TWI353370B - Cellulose composition, cellulose film, modifier fo - Google Patents

Description

1353370 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種纖維素體組成物及纖維素體薄膜， 詳言之，關於一種顯示良好透濕性、光學異方向性大的纖 維素體薄膜用改質劑、含有該改質性劑而成的纖維素體組 成物及纖維素體薄膜。另外，本發明亦關於使用該纖維素 體薄膜之偏光板保護膜、液晶顯示裝置及鹵化銀照相感光 材料。 【先前技術】 由於習知纖維素體薄膜之強韌性與難燃性，已將纖維 素體薄膜應用於照片用支持體或各種光學材料。尤其，近 年來已多應用於液晶顯示裝置用之光學透明薄膜。由於醯 化纖維素薄膜之光學透明性高與光學異方向性高，例如， 極爲優異地作爲液晶顯示裝置之處理偏光裝置用的光學材 料，現今已作爲偏光子之保護膜或是作爲能夠改善從斜方 向觀賞畫面（視野角補償）的光學補償膜支持體之使用。 液晶顯示裝置用構件之一的偏光板上，至少於偏光子 之單側，藉由貼合而形成偏光子之保護膜。一般之偏光子 係藉由利用碘或二色性色素，進行已拉伸之聚乙烯醇 (PVA )系薄膜之染色而得到的。 大多之情形，可以使用對PVA能夠直接貼合的醯化纖 維素薄膜，尤其是三乙醯基纖維素體薄膜作爲偏光子之保 護膜。此偏光子保護膜之光學特性極影響偏光板之特性。 另一方面，相較於一般性其他之透明支持體，例如聚 對苯二甲酸乙二醇酯薄膜，醯化纖維素薄膜於高溫高濕下 1353370 至少一種選自於下述通式（1)或通式（2)所表示之化合物， 【化3】 通式（1) OR3 Λ II I - R-C-N-R21353370 IX. Description of the Invention: [Technical Field] The present invention relates to a cellulose body composition and a cellulose body film, and more particularly to a cellulose body exhibiting good moisture permeability and optical anisotropy A modifying agent for a film, a cellulose body composition containing the modifying agent, and a cellulose film. Further, the present invention relates to a polarizing plate protective film, a liquid crystal display device and a silver halide photographic light-sensitive material using the cellulose film. [Prior Art] Due to the toughness and flame retardancy of the conventional cellulose body film, the cellulose film has been applied to a photo support or various optical materials. In particular, it has been widely used in optical transparent films for liquid crystal display devices in recent years. Since the deuterated cellulose film has high optical transparency and high optical anisotropy, for example, it is an optical material for processing a polarizing device which is extremely excellent as a liquid crystal display device, and has been used as a protective film for a polarizer or as an improvement. Use of an optical compensation film support for viewing the picture (viewing angle compensation) in an oblique direction. A polarizing plate protective film is formed on the polarizing plate of one of the members for a liquid crystal display device by bonding at least on one side of the polarizer. A general polarizer is obtained by dyeing a stretched polyvinyl alcohol (PVA) film using iodine or a dichroic dye. In many cases, a bismuth cellulose film which can be directly bonded to PVA, in particular, a triethylene fluorene-based cellulose film can be used as a protective film for a polarizer. The optical properties of this polarizer protective film greatly affect the characteristics of the polarizing plate. On the other hand, compared to a general transparent support such as a polyethylene terephthalate film, the deuterated cellulose film is under high temperature and high humidity, 1353370, at least one selected from the following formula (1) Or a compound represented by the formula (2), a formula (1) OR3 Λ II I - RCN-R2

[通式（1)中' Rl係表示烷基或芳基、…及R3係分別獨 立表示氫原子、烷基或芳基，又烷基及芳基亦可含有取代 基’ R1、R2及R3之中2個以上的基可互相鍵結以形成環] (2) —種纖維素體薄膜，其特徵係包括至少一種選自於 上述通式（1)或通式（2)所表示之化合物。 (3) 如（2)項之纖維素體薄膜，其中上述通式（1)所示之 化π物爲下述通式（2)所示之化合物。 【化4】 通式（2) 0 r4-c-n-r5 Η [式中’ R4及R5係各別表示芳基，可具有各別獨立的取 代基。R4及R5係可形成縮合環] (4)如（2)或（3)項之纖維素體薄膜，其中纖維素體爲醯 化纖維素。 (5)—種醯化纖維素薄膜，其特徵係含有醯化纖維素、 與醯化纖維素之1至30質量％的量爲上述通式（1)及通式（2) 所示之至少1種化合物。 1353370 (6) 如（5)項之纖維素體薄膜，其中醯化纖維素的醯化取 代度爲2.60至3.00。 (7) 如（5)項之纖維素體薄膜，其中醯化纖維素的醯化取 代度爲2.80至2.95。 (8) 如（5)項之纖維素體薄膜，其中醯化纖維素中以乙醯 基取代的取代度爲2.60至3.00。 (9) 如（5)項之纖維素體薄膜，其中醯化纖維素中以碳原 子數3至22的醯基取代之取代度爲0.00至0.80。 (10) 如（5)項之纖維素體薄膜，其中醯化纖維素係以乙 醯基及碳原子數爲3至22的醯基取代，且存在碳原子數3至 22的醯基30%以上爲第6位置羥基之取代基。 (11) 如（5)項之纖維素體薄膜，其中醯化纖維素第6位置 的醯化取代度爲0.80至1.00。 (12) 如（5)項之纖維素體薄膜，其中醯化纖維素第6位置 的醯化取代度爲0.85至1.00。 (13) —種纖維素體薄膜用改質劑，其特徵係如上述通 式（1)及通式（2)所表示者。 (14) 一種偏光板保護膜，其特徵係包括至少一層 (2)〜（I2)項中任一項之纖維素體薄膜。 (15) —種液晶顯示裝置，其特徵係包括至少一層（2)~( 12)項中任一項之纖維素體薄膜。 (1 6) —種鹵化銀照相感光材料，其特徵係使用至少一 層（2)〜（12)項中任一項之纖維素體薄膜作爲支持體。 【發明效果】 添加上述通式（1)及通式（2)所示化合物的纖維素體薄 1353370 膜係透濕性小、具有光學異方向性分常大的優異效果。a 此，該纖維素體薄膜亦可使用於偏光板保護膜、液晶顯$ 裝置、鹵化銀照相感光材料。 【實施發明之最佳形態】 本發明係使用至少一種下述通式（1)所示之化合物# 爲纖維素體用改質劑。 【化5】 通式（1) • OR3 R1-C-N-R2 _ 以下係詳細說明本發明通式（1)所示之化合物。上述通 -式（1)中，R1係表示烷基或芳基、更佳爲芳基。R2及R3係表 示分別獨立地氫原子、烷基或芳基，更隹爲分別獨立地氫 原子或芳基。此處，烷基可爲直鎖、分支或環狀，以碳原 子數1至25者爲佳、6至25者爲更佳、6至20者爲最佳。芳基 ^ 係爲碳原子數6至36者爲佳、10至36者爲更佳。又，R1、R2 及R3係分別2個以上之基可彼此鍵結形成環。 上述的烷基及芳基可具有取代基，取代基係以鹵素原 子（例如，氯、溴、氟及碘）、烷基、芳基、烷氧基、芳氧 基、醯基、烷氧羰基、芳氧羰基、醯氧基、磺醯胺基、羥 基、氰基、胺基及醯基胺基爲佳，更佳爲烷基 '芳基、烷 氧基、芳氧基及鹵素原子，特佳爲烷基及芳基。 上述通式（1)較佳係爲下述通式（2)所示之化合物。 【化6】 -10- 1353370 Ο r4-c-n-r5 Η 上述通式（2)中，R4及R5係表示分別獨立句 係以碳原子數6至3 6者爲佳、10至3 6者爲更佳 又，R4及R5可形成縮合環。 上述芳基可具有各取代基，取代基可舉任 (例如，氯、溴、氟及碘）、烷基 '芳基、烷氧: 醯基、烷氧羰基、芳氧羰基、醯氧基、磺醯® 氰基、胺基及醯基胺基爲佳，更佳爲烷基、芳 芳氧基及鹵素原子，特佳爲烷基及芳基。 又，本發明的纖維素體改質劑的添加量， 素體以2至30質量％爲佳、2至25質量％爲較佳、 爲最佳。 通式（1)或通式（2)任一者所示之化合物的 如下述所示，但是本發明係不限制此等具體倒 豆芳基，芳基 〇 ϋ如鹵素原子 基、芳氧基、 ¥基、羥基、 基、烷氧基、 相對於纖維 2至2 0質量％ J較佳實例係[In the formula (1), R1 means an alkyl group or an aryl group, ... and R3 each independently represents a hydrogen atom, an alkyl group or an aryl group, and the alkyl group and the aryl group may further have a substituent 'R1, R2 and R3. Two or more groups may be bonded to each other to form a ring] (2) a cellulose body film characterized by at least one compound selected from the group consisting of the above formula (1) or formula (2) . (3) The cellulose film according to (2), wherein the π compound represented by the above formula (1) is a compound represented by the following formula (2). [Chemical Formula 4] Formula (2) 0 r4-c-n-r5 Η [wherein R4 and R5 each represent an aryl group and may have independent substituents. R4 and R5 may form a condensed ring] (4) A cellulosic film of the item (2) or (3), wherein the cellulosic body is fluorene cellulose. (5) a seedized cellulose film characterized in that it contains at least 1 to 30% by mass of deuterated cellulose and deuterated cellulose, and is at least represented by the above formula (1) and formula (2) 1 compound. 1353370 (6) The cellulosic film of (5), wherein the deuterated cellulose has a deuteration substitution of 2.60 to 3.00. (7) The cellulosic film of (5), wherein the deuterated cellulose has a deuteration substitution of 2.80 to 2.95. (8) The cellulosic film of (5), wherein the degree of substitution by the thiol group in the deuterated cellulose is 2.60 to 3.00. (9) A cellulosic film according to item (5), wherein the degree of substitution of the fluorenyl group having a carbon atom number of 3 to 22 in the deuterated cellulose is from 0.00 to 0.80. (10) The cellulosic film of (5), wherein the deuterated cellulose is substituted with an ethyl fluorenyl group and a fluorenyl group having 3 to 22 carbon atoms, and a fluorenyl group having 3 to 22 carbon atoms is present in 30%. The above is a substituent of the hydroxyl group at the sixth position. (11) A cellulosic film according to item (5), wherein the degree of substitution of the fluorinated cellulose at the sixth position is from 0.80 to 1.00. (12) A cellulosic film according to item (5), wherein the degree of substitution of the fluorinated cellulose at the sixth position is from 0.85 to 1.00. (13) A modifying agent for a cellulose film, which is characterized by the above formula (1) and formula (2). (14) A polarizing plate protective film comprising at least one layer of the cellulose body film of any one of (2) to (I2). (15) A liquid crystal display device characterized by comprising at least one of the cellulose body films of any one of (2) to (12). (1) A silver halide photographic light-sensitive material characterized by using at least one of the cellulose film of any one of (2) to (12) as a support. [Effect of the Invention] The cellulose body having a compound represented by the above formula (1) and the formula (2) is thin. 1353370 The film has a small moisture permeability and an excellent effect that the optical anisotropy is often large. a The cellulose film can also be used for a polarizing plate protective film, a liquid crystal display device, or a silver halide photographic light-sensitive material. BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, at least one compound # represented by the following formula (1) is used as a modifier for a cellulose body. Formula (1) • OR3 R1-C-N-R2 _ The following is a detailed description of the compound of the formula (1) of the present invention. In the above formula (1), R1 represents an alkyl group or an aryl group, more preferably an aryl group. R2 and R3 are each independently a hydrogen atom, an alkyl group or an aryl group, and more specifically a hydrogen atom or an aryl group, respectively. Here, the alkyl group may be a straight lock, a branch or a ring, preferably one having a carbon number of from 1 to 25, more preferably from 6 to 25, most preferably from 6 to 20. The aryl group is preferably a carbon number of 6 to 36, more preferably 10 to 36. Further, two or more groups of R1, R2 and R3 may be bonded to each other to form a ring. The above alkyl group and aryl group may have a substituent, and the substituent is a halogen atom (for example, chlorine, bromine, fluorine, and iodine), an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a decyl group, or an alkoxycarbonyl group. An aryloxycarbonyl group, a decyloxy group, a sulfonylamino group, a hydroxyl group, a cyano group, an amine group and a mercaptoamine group, more preferably an alkyl 'aryl group, an alkoxy group, an aryloxy group and a halogen atom. Preferred are alkyl and aryl groups. The above formula (1) is preferably a compound represented by the following formula (2). [Chemical 6] -10- 1353370 Ο r4-cn-r5 Η In the above formula (2), R4 and R5 represent that the independent sentence is preferably 6 to 36, and 10 to 3 6 More preferably, R4 and R5 form a condensed ring. The above aryl group may have each substituent, and the substituent may be (for example, chlorine, bromine, fluorine, and iodine), an alkyl 'aryl group, an alkoxy group: a mercapto group, an alkoxycarbonyl group, an aryloxycarbonyl group, a decyloxy group, The sulfonium® cyano group, the amine group and the mercaptoamine group are preferred, and an alkyl group, an aryl aryloxy group and a halogen atom are more preferred, and an alkyl group and an aryl group are particularly preferred. Further, the amount of the cellulose body modifier to be added in the present invention is preferably from 2 to 30% by mass, preferably from 2 to 25% by mass, based on the amount of the element body. The compound represented by any one of the formula (1) or the formula (2) is as shown below, but the present invention is not limited to these specific inverted aryl groups, such as a halogen atom group or an aryloxy group. , a base group, a hydroxyl group, a base group, an alkoxy group, and 2 to 20% by mass relative to the fiber.

