200428043 Ο) 玖、發明說明 【發明所屬之技術領域】 本發明係有關層合保護膜於至少單面之偏光膜上的偏 光板及其製造方法者。 【先前技術】 先行做爲偏光膜者係於聚乙烯醇系樹脂膜使用使雙色 性色素進行吸著配向者。而以碘做爲雙色性色素之碘系偏 光膜，以雙色性染料做爲雙色性色素之染料系偏光膜爲 公知者。此等偏光膜一般，於其至少單面，較佳者雙面 上介著由聚乙烯醇系樹脂水溶液所成之粘合劑進行粘合 三乙醯纖維素等保護膜後，做成偏光板。惟，此所構成 之偏光板於濕熱下長時間使用時，將極易降低偏光性能 ，且，易剝離保護膜與偏光膜之端面等問題產生。 針對此問題被提出，以熱塑性環烯烴系樹脂做爲偏光 板保護膜之使用。如：特開平5-212828號公報（專利文獻 1)中揭示介著丙烯系粘合劑於至少單面之聚乙烯醇系薄 片上層合熱塑性飽和原菠烯系樹脂薄片後，加熱壓延後 做成偏光板者。又，於特開2000-321430號公報（專利文 獻2)中揭示介著聚乙烯醇系粘著劑與2液型粘合劑之混合 物粘合劑層於至少單面之聚乙烯醇系偏光膜上層合由環狀 嫌煙系樹S曰所成保護膜之偏光板者。更於特開2000·* 321432號公報（專利文獻3)中揭示聚乙烯醇系偏光膜與 熱塑性飽和原菠烯系樹脂所成之保護膜藉由聚胺基甲酸 -4 - (2) (2)200428043 乙酯系粘合劑所粘合之偏光板者。 惟，丙烯系等粘合劑（亦稱感壓粘合劑）中，其本身 厚度爲10〜50 μπι時，將無法取得某種程度之厚度。又，使 用一般公知之聚乙烯醇系，胺基甲酸乙酯系、丙烯系、 醋酸乙烯酯系等之粘合劑後，進行粘合聚乙烯醇系偏光 膜與環烯烴系樹脂薄膜時，藉由組合兩膜後，未必能有效 取得充份之粘合性者。 另外，先行者主要意圖以三乙醯纖維素等做爲保護 膜者，亦針對其與聚乙烯醇系偏光膜之粘合進行各種提案 。如：特開平8- 1 01 307號公報（專利文獻4)中揭示聚乙烯醇 系偏光膜與載體（保護膜）介著由聚酯聚醇與脂肪族多價 異氰酸酯所成之粘合劑所層合之偏光板者。又，特開平9-25 8023號公報（專利文獻5)中揭示介著含有水溶性環氧化 合物之聚乙烯醇系粘合劑粘合保護膜於至少單面之聚乙烯 醇系偏光膜之偏光板者。 [專利文獻1]特開平5-2 1 2828號公報 [專利文獻2]特開平2000-32 1430號公報 [專利文獻3]特開平2000-32 1432號公報 [專利文獻4]特開平8- 1 0 1 307號公報 [專利文獻5]特開平9-258023號公報 【發明內容】 本發明目的係於聚乙烯醇系偏光膜層合由聚烯烴系樹 脂所成之保護膜後做成偏光板時，利用適當之粘合劑，提 -5· (3) (3)200428043 局兩者粘者力者。 本發明者，以該目的爲基準，進行精密硏討結果發現， 於聚乙烯醇系偏光膜進行層合由環烯烴系樹脂所成之保護 膜時’做爲粘合劑者，藉由使用胺基甲酸乙酯系粘合劑與特 定組成之聚乙烯醇系樹脂混合物後，可取得偏光膜與保護 膜之粘合性良好之偏光板者，進而完成本發明。 亦即’本發明係提供一種於聚乙烯醇系偏光膜之單面 或雙面上介著粘合劑層進行層合由環烯烴系樹脂所成之保護 膜後所成之偏光板者，粘合劑層爲含有胺基甲酸乙酯系粘 合劑與聚乙烯醇系樹脂，此聚乙烯醇系樹脂係提供醋酸乙 烯酯與可於此共聚之其他單體相互之共聚物皂化物的偏光 板者。 此偏光板係於聚乙烯醇系偏光膜之單面或雙面上介著 粘合劑層進行層合由環烯烴系樹脂所成保護膜時，做爲粘合 劑者，使用胺基甲酸乙酯系粘合劑及醋酸乙烯酯與可於此共 聚之其他單體相互共聚物皂化物之聚乙烯醇系樹脂之水溶 液混合物，且，混合胺基甲酸乙酯系粘合劑及聚乙烯醇系 樹脂之水溶液後5分鐘內，適用於偏光膜或保護膜表面後， 藉由附與層合兩者步驟之方法後可有效製造之。 藉由本發明，相較於使用先行粘合劑時，較可製造與 聚乙烯醇系偏光膜與環烯烴系樹脂所成保護膜相互粘合性 良好之偏光板。 【實施方式】 -6- (4) (4)200428043 [發明實施之最佳形態] 以下，進行本發明之詳細說明，偏光膜係由聚乙烯醇 系樹脂所成者，如：於聚乙烯醇系樹脂薄膜中進行碘之吸附 定向之碘系偏光膜，於聚乙烯醇系樹脂膜中進行雙色性染 料之吸附定向之染料與偏光膜，將此等膜進行部份脫水 處理之聚烯系偏光膜等例。聚乙烯醇系樹脂通常藉由皂化 聚醋酸乙烯酯系樹脂後取得者。做爲聚醋酸乙烯酯系樹脂例 者，除醋酸乙烯酯之單獨聚合物之聚醋酸乙烯酯之外，有醋 酸乙烯酯及可於此共聚之其他單量體之共聚物，如：聚（乙 烯-醋酸乙烯酯）共聚物等例者。此等聚乙烯醇系樹脂亦可 被改性，如：以醛類被改性之聚乙烯醇縮甲醛水、聚乙烯醇 縮乙醛、聚乙烯醇縮丁醛等亦可使用之。 碘系偏光膜、染料系偏光膜係於此等聚乙烯醇系樹脂 所成之壞體膜藉由單軸延伸及碘或雙色性染料之染色後，使 碘或雙色性染料進行吸附定向者。聚乙烯醇系偏光膜之厚 度約爲5〜50 μπι者。 本發明係於此聚乙烯醇系偏光膜之單面或雙面上層合 由環烯烴系樹脂所成之保護膜後，做成偏光板者。環烯烴 系樹脂係指如：具有原菠烯、多環原菠烯系單體類之環狀烯 烴（環烯烴）所成之單體單位的熱塑性樹脂者。此環烯烴 系樹脂亦可爲環烯烴與鏈狀烯烴、具乙烯基之芳香族化合物 相互之共聚物者。另外，導入極性基者亦有效者。 做爲環烯烴與鏈狀烯烴，具乙烯基之芳香族化合物相互 共聚物者時，其鏈狀烯烴例如：乙烯、丙烯等例者。又，做 (5) (5)200428043 爲具有乙烯基之芳香族化合物例者如：苯乙烯、甲基苯乙 烯、核烷基取代苯乙烯等例。此共聚物中’由環烯烴所成單 體之單位爲50莫耳％以下者宜，亦可爲15〜50莫耳％者。特別 是做爲環烯烴與鏈狀烯烴及具乙烯基之芳香族化合物相互之 三元共聚物時，其由環狀烯烴所成單體之單位可爲如此較少 量者。該三元共聚物中’由鏈狀烯烴所成單體之單位一般爲 5〜80莫耳％，具乙烯基之芳香族化合物所成單體之單位一般 爲5〜80莫耳％者。 做爲市販熱塑性環烯烴系樹脂例者如：德國之 Ticona 公司所販賣之、Topas〃 、JES A1 (股份）所販賣之>Aton 、曰本 Zeon (股份）所販賣之"ZEONOR" 、" ZEONEX 〃、由三井化學（股份）所販賣之'Aper等。進行此環烯 烴系樹脂之製膜後，做成薄膜所成者，而，於製膜中，可適 用溶劑鑄造法、熔融擠壓法等’公知方法者。所製膜之環烯 烴系樹脂薄膜亦被市販之，如：由積水化學工業（股份）所 販賣之A Seine〆、、SCA4 0 "等者。 保護膜之厚度以較薄者宜，惟，太薄將降低強度，使加 工性變差，反之，太厚則降低透明性，層合後必要之養護時 間變長等問題點出現。因此，保護膜理想之厚度以5〜200μιη ，較佳者爲10〜150 μιη，更佳者爲20〜100 μιη。 該環烯烴系樹脂所成之保護膜亦可貼合於偏光膜之單 面上，亦可貼於雙面。於偏光膜雙面貼合環烯烴系樹脂 所成保護膜時，該2片保護膜可爲相同或不同類均可。於 偏光膜之單面貼合環烯烴系樹脂所成之保護膜時，可於 -8- (6) (6)200428043 其反面貼合環烯烴系樹脂以外之樹脂所成之保護膜者。做 爲環烯烴系樹脂以之樹脂所成之保護膜者如：三乙醯纖維 素、二乙醯纖維素類之乙醯纖維素系樹脂所成之薄膜、 聚對苯二甲酸乙二醇酯、聚乙烯萘酸酯、聚對苯二甲酸 丁二醇酯類之聚酯系樹脂所成之薄膜、聚碳酸酯系樹脂所 成之薄膜等，具良好光學性透明性之薄膜例者。 偏光膜與環烯烴系樹脂所成之保護膜係指使用胺基甲 酸乙酯系粘合劑與聚乙烯醇系樹脂之混合粘合劑後被層合 者。於偏光膜雙面層合環烯烴系樹脂所成之保護膜時，介著 此混合粘合劑於偏光膜雙面粘合環烯烴系樹脂所成之保護膜 。另外，於偏光膜單面層合環烯烴系樹脂所成之保護膜後， 另一面層合其他樹脂所成之保護膜時，於偏光膜雙面亦適 用相同粘合劑，偏光膜與環烯烴系樹脂所成之保護膜相 互粘著時適用該混合粘合劑，偏光膜與環烯烴系樹脂以外 之樹脂所成之保護膜相互之粘合時，亦可適用別種粘合劑。 如：於偏光膜之單面層合乙醯纖維素系樹脂所成之保護膜時 ，於兩者粘合時，實質上亦可使用聚乙烯醇系樹脂所成之粘 合劑。 胺基甲酸乙酯系粘合劑有由具末端異氰酸酯基之預聚物 所成之一液型，及與異氰酸酯基反應者，特別以具有羥基之 主劑與具有異氰酸酯基之硬化劑所成之二液型者，而，本發 明中可任意使用之。一液型中，末端異氰酸酯基與周圍水份 ，如：偏光膜中之水份、空氣中之水份反應之，或與膜表面 之活性氫基反應後出現粘著性。 (7) (7)200428043 做爲構成二液型胺基甲酸乙酯系粘合劑一方之具羥基之 主劑者如：聚醚聚醇、聚酯聚醇、丙烯系聚醇、乙烯·醋酸乙 烯酯系聚醇、聚醯胺系聚醇等例。聚醚聚醇如：聚乙二醇、 聚丙二醇、環氧乙烷/環氧丙烷共聚物者。聚酯聚醇如：二鹽 基酸與二醇相互之縮聚物者。丙烯系聚醇如：（甲基）丙烯 酸羥乙酯、（甲基）丙烯酸羥丙酯、（甲基）丙烯酸羥丁 酯類之具有羥基之（甲基）丙烯酸酯與（甲基）丙烯酸或 其烷酯相互之共聚物者。乙烯·醋酸乙烯酯系聚醇如：乙烯· 醋酸乙烯酯共聚物或更可於此共聚之其他單體被共聚之三元 以上共聚物的部份皂化物者，做爲此時所使用之第三單體者 如：不飽和羧酸類及其鹽、丙烯酸酯類、乙烯以外之鏈狀烯 烴、乙烯醚類、不飽和腈類、鹵化乙烯、丙烯化合物、乙烯 矽烷基化合物，具乙烯基之芳香族化合物等，可自由基聚合 者之例。聚醯胺系聚醇於製造該聚酯聚醇時，倂用以乙烯二 胺、丙烯二胺、六亞甲基二胺等之二胺做爲原料後，形成醯 胺鍵者。 胺基甲酸乙酯系粘合劑之主劑有溶解聚醇於有機溶劑之 有機溶劑系者與溶解聚醇於水中之水系者，惟，本發明中由 此胺基甲酸乙酯系粘合劑與聚乙烯醇系樹脂之水溶液相互混 合下，以水系爲較理想之使用者。做爲二液型胺基甲酸乙酯 系粘合劑之主劑的市販品時，如：做爲聚酯聚醇者由東洋 moton (股份）所販賣之，EL-436A 〃，做爲丙烯系聚醇者由 東洋moton (股份）所販賣之AEA-W15 1A〃等者。 構成另一二液型胺基甲酸乙酯系粘合劑之硬化劑爲具有 •10· (8) (8)200428043 異氰酸酯基於分子末端之化合物者’如：甲苯烯二異氰酸酯 '二苯基甲烷二異氰酸酯、六亞甲基二異氰酸酯、異弗爾酮 二異氰酸酯類之聚異氰酸酯單量體之外，此等複數分子附加 於三羥甲基丙烷類之多價醇的加成化合物、二異氰酸酯3分 子分別於單末端異氰酸酯基之部份形成三聚異氰酸酯環之3 官能三聚異氰酸酯體、二異氰酸酯3分子分別於單末端異氰 酸酯基之部份進行水合、脫碳酸後所形成之縮二脲體類之聚 異氰酸酯改性體等。 二液型胺基甲酸乙酯系粘合劑之硬化劑以分散於水後， 可使用之型態者宜。做爲二液型胺基甲酸乙酯系粘合劑之硬 化劑市販品者如：東洋rnoton (股份）所販賣之''EL-436B〃 、及、EA-W151B"等者。 與胺基甲酸乙酯系粘合劑混合之聚乙烯醇系樹脂以水溶 液之形態使用之。做爲粘合劑之聚乙烯醇系樹脂有醋酸乙烯 酯單獨聚合物之聚醋酸乙烯酯經過皂化處理後取得之乙烯醇 均聚合物之外，醋酸乙烯酯與於此可共聚之其他單體相互之 共聚物進行皂化處理後取得之乙烯醇系共聚物、更有此等羥 基經過部份改性之改性聚乙烯醇系聚合物、如：以公知之方 法反應醋酸乙烯酯之單獨聚合物或共聚物之皂化物後，取得 之乙醯乙醯基改性聚乙烯醇等。本發明該聚乙烯醇系粘著劑 中，亦使用醋酸乙烯酯與可於此共聚之其他單體之相互共聚 物的皂化物之乙烯醇系共聚物。使用乙烯醇均聚合物時，其 聚乙烯醇系偏光膜與環烯烴系樹脂相互間無法取得足夠之粘 著力。 -11 - (9) (9)200428043 醋酸乙烯酯與其他單體共聚物中，其醋酸乙烯酯爲主體 ，兩者共聚比例其醋酸乙烯酯爲70〜99.9莫耳％，其他單體爲 〇·1〜30莫耳％。共聚於醋酸乙烯酯之其他單體中，有不飽和 羧酸類及其鹽、丙烯酸酯類、鏈狀烯烴類、乙烯醚類、不飽 和腈類、鹵化乙烯、烯丙基化合物、乙烯矽烷基化合物、具 乙烯基之芳香族化合物等者，其中又以不飽和羧酸類或共聚 其鹽者爲較佳。因此，本發明做爲構成粘合劑之聚乙烯醇系 樹脂者可使用醋酸乙烯酯與具羧基之單體相互共聚物之皂化 物，亦即，羧基改性聚乙烯醇爲理想使用者。另外，本明細 書中「羧基」係指含有-COOH及其鹽之槪念者。 做爲市販之羧基改性聚乙烯醇者如：分別爲（股份） Klare 所販售之 ^Klare pobal KL506" 、 Klare pobal KL3 18 "及 、Klare pobal KL1 18 "，分別由日本合成化學 工業（股份）所販售之'gocenal Τ-3 30 〃及Ag0cenal Τ-3 5 0 〃 、電氣化學工業（股份）所販售之' DR-0415〃 、分 別由日本醋 vi · pobal (股份）所販售之、AF-17〃 、、 AT-17〃 、及、AP-17〃 等例。 聚乙烯醇系樹脂之分子量通常爲1萬至100萬者，較佳者 爲2萬至40萬，更佳者爲4萬至12萬。此聚乙烯醇系樹脂溶於 水後做成粘合劑時，其聚乙烯醇系樹脂濃度並未特別限定， 通常如以聚乙烯醇系樹脂/水之重量比下爲（0.1〜10) /100 者宜，較佳者爲（1〜5) /100者。 胺基甲酸乙酯系粘合劑與聚乙烯醇系樹脂相互混合物 之粘合劑中更可混合水溶性環氧化合物、乙二醛、戊二醛、 -12- (10) (10)200428043 氯化鋅、蜜胺系化合物等。此等成份一般被混合於聚乙烯醇 系樹脂之水溶液中。特別是爲提昇保護膜與偏光膜之粘合 性，以配合水溶性環氧化合物爲較佳者。 