 - 201107801 專利文獻2中對於以往的纖維素酯薄膜，提案混合可 塑劑或控制光學性能而混合較低分子量之丙烯酸樹脂的技 術。專利文獻3中提案一種熔融混合分子量較大的丙烯酸 樹脂與纖維素酯樹脂的光學薄膜，但是此技術係丙烯酸樹 脂與纖維素酯樹脂之相溶性有時不充分，欠缺泛用性的技 術，且硬度不足。 此外，提案光學薄膜以複層構成，同時賦予新的特性 ，或相反的特性的技術。例如專利文獻4提案藉由使用無 機微粒子之薄膜表層中的濃度大於該無機微粒子之薄膜中 之平均濃度之2軸性的光學補償薄膜，可提供在廣範圍之 視角可顯示高對比的圖像，且可減輕色彩偏移（由斜方向 觀看時的色調變化）的液晶顯示裝置，特別是V A模式的 液晶顯示裝置、賦予該特性的光學補償薄膜及偏光板及光 學補償薄膜之製造方法的技術。此等技術係有關相同樹脂 組成之層之厚度方向之一部份的層中含有添加劑的技術， 但是完全未提及藉由改變樹脂組成以改善特性的技術。 專利文獻5提案藉由可溶或可分散於有機溶劑或水中 之聚合物所構成之芯層與於該芯層之至少單面具有由0.1〜 20 μηι膜厚之纖維素衍生物所構成之表層爲特徴的偏光板用 保護薄膜，可提供低延遲（retardation )，且光學變形較 少’亮點異物較少，高濕度下之尺寸安定性佳，捲曲較少 ’與玻璃基板之接著性佳的偏光板用保護薄膜的技術。此 技術係設置芯層的技術，該芯層之特徵係含有主要由纖維 素衍生物所構成之表層與纖維素衍生物與具有乙烯性雙鍵 201107801 的化合物與光重合起始劑。此技術並未提及因樹脂組成而 改變的特性，藉由設置樹脂組成不同之複數層，可提供較 佳特性的光學薄膜的技術。此外，也未記載特別是使用丙 烯酸樹脂與纖維素樹脂時，即使設置具有複數層的光學薄 膜，但是設置樹脂比率不同之層時，在層間會因樹脂組成 不同產生界面，而無法得到光學薄膜所需要的光學特性。 [先行技術文獻] [專利文獻] [專利文獻1 ]特開平5 -1 1 9 2 1 7號公報 [專利文獻2 ]特開2 0 0 3 - 1 2 8 5 9號公報 [專利文獻3]特開2008-8 84 1 7號公報 [專利文獻4 ]特開2 0 0 8 - 2 6 2 1 6 1號公報 [專利文獻5 ]特開2 0 0 1 - 2 1 5 3 3號公報 【發明內容】 [發明槪要] [發明欲解決的課題] 本發明係有鑑於上述問題·狀況而完成者，其解決課 題係提供改善薄膜之硬度及使用性的光學薄膜。此外提供 使用該光學薄膜之偏光板及液晶顯示裝置。 [解決課題的手段] 本發明的上述課題係藉由以下手段來解決^ -8 - 201107801 ι·一種光學薄膜，其係具有至少二層以上之樹脂組成 彼此不同之層的光學薄膜，其特徵係（i)構成該光學薄 膜表面之層的至少一層爲以95: 5〜85 : 15之質量比含有丙 烯酸樹脂（A)與纖維素酯樹脂（B) ，（U)構成該表面 之層以外的層爲以80: 20~50: 50之質量比含有丙烯酸樹 脂（A)與纖維素酯樹脂（B ) ， （iii)前述丙烯酸樹脂 (A)之重量平均分子量爲80000以上，（iv)前述纖維素 酯樹脂（B )之醯基的總取代度爲2.0~3.0、碳數3〜7之醯 基的取代度爲1.2-3.0，該纖維素酯樹脂（Β)之重量平均 分子量爲75 000以上者。 2·如前述第1項之光學薄膜，其中構成前述表面之層 的厚度爲前述光學薄膜整體厚度的5~20 %。 3. 如前述第1或2項之光學薄膜，其中相對於構成該表 面之層的全質量，在構成前述表面之層上含有0.01〜丨質量 %之平均粒徑爲50~300μπι之範圍內之無機化合物或有機化 合物之微粒子。 4. 如前述第1~3項中任一項之光學薄膜，其係含有防 靜電劑。 5. 如前述第1〜4項中任一項之光學薄膜，其中前述光 學薄膜之寬度方向之長度之至少10〜90%的範圍內，且含有 該薄膜寬度方向之中心的部分爲含有至少二層以上之前述 樹脂組成不同的層者。 6. 如前述第1〜5項中任一項之光學薄膜，其中前述樹 脂組成彼此不同之層在薄膜製膜時同時形成。 ~ 9 - 201107801 7.—種偏光板，其特徵係使用如前述第1〜6項中任一 項之光學薄膜者。 8 · —種液晶顯示裝置，其特徵係使用如前述第1〜6項 中任一項之光學薄膜者。 發明效果 藉由本發明之手段可提供改善薄膜之硬度及使用性的 光學薄膜。此外可提供使用該光學薄膜之偏光板及液晶顯 示裝置。 [實施發明之形態] 本發明之光學薄膜，其係具有至少二層以上之樹脂組 成彼此不同之層的光學薄膜，其特徵係（i)構成該光學 薄膜表面之層的至少一層爲以95 : 5~85 : 15之質量比含有 丙烯酸樹脂（A)與纖維素酯樹脂（B) ，（ii)構成該表 面之層以外的層爲以80 : 20〜50 : 50之質量比含有丙烯酸 樹脂（A )與纖維素酯樹脂（B ) ，（iii)前述丙烯酸樹 脂（A)之重量平均分子量爲80000以上，（iv)前述纖維 素酯樹脂（B )之醯基的總取代度爲2.0〜3.0、碳數3〜7之 醯基的取代度爲1 .2~3.0 ’該纖維素酯樹脂（B )之重量平 均分子量爲75000以上者。此特徵係申請專利範圍第1~8項 的共同技術特徵。 本發明之光學薄膜可適用於偏光板。因此也適用於液 晶顯示裝置。 -10- 201107801 以下詳細說明本發明與其構成要素及實施本發明之形 態·態樣等。 〔光學薄膜之構成槪要〕 本發明之光學薄膜可採用各種之層構成態樣，其特徵 係具有至少二層以上之樹脂組成彼此不同之層的光學薄膜 。此外，其特徵係滿足下述要件（丨）〜（iv)。 (i )構成該光學薄膜表面之層的至少一層爲以95 : 5〜85 : 15之質量比含有丙烯酸樹脂（A)與纖維素酯樹脂 (B )。 (ii) 構成該表面之層以外的層爲以80: 20〜50: 50之 質量比含有丙烯酸樹脂（A)與纖維素酯樹脂（B)。 (iii) 前述丙烯酸樹脂（A)之重量平均分子量爲 8 0 0 0 0以上。 (iv) 前述纖維素酯樹脂（B)之醯基的總取代度爲 2.0〜3.0、碳數3〜7之醯基的取代度爲1.2〜3.0，該纖維素酯 樹脂（B)之重量平均分子量爲75000以上者。 本發明之實施態樣從本發明之效果顯現的觀點，構成 前述表面之層的厚度較佳爲前述光學薄膜整體厚度的 5〜2 0%。其中相對於構成該表面之層的全質量，在構成前 述表面之層上較佳爲含有0.01〜1質量％之平均粒徑爲50~ 3 00 μηι之範圍內之無機化合物或有機化合物之微粒子的態 樣。本發明之光學薄膜較佳爲含有防靜電劑。 本發明中，該光學薄膜之寬度方向之長度之至少10〜 -11 - 201107801 90%的範圍內，且含有該薄膜寬度方向之中心的部分爲含 有至少二層以上之前述樹脂組成不同的層較佳。其中該樹 脂組成彼此不同之層在薄膜製膜時同時形成較佳。 以下詳細說明各構成要素。 (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。 可共聚合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α，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（A )特別是 從改善光學薄膜之脆性及改善與纖維素酯樹脂（B )相溶 -12- 201107801 時之透明性的觀點，重量平均分子量（Mw)爲80000以上 。丙烯酸樹脂（A)之重量平均分子量（Mw)爲800 00以 下時，無法充分改善脆性，與纖維素酯樹脂（B )之相溶 性差。丙烯酸樹脂（A)之重量平均分子量（Mw)更佳爲 80000-1 000000之範圍內，特佳爲100000〜600000之範圍內 ，最佳爲1 50000~400000之範圍。丙烯酸樹脂（A)之重量 平均分子量（Mw )的上限値無特別限定，但是從製造上 的觀點，1 0 0 0 0 0 0以下爲較佳的形態。 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。 溶劑：二氯甲烷 柱：Shodex K806 、 K805 、 K803G ( 0召和電工（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 5 04 ( GL Science公司製） 幫浦：L6000 (日立製作所（股）製） 流量：l.Oml/min 校正曲線：使用標準聚苯乙烯STK standard 聚苯乙 烯（東曹（股）製）Mw = 2,800,000-500之13個試樣的校正 曲線。1 3個試樣以大致等間隔使用較佳。 本發明之丙烯酸樹脂（A )的製造方法並無特別限制 ，可使用懸浮聚合、乳化聚合、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 -13- 201107801 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3 0〜1 00°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 。下述表示本發明之丙烯酸樹脂與其製造方法之一例。 A1 :單體質量比（MMA : MA = 98 : 2 ) 、Mw70000 A2:單體質量比（MMA: MA = 97: 3) 、Mwl60000 A3 :單體質量比（MMA : MA = 97 : 3 ) 、Mw3 50000 A4:單體質量比（MMA: MA = 97: 3) 、Mw550000 A5:單體質量比（MMA: MA = 97: 3) 、Mw800000 A6:單體質量比（MMA: MA = 97: 3) 、Mw930000[Technical Field] The present invention relates to an optical film for improving hardness and usability, a polarizing plate using the optical film, and a liquid crystal display device. [Prior Art] The liquid crystal display device is in demand for use in liquid crystal televisions and liquid crystal displays of personal computers. Generally, a liquid crystal display device is formed by arranging a liquid crystal cell such as a transparent electrode, a liquid crystal layer, a color filter or the like on a glass plate with two polarizing plates provided on both sides thereof, and each polarizing plate is made of two optical films ( The polarizing plate protective film is composed of a polarizer (also called a polarizer and a polarizing film). This polarizing plate protective film is usually a cellulose triacetate film. In addition, due to technological advances in recent years, liquid crystal display devices have been accelerated and large-sized. At the same time, the use of liquid crystal display devices has also diversified. For example, it can be used as an advertisement display that is installed on a large display on a street or a store or used in a public place where a display device called a digital signage is used. This use is assumed to be used outdoors, and therefore, the polarizing plate protective film requires higher moisture resistance due to the problem of deterioration due to moisture absorption of the polarizing film. However, it has been difficult to obtain sufficient moisture resistance of a cellulose ester film such as a cellulose triacetate film which has been conventionally used. In order to obtain moisture resistance and thicken the film, there is a problem that the optical influence is large. In recent years, since the thickness of the device is required to be thinned, there is a problem that the thickness of the polarizing plate itself is increased. In addition, polymethyl methacrylate (hereinafter abbreviated as "PMMA"), which is an acrylic resin of a low-absorption optical film material, exhibits excellent transparency and size in addition to low humidity. It is stable and therefore suitable for optical films. However, as described above, with the increase in size of liquid crystal display devices and the expansion of outdoor applications, it is necessary to fully recognize images even outside the house. Therefore, it is necessary to increase the amount of backlight light, and when used under more severe conditions, it is required to have a high temperature. Heat resistance and long-term heat resistance. However, the PMMA film has a problem of shape change due to lack of heat resistance, use at high temperatures, long-term use, and the like. This problem is not only the physical properties of the film monomer, but also a polarizing plate or a display device using such a film is an important subject. In other words, in the liquid crystal display device, the polarizing plate is curled as the film is deformed, so that the entire panel is deformed. The problem caused by the deformation of the film has a problem on the backlight side, and the phase difference in design due to deformation when the position of the side surface is recognized is changed, so that there is a problem that the angle of view changes or the color tone changes. Further, when the acrylic resin film is more likely to be broken or brittle than the cellulose ester film or the like, it is difficult to perform operations such as cutting (cutting), and it is difficult to stably manufacture optical for a large liquid crystal display device. In view of the above-mentioned problems, etc., for example, Patent Document 1 proposes a technique for improving moisture resistance and heat resistance, which is an acrylic resin combined impact-resistant acrylic rubber-methyl methacrylate copolymer or butyl-modified acetamidine. A cellulose based resin. -6 - 201107801 Patent Document 2 proposes a technique of mixing a plasticizer or controlling an optical property to mix a lower molecular weight acrylic resin with respect to a conventional cellulose ester film. Patent Document 3 proposes an optical film in which an acrylic resin having a relatively large molecular weight and a cellulose ester resin are melt-mixed, but this technique is incompatible with the compatibility of the acrylic resin and the cellulose ester resin, and lacks a general-purpose technique, and Insufficient hardness. Further, it is proposed that the optical film is composed of a plurality of layers while imparting new characteristics or opposite characteristics. For example, Patent Document 4 proposes to provide an image in which a high contrast ratio can be displayed over a wide range of viewing angles by using an optical compensation film in which a concentration in a film surface layer of inorganic fine particles is larger than an average concentration in a film of the inorganic fine particles. Further, it is possible to reduce the color shift (change in color tone when viewed in an oblique direction), in particular, a VA mode liquid crystal display device, an optical compensation film that imparts such characteristics, and a technique for manufacturing a polarizing plate and an optical compensation film. These techniques are techniques for containing an additive in a layer relating to a part of the thickness direction of the layer of the same resin composition, but there is no mention of a technique for improving the characteristics by changing the resin composition. Patent Document 5 proposes a core layer composed of a polymer soluble or dispersible in an organic solvent or water, and a surface layer composed of a cellulose derivative having a film thickness of 0.1 to 20 μm on at least one side of the core layer. It is a special protective film for polarizing plates, which provides low retardation and less optical distortion. 'There are fewer bright spots, good dimensional stability under high humidity, less curling' and better polarization with glass substrate. The technology of protective film for boards. This technique is a technique for providing a core layer characterized by a surface layer mainly composed of a cellulose derivative and a cellulose derivative and a compound having a vinyl double bond 201107801 and a photorecoupling initiator. This technique does not mention a property which is changed by the resin composition, and a technique of providing an optical film having better characteristics by providing a plurality of layers having different resin compositions. Further, when an acrylic resin and a cellulose resin are used in particular, even if an optical film having a plurality of layers is provided, when a layer having a different resin ratio is provided, an interface is formed between layers due to a difference in resin composition, and an optical film cannot be obtained. The required optical properties. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. Hei 2 0 0 3 - 1 2 8 5 9 [Patent Document 3] JP-A-2008-8 84 No. 7 (Patent Document 4) Japanese Patent Publication No. 2 0 0 8 - 2 6 2 1 6 1 [Patent Document 5] Japanese Patent Publication No. 2 0 0 1 - 2 1 5 3 Disclosure of the Invention [Problems to be Solved by the Invention] The present invention has been made in view of the above problems and circumstances, and an object of the invention is to provide an optical film which improves the hardness and usability of a film. Further, a polarizing plate and a liquid crystal display device using the optical film are provided. [Means for Solving the Problem] The above-described problem of the present invention is solved by the following means: an optical film having at least two or more layers of resin compositions different from each other, the characteristics of which are (i) at least one layer constituting the surface of the optical film is composed of an acrylic resin (A) and a cellulose ester resin (B) in a mass ratio of 95:5 to 85:15, and (U) constitutes a layer other than the layer The layer is composed of an acrylic resin (A) and a cellulose ester resin (B) in a mass ratio of 80:20 to 50:50, (iii) the weight average molecular weight of the acrylic resin (A) is 80,000 or more, (iv) the aforementioned fiber The total substitution degree of the thiol group of the ester resin (B) is 2.0 to 3.0, the degree of substitution of the fluorenyl group having 3 to 7 carbon atoms is 1.2 to 3.0, and the weight average molecular weight of the cellulose ester resin (Β) is 75,000 or more. By. The optical film according to the above item 1, wherein the thickness of the layer constituting the surface is 5 to 20% of the entire thickness of the optical film. 3. The optical film according to item 1 or 2 above, wherein the total mass of the layer constituting the surface is in a range of 0.01 to 丨% by mass and the average particle diameter is 50 to 300 μm. A fine particle of an inorganic compound or an organic compound. 4. The optical film according to any one of items 1 to 3 above which contains an antistatic agent. 5. The optical film according to any one of items 1 to 4, wherein the optical film has a length in the width direction of at least 10 to 90%, and a portion including a center of the film width direction contains at least two The foregoing resin above the layer constitutes a different layer. 6. The optical film according to any one of the preceding items, wherein the layers having the different resin compositions are formed simultaneously at the time of film formation. ~ 9 - 201107801 7. A polarizing plate characterized by using the optical film according to any one of items 1 to 6 above. A liquid crystal display device characterized in that the optical film according to any one of the above items 1 to 6 is used. EFFECT OF THE INVENTION An optical film which improves the hardness and usability of a film can be provided by the means of the present invention. Further, a polarizing plate and a liquid crystal display device using the optical film can be provided. [Embodiment of the Invention] The optical film of the present invention is an optical film having at least two or more layers of resin compositions different from each other, and characterized in that (i) at least one layer constituting a layer of the surface of the optical film is 95: a mass ratio of 5 to 85:15 containing an acrylic resin (A) and a cellulose ester resin (B), and (ii) a layer other than the layer constituting the surface is an acrylic resin in a mass ratio of 80:20 to 50:50 ( A) with the cellulose ester resin (B), (iii) the weight average molecular weight of the acrylic resin (A) is 80,000 or more, and (iv) the total substitution degree of the thiol group of the cellulose ester resin (B) is 2.0 to 3.0. The degree of substitution of the fluorenyl group having a carbon number of 3 to 7 is 1.2 to 3.0. The weight average molecular weight of the cellulose ester resin (B) is 75,000 or more. This feature is a common technical feature of claims 1 to 8 of the patent application. The optical film of the present invention can be applied to a polarizing plate. Therefore, it is also applicable to liquid crystal display devices. -10- 201107801 The present invention and its constituent elements, and the aspects and aspects for carrying out the invention will be described in detail below. [Configuration of Optical Film] The optical film of the present invention may have various layer constitutions, and is characterized in that it has an optical film having at least two or more layers of resin compositions different from each other. Further, its characteristics satisfy the following requirements (丨) to (iv). (i) At least one layer constituting the surface of the optical film contains the acrylic resin (A) and the cellulose ester resin (B) in a mass ratio of 95:5 to 85:15. (ii) The layer other than the layer constituting the surface contains the acrylic resin (A) and the cellulose ester resin (B) in a mass ratio of 80:20 to 50:50. (iii) The weight average molecular weight of the acrylic resin (A) is 8000 or more. (iv) The total degree of substitution of the thiol group of the cellulose ester resin (B) is 2.0 to 3.0, the degree of substitution of the fluorenyl group having 3 to 7 carbon atoms is 1.2 to 3.0, and the weight average of the cellulose ester resin (B) The molecular weight is 75,000 or more. In the embodiment of the present invention, the thickness of the layer constituting the surface is preferably from 5 to 20% of the entire thickness of the optical film from the viewpoint of the effect of the present invention. In the layer constituting the surface, it is preferable that the layer constituting the surface contains 0.01 to 1% by mass of the inorganic compound or the organic compound in the range of 50 to 300 μm. Aspect. The optical film of the present invention preferably contains an antistatic agent. In the present invention, the length of the optical film in the width direction is at least 10 to -11 - 201107801 90%, and the portion containing the center of the film in the width direction is a layer containing at least two or more layers different in resin composition. good. Among them, the layers in which the resin compositions are different from each other are preferably formed at the same time in film formation. Each component will be described in detail below. (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 which can be copolymerized include, for example, an alkyl methacrylate having an alkyl group having 2 to 18 carbon atoms, an alkyl group having an alkyl group