-11 - 1353370 化7】 A-1 A- 2 Λ-3 A-4-11 - 1353370 7] A-1 A- 2 Λ-3 A-4

Q-U^y^ Q-^ta^Q-Q ' Pt1 A—5 A— 6 A— 7 0^Q~^~0 -t A-8 A-9Q-U^y^ Q-^ta^Q-Q ' Pt1 A—5 A— 6 A— 7 0^Q~^~0 −t A-8 A-9

A- 1 0 A- 1 0^1¾ o 〇^"〇"6-口-〇 A- 1 3 a A- 1 4 A-l 2A- 1 0 A- 1 0^13⁄4 o 〇^"〇"6-port-〇 A- 1 3 a A- 1 4 A-l 2

C4H9-^-n-c-^^-cn-^^-c4h8 a- 1 6 〇·έ^^Ο 0CeH«j3C4H9-^-n-c-^^-cn-^^-c4h8 a- 1 6 〇·έ^^Ο 0CeH«j3

A-l 8 A- 1 7A-l 8 A- 1 7

IwIw

A-l 9A-l 9

g-^-w-O A-2G-^-w-O A-2

A-2 2A-2 2

SiSi

丨邮13 A-23 Q-6-n-Q-n0-^) A-24 A-2 ! 〇CeH13 Λ-2 6 -12- 1353370 可以於膠漿製作步驟之最後調製步驟時，額外進行添加劑 之添加、調製的步驟。另外，只要能發現各材料添加量之 功能，並無特別之限定。此外，醯化纖維素薄膜爲由多層 所形成的情形，各層之添加物的種類或添加量也可以不 同。例如，揭示於日本公開專利第2001-151902號公報等， 此等爲習知之技術。 此等之更詳細說明，較佳爲已詳細記載於日本發明協 會公開技報（公技編號：20CU-1745，2001年3月15日發 行，發明協會），第16~22頁的材料。 接著，針對進行用於本發明纖維素體溶解的有機溶劑 進行說明。 首先，針對於製作纖維素體溶液時之較佳所用的非氯 系有機溶劑進行說明》能進行於本發明纖維素體之溶解、 流延、製膜的範圍內，只要能達成此目的，所用之非氯系 有機溶劑並無特別之限定。本發明所用之非氯系有機溶 劑，較佳由碳原子數爲3〜12之酯、酮與醚所選出的溶劑。 酯、酮與醚也可以具有環狀構造。可以將具有二個以上之 酯、酮與醚之官能基（亦即，·〇_、-CO-與-COO-)的化合 物作爲主溶劑使用，也可以具有例如醇性羥基般之其他官 能基。具有二種以上官能基之主溶劑的情形，只要其碳原 子數爲具有任一官能基的化合物之規定範圍內的話皆可。 以碳原子數爲3〜12之酯類爲例，可舉例如乙基甲醯 酯、丙基甲醯酯、戊基甲醯酯、甲基乙酸酯、乙基乙酸酯 與戊基乙酸酯。以碳原子數爲2之酮類爲例，可舉例如 丙酮、甲基乙基酮、二乙基酮、二異丁基酮、環戊酮、環 -18 - 1353370 己嗣與甲基環己酮。以碳原子數爲3〜12之醚類爲例，可舉 例如二異丙基醚、二甲氧基甲烷、二甲氧基乙烷、1，4-二 頓院、1,3 -二氧雜戊環、四氫呋喃、苯甲醚與苯***。以 具有二種以上官能基之有機溶劑爲例，可舉例如2 -乙氧基 乙基乙酸酯、2-甲氧基乙醇以及2-丁氧基乙醇。 針對用於以上之纖維素體的非氯系有機溶劑，基於該 各式各樣之觀點進行選擇，較佳爲相互不同的三種以上之 混合溶劑。 第1溶劑係由乙酸甲酯、乙酸乙酯、甲酸甲酯、甲酸 乙酯、丙酮、二氧雜戊環、二噁烷所選出之至少一個或此 等之混合液，較佳爲乙酸甲酯、丙酮、甲酸甲酯、甲酸乙 酯或此等之混合液。 第2溶劑係由碳原子數爲4〜7之酮類或乙醯乙酸酯所 選出之至少一個或此等之混合液，較佳爲甲基乙基酮、環 戊酮、環己酮、乙醯基乙酸甲酯或此等之混合液。 還有，第1溶劑爲二種以上溶劑之混合液的情形，即使 無第2溶劑也可以。 第3溶劑最好碳數爲1〜10之醇類或碳氫化合物所選出 的，最好碳數爲1〜8之醇類。 第3溶劑爲醇類之羥基以外的部分，可以爲直鏈、分 枝或環狀’其中較佳爲飽和脂環族碳氫化合物。醇類可舉 例如甲醇、乙醇、1-丙醇、2 -丙醇' 1-丁醇、2 -丁醇、第三 丁醇、1-戊醇、2-甲基-2-丁醇與環己醇。還有，醇類也可 以使用氟系醇類。例如’可舉例如2·氟乙醇、2，2,2-三氟乙 醇、2,2,3,3-四氟-1-丙醇等。 -19 - 1353370 作爲第3溶劑之碳氫化合物，可以爲直鏈、分枝或環 狀。可以使用芳香族碳氫化合物與脂肪族碳氫化合物之任 一種。脂肪族碳氫化合物可以爲飽和的、也可以爲不飽和 的。碳氫化合物之例中，包含環己烷、己烷、苯、甲苯與 二甲苯。 此等第3溶劑之醇類與碳氫化合物可以爲單獨的、也 可以爲二種以上之混合物，並無特別之限定。作爲第3溶 劑之較佳具體化合物，可舉例如醇類之甲醇、乙醇、1-丙 醇、2_丙醇、1-丁醇、2-丁醇與環己醇；環己烷、己烷。尤 以甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇較爲理想。 以上三種混合溶劑之比例，較佳爲含有第1溶劑： 20〜95質量％、第2溶劑：2〜60質量％、且第3溶劑：2~30 質量％。更佳爲含有第1溶劑：3 0~9 0質量％、第2溶劑： 3〜50質量％，且第3溶劑含有醇3~25質量％者。尤以含有 第1溶劑：3 0〜9 0質量％、第2溶劑：3 ~ 3 0質量％、第3溶 劑爲含有醇類3〜15質量％者爲最佳。 再者，第1溶劑爲混合液且不使用第2溶劑之情形，較 佳爲含有第1溶劑：20~90質量％、第3溶劑：5~30質量％。 更佳爲含有第1溶劑：30〜86質量％、第3溶劑：7~25質量％。 用於以上本發明的非氯系有機溶劑，更詳細之說明已 詳細揭示於日本發明協會公開技報（公技編號： 2001-1745，2001年3月15日發行，發明協會），第12〜16 頁。本發明之較佳非氯系有機溶劑的組合，可列舉如下之 所示，但是並非限定於此等非氯系有機溶劑。 *乙酸甲酯/丙酮/甲醇/乙醇/ 丁醇（75/10/5/5/5、質量份）、 -20- 1353370 癱乙酸甲酯/丙酮/甲醇/乙醇/丙醇（75/1 0/5/5/5、質量份）、 *乙酸甲酯/丙酮/甲醇/ 丁醇/環己烷（75/10/5/5/5、質量 份）、 ♦乙酸甲酯/丙酮/乙醇/丁醇（81/8/7/4、質量份）、 *乙酸甲酯/丙酮/乙醇/丁醇（82/10/4/4、質量份）、 籲乙酸甲酯/丙酮/乙醇/丁醇（80/10/4/6、質量份）、 «乙酸甲酯/甲基乙基酮/甲醇/丁醇（8 0/10/5/5、質量份）、 *乙酸甲酯/丙酮/甲基乙基酮/乙醇/異丙醇 (75/1 0/1 0/5/7、質量份）、 籲乙酸甲酯/環戊酮/甲醇/異丙醇（80/10/5/8、質量份）、 參乙酸甲酯/丙酮/丁醇（85/5/5、質量份）、 春乙酸甲酯/環戊酮/丙酮/甲醇/ 丁醇（6 0/15/15/5/6、質量 份）、 •乙酸甲酯/環己酮/甲醇/己烷（70/20/5/5、質量份）、 *乙酸甲酯/甲基乙基酮/丙酮/甲醇/乙醇（ 50/20/20/5/5、 質量份）、 籲乙酸甲酯/1,3-二氧雜戊環/甲醇/乙醇（7〇/2〇/5/5、質量 份）、 籲乙酸甲酯/二噁烷/丙酮/甲醇/乙醇（60/20/ 1 0/5/5、質量 份）、 *乙酸甲酯/丙酮/環戊酮/乙醇/異丁醇/環己烷 (65/1 0/1 0/5/5/5、質量份）、 •甲酸甲酯/甲基乙基酮/丙酮/甲醇/乙醇（ 50/20/20/5/5、 質量份）、 參甲酸甲酯/丙酮/乙酸乙酯/乙醇/ 丁醇/己烷 -21- 1353370 (65/1 0/10/5/5/5、質量份）、 籲丙酮/乙醯基乙酸甲酯/甲醇/乙醇（ 65/2 0/1 0/5、質量 份）、 •丙萌/環戊酮/乙醇/ 丁醇（ 65/20/ 1 0/5、質量份）、 •丙酮/1,3-二氧雜戊環/乙醇/丁醇（65/2 0/1 0/5、質量份）、 ♦ 1，3 -二氧雜戊環/環己酮/甲基乙基酮/甲醇/ 丁醇 (5 5/20/1 0/5/5、質量份）等。 再者，也可以利用下列方法，使用醯化纖維素溶液。 用於本發明之膠漿中，除了該非氯系有機溶劑之外， 也可以含有全部有機溶劑量10質量％以下之二氯甲烷。 另外，於製作本發明之醯化纖維素溶液時，依情形而 定，也可以使用氯系有機溶劑作爲主溶劑。於本發明能夠 進行纖維素體之溶解、流延、製膜的範圍內，其氯系有機 溶劑並無特別之限定。此等氯系有機溶劑較隹爲二氯甲烷 、氯仿。尤以二氯甲烷較爲理想。另外，混合氯系有機溶 劑以外之有機溶劑也無特別之問題。此情形下，二氯甲烷 較佳使用至少50質量％。 作爲合倂使用之非氯系有機溶劑，較佳爲由碳原子數 3〜12之酯、酮、醚、碳氫化合物等所選出之溶劑。酯、酮 、醚與醇也可以具有環狀構造。也可以將具有任意二個以 上之酯、酮與醚的官能基（亦即，-0-、-CO -與- COO-)的 化合物作爲溶劑使用，也可以同時具有例如醇性羥基般之 其他的官能基。具有二種以上官能基之溶劑的情形，只要 其碳原子數爲具有任一官能基的化合物之規定範圍內的話 皆可。 -22- 1353370 倂使用之非氯系有機溶劑，可舉例如乙酸甲酯、丙酮、甲 酸甲酯'甲酸乙酯、甲基乙基酮、環戊酮、環己酮、乙醯 基乙酸甲酯、甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、環己醇、環己烷與己烷。與本發明較佳的主溶劑之 氯系有機溶劑組合，可列舉如下，但是並不受限於此等之 組合，可舉例如 • 二氯甲烷/甲醇/乙醇/ 丁醇（75/10/5/5/5、質量份）、 • 二氯甲烷/丙酮/甲醇/丙醇（80/10/5/5/5、質量份）、 • 二氯甲烷/甲醇/ 丁醇/環己烷（75/10/5/5、質量份）、 • 二氯甲烷/甲基乙基酮/甲醇/ 丁醇（80/10/5/5、質量份）、 • 二氯甲烷/丙酮/甲基乙基酮/乙醇/異丙醇 (75/10/10/5/7、質量份）、 • 二氯甲烷/環戊酮/甲醇/異丙醇（80/10/5/8、質量份）、 • 二氯甲烷/乙酸甲酯/ 丁醇（80/10/10、質量份）、 • 二氯甲烷/環己酮/甲醇/己烷（ 70/20/5/5、質量份）' •二氯甲烷/甲基乙基酮/丙酮/甲醇/乙醇（50/20/20/5/5、 質量份）、 •二氯甲烷/1,3-二氧雜戊環/甲醇/乙醇（ 70/20/5/5、質量 份）' ♦二氯甲烷/二噁烷/丙酮/甲醇/乙醇（60/20/10/5/5、質量 份）、 •二氯甲烷/丙酮/環戊酮/乙醇/異丁醇/環己烷 (65/10/10/5/5/5 、質量份）、 *二氯甲烷/甲基乙基酮/丙酮/甲醇/乙醇（7〇/1〇/1〇/5/5、 質量份）、 -24- 1353370 黏度爲10〜2 00 Pa· s，於15 °c之動態貯藏彈性率較佳爲 100-100萬Pa。再者，於低溫之動態貯藏彈性率越大越好， 例如，流延支持體於-5 °C之情形，於-5 °C之動態貯藏彈性 率較佳爲1萬〜100萬Pa，支持體於-50 °C之情形，於-50 °C 之動態貯藏彈性率較佳爲1萬~5 〇〇萬Pa。 接著，針對利用醯化纖維素溶液之薄膜的製造方法加 以說明。製造本發明之纖維素體薄膜的方法及設備，可以 使用供習知三乙酸纖維素體薄膜製造之溶液流延製膜方法 及溶液流延製膜裝置。利用貯藏鍋暫時貯藏由溶解機（鍋） 所調製的膠漿（醯化醯化纖維素溶液），脫除於膠漿中所 含之氣泡而進行最後調製。例如，將膠漿從膠漿排出口， 藉由旋轉數而通過能夠高精確度定量送液的加壓型定量齒 輪幫浦，移送至加壓型模頭，再由加壓型模頭之噴嘴（狹 縫），於環形移動中之流延部的金屬支持體上進行均勻地 流延，於金屬支持體約繞一周的剝離點，將半乾之膠漿薄 膜（也稱爲纖維膜）從金屬支持體予以剝離。以夾子夾住 所得到的纖維膜之兩端，一面保持寬度，一面利用鍊式烘 乾機，進行移送與乾燥，接著，利用乾燥裝置的數個滾筒 進行移送，結束乾燥之後，利用捲取機捲取所要之長度。 鍊式烘乾機與數個滾筒乾燥裝置之組合，因應於其目的而 有所改變。用於鹵化銀照相感光材料或電子顯示噴霧用功 能性保護膜的溶液流延製膜方法，除了溶液流延製膜裝置 之外，爲了對底層、抗靜電層、防眩層、保護層等薄膜之 表面加工，大多附加塗布裝置。針對此等之各製造步驟， 已詳細揭示於日本發明協會公開技報（公技編號： -28- 1353370 爲含有至少一種液體或固體之可塑劑0.1〜20質量％的醯化 纖維素溶液；及/或相對於醯化纖維素，爲含有至少一種液 體或固體之紫外線吸收劑0.001~5質量％的醯化纖維素溶 液；及/或相對於醯化纖維素，爲含有至少一種之固體，其 平均粒徑爲5~ 3 OOOnm之微粒粉末0.001〜5質量的醯化纖維 素溶液：及/或相對於醯化纖維素，爲含有至少一種氟系界 面活性劑0.001〜2質量％的醯化纖維素溶液；及/或相對於 醯化纖維素，爲含有至少一種剝離劑0·0001~2質量％的醯 化纖維素溶液；及/或相對於醯化纖維素，爲含有至少一種 抗劣化劑0.0001〜2質量％的醯化纖維素溶液；及/或相對於 醯化纖維素，爲含有至少一種光學異方向性控制劑0.1 ~ 1 5 質量％的醯化纖維素溶液；及/或相對於醯化纖維素，爲含 有至少一種紅外線吸收劑〇·1〜5質量％的醯化纖維素溶液。 於流延步驟，可以進行一種醯化纖維素溶液之單層流 延，也可以同時及/或逐次共流延二種以上之醯化纖維素溶 液。共流延能夠利用例如於特開昭56-162617、開昭 2002-316387所揭示之態樣而進行。藉由共流延，製造本發 明纖維素膜之情形的層數，較佳爲2〜5層，更佳爲2〜4層， 尤以2〜3層更爲理想。 較佳之一種醯化纖維素溶液及由它所製作之醯化纖維 素薄膜，其特徵爲：具有由2層以上而成的流延步驟之情 形，於所製作的醯化纖維素溶液及醯化纖維素薄膜中，各 層之氯系溶劑組成爲相同的或不同的組成之任一情形；各 層之添加劑爲一種或二種以上之任一情形；對各層之添加 劑的添加位置爲同一層或不同層之任一情形；添加劑之溶 -30- 1353370 液中的濃度各層均爲相同濃度或不同濃度之任 層之締合體分子量爲相同的或不同的締合體分 情形；各層溶液之溫度爲相同的或不同的溫, 形：另外，各層的塗布量爲相同的或不同的塗 情形：各層的黏度爲相同的或不同的黏度之任 層乾燥後的膜厚爲相同的或不同的厚度之任 者，存在於各層之原料爲相同狀態與分布或不 布之任一情形；各層物性爲同一或不同的物性2 此處所謂之物性係包含已詳細揭示於曰本 開技報（公技編號：2001-1745，2001年3月15 明協會），第6~7頁的物性，例如，Hz、透過率 、遲滯Re値、遲滯Rth値、分子配向軸、軸偏移 、耐折強度、拉伸強度、捲繞內外Rt差、磨擦 擦、鹼加水分解、捲曲値、含水率、殘留溶劑 率、高濕尺寸評估、透濕度、基材之平面性、 、熱收縮開始溫度、彈性率及輝點異物之測定 也包含用於基材評估之電阻、表面狀態。另外 舉：已詳細揭示於日本發明協會公開技報（公 01-1745，2001年3月15日發行，發明協會）， 化纖維素之黃色指標、透明度、熱物性（Tg、 等。 還有，本發明之醯化纖維素薄膜，基於調 之目的，也可以於流延時及乾燥後，向任意方 〇 醯化纖維素薄膜係藉由進行視情形而定之 一情形；各 子量之任一 f之任一情 布量之任一 一情形；各 一情形；再 同狀態與分 :任一情形。 發明協會公 曰發行，發 、分光特性 、扯裂強度 聲響、動摩 量、熱收縮 尺寸安定性 等，再者， ，也可以列 技編號：20 第1 1頁的醯 結晶化熱） 節光學性能 向進行拉伸 表面處理， -31· 1353370 能夠達成改善醯化纖維素薄膜與各機能性層（例如，底塗 層與背面層）之黏著。例如，可以利用輝光放電處理、紫 外線照射處理、電暈處理、火焰處理、酸或鹼處理。此處 所謂輝光放電處理係於ΠΓ3〜20Torr(0.1Pa〜2.7kPa)之低壓 氣體下所進行的，所謂的低溫電漿。另外，最好於一大氣 壓力下進行電漿處理。 所謂電漿激發性氣體係指如該條件下被電漿所激發的 氣體，可舉例如氬、氦、氖、氪、氙、氮、二氧化碳、四 氟甲烷般之有機氟化物類及此等之混合物等。針對此等氣 體，已詳細揭示於日本發明協會公開技報（公技編號： 2001-.1 745’ 2001年3月15日發行，發明協會），第30~32頁。 還有，近年來備受矚目之一大氣壓力下的電漿處理，例如， 於10〜lOOOKev下，使用20〜500kGy之照射能量，較佳於 30〜5 00Kev下，使用20~3 00kGy之照射能量。此等之中，尤 以鹼液皂化處理更爲理想，對於纖維素膜之表面處理極爲 有效。 鹼液皂化處理係藉由塗布皂化液而進行的。塗布方法 ’可舉例如浸漬塗布法、簾流塗布法、擠壓塗布法、桿式 塗布法及E型塗布法。鹼液皂化處理塗布液之溶劑較佳選擇 :爲了對於透明支持體進行皂化液之塗布，具有良好之濕 潤性，另外，利用皂化液溶劑，不會於透明支持體表面上 形成凹凸’保持良好之表面狀態。丨邮13 A-23 Q-6-nQ-n0-^) A-24 A-2 ! 〇CeH13 Λ-2 6 -12- 1353370 Additional additives can be added during the final preparation step of the glue making step , the steps of modulation. Further, there is no particular limitation as long as the function of adding the amount of each material can be found. Further, the deuterated cellulose film is formed of a plurality of layers, and the type or addition amount of the additives of the respective layers may be different. For example, it is disclosed in Japanese Laid-Open Patent Publication No. 2001-151902, etc., which are known techniques. A more detailed description of these is preferably described in detail in the Japanese Invention Association Open Technical Bulletin (public technology number: 20CU-1745, issued on March 15, 2001, Invention Association), pages 16-22. Next, the organic solvent used for the dissolution of the cellulose body of the present invention will be described. First, the description of the non-chlorine-based organic solvent preferably used in the production of the cellulose body solution can be carried out in the range of dissolution, casting, and film formation of the cellulose body of the present invention, as long as the object can be achieved. The non-chlorine organic solvent is not particularly limited. The non-chlorine-based organic solvent used in the present invention is preferably a solvent selected from esters, ketones and ethers having 3 to 12 carbon atoms. The esters, ketones and ethers may also have a cyclic structure. A compound having two or more functional groups of an ester, a ketone and an ether (that is, 〇_, -CO- and -COO-) may be used as a main solvent, and may have other functional groups such as an alcoholic hydroxyl group. . The main solvent having two or more functional groups may be any one as long as the number of carbon atoms is within a predetermined range of the compound having any functional group. Examples of the ester having 3 to 12 