做爲水溶性環氧化合物例者如於二乙烯三胺、三乙烯 四胺類之聚亞胺基聚胺與己二酸類之二羧酸相互反應取 得之聚醯胺聚胺中使環氧氯丙烷反應後取得之聚醯胺環 氧樹脂等例。做爲此聚醯胺環氧樹脂之市販品者，如：由 住友化學工業（股份）所販售之'Sumi less resin 650〃及 "Sumi less resin 675 "、由日本PMC (股份）所販售之、 WS_525 〃 等。 配合水溶性環氧化合物於聚乙烯醇系樹脂水溶液時，一 般水溶性環氧化合物/聚乙烯醇系樹脂之比例以固形份重量 比下爲（5〜100) /100者宜，較佳者爲 （5〜50) /100。當水溶 性環氧化合物之量少於該範圍時，則將減少防止保護膜剝離 之效果，反之，量太大則粘著劑層將易脆。更且，此聚乙 烯醇系樹脂水溶液中加入水溶性環氧化合物後，亦可添加 氯化鋅、氯化錫、硼氟化鋅、三級胺、四級銨鹽、咪唑化合 物等。 本發明係以胺基甲酸乙酯系粘合劑與聚乙烯醇系樹脂 之混合物做爲粘合劑者，而兩者比例爲針對1 〇〇重量份胺 基甲酸乙酯系粘著劑之固形份時，則使用1〜500重量份之 聚乙烯醇系樹脂之固形份者宜。較佳者爲5〜200重量份， 更佳者爲10〜100重量份。胺基甲酸乙酯系粘合劑中可依其 主劑與硬化劑之官能基比等進行適當選取之。 •13- (11) (11)200428043 做爲提昇粘著劑與偏光膜及/或保護膜相互之粘著性的 方法者亦可於偏光膜及/或保護膜中進行電暈處理，火焰 處理、電漿處理、紫外線照射、底漆塗佈處理、皂化處 理等表面處理。 貼合聚乙稀醇系偏光膜與保護膜之方法並未特別限定 ’一般如：均勻塗佈粘合劑於聚乙烯醇系偏光膜或保護膜之 表面後，於塗佈面重疊另一面之薄膜後，藉由滾輥等進行貼 合後，進行乾燥之方法等例。 混合胺基甲酸乙酯系粘合劑與聚乙烯醇系樹脂水溶液後 進行調製粘合劑後，利用此層合偏光膜與保護膜者，混合胺 基甲酸乙酯系粘合劑與聚乙烯醇系樹脂水溶液後，將此適 用於偏光膜與保護膜間至層合爲止之時間以5分鐘以內者宜 。混合至層合爲止之時間太長時，則於混合粘著劑中產生沈 澱、分離，降低粘合性，造成外觀不良之問題。混合至層合 爲止之時間較佳者爲3分鐘以內，更佳者1分鐘以內。 通常，調製混合粘著劑後，於15〜40 °C之溫度下進行 塗佈、貼合溫度一般爲15〜30 °C之範圍者。貼合後進行乾 燥處理後，去除含於粘合劑中之水等溶劑，而，此時之乾燥 溫度一般爲30〜85 °C者宜，較佳者爲40〜80 °C。隨後，於 15〜85 °C之溫度環境下，較佳者於20〜50 °C，更佳者35〜45 °C，進行0·1〜100日之養護後，使粘合劑硬化之。此養護時 間太長時將造成生產性不良，理想之養護時間爲0.5〜30日、 更理想者爲1〜7日。 介著該胺基甲酸乙酯系粘合劑與含聚乙烯醇系樹脂之 • 14 - (12) (12)200428043 粘合劑層，於聚乙烯醇系偏光膜之單面或雙面取得由環燒 烴系樹脂所成之保護膜所貼合之偏光板。 本發明之保護膜，特別是由環烯烴系樹脂所成之保護膜 具有做爲位相差膜之機能，提昇亮度膜之機能，做爲反射膜 之機能，做爲半透光反射膜之機能，做爲擴散膜之機能’做 爲光學補償膜之機能等，光學機能者。此時，如於保護膜表 面藉由層合位相差膜、提昇亮度膜、反射膜、半透光反射膜 、擴散膜、光學補償膜等光學機能性膜後，可具此機能之外 ，於保護膜本身亦附與此機能者。如：於該保護膜上進行延 伸處理後，可附與做爲位相差膜之機能者。於該保護膜中以 特開2002- 1 69025號公報、特開2003-29030號公報所載之方法 形成微細孔後，選擇反射之中心波長藉由重疊不同2層以上 膽固醇型液晶層後，可附與做爲提昇亮度膜之機能者。於該 保護膜上以蒸鑛、濺射等形成金屬護膜後，可附與做爲反射 膜或半透光反射膜之機能者。於該保護膜塗佈含有微粒子之 樹脂溶液後，可附與做爲擴散膜之機能者。更於該保護膜塗 佈液晶性化合物後進行定向之後，可附與做爲光學補償膜之 機能者。 [實施例] 以下以實施例進行本發明更具體之說明，惟，本發明並 未受限於此等例者。例中，含量及使用量所示之％及份末特 別記載下代表重量基準者。 -15- (13) (13)200428043 [實施例1] (a) 偏光膜之製作 於厚度75 μπι之聚乙烯醇薄膜（聚合度2,4〇〇、皂化度 99.9莫耳％以上）以乾式進行延伸倍率5倍之單軸延伸後’直 接保持於緊張狀態、60 °C之純水中浸漬60秒後’再於碘/碘 化鉀/水以重量比0.05/5/1 00之水溶液中浸漬60秒進行染色之 。之後，碘化鉀/硼酸/水之重量比爲6/7.5/100之水溶液中’ 73 °C下進行浸漬300秒。更於15 °C之純水進行洗淨10秒後 ，50 °C下進行乾燥後，取得碘系偏光膜。 (b) 粘著劑之調製 於1 00份之做爲胺基甲酸乙酯系粘合劑之主劑聚酯聚醇 預聚物之東洋 moton (股份）製之’ EL-436A〃 （固形份濃 度35%之水溶液）中，配合30份異氰酸酯系硬化劑之東洋 moton (股份）製之、EL-436B "(有效成份1 0 0 °/〇者）後， 更加入水使固形份濃度稀釋呈2 0 %。又，進行調製做爲聚乙 烯醇系粘合劑之（股份）Klare製之羧基改性聚乙燒醇、 Klera pobal KL318〃 （醋酸乙烯酯與衣康酸鈉之莫耳比約 98:2之共聚物皂化物、皂化度85〜90莫耳％、分子量85,〇〇〇) 之3%水溶液。以重量比1:1 (固形份重量比爲2〇:3)混合所取 得之胺基甲酸乙酯系粘合劑與聚乙烯醇系水溶液後，做爲混 合粘合劑。 (C)保護膜 -16- (14) (14)200428043 以日本 Zeon (股份）製之環烯烴系樹脂、Zeonor 〃所 製膜之厚度40 μιη薄膜做成第一保護膜。更以富士相片膠卷 (股份）製厚度8〇 μιη之三乙醯纖維素膜之、fujituck UV80 〃做成第二保護膜。 (d)附保護膜之偏光板的製作 以（b)之方法將所調製之混合混合粘合劑後於1分鐘 以內塗佈於 U)取得碘系偏光膜之兩面後，其一面於該環 烯烴系樹脂所成第一保護膜之單面以250W · min/m2之條件進 行電暈處理後，於其電暈處理後30秒內以其電暈處理面進行 貼合，另一面將進行皂化處理於表面之該三乙醯纖維素所成 第二保護膜以其皂化處理面進行貼合後，於70 °C下進行乾 燥5分鐘後，做成偏光板。此偏光板更於40 °C下進行養護2 曰。 (e)粘著力之評定：剝離試驗 養護後偏光板之環烯烴系樹脂所成之第一保護膜表面 上針對薄膜法線方向由斜度45 °往透光軸方向置入切割刀之 後，嘗試剝離偏光膜與此保護膜，而無法剝離之。針對三乙 醯纖維素所成之第二保護膜表面亦進行相同剝離試驗，結果 仍無法剝離之。 [實施例2] 於1 00份做爲胺基甲酸乙酯系粘合劑之主劑丙烯系聚醇 -17- (15) (15)200428043 之東洋 moton (股份）製之a EA-W151 A〃 （固形份濃度 45 %之水溶液）中配合20份異氰酸酯系硬化劑之東洋 moton (股份）製之'EA-W151B〃 （有效成份100%) 後，更加入 水使固形份濃度稀釋呈40%。除使胺基甲酸乙酯系粘合劑以 此變更所調製者之外，與實施例1同法以重量比1 : 1混合此 胺基甲酸乙酯系粘合劑與聚乙烯醇系水溶液後做成混合粘 合劑，利用此，與實施例1同法製作偏光板。 於取得偏光板之環烯烴系樹脂所成之第一保護膜表面 針對薄膜法線方向由斜度45 °往透光軸方向置入切割刀之後 ，嘗試剝離偏光膜與此保護膜，而無法剝離之。針對三乙 醯纖維素所成之第二保護膜表面亦進行相同剝離試驗， 結果仍無法剝離之。 [實施例3] 針對100份水進行溶解3份之（股份）Klare製之羧基 改性聚乙烯醇、Klare pobal KL318〃後，更於其中加入1.5 份水溶性聚醯胺環氧樹脂之住友化學工業（股份）製之> Sumi less resin 650 ^ (固形份3 0 %之水溶液）後，做成粘 合劑。除將聚乙烯醇系粘合劑以此變更調製者之外，與實 施例1同法製作偏光板。 於取得偏光板之環烯烴系樹脂所成第一保護膜表面’ 針對薄膜法線方向由斜度45 °往透光軸方向置入切割刀’嘗 試剝離偏光膜與此保護，而，無剝離之。針對三乙醯纖維素 所成第二保護膜表面亦進行相同剝離試驗，結果仍無法剝離 -18- (16) (16)200428043 之。 [實施例4] 於積水化學工業（股份）製之環烯烴系樹脂薄膜、商 品名、、SCA40"(厚度40 μιη)以250W · min/m2之條件進行 電暈處理後，以此做成保護膜。與實施例1相同使用偏光膜 及粘著劑，除使該保護膜適用於偏光膜之兩面之外’與實施 例1於同條件下進行製作偏光板。所取得偏光板之單面針對 薄膜法線方向由斜度4 5 °往透光軸方向置入切割刀，嘗試剝 離偏光膜與單側之保護膜’而未剝離之。 [實施例5] 乙烯：厚菠烯：苯乙烯之莫耳比爲49:22:29之共聚物經 加壓成型後厚度40 μιη之薄膜中以2 50W · min/m2之條件下 進行電暈處理後，將此做爲保護膜，與實施例1使用相同 之偏光膜及粘合劑，該保護膜適用於偏光膜兩面之外， 與實施例1相同條件下製作偏光板。於取得偏光板之單面 針對薄膜法線方向由斜度45 °往透光軸方向置入切割刀， 嘗試剝離偏光膜與單側之保護膜，而未出現剝離。 [比較例1 ] 單獨使用主劑之東洋 moton (股份）製之’EA-W151A 〃、硬化劑之東洋 moton (股份）製之' EA-W151B〃之胺 基甲酸乙酯系粘合劑，未添加聚乙烯醇系樹脂水溶液之外， (17) (17)200428043 與實施例2同法製作偏光板。於取得偏光板之環烯烴系樹脂 所成之第一保護膜針對薄膜法線方向由斜度45 °往透光軸方 向置入切割刀，嘗試剝離偏光膜與此保護膜，結果剝離之。 以相同剝離試驗，針對三乙醯纖維素所成之第二保護膜表面 結果其保護膜無剝離現象。 [比較例2 ] 單獨使用於羧基改性聚乙烯醇水溶液中添加水溶性聚 醯胺環氧樹脂之聚乙烯醇系粘合劑，未添加胺基甲酸乙 酯系粘合劑之外，與實施例3同法製作偏光板。於取得 偏光板之環烯烴系樹脂所成之第一保護膜表面，針對薄 膜法線方向由斜度45 °往透光軸方向置入切割刀，嘗試剝 離偏光膜與此保護膜，結果可剝離之。針對三乙醯纖維 素所成之第二保護膜表面以相同剝離試驗，結果該保護 膜未剝離之。 [比較例3] 以和光純藥工業（股份）取得之聚乙烯醇a 163-03 045 〃 （皂化度約88%，聚合度約500)之4.8%溶液做爲聚 乙烯醇系粘合劑之使用之外，與實施例1相同條件下製作偏 光板。於取得偏光板之環烯烴系樹脂所成之第一保護膜表 面，針對薄膜法線方向由斜度45°往透光軸方向置入切割刀 ，嘗試剝離偏光膜與此保護膜，結果可剝離之。針對三乙 醯纖維素所成之第二保護膜表面，以相同剝離試驗，結 -20- (18) (18)200428043 果未剝離保護膜。 [比較例4] 混合胺基甲酸乙酯系粘合劑與聚乙烯醇系樹脂水溶液 後1小時後粘合偏光膜與保護膜之外，與實施例3同法製作 偏光板。其結果於混合液中產生沈澱，所取得偏光板之外 觀爲不良者。200428043 〇). Description of the invention [Technical field to which the invention belongs] The present invention relates to a polarizing plate with a protective film laminated on at least one side of a polarizing film and a method for manufacturing the same. [Prior art] Those who first used polarizing films were those based on polyvinyl alcohol resin films, which used dichroic pigments for absorbing alignment. Iodine-based polarizing films using iodine as a dichroic pigment, and dye-based polarizing films using dichroic dye as a dichroic pigment are known. These polarizing films are generally, on at least one side, preferably on both sides, a protective film such as triethyl cellulose is bonded through an adhesive made of a polyvinyl alcohol-based resin aqueous solution to form a polarizing plate. . However, when the polarizing plate constituted by this is used for a long time under moist heat, the polarizing performance