TW201213409A - Cellulose ester film, polarizing plate and liquid-crystal display - Google Patents

Abstract

A cellulose ester film is provided, which includes cellulose ester, aromatic sugar ester compounds represented by general formula (I), aromatic sugar ester compounds represented by general formula (II), and aliphatic sugar ester compounds represented by general formula (III) and the average ester substitution degree of the aromatic sugar ester compounds represented by general formula (I) and the aromatic sugar ester compounds represented by general formula (II) is less than 94%. (I) (HO)m-G-(L-R1)n; (II) (HO)p-G-(L-R1)q; (III) (HO)t-G'-(L'-R2)r; (G and G' represent monosaccharide residue or disaccharide residue; R1 represents an aliphatic group or an aromatic group, and at least one of which is an aromatic group; R2 is an aliphatic group; L and L' are divalent linking groups; m and t are integers greater than 0; n, p and q are integers greater than 1; r is an integer greater than 3; wherein m+n ≥ 4; p+q ≥ 4; m > p; n < q).

Description

201213409 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種纖維素醋膜、偏光板及液晶顯示 裝置。 【先前技術】 境變化之偏光元件保護（偏光板耐久性），須要膜之疏水 =。疏水化中通常使用添加劑。然而，於作為製造纖維素201213409 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a cellulose acetate film, a polarizing plate, and a liquid crystal display device. [Prior Art] The polarization of the polarized element (polarized plate durability) requires the hydrophobicity of the film. Additives are commonly used in hydrophobization. However, as a manufacturing cellulose

為面狀故障之原因之一而成為問題。 於鹵化銀照相感光材料、相位差膜、偏光板及影像顯 示裝置中使用有以纖維素酯、聚酯、聚碳酸酯·、環烯烴聚 合物、乙烯系聚合物及聚醯亞胺等為代表之聚合物膜。由 該些聚合物可製造於平面性或均一性之方面更優異之膜， 因此被廣泛用作光學用途之膜。例如，具有適宜之透濕度 的纖維素酯膜可在線（online)與最一般的包含聚乙歸醇 (PVA) /碘之偏光元件（polarizer)直接貼合。因此，纖 維素酯、特別是乙酸纖維素被廣泛用作偏光板之保護膜。 於將纖維素醋膜用於液晶顯示裝置之情形時，為了環 於近年已矣口右以止丨1It becomes a problem for one of the causes of the planar failure. Used in silver halide photographic light-sensitive materials, retardation films, polarizing plates, and image display devices, which are represented by cellulose ester, polyester, polycarbonate, cycloolefin polymer, vinyl polymer, and polyimine. Polymer film. These polymers can be produced as a film which is more excellent in planarity or uniformity, and thus are widely used as a film for optical use. For example, a cellulose ester film having a suitable moisture permeability can be directly bonded to the most common polarizer comprising polyacetal (PVA) / iodine. Therefore, cellulose esters, particularly cellulose acetate, are widely used as a protective film for polarizing plates. When the cellulose vinegar film is used in a liquid crystal display device, in order to ring the mouth in recent years, it is closed to the right.

量的 out) 之情9 4 201213409 對此，於國際公開W02009/011228號公報（專利文獻 1) 中揭不了成膜纖維素酯膜的方法，藉由使作為蔗糖骨架 之糖之衍生物的化合物之〇11基之一部分殘存，進一步組 合OH基數不同之至少2種以上取代物，從而於成膜時揮 發成分少、且不產生滲出。而且，於專利文獻丨中存在如 下之記載：藉由使用低取代物與高取代物之糖酯的混合 物可有效地補償纖維素酯分子之醯基取代度的實質性偏 差因此所付之膜之皂化（saponification)後之财久性高， 且與偏光元件之密接性、偏光板耐久性變良好。然而，於 專利文獻1巾並未提及任何關料祕麟無肪族糖酿 之組合。另外’於專利文獻1之實例中，作為糖酯塑化劑， 主要使=蔗糖笨甲酸酯（其是於側鏈具有芳香族基作為取 代基^芳香族糖I旨）之取代度不同的3種取代物之混合物 而進行研究H於專利文獻丨中雖然亦揭示了其他實 例，但均為僅僅併用數種芳香族糖酯之組合、或者僅僅併 用數種脂肪族糖酯之組合。 而且，於國際公開W02009/031464號公報（專利文獻 2) 中揭不了藉由使用使作為蔗糖骨架糖之衍生物的化合物 之0H基之一部分殘存的低取代物，可減低霧度，藉由改 善硬塗層之塗佈不均而提高漏域對比度。鱗利文獻2 中作為糖醋塑化劑，除了芳香族糖醋以外，亦使用於側 鏈具有脂肪族基作為取代基的脂肪族糖酯 ，但並未揭示將 兩者混合之例，且亦無暗示將兩者加以混合之記載。 另一方面，於液晶顯示裝置中使用用以擴大視角、改 201213409 -- -IT -- 善影像著色、及提高對比度之光學補償膜是廣為人知之技 術。於最為普及之VA (Vertically Aligned)模式（垂直配 向模式）、TN模式等中需求可將特別是光學特性（例如Re 值及Rth值）控制為所期望之值的光學補償膜。 於適於VA模式之光學特性之調整中須要延伸處理， 故，烈需麵於目製造時的步驟污染所造狀面狀故障的 對策。 . 對此，本發明者等人使用該些文獻中所記載之糖酯塑 化劑時，作為先前由於添加劑之揮發所造成的製造設備之 動作異常或叙面狀故障之產生並未得到滿足。另外，本 發明者等人賴之Rth或於偏光板雜下之正交透射率， 研究於濕熱環境下隨相㈣時雜能，絲可知關於今 些之性能亦未得到滿足。 【發明内容】 本發明之目的在於提供面狀故障少、光學性能經時變 =小、且作為賴膜_裝至偏光板時偏光板之經時性 月良化小的纖維素g旨膜。 ^發明者等人為了解決上述問題而進行了銳意研究， 二果發現於使用芳香族糖s旨時，變得容易產生於使用時隨 =間^勒造成之光學舰之變動。因此，對於取代度不 杈？酯之2種以上混合體而混合脂肪族糖酯時， :而:於使用芳香族糖酯時所產生之隨時間經 構成，可同時滿騎有上述 籍由此種 6 201213409 亦即，本發明者等人進行銳意研究之結果是發現上述 課題可藉由以下構成之本發明而得到解決。 Π] —種纖維素酯膜，其含有纖維素酯、下述通式（1) 所表示之芳香族糖酯化合物、下述通式（11)所表示之芳 香族糖s旨化合物以及下述通式所表示之脂肪族糖酿 化合物，其特徵在於：所述通式所表示之芳香族糖酯 化合物與所述通式（π)所表示之芳香族糖酯化合物之平 均酯取代度不足94%， (1) (H〇)m-G-(L-R1)n (Π) (HOVG-CL-R1^ (III) (H〇)t-G’-(L，-R2)r (於通式（I)〜通式（m)中，〇及G，分別獨立地表 示單糖殘基或二賊H分職立地表示㈣族基或芳 香族基，至少一個表示芳香族基；R2分別獨立地表示脂肪 族基；L及L，分別獨立地表示2價之連結基；m表示〇以 上之整數，n、p&amp;q分別獨立地表示丨以上之整數，犷表 示3以上之整數，t表示〇以上之整數；其中，m + ng4， p + ，m&gt;p，n〈q ;而且，m + n及p + q分別與假定 所述G並非殘基而是相同骨架之環狀縮醛結構之未經取代 之糠類之情形時的羥基數相等，r+t與假定所述G，並非殘 基而是相同骨架之環狀縮醛結構之未經取代之糖類之情形 時的羥基數相等）。 [2] 如[1]所述之纖維素酯膜，其特徵在於，所述通式 (III)中之所述R2表示2種以上之脂肪族基。 201213409, [3] 如Π]或[2]所述之纖維素酯膜，其特徵在於，所述 通式（III)中之所述G，表示二糖殘基。 [4] 如[1]〜[3]中任一項所述之纖維素酯膜，其特徵在 於，所述通式（I)及所述通式（II)中之所述G為蔗糖骨 架，所述通式（I)所表示之芳香族糖酯化合物與所述通式 (II)所表示之芳香族糖酯化合物之平均酯取代度為5〜 7.5。 [5] 如[4]所述之纖維素酯膜，其特徵在於，所述通式 (II)中之q為8之芳香族糖酯之添加量相對於所述通式 (I)所表示之芳香族糖酯化合物及所述通式（Π)所表示 之芳香族糖酯化合物之合計添加量而言不足20 wt%。 [6] 如[1]〜[5]中任一項所述之纖維素酯膜，其特徵在 於’所述通式（I)以及所述通式（II)中之所述L、及所 述通式（III)中之所述U分別獨立地表示單鍵、·〇_、_(；；〇_、 (R11表示1價之取代基）之任一個。 [7] 如[1]〜[6]中任一項所述之纖維素酯膜，其特徵在 於，所述通式（I)以及所述通式（Π)中之所述ri、及所 述通式（III)中之所述R2分別獨立地表示醯基。 [8] 如[1]〜[7]中任一項所述之纖維素酯膜，其特徵在 於，所述通式（I)及所述通式（II)中之所述Ri表示苯甲 醯基。 [9] 如[1]〜[8]中任一項所述之纖維素酯膜’其特徵在 於，所述通式（III)中之所述R2分別獨立地表示非環式脂 肪族。 8 201213409 [10] 如[1]〜[9]中任一項所述之纖維素醋膜，其特徵 在於，所述通式（III)中之所述R2中之至少一種表示分支 狀之脂肪族基。 [11] 如[1]〜[1〇]中任一項所述之纖維素醋膜，其特徵 在於’所述通式（III)中之所述!^2僅包含乙醯基與異丁醯 基。 [12] -種偏光板，其具有偏光元件、與配置於該偏光 元件之兩側的保護膜，其特徵在於：該保護膜之至少i牧 是如[1]〜[11]中任一項所述之纖維素酯膜。 [13] —種液晶顯示裝置，其具有液晶單元及配置於該 液晶單元之兩侧的偏光板，其特徵在於：該偏光板中之至 少1牧是如[12]所述之偏光板。 [發明的效果] 藉由本發明可提供面狀故障少、光學性能經時變化亦 小、且作為保濩膜而内裝至偏光板時偏光板之經時性能變 化小的纖維素酯膜。而且，可提供使用該纖維素酯膜之經 時性能變化小的偏光板。而且，可提供使用上述膜或偏光 板的顯示品質良好之液晶顯示裝置。 【實施方式】 於以下，對本發明之内容加以詳細說明。以下所記载 之構成要素之說明是基於本發明之代表性實施態樣而進行 的，但本發明並不限定於此種實施態樣。另外，於本申請 說明書中’「〜」是以包含其前後所記載之數值而作為下限 值及上限值的含義而使用。 201213409 ·* [纖維素酯膜] 本發明之纖維素酯膜（以下亦稱為本發明之膜）含有 纖維素酯、下述通式（1)所表示之芳香族糖酯化合物、下 述通式（II)所表示之芳香族糖酯化合物、以及下述通式 (III)所表示之脂肪族糖酯化合物，其特徵在於：所述通 式U)所表示之芳香族糖酯化合物與所述通式（η)所表 示之芳香族糖酯化合物之平均酯取代度不足94%。· (I) (hol-g-cl-r、 (II) (HO)p-G-(L-Rl)q (III) (HO)t-G 丨-(L，-R2)r 一 0 (於通式（i)〜通式（m)中，G&amp;G，分別獨立地表 不單糖殘基或二糖殘基。R1分別獨立地表示脂肪族基或芳 香族基，至少-録衫_基。R2分糊立地表示脂肪 族基。L及L’分別獨立地表示2價之連結基。m表示〇以 上之整數，n、p&amp;q分別獨立地表示丨以上之整數，^表 示3以上之整數，t表示〇以上之整數。其中，m + n^4， P + qd ’ m&gt;p ’ n&lt;q。*且’ m + n及p + q分別與假定 所述G並非殘基而是相同骨架之環狀縮醛結構之未經取代 之糖類之情形時的經基數相等，r + t與假定所述g,並非殘 基而是相同骨架之環狀縮酸結構之未經取代之糖 時的羥基數相等。） 以下’對本發明之纖維素酯膜加以說明。 &lt;糖酯化合物&gt; 本發明之膜含有下述通式⑴所表示之芳香族糖酷化 201213409 a物下述通式（H)所表示之芳香族糖酯化合物、下述 通式（πι)所表示之脂肪族糖酯化合物，且所述通式（ι) 所表不之芳香族糖酯化合物與所述通式（π)所表示之芳 香族糖酯化合物之平均酯取代度不足94%。 ⑴（HCOm-G-A-R、 (II) (UO)rG-(L-Rl)q (ΙΠ) (H〇)rG，-(L，-R2)r 一（於通式（1)〜通式（III)中，G及G，分別獨立地表 示單糖殘基或二_基。W分職立地表㈣肪族基或芳 香族基’至少-個表示料族基。r2分賴立地表示脂肪 族基。L及L，分別獨立地表示2價之連結基。m表示〇以 上之整數’ η、p及q分別獨立地表示1以上之整數，r表 示3以上之整數，（表示〇以上之整數。其中，m + ， P + q^4，m&gt;p ’ n&lt;q。而且，m + n及p + q分別與假定 所述G並械基而是相时架之環狀祕結構之未經取代 之糖，之情形時的經基數相等，出與假定所述G，並非殘 基而疋相同骨架之環狀祕結構之未經取代之糖類之情形 時的羥基數相等。） 具體而言’於本發明中，特徵在於使用糖醋化合物混 合體’其是以滿足上述條件之方式混合有g|取代度不同之 多種芳香族㈣化合物與脂肪族糖0旨化合物。藉由將所述 糖醋化合物混合體杨錢維素⑽巾，可獲得面狀故障 少、光學性能之㈣變化亦小、且作為保賴而内裝至偏 光板時偏光板之經時性能變化小喊維素醋膜。 201213409 以下’對所述糖酯化合物混合體中所使用之各糖酯化 合物所共用之較佳範圍、及分別滿足通式（1)〜通式（ΠΙ) 之各糖酯化合物所特有之較佳範圍加以說明。 (各糖酯化合物所共用之性質） 所述糖醋化合物混合體中所使用之各糖酯化合物以單 糖殘基或一糖殘基為骨架。亦即，於所述通式（〗）〜通式 (III)中，G及G’分別獨立地表示單糖殘基或二糖殘基。 所述糖酯化合物是指構成該化合物之糖骨架結構中的 可經取代之基（例如羥基、羧基）之至少一個與至少一種 取代基進行酯鍵結而成之化合物。亦即，此處所謂糖酯化 合物亦包含廣義之糖衍生物類，例如亦包含如葡萄糖酸 (gluconic acid)這樣的包含糖殘基作為結構之化合物。亦 即，所述糖酯化合物亦包含葡萄糖與羧酸之酯體、葡萄糖 酸與醇之酯體。 可於本發明中使用之所述通式（I)〜通式（III)所表 示之所述触化合物較佳的是具㈣喃糖結構或吼喃糖結 構之化合物。於具有呋喃糖結構或吡喃糖結構作為糖骨架 之情形時，於所述通式（I)〜通式（III)中，可滿足m+ n24，p + qg4且]：為3以上之條件。 而且，於具有呋喃糖結構或„比喃糖結構作為糖骨架之 情形時、’ $可滿足如下之條件：m + n及p + q分別與假定 所述G並麵基而是相时架之環狀_結構之未經取代 之糠，之情形時馳基數相等，⑴與假定所述G，並非殘 基而疋相同θ架之環狀祕結構之未經取代之糖類之情开) 12 201213409 時的羥基數相等。 所述' P + q及…之上限值可採用根據 成為5 m&amp;Aa， 或G為早糖殘基則 右為一糖殘基則成為8。 較佳通式⑴〜通式（ΙΠ)所表示之所述細旨化合物 Γ,Ι疋财—個料糖結構或，糖結構之所述G或 槿^糖絲的化合物（Α)巾、或鍵結有2個吱喃糖結 人喃糖結構之至少—種的所述G^G，為二糖殘基的化 :B) +之0H基之全部或一部分進行醋化而成的 化化合物。 然而，本發明中所使用之糖酯化合物混合體之特徵在 於：於所述通式（I)及通式（11)中，滿sm&gt;p&amp;n&lt;q， 亦=，至少所述通式（I)所表示之糖酯化合物之〇H基並 ^完全被酯化。藉由如上所述而使用酯取代度不同之多種 芳香族糖酯化合物，於製造步驟中之揮發性變低，且於成 膜後變得難以自纖維素酯膜滲出。 化合物（A)之例可列舉葡萄糖、半乳糖、甘露糖、 果糖、木糖或***糖，但並不限定於該些化合物。 化合物（B)之例可列舉乳糖、蔗糖、蔗果四糖 (nystose)、蔗果五糖（IF· fructosyl nystose)、水蘇糖 (stachyose)、麥芽糖醇、乳糖醇、乳酮糖（iactul〇se)、 纖維雙糖（cellobiose)、麥芽糖、纖維三糖、麥芽三糖、 棉子糖（raffinose)或蔗果三糖（kestose)。除此以外，亦 可列舉龍膽二糖、龍膽三糖、龍膽四糖、木三糖 13 201213409 t ▲丄 (xylotriose )、乳果寡醣（iact〇sucr〇se )等，但並不限 於該些化合物。 於該些化合物（A)及化合物（B)中’特佳的是具有 呋喃糖結構與吡喃糖結構雙方之化合物。例子較佳的^蔗 糖、蔗果三糖、蔗果四糖、蔗果五糖、水蘇糖等，更佳的' 是蔗糖。而且，於化合物（B)中，鍵結有2個呋喃糖結 構或°比喃糖結構之至少一種的化合物亦是較佳之態樣之 〇 用以對化合物（A)及化合物（B)中之〇H基之全部 ，一部分進行酯化的取代基並無特別限制。其中，較佳^ 是使用單舰。亦即’較佳的是所述通式⑴以及所述通 式（Π)中之所述Ri、及所述通式（ΠΙ)中之所述R2分別 獨立地表示醯基。 所述單羧酸並無特別之限制，可使用公知之脂肪族單 羧酸、脂環族單叛酸、芳香族單羧酸等。所使用之叛酸可 為一種，亦可為2種以上之混合。於所述Rl或所述R2為 多種之情形時，可相互相同亦可不同。 另一方面，較佳的是所述通式（D以及所述通式（11) 中之所述L、及所述通式（πΐ)中之所述l，分別獨立地表 不單鍵、-〇-、-C〇-、-NR11- (R11表示1價之取代基）之 任一個；而且，於所述L1或所述L'為多個之情形時，可相 互相同亦可不同。其中，自所述以1及R2可容易地被醯基 取代之觀點而言，較佳的是所述L1或所述l，表示-0-。 (通式（I)及通式（II)所表示之芳香族糠酯化合物 201213409 之混合體） 其次，對所述通式⑴及通式（π)所表示之芳香族 糖酯化合物之較佳態樣加以說明。 於所述通式（I)及通式（11)中，所述Rl分別獨立地 表示脂肪族基或芳香族基，至少一個表示芳香族基。其中， 較佳的是職R1分職立地僅表*料族基，更佳的是所 有R1均表示相同之芳香族基。. 其特徵在於所述通式⑴所表示之芳香族糖醋化合物 與所述通式（II)所表示之芳香族糖酯化合物之平均醋取 代度不足94%。藉由如上所述而使2種以上之芳香族糖醋 化合物之混合體的平均酯取代度不足94%，可使所得之纖 維素酯膜之霧度顯著變小，且可作為光學膜而良好地用於 偏光板或液晶顯示裝置中。 自可減少於内裝至偏光板時於濕熱環境下之正交透射 率的經時變化的觀點考慮，較佳的是所述所述通式（ι)所 表示之芳香族糖酯化合物與所述通式（11)所表示之芳香 族糖酯化合物之平均酯取代度為62%以上且不足94%。 一另外，自可減少於内裝至偏光板時於濕熱環境下之正 父透射率的經時變化的觀點考慮，更佳的是所述通式 及所述通式（II)中之所述G為蔗糖骨架，所述通式（1) 所表示之芳香族糖酯化合物與所述通式（n)所表示之芳 香族糖酯化合物之平均酯取代度為5〜75，特佳的是5 5 〜7.0。 而且，於所述通式（I)及通式（11)中，m表示〇以 15 201213409 、 上之整數，n、pgq分別獨立地表示丨以上之 &gt;p，n&lt;q。 於本發明中’自所得之纖維素醋膜之霧度顯著變小的 觀點考慮，較佳的是於所述G為二糖殘基之情形時，所述 通式（II)中之q為8之芳香族糖酯之添加量相對於所述 通式（I)所表示之芳香族糖酯化合物及所述通式所 表示之芳香族糖酯化合物之合計添加量而言為不足2〇 wt%。於所述G為二糖殘基之情形時，並不具有—個羥基 作為取代基的芳香族糖酯化合物之含量相對於所有芳香族 糖酯之含量而言較佳的是20 wt%以下，更佳的是15 wt% 以下，特佳的是10 wt%以下，進一步特佳的是5 wt%以下。 另一方面，於本發明中，所述通式（1)所表示之芳香 族糖酯化合物與所述通式（II)所表示之芳香族糖酯化合 物於所述G為二糖殘基之情形時，較佳的是11為3以上， 5以上亦較佳。亦即，於本發明中，較佳的是至少所述芳 香族糖酯化合物混合體中所含之芳香族糖酯化合物為至少 3取代物以上，至少5取代物以上亦較佳。 於所述芳香族糖酯化合物為2糖類之情形時，被醋化 之取代基為3個〜5個之3取代物〜5取代物的含有率相對 於芳香族糖S旨化合物全體而言較佳的是10%〜7〇%，更佳 的是20%〜50%。6取代物〜7取代物之含量相對於芳香族 糖酯化合物全體而言較佳的是20%〜85%，更佳的是20% 〜75% 〇 於由R1取代時所使用之較佳之芳香族單竣酸之例可 201213409 列舉苯曱酸、曱苯曱酸（toluic acid)等於苯曱酸之苯環導 入有烷基或烷氧基之芳香族單羧酸，肉桂酸 (cinnamic acid) ’二苯經乙酸（benzilic acid)、聯苯缓酸、萘銳酸、 四氫萘緩酸（tetralincarboxylic acid )等具有2個以上苯環 之芳香族單羧酸，及該些化合物之衍生物；更具體而言可 列舉：二曱基苯曱酸（xylic acid )、2,3-二甲基苯曱酸 (hemellitic acid)、3,5-二曱基苯曱酸（mesitylenic acid)、 2，M-三甲基苯曱酸（prehnitylic acid)、2,3,5-三曱基苯曱 酸（γ-isodurylic acid )、2,4,5-三曱基苯曱酸（durylic acid )、 2,4,6-三曱基苯曱酸（mesitoic acid )、3,4,5-三曱基苯曱酸 (α-isodurylic acid )、小菌香酸（cuminic acid )、α-甲苯曱 酸、氫化阿托酸（hydratropic acid)、阿托酸、氫肉桂酸、 水揚酸、鄰茴香酸（o-anisic acid)、間茴香酸（ m-anisic acid)、對茴香酸（p-anisic acid)、木顧油酸（creosote oil acid )、鄰升柳酸（〇-homosalicylic acid )、間升柳酸 (m-homosalicylic acid )、對升柳酸（p-homosalicylic acid)、鄰焦兒茶酸（o-pyrocatechuic acid) ' 2,4-二羧基苯 甲酸（β-resorcylic acid)、香草酸（vanillic acid)、異香草 酸（isovanillic acid )、3,4-二曱氧基苯曱酸（veratric acid )、 2,3-二曱氧基苯曱酸（o-veratric acid)、沒食子酸、細辛酸 (asaronic acid)、苦杏仁酸（mandelic acid)、4-曱氧基苯 乙酸（homoanisic acid)、高香草酸（homovanillic acid)、 升蘇董酸（homoveratric acid )、2,3 -二曱氧基苯乙酸 (o-homoveratric acid)、敌酮酸（phthalonic acid)、對闊馬 17 201213409 / V/Jpli 所述通式（II)中之所述R1表示苯甲酿基。 i方去並無特別限制，可使用公知之方法。而且， 少種所相取代衫同之㈣族糖合物之混合時序為 :::抹用溶液成膜法之情形時，可為添加於纖維素酯摻 雜物中之前’亦可為於將多種糖·合物_地添加於纖 維素@旨摻雜物中之後。 (脂肪族糖酯化合物之較佳態樣） 其次，對所述通式（III)所表示之脂肪族糖酯化合物 之較佳態樣加以說明。於所述通式（ΙΠ)中，所述R2分別 獨立地表示脂肪族基。 於由R2取代時所使用之較佳之脂肪族單羧酸可列舉 乙酸、丙酸、丁酸、異丁酸、吉草酸（valeric acid)、己酸 (caproic acid)、庚酸、辛酸、壬酸、癸酸、2-乙基-己竣 酸、Ί 酸、月桂酸、十三酸、肉豆謹酸（myristic acid )、 十五酸、標糊酸（palmitic acid)、十七酸、硬脂酸、十九 酸（nonadecanoic acid )、花生酸（arachidic acid )、二十二 酸（behenic acid )、二十四酸（lignoceric acid )、二十六酸 (cerotic acid )、二十七酸（heptacosanic acid )、褐煤酸 (montanic acid )、蜂蠛酸（melissic acid )、三十二酸 (lacceric acid)等飽和脂肪酸；十一烯酸（undecylenic acid)、油酸（oleic acid)、己二烯酸（sorbic acid)、亞麻 油酸（linolicacid)、次亞麻油酸（linolenic acid)、花生油 201213409 酸（arachidonic acid)、辛烯酸（octen〇ic acid)等不飽和 脂肪酸等。 較佳之脂環族單羧酸之例可列舉環戊烷曱酸、環己烷 曱酸、環辛烷曱酸、或該些酸之衍生物。 較佳的是所述R2分別獨立地表示非環式脂肪族基，較 佳的是所有之R2均表示非環式脂肪族基。 較佳的是所述R2表示2種以上脂肪族基。 於脂肪族單羧酸中，較佳的是所述通式（III)所表示 之脂肪族糖酯化合物至少經乙酸取代。亦即，較佳的是所 述通式（III)中之所述]^2之至少一個表示乙醯基。 匕另一方面，更佳的是所述R2中之至少一種表示分支狀 之脂肪族基，特佳岐於賴R2纟示2種以上脂肪族基之 情形時僅僅—種表示分支狀脂職基。其巾’所述通式 (ΙΠ)所表示之脂肪族糖酯化合物較佳的是除乙酸以外亦 3經2異7取代。亦即’較佳的是所述通式（III)中之所 f R包含乙醯基與異丁醯基，自光學性能經時 考慮，較佳的是僅僅包含㈣基與異了醯基。k匕之觀點In the case of the method of forming a cellulose ester film, a compound which is a derivative of a sugar which is a sucrose skeleton is disclosed in International Publication No. WO2009/011228 (Patent Document 1). Then, one part of the base 11 remains, and at least two or more substituents having different numbers of OH groups are further combined, so that the volatile component is small at the time of film formation, and no bleeding occurs. Further, in the patent document, there is a description that by using a mixture of a low-substrate and a high-substituted sugar ester, the substantial deviation of the degree of thiol substitution of the cellulose ester molecule can be effectively compensated. After saponification, the long-lasting property is high, and the adhesion to the polarizing element and the durability of the polarizing plate are improved. However, there is no mention in the patent document 1 that any combination of the secret and non-fat sugar can be mentioned. Further, in the example of Patent Document 1, as the sugar ester plasticizer, the degree of substitution of the sucrose meta-formate (which has an aromatic group as a substituent in the side chain) is mainly different. Studies on a mixture of three types of substituents. Although other examples are disclosed in the patent literature, all combinations of several kinds of aromatic sugar esters are used in combination, or only a combination of several kinds of aliphatic sugar esters are used in combination. Further, it is disclosed in International Publication No. WO2009/031464 (Patent Document 2) that the haze can be reduced by using a low-substituent which remains as a part of the OH group of the compound which is a derivative of the sucrose skeleton sugar, and is improved by The coating of the hard coat layer is uneven and the contrast of the drain region is improved. In the scaly literature 2, as a sweet and sour plasticizer, in addition to the aromatic sweet and sour vinegar, an aliphatic sugar ester having an aliphatic group as a substituent in the side chain is also used, but the case of mixing the two is not disclosed. There is no indication that the two are mixed. On the other hand, an optical compensation film for expanding the viewing angle, changing the 201213409--IT-good image coloring, and improving the contrast in the liquid crystal display device is a well-known technique. In the most widely used VA (Vertically Aligned) mode (vertical alignment mode), TN mode, etc., an optical compensation film in which optical characteristics (for example, Re value and Rth value) can be controlled to a desired value can be required. In the adjustment of the optical characteristics suitable for the VA mode, it is necessary to extend the processing. Therefore, it is necessary to face the problem of the surface failure caused by the surface manufacturing process. On the other hand, when the inventors of the present invention used the sugar ester plasticizer described in the above documents, the occurrence of an abnormal operation or a surface failure of the manufacturing apparatus due to the volatilization of the additive was not satisfied. Further, the inventors of the present invention and the Rt or the orthogonal transmittance of the polarizing plate are studied in the wet heat environment with the phase (4) impurity energy, and it is known that the performance of the wire is not satisfied. SUMMARY OF THE INVENTION An object of the present invention is to provide a cellulose g film having a small surface failure, a small optical property change over time, and a small amount of time-dependent change in the polarizing plate when the film is attached to a polarizing plate. Inventors and others have made intensive studies to solve the above problems, and two have found that when using aromatic sugars, it is easy to cause changes in the optical ship caused by the use of the same. So, what about the degree of substitution? When two or more kinds of esters are mixed and an aliphatic sugar ester is mixed, the composition may be formed over time when the aromatic sugar ester is used, and the present invention may be simultaneously carried out. 6 201213409 As a result of intensive research, it has been found that the above problems can be solved by the present invention having the following constitution.纤维素] a cellulose ester film containing a cellulose ester, an aromatic sugar ester compound represented by the following formula (1), an aromatic sugar s compound represented by the following formula (11), and the following An aliphatic saccharide compound represented by the formula, wherein an average ester substitution degree of the aromatic sugar ester compound represented by the formula and the aromatic sugar ester compound represented by the formula (π) is less than 94 %, (1) (H〇)mG-(L-R1)n (Π) (HOVG-CL-R1^ (III) (H〇)t-G'-(L,-R2)r (in the formula (I)~ In the general formula (m), hydrazine and G each independently represent a monosaccharide residue or a second thief H, and represent a (qua) group or an aromatic group, at least one represents an aromatic group; and R2 independently An aliphatic group; L and L each independently represent a divalent linking group; m represents an integer above 〇, n, p&q independently represent an integer above 丨, 犷 represents an integer of 3 or more, and t represents 〇 The above integer; wherein m + ng4, p + , m &gt; p, n < q ; and m + n and p + q are respectively associated with a cyclic acetal structure which assumes that the G is not a residue but the same skeleton Unsubstituted In the case of the oxime, the number of hydroxyl groups is equal, and r+t is equal to the number of hydroxyl groups in the case of the unsubstituted saccharide of the cyclic acetal structure which assumes the G, not the residue but the same skeleton. The cellulose ester film according to the above [1], wherein R2 in the formula (III) represents two or more aliphatic groups. 201213409, [3] 如Π] or [2] The cellulose ester film according to the above formula (III), wherein the fiber of the formula (III) represents a disaccharide residue. [4] The fiber according to any one of [1] to [3] The ester film of the above formula (I) and the formula (II) is a sucrose skeleton, and the aromatic sugar ester compound represented by the formula (I) The average ester substitution degree of the aromatic sugar ester compound represented by the formula (II) is 5 to 7.5. [5] The cellulose ester film according to [4], wherein the formula (II) The amount of the aromatic sugar ester in which q is 8 is the total amount of the aromatic sugar ester compound represented by the above formula (I) and the aromatic sugar ester compound represented by the above formula (Π). Less than 20 wt%. [6] as [ The cellulose ester film according to any one of [1], wherein the formula (I) and the formula (II) are L, and the formula (III) Said U in each of them independently represents a single bond, 〇_, _(;; 〇_, (R11 represents a substituent of one valence). [7] As in [1]~[6] A cellulose ester film according to any one of the preceding claims, wherein said ri of said formula (I) and said formula (Π), and said R2 of said formula (III) are each independently The ground represents the base. [8] The cellulose ester film according to any one of [1] to [7], wherein the Ri in the general formula (I) and the general formula (II) represents a beryl醯基. [9] The cellulose ester film according to any one of [1] to [8] wherein R2 in the formula (III) independently represents an acyclic aliphatic group. The cellulose vine film according to any one of [1] to [9] wherein at least one of the R2 in the formula (III) represents a branched fat. Family base. [11] The cellulose vinegar film according to any one of [1] to [1], characterized in that the above-mentioned formula (III) contains only an ethylene group and an isobutyl group. . [12] A polarizing plate having a polarizing element and a protective film disposed on both sides of the polarizing element, wherein at least one of the protective films is any one of [1] to [11] The cellulose ester film. [13] A liquid crystal display device comprising a liquid crystal cell and a polarizing plate disposed on both sides of the liquid crystal cell, wherein at least one of the polarizing plates is a polarizing plate according to [12]. [Effects of the Invention] According to the present invention, it is possible to provide a cellulose ester film having a small surface failure, a small change in optical properties over time, and a small change in the temporal performance of the polarizing plate when incorporated into a polarizing film as a film. Further, a polarizing plate using a small change in the temporal properties of the cellulose ester film can be provided. Further, a liquid crystal display device having good display quality using the above film or polarizing plate can be provided. [Embodiment] Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below is based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In addition, in the specification of the present application, "~" is used as a lower limit value and an upper limit value inclusive of numerical values described before and after. 201213409 ** [Cellulose ester film] The cellulose ester film of the present invention (hereinafter also referred to as the film of the present invention) contains a cellulose ester, an aromatic sugar ester compound represented by the following formula (1), and the following The aromatic sugar ester compound represented by the formula (II) and the aliphatic sugar ester compound represented by the following formula (III), characterized in that the aromatic sugar ester compound represented by the above formula U) The average ester substitution degree of the aromatic sugar ester compound represented by the above formula (η) is less than 94%. · (I) (hol-g-cl-r, (II) (HO) pG-(L-Rl)q (III) (HO)tG 丨-(L,-R2)r - 0 (in general formula ( i)~ In the general formula (m), G&G independently represents a monosaccharide residue or a disaccharide residue, and R1 independently represents an aliphatic group or an aromatic group, at least - a lining-based group. The ground represents an aliphatic group. L and L' each independently represent a divalent linking group. m represents an integer above 〇, and n, p&q independently represent an integer above 丨, ^ represents an integer of 3 or more, and t represents 〇 the above integer, where m + n^4, P + qd ' m > p ' n &lt; q. * and ' m + n and p + q respectively with the ring that assumes that G is not a residue but the same skeleton The number of hydroxyl groups in the case of an unsubstituted saccharide having an unsubstituted saccharide structure, r + t and an unsubstituted sugar of a cyclic acid-reducing structure which assumes the g, which is not a residue but the same skeleton In the following, the cellulose ester film of the present invention will be described. <Sugar ester compound> The film of the present invention contains the aromatic sugar-cooled 201213409 represented by the following formula (1). Aromatic sugar a compound, an aliphatic sugar ester compound represented by the following formula (πι), and an aromatic sugar ester compound represented by the above formula (1) and an aromatic sugar ester represented by the above formula (π) The average ester substitution degree of the compound is less than 94%. (1) (HCOm-GAR, (II) (UO)rG-(L-Rl)q (ΙΠ) (H〇)rG, -(L,-R2)r In the general formulae (1) to (III), G and G each independently represent a monosaccharide residue or a di-based group. W is divided into a surface (4) an aliphatic group or an aromatic group 'at least one of which indicates a material group. The radical r2 represents an aliphatic group. L and L each independently represent a divalent linking group. m represents an integer above 〇, η, p and q each independently represent an integer of 1 or more, and r represents 3 or more. An integer, (indicating an integer above 〇, where m + , P + q^4, m &gt; p ' n &lt; q. Moreover, m + n and p + q are respectively assumed to be the mechanical basis of the G The unsubstituted sugar of the cyclic structure of the time frame, in the case where the base number is equal, and the unsubstituted sugar of the ring-like secret structure of the same skeleton is assumed to be the G, not the residue, and the same skeleton. Hydroxyl number Specifically, in the present invention, a mixture of a sweet and sour compound is used, and a plurality of aromatic (tetra) compounds and aliphatic sugar compounds having different degrees of substitution of g| are mixed so as to satisfy the above conditions. By adding the sweet and sour compound mixture to the citric acid (10) towel, it is possible to obtain a small surface failure, a small change in optical properties, and a change in the temporal property of the polarizing plate when it is incorporated into the polarizing plate as a warranty. Shouted the vegetarian vinegar film. 201213409 The following is a preferred range for the respective sugar ester compounds used in the mixture of the sugar ester compounds, and a preferred one of the sugar ester compounds each satisfying the formula (1) to the formula (ΠΙ). The scope is explained. (Protection of the respective sugar ester compounds) Each of the sugar ester compounds used in the mixture of the sweet and sour compound has a monosaccharide residue or a sugar residue as a skeleton. That is, in the above formula () to formula (III), G and G' each independently represent a monosaccharide residue or a disaccharide residue. The sugar ester compound means a compound obtained by ester-bonding at least one of a substituent group (e.g., a hydroxyl group or a carboxyl group) constituting the sugar skeleton structure of the compound to at least one substituent. That is, the sugar ester compound herein also includes a generalized sugar derivative, and for example, a compound containing a sugar residue such as gluconic acid as a structure. That is, the sugar ester compound also contains an ester of glucose and a carboxylic acid, and an ester of gluconic acid and an alcohol. The tactile compound represented by the above formula (I) to formula (III) which can be used in the present invention is preferably a compound having a (tetra) sucrose structure or a sucrose structure. In the case of having a furanose structure or a pyranose structure as a sugar skeleton, in the above formulae (I) to (III), m + n24, p + qg4 and ]: may be satisfied. Moreover, in the case of having a furanose structure or a sucrose structure as a sugar skeleton, '$ can satisfy the following conditions: m + n and p + q are respectively assumed to be phased with the G-plane The unsubstituted enthalpy of the ring structure, in which case the number of radix is equal, (1) the unsubstituted saccharide of the ring-shaped secret structure of the same θ frame assumed to be the G, not the residue) 12 201213409 The number of hydroxyl groups is equal. The upper limit of 'P + q and ... can be determined to be 5 m &amp; Aa, or G is a early sugar residue, and then the right is a sugar residue to become 8. Preferred formula (1) - The compound of the formula (ΙΠ) represented by the formula (ΙΠ), the compound of the sugar structure or the compound of the G or the sugar of the sugar structure, or two of the bonds The G^G of at least one of the sucrose-glycodose structure is a compound of a disaccharide residue: B) + or a part of the OH group is acetated. However, the present invention The mixture of sugar ester compounds used in the above formula is characterized in that, in the general formula (I) and the general formula (11), full sm &gt; p &amp; n &lt; q, also =, at least said The oxime H group of the sugar ester compound represented by the formula (I) is completely esterified. By using a plurality of aromatic sugar ester compounds having different degrees of ester substitution as described above, the volatility in the production step is low. Further, it becomes difficult to exude from the cellulose ester film after film formation. Examples of the compound (A) include glucose, galactose, mannose, fructose, xylose or arabinose, but are not limited to these compounds. Examples of (B) include lactose, sucrose, nystose, IF fructosyl nystose, stachyose, maltitol, lactitol, and lactulose (iactul〇se) ), cellobiose, maltose, cellotriose, maltotriose, raffinose or kestose. In addition, gentiobiose, gentian three can also be mentioned. Sugar, gentiantetraose, xylotriose 13 201213409 t ▲ 丄 (xylotriose), lacto-oligosaccharide (iact〇sucr〇se), etc., but not limited to these compounds. Among these compounds (A) and compounds ( B) is particularly good for both furanose structure and pyranose structure The compound is preferably sucrose, canetriose, cane sugar, cane, pentasaccharide, stachyose, etc., more preferably 'sucrose. Moreover, in compound (B), there are 2 bonds. A compound having at least one of a furanose structure or a ?-orose structure is also preferred. The substituents used for esterification of all of the oxime H groups in the compound (A) and the compound (B) are There is no particular limitation. Among them, it is preferred to use a single ship. That is, it is preferable that the above formula (1) and the above-mentioned formula (Π) are in Ri, and in the formula (ΠΙ) The R2 independently represents a sulfhydryl group. The monocarboxylic acid is not particularly limited, and a known aliphatic monocarboxylic acid, alicyclic monorexic acid, aromatic monocarboxylic acid or the like can be used. The tickic acid used may be one type or a mixture of two or more types. In the case where the R1 or the R2 is plural, they may be the same or different from each other. On the other hand, it is preferred that the above formula (D and the above-mentioned L in the formula (11) and the above-mentioned formula (πΐ) independently represent a single bond, -〇 -, -C〇-, -NR11- (wherein R11 represents a monovalent substituent); and when the L1 or the L' is plural, they may be the same or different. From the viewpoint that 1 and R2 can be easily substituted by a mercapto group, it is preferred that the L1 or the l represents -0-. (Expressed by the general formula (I) and the general formula (II) A mixture of the aromatic oxime ester compound 201213409) Next, a preferred aspect of the aromatic sugar ester compound represented by the above formula (1) and formula (π) will be described. In the formula (11), the R1 each independently represents an aliphatic group or an aromatic group, and at least one represents an aromatic group. Among them, it is preferred that the R1 is only a member of the group, and more preferably All the aromatic groups represented by the above formula (1) and the aromatic sugar ester compound represented by the above formula (II) are characterized in that all of R1 represents the same aromatic group. The average vinegar substitution degree is less than 94%. By the above, the average ester substitution degree of the mixture of two or more kinds of aromatic sweet and sour compounds is less than 94%, and the haze of the obtained cellulose ester film can be remarkably changed. It is small and can be suitably used as an optical film in a polarizing plate or a liquid crystal display device. It is preferable from the viewpoint of reducing the temporal change of the orthogonal transmittance in a moist heat environment when incorporated into a polarizing plate. The average ester substitution degree of the aromatic sugar ester compound represented by the above formula (1) and the aromatic sugar ester compound represented by the above formula (11) is 62% or more and less than 94%. From the viewpoint of being able to reduce the temporal change of the positive-parent transmittance in a hot and humid environment when incorporated into a polarizing plate, it is more preferable that the G in the above formula and the formula (II) is The sucrose skeleton, the average ester substitution degree of the aromatic sugar ester compound represented by the above formula (1) and the aromatic sugar ester compound represented by the formula (n) is 5 to 75, and particularly preferably 5 5 ～7.0. Further, in the above formula (I) and formula (11), m represents 〇 to 15 201213409 In the present invention, the above-mentioned integers, n and pgq, respectively, represent &gt;p, n &lt; q. In the present invention, it is preferable from the viewpoint that the haze of the obtained cellulose vinegar film is remarkably small. In the case where G is a disaccharide residue, the amount of the aromatic sugar ester in which q is 8 in the formula (II) is relative to the aromatic sugar ester compound represented by the formula (I) The total amount of the aromatic sugar ester compound represented by the above formula is less than 2% by weight. When the G is a disaccharide residue, it does not have a hydroxyl group as a substituent. The content of the sugar ester compound is preferably 20 wt% or less, more preferably 15 wt% or less, particularly preferably 10 wt% or less, and further preferably 5 wt% with respect to the content of all the aromatic sugar esters. %the following. On the other hand, in the present invention, the aromatic sugar ester compound represented by the above formula (1) and the aromatic sugar ester compound represented by the above formula (II) are wherein the G is a disaccharide residue. In the case, it is preferable that 11 is 3 or more, and 5 or more is also preferable. That is, in the present invention, it is preferred that at least the aromatic sugar ester compound contained in the aromatic sugar ester compound mixture is at least 3 substituents or more, and at least 5 substituents or more is also preferable. When the aromatic sugar ester compound is a saccharide, the content of the acetated substituent is 3 to 5, and the substitution ratio of the 1-5 substituent is higher than that of the aromatic sugar S. The best is 10% ~ 7〇%, and more preferably 20% ~ 50%. The content of the 6 substituents to 7 substituents is preferably from 20% to 85%, more preferably from 20% to 75%, based on the total of the aromatic sugar ester compound. An example of a family of monodecanoic acid can be 201213409. The benzene phthalic acid, toluic acid is equal to the benzene ring of benzoic acid, and an aromatic monocarboxylic acid having an alkyl or alkoxy group introduced therein, cinnamic acid An aromatic monocarboxylic acid having two or more benzene rings, such as benzolic acid, biphenyl acid, naphthic acid, tetralincarboxylic acid, and derivatives thereof; Specific examples thereof include: xylic acid, 2,3-dimethylbenzoic acid, 3,5-dimercaptobenzoic acid, 2, M -prehnitylic acid, 2,3,5-trimethyl benzoic acid, 2,4,5-triphenyl benzoic acid, 2, 4,6-trimethyl benzoic acid, α-isodurylic acid, cuminic acid, α-toluene acid, hydrogenation Ato acid (hydratropic acid), atropic acid, hydrogen cinnamic acid, salicylic acid, o-anisic acid, m-anisic acid, p-anisic acid, mucha oil Creosote oil acid, 〇-homosalicylic acid, m-homosalicylic acid, p-homosalicylic acid, o-pyrocatechuic acid ''2'-resorcylic acid, vanillic acid, isovanillic acid, 3,4-dimethoxybenzoic acid, 2,3 -o-veratric acid, gallic acid, asaronic acid, mandelic acid, homoanisic acid, high vanillic acid (homovanillic acid), homoveratric acid, o-homoveratric acid, phthalonic acid, to the broad horse 17 201213409 / V/Jpli R1 in the formula (II) represents a benzoyl group. There is no particular limitation on the i side, and a known method can be used. Moreover, the mixing timing of the rare species of the substituted shirt and the (four) family of saccharides is:: in the case of the solution solution filming method, it may be before adding to the cellulose ester dopant. A variety of sugar complexes were added after the cellulose@thinking dopant. (Preferred aspect of aliphatic sugar ester compound) Next, a preferred aspect of the aliphatic sugar ester compound represented by the above formula (III) will be described. In the above formula (ΙΠ), the R 2 independently represents an aliphatic group. Preferred aliphatic monocarboxylic acids for use in the replacement of R2 include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, and citric acid. , citric acid, 2-ethyl-hexanoic acid, citric acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid Acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, heptacannic acid Acid), montanic acid, melissic acid, laccolic acid, etc.; undecylenic acid, oleic acid, sorbic acid ), linolic acid, linolenic acid, peanut oil 201213409 acid (arachidonic acid), octenoic acid (octen ic acid) and other unsaturated fatty acids. Examples of preferred alicyclic monocarboxylic acids include cyclopentane decanoic acid, cyclohexane decanoic acid, cyclooctane decanoic acid, or derivatives of these acids. Preferably, said R2 independently represents an acyclic aliphatic group, and preferably all of R2 represents an acyclic aliphatic group. Preferably, R2 represents two or more aliphatic groups. In the aliphatic monocarboxylic acid, it is preferred that the aliphatic sugar ester compound represented by the above formula (III) is substituted with at least acetic acid. That is, it is preferred that at least one of the above-mentioned formulas of the formula (III) represents an ethyl group. On the other hand, it is more preferable that at least one of the R2 represents a branched aliphatic group, and particularly preferably, when the R2 represents two or more aliphatic groups, only the branched fatty group is represented. . The aliphatic sugar ester compound represented by the above formula (ΙΠ) is preferably substituted with 2 and 7 in addition to acetic acid. That is, it is preferred that f R in the above formula (III) contains an ethyl fluorenyl group and an isobutyl fluorenyl group, which are considered from the viewpoint of optical properties over time, and preferably contain only a (tetra) group and an isomeric fluorenyl group. K匕's point of view