having 1 to 18 carbon atoms, acrylic acid, methacrylic acid, or the like. An aromatic vinyl compound such as an unsaturated group-containing dicarboxylic acid such as β-unsaturated acid, maleic acid, fumaric acid or itaconic acid, styrene or α-methylstyrene, acrylonitrile or the like α,β-unsaturated nitrile such as acrylonitrile, maleic anhydride, maleimide, fluorene-substituted maleimide, glutaric anhydride, etc., which may be used alone or in combination of two or more Body use. Among them, from the viewpoint of heat decomposition resistance and fluidity of the copolymer, methacrylate, ethyl acrylate, η-propyl acrylate, η-butyl acrylate, s-butyl acrylate, and 2 are preferable. _Ethylhexyl acrylate or the like, particularly preferably methacrylate or η-butyl acrylate. The acrylic resin (A) used in the optical film of the present invention has a weight average molecular weight (Mw) from the viewpoint of improving the brittleness of the optical film and improving the transparency when it is compatible with the cellulose ester resin (B) -12-201107801. It is more than 80,000. When the weight average molecular weight (Mw) of the acrylic resin (A) is 800 Å or less, the brittleness cannot be sufficiently improved and the compatibility with the cellulose ester resin (B) is inferior. The weight average molecular weight (Mw) of the acrylic resin (A) is more preferably in the range of 80000-1000000, particularly preferably in the range of 100,000 to 600,000, and most preferably in the range of 150,000 to 400,000. The weight of the acrylic resin (A) is not particularly limited as long as it is an average molecular weight (Mw). However, from the viewpoint of production, it is preferable that it is not more than 1,000. The weight average molecular weight of the acrylic resin of the present invention can be determined by gel permeation chromatography. The measurement conditions are as follows. Solvent: Dichloromethane column: Shodex K806, K805, K803G (3 calls and electrician (share) system connection 3) Column temperature: 2 5 °C Sample concentration: 〇. 1 mass% Detector: RI Model 5 04 ( GL Science Co., Ltd.) Pump: L6000 (Hitachi, Ltd.) Flow: l.Oml/min Calibration curve: Standard polystyrene STK standard polystyrene (made by Tosoh Corporation) Mw = 2,800,000-500 Calibration curve for 13 samples. It is preferred to use 13 samples at substantially equal intervals. The method for producing the acrylic resin (A) of the present invention is not particularly limited, and any of known methods such as suspension polymerization, emulsion polymerization, bulk polymerization or solution polymerization can be used. As the polymerization initiator, a general peroxidation-13-201107801 system and an azo-based polymerization initiator may be used, and a redox system may also be used. The polymerization temperature may be 30 to 100 ° C for suspension or emulsion polymerization, and the polymerization may be carried out at 80 to 160 ° C in bulk or solution polymerization. In order to control the reducing viscosity of the obtained copolymer, an alkylthiol or the like may be used as a chain transfer agent to carry out polymerization. An example of the acrylic resin of the present invention and a method for producing the same will be described below. A1 : monomer mass ratio (MMA : MA = 98 : 2 ) , Mw70000 A2 : monomer mass ratio (MMA: MA = 97: 3), Mwl60000 A3 : monomer mass ratio (MMA : MA = 97 : 3 ), Mw3 50000 A4: monomer mass ratio (MMA: MA = 97: 3), Mw550000 A5: monomer mass ratio (MMA: MA = 97: 3), Mw800000 A6: monomer mass ratio (MMA: MA = 97: 3 ), Mw930000

A7:單體質量比（MMA: MA = 94: 6) 、MwllOOOOOA7: monomer mass ratio (MMA: MA = 94: 6), MwllOOOOO

MSI ：單體質量比（MMA: ST = 60: 40) 、MwlOOOOOMSI: monomer mass ratio (MMA: ST = 60: 40), MwlOOOO

MS2 ：單體質量比（MMA: ST = 40: 60) 、MwlOOOOO MMA :甲基丙烯酸甲酯 ΜΑ :甲基丙烯酸酯 ST :苯乙烯 (A 8之合成例） 首先將甲基丙烯酸甲酯/丙烯醯胺共聚合物系懸濁劑 如下述調整。 甲基丙烯酸甲酯 20質量份 丙烯醯胺 80質量份 過硫酸鉀 〇.3質量份 -14- 201107801 離子交換水 1 500質量份 將上述成分投入反應器中，反應器中以氮氣體取代同 時保持70°C進行反應使單體完全轉變成聚合物爲止。所得 之水溶液作爲懸浮劑。將上述懸浮劑0 · 〇 5質量份溶解於離 子交換水165質量份之溶液供給容量爲5L，且具備擋板及 pfauder (反向葉輪）型攪拌翼之不鏽鋼製高壓鍋中，體系 內以氮氣體取代同時以400rpm進行攪拌。 其次，將下述投入組成之混合物質在攪拌反應系的狀 態進行添加。 27質量份 73質量份 甲基丙烯酸 甲基丙烯酸甲酯 t-十二碳烷硫醇 1.2質量份 2，2’-偶氮雙異丁腈 0.4質量份 添加後，昇溫至7 0 °C，當內溫達到7 〇 °C之時點作爲聚 合開始時點，然後保持180分鐘進行聚合。 然後依據通常的方法進行反應系之冷却、聚合物之分 離、洗淨、乾燥，得到顆粒狀的共聚合物。此共聚合物之 聚合率爲97%，重量平均分子量爲13萬。 此共聚合物中添加0.2質量％之添加劑（Na〇CH3 ), 使用2軸擠出機（TEX30 (日本製鋼公司製、L/D = 44.5 )) ’由供料斗部將氮氣以10L/分鐘的量清洗（purge)，同時 以螺旋轉數1 OOrpm、原料供給量5kg/小時、汽缸溫度290 °C下進行分子內環化反應，製作顆粒，以80〇C真空乾燥8 小時得到丙烯酸樹脂A 8。丙烯酸樹脂A 8之重量平均分子 -15- 201107801 量（1^^)係 130000，丁§係140。〇。 本發明之丙烯酸樹脂可使用市售品。例如有Delpet 60N、8 0N (旭化成化學（股）製）、Dianal BR52、BR80 、BR83、BR85、B R 8 8 (三菱 R a y 〇 η (股）製）' ΚΤ75 ( 電化學工業（股）製）等。丙烯酸樹脂也可併用二種以上 (纖維素酯樹脂（Β )) 本發明之纖維素酯樹脂（Β )，特別是從改善脆性或 與丙烯酸樹脂（Α)相溶時之透明性的觀點，較佳爲醯基 之總取代度（Τ )爲2.0〜3.0，碳數3~7之醯基的取代度爲 1.2-3.0，碳數3~7之醯基的取代度爲2.0〜3.0。換言之，本 發明之纖維素酯樹脂係被碳數3〜7之醯基取代的纖維素酯 樹脂，具體而言，較佳爲使用丙醯基、丁醯基等，特佳爲 使用丙醯基。 纖維素酯樹脂（Β )之醯基的總取代度爲低於2.0時， 換言之，纖維素酯分子之2,3,6位之羥基殘度高於1.0時， 丙烯酸樹脂（A)與纖維素酯樹脂（Β )無法充分相溶，作 爲光學薄膜用時會有混濁的問題。此外，即使醯基之總取 代度爲2.0以上，但碳數3~7之醯基的取代度低於1.2時，仍 無法得到充分的相溶性，或脆性降低。例如即使醯基之總 取代度爲2.0以上，但碳數2之醯基’即乙醯基之取代度較 高，碳數3〜7之醯基的取代度低於〗.2時’相溶性會降低， 混濁上升。又，即使醯基之總取代度爲2.0以上’但碳數8 -16- 201107801 以上之醯基的取代度較高，碳數3 ~7之醯基的取代度低於 1.2時，脆性變差而無法得到所希望的特性。 本發明之纖維素酯樹脂（B )的醯基取代度係總取代 度（T)爲2.0〜3.0，碳數爲3~7之醯基的取代度爲1.2〜3.0 時，不會有問題，但是碳數3〜7以外之醯基，即乙醯基及 碳數爲8以上之醯基的取代度總計較佳爲1 .3以下。 又，纖維素酯樹脂（B )之醯基的總取代度（T )更佳 爲2.5 ~ 3 · 0的範圍。 本發明中，前述醯基可爲脂肪族醯基或芳香族醯基。 其爲脂肪族醯基時，可爲直鏈或支鏈，尙可具有取代基。 本發明之醯基的碳數係包含醯基之取代基者。 上述纖維素酯樹脂（B)爲具有芳香族醯基作爲取代 基時，在芳香族環上取代之取代基X的數量較佳爲0〜5個。 此時仍需留意使包含取代基之碳數爲3 ~7之醯基的取代度 成爲1.2〜3.0。例如因爲苯醯基之碳數成爲7，因此具有含 碳之取代基時，苯醯基之碳數成爲8以上，而不含在碳數 爲3~7的醯基內。 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）。 如上述之纖維素酯樹脂（B )係具有含有碳數3〜7之脂 肪族醯基之至少1種的構造，可作爲用於本發明之纖維素 樹脂的構造使用。 -17- 201107801 本發明之纖維素酯樹脂（B )的取代度係醯基之總取 代度（T)爲2.0~3.0，碳數爲3〜7之醯基的取代度爲1.2〜 3.0。 另外，碳數爲3〜7之醯基以外，即乙醯基與碳數爲8以 上之醯基之取代度的總和爲1.3以下者爲較佳的構造。 本發明之纖維素酯樹脂（B )特佳爲選自纖維素乙酸 酯丙酸酯、纖維素乙酸酯丁酸酯、纖維素乙酸酯苯甲酸酯 、纖維素丙酸酯、纖維素丁酸酯中之至少一種，較佳爲具 有碳原子數3或4的醯基作爲取代基者。 此等中特佳的纖維素酯樹脂爲纖維素乙酸酯丙酸酯或 纖維素丙酸酯。 未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。 本發明之纖維素酯樹脂的重量平均分子量（Mw)， 特別是從與丙烯酸樹脂（A )之相溶性、改善脆性的觀點 爲75000以上，較佳爲75000〜300000的範圍，更佳爲 1 00000~240000的範圍，特佳爲1 60000〜240000者。纖維素 醋樹脂之重量平均分子量（Mw)低於75000時，耐熱性及 脆性之改善效果不佳，無法得到本發明的效果。本發明可 混合使用二種以上的纖維素樹脂。 本發明之光學薄膜係具有至少二層以上之樹脂組成彼 此不同之層的光學薄膜，但是需要（i)構成該光學薄膜 -18- 201107801 表面之層的至少一層爲以95: 5〜85: 15之質量比含有丙烯 酸樹脂（A)與纖維素酯樹脂（B) ，（ii)構成該表面之 層以外的層爲以80 : 20~5 0 : 50之質量比含有丙烯酸樹脂 (A)與纖維素酯樹脂（B )。而且以相溶狀態含有丙烯酸 樹脂（A)與纖維素酯樹脂（B )較佳。 本發明之光學薄膜必須以相溶狀態含有丙烯酸樹脂（ A)與纖維素酯樹脂（B)。使不同的樹脂相溶、互補可達 成作爲光學薄膜所必要之物性或品質。 例如可藉由玻璃轉化溫度T g來判斷丙烯酸樹脂（a ) 與纖維素酯樹脂（B )是否成爲相溶狀態。 例如兩者之樹脂的玻璃轉化溫度不同時，混合兩者的 樹脂時，因有各自樹脂之玻璃轉化溫度，因此混合物之坡 璃轉化溫度也有2個以上，但兩者之樹脂相溶時，各自樹 脂固有的玻璃轉化溫度消失，成爲1個玻璃轉化溫度，成 爲相溶後之樹脂的玻璃轉化溫度。 又，此處所謂的玻璃轉化溫度係指使用差示掃描熱量 測定器（Perkin E1 m e r公司製D S C - 7型），以升溫速度 2〇°C/分鐘測定後，依JIS K7 1 21 ( 1 987 )得到的中間點坡 璃轉化溫度（Tmg) ^ 丙烯酸樹脂（A)與纖維素酯樹脂（B )各自爲非結晶 性樹脂較佳’又’其中一方可爲結晶性高分子，或—部分 具有結晶性的高分子，但本發明之丙烯酸樹脂（A )與纖 維素酯樹脂（B )相溶，成爲非結晶性樹脂較佳。 本發明之光學薄膜中之丙烯酸樹脂（A)的重量平均 -19- 201107801 分子量（Mw)或纖維素酯樹脂（B)之重量平均分子量（ Mw )或取代度係使用兩者之樹脂對於溶劑之溶解性的差 異，進行區分後，各自進行測定而得。區分樹脂時，藉由 添加相溶於僅溶解其中之一之溶劑中的樹脂，再萃取溶解 的樹脂來區分，此時可進行加熱操作或回流。可以2個步 驟以上組合此等溶劑之組合，來區分樹脂。將溶解後之樹 脂與以不溶物殘留的樹脂進行過濾，對於含有萃取物之溶 液可藉由使溶劑蒸發、乾燥的步驟以區分樹脂。此等區分 後的樹脂可藉由高分子之一般結構解析來限定。本發明之 光學薄膜含有丙烯酸樹脂（A)及纖維素酯樹脂（B)以外 的樹脂時，也可以相同方法區分。 又，相溶後之樹脂的重量平均分子量（Mw)各自不 同時，可藉由凝膠滲透色譜法（GPC )，高分子量物先被 溶離’越低分子量物需經過越長時間後始被溶離，故容易 區分且可測定分子量。 又’藉由GPC測定相溶後樹脂之分子量，同時可分開 取得每段時間溶離後之樹脂溶液，餾除溶劑，經乾燥後的 樹脂以定量進行結構解析，檢出不同分子量之每一分區的 樹脂組成’可分別限定相溶之樹脂。又，將預先以對溶劑 之溶解性之差異分開取得的樹脂，各自以GPC測定分子量 分布，可各自檢出相溶的樹脂。 又’本發明中，「以相溶狀態含有丙烯酸樹脂（A ) 與纖維素酯樹脂（B )」係指混合各樹脂（聚合物），結 果成爲相溶的狀態，並不包含纖維素酯樹脂（B )中混合 -20- 201107801 單體、二聚物或低聚物等之丙烯酸樹脂的前驅物後，藉由 聚合而爲混合樹脂的狀態。 例如，在纖維素酯樹脂（B )中混合單體、二聚物或 低聚物等之丙烯酸樹脂的前驅物後，藉由聚合得到混合樹 脂的步驟係聚合反應複雜，且此方法所製作之樹脂，難以 控制反應，分子量調整也困難。又，以此種方法合成樹脂 時，大多會產生接枝聚合、交聯反應或環化反應，且常有 不溶解於溶劑的情形或無法藉由加熱熔融，因此很難將混 合樹脂中之丙烯酸樹脂予以溶離測定重量平均分子量（ Mw )，故難以控制物性，無法作爲可安定製造光學薄膜 的樹脂使用。 本發明之光學薄膜在不損及光學薄膜的功能時，可由 含有丙烯酸樹脂（A )、纖維素酯樹脂（B )以外之樹脂及 添加劑所構成。 含有丙烯酸樹脂（A)、纖維素酯樹脂（B)以外的樹 脂時’所添加之樹脂可爲相溶狀態，或不溶解狀態下混合 〇 本發明之光學薄膜中之丙烯酸樹脂（A)與纖維素酯 樹脂（B )的總質量較佳爲光學薄膜之5 5質量％以上，更 佳爲60質量％以上，特佳爲70質量％以上。 使用丙烯酸樹脂（A)及纖維素酯樹脂（B )以外之樹 脂及添加劑時，在不損及本發明之光學薄膜功能的範圍內 調整添加量爲佳。 -21 - 201107801 (丙烯酸粒子（c)) 本發明之光學薄膜較佳爲含有丙烯酸粒子。 本發明之丙烯酸粒子（C )係指以相溶狀態含有前述 丙烯酸樹脂（A)及纖維素酯樹脂（B)之光學薄膜中，以 粒子狀態（也稱非相溶狀態）存在的丙烯酸成分。 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由中心部向外周部 ，具有最內硬質層聚合物、顯示橡膠彈性之交聯軟質層聚 合物及最外硬質層聚合物以層狀重疊所成之構造的粒子狀 丙烯酸聚合物。 換言之’多層構造丙烯酸系粒狀聚合物係指由中心部 朝向外周部，由最內硬質層、交聯軟質層及最外硬質層所 構成的多層構造丙烯酸系粒狀聚合物。較佳爲使用此3層 芯殻構造之多層構造丙烯酸系粒狀複合物。 本發明之丙烯酸系樹脂組成物所使用的多層構造丙烯 酸系粒狀複合物之較佳形態，例如有下述者。例如由（a )由甲基丙烯酸甲酯8 0〜98.9質量％、烷基之碳數爲1〜8的 -22- 201107801 烷基丙烯酸酯1 ~2 0質量％、及多官能性接枝劑ο · ο 1〜〇. 3質 量％所構成之單體混合物進行聚合而得的最內硬質層聚合 物；（b)在上述最內硬質層聚合物之存在下，由烷基之 碳數爲4〜8的烷基丙烯酸酯75〜98.5質量％、多官能性交聯 劑0.01〜5質量％及多官能性接枝劑〇.5〜5質量％所構成之單 體混合物進行聚合而得的交聯軟質層聚合物；（c)在上 述最內硬質層及交聯軟質層所構成的聚合物存在下，由甲 基丙烯酸甲酯80〜99質量％與烷基之碳數爲之烷基丙烯 酸酯1〜2 0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) 20~50質量％ 所構成’以丙酮區分時有不溶部分，該不溶部分之甲基乙 基酮膨潤度爲1 .5〜4 _0的丙烯酸系粒狀聚合物。 又如日本特公昭60-174〇6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。 構成多層構造丙嫌酸系粒狀複合物之最內硬質層聚合 物（a)較佳爲由甲基丙烧酸甲醋8〇〜98.9質量❶/〇、院基之 碳數爲1〜8的烷基丙烯酸酯1〜2 0質量％及多官能性接枝劑 0.01 ~〇.3質量％所構成之單體混合物進行聚合所得者。 -23- 201107801 院基之碳數爲1~8的院基丙嫌酸醋，例如有甲基丙烧 酸酯、乙基丙烯酸酯、η-丙基丙烯酸酯、η-丁基丙嫌酸醋 、s-丁基丙烯酸酯、2-乙基己基丙烯酸酯等，較佳爲使用 甲基丙烯酸酯及η-丁基丙烯酸酯。 最內硬質層聚合物（a)中之烷基丙烯酸酯單位的比 例爲1〜20質量％，該單位未達1質量％時，聚合物之熱分解 性變大，又該單位超過20質量％時，最內硬質層聚合物（c )之玻璃轉化溫度降低，3層構造丙烯酸系粒狀複合物之 耐衝擊性賦予效果降低，故均不佳。 多官能性接枝劑係具有不同之可聚合之官能基的多官 能性單體，例如丙烯酸、甲基丙烯酸、馬來酸、富馬酸之 烯丙酯等，較佳爲使用烯丙基甲基丙烯酸酯。多官能性接 枝劑係用於使最內硬質層聚合物與軟質層聚合物進行化學 性結合，因此，該最內硬質層聚合時所用的比例爲〇.〇 1 〜〇 . 3質量％。 構成丙烯酸系粒狀複合物之交聯軟質層聚合物》(b) 較佳爲在上述最內硬質層聚合物（a)之存在下’由院基 之碳數爲1~8的烷基丙烯酸酯75~98.5質量％、多官能性交 聯劑0.0 1 ~ 5質量％及多官能性接枝劑0.5〜5質量％所構成之 單體混合物進行聚合而得者。 其中烷基之碳數爲4〜8的烷基丙烯酸酯’較彳圭胃使 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％以下@胃# % & 之其他單官能性單體共聚合。 • 24- 201107801 可共聚合之其他單官能性單體，例如有苯乙烯及取代 苯乙烯衍生物。烷基之碳數爲4〜8的烷基丙烯酸酯與苯乙 烯之比例係當前者越多時，聚合物（b )之玻璃轉化溫度 越低，即越能軟質化。 又從樹脂組成物之透明性的觀點，軟質層聚合物（b )之常溫下的折射率越接近最內硬質層聚合物（a)、最 外硬質層聚合物（c)及硬質熱塑性丙烯酸樹脂越佳，考 慮這些後選定兩者的比例。 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2 〇〇〜 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0. 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 -25- 201107801 物（C)較佳爲在上述最內硬質層聚合物（a)及軟質層聚 合物（b)之存在下，由甲基丙烯酸甲酯80~99質量％及烷 基之碳數爲1〜8的烷基丙烯酸酯1〜20質量％所構成之單體混 合物進行聚合而得者。 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， 可使形成最外硬質層之聚合物的分子量，由多層構造丙烯 酸系粒狀複合物之內側往外側減少。 此時所形成的分子量可藉由測定將每次使用之單體混 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。 本發明較適合使用的丙烯酸粒子（C)之粒徑並無特 別限定，較佳爲l〇nm以上、l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，芯與殻之質量比並無特別限定，但是多層構造 -26- 201107801 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。此 芯層係指最內硬質層。 這種多層構造丙烯酸系粒狀複合物之市售品，例如有 三菱Rayon公司製“metablen”、鐘淵化學工業公司製 “kanes”、吳羽化學工業公司製 “Paraloid”、Rohm and Haas 公司製“Acryloid”、ganz化成工業公司製“staphiloid”及 kuraray公司製“parapet SA”等，此等可單獨使用或使用2種 以上。 又’本發明較適合使用之丙烯酸粒子（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之其 他乙烯基系單體所構成之單體混合物進行共聚而得的接枝 共聚物。 接枝共聚物之丙烯酸粒子（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-丁二烯共聚 物、苯乙烯-丁二烯之嵌段共聚物、丙烯腈-丁二烯共聚物 、丙烯酸丁酯-丁二烯共聚物、聚異戊二烯、丁二烯-甲基 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、乙烯-丙 烯-二烯系共聚物、乙烯-異戊二烯共聚物、及乙烯-丙烯酸 甲酯共聚物等。此等橡膠質聚合物可使用1種或2種以上的 -27- 201107801 混合物。 又，本發明之光學薄膜中添加丙烯酸粒子（C)時， 從可得到透明性較高之薄膜的觀點，丙烯酸樹脂（A )與 纖維素酯樹脂（B )之混合物的折射率與丙烯酸粒子（c ) 之折射率接近較佳。具體而言，丙烯酸粒子（C)與丙烯 酸樹脂（A )之折射率差較佳爲〇.〇5以下，更佳爲〇.〇2以 下，特佳爲0.01以下。 爲了滿足這種折射率條件時，可藉由調整丙烯酸樹脂 (A)之各單體單位組成比的方法，及/或調整丙烯酸粒子 (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（ 23°C、測定波長：550nm)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)及纖維素酯樹脂（B )的溶 -28- 201107801 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。 以下表示本發明之丙烯酸粒子與其製造方法之一例。 <調製丙烯酸粒子（C1) > 將離子交換水38.2L、二辛基磺基琥珀酸鈉i丨丨.6g投入 內容積60L之附回流冷卻器的反應器中，以250rpm轉數攪 拌同時在氮氣氛下升溫至75°C而形成事實上不受氧影響的 狀態。添加APS 0.3 6g攪拌5分鐘後，以一次添加由MMA 1 65 7g、BA 21.6g及ALMA 1.68g所構成之單體混合物，檢 測出發熱波峰後再保持20分鐘完成最內硬合層之聚合。 其次添加APS 3.48g，攪拌5分鐘後以120分鐘連續添 力口由 BA 8 1 05g ' PEGDA ( 200 ) 31.9g及 ALMA 264.0g所構 成的單體混合物，添加結束後再保持1 20分鐘完成軟質層 之聚合。 接著添加APS 1.32g，攪拌5分鐘後以20分鐘連續添加 由MMA 2106g、BA 201.6g所構成的單體混合物，添加結 束後再保持20分鐘完成最外硬質層1之聚合。 其次添加APS 1.32g，5分鐘後以20分鐘連續添加由 MMA 3148g、BA 201.6g及n-OM lO.lg所構成的單體混合 物，添加結束後再保持20分鐘。升溫至95°C後保持60分鐘 ，完成最外硬質層2之聚合。 將上述所得之聚合物乳膠投入3質量％硫酸鈉溫水溶液 -29- 201107801 中，重覆鹽析、凝固’接著脫水、洗淨後，進行乾燥得到 3層構造之丙烯酸粒子（C1)。藉由吸光度法得到平均粒 徑爲1 0 0 n m。 上述簡稱係各自爲下述材料。 MMA :甲基丙烯酸甲酯 MA :甲基丙烯酸酯 BA : η-丁基丙烯酸酯 ALMA :嫌丙基甲基丙烯酸酯 PEGDA :聚乙二醇二丙烯酸酯（分子量200 ) n-OM : 辛基硫醇 APS :過硫酸銨 本發明之丙烯酸粒子可使用市售品。例如有metablen W-341(C2)(三菱 Rayon (股）製）、chemisnowMR-2G(C3) 、MS-300X(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0.5〜30質量％之丙烯酸粒子（C )，更佳爲 含有1.0~1 5質量％的範圍。 <防靜電劑> 本發明之光學薄膜較佳爲含有防靜電劑，相對於構成 該薄膜之樹脂100質量份，較佳爲含有0.001〜2.0質量份的 防靜電劑。 防靜電劑無特別限定，可使用公知的防靜電劑，但是 較佳爲選自陰離子性防靜電劑、陽離子性防靜電劑、非離 -30- 201107801 子性防靜電劑、兩性離子性防靜電劑、 導電性微粒子之至少一種，更佳爲導電 選自氧化铈、氧化銦、氧化錫、氧化銨 種。 陰離子性防靜電劑例如有脂肪酸鹽 鹽類、液體脂肪油硫酸酯鹽類、脂肪族 硫酸鹽類、脂肪族醇磷酸酯鹽類、二鹽 酸鹽類、脂肪族醯胺磺酸鹽類、烷基烯 醛液縮合之萘磺酸鹽類等，陽離子性防 族胺鹽類、4級銨鹽類、烷基吡啶鑰鹽; 電劑例如有聚氧化乙烯烷醚類、聚氧化 聚氧化乙烯烷基酯、山梨糖醇酐烷基酯 糖醇酐烷基酯等，兩性離子性防靜電劑 物、甜菜鹼型高級烷基胺基衍生物、硫 酯衍生物等，具體的化合物係劑載於九 劑高分子之表面改質」幸書房、增補 加劑實用便覽P3 3 3〜p455」化學工業 2 5 6 1 4 3號、特公昭5 2 - 3 2 5 7 2號、特開平1 較佳之防靜電劑例如有陰離子性防 防靜電劑等的離子性高分子化合物。離 例如特公昭49-23828號、同49-23827號 示之陰離子性高分子化合物；特公昭55-54672號、特公昭 59-14735號、同 57-181 號、同57-5 605 9號等所記載之主鏈中具 高分子防靜電劑及 性微粒子，特佳爲 及氧化矽之至少一 類、高級醇硫酸酯 胺及脂肪族醯胺之 基性脂肪酸酯之磺 丙基磺酸鹽類、甲 靜電劑例如有脂肪 ，。非離子性防靜 乙烯烷基酚醚類、 、聚氧化乙烯山梨 例如有咪唑啉衍生 酸酯衍生物、磷酸 茂秀雄著「防靜電 「塑膠及橡膠用添 社刊、特開平1 1 -0-1 5 8484號等。 靜電劑或陽離子性 子性高分子化合物 '同4 7 - 2 8 9 3 7號所 -73 4號、特開昭50-75號、同 57-18176 有解離基之陽離子 -31 - 201107801 (ionene)型聚合物：特公昭53-13223號、同57-15376號 、特公昭 53-45231號、同 55-145783號、同 55-65950號、同 55-67746 號、同 57-11342號、同 57-19735號、特公昭 58- 56858號、特開昭61-27853號、同62_9346號各公報所記載 之側鏈中具有陽離子性解離基之陽離子性甜菜鹼型聚合物 、特開平5-2301 61號公報所記載之接枝共聚合物等。 此外，本發明之光學薄膜中，特別適用枝導電性微粒 子，其中金屬氧化物較佳爲例如有ZnO、Ti02、Sn02、MS2: monomer mass ratio (MMA: ST = 40: 60), MwlOOOOOO MMA: methyl methacrylate ΜΑ: methacrylate ST: styrene (combination of A 8) First, methyl methacrylate / propylene The guanamine copolymer-based suspension was adjusted as described below. Methyl methacrylate 20 parts by mass of acrylamide 80 parts by mass of potassium persulfate 〇. 3 parts by mass - 14 - 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 The reaction was carried out at 70 ° C to completely convert the monomer into a polymer. The resulting aqueous solution was used as a suspending agent. 5 parts by mass of the above suspension agent is dissolved in 165 parts by mass of ion-exchanged water, and the solution supply capacity is 5 L, and a stainless steel pressure cooker having a baffle plate and a pfauder type (a reverse impeller) type stirring blade is used. Instead of stirring at 400 rpm at the same time. Next, the mixed substance having the following input composition was added in the state of stirring the reaction system. 27 parts by mass of 73 parts by mass of methyl methacrylate t-dodecanethiol 1.2 parts by mass of 2,2'-azobisisobutyronitrile 0.4 parts by mass, and then heated to 70 ° C, when The point at which the internal temperature reached 7 〇 ° C was taken as the polymerization start point, and then the polymerization was carried out for 180 minutes. Then, the reaction system is cooled, the polymer is separated, washed, and dried according to a usual method to obtain a pelletized copolymer. The copolymer had a polymerization ratio of 97% and a weight average molecular weight of 130,000. To the copolymer, 0.2% by mass of an additive (Na〇CH3) was added, and a 2-axis extruder (TEX30 (manufactured by Nippon Steel Co., Ltd., L/D = 44.5)) was used, and nitrogen gas was supplied from the supply hopper portion at 10 L/min. Purge, and simultaneously carry out intramolecular cyclization reaction at a screw rotation number of 1 OO rpm, a raw material supply amount of 5 kg / hr, and a cylinder temperature of 290 ° C to prepare granules, which were vacuum dried at 80 ° C for 8 hours to obtain an acrylic resin A 8 . . The weight average molecular weight of acrylic resin A 8 -15- 201107801 The quantity (1^^) is 130000, and the Ding is 140. Hey. A commercially available product can be used for the acrylic resin of the present invention. For example, there are Delpet 60N, 80N (made by Asahi Kasei Chemicals Co., Ltd.), Dianal BR52, BR80, BR83, BR85, and BR 8 8 (Mitsubishi R ay 〇η (share) system) ΚΤ75 (Electrochemical Industry Co., Ltd.) Wait. The acrylic resin may be used in combination of two or more kinds (cellulose ester resin (Β)), the cellulose ester resin (Β) of the present invention, in particular, from the viewpoint of improving the brittleness or the transparency when it is compatible with the acrylic resin. The total degree of substitution (Τ) of the sulfhydryl group is 2.0 to 3.0, the degree of substitution of the fluorenyl group having 3 to 7 carbon atoms is 1.2 to 3.0, and the degree of substitution of the fluorenyl group having 3 to 7 carbon atoms is 2.0 to 3.0. In other words, the cellulose ester resin of the present invention is a cellulose ester resin substituted with a mercapto group having 3 to 7 carbon atoms. Specifically, a propenyl group or a butyl group is preferably used, and a propyl group is particularly preferably used. The total degree of substitution of the thiol group of the cellulose ester resin (Β) is less than 2.0, in other words, when the hydroxyl residue at the 2, 3, and 6 positions of the cellulose ester molecule is higher than 1.0, the acrylic resin (A) and cellulose The ester resin (Β) is not sufficiently soluble, and there is a problem of turbidity when used as an optical film. Further, even if the total substitution degree of the fluorenyl group is 2.0 or more, when the degree of substitution of the fluorenyl group having 3 to 7 carbon atoms is less than 1.2, sufficient compatibility or brittleness is not obtained. For example, even if the total substitution degree of the fluorenyl group is 2.0 or more, the degree of substitution of the fluorenyl group of the carbon number 2, that is, the thiol group is higher, and the degree of substitution of the fluorenyl group having 3 to 7 carbon atoms is lower than that of the 〗 〖2. It will decrease and the turbidity will rise. Further, even if the total substitution degree of the fluorenyl group is 2.0 or more 'but the substitution degree of the fluorenyl group having a carbon number of 8 -16 to 201107801 or more is high, and the degree of substitution of the fluorenyl group having 3 to 7 carbon atoms is less than 1.2, the brittleness is deteriorated. It is impossible to get the desired characteristics. The cellulose ester resin (B) of the present invention has a thiol substitution degree of a total degree of substitution (T) of 2.0 to 3.0, and a substitution degree of a ruthenium group having a carbon number of 3 to 7 of 1.2 to 3.0 is not problematic. However, the degree of substitution of the fluorenyl group other than the carbon number of 3 to 7 and the fluorenyl group having 8 or more carbon atoms is preferably 1.3 or less. Further, the total degree of substitution (T) of the thiol group of the cellulose ester resin (B) is more preferably in the range of 2.5 to 3.9. In the present invention, the above mercapto group may be an aliphatic mercapto group or an aromatic mercapto group. When it is an aliphatic fluorenyl group, it may be a straight chain or a branched chain, and hydrazine may have a substituent. The carbon number of the fluorenyl group of the present invention is a substituent containing a fluorenyl group. When the cellulose ester resin (B) has an aromatic fluorenyl group as a substituent, the number of substituents X substituted on the aromatic ring is preferably from 0 to 5. At this time, it is necessary to note that the degree of substitution of the fluorenyl group having a carbon number of 3 to 7 containing a substituent is 1.2 to 3.0. For example, since the carbon number of the phenylhydrazine group is 7, when the carbon-containing substituent is present, the carbon number of the phenylhydrazine group is 8 or more, and it is not contained in the fluorenyl group having 3 to 7 carbon atoms. 