200800604 (1) 九、發明說明 【發明所屬之技術領域】 本發明係關於’於由聚乙烯醇系樹脂所成之偏光薄膜 的一側的面上，介由黏著劑使環嫌烴系樹脂薄膜層合，於 另一側的面上，介由黏著劑使乙酸纖維素系薄膜層合而成 之偏光板，以及該偏光板的製造方法。更詳細地說是關於 相關構成之中’其係可抑制彎曲，且在黏貼於液晶晶胞時 Φ ，較難發生氣泡混入之偏光板及其製造方法。 【先前技術】 偏光板通常於由有二色性色素吸附配向的聚乙烯醇系 樹脂所成之偏光薄膜的兩面上，介由黏著劑來層合透明樹 脂薄膜例如三乙醢基纖維素所代表之乙酸纖維素系的保護 薄膜所構成。此外，因使環烯烴系樹脂薄膜等被延伸之光 學薄膜透過黏著劑黏貼於偏光板上，可使適用於液晶晶胞 ® 上而成爲液晶顯示裝置時來自各個角度的視覺辨識性得以 改良，以得到良好的視野角。 , 於聚乙烯醇系之偏光薄膜上黏貼環烯烴系樹脂薄膜亦 _ 已多爲大眾所知，例如，特開平5-2 1 2828號公報（專利 文獻1 )中係記載著，於聚乙烯醇系薄膜的至少單面上， 介由丙烯酸系黏著劑而層合熱可塑性飽和降冰片烯系樹脂 薄膜，經過加熱壓著後成爲偏光板。但是，丙烯酸系等之 黏著劑（亦稱爲感壓黏著劑）因爲本體的厚度爲1〇〜50 μπι程度’不得不使液晶顯示裝置也變厚，而且，爲使偏 -5- (2) (2)200800604 光薄膜與環烯烴系樹脂薄膜一片一片地黏貼也極其煩雜。 另一方面，於由聚乙烯醇系樹脂所成之偏光薄膜上， 介由黏著劑黏貼環烯烴系樹脂薄膜既已爲大眾所知，例如 ，特開2 0 0 5 - 7 0 1 4 0號公報（專利文獻2 )、特開2 0 0 5 -181817號公報（專利文獻3 )以及特開2005-208456號公 報（專利文獻4 )中係記載著，於由聚乙烯醇系樹脂所成 之偏光薄膜上，介由胺基甲酸乙酯，特別是含有聚酯系離 子鍵聚合物型胺基甲酸乙酯樹脂之水系黏著劑，來層合環 嫌烴系樹脂薄膜。根據此等公報上所記載之技術，係可藉 由連續製程（roll to roll )之方法，於聚乙烯醇系偏光薄 膜上直接層合環烯烴系保護薄膜。 此外，於偏光薄膜的兩面上層合保護薄膜之偏光板中 ，其偏光板係有單方面側捲曲，意即彎曲之問題。對於此 類彎曲，例如特開2004- 1 84809號公報（專利文獻5 )中 ，揭示有將呈彎曲的2片保護薄膜分別以逆於彎曲方向黏 貼於偏光薄膜之兩面上的方法。 再者，已知例如，前述專利文獻 4或特開 2005-3 5 20 1 1號公報（專利文獻6 )係揭示有，於由聚乙烯醇系 樹脂所成的偏光薄膜之一側的面上黏貼環烯烴系樹脂薄膜 ，於該偏光薄膜另一側的面上黏貼乙酸纖維素系薄膜之構 成。於由聚乙烯醇系樹脂所成的偏光薄膜之一側的面上黏 貼環烯烴系樹脂薄膜，於該偏光薄膜另一側的面上黏貼乙 酸纖維素系薄膜之偏光板，係非對稱構成，而且，因爲環 烯烴系樹脂薄膜本身的彎曲極小，與具有於聚乙烯醇系偏 -6 - 200800604 (3) 光薄膜的兩面上層合乙酸纖維素系薄膜之對稱構成的偏光 板比較之下，彎曲量容易變大，黏貼於液晶晶胞時則容易 有氣泡混入的問題。 〔專利文獻1〕特開平5-2 1 2828號公報 〔專利文獻2〕特開2005-70 1 40號公報 〔專利文獻3〕特開2 0 0 5 - 1 8 1 8 1 7號公報 〔專利文獻.4〕特開2005-208456號公報 Φ 〔專利文獻5〕特開2004-184809號公報 〔專利文獻6〕特開2005-35 2 0 11號公報 【發明內容】 〔發明所欲解決之課題〕 本發明的目的在於，在由聚乙烯醇系樹脂所成之偏光 薄膜之一側的面上，介由黏著劑層合環烯烴系樹脂薄膜， 且在該偏光薄膜另一側的面上，介由黏著劑層合乙酸纖維 ® 素系薄膜所構成之偏光板中，係可抑制彎曲的發生。 本發明者們係以相關目的之基礎致力於硏究的結果， 係在由聚乙烯醇系樹脂所成之偏光薄膜之一側的面上，介 ^ 由黏著劑層合環烯烴系樹脂薄膜，且在該偏光薄膜另一側 的面上’介由黏著劑層合乙酸纖維素系薄膜所構成之偏光 板中’係著眼於乙酸纖維素系薄膜對偏光板之黏著面，遂 達成本發明。 〔解決課題之方法〕 -7- (4) (4)200800604 也就是說，根據本發明，係可提供一種偏光板，其係 在由聚乙烯醇系樹脂所成之偏光薄膜的一側的面上，介由 黏著劑層合環烯烴系樹脂薄膜，且在另一側的面上，介由 黏著劑層合乙酸纖維素系薄膜而成，其中，該乙酸纖維素 系薄膜係以於80°C下經24小時放置後會發生彎曲的凸面 側作爲對前述偏光薄膜之黏著面。 此外，依本發明，亦可提供一種偏光板的製造方法， 其係在由聚乙烯醇系樹脂所成之偏光薄膜的一側的面上， 介由黏著劑層合環烯烴系樹脂薄膜，且在另一側的面上， 介由黏著劑層合乙酸纖維素系薄膜而製造偏光板時，該乙 酸纖維素系薄膜係以於80°C下經24小時放置後會發生彎 曲的凸面側黏貼於前述偏光薄膜上。 〔發明的效果〕 根據本發明，在由聚乙烯醇系樹脂所成之偏光薄膜之 -側的面上，介由黏著劑層合環烯烴系樹脂薄膜，且在該 偏光薄膜另一側的面上，介由黏著劑層合乙酸纖維素系薄 膜所構成之偏光板中，係可減少彎曲的發生。 〔實施發明的最佳型態〕 以下，詳細說明本發明。本發明的偏光板，係在由聚 乙烯醇系樹脂所成之偏光薄膜的一側的面上，介由黏著劑 層合環烯烴系樹脂薄膜，且在另一側的面上，介由黏著劑 層合乙酸纖維素系薄膜所成。 -8- (5) 200800604 由聚乙烯醇系樹脂所成的偏光薄膜，具體地說，其 於單軸延伸之聚乙烯醇系樹脂薄膜中吸附配向有二色性 素者。 構成偏光薄膜之聚乙烯醇系樹脂，係藉由皂化聚乙 乙烯系樹脂而得。聚乙酸乙烯系樹脂方面，除了有乙酸 烯之單一聚合物之聚乙酸乙烯外，亦有乙酸乙烯與可與 共聚合之單體的共聚物等例示。可與乙酸乙烯共聚合之 體方面，係可舉出例如，不飽和羧酸類、不飽和磺酸類 烯烴類、乙烯醚類、具有銨基之丙烯醯胺類等。聚乙烯 系樹脂的皂化度一般係8 5〜1 0 0莫耳％之程度，較佳爲 莫耳％以上。此聚乙烯醇系樹脂，亦可進一步改性，例 亦可使用以醛類所改性之聚乙烯醇縮甲醛、或聚乙烯醇 醒等。此外，聚乙烯醇系樹脂的聚合度，通常爲ι，000 10,000之程度，較佳爲1，5〇〇〜5,000之程度。 將相關聚乙烯醇系樹脂製膜後，係用以爲偏光薄膜 原料素材薄膜。聚乙嫌醇系樹脂進行製膜之方法並無特 限制’可以習知的方法製膜。聚乙烯醇系原料素材薄膜 膜厚並無特別限定，可爲例如10 μιη〜15〇 μιη。 偏光薄膜一般，係經過如此將聚乙烯醇系樹脂薄膜 行單軸延伸之步驟、將聚乙烯醇系樹脂薄膜以二色性色 染色使其吸附二色性色素之步驟、將吸附有二色性色素 聚乙烯醇系樹脂薄膜以硼酸水溶液處理之步驟、以及經 硼酸水溶液處理後進行水洗之步驟，而予以製造。 單軸延伸可於染色之前進行，亦可與染色同時進行 係 色 酸 乙 其 單 、 醇 98 如 縮 的 別 的 進 素 之 此 -9 - (6) 200800604 也可於染色之後進行。若於染色後進行單軸延伸時 軸延伸係可於硼酸處理之前進行，亦可於硼酸處理 。當然，在此些複數個階段當中，也可進行單軸延 單軸延伸中，可於圓周速度不同的輥軸之間進行單 ，亦可使用熱輥進行單軸延伸。此外，可爲於大氣 行延伸等之乾式延伸，亦可爲於溶劑中使呈膨潤狀 行延伸之濕式延伸。延伸倍率通常爲2〜8倍之程虔 # 以二色性色素使聚乙烯醇系樹脂薄膜進行染色 如，若可將聚乙烯醇系樹脂薄膜浸漬於含有二色性 水溶液中即佳。二色性色素方面，具體地係使用碘 性染料。此外，聚乙烯醇系樹脂薄膜最好在染色處 ，預先施以對水的浸漬處理。 使用碘作爲二色性色素時，通常採用將聚乙烯 脂薄膜浸漬於含有碘及碘化鉀之水溶液中進行染色 。此水溶液中的碘含量，一般係以每丨〇 〇重量份的 ® 0·01〜1重量份之程度，而碘化鉀的含量一般則以 重量份的水中含0.5〜20重量份之程度。用於.染色 液溫度通常爲20〜40t：之程度，且對此水溶液的浸 (染色時間）一般爲20〜1，800秒之程度。 另一方面，使用二色性染料作爲二色性色素時 採用將聚乙燦醇系樹脂薄膜浸漬於含有水溶性二色 之水溶液中進行染色之方法。此水溶液中二色性染 量’於每100重量份的水中通常爲1χ1〇-4〜1〇重量 度，較佳爲lxl 〇·3〜1重量份之程度。此水溶液亦 ，此單 中進行 伸。在 軸延伸 當中進 態下進 〇 時，例 色素之 或二色 理之前 醇系樹 之方法 水中含 每 10 0 的水溶 漬時間 ，通常 性染料 料之含 份之程 可含有 -10- (7) (7)200800604 硫酸鈉等之無機鹽作爲助染劑。用於染色之染料水溶液的 溫度一般爲20〜80 °C之程度，而且對此水溶液的浸漬時間 (染色時間）一般爲10〜1，8 00秒之程度。 經二色性色素染色後的硼酸處理，係藉由使已染色的 聚乙烯醇系樹脂薄膜浸漬於含有硼酸之水溶液中予以進行 。含硼酸之水溶液中的硼酸含量，於每1 〇 〇重量份的水中 ，通常爲2〜15重量份之程度，較佳爲5〜12重量份之程 度。使用碘作爲二色性色素時，此含硼酸之水溶液係以含 有碘化鉀者爲佳。含硼酸之水溶液中的碘化鉀含量，每 1〇〇重量份的水中通常爲〇·1〜15重量份之程度，較佳爲 5〜1 2重量份之程度。對含硼酸之水溶液的浸漬時間，一 般爲60〜1，200秒之程度，較佳爲150〜600秒之程度， 而2 0 0〜4 0 0秒之程度則更佳。含硼酸之水溶液的溫度一 般爲50°C以上，較佳爲50〜85°C之程度，而60〜80°C則 更佳。 硼酸處理後的聚乙烯醇系樹脂薄膜，一般以水洗處理 。水洗處理可藉由例如’將經過硼酸處理之聚乙烯醇系樹 脂薄膜浸漬於水中予以進行。水洗處理中的水溫通常爲5 〜4〇t：之程度，浸漬時間一般爲1〜〗2〇秒之程度。水洗 後，實施乾燥處理’可得偏光薄膜。乾燥處理一般係使用 熱風乾燥機或遠紅外線加熱器進行。乾燥處理的溫度一般 爲30〜100°C之程度，較佳爲50〜8 〇°C。乾燥處理的時間 一般爲60〜600秒之程度，較佳爲120〜600秒程度。 如此，於聚乙烯醇系樹脂薄膜上施以單軸延伸、藉二 -11 - (8) 200800604 色性色素之染色以及硼酸處理後，可得 薄膜的厚度係5〜40 μηι之程度。本發 膜之一側的面上係介由黏著劑層合環烯 另一側的面上介由黏著劑層合乙酸纖維 所謂環烯烴系樹脂，例如，具有像 冰片烯系單體之環狀烯烴（環烯烴）所 可塑性樹脂。此環烯烴系樹脂除了有上 合物及使用2種以上之環烯烴之開環共 ，亦有環烯烴與鏈狀烯烴或具有乙烯基 之加成共聚物。而且，導入有極性基者 若爲環烯烴與鏈狀烯烴或具有乙烯 之共聚物時，鏈狀烯烴的例子方面，係 等，又具有乙烯基之芳香族化合物的例 苯乙烯、α-甲基苯乙烯、經核烷基取代 之共聚物中，由環烯烴所成之單體的單 ，例如可爲1 5〜5 0莫耳％之程度。特別 鏈狀烯烴與具有乙烯基之芳香族化合物 由環烯烴所成之單體的單位係可爲較少 共聚物中，由鏈狀烯烴所成之單體的單 耳％之程度，由具有乙烯基之芳香族化 單位一般爲5〜80莫耳％之程度。 市售的熱可塑性環烯烴系樹脂j Tic〇na公司所販售的「Topas」、JSR ARTON」、日本 ΖΕΟΝ所販售的「 偏光薄膜。此偏光 明中，於此偏光薄 烴系樹脂薄膜，於 素系薄膜。 降冰片烯或多環降 成之單體單位的熱 述環烯烴之開環聚 聚物的氫化物之外 之芳香族化合物等 也有效。 基之芳香族化合物 可舉出乙烯或丙烯 子方面，可舉出有 之苯乙基等。如此 位係50莫耳％以下 丨是當其爲環烯烴與 之三元共聚物時， 的量。相關的三元 位一'般爲5〜80莫 合物所成之單體的 ί面，係有德國的 (股）所販售的「 ZEONOR」以及「 -12- 200800604 (9) ZEONEX」、三井化學（股）所販售的「APL」等（任一 者均爲商品名）。如此之環烯烴系樹脂進行製膜後雖成爲 薄膜，但於製膜時，係以使用溶劑澆鑄法、熔融擠壓法等 習知的方法爲適。經過製膜的環烯烴系樹脂薄膜既已販售 ’係有例如，積水化學工業（股）所販售之「S西拿」以 及「SCA40」、（股）OPTES所販售的「ZeonorFilm」等 (任一者皆爲商品名）。 Φ 環烯烴系樹脂薄膜係可予以單軸或二軸延伸，亦可爲 顯示所定的多折射特性者。此時的延伸倍率一般爲1 . 1〜5 倍之程度，較佳爲1 · 1〜3倍。 本發明中，爲另一側之保護薄膜的乙酸纖維素系薄膜 ，係纖維素的部分或完全乙酸酯化物，可舉出有例如，三 乙醯纖維素薄膜或二乙醯纖維素薄膜等。市售的三乙醯纖 維素薄膜方面，係有富士寫真薄膜（股）所販售的「 FUJITAC TD80」、「FUJITAC TD80UF」及「FUJITAC _ TD80UZ」、KONICA Μ IN Ο L Τ Α Ο Ρ Τ Ο (股）所販售的「 KC8UX2MW」及「KC8UY」等。 爲了提高與黏著劑的黏著力，係以於乙酸纖維素系薄 膜之表面預先實施島化處理爲佳。巷化處理係可藉由浸漬 於如氫氧化鈉或氫氧化紳等鹼性水溶液中之方法而得以進 行。 此外，爲了先行對偏光薄膜進行黏貼，預先浸漬於水 中，接著實施乾燥之前處理，係可使彎曲變少而較佳。在 前處理的第一步驟中，係將乙酸纖維素系薄膜於1 0〜5 0 °c -13- 200800604 (10) 之溫度下浸漬於水中5〜1 0秒使其膨潤。此時，若溫度變 高，薄膜上會產生筋線狀之缺陷，故最好於2 0〜4 5 °C下進 行。於第二處理步驟中，即是進行乙酸纖維素系薄膜表面 的乾燥處理。乾燥處理通常使用熱風乾燥機或遠紅外線加 熱器進行。乾燥處理的溫度通常爲30〜100 °C，較佳爲40 〜60。乾燥處理的時間一般在20〜600秒之程度，較佳 爲20〜60秒之程度。此時，乙酸纖維素系薄膜與偏光薄 膜的黏貼面係可藉由適當地變更輥筒的送出方向予以調整 〇 乙酸纖維素系薄膜，係可於其與偏光薄膜黏貼之面上 與其反側之面上實施防眩處理、硬塗膜處理、防靜電處理 、防反射處理等之表面處理。而且，亦可形成由液晶性化 合物或其高分子化合物等所成之塗膜層。 本發明中，係以使乙酸纖維素系薄膜在8 0 °C下放置 24小時之後會發生彎曲的凸面側，黏貼於聚乙烯醇系偏光 薄膜上。用以爲偏光板保護薄膜之乙酸纖維素系薄膜，一 般係可藉由使樹脂溶解於溶劑之狀態下，流延於由金屬帶 所成的支持體上，再將溶劑揮發之溶劑澆鑄法而製造。當 下，爲空氣側的一面稱爲A面，爲相反的支持體的一面稱 爲B面。後述之實施例所使用的薄膜，A面側呈凸起。如 上述，因使凸面側爲對偏光薄膜之黏著面，因此當其與相 反的情況比較時，所製得的偏光板彎曲量將會變小。 配置於偏光薄膜的兩面上之環烯烴系樹脂薄膜以及乙 酸纖維素系薄膜各別的厚度，係以薄的爲佳，但若過薄， •14- 200800604 (11) 則強度將會降低，使加工性變差，另外，若過厚，則容易 發生透明性降低，偏光板重量變大等問題。因此，環烯烴 系樹脂薄膜的適當厚度，例如爲5〜200 μηι之程度，較佳 爲10〜150 μιη，而20〜100 μηι又更佳。此外，乙酸纖維 素系薄膜的適當厚度係爲20〜200 μηι之程度，較佳爲20 〜1 0 0 μηι 〇 在偏光薄膜之一側的面與另一側的面上，均藉由黏著 劑並如以上所說明地分別層合環烯烴系樹脂薄膜與乙酸纖 維系薄膜而形成偏光板。 用於黏合偏光薄膜與環烯烴系樹脂薄膜之黏著劑，以 及用於黏合偏光薄膜與乙酸纖維素系薄膜之黏著劑，若由 使黏著劑層爲薄之觀點來看，係以水系者，意即使黏著劑 成分溶解於水者或分散於水者爲佳。例如，較佳的黏著劑 方面，係可舉出有使用聚乙烯醇系樹脂或胺基甲酸乙酯樹 脂之組成物作爲主要成分之黏著劑。此外，只要可獲得適 當的黏著性，適用於偏光薄膜兩面上之黏著劑以使用相同 組成者爲佳，因如此係可簡化製造步驟。 使用聚乙烯醇系樹脂作爲黏著劑的主要成分時，其聚 乙烯醇系樹脂除了部分皂化之聚乙烯醇或完全皂化之聚乙 烯醇之外，亦可爲羧基改性聚乙烯醇、乙醯乙醯基改性聚 乙烯醇、羥甲基改性聚乙烯醇、胺基改性聚乙烯醇等之經 改性的聚乙烯醇系樹脂。使用聚乙烯醇系樹脂的情況下， 係以其水溶液爲黏著劑。