耐久纖維素賴之面狀故障，錢善偏光板 表示二糖^考慮，較佳的是所述通式（ΠΙ)中之所述GI 1/7〜4/4,更佳的是1/7〜3/5 之情ίΐΊ111)中之所㈣僅包含乙醯基與異丁醒基 乙酿基/里於所述G，為二糖殘基時，其比例較佳的是 是2/6 特佳的 201213409 該些經脂肪族單羧酸取代之脂肪族糖醋化合物之製造 方法例如於曰本專利特開平8-245678號公報中所記載。 所述酯化化合物之製造例之一例如下所述。 於葡萄糖（29.8 g、166 mmol)中添加有吡啶（1〇〇 ml) 之溶液中滴加乙酸酐（200 ml)，使其反應24小時。其後， 藉由蒸發對溶液加以濃縮而投入至冰水中。放置1小時 後，以玻璃過濾器進行過濾，將固體與水分離，使玻璃過 遽器上之固體溶解於氣仿中，藉由冷水進行分液直至其成 為中性為止。將有機層分離後，藉由無水硫酸鈉加以乾燥。 以過濾除去無水硫酸鈉後，藉由蒸發除去氣仿，進一步藉 由減壓乾燥而獲得葡萄糖五乙酸酯（glucose pentaacetate ) (58.8 g、150 mmo卜90.9%)。另外，可使用上述單羧酸 而代替上述乙酸肝。 以下 一 列舉可於本發明中使用之通式（D〜通式（m 所表不之細旨化合物之具㈣，但本發明並不限定於此。 =且。於下述之具體例中未記載各糖酯化合物之酯取+ ;=於不違反本發明之主旨之範圍内使用任意之酯取+ 糖自旨化合物’可設為糖酯化合物混合體。特別是㈤ mi通式（Π)所表㈣錄§旨化合物可選擇滿力 本發明之轉條件之任纽合而使用。 20 201213409 —· — 1— 化合物The surface of the durable cellulose is faulty, and the Qianliang polarizer indicates a disaccharide. Preferably, the GI 1/7 to 4/4 in the formula (ΠΙ) is more preferably 1/7. ~ 3/5 ΐΊ ΐΊ ) ) ) ) ) ) ) ) ) ) ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ ΐΊ 201213409 The method for producing an aliphatic sweet and sour compound substituted with an aliphatic monocarboxylic acid is described in, for example, JP-A-H08-245678. One of the production examples of the esterified compound is as follows. Acetic anhydride (200 ml) was added dropwise to a solution of pyridine (1 〇〇 ml) added to glucose (29.8 g, 166 mmol), and allowed to react for 24 hours. Thereafter, the solution was concentrated by evaporation and poured into ice water. After standing for 1 hour, it was filtered with a glass filter to separate the solid from water, and the solid on the glass filter was dissolved in the air-mesh, and the liquid was separated by cold water until it became neutral. After separating the organic layer, it was dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the gas-like form was removed by evaporation, and further dried under reduced pressure to obtain glucose pentaacetate (58.8 g, 150 mmo, 90.9%). Further, the above monocarboxylic acid may be used instead of the above-mentioned acetic acid liver. The following formula (D) which can be used in the present invention can be used in the present invention (d), but the present invention is not limited thereto. The ester of each of the sugar ester compounds is described as +; = the use of any of the esters in the range which does not violate the gist of the present invention is as follows: the sugar compound compound can be used as a mixture of sugar ester compounds. In particular, (5) mi formula (Π) The compound of Table (4) can be used as a compound of the conditions of the invention. 20 201213409 —· — 1— Compound

R1«R1«

Ο tl -C-CHSTl tl -C-CHS

化合物2 CH2OCOCH3 -Q CH2OR2 Μ I /〇 R20Compound 2 CH2OCOCH3 -Q CH2OR2 Μ I /〇 R20

OR2OR2

Ej| R20/CHi〇COCH3 R2« —C-CHCH3 ' ' CHj OR2 H 化合物3Ej| R20/CHi〇COCH3 R2« —C-CHCH3 ' ' CHj OR2 H Compound 3

化合物4Compound 4

R4= O ti -C-〇2Hs 21 201213409 化合物5R4= O ti -C-〇2Hs 21 201213409 Compound 5

°n 化合物6°n Compound 6

Rfi= II -C-CH3 化合物7Rfi= II -C-CH3 Compound 7

Ο R7« 一C-CH3 化合物8Ο R7« a C-CH3 compound 8

R8« —C-CHj 22 201213409 化合物9R8« —C-CHj 22 201213409 Compound 9

化合物10Compound 10

化合物11 CH2〇R11 i—-0 CH2〇R11 hA \ R11i\〇R11 H/ 0 \H Κ11〇/〇Η,〇Κ11 l 0R11 I f 0R11 H 化合物12Compound 11 CH2〇R11 i--0 CH2〇R11 hA \ R11i\〇R11 H/ 0 \H Κ11〇/〇Η,〇Κ11 l 0R11 I f 0R11 H Compound 12

〇CHs CH2OR12 CH2OR12 R120〇CHs CH2OR12 CH2OR12 R120

CH2〇R12 0M2 0R12 HCH2〇R12 0M2 0R12 H

0 u R12« —C OCHa 23 201213409 «;υ / ν^ριι. 化合物13 CH2OR13 R1300 u R12« —C OCHa 23 201213409 «;υ / ν^ριι. Compound 13 CH2OR13 R130

CH2〇R13 OR13 H R13= _C — ch2 化合物14CH2〇R13 OR13 H R13= _C — ch2 Compound 14

化合物15Compound 15

化合物16Compound 16

ο rig= —c—CHzο rig= —c—CHz

24 201213409 於以下之結構式中，R分別獨立地表示任意之取代 基，多個R可相同亦可不同。24 201213409 In the following structural formulae, R independently represents an arbitrary substituent, and a plurality of R's may be the same or different.

[表1] 化合物 取代基1 取代基2 分子量 種類 取代度 種類 取代度 101 乙醯基 7 苄基 1 727 102 乙酿基 6 苄基 2 775 103 乙醯基 7 苯甲醯基 1 741 104 乙醯基 6 笨曱醯基 2 802 105 苄基 2 無 0 523 106 苄基 3 無 0 613 107 苄基 4 無 0 702 108 乙醯基 7 苯基乙醯基 1 771 109 乙醯基 6 笨基乙醯基 2 847 110 苯甲醯基 1 無 - 446 111 笨曱醯基 2 無 - 550 112 苯曱醯基 3 無 - 654 113 苯甲醯基 4 無 - 758 114 苯曱醯基 5 無 - 862 115 苯甲醯基 6 無 - 966 116 苯曱醯基 7 無 - 1070 117 笨甲醯基 8 無 - 1174 25 201213409[Table 1] Compound Substituent 1 Substituent 2 Molecular Weight Species Degree of Substitution Degree of Substitution Degree 101 Ethyl 7 Benzyl 1 727 102 Ethylene 6 Benzyl 2 775 103 Ethyl 7 Benzopyridyl 1 741 104 Ethylene Base 6 Awkward base 2 802 105 Benzyl 2 No 0 523 106 Benzyl 3 No 0 613 107 Benzyl 4 No 0 702 108 Ethyl 7 Phenylethyl 1 771 109 Ethyl 6 Styrene Base 2 847 110 Benzopyridinyl 1 None - 446 111 Clumdolyl 2 None - 550 112 Phenylhydrazyl 3 None - 654 113 Benzopyridinyl 4 None - 758 114 Phenylhydrazyl 5 None - 862 115 Benzene醯基基6 无 - 966 116 phenyl hydrazino 7 no - 1070 117 笨甲甲基8 No - 1174 25 201213409

[表2] 化合物 取代基1 取代基2 分子量 種類 取代度 種類 取代度 301 乙酿基 6 笨甲醯基 2 803 302 乙醯基 6 苄基 2 775 303 乙酿基 6 苯基乙醯基 2 831 304 苯曱醯基 2 無 0 551 305 苄基 2 無 0 522 306 苯基乙ΘΙ基 2 無 0 579[Table 2] Compound Substituent 1 Substituent 2 Molecular Weight Species Degree of Substitution Degree of Substitution Degree 301 Ethyl Acrylate 6 Strepto-Methyl 2 803 302 Ethyl 6 Benzyl 2 775 303 Ethyl 6 Phenyl Ethyl 2 831 304 phenyl fluorenyl 2 no 0 551 305 benzyl 2 no 0 522 306 phenyl ethyl fluorenyl 2 no 0 579

H OR 26 201213409 [表3]H OR 26 201213409 [Table 3]