will be extremely reduced, and problems such as easy peeling of the protective film and the end face of the polarizing film will occur. In response to this problem, a thermoplastic cycloolefin-based resin has been proposed as a protective film for polarizing plates. For example, Japanese Unexamined Patent Publication No. 5-212828 (Patent Document 1) discloses that a thermoplastic saturated orthospinene resin sheet is laminated on a polyvinyl alcohol sheet having at least one side through a propylene-based adhesive, and then heated and calendered. Polarizer. Also, Japanese Patent Application Laid-Open No. 2000-321430 (Patent Document 2) discloses a polyvinyl alcohol-based polarizing film having a PSA layer interposed between a polyvinyl alcohol-based adhesive and a two-component adhesive on at least one side. The upper layer is a polarizing plate made of a protective film formed by a ring-like smoke tree S. Furthermore, Japanese Patent Application Laid-Open No. 2000 · * 321432 (Patent Document 3) discloses that a protective film made of a polyvinyl alcohol-based polarizing film and a thermoplastic saturated orthospinene-based resin is made of polyurethane-4-(2) (2 ) 200428043 A polarizer with an ethyl-based adhesive. However, in the case of an adhesive such as acrylic (also called a pressure-sensitive adhesive), if the thickness is 10 to 50 μm, it cannot achieve a certain thickness. In addition, when using generally known adhesives such as polyvinyl alcohol-based, urethane-based, propylene-based, vinyl acetate-based, and the like, when bonding a polyvinyl alcohol-based polarizing film and a cycloolefin-based resin film, The combination of two films may not be able to effectively obtain sufficient adhesion. In addition, the pioneers mainly intended to use triethyl cellulose as a protective film, and also made various proposals for their adhesion to polyvinyl alcohol-based polarizing films. For example, Japanese Unexamined Patent Publication No. 8- 1 01 307 (Patent Document 4) discloses that a polyvinyl alcohol-based polarizing film and a carrier (protective film) are interposed between a polyester polyol and an aliphatic polyvalent isocyanate. Laminated polarizer. Also, Japanese Patent Application Laid-Open No. 9-25 8023 (Patent Document 5) discloses polarized light of a polyvinyl alcohol-based polarizing film on at least one side through a polyvinyl alcohol-based adhesive-bonding protective film containing a water-soluble epoxy compound. Board. [Patent Document 1] JP 5-2 1 2828 [Patent Document 2] JP 2000-32 1430 [Patent Document 3] JP 2000-32 1432 [Patent Document 4] JP 8- 1 0 1 307 [Patent Document 5] Japanese Patent Application Laid-Open No. 9-258023 [Summary of the Invention] The object of the present invention is to make a polarizing plate by laminating a protective film made of a polyolefin resin with a polyvinyl alcohol-based polarizing film. Using the appropriate adhesive, mention -5 (3) (3) 200428043. Based on this objective, the present inventors conducted precise investigations and found that when a polyvinyl alcohol-based polarizing film is laminated with a protective film made of a cycloolefin-based resin, as a binder, an amine is used. After a mixture of a urethane-based adhesive and a polyvinyl alcohol-based resin having a specific composition, a polarizing plate with good adhesion between a polarizing film and a protective film can be obtained, and the present invention has been completed. That is, the present invention provides a polarizing plate formed by laminating a protective film made of a cycloolefin resin on one or both sides of a polyvinyl alcohol-based polarizing film with an adhesive layer interposed therebetween. The mixture layer is a polarizing plate containing a urethane-based adhesive and a polyvinyl alcohol-based resin. The polyvinyl alcohol-based resin is a polarizer that provides a saponified copolymer of vinyl acetate and other monomers copolymerizable therewith. By. This polarizer is based on one or both sides of a polyvinyl alcohol-based polarizing film. A protective film made of a cycloolefin resin is laminated with an adhesive layer on one or both sides. As the adhesive, ethyl carbamate is used. An ester-based adhesive and an aqueous solution mixture of polyvinyl acetate and a polyvinyl alcohol-based resin which are copolymerized with other monomers which can be copolymerized with each other, and a urethane-based adhesive and a polyvinyl alcohol-based Within 5 minutes after the aqueous solution of the resin is applied to the surface of the polarizing film or the protective film, it can be effectively manufactured by the method of attaching and laminating both steps. According to the present invention, it is possible to manufacture a polarizing plate having good adhesion with a protective film made of a polyvinyl alcohol-based polarizing film and a cycloolefin-based resin, as compared with a case where a prior adhesive is used. [Embodiment] -6- (4) (4) 200428043 [Best Mode for Implementing the Invention] Hereinafter, the present invention will be described in detail. The polarizing film is made of a polyvinyl alcohol resin, such as in polyvinyl alcohol. An iodine-based polarizing film for iodine adsorption orientation in a resin film, a dye and a polarizing film for dichroic dye adsorption orientation in a polyvinyl alcohol-based resin film, and a polyene-based polarizing film for partially dehydrating the films Examples of films. Polyvinyl alcohol resin is usually obtained by saponifying a polyvinyl acetate resin. As examples of polyvinyl acetate-based resins, in addition to