黏著劑中之聚乙烯醇系樹脂的濃 度，相對於1 0 0重量份的水而言，一般爲1〜1 0重量份之 -15- 200800604 (12) 程度，較佳爲1〜5重量份。 由聚乙烯醇系樹脂之水溶液所成之黏著劑中，爲了提 高黏著性，係以添加乙二醛或水溶性環氧樹脂等之硬化性 成分乃至交聯劑爲佳。水溶性環氧樹脂係例如在像二乙撐 三胺、三乙撐四胺之聚烷撐多元胺與像己二酸之二羧酸反 應所得的聚醯胺多元胺中，使環氧氯丙烷反應而可得之聚 醯胺環氧樹脂。相關的聚醯胺環氧樹脂之市售品方面，係 • 有住友化學（股）所販售之 「Sumirez Resin 650」或「 Sumirez Resin 675」、日本 P M C (股）所販售之「W S-5 25」等。此等硬化性成分乃至交聯劑的添加量，相對於 1 00重量份的聚乙烯醇系樹脂，作爲固體成分一般爲1〜 1 00重量份，較佳爲1〜50重量份。若添加量太少的話， 則黏著性提升的效果變小，另一方面，若其添加量太多， 則黏著劑層會有變脆的傾向。 使用胺基甲酸乙酯樹脂作爲黏著劑的主要成分時，適 Φ 當的黏著劑組成物的例子方面，係可舉出聚酯系離子鍵聚 合物型胺基甲酸乙酯樹脂與含有縮水甘油基羥基之化合物 的混合物。在此所述之聚酯系離子鍵聚合物型胺基甲酸乙 酯樹脂，係指於具有聚酯骨架之胺基甲酸乙酯樹脂中導入 少量離子性成分（親水成分）者。相關的離子鍵聚合物型 胺基甲酸乙酯樹脂，因可於不使用乳化劑之下直接在水中 乳化爲乳劑，故適用爲水系的黏著劑。聚酯系離子鍵聚合 物型胺基甲酸乙酯樹脂本身既已爲習知，例如特開平7-975 04號公報中，係有以使苯酚系樹脂分散於水性溶劑中 -16- 200800604 (13) 用的高分子分散劑爲例之記載，而且在前述的專利文獻2 〜4中，係顯示有以聚酯系離子鍵聚合物型胺基甲酸乙酯 樹脂與含有縮水甘油基羥基之化合物的混合物作爲黏著劑 ，於由聚乙烯醇系樹脂所成之偏光薄膜上黏貼環烯烴系樹 U 脂薄膜之型態。 聚酯系離子鍵聚合物型胺基甲酸乙酯樹脂，係可藉由 使含親水性基之化合物、聚酯多元醇以及聚異氰酸酯反應 φ 所得之含親水性基胺基甲酸乙酯於水中乳化之方法而製造 。此時，除了聚酯多元醇，還可倂用其他高分子量多元醇 成分或者低分子量之含活性氫化合物。高分子量多元醇方 面，係可舉出例如聚醚多元醇、聚碳酸酯多元醇、聚甲醛 多元醇、聚丙烯酸酯多元醇、聚酯醯胺多元醇、聚硫醚多 元醇等。此外，低分子量之含活性氫化合物方面，係可舉 出例如乙二醇、季戊二醇、1，6-己二醇、丙三醇、三羥甲 基丙烷之聚羥基化合物；如乙撐二胺、哌嗪之二胺化合物 • 等。其中，更以倂用低分子量之含活性氫化合物爲較佳之 型態。 聚酯系離子鍵聚合物型胺基甲酸乙酯樹脂，係以重量 平均分子量爲5，00 0以上爲佳，重量平均分子量爲1〇, 〇〇G 以上300,000以下則更佳。當其重量平均分子量小於 5，00 0時，其黏著劑無法獲得足夠的強度，而當重量平均 分子量大於3 00,000時，以其當作水分散液時的黏度變高 ，使用變得困難。 相關的聚酯系離子鍵聚合物型胺基甲酸乙酯樹脂分散 -17 - 200800604 (14) 於水中之狀_下，係可作爲水系黏著劑。此水系黏著劑的 黏度係以2,000 mPa· sec以下時在使用上較佳，而於 1，000 mPa· sec以下，特別於5〇〇 mpa· _以下時更好 。黏度愈低，則黏著劑的塗佈愈容易進行，而且，所得的 偏光板的外觀亦隨之變佳。此水系黏著劑中之聚酯系離子 鍵聚合物型胺基甲酸乙酯樹脂的固體成分濃度，若由黏度 與黏著強度的觀點來看’係以丨〇〜7 〇重量％之範圍爲佳， 特別是2 0重量％以上，且5 0重量％以下更佳。 聚酯系離子鍵聚合物型胺基甲酸乙酯樹脂的水分散液 中，亦可進一步添加聚乙二醇或聚氧乙烯等，或是界面活 性劑等。甚至，亦可添加聚羥基乙基甲基丙烯酸酯、聚羥 基乙基丙烯酸酯、聚丙烯酸、聚乙烯醇系樹脂等之水溶性 樹脂。 市售的聚酯系離子鍵聚合物型胺基甲酸乙酯樹脂方面 ’係可舉出大日本油墨化學工業（股）所販售的「 HYDRAN AP-20」、「HYDRAN APX-1 0 1 Η」等。 由聚酯系離子鍵聚合物型胺基甲酸乙酯樹脂之水分散 液所成之黏著劑係更進一步以含具有縮水甘油基羥基之化 合物者爲佳。藉由具有縮水甘油基羥基之化合物之倂用， 係使偏光薄膜與層合於其上之環烯烴系樹脂薄膜或乙酸纖 維素系薄膜之黏著性向上提升。此處所謂的縮水甘油基羥 基，在純化學領域中應是被稱爲2,3-環氧丙氧基者。具有 縮水甘油基羥基之化合物的例子方面，係可舉出聚乙二醇 二縮水甘油醚、聚丙二醇二縮水甘油醚、聚四甲二醇二縮 -18- 200800604 (15) 水甘油醚、季戊二醇二縮水甘油醚、二丙三醇二縮水甘油 醚、乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、1，4· 丁 二醇二縮水甘油醚、1，6 -己二醇二縮水甘油醚、雙苯酚A 二縮水甘油醚、雙苯酚F二縮水甘油醚、間苯二酚二縮水 甘油醚、丙三醇三縮水甘油醚、三羥甲基丙烷三縮水甘油 ' 醚、季戊四醇聚縮水甘油醚、山梨糖醇聚縮水甘油醚、山 梨糖醇酐聚縮水甘油醚、聚丙三醇聚縮水甘油醚等。 φ 聚酯系離子鍵聚合物型胺基甲酸乙酯樹脂與具縮水甘 油基羥基化合物的混合比，相對於聚酯系離子鍵聚合物型 胺基甲酸乙酯樹脂的固體成分100質量份而言，具有縮水 甘油基羥基之化合物係以5〜1 00重量份程度之範圍適當 選擇爲宜，而較佳是選擇具有縮水甘油基羥基之化合物爲 5〜60重量份，特別是以5〜30重量份最好。若是具有縮 水甘油基羥基之化合物的比率過低，就無法獲得充分的黏 著強度，而若其比率過大’則黏著劑黏度變高，使用上將 # 變得困難。 含有聚酯系離子鍵聚合物型胺基甲酸乙酯樹脂與具縮 水甘油基羥基化合物之水系黏著劑’因爲在實質上並無需 使用有機溶劑，所以不管是從環境上或從業者健康上的觀 點來看均較佳，且因倂用具縮水甘油基羥基化合物而賦予 其高黏著力。 使用聚酯系離子鍵聚合物型胺基甲酸乙酯樹脂作爲黏 著劑時，爲了提昇對乙酸纖維素系薄膜之黏著性，係以倂 用具有異氰酸根基之化合物，特別是分子內具有至少2個 -19- 200800604 (16) 異氰酸根基之聚異氰酸酯化合物爲佳。相關的具異氰 基之化合物方面，係可舉出例如2,4_甲苯撐二異氰酸 苯撑二異氨酸酯、4，4’-二苯基甲院一異氰酸酯、1，6-撐二異氰酸酯、異佛爾酮二異氰酸酯等之單體或寡聚 * 或是此等化合物與多元醇之反應物。此處所使用之多 • 方面，係可舉出1，3-丙二醇、1，3-丁二醇、1，4-丁二 1，5-戊二醇等。此等含異氰酸根基之化合物的分子量 φ 使爲上述的寡聚物或是與多元醇之反應物時，係以重 均分子量5,000以下爲佳。較適的市售之含異氰酸根 化合物方面，可舉出例如大日本油墨化學工業（股） 售的「HYDRAN ASISTA-C1」等。 聚酯系離子鍵聚合物型胺基甲酸乙酯樹脂與含異 根基之化合物的混合比，相對於1 〇〇重量份聚酯系離 聚合物型胺基甲酸乙酯樹脂的固體成分而言，係以適 選擇5〜100重量份程度範圍的含異氰酸根基之化合 φ 佳，而選擇5〜60重量份，特別是5〜3 0重量份範圍 異氰酸根基之化合物者又更佳。若含異氰酸根基之化 的比率過低，將無法獲得充分的黏著強度，而若其比 高，將使黏著劑的黏度變高，使用上變難。 在偏光薄膜上以黏著劑黏合環烯烴系樹脂薄膜或 纖維素薄膜之方法，係以一般習知之方法進行即可， 出有例如流延法、輥塗佈法、凹板塗佈法、擠壓塗佈 浸漬塗佈法、噴霧法等，於偏光薄膜及/或黏合於其 薄膜的黏著面上塗佈黏著劑，使兩者重疊貼合之方法 酸根 酯、 —·ι“ ΓΠ /、中 物、 元醇 醇、 ，即 量平 基之 所販 氰酸 子鍵 當地 物爲 的含 合物 率過 乙酸 可舉 法、 上之 。所 -20- 200800604 (17) 謂的流延法係將被塗佈物之薄膜呈槪略垂直方向、槪略水 平方向、或介於兩者之間的傾斜方向，邊使其移動邊於其 表面上使黏著劑流下而擴散分佈之方法。塗佈黏著劑之後 ，係使偏光薄膜與黏合於其上之薄膜以壓延輥挾持後使其 • 貼合。 ^ 接著，爲提升黏著性，亦可對黏著表面適當地施以電 漿處理、電暈放電處理、紫外線照射處理、火焰處理、皂 φ 化處理等之表面處理。 在偏光薄膜之一側的面上層合環烯烴系樹脂薄膜，於 另外一側的面上層合乙酸纖維素系薄膜之後，係實施乾燥 處理。乾燥處理例如可藉由熱風吹拂來進行，當下的溫度 可適當地選擇於40〜100 °C程度，較佳爲60〜100 °C之範 圍。乾燥時間爲20〜1，200秒之程度。乾燥後之黏著劑層 的厚度，一般爲0.001〜5 μιη之程度，較佳爲0.01 μιη以 上，而以2 μπι以下爲佳，更好是1 μηι以下。黏著劑層的 # 厚度若過大，易導致偏光板的外觀不良。 貼合之後，置於室溫以上的溫度至少半天，一般係以 實施數曰間以上的熟成，可得充分的黏著強度。較佳的熟 成溫度係30〜50°C，更佳爲35〜45°C。當熟成溫度爲50 °C以上時，輥捲取狀態中容易發生「捲曲」。此外，熟成 時的溼度不管是否適當，若相對溼度爲0%RH〜70 %RH程 度之範圍即可。熟成時間通常要1〜1〇日，較佳爲2〜7 曰。 本發明的偏光板中，環烯烴系樹脂薄膜與配置於另一 -21 - 200800604 (18) 側的乙酸纖維素薄膜之表面上，亦可介由黏著劑黏貼光學 機能性薄膜。光學機能性薄膜方面，係可舉出例如，於基 材表面塗佈液晶性化合物而配向之光學補償薄膜、使某種 偏光的光透過，而與該性質呈相反地使偏光的光反射之反 ^ 射型偏光分離薄膜、表面具有凹凸形狀之附防眩機能薄膜 * 、附表面防反射處理之薄膜、具有反射機能之反射薄膜、 兼具反射機能與透過機能之半透過反射薄膜等。與於基材 Φ 表面塗佈液晶性化合物而配向之光學補償薄膜相當的市售 品方面，係有富士寫真薄膜（股）所販售的「WV FILM」 、新曰本石油（股）所販售的「NH FILM」或「NR FILM 」（任一者皆爲商品名）等。相當於使某種偏光的光透過 ，而與該性質呈相反地使偏光的光反射之反射型偏光分離 薄膜之市售品方面，係有Minnesota Mining and Manufacturing公司（3M公司）（在日本爲住友3M (股 ))所販售之「DBEF」（商品名）等。 【實施方式】 〔實施例〕 以下，藉由實施例更詳細地說明本發明，但本發明不 受限於此等之例。例中，表示含量乃至使用量之r %」及 「份」，若無特別說明下，即爲重量基準。 〔製造例1〕偏光薄膜的製作 在平均聚合度約2,400、皂化度99.9莫耳％以上，將 -22- (19) (19)200800604 厚度75 μιη的聚乙烯醇薄膜以乾式進行約5倍之單軸延伸 ，進而在持續保持其拉緊狀態下，浸漬於60 Τ：的純水1分 鐘之後，在28 °C下浸漬於碘/碘化鉀/水之重量比爲 0 · 0 5 / 5 / 1 0 0的水溶液中6 0秒。然後，在7 2 °C下浸漬於 碘化鉀/硼酸/水之重量比爲8·5/ 8.5/ 1〇〇的水溶液中 3〇〇秒。接著，以26°C的純水進行20秒之洗淨後，於65 °C下進行乾燥後，可得聚乙烯醇樹脂中有碘吸附配向之偏 光薄膜。 〔製造例2〕黏著劑的調製 於1 00份的水中，添加3份的羧基改性聚乙烯醇（自 (股）Kuraray 公司取得之「Kuraray Poval KL318」）與 1 · 5份的水溶性聚醯胺環氧樹脂（自住友化學（股）取得 之「Sumirez Resin 650」（固體成分濃度30%的水溶液） )，調製成聚乙烯醇系黏著劑。 〔實施例1〕 將厚度80 μπι的三乙醯基纖維素薄膜（自 KONICA MINOLTA OPTO (股）取得之「KC8UX2MW」）進行皂化 處理，接著於3 0°C下浸漬於水中1 〇秒鐘進行膨潤處理， 其後，在8(TC下乾燥53秒鐘。此薄膜於8〇 °C下放置24 小時後，觀察其彎曲，並確認呈凸面之側。此呈凸面之側 若參照製造商所提供之資訊，係爲A面（溶劑澆鑄時的空 氣側）。 -23 - 200800604 (20) 於製造例1中所得偏光薄膜的單一面上，介由製造例 2中所製作之黏著劑，將上述三乙醯基纖維素薄膜以其彎 曲的凸面側進行黏貼，而偏光薄膜的另一面上，係介由相 同的黏著劑黏貼由降冰片烯系樹脂所成厚度73 μιη的保護 膜。其後，以6 0〜9 0 °C之溫度乾燥5分鐘，再於4 0 °C的 . 環境下，經7日的熟成後獲得偏光板。 相對於其吸收軸（延伸方向）而言，將所得的偏光板 • 以各邊呈45 之角度切成15 cm X 15 cm大小的正方形 ，於溫度23 °C、相對溼度5 0%下調節溼度1個小時之後， 測定彎曲墓。其結果係偏光板4角的彎曲爲〇〜2 〇 m m。 偏光板的彎曲量係如下述進行測定。意即，如圖1所 示，於基準面5 (例如，桌子上的平面等）上，使已經彎 曲的偏光板1以凹面向上來放置。此圖中，係表示假設偏 光板上無彎曲時的面作爲四角形ABCD所表示之假想面3 。接著，假想面3中的一個角A係位於彎曲偏光板1中的 • A1位置；另一角C係位於彎曲偏光板1中的c 1位置·，又 別的角B、D位於彎曲偏光板1中的B1、D1位置，其係 表示B1與B在相同的位置，而D1與D在相同的位置（ 也就是說，偏光板的角B與角D相當於無浮起之狀態）。 但是實際上，亦有偏光板的4個角中的3個角或4個角全 部浮起的情況。因此’就偏光板的4個角A1、B1、C1、 D 1分別自基準面測定其高度Η，並以其値爲彎曲量。 〔比較例1〕 -24- 200800604 (21) 除了使三乙醯基纖維素薄膜對偏光薄膜的黏著面作爲 彎曲的凹面側之外，其餘與實施例1同樣進行而獲得偏光 板。就所得之偏光板，進行與實施例1相同的剪切、調溼 之後，測定彎曲量。其結果顯示，偏光板4角的彎曲爲0 〜60 mm，與實施例1相比之下，彎曲量的最大値變爲3 ’ 倍。 〔實施例2〕 於三乙醯基纖維素薄膜的皂化處理以及膨潤處理之後 ，除了以60°C進行53秒鐘的乾燥之外，其餘係與實施例 1同樣地進行而獲得偏光板。就所得的偏光板，以與實施 例1相同地進行剪切、調溼之後，測定彎曲量。其結果顯 示，偏光板4角的彎曲爲0〜3 mm。 〔比較例2〕 # 除了使三乙醯基纖維素薄膜對偏光薄膜的黏著面作爲 彎曲的凹面側之外，其餘與實施例2同樣進行而獲得偏光 板。就所得之偏光板，進行與實施例1相同的剪切、調溼 之後，測定彎曲量。其結果顯示，偏光板4角的彎曲爲0 〜10 mm，與實施例2相比之下，彎曲量的最大値超過了 3倍。 【圖式簡單說明】 〔圖1〕使實施例中偏光板的彎曲量測定狀態以模式 -25- (22) (22)200800604 圖所示之側視圖。 【主要元件之符號說明】 1 :彎曲的偏光板； 3 :假設偏光板上無彎曲時，基準面上的假想面； 5 :基準面； A，B，C，D :假想面上的角； A1，B1，C1，D1 :彎曲偏光板的角； Η :彎曲量（自基準面至偏光板的角爲止之高度）。