(方香族_化合物與脂肪族糖酯化合物 人从將多種滿足以上條件之8旨取代度不同之芳香族二化 :物f斤述脂肪族糖醋化合物混合而添加於纖唯;二 二=僅僅輯取代度不同之芳香族糖醋化== _ 13彳進—步改善賴環境下之膜之光學性能耐 久性與偏光板耐久性。另外，對於所謂Tpp/BDp等公知之 填酸S旨系塑化劑，亦理所當然地可改域之絲性能对久 性與偏光板耐久性。而且，於與硬塗層積層之情形時，亦 可獲得密接性優異、鉛筆硬度亦良好之膜。 本發明之纖維素酯膜較佳的是相對於纖維素酯而言包 含合計lwt%〜30wt%之所述通式（I)及通式（π)所表 示之芳香族糖酯化合物，更佳的是包含5 wt%〜20 wt%， 特佳的是包含5 wt%〜15 wt%。 本發明之纖維素醋膜較佳的是相對於纖維素酯而包含 1 wt%〜3〇 wt%之所述通式（III)所表示之脂肪族糖酯化 合物’更佳的是包含1 wt%〜10 wt%，特佳的是包含1 wt% 〜5 wt%。 27 201213409 物與:ίί)及通式(Π)所表示之芳香族糖醋化合 通式（ΙΠ)所表示之脂肪族糖®1化合物之混人比 加奮/沪#/、中較佳的疋方香族糖酯化合物之添 曰f日肪喊化合物之添加量（重量比）S過卜更佳的 疋2〜1〇，特佳的是3〜5。 更1的 f發明之纖維素g旨難佳岐相躲齡相而包含 a计1 wt%〜30 wt%之所述通&lt; ⑴〜通式（叩所表干 之糖醋化合物，更佳的是包含5 wt%〜3() wt%，特佳 含有W%〜20 wt%，進一步特佳的是含有$ *伙〜^ wt%。若為該範圍内，則無滲出等而較佳。 、而且’於將後述之聚縮合醋塑化劑與所述糖醋化合物 併用之情形時，所歸s旨化合物之添加量（重量份）相 於聚縮合_化劑之添加量（重量份）而言，較佳 加2〜K)倍（重量比），更佳的是添加3〜8倍（重量比^ …而且，於將後述之具有至少2個芳香環的化合物與所 述糖酯化合物㈣之情料，所賴雜合物之添加量（重 量伤）相對於具有至少2個料環之化合物的添加量（重 量份）而言，較佳的是添加2〜1〇倍（重量比），更佳的是 添加3〜8倍（重量比）。 而且，作為多種所述芳香族糖酯化合物與所述脂肪族 糖酯化合物之混合時序，例如於採用溶液成膜法之情形 時，可為添加於纖維素酯摻雜物中之前，亦可為於將多種 糖酯化合物個別地添加於纖維素酯摻雜物中之後。 &lt;聚縮合酯&gt; 28 201213409 可於不違反本發明之主旨之範圍内包含 4縮合s9 (以下亦稱為寡聚物塑化劑）。 所述聚縮合酯可以包含至少一· ，環之二紐）與至少—種脂肪族二魏、= 肪知二醇、至少—種單魏之混合物為原料而獲得。曰 =物塑化劑之較佳例包含：二醇成分與二_成分 之Us旨及其何生物、以及丙烯酸f g| (ma)之 物及其衍生物（以下有時稱為「μα寡聚物塑化劑」） 所述聚縮合醋是二竣酸成分與二醇成分之聚縮合酉，。 -緩酸成分可健包含—種二賊，或者亦可 以上二魏之混合物。其巾，作為二麟成分，較佳 使用包含至少-種芳香族性二親及至少—種脂肪族二= 酸的二鏡成分。另-方面，關於二醇成分錢可勺 含一種二醇成分，或者亦可為2種以上二醇之混合物。= 中，作為二醇成分，較佳的是使用乙二醇及/或平均碳^ 數大於2.0且為3.0以下之脂肪族二醇。 ’、 所述聚縮合酯可較佳地使用日本專利 2010-079241號公報之[0029]〜[0045]中所記載之化合物$ &lt;具有至少2個芳香環的化合物&gt; 本發明之纖維素酯膜亦可於不違反本發明之主旨&quot; 圍内進一步含有具有至少2個芳香環的化合物。3之範 以下，對具有至少2個以上芳香環的化合物加以 較佳的疋具有至少2個以上芳香環的化合物於均勻配 向（uniform alignment)之情形時光學性地表現出正的^ 29 201213409 軸性。 具有至少2個以上芳香環的化合物之分子量較佳的是 300〜1200，更佳的是400〜1〇〇〇。 於將本發明之纖維素酯膜用作光學補償膜之情形時， 為了將光學特性特別是Re控制為較佳之值，有效的是進 行延伸。Re之上升必須增大膜面内之折射率異向性，一個 方法是藉由延伸而提高聚合物膜之主鏈配向。而且，藉由 將折射率異向性大的化合物用作添加劑，可進一步使膜之 折射率異向性上升。例如上述具有2個以上芳香環之化合 物可藉由延伸而傳遞聚合物主鏈排列之力，由此亦可提高 該化合物之配向性，變得容易控制為所期望之光學特性， 具有至少2個芳香環的化合物例如可列舉日本專利 ^ 2〇〇3_344655號公報+所記载之三嗓化合物、日本專利 特=纖·迎43㉟公報中所記载之棒狀化合物、日本^ =特開屬-m884及日本專利特開2_19?37號公報 棒液晶性化合物等。更佳的是上述三嗪化合物或 用。具有至4 2個4香環的化合物亦可併用2種以上而使 &lt;纖維素酯&gt; 發明之纖輪旨财’纖輸旨可列舉：纖唯青 Mb合物，以及以纖維素為 ⑺牛纖維素 官能基而所得的具1 學性地導入 射藝去^ 代之纖維素骨架的化合物。 所述纖維素酷是纖維去伽μ &gt; 难素〃馱之酯。構成所述酯之酸較 201213409 佳的是有機酸，更佳的是幾酸，(Fangxiang nationality _ compound and aliphatic sugar ester compound from a variety of aromatic dimerizations with different degrees of substitution satisfying the above conditions: the mixture of fatty vinegar compounds is added to the fiber and vinegar compound; Only the aromatic saccharification with different degrees of substitution == _ 13 — — — 改善 改善 改善 改善 改善 改善 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学The plasticizer can also be used to change the durability of the filament properties and the durability of the polarizing plate. Moreover, in the case of laminating with the hard coat layer, a film excellent in adhesion and good in pencil hardness can be obtained. The cellulose ester film of the invention preferably contains a total of 1% by weight to 30% by weight of the aromatic sugar ester compound represented by the above formula (I) and the formula (π) with respect to the cellulose ester, more preferably It is contained in an amount of 5 wt% to 20 wt%, particularly preferably 5 wt% to 15 wt%. The cellulose acetate film of the present invention preferably contains 1 wt% to 3 wt% relative to the cellulose ester. The aliphatic sugar ester compound represented by the formula (III) is more preferably contained in an amount of from 1% by weight to 10% by weight. The inclusion ratio is 1 wt% to 5 wt%. 27 201213409 The ratio of the aliphatic sugar to the compound represented by the formula (ΙΠ) represented by the formula (ΙΠ) Jiafen/Shanghai#/, the best addition of the scented aromatic sugar ester compound, the addition amount of the compound (weight ratio) S is better than 疋2~1〇, especially good 3 ~5. The cellulose g of the invention of the first aspect of the invention comprises the above-mentioned 1 wt% to 30 wt% of the above-mentioned &lt; (1) to the formula (the dried sweet and sour compound, preferably It is composed of 5 wt%~3() wt%, especially preferably contains W%~20 wt%, and further preferably contains $* 伙~^ wt%. If it is within the range, it is preferably no bleed, etc. And when the polycondensation vinegar plasticizer described later is used in combination with the sweet and sour compound, the amount of the compound (parts by weight) added to the polycondensation-chemical agent (parts by weight) In addition, it is preferable to add 2 to K times (weight ratio), more preferably 3 to 8 times (weight ratio) and further, a compound having at least two aromatic rings to be described later and the sugar ester In the case of the compound (4), the amount of the hybrid (weight injury) to be added is preferably 2 to 1 times (weight) relative to the amount (parts by weight) of the compound having at least 2 rings. More preferably, it is added 3 to 8 times (by weight). Moreover, as a mixing timing of a plurality of the aromatic sugar ester compounds and the aliphatic sugar ester compound For example, in the case of using a solution film forming method, it may be added before the cellulose ester dopant, or after a plurality of sugar ester compounds are individually added to the cellulose ester dopant. Ester &gt; 28 201213409 may include 4 condensation s9 (hereinafter also referred to as an oligomer plasticizer) within a range not departing from the gist of the present invention. The polycondensation ester may contain at least one and two rings At least a mixture of an aliphatic diwei, an adipic diol, and at least a mono-wei is obtained as a raw material. Preferred examples of the 曰=physical plasticizer include: a diol component and a U-component of the bis component, and a substance thereof, and an acrylic acid fg|(ma) and a derivative thereof (hereinafter sometimes referred to as "μα oligomerization" Plasticizing agent") The polycondensed vinegar is a polycondensation enthalpy of a diterpene acid component and a diol component. - The acid-lowering ingredient can contain a second thief, or a mixture of the above two. As the towel, as the two-component component, a two-mirror component containing at least one aromatic di-parent and at least one aliphatic di-acid is preferably used. On the other hand, the diol component may contain a diol component or a mixture of two or more diols. In the middle of the diol component, it is preferred to use ethylene glycol and/or an aliphatic diol having an average carbon number of more than 2.0 and 3.0 or less. The polycondensation ester is preferably a compound of the formula [0029] to [0045] of the Japanese Patent Publication No. 2010-079241, &lt;a compound having at least two aromatic rings&gt; The ester film may further contain a compound having at least two aromatic rings, without departing from the gist of the present invention. 3 or less, a compound having at least two or more aromatic rings is preferably a compound having at least two or more aromatic rings, and optically exhibits a positive axis in the case of uniform alignment. Sex. The molecular weight of the compound having at least two aromatic rings is preferably from 300 to 1200, more preferably from 400 to 1 Torr. In the case where the cellulose ester film of the present invention is used as an optical compensation film, in order to control the optical characteristics, particularly Re, to a preferable value, it is effective to carry out the stretching. The rise of Re must increase the refractive index anisotropy in the film surface. One method is to increase the main chain alignment of the polymer film by stretching. Further, by using a compound having a large refractive index anisotropy as an additive, the refractive index anisotropy of the film can be further increased. For example, the compound having two or more aromatic rings can transfer the force of the polymer main chain by stretching, thereby improving the alignment of the compound and easily controlling the desired optical characteristics, and has at least two Examples of the compound of the aromatic ring include a triterpenoid compound described in Japanese Patent Publication No. 2-3-344655, a rod-shaped compound described in Japanese Patent Publication No. 4335, and a Japanese genus-specific genus- M884 and Japanese Patent Laid-Open Publication No. Hei 2-19-37. More preferably, the above triazine compound is used. The compound having up to 42 four-fragrance rings may be used in combination of two or more kinds, and the cellulose ester of the invention may be exemplified by a fiber-optic Mb compound and a cellulose. (7) A bovine cellulose functional group obtained by a method of introducing a cellulose skeleton into the art. The cellulose is a fiber degreased &gt; The acid constituting the ester is better than the organic acid in 201213409, and more preferably the acid.

酸之纖維素酯。 進一步更佳的是碳原子數 ί子數為2〜4之低級脂肪 作為本發明中所使用之纖維素S旨原料的纖維素 織（c_n Hnter)或木聚（w〇〇d pulp)(闊葉樹聚 ，有棉 、針葉 樹聚）等’峰意之原料纖维素所得之纖維素酯均可使用) 亦可根據情況*混合使用。關於該麵料纖維素之詳細記 載，例如可使用「轉材料講座（丨7 )纖維料樹脂」（丸 澤、宇田著、日刊工業新聞社、聊年發行）絲明協會 公開技術報告2001-1745 (第7頁〜第8頁）中所記載之 纖、、隹素對於本發明之纖維素酯膜而言並無特別之限定。 其次，對以上述之纖維素為原料而製造之本發明中適 宜之纖維素酯進行記載。 本發明中所使用之纖維素酯是纖維素之羥基被醯化而 成的纖維素酯，其取代基可使用醯基之碳數為2之乙醯基 至碳數為22之醯基之任意基。於本發明中，關於纖維素酯 中的對纖維素之羥基之取代度，並無特別限定，可測定對 纖維素之羥基進行取代之乙酸及/或碳數為3〜22之脂肪 酸的結合度，藉由計算而獲得取代度。測定方法可基於 ASTMD-817-91 而實施。 如上所述，關於對纖維素之羥基之取代度，並無特別 之限疋’對纖維素之羥基的醯基取代度較佳的是2.〇〇〜 2.95。 對纖維素之羥基進行取代之乙酸及/或碳數為3〜22 201213409 Λ. ，脂^酸中’料碳數為2〜22之醯基，▼為脂肪族基亦 可為芳基，並無特別之限定，可單一亦可為2種以上之混 合，。該些例如為纖維素之烷基羰基酯、烯基羰基酯、芳 香族羰基酯、或芳香族烷基羰基酯等，亦可分別具有進一 步被取代之基。該些較佳之醯基可列舉乙醯基、丙醯基、 丁醯基、庚醯基、己醯基、辛醯基、癸醯基、十二醯基、 士二醯基、十四醯基、十六醯、十八醯基、異丁醯基、第 二丁醯基、環己基甲醯基、油醯基、苯甲 肉桂醯基等。該些中較佳的是乙醯基、㈣基Γϋί、 十二醯基、十八醯基、第三丁醯基、油醯基、苯甲醯基、 萘甲醯基、肉桂醯基等，更佳的是乙醯基、丙醯基、丁酿 基。最佳之基為乙醯基。 …於上述對纖維素之羥基進行取代之醯基取代基中，於 實質上包含乙醯基/丙醯基/丁醯基之至少2種之情形時，、 較佳的是其總取代度為2.50〜2·95，更佳的是醯▲取代度 為2.60〜2.95，進一步更佳的是2.65〜2,95。 上述纖維素酯之醯基取代基僅包含乙醯基之情形時， 較佳的是其總取代度為，〜2.95。更佳的是取代度為 2.40〜2.95，進一步更佳的是2.85〜2.95。 本發明中較佳使用之纖維素醋之聚合度以黏度平均聚 合度計而言為180〜700，於乙酸纖維素中更佳的是18〇〜 550，進一步更佳的是180〜4〇〇，特佳的是18〇〜35〇。若 ，合度為該上限值以下’則纖維素_之摻雜物溶液的黏度 並不過於變高，可容易地藉由流鑄（easting)而製作膜， 32 201213409Acidic cellulose ester. Further more preferably, the lower fat having a carbon number of 2 to 4 is a cellulose woven (c_n Hnter) or a wood poly (w〇〇d pulp) (a broad-leaved tree) which is a raw material of the cellulose S used in the present invention. Poly, cotton, conifer poly), etc., can be used as a cellulose ester obtained from the raw material of the peak. For the detailed description of the cellulose in this fabric, for example, the "Transfer Materials Lecture (丨7) Fiber Resin" (Maruzawa, Uda, Nikkan Kogyo Shimbun, and the Year of the Year) can be used. The cellulose and alizarin described in the seventh to eighth pages are not particularly limited to the cellulose ester film of the present invention. Next, a cellulose ester suitable for the present invention produced by using the above cellulose as a raw material will be described. The cellulose ester used in the present invention is a cellulose ester obtained by deuteration of a hydroxyl group of cellulose, and the substituent may be any of a fluorenyl group having a carbon number of 2 to an alkyl group having a carbon number of 22. base. In the present invention, the degree of substitution of the hydroxyl group of the cellulose in the cellulose ester is not particularly limited, and the degree of binding of the acetic acid substituted for the hydroxyl group of the cellulose and/or the fatty acid having the carbon number of 3 to 22 can be measured. , the degree of substitution is obtained by calculation. The measurement method can be carried out based on ASTM D-817-91. As described above, there is no particular limitation on the degree of substitution of the hydroxyl group of the cellulose. The degree of substitution of the thiol group for the hydroxyl group of the cellulose is preferably 2. 〇〇 to 2.95. The acetic acid and/or the carbon number of the cellulose hydroxy group is 3~22 201213409 ,. In the fatty acid, the carbon number of the material is 2 to 22, and the aliphatic group may be an aryl group, and There is no particular limitation, and a single or a mixture of two or more types may be used. These alkyl carbonyl esters, alkenyl carbonyl esters, aromatic carbonyl esters, or aromatic alkyl carbonyl esters such as cellulose may each have a further substituted group. Preferred examples of the sulfhydryl group include an ethyl group, a propyl group, a butyl group, a butyl group, a fluorenyl group, a hexyl group, a decyl group, a fluorenyl group, a fluorenyl group, a bismuth group, a tetradecyl group, and a hexadecanthene group. , 18 fluorenyl, isobutyl decyl, second butyl fluorenyl, cyclohexylmethyl fluorenyl, oleoreyl, benzyl cinnamyl and the like. Preferred among these are ethyl ketone, (iv) ruthenium, ruthenium, octadecyl, tert-butyl, ruthenium, benzylidene, naphthyl, cinnamyl, etc., more preferably It is an ethyl group, a propyl group, and a butyl group. The best base is acetamidine. In the case where the above-mentioned thiol substituent substituted for the hydroxyl group of the cellulose substantially contains at least two kinds of an ethyl group, a fluorenyl group, and a butyl group, the total degree of substitution is preferably 2.50. 2.95, more preferably 醯▲ degree of substitution is 2.60~2.95, and even more preferably 2.65~2,95. When the thiol substituent of the above cellulose ester contains only an ethyl fluorenyl group, it is preferred that the total degree of substitution is 〜2.95. More preferably, the degree of substitution is 2.40 to 2.95, and further preferably 2.85 to 2.95. The cellulose vinegar preferably used in the present invention has a degree of polymerization of from 180 to 700 in terms of viscosity average degree of polymerization, more preferably from 18 Å to 550 in cellulose acetate, and still more preferably from 180 to 4 Å. The best one is 18〇~35〇. If the degree of bonding is below the upper limit, the viscosity of the cellulose-based dopant solution is not too high, and the film can be easily formed by easting. 32 201213409

--- - - r --L &gt; 因此較佳。若聚合度為該下限值以上，則並不產生所製作 之膜之強度降低等不良情況而較佳。黏度平均聚合度可藉 由宇田等人之極限黏度法{宇田和夫、齊藤秀夫、「纖維學 會刊」、第18卷第i號、第105頁〜第ι2〇頁（1%2年）} 而測定。該方法於日本專利特開平9—95538號公報中亦有 所詳細記載。 而且，本發明中較佳使用之纖維素酯之分子量分布可 藉由凝膠滲透層析法而評價，較佳的是其多分散性指數 Mw/Mn (Mw為重量平均分子量、Mn為數量平均分子量） 小’分子量分布狹窄。具體之Mw/Mn之值較佳的是1.〇〜 4.0 ’更佳的是2.0〜4.0，最佳的是2.3〜3.4。 &lt;纖維素酯膜之製造方法&gt; 本發明之纖維素酯膜可藉由溶劑澆鑄法而製造。於溶 劑澆鑄法中，使用於有機溶劑中溶解有纖維素酯之溶液（摻 雜物）而製造膜。 有機溶劑較佳的是包含選自碳原子數為3〜12之趟、 碳原子數為3〜12之酮、碳原子數為3〜12之酯及碳原子 數為1〜6之鹵化烴（halohydrocarbon)之溶劑。 驗、酮及酯亦可具有環狀結構。具有二個以上醚、酉同 及酯之官能基（亦即-0-、-CO-及-COO-)之任意者的化合 物亦可作為有機溶劑而使用。有機溶劑亦可具有如醇性經 基之其他官能基。具有二種以上之官能基的有機溶劑之情 形時，較佳的是其奴原子數為具有任意之官能基的溶劑之 上述較佳之碳原子數範圍内。 33 201213409 jo t u^uii 碳原子數為3〜12之_類之例包括二異丙趟、二曱氧 基甲烷、二曱氧基乙烷、1，4-二噁烷、1，3-二氧戊環 (dioxolan)、四氫呋喃、苯甲醚及苯基乙基醚。 碳原子數為3〜12之酮類之例包括丙酮、曱基乙基 酮、二乙基酮、二異丁基酮、環己酮及曱基環己酮。 碳原子數為3〜12之酯類之例包括曱酸乙酯、甲酸丙 酯、曱酸戊酯、乙酸曱酯、乙酸乙酯及乙酸戊酯。 具有二種以上官能基之有機溶劑之例包括乙酸乙 氧基乙酯、2-曱氧基乙醇及2-丁氧基乙醇。 鹵化烴之碳原子數較佳的是1或2，最佳的是丨。鹵化 烴之齒素較佳的是氣。齒化烴之氫原子被取代為_素之比 例較佳的是25 mol%〜75 mol%，更佳的是3〇 m〇1%〜7〇 mol%，進一步更佳的是35 m〇1%〜幻m〇1%，最佳的是4〇 mol%〜60 mol%。二氯甲烷是代表性的鹵化烴。 亦可將二種以上有機溶劑混合使用。 曰由包含於GC以上之溫度（常溫或高溫）下進行 理之-般性方法，可㈣纖維麵驗。溶液之調製可 用通常之溶誠鑄法中之摻雜物之調製方法及裝置而 1牯ίι: ’於一般性方法之情形時’較佳的是使用鹵化 (特別疋二氯甲烷）而作為有機溶劑。 纖，钱之量可霞為於所叙溶 二=纖維素醋之量更佳的是10wt%〜30— =主，）中，亦可添加後述之任意添加劑。 各液可藉由於常溫⑽〜价㈡下對纖維素醋與有 34 201213409 溶劑進行攪拌而調製。高濃度之溶液可於加壓及加熱條件 下進行攪拌。具體而言，將乙酸纖維素與，有機溶劑放入至 加壓容器中而加以密閉，於加壓下一面加熱至溶劑於常溫 下之沸點以上、且溶劑不沸騰之範圍的溫度一面進行攪拌。 加熱溫度通常為4〇。(：以上，較佳的是60。(：〜200。(：， 更佳的是80°C〜ll〇°e。 各成分亦可預先粗混合後放入至容器中。而且，亦可 依序投入至容器中。容器必須以可進行攪拌之方式構成。 可注入氮氣等惰性氣體而對容器進行加壓。而且，亦可利 用藉由加熱之溶劑之蒸汽壓之上升。或者，亦可於將容器 密閉後，於壓力下添加各成分。 ^ 於進行加熱之情形時，較佳的是自容器之外部進行加 熱。例如，可使用套箱式（jacket type)之加熱震置。而且， 亦可藉由於容器之外部設置加熱板，進行配管使液體循環 而對容器全體進行加熱。 /季又佳的疋於容器内部設置勝翼，使用該鮮翼而進 行授拌。獅翼較麵是達耽輕附近之長度。較佳 是於猜翼之末端設置麻翼錢财器壁之液膜。 容f中亦可設置壓力計、溫度計等計量儀器類。於容 器内將各成分轉於溶射1_之 自容器中取出，或者取出後仙熱交換轉而 藉由溶劑洗鑄法由所調製之纖維素醋 ς =纖維翻旨膜。較佳的是於摻雜物中添加所述--- - - r --L &gt; is therefore preferred. When the degree of polymerization is at least the lower limit value, it is preferable that the strength of the produced film is not lowered. The viscosity average degree of polymerization can be determined by the limit viscosity method of Uda et al. {Uda Kazuo, Saito Hideo, "Fiber Society Journal", Vol. 18, No. i, p. 105 ~ page 1 (1% 2 years)} Determination. This method is also described in detail in Japanese Laid-Open Patent Publication No. Hei 9-95538. Further, the molecular weight distribution of the cellulose ester preferably used in the present invention can be evaluated by gel permeation chromatography, preferably its polydispersity index Mw/Mn (Mw is a weight average molecular weight, and Mn is a number average). Molecular weight) small 'molecular weight distribution is narrow. The specific value of Mw/Mn is preferably 1. 〇 to 4.0 Å, more preferably 2.0 to 4.0, and most preferably 2.3 to 3.4. &lt;Method for Producing Cellulose Ester Film&gt; The cellulose ester film of the present invention can be produced by a solvent casting method. In the solvent casting method, a film (doped matter) in which a cellulose ester is dissolved in an organic solvent is used to produce a film. The organic solvent preferably contains a ketone having a carbon number of 3 to 12, a ketone having 3 to 12 carbon atoms, an ester having 3 to 12 carbon atoms, and a halogenated hydrocarbon having 1 to 6 carbon atoms ( Halohydrocarbon) solvent. The test, ketone and ester may also have a cyclic structure. A compound having two or more functional groups of an ether, a hydrazine, and an ester (i.e., -0-, -CO-, and -COO-) can also be used as an organic solvent. The organic solvent may also have other functional groups such as an alcoholic group. In the case of an organic solvent having two or more functional groups, it is preferred that the number of slave atoms is within the above-mentioned preferred number of carbon atoms of a solvent having an arbitrary functional group. 33 201213409 jo tu^uii Examples of the class of carbon atoms 3 to 12 include diisopropyl hydrazine, dimethoxy methoxy methane, dimethoxy ethane, 1,4-dioxane, 1,3- Dioxolane, tetrahydrofuran, anisole and phenylethyl ether. Examples of the ketone having 3 to 12 carbon atoms include acetone, mercaptoethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone, and nonylcyclohexanone. Examples of the ester having 3 to 12 carbon atoms include ethyl decanoate, propyl formate, amyl decanoate, decyl acetate, ethyl acetate and amyl acetate. Examples of the organic solvent having two or more functional groups include ethoxyethyl acetate, 2-methoxyethanol, and 2-butoxyethanol. The number of carbon atoms of the halogenated hydrocarbon is preferably 1 or 2, and most preferably ruthenium. The dentate of the halogenated hydrocarbon is preferably gas. The proportion of the hydrogen atom of the toothed hydrocarbon to be substituted with _ is preferably from 25 mol% to 75 mol%, more preferably from 3 〇m 〇 1% to 7 〇 mol%, still more preferably 35 m 〇 1 %~ illusion m〇1%, the best is 4〇mol%~60 mol%. Dichloromethane is a representative halogenated hydrocarbon. Two or more organic solvents may also be used in combination.曰 It is a general method based on the temperature (normal temperature or high temperature) contained above the GC, and can be tested on the fiber surface. The preparation of the solution can be carried out by using a method and a device for preparing a dopant in a conventional solution casting method. 1 牯 ιιι: 'In the case of a general method, it is preferred to use a halogenated (particularly 疋 dichloromethane) as an organic Solvent. The amount of fiber, the amount of money can be dissolved in the second solution = the amount of cellulose vinegar is more preferably 10wt% ~ 30 - = main,), can also add any of the additives described later. Each liquid can be prepared by stirring the cellulose vinegar with a solvent of 34 201213409 at room temperature (10) to price (2). The high concentration solution can be stirred under pressure and heating. Specifically, the cellulose acetate and the organic solvent are placed in a pressurized container and sealed, and heated under pressure while being heated to a temperature equal to or higher than the boiling point of the solvent at a normal temperature, and the solvent is not boiled. The heating temperature is usually 4 Torr. (: Above, preferably 60. (: ~200. (:, more preferably 80 ° C ~ ll 〇 ° e. The ingredients can also be coarsely mixed beforehand and put into the container. Also, depending on The container is placed in a container. The container must be stirred. The container can be pressurized by injecting an inert gas such as nitrogen, or the vapor pressure of the solvent by heating can be used. After the container is sealed, the components are added under pressure. ^ In the case of heating, it is preferred to heat from the outside of the container. For example, a jacket type heating can be used. The heating plate can be placed outside the container, and the pipe can be circulated to heat the entire container. The season is better than the inner wing of the container, and the fresh wing is used for mixing. It is better to set the length of the light near the end of the guessing wing. The pressure gauge, thermometer, etc. can also be set in the volume f. The components are transferred to the spray in the container. _ taken out of the container, or After the removal, the heat exchange is transferred to the cellulose vinegar 纤维 = fiber by the solvent washing method. It is preferred to add the above to the dopant.

戶IJ 35 201213409. 使摻雜物流轉於誌―、姓，^ 佳的是對流鑄前之摻雜 成較 18%〜35%。 1史固形物I成為 的是使摻雜物流;工為鏡面狀態。較佳 於彻，於t:雜 上之情形時，於剝下前乾燥之前半 鑄於帶 乾燥！〇秒以上％秒以下、較佳的是m無風下 乾燥之前半中，較佳的是進行於實f ^於剝下前 10秒以下、較佳的是2秒‘下乾燦1秒以上 於本發明中，所袖以下之時間的步驟。 佈於帶或鼓上之後 而且，所謂「前半」是指自：=== 有時間之-半之前的步驟。所謂4=下=之所 ί:===：τ中未能檢測二= 秒左秒〜3。。 秒以上⑽料下之時間是於缺下妨賴 ^時通常為5秒〜30秒左右之時間，其中之 月 秒以下、較佳的是2秒以上5細下之時暇於^上= 行乾燥。環境溫度較佳的是〇ΐ〜18〇ΐ，更佳的是、2進 1耽。於無風下進行錢之操作可於剝下前絲= 36 201213409 任意階段進行，較佳的是於流鑄之後立即進行。於無風下 進行乾燥之時間於帶上之情形時，若不足1〇秒（於鼓上之 情形時不足1秒），則添加劑難以均一地分布於膜内，若超 過90秒（於鼓上之情形時超過1〇秒），則乾燥不充分而變 得剝下，膜之面狀惡化。 剝下剷乾燥中之於無風下進行乾燥以外的時間可藉由 送風惰性氣體而進行乾燥。此時之風溫較佳 18〇°C，更佳的是 4(rc〜150t：。 β關於溶舰鑄法巾之乾燥方法，於美國專利2336310 號美國專利2367603號、美國專利2492078號、美國專 =2492977號、美國專利2492978號、美國專利姻 '、美國專利2739069號、美國專利2739〇7〇號、英國專 =073!號、英國專利乃舰號之各朗書，日本專利 =ΓΛ4554號、日本專利特公昭49·5614號、日本專 6(Μ76834號、日本專利制昭你綱％號、 鼓上2 = =2_115()35號各公報中有所記載。於帶或 可藉由送風空氣、氮氣等惰性氣體而進行。Household IJ 35 201213409. Turn the doping logistics into Zhi-, surname, ^ is better than the doping before casting is 18% ~ 35%. 1 The history of solid matter I becomes the doping stream; the work is mirrored. It is better to use it in the case of t: miscellaneous, before the peeling is dried before the half is cast in the belt to dry! Preferably, the second half or less, preferably less than 10 seconds before the stripping, and preferably less than 1 second before the stripping, is preferably performed for 1 second or more. In the present invention, the steps of the following time are sleeved. After being placed on a belt or a drum, the so-called "first half" refers to the step from: === having time - half before. The so-called 4 = lower = where ί: ===: τ failed to detect two = seconds left seconds ~ 3. . The time under the second (10) is the time of 5 seconds to 30 seconds, which is usually less than 2 seconds to 30 seconds, and it is preferably 2 seconds or more and 5 seconds. dry. The ambient temperature is preferably 〇ΐ 18 〇ΐ, more preferably 2 耽 1 耽. The operation of the money in the absence of the wind can be carried out at any stage of stripping the front yarn = 36 201213409, preferably immediately after the casting. When the drying time is not carried out under the wind, if it is less than 1 second (in less than 1 second on the drum), the additive is difficult to uniformly distribute in the film, if it is more than 90 seconds (on the drum) In the case of more than one 〇 second, the drying is insufficient and the peeling is performed, and the surface of the film is deteriorated. The time other than drying in the shovel drying in the absence of wind can be dried by blowing the inert gas. The wind temperature at this time is preferably 18 〇 ° C, and more preferably 4 (rc 〜 150 t: 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Patent No. 2492977, US Patent No. 2492978, US Patent Marriage ', US Patent 2739069, US Patent 2739〇7〇, UK Special =073!, British Patent is the title of each ship, Japanese Patent=ΓΛ4554 Japanese Patent Special Publication No. Sho 49.5614, Japanese Special 6 (Μ76834, Japanese Patent No. ZHAO Yougang%, and Drum 2 ==2_115() No. 35 are published in each bulletin. It is carried out by an inert gas such as air or nitrogen.