polyvinyl acetate, which is a separate polymer of vinyl acetate, there are copolymers of vinyl acetate and other monomers that can be copolymerized here, such as: poly (ethylene -Vinyl acetate) copolymer. These polyvinyl alcohol-based resins can also be modified, such as polyvinyl formal water modified with aldehydes, polyvinyl acetal, polyvinyl butyral, and the like. An iodine-based polarizing film and a dye-based polarizing film are made of these polyvinyl alcohol-based resins, and the bad film is uniaxially stretched and dyed with iodine or a dichroic dye, and the iodine or dichroic dye is adsorbed and oriented. The thickness of the polyvinyl alcohol-based polarizing film is about 5 to 50 μm. In the present invention, a polarizing plate is formed by laminating a protective film made of a cycloolefin resin on one or both sides of the polyvinyl alcohol-based polarizing film. Cycloolefin-based resins are thermoplastic resins having monomer units made of cyclic olefins (cycloolefins) of orthocyclone and polycyclic orthospinene monomers. This cycloolefin-based resin may be a copolymer of a cycloolefin, a chain olefin, and an aromatic compound having a vinyl group. It is also effective to introduce a polar group. When the cyclic olefin and the chain olefin are copolymerized with the aromatic compound having a vinyl group, examples of the chain olefin include ethylene and propylene. In addition, (5) (5) 200428043 is an example of an aromatic compound having a vinyl group such as styrene, methylstyrene, or a nucleoalkyl-substituted styrene. In this copolymer, the unit of the monomer made of cyclic olefin is preferably 50 mol% or less, and may be 15 to 50 mol%. In particular, when used as a terpolymer of a cyclic olefin, a chain olefin, and an aromatic compound having a vinyl group, the unit of the monomer formed from the cyclic olefin may be such a small amount. In the terpolymer, the unit of the monomer made of a chain olefin is generally 5 to 80 mol%, and the unit of the monomer made of an aromatic compound having a vinyl group is generally 5 to 80 mol%. Examples of commercially available thermoplastic cyclic olefin resins include those sold by Ticona in Germany, Topas〃, JES A1 (shares), > Aton, and Zeon (shares), which are sold by " ZEONOR ", "; ZEONEX 〃, 'Aper, etc. sold by Mitsui Chemicals Co., Ltd .; After the film formation of the cycloolefin resin is carried out, a thin film is formed. For the film formation, a known method such as a solvent casting method or a melt extrusion method can be applied. The produced cycloolefin resin film is also sold by the market, such as A Seine〆, SCA4 0 ", etc., sold by Sekisui Chemical Industry Co., Ltd. The thickness of the protective film is preferably thin, but too thin will reduce the strength and make the processability worse. On the other hand, too thick will reduce the transparency, and the necessary curing time after lamination will become longer. Therefore, the ideal thickness of the protective film is 5 to 200 μm, preferably 10 to 150 μm, and more preferably 20 to 100 μm. The protective film made of the cycloolefin-based resin may be laminated on one side of a polarizing film or on both sides. When a protective film made of a cycloolefin resin is laminated on both sides of a polarizing film, the two protective films may be the same or different types. When a protective film made of a cycloolefin-based resin is laminated on one side of a polarizing film, a protective film made of a resin other than a cycloolefin-based resin can be laminated on the reverse side of (-8) (6) (2004) 200428043. Examples of protective films made of resins made from cycloolefin resins include films made of triethyl cellulose, ethyl acetate cellulose resins of diethyl cellulose, and polyethylene terephthalate. Films made of polyester resins such as polyethylene naphthalate and polybutylene terephthalate, films made of polycarbonate resins, and other examples of films with good optical transparency. A protective film made of a polarizing film and a cycloolefin-based resin refers to a layer obtained by using a mixed adhesive of an urethane-based adhesive and a polyvinyl alcohol-based resin. When a protective film made of a cycloolefin-based resin is laminated on both sides of a polarizing film, a protective film made of a cycloolefin-based resin on both sides of the polarizing film is bonded through this mixed adhesive. In addition, when a protective film made of a cycloolefin resin is laminated on one side of the polarizing film and a protective film made of another resin is laminated on the other side, the same adhesive is also applied to both sides of the polarizing film. The polarizing film and the cycloolefin The mixed adhesive is applicable when the protective films made of the resin are adhered to each other, and other adhesives may be applied when the protective film made of the polarizing film and the resin other than the cycloolefin resin is adhered to each other. For example, when a protective film made of an ethyl acetate cellulose resin is laminated on one side of a polarizing film, an adhesive made of a polyvinyl alcohol resin can also be substantially used when the two are bonded. Urethane-based adhesives have a liquid type made of a prepolymer having a terminal isocyanate group, and those reacting with an isocyanate group, especially a main agent having a hydroxyl group and a hardener having an isocyanate group. The two-liquid type can be used arbitrarily in the present invention. In one-liquid type, the terminal isocyanate group reacts with the surrounding water, such as: the water