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 cellulose ester resin (B) as described above has a structure containing at least one of aliphatic aliphatic groups having 3 to 7 carbon atoms, and can be used as a structure for the cellulose resin of the present invention. -17-201107801 The degree of substitution of the cellulose ester resin (B) of the present invention is that the total degree of substitution (T) of the thiol group is from 2.0 to 3.0, and the degree of substitution of the fluorenyl group having a carbon number of from 3 to 7 is from 1.2 to 3.0. Further, in addition to the fluorenyl group having a carbon number of 3 to 7, the sum of the degree of substitution of the fluorenyl group and the fluorenyl group having a carbon number of 8 or more is preferably 1.3 or less. The cellulose ester resin (B) of the present invention is particularly preferably selected from the group consisting of cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate benzoate, cellulose propionate, fiber At least one of the butyrate esters preferably has a fluorenyl group having 3 or 4 carbon atoms as a substituent. Particularly preferred cellulose ester resins are cellulose acetate propionate or cellulose propionate. 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. The weight average molecular weight (Mw) of the cellulose ester resin of the present invention is, in particular, from the viewpoint of compatibility with the acrylic resin (A) and improvement of brittleness, in the range of 75,000 or more, preferably 75,000 to 300,000, more preferably 100,000. The range of ~240000 is particularly good for 1 60000~240000. When the weight average molecular weight (Mw) of the cellulose vinegar resin is less than 75,000, the effect of improving heat resistance and brittleness is not good, and the effects of the present invention cannot be obtained. In the present invention, two or more kinds of cellulose resins may be used in combination. The optical film of the present invention is an optical film having at least two or more layers of resin compositions different from each other, but it is required that (i) at least one layer constituting the surface of the optical film -18-201107801 is 95: 5 to 85: 15 The mass ratio includes the acrylic resin (A) and the cellulose ester resin (B), and (ii) the layer other than the layer constituting the surface contains the acrylic resin (A) and the fiber in a mass ratio of 80:20 to 50:50. Alkyl ester resin (B). Further, it is preferable to contain the acrylic resin (A) and the cellulose ester resin (B) in a compatible state. The optical film of the present invention must contain the acrylic resin (A) and the cellulose ester resin (B) in a compatible state. The different resins are compatible and complementary to the physical properties or qualities necessary for the optical film. For example, whether or not the acrylic resin (a) and the cellulose ester resin (B) are in a compatible state can be determined by the glass transition temperature T g . For example, when the glass transition temperatures of the resins of the two are different, when the resins of the two are mixed, the glass transition temperature of the respective resins is different, so that the glass transition temperature of the mixture is also two or more, but when the resins of the two are compatible, The glass transition temperature inherent in the resin disappears and becomes one glass transition temperature, which becomes the glass transition temperature of the resin after the compatibility. In addition, the term "glass transition temperature" as used herein refers to a differential scanning calorimeter (DSC-7 type manufactured by Perkin E1mer Co., Ltd.), and is measured at a temperature increase rate of 2 〇 ° C/min, according to JIS K7 1 21 (1 987). The obtained intermediate point glass transition temperature (Tmg) ^ The acrylic resin (A) and the cellulose ester resin (B) are each preferably a non-crystalline resin, and one of them may be a crystalline polymer, or a portion thereof Although the crystalline polymer is compatible with the cellulose ester resin (B), the acrylic resin (A) of the present invention is preferably an amorphous resin. The weight average of the acrylic resin (A) in the optical film of the present invention is -19-201107801. The molecular weight (Mw) or the weight average molecular weight (Mw) or degree of substitution of the cellulose ester resin (B) is a resin using both. The difference in solubility is determined by each of the differences. When the resin is distinguished, it is distinguished by adding a resin in which the phase is dissolved in a solvent which dissolves only one of them, and then extracting the dissolved resin, and at this time, heating operation or reflux can be performed. The combination of these solvents can be combined in two steps to distinguish the resins. The dissolved resin is filtered with a resin remaining as an insoluble matter, and the solution containing the extract can be distinguished from the resin by a step of evaporating and drying the solvent. These differentiated resins can be defined by general structural analysis of the polymer. When the optical film of the present invention contains a resin other than the acrylic resin (A) and the cellulose ester resin (B), it can be distinguished in the same manner. Further, when the weight average molecular weight (Mw) of the resin after the dissolving is different, the high molecular weight substance can be first dissolved by gel permeation chromatography (GPC). The lower the molecular weight, the longer the time is required to be dissolved. Therefore, it is easy to distinguish and the molecular weight can be measured. In addition, the molecular weight of the resin after dissolving is determined by GPC, and the resin solution after each period of time is separately obtained, the solvent is distilled off, and the dried resin is quantitatively analyzed for structure, and each partition of different molecular weight is detected. The resin composition 'is individually defined as a compatible resin. Further, each of the resins obtained in advance in the difference in solubility of the solvent was measured for molecular weight distribution by GPC, and each of the resins was found to be soluble. In the present invention, the "containing the acrylic resin (A) and the cellulose ester resin (B) in a compatible state means that the respective resins (polymers) are mixed, and as a result, they are in a compatible state, and do not contain the cellulose ester resin. (B) Mixing -20-201107801 A precursor of an acrylic resin such as a monomer, a dimer or an oligomer, followed by polymerization to form a state of a mixed resin. For example, after mixing a precursor of an acrylic resin such as a monomer, a dimer or an oligomer in the cellulose ester resin (B), the step of obtaining a mixed resin by polymerization is complicated in polymerization, and the method is produced. Resin, it is difficult to control the reaction, and molecular weight adjustment is also difficult. Moreover, when a resin is synthesized by such a method, a graft polymerization, a crosslinking reaction, or a cyclization reaction often occurs, and it is often insoluble in a solvent or melted by heating, so that it is difficult to mix acrylic acid in a resin. Since the resin is dissolved and the weight average molecular weight (Mw) is measured, it is difficult to control the physical properties, and it cannot be used as a resin capable of stably producing an optical film. The optical film of the present invention may be composed of a resin other than the acrylic resin (A) or the cellulose ester resin (B) and an additive, without impairing the function of the optical film. When the resin other than the acrylic resin (A) or the cellulose ester resin (B) is contained, the resin to be added may be in a compatible state, or the acrylic resin (A) and the fiber in the optical film of the present invention may be mixed in an insoluble state. The total mass of the ester resin (B) is preferably 55 mass% or more, more preferably 60 mass% or more, and particularly preferably 70 mass% or more. When a resin other than the acrylic resin (A) and the cellulose ester resin (B) and an additive are used, it is preferred to adjust the amount of addition within a range that does not impair the function of the optical film of the present invention. -21 - 201107801 (Acrylic Particles (c)) The optical film of the present invention preferably contains acrylic particles. The acrylic particles (C) of the present invention are acrylic components which are present in a particulate state (also referred to as an incompatible state) in an optical film containing the acrylic resin (A) and the cellulose ester resin (B) in a compatible 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, particularly preferably a multilayered structural acrylic granular composite. The multilayered acrylic granulated composite refers to a structure in which the innermost peripheral portion has the innermost hard layer polymer, the crosslinked soft layer polymer exhibiting rubber elasticity, and the outermost hard layer polymer are layered and overlapped. A particulate acrylic polymer. In other words, the "multilayer structure acrylic granulated polymer" refers to a multilayer structure acrylic granulated polymer composed of an innermost hard layer, a crosslinked soft layer and an outermost hard layer from the center portion toward the outer peripheral portion. It is preferable to use the multilayer structure of the three-layer core-shell structure to form an acrylic granular composite. A preferred embodiment of the multilayer structure acrylic-based particulate composite used in the acrylic resin composition of the present invention is, for example, the following. For example, (a) -20-201107801 alkyl acrylate having a molecular weight of 80 to 98.9 mass% of methyl methacrylate and a carbon number of 1 to 8 of an alkyl group, and a polyfunctional grafting agent ο · ο 1~〇. The innermost hard layer polymer obtained by polymerizing a monomer mixture composed of 3 mass%; (b) in the presence of the innermost hard layer polymer, the carbon number of the alkyl group is The polymerization of a monomer mixture composed of 4 to 8 alkyl acrylates of 75 to 98.5% by mass, a polyfunctional crosslinking agent of 0.01 to 5% by mass, and a polyfunctional grafting agent of 5 to 5 % by mass a soft layer polymer; (c) an alkyl acrylate having a carbon number of 80 to 99% by mass of methyl methacrylate and an alkyl group in the presence of a polymer composed of the innermost hard layer and the crosslinked soft layer An outermost hard layer polymer obtained by polymerizing a monomer mixture composed of 1 to 20% by mass of an ester; having a three-layer structure and having the obtained three-layer structure polymer as the innermost hard layer polymer (a ) 5 to 40% by mass, soft layer polymer (b) 30 to 60% by mass and outermost hard layer polymer (c) 20 to 50 mass The configuration 'when the insoluble portion distinguish acetone, the insoluble portion of the methyl ethyl ketone swelling degree of the particulate acrylic polymer in 1 .5~4 _0. Further, as disclosed in Japanese Patent Publication No. Sho 60-174-6, or Japanese Patent Publication No. Hei-3-39095, the composition and particle diameter of each layer of the multilayered acrylic particulate composite are not limited. The tensile modulus of the article and the methyl ethyl ketone swelling degree of the acetone-insoluble portion are set within a specific range 'by this, a balance of more sufficient impact resistance and stress whitening resistance can be achieved. The innermost hard layer polymer (a) constituting the multilayer structure of the acrylic acid-like granular composite is preferably composed of methyl acetoacetic acid methyl vinegar 8 〇 98.9 mass ❶ / 〇, and the carbon number of the hospital base is 1 -8 The monomer mixture obtained by polymerizing the alkyl acrylate 1 to 20% by mass and the polyfunctional grafting agent 0.01 to 0.3% by mass. -23- 201107801 The base of the hospital has a carbon number of 1~8, such as methyl propionate, ethyl acrylate, η-propyl acrylate, η-butyl acrylate vinegar As the s-butyl acrylate, 2-ethylhexyl acrylate or the like, methacrylate and η-butyl acrylate are preferably used. The ratio of the alkyl acrylate unit in the innermost hard layer polymer (a) is 1 to 20% by mass, and when the unit is less than 1% by mass, the thermal decomposition property of the polymer becomes large, and the unit exceeds 20% by mass. At this time, the glass transition temperature of the innermost hard layer polymer (c) is lowered, and the impact resistance imparting effect of the three-layer structure acrylic type granular composite is lowered, so that it is not preferable. The polyfunctional grafting agent is a polyfunctional monomer having different polymerizable functional groups, such as acrylic acid, methacrylic acid, maleic acid, allyl fumarate, etc., preferably using allyl group. Acrylate. The polyfunctional grafting agent is used for chemically bonding the innermost hard layer polymer to the soft layer polymer. Therefore, the ratio of the innermost hard layer to be polymerized is 〇.〇 1 to 〇. 3 mass%. The crosslinked soft layer polymer constituting the acrylic granular composite (b) is preferably an alkylacrylic acid having a carbon number of from 1 to 8 in the presence of the innermost hard layer polymer (a). A monomer mixture composed of 75 to 98.5% by mass of an ester, 0.01 to 5% by mass of a polyfunctional crosslinking agent, and 0.5 to 5% by mass of a polyfunctional grafting agent is obtained by polymerization. The alkyl acrylate having a carbon number of 4 to 8 in the alkyl group is η-butyl acrylate and 2-ethylhexyl acrylate as compared with the stomach. Further, these polymerizable monomers may be copolymerized with 25% by mass or less of other monofunctional monomers of @胃# % & • 24- 201107801 Other monofunctional monomers that can be copolymerized, such as styrene and substituted styrene derivatives. The ratio of the alkyl acrylate having a carbon number of 4 to 8 to the styrene is as high as possible, and the lower the glass transition temperature of the polymer (b), the softer it is. Further, from the viewpoint of the transparency of the resin composition, the refractive index of the soft layer polymer (b) at normal temperature is closer to the innermost hard layer polymer (a), the outermost hard layer polymer (c), and the hard thermoplastic acrylic resin. The better, consider the ratio of the two after considering these. As the polyfunctional grafting agent, those enumerated as mentioned in the above-mentioned innermost hard layer polymer (a) can be used. The polyfunctional grafting agent used herein is for chemically bonding the soft layer polymer (b) to the outermost hard layer polymer (c), and the ratio of the innermost hard layer used for polymerization is resistant. The viewpoint of the impact imparting effect is preferably 0.5 to 5% by mass. As the polyfunctional crosslinking agent, a generally known crosslinking agent such as a divinyl compound, a diallyl compound, a diacrylic compound, or a dimethacrylic compound can be used. Preferably, polyethylene glycol diacrylate (molecular weight 2) is used. 