至所得之膜自鼓或帶刺下’進一步藉由於100°C 装發。m逐纽變溫度的高溫風騎乾燥較殘留溶劑 二載於日本專利特公平M购號公報中有 為ΐΐ施=該方法，則可縮短自流铸至剝下的時間。 了實施該方法，必須於流鑄時之鼓 摻雜物凝膠化。 之表面咖·度下使 亦可使用調整之纖維素醋溶液（摻雜物）進行二層以 37 201213409 上之流鑄而後進行膜化。於此情形時，較佳的是藉由溶劑 澆鑄法製作纖維素酯膜。使摻雜物流鑄於鼓或帶上，使溶 劑蒸發而形成膜。較佳的是對流鑄前之摻雜物進行濃度調 整以使固形物量成為10%〜40%之範圍。鼓或帶之表$較 佳的是預先精加工為鏡面狀態。 本發明之纖維素酯膜之較佳之寬度為0 5 m〜5 m，更 佳的是0.7 m〜3 m。膜之較佳之卷長為3〇〇 m〜3〇〇〇〇爪， 更佳的是500 m〜10000 m’進一步更佳的是1〇〇〇 m〜7〇〇〇 m ° (膜厚） 本發明之纖維素酯膜之膜厚較佳的是2〇 μιη〜18〇 μπι，更佳的是30μιη〜120μηι，進一步更佳的是4〇μιη〜 1〇〇 μιη。若膜厚為20 μηι以上，則於加工為偏光板等時之 處理特性（handling property)或偏光板之捲曲（curl)抑 制之方面而言較佳。而且，本發明之纖維素酯膜之膜厚不 均較佳的是於搬送方向及寬度方向均為〇%〜2%， 是㈧〜L5%，特佳的是0%〜1%。 細 (添加劑） 於纖維素酯膜中亦可添加劣化抑制劑（例如抗氧化 劑、過氧化物分解劑、自由基禁止劑、金屬鈍化劑、酸清 除劑、胺）。關於劣化抑制劑’於曰本專利特開平3_1992〇1 號、曰本專利特開平5-194789號、曰本專利特開平 5-271471號、曰.本專利特開平6_1〇7854號之各公報中有所 記載。劣化抑制劑之添加量，自表現效果及抑制劣化抑制 38 201213409 劑滲出（bleed out)至膜表面之觀點考慮，較佳的是所調 製之溶液（摻雜物）之〇·〇〗 wt%，更佳的是咖 wt%〜0.2 wt%。 特佳之劣化抑制劑之例可列舉丁基化羥基甲 (BHT)、三节基胺（TBA)。 本發明之纖維素酯膜中亦可添加紫外線吸收劑。紫外 線吸收劑較佳的是使用日本專利特開篇Μα979號公報 中所記載之化合物（二苯甲酮、苯并三如三嗪&gt; 紫外線 吸收劑亦可併用2種以上而使用。 紫外線吸收劑較佳的是苯并***，具體而言可列舉 TINUVIN328、TINUVIN326、TINUVIN329、TINUVIN57 卜The resulting film was drummed or punctured' further by means of 100 °C. The high-temperature wind-driving drying of the m-to-new temperature is more than the residual solvent. In the Japanese Patent Special Fair M purchase bulletin, it is possible to shorten the time from the casting to the stripping. To carry out the process, the drum dopant must be gelled during casting. The surface of the coffee can also be film-formed by using a modified cellulose vinegar solution (dopant) for two-layer casting on 37 201213409. In this case, it is preferred to prepare a cellulose ester film by a solvent casting method. The doping stream is cast onto a drum or belt to evaporate the solvent to form a film. It is preferred to adjust the concentration of the dopant before casting to have a solid content of 10% to 40%. The drum or belt watch $ is preferably pre-finished to a mirrored state. The preferred width of the cellulose ester film of the present invention is from 0 5 m to 5 m, more preferably from 0.7 m to 3 m. The preferred roll length of the film is 3〇〇m~3 jaws, more preferably 500m~10000 m', and even more preferably 1〇〇〇m~7〇〇〇m ° (film thickness) The film thickness of the cellulose ester film of the present invention is preferably 2 μm to 18 μm, more preferably 30 μm to 120 μm, still more preferably 4 μm to 1 μm. When the film thickness is 20 μηι or more, it is preferable in terms of handling property when processed into a polarizing plate or the like, or curl suppression of a polarizing plate. Further, the film thickness unevenness of the cellulose ester film of the present invention is preferably 〇% to 2% in the conveyance direction and the width direction, and is (eight) to L5%, particularly preferably 0% to 1%. Fine (Additive) A deterioration inhibitor (e.g., an antioxidant, a peroxide decomposer, a radical inhibitor, a metal deactivator, an acid remover, an amine) may be added to the cellulose ester film. Regarding the deterioration inhibitors, in the publications of the Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. There are records. The addition amount of the deterioration inhibitor, the self-expression effect, and the suppression of the deterioration inhibition 38 201213409 From the viewpoint of bleeding out to the surface of the film, it is preferable that the prepared solution (dopant) is wt·〇 wt%, More preferably, the coffee is wt%~0.2 wt%. Examples of the particularly preferable deterioration inhibitor include butylated hydroxymethyl (BHT) and trisylamine (TBA). An ultraviolet absorber may also be added to the cellulose ester film of the present invention. The ultraviolet absorber is preferably a compound (benzophenone or benzotriazine such as triazine) as disclosed in Japanese Laid-Open Patent Publication No. 979. The ultraviolet absorber may be used in combination of two or more kinds. The best is benzotriazole, specifically TINUVIN328, TINUVIN326, TINUVIN329, TINUVIN57

Adekastab LA-31 等。 I外線吸收劑之使用量相對於纖維素酯之重量比較佳 的是10%以下’更佳的是3%以下，最佳的是2%以下〇 〇5% 以上。 (消光劑微粒子） 本發明之纖維錢雌佳的是含有微粒子作為消光 劑。本發明中所使狀微粒子可列舉二氧切、二氧化鈦、 氧化銘、氧化錯、碳酸約、滑石、黏土、锻燒高屬土、般 燒石夕酸飼、水合、魏紹、魏鎂及雜轉。作為 U粒子，於/蜀度變低之方面而言，較佳的是包含碎之微粒 子，特佳的是二氧化;^。二氧切之微粒子較佳的是一次 平均粒徑為20 nm以下，且視比重為7〇抑以上。一次粒 子之平均錄小於5 nm〜16 nm者可降倾之霧度而更 39 201213409 JU f 〜200 /T g/L〜200 g/L，更佳的是100叭 :。視比重越大，越變得可能製作高濃度之分散 度、凝聚物良化而較佳。較理想之實施態樣於發明 協會么開技術報告（公職術職2GGM745、2001年3 發明協會）第35 f〜第36頁中有所詳細記 載，於本發明之纖較s旨财亦可較佳地使用。 (延伸） 本發明之纖維素醋膜可藉由延伸處理而調整延遲。稽 極地於寬度方向（相對於搬送方向而言垂直之方向）進行 延伸之方法例如於日本專利特開昭62 115()35號、日本 利特開平4·152125號、日本專利制平4_284211號、日 本專利特開平4_29831G號、及日本專繼開平11-48271 號^各公報等巾有所記載。膜之延伸可於常溫或加熱條件 下實施。加熱溫度較佳的是膜之玻璃轉移溫度±2〇°C。其 原因在於：若於較玻璃轉移溫度極其低之溫度下進行延 伸，變得谷易破斷而不能表現出所期望之光學特性。而且， 右於較玻璃轉移溫度極其高之溫度下進行延伸，則於藉由 1伸而對分子配向之膜進行熱固定之前’由於延伸時之熱 緩和而無法使配向固定化，光學特性之表現性變差。 另外，於延伸區域（例如拉幅區域）中，於咬入膜， 進行搬送而經過最大展寬率後，通常設置有使其緩和之區 域。此為減低軸偏斜所必須之區域。於通常之延伸中，於 經過該最大展寬率之後的緩和率區域中，直至通過拉幅區 域之時間短於1分鐘，膜之延伸可為僅僅於搬送方向或寬 201213409 度方向上之單軸延伸，亦可為_或逐次雙軸延伸，較佳 的是較寬度方向更多地延伸。寬度方向之延伸較佳的是5% 〜100%之延伸，特佳的是進行5%〜80%之延伸。而且， 延伸處理可於賴步驟之射進行，亦可對細而捲取之 胚片進行延魏理。於前者讀科，可於包含殘留溶劑 莖之狀,％下物延伸，於殘留溶缝=(殘存揮發成分重 量/加熱處理後之膜重量）&gt;&lt;100%為0 05%〜50%下可較佳 地進行延伸。特佳的是於殘留溶劑量為G规〜抓之狀離 下進行5%〜80%之延伸。 而且，本發明之纖維素酯膜亦可進行雙軸延伸。 雙轴延伸存在有同時雙轴延伸法與逐次雙轴延伸法， 自連續製造讀財餘佳的是逐:欠雙軸延伸方法，於产 鑄摻雜物之後，自帶或鼓上剝下膜，於寬度方向上進行^ 伸後於長度方向上進行延伸’或者於長度方向上進行延 後於寬度方向上進行延伸。 該些流鑄至後乾燥為止之步驟可於空氣環境下進行亦 可於氮氣等惰性氣體環境下進行。於本發明之纖維素醋膜 之製造中所使狀捲繞機為通常所使时即可，可藉由定 張力法、定扭矩法、_張力法、内部應力固定之^ 力控制法等捲取方法而進行捲取。 、 (纖維素酯臈之表面處理） f維素酯難佳岐實絲面處理。具體之方法可列 舉電軍放電處理、輝光放電處理、火焰處理、酸處理、驗 處理或紫外線照射處理。而且，如日本專利特開平m 3极 201213409 、自:樣設置下塗層之方法亦較佳。 中，將的是於該些處理 具體而言為1卿町Γ _移溫度）以下、 光元透明保護膜而使用之情形時，自與偏 理亦即對於纖維素輯的是實施酸處理或驗處 以上’更佳的是60 mN/m 、表面能量較佳的是55mN/m 以上75 mN/m以下。 、下以糾生驗化處理為例而力口以 纖之錄驗化處理較麵是以如^循環而 進行水=== 於鹼錄愤，以雜絲騎中和， 驗岭液可列舉氫氧化鉀溶液、氫氧化納溶液，氮氧根 =濃度較佳的是處於G.l mol/L〜3.G mol/L之範圍，更佳 ，疋處於0.5 mol/L〜2.0 m〇i/L之範圍。驗溶液溫度較佳的 是處於室溫〜90°C之範圍，更佳的是處於40。(：〜70Ϊ之範 圍。 固體之表面能量可藉由如「潤濕之基礎與應用」 (Realize C〇rporation ’ 1989.12.10 發行）中所記載之接觸 角法、濕潤熱法、及吸附法而求出。本發明之纖維素賴膜 之情形時，較佳的是使用接觸角法。 具體而言，將表面能量已知之2種溶液滴加至纖維素 酯膜上，將於液滴之表面與膜表面之交點中，向液滴所引 42 201213409 r:與：：膜之之=液_ 〈纖維素酯膜之特性&gt; 化亦ΓΓί纖維素醋膜之面狀故障少，光學性能經時變 性能變化小:ί保，而内*至偏光板時偏光板之經時 丨。此處，此種面狀故障少主要藉由如 冲h糟由使用所述細旨化合物混合體作為添加劑，從而 改善成膜時之揮發性或滲出。而且，於 從而 ===·情形時，不僅可抑制於 膜於濕熱環境下隨得之纖維素顆 素：特==?特性合在-起而對本發明之纖維 (膜之延遲） 於本說明書中，Re⑴及Rth⑴分別表示於 1 之料⑽侧°Re⑴以職^ 2 ADH或WR (商品名、王子計測機器公司製造 ^長λ肺之光向膜之法線方向入射而測定。於選擇測定 波長λ nm時，可手動交換波長選擇型濾波器，藓 程式等對測定值進行轉換而測定。 —曰 料3 = 單軸或雙軸之折射率橢球而表示之情 形時藉由以下之方法而算出Rth (λ)。 (λ)是相對於將面内之遲相軸（藉 21ADH或WR而判斷）作為傾斜軸（旋轉軸）（於無遲相 43 201213409 JO / V-7U11 轴之情形時，將膜之面内之任意方向作為旋軸 法線方向，對自法線方向至單側5G度處每隔ω 乂 自該傾斜之方向人射波長為“之光，總制定6點= 述Re (λ) ’基於該測定之延遲值與平均折射率之 所輸入之膜厚值而由^：06^21入011或WR算出。值及 於上述中，於具有以面内之遲相轴為旋難，° 方向起某傾斜角度處延遲值成為零之方向_之昧線 較該傾斜角度更大之傾斜角度的延遲值，是將其^號=更 為負之後’由KOBRA 21ADH或WR而算出。 另外’將遲相軸作為傾斜轴（旋轉轴）（於無遲 情形時’將膜面内之任意方向作為旋_)，自任意之 之2個方向測定延遲值，基於該值與平均折射率之假 及所輸入之膜厚值，藉由以下之式（21)及式（22 出Rth。 井 式（21)Adekastab LA-31 et al. The amount of the external absorbent to be used is preferably 10% or less with respect to the weight of the cellulose ester, more preferably 3% or less, and most preferably 2% or less 〇 5% or more. (Matting agent fine particles) The fiber of the present invention preferably contains fine particles as a matting agent. The microparticles to be used in the present invention include dioxins, titania, oxidized imprints, oxidized faults, carbonic acid, talc, clay, calcined high genus, general burnt stone acid, hydrated, Weishao, Wei magnesium and miscellaneous turn. As the U particles, it is preferable to contain fine particles in terms of a low degree of enthalpy, and particularly preferred is oxidization; The diced microparticles preferably have a primary average particle diameter of 20 nm or less and an apparent specific gravity of 7 Å or more. If the average particle size of a single particle is less than 5 nm~16 nm, the haze of the tilting lens can be lowered. 39 201213409 JU f 〜200 /T g/L~200 g/L, more preferably 100 mp:. The larger the specific gravity, the more likely it is to produce a high concentration dispersion and a good agglomerate. The preferred embodiment is described in detail in the 35th ~ 36th page of the Invention Association's technical report (public service 2GGM745, 2001 3 Invention Association), and the fiber of the invention can be compared with the s Good to use. (Extension) The cellulose vinegar film of the present invention can be adjusted in retardation by elongation treatment. The method of extending the polarity in the width direction (the direction perpendicular to the transport direction) is, for example, Japanese Patent Laid-Open No. Sho 62 115 ( ) No. 35, Japanese Patent No. 4,152,125, Japanese Patent No. 4_284211, Japanese Patent Laid-Open No. 4_29831G, and Japan's special Kaiping No. 11-48271, each bulletin, etc. are described. The extension of the film can be carried out under normal temperature or under heating. The heating temperature is preferably a glass transition temperature of the film of ± 2 〇 ° C. The reason for this is that if the stretching is carried out at a temperature extremely lower than the glass transition temperature, the grain becomes easily broken and the desired optical characteristics are not exhibited. Further, when stretching is performed at a temperature extremely higher than the glass transition temperature, the film is thermally fixed by the stretching of the molecule, and the film is prevented from being fixed by the heat relaxation during the stretching, and the optical characteristics are expressed. Sexual deterioration. Further, in the extended region (e.g., the tenter region), after the film is bitten into the film and transported to the maximum stretch ratio, a region to be relaxed is usually provided. This is the area necessary to reduce the axis skew. In a typical extension, in the region of the relaxation rate after the maximum stretch ratio, until the time passing through the tenter region is shorter than 1 minute, the film extension may be a uniaxial extension only in the direction of transport or in the direction of 201213409 degrees. It may also be _ or successive biaxial extension, preferably extending more in the width direction. The extension in the width direction is preferably an extension of 5% to 100%, and particularly preferably an extension of 5% to 80%. Moreover, the stretching process can be performed by the spraying of the steps, and the finely wound sheets can be subjected to the extension. In the former, it can be used in the form of residual solvent stems, and the material is extended in the residual solution = (remaining volatile component weight / film weight after heat treatment) &gt;&lt; 100% is 0 05% to 50% The extension can be preferably carried out. It is particularly preferable to carry out the extension of 5% to 80% under the condition that the residual solvent amount is G gauge-grab. Moreover, the cellulose ester film of the present invention can also be biaxially stretched. Biaxial stretching exists in the simultaneous biaxial stretching method and the sequential biaxial stretching method. The self-continuous manufacturing reading is better than the under-biaxial stretching method. After the casting dopant is produced, the film is peeled off from the belt or the drum. , extending in the width direction and extending in the longitudinal direction or extending in the longitudinal direction to extend in the width direction. The steps from the casting to the post-drying may be carried out in an air atmosphere or in an inert gas atmosphere such as nitrogen. In the manufacture of the cellulose vinegar film of the present invention, the winding machine can be used as usual, and can be wound by a constant tension method, a constant torque method, a _ tension method, an internal stress fixed method, and the like. Take the method and take the roll. (Finishing of cellulose ester oxime) F-dimensional ester is difficult to be treated with silk surface. The specific method may be an electric discharge treatment, a glow discharge treatment, a flame treatment, an acid treatment, a treatment treatment or an ultraviolet irradiation treatment. Further, as in the case of the Japanese Patent Laid-Opening M 3 pole 201213409, the method of providing the undercoat layer from the sample is also preferable. In the case where the treatment is specifically performed under the above-mentioned treatment, and the photo-transparent protective film is used, the self-contrast, that is, the cellulose treatment is acid treatment or The above is better than 60 mN/m, and the surface energy is preferably 55 mN/m or more and 75 mN/m or less. Take the correction test as an example and use the fiber to record the treatment. The water is treated as the water cycle === The alkali is recorded in the anger, and the silk is neutralized. Potassium hydroxide solution, sodium hydroxide solution, nitrogen oxide = concentration is preferably in the range of Gl mol / L ~ 3. G mol / L, more preferably, 疋 is 0.5 mol / L ~ 2.0 m〇i / L The scope. The temperature of the test solution is preferably in the range of room temperature to 90 ° C, more preferably 40. (: ~70Ϊ range. The surface energy of solids can be obtained by the contact angle method, humidification method, and adsorption method as described in "Basic and Application of Wetting" (released by Realize C〇rporation '1989.12.10). In the case of the cellulose film of the present invention, it is preferred to use a contact angle method. Specifically, two kinds of solutions having known surface energies are added dropwise to the cellulose ester film, which will be on the surface of the droplets. In the intersection with the surface of the film, the liquid droplets are led to the liquid droplets. 42 201213409 r: and :: film of the liquid = liquid _ _ characteristics of the cellulose ester film 〉 ΓΓ 纤维素 纤维素 cellulose vinegar film surface failure, optical properties The variation of the time-varying property is small: ί保, and the time 丨 of the polarizing plate in the inner * to the polarizing plate. Here, such a planar failure is mainly caused by the use of the compound of the compound as an additive. , thereby improving the volatility or bleed out during film formation. Moreover, in the case of the ratio ===·, not only can the cellulose granules obtained in the hot and humid environment be restrained: For the fiber of the present invention (delay of film) in the present specification, Re(1) and Rth(1) It is measured on the side of the material (10) of the material (1), and the measurement is performed at the normal wavelength of the film. The wavelength selective filter can be manually exchanged, and the measured value can be measured by converting the measured value. - When the material 3 = the uniaxial or biaxial refractive index ellipsoid is expressed, the Rth (λ) is calculated by the following method. (λ) is the tilt axis (rotation axis) with respect to the in-plane retardation axis (determined by 21ADH or WR) (when there is no delay phase 43 201213409 JO / V-7U11 axis, the film is Any direction in the plane is used as the normal direction of the rotation axis. For every ω 乂 from the normal direction to the single-sided 5G degree, the wavelength of the human shot is “light” from the direction of the tilt. The total is 6 points = Re (λ) 'Based on the input film thickness value of the measured retardation value and the average refractive index, it is calculated from 011 or WR by ^:06^21. The value and the above are the rotation of the late phase axis in the plane. ° The angle at which the delay value becomes zero at a certain inclination angle _ the slant angle of the 昧 line is larger than the inclination angle The delay value of the degree is calculated by KOBRA 21ADH or WR after the ^ number = more negative. In addition, 'the slow phase axis is used as the tilt axis (rotary axis) (when there is no delay) The direction is taken as the rotation _), and the retardation value is measured from any two directions. Based on the value and the average refractive index and the input film thickness value, the following equations (21) and (22) Rth. Formula (21)

Re($)a )))a (nc cos(boi c〇g(sax ^ 式（22)Re($)a )))a (nc cos(boi c〇g(sax ^ 式(22)

Rth={ (nx+ny) /2-nz}xd 於式中’ Re (Θ)表示自法線方向傾斜角度θ之方向 44 201213409 面内之遲相軸方向之折射率，ny表示於 ^方向崎料，nz表賴nx切正交 之方向之折射率，d表示層之厚度（nm)。 之膜所疋無法以單軸或雙軸之折射率橢球而表現 之方法f卩^軸（Gptleaxis)之膜之情形時，藉由以下 之方法而异出IUh (λ)。 二Λ將面内之遲相轴（藉由K0BRA2iadh或 ^而^斷）作為傾斜軸（旋轉軸），相對於膜之法線方向 α二至+5G度處每隔1G度地分別自該傾斜之方向入射 ίίΐΥΓ之光而測定11點之所Ue⑴，基於該測定 ^遲值與平騎料之假定值及所輸人之财值，由 KOBRA 21ADIi 或 WR 而算出。 於上述測定巾’平均折射率之假定值可使用聚合物手 JOHN WILEY &amp; SONS，INC)巾各種光學膜之目錄 。，於平均折射率之值並非已知者，可藉由阿貝折射計 而測疋冑主要之光學膜之平均折射率之值例示 於以下： 酉化纖維素（1.48)、料烴聚合物（152)、聚碳酸醋 (1-59)、聚甲基丙婦酸甲冑（149)、聚苯乙烯（1別。 藉由輸入平均折射率之假定值無厚，可由KOBRA 21ADH或WR而算出nx、ny、取。 本發明之纖維素醋膜可作為偏光板之保護膜而使用， 特別是可作為與各機晶模讀狀她錢而較佳地使 用0 於將本發明之纖維素酯膜用作相位差膜之情形時，纖 45 201213409 維素酯膜之較佳之光學特性因液晶模式而異。 作為VA模式用而於590 nm下所測定之！^較佳的是 20 nm〜150 nm，更佳的是5〇 nm〜i3〇 nm，進一步更佳的 是70 nm〜120 nm。Rth較佳的是100 nm〜3〇〇 nm，更佳 的是120nm〜280nm，進一步更佳的是15〇nm〜25〇nm。 作為TN模式用而於59〇 nm下所測定之Re較佳的是 〇11111〜1〇〇11111，更佳的是111111〜5〇11111，進一步更佳的是 2 nm〜20 nm。Rth較佳的是2〇 nm〜2〇〇 nm，更佳的是3〇 nm〜150mn，進一步更佳的是4〇nm〜12〇nm。 於TN模式用中，可於具有所述延遲值之纖維素酿膜 上塗佈光學異向性層而作為相位差膜使用。 (光學性能經時變化） 本發明之纖維素醋膜之特徵在於：不僅可良好地表現 f Rth，而且於濕熱環境下隨時間經過前後之她之 量小。 又 (膜之霧度） 作 本發明之纖料®旨膜之霧賴佳的是魏％〜2仰 更佳的是G.G5%〜1.5%，進—步更佳的是Q 1%叫〇% 〇 為光學膜’膜之透明性是重要的。 (纖維素酯膜之構成） 本發明之纖維素酿膜可為單層結構亦 成，較佳的是單層結構。此處，所謂「單層結構」^構 並非多種膜材料貼合而成之膜，而是表示纖$ 膜。而且，亦包括由多種纖維素液， 46 201213409 式或共流鑄方式而製造一枚纖維素酯膜之情形。 旦二此情形時’可藉由適宜調整添加劑之種類或調配 罝、纖維素i旨之分子量分布或纖維㈣之麵等而獲得於 厚度方向上具有分布之纖維素賴。而且，亦包含於該些 -枚膜中具有光學異向性部、防眩部、^ 等各種功能性部者。 ”Rth={ (nx+ny) /2-nz}xd In the formula, 'Re (Θ) denotes the direction of the inclination angle θ from the normal direction 44 201213409 The refractive index of the slow phase axis in the plane, ny is expressed in the direction of ^ In the case of bake, nz represents the refractive index of the direction in which nx is orthogonal, and d represents the thickness (nm) of the layer. In the case where the film cannot be expressed by a uniaxial or biaxial refractive index ellipsoid, the film is in the form of a film of Gptle axis, and IUh (λ) is different by the following method. The second axis is the retardation axis (by K0BRA2iadh or ^^^) as the tilt axis (rotation axis), which is inclined from the normal direction of the film from the normal direction α to +5G degrees. The Ue(1) at the 11th point is measured by the incident light of the ίίΐΥΓ light, and is calculated based on the measured value of the late value and the flat riding material and the value of the input person, and is calculated by KOBRA 21ADIi or WR. The assumed value of the average refractive index of the above-mentioned measuring towel can be used in the catalogue of various optical films of the polymer hand JOHN WILEY &amp; SONS, INC. The value of the average refractive index is not known, and the average refractive index of the main optical film can be measured by an Abbe refractometer as exemplified below: Deuterated cellulose (1.48), hydrocarbon polymer ( 152), polycarbonate (1-59), polymethyl propyl ketone (149), polystyrene (1. By the input of the average refractive index, the assumed value is not thick, can be calculated by KOBRA 21ADH or WR nx The cellulose vinegar film of the present invention can be used as a protective film for a polarizing plate, and in particular, it can be used as a crystal film of the present invention. When used as a retardation film, the preferred optical properties of the fiber 45 201213409 vegetal ester film vary depending on the liquid crystal mode. Measured at 590 nm as the VA mode! ^20 nm to 150 nm is preferred. More preferably, it is 5 〇 nm to i3 〇 nm, and further preferably 70 nm to 120 nm. Rth is preferably 100 nm to 3 〇〇 nm, more preferably 120 nm to 280 nm, and even more preferably 15 〇 nm 〜 25 〇 nm. As the TN mode, the Re measured at 59 〇 nm is preferably 〇11111~1〇〇11111, more It is 111111~5〇11111, and further preferably 2 nm~20 nm. Rth is preferably 2〇nm~2〇〇nm, more preferably 3〇nm~150mn, and even more preferably 4〇. In the TN mode, an optically anisotropic layer can be coated on the cellulose granule film having the retardation value and used as a retardation film. (Optical properties change over time) The fiber of the present invention The vinegar film is characterized in that it not only satisfactorily expresses f Rth, but also has a small amount in the wet heat environment before and after the passage of time. (Haze of the film) is the mist of the fiber of the present invention. It is better that the %%2 is better than G.G5%~1.5%, and the better the step is Q 1% is 〇% 〇 is the optical film 'transparency of the film is important. (cellulose ester film The cellulose granulated film of the present invention may have a single layer structure or a single layer structure. Here, the "single layer structure" is not a film obtained by laminating a plurality of film materials, but Represents the fiber $ film. Also, it includes the case of producing a cellulose ester film from a variety of cellulosic liquids, 46 201213409 or co-casting. In this case, it is possible to obtain a cellulose ray having a distribution in the thickness direction by appropriately adjusting the kind of the additive or the blending of hydrazine, the molecular weight distribution of the cellulose i or the surface of the fiber (4), and the like. - There are various functional parts such as optical anisotropy, anti-glare, and ^ in the film."