200800604 (1) EMBODIMENT OF THE INVENTION [Technical Field] The present invention relates to a ring-like hydrocarbon resin film on the side of one side of a polarizing film made of a polyvinyl alcohol-based resin via an adhesive. A polarizing plate obtained by laminating a cellulose acetate-based film via an adhesive on the other side, and a method of producing the polarizing plate. More specifically, in the related configuration, a polarizing plate which is capable of suppressing bending and which is Φ when adhered to a liquid crystal cell, is less likely to cause bubbles to enter, and a method for producing the same. [Prior Art] A polarizing plate is usually laminated on both sides of a polarizing film made of a polyvinyl alcohol-based resin having a dichroic dye adsorption alignment, and a transparent resin film such as triethylenesulfonyl cellulose is laminated via an adhesive. It is composed of a cellulose acetate-based protective film. In addition, when the optical film which is stretched by a cycloolefin-based resin film or the like is adhered to the polarizing plate through an adhesive, the visibility of the liquid crystal display device can be improved, and the visibility from each angle can be improved. Get a good viewing angle. In the case of a polyvinyl alcohol-based polarizing film, a cycloalkene-based resin film is also known, and it is known in the art. For example, Japanese Laid-Open Patent Publication No. Hei 5-2 1 2828 (Patent Document 1) discloses a polyvinyl alcohol. On at least one side of the film, a thermoplastic saturated norbornene-based resin film is laminated via an acrylic adhesive, and after heating and pressing, it becomes a polarizing plate. However, acrylic adhesives (also known as pressure sensitive adhesives) have to thicken the liquid crystal display device because the thickness of the body is 1 〇 to 50 μπι, and, in order to make the bias -5 - (2) (2) 200800604 The light film and the cycloolefin resin film are adhered one by one and are extremely cumbersome. On the other hand, on a polarizing film made of a polyvinyl alcohol-based resin, a cycloolefin-based resin film is adhered to the adhesive film by an adhesive, for example, JP-A-N 0 0 5 - 7 0 1 4 0 Japanese Patent Publication No. 2005-208456 (Patent Document 4) and JP-A-2005-208456 (Patent Document 4) disclose that it is made of a polyvinyl alcohol-based resin. On the polarizing film, a ring-like hydrocarbon resin film is laminated via an aqueous urethane, particularly a water-based adhesive containing a polyester-based ionomer-type urethane resin. According to the technique described in these publications, a cycloolefin-based protective film can be directly laminated on a polyvinyl alcohol-based polarizing film by a roll to roll method. Further, in the polarizing plate in which the protective film is laminated on both sides of the polarizing film, the polarizing plate has a unilateral side curl, which means a problem of bending. In the case of such a bending, for example, a method in which two protective films which are curved are adhered to both surfaces of the polarizing film in a direction opposite to the bending direction are disclosed. In addition, for example, the above-mentioned Patent Document 4 or JP-A-2005-3 5 20 1 1 (Patent Document 6) discloses a surface on one side of a polarizing film made of a polyvinyl alcohol-based resin. A cycloolefin resin film is adhered, and a cellulose acetate film is adhered to the other surface of the polarizing film. a cycloolefin-based resin film is adhered to one surface of a polarizing film made of a polyvinyl alcohol-based resin, and a polarizing plate of a cellulose acetate-based film is adhered to the other surface of the polarizing film, and is asymmetrically formed. In addition, since the bending of the cycloolefin-based resin film itself is extremely small, it is curved in comparison with a polarizing plate having a symmetrical structure of a cellulose acetate-based film laminated on both sides of a polyvinyl alcohol-based -6 - 200800604 (3) light film. The amount tends to become large, and when it is adhered to the liquid crystal cell, the problem of air bubbles is likely to be mixed. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2005-70 No. 40 (Patent Document 3). Patent Publication No. 2 0 0 5 - 1 8 1 8 1 literature. [Patent Document 5] JP-A-2004-184809 (Patent Document 6) JP-A-2005-35 2 0 11 SUMMARY OF INVENTION [Problems to be Solved by the Invention] An object of the present invention is to laminate a cycloolefin-based resin film on the surface of one side of a polarizing film made of a polyvinyl alcohol-based resin via an adhesive, and to pass the surface on the other side of the polarizing film. In the polarizing plate composed of the adhesive layer laminated with the cellulose acetate film, the occurrence of bending can be suppressed. The inventors of the present invention have been working on the surface of one side of the polarizing film made of a polyvinyl alcohol-based resin, and laminated the cycloolefin-based resin film with an adhesive. Further, in the polarizing plate comprising the cellulose acetate-based film laminated with an adhesive on the other surface of the polarizing film, the present invention was achieved by focusing on the adhesion surface of the cellulose acetate-based film to the polarizing plate. [Means for Solving the Problem] -7- (4) (4) 200800604 In other words, according to the present invention, it is possible to provide a polarizing plate which is on the side of one side of a polarizing film made of a polyvinyl alcohol-based resin. First, a cycloolefin-based resin film is laminated via an adhesive, and a cellulose acetate-based film is laminated on the other surface by an adhesive, wherein the cellulose acetate-based film is 80°. The convex side which is bent after being placed under C for 24 hours serves as an adhesive surface to the polarizing film. Further, according to the present invention, a method for producing a polarizing plate may be provided, in which a cycloolefin-based resin film is laminated via an adhesive on a surface of one side of a polarizing film made of a polyvinyl alcohol-based resin, and On the other side, when a polarizing plate is produced by laminating a cellulose acetate-based film with an adhesive, the cellulose acetate-based film is a convex side-side adhesive which is bent after being left at 80 ° C for 24 hours. On the aforementioned polarizing film. [Effect of the Invention] According to the present invention, a cycloolefin-based resin film is laminated on the surface of the polarizing film formed of a polyvinyl alcohol-based resin on the other side of the polarizing film. In the polarizing plate comprising a cellulose acetate-based film laminated with an adhesive, the occurrence of bending can be reduced. [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in detail. In the polarizing plate of the present invention, a cycloolefin-based resin film is laminated on the surface of the polarizing film made of a polyvinyl alcohol-based resin via an adhesive, and adhered to the other surface. The agent is laminated with a cellulose acetate film. -8- (5) 200800604 A polarizing film