〇〇~600) The polyfunctional crosslinking agent used herein is used to form a crosslinked structure when the soft layer (b) is polymerized to impart an impact resistance. However, when the conventional polyfunctional grafting agent is used for the polymerization of the soft layer, the crosslinked structure of the soft layer (b) is formed to some extent, so that the polyfunctional crosslinking agent is not essential, but from the viewpoint of imparting impact resistance, The ratio of the polyfunctional crosslinking agent used in the polymerization of the soft layer is preferably 0. 〇1 to 5 mass% » The outermost hard layer polymerization constituting the multilayer structure acrylic granular composite -25-201107801 Preferably, in the presence of the innermost hard layer polymer (a) and the soft layer polymer (b), the alkyl acrylate is 80 to 99% by mass of methyl methacrylate and the carbon number of the alkyl group is 1 to 8. The monomer mixture composed of 1 to 20% by mass of the ester is polymerized. Among them, the alkyl acrylate may be used as described above, and it is preferred to use methacrylate and ethacrylate. The proportion of the alkyl acrylate unit in the outermost hard layer (c) is preferably from 1 to 20% by mass. Further, in the polymerization of the outermost hard layer (c), in order to improve the compatibility with the acrylic resin (A), in order to adjust the molecular weight, an alkyl mercaptan or the like may be used as a chain transfer agent for polymerization. In particular, it is preferable that the outermost hard layer has a slope (slope) in which the molecular weight is gradually decreased from the inner side to the outer side, and the balance between the elongation and the impact resistance can be improved. The specific method is to divide the monomer mixture for forming the outermost hard layer into two or more, and sequentially increase the chain transfer dose per addition, so that the molecular weight of the polymer forming the outermost hard layer can be made of a multilayer structure. The inner side of the acrylic granular composite is reduced to the outside. The molecular weight formed at this time can be known by measuring the molecular weight of the polymer obtained by polymerizing each of the monomer mixtures used each time under the same conditions. The particle diameter of the acrylic particles (C) which is suitably used in the present invention is not particularly limited, but is preferably 10 nm or more and 10 nm or less, more preferably 20 nm or more and 500 nm or less, and most preferably 50 nm or more and 400 nm. the following. 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 polymer is 100 parts by mass in the multilayer structure -26-201107801, the core layer is preferably It is 50 parts by mass or more, 90 parts by mass or less, more preferably 60 parts by mass or more and 80 parts by mass or less. This core layer refers to the innermost hard layer. Commercial products of such a multilayer structure of the acrylic granular composite are, for example, "metablen" manufactured by Mitsubishi Rayon Co., Ltd., "kanes" manufactured by Kaneka Chemical Industry Co., Ltd., "Paraloid" manufactured by Kureha Chemical Industry Co., Ltd., and manufactured by Rohm and Haas Co., Ltd. "Acryloid", "staphiloid" manufactured by ganz Chemical Industry Co., Ltd., and "parapet SA" manufactured by Kuraray Co., Ltd., etc., may be used alone or in combination of two or more. Further, a specific example of the acrylic particles (C) which are more suitable for use in the present invention, and a suitable graft copolymerized acrylic particle (c-1), are in the presence of a rubbery polymer, and are derived from an unsaturated carboxylic acid ester. A graft copolymer obtained by copolymerizing a monomer, an unsaturated carboxylic acid monomer, an aromatic vinyl monomer, and, if necessary, a monomer mixture composed of other vinyl 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 ethacrylate copolymer, ethylene-propylene copolymer, ethylene-propylene-diene A copolymer, an ethylene-isoprene copolymer, and an ethylene-methyl acrylate copolymer. These rubbery polymers may be used alone or in combination of two or more of -27-201107801. Further, when the acrylic particles (C) are added to the optical film of the present invention, the refractive index of the mixture of the acrylic resin (A) and the cellulose ester resin (B) and the acrylic particles are from the viewpoint of obtaining a film having high transparency. The refractive index of c) is close to better. Specifically, the difference in refractive index between the acrylic particles (C) and the acrylic resin (A) is preferably 〇. 5 or less, more preferably 〇. 〇 2 or less, 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. The method of reducing the refractive index difference, etc., can obtain an optical film excellent in transparency. 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. The insoluble portion (acrylic resin (A)) and the insoluble portion (acrylic acid particles (C)) were separately purified from the insoluble portion, and the difference between the measured refractive index (23 ° C, measurement wavelength: 550 nm) was shown. 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 an acrylic resin (A) and other optional components in advance, usually at 200 to 3 50 ° C. A method of uniformly adding melt-kneading by adding a acryl particle (C) while being uniaxially or biaxially extruded. Further, a solution in which acrylic particles (C) are dispersed in advance may be used to dissolve the acrylic resin (A) and A method of mixing a solution of a cellulose ester resin (B), a solution of a solution of a solution of the acrylic acid (C) and any other additives, and in-line addition, etc. . An example of the acrylic particles of the present invention and a method for producing the same are shown below. <Preparation of acrylic acid particles (C1) > 38.2 L of ion-exchanged water and sodium dioctylsulfosuccinate i.6 g were placed in a reactor equipped with a reflux condenser at an internal volume of 60 L, and stirred at 250 rpm while stirring The temperature was raised to 75 ° C under a nitrogen atmosphere to form a state which was virtually unaffected by oxygen. After adding APS 0.3 6 g and stirring for 5 minutes, a monomer mixture composed of MMA 1 65 7 g, BA 21.6 g, and ALMA 1.68 g was added in one portion, and the polymerization of the innermost hard layer was completed after detecting the onset heat peak for 20 minutes. Next, add ABS 3.48g, stir for 5 minutes, and continuously add a monomer mixture consisting of BA 8 1 05g 'PEGDA (200) 31.9g and ALMA 264.0g for 120 minutes. After the addition, keep it for 20 minutes to complete the softness. Polymerization of layers. Next, 1.32 g of APS was added, and after stirring for 5 minutes, a monomer mixture composed of MMA 2106 g and BA 201.6 g was continuously added over 20 minutes, and after completion of the addition, polymerization of the outermost hard layer 1 was completed for 20 minutes. Next, 1.32 g of APS was added, and after 5 minutes, a monomer mixture composed of MMA 3148g, BA 201.6g, and n-OM 10g was continuously added for 20 minutes, and the addition was continued for 20 minutes. After heating to 95 ° C for 60 minutes, the polymerization of the outermost hard layer 2 was completed. The polymer latex obtained above was placed in a 3 mass% sodium sulfate warm aqueous solution -29-201107801, and the salting-out and solidification were repeated, followed by dehydration and washing, followed by drying to obtain a three-layer structure of acrylic particles (C1). The average particle diameter was obtained by absorbance method to be 100 nm. The above abbreviations are each of the following materials. MMA: methyl methacrylate MA: methacrylate BA: η-butyl acrylate ALMA: propyl methacrylate PEGDA: polyethylene glycol diacrylate (molecular weight 200) n-OM : octyl sulphide Alcohol APS: Ammonium Persulfate A commercially available product can be used for the acrylic particles of the present invention. For example, there are metablen W-341 (C2) (manufactured by Mitsubishi Rayon Co., Ltd.), chemisnow MR-2G (C3), and MS-300X (C4) (manufactured by Suga Chemical Co., Ltd.). In the optical film of the present invention, the acrylic resin particles (C) are preferably contained in an amount of from 0.5 to 30% by mass, more preferably from 1.0 to 15% by mass, based on the total mass of the resin constituting the film. <Antistatic agent> The optical film of the present invention preferably contains an antistatic agent, and preferably contains 0.001 to 2.0 parts by mass of an antistatic agent based on 100 parts by mass of the resin constituting the film. The antistatic agent is not particularly limited, and a known antistatic agent can be used, but is preferably selected from an anionic antistatic agent, a cationic antistatic agent, a nonionic -30-201107801 sub-static antistatic agent, and a zwitterionic antistatic agent. At least one of the agent and the conductive fine particles, more preferably, the conductive material is selected from the group consisting of cerium oxide, indium oxide, tin oxide, and ammonium oxide. Examples of the anionic antistatic agent include fatty acid salt salts, liquid fatty oil sulfate salts, aliphatic sulfates, aliphatic alcohol phosphate salts, dihydrochloride salts, aliphatic guanamine sulfonates, and alkyl groups. a naphthalene sulfonate such as a condensation of an alkenal liquid, a cationic anti-steroidal salt, a 4-grade ammonium salt, an alkyl pyridyl salt; an electric agent such as a polyoxyethylene alkyl ether or a polyoxyethylene oxide alkyl group Ester, sorbitan alkyl saccharide alkyl ester, etc., amphoteric ionic antistatic agent, betaine type higher alkyl amino derivative, thioester derivative, etc., specific compound agents are contained in Surface modification of polymer polymer "Fortunate study room, supplementary additives practical notes P3 3 3 ~ p455" Chemical industry 2 5 6 1 4 3, special public Zhao 5 2 - 3 2 5 7 2, special Kaiping 1 better defense The electrostatic agent is, for example, an ionic polymer compound such as an anionic antistatic agent. For example, an anionic polymer compound shown in Japanese Patent Publication No. Sho 49-23828, No. 49-23827; No. Sho 55-54672, No. 59-14735, No. 57-181, No. 57-5 605, etc. The main chain described therein has a polymer antistatic agent and fine particles, particularly preferably at least one type of cerium oxide, a higher alcohol sulphate amine, and a sulfopropyl sulfonate of a fatty acid ester of an aliphatic decylamine. The electrostatic agent is, for example, fat. Non-ionic antistatic vinyl vinyl phenol ethers, and polyoxyethylene sorbes, for example, imidazoline-derived acid ester derivatives, and phosphoric acid, Xiu Xiong, "Antistatic" Plastics and Rubber Additions, Special Kaiping 1 1 -0- 1 5 8484, etc. Electrostatic agent or cationic polymer compound 'the same as 4 7 - 2 8 9 3 7-73 4, special open 50-75, the same 57-18176 with cations of the dissociation group - 31 - 201107801 (ionene) type polymer: special public Zhao 53-13223, same as 57-15376, special public Zhao 53-45231, the same 55-145783, the same 55-65950, the same 55-67746, the same 57 a cationic betaine-based polymer having a cationic dissociative group in a side chain described in each of the publications of the Japanese Patent Publication No. -11342, No. 57-19735, No. 57-19565, No. Sho 58-56858, No. 61-27853, and No. 62-9346 Further, in the optical film of the present invention, the branch conductive fine particles are particularly preferably used, and the metal oxide is preferably ZnO, TiO 2 or Sn 02, for example.

Al2〇3、In203、Si〇2、MgO、BaO、Ce〇2、Sb203、Mo〇2、 V2〇5等、或此等之複合氧化物，特佳爲Ce〇2、In2〇3、 Sn02、Sb203、及Si02。含有雜原子之例有對於ZnO添加A1 、in等，對於Ti02添加Nb、Ta等，對於Sn02添加Sb、Nb 、鹵素元素等具有效果。此等異種原子之添加量較佳爲 0 · 0 1 ~ 2 5 m ο 1 %的範圍，特佳爲0.1〜1 5 m ο 1 %的範圍。 該導電性微粒子之平均微粒徑較佳爲1 〇〇nm以下’更 佳爲5〜lOOnm。導電性微粒子之平均微粒徑爲lOOnm以下 時，含於樹脂材料中時，可賦予充分的防靜m特性，同時 不影響樹脂材料之透明性，故較佳。 特佳的防靜電劑從防靜電性能與添加量的關係，表面 固有電阻値爲1x1 〇1()Ω以下者較佳。表面固有抵抗値係將 試料在23t、50%RH之氣氛中，調濕24小時後，使用超絶 緣計依據ASTM D25 7測定。 本發明中，較適用的防靜電劑係特開平9-203 8 1 0號所 記載之陽離子導電性聚合物或分子間具有交聯的4級銨陽 -32- 201107801 離子導電性聚合物等。 交聯型陽離子導電性聚合物之特徴係所得之分散性粒 狀聚合物’可以高濃度、高密度具有微粒子內的陽離子成 分，因此不僅具有優異的導電性，且與樹脂之相溶性良好 ’可得到高的透明性，而即使在更低相對濕度下，也未見 導電性劣化。 防靜電用之交聯型陽離子導電性聚合物之分散性粒狀 聚合物，一般使用約0.01〜0.3/zm之微粒子尺寸範圍，較 佳爲〇.〇5〜0.15# m之範圍的微粒子尺寸。 本發明中，上述說明之各防靜電劑係相對於本發明之 光學薄膜100質量份，較佳爲添加0.001~2.0質量份的範圍 ’防靜電劑之添加量爲0.001質量份以上、2.0質量份以下 時’可有效抑制塵埃附著於樹脂材料，樹脂材料之光透過 率可維持在所希望的數値。防靜電劑之添加量係相對於具 有脂環式構造之聚合物100質量份，較佳爲0.00 5〜1.0質量 份，更佳爲0.01 ~0.5質量份。 本發明中，在樹脂上設置上述防靜電劑及一般防污用 之具有氟化合物的層，也可得到同樣的效果。 爲了得到本發明之光學薄膜的性能，可在薄膜表面設 置含有防靜電劑之至少一種的層（防靜電層）。 防靜電層可藉由將前述具有防靜電劑之混合物塗佈於 光學元件表面來設置，或藉由如蒸鍍的方法來設置。此外 ，防靜電層之厚度較佳爲50~300 //m。 -33- 201107801 (消光劑） 爲了賦予本發明之光學薄膜滑潤性或光學性、機械功 能’可添加無機化合物之微粒子或有機化合物之微粒子作 爲消光劑。 較佳爲使用消光劑的形狀爲球狀、棒狀、針狀、層狀 、平板狀等的形狀者。 消光劑例如有二氧化矽、二氧化鈦、氧化鋁、氧化锆 、碳酸鈣、陶土、滑石、燒成矽酸鈣、水和矽酸鈣、矽酸 鋁、矽酸鎂、磷酸鈣等金屬原子的氧化物、磷酸鹽、矽酸 鹽、碳酸鹽等之無機微粒子。 有機化合物之微粒子可使用例如美國專利第2,322,03 7 號說明書等所記載之澱粉、比利時專利第62 5,45 1號說明 書或英國專利第98 1，1 98號說明書等所記載之澱粉衍生物 、特公昭44-3 643號公報等所記載之聚乙烯醇、瑞士專利 第330,158號公報等所記載之聚苯乙烯或聚甲基丙烯酸酯 、美國專利第3,079,2 5 7號說明書等所記載之聚丙烯腈、美 國專利第3,022,169號說明書等所記載之聚碳酸酯的有機微 粒子。 換言之，有機化合物之微粒子的例子，其中水分散性 乙烯聚合物例如有聚甲基丙烯酸酯、聚甲基丙烯酸甲酯、 聚丙烯腈、丙烯腈-α-甲基苯乙烯共聚合物、聚苯乙烯、 苯乙烯-二乙烯基苯共聚合物、聚乙烯基乙酸酯、聚乙烯 碳酸酯、聚四氟乙烯等、纖維素衍生物例如有甲基纖維素 、纖維素乙酸酯、纖維素乙酸酯丙酸酯等、澱粉衍生物例 -34- 201107801 如有羧基澱粉、羧基硝基苯基澱粉、尿素-甲醛-澱粉反應 物等、以公知硬化劑硬化的明膠及凝聚層硬化形成微小膠 囊中空粒體的硬化明膠等可適合使用。 以上之無機微粒子微粒子或有機化合物微粒子中，二 氧化矽可降低薄膜之霧値，故較佳。此等微粒子藉由有機 物進行表面處理，可降低薄膜之霧値，故較佳。 較佳爲以鹵矽烷類、烷氧基矽烷類、矽胺烷、矽氧烷 等進行表面處理。微粒子之平均粒徑越大，滑潤性效果越 大，相反地，平均粒徑越小透明性越優異。 又，微粒子之一次粒子的平均粒徑爲0.01〜Ι.Ομηι之範 圍。較佳微粒子之一次粒子的平均粒徑較佳爲5〜5 Onm，更 佳爲7〜1 4 n m。 這些微粒子可於光學薄膜表面上產生0.01〜Ι.Ομηι之凹 凸，故較適用。 二氧化矽之微粒子例如有日本AEROSIL (股）製之 AEROSIL 200、200V、300、R972、R972V、R974、R202 ' R812、0X50、ΤΤ600、ΝΑΧ50等、日本觸媒（股）製之 ΚΕ-Ρ10、ΚΕ-Ρ30、ΚΕ-Ρ100、ΚΕ-Ρ150 等，較佳爲 AEROSIL200V、R972V、N A X 5 0、Κ Ε - Ρ 3 0、Κ Ε - Ρ 1 0 0。這 些微粒子可倂用2種以上。 倂用2種以上時，可以任意比率混合使用。此時，可 以質量比0.1: 99.9~99.9: 0.1之範圍使用平均粒徑或材質 相異的微粒子，例如AEROSIL 200V與R972V。 這些消光劑之添加方法較佳爲藉由混煉等方法添加。 -35- 201107801 又，另外的形態爲將預先分散於溶劑之消光劑與樹脂及/ 或可塑劑及/或抗氧化劑及/或紫外線吸收劑經混合分散後 ，得到溶劑揮發或沈澱的固形物，將此使用於樹脂熔融物 之製造過程，此從消光劑可均勻地分散於樹脂中的觀點， 較佳。 欲改善薄膜的機械性、電氣、光學特性，可添加上述 消光劑。 添加這些微粒子可提高所得之薄膜的滑潤性，但添加 後霧値會上昇，因此相對於樹脂，含量較佳爲0.001〜5質 量％，更佳爲〇.〇〇5〜1質量％，更佳爲〇.〇1〜〇.5質量％。 本發明之光學薄膜係霧値若超過1 . 0 %時作爲光學用材 料會有影響，較佳爲霧値未達1.0%，更佳爲未達0.5%。霧 値可以JIS-K7136行測定。 <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 -36- 201107801 應物，但主要係使用二價羧酸與甘醇反應而得者。代表性 之二價羧酸例如有戊二酸 '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-丁烯、1，6-己 烯、新戊烯、二乙烯、三乙烯、二丙烯等之甘醇。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600~3 000的範 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200〜5〇〇〇MPa*s ( 25°C )的範圍。另外，可倂用數個聚 酯系可塑劑。 可塑劑係相對於本發明之光學薄膜1 0 0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 酸苯基酯系者等。例如有2-(5-甲基-2-羥基苯基）苯并三 唑、2-[2 -羥基- 3,5 -雙（α，α -二甲基苯甲基）苯基]-2H -苯 并三哩、2- (3,5-二-t -丁基-2-經基苯基）苯并三卩坐等三哩 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。 -37- 201107801 此等紫外線吸收劑中，分子量爲4 0 0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。 分子量爲400以上之紫外線吸收劑例如有2- ( 2-羥基-3,5-雙（〇1，(1-二甲基苯甲基）苯基）-2-苯并三唑、2,2_亞 甲基雙[4- ( 1，1，3,3-四丁基）-6- ( 2Η-苯并三唑-2-基）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-羥基苯甲基）-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-羥基苯基）丙醯氧基]乙基卜4_[3- ( 3,5_二4_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。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、二芳基磷酸酯、單芳基磷酸酯、芳基膦酸化合物、芳 基膦氧化物化合物、縮合芳基磷酸酯、鹵化烷基磷酸酯、 • 38 · 201107801 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（氯乙基）磷酸酯、三（二 氯丙基）磷酸酯、三（三溴新戊基）磷酸酯等。 依據本發明之光學薄膜時，可同時達成以往樹脂薄膜 無法完成之改善低吸濕性、透明性、高耐熱性及脆性。 本發明中，脆性之指標係以是否爲「不會產生延性破 壞的光學薄膜」爲基準來判斷。可得到不會產生延性破壞 ’改善脆性的光學薄膜，即使製作大型液晶顯示裝置用之 偏光板時，也不會發生斷裂或龜裂，可形成使用操作性優 異的光學薄膜。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時會造成斷裂，且最終斷裂前伴隨著 材料之明顯之延伸或收縮的破壞。該斷面之特徵爲形成無 數被稱爲窩的凹洞。 本發明中，是否爲「不會產生延性破壞的光學薄膜」 係藉由即使施加將薄膜折彎成2片之大應力作用，也未出 現斷裂等之破壞來評價者。即使施加這種較大應力也不會 產生延性破壞的光學薄膜時，即使作爲大型化液晶顯示裝 置用之偏光板使用時，也可充分減少製造時斷裂等問題， 此外，即使經過一次貼合後再剝離，使用光學薄膜時，也 不會發生斷裂，可充分適用於光學薄膜之薄型化。 本發明係使用張力軟化點作爲耐熱性指標。隨著液晶 顯示裝置大型化、背光光源亮度日益提高，以及將數字標 -39- 201107801 牌運用於屋外用途而要求更高亮度，因此光學薄膜需要具 有耐更高溫環境之特性，但張力軟化點爲時即 可判斷爲具有充分耐熱性。特佳爲控制於110〜1 3 〇°C。 顯示光學薄膜之張力軟化點之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- 1 22 5A )，將光學薄膜切成120mm (長）X 10mm (寬）後，以 10N之張力拉伸，同時以30°C /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，從耐熱性觀點，光學薄膜之玻璃轉化溫度（Tg ) 較佳爲1 1 〇 °C以上。更佳爲1 2 0 °C以上。特佳爲1 5 0 °C以上 〇 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JIS K7121 ( 1 98 7 )求得的中間點玻璃轉化溫度（Tmg) 〇 判斷本發明之光學薄膜之透明性的指標係使用霧度値 (濁度）。特別是於屋外使用之液晶顯示裝置，即使於明 亮場所也要求可得到充分亮度及高對比，因此霧度値必須 在1.0%以下，更佳爲0.5%以下。 依據含有丙烯酸系樹脂（A)與纖維素酯樹脂（B)之 本發明的光學薄膜時，可得高透明性，但爲了改善其他物 性而使用丙烯酸粒子時，藉由降低樹脂（丙烯酸系樹脂（ A)與纖維素酯樹脂（B))與丙烯酸粒子（C)之折射率 差，可防止霧度値上升。 -40- 201107801 又，表面粗糙度也以表面霧度的形態影響霧度値，因 此將丙烯酸粒子（C )之粒徑及添加量控制於前述範圍內 ，可有效降低製膜時之薄膜接觸部的表面粗糙度。 又，本發明之光學薄膜的吸濕性係藉由相對於濕度變 化之尺寸變化來評價。 相對於濕度變化之尺寸變化的評價方法可使用下述方 法。 在製作之光學薄膜之流延方向，於2處作記號（十字 )，以60t、90%RH下處理1 000小時，使用光學顯微鏡測 定處理前與處理後之記號（十字）的距離，求得尺寸變化 率（％)。尺寸變化率（％ )如下述式表示。 尺寸變化率（％) = [(al-a2)/al]xl00 al :熱處理前之距離 a2 :熱處理後之距離 使用光學薄膜作爲液晶顯示裝置的偏光板用保護薄膜 時，因吸濕造成之尺寸改變，因而使光學薄膜發生不均（ 色斑）或相位差値變化，故會產生對比降低或色斑的問題 。特別是使用於屋外用之液晶顯示裝置的偏光板保護薄膜 時，上述問題會更明顯。但上述條件之尺寸變化率（％ ) 未達0.5 %時，評價爲顯示充分低吸濕性的光學薄膜。更佳 爲未達0.3 %者。 又，本發明之光學薄膜係在薄膜面內之直徑5μηι以上 的缺點較佳爲1個/l〇cm四方以下。更佳爲0.5個/10cm四方 以下，更佳爲0.1個/l〇cm四方以下。 -41 - 201107801 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。 缺點個數多於1個/1 0cm四方時，例如於其後步驟之加 工時等對薄膜施加張力時，有時以缺點爲起點，薄膜斷裂 ’生產性有明顯降低的情形。又，缺點的直徑爲5μπι以上 時’可以偏光板觀察等以目視確認，有時作爲光學構件使 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硬塗層 等時’塗劑無法均一形成，成爲缺點（未被塗佈）的情形 。缺點係指在溶液製膜之乾燥步驟中，因溶劑之急速蒸發 所產生之薄膜中的空洞（發泡缺陷）或因製膜原液中之異 物或製膜中混入之異物所產生之薄膜中的異物（異物缺點 -42- 201107801 又’本發明之光學薄膜依據JIS-K7127-1999測定時， 至少一方向之斷裂伸度較佳爲1 0 %以上，更佳爲2 0 %以上 〇 斷裂伸度之上限並無特別限制，實際上爲約250%。欲 提高斷裂伸度時，可藉由抑制因異物或發泡所造成之薄膜 中的缺點。 本發明之光學薄膜的厚度較佳爲20 μηι以上。更佳爲 3 Ομηι以上。 厚度上限並無特別限定，但從塗佈性、發泡、溶劑乾 燥等的觀點，上限爲250μιη。又薄膜厚度可依據用途來適 當選擇。 本發明之光學薄膜之光線透過率較佳爲90%以上，更 佳爲93%以上。又實際的上限爲99%。