in the polarizing film, the water in the air, or the reaction with the active hydrogen groups on the surface of the film. (7) (7) 200428043 As the main agent with a hydroxyl group that constitutes one side of the two-liquid urethane-based adhesive, such as: polyetherpolyol, polyesterpolyol, propylenepolyol, ethylene · acetic acid Examples are vinyl ester-based polyols and polyamine-based polyols. Polyether polyols such as: polyethylene glycol, polypropylene glycol, ethylene oxide / propylene oxide copolymer. Polyester polyols such as: polycondensates of dibasic acids and diols. Acrylic polyols such as: hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, (meth) acrylic acid esters and (meth) acrylic acid, or Copolymers of their alkyl esters. Ethylene · vinyl acetate-based polyols such as: ethylene · vinyl acetate copolymers or those partially copolymerized with other ternary copolymers in which other monomers copolymerizable here are copolymerized are used as the first Three monomers such as: unsaturated carboxylic acids and their salts, acrylates, chain olefins other than ethylene, vinyl ethers, unsaturated nitriles, halogenated ethylene, propylene compounds, ethylene silane compounds, and aromatic vinyls Group compounds and the like are examples of those capable of radical polymerization. In the production of the polyester polyol, polyamines are formed by using diamines such as ethylene diamine, propylene diamine, and hexamethylene diamine as raw materials to form amine bonds. The main agent of the urethane-based adhesive is an organic solvent-based one that dissolves a polyalcohol in an organic solvent and an aqueous system that dissolves a polyalcohol in water. However, in the present invention, the urethane-based adhesive When mixed with an aqueous solution of a polyvinyl alcohol resin, a water system is preferred. When it is marketed as the main agent of two-liquid urethane-based adhesives, for example, as a polyester polyol, it is sold by Toyo Moton Co., Ltd., EL-436A 〃, as acrylic Polyols are AEA-W15 1A〃 sold by Toyo moton (shares). The hardening agent that constitutes another two-liquid urethane-based adhesive is a compound having • 10 · (8) (8) 200428043 Isocyanate-based compounds at the molecular end, such as: toluene diisocyanate, diphenylmethane di Isocyanate, hexamethylene diisocyanate, isophorone diisocyanate and other polyisocyanate monomers, these molecules are added to trimethylolpropane polyhydric alcohol addition compounds, diisocyanate 3 molecules The trifunctional isocyanate body and the diisocyanate 3 molecules that form a trimeric isocyanate ring on the part of the single-terminal isocyanate group are respectively biuret bodies formed by hydrating and decarbonating the single-terminal isocyanate group. Polyisocyanate modified body and the like. The two-liquid urethane-based adhesive hardener is suitable for use after being dispersed in water. As the hardener of two-liquid urethane-based adhesives, marketers such as "EL-436B", EA-W151B ", etc. sold by Toyo rnoton (shares). The polyvinyl alcohol-based resin mixed with the urethane-based adhesive is used in the form of an aqueous solution. The polyvinyl alcohol-based resin used as a binder is a vinyl acetate homopolymer obtained by saponification of polyvinyl acetate alone polymer, and vinyl acetate and other monomers copolymerizable therewith each other. The vinyl alcohol copolymer obtained after saponification of the copolymer, and the modified polyvinyl alcohol polymer having such hydroxyl groups partially modified, such as a single polymer that reacts vinyl acetate by a known method or After saponification of the copolymer, acetoacetate-modified polyvinyl alcohol and the like are obtained. In the polyvinyl alcohol-based adhesive of the present invention, a vinyl alcohol-based copolymer of a saponified product of vinyl acetate and other monomers copolymerizable therewith is also used. When a vinyl alcohol homopolymer is used, sufficient adhesion between the polyvinyl alcohol-based polarizing film and the cycloolefin-based resin cannot be obtained. -11-(9) (9) 200428043 In the copolymer of vinyl acetate and other monomers, the vinyl acetate is the main component, and the copolymerization ratio of the two is 70 to 99.9 mol% of vinyl acetate, and the other monomers are 0 · 1 ~ 30 mole%. Among other monomers copolymerized in vinyl acetate are unsaturated carboxylic acids and their salts, acrylates, chain olefins, vinyl ethers, unsaturated nitriles, halogenated ethylene, allyl compounds, and ethylene silane compounds And aromatic compounds having a vinyl group, among which unsaturated carboxylic acids or copolymerized salts thereof are preferred. Therefore, as the polyvinyl alcohol-based resin constituting the adhesive of the present invention, a saponified product of a copolymer of vinyl acetate and a monomer having a carboxyl group can be used, that is, a carboxyl-modified polyvinyl alcohol is an ideal user. In addition, the "carboxyl group" in this manual refers to those who contain -COOH and its salts. As carboxy modified polyvinyl alcohols sold by the market, such as: ^ Klare pobal KL506 ", Klare pobal KL3 18 " and Klare pobal KL1 18 " sold by Klare, respectively, by Japan Synthetic Chemical Industry (Stock) sold 'gocenal Τ-3 30 30 and Ag0cenal Τ-3 50 0, and' DR-0415〃 sold by Denki Kogyo Co., Ltd., respectively, by Japanese vinegar vi · pobal (shares) Examples of AF-17〃, AT-17〃, and AP-17〃 sold. The molecular weight of the polyvinyl alcohol resin is usually 10,000 to 1 million, preferably 20,000 to 400,000, and more preferably 40,000 to 