made of a polyvinyl alcohol-based resin, specifically, a fluorochromic resin film which is uniaxially stretched and adsorbed to have a dichroic property. The polyvinyl alcohol-based resin constituting the polarizing film is obtained by saponifying a polyethylene-based resin. In the case of the polyvinyl acetate-based resin, in addition to polyvinyl acetate having a single polymer of acetylene, a copolymer of vinyl acetate and a copolymerizable monomer may be exemplified. Examples of the copolymerizable with vinyl acetate include unsaturated carboxylic acids, unsaturated sulfonic acid olefins, vinyl ethers, and acrylamides having an ammonium group. The degree of saponification of the polyethylene-based resin is generally from 8 5 to 1% by mole, preferably more than mol%. Further, the polyvinyl alcohol-based resin may be further modified. For example, a polyvinyl formal modified with an aldehyde or a polyvinyl alcohol may be used. Further, the degree of polymerization of the polyvinyl alcohol-based resin is usually about 10,000 10,000, preferably about 1,5 Torr to 5,000. After the film of the related polyvinyl alcohol-based resin is formed, it is used as a material for the polarizing film raw material. There is no particular limitation on the method of forming a film by using a polyethyl alcohol-based resin. The film can be formed by a conventional method. The film thickness of the polyvinyl alcohol-based raw material material film is not particularly limited, and may be, for example, 10 μm to 15 μm μη. In the polarizing film, the polyvinyl alcohol-based resin film is uniaxially stretched in this manner, and the polyvinyl alcohol-based resin film is dyed in a dichroic color to adsorb the dichroic dye, and the dichroic property is adsorbed. The pigment polyvinyl alcohol-based resin film is produced by a step of treating with a boric acid aqueous solution and a step of washing with a boric acid aqueous solution and then washing with water. The uniaxial extension can be carried out prior to dyeing, or it can be carried out simultaneously with the dyeing of the acid, and the alcohol 98, such as the other -9 - (6) 200800604, can also be carried out after dyeing. If uniaxial stretching is performed after dyeing, the shaft extension can be carried out before boric acid treatment or boric acid treatment. Of course, in the plurality of stages, the single-axis extension can also be performed in a single-axis extension, which can be performed between the rolls having different circumferential speeds, or can be uniaxially extended by using a heat roll. Further, it may be a dry stretching such as stretching in the atmosphere, or may be a wet stretching in which a swelling is extended in a solvent. The stretching ratio is usually 2 to 8 times. 虔 The polyvinyl alcohol resin film is dyed with a dichroic dye. For example, the polyvinyl alcohol resin film may be immersed in a dichroic aqueous solution. In the case of dichroic dyes, iodine dyes are specifically used. Further, it is preferable that the polyvinyl alcohol-based resin film is subjected to immersion treatment of water in advance at the dyeing place. When iodine is used as the dichroic dye, it is usually dyed by immersing the polyethylene film in an aqueous solution containing iodine and potassium iodide. The iodine content in the aqueous solution is generally in the range of 0.001 to 1 part by weight per part by weight, and the potassium iodide is generally present in parts by weight of water. 5 to 20 parts by weight. Used for. The temperature of the dyeing solution is usually about 20 to 40 t: and the immersion (dyeing time) of the aqueous solution is generally about 20 to 1,800 seconds. On the other hand, when a dichroic dye is used as the dichroic dye, a method of immersing the polyglycolic alcohol resin film in an aqueous solution containing water-soluble two colors for dyeing is employed. The dichroic dyeing amount in the aqueous solution is usually from 1 χ 1 〇 to 4 Torr per 100 parts by weight of water, preferably from 1 x 1 〇 3 to 1 part by weight. This aqueous solution is also stretched in this sheet. In the process of advancing in the middle of the shaft extension, the method of alcoholic tree before the pigment or the two-color method contains water soaking time per 10 0, and the range of the usual dye material may contain -10- (7) (7) 200800604 An inorganic salt such as sodium sulfate is used as a dyeing aid. The temperature of the dye aqueous solution used for dyeing is generally about 20 to 80 ° C, and the immersion time (dyeing time) of the aqueous solution is generally about 10 to 1,800 seconds. The boric acid treatment after dyeing with the dichroic dye is carried out by immersing the dyed polyvinyl alcohol resin film in an aqueous solution containing boric acid. The boric acid content in the aqueous solution containing boric acid is usually from 2 to 15 parts by weight, preferably from 5 to 12 parts by weight, per 1 part by weight of water. When iodine is used as the dichroic dye, the aqueous solution containing boric acid is preferably one containing potassium iodide. The potassium iodide content in the aqueous solution containing boric acid is usually from 1 to 15 parts by weight, preferably from 5 to 12 parts by weight, per 1 part by weight of water. The immersion time for the aqueous solution containing boric acid is generally 60 to 1,200 seconds, preferably 150 to 600 seconds, and more preferably 2 to 60 seconds. The temperature of the aqueous solution containing boric acid is usually 50 ° C or higher, preferably 50 to 85 ° C, and more preferably 60 to 80 ° C. The polyvinyl alcohol-based resin film after boric acid treatment is generally washed with water. The water washing treatment can be carried out, for example, by immersing a boric acid-treated polyvinyl alcohol-based resin film in water. The water temperature in the water washing treatment is usually 5 to 4 〇 t:, and the immersion time is generally 1 to 2 seconds. After washing with water, a drying treatment was carried out to obtain a polarizing film. The drying treatment is generally carried out using a hot air dryer or a far infrared heater. The drying treatment temperature is usually from 30 to 100 ° C, preferably from 50 to 8 ° C. The drying treatment time is usually about 60 to 600 seconds, preferably about 120 to 600 seconds. Thus, the thickness of the film is 5 to 40 μηι after the uniaxial stretching is carried out on the polyvinyl alcohol-based resin film, and the dyeing by the chromatic dye and the boric acid treatment are carried out. The surface on one side of the hair mask is laminated on the other side of the surface of the cycloolefin by an adhesive, and the acetate fiber is laminated with