爲了達成此種以全 光線透過率表示之優異的透明性時，可藉由避免導入會吸 收可見光之添加劑或共聚合成份、或藉由高精度過濾去除 聚合物中的異物，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（冷卻輥、壓 延輥、滾筒、輸送帶、溶液製膜之塗佈基材、搬運輥等） 之表面粗糙度，以降低薄膜表面之表面粗糙度，或降低丙 烯酸樹脂之折射率，減少薄膜表面之光擴散或反射。 本發明之光學薄膜滿足如上述的物性時，特別適合作 爲大型液晶顯示裝置或屋外用途之液晶顯示裝置用的偏光 板保護薄膜使用。 -43- 201107801 <光學薄膜之製膜> 以下說明光學薄膜之製膜方法例，但本發明不限定於 此等。 本發明之光學薄膜之製膜方法，可使用例如吹塑法、 τ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β 本發明之光學薄膜’其係具有至少二層以上之樹脂組 成彼此不同之層的光學薄膜’其特徵係（i)構成該光學 薄膜表面之層的至少一層爲以50: 5 0〜30: 70之質量比含 有丙烯酸樹脂（A)與纖維素酯樹脂（b) ，（ii)構成該 表面之層以外的層爲以80: 20〜50: 50之質量比含有丙稀 酸樹脂（A)與纖維素酯樹脂（b) ， （iii)前述丙烯酸 樹脂（A )之重量平均分子量爲80000以上，（iv )前述纖 維素酯樹脂（B)之醯基的總取代度爲2.0〜3.0、碳數3〜7 之醯基的取代度爲1 .2〜3.0 ’該纖維素酯樹脂（b )之重量 平均分子量爲75000以上者。因此實現這種特徵的方法係 採用以下詳述之薄膜製膜步驟時同時形成該樹脂組成彼此 不同之層的方法較佳。例如有預先製作複數之該樹脂組成 彼此不同之膠漿’然後供給的方法、製作各自之樹脂的膠 漿’在流延前適當混合製作複數樹脂組成之膠漿的方法， 但是從膠漿之均一性的觀點’較佳爲預先製作複數之該樹 脂組成彼此不同之膠漿，然後供給的方法。 例如製造本發明之光學薄膜係將樹脂組成不同之複數 -44- 201107801 的膠漿液使用具有複數狹縫之模縫，直接流延於流延帶（ belt )上進行共流延（鑄膜步驟），接著加熱除去溶劑之 一部份（流延帶上之乾燥步驟）後，從流延帶上剝離，將 剝離後的薄膜乾燥（薄膜乾燥步驟），可得到本發明之樹 脂組成不同之具有複數層的光學薄膜。 本發明所謂的表面側係指從薄膜表面，薄膜厚度之5% 以上20%以下之深度的部分。 圖1爲本發明用之可同時流延、連續流延之裝置的較 佳例。 1 a~ 1 c係分別表示膠漿液槽，2 a~ 2 c係分別表示泵，3 係表示共流延用的模。共流延用之模的放大剖面圖如圖2 所示，具有10、11a、lib、及12之4支的模縫。 各自之流延用的膠漿分別供給模縫1 0、1 1 a、1 1 b，在 合流點形成層流，由1 2之模縫供給流延用帶上。5爲流延 用之支持體（帶），4爲旋轉的滾筒，7係表示流延後，適 度的使溶劑蒸發後，剝離後的光學薄膜，6係表示搬送此 光學薄膜的滾筒。 例如將樹脂組成不同之膠漿A、膠漿B、膠漿C分別充 滿於膠獎液槽la、lb、lc，改變栗2a~2c的流量，由流延 用之3個細縫供給，可得到三層的共流延薄膜。 該光學薄膜之寬度方向之長度之至少10〜90%的範圍內 ，且含有該薄膜寬度方向之中心的部分爲含有至少二層以 上之前述樹脂組成不同之層的態樣較佳。 -45- 201107801 (有機溶媒） 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’只要是可同時溶解丙烯酸樹脂（A)、纖維 素醋樹脂（B )、其他的添加劑者時，無特別限制均可使 用。 例如氯系有機溶劑有二氯甲烷，非氯系有機溶劑例如 有乙酸甲酯、乙酸乙酯、乙酸戊酯 '丙酮、四氫呋喃、 1，3-二氧雜環戊烷、ι，4-二噁烷、環己酮、甲酸乙酯、 2,2,2-三氟乙醇、2,2,3,3-六氟-1-丙醇、ι，3-二氟-2-丙醇' 1，1，1，3,3,3-/、氣-2 -甲基-2-丙醇、1，ΐ，ι，3,3,3 -六氟-2-丙醇 、2,2,3,3,3 -五氟-1-丙醇、硝基乙烷等，較佳爲使用二氯 甲烷、乙酸甲酯、乙酸乙酯、丙酮。 膠漿中除了上述有機溶劑外，較佳爲含有1~40質量％ 之碳原子數1〜4之直鏈或支鏈狀之脂肪族醇。膠漿中之醇 的比率升高時，纖維網（web )產生凝膠化，容易由金屬 支持體上剝離，而醇的比例較少時，非氯素系有機溶劑系 也有促進溶解丙烯酸樹脂（A)、纖維素酯樹脂（B)的功 用。 特別是使丙烯酸樹脂（A)與纖維素酯樹脂（B )與丙 烯酸粒子（C )之3種至少共計1 5〜45質量％溶解於含有二 氯甲烷及碳數1 ~4之直鏈或支鏈狀之脂肪族醇的溶劑中的 膠漿組成物較佳。 碳數1〜4之直鏈或支鏈狀之脂肪族醇，例如有甲醇、 乙醇、η-丙醇、iso-丙醇、η-丁醇、sec-丁醇' tert-丁醇》 -46- 201107801 此等當中’考慮膠發之安定性、沸點較低、乾燥性佳等， 較佳爲甲醇。 以下說明本發明之光學薄膜之較佳的製膜方法。 1 )溶解步驟 在以對於丙烯酸樹脂（A)、纖維素酯樹脂（B)之良 溶劑爲主的有機溶劑中，在溶解鍋中將該丙烯酸樹脂（A )、纖維素酯樹脂（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)、纖維素酯樹脂（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)、纖維素酯樹脂（B)之溶解可使用 常壓下溶解的方法、在主溶劑之沸點以下溶解的方法、在 主溶劑之沸點以上進行加壓溶解的方法、如特開平9-95544號公報、特開平9-95 5 5 7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 79號公報所記載，以高壓溶解的方法等各種的溶解方 法’特佳爲在主溶劑之沸點以上進行加壓溶解的方法。 膠漿中之丙烯酸樹脂（A)與纖維素酯樹脂（B)合計 爲15〜4 5質量％的範圍較佳。溶解中或溶解後之膠漿中加入 添加劑，經溶解及分散後，以過濾材過濾、脫泡’並以送 液泵送至下一步驟。 過濾係使用捕集粒徑〇 · 5〜5 // m，且據水時間1 0〜2 5 s e c -47- 201107801 /1 0 0 m 1的濾材較佳。 此方法係將粒子分散時殘留之凝集 所發生之凝集物，使用捕集粒徑0.5〜5 # ~25seC/100ml的濾材可僅除去凝集物。 濃度相較於添加液爲非常低，因此過濾 物彼此黏結，造成急速的濾壓上昇。 圖3係表示本發明較佳之溶液流延！ 製步驟、流延步驟及乾燥步驟之一例的| 必要時，由丙烯酸粒子投入鍋4 1以 的凝集物，然後送液至儲存鍋42。其後 烯酸粒子添加液加入主膠漿溶解鍋1 x中. 其後，主膠漿液係主過濾器3 X過濾 線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, 有時含有丙烯酸粒子，此時配合回料之 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 0 · 5〜1 0質量％，更佳爲含有丨〜丨〇質量％， 量％ 0 上述範圍內時，添加液係低黏度， ’也容易添加至主膠漿中，故較佳。 回料係指將光學薄膜經過微細粉碎 薄膜時所發生之將薄膜之兩端部分切掉 等’當作規格外之光學薄膜原料使用者 物或主膠漿添加時 m、且濾水時間1 0 主膠漿中，粒子之 時不會產生因凝集 製膜方法之膠漿調 莫式圖。 過濾器44除去較大 ，由儲存鍋42將丙 〇 ，然後藉由16x連 -5 0質量％。回料中 添加量控制丙烯酸 爲含有丙烯酸粒子 最佳爲含有1~5質 且操作使用較容易 之物品，製膜光學 後的物品或因擦傷 -48- 201107801 預先將丙烯酸樹脂、纖維素酯樹脂及必要時之丙烯酸 粒子混練形成顆粒化者，較適用。 2 )流延步驟 將膠漿通過送液泵（例如加壓型定量齒輪泵）送液至 加壓模3 0，再由加壓模縫將膠漿流延至無限移送之無終端 的金屬帶31、例如有不鏽鋼帶、或旋轉之金屬滾筒等的金 屬支持體上之流延位置的流延步驟。 可調整模之模頭部分的細縫形狀，且容易使膜厚均一 之加壓模較佳。加壓模有衣架型模（coat hanger die)或T 模等均可使用。金屬支持體之表面成爲鏡面。爲了提高製 膜速度’可在金屬支持體上設置2座加壓模，將膠漿量分 割進行層合。或可藉由將複數之膠漿同時流延的共流延法 ’可得到層合構造的薄膜。 3 )溶劑蒸發步驟 將纖維網（使膠漿流延至流延用支持體上所形成的膠 發膜稱爲「纖維網」）在流延用支持體上加熱，使溶劑蒸 發的步驟。 欲使溶劑蒸發時’有由纖維網側吹風的方法及/或由 支持體之內面藉由液體傳熱的方法、藉由輻射熱由表裏傳 熱的方法等，但是內面液體傳熱方法乾燥效率高，故較佳 。也可使用組合彼等的方法。使流延後之支持體上的纖維 網在40〜l〇(TC之氣氛下’在支持體上乾燥較佳。欲維持4〇 -49- 201107801 〜100 °c之氣氛下時，將此溫度之熱風吹纖維網上面，或藉 由紅外線等的手段加熱較佳。 從面品質 '透濕性、剝離性的觀點，較佳爲在3 0〜1 2 0 秒以內，將該纖維網由支持體上剝離。 4 )剝離步驟 將在金屬支持體上使溶劑蒸發後的纖維網在剝離位置 剝離的步驟。剝離後的纖維網係被送至下一步驟。 金屬支持體上之剝離位置的溫度較佳爲10〜4(TC，更 佳爲1 1〜3 0°C。 剝離之時點之金屬支持體上之纖維網的剝離時殘留溶 劑量係依乾燥條件之強弱、金屬支持體之長度等，在5 Ο-ΐ 2 0質 量 ％之範圍 進行剝 離較佳 ，但是 殘留溶 劑量更 多的時 點進行剝離時，若纖維網太柔軟時，會損害剝離時平面性 ，因剝離張力容易產生鬆弛或直線條，因此以兼顧經濟速 度與品質，來決定剝離時的殘留溶劑量。 纖維網之殘留溶劑量係下述式定義。 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 1〇〇 此外，測定殘留溶劑量時之加熱處理係表示以1〗5 °C 加熱處理1小時。 剝離金屬支持體與薄膜時之剝離張力通常爲19 6〜24 5 N/m，但是剝離時易產生皴紋時，以190N/m以下的張力進 行剝離較佳，更佳爲以可剝離之最低張力〜166.6N/m '接 -50- 201107801 著以最低張力〜137.2N/m剝離，特佳爲以最低張力〜100N/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°C。 5)乾燥及延伸步驟 剝離後，使用將纖維網交互通過在乾燥裝置內複數配 置之輥，進行搬送之乾燥裝置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40〜2 5 0t 乾燥。特佳爲以4 0 ~ 1 6 0 °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 -51 - 201107801 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 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><1.〇1倍~><1.5倍的範 圍。 進行拉幅延伸時之纖維網的殘留溶劑量，在拉幅延伸 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％以下爲止進行拉幅同時乾燥較佳，更佳爲5質量 %以下。 進行拉幅延伸時之乾燥溫度較佳爲30〜160°C，更佳爲 50〜150°C，最佳爲 70~140°C。 拉幅步驟中，氣氛之寬度方向的溫度分布較少，從提 高薄膜之均一性的觀點較佳，拉幅步驟之寬度方向之溫度 分布較佳爲± 5 °C以內，更佳爲± 2 °C以內，最佳爲± 1 °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 -52- 201107801 膜的形態藉由捲繞機3 7捲繞的步驟，使殘留溶劑量在〇 4 質量％以下，可得到尺寸安定性良好的薄膜。特別胃& 0.00〜0.10質量％進行捲繞較佳。 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l〇〇m 〜5 000m程度者，通常以筒狀提供的形態者。此外，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20〜200 ym，更佳爲25〜1〇〇 仁m，特佳爲30~80//m。 [偏光板] 以本發明之光學薄膜作爲偏光板用保護薄膜使用時， 可以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、 KC8UE 、 KC4UE 、 KC4FR-3 、 KC4FR-4 、 KC4HR-1 、 KC8UY-HA、KC8UX-RHA，以上爲 KonicaMinolta Opto ( -53- 201107801 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 —部分使用在25 °C之貯藏彈性率爲1.0 X104〜1 .0x1 09Pa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 -54- 201107801 %。 [液晶顯示裝置] 將貼合本發明之光學薄膜的偏光板組裝於 置後’可製作各種辨識性優之液晶顯示裝置， 大型液晶顯示裝置或數字標識等屋外用途之液 本發明之偏光板係介於前述黏著層等貼合於液^ 本發明之偏光板適用於反射型、透過型 LCD 或 TN 型、STN 型、OCB 型、HAN 型、VA 型 MVA型）、IPS型（包含FFS方式）等各種驅動 。特別是畫面爲30吋以上，更佳爲30吋〜54吋 顯示裝置’在畫面周邊部無泛白等，可長時間 〇 而且色斑、眩光或凹凸不句較少，具有即 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 等。 實施例1 〔光學薄膜之製作〕 <光學薄膜1之製作> 液晶顯示裝 特別適用於 晶顯不器。 Pb胞上。 、半透過型 (PVA 型、 方式的LCD 之大畫面的 維持該效果 使長時間觀 非限定於此 -55- 201107801 (膠漿液1組成） DIANAL BR85(Mitsubishi Rayon(股）製） 65 質量份 丙烯酸粒子（C1) 5質量份 纖維素酯（纖維素乙酸酯丙酸酯醯基總取代度2.75、 乙醯基取代度0.19、丙醯基取代度2.56、Mw = 200〇〇〇) 3〇質量份 二氯甲烷 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1。 同樣地，除了將樹脂組成變更如下述外，同樣製作膠 漿液2。 (膠漿液2組成） DIANAL BR85(Mitsubishi Rayon(股）製） 85 質量份 丙烯酸粒子（C1) 5質量份 纖維素酯（纖維素乙酸酯丙酸酯醯基總取代度2.75、 乙醯基取代度0.19、丙醯基取代度2.56、Mw = 200000) 10質量份 二氯甲烷 300質量份 乙醇 40質量份 (丙烯酸樹脂薄膜之製膜） 使用帶狀流延裝置（参照圖1 )，以溫度22°C、2m寬 度，將上述製作的膠漿液1、2均勻地流延於不銹鋼帶支持 -56- 201107801 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100%爲止，自不銹鋼帶支持體上以剝離張力160N/m剝 離。其次，適當控制膠漿液1及2之流延量得到所希望之層 厚的薄膜。使剝離後之薄膜的纖維網以3 5 t使溶劑蒸發， 使用拉幅器在寬度方向延伸1.5倍，同時以140°C之乾燥溫 度乾燥。此時，使用拉幅延伸開始時的殘留溶劑量爲1 0% 。使用拉幅延伸後，以1 3 0 °C緩和5分鐘後，以多數輥搬送 通過100°C、120°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 ΙΟΝ/m捲繞於內徑 15.24cm的芯上，得到本發明之光學薄膜1。 <本發明之光學薄膜2〜13及比較例之光學薄膜1〜7之製作> 上述光學薄膜1之製作中，除了將丙烯酸樹脂（A)、 纖維素酯樹脂（B )之種類與組成比改爲如表1及表2所記 載外，同樣地製作本發明之光學薄膜2〜13及比較例之光學 薄膜1〜7。丙烯酸樹脂之DIANALBR85與丙烯酸粒子（C1 )之比率爲一定。 本發明之光學薄膜1之製作中，除了將丙烯酸樹脂改 爲旭化成Chemicals (股）製之Delpet80N，丙烯酸樹脂（ A )、纖維素樹脂（B )之組成比改爲表2所記載外，同樣 地製作本發明之光學薄膜14〜20。丙烯酸樹脂之Delpet 8 ON 與丙烯酸粒子（Cl)之比率爲一定。 -57- 201107801 《評價方法》 對於所得之光學薄膜以下述評價。 (折彎評價） 將光學薄膜切成100mm (長）xlOmm (寬），在縱方 向之中央部分別以外折、內折各折1次，此評價測定1 〇次 ，以折的次數評價。此處之評價之破裂係表示破裂分離成 2片以上的片段。 (鉛筆硬度） 對於上述製作的實施例卜20及比較例1〜7之各光學薄 膜，使用JIS S 6006所規定之試驗用鉛筆’依據JIS K 54〇0 所規定之鉛筆硬度評價法’使用1kg之荷重’以各硬度的 鉛筆劃在實施例1〜20及比較例1~7之各光學薄膜的表面’ 測定鉛筆硬度。本發明之光學薄膜係劃在層2側表面進行 評價。所得的結果如下述表1及表2所示。 -58- 201107801 【iAl2〇3, In203, Si〇2, MgO, BaO, Ce〇2, Sb203, Mo〇2, V2〇5, etc., or a composite oxide thereof, particularly preferably Ce〇2, In2〇3, Sn02, Sb203, and SiO2. Examples of the hetero atom include addition of A1 and in to ZnO, addition of Nb or Ta to Ti02, and addition of Sb, Nb, and halogen to Sn02. The amount of such hetero atoms added is preferably in the range of 0 · 0 1 to 2 5 m ο 1 %, particularly preferably in the range of 0.1 to 15 m ο 1 %. The average fine particle diameter of the conductive fine particles is preferably 1 〇〇 nm or less', more preferably 5 to 100 nm. When the average fine particle diameter of the conductive fine particles is 100 nm or less, it is preferable to provide sufficient antistatic m characteristics when it is contained in a resin material, and does not affect the transparency of the resin material. The excellent antistatic agent is preferably one in which the surface specific resistance 1 is 1 x 1 〇 1 () Ω or less in terms of the relationship between the antistatic property and the added amount. The surface was inherently resistant to lanthanide. The sample was conditioned for 24 hours in an atmosphere of 23t, 50% RH, and then measured using an ultrasonic insulation meter in accordance with ASTM D25 7. In the present invention, a more suitable antistatic agent is a cationic conductive polymer described in JP-A-H09-203801 or a 4-stage ammonium cation-32-201107801 ion conductive polymer having a crosslink between molecules. The dispersible granular polymer obtained by the characteristics of the cross-linked cationic conductive polymer can have a cationic component in the fine particles at a high concentration and a high density, and therefore has excellent conductivity and good compatibility with the resin. High transparency was obtained, and even at a lower relative humidity, no deterioration in conductivity was observed. The dispersible granular polymer of the cross-linked cationic conductive polymer for antistatic is generally used in the range of fine particle size of about 0.01 to 0.3 / zm, more preferably in the range of 〇. 5 to 0.15 # m. In the present invention, each of the antistatic agents described above is preferably added in an amount of 0.001 to 2.0 parts by mass, and the amount of the antistatic agent added is 0.001 part by mass or more and 2.0 parts by mass, based on 100 parts by mass of the optical film of the present invention. In the following case, dust can be effectively prevented from adhering to the resin material, and the light transmittance of the resin material can be maintained at a desired number. The amount of the antistatic agent added is preferably from 0.005 to 1.0 part by mass, more preferably from 0.01 to 0.5 part by mass, per 100 parts by mass of the polymer having an alicyclic structure. In the present invention, the same effect can be obtained by providing the above-mentioned antistatic agent and a layer having a fluorine compound for general antifouling on the resin. In order to obtain the properties of the optical film of the present invention, a layer (antistatic layer) containing at least one of an antistatic agent may be provided on the surface of the film. The antistatic layer can be provided by applying the aforementioned mixture having an antistatic agent to the surface of the optical member, or by a method such as evaporation. Further, the thickness of the antistatic layer is preferably from 50 to 300 //m. -33-201107801 (matting agent) In order to impart the smoothness, optical, and mechanical function of the optical film of the present invention, fine particles of an inorganic compound or fine particles of an organic compound may be added as a matting agent. It is preferable to use a shape in which the shape of the matting agent is a spherical shape, a rod shape, a needle shape, a layer shape, a flat shape or the like. The matting agent is oxidized by metal atoms such as cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, calcium carbonate, clay, talc, calcined calcium citrate, water and calcium citrate, aluminum silicate, magnesium citrate and calcium phosphate. Inorganic fine particles such as phosphates, citrates, carbonates, and the like. As the fine particles of the organic compound, for example, the starch described in the specification of the U.S. Patent No. 2,322,03, etc., the specification of the Belgian Patent No. 62 5,45 1 or the specification of the British Patent No. 98 1,1 98, etc., may be used. Polyvinyl alcohol described in Japanese Patent Publication No. Sho 44-3, 643, and the like, and polystyrene or polymethacrylate described in Swiss Patent No. 330,158, and the like, and the specification of U.S. Patent No. 3,079,257, and the like. The organic fine particles of the polycarbonate described in the polyacrylonitrile, the specification of U.S. Patent No. 3,022,169, and the like. In other words, examples of the fine particles of the organic compound, wherein the water-dispersible ethylene polymer is, for example, polymethacrylate, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-α-methylstyrene copolymer, polyphenylene Ethylene, styrene-divinylbenzene copolymer, polyvinyl acetate, polyethylene carbonate, polytetrafluoroethylene, etc., cellulose derivatives such as methyl cellulose, cellulose acetate, cellulose Acetate propionate, etc., starch derivative Example -34- 201107801 If there are carboxyl starch, carboxyl nitrophenyl starch, urea-formaldehyde-starch reactant, etc., gelatin hardened by a known hardener and hardened by a coacervate Hardened gelatin or the like of the capsule hollow granules can be suitably used. Among the above inorganic fine particle fine particles or organic compound fine particles, cerium oxide is preferred because it can reduce the haze of the film. It is preferred that these fine particles are surface-treated by an organic substance to reduce the haze of the film. It is preferred to carry out surface treatment with a halodecane, an alkoxydecane, a guanamine, a decane or the like. The larger the average particle diameter of the fine particles, the larger the smoothness effect, and conversely, the smaller the average particle diameter, the more excellent the transparency. Further, the average particle diameter of the primary particles of the fine particles is in the range of 0.01 to Ι.Ομηι. The average particle diameter of the primary particles of the preferred fine particles is preferably 5 to 5 Onm, more preferably 7 to 1 4 n m. These fine particles are more suitable for producing a concave protrusion of 0.01 to Ι.Ομηι on the surface of the optical film. The fine particles of cerium oxide are, for example, AEROSIL 200, 200V, 300, R972, R972V, R974, R202 'R812, 0X50, ΤΤ600, ΝΑΧ50, etc. manufactured by Japan AEROSIL Co., Ltd., and 日本-Ρ10 manufactured by Nippon Shokubai Co., Ltd. ΚΕ-Ρ30, ΚΕ-Ρ100, ΚΕ-Ρ150, etc., preferably AEROSIL200V, R972V, NAX 5 0, Κ Ε - Ρ 3 0, Κ Ε - Ρ 1 0 0. These fine particles can be used in two or more types. When two or more types are used, they can be used in any ratio. At this time, fine particles having an average particle diameter or material, such as AEROSIL 200V and R972V, can be used in a mass ratio of 0.1: 99.9 to 99.9: 0.1. The method of adding these matting agents is preferably added by a method such as kneading. -35-201107801 Further, in another embodiment, a matting agent previously dispersed in a solvent and a resin and/or a plasticizer and/or an antioxidant and/or an ultraviolet absorber are mixed and dispersed to obtain a solid substance in which a solvent volatilizes or precipitates. This is preferably used in the production process of the resin melt, which is preferable from the viewpoint that the matting agent can be uniformly dispersed in the resin. To improve the mechanical, electrical, and optical properties of the film, the above matting agent may be added. The addition of these fine particles can improve the smoothness of the obtained film, but the haze increases after the addition, so the content is preferably 0.001 to 5% by mass, more preferably 〇. 5 to 1% by mass, more preferably, relative to the resin. It is 〇.