(功能性層V 本發明之膜可為單層膜，亦可具有2層以上之積層社 構。此處，較佳的是後述之本發明之偏光板包含功能性層， 可為本發明之膜具有魏性狀祕，亦可於將本發明之 膜内裝至本發明之偏光板中時疊合其他功能性膜。 所述功能性層只要不違反本發明之主旨則並無特別之 限制’例如可列舉以下之態樣之功能性層。其中，於將本 發明之膜作為紐膜而使用之情形日$，制是直接於其上 形成硬塗層較佳，較佳的是藉由塗佈而設置硬塗層。八 基材膜/硬塗層/中折射率層/低折射率層 曰 基材膜/硬塗層/中折射率層/高折射率層/低折射率層 基材膜/硬塗層/低折射率層 基材膜/硬塗層/導電性層/低折射率層 基材膜/硬塗層/高折射率層（導電性層口低折射率層 基材膜/硬淦層/防眩性層/低折射率層 本發明之纖維素酿膜較佳的是於塗佈硬塗層時塗佈不 均少。 於形成所述硬塗層時的石更塗層帛塗佈液中所使用之光 201213409 集合性多官能單體存在有烧二醇之（甲基)丙稀酸二酯類、 聚氧烧一醇之（甲基)丙烯酸二s旨類、多元醇之（甲基)丙稀酸 二酯類、環氧乙烧或環氧丙烧加成物之（甲基）丙婦酸二酯 類等，且存在有（甲基)丙烯酸環氧酯類、（甲基)丙烯酸胺基 甲酸酯類、聚酯（甲基）丙婦酸酯類等，並不限定於該些化 合物，可單一地使用亦可併用數種。 光自由基聚合起始劑可列舉苯乙酮類、安息香類、二 苯甲酮類、膦氧化物類、縮酮類、蒽醌類、噻噸酮類、偶 氮化合物、過氧化物類（日本專利特開2〇〇1_139663號 等）、2,3-二烷基二酮化合物類、二硫醚化合物類、氟胺化 合物類、芳香族錡（sulf〇nium)類、咯吩二聚物（丨叩⑴此 dimer)類、鏽鹽類、硼酸鹽類、活性酯類、活性鹵素類、 無機錯合物、香豆素類等，但並不限定於該些化合物。 口一塗佈溶劑可使用根據如下之觀點而選擇之各種溶劑： Z解或分散各成分，於塗佈步驟、乾鮮射容易成為 &quot;之面狀，可確保液體保存性，具有適度之飽和蒸汽壓 等。 心劑可將2種以上溶劑混合使用。特別是自乾燥負荷 於#,點考慮，較佳的是以常壓室溫下沸點為100°C以下之 ιοα。!^主成分，為了調整乾燥速度而少量含有沸點為 以上之溶劑。而且’為了對溶解度參數進行微調整亦 進仃溶劑之混合。 68 7^點為WC以下之溶劑例如存在有己炫（沸點為 庚烧（98.4。(：）、環己烧（8〇.7。(：）、苯（80.1°C ) 48(Functional Layer V The film of the present invention may be a single layer film or a laminated structure of two or more layers. Here, it is preferable that the polarizing plate of the present invention described later contains a functional layer, which may be the present invention. The film has a Wei-like property, and may also laminate other functional films when the film of the present invention is incorporated into the polarizing plate of the present invention. The functional layer is not particularly limited as long as it does not violate the gist of the present invention. For example, a functional layer in which the film of the present invention is used as a film may be used, and it is preferable to form a hard coat layer directly thereon, preferably by coating. A hard coating is provided for the cloth. Eight base film / hard coat / medium refractive index layer / low refractive index layer / base material film / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer substrate Film/hard coat layer/low refractive index layer base film/hard coat layer/conductive layer/low refractive index layer base film/hard coat layer/high refractive index layer (conductive layer low refractive index layer base film /hard layer/anti-glare layer/low-refractive layer The cellulose-dyed film of the present invention preferably has less uneven coating when the hard coat layer is applied. The light used in the coating layer of the stone coating layer in the hard coat layer 201213409 The polyfunctional monomer in the presence of the diol is a (meth) acrylate diester, a polyoxyl oleanol. a (meth)acrylic acid s-type, a (meth)acrylic acid diester of a polyhydric alcohol, an epoxy bromide or a propylene-acrylic acid adduct (meth)-propyl acetoic acid diester, etc. There are (meth)acrylic acid epoxy esters, (meth)acrylic acid urethanes, polyester (methyl) propionate, and the like, and are not limited to these compounds, and may be used singly or in a single manner. A plurality of kinds of photoradical polymerization initiators include acetophenones, benzoin, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, and Oxide (Japanese Patent Laid-Open Publication No. 2-139663, etc.), 2,3-dialkyldione compound, disulfide compound, fluoroamine compound, aromatic sulfonium (sulfonium), Phtha dimer (丨叩(1) dimer), rust salt, borate, active ester, active halogen, inorganic complex, coumarin, etc. However, it is not limited to these compounds. The solvent-coating solvent can use various solvents selected according to the following viewpoints: Z-dissolving or dispersing each component, and it is easy to become a "face" in the coating step and the dry fresh shot. To ensure liquid preservability, moderate vapor pressure, etc. The heart can be used in combination with two or more solvents. Especially from the drying load of #, it is preferable to have a boiling point of 100 ° C at room temperature and atmospheric pressure. The following ιοα.!^ main component, in order to adjust the drying speed, a small amount of a solvent having a boiling point of above, and 'in order to finely adjust the solubility parameter, the solvent is mixed. 68 7^ The solvent below WC, for example, exists. Hyun (boiling point is heptane (98.4. (:), cyclohexane (8〇.7. (:), benzene (80.1 °C) 48

201213409 X 等烴類，二氣甲烷（39.8°c )、氣仿（61.2°C )、四氯化碳 (76.8Ό)、1，2_二氯乙烷（83.5°〇、三氯乙烯（87.2°C) 等鹵化烴類’二***（34.6°C )、二異丙醚（68.5°C )、二丙 謎（90.5°C )、四負/夫喃（66°C )等趟類，曱酸乙醋（54.2〇C )、 乙酸甲酯（57.8°C)、乙酸乙酯（77.1°C)、乙酸異丙酯（89。〇 等酯類，丙酮（56.1°(：)、2-丁_(與甲基乙基酮相同、79.6。〇 等酮類，甲醇（64.5°C)、乙醇（78.3°C)、2-丙醇（82.4〇C)、 1-丙醇（97.2°C)等醇類，乙腈（81.6。〇、丙腈（97.4°C) 等氰基化合物類’二硫化碳（46.2°C)等；沸點為l〇〇t：以 上之溶劑例如存在有辛烷（125.7°C)、甲苯（11〇.6。(：）、二 甲苯（138〇C)、四氯乙烯（121.2°C)、氣苯（131.7°C)、二 噁烷（101.3°C)、二丁醚（142.4°C)、乙酸異丁酯（118°C)、 環己酮（155.7°C )、2-甲基-4-戊酮（與MIBK相同、 115.9°C )、1-丁醇（117.7°C )、N，N-二曱基曱醯胺（153。(：）、 N，N-二曱基乙醯胺（166°C )、二曱基亞石風（189°C )等，但 並不限定於該些溶劑。 (相位差膜） 本發明之纖維素酯膜可作為相位差膜而使用。另外， 所謂「相位差膜」是表示於通常用於液晶顯示裝置等顯示 裝置中，具有光學異向性之光學材料，與相位差板、光學 補4員膜、光學補償板等同義。於液晶顯示裝置中，以提高 顯不晝面之對比度，改善視角特性或色調之目的而使用相 位差膜。 藉由使用本發明之透明纖維素酯膜，可容易地製作Re 49 201213409: 值及Rth值得到自由地控制的相位差膜。 而且’亦可將多牧本發明之纖維素酯膜積層，或者將 本發明之纖維素酯膜與本發明以外之膜積層.而適宜調整 Re或Rth ’作為相位差膜而使用。膜之積層可使用黏著劑 或接著劑而實施。 而且’亦可根據情況將本發明之纖維素酯膜用作相位 差膜之支撐體’於其上設置包含液晶等之光學異向性層而 作為相位差膜使用。於本發明之相位差膜中適用之光學異 向性層例如可由含有液晶性化合物之組成物而形成，亦可 由具有雙折射之纖維素酯膜而形成，亦可由本發明之纖維 素酯膜而形成。 所述液晶性化合物較佳的是盤形（disc〇tic)液晶性化 合物或棒狀液晶性化合物。 [偏光板] 本發明之纖維素酯臈或相位差膜可作為偏光板（本發 明之偏光板）之保護臈而使用。本發明之偏光板包含偏光 兀件與對其兩個面進行保護的二枚偏光板保護膜（透明 膜），本發明之纖維素醋膜或相位差膜可作為至少一個偏光 板保護膜而使用。 ，於將本發明之纖維素酿膜用作所述偏光板保護膜之情 形時，較佳的是預先對本發明之纖維素醋膜實施所述表面 處理（於日本專利特開平Μ·號公報、日本專利 平6-118232號公報中亦有所記載）而進行親水化，例 佳的疋實施輝光放電處理、電暈放電處理、或驗性驗化處 50 201213409 ，等。制是構成之纖維素㈣的_相為釀化 纖維素之_時’最_是使驗冊化處理作為所述 面處理。 而且，所述偏光元件例如可使用將聚乙烯醇膜浸潰於 蛾溶液中進行延伸而成者等。於使用將聚乙婦醇膜浸潰於 破溶液中進行延伸而成之偏光元件之情形時，可使用接著 劑而於偏光元件之兩個面直接貼合本發明之透明纖維素醋 膜之表面處理面。於本發明之製造方法巾，較佳的是如上 =述那樣將所述齡素§旨難絲元件直接貼合。所述接 著，可使用聚乙烯醇或聚乙稀祕（例如聚乙烯丁搭）之 水溶液、或者乙稀系聚合物（例如聚丙稀酸丁醋）之乳膠。 特佳之接著劑是完全鹼化聚乙烯醇之水溶液。 曰⑽-般情況下’液晶顯示裝置於二枚偏光板之間設有液 晶單元，因此具有4枚偏光板保龍。本發明之纖維素醋 膜可用於4枚偏光祕制之任紐，但本㈣之纖維素 ，膜可作為於液晶顯示裝置中的偏光元件與液晶層（液晶 單元）之間所配置之保護膜而特別有利地使用。而且，於 夾持所述偏光元件㈣置於本發明之纖維素賴之相反側 的保濩膜上可没置透明硬塗層、防眩層、抗反射層等，特 別疋可作為液_示裝置之顯示侧最表面之偏光板保護膜 而較佳地使用。 [液晶顯示裝置] 一本發明之纖較賴、相位麵及偏光板可用於各種 顯不模式之液晶顯示裝置巾。町，對使㈣些膜之各液 51 201213409 w / v Λ. a 晶模式加以說明。於該些模式中，本發明之纖維素酯膜、 相位差膜及偏光板特別是可較佳地用於VA模式及IPS楔 式之液晶顯不裝置中。該些液晶顯示裝置可為透射型、反 射型及半透射型之任意種。 (TN型液晶顯示裝置） 本發明之纖維素酯臈亦可作為具有TN模式之液晶單 元的TN魏晶顯示裝置之相位差膜之支撐體而使用。關 於TN模式之液晶單元與TN型液晶顯示裝置，自先前以 來已廣為人知。關於TN型液晶顯示裝置中所使用之相位 差膜，除了曰本專利特開平3_9325號、曰本專利特開平 6-148429號、曰本專利特開平8_5〇2〇6號及日本專利特開 平9-26572號之各公報以外，於M〇ri以及其他人之論文 (Jpn. J. Appl. Phys. V〇l. 36 ( 1997) p.143 Jpn. J. Appl. Phys.Vol. 36 ( 1997) p.i068)中有所記載。 (VA型液晶顯示裝置） 本發明之纖維素酯膜可作為具有VA模式之液晶單元 的VA型液晶顯示裝置之相位差膜或相位差膜之支樓體而 特別有利地使用。VA型液晶顯示裝置例如亦可為日本專 利特開平10-123576號公報中所記載之配向分割之方式。 於該些態樣巾，使用本發明之纖㈣賴的偏光板有助於 視角擴大、對比度良化。 (IPS型液晶顯示農置及ECB型液晶顯示裝置） 本發明之纖維素酯膜可作為具有IPS模式及ECB模式 之液晶單元的IPS型液晶顯示裝置及EC_液晶顯示裝置 52 201213409 w w f v w J^e Λ ^ 之相位差膜或相位差膜之支撐體、或偏光板之保護膜而特 別有利地使用。該些模式是於黑顯示時液晶材料略平行地 配向之態樣，於未施加電壓之狀態下使液晶分子相對於基 板面而&amp;平行配向，進行黑顯示。於該些態樣中，使用本 發明之纖維素酯膜之偏光板有助於視角擴大、對比度良化。 (反射型液晶顯示裝置） 本發明之纖維素酯膜亦可作為ΤΝ型、§ΤΝ型、ΗΑΝ 型、GH (Guest-Host)型之反射型液晶顯示裝置之相位差 膜而有利地使用。該些顯示模式自先前以來已廣為人知。 關於TN型反射型液晶顯示裝置，於日本專利特開平 10-123478號、國際公開第98/48320號說明書、日本專利 第3022477號公報令有所記載。關於反射型液晶顯示裝置 中所使用之相位差膜，於國際公開第〇〇/65384號說明書中 有所記載。 (其他液晶顯示裝置） 本發明之纖維素酯膜亦可作為具有ASM(Axially Symmetric Aligned Microcell)模式之液晶單元的 ASM 型 液晶顯不裝置之相位差膜之支撐體而有利地使用。ASM模 式之液晶單元之特徵在於：單元之厚度由可進行位置調整 之樹脂間隔物而維持。其他性質與TN模式之液晶單元相 同。關於ASM模式之液晶單元與ASM型液晶顯示裝置， 於Kume以及其他人之論文（Kume et ai” SID 98 Digest 1089 (1998))中有所記載。 (硬塗膜、防眩膜、抗反射膜） 53201213409 X and other hydrocarbons, two gas methane (39.8 ° c), gas (61.2 ° C), carbon tetrachloride (76.8 Ό), 1,2-dichloroethane (83.5 ° 〇, trichloroethylene (87.2 °C) Halogenated hydrocarbons such as 'diethyl ether (34.6 ° C), diisopropyl ether (68.5 ° C), dipropanol (90.5 ° C), tetra-negative/fusane (66 ° C), etc. Ethyl acetate (54.2 〇C), methyl acetate (57.8 ° C), ethyl acetate (77.1 ° C), isopropyl acetate (89. oxime and other esters, acetone (56.1 ° (:), 2-butyl) _ (same as methyl ethyl ketone, 79.6. ketones such as hydrazine, methanol (64.5 ° C), ethanol (78.3 ° C), 2-propanol (82.4 〇C), 1-propanol (97.2 ° C) Alcohols, acetonitrile (81.6. hydrazine, propionitrile (97.4 ° C) and other cyano compounds such as carbon disulfide (46.2 ° C); boiling point l〇〇t: above solvents such as octane (125.7 ° C ), toluene (11〇.6. (:), xylene (138〇C), tetrachloroethylene (121.2 ° C), gas benzene (131.7 ° C), dioxane (101.3 ° C), dibutyl ether (142.4 ° C), isobutyl acetate (118 ° C), cyclohexanone (155.7 ° C), 2-methyl-4-pentanone (same as MIBK, 115.9 ° C), 1- Alcohol (117.7 ° C), N,N-didecylguanamine (153. (:), N,N-dimercaptoacetamide (166 ° C), diterpene sulphite (189 ° C (Retardation film) The cellulose ester film of the present invention can be used as a retardation film. The term "retardation film" is used in a liquid crystal display device or the like. In the display device, an optical material having optical anisotropy is equivalent to a phase difference plate, an optical complement film, and an optical compensation plate. In the liquid crystal display device, the contrast of the visible surface is improved, and the viewing angle characteristics or color tone are improved. A retardation film is used for the purpose of the present invention. By using the transparent cellulose ester film of the present invention, it is possible to easily produce a retardation film in which Re 49 201213409: value and Rth value are freely controlled. The cellulose ester film layer or the cellulose ester film of the present invention may be laminated with a film other than the present invention, and Re or Rth' may be suitably used as a retardation film. The film may be laminated using an adhesive or an adhesive. And 'the fiber of the invention can also be used according to the situation The ester film is used as a support for a retardation film, and an optically anisotropic layer containing a liquid crystal or the like is provided thereon as a retardation film. The optically anisotropic layer to be used in the retardation film of the present invention may be contained, for example. It may be formed of a composition of a liquid crystal compound, may be formed of a cellulose ester film having birefringence, or may be formed of the cellulose ester film of the present invention. The liquid crystalline compound is preferably a discotic liquid crystalline compound or a rod-like liquid crystalline compound. [Polarizing Plate] The cellulose ester oxime or retardation film of the present invention can be used as a protective film for a polarizing plate (polarizing plate of the present invention). The polarizing plate of the present invention comprises a polarizing element and two polarizing plate protective films (transparent films) for protecting the two faces thereof, and the cellulose acetate film or the retardation film of the present invention can be used as at least one polarizing plate protective film. . When the cellulose granulated film of the present invention is used as the protective film for the polarizing plate, it is preferred to subject the cellulose vinegar film of the present invention to the surface treatment in advance (in Japanese Patent Laid-Open Publication No. Japanese Patent No. 6-118232 (also described in Japanese Patent Laid-Open No. Hei 6-118232) is hydrophilized, and a good example of yttrium is subjected to glow discharge treatment, corona discharge treatment, or inspection and verification at 50 201213409, and the like. The _ phase of the cellulose (4) of the composition is _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Further, as the polarizing element, for example, a polyvinyl alcohol film may be impregnated into a moth solution to be stretched. When a polarizing element obtained by immersing a polythyl alcohol film in a breaking solution is used, an adhesive may be used to directly adhere the surface of the transparent cellulose vine film of the present invention to both faces of the polarizing element. Processing surface. In the method of manufacturing a napkin of the present invention, it is preferred that the aging element is directly bonded to the imaginary element as described above. Alternatively, an aqueous solution of polyvinyl alcohol or polyethylene (e.g., polyethylene butadiene) or a latex of an ethylene-based polymer (e.g., polybutyl acrylate) may be used. A particularly preferred adhesive is an aqueous solution of fully alkalized polyvinyl alcohol.曰(10)-Generally, the liquid crystal display device is provided with a liquid crystal unit between two polarizing plates, so that it has four polarizing plates. The cellulose vinegar film of the invention can be used for four polarizing secrets, but the cellulose of the invention (4) can be used as a protective film disposed between the polarizing element and the liquid crystal layer (liquid crystal cell) in the liquid crystal display device. It is particularly advantageous to use. Further, a transparent hard coat layer, an anti-glare layer, an anti-reflection layer, or the like may be omitted on the film on which the polarizing element (4) is placed on the opposite side of the cellulose sheet of the present invention, and may be used as a liquid. The polarizing plate protective film on the display surface of the display side is preferably used. [Liquid Crystal Display Device] A fiber-releasing device, a phase surface, and a polarizing plate of the present invention can be used for various liquid crystal display device tissues of the display mode.町,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Among these modes, the cellulose ester film, retardation film and polarizing plate of the present invention are particularly preferably used in a VA mode and IPS wedge type liquid crystal display device. The liquid crystal display devices may be of any of a transmissive type, a reflective type, and a semi-transmissive type. (TN type liquid crystal display device) The cellulose ester oxime of the present invention can also be used as a support for a retardation film of a TN seed crystal display device having a TN mode liquid crystal cell. Liquid crystal cells and TN type liquid crystal display devices in the TN mode have been widely known since. Regarding the phase difference film used in the TN type liquid crystal display device, in addition to the Japanese Patent Laid-Open No. Hei 3_9325, the Japanese Patent Laid-Open No. 6-148429, the Japanese Patent Laid-Open No. 8_5〇2〇6, and the Japanese Patent Laid-Open 9 In addition to the bulletins No. -26572, papers by M〇ri and others (Jpn. J. Appl. Phys. V〇l. 36 (1997) p.143 Jpn. J. Appl. Phys.Vol. 36 ( 1997 ) is described in p.i068). (VA type liquid crystal display device) The cellulose ester film of the present invention can be used particularly advantageously as a retardation film of a VA type liquid crystal display device having a VA mode liquid crystal cell or a support structure of a retardation film. The VA type liquid crystal display device can be, for example, an alignment division method described in Japanese Laid-Open Patent Publication No. Hei 10-123576. In the pattern towels, the use of the polarizing plate of the fiber of the present invention contributes to an increase in viewing angle and a favorable contrast. (IPS type liquid crystal display farm and ECB type liquid crystal display device) The cellulose ester film of the present invention can be used as an IPS type liquid crystal display device having an IPS mode and an ECB mode liquid crystal cell, and an EC_liquid crystal display device 52 201213409 wwfvw J^e The retardation film of Λ ^ or the support of the retardation film or the protective film of the polarizing plate is particularly advantageously used. These modes are in such a manner that the liquid crystal material is aligned in a slightly parallel manner in the black display, and the liquid crystal molecules are aligned in parallel with the substrate surface in a state where no voltage is applied, and black display is performed. Among these aspects, the polarizing plate using the cellulose ester film of the present invention contributes to an increase in viewing angle and a favorable contrast. (Reflective liquid crystal display device) The cellulose ester film of the present invention can be advantageously used as a retardation film of a reflective liquid crystal display device of a ΤΝ-type, ΤΝ-type, ΗΑΝ-type, or GH (Guest-Host) type. These display modes have been widely known since. The TN-type reflective liquid crystal display device is described in Japanese Patent Laid-Open No. Hei 10-123478, International Publication No. 98/48320, and Japanese Patent No. 3022477. The retardation film used in the reflective liquid crystal display device is described in the specification of International Publication No. /65384. (Other liquid crystal display device) The cellulose ester film of the present invention can be advantageously used as a support of a retardation film of an ASM type liquid crystal display device having an ASM (Axially Symmetric Aligned Microcell) mode liquid crystal cell. The liquid crystal cell of the ASM mode is characterized in that the thickness of the cell is maintained by a resin spacer which can be positionally adjusted. Other properties are the same as those of the TN mode. The ASM mode liquid crystal cell and the ASM type liquid crystal display device are described in Kume et al. (Kume et ai) SID 98 Digest 1089 (1998). (Hard film, anti-glare film, anti-reflection film) ) 53

201213409 U\J / \J^UiK 本發明之纖維素酯膜亦可根據情況而適用於硬塗膜、 防眩膜、抗反射膜中。為了提高LCD、PDP、CRT、EL等 平面顯示器之視認性，可於本發明之透明纖維素酯膜之單 面或雙面賦予硬塗層、防眩層、抗反射層之任意種或全部。 作為此種防眩膜、抗反射膜之理想之實施態樣於發明協會 公開技術報告（公開技術編號2001-1745、2001年3月15 曰發行、發明協會）之第54頁〜第57頁中有所詳細記載， 於本發明之纖維素酯膜中亦可較佳地使用。 [實例] 以下列舉實例與比較例而對本發明之特徵加以更具體 之說明。以下實例中所示之材料、使用量、比例、處理内 容、處理順序等可於不脫離本發明之主旨之範圍内適宜變 更。因此，本發明之範圍並不藉由以下所示之具體例而進 行限定性解釋。 [實例1 :纖維素酯膜101之製作] (纖維素酯溶液A-1之調製） 將下述組成物投入至混合槽中，一面加熱一面進行撥 拌，使各成分溶解而調製纖維素酯溶液A-1。乙醯基取代 度可基於ASTM D-817-91而進行測定。黏度平均聚合度可 藉由宇田等人之極限黏度法{宇田和夫、齊藤秀夫、「纖維 學會刊」、第18卷第1號、第105頁〜第12〇頁（1962年）} 而測定。 纖維素醋溶液A-1之組成 •纖維素醋（乙酿基取代度2.86、黏度平均聚合度 54 201213409 310) 100重量份 •通式（I)、通式（π)之糖酯化合物表4中所 載之添加量 •通式（III)之糖酯化合物 表4中所記載之添 加量 ' •二氣曱烷 •曱醇 •丁醇 384重量份 69重量份 9重量份 (消光劑分散液B-1之調製） 將下述之組成物投入至分散機中，進行攪拌使各成分 溶解，調製消光劑分散液B-1。 消光劑分散液B-1之組成 •二氧化矽粒子分散液（平均粒徑為16 nm) “AEROSIL R972”、曰本Aerosil股份有限公司製造 10.0重量份 72.8重量份 3.9重量份 0.5重量份 10.3重量份 •二氯曱烷 •曱醇 •丁醇 •纖維素酯溶液A-1 (紫外線吸收劑溶液C-1之調製） 將下述之組成物投入至其他之混合槽中，一面加熱一 面進行攪拌，使各成分溶解而調製紫外線吸收劑溶液C-1。 紫外線吸收劑溶液c-1之組成 •紫外線吸收劑（下述UV-1) 10.0重量份 55 201213409201213409 U\J / \J^UiK The cellulose ester film of the present invention can also be applied to a hard coat film, an anti-glare film, and an anti-reflection film depending on the case. In order to improve the visibility of a flat panel display such as an LCD, a PDP, a CRT or an EL, any or all of the hard coat layer, the antiglare layer and the antireflection layer may be provided on one or both sides of the transparent cellulose ester film of the present invention. An ideal embodiment of such an anti-glare film or an anti-reflection film is disclosed in the 54th page to the 57th page of the Open Association Technical Report of the Invention Association (Open Art No. 2001-1745, March 15, 2001, Issue, Invention Association) As described in detail, it can also be preferably used in the cellulose ester film of the present invention. [Examples] The features of the present invention will be more specifically described below by way of examples and comparative examples. The materials, the amounts of use, the ratios, the contents of the treatment, the order of treatment, and the like, which are shown in the following examples, may be suitably changed within the scope of the gist of the invention. Therefore, the scope of the invention is not limited by the specific examples shown below. [Example 1: Preparation of cellulose ester film 101] (Preparation of cellulose ester solution A-1) The following composition was placed in a mixing tank, and the mixture was heated while being mixed, and the components were dissolved to prepare a cellulose ester. Solution A-1. The degree of substitution of ethyl thiol can be determined based on ASTM D-817-91. The viscosity average degree of polymerization can be measured by the limit viscosity method of Uda et al. {Uda Kazuo, Saito Hideo, "Fibre Society Journal", Vol. 18, No. 1, p. 105 - p. 12 (1962)}. Composition of Cellulose Vinegar Solution A-1 • Cellulose Vinegar (Ethylene Substrate Degree of 2.86, Viscosity Average Degree of Polymerization 54 201213409 310) 100 parts by weight • Sugar ester compounds of general formula (I) and formula (π) Table 4 Addition amount contained in the formula: The sugar ester compound of the formula (III) The amount of addition described in Table 4 • Dioxane • sterol • Butanol 384 parts by weight 69 parts by weight 9 parts by weight (mater dispersion) Preparation of B-1) The following composition was placed in a dispersing machine, and the components were dissolved by stirring to prepare a matting agent dispersion liquid B-1. Composition of Matting Agent Dispersion B-1 • Separation of cerium oxide particles (average particle size: 16 nm) “AEROSIL R972”, manufactured by A本 Aerosil Co., Ltd. 10.0 parts by weight, 72.8 parts by weight, 3.9 parts by weight, 0.5 parts by weight, 10.3 parts by weight • Dichlorodecane • decyl alcohol • Butanol • Cellulose ester solution A-1 (Preparation of UV absorber solution C-1) The following components are put into other mixing tanks and stirred while heating. The components were dissolved to prepare an ultraviolet absorber solution C-1. Composition of UV absorber solution c-1 • UV absorber (UV-1 below) 10.0 parts by weight 55 201213409

10.0重量份 55.7重量份 10重量份 1.3重量份 12.9重量份 •紫外線吸收劑（下述UV-2) •二氯曱烷 •曱醇 •丁醇 •纖維素酯溶液A-1 (UV- 1)10.0 parts by weight 55.7 parts by weight 10 parts by weight 1.3 parts by weight 12.9 parts by weight • UV absorber (UV-2 described below) • Dichlorodecane • Sterol • Butanol • Cellulose ester solution A-1 (UV-1)

C5H1 i_tert (UV-2)C5H1 i_tert (UV-2)

(纖維素酯膜（101)之製作） 於纖維素酯溶液A-1中，以使每100重量份纖維素酯 中之通式（I)〜通式（III)之糖酯化合物成為表4中所記 載之添加量之方式添加消光劑分散液B-1，進一步以紫外 56 201213409 線吸收劑（uv-1)及紫外線吸收劑（uv_2)分別成為1〇 重量份之方式添加紫外線吸收劑溶液C-1，一面加熱一面 充分攪拌而使各成分溶解’調製摻雜物。將所得之&amp;雜物 加溫至30°c ’通過流鑄成型機而流鱗於作*吉僻盔 鼓的鏡面残鋼支«上。支撐體之 -5 C，塗佈寬度設為1470 mm。流鑄部整體之空間溫度言免 定為i5°c。繼而，於流鑄部之終點部之侧的50cm處，ς 流鑄而旋轉之_素自旨膜自鼓上财，紐崎梳拉幅機 (pm tenter)夾住兩端。剝下之後的纖維素g旨腹 溶劑量為70%且纖維素酷腹板之膜面溫度為穴。 送至St幅機a·)所保持之纖輸旨腹板搬 ^於靴下乾燥5分鐘，進—步於赋下=ι〇; 作為=膜厚為¥。將該膜試樣皿 [ΓΙ列2〜實例9、比㈣1〜比較例6] 使膜102〜纖維素醋膜115之製作） 維素酯獏10i 示之糖酯化合物或比較化合物代替於纖 細旨化合物而所使用之通式⑴〜通式⑽之 酯膜115。碉1摻雜物，製作纖維素酯膜丨〇2〜纖維素 [測定法] (嚴糖笨甲_ ^ Τ ^酯之平均取代度之測定法） 57 201213409 你ΐί 及通式（π)所表示之芳香族糖醋化合 物之取代物之分布與平均取代度，藉由於以下之ΗΡ 件下之測定而將滞科間處於31.5 mi續近之峰值作為8 取代物、處於27 mm〜29 minw近之峰值群作為7取代 物、處於22 min〜25 min附近之峰值群作為6取代物、處 於15 min〜20 min附近之峰值群作為5取代物、處於8 $ min〜13 min附近之峰值群作為4取代物、處於3 _〜6 ππη附近之峰值群作為3取代物，算出相對於各個面積比 之合計值的平均取代度。將其結果記載於下述表4中。 《HPLC測定條件》 管柱.TSK-gel ODS-IOOZ (Tosoh)、4.6x150 mm、批 號（P0014) 溶離液 A : H2〇=l〇〇、 溶離液B : AR= 1〇〇。A、B中均放入AcOH、NEt3 各 0.1% 流量：1 ml/min、 管柱溫度：40°C、 波長：254 nm、 感光度：AUX2、 注入量：10 μΐ、 淋洗液：THF/H2O =9/1 (體積比） 樣品濃度：5mgM0ml (THF) [評價] (面狀故障） 58 201213409(Production of cellulose ester film (101)) In the cellulose ester solution A-1, the sugar ester compound of the formula (I) to the formula (III) per 100 parts by weight of the cellulose ester is shown in Table 4. The matting agent dispersion liquid B-1 is added in such a manner as to be added, and the ultraviolet absorber solution is further added in such a manner that the ultraviolet ray 56 201213409 line absorbent (uv-1) and the ultraviolet absorbing agent (uv_2) are respectively 1 part by weight. C-1 is prepared by dissolving each component while heating and dissolving the dopant. The obtained &amp; muffs were warmed to 30 ° C ' and flowed through a cast molding machine to make a mirror-remaining steel rod of the girders. The support is -5 C and the coating width is set to 1470 mm. The space temperature of the entire casting part is exempt from i5 °c. Then, at the 50 cm side of the end portion of the casting portion, the ς 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自The amount of cellulose g after peeling was 70%, and the film surface temperature of the cellulose cool web was a hole. Send to the St-frame machine a·) to maintain the fiber loss of the web. Move under the boots for 5 minutes, and then enter the step = 〇; as = film thickness is ¥. This film sample dish [ΓΙ column 2 to Example 9, ratio (4) 1 to Comparative Example 6] was used to prepare the film 102 to the cellulose vine film 115). The sugar ester compound or the comparative compound of the vitamin ester ester 10i was used instead of the fine particle. The ester film 115 of the formula (1) to the formula (10) used as the compound.碉1 dopant, cellulose ester film 丨〇 2 ~ cellulose [assay] (measured by the average degree of substitution of sulphate _ ^ Τ ^ ester) 57 201213409 you ΐ and general formula (π) The distribution and average degree of substitution of the aromatic sweet and sour compound represented by the following conditions are determined by the following conditions, and the peak of 31.5 mi in the stagnation is taken as an 8-alternate, which is in the vicinity of 27 mm to 29 minw. The peak group is a 7-substituent, the peak group in the vicinity of 22 min to 25 min is a 6-substituent, the peak group in the vicinity of 15 min to 20 min is a 5-substituent, and the peak group is in the vicinity of 8 $ min to 13 min. The 4 substituents and the peak group in the vicinity of 3 _ to 6 ππη were used as the 3 substituents, and the average degree of substitution with respect to the total value of the respective area ratios was calculated. The results are shown in Table 4 below. <<HPLC measurement conditions>> Tube column. TSK-gel ODS-IOOZ (Tosoh), 4.6 x 150 mm, batch number (P0014) Dissolution liquid A: H2 〇 = l 〇〇, dissolving solution B: AR = 1 〇〇. Both A and B were placed in AcOH and NEt3 at 0.1% flow rate: 1 ml/min, column temperature: 40 ° C, wavelength: 254 nm, sensitivity: AUX2, injection amount: 10 μΐ, eluent: THF/ H2O = 9/1 (volume ratio) Sample concentration: 5 mg M0 ml (THF) [Evaluation] (face failure) 58 201213409