a so-called cycloolefin resin, for example, having a ring shape like a norbornene monomer. An olefin (cycloolefin) plastic resin. The cycloolefin-based resin has a ring-opening olefin and a chain olefin or an addition copolymer having a vinyl group in addition to the above compound and ring-opening using two or more kinds of cyclic olefins. Further, when a polar group is introduced as a cyclic olefin and a chain olefin or a copolymer having ethylene, examples of the chain olefin are, for example, a styrene or α-methyl group having a vinyl aromatic compound. In the styrene or the nuclear alkyl-substituted copolymer, the monomer of the cycloolefin may be, for example, about 15 to 50 mol%. The unit system of the monomer of the special chain olefin and the aromatic compound having a vinyl group derived from the cyclic olefin may be a copolymer of a chain olefin, and the degree of the monomer of the monomer is less than The aromatic unit of the base is generally from 5 to 80 mol%. "Topas", JSR ARTON, which is sold by the company, and the "polarized film" sold by Nippon Steel Co., Ltd., which is sold by the company. Ordinary film. Oral compound other than the hydride of the ring-opening polymer of the ring-opening polymer of the norbornene or the polycyclic ring-forming monomer. The aromatic compound of the group is also effective. The propylene group may, for example, be a phenethyl group or the like. Such a content of 50 mol% or less is an amount when it is a cycloolefin and a terpolymer thereof. The related ternary position is generally The monomer of the 5~80 Mo compound is sold by the "ZEONOR" and "-12-200800604 (9) ZEONEX" sold by the German company. "APL", etc. (either is a product name). Although the cycloolefin-based resin is formed into a film after film formation, a conventional method such as a solvent casting method or a melt extrusion method is suitable for film formation. The film-formed cycloolefin-based resin film has been sold, for example, "S Senna" sold by Sekisui Chemical Industry Co., Ltd., "Zeonor Film" sold by "SCA40", and "OPTES". (Either are the product names). The Φ cycloolefin resin film may be uniaxially or biaxially stretched, or may exhibit a predetermined multirefractal property. The stretching ratio at this time is generally 1 . 1 to 5 times, preferably 1 · 1 to 3 times. In the present invention, the cellulose acetate-based film which is the protective film on the other side is a partial or complete acetate ester of cellulose, and examples thereof include a triacetyl cellulose film or a diethyl cellulose film. . For the commercially available triacetone cellulose film, "FUJITAC TD80", "FUJITAC TD80UF" and "FUJITAC _ TD80UZ" sold by Fuji Photo Film Co., Ltd., KONICA Μ IN Ο L Τ Α Ο Ρ Τ Ο (KC8UX2MW) and "KC8UY" sold by the company. In order to improve the adhesion to the adhesive, it is preferred to carry out the islanding treatment on the surface of the cellulose acetate-based film in advance. The roadway treatment can be carried out by immersing in an alkaline aqueous solution such as sodium hydroxide or barium hydroxide. Further, in order to adhere the polarizing film in advance, it is preferable to immerse it in water in advance and then perform the treatment before drying to reduce the bending. In the first step of the pretreatment, the cellulose acetate-based film is immersed in water at a temperature of 10 to 50 ° c -13 to 200800604 (10) for 5 to 10 seconds to be swollen. At this time, if the temperature becomes high, rib-line defects are generated on the film, so it is preferable to carry out at 20 to 4 5 °C. In the second treatment step, the surface of the cellulose acetate-based film is dried. The drying treatment is usually carried out using a hot air dryer or a far infrared heater. The drying treatment temperature is usually from 30 to 100 ° C, preferably from 40 to 60. The drying treatment time is usually from 20 to 600 seconds, preferably from 20 to 60 seconds. In this case, the adhesion surface of the cellulose acetate-based film and the polarizing film can be adjusted by appropriately changing the feeding direction of the roll, and the cellulose acetate-based film can be attached to the surface on which the polarizing film is adhered and the opposite side thereof. The surface is subjected to surface treatment such as anti-glare treatment, hard coating treatment, antistatic treatment, and anti-reflection treatment. Further, a coating layer formed of a liquid crystal compound or a polymer compound thereof may be formed. In the present invention, the cellulose acetate-based film is adhered to a polyvinyl alcohol-based polarizing film by being bent at a temperature of 80 ° C for 24 hours. The cellulose acetate-based film for protecting a film of a polarizing plate is generally produced by a solvent casting method in which a resin is dissolved in a solvent, cast on a support made of a metal strip, and a solvent is volatilized. . In the present case, the side on the air side is referred to as the A side, and the side on the opposite side is referred to as the B side. The film used in the examples described later has a convex surface on the A side. As described above, since the convex side is the adhesion surface to the polarizing film, when compared with the opposite case, the amount of bending of the polarizing plate produced becomes small. The thickness of each of the cycloolefin-based resin film and the cellulose acetate-based film disposed on both surfaces of the polarizing film is preferably thin, but if it is too thin, the strength will be lowered from 14 to 200800604 (11). When the workability is deteriorated, if the thickness is too large, the transparency is lowered and the weight of the polarizing plate is increased. Therefore, the appropriate thickness of the cycloolefin-based resin film is, for example, about 5 to 200 μm, preferably 10 to 150 μm, and more preferably 20 to 100 μm. Further, the cellulose acetate-based film has a suitable thickness of 20 to 200 μm, preferably 20 to 1 0 0 μηι 〇 on one side of the polarizing film and the other side, by an adhesive. Further, as described above, a cycloolefin resin film and a cellulose acetate film are laminated, respectively, to form a polarizing plate. An adhesive for bonding a polarizing film and a cycloolefin resin film, and an adhesive for bonding a polarizing film and a cellulose acetate film, if the adhesive layer is made thin, it is a water system, meaning It is preferred that the adhesive component is dissolved in water or dispersed in water. For example, a preferred adhesive agent is an adhesive containing a composition of a polyvinyl alcohol resin or a urethane resin as a main component. Further, as long as the proper adhesion