〇1~〇.5 mass%. When the optical film of the present invention has a haze of more than 1.0%, it may have an influence as an optical material, and it is preferable that the haze is less than 1.0%, more preferably less than 0.5%. The mist can be measured by JIS-K7136. <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 compound 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 divalent carboxylic acids are, for example, glutaric acid 'itaconic acid, adipic acid, citric 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-butene, 1,6-hexene, neopentene, diethylene, triethylene or dipropylene. These divalent carboxylic acids and glycols may 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, and a plasticizing effect. Further, the viscosity of the plasticizer is related to the molecular structure or molecular weight, but when it is an adipic acid plasticizer, the relationship between compatibility and plasticizing efficiency is preferably 200 to 5 MPa*s (25 ° C). The scope of). In addition, several polyester-based plasticizers can be used. The plasticizer is preferably added in an amount of from 0.5 to 30 parts by mass based on 100 parts by mass of the optical film of the invention. When the amount of the plasticizer added exceeds 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 to be used may, for example, be a benzotriazole-based, 2-hydroxybenzophenone-based or phenyl salicylate-based compound. For example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H - benzotriazine, 2-(3,5-di-t-butyl-2-ylphenyl)benzotriazine, triterpenoids, 2-hydroxy-4-methoxybenzophenone, A benzophenone such as 2-hydroxy-4-octyloxybenzophenone or 2,2'-dihydroxy-4-methoxybenzophenone. -37- 201107801 Among these ultraviolet absorbers, the ultraviolet absorber having a molecular weight of 400 or more is not easily volatilized at a high boiling point, and is not easily scattered when formed at a high temperature, so that it can be effectively improved in weather resistance by being added in a small amount. The ultraviolet absorber having a molecular weight of 400 or more is, for example, 2-(2-hydroxy-3,5-bis(indenyl-1,(1-dimethylbenzyl)phenyl)-2-benzotriazole, 2,2 _Methylene bis[4-( 1,1,3,3-tetrabutyl)-6-( 2 Η-benzotriazol-2-yl) phenol] benzotriazole-type bis (2, Blocking of 2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate Amines and 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis(1,2,2,6,6-pentamethyl 4-piperidinyl ester), 1-[2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propenyloxy]ethyl b 4_[3- (3, a mixed system of a hindered phenol and a hindered amine structure in a molecule such as 5_bis 4-butyl-4-hydroxyphenyl)propanoxy]-2,2,6,6-tetramethylpiperidine. These may be used alone or in combination of two or more. Among them, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]_2-benzotriazole and 2,2-methylenebis[4-( 1,1,3,3 -tetrabutyl)-6-(2Η-benzotriazol-2-yl)phenol]» In addition, the optical film of the present invention is Improve thermal decomposition during forming Various anti-oxidants can be added to the thermal coloring property, and an antistatic agent can be added to impart antistatic properties to the optical film. The optical film of the present invention can also be a flame-retardant acrylic resin composition to which a phosphorus-based flame retardant is added. The phosphorus-based flame retardant used is, for example, selected from the group consisting of red phosphorus, triaryl phosphate, diaryl phosphate, monoaryl phosphate, arylphosphonic acid compound, arylphosphine oxide compound, condensed aryl phosphate, Halogenated alkyl phosphate, • 38 · 201107801 One or a mixture of two or more of a halogen-containing condensed phosphate, a halogen-containing condensed phosphonate, a halogen-containing phosphite, etc. Specifically, for example, triphenyl phosphate, 9,10 -Dihydro-9-oxo-10-phosphaphenanthrene- 10-oxide, phenylphosphonic acid, tris(chloroethyl)phosphate, tris(dichloropropyl)phosphate, tris(tribromoneopentyl) Phosphate ester or the like. According to the optical film of the present invention, it is possible to simultaneously achieve improvement in low hygroscopicity, transparency, high heat resistance and brittleness which cannot be achieved by the conventional resin film. In the present invention, the index of brittleness is whether or not Optical film that produces ductile damage It is judged by the standard. It is possible to obtain an optical film which does not cause ductile damage and improve the brittleness. Even when a polarizing plate for a large liquid crystal display device is produced, cracking or cracking does not occur, and an optical film excellent in handleability can be formed. A ductile failure system is defined as a fracture that occurs when a stress greater than the strength of a material is applied, and which is accompanied by a significant extension or contraction of the material before the final fracture. The section is characterized by the formation of numerous In the present invention, the "optical film which does not cause ductile fracture" is evaluated by the fact that even if a large stress is applied to bend the film into two pieces, no damage such as cracking occurs. Even when an optical film which does not cause ductile damage is applied even when such a large stress is applied, even when it is used as a polarizing plate for a large-sized liquid crystal display device, problems such as breakage during production can be sufficiently reduced, and even after one bonding Further, when the optical film is used, the optical film is not broken, and it can be sufficiently applied to the thinning of the optical film. In the present invention, a tension softening point is used as an index of heat resistance. As the liquid crystal display device is enlarged, the brightness of the backlight source is increasing, and the digital standard -39-201107801 is used for outdoor use, higher brightness is required. Therefore, the optical film needs to have a higher temperature environment, but the tension softening point is It can be judged that it has sufficient heat resistance. Very good for control at 110~1 3 〇 °C. A specific measurement method for displaying the temperature at the tension softening point of the optical film, for example, using a universal tensile tester (RTC-1225 5A manufactured by ORIENTEC Co., Ltd.), and cutting the optical film into 120 mm (length) X 10 mm (width), and then 10 N The tension was stretched, and the temperature was continuously raised at a temperature increase rate of 30 ° C /min, and the temperature at the point of reaching 9 N was measured three times, and the average enthalpy was obtained. Further, from the viewpoint of heat resistance, the glass transition temperature (Tg) of the optical film is preferably 1 1 〇 ° C or more. More preferably, it is above 1 20 °C. Particularly preferred is a glass transition temperature of 150 ° C or higher, which is measured by a differential scanning calorimeter (Model DSC-7 manufactured by Perkin Elmer Co., Ltd.) at a temperature rising rate of 20 ° C /min, in accordance with JIS K7121 (1 98 7). The obtained intermediate point glass transition temperature (Tmg) 指标 The index for judging the transparency of the optical film of the present invention is haze (turbidity). In particular, a liquid crystal display device used outside the house is required to have sufficient brightness and high contrast even in a bright place, and therefore the haze must be 1.0% or less, more preferably 0.5% or less. According to the optical film of the present invention containing the acrylic resin (A) and the cellulose ester resin (B), high transparency can be obtained, but when acrylic particles are used to improve other physical properties, the resin (acrylic resin) is lowered. A) The difference in refractive index between the cellulose ester resin (B) and the acrylic particles (C) prevents the haze from rising. -40- 201107801 In addition, since the surface roughness also affects the haze in the form of surface haze, the particle size and the addition amount of the acrylic particles (C) are controlled within the above range, and the film contact portion at the time of film formation can be effectively reduced. Surface roughness. Further, the hygroscopicity of the optical film of the present invention is evaluated by dimensional change with respect to humidity change. The following method can be used for the evaluation method of the dimensional change with respect to the change in humidity. In the casting direction of the produced optical film, mark (cross) at two places, and treat it at 60 t, 90% RH for 1 000 hours, and measure the distance between the mark (cross) before and after the treatment using an optical microscope. Dimensional change rate (%). The dimensional change rate (%) is expressed by the following formula. Dimensional change rate (%) = [(al-a2)/al]xl00 al : distance before heat treatment a2 : distance after heat treatment When an optical film is used as a protective film for a polarizing plate of a liquid crystal display device, the size due to moisture absorption The change causes unevenness (stain) or phase difference 光学 of the optical film, so that a problem of contrast reduction or staining occurs. Especially in the case of a polarizing plate protective film for a liquid crystal display device for outdoor use, the above problems are more conspicuous. However, when the dimensional change rate (%) of the above conditions was less than 0.5%, it was evaluated as an optical film showing sufficiently low hygroscopicity. More preferably, it is less than 0.3%. Further, the optical film of the present invention has a defect of 5 μm or more in diameter in the film surface, and is preferably 1/l〇cm or less. More preferably, it is 0.5 /10 cm square or less, more preferably 0.1 / l 〇 cm square. -41 - 201107801 The diameter of this defect refers to the diameter when the defect is circular, and the non-circular shape can be determined by the following method using the microscope to observe the defect as the maximum diameter (diameter of the circumscribed circle). The scope of the disadvantage is that when the defect is a bubble or a foreign matter, it refers to the size of the shadow when the defect is observed by differentially observing the transmitted light of the microscope. The disadvantage is that when the surface shape such as transfer or scratch of the roll is changed, the reflected light of the microscope can be differentially observed to confirm the size. Further, when observing the reflected light, if the size of the defect is not clear, aluminum or platinum may be deposited on the surface to observe. In order to obtain a film excellent in quality with such a defect frequency with better productivity, 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 casting in stages. The drying conditions are followed by drying with high efficiency and suppression of foaming. When the number of defects is more than one/10 cm square, for example, when tension is applied to the film during processing such as the subsequent step, the film breakage may be significantly lowered from the viewpoint of the defect. Further, when the diameter of the defect is 5 μm or more, it can be visually confirmed by observation of a polarizing plate or the like, and a bright spot may be generated when used as an optical member. When it is not possible to visually confirm, a hard coat layer or the like may be formed on the film, and the coating agent may not be uniformly formed, which may be a disadvantage (uncoated). Disadvantages refer to voids (foaming defects) in a film produced by rapid evaporation of a solvent in a drying step of a solution film formation, or a film generated by a foreign matter in a film forming solution or a foreign matter mixed in a film forming film. Foreign matter (foreign matter defect-42-201107801 Further, when the optical film of the present invention is measured in accordance with JIS-K7127-1999, the elongation at break in at least one direction is preferably 10% or more, more preferably 20% or more. The upper limit is not particularly limited and is actually about 250%. When the elongation at break is to be increased, the disadvantage in the film due to foreign matter or foaming can be suppressed. The thickness of the optical film of the present invention is preferably 20 μm. The upper limit of the thickness is not particularly limited, but the upper limit is 250 μm from the viewpoints of coatability, foaming, solvent drying, etc. Further, the film thickness can be appropriately selected depending on the use. The light transmittance is preferably 90% or more, more preferably 93% or more, and the actual upper limit is 99%. In order to achieve such excellent transparency as the total light transmittance, the introduction can be avoided. Adding visible light additives or copolymerized components, or removing foreign matter in the polymer by high-precision filtration, or reducing light diffusion or absorption inside the film. Further, by reducing the film contact portion during film formation (cooling roll, calendering) Surface roughness of rolls, rollers, conveyor belts, coating substrates, transfer rolls, etc.) to reduce the surface roughness of the film surface, or to reduce the refractive index of the acrylic resin, and reduce the light diffusion or reflection on the surface of the film. When the optical film of the present invention satisfies the above physical properties, it is particularly suitable for use as a polarizing plate protective film for a large liquid crystal display device or a liquid crystal display device for outdoor use. -43- 201107801 <Film film formation of optical film> An example of a film formation method of an optical film will be described below, but the present invention is not limited thereto. In the film forming method of the optical film of the present invention, for example, a production method such as a blow molding method, a τ mold method, a calendering method, a cutting method, a casting method, an emulsification method, or a hot pressing method can be used, but from the viewpoint of suppressing coloring and suppressing foreign matter defects, From the viewpoint of suppressing optical defects such as mold marks and the like, it is preferable to form a film by a solution of a casting method. The optical film of the present invention has an optical film having at least two or more layers of resin compositions different from each other. (i) at least one layer constituting the surface of the optical film is composed of an acrylic resin (A) and a cellulose ester resin (b) in a mass ratio of 50:50 to 30:70, (ii) a layer constituting the surface The layer is composed of an acrylic resin (A) and a cellulose ester resin (b) in a mass ratio of 80:20 to 50:50, (iii) the weight average molecular weight of the acrylic resin (A) is 80,000 or more, (iv) The total degree of substitution of the thiol group of the cellulose ester resin (B) is 2.0 to 3.0, and the degree of substitution of the fluorenyl group having 3 to 7 carbon atoms is 1.2 to 3.0 'the average weight of the cellulose ester resin (b) The molecular weight is 75,000 or more. Therefore, the method for realizing such a feature is preferably a method of simultaneously forming a layer in which the resin compositions are different from each other by the film forming step described in detail below. For example, there is a method in which a plurality of different compositions of the resin are prepared in advance, and then a method of supplying the same, and a method of supplying the respective resins, and preparing a paste of a plurality of resins before casting, but uniforming from the glue The point of view 'preferably' is a method of preliminarily preparing a plurality of layers of the resin which are different from each other and then supplied. For example, the optical film of the present invention is obtained by using a mold having a plurality of slits and using a mold having a plurality of slits for co-casting (cast film step) using a plurality of slits having a plurality of slits. Then, one part of the solvent is removed by heating (drying step on the casting tape), and then peeled off from the casting tape, and the peeled film is dried (film drying step), and the resin composition of the present invention has a plural An optical film of the layer. The term "surface side" as used in the present invention means a portion having a depth of 5% or more and 20% or less of the thickness of the film from the surface of the film. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a preferred embodiment of a device for simultaneous casting and continuous casting for use in the present invention. 1 a~ 1 c are the glue tanks respectively, 2 a~ 2 c are the pumps, and 3 are the molds for co-casting. An enlarged cross-sectional view of the mold for co-casting is shown in Fig. 2, and has a die slit of four of 10, 11a, lib, and 12. The respective mortars for casting are supplied to the die slits 10, 1 1 a, and 1 1 b, respectively, and a laminar flow is formed at the joining point, and the casting tape is supplied from the die slit of 12. 5 is a support for casting (belt), 4 is a rotating drum, and 7 is an optical film after stripping after moderately evaporating the solvent, and 6 is a drum for conveying the optical film. For example, the glue A, the glue B, and the glue C having different resin compositions are respectively filled in the glue liquid tanks la, lb, and lc, and the flow rates of the pumps 2a to 2c are changed, and are supplied by the three slits for casting. A three-layer co-cast film was obtained. The optical film has a length in the width direction of at least 10 to 90%, and a portion containing the center of the film in the width direction is preferably a layer containing at least two or more layers having different resin compositions. -45-201107801 (Organic solvent) When the optical film of the present invention is produced by a solution casting method, an organic solvent for forming a paste is used as long as it can simultaneously dissolve the acrylic resin (A), cellulose vinegar resin (B), and the like. When the additive is used, it can be used without particular limitation. For example, a chlorine-based organic solvent is dichloromethane, and a non-chlorine-based organic solvent is, for example, methyl acetate, ethyl acetate, amyl acetate 'acetone, tetrahydrofuran, 1,3-dioxolane, iota, dioxole Alkane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, iota, 3-difluoro-2-propanol' 1, 1,1,3,3,3-/, gas-2-methyl-2-propanol, 1, hydrazine, ι, 3,3,3-hexafluoro-2-propanol, 2, 2, 3, 3,3-pentafluoro-1-propanol, nitroethane or the like is preferably dichloromethane, methyl acetate, ethyl acetate or acetone. In addition to the above organic solvent, the dope preferably contains 1 to 40% by mass of a linear or branched aliphatic alcohol having 1 to 4 carbon atoms. When the ratio of the alcohol in the dope is increased, the web is gelated and easily peeled off from the metal support, and when the proportion of the alcohol is small, the non-chlorinated organic solvent also promotes dissolution of the acrylic resin ( A), the function of the cellulose ester resin (B). In particular, at least a total of 15 to 45 mass% of the acrylic resin (A), the cellulose ester resin (B) and the acrylic acid particles (C) are dissolved in a straight chain or a branch containing methylene chloride and a carbon number of 1 to 4. The dope composition in the solvent of the chain aliphatic alcohol is preferred. A linear or branched aliphatic alcohol having 1 to 4 carbon atoms, for example, methanol, ethanol, η-propanol, iso-propanol, η-butanol, sec-butanol 'tert-butanol" -46 - 201107801 Among these, 'considering the stability of the rubber, low boiling point, good drying property, etc., methanol is preferred. A preferred film forming method of the optical film of the present invention will be described below. 