carbon atoms include ethyl methyl decyl ester, propyl methyl decyl methacrylate, amyl decyl methyl ester, methyl acetate, ethyl acetate, and amyl B. Acid ester. Examples of the ketone having 2 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, and ring -18 - 1353370 hexane and methylcyclohexane. ketone. Examples of the ether having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-diton, and 1,3-diox. Heteropentane, tetrahydrofuran, anisole and phenylethyl ether. The organic solvent having two or more functional groups may, for example, be 2-ethoxyethyl acetate, 2-methoxyethanol or 2-butoxyethanol. The non-chlorine-based organic solvent used for the above-mentioned cellulose body is selected based on the various viewpoints, and preferably three or more mixed solvents different from each other. The first solvent is at least one selected from the group consisting of methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetone, dioxolane, dioxane or a mixture thereof, preferably methyl acetate. , acetone, methyl formate, ethyl formate or a mixture of these. The second solvent is at least one selected from the group consisting of ketones or acetonitrile acetate having 4 to 7 carbon atoms, or a mixture thereof, preferably methyl ethyl ketone, cyclopentanone, cyclohexanone, Methyl acetoxyacetate or a mixture of these. Further, in the case where the first solvent is a mixture of two or more solvents, the second solvent may be used. The third solvent is preferably an alcohol selected from an alcohol or a hydrocarbon having a carbon number of 1 to 10, preferably an alcohol having a carbon number of 1 to 8. The third solvent is a moiety other than the hydroxyl group of the alcohol, and may be linear, branched or cyclic. Among them, a saturated alicyclic hydrocarbon is preferable. The alcohol may, for example, be methanol, ethanol, 1-propanol, 2-propanol '1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol and a ring. Hexanol. Further, as the alcohol, a fluorine-based alcohol can also be used. For example, fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol or the like can be mentioned. -19 - 1353370 Hydrocarbon as a third solvent, which may be linear, branched or cyclic. Any of an aromatic hydrocarbon and an aliphatic hydrocarbon can be used. Aliphatic hydrocarbons may be saturated or unsaturated. Examples of the hydrocarbon include cyclohexane, hexane, benzene, toluene and xylene. The alcohol and the hydrocarbon of the third solvent may be used singly or in combination of two or more kinds, and are not particularly limited. Preferred specific compounds of the third solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and cyclohexanol; cyclohexane and hexane; . In particular, methanol, ethanol, 1-propanol, 2-propanol and 1-butanol are preferred. The ratio of the above three mixed solvents is preferably 20% by mass to 95% by mass of the first solvent, 2 to 60% by mass of the second solvent, and 2 to 30% by mass of the third solvent. More preferably, it contains the first solvent: 30 to 90% by mass, the second solvent: 3 to 50% by mass, and the third solvent contains 3 to 25% by mass of the alcohol. In particular, it is preferable to contain the first solvent: 30 to 90% by mass, the second solvent: 3 to 30% by mass, and the third solvent to contain 3 to 15% by mass of the alcohol. Further, when the first solvent is a mixed solution and the second solvent is not used, it is preferable to contain the first solvent: 20 to 90% by mass, and the third solvent: 5 to 30% by mass. More preferably, it contains a 1st solvent: 30-86 mass %, and a 3rd solvent: 7-25 mass %. The non-chlorinated organic solvent used in the above invention is described in detail in the Japanese Invention Association Open Technical Bulletin (public technology number: 2001-1745, issued on March 15, 2001, Invention Association), No. 12~ 16 pages. The combination of the preferred non-chlorine-based organic solvent of the present invention is as follows, but is not limited to such a non-chlorine-based organic solvent. *Methyl acetate / acetone / methanol / ethanol / butanol (75/10/5/5/5, parts by mass), -20- 1353370 methyl acetate / acetone / methanol / ethanol / propanol (75 / 1 0 /5/5/5, parts by mass), *methyl acetate/acetone/methanol/butanol/cyclohexane (75/10/5/5/5, parts by mass), ♦ methyl acetate/acetone/ethanol/ Butanol (81/8/7/4, parts by mass), *methyl acetate/acetone/ethanol/butanol (82/10/4/4, parts by mass), methyl acetate/acetone/ethanol/butanol (80/10/4/6, parts by mass), «methyl acetate/methyl ethyl ketone/methanol/butanol (8 0/10/5/5, parts by mass), *methyl acetate/acetone/A Ethyl ketone / ethanol / isopropanol (75 / 1 0/1 0/5 / 7, parts by mass), methyl acetate / cyclopentanone / methanol / isopropanol (80/10/5 / 8, Parts by mass), methyl acetate/acetone/butanol (85/5/5, parts by mass), methyl acetoxy/cyclopentanone/acetone/methanol/butanol (6 0/15/15/5/6 , parts by mass), • methyl acetate/cyclohexanone/methanol/hexane (70/20/5/5, parts by mass), *methyl acetate/methyl ethyl ketone/acetone/methanol/ethanol (50/ 20/20/5/5, parts by mass), methyl acetate/1,3-two Heteropentane/methanol/ethanol (7〇/2〇/5/5, parts by mass), methyl acetate/dioxane/acetone/methanol/ethanol (60/20/ 1 0/5/5, parts by mass) ), *methyl acetate / acetone / cyclopentanone / ethanol / isobutanol / cyclohexane (65 / 1 0/1 0/5 / 5 / 5 parts by mass), • methyl formate / methyl ethyl Ketone/Acetone/Methanol/Ethanol (50/20/20/5/5, parts by mass), methyl formate/acetone/ethyl acetate/ethanol/butanol/hexane-21- 1353370 (65/1 0/ 10/5/5/5, parts by mass), Acetone/Ethyl mercaptoacetate/methanol/ethanol (65/2 0/1 0/5, parts by mass), • Propylene/cyclopentanone/ethanol/ Butanol (65/20/1 0/5, parts by mass), • Acetone/1,3-dioxolane/ethanol/butanol (65/2 0/1 0/5, parts by mass), ♦ 1 , 3 - dioxapentane / cyclohexanone / methyl ethyl ketone / methanol / butanol (5 5 / 20/1 0/5 / 5, parts by mass). Further, the deuterated cellulose solution can also be used by the following method. The dope used in the present invention may contain, in addition to the non-chlorine-based organic solvent, methylene chloride in an amount of 10% by mass or less based on the total amount of the organic solvent. Further, in the case of producing the deuterated cellulose solution of the present invention, a chlorine-based organic solvent may be used as the main solvent, as the case may be. In the range in which the cellulose body can be dissolved, cast, or formed into a film, the chlorine-based organic solvent is not particularly limited. These chlorine-based organic solvents are more preferably dichloromethane or chloroform. Especially dichloromethane is ideal. Further, there is no particular problem in mixing an organic solvent other than the chlorine-based organic solvent. In this case, dichloromethane is preferably used in an amount of at least 50% by mass. The non-chlorine organic solvent to be used in combination is preferably a solvent selected from esters, ketones, ethers, hydrocarbons and the like having 3 to 12 carbon atoms. The esters, ketones, ethers and alcohols may also have a cyclic structure. A compound having any two or more functional groups of an ester, a ketone and an ether (that is, -0-, -CO-, and -COO-) may be used as a solvent, or may have, for example, an alcoholic hydroxyl group. Functional group. The solvent having two or more functional groups may be any one as long as the number of carbon atoms is within a predetermined range of the compound having any functional group. -22- 1353370 非 The non-chlorine organic solvent used in the hydrazine may, for example, be methyl acetate, acetone, methyl formate 'ethyl formate, methyl ethyl ketone, cyclopentanone, cyclohexanone or methyl acetoxyacetate. Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, cyclohexanol, cyclohexane and hexane. The combination with the chlorine-based organic solvent of the preferred main solvent of the present invention is as follows, but is not limited thereto, and may be, for example, methylene chloride/methanol/ethanol/butanol (75/10/5) /5/5, parts by mass), • dichloromethane/acetone/methanol/propanol (80/10/5/5/5, parts by mass), • dichloromethane/methanol/butanol/cyclohexane (75 /10/5/5, parts by mass), • dichloromethane/methyl ethyl ketone/methanol/butanol (80/10/5/5, parts by mass), • dichloromethane/acetone/methylethyl Ketone/Ethanol/Isopropanol (75/10/10/5/7, parts by mass), • Dichloromethane/cyclopentanone/methanol/isopropanol (80/10/5/8, parts by mass), • Dichloromethane/methyl acetate/butanol (80/10/10, parts by mass), • dichloromethane/cyclohexanone/methanol/hexane (70/20/5/5, parts by mass)' • Dichloro Methane/methyl ethyl ketone/acetone/methanol/ethanol (50/20/20/5/5, parts by mass), • dichloromethane/1,3-dioxolane/methanol/ethanol (70/20 /5/5, parts by mass) ' ♦ dichloromethane / dioxane / acetone / methanol / ethanol (60 / 20/10/5 / 5 parts by mass), • dichloromethane / acetone / cyclopentane Ketone/Ethanol/Isobutanol/Cyclohexane (65/10/10/5/5/5, parts by mass), *Dichloromethane/Methyl Ethyl Ketone/Acetone/Methanol/Ethanol (7〇/1〇) /1〇/5/5, parts by mass), -24-1353370 The viscosity is 10~2 00 Pa·s, and the dynamic storage modulus at 15 °c is preferably 100-100,000 Pa. Furthermore, the higher the dynamic storage modulus at low temperatures, the better, for example, the casting support at -5 ° C, the dynamic storage elastic modulus at -5 ° C is preferably 10,000 to 1 million Pa, support At -50 °C, the dynamic storage modulus at -50 °C is preferably 10,000 to 50,000 Pa. Next, a description will be given of a method for producing a film using a deuterated cellulose solution. The method and apparatus for producing the cellulose body film of the present invention may be a solution casting film forming method and a solution casting film forming apparatus which are prepared by a conventional cellulose acetate film. The slurry prepared by the dissolving machine (pot) is temporarily stored in a storage pot, and the bubbles contained in the dope are removed for final preparation. For example, the glue is discharged from the glue discharge port, and the pressure type quantitative gear pump capable of quantitatively feeding the liquid by high rotation is transferred to the pressure type die, and then the nozzle of the pressure type die is transferred. (slit), which is uniformly cast on the metal support of the casting portion in the circular movement, and the semi-dry dope film (also referred to as a fiber membrane) is removed from the metal support at a peeling point of about one round. The metal support is peeled off. The both ends of the obtained fiber membrane are sandwiched by a clip, and the width is maintained, and the mixture is transferred and dried by a chain dryer, and then transferred by a plurality of rollers of the drying device, and after drying, the coiler is used. Take the desired length. The combination of a chain dryer and several drum dryers varies depending on its purpose. A solution casting film forming method for a silver halide photographic light-sensitive material or a functional protective film for electronic display spray, in addition to a solution casting film forming device, for a film such as a bottom layer, an antistatic layer, an antiglare layer, a protective layer, or the like For the surface processing, a coating device is often added. For each of the manufacturing steps, it has been disclosed in detail in the Japanese Invention Association published technical report (public technology number: -28-1353370 is a deuterated cellulose solution containing at least one liquid or solid plasticizer 0.1 to 20% by mass; and Or 0.001 to 5% by mass of a deuterated cellulose solution containing at least one liquid or solid ultraviolet absorber relative to the deuterated cellulose; and/or containing at least one solid relative to the deuterated cellulose, a bismuth cellulose solution having an average particle diameter of 5 to 3 OOOnm of 0.001 to 5 masses of fine particles: and/or 0.001 to 2% by mass of deuterated fiber containing at least one fluorine-based surfactant relative to deuterated cellulose. And a solution of deuterated cellulose containing at least one stripping agent in an amount of 0. 0001 to 2% by mass relative to the deuterated cellulose; and/or containing at least one anti-deteriorating agent relative to the deuterated cellulose. 0.0001 to 2% by mass of a deuterated cellulose solution; and/or a deuterated cellulose solution containing at least one optical anisotropic control agent in an amount of 0.1 to 15% by mass relative to the deuterated cellulose; and/or relative to醯Chemical fiber a bismuth cellulose solution containing at least one infrared absorbing agent 1·1 to 5% by mass. In the casting step, a single layer casting of a bismuth cellulose solution may be carried out, or may be simultaneously and/or successively Two or more kinds of deuterated cellulose solutions are cast, and the co-casting can be carried out, for example, in the form disclosed in JP-A-56-162617, and JP-A-2002-316387. The cellulose of the present invention is produced by co-casting. The number of layers in the case of the film is preferably 2 to 5 layers, more preferably 2 to 4 layers, and particularly preferably 2 to 3 layers. A preferred deuterated cellulose solution and deuterated fiber produced therefrom A film having a casting step of two or more layers, wherein the chlorine-based solvent compositions of the layers are the same or different in the produced deuterated cellulose solution and the deuterated cellulose film. In any case of the composition; the additive of each layer is one or more of the above; the additive of each layer is added in the same layer or in any of the different layers; the concentration of the additive in the solution -30 - 1353370 Are the same concentration or different concentrations The molecular weight of the association of any layer is the same or different associations; the temperature of each layer solution is the same or different temperature, and the shape: the coating amount of each layer is the same or different coating conditions: the viscosity of each layer is Any of the same or different viscosities, the film thickness after drying is the same or different thickness, and the materials present in each layer are in the same state and distributed or not. The physical properties of the layers are the same or different. Physical property 2 The physical property system here contains the physical properties that have been disclosed in detail in the 曰本开技报 (public technology number: 2001-1745, March 15, 2001), pages 6-7, for example, Hz, transmittance Hysteresis Re値, hysteresis Rth値, molecular alignment axis, axis offset, folding strength, tensile strength, Rt difference inside and outside the winding, friction rubbing, alkali hydrolysis, curling, moisture content, residual solvent rate, high humidity The dimensional evaluation, the moisture permeability, the planarity of the substrate, the heat shrinkage onset temperature, the modulus of elasticity, and the measurement of the foreign matter of the bright spot also include the resistance and surface state for evaluation of the substrate. In addition, it has been disclosed in detail in the Japanese Invention Association's Open Technical Bulletin (public 01-1745, issued on March 15, 2001, Invention Association), yellow index of cellulose, transparency, thermal properties (Tg, etc. Also, The deuterated cellulose film of the present invention may be subjected to any of the sub-quantity by any of the sub-quantity of the cellulose film according to the purpose of the adjustment, after the flow-delay and drying. Any one of the circumstances; each situation; the same state and points: any situation. The invention association issued, hair, spectroscopic characteristics, tear strength, dynamic friction, heat shrink size stability Sex, etc., can also be listed in the number: 20, page 1 of the crystallization heat of the )) optical performance of the tensile surface treatment, -31· 1353370 can achieve improved cellulose film and various functionalities Adhesion of the layer (eg, the undercoat layer and the back layer). For example, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be utilized. Here, the glow discharge treatment is carried out under a low pressure gas of 3 to 20 Torr (0.1 Pa to 2.7 kPa), so-called low temperature plasma. In addition, it is preferred to carry out the plasma treatment at an atmospheric pressure. The plasma-excited gas system refers to a gas excited by the plasma under such conditions, and examples thereof include argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, tetrafluoromethane-like organic fluorides, and the like. Mixture, etc. For these gases, they have been disclosed in detail in the Japan Invention Association Open Technical Bulletin (public technology number: 2001-.1 745' issued on March 15, 2001, Invention Association), pp. 30-32. In addition, in recent years, the plasma treatment under atmospheric pressure has been attracting attention. For example, under 10~100 OKev, the irradiation energy of 20~500kGy is used, preferably 30~500 00Kev, and the irradiation of 20~300 00Ky is used. energy. Among these, saponification by alkali is more preferable, and it is extremely effective for the surface treatment of the cellulose film. The alkali saponification treatment is carried out by coating a saponification liquid. The coating method is exemplified by a dip coating method, a curtain flow coating method, an extrusion coating method, a rod coating method, and an E-type coating method. The solvent for the alkali saponification treatment coating liquid is preferably selected to have good wettability in order to apply the saponification liquid to the transparent support, and to prevent the formation of irregularities on the surface of the transparent support by the saponification solution solvent. surface condition.