is obtained, it is preferred that the adhesive applied to both sides of the polarizing film is the same composition, so that the manufacturing steps can be simplified. When a polyvinyl alcohol-based resin is used as a main component of the adhesive, the polyvinyl alcohol-based resin may be a carboxyl-modified polyvinyl alcohol or a acetonitrile, in addition to a partially saponified polyvinyl alcohol or a fully saponified polyvinyl alcohol. A modified polyvinyl alcohol-based resin such as a mercapto-modified polyvinyl alcohol, a hydroxymethyl-modified polyvinyl alcohol, or an amine-modified polyvinyl alcohol. When a polyvinyl alcohol-based resin is used, an aqueous solution is used as an adhesive. The concentration of the polyvinyl alcohol-based resin in the adhesive is generally from 1 to 10 parts by weight, preferably from 1 to 5 parts by weight, preferably from 1 to 5 parts by weight, per 100 parts by weight of water. . In order to improve the adhesiveness, an adhesive made of an aqueous solution of a polyvinyl alcohol-based resin is preferably a curable component such as glyoxal or a water-soluble epoxy resin or a crosslinking agent. The water-soluble epoxy resin is, for example, an epichlorohydrin in a polyamidamine polyamine obtained by reacting a polyalkylene polyamine such as diethylenetriamine or triethylenetetramine with a dicarboxylic acid such as adipic acid. A polyamine epoxy resin obtainable by reaction. For the commercial products of the related polyamine epoxy resin, the "W S sold by Sumitez Resin 650" or "Sumirez Resin 675" sold by Sumitomo Chemical Co., Ltd. and the Japanese PMC (share) -5 25" and so on. The amount of the curable component or the crosslinking agent to be added is usually 1 to 100 parts by weight, preferably 1 to 50 parts by weight, per 100 parts by weight of the polyvinyl alcohol-based resin. If the amount added is too small, the effect of improving the adhesion is small. On the other hand, if the amount of addition is too large, the adhesive layer tends to become brittle. When a urethane resin is used as a main component of the adhesive, an example of the adhesive composition is exemplified by a polyester-based ionomer type urethane resin and a glycidyl group. A mixture of compounds of a hydroxyl group. The polyester-based ionomer-type urethane resin described herein refers to a small amount of an ionic component (hydrophilic component) introduced into a urethane resin having a polyester skeleton. The related ionomer type urethane resin is suitable for use as an aqueous adhesive because it can be directly emulsified in water as an emulsion without using an emulsifier. The polyester-based ionomer-type urethane resin itself is conventionally known, for example, in Japanese Laid-Open Patent Publication No. Hei 7-975-04, the phenol resin is dispersed in an aqueous solvent - 16 - 200800604 (13 The polymer dispersant used is exemplified, and in the above-mentioned Patent Documents 2 to 4, a polyester-based ionomer-type urethane resin and a compound containing a glycidyl group-containing hydroxyl group are shown. The mixture acts as an adhesive on the polarizing film made of a polyvinyl alcohol-based resin and adheres to a form of a cycloolefin-based U-lip film. The polyester-based ionomer-type urethane resin can be emulsified in water by reacting a hydrophilic group-containing ethyl urethane obtained by reacting a hydrophilic group-containing compound, a polyester polyol, and a polyisocyanate. Manufactured by the method. At this time, in addition to the polyester polyol, other high molecular weight polyol components or low molecular weight active hydrogen-containing compounds may be used. The high molecular weight polyol may, for example, be a polyether polyol, a polycarbonate polyol, a polyoxymethylene polyol, a polyacrylate polyol, a polyester decylamine polyol, a polythioether polyol or the like. Further, examples of the low molecular weight active hydrogen-containing compound include polyhydroxy compounds such as ethylene glycol, pentaerythritol, 1,6-hexanediol, glycerin, and trimethylolpropane; Diamine, piperazine diamine compound, etc. Among them, it is preferred to use a low molecular weight active hydrogen-containing compound. The polyester-based ionomer type urethane resin preferably has a weight average molecular weight of 5,000 or more, a weight average molecular weight of 1 Å, and more preferably 〇〇G or more and 300,000 or less. When the weight average molecular weight is less than 5,000, the adhesive cannot obtain sufficient strength, and when the weight average molecular weight is more than 30,000, the viscosity at the time of using it as an aqueous dispersion becomes high, and the use becomes difficult. Related polyester-based ionomer type urethane resin dispersion -17 - 200800604 (14) In water, it can be used as a water-based adhesive. When the viscosity of the water-based adhesive is 2,000 mPa·sec or less, it is preferably used, and it is preferably 1,000 mPa·sec or less, particularly preferably 5 〇〇 mpa· _ or less. The lower the viscosity, the easier the application of the adhesive is, and the appearance of the obtained polarizing plate is also improved. The solid content concentration of the polyester-based ionomer type urethane resin in the water-based adhesive is preferably in the range of 丨〇 to 7 〇% by weight from the viewpoint of viscosity and adhesion strength. In particular, it is preferably 20% by weight or more, and more preferably 50% by weight or less. In the aqueous dispersion of the polyester-based ionomer type urethane resin, polyethylene glycol, polyoxyethylene or the like may be further added, or an interface active agent or the like may be added. Further, a water-soluble resin such as polyhydroxyethyl methacrylate, polyhydroxyethyl acrylate, polyacrylic acid or polyvinyl alcohol-based resin may be added. "HYDRAN AP-20" and "HYDRAN APX-1 0 1 Η" sold by Dainippon Ink Chemical Industry Co., Ltd. are available for the polyester-based ionomer-type urethane resin. "Wait. The adhesive agent formed from the aqueous dispersion of the polyester-based ionomer type urethane resin is more preferably a compound having a glycidyl group-containing hydroxyl group. By the use of a compound having a glycidyl group-containing hydroxyl group, the adhesion of the polarizing film to the cycloolefin-based resin film or the cellulose acetate-based film laminated thereon is increased upward. The glycidylhydroxy group referred to herein should be referred to as 2,3-epoxypropoxy in the field of purification. Examples of the compound having a glycidyl hydroxyl group include polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol dimethyl-18-200800604 (15) glyceryl ether, season Pentyl