N 將纖維素醋膜捲取為輥狀，自該圓捲而裁斷l〇〇 mmxlOO mm之尺寸，使用偏光顯微鏡於正交偏光下倍 ^0倍下騎觀察，㈣㈣產生部位之錄而進行下述 則貝。異物是源自添加劑之滲出成分、表面之污垢、或膜 内部或表面之析^物，於偏光麵鏡下觀察為亮點。 〇 :異物之個數為〇〜9個 △:異物之個數為1.〇〜5〇個 X :異物之個數為51個以上 將所得之結果記載於下述表4。 (光學性能經時變化） 一藉由自動雙折射率計（KOBRA-WR、王子計測機器公 司製造）而測定纖維素酯膜於25°c下、相對濕度為6〇%下 之波長590 nm之Rth。進一步於63°C、相對濕度90%之 條件下保存20曰之後，藉由相同之測定條件而測定尺出。 將於高溫高濕條件下之保存前後之Rth之差作為光學性能 經時變化而記載於下述表4中。 (偏光板經時變化） 1)膜之鹼化 將所得之膜於保持為55。(：之1.5 mol/L之NaOH水溶 液（鹼化液）中浸潰2分鐘後，對膜進行水洗，其後，於 25°C之0.05 mol/L之硫酸水溶液中浸潰30秒之後，進一步 於流水下通過水洗浴3〇秒’使膜成為中性之狀態。而且， 重覆3次利用氣刀之脫水，使水落下後於70〇c之乾燥區域 滞留15秒而使其乾燥，製作進行了鹼化處理之膜。 59 201213409l 2) 偏光元件之製作 依照日本專利特開2001-141926號公報之實例〖而使 碘吸附於進行了延伸之聚乙烯醇膜上而製作厚度為2〇 之偏光元件。 3) 貼合 使用聚乙烯醇系接著劑，於偏光元件之兩側貼附所掣 作之纖維素酯膜101，於7(rc下乾燥10分鐘以上。將所^ 之偏光板作為偏光板101。同樣地使用纖維素酯膜102〜纖 維素酯膜125，製作偏光板102〜偏光板125。 4) 偏光板之評價 製作二組將偏光板之其中一個膜側藉由黏著劑貼合於 玻璃板上而成之樣品，將其配置為正交偏光而測定透射率 (初始透射率，於25°C、相對濕度60°/。下測定）。進一步 將上述樣品於63°c、相對濕度9〇%之條件下放置1〇〇〇小 時其後進一步於25。〇相對濕度60%下放置5小時以上， 然後再次配置為正交偏光而測定透射率（經時透射率）。將 初始透射率與經時透射率之於波長400 nm〜500 nm之範 圍内的最大變化幅度乘以100而所得之值作為偏光板經時N The cellulose vinegar film is taken up into a roll shape, and the size of l〇〇mmxlOO mm is cut from the round shape, and the polarizing microscope is used to observe the magnification under the orthogonal polarized light by 0 times, and (4) (4) the recording of the production site is performed. Said the shell. The foreign matter is derived from the exudation component of the additive, the dirt on the surface, or the analyte inside or on the surface, and is observed as a bright spot under a polarizing mirror. 〇 : The number of foreign matter is 〇~9 △: The number of foreign matter is 1. 〇~5〇 X: The number of foreign substances is 51 or more The results obtained are shown in Table 4 below. (Optical properties change over time) The cellulose ester film was measured at a wavelength of 590 nm at 25 ° C and a relative humidity of 6〇% by an automatic birefringence meter (KOBRA-WR, manufactured by Oji Scientific Instruments Co., Ltd.). Rth. Further, after storage for 20 63 under conditions of 63 ° C and a relative humidity of 90%, the ruler was measured by the same measurement conditions. The difference in Rth before and after storage under high temperature and high humidity conditions is described in Table 4 below as optical properties with time. (Polarization of the polarizing plate over time) 1) Alkalinization of the film The obtained film was kept at 55. (: 1.5 min of 1.5 mol/L NaOH aqueous solution (basified solution) was immersed for 2 minutes, then the membrane was washed with water, and then immersed in a 0.05 mol/L sulfuric acid aqueous solution at 25 ° C for 30 seconds, and further The film was brought to a neutral state by water bathing for 3 sec seconds under running water. Further, the water was dehydrated three times by air knife, and the water was dropped, and then dried in a drying area of 70 〇c for 15 seconds to be dried. The film which was subjected to the alkalization treatment. 59 201213409l 2) The production of the polarizing element was carried out in accordance with the example of JP-A-2001-141926, and iodine was adsorbed on the stretched polyvinyl alcohol film to have a thickness of 2 Å. Polarized component. 3) A polyvinyl alcohol-based adhesive is applied to each other, and the cellulose ester film 101 thus prepared is attached to both sides of the polarizing element, and dried at 7 (r) for 10 minutes or more. The polarizing plate is used as the polarizing plate 101. Similarly, the cellulose ester film 102 to the cellulose ester film 125 were used to prepare the polarizing plate 102 to the polarizing plate 125. 4) Evaluation of the polarizing plate Two sets of the film side of the polarizing plate were bonded to the glass by an adhesive. The sample formed on the plate was placed in a crossed polarized light to measure the transmittance (initial transmittance, measured at 25 ° C, relative humidity of 60 ° /.). Further, the above sample was allowed to stand at 63 ° C and a relative humidity of 9 % for 1 hour and then further at 25. The crucible was allowed to stand for 60 hours or more at a relative humidity of 60%, and then the polarized light was measured again to measure the transmittance (transmissive transmittance). The value obtained by multiplying the initial transmittance and the temporal transmittance by a maximum variation in the range of wavelengths from 400 nm to 500 nm by 100 is used as a polarizing plate elapsed time.

變化。透射率測定中使用分光光度計“ U-mO” {曰立製作 所股份有限公司} C 將所得之結果作為偏光板經時變化，記載於下述表4 中。 (霧度） 霧度之測定是於25Ϊ、相對濕度60%下，藉由霧度計 201213409Variety. In the measurement of the transmittance, a spectrophotometer "U-mO" was used. {U.S. Co., Ltd.} C The results obtained were changed as a polarizing plate over time, and are described in Table 4 below. (Haze) The haze is measured at 25 Ϊ and 60% relative humidity by haze meter 201213409

(HGM-2DP、suga test instruments C〇.，Ltd )，依照 JIS K-6714而對膜試樣4〇 mmX8〇 mm進行測定。關於霧度為 1.0%以上者，評價為霧度增大，關於霧度增大者，將其要 點示於下述表4中。 (滲出） 滲出是評價於摻雜物流鑄、乾燥後，於溫度6〇°c濕度 • 90%、溫度80%濕度10°/。之濕熱條件下經過1〇〇〇 h後時， 疋否產生添加劑之析出。關於滲出者，將其要點記戴於表 201213409 J'as 卜οο£ 偏光板 經時變 化 VO οο v〇 VO 00 S? ^ &lt; 铱 Ή 〇 〇〇 ο 卜 卜 ±i Q ^ 當§ 霧度增大 m ο 00 1 面狀 故障 〇 ο 〇 〇 〇 〇 〇 〇 Ο &lt; ο 〇 比較化合物（添加量〕 •*1) 1 I 1 1 1 1 1 1 I 1 I 通式（III)之脂肪族糖酯化合物 添加量 (重量 份） CO m m ΓΛ CO I 1 平均 取代 度 cs &lt;N v〇 CN i〇 cs ν〇 v〇 ϊ〇 CN v〇 CN 00 in I 1 取代基 乙醯基/ 異丁醯基 乙醯基/ 異丁醯基 乙醯基/ 異丁醯基 乙醯基/ 異丁醯基 乙醯基/ 異丁醯基 乙醯基/ 異丁醯基 乙醯基/ 異丁醯基 乙醯基/ 異丁醯基 1乙醯基i |乙醯基1 1 1 糖結構 蔗糖 蔗糖 蔗糖 蔗糖 蔗糖 蔗糖 1 蔗糖 蔗糖 蔗糖 l葡萄糖l 1 1 通式（I)、通式（Π)之芳香族糖酯化合物之混合體 添加量 (重量 份） CN 〇 CN CS 〇 〇 〇 rs &lt;N &lt;N 5〜3取 代物 m m cn m 寸 〇 1 艺 cn m ro m 艺 7〜6取 代物 w-&gt; v〇 v〇 cn in 00 〇\ &lt; (N CN m v〇 VO CN CN in 8取 代物 (N (N in 寸 〇〇 〇 寸 CN CN 寸 ν-ϊ 平均 取代度 卜 卜 卜 CN cn 1&gt; 卜 〇 〇〇 〇 — 卜 卜 Ο — 卜 in 取代基 苯甲醯基 苯甲醯基 苯甲醯基 1 :苯甲醯基 笨甲醯基 笨甲醯基 苯甲醯基 笨曱醯基 |笨曱醯基| 1笨曱醯基1 笨甲醯基 笨曱醯基 糖結 構 蔗糖 蔗糖 蔗糖 蔗糖 蔗糖 蔗糖 蔗糖 蔗糖 蔗糖 蔗糖 蔗糖 蔗糖 教 %ui 1)01 紱3♦鹊 Ο 〇 S S g ψ Η ο 1—^ CN 實例1 實例2 實例3 實例4 實例5 實例6 實例q 實例8 比較 例3 比較 例4 ΰ 201213409 J-as 卜οοε Η 00 ο /-~Ν 拿 t〇H ΦΊ φ| 费 μ ±3 33 〇 0 X 1 1 3械 ^ 3 w »1 ^ ®- 5 ijm ¢^1 ^ 11 Aim ^ Γ U ^ 械价一掛t〇 S雪， 锌 t ο 1 CS 1 v〇 1 乙醯基/ 異丁醯基 1 蔗糖 1 1 1 1 1 ο 1 ο οό 1 瘤 φ( ifhil ψ&gt;Ί ο 苯甲醯基 1 蔗糖 1 cm ϊ &lt; ε 饀 Η〇 &lt;η 比較 例5 錄ο 磁Γ-£ 5 /•&quot;Ν * 201213409 JO /Ujpn' 根據表4可知：含有混合有滿足本發明之範圍的芳香 族糖酯與脂肪族糖酯者的纖維素酯膜之面狀故障少，光學 性能經時變化亦小，且偏光板之經時性能變化亦小，作為 保護膜而言優異。另外，根據實例7可知：於作為通式（1)、 通式（II)之化合物使用芳香族糖酯之蔗糖苯曱酸酯之平 均取代度為4.0之取代物之情形時’存在偏光板經時變化 變大之傾向。而且，根據實例9可知：於作為通式（ΠΙ) 之化合物的脂肪族糖醋使用糖結構為單糖骨架（吡喃糖骨 架）的葡萄糖殘基之化合物之情形時，存在偏光板經時變 化變大之傾向。 另一方面，根據比較例1及比較例2可知：於作為通 式（I)、通式（II)之化合物使用芳香族糖酯之嚴糖^甲 酸酉旨之平均取代度7.5以上的取代物或者僅使用8置換之^ 情形時，分別引起霧度增大、產生渗出之問題。 ' 根據比較例3〜比較例5可知：於僅僅單獨使用作為 通式（I)、通式（Π)之化合物的芳香族糖酯，未使用作 為通式（III)之化合物的脂肪族糖酯之情形時，光學性〜 經時變化變大。 根據比較例6可知：於僅僅單獨使用作為通式（Ιπ) 之化合物的脂肪族糖酯’並未使用作為通式（I)、通式（π) 之化合物的芳香族糖酯之情形時，光學性能經時變化變大。(HGM-2DP, suga test instruments C〇., Ltd), the film sample 4〇 mmX8〇 mm was measured in accordance with JIS K-6714. When the haze is 1.0% or more, the haze is evaluated to be increased, and the haze is increased as shown in Table 4 below. (Exudation) Exudation is evaluated after the doping stream is cast and dried at a temperature of 6 ° C humidity • 90%, temperature 80% humidity 10 ° /. The precipitation of the additive occurs after 1 〇〇〇 h under humid and hot conditions. Regarding the exuder, record the main points on the table 201213409 J'as Bu οο £ Polarimetric change over time VO οο v〇VO 00 S? ^ &lt; 铱Ή 〇〇〇ο Bub ±i Q ^ When § Haze Increase m ο 00 1 Surface failure 〇ο 〇〇〇〇〇〇Ο &lt; ο 〇Comparative compound (addition amount) •*1) 1 I 1 1 1 1 1 1 I 1 I Fat of formula (III) Addition amount of the sugar ester compound (parts by weight) CO mm ΓΛ CO I 1 Average degree of substitution cs &lt;N v〇CN i〇cs ν〇v〇ϊ〇CN v〇CN 00 in I 1 Substitudinyl group / different醯丁基乙醯基/ Isobutyl Group Ethyl / Isobutyl Ethyl Acetyl / Isobutyl Ethyl Acetyl / Isobutyl Ethyl Acetyl / Isobutyl Ethyl Acetyl / Isobutyl Ethyl Ethyl / Isobutyl 1 Ethyl I | B Mercapto 1 1 1 sugar structure sucrose sucrose sucrose sucrose sucrose 1 sucrose sucrose sucrose l 1 1 a mixture of aromatic sugar ester compounds of the formula (I), formula (Π) (wt parts) CN 〇 CN CS 〇〇〇rs &lt;N &lt;N 5~3 Substitute mm cn m Inch 〇 1 Art cn m ro m Art 7~6 Substitute w-&gt; v〇v〇cn in 00 〇\ &lt; (N CN mv〇VO CN CN in 8 Substitute (N (N in inch inch CN CN inch ν-ϊ average Substitution degree 卜卜卜CN cn 1&gt; 〇〇〇〇 〇〇〇〇 卜 Ο 卜 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代 取代甲基基笨曱醯基 | 笨曱醯基 | 1 曱醯基基1 Stupid 醯 醯 曱醯 曱醯 曱醯 曱醯 sucrose sucrose sucrose sucrose sucrose sucrose sucrose sucrose sucrose sucrose sucrose %ui 1) 01 绂 3♦鹊Ο 〇 SS g ψ Η ο 1—^ CN Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example q Example 8 Comparative Example 3 Comparative Example 4 ΰ 201213409 J-as 卜οοε Η 00 ο /-~Ν Take t 〇H ΦΊ φ| Fee μ ±3 33 〇0 X 1 1 3 机械 ^ 3 w »1 ^ ®- 5 ijm ¢^1 ^ 11 Aim ^ Γ U ^ Price hangs t〇S snow, zinc t ο 1 CS 1 v〇1 Ethyl group / Isobutyl group 1 Sucrose 1 1 1 1 1 ο 1 ο οό 1 Tumor φ ( ifhil ψ > Ί ο Benzyl thiol 1 sucrose 1 cm ϊ &lt; ε 饀Η〇 &lt;η Comparative Example 5 Recording Γ Magnetic Γ - £ 5 /•&quot; Ν * 201213409 JO /Ujpn' According to Table 4, it is known that fibers containing an aromatic sugar ester and an aliphatic sugar ester which satisfy the range of the present invention are contained. The surface loss of the polyester film is small, the optical performance changes little with time, and the change in the temporal performance of the polarizing plate is small, which is excellent as a protective film. Further, according to Example 7, it is understood that in the case where the average degree of substitution of the sucrose benzoate of the aromatic sugar ester is 4.0 as a compound of the formula (1) or the formula (II), the polarizing plate is present. The tendency to change when it changes. Further, according to Example 9, it is understood that when a compound having a sugar structure of a glucose residue of a monosaccharide skeleton (pyranose skeleton) is used as the aliphatic sweet and sour vinegar of the compound of the formula (ΠΙ), there is a change in the polarizing plate over time. The tendency to become bigger. On the other hand, according to Comparative Example 1 and Comparative Example 2, it is understood that a substituent having an average degree of substitution of 7.5 or more is used as the compound of the general formula (I) or the formula (II) using an aromatic sugar ester. Or, when only the case of 8 replacement is used, the problem of an increase in haze and occurrence of bleeding is caused. According to Comparative Example 3 to Comparative Example 5, an aliphatic sugar ester which is a compound of the formula (I) or a compound of the formula (III) is used alone, and an aliphatic sugar ester which is a compound of the formula (III) is not used. In the case of the optical property, the change over time becomes large. According to the comparative example 6, when the aliphatic sugar ester which is a compound of the general formula (I) and the aromatic sugar ester of the compound of the general formula (I) is not used alone, The optical properties change over time.

根據比較例7可知：於使用通式（I)〜通式（班）之 糖酯以外的比較化合物之情形時，產生由於添加劑之揮發 性所造成之面狀故障0 X 64 201213409, I \JU IJiM.According to Comparative Example 7, when a comparative compound other than the sugar ester of the general formula (I) to the general formula (ban) was used, a planar failure due to the volatility of the additive was generated. 0 X 64 201213409, I \JU IJiM.

[實例9] 於實例1之試樣103中，將纖維素酯替換為乙醯基取 代度為2.94之材料，除此以外同樣地進行而製作試樣 401。試樣401與試樣103同樣地獲得良好之結果。 [實例101〜實例103] (硬塗層塗佈膜之塗設） 對實例1、實例2、實例8中所得之試樣101、試樣1〇2、 試樣109以如下之態樣進行硬塗層塗佈。另外，於下述硬 塗1〜硬塗4中’於試樣101中使用硬塗1，於試樣1〇2 中使用硬塗4，於試樣109中使用硬塗3。 硬塗1〜硬·塗4為下述表3中所示之組成物，uv起始 劑1為下表中所7F之結構。 [表5] 單體1 單體2 單體1/ 單體2 UV起始 劑 單體/UV 起始劑比 固形物濃度 溶劑1 溶劑2 溶劑1/ 硬塗1 季戊四醇三 丙烯酸δ旨 季戊四醇 四丙稀酸 酯 3/2 trv起始 劑1 53.5/1.5 55 乙酸乙酯 硬塗2 季戊四醇三 丙烯酸酯 季戊四醇 四丙婦酸 3/2 UV起始 劑1 53.5/1.6 55 乙酸乙酯 甲基乙基 酮 ---- 1/1 硬塗3 季戊四醇三 丙烯酸酯 季戊四醇 四丙稀酸 酯 3/2 UV起始 劑1 53.5/1.7 55 甲笨 曱基異丁 基_ 9/1 硬塗4 二季戊四醇 六丙烯酸酯 - UV 起ii&quot; 劑1 53.5/1.8 55 甲笨 ~甲基異丁~ 基酿I 9/1 硬塗1〜硬塗3中所使用之光聚合性單體是日本化藥 股份有限公司之PET30，硬塗4中所使用之單體是日本化 藥股份有限公司之KAYARAD DPHA。 65 201213409, JO /U-7pl^[Example 9] A sample 401 was produced in the same manner as in the sample 103 of the example 1, except that the cellulose ester was replaced with a material having an ethylene group substitution of 2.94. The sample 401 obtained good results in the same manner as the sample 103. [Example 101 to Example 103] (Coating of the hard coat coating film) The sample 101, the sample 1〇2, and the sample 109 obtained in Example 1, Example 2, and Example 8 were hardened as follows. Coating coating. Further, in the following hard coat 1 to hard coat 4, hard coat 1 was used for sample 101, hard coat 4 was used for sample 1〇2, and hard coat 3 was used for sample 109. Hard coating 1 to hard coating 4 are the compositions shown in Table 3 below, and uv initiator 1 is the structure of 7F in the following table. [Table 5] Monomer 1 Monomer 2 Monomer 1 / Monomer 2 UV initiator monomer / UV initiator ratio solid concentration solvent 1 Solvent 2 Solvent 1 / Hard coating 1 Pentaerythritol triacrylic acid δ pentaerythritol tetrapropyl Dilute ester 3/2 trv starter 1 53.5/1.5 55 Ethyl acetate hard coat 2 Pentaerythritol triacrylate pentaerythritol tetrapropanoic acid 3/2 UV starter 1 53.5/1.6 55 ethyl acetate methyl ethyl ketone ---- 1/1 Hard Coating 3 Pentaerythritol Triacrylate Pentaerythritol Tetraacrylate 3/2 UV Starter 1 53.5/1.7 55 Alum-based Isobutyl _ 9/1 Hard Coat 4 Dipentaerythritol Hexa Acrylic Acid Ester-UV from ii&quot; Agent 1 53.5/1.8 55 甲笨~Methyl butyl ketone ~ Base I 9/1 Hard coating 1 ~ Hard coating 3 The photopolymerizable monomer used is Nippon Chemical Co., Ltd. The monomer used in PET30, Hard Coating 4 is KAYARAD DPHA of Nippon Kayaku Co., Ltd. 65 201213409, JO /U-7pl^

UV 起始劑 1 使用 Ciba Japan K.K.之 IRGACiURE 127。 硬塗之塗佈條件是於利用支數（yarn count) 8之棒式 塗佈機之手塗佈後’於1〇〇。(：下乾燥60秒，於氮氣0.1% 以下之條件下以1.5 kW、300mJ照射UV而使其硬化。 (密接性評價） 藉由下述之方法進行光照射後之密接性評價。 進行以JIS K 5600為基準之栅格試驗。具體而言，於 破塗塗佈及uv硬化後之樣品表面上以i mm之間隔縱相 各切入11根切痕而製作100個i mm見方之栅格。於其』 貝占附透明膠帶及瑪拉膠帶（mylar tape)，藉由目視觀察却 速剝下而娜之部位，進行密接評價。樣品 濕度帆之相進行2小相上之濕度控綱 於切入城前騎Xe 24㈣躺 是表1中之狀⑽密接結果，如Μ、=進行ί 换48 h密接結果。未進行心照射而進 行雄、接评彳貝之結果是初始密接評價。 密接性〇 :剝離部位為〇塊〜1〇塊 66 201213409 密接性△:剝離部位為u塊〜49塊 密接性X :剝離部位為50塊〜99塊 密接性XX : _部位為廳塊以上（貼有 部分UV initiator 1 IRAACiURE 127 from Ciba Japan K.K. The coating conditions of the hard coat were applied after hand coating using a yarn counter of a yarn count of 8 . (: After drying for 60 seconds, UV was irradiated by irradiating UV at 1.5 kW and 300 mJ under conditions of 0.1% or less of nitrogen gas. (Evaluation of adhesion) The adhesion after light irradiation was evaluated by the following method. K 5600 is a reference grid test. Specifically, on the surface of the sample after the spray coating and the uv hardening, 11 slits were cut in the longitudinal direction at intervals of i mm to prepare a grid of 100 i mm squares. In its "Bai Zhan attached scotch tape and mylar tape", by visual observation, it quickly peeled off the part of Na, and made a close evaluation. The phase of the sample humidity sail was carried out on the 2 small phase of the humidity control. The Xe 24 (four) lying in front of the city is the result of the close connection in Table 1 (10), such as Μ, = ί for 48 h. The results of the male and the evaluation of the mussel without the heart irradiation are the initial close evaluation. : Peeling part is 〇 block ~ 1 〇 block 66 201213409 Adhesion △: Peeling part is u block ~ 49 pieces of adhesion X: Peeling part is 50 pieces ~ 99 pieces of adhesion XX : _ part is above the block (with part

的全部） VAll) V

Xe之照射中使用suga test instrumems c〇山纪製造厶 super xenon weather meter SX75 〇 其結果可知：於Xe 24小時下均成為〇之評價。 (鉛筆硬度評價） 藉由下述方法進行鉛筆硬度評價。 將硬塗塗佈及UV硬化後之樣品於25ΐ、相對濕度 60%之條件下進行2小時之濕度控制後使用瓜§ 6_ =定之試驗用錯筆’依照JISK54⑻所規定之錯筆硬度 «平使用500 g之砝碼而以各硬度之鉛筆反覆劃$次， 將4 ^以上無傷痕之硬度測定為0K。另外，JIS K 5400 :斤疋義之傷痕疋塗膜之破裂、塗膜之擦傷，塗膜之凹下 為對象而§己載’但於此處’包括塗膜之凹下亦被判 斷為傷痕。數字越大，表示硬度越高。 其結果可知：均為良好（全部於3Η下為ΟΚ評價）。 例301 .於IPS模式液晶顯示裝置中之封裝實驗] + 纖維素㉖膜1G1與市售之纖維素賴（Z-tack、富 理=份有限公司製造）進行與實例1同樣之驗化處 中所制/Λ·步使用聚乙稀醇系接著劑，以2個膜夾入實例1 ^作之偏光元件，於贼下賴1G分鐘以上。 乂偏光7L件之透射軸與如上所述而製作之纖維素酯膜 67 201213409 JO/ WJJJif s 之遲相軸平行之方式進行配置。以偏光元件之透射軸與市 售之二醯化纖維素膜之遲相軸正交之方式進行配置。 (液晶單元） 液晶單元或電極、基板可直接使用自先前用作;[PS之 液晶單元或電極、基板。液晶單元之配向為水平配向’可 使用開發、市售為IPS液晶用之液晶單元。液晶單元之物 性是液晶之△!!·為0.099、液晶層之單元間隙為3.0 μπι、預 傾角為5。、摩擦方向為基板上下均為75。。 (於IPS面板中之封裝） 將使用有上述垂直配向型液晶單元之液晶顯示裝置的 於上側偏光板、下側偏光板（背光源側）上具有上述纖維 素酉曰膜101之偏光板，以該纖維素醋膜Z_tack成為液晶單 凡側之方式進行設置。上側偏光板及下侧偏光板經由黏著 劑而貼附於液晶單元上。上側偏光板之透射軸成為上下方 向，且下側偏光板之透射軸成為左右方向，從而設為正交 偏光配置。 將透射率之比（白顯示/黑顯示）作為對比率，使用測 疋機（EZ-Contrast 160D、ELDIM公司製造）’以黑顯示（li ) 至白顯示（L8)之8個階段測定視角（對比率為1〇以上 且無黑側之灰階反轉之極角範圍）。 對所製作之液晶顯示裝置進行觀察之結果，使用本發 明之膜的液晶面板於正面方向及視角方向之任意方向中均 實現中性之黑顯示。 [實例302] 68 201213409 於實例1之試樣101中，將膜厚設為4〇 μιη，除此以 外同樣地進行而製作試樣501。使用此試樣5〇1而與 301—同樣地製作偏光板，進行於ips模式液晶顯示 裝實驗。封裝有該偏光板之IPS液晶面板於正&lt; 封 中性之黑顯示，是良好的液晶面板。 向幾得 【圖式簡單說明】 〇 【主要元件符號說明】 M. 〇 69In the Xe irradiation, suga test instrumems was used. 〇 super xenon weather meter SX75 〇 The results showed that it was evaluated as X〇 at 24 hours. (Evaluation of pencil hardness) Pencil hardness evaluation was performed by the following method. The sample after hard coating and UV hardening is subjected to humidity control for 2 hours under conditions of 25 ΐ and relative humidity of 60%, and then the test erroneous pen 'in accordance with JIS K54 (8) The weight of 500 g is reversed by a pencil of each hardness for $0, and the hardness of 4^ or more without scratch is measured as 0K. In addition, JIS K 5400: rupture of the scar film of the 疋 疋 、 、 、 、 、 、 、 、 、 、 、 、 、 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The higher the number, the higher the hardness. As a result, it was found that all of them were good (all were evaluated at 3Η). Example 301. Packaging experiment in IPS mode liquid crystal display device] + Cellulose 26 film 1G1 and commercially available cellulose Lai (manufactured by Z-tack, Fuli = Co., Ltd.) were subjected to the same test procedure as in Example 1. The prepared / Λ step was made using a polyethylene glycol-based adhesive, and the polarizing element of Example 1 was sandwiched between two films, and the thief was allowed to stand for 1 G min or more. The transmission axis of the 乂-polarized 7L member is arranged in parallel with the retardation axis of the cellulose ester film 67 201213409 JO/ WJJJif s prepared as described above. The transmission axis of the polarizing element is disposed so as to be orthogonal to the late phase axis of the commercially available dibasic cellulose film. (Liquid Crystal Cell) The liquid crystal cell or electrode and the substrate can be used directly from the previous ones; [PS liquid crystal cell or electrode, substrate. The alignment of the liquid crystal cell is horizontal alignment. A liquid crystal cell that is developed and commercially available as an IPS liquid crystal can be used. The physical properties of the liquid crystal cell are Δ!!· of the liquid crystal layer of 0.099, the cell gap of the liquid crystal layer is 3.0 μm, and the pretilt angle is 5. The rubbing direction is 75 on both the upper and lower sides of the substrate. . (Package in the IPS panel) A polarizing plate having the above-described cellulose film 101 on the upper polarizing plate and the lower polarizing plate (backlight side) of the liquid crystal display device having the above-described vertical alignment type liquid crystal cell is used. The cellulose vinegar film Z_tack is set in such a manner as to be a single side of the liquid crystal. The upper polarizing plate and the lower polarizing plate are attached to the liquid crystal cell via an adhesive. The transmission axis of the upper polarizing plate is up and down, and the transmission axis of the lower polarizing plate is in the left-right direction, so that it is arranged in an orthogonal polarization. The transmittance ratio (white display/black display) was used as a contrast ratio, and the angle of view was measured using eight stages of black display (li) to white display (L8) using a measuring machine (EZ-Contrast 160D, manufactured by ELDIM). The contrast ratio is 1 〇 or more and there is no polar angle range of gray scale inversion on the black side). As a result of observing the liquid crystal display device produced, the liquid crystal panel using the film of the present invention realized a neutral black display in any of the front direction and the viewing angle direction. [Example 302] 68 201213409 In the sample 101 of the example 1, the film thickness was set to 4 μm, and the sample 501 was produced in the same manner. Using this sample 5〇1, a polarizing plate was produced in the same manner as in 301-, and an ips mode liquid crystal display mounting experiment was performed. The IPS liquid crystal panel encapsulating the polarizing plate is a positive liquid crystal panel in a positive black display. Toward a few [Simplified description of the drawing] 〇 [Description of main component symbols] M. 〇 69