具體而言，較佳爲醇系溶劑，尤以異丙醇更爲理想。 另外’也可以將界面活性劑之水溶液作爲溶劑使用。鹼液 皂化塗布液之鹼液，較佳溶於該溶劑之鹼液，更佳者爲KO -32- 1353370 Η、NaOH。皂化塗布液之pH値較佳爲10以上、更佳爲12以 上。鹼液皂化時之反應條件，於室溫下’較佳爲1秒鐘以上 、5分鐘以下，更佳爲5秒鐘以上、5分鐘以下’尤以20秒鐘 以上、3分鐘以下更爲理想。鹼液皂化反應後，較佳利用水 洗或是以酸洗淨皂化液塗布面之後再進行水洗。 另外，能夠連續進行塗布式皂化處理與後述之配向膜 底塗層之設置，故能夠減少製程步驟之數目。 爲了達成乳劑層等之機能性層與膜之黏著，一種方法 係於進行表面活性化處理之後，將機能性層直接塗布於醯 化纖維素薄膜上而得到黏著力；與另一種方法係一旦進行 任何表面處理之後，或是不進行表面處理，設置底塗層（ 黏著層），再於其上進行機能性層之塗布。針對此等之底 塗層，已詳細揭示於日本發明協會公開技報（公技編號：2 00卜1745，2001年3月15日發行，發明協會），第32頁。另 外，針對本發明之醯化纖維素薄膜的機能性層，各種機能 性層已詳細揭示於日本發明協會公開技報（公技編號：20 01-1745，2001年3月15日發行，發明協會），第32〜45頁。 本發明的醯化纖維素薄膜之透濕度，係以200~2000克 /(m2 ·日）爲佳、400〜2000克/(m2 ·曰）爲更佳、400〜1800 克/(m2·曰）爲最佳。 本發明中的透濕度，爲裝入氯化鉀的杯子係使用各種 的薄膜試料之蓋、且密閉者，於60°C及95%RH的條件下， 根據放置24小時前後的重量變化（克/(m2 .日）），基於氯化 鉀的吸濕性而評價纖維素三乙酸酯薄膜透濕度之數値。 以下係說明書醯化纖維素薄膜的光學性能。本發明醯 -33- 1353370 化纖維素薄膜的光學性能之面内遲滯値（Re)、遲滯値（以下 Rth)，係利用橢圓儀（Ellipsometer)(AEP-l〇〇、島津製作所 (股）製）來加以測定。 具體而言，Re係爲以波長632.8nm測定的面内縱横折射 率差’乘上薄膜膜厚之値，可根據下述式而求得。Specifically, an alcohol solvent is preferred, and isopropyl alcohol is more preferred. Further, an aqueous solution of a surfactant may be used as a solvent. The alkali solution of the saponification coating liquid is preferably dissolved in the alkali solution of the solvent, more preferably KO-32-1353370 hydrazine or NaOH. The pH of the saponified coating liquid is preferably 10 or more, more preferably 12 or more. The reaction conditions at the time of saponification of the alkali liquid are preferably at least 1 second or more and 5 minutes or less at room temperature, more preferably 5 seconds or more and 5 minutes or less, and more preferably 20 seconds or more and 3 minutes or less. . After the lyophilization reaction of the alkali solution, it is preferred to wash the surface with water or to wash the surface with an acid saponification solution, followed by water washing. Further, since the coating saponification treatment and the aligning film undercoat layer described later can be continuously performed, the number of process steps can be reduced. In order to achieve adhesion of the functional layer of the emulsion layer to the film, one method is to apply the functional layer directly to the deuterated cellulose film to obtain adhesion after the surface activation treatment; After any surface treatment, or without surface treatment, an undercoat layer (adhesive layer) is provided, and then the functional layer is coated thereon. The undercoat for these has been disclosed in detail in the Japanese Invention Association's Open Technical Bulletin (public technology number: 00b 1745, issued on March 15, 2001, Invention Association), p. 32. In addition, with regard to the functional layer of the deuterated cellulose film of the present invention, various functional layers have been disclosed in detail in the Japanese Invention Association Open Technical Bulletin (public technology number: 20 01-1745, issued on March 15, 2001, Invention Association ), pp. 32~45. The moisture permeability of the deuterated cellulose film of the present invention is preferably 200 to 2000 g/(m2·day), more preferably 400 to 2000 g/(m2·曰), and more preferably 400 to 1800 g/(m2·曰). ) is the best. The moisture permeability in the present invention is a cover for various types of film samples used in a cup containing potassium chloride, and is sealed, at 60 ° C and 95% RH, depending on the weight change before and after standing for 24 hours (g / (m2. day)), the number of moisture permeability of the cellulose triacetate film was evaluated based on the hygroscopicity of potassium chloride. The following is a description of the optical properties of the cellulose film. In-plane retardation Re(Re) and hysteresis 以下 (hereinafter Rth) of the optical properties of the 醯-33- 1353370 cellulose film of the present invention are based on an Ellipsometer (AEP-l〇〇, Shimadzu Corporation) ) to determine. Specifically, Re is obtained by multiplying the in-plane longitudinal and lateral refractive index difference ‘ measured at a wavelength of 632.8 nm by the thickness of the film, and can be obtained by the following formula.