glycol diglycidyl ether, diglycerol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4·butylene glycol diglycidyl ether, 1,6-hexanediol Diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, resorcinol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol Polyglycidyl ether, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, polyglycerol polyglycidyl ether, and the like. The mixing ratio of the φ polyester-based ionomer type urethane resin and the glycidyl group-containing hydroxy compound is 100 parts by mass based on the solid content of the polyester-based ionomer type urethane resin. The compound having a glycidyl hydroxy group is suitably selected in the range of 5 to 100 parts by weight, and preferably the compound having a glycidyl hydroxy group is selected in an amount of 5 to 60 parts by weight, particularly 5 to 30 parts by weight. The best. If the ratio of the compound having a glycidyl hydroxyl group is too low, sufficient adhesive strength cannot be obtained, and if the ratio is too large, the viscosity of the adhesive becomes high, and it becomes difficult to use #. Containing a polyester-based ionomer-type urethane resin and a water-based adhesive having a glycidyl hydroxy compound, because it does not require the use of an organic solvent, it is environmentally or practically Both are preferred, and they are highly adhesive due to the glycidyl hydroxy compound. When a polyester-based ionomer-type urethane resin is used as the adhesive, in order to improve the adhesion to the cellulose acetate-based film, a compound having an isocyanate group is used, particularly at least in the molecule. 2-19-200800604 (16) An isocyanato group-based polyisocyanate compound is preferred. Examples of the compound having an isocyano group include, for example, 2,4-toluene diisocyanate, diisocyanato, 4,4'-diphenylmethyl isocyanate, 1,6- A monomer or oligo* of diisocyanate, isophorone diisocyanate or the like or a reaction of such a compound with a polyol. As used herein, 1,3-propanediol, 1,3-butanediol, 1,4-butane 1,5-pentanediol, and the like can be mentioned. When the molecular weight φ of the isocyanate group-containing compound is the above oligomer or a reaction product with a polyol, the weight average molecular weight is preferably 5,000 or less. For the commercially available isocyanate-containing compound, for example, "HYDRAN ASISTA-C1" sold by Dainippon Ink Chemical Industry Co., Ltd., and the like can be mentioned. The mixing ratio of the polyester-based ionomer-type urethane resin to the hetero-base-containing compound is relative to 1 part by weight of the solid component of the polyester-based polymer urethane resin. It is preferable to select a compound having an isocyanate group in a range of from 5 to 100 parts by weight, and preferably from 5 to 60 parts by weight, particularly preferably from 5 to 30 parts by weight, of the isocyanate group. If the ratio of the isocyanato group-containing radical is too low, sufficient adhesive strength cannot be obtained, and if the ratio is high, the viscosity of the adhesive becomes high, and it becomes difficult to use. The method of bonding a cycloolefin-based resin film or a cellulose film to an adhesive film by an adhesive may be carried out by a conventional method, for example, a casting method, a roll coating method, a concave coating method, and extrusion. Applying a dip coating method, a spray method, or the like, applying an adhesive to a polarizing film and/or an adhesive surface adhered to the film, and laminating the two together. The acid ester, —·ι “ ΓΠ /, middle material , the alcoholic alcohol, that is, the amount of the cyanide bond localized by the amount of the content of the peracetic acid is a method of peracetic acid, -20- 200800604 (17) that the casting method will be The film of the coating is in a direction perpendicular to the vertical direction, slightly horizontal direction, or an oblique direction therebetween, and the method of moving the adhesive layer on the surface thereof to diffuse and distribute the adhesive. Thereafter, the polarizing film and the film adhered thereto are held by a calender roll and then bonded. ^ Next, in order to improve the adhesion, the adhesive surface may be appropriately subjected to plasma treatment, corona discharge treatment, UV irradiation treatment, flame treatment, soap Surface treatment such as chemical treatment. The cycloolefin resin film is laminated on one surface of the polarizing film, and the cellulose acetate film is laminated on the other surface, followed by drying treatment. The drying treatment can be performed, for example, by hot air. By blowing, the current temperature can be appropriately selected to be in the range of 40 to 100 ° C, preferably 60 to 100 ° C. The drying time is 20 to 1,200 seconds. The thickness of the adhesive layer after drying. , generally 0. The degree of 001 to 5 μιη, preferably 0. 01 μιη or more is preferably 2 μπι or less, more preferably 1 μηι or less. If the thickness of the adhesive layer is too large, the appearance of the polarizing plate may be poor. After the bonding, the temperature is allowed to stand at room temperature or higher for at least half a day, and generally, a plurality of mashings are carried out to obtain a sufficient adhesive strength. The preferred ripening temperature is 30 to 50 ° C, more preferably 35 to 45 ° C. When the aging temperature is 50 ° C or more, "curl" tends to occur in the winding state of the roll. Further, the humidity at the time of ripening may be any range, and the relative humidity may be in the range of 0% RH to 70% RH. The ripening time usually takes 1 to 1 day, preferably 2 to 7 inches. In the polarizing plate of the present invention, the cycloolefin-based resin film and the surface of the cellulose acetate film disposed on the other side of the -21 - 200800604 (18) layer may be adhered to the optical functional film via an adhesive. In the optical functional film, for example, an optical compensation film which is coated with a liquid crystal compound on the surface of the substrate and which transmits light of a certain polarized light, and which is opposite to the property, reflects the polarized light. ^ An image-type polarized separation film, an anti-glare functional film* having a concave-convex shape on the surface, a film with an anti-reflection treatment, a reflective film having a reflection function, and a semi-transmissive reflection film having both a reflection function and a transmission function. "WV FILM" sold by Fuji Photo Film Co., Ltd., and Sakamoto Oil Co., Ltd. are sold in the same way as the optical compensation film in which the liquid crystal compound is applied to the surface of the substrate Φ. "NH FILM" or "NR FILM" (any one is a trade name) sold. Minnesota Mining and Manufacturing Co., Ltd. (3M Company) is a commercial product of a reflective polarized light separation film that transmits light of a certain polarized light and reflects the polarized light in the opposite direction. "DBEF" (trade name) sold by 3M (shares). [Embodiment] [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. In the examples, "%" and "parts" of the content and the amount used are based on the weight basis unless otherwise specified. [Production Example 1] Preparation of a polarizing film The average polymerization degree was about 2,400 and the degree of saponification was 99. 