Claims (1)

201213409 / ν/^μ;ιΓ 七、申請專利範圍： 1· 一種纖維素醋膜，其含有纖維素醋、 所表不之芳香族糖酯化合物、下述通式⑻ : 香族糖酯化合物、下述通式不方 合物，其特徵在於·· ）所表不之脂肪族糖酯化 an所戶 =式⑴示之芳麵糖s旨化合物與所述通式 9=所表不之方㈣_化合物之平均酯取代度不足 (I) (HO^-G-CL-R1^ (II) (HO^-G-CL-R1^ (III) (HO)rG，-(IAR2)r (於所述通式⑴〜所述通式（ΙΠ)中，〇及 殘基或二糖殘基；R1分別獨立地表示脂肪 Ϊ 一個表示芳香族基;R2分別獨立地 =月曰肪族基；L及立地表示2價之連結基；瓜 f不=上之整數’n、p及q分別獨立地表示1以上之整 數’Γ表不3以上之整數，t表示。以上之整數；其中，m +n:4，P+_’m&gt;p’n&lt;q;g，m+n4 =與假定所述G並非殘基而是相同骨架之環狀祕結構之 未經取代之糖類之情形時的經基數相等，r+t血假定所述 G’並非殘基而是相同骨架之環狀祕結構之未經取代之糠 類之情形時的羥基數相等）。 2.如申請專利範圍第！項所述之纖維素醋膜，其中， 所述通式（III)中之所述厌2表示2種以上之脂肪族基。 201213409 3. 如申請專利範圍第1項所述之纖維素醋膜，其中， 所述通式（III)中之所述G，表示二糖殘基。、 4. 如申請專利範圍第1項所述之纖維素酉旨膜，1中， 所述通式（I)及所述通式㈤中之所述〇為簾糖骨 架，所述通式（I)絲示之芳钱細旨化合物與所述通式 (II)所表示之芳香族糖酯化合物之平均酯取代度為5〜 7.5。 · 又’’、、〜 5. 如申請專利範圍第4項所述之纖維素酯膜，其中， 所述通式（II)中之q為8之芳香族糖g旨之添加量相 對於所述通式（I)所表示之芳香族糖醋化合物及所述通式 (II)所表示之芳香族糖酯化合物之合計添加量而言不足 20 wt% 〇 6·如申請專利範圍第1項至第5項中任一項所述之纖 維素酯膜，其中， 所述通式（I)以及所述通式（n)中之所述L、及所 述通式（III)中之所述L，分別獨立地表示單鍵、_〇_、_c〇_、 -NR11- (R11表示1價之取代基）之任一個。 7. 如申請專利範圍第1項至第5項中任一項所述之纖 維素酯膜，其中， 所述通式（0以及所述通式（II)中之所述R1、及所 述通式（III)中之所述^2分別獨立地表示醯基。 8. 如申凊專利範圍第1項至第5項中任一項所述之纖 維素酯膜，其中， 所述通式（I)及所述通式（Π)中之所述R1表示苯甲 71 201213409 醯基。 9·如申請專利範圍第1項至第5項中任—項所述之纖 維素酯膜，其中， 所述通式（III)中之所述尺2分別獨立地表示非環式脂 肪族。 10. 如中料郷圍第i項至第5項巾任—項所述之 纖維素酯膜，其中， 所述通式（m)中之所教2中之至少一種表示分支狀 之脂肪族基。 11. 如中料利範圍第i項至第5項巾任—項所述之 纖維素酯膜，其中， 所述通式⑽中之所述反2僅包含乙酿基與異丁酿基。 12. -種偏光板’其具有㈣元件、與配置於所述偏 光元件之兩侧的保護膜，其特徵在於： 所述保護膜之至少1枚是如申請專利範圍第i項至 11項中任一項所述之纖維素酯膜。 H1 曰3.二種液晶齡裝置’其具有液晶單元及配置於所 述液晶單元之兩側的偏光板，其特徵在於. 述之:=光板中之至少1枚是”請專利範圍㈣項所 72 201213409 1 L 四、 指定代表圖： (一) 本案指定代表圖為：無。 (二) 本代表圖之元件符號簡單說明： 益。 五、 本案若有化學式時，請揭示最能顯示發明特徵 的化學式： (HO^-G-CL-R1^ 201213409, , 爲第10G127G33 1¾巾文麵 期:100 年 U#表年月曰 發明專利說明書^ (本說明書格式、順序’請勿任意更動’※記號部分請勿填寫） ※申請案號^ ^ &lt;2006.0 υ ※申請日：\。。、。）” PC ： CJL &lt;2006.0 υ -'發明名稱··（中文，英文） ㈣£二:::1 ❹ 纖維素酯膜、偏光板及液晶顯示裝置 CELLULOSE ESTER FILM, POLARIZING PLATE AND LIQUID-CRYSTAL DISPLAY 二、中文發明摘要： 一種纖維素酯膜’其含有纖維素酯、通式（j)所表示 之芳香族糖酯化合物、通式（II)所表示之芳香族糖酯化 5物通式（hi)所表示之脂肪族糖醋化合物，且所述通 式（I)所表示之芳香族糖酯化合物與所述通式（11)所表 不之芳香族糖酯化合物之平均酯取代度不足94%。 Ο 曰 (1) (HOk-G-a-R、；（II) (H0) g_(l_r1) (HO)rG'-(L^R2)r ； ；q U ； G’表示單賊基或二糖錄；&amp;表示脂肪族基 ίΓ2 ΐ 少—個為芳香族基；R2為脂肪族基；L及 一貝之連結基；m、t為〇以上之整數；n 以上之整數;…以上之整數;其中，心二么 m&gt;P ； n&lt;q 〇 ) P^q== 1 201213409 爲第100127033號中文說明書無劃線修正頁修正日期:100年丨〇月14日 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種纖維素酯膜、偏光板及液晶顯示 裝置。 【先前技術】 於鹵化銀照相感光材料、相位差膜、偏光板及影像顯 示裝置中使用有以纖維素酯、聚酯、聚碳酸酯、環烯烴聚 合物、乙烯系聚合物及聚醯亞胺等為代表之聚合物膜。由 該些聚合物可製造於平面性或均一性之方面更優異之膜， 因此被廣泛用作光學用途之膜。例如，具有適宜之透濕度 的纖維素酯膜可在線（online)與最一般的包含聚乙烯醇 (PVA) /蛾之偏光元件（Polarizer)直接貼合。因此，纖 維素酯、特別是乙酸纖維素被廣泛用作偏光板之保護膜。 於將纖維素酯膜用於液晶顯示裝置之情形時，為了罈 境變化之偏光元件保護（偏光板耐久性），須要膜之疏= =。疏水化中通常使用添加劑。然而，於作為製造纖維素 酯膜之方法而廣泛使用的溶液成膜法中，為了於短時間内 使溶劑揮發而包含乾齡驟ϋ疏水化用添加 燥步驟中揮發_著於製造機上，再次冷卻㈣污垢之= 式附著於膜上，作為面狀故障之原因之—而成為問題。） 旦於近年已知有以抑制揮發為目的而增大添加劑之分 1的方法，但存在分子量大之添加劑產生自膜渗出（J 題物系之塑化劑而作為添加劑 201213409 修正日期:100年月14日 爲第100127033號中文說日月書無劃線修JE頁 時的經基數相等。 所述斤述m+n、p+q及出之上限值可採用根據 ^之種類而決定之值’若G^’為單糖殘基則 成為5，右為二糖殘基則成為8。 0 紗社通式⑴〜通式（ΠΙ)所表示之所述細旨化合物 义土。〇'疋具有一個呋喃搪結構或吡喃糖結構之所述G或 G’為單糖殘基的化合物（Α)巾、紐結有2個吱喃糖結 構或吼喃糖結構之至少—種的所述G或G，為二糖殘基的化 合物（B)中之0H基之全部或一部分進行醋化而成的酯 化化合物。 然而，本發明中所使用之糖酯化合物混合體之特徵在 於··於所述通式（I)及通式（11)中，滿足m&gt;p&amp;n&lt;q， 亦即’至少所述通式（I)所表示之糖酯化合物之OH基並 未完全被酯化。藉由如上所述而使用酯取代度不同之多種 芳香族糖酯化合物，於製造步驟中之揮發性變低，且於成 膜後變得難以自纖維素酯膜滲出。 〇 化合物（A)之例可列舉葡萄糖、半乳糖、甘露糖、 果糖、木糖或***糖，但並不限定於該些化合物。 化合物（B)之例可列舉乳糖、蔗糖、蔗果四糖 (nystose)、庶果五糖（IF- fructosyl nystose)、水蘇糖 (stachyose)、麥芽糖醇、乳糖醇、乳酮糖（lactulose)、 纖維雙糖（cellobiose)、麥芽糖、纖維三糖、麥芽三糖、 棉子糖（raffinose)或蔗果三糖（kestose)。除此以外，亦 可列舉龍膽二糖、龍膽三糖、龍膽四糖、木三糖 13 201213409 、修正日期:100年1〇月14日 i第100127033號中文說明書無劃線修^胃 (xylotriose )、乳果寡聽（iact〇sucr〇se )等但並不限定 於該些化合物。 於該些化合物（A)及化合物（B)中，特佳的是具有 〇夫喃糖結構與°比喃糖結構雙方之化合物。例子較佳的是蔗 ，三蔗果二糖、蔗果四糖、蔗果五糖、水蘇糖等，更佳的 是蔗糖。而且’於化合物（Β)申，鍵結有2個呋喃糖結 構或吼喃糖結構之至少一種的化合物亦是較佳之態樣之 用以對化合物（Α)及化合物（Β)中之ΟΗ基之全部 或一部分進行酯化的取代基並無特別限制。其中，較佳的 是使用單羧酸。亦即’較佳的是所述通式以及所述通 式（Π)中之所述R1、及所述通式（111)中之所述尺2分別 獨立地表示醯基。 所述單缓酸並無特別之限制，可使用公知之脂肪族單 叛酸、脂環族單羧酸、芳香族單羧酸等。所使用之鲮酸可 為一種，亦可為2種以上之混合。於所述R1或所述圮為 多種之情形時’可相互相同亦可不同。 另一方面’較佳的是所述通式（I)以及所述通式（11) 中之所述L、及所述通式（ΠΙ)中之所述L，分別獨立地表 示單鍵、-Ο-、_CO-、-NR11- (R11表示1價之取代基）之 任一個；而且，於所述L或所述L，為多個之情形時，可相 互相同亦可不同。其中，自所述R1及R2可容易地被醯基 取代之觀點而言，較佳的是所述L或所述L，表示-〇_。 (通式（I)及通式（II)所表示之芳香族糖酯化合物 14 201213409 修正日期:年10月14日 爲第100127033號中文說明書無劃線修正頁 之混合體） 其次，對所述通式（I)及通式（π) 糖酯化合物之較佳態樣加以說明。 所表示之芳香族 笮，所述R1分別獨立地 個表示芳香族基。其中， 示芳香族基，更佳的是所 於所述通式（I)及通式（π)令， 表示脂肪族基或芳香族基，至少一値 較佳的是所述R1分別獨立地僅表示 有R1均表示相同之芳香族基。 〇 祕徵在於所料式⑴職示之料絲S旨化合物 與所述通式（II)所表示之芳香族糖醋化合物之平均醋取 代度不；194%。藉由如上所述而使2種社之芳香族糖醋 化合物之混合體的平均酯取代度不足94%，可使所得之纖 維素酯膜之霧度顯著變小，且可作為光學膜而良好地用於 偏光板或液晶顯示裝置中。 自可減少於内裝至偏光板時於濕熱環境下之正交透射 率的經時變化的觀點考慮’較佳的是所述通式所表示 之芳香族糖酯化合物與所述通式（II)所表示之芳香族糖 Ο 酯化合物之平均酯取代度為62%以上且不足94%。 另外，自可減少於内裝至偏光板時於濕熱環境下之正 交透射率的經時變化的觀點考慮，更佳的是所述通式（I) 及所述通式（II)中之所述G為蔗糖骨架，所述通式（I) 所表示之芳香族糖酯化合物與所述通式（II)所表示之芳 香族糖酯化合物之平均酯取代度為5〜7.5，特佳的是5.5 〜7.0。 而且，於所述通式（I)及通式（II)中，m表示0以 15 201213409 爲第麵細號中文說明書無畫臟修頭 修正日期:⑽年10月14日 上之整數，n、P&amp;q分別獨立地表示丨以上之整數，真m &gt;p，n&lt;q。 於本發明中，自所得之纖維素醋膜之霧度顯著變小的 觀點考慮，較佳的是於所述G為二糖殘基之情形時，所述 通式（II)中之q為8之芳香族糖酯之添加量相對於所述 通式（I)所表示之芳香族糖酯化合物及所述通式（II)戶斤 表示之芳香族糖酯化合物之合計添加量而言為不足2〇 wt%。於所述G為二糖殘基之情形時，並不具有—個羥基 作為取代基的芳香族糖酯化合物之含量相對於所有芳香族 糖酯之含量而言較佳的是20 wt%以下，更佳的是15 wt% 以下’特佳的是10 wt%以下，進一步特佳的是5 wt%以下。 另一方面，於本發明中，所述通式（1)所表示之芳香 族糖酯化合物與所述通式（II)所表示之芳香族糖酯化合 物於所述G為二糖殘基之情形時，較佳的是11為3以上， 5以上亦較佳。亦即，於本發明中，較佳的是至少所述芳 香族糖酯化合物混合體中所含之芳香族糖酯化合物為至少 3取代物以上，至少5取代物以上亦較佳。 於所述方香族糖醋化合物為2糖類之情形時，被g旨化 之取代基為3個〜5個之3取代物〜5取代物的含有率相對 於芳香族糖酯化合物全體而言較佳的是10%〜，更佳 的是20%〜50%。6取代物〜7取代物之含量相對於芳香族 糖酯化合物全體而言較佳的是20%〜85%，更佳的是2〇% 〜75%。 於由R1取代時所使用之較佳之芳香族單綾酸之例可 16 201213409 修正日期:100年10月14日 爲第謂127G33號巾織鴨細線修正頁 任意階段進行，較佳的是於流鑄之後立即進行。於盔風下 =行^燥之時間於帶上之情形時，若不足10秒（於鼓上之 情形時不足1秒），則添加劑難以均一地分布於膜内，若超 過90心（於豉上之情形時超過1〇秒），則乾燥不充分而 得剝下，臈之面狀惡化。 、，韌下剷乾燥中之於無風下進行乾燥以外的時間可藉由 达風惰性氣體^騎錢。此時之風溫較佳的是〇t〜 0 18〇C ’ 更佳的是 40°C 〜150°C。 關於溶劑繞鑄法中之乾燥方法，於美國專利則训 ，、吳國專利2367603號、美國專利2492078號、美國專 號、美國專利膽78號、美國專利厕^ ί Γ Μ%69號、美國專利2739070號、英國專 ^Γ4 國專利736892號之各說明書，日本專利 特a昭45-4554號、日本專利特公昭49 5614號、日 bT^T176834 ^ 6〇·2〇343〇 ^ ο鼓上之，择=:2-115035號各公報中有所記載。於帶或 得之膜自鼓或帶剝下，進一步藉由於；0。。 _(:㈣姐變溫度的高溫簡行 所【載;=1本專利特公平5,號二1 榜雜IS:，流鱗時之鼓或帶之表*溫度下使 亦可使用調製之纖維素酯溶液（摻雜物）進行二層以 37 201213409 修正日期:100年1〇月丨4臼 爲第100127033號中文說明書無畫丨i線修正頁 上之流_錢㈣化。於此情科，較麵是藉由溶刻 洗鑄法製作纖維素酯膜。使摻雜物流鑄於鼓或帶上，使溶 劑蒸發而形賴。較佳的是對流鑄前之_物進行濃产调 整以使固形物量成為〜4〇%之。鼓或帶之表ς較 佳的是預先精加工為鏡面狀態。 本發明之纖維素酯膜之較佳之寬度為05m〜5m，更 佳的是0.7 m〜3 m。膜之較佳之卷長為3〇〇 m〜3〇_ m， 更佳的是5GG m〜1GGGG m，進-步更佳的是職m〜7〇〇〇 m ° (膜厚） 本發明之纖維素酯膜之膜厚較佳的是2〇 μιη〜ι8〇 μιη，更佳的是30μιη〜12〇μιη，進一步更佳的是〜 100 =。若膜厚為2G μιη以上，則於加工為偏光板等時之 2理特性（handling property)或偏光板之捲曲（euri)抑 言較佳。而且，本發明之纖維素酯膜之膜厚不 f父仏的疋於搬送方向及寬度方向均為〇%〜2%，更佳的 疋〇%〜1.5%，特佳的是〇%〜1%。 (添加劑） 劑、旨膜令亦可添加劣化抑制劑（例如抗氧化 除劑、胺）劑、自由基禁止劑、金屬純化劑、酸清 ^版）。關於劣化抑制劑，於日本專利 專利特開平5_19侧號、日本專利特開平 钱4 ^日本專利特開平6_顚54號之各公報中有所 $化抑咖之添加量，自表現效果及抑制劣化抑制 38 201213409 修正日期:1〇〇年10月14臼 爲弟ΗΧΠ27033號中文說明書 式或共流鑄方式而製造一牧纖維素酯膜之情形。 旦形時’可藉由適宜調整添加劑之種類或調配 =、纖維素g旨之分子量分布或旨之種㈣而獲得於 厚度方向上具有分布之纖維素㈣。而且，亦包含於該些 具有光學異向性部、防眩部、阻氣部、耐濕性部 4各種功能性部者。 (功能性層） · 〇 〇 ，發明之膜可為單制，亦可具有2相上之積層結 ^此處，較佳的是後述之本發明之偏光板包含功能性層， :為本發明之·有魏性層之籠，亦可於將本發明之 、内裝至本發明之偏光板巾時Φ合其他功能性膜。 所述魏性層W不違反本剌之主旨職無特別之 限制’例如可列舉以下之態樣之魏性層。其中，於 ，明之膜作為基獅而使狀情料，制是直接於其上 形成硬塗層較佳，較佳的是#由塗佈而設置硬塗層。、 基材膜/硬塗層/中折射率層/低折射率層 基材臈/硬塗層/中折射率層/高折射I 基材膜/硬塗層/低折射率層 牛層 基材膜/硬塗層/導電性層/低折射率層 基材膜/硬塗層/高折射率層（導電性層）/低折射率層 基材膜/硬塗層/防眩性層/低折射率層 均少 本發明之纖維素醋膜較佳的是於塗二硬塗層時塗佈不 〇 於形成所述硬㈣時的硬塗層驗佈液中所使用之光 47 201213409 修正日期:100年10月14日 爲第100127〇33號中文說明書無劃線修正頁 重合性多官能單體存在有炫二醇之（甲基)丙稀酸二醋類、 聚氧烷二醇之（甲基)丙烯酸二酯類、多元醇之（甲基)丙烯酸 二酯類、環氧乙烷或環氧丙烷加成物之（甲基）丙烯酸二酯 類等，且存在有（甲基)丙烯酸環氧酯類、（甲基)丙烯酸胺基 甲酸酯類、聚酯（甲基）丙烯酸酯類等，並不限定於該些化 合物，可單一地使用亦可併用數種。 ^光自由基聚合起始劑可列舉苯乙酮類、安息香類、二 苯甲酮類、膦氧化物類、縮酮類、蒽醌類、噻噸酮類、偶 氮化合物、過氧化物類（日本專利特開200M39663號 等）、2,3-二烷基二酮化合物類、二硫醚化合物類、氟胺化 合物類、芳香族銃（sulf0nium)類、哈吩二聚物（l〇phine dlmer)類、鑌贿、侧酸鹽類、活性g旨類、活性鹵素類、 無機錯合物、香讀類等，但並不限定於該些化合物。 口☆塗佈溶劑可使用根據如下之觀點而選擇之各種溶劑： 可冷解或分散各成分，於塗佈步驟、乾燥步驟中 之面狀’可確保液魏存性，具有適度之飽和装汽壓 ^ ° *、、、 “溶劑可將2種以上溶劑混合使用。特別是自乾燥負荷 ^觀點考慮’較佳的是以常壓室溫下彿點為lOOU下之 H為主成分，為了調整乾燥速度而少量含有彿點為 &gt;以上之溶劑。而且，為了對溶解度參數進行微調整亦 J進行溶劑之混合。 =弗點為10(rc以下之溶劑例如存在有己烷（沸點為 UC)、庚烷（98.4°c)、環己烷（8〇n：)、苯（8〇 rc) 48 201213409 爲第100127033號中文說明書無«I線修正頁 修正日期:100年10月14臼 (HGM-2DP、suga test instruments C〇., Ltd.)，依照 JIS K-67l4 *對膜試樣4〇麵塌mm進行測定 霧度 為霧度增大’關，霧度增大者，將其要 (滲出） 滲出是評價於摻雜物流鑄、乾燦201213409 / ν/^μ;ιΓ VII. Patent application scope: 1. A cellulose vinegar film containing cellulose vinegar, an aromatic sugar ester compound, and the following general formula (8): a fragrant sugar ester compound, The following general formula is characterized by the fact that the aliphatic sugar esterification of the formula is represented by the formula (1) and the formula of the formula (1) and the formula 9 = (4) The average ester substitution degree of the compound is insufficient (I) (HO^-G-CL-R1^ (II) (HO^-G-CL-R1^ (III) (HO)rG,-(IAR2)r (in In the above formula (1) to the above formula (ΙΠ), hydrazine and a residue or a disaccharide residue; R1 each independently represents a fatty hydra group, and one represents an aromatic group; and R2 is independently a sulphate aliphatic group; And the base indicates a two-valent linkage; the melon f does not = the upper integer 'n, p and q each independently represent an integer of 1 or more, and the integer is not more than 3, and t represents the above integer; wherein, m + n:4, P+_'m&gt;p'n&lt;q;g,m+n4 = in the case of an unsubstituted saccharide which assumes that the G is not a residue but a cyclic structure of the same skeleton The cardinalities are equal, r+t blood assumes the G' and The non-residue group is the same as the unsubstituted hydrazine of the cyclic structure of the same skeleton, and the number of hydroxyl groups is the same. The acne 2 in the formula (III) represents two or more kinds of aliphatic groups. The cellulose vine film according to claim 1, wherein the formula (III) is as described in the above formula (III) G, which represents a disaccharide residue. 4. The cellulose ruthenium film according to claim 1, wherein the oxime of the formula (I) and the formula (5) is a curtain The sugar skeleton, the average ester substitution degree of the compound of the formula (I) and the aromatic sugar ester compound represented by the formula (II) is 5 to 7.5. The cellulose ester film according to claim 4, wherein the aromatic sugar g in which q is 8 in the formula (II) is added in an amount relative to the formula (I) The total addition amount of the aromatic sweet and sour compound represented by the above formula (II) and the aromatic sugar ester compound represented by the above formula (II) is less than 20% by weight. The cellulose ester film according to any one of the above-mentioned item (1), wherein the L in the formula (I) and the formula (n), and the formula (III) In the above, each of L represents independently a single bond, _〇_, _c〇_, -NR11- (wherein R11 represents a monovalent substituent). 7. Patent application No. 1 to 5 The cellulose ester film according to any one of the above formula (0, wherein R1 in the formula (II) and the above-mentioned ^2 in the formula (III) are respectively Independently represents a sulfhydryl group. 8. The cellulose ester film according to any one of the items 1 to 5, wherein the R1 in the formula (I) and the formula (Π) represents benzene A 71 201213409 醯基. The cellulosic ester film according to any one of the preceding claims, wherein the rule 2 in the formula (III) independently represents an acyclic aliphatic group. 10. The cellulose ester film according to any one of the items (i) to (5), wherein at least one of the two taught in the formula (m) represents a branched aliphatic group. base. 11. The cellulose ester film according to the above item, wherein the reverse 2 in the formula (10) comprises only an ethyl ketone group and an isobutyl aryl group. 12. A polarizing plate having a (four) element and a protective film disposed on both sides of the polarizing element, wherein: at least one of the protective films is as in items i to 11 of the patent application scope A cellulose ester film according to any one of the preceding claims. H1 曰3. Two liquid crystal age devices having a liquid crystal cell and a polarizing plate disposed on both sides of the liquid crystal cell are characterized in that: at least one of the light plates is "the scope of the patent (4) 72 201213409 1 L IV. Designated representative map: (1) The representative representative of the case is: No. (2) The symbol of the symbol of the representative figure is simple: Benefit. 5. If there is a chemical formula in this case, please reveal the characteristics that can best show the invention. Chemical formula: (HO^-G-CL-R1^ 201213409, , for the 10th G127G33 13⁄4 towel text period: 100 years U# table year month 曰 invention patent specification ^ (This manual format, order 'do not change arbitrarily' ※ Please do not fill in the mark) ※Application number ^ ^ &lt;2006.0 υ ※Application date: \..,.)" PC : CJL &lt;2006.0 υ - 'Invention name ··(Chinese, English) (4) £2:: :1 纤维素 cellulose ester film, polarizing plate and liquid crystal display device CELLULOSE ESTER FILM, POLARIZING PLATE AND LIQUID-CRYSTAL DISPLAY II. Abstract of Chinese invention: A cellulose ester film containing cellulose ester, represented by the formula (j) Aromatic sugar ester An aromatic sugar-ester compound represented by the formula (hi) represented by the aromatic sugar ester represented by the formula (II), and the aromatic sugar ester compound represented by the above formula (I) The average ester substitution degree of the aromatic sugar ester compound represented by the above formula (11) is less than 94%. Ο 曰(1) (HOk-GaR,; (II) (H0) g_(l_r1) (HO)rG'-(L^R2)r ; ;q U ; G' denotes a single thief or disaccharide; &amp ; represents an aliphatic group Γ 2 ΐ — — — 个 个 个 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; 脂肪 脂肪 脂肪 脂肪 脂肪 脂肪 脂肪 脂肪 脂肪 脂肪 脂肪 脂肪 脂肪 脂肪 脂肪 脂肪心二的m&gt;P ; n&lt;q 〇) P^q== 1 201213409 is No. 100127033 Chinese manual without scribe correction page Revision date: 100 years 丨〇月14日六, invention description: [Technology to which the invention belongs FIELD OF THE INVENTION The present invention relates to a cellulose ester film, a polarizing plate, and a liquid crystal display device. [Prior Art] In the silver halide photographic light-sensitive material, retardation film, polarizing plate, and image display device, cellulose ester, polyester, polycarbonate, cycloolefin polymer, vinyl polymer, and polyimine are used. Such as the representative of the polymer film. These polymers can be produced as a film which is more excellent in planarity or uniformity, and thus are widely used as a film for optical use. For example, a cellulose ester film having a suitable moisture permeability can be directly bonded to the most general polarizing element comprising a polyvinyl alcohol (PVA) / moth (Polarizer). Therefore, cellulose esters, particularly cellulose acetate, are widely used as a protective film for polarizing plates. In the case where a cellulose ester film is used for a liquid crystal display device, for the protection of the polarizing element of the algae (polarizer durability), the film is required to be ==. Additives are commonly used in hydrophobization. However, in the solution film forming method widely used as a method for producing a cellulose ester film, in order to volatilize the solvent in a short time, the dry phase is contained, and the hydrophobization is volatilized in the drying step, on the manufacturing machine. Cooling again (4) The dirt = type attached to the film, which is the cause of the planar failure - becomes a problem. In recent years, it has been known that a method of increasing the amount of the additive by suppressing volatilization is known, but an additive having a large molecular weight is generated from the film (the plasticizer of the J system is used as an additive 201213409) Date of revision: 100 On the 14th of the year, the number of the 100th day is the same as the number of bases when the JE page is not marked with a line. The above mentioned m+n, p+q and the upper limit can be determined according to the type of ^. When the value 'G^' is a monosaccharide residue, it becomes 5, and when it is a disaccharide residue, it becomes 8. 0. The yarn of the general formula (1) to the formula (ΠΙ) represents the compounded compound. 'A compound having a furan structure or a pyranose structure, wherein the G or G' is a monosaccharide residue, and the kink has at least one of a sucrose structure or a sucrose structure. The G or G is an esterified compound obtained by acetating all or a part of the OH group in the compound (B) of the disaccharide residue. However, the mixture of the sugar ester compounds used in the present invention is characterized by ·············· The OH group of the sugar ester compound represented by the formula (I) is not completely esterified. By using a plurality of aromatic sugar ester compounds having different degrees of ester substitution as described above, the volatility in the production step becomes low, Further, it is difficult to bleed out from the cellulose ester film after film formation. Examples of the ruthenium compound (A) include glucose, galactose, mannose, fructose, xylose or arabinose, but are not limited to these compounds. Examples of (B) include lactose, sucrose, nystose, IF-fructosyl nystose, stachyose, maltitol, lactitol, lactulose, Cellobiose, maltose, cellotriose, maltotriose, raffinose or kestose. In addition, gentiobiose, gentian triose, Gentiantetraose, xylotriose 13 201213409, date of revision: 100 years, 1 month, 14th, i, 100127033, Chinese manual, no scribe, xylotriose, iact〇sucr〇se, etc. It is not limited to these compounds. And the compound (B) is particularly preferably a compound having both a ruthenium sugar structure and a quaternary sugar structure. Preferred examples are sugar cane, cane fruit disaccharide, cane sugar, sugar cane and pentasaccharide More preferably, sucrose, and a compound having at least one of a furanose structure or a ruthenium saccharide structure bonded to the compound is also preferably used in the compound. The substituent which esterifies all or a part of the fluorenyl group in (化合物) and the compound (Β) is not particularly limited. Among them, it is preferred to use a monocarboxylic acid. That is, it is preferable that the above-mentioned formula and the above-mentioned R1 in the above formula (Π) and the ruler 2 in the above formula (111) each independently represent a mercapto group. The monobasic acid is not particularly limited, and a known aliphatic monoterpictic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid or the like can be used. The tannic acid to be used may be one type or a mixture of two or more types. In the case where the R1 or the enthalpy is plural, 'may be the same or different from each other. On the other hand, it is preferred that L in the above formula (I) and the formula (11), and L in the formula (ΠΙ) independently represent a single bond, - Ο-, _CO-, -NR11- (wherein R11 represents a monovalent substituent); and in the case where the L or the L is plural, they may be the same or different. Among them, from the viewpoint that R1 and R2 can be easily substituted by a mercapto group, it is preferred that L or L represents -〇. (Aromatic Sugar Ester Compound 14 represented by the general formula (I) and the general formula (II) 201213409 Revision date: October 14, 2014 is a mixture of the Chinese specification of the No. 100127033, which has no scribe correction page. Preferred aspects of the general formula (I) and the general formula (π) sugar ester compound are illustrated. In the aromatic oxime represented, each of R1 independently represents an aromatic group. Wherein, the aromatic group is more preferably an aliphatic group or an aromatic group in the formula (I) and the formula (π), and at least one is preferably the R1 independently It is only indicated that R1 represents the same aromatic group.