Re=(nx-ny)xd [式中，nx係爲遲相軸方向（折射率最大的方向）的折射 率；ny係爲遲相軸直交方向的折射率；然後，d係爲薄膜的厚 度（單位：nm)] 纖維素酯薄膜的面向遲滯値（Re)係以5 Onm以下爲佳、 40nm以下爲較佳、30nm以下爲更佳、20nm以下爲最佳。 薄膜厚度方向的遲滯値（Rth)，具體而言係爲以波長 632.8nm測定的厚度方向複折射率，乘上薄膜膜厚之値，可 根據下述式而求得。Re=(nx-ny)xd [wherein nx is the refractive index of the slow axis direction (the direction in which the refractive index is the largest); ny is the refractive index of the direction of the late phase axis; then, d is the thickness of the film (Unit: nm)] The retardation Re (Re) of the cellulose ester film is preferably 5 Onm or less, preferably 40 nm or less, more preferably 30 nm or less, and most preferably 20 nm or less. The retardation 値(Rth) in the thickness direction of the film is specifically a thickness direction complex refractive index measured at a wavelength of 632.8 nm, which is obtained by multiplying the film thickness of the film by the following formula.

Rth = {(nx + ny)/2-nz }xd [式中，nx係爲遲相軸方向（折射率爲最大的方向）的折 射率；ny係爲遲相軸直交方向的折射率；nz係爲厚度方向的 折射率；然後，d爲薄膜的厚度（單位：nm)] 纖維素酯薄膜厚度方向的遲滯値（Rth)，係以 1 00nm~3 OOnm 爲佳、1 2 Onm〜3 0 Onm 爲更佳、150nm~300nm 爲最佳。 首先，針對本發明所製作的纖維素體之用途，進行龠 單的描述。本發明之光學薄膜作爲偏光板保護膜用係爲有 用，作爲偏光板保護膜使用之情形下，偏光板之製作方法 並無特別之限定，能夠利用一般方法進行製作。例如，進 -34- 1353370 行所得到的醯化纖維素薄膜之鹼液處理，於碘溶液中進行 聚乙烯醇膜之浸漬拉伸而製成的偏光子兩面，利用完全凝 膠化之聚乙烯醇水溶液進行貼合的方法。也可以進行如特 開平6-94915、同6-118232號之各公報所揭示的易黏著加工 以取代鹼液處理。用於保護膜處理面與偏光子之貼合的黏 著劑，例如，可舉例如聚乙烯醇、聚乙烯丁縮醛等之聚乙 烯醇系黏著劑，或是丙烯酸丁酯等之乙烯系乳膠等。偏光 板係由保護偏光子及其兩面之保護膜所構成的，再者構造 上，係於該偏光板之一側面貼合防護膜，於反面貼合隔離 膜。防護膜及隔離膜之目的係用於偏光板出貨時、產品檢 查時等進行保護。此情形下，防護膜之目的在於保護偏光 板表面而進行貼合，用於將偏光板貼合於液晶板之相反面 側。另外，隔離膜之目的在於用以覆蓋貼合於液晶板之黏 著層，用於將偏光板貼合於液晶板之表面側。於液晶顯示 裝置中，通常於二片偏光板之間配置含有液晶之基板，適 用本發明光學薄膜之偏光板保護膜，不論配置於那一部位 ，均可以得到優異的顯示性。尤其，由於液晶顯示裝置之 顯示側最表面的偏光板保護膜上設置透明硬質塗布層、防 眩層、抗反射層等，尤以將偏光板保護膜用於此部分更爲 理想。 本發明之纖維素體薄膜，可適用於各式各樣之用途， 作爲液晶顯示裝置之光學補償片材使用特別有效。本發明 之纖維素體薄膜，可適用於各式各樣顯示模式之液晶儲存 格。如 TN(Twisted Nematic;扭曲配向）、ISP(In-Plane Swi tching;面內切換）、FLC(Ferroelectric Liquid Crystal;鐵電 -35- 1353370 液晶）、AFLC(Anti-ferroelectric Liquid Crystal;抗鐵電液 晶）、OCB(Optically Compensatory Bend;光學補償彎曲） 、STN(Supper Twisted Nematic;超扭曲配向）、VA(Vertic ally Aligned;垂直排列）及 HAN(Hybrid Aligned Nematic; 混成排列扭曲）之各式各樣顯示模式。另外，如該顯示模 式之配向分割顯示模式。纖維素體薄膜對任一顯示模式之 液晶顯示裝置均爲有效的。另外，透過型、反射型、半透 過型之任一液晶顯示裝置也均爲有效的。也可以將本發明 之纖維素體薄膜，作爲具有TN模式液晶儲存格之TN型液晶 顯示裝置的光學補償片材之支持體使用。也可以將本發明 之纖維素體薄膜，作爲具有STN模式液晶儲存格之STN型液 晶顯示裝置的光學補償片材之支持體使用。一般之STN型 液晶顯示裝置，液晶儲存格中的棒狀液晶性分子於90〜3 60 度之範圍被扭曲，棒狀液晶性分子之折射率異方向性（Δη )與儲存格間隙（d)之乘積（Δηίΐ)於300-1500nm之範圍 。針對用於STN型液晶顯示裝置的光學補償片材，已揭示 於特開2000-105316號公報。本發明之纖維素體薄膜，有利 於作爲具有VA模式之液晶儲存格之VA型液晶顯示裝置的 光學補償片材之支持體使用。本發明之纖維素體薄膜，也 有利於作爲具有OCB模式之液晶儲存格之OCB型液晶顯示 裝置或是HAN模式之液晶儲存格之HAN型液晶顯示裝置的 光學補償片材之支持體使用。 本發明之纖維素體薄膜’均有利於作爲具有TN型、ST N型、Η AN型、GH ( Guest-Host ;主客）型之反射型液晶顯 示裝置的光學補償片材之支持體使用。此等顯示模式均已 -36- 1353370 習知良久。針對TN型反射型液晶顯示裝置，已揭示於特開 平1 0-1 23478號公報、國際公報WO98/48320號手冊、特許3 022477說明書之中。針對用於反射型液晶顯示裝置之光學 補償片材，已揭示於國際公報WOOO/653 84號手冊。 本發明之纖維素體薄膜有利於作爲具有ASM(Axially Symmetric Aligned Microcell;軸向對稱對準微儲存格） 模式之液晶儲存格的AS Μ型液晶顯示裝置之光學補償片材 之支持體使用。ASM模式之液晶儲存格所具備之特徵爲： 藉由可調整位置之樹脂間隙物維持儲存格的厚度。其他之 性質則相同於TN模式之液晶儲存格。針對AS Μ模式液晶儲 存格與ASM型液晶顯示裝置，已揭示於Kume等人之論文（Κ ume et al·， SID 98 Digest 1 089( 1 998))。 如上所述此等詳細之纖維素體薄膜的用途，已詳細揭 示於日本發明協會公開技報（公技編號：2001-1745，2001年3 月15曰發行，發明協會），第45〜5 9頁。 再者，本發明的纖維素體薄膜亦可適用於作爲鹵化銀 照相感光材料的支持體，視用「照相工學的基礎」、曰本 照相學會（社）編、可樂麗社、第276〜291頁、及第291頁 記載的參考文獻中所記載之各種材料或處方，以及處理方 法。關於此等技術，可舉例如有特開2000-105445號公報 中詳細記載的彩色底片，使用本發明的纖維素體薄膜爲 佳。又，亦可適用於作爲彩色反轉鹵化銀照相感光材料的 支持體，適用特開平11-282119號公報中記載的各種材料 或處方、以及處理方法。 【實施方式】 -37- 1353370 【實施例】 接著，根據實施例，更詳細說明本發明，本發明係依 據該實施例，並無特別之限定。 <實施例ι>纖維素體薄膜及纖維素體薄膜用改質劑 (1-1)醯化纖維素溶液之製作 在具有攪拌翼之5L玻璃容器中，使下述的溶劑混合溶 液攪拌·分散，且緩慢地添加下述的纖維素三乙酸酯粉體A (薄片），進料至全體爲2公斤。此外，溶劑之乙酸甲酯、丙 酮及乙醇係利用其總含水率爲0 · 2質量％以下者。首先，纖 維素三乙酸酯之粉末係將粉體投入分散槽封入氮氣、以溶 解器類型的偏芯攪拌軸、及中心軸具有錨形葉片之攪拌機 攪拌30分鐘。分散起始溫度爲3(TC »分散終了後、停止高 速攪拌、錨形葉片的周速爲〇.5m/sec而進一步攪拌100分鐘 ，膨潤纖維素三乙酸酯薄片。直至膨潤終了爲止，氮氣槽 内係加壓成〇.l2MPa。此時槽内的氧濃度爲低於2vol%，維 持在防爆上沒有問題之狀態。另外，確認膠漿中的水分量 爲0.2質量％以下。醯化纖維素溶液的組成係如以下所示： 使用纖維素三乙酸酯八（用8八+ 88爲2.78、5入爲2.78、 SB爲0、黏度平均聚合度303、含水率爲1質量％以下的醯化 纖維素薄片。又，使用醯化纖維素的第6位取代度爲0.90 者）（15質量份）、乙酸甲酯（87.0質量份）、丙酮（8.0質量份）、 乙醇（5.0質量份）、TPP/BDP(8.0質量份）以製造第1表所記載 的試料1。接著除了試料1的TPP/BDP爲12.0質量份以外，製 成與試料1相同組成之試料2。再者’將試料1的TPP/BDP以 表1記載的改質劑替換，添加表1記載的添加量以製作試料 -38 - 1353370 3~1 5。 (1-2)纖維素三乙酸酯膜溶液 所得不均勻的凝膠狀溶液係以螺旋泵送液，在-70°C下 3分鐘通過冷却部分。冷却係使用以冷凍機冷却的-8 0 °C冷 媒而實施。由冷却所得溶液係移送至不銹鋼製之容器中， 以50 °C攪拌2小時成均勻溶液後，以絶對濾過精度0.01 mm 的濾紙（東洋濾紙（股）製、#6 3)過濾，且更以絶對濾過精度 2.5μπι的濾紙（Pole社製、FH02 5)過濾。 (1-3)纖維素三乙酸酯膜的製作 過濾完成之50 °C的纖維素三乙酸酯溶液係通過流延 器、在鏡面不銹鋼支持體上加以流延。以支持體的溫度5 °C，流延速度3m/分形成塗布寬爲3 0 cm。於室溫下放置1分 鐘，之後爲了乾燥於55 °C的乾燥風加以送風。5分鐘後從鏡 面不銹鋼支持體剝取、之後在133°C下乾燥27分鐘，以得到 膜厚60μιη的纖維素三乙酸酯膜。 (1-4)纖維素三乙酸酯膜的透濕度測定 所得之纖維素三乙酸酯薄膜的透濕度，爲裝入氯化鉀 的杯子係使用各種的薄膜試料之蓋、且密閉者，於6〇°C及 95 %RH的條件下，根據放置24小時前後的重量變化（克 /(m2 .日）），基於氯化鉀的吸濕性而評價纖維素三乙酸酯薄 膜透濕度之數値。 (1-5)纖維素三乙酸酯膜的Rth測定 使用橢圓儀（AEP-100、島津製作所（股）製）’以波長 6 3 2.8 nm測定的面内縱横折射率差，乘上薄膜膜厚之値，可 由下述式而求得。 -39- 1353370Rth = {(nx + ny)/2-nz }xd [wherein nx is the refractive index in the direction of the slow axis (the direction in which the refractive index is maximum); ny is the refractive index in the direction orthogonal to the slow axis; nz The refractive index in the thickness direction; then, d is the thickness of the film (unit: nm)] The retardation R(Rth) in the thickness direction of the cellulose ester film is preferably from 100 nm to 300 nm, and is 1 2 Onm to 3 0 Onm is better, and 150nm~300nm is the best. First, a description will be given of the use of the cellulose body produced by the present invention. The optical film of the present invention is useful as a protective film for a polarizing plate. When it is used as a protective film for a polarizing plate, the method for producing the polarizing plate is not particularly limited, and it can be produced by a general method. For example, the lyophilized film of the deuterated cellulose film obtained in the line of -34-1353370 is subjected to the immersion stretching of the polyvinyl alcohol film in the iodine solution to form both sides of the polarizer, and the fully gelled polyethylene is used. A method in which an aqueous alcohol solution is applied. It is also possible to carry out an easy adhesion process as disclosed in the publications of JP-A-6-94915 and No. 6-118232 in place of the alkali treatment. For the adhesive to be applied to the protective film-treated surface and the polarizer, for example, a polyvinyl alcohol-based adhesive such as polyvinyl alcohol or polyvinyl butyral, or a vinyl latex such as butyl acrylate may be used. . The polarizing plate is composed of a protective polarizer and a protective film on both sides thereof. Further, the protective film is attached to one side of the polarizing plate, and the insulating film is attached to the reverse side. The purpose of the protective film and the separator is to protect the polarizing plate when it is shipped, during product inspection, etc. In this case, the purpose of the pellicle film is to protect the surface of the polarizing plate and to bond the polarizing plate to the opposite side of the liquid crystal panel. Further, the purpose of the separator is to cover the adhesive layer attached to the liquid crystal panel for bonding the polarizing plate to the surface side of the liquid crystal panel. In the liquid crystal display device, a substrate containing a liquid crystal is usually disposed between two polarizing plates, and a polarizing plate protective film of the optical film of the present invention is used, and excellent display properties can be obtained regardless of the portion disposed therein. In particular, since a transparent hard coating layer, an antiglare layer, an antireflection layer or the like is provided on the polarizing plate protective film on the outermost surface of the display side of the liquid crystal display device, it is more preferable to use a polarizing plate protective film for this portion. The cellulose body film of the present invention can be suitably used for various purposes, and is particularly effective as an optical compensation sheet for a liquid crystal display device. The cellulose body film of the present invention can be applied to liquid crystal cells of various display modes. Such as TN (Twisted Nematic), ISP (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), AFLC (Anti-ferroelectric Liquid Crystal) ), OCB (Optically Compensatory Bend), STN (Supper Twisted Nematic), VA (Vertic ally Aligned), and HAN (Hybrid Aligned