120,000. When the polyvinyl alcohol-based resin is dissolved in water to make a binder, the concentration of the polyvinyl alcohol-based resin is not particularly limited. Generally, the weight ratio of the polyvinyl alcohol-based resin / water is (0.1 to 10) / 100 is preferred, and (1 ~ 5) / 100 is preferred. Water-soluble epoxy compounds, glyoxal, glutaraldehyde, -12- (10) (10) 200428043 chlorine can be mixed into the adhesive of the mixture of urethane-based adhesive and polyvinyl alcohol-based resin. Zinc compounds, melamine compounds, etc. These ingredients are generally mixed in an aqueous solution of a polyvinyl alcohol-based resin. In particular, in order to improve the adhesion between the protective film and the polarizing film, it is preferable to mix a water-soluble epoxy compound. As an example of a water-soluble epoxy compound, epoxy polychloride is used in polyamine polyamine obtained by the reaction of polyimide polyamines of diethylene triamine and triethylene tetramine with adicarboxylic acid dicarboxylic acid. Examples of polyamine epoxy resins obtained after propane reaction. As a marketer of polyamine epoxy resins, such as: 'Sumi less resin 650' and " Sumi less resin 675 " sold by Sumitomo Chemical Industries (Stock), and Japan PMC (Stock) For sale, WS_525 〃, etc. When blending a water-soluble epoxy compound in a polyvinyl alcohol-based resin aqueous solution, the ratio of the water-soluble epoxy compound / polyvinyl alcohol-based resin is generally (5 to 100) / 100 in terms of solid content weight ratio, and more preferably (5 ~ 50) / 100. When the amount of the water-soluble epoxy compound is less than this range, the effect of preventing the peeling of the protective film will be reduced. On the other hand, if the amount is too large, the adhesive layer will be brittle. Furthermore, after adding a water-soluble epoxy compound to this polyvinyl alcohol-based resin aqueous solution, zinc chloride, tin chloride, zinc borofluoride, tertiary amine, quaternary ammonium salt, imidazole compound, and the like may be added. In the present invention, a mixture of a urethane-based adhesive and a polyvinyl alcohol-based resin is used as the adhesive, and the ratio of the two is based on the solid form of the urethane-based adhesive in an amount of 100 parts by weight. In the case of 1 part by weight, 1 to 500 parts by weight of the solid content of the polyvinyl alcohol resin is preferably used. It is preferably 5 to 200 parts by weight, and more preferably 10 to 100 parts by weight. The urethane-based adhesive can be appropriately selected according to the functional group ratio of the main agent and the hardener. • 13- (11) (11) 200428043 As a method to improve the adhesion between the adhesive and the polarizing film and / or protective film, corona treatment and flame treatment can also be performed in the polarizing film and / or protective film. , Plasma treatment, ultraviolet irradiation, primer coating treatment, saponification treatment and other surface treatments. The method of laminating a polarizing film based on polyvinyl alcohol and a protective film is not particularly limited. 'Generally, for example, after uniformly applying an adhesive to the surface of a polarizing film or protective film based on polyvinyl alcohol, the coated surface is overlapped with the other surface. After the film is adhered by a roll or the like, a method such as drying is performed. After mixing an urethane-based adhesive and a polyvinyl alcohol-based resin aqueous solution, and then preparing an adhesive, the laminated polarizing film and the protective film are used to mix the urethane-based adhesive and polyvinyl alcohol. After the resin aqueous solution, it is suitable to apply this time within 5 minutes between the polarizing film and the protective film until lamination. When the time between mixing and lamination is too long, precipitation and separation occur in the mixed adhesive, which reduces the adhesiveness and causes a problem of poor appearance. The time from mixing to lamination is preferably within 3 minutes, and more preferably within 1 minute. Generally, after preparing a mixed adhesive, coating is performed at a temperature of 15 to 40 ° C, and the bonding temperature is generally in a range of 15 to 30 ° C. After lamination, the solvent such as water contained in the adhesive is removed after the drying treatment, and the drying temperature at this time is generally 30 ~ 85 ° C, more preferably 40 ~ 80 ° C. Then, under a temperature environment of 15 to 85 ° C, preferably 20 to 50 ° C, and more preferably 35 to 45 ° C, after curing for 0.1 to 100 days, the adhesive is hardened. If this curing time is too long, it will cause poor productivity. The ideal curing time is 0.5 ~ 30 days, and the ideal curing time is 1 ~ 7 days. • 14-(12) (12) 200428043 adhesive layer between this urethane-based adhesive and polyvinyl alcohol-based resin, obtained on one or both sides of the polyvinyl alcohol-based polarizing film A polarizing plate to which a protective film made of a naphthenic hydrocarbon resin is bonded. The protective film of the present invention, especially a protective film made of a cycloolefin resin, has the function of a phase difference film, enhances the function of a brightness film, functions of a reflective film, and functions of a translucent reflective film. Function as a diffusion film 'Optical function as an optical compensation film. At this time, if the surface of the protective film is laminated with an optical functional film such as a phase difference film, a brightness enhancement