秘 The secret is that the average vinegar substitution of the compound of the formula (1) and the aromatic sweet and sour compound represented by the formula (II) is not 194%. When the average degree of ester substitution of the mixture of the two kinds of aromatic sweet and sour compounds is less than 94% as described above, the haze of the obtained cellulose ester film can be remarkably reduced, and it can be excellent as an optical film. It is used in polarizing plates or liquid crystal display devices. From the viewpoint of being able to reduce the temporal change of the orthogonal transmittance in a moist heat environment when incorporated into a polarizing plate, it is preferable that the aromatic sugar ester compound represented by the above formula is the same as the above formula (II). The average degree of ester substitution of the aromatic glycoside ester compound represented by the compound is 62% or more and less than 94%. In addition, from the viewpoint of being able to reduce the temporal change of the orthogonal transmittance in a moist heat environment when incorporated into a polarizing plate, it is more preferable in the above formula (I) and the formula (II) The G is a sucrose skeleton, and the average ester substitution degree of the aromatic sugar ester compound represented by the formula (I) and the aromatic sugar ester compound represented by the formula (II) is 5 to 7.5, which is particularly preferable. It is 5.5 to 7.0. Further, in the above formula (I) and formula (II), m represents 0 with 15 201213409 as the first detailed Chinese manual without a dirty shave correction date: (10) on October 14, the integer, n And P&amp;q independently represent the integer above ,, true m &gt; p, n &lt; q. In the present invention, from the viewpoint that the haze of the obtained cellulose vinegar film is remarkably small, it is preferred that in the case where the G is a disaccharide residue, q in the general formula (II) is The amount of the aromatic sugar ester added in the case of the total amount of the aromatic sugar ester compound represented by the above formula (I) and the aromatic sugar ester compound represented by the above formula (II) is Less than 2〇wt%. When the G is a disaccharide residue, the content of the aromatic sugar ester compound having no hydroxyl group as a substituent is preferably 20 wt% or less with respect to the content of all the aromatic sugar esters. More preferably, it is 15 wt% or less, particularly preferably 10 wt% or less, and further preferably 5 wt% or less. On the other hand, in the present invention, the aromatic sugar ester compound represented by the above formula (1) and the aromatic sugar ester compound represented by the above formula (II) are wherein the G is a disaccharide residue. In the case, it is preferable that 11 is 3 or more, and 5 or more is also preferable. That is, in the present invention, it is preferred that at least the aromatic sugar ester compound contained in the aromatic sugar ester compound mixture is at least 3 substituents or more, and at least 5 substituents or more is also preferable. When the square-flavored sweet and sour compound is a saccharide, the content of the substituted substituent is 3 to 5, and the content of the 3 to 5 substituent is relative to the entire aromatic sugar ester compound. It is preferably 10%~, more preferably 20%~50%. The content of the 6 substituents to 7 substituents is preferably 20% to 85%, more preferably 2% to 75%, based on the total amount of the aromatic sugar ester compound. An example of a preferred aromatic monoterpene acid used in the replacement of R1 may be 16 201213409. The date of revision: October 14, 100 is the arbitrary stage of the 127G33 towel woven duck thin line correction page, preferably in the flow. Immediately after casting. Under the hood wind = when the drying time is on the belt, if it is less than 10 seconds (less than 1 second on the drum), the additive is difficult to uniformly distribute in the film, if more than 90 hearts (on the raft In the case of more than one 〇 second, the drying is insufficient and the peeling is performed, and the surface of the sputum is deteriorated. The time outside the drying of the tough shovel in the absence of wind can be carried out by the inert gas of the wind. The wind temperature at this time is preferably 〇t 0 0 〇C ' more preferably 40 ° C to 150 ° C. The drying method in the solvent casting method is disclosed in U.S. Patent, U.S. Patent No. 2,367,603, U.S. Patent No. 2,492,078, U.S. Patent No., U.S. Patent No. 78, U.S. Patent Toilet ^ 69 69%69, U.S. Patent No. 2739070, the specification of the British Patent No. 736892, the Japanese Patent No. A-45-4554, the Japanese Patent Special Publication No. 49 5614, the Japanese bT^T176834 ^ 6〇·2〇343〇^ ο , Option =: No. 2-11535, each bulletin is described. The film taken with or obtained is peeled off from the drum or the belt, and further relies on; . _ (: (4) Sister temperature change high temperature routine [Load; =1 this patent special fair 5, No. 2 1 list miscellaneous IS:, the drum or belt table when the scales * temperature can also use the modulated fiber The ester solution (dopant) is carried out in two layers to 37 201213409. The date of revision: 100 years, 1 month, 4 days, the number 100127033, the Chinese manual, no picture, the line on the correction page, the money (four). On the other hand, the cellulose ester film is formed by the immersion washing method, and the doping stream is cast on the drum or the belt to evaporate and shape the solvent. It is preferable to adjust the concentration of the material before the casting. The amount of solid matter is made to be ~4%. The surface of the drum or belt is preferably pre-finished into a mirror state. The preferred width of the cellulose ester film of the present invention is 05 m 5 m, more preferably 0.7 m. 3 m. The preferred roll length of the film is 3〇〇m~3〇_ m, more preferably 5GG m~1GGGG m, and the better step is m~7〇〇〇m ° (film thickness) The film thickness of the cellulose ester film of the present invention is preferably 2 〇 μηη to ι 8 〇 μηη, more preferably 30 μm to 12 〇 μηη, still more preferably 〜 100 = if the film thickness is 2G When it is more than μηη, it is preferable to carry out the handling property of the polarizing plate or the like or the curling of the polarizing plate (euri). Moreover, the film thickness of the cellulose ester film of the present invention is not the father's flaw. In the direction of transport and the width direction are 〇%~2%, more preferably 疋〇%~1.5%, particularly preferably 〇%~1%. (Additive) agent, film order can also add deterioration inhibitor (for example Antioxidant remover, amine), free radical inhibitor, metal purifying agent, acid acid version). Regarding the deterioration inhibitor, in the publications of Japanese Patent Laid-Open No. 5_19, Japanese Patent Laid-Open No. 4, Japanese Patent Laid-Open No. 6_顚54, there is an increase in the amount of the coffee, self-performance and suppression. Deterioration inhibition 38 201213409 Revision date: The case of the production of a cellulose ester film in the Chinese manual or co-casting method of the sister-in-law No. 27033 in October of the next year. In the case of denier, cellulose having a distribution in the thickness direction can be obtained by appropriately adjusting the kind or blending of the additive = the molecular weight distribution of cellulose g or the species (4). Further, it is also included in the various functional portions having the optical anisotropy portion, the anti-glare portion, the gas barrier portion, and the moisture resistance portion. (Functional layer) · 〇〇, the film of the invention may be a single system, or may have a laminated layer on two phases. Here, it is preferable that the polarizing plate of the present invention described later contains a functional layer, which is the present invention. The cage having the Wei layer can also be combined with other functional films when the invention is incorporated into the polarizing plate of the present invention. The Wei layer W is not inconsistent with the subject matter of the present invention, and there is no particular limitation. For example, the following layer may be mentioned. Among them, the film of Yu, Ming is made as a base lion, and it is preferable to form a hard coat layer directly thereon, and it is preferable to provide a hard coat layer by coating. , base film / hard coat / medium refractive index layer / low refractive index layer substrate / hard coat / medium refractive index layer / high refractive I substrate film / hard coat / low refractive index layer of cattle layer substrate Film/hard coat layer/conductive layer/low refractive index layer base film/hard coat layer/high refractive index layer (conductive layer)/low refractive index layer base film/hard coat layer/anti-glare layer/low The refractive index layer is less than the cellulose vinegar film of the present invention. It is preferred to apply the light used in the hard coating inspection liquid when the hard coating layer is applied. : October 14th, 100th, No. 100127〇33 Chinese manual, no sizing correction page, a polyfunctional monomer, a (meth)acrylic acid diacetate, a polyoxyalkylene glycol (meth)acrylic acid diesters, (meth)acrylic acid diesters of polyhydric alcohols, (meth)acrylic acid diesters of ethylene oxide or propylene oxide adducts, etc., and (meth)acrylic acid The epoxy esters, (meth)acrylic acid urethanes, polyester (meth)acrylates, and the like are not limited to these compounds, and may be used singly or in combination. Several. ^Photoradical polymerization initiators include acetophenones, benzoin, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides (Japanese Patent Laid-Open No. 200M39663, etc.), 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, hexaphene dimers (l〇phine) Dlmer), bribery, side acid salts, active g-types, active halogens, inorganic complexes, fragrant readings, etc., but are not limited to these compounds. The mouth ☆ coating solvent can use various solvents selected according to the following points: The components can be cold-dissolved or dispersed, and the surface in the coating step and the drying step can ensure the fluid's consistency and have a moderately saturated steam. Pressure ^ ° *,,, "The solvent can be used in combination of two or more solvents. Especially from the viewpoint of drying load ^", it is preferable to use H as the main component at room temperature under normal pressure at room temperature, in order to adjust The drying rate is small, and the solvent is added in a small amount. In addition, in order to finely adjust the solubility parameter, J is mixed with a solvent. = The point is 10 (the solvent below rc is, for example, hexane (boiling point is UC), Heptane (98.4°c), cyclohexane (8〇n:), benzene (8〇rc) 48 201213409 is No. 100127033 Chinese manual No «I-line correction page Revision date: October 14th, 100 years (HGM- 2DP, suga test instruments C〇., Ltd.), according to JIS K-67l4 * For the film sample 4 〇 surface collapse mm to measure the haze as the haze increases 'off, the haze increases, it will ( Exudation) exudation is evaluated in doped logistics casting, dry can ，於溫度60°C濕度 經過1000 h後時， 將其要點記載於表 90%、溫度8(rc濕度10%之濕熱條件下 疋否產生添加劑之析出。關於滲出 4中。 ， 201213409 冚寸 Im:o 一 壯 ο 〇 一 :a&gt;ra3rsΚ3Γ 崔5«摧«1郜盔扒旮龌 ε ε ολΙΝι ο 〇 一 聛脈 u-a£0A8£ 【寸 偏光板 經時變 化 Ό 00 00 S? Η &lt; 蛛 Ή 〇 00 Ο 卜 ^ W ·&amp; § r— 霧度增大 -¾ ί—Η IT) Η 〇 〇〇 面狀 故障 〇 〇 〇 〇 〇 〇 〇 〇 〇 &lt;] 〇 〇 比較化合物（添加量〕 *1) 1 ·· 1 1 1 1 1 1 1 1 1 1 ( 1 通式（III)之脂肪族糖酯化合物 添加量 (重量 份） CO IT) CO m -W-1 KD m m ro 1 1 平均 取代 度 VO CN CS &lt;s VO CS rs 00 in 1 1 取代基 乙醯基/ 異丁醯基 乙醯基/ 異丁醯基 乙醢基/ 異丁醯基 乙醯基/ 異丁醯基 乙醯基/ 異丁醯基 乙醯基/ 異丁醯基 乙酿基/ 異丁醯基 乙醯基/ 異丁醯基 乙醯基 1乙醯基1 1 1 糖結構 1 蔗糖： 蔗糖 蔗糖 蔗糖 ... 1 蔗糖 蔗糖 蔗糖 蔗糖 1蔗糖 葡萄糖 J 1 審 Λ3 添加量 (重量 份） CN Ο fN CN 〇 〇 〇 rj CS CN 5〜3取 代物 m m m m Μ 宕 寸 〇 1 CO ΓΛ cn Μ 沐r /-&quot;N Η /^Ν 1—Η 7〜6取 代物 Ό CO νη 00 σ\ m 1 (N ίΝ in νο iT) vo CS (Ν m ir&gt; ! 8取丨 代物: (N cs in 寸 00 -H 〇 寸 CN (N 寸 V) 平均 取代度 1 卜 iri 卜 v-j (N \6 cn 卜 〇 00 〇 卜 Γ ΙΟ 〇 寸· 卜 κή 取代基 苯甲醯基 苯甲醯基 苯甲醯基 苯曱醯基 1 1- 1苯甲醯基 苯甲醯基 i苯甲醯基 1 1 苯甲醯基 1苯曱醯基1 |苯甲醯基| 苯甲醯基 ι- 苯曱醯基 糖結 構 蔗糖 蔗糖 嚴糖 蔗糖 蔗糖 蔗糖 蔗糖 蔗糖 蔗糖 蔗糖 1- 蔗糖 1- 蔗糖 教 «Aji -«V jjm 黎遂《I 一 s s y—t S 1—( »—Η g ο 1—Η Τ-Η CS Η 實例1: 實例2 m 苳 Ik 實例4 1 實例5 比較 例1 實例6 實例7 實例8| 比較 例3 比較 例4 201213409/ , 爲第100127033號中文說明書無劃線修正頁 修正日期:100年10月14曰 [實例9] 於實例1之試樣103中，將纖維素醋替換為乙酿基取 代度為2.94之材料’除此以外同樣地進行而製作試樣 401。試樣401與試樣103同樣地獲得良好之結果。 [實例101〜實例103] (硬塗層塗佈膜之塗設） 對實例1、實例2、實例8中所得之試樣1〇1、試樣1〇2、 ◎ 試樣109以如下之態樣進行硬塗層塗佈。另外，於下述硬 塗1〜硬塗4中，於試樣101中使用硬塗丨，於試樣1〇2 中使用硬塗4，於試樣109中使用硬塗3。 硬塗1〜硬塗4為下述表3中所示之組成物，uv起始 劑1為下表中所示之結構。 [表5] 單體1 單體2 單體1/ 單體2 UV起始 劑 單體/UV 起始劑比 固形物濃度 溶劑1 溶劑2 溶劑1/ 硬塗1 季戊四醇三 丙烯酸酯 季戊四醇 四丙婦酸 酯 3/2 UV起始 劑1 53.5/1.5 55 乙酸乙酯 - 冷H’J厶 硬塗2 季戊四醇三 丙烯酸酯 季戊四δί 四丙烯酸 酯 3/2 UV起始 劑1 53.5/1.6 55 乙酸乙酯 甲基乙基 酮 1/1 硬塗3 季戊四醇三 丙烯酸酯 季戊四醇 四丙歸酸 酯 3/2 UV起始 劑1 53.5/1.7 55 甲苯 甲基異丁 基酮 9/1 硬塗4 二季戊四醇 六丙烯酸酯 - - UV起始 劑1 53.5/1.8 55 甲笨 甲基異丁 基阑 9/1 〇 硬塗1〜硬塗3中所使用之光聚合性單體是日本化藥 股份有限公司之PET30，硬塗4中所使用之單體是日本化 藥股份有限公司之KAYARAD DPHA。 65 201213409 修正日期:100年10月14曰 爲第1^012則號巾文說明書無_修正頁When the temperature is 60 ° C and the humidity is over 1000 h, the main points are described in Table 90%, temperature 8 (the humidity of rc is 10% under the conditions of damp heat, whether or not the precipitation of the additive occurs. About the exudation 4, 201213409 冚Inm :o 一壮ο 〇一: a&gt;ra3rsΚ3Γ Cui 5«摧«1郜Helmet 扒旮龌ε ε ολΙΝι ο 〇一聛脉ua£0A8£ [Inch polarizer changes over time Ό 00 00 S? Η &lt; Ή 〇00 Ο 卜 ^ W ·&amp; § r - haze increase -3⁄4 ί—Η IT) 〇〇〇 〇〇〇 〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇 ] 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〕 *1) 1 ·· 1 1 1 1 1 1 1 1 1 1 (1 Addition amount of the aliphatic sugar ester compound of the formula (III) (parts by weight) CO IT) CO m -W-1 KD mm ro 1 1 Average degree of substitution VO CN CS &lt;s VO CS rs 00 in 1 1 Substitudinyl group / Isobutyl ethane group / Isobutyl ethane group / Isobutyl ethane group / Isobutyl acetyl group / Isobutyl group Base / Isobutyl ketone / Isobutyl fluorenyl / Isobutyl thioglycolyl 1 ethyl hydrazide 1 1 1 Sugar structure 1 Sucrose: Sucrose Sucrose sucrose... 1 Sucrose sucrose Sucrose Sucrose 1 Sucrose glucose J 1 Review 3 Add amount (parts by weight) CN Ο fN CN 〇〇〇rj CS CN 5~3 Substitute mmmm Μ 宕 inch 〇 1 CO ΓΛ cn Μ 沐/-&quot;N Η /^Ν 1—Η 7~6 Substitute Ό CO νη 00 σ\ m 1 (N ίΝ in νο iT) vo CS (Ν m ir> 8 Take the surrogate: (N cs in inch 00 -H 〇 inch CN (N inch V) average degree of substitution 1 iri iv vj (N \6 cn 〇 〇 〇 Γ Γ ΙΟ · · · · · · · 取代 取代 取代 取代 取代 苯 苯 苯 苯 苯 苯 苯 苯 苯 取代 取代 取代Benzoyl 1 1- 1 benzylidene benzoyl fluorenyl i phenyl fluorenyl 1 1 benzhydryl 1 benzoin 1 | benzhydryl | benzhydryl iota Structure sucrose sucrose sucrose sucrose sucrose sucrose sucrose sucrose sucrose 1- sucrose 1- sucrose teaching «Aji - «V jjm Li Wei "I a ssy-t S 1 - ( » - Η g ο 1 - Η Τ - Η CS Η Example 1: Example 2 m 苳Ik Example 4 1 Example 5 Comparative Example 1 Example 6 Example 7 Example 8 | Comparative Example 3 Comparative Example 4 201213409/ , No. 100127033 Chinese specification Amendment page revision date: October, 2014, 曰 [Example 9] In the sample 103 of Example 1, the cellulose vinegar was replaced with a material having an ethylenic acid substitution degree of 2.94, and the sample was prepared in the same manner. 401. The sample 401 obtained good results in the same manner as the sample 103. [Example 101 to Example 103] (Coating of the hard coat coating film) The sample 1〇1, the sample 1〇2, and the ◎ sample 109 obtained in Example 1, Example 2, and Example 8 were as follows. The coating was applied as a hard coat. Further, in the following hard coat 1 to hard coat 4, a hard coat was used for the sample 101, a hard coat 4 was used for the sample 1〇2, and a hard coat 3 was used for the sample 109. Hard coating 1 to hard coating 4 are compositions shown in Table 3 below, and uv initiator 1 is the structure shown in the following table. [Table 5] Monomer 1 Monomer 2 Monomer 1 / Monomer 2 UV initiator monomer / UV initiator ratio solid concentration solvent 1 Solvent 2 Solvent 1 / Hard coating 1 Pentaerythritol triacrylate Pentaerythritol tetrapropyl Acid ester 3/2 UV starter 1 53.5/1.5 55 ethyl acetate - cold H'J厶 hard coat 2 pentaerythritol triacrylate pentaerythritol δί tetraacrylate 3/2 UV starter 1 53.5/1.6 55 acetic acid Ethyl methyl ethyl ketone 1/1 hard coating 3 pentaerythritol triacrylate pentaerythritol tetrapropyl acid ester 3/2 UV initiator 1 53.5/1.7 55 toluene methyl isobutyl ketone 9/1 hard coating 4 dipentaerythritol Hexaacrylate--UV initiator 1 53.5/1.8 55 methyl acetophenone 9/1 〇 hard coating 1 ~ hard coating 3 used in photopolymerizable monomer is Nippon Chemical Co., Ltd. The monomer used in PET30, Hard Coating 4 is KAYARAD DPHA of Nippon Kayaku Co., Ltd. 65 201213409 Revision date: October 14th, 100th, for the 1st and 12th, the towel manual has no _ correction page UV 起始劑 1 使用 Ciba Japan K.K·之 IRGACURE 127。 硬塗之塗佈條件是於利用支數（yarn c〇unt) 8之棒式 塗佈機之手塗佈後，於100〇c下乾燥6〇秒，於氮氣〇 1% 以下之條件下以1.5 kW、300 mJ照射UV而使其硬化。 (密接性評價） 藉由下述之方法進行光照射後之密接性評價。 進行以JIS K 5600為基準之柵格試驗。具體而言，於 硬塗塗佈及UV硬化後之樣品表面上以1 之間隔縱橫 各切入11根切痕而製作100個lmm見方之柵格。於其上 貼附透明膠帶及瑪拉膠帶（mylar tape)，藉由目視觀察迅 速剝下而剝離之部位，進行密接評價。樣品於密接評價前， 於溫度25 C濕度60%之房間進行2小時以上之濕度控制後 進行評價。 於切入切痕前照射Xe 24小時後進行密接評價之結果 是财光24 h密接結果，照射xe 48小時後進行密接評價之 結果是耐光48 h密接結果。未進行又6照射而進行密接評 價之結果是初始密接評價。 密接性〇 :剝離部位為〇塊〜1〇塊 66 201213409, , 爲第10G127G33 1¾巾文麵 期:100 年 U#表年月曰 發明專利說明書^ (本說明書格式、順序’請勿任意更動’※記號部分請勿填寫） ※申請案號^ ^ &lt;2006.0 υ ※申請日：\。。、。）” PC ： CJL &lt;2006.0 υ -'發明名稱··（中文，英文） ㈣£二:::1 ❹ 纖維素酯膜、偏光板及液晶顯示裝置 CELLULOSE ESTER FILM, POLARIZING PLATE AND LIQUID-CRYSTAL DISPLAY 二、中文發明摘要： 一種纖維素酯膜’其含有纖維素酯、通式（j)所表示 之芳香族糖酯化合物、通式（II)所表示之芳香族糖酯化 5物通式（hi)所表示之脂肪族糖醋化合物，且所述通 式（I)所表示之芳香族糖酯化合物與所述通式（11)所表 不之芳香族糖酯化合物之平均酯取代度不足94%。 Ο 曰 (1) (HOk-G-a-R、；（II) (H0) g_(l_r1) (HO)rG'-(L^R2)r ； ；q U ； G’表示單賊基或二糖錄；&amp;表示脂肪族基 ίΓ2 ΐ 少—個為芳香族基；R2為脂肪族基；L及 一貝之連結基；m、t為〇以上之整數；n 以上之整數;…以上之整數;其中，心二么 m&gt;P ； n&lt;q 〇 ) P^q== 1 201213409 爲箄1^0127033號中文說明書無劃線修正頁修正曰期:100年10月14曰 三、英文發明摘要： A cellulose ester film is provided, which includes cellulose ester, aromatic sugar ester compounds represented by general formula (I), aromatic sugar ester compounds represented by general formula (II), and aliphatic sugar ester compounds represented by general formula (III) and the average ester substitution degree of the aromatic sugar ester compounds represented by general formula (I) and the aromatic sugar ester compounds represented by general formula (II) is less than 94%. (I) (HOVG-CL-R1^ ; (II) (HOVGKL-Rbq ; (III) (HO)t_G，-(L，-R2)r; (G and G' represent monosaccharide residue or disaccharide residue; R1 represents an aliphatic group or an aromatic group, and at least one of which is an aromatic group; R2 is an aliphatic group; L and L' are divalent linking groups; m and t are integers greater than 0; n, p and q are integers greater than 1; r is an integer greater than 3; wherein m + n^4;p + q^4;m&gt;p;n&lt;q). 201213409— 爲第100127033號中文說明書無劃線修正頁修正日期:100年1、〇月14日 四、指定代表圖： (一) 本案指定代表圖為：無。 (二) 本代表圖之元件符號簡單說明： 無。 五、本案若有化學式時，請揭示最能顯示發明特徵 的化學式： 〇 (HO^-G-CL-R1),,UV initiator 1 Use IRGACURE 127 from Ciba Japan K.K. The coating conditions of the hard coating are applied by hand coating using a rod coater of 8 to 100 〇c for 6 sec seconds, and under conditions of nitrogen 〇 1% or less. 1.5 kW, 300 mJ is irradiated with UV to harden it. (Adhesion evaluation) The adhesion evaluation after light irradiation was performed by the following method. A grid test based on JIS K 5600 was performed. Specifically, on the surface of the sample after hard coating and UV hardening, 11 slits were cut at intervals of 1 to make 100 grids of 1 mm square. A scotch tape and a mylar tape were attached thereto, and the portion peeled off by rapid peeling was visually observed to evaluate the adhesion. Before the sample was evaluated for adhesion, the humidity was controlled for 2 hours or more in a room with a temperature of 25 C and a humidity of 60%. The result of the adhesion evaluation after Xe irradiation for 24 hours before cutting into the incision was the result of the close contact of Caiguang 24 h, and the result of the adhesion evaluation after 48 hours of irradiation with xe was the result of the light-resistant 48 h adhesion. The result of the close evaluation without performing the 6-invention was the initial close evaluation. Adhesive 〇: The peeling part is 〇 block~1〇 block 66 201213409, , is the 10th G127G33 13⁄4 towel writing period: 100 years U#表年月曰 invention patent specification ^ (This manual format, order 'Do not change any more' ※Please do not fill in the number of the mark. ※Application number ^ ^ &lt;2006.0 υ ※Application date:\. . ,. ) PC : CJL &lt;2006.0 υ - 'Invention name · · (Chinese, English) (4) £2:::1 纤维素 Cellulose ester film, polarizing plate and liquid crystal display device CELLULOSE ESTER FILM, POLARIZING PLATE AND LIQUID-CRYSTAL DISPLAY 2. Abstract of the Invention: A cellulose ester film comprising a cellulose ester, an aromatic sugar ester compound represented by the formula (j), and an aromatic sugar esterification 5 compound represented by the formula (II) Hi) the aliphatic sweet and sour compound represented by the above, and the average ester substitution degree of the aromatic sugar ester compound represented by the above formula (I) and the aromatic sugar ester compound represented by the above formula (11) is insufficient 94%. Ο 曰(1) (HOk-GaR,; (II) (H0) g_(l_r1) (HO)rG'-(L^R2)r ; ;q U ; G' denotes a single thief base or disaccharide Record; &amp; represents aliphatic group Γ 2 ΐ less - one is an aromatic group; R2 is an aliphatic group; L and a shell of a bond; m, t is an integer above ;; an integer above n; ; Among them, the heart two m> p; n&lt;q 〇) P^q== 1 201213409 is 箄1^0127033 Chinese manual no line correction page correction曰A cellulose ester film is provided, which includes cellulose ester, aromatic sugar ester compounds represented by general formula (I), aromatic sugar ester compounds by general formula (II), And an alternative to the formula (I) and the aromatic sugar ester compounds represented by general formula (I) and the aromatic sugar ester compounds represented by general formula (II) is less than 94%. (I) (HOVG-CL-R1^; (II) (HOVGKL-Rbq; (III) (HO)t_G,-(L,-R2)r; (G and G' represent monosaccharide residue or disaccharide residue; R1 An aliphatic group or an aromatic group, and at least one of which is an aromatic group; R2 is an aliphatic group; L and L' are divalent linking groups; m and t are integers greater than 0; n, p and q are integers Greater than 1; r is an integer greater than 3; m + n^4; p + q^4; m&gt;p;n&lt;q). 201213409 100 In January, four billion January 14, designated representative map:: (a) case designated representative Pictured: No. 100,127,033 for the Chinese manual correction page scoreless date of amendment no. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 〇 (HO^-G-CL-R1),