Nematic) mode. In addition, the display mode is divided as shown in the display mode. The cellulose body film is effective for any display mode liquid crystal display device. Further, any liquid crystal display device of a transmissive type, a reflective type, or a semi-transmissive type is also effective. The cellulose body film of the present invention can also be used as a support for an optical compensation sheet of a TN type liquid crystal display device having a TN mode liquid crystal cell. The cellulose body film of the present invention can also be used as a support for an optical compensation sheet of an STN type liquid crystal display device having an STN mode liquid crystal cell. In a general STN type liquid crystal display device, the rod-like liquid crystal molecules in the liquid crystal cell are distorted in the range of 90 to 3 60 degrees, and the refractive index anisotropy (Δη) of the rod-like liquid crystal molecules and the cell gap (d) The product (Δηίΐ) is in the range of 300-1500 nm. An optical compensation sheet for an STN type liquid crystal display device is disclosed in Japanese Laid-Open Patent Publication No. 2000-105316. The cellulose body film of the present invention is advantageously used as a support for an optical compensation sheet of a VA type liquid crystal display device having a VA mode liquid crystal cell. The cellulose body film of the present invention is also advantageously used as a support for an optical compensation sheet of an OCB type liquid crystal display device having an OCB mode liquid crystal cell or a HAN mode liquid crystal display device of a HAN mode. The cellulose film of the present invention is advantageously used as a support for an optical compensation sheet of a reflective liquid crystal display device having a TN type, an ST N type, a Η AN type, and a GH (Guest-Host) type. These display modes have been -36- 1353370 for a long time. The TN type reflective liquid crystal display device is disclosed in the specification of Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. An optical compensation sheet for a reflective liquid crystal display device has been disclosed in International Publication WOOO/653 84. The cellulose body film of the present invention is advantageously used as a support for an optical compensation sheet of an AS Μ type liquid crystal display device having an ASM (Axially Symmetric Aligned Microcell) mode liquid crystal cell. The ASM mode liquid crystal cell has the following features: The thickness of the cell is maintained by a resin spacer in an adjustable position. The other properties are the same as those in the TN mode. The AS Μ mode liquid crystal cell and the ASM type liquid crystal display device have been disclosed in the paper by Kume et al. (Κ ume et al., SID 98 Digest 1 089 (1 998)). The use of such detailed cellulosic film as described above has been disclosed in detail in the Japanese Invention Association Open Technical Bulletin (public technology number: 2001-1745, issued March 15, 2001, Invention Association), No. 45~5 9 page. Furthermore, the cellulose body film of the present invention can also be suitably used as a support for a silver halide photographic light-sensitive material, and is based on "the basis of photographic engineering", edited by Sakamoto Photographic Society (Society), Kuraray, 276~ Various materials, prescriptions, and treatment methods described in the references described on pages 291 and 291. For the above-mentioned techniques, for example, a color negative film described in detail in JP-A-2000-105445 is preferably used, and the cellulose body film of the present invention is preferably used. Further, it can be applied to a support for a color reversed silver halide photographic light-sensitive material, and various materials, prescriptions, and treatment methods described in JP-A-11-282119 can be applied. [Embodiment] -37-1353370 [Embodiment] Next, the present invention will be described in more detail based on examples, and the present invention is not particularly limited in accordance with the embodiment. <Example 1> Preparation of Cellulose Film and Cellulose Film for Modifier (1-1) Deuterated Cellulose Solution In a 5 L glass vessel equipped with a stirring blade, the following solvent mixture solution was stirred. The following cellulose triacetate powder A (flakes) was dispersed and slowly added, and the total amount was 2 kg. Further, the solvent methyl acetate, acetone, and ethanol are used in a total water content of 0.2% by mass or less. First, the powder of cellulose triacetate was put into a dispersion tank and sealed with nitrogen gas, stirred with a dissolver type eccentric stirring shaft, and a mixer having an anchor blade at the center axis for 30 minutes. The dispersion initiation temperature was 3 (TC » after the dispersion was completed, the high-speed stirring was stopped, the peripheral speed of the anchor blade was 〇.5 m/sec, and the mixture was further stirred for 100 minutes to swell the cellulose triacetate sheet until the end of the swelling, nitrogen gas. The inside of the tank is pressurized to 〇1. 2 MPa. At this time, the oxygen concentration in the tank is less than 2 vol%, and the state of the explosion is maintained at no problem. Further, it is confirmed that the amount of water in the sizing is 0.2% by mass or less. The composition of the prime solution is as follows: Cellulose triacetate VIII (8-8 + 88 is 2.78, 5 is 2.78, SB is 0, viscosity average degree of polymerization 303, and water content is 1% by mass or less). Deuterated cellulose flakes. Further, the use of deuterated cellulose has a degree of substitution of 0.90 (15 parts by mass), methyl acetate (87.0 parts by mass), acetone (8.0 parts by mass), and ethanol (5.0 parts by mass). And TPP/BDP (8.0 parts by mass) was used to produce the sample 1 described in the first table. Next, the sample 2 having the same composition as the sample 1 was prepared except that the TPP/BDP of the sample 1 was 12.0 parts by mass. The TPP/BDP of the sample 1 was replaced with the modifier described in Table 1, and the addition of Table 1 was described. The amount was added to prepare a sample -38 - 1353370 3~1 5. (1-2) The uneven gel-like solution obtained from the cellulose triacetate film solution was pumped by a screw, and was heated at -70 ° C for 3 minutes. Passing through the cooling section, the cooling system is carried out using a refrigerant cooled at 9.0 ° C. The solution obtained by cooling is transferred to a container made of stainless steel, and stirred at 50 ° C for 2 hours to form a homogeneous solution, with absolute filtration accuracy. 0.01 mm filter paper (made by Toyo Filter Paper Co., Ltd., #6 3) was filtered, and filtered with a filter paper of absolute filtration accuracy of 2.5 μm (manufactured by Pole Co., Ltd., FH02 5). (1-3) Cellulose triacetate film The 50 °C cellulose triacetate solution was cast through a caster and cast on a mirror-finished stainless steel support. The support was heated at a temperature of 5 ° C and a casting speed of 3 m / min to form a coating width. It was 30 cm. It was allowed to stand at room temperature for 1 minute, and then air was blown for drying at 55 ° C. After 5 minutes, it was peeled off from the mirror stainless steel support, and then dried at 133 ° C for 27 minutes to obtain a film. 60 μιη thick cellulose triacetate film. (1-4) Cellulose triacetate film moisture permeability The moisture permeability of the obtained cellulose triacetate film is measured by using a cover of various film samples for the cup containing potassium chloride, and sealed, at 6 ° C and 95 % RH, according to The weight change (g/(m2.day)) before and after standing for 24 hours, and the moisture permeability of the cellulose triacetate film was evaluated based on the hygroscopicity of potassium chloride. (1-5) Cellulose triacetate The Rth measurement of the ester film was carried out by using the ellipsometer (AEP-100, manufactured by Shimadzu Corporation), the in-plane vertical and horizontal refractive index difference measured at a wavelength of 6 3 2.8 nm, and the film thickness was multiplied by the following formula. Got it. -39- 1353370