film, a reflective film, a translucent reflective film, a diffusion film, and an optical compensation film, it can have this function in addition to The protective film itself is also attached to this function. For example, after performing an extension treatment on the protective film, it can be attached as a function of a phase difference film. After forming fine pores in the protective film by the methods described in JP 2002-1 69025 and JP 2003-29030, the center wavelength of reflection is selected and two or more different cholesterol-type liquid crystal layers can be overlapped. Attached as a function to enhance the brightness film. After forming a metal protective film on the protective film by evaporation, sputtering, etc., it can be attached as a function of a reflective film or a semi-transparent reflective film. After coating the resin solution containing fine particles on the protective film, it can be attached as a function of a diffusion film. After the protective film is coated with a liquid crystal compound and aligned, it can be attached as a function of an optical compensation film. [Examples] The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples. In the examples, the percentages and parts shown in the contents and the amount used are specifically stated on a weight basis. -15- (13) (13) 200428043 [Example 1] (a) Production of polarizing film on a polyvinyl alcohol film with a thickness of 75 μm (degree of polymerization of 2,400, degree of saponification of 99.9 mole% or more) in dry type After performing uniaxial stretching at a stretching ratio of 5 times, 'directly maintained in tension, immersed in pure water at 60 ° C for 60 seconds', and then immersed in an aqueous solution of iodine / potassium iodide / water at a weight ratio of 0.05 / 5/1 00 for 60 seconds. Stain it in seconds. Thereafter, the solution was immersed in an aqueous solution having a weight ratio of potassium iodide / boric acid / water of 6 / 7.5 / 100 at '73 ° C for 300 seconds. After washing with pure water at 15 ° C for 10 seconds, and drying at 50 ° C, an iodine-based polarizing film was obtained. (b) The adhesive is prepared in 100 parts of Toyo Moton Co., Ltd. (EL-436A〃) (solid content) as the main agent of the urethane-based adhesive polyester polyester prepolymer. Aqueous solution with a concentration of 35%), after adding 30 parts of isocyanate-based hardener made by Toyo Moton Co., Ltd., EL-436B " (effective ingredient 100 ° / 〇), add water to dilute the solid content concentration It was 20%. In addition, it is prepared as a (share) carboxyl-modified polyethylene glycol produced by Klare, a polyvinyl alcohol-based adhesive, and Klera pobal KL318〃 (the molar ratio of vinyl acetate to sodium itaconate is about 98: 2). Copolymer saponification, a 3% aqueous solution with a saponification degree of 85 to 90 mole% and a molecular weight of 85,000. The obtained urethane-based adhesive and polyvinyl alcohol-based aqueous solution were mixed at a weight ratio of 1: 1 (solid content weight ratio was 20: 3), and then used as a mixed adhesive. (C) Protective film -16- (14) (14) 200428043 The first protective film is made of a 40 μm thick film made of a cycloolefin resin made by Zeon (stock) of Japan and Zeonor (R). A second protective film was made of Fujitsu Film 80 (three ethyl acetate cellulose film with a thickness of 80 μm, made by Fuji Photo Film). (d) Fabrication of a polarizing plate with a protective film The method of (b) applies the prepared mixed adhesive to the U within 1 minute.) After obtaining two sides of the iodine-based polarizing film, one side is on the ring One side of the first protective film made of olefin resin is corona-treated under the condition of 250W · min / m2, and the corona-treated surface is bonded within 30 seconds after the corona treatment, and the other side is saponified. The second protective film made of the triethylammonium cellulose treated on the surface was bonded on the saponified surface, and then dried at 70 ° C for 5 minutes to prepare a polarizing plate. This polarizer is cured at 40 ° C for 2 days. (e) Evaluation of adhesion: After the peel test, the first protective film made of the cycloolefin resin of the polarizer after curing was placed on the surface of the film from the slope of the film normal direction at an angle of 45 ° to the direction of the light transmission axis. The polarizing film and the protective film cannot be peeled off. The same peeling test was also performed on the surface of the second protective film made of triethylcellulose cellulose, and as a result, it could not be peeled off. [Example 2] In 100 parts of propylene-based polyol as the main agent of urethane-based adhesive -17- (15) (15) 200428043 a EA-W151 A made by Toyo Moton Co., Ltd. 