9 mol% or more, -22-(19) (19)200800604 A 75 μm thick polyvinyl alcohol film was dry-dried about 5 times uniaxially, and then immersed in 60 在 while continuously maintaining its tension. After 1 minute of pure water, it was immersed in an aqueous solution of iodine/potassium iodide/water in a weight ratio of 0 · 0 5 / 5 / 1 0 at 60 ° C for 60 seconds. Then, the weight ratio of immersion in potassium iodide/boric acid/water at 7 2 ° C is 8·5/8. 5 / 1 〇〇 in an aqueous solution for 3 sec. Subsequently, the film was washed with pure water at 26 ° C for 20 seconds, and then dried at 65 ° C to obtain a polarizing film having an iodine adsorption alignment in the polyvinyl alcohol resin. [Production Example 2] The adhesive was prepared in 100 parts of water, and 3 parts of carboxyl-modified polyvinyl alcohol ("Kuraray Poval KL318" obtained from Kuraray Co., Ltd.) and 1.5 parts of water-soluble poly were added. Indoleamine epoxy resin (Sumirez Resin 650 (a 30% solid solution) obtained from Sumitomo Chemical Co., Ltd.) was prepared into a polyvinyl alcohol-based adhesive. [Example 1] A triacetonitrile-based cellulose film ("KC8UX2MW" obtained from KONICA MINOLTA OPTO) having a thickness of 80 μm was subjected to saponification treatment, followed by immersion in water at 30 ° C for 1 〇 second. After swelling treatment, it was dried at 8 (TC for 53 seconds). After the film was allowed to stand at 8 ° C for 24 hours, the film was observed to be bent and confirmed to be on the convex side. The side of the convex surface was referred to the manufacturer. The information provided is the A side (the air side at the time of solvent casting). -23 - 200800604 (20) On the single surface of the polarizing film obtained in Production Example 1, the adhesive prepared in Production Example 2 will be used. The triethylene fluorene-based cellulose film was adhered to the curved convex side thereof, and the other surface of the polarizing film was adhered with a protective film of 73 μm thick by a norbornene-based resin through the same adhesive. Dry at a temperature of 60 to 90 ° C for 5 minutes and then at 40 ° C. Under the environment, a polarizing plate was obtained after the ripening on the 7th. Relative to the absorption axis (extension direction), the obtained polarizing plate is cut into a square of 15 cm X 15 cm at an angle of 45 at each side, and the humidity is adjusted at a temperature of 23 ° C and a relative humidity of 50%. After 1 hour, the curved tomb was measured. As a result, the bending of the corners of the polarizing plate 4 is 〇~2 〇 m m. The amount of bending of the polarizing plate was measured as follows. That is, as shown in Fig. 1, on the reference surface 5 (e.g., the plane on the table, etc.), the already-curved polarizing plate 1 is placed with the concave surface facing up. In the figure, it is assumed that the face when the polarizing plate is not bent is assumed to be the imaginary face 3 represented by the quadrilateral ABCD. Next, one corner A of the imaginary plane 3 is located at the position A1 of the curved polarizing plate 1; the other corner C is located at the position c1 of the curved polarizing plate 1, and the other corners B, D are located at the curved polarizing plate 1 The B1 and D1 positions in the system indicate that B1 and B are at the same position, and D1 and D are at the same position (that is, the angle B and the angle D of the polarizing plate correspond to a state in which no floating is performed). However, in actuality, there are cases in which three or four of the four corners of the polarizing plate are floated. Therefore, the heights Η of the four corners A1, B1, C1, and D1 of the polarizing plate are measured from the reference plane, respectively, and the ridge is used as the amount of bending. [Comparative Example 1] -24-200800604 (21) A polarizing plate was obtained in the same manner as in Example 1 except that the adhesion surface of the triacetyl cellulose film to the polarizing film was the curved concave side. The obtained polarizing plate was subjected to the same shearing and humidity conditioning as in Example 1, and then the amount of bending was measured. As a result, the bending of the corners of the polarizing plate 4 was 0 to 60 mm, and the maximum enthalpy of the amount of bending was 3' times as compared with Example 1. [Example 2] A polarizing plate was obtained in the same manner as in Example 1 except that after the saponification treatment and the swelling treatment of the triethylenesulfonated cellulose film, the film was dried at 60 ° C for 53 seconds. The obtained polarizing plate was subjected to shearing and humidity conditioning in the same manner as in Example 1, and then the amount of bending was measured. As a result, the bending of the corners of the polarizing plate 4 was 0 to 3 mm. [Comparative Example 2] # A polarizing plate was obtained in the same manner as in Example 2 except that the adhesion surface of the triacetyl cellulose film to the polarizing film was the curved concave side. The obtained polarizing plate was subjected to the same shearing and humidity conditioning as in Example 1, and then the amount of bending was measured. As a result, the bending of the corners of the polarizing plate 4 was 0 to 10 mm, and the maximum amount of bending of the bending amount was more than 3 times as compared with the second embodiment. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] The state in which the amount of bending of the polarizing plate in the embodiment is measured is shown in the side view of the mode -25-(22) (22)200800604. [Symbol description of main components] 1 : Curved polarizing plate; 3: Hypothetical surface on the reference plane when there is no bending on the polarizing plate; 5: Datum plane; A, B, C, D: Angle on the imaginary plane; A1, B1, C1, D1: the angle of the curved polarizing plate; Η: the amount of bending (the height from the reference surface to the corner of the polarizing plate).
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