Rth = {(nx + ny)/2-nz } xd nx:遲相軸方向（折射率爲最大的方向）的折射率 ny:遲相軸直交方向的折射率 nz:厚度方向的折射率 d:薄膜的厚度（單位：nm) -40- 1353370Rth = {(nx + ny)/2-nz } xd nx: refractive index in the direction of the slow axis (the direction in which the refractive index is maximum) ny: refractive index in the direction orthogonal to the slow axis nz: refractive index d in the thickness direction: Thickness of film (unit: nm) -40- 1353370

【表1】 試料 内容 改質劑 添加量 (質量％) Rth (nm) 透濕度 (g/m2 ·日） 試料1 比較 — 一 76 2900 試料2 比較 TPP/BDP 8 76 2200 試料3 比較 TPP/BDP 12 77 2200 試料4 比較 C - 1 12 120 2 100 試料5 比較 C - 2 12 100 2200 試料6 比較 C — 3 12 90 2200 試料7 本發明 A- 1 8 140 1750 試料8 本發明 A- 1 12 175 1700 試料9 本發明 A - 8 8 2 10 1750 試料1 0 本發明 A— 8 12 190 1700 試料1 1 本發明 A- 10 8 1 80 1700 試料12 本發明 A- 13 8 180 1700 試料13 本發明 A - 2 1 12 174 1730 試料1 4 本發明 A - 3 1 12 230 1740 試料1 5 本發明 A- 34 12 202 1750 【化9】 比較化合物 -41 - 1353370[Table 1] Sample content modifier addition amount (% by mass) Rth (nm) Moisture permeability (g/m2 · day) Sample 1 Comparison - A 76 2900 Sample 2 Comparison TPP/BDP 8 76 2200 Sample 3 Comparison TPP/BDP 12 77 2200 Sample 4 Comparison C - 1 12 120 2 100 Sample 5 Comparison C - 2 12 100 2200 Sample 6 Comparison C - 3 12 90 2200 Sample 7 A- 1 8 140 1750 Sample 8 of the Invention A- 1 12 175 of the Invention 1700 Sample 9 Inventive A A-8 8 2 10 1750 Sample 1 0 A-8 12 190 1700 Sample 1 1 A- 10 8 1 80 1700 Sample 12 A- 13 8 180 1700 Sample 13 of the Invention Invention A - 2 1 12 174 1730 Sample 1 4 Invention A - 3 1 12 230 1740 Sample 1 5 A-34 12 202 1750 of the invention [Chemical 9] Comparative compound -41 - 1353370

根據表1，藉由添加本發明的化合物，可製造出比廣泛 使用之TPP/BDP或具有類似骨格之C— 1、C一 2及C—3、透 濕度小、光學異方向性大的（Rth大）纖維素乙酸酯薄膜。特 別是藉由添加本發明的改質劑，光學異方向性係對於 TPP/BDP可大幅度地飛躍。 <實施例2> 以與實施例1同樣的方法使用下述的組成物、製作醯化 纖維素薄膜。此時亦可得到與實施例1同樣良好的結果。 纖維素三乙酸酯（乙醯化度60.9%)(100質量份） 二氯甲烷（300質量份） 甲醇（45質量份） 實施例1記載的試料1〜15(11.7質量份） <實施例3>偏光板保護膜 關於實施例1的試料1〜15，係藉由特開平11-316378號 公報的實施例1所記載之方法，以製做試料2 0 1〜2 0 5來加以 評價。由本發明的纖維素體薄膜所得楕圓偏光板之光學特 性係爲優異。又’經時耐久性即使與比較試料2比較亦沒有 特別的問題。 <實施例4>液晶顯示裝置 關於實施例1的試料1〜15,製作特開平10-48420號公報 的實施例1中所記載之液晶顯示裝置、含有特開平9-26 5 72 號公報的實施例1中所記載之碟狀液晶分子的光學異方向 -42- 1353370 性層、塗布聚乙烯醇之配向膜、特開20004 5426 1號公報的 第2〜9圖中所記載之▽八型液晶顯示裝置、特開2〇〇〇_ 1 542 6 1 號公報的第1 0〜1 5圖中所記載之〇 C B型液晶顯示裝置，並加 以評價。使用本發明的纖維素體薄膜之所得裝置，係得到 即使在任何場合下均良好之性能。 <實施例5 >鹵化銀照相感光材料 關於實施例1的試料1~15，除了該膜厚爲12〇nm以 外’與實施例1同様地行’以製做試料4 〇 i〜4 〇 5。在所得 φ 膜—方之面上，賦予特開平4- 73 7 3 6號公報的實施例1記 載之第1層及第2層，以做成陽離子系聚合物作爲導電性 層之背面層。再者’在賦予所得背面層之膜基的反對面上， ，塗布具有與特開平"。。㈠號公報的實施例1中所記載的 -試料1 0 5相同組成之各層’以製做鹵化銀照相感光材料。 使用本發明的纖維素體薄膜所得之鹵化銀照相感光材料， 可得到均優異的影像且其亦沒有關於操作性方面之問題。 【圖式簡單說明】：According to Table 1, by adding the compound of the present invention, it is possible to produce a TPP/BDP or a similarly shaped C-1, C-2, and C-3, having a small moisture permeability and a large optical anisotropy ( Rth large) cellulose acetate film. In particular, by adding the modifier of the present invention, the optical anisotropic system can greatly leap for TPP/BDP. <Example 2> The following composition was used in the same manner as in Example 1 to prepare a cellulose-deposited cellulose film. In this case, the same good results as in Example 1 were obtained. Cellulose triacetate (degree of acetylation 60.9%) (100 parts by mass) dichloromethane (300 parts by mass) methanol (45 parts by mass) Samples 1 to 15 (11.7 parts by mass) described in Example 1 < Example 3> The polarizing plate protective film The samples 1 to 15 of the first embodiment were evaluated by the method described in the first embodiment of JP-A-11-316378, and the samples were prepared for the samples 2 0 1 to 2 0 5 . . The optical characteristics of the circularly polarizing plate obtained from the cellulose body film of the present invention are excellent. Further, there is no particular problem with the durability over time even when compared with the comparative sample 2. <Example 4> Liquid crystal display device The liquid crystal display device described in Example 1 of the Japanese Patent Publication No. Hei 10-48420, and the Japanese Patent Publication No. Hei 9-26 5 72 The optically different direction -42 - 1353370 layer of the discotic liquid crystal molecules described in the first embodiment, the alignment film coated with polyvinyl alcohol, and the octagonal type described in the second to ninth drawings of JP-A No. 20004 5426 1 The liquid crystal display device and the 〇CB type liquid crystal display device described in the drawings 1 to 10 of the Japanese Patent Laid-Open Publication No. Hei. The resulting apparatus using the cellulose body film of the present invention is excellent in performance even in any case. <Example 5> Silver halide photographic light-sensitive material The samples 1 to 15 of Example 1 were prepared in the same manner as in Example 1 except that the film thickness was 12 〇 nm to prepare a sample 4 〇i~4 〇 5. On the surface of the obtained φ film, the first layer and the second layer described in Example 1 of JP-A-4-73 7 3 6 were used to form a cationic polymer as a back layer of the conductive layer. Further, 'on the opposite side of the film base to which the obtained back surface layer is applied, the coating has a special opening degree ". . The layer 1 of the same composition of the sample 1 0 5 described in the first embodiment of the publication is made into a silver halide photographic light-sensitive material. The silver halide photographic light-sensitive material obtained by using the cellulose body film of the present invention can provide excellent images and has no problem in terms of workability. [Simple description of the diagram]:

Arrr. _ Ws -43-Arrr. _ Ws -43-

Claims (1)

修正本 13533¾)- /公告本 第094 1 01 752號「纖維素體組成物、纖維素體薄膜、纖維素 體薄膜用改質劑、偏光板保護膜、液晶顯示裝置、鹵化銀照 相感光材料」專利案 (201 1年7月12日修正） 十、申請專利範圍： 1. 一種纖維素體組成物，其特徵係含有纖維素體、及至少 一種選自於下述通式（1)所示之化合物， 通式（1)Amendment 135333⁄4)- / Announcement No. 094 1 01 752 "Cellulose composition, cellulose film, modifier for cellulose film, polarizing plate protective film, liquid crystal display device, silver halide photographic light-sensitive material" Patent case (amended on July 12, 2011) X. Patent application scope: 1. A cellulose body composition characterized in that it contains a cellulose body, and at least one selected from the group consisting of the following formula (1) Compound, general formula (1) OR3 II I R1—C-N —R2 [通式（1)中、R1係表示烷基或芳基、R2及R3係分別獨立表 示氫原子、烷基或芳基，又烷基及芳基亦可含有取代基， 烷基的碳原子數爲6至25,芳基的碳原子數爲6至36’ R1、 R2及R3之中2個以上的基可互相鍵結以形成環] ，其中該纖維素體爲醯化纖維素’該醯化纖維素對纖維 素羥基的取代度爲可以滿足所有下式（1)〜（ΠΙ)之醯化纖 維素： (I) 2.6 S SA + SB S 3.0 (II) 2.0 ^ SA ^ 3.0 (III) 0 ^ SB ^ 0.8 其中，式中SA + SB係表示被纖維素之經基所取代之酿基 的取代度’ SA爲乙醯基之取代度，另外’ SB係碳原子數 3~22之醯基的取代度。 2.—種纖維素體薄膜，其特徵係含有纖維素體、及至少一 種選自於下述通式（1)所示之化合物’ 1353370 修正本 通式（1) O R3 R1 —C — N-R2 [通式（1)中、R1係表示烷基或芳基、R2及R3係分別獨& _ 示氫原子、烷基或芳基，又烷基及芳基亦可含有取代_， 烷基的碳原子數爲6至25,芳基的碳原子數爲6至36, R1 \ R2及R3之中2個以上的基可互相鍵結以形成環]。 • 3.如申請專利範圍第2項之纖維素體薄膜，其中通式 示之化合物爲下述通式（2)所示之化合物， 通式（2) 〇 R4 —C — N-R5 Η [式中’ R4及R5係各別表示芳基，可具有各別獨立的取代 基’ R4及R5係可形成縮合環]。 • 4.~種纖維素體薄膜用改質劑，其係爲如申請專利範圍第丄 項通式（1)所示者。 —種偏光板保護膜，其特徵係含有至少—層如申請專利 範圍第2項之纖維素體薄膜。 6·如申請專利範圍第2項之纖維素體薄膜，其係用於液晶顯 示裝置。OR3 II I R1—CN—R2 [In the formula (1), R1 represents an alkyl group or an aryl group, and R2 and R3 each independently represent a hydrogen atom, an alkyl group or an aryl group, and the alkyl group and the aryl group may also contain a substituent having an alkyl group having 6 to 25 carbon atoms, an aryl group having 6 to 36' carbon atoms, and 2 or more groups of R2 and R3 bonded to each other to form a ring], wherein the cellulose The body is deuterated cellulose. The degree of substitution of the deuterated cellulose to the cellulose hydroxyl group is such that all the celluloses of the following formula (1) to (ΠΙ) can be satisfied: (I) 2.6 S SA + SB S 3.0 (II 2.0 ^ SA ^ 3.0 (III) 0 ^ SB ^ 0.8 where SA + SB is the degree of substitution of the brewing group substituted by the cellulose radical, 'SA is the degree of substitution of the ethyl group, and 'SB The degree of substitution of a fluorenyl group having 3 to 22 carbon atoms. 2. A cellulosic film comprising a cellulosic body and at least one compound selected from the group consisting of the following formula (1) '1353370. The formula (1) O R3 R1 - C - N -R2 [In the formula (1), R1 represents an alkyl group or an aryl group, and R2 and R3 are each independently represented by a hydrogen atom, an alkyl group or an aryl group, and the alkyl group and the aryl group may further contain a substituent _, The alkyl group has 6 to 25 carbon atoms, the aryl group has 6 to 36 carbon atoms, and 2 or more of R1 \ R2 and R3 may be bonded to each other to form a ring. 3. The cellulosic film according to claim 2, wherein the compound represented by the formula is a compound represented by the following formula (2), and the formula (2) 〇R4 - C - N-R5 Η [ Wherein 'R4 and R5 each represent an aryl group and may have a separate substituent 'R4 and R5 form a condensed ring>. • 4.~ A modifier for a cellulose film, which is represented by the general formula (1) of the scope of the patent application. A polarizing plate protective film characterized by containing at least a layer of a cellulosic film as in the second aspect of the patent application. 6. A cellulosic film as claimed in claim 2, which is used in a liquid crystal display device.