〃 "EA-W151B" (100% active ingredient) made by Toyo Moton (shares) with 20 parts of isocyanate-based hardener in an aqueous solution of 45% solid content concentration, and then add water to dilute the solid content concentration to 40% . This urethane-based adhesive was mixed with the polyvinyl alcohol-based aqueous solution in the same manner as in Example 1 except that the urethane-based adhesive was modified in the same manner as in Example 1. A mixed adhesive was prepared, and a polarizing plate was produced in the same manner as in Example 1 using this. After the surface of the first protective film made of the cycloolefin-based resin obtained the polarizing plate was placed in a cutting blade with an inclination of 45 ° toward the direction of the light transmission axis with respect to the normal direction of the film, the polarizing film and the protective film were attempted to be peeled off. Of it. The same peeling test was also performed on the surface of the second protective film made of triethylammonium cellulose, and as a result, it could not be peeled off. [Example 3] After dissolving 3 parts (shares) of carboxy-modified polyvinyl alcohol made by Klare and Klare pobal KL318〃 for 100 parts of water, 1.5 parts of water-soluble polyamine epoxy resin was added to Sumitomo Chemical Industrial (shares) system > Sumi less resin 650 ^ (30% solid solution in water), then made into an adhesive. A polarizing plate was produced in the same manner as in Example 1 except that the polyvinyl alcohol-based adhesive was changed in this way. On the surface of the first protective film made of a cycloolefin-based resin obtained with a polarizing plate, a cutting knife was placed in the direction of the film normal from an inclination of 45 ° to the direction of the light transmission axis. . The same peeling test was also performed on the surface of the second protective film made of triethylammonium cellulose, and the result still could not be peeled off. -18- (16) (16) 200428043. [Example 4] Corona treatment was performed on a cycloolefin resin film, trade name, SCA40 " (thickness: 40 μιη) made by Sekisui Chemical Industry Co., Ltd. under the conditions of 250 W · min / m2 to make protection. membrane. A polarizing film and an adhesive were used in the same manner as in Example 1. A polarizing plate was produced under the same conditions as in Example 1 except that the protective film was applied to both sides of the polarizing film. A single side of the obtained polarizing plate was placed in the direction of the film normal from an inclination of 45 ° to the direction of the light transmission axis, and a cutting blade was placed to try to peel off the polarizing film and the protective film on one side without peeling it off. [Example 5] Coronation of a film having a thickness of 40 μm after compression molding of a copolymer having a molar ratio of 49:22:29 of ethylene: thick spinene: styrene was subjected to corona at a temperature of 2 50 W · min / m 2 After the treatment, this was used as a protective film. The same polarizing film and adhesive were used as in Example 1. The protective film was applied to both sides of the polarizing film, and a polarizing plate was produced under the same conditions as in Example 1. On one side of the obtained polarizing plate, a cutting blade was placed in the direction of the film normal from an inclination of 45 ° to the direction of the light transmission axis, and an attempt was made to peel off the polarizing film and the protective film on one side without peeling. [Comparative Example 1] 'EA-W151A' manufactured by Toyo Moton Co., Ltd. and EA-W151B manufactured by Toyo Moton Co. (17) (17) 200428043 A polarizing plate was produced in the same manner as in Example 2 except that the polyvinyl alcohol-based resin aqueous solution was added. The first protective film formed from the cycloolefin-based resin obtained from the polarizing plate was placed with a cutting blade at an inclination of 45 ° toward the normal axis of the film in the direction of the film normal, and an attempt was made to peel the polarizing film and the protective film. The same peeling test was performed on the surface of the second protective film made of triethylammonium cellulose. As a result, there was no peeling of the protective film. [Comparative Example 2] A polyvinyl alcohol-based adhesive in which a water-soluble polyamine epoxy resin was added to an aqueous solution of a carboxyl-modified polyvinyl alcohol alone was used, except that no urethane-based adhesive was added. Example 3 The polarizing plate was made in the same way. A cutting blade was placed on the surface of the first protective film made of a cycloolefin-based resin obtained from a polarizing plate with an inclination of 45 ° toward the direction of the light transmission axis in the direction of the film normal, and the polarizing film and the protective film were peeled off as a result. Of it. The same peeling test was performed on the surface of the second protective film made of triethylammonium cellulose. As a result, the protective film was not peeled. [Comparative Example 3] A 4.8% solution of polyvinyl alcohol a 163-03 045 〃 (degree of saponification about 88%, degree of polymerization of about 500) obtained by Wako Pure Chemical Industries (stock) was used as the polyvinyl alcohol-based adhesive Except for use, a polarizing plate was produced under the same conditions as in Example 1. A cutting blade was placed on the surface of the first protective film made of a cycloolefin resin obtained from a polarizing plate with a slope of 45 ° toward the direction of the light transmission axis from the normal direction of the film. The polarizing film and the protective film were peeled off as a result. Of it. The same peeling test was performed on the surface of the second protective film made of triethylcellulose cellulose, and the result was -20- (18) (18) 200428043 without peeling the protective film. [Comparative Example 4] A polarizing plate was produced in the same manner as in Example 3 except that the polarizing film and the protective film were adhered to each other 1 hour after the urethane-based adhesive and the polyvinyl alcohol-based resin aqueous solution were mixed. As a result, a precipitate was generated in the mixed solution, and the obtained polarizing plate was defective in appearance.
-21 --twenty one -