1) Dissolution step In an organic solvent mainly composed of a good solvent for the acrylic resin (A) or the cellulose ester resin (B), the acrylic resin (A), the cellulose ester resin (B), and the like are dissolved in a dissolution pot. And if necessary, the acrylic particles (C) and other additives are stirred and dissolved to form a dope, or the acrylic resin (A) or the cellulose ester resin (B) solution may be mixed with acrylic particles (C) as necessary. The solution, the other additive solution, forms the dope of the main solution. The dissolution of the acrylic resin (A) or the cellulose ester resin (B) can be carried out by a method of dissolving under normal pressure, a method of dissolving below the boiling point of the main solvent, or a method of performing pressure dissolution at a boiling point or higher of the main solvent, such as a special opening. A method of dissolving in a cooling and dissolving method, such as JP-A No. 1 1 - 2 1 3 79, as disclosed in Japanese Laid-Open Patent Publication No. Hei 9-95-5-5 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 cellulose ester resin (B) in the dope preferably have a total range of 15 to 45 mass%. The additive is added to the dissolved or dissolved cement, dissolved and dispersed, filtered through a filter material, defoamed, and pumped to the next step by liquid. The filtration system is preferably a filter material having a particle size of 〇 · 5 to 5 // m and a water time of 10 0 to 2 5 s e c -47 to 201107801 /1 0 0 m 1 . This method is an agglomerate generated by agglutination remaining when the particles are dispersed, and only the agglomerates can be removed by using a filter medium having a particle diameter of 0.5 to 5 # to 25 seC/100 ml. The concentration is very low compared to the addition solution, so the filters stick to each other, causing a rapid increase in filtration pressure. Figure 3 shows a preferred solution casting of the present invention! As an example of the production step, the casting step, and the drying step, if necessary, the agglomerates of the acrylic particles are put into the pot 4 1 and then fed to the storage pot 42. Thereafter, the olefinic acid particle addition liquid is added to the main dope dissolving pot 1 x. Thereafter, the main colloidal liquid main filter 3 X filter line is added with a UV absorbent addition liquid. In many cases, the main rubber contains the returning material 10, and sometimes contains acrylic acid particles. In this case, the amount of the particulate additive liquid to be added to the recycled material is preferably increased. The additive liquid containing the acrylic particles is preferably 0·5 to 10% by mass, more preferably 丨% to 丨〇% by mass, and the amount % is 0. When the above range is satisfied, the liquid is added to have a low viscosity, and 'it is easy to add to the main It is preferred in the glue. The return material refers to the fact that when the optical film is passed through the finely pulverized film, the two ends of the film are cut off, etc., when the optical film raw material or the main glue is added as the specification, m is added, and the filtering time is 10 In the main dope, the particles do not produce a gel-adjusting pattern due to the agglutination film forming method. The filter 44 is removed to a larger extent, and is stored by the storage pot 42 and then by 16x to -50% by mass. The amount of added acrylic in the return material is preferably an acrylic resin, a cellulose ester resin, and an article containing 1-5 masses which is easy to handle and which is easy to handle, and which is made by optical filming or scratching -48-201107801 If necessary, the acrylic particles are mixed and formed into granules, which is more suitable. 2) The casting step feeds the glue to the pressurizing die 30 through a liquid feeding pump (for example, a pressurized quantitative gear pump), and then casts the cement to the endless metal strip 31 by the press die slit. For example, there is a casting step of a casting position on a metal support such as a stainless steel belt or a rotating metal drum. It is possible to adjust the shape of the slit of the die portion of the mold, and it is easy to make the pressurizing die having a uniform film thickness. The press mold can be used with a coat hanger die or a T die. The surface of the metal support becomes a mirror surface. In order to increase the film forming speed, two press molds may be provided on the metal support, and the amount of the glue may be divided and laminated. Alternatively, a film of a laminated structure can be obtained by a co-casting method in which a plurality of cements are simultaneously cast. 3) Solvent evaporation step The step of heating the solvent on the casting support by ejecting the fiber web (the film formed by casting the paste onto the support for casting is referred to as "web") to evaporate the solvent. When the solvent is to be evaporated, there is a method of blowing from the side of the fiber web and/or a method of transferring heat from the inner surface of the support by liquid, a method of transferring heat from the surface by radiant heat, etc., but the inner liquid heat transfer method is dried. It is more efficient and therefore better. It is also possible to use a combination of these methods. The web on the cast support is preferably dried on a support at 40 to 1 Torr (the atmosphere of TC). To maintain the atmosphere of 4〇-49-201107801 to 100 °c, the temperature is maintained. The hot air blows the surface of the fiber web or is heated by means of infrared rays or the like. From the viewpoint of surface quality 'moisture permeability and peelability, it is preferably within 30 to 120 seconds to support the fiber web. The body is peeled off. 4) The peeling step is a step of peeling the web after evaporation of the solvent on the metal support at the peeling position. The stripped web is sent to the next step. The temperature at the peeling position on the metal support is preferably 10 to 4 (TC, more preferably 1 to 30 ° C. The amount of residual solvent at the time of peeling off the web on the metal support at the time of peeling is based on drying conditions When the strength is weak, the length of the metal support, etc., peeling is preferably performed in the range of 5 Ο-ΐ 20% by mass, but when the amount of residual solvent is more, when the web is too soft, the plane at the time of peeling is impaired. Since the peeling tension tends to cause slack or straight lines, the amount of residual solvent at the time of peeling is determined by taking into consideration the economic speed and quality. The amount of residual solvent in the fiber web is defined by the following formula: Residual solvent amount (%) = (fiber Mass before heat treatment of the web - mass after heat treatment of the fiber web) / (mass after heat treatment of the fiber web) x 1 〇〇 In addition, the heat treatment at the time of measuring the amount of residual solvent means heat treatment at 1 5 5 ° C When the metal support and the film are peeled off, the peeling tension is usually 19 6 to 24 5 N/m, but when crepe is likely to occur during peeling, peeling is preferably performed at a tension of 190 N/m or less, and more preferably peelable. Lowest Tension ~166.6N/m 'connected -50-201107801 peeled off at a minimum tension of ~137.2 N/m, particularly preferably at a minimum tension of ~100 N/m. In the present invention, the temperature at the peeling position on the metal support is higher. Preferably, it is -50 to 40 ° C, more preferably 10 to 40 ° C, and most preferably 15 to 30 ° C. 5) After the drying and stretching steps are peeled off, the fiber web is alternately passed through a roller arranged in a drying device. The drying device 35 for carrying the conveyance and/or the tenter stretching device 34 for holding the both ends of the fiber web by the jig are transported to dry the fiber web. The drying means generally uses hot air to blow both sides of the fiber web, or a microwave oven can be used instead of heating to replace the hot air for heating. Too fast drying tends to damage the planarity of the finished film. The residual solvent may be about 8% by mass or less by drying at a high temperature. The overall dry sputum is dried at 40~2 50t. It is especially dry at 40 to 160 °C. When the tenter extension device is used, it is preferable to use a device for controlling the holding length of the film (the distance from the start of gripping to the end of gripping) by the right and left holding means of the tenter. In the tentering step, intervals having different temperatures can also be intentionally made in order to improve planarity. Neutral regions can be set so that there is no interference between the respective intervals in different temperature ranges. The extension operation can be divided into a multi-stage implementation, and the two-axis extension can also be performed in the casting direction and the width direction. For two-axis extension, two-axis extension or phased implementation can be performed simultaneously. In this case, the staged system may, for example, be extended in different directions from -51 to 201107801, or divide the extension in the same direction into multiple stages, and extensions in different directions may be applied to any of the stages. In other words, for example, the following extension steps are possible. • Casting direction extension - width direction extension - casting direction extension - casting direction extension / width direction extension - width direction extension - casting direction extension · casting direction extension. After that, the other side relaxes the tension and produces a contraction. At the same time, the preferred extension ratio of the 2-axis extension is both the width direction and the length direction. <1.〇1 times~><1.5 times the range. The amount of residual solvent of the fiber web at the time of tenter stretching is preferably 20 to 100% by mass at the start of tenter stretching, and it is preferred to carry out tentering while drying at a residual solvent amount of the fiber web of 1% by mass or less. More preferably, it is 5% by mass or less. The drying temperature at the time of tenter stretching is preferably from 30 to 160 ° C, more preferably from 50 to 150 ° C, most preferably from 70 to 140 ° C. In the tentering step, the temperature distribution in the width direction of the atmosphere is small, and from the viewpoint of improving the uniformity of the film, the temperature distribution in the width direction of the tentering step is preferably within ± 5 ° C, more preferably ± 2 °. Within C, preferably within ± 1 °C. 6) The amount of residual solvent in the fiber web after the winding step is 2% by mass or less, and then wound by a winder 37 in the form of an optical thin-52-201107801 film. In the step, the amount of the residual solvent is 〇4% by mass or less, and a film having good dimensional stability can be obtained. It is preferred to carry out the winding in a special stomach & 0.00~0.10% by mass. The winding method may be 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 fixing, etc., and these may be used separately. The optical film of the present invention is preferably a long film, specifically, a film of the order of 10 μm to 5,000 m, usually in the form of a cylinder. Further, the width of the film 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 1 barium, and particularly preferably 30 to 80/m when used in a protective film for a polarizing plate to be described later. . [Polarizing Plate] When the optical film of the present invention is used as a protective film for a polarizing plate, a polarizing plate can be produced by a general method. Preferably, 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 a polarizer formed by stretching in an 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, KC8UE, KC4UE, KC4FR-3, KC4FR -4, KC4HR-1, KC8UY-HA, KC8UX-RHA, the above is KonicaMinolta Opto (-53-201107801 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, and the polarizing film has iodine-made 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. Preferably, the adhesive used in the adhesive layer is an adhesive which is at least partially used at a storage modulus of 1.0 X104 to 1.0x1 09Pa at 25 ° C, and is coated with an adhesive after bonding. A hardening type adhesive which forms a high molecular weight substance or a crosslinked structure by various chemical reactions is suitable. 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 generally 0.1 to 50 mass -54 to 201107801%. [Liquid crystal display device] The polarizing plate to which the optical film of the present invention is bonded is assembled, and a liquid crystal display device having various excellent visibility can be produced, and a liquid crystal display device such as a large liquid crystal display device or a digital sign can be used. The adhesive layer or the like is bonded to the liquid. The polarizing plate of the present invention is suitable for a reflective type, a transmissive LCD or a TN type, an STN type, an OCB type, a HAN type, or a VA type MVA type), and an IPS type (including an FFS method). And so on. In particular, the screen is 30 吋 or more, and more preferably 30 吋 to 54 吋. The display device 'has no whitening at the periphery of the screen, and can be smashed for a long time, and the color spots, glare, or unevenness are less, and the eyes are also Not tired of the effect. [Embodiment] EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention and the like. Example 1 [Production of Optical Film] <Production of Optical Film 1> The liquid crystal display device is particularly suitable for use in crystal display devices. Pb on the cell. The semi-transmissive type (PVA type, the large screen of the LCD maintains this effect, so that the long-term view is not limited to this -55-201107801 (Melted by the glue 1) DIANAL BR85 (manufactured by Mitsubishi Rayon) 65 parts by mass of acrylic acid Particle (C1) 5 parts by mass of cellulose ester (cellulose acetate propionate decyl group total substitution degree 2.75, acetyl group substitution degree 0.19, propyl thiol substitution degree 2.56, Mw = 200 〇〇〇) 3 〇 mass 40 parts by mass of methylene chloride, 40 parts by mass of ethanol, and the above composition was sufficiently dissolved by heating to prepare a dope 1. Similarly, the dope 2 was prepared in the same manner except that the resin composition was changed as follows. (Mixed liquid 2 composition) DIANAL BR85 (Mitsubishi Rayon Co., Ltd.) 85 parts by mass of acrylic particles (C1) 5 parts by mass of cellulose ester (cellulose acetate propionate thiol group total substitution degree 2.75, acetyl group substitution degree 0.19, propyl ketone substitution degree 2.56, Mw = 200000) 10 parts by mass of dichloromethane, 300 parts by mass of ethanol, 40 parts by mass (film formation of acrylic resin film), using a belt-shaped casting device (see Fig. 1), at a temperature of 22 ° C and a width of 2 m Made glue 1, 2 It is uniformly cast on the stainless steel belt support -56-201107801. The solvent is evaporated on the stainless steel belt support until the residual solvent amount becomes 100%, and the peeling tension is 160 N/m from the stainless steel belt support. Secondly, appropriate Controlling the casting amount of the dope 1 and 2 to obtain a film having a desired layer thickness. The web of the peeled film was allowed to evaporate the solvent at 35 t, and was extended 1.5 times in the width direction using a tenter while being 140°. The drying temperature of C was dried. At this time, the amount of residual solvent at the start of tenter stretching was 10%. After stretching with a tenter, it was relaxed at 130 ° C for 5 minutes, and then conveyed to 100 ° C with a plurality of rolls. The drying zone at 120 ° C, at the same time of drying, was cut into 1.5 m width, and embossing was applied to both ends of the film by a width of 10 mm and a height of 5 μm, with an initial tension of 220 N/m and a final tension of 1 ΙΟΝ/m. The optical film 1 of the present invention was obtained by winding on a core having an inner diameter of 15.24 cm. <Production of Optical Films 2 to 13 of the Present Invention and Optical Films 1 to 7 of Comparative Example> In the production of the above optical film 1, except for the type and composition of the acrylic resin (A) and the cellulose ester resin (B) The optical films 2 to 13 of the present invention and the optical films 1 to 7 of the comparative examples were produced in the same manner as described in Tables 1 and 2. The ratio of DIANALBR85 to acrylic particles (C1) of acrylic resin is constant. In the production of the optical film 1 of the present invention, except that the acrylic resin was changed to Delpet 80N manufactured by Asahi Kasei Chemicals Co., Ltd., the composition ratio of the acrylic resin (A) and the cellulose resin (B) was changed to that shown in Table 2, and the same. The optical films 14 to 20 of the present invention were produced. The ratio of Delpet 8 ON to acrylic particles (Cl) of acrylic resin is constant. -57-201107801 "Evaluation method" The obtained optical film was evaluated as follows. (Evaluation of Bending) The optical film was cut into 100 mm (length) x 10 mm (width), and folded in the center of the longitudinal direction, and folded in half, and the evaluation was measured 1 time, and the number of folds was evaluated. The rupture evaluated here indicates that the rupture is separated into two or more fragments. (Pencil Hardness) For each of the optical films of the above-described Example 20 and Comparative Examples 1 to 7, a test pencil defined in JIS S 6006 was used, and 1 kg was used in accordance with the pencil hardness evaluation method prescribed in JIS K 54〇0. The load was measured by pencils of the hardness of each of the optical films of Examples 1 to 20 and Comparative Examples 1 to 7 to determine the pencil hardness. The optical film of the present invention was evaluated on the side of the layer 2 side. The results obtained are shown in Tables 1 and 2 below. -58- 201107801 【i

m \taj 蠶 <Pr r CM I OJ 工 CVJ I 04 工 CM X CM 工 CM X CNJ X CNJ 工 (N X. CM X CNJ 工 ώ co: X CO X CD CO X CQ d3 CM ir靈怪 it-® 〇 o Ο 〇 〇 Ο 〇 〇 〇 〇 〇 . ο σ» 一 mi ΓΟ CO m f 幽 <N m a 铿 m N < § g s S LO 〇 次 LO 00 § 〇 〇> § s 1 ' 1 s 次 § CO s 次 o 次 P 次 2 m 次 w> 〇 Ό S 〇 〇 Ο ο 1 1 1 1 次 s ο ο 掛 ia：s , in CO ·—· s C0 CO *«— 2 ro ΓΟ in in ΙΟ tn <VJ s 1 1 1 i CO . CO CO ··— ft ^ 豳3 CM in α〇 in in ΙΟ in .in 一 C0 对 p 8 1 1 1 1 ΊΛ m ΙΟ 幽 s 褂 ia Si m y—·» < >w/ 次 o 次 ο 〇 次 ο ο § S S 次 S S 次 o Ο 次 ο 次 ο 次 ο 次 in 次 Ο 次 tn 次 ω 另 S 次 S 次 S 次 S 次 ο 次 ο s 另 次 ιο m 次 s 掛 m：b I® CO oo s S 00 00 CO GO S 00 00 S tn σ> in S ο ο ο ^-. · ο GO 00 00 00 oo oo 1¾ ^ 购=4 茺 in ro CM ΓΟ in CO in ΓΟ S 〇> K VO s ο ο ο ο in ΓΟ in 00 tn CO tt fg i? J σ o ο 〇 ο xj* ό 〇 〇 S § o 〇 ο ο ο ο ο o o i m 件 CM 粼 恃 CO 粼 恃 m 恃 in 微 * (Ο 镟 f< 镞 •14 00 餾 •14 cn 匪 m 〇 m i 粼 <y 鄹 掩 CO i m 恃 ί. OJ CSJ 鑑 C0 鎰 寸 in 鎰 <〇 卜 m 鎰 JJ JA i雲Μ : (V)ii " - ω- -59- 201107801 【sm \taj silkworm <Pr r CM I OJ work CVJ I 04 work CM X CM work CM X CNJ X CNJ work (N X. CM X CNJ work co: X CO X CD CO X CQ d3 CM ir genius it- ® 〇o Ο 〇〇Ο 〇〇〇〇〇. ο σ» a mi ΓΟ CO mf 幽<N ma 铿m N < § gs S LO 〇LO 00 § 〇〇> § s 1 ' 1 s Times § CO s times o times times P times 2 m times w> 〇Ό S 〇〇Ο ο 1 1 1 1 time s ο ο hang ia:s , in CO ·—· s C0 CO *« — 2 ro ΓΟ in in ΙΟ tn <VJ s 1 1 1 i CO . CO CO ··· ft ^ 豳3 CM in α〇in in ΙΟ in .in a C0 pair p 8 1 1 1 1 ΊΛ m ΙΟ s s 褂ia Si my— ·» <>w/ times o times ο 〇 ο ο § SS times SS times o Ο times ο times ο times ο times in times t times tn times ω another S times S times S times ο times ο s Another time ιο m times s hang m:b I® CO oo s S 00 00 CO GO S 00 00 S tn σ> in S ο ο ο ^-. · ο GO 00 00 00 oo oo 13⁄4 ^ Purchase = 4 茺in Ro CM ΓΟ in CO in ΓΟ S 〇> K VO s ο ο ο ο ΓΟ in 00 tn CO tt fg i? J σ o ο 〇ο Xj* ό 〇〇S § o 〇ο ο ο ο ο oo oo oo oo oo 件 CM 微 微 微 & & & 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 CO im 恃ί. OJ CSJ 鉴 C0 镒 inch in 镒<〇卜m 镒JJ JA i云Μ : (V)ii " - ω- -59- 201107801 [s

UnJ © 槲 鋪 -fi- g 〇〇 ffi CNJ X CQ X C0 〇] X 03 X οα X CO ΙΓ g 〇 Ο 〇 〇 ο ο ο CS 雠 褂 鋰 m ^ ΓΠ <次 一 L_l § § LO σ> § § § § 一鬥 PQ ^ 〇 ο in 〇 ο ο ο μ：色 _ to CO i〇 ιο LO ϋ； ^ ^ 1__1 CNJ 00 00 in ιΗ CO 寸 Μ 1I < έ? 一 ι_ι Ο ο ο s s S s ^门 PQ ^ W u 另 另 s s S s 稱· _ Β： S tn σ> g § s ΙΟ <ji it ^ [to ^ L·-! 00 co 3 LO Ml Q _ Μ ο 寸 宕 § § 鏹 LO S 粼 恃 CO i 餾 恃 S 餾 恃 00 S 微 恃 2 i 鹬 微 (V)S5艇趑裝E:: (V) II .· s- ’ 均 高爲 度成 .硬組 係脂 膜樹 薄之 學向 光方 之度 明厚 發到 本得 ’ 可 知 ， 。 得少性 載較特 記裂的 ί破現 之實 成法 表造無 如所所 彎時 折一 表 及 -60- 201107801 實施例2 實施例1之膠漿液2調製時，除了如表3添加追加化合 物外，同樣地，可提供改善光學薄膜之接著性及硬度的光 學薄膜。提供使用該光學薄膜之偏光板及液晶顯示器。 製作薄膜21~28。表3中之P-1、P-2係特開平9-203810 號公報之實施例所記載的防靜電劑。將製作的光學薄膜進 行實施例1之折彎評價、鉛筆硬度評價、下述污垢附著試 驗。所得的結果如下述表3所示。 (污垢附著試驗） 將薄膜之a面側以1 0秒靠近香煙灰直到高度1 cm爲止， 觀察污垢附著。 〇：完全未看見污垢附著。 △:有少許污垢附著。 X :污垢附著明顯。 -61 - 201107801 【8】 污垢 附著 〇 O 。 O Ο d 0 鉛筆硬 度單體 X CM 2 H I X CM X to X CNJ I CO 2 Η 折彎10次 中斷裂次數 [次] d o 〇 0 ό ό ό 〇 第2層(表面層） <Π η 9 _ in o CSI in. ci <SJ； Ο rr, d CSJ .* 〇 魃 郷 1 CL QL CNJ 1 a CM I QL § δ 〇c >r'· f 」: 〇 oc 1 AEROSIL 972V 'δ； ε； to i ·< 樹脂比率 (Λ) 次 9〇%1 \m\ 90%. \sm\ •ο σ>： :C5· σι s GO 1¾ to% 1.0%. i〇K ο k ;ο： ym\ 層厚比率 C%] in 2? in m in 家 in s? in tn ir> 層厚 CM csi csi CM cy 第1層 ! 樹脂比率 70% 70% 〇 次 ο 家 | 70% 0 30%! 30% 30%: 30%, 次 ο ΓΟ 層厚比率 C%] in cr> ιό Oi in 〇> ύή Φ in 〇> (Λ σ> % 層厚 [Am] 00 f〇 00 CO GO CO 00 Γ〇 00 rr> % 全層厚 o ό 穿 ο ό ο ο |本發明21 I _ 明 22| |本發明231 1本發明24| 1本發明25| 1本發明2$| 鏃 讲 本發明28 sssi.: (V) Φ_Μ:«; is -62- 201107801 如表3記載得知’使用防靜電劑或消光劑之本發明的 光學薄膜係具有硬度高，折彎之破裂少，且污垢附著性優 異之特徴的光學薄膜。 實施例3 實施例1之光學薄膜1之製作時，除了僅在薄膜之兩端 部部分以比較例1之膠漿以單一層流延，改變拉幅器部分 之薄膜的把持方法外，同樣地，製作光學薄膜。本發明之 光學薄膜30係藉由金屬塊（block)由上下挾壓薄膜端部 來把持的挾具方式，光學薄膜31係使用針（pin)刺薄膜 端部，藉由貫穿的針把持薄膜，以拉幅器進行延伸。此等 薄膜之搬送性如下表4所示。 (搬送性試驗） 將拉幅器內部溫度分別設定爲1 0 0 °c、1 3 0 °c、1 5 0。(： ，延伸率1.5倍下搬送薄膜，觀察薄膜。 〇：薄膜可在無破裂、變形下搬送。 △:薄膜雖未破裂，但是產生變形。 X :薄膜有破裂、變形，無法搬送。 [表4] 薄膜之寬度方向之構j 成 拉幅器 保持方法 薄膜 搬送 0〜100[mm] 100〜1400「mml 1400〜1500『mml 本發明30 比較例1的構成 實施例1的構成 比較例1的構成 挾具 〇 本發明31 比較例1的構成 實施例1的構成 比較例1的構成 針 〇 -63- 201107801 如表4記載，本發明之光學薄膜顯示以拉幅器之把持 手段在挾具、針兩者可安定的搬送性。 (液晶顯示裝置之特性評價） <偏光板之製作> 如下述製作將各光學薄膜作爲偏光板保護薄膜的偏光 板。 將厚度120 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1 0 0質量份中，5 0 °C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1製作的光學薄 膜1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 KonicaMinoltaOpto公司製KC8UX，經乾燥製作偏光板。同 樣的，使用本發明之光學薄膜2〜13、比較例之光學薄膜 1~7製作偏光板。 使用本發明之光學薄膜的偏光板係薄膜切割性優異， 容易加工。 <液晶顯示裝置之製作> 使用上述製作的各偏光板評價光學薄膜之顯示特性。 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避免使各自 K C 8 U X在液晶胞之玻璃面側，且使吸收軸朝向於與預先貼 -64- 201107801 合之偏光板相同方向來貼合，分別製作液晶顯示裝置。 (顯示品質評價） 關於上述製作的液晶顯示裝置，使顯示各種圖{ s,、 冢’ g平 價在23°C、55%RH之環境下之顯示圖像的品質。 〇：良好的顯示 △:顯示之圖像欠缺均一性，有色斑（不均）。 X:—部份產生極端地色變化。 (色彩偏移：偏光板之耐熱•耐濕性評價） 關於上述製作的液晶顯示裝置，在23 t、55 %RH之環 境下，使顯示器顯示黑色，由斜方向45。之角度觀察。接 者’同樣觀察將上述偏光板經過以60 °C、90 % RH處理1000 小時者，並以下述基準評價色變化。 〇：完全無色變化。 △:稍微有色變化。 X :色變化大。 -65 - 201107801UnJ © 槲 shop-fi- g 〇〇ffi CNJ X CQ X C0 〇] X 03 X οα X CO ΙΓ g 〇Ο 〇〇ο ο ο CS 雠褂 Li m ^ ΓΠ <Second L_l § § LO σ> § § § § 一斗 PQ ^ 〇ο in 〇ο ο ο μ:色_ to CO i〇ιο LO ϋ; ^ ^ 1__1 CNJ 00 00 in ιΗ CO Μ Μ 1I < έ? 一ι_ι Ο ο ο ss S s ^门 PQ ^ W u Another ss S s called · _ Β: S tn σ> g § s ΙΟ <ji it ^ [to ^ L·-! 00 co 3 LO Ml Q _ Μ ο 宕 § §镪LO S 粼恃CO i Distillation 恃 S Distillation S S S i i i i i i i i i : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : The thinness of the tree to the light side of the degree to the original can be known. In the case of the sizing of the sizing solution of the first embodiment, in addition to the addition of the compound as shown in Table 3, the addition of the singularity of the singularity of the singularity is not as good as that of the case Further, similarly, an optical film which improves the adhesion and hardness of the optical film can be provided. A polarizing plate and a liquid crystal display using the optical film are provided. Films 21 to 28 were produced. The antistatic agent described in the examples of the Japanese Patent Publication No. Hei 9-203810. The produced optical film was subjected to the bending evaluation of Example 1, the pencil hardness evaluation, and the following soil adhesion test. The results obtained are shown in Table 3 below. (Fouling adhesion test) The surface of the a side of the film was placed close to the cigarette ash at a height of 1 cm for 10 seconds, and the adhesion of the dirt was observed. 〇: No dirt was observed at all. △: A little dirt adhered. X: The dirt adheres significantly. -61 - 201107801 [8] Dirt adhesion 〇 O . O Ο d 0 Pencil hardness monomer X CM 2 HIX CM X to X CNJ I CO 2 Η Number of breaks in 10 bends [times] do 〇0 ό ό ό 〇 Layer 2 (surface layer) <Π η 9 _ in o CSI in. ci <SJ; Ο rr, d CSJ .* 〇魃郷1 CL QL CNJ 1 a CM I QL § δ 〇c >r'· f ”: 〇oc 1 AEROSIL 972V 'δ; ε; to i ·< Resin ratio (Λ) times 9〇%1 \m\ 90%. \sm\ •ο σ>: :C5· σι s GO 13⁄4 to% 1.0%. i〇K ο k ;ο : ym\ layer thickness ratio C%] in 2? in m in home in s? in tn ir> layer thickness CM csi csi CM cy layer 1! Resin ratio 70% 70% 〇次ο 家 | 70% 0 30% 30% 30%: 30%, times ο 层 layer thickness ratio C%] in cr> ιό Oi in 〇> ύή Φ in 〇> (Λ σ> % layer thickness [Am] 00 f〇00 CO GO CO 00 Γ〇00 rr>% full layer thickness o 穿 wear ο ό ο ο | The present invention 21 I _ Ming 22 | | The present invention 231 1 The present invention 24 | 1 The present invention 25 | 1 The present invention 2$| 镞 本 本28 sssi.: (V) Φ_Μ: «; is -62- 201107801 As shown in Table 3, the optical film system of the present invention using an antistatic agent or a matting agent is known. There is a special optical film having high hardness, less cracking of the bend, and excellent stain adhesion. Example 3 In the production of the optical film 1 of Example 1, except that the glue of Comparative Example 1 was only used at both end portions of the film. The film is cast in a single layer and the film holding method of the tenter portion is changed. Similarly, an optical film is produced. The optical film 30 of the present invention is held by the end of the film by a metal block. In the cooker method, the optical film 31 is formed by a pin-punching film end portion, and is stretched by a tenter by a penetrating needle. The film transportability is as shown in Table 4 below. (Transportability test) The internal temperature of the tenter is set to 1 0 0 °c, 1 30 °c, and 150. (:, the film is conveyed at an elongation of 1.5 times, and the film is observed. 〇: The film can be transported without cracking or deformation. . △: Although the film was not broken, it was deformed. X: The film is cracked and deformed and cannot be transported. [Table 4] The configuration of the film in the width direction of the film is a tenter holding method. The film transport is 0 to 100 [mm] 100 to 1400 "mml 1400 to 1500" mml. 30. Comparative Example of the configuration example 1 of the comparative example 1 of the present invention The composition of the first embodiment of the present invention 31 The composition of the first embodiment of the comparative example 1 is the configuration of the comparative example 1. The needle-63-201107801 is as shown in Table 4, and the optical film of the present invention shows the holding means by the tenter. (Evaluation of characteristics of liquid crystal display device) <Production of polarizing plate> A polarizing plate in which each optical film is used as a protective film for a polarizing plate is produced as follows. The polyvinyl alcohol film 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 5 times in the transport direction at 50 ° C. Next, an acrylic adhesive was used to carry out the film. The optical film 1 produced in Example 1 was attached to the single side of the polarizing film after being subjected to a corona treatment. KC8UX manufactured by Konica Minolta Opto Co., Ltd., which was subjected to alkali saponification, was attached to the other side of the polarizing film, and dried. In the same manner, the polarizing plate was produced by using the optical films 2 to 13 of the present invention and the optical films 1 to 7 of the comparative example. The polarizing plate film using the optical film of the present invention is excellent in cutting property and easy to process. [Production of the device] The display characteristics of the optical film were evaluated using the polarizing plates produced as described above. The polarizing plate of the 32-inch TV 32H2000 manufactured by Tosoh Corporation was bonded to the polarizing plates of both sides in advance, and the polarizing plates produced above were prevented from being respectively made KC 8 UX is attached to the glass surface side of the liquid crystal cell, and the absorption axis is bonded to the same direction as the polarizing plate of the pre-bonded-64-201107801, and a liquid crystal display device is produced. (Display quality evaluation) The liquid crystal display device produced as described above To display the quality of the displayed image in various environments where the graphs { s, 冢 ' g are at 23 ° C and 55% RH. 〇: Good display △: The displayed image lacks uniformity and has color spots ( X: - Partially extreme color change. (Color shift: heat resistance and moisture resistance evaluation of polarizing plate) About the liquid crystal display device produced above, at 23 t, 55 % RH In the environment, the display is displayed in black and viewed from the oblique direction of 45. The receiver's observation of the polarizing plate was carried out at 60 ° C and 90 % RH for 1000 hours, and the color change was evaluated on the basis of the following criteria. Completely colorless change. △: Slight color change. X: Color change is large. -65 - 201107801

[表5] _示品質 色彩偏移 本發明1 〇 〇 本發明2 〇 〇 本發明3 〇 〇 本發明4 〇 〇 本發明5 〇 〇 本發明6 〇 〇 本發明？ 〇 1 δ— 本發明8 〇 〇 本發明9 〇 〇 本發明10 〇 〇 本發明η 〇 〇 本發明12 〇 〇 本發明13 〇 〇 比較例1 △ X 比較例2 〇 X 比較例3 〇 X 比較例4 Δ Δ 比較例5 △ Δ X △ X X 使用本發明之光學薄膜製作的偏光板、液晶顯示裝置 具有顯示品質及色彩偏移優異的特性。 【圖式簡單說明】 [圖1]表示可同時流延複數膠漿之樹脂薄膜製造裝置的 槪略圖。 [圖2]共流延用模的剖面圖 [圖3]表示溶液流延製膜方法之膠獎調製步驟、流延步 驟及乾燥步驟之一例的模式圖。 【主要元件符號說明】 la〜Id :膠漿液槽 2 a~2 c :栗 -66- 201107801 4 ： 5 ： 6 ·· 7 ： 10、 lx: 3 x、 4 x、 5 x、 8x、 1 Ox 20 : 21 : 30 : 3 1: 3 2 ： 33 : 34 : 35 : 41 : 42 : 43 : 44 : 流延用模 筒 流延帶 滾筒 樹脂薄膜 1 1 a、1 1 b、1 2 :模縫 溶解鍋 6x、 12x、 15x:過濾器 1 3 x :儲存槽 1 4 X :送液泵 1 6x :導管 :紫外線吸收劑投入鍋 合流管 混合機 模 金屬支持體 纖維網 剝離位置 拉幅器裝置 輥乾燥裝置 粒子投入鍋 儲存槽 泵 過濾器 -67[Table 5] _ indicates quality color shifting The present invention 1 〇 〇 2nd invention 〇 〇 3rd invention 4 〇 发明 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇1 δ - the present invention 8 〇〇 the present invention 9 〇〇 the present invention 10 〇〇 the present invention η 〇〇 the present invention 12 〇〇 the present invention 13 〇〇 comparative example 1 Δ X Comparative Example 2 〇 X Comparative Example 3 〇 X Comparison Example 4 Δ Δ Comparative Example 5 Δ Δ X Δ XX The polarizing plate and the liquid crystal display device produced by using the optical film of the present invention have excellent display quality and color shift. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] is a schematic view showing a resin film manufacturing apparatus capable of simultaneously casting a plurality of dopes. Fig. 2 is a cross-sectional view showing a mold for co-casting. Fig. 3 is a schematic view showing an example of a glue-modulating step, a casting step, and a drying step of the solution casting film forming method. [Description of main component symbols] la~Id: glue tank 2 a~2 c: chestnut-66- 201107801 4 : 5 : 6 ·· 7 : 10, lx: 3 x, 4 x, 5 x, 8x, 1 Ox 20 : 21 : 30 : 3 1: 3 2 : 33 : 34 : 35 : 41 : 42 : 43 : 44 : Casting film for casting with roll film 1 1 a, 1 1 b, 1 2 : Mold seam Dissolving pot 6x, 12x, 15x: filter 1 3 x : storage tank 1 4 X : liquid feeding pump 1 6x : conduit: UV absorber into the pot mixing tube mixer machine metal support fiber web stripping position tenter device roll Drying device particles into the pot storage tank pump filter -67

Claims (1)

201107801 七、申請專利範圍： 1. 一種光學薄膜，其係具有至少二層以上之樹脂組成 彼此不同之層的光學薄膜’其特徵係（i)構成該光學薄 膜表面之層的至少—層爲以95 : 5〜85 : 15之質量比含有丙 烯酸樹脂（A)與纖維素酯樹脂（B) ’ （ii)構成該表面 之層以外的層爲以80: 20〜50: 50之質量比含有丙烯酸樹 脂（A )與纖維素酯樹脂（B ) ’ （iii)前述丙烯酸樹脂 (A )之重量平均分子量爲80000以上，（iv )前述纖維素 酯樹脂（B)之醯基的總取代度爲2.0~3.0、碳數3〜7之醯 基的取代度爲1.2~3.0，該纖維素酯樹脂（B)之重量平均 分子量爲7 5000以上者。 2. 如申請專利範圍第1項之光學薄膜，其中構成前述 表面之層的厚度爲前述光學薄膜整體厚度的5~2 0%。 3. 如申請專利範圍第1或2項之光學薄膜，其中相對於 構成該表面之層的全質量，在構成前述表面之層上含有 0.01〜1質量％之平均粒徑爲5 0〜3 00 μιη之範圍內之無機化合 物或有機化合物之微粒子。 4. 如申請專利範圍第1 ~3項中任一項之光學薄膜，其 係含有防靜電劑。 5 .如申請專利範圍第1〜4項中任一項之光學薄膜，其 中前述光學薄膜之寬度方向之長度之至少10~90%的範圍內 ，且含有該薄膜寬度方向之中心的部分爲含有至少二層以 上之前述樹脂組成不同的層者。 6.如申請專利範圍第1〜5項中任一項之光學薄膜，其 -68- 201107801 中前述樹脂組成彼此不同之層在薄膜製膜時同時形成。 7. —種偏光板，其特徵係使用如申請專利範圍第1 ~6 項中任一項之光學薄膜者。 8 · —種液晶顯示裝置，其特徵係使用如申請專利範圍 第1〜6項中任一項之光學薄膜者。201107801 VII. Patent application scope: 1. An optical film which is an optical film having at least two or more layers of resin layers different from each other, characterized in that (i) at least a layer constituting a layer of the surface of the optical film is 95 : 5 to 85 : 15 mass ratio containing acrylic resin (A) and cellulose ester resin (B) ' (ii) layers other than the layer constituting the surface are contained in an 80:20 to 50:50 mass ratio of acrylic acid Resin (A) and cellulose ester resin (B) ' (iii) The weight average molecular weight of the aforementioned acrylic resin (A) is 80,000 or more, and (iv) the total substitution degree of the thiol group of the cellulose ester resin (B) is 2.0. The degree of substitution of ~3.0, a fluorenyl group having 3 to 7 carbon atoms is 1.2 to 3.0, and the weight average molecular weight of the cellulose ester resin (B) is 75,000 or more. 2. The optical film of claim 1, wherein the thickness of the layer constituting the surface is 5 to 20% of the entire thickness of the optical film. 3. The optical film according to claim 1 or 2, wherein an average particle diameter of 0.01 to 1% by mass on the layer constituting the surface is 50 to 30,000 with respect to the total mass of the layer constituting the surface. A fine particle of an inorganic compound or an organic compound within the range of μιη. 4. An optical film according to any one of claims 1 to 3, which contains an antistatic agent. The optical film according to any one of claims 1 to 4, wherein the optical film has a length in the width direction of at least 10 to 90%, and a portion including a center of the film width direction is contained. At least two or more layers of the foregoing resins constitute different layers. 6. The optical film according to any one of claims 1 to 5, wherein the layer having the different resin compositions described above in -68-201107801 is simultaneously formed at the time of film formation. 7. A polarizing plate characterized by using an optical film according to any one of claims 1 to 6. A liquid crystal display device characterized by using an optical film according to any one of claims 1 to 6.
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