200923444 九、發明說明 【發明所屬之技術領域】 本發明係有關在聚乙烯醇系樹脂所形成之偏光膜之至 少單面隔介接著劑層積層保護膜而成之偏光板及其製造方 法。 【先前技術】 偏光板一般係於經二色性色素吸著配向之聚乙烯醇系 樹脂所形成的偏光膜之至少單面或兩面，隔介接著劑層積 層保護膜而構成。偏光板作爲液晶顯示裝置之構成部件， 必要時亦可隔介其他光學系薄膜，以黏著劑貼合於液晶元 件（liquid crystal cell)。 液晶顯示裝置隨著其用途擴大，而要求可於各種各樣 的環境使用。因而，對構成液晶顯示裝置之部件要求高度 之耐環境性。 例如’對以行動電話爲代表之攜帶用液晶顯示裝置， 要求即使於溼熱下亦可使用，對其中使用之偏光板，要求 高度之耐溼熱耐久性。然而，以往構成之偏光板，特別是 長時間曝露於溼熱環境下時，有偏光性能容易降低，且偏 光膜與保護膜之界面容易剝離的問題。 針對此種問題，有提案使用熱塑性環烯烴系樹脂作爲 偏光膜的保護膜。例如，日本特開平5 - 2 1 2 8 2 8號公報（ 專利文獻1)揭示於聚乙烯醇系片之至少單面隔介丙烯酸 系黏著劑層積層熱塑性飽和降冰片烯系樹脂片，並加熱壓 -5- 200923444 著而作成偏光板（複合片）之技術。然而，丙烯酸系等黏 著劑（亦稱爲感壓接著劑），由於本身厚度爲1 0至5〇μιη 左右，因而液晶顯示裝置不得不變厚。又，乾積層（dry laminate )用接著劑、苯乙烯丁二烯橡膠系接著劑、環氧 系二液硬化型接著劑等，含有有機溶劑，而有環境上、從 業者健康上的問題。再者，將此種含有有機溶劑的接著劑 使用於以往不使用有機溶劑的偏光板製造設備時，伴隨著 需新設防爆設備等、設備改造等繁雜事務。 又’已知於聚乙烯醇系樹脂所形成之偏光膜隔介接著 劑貼合環烯烴系樹脂膜，例如，日本特開2005-7014〇號 公報（專利文獻2 )、特開2 0 0 5 - 1 8 1 8 1 7號公報（專利文 獻3)及特開2005-208456號公報（專利文獻4)記載於 聚乙烯醇系樹脂所形成之偏光膜隔介胺基甲酸酯（ urethane)樹脂’特別是含聚酯系離子聚合物（i〇norner) 型胺基甲酸酯樹脂的水系接著劑，積層環烯烴系樹脂膜。 據此’以輥對輥（roll to roll )之方法，即可於聚乙烯醇 系樹脂所形成之偏光膜直接積層環烯烴系保護膜。 一方面’日本特開平9-318814號公報（專利文獻5) 、曰本特開200 5 - 1 73440號公報（專利文獻6)、日本特 開20〇5 - 1 0760號公報（專利文獻7 )提案使用以三乙醯基 纖維素爲代表之纖維素系樹脂所形成之透明樹脂膜作爲偏 光板之保護膜，及用於將該保護膜貼合於聚乙烯醇系樹脂 所形成之偏光膜用的各種接著劑。此處，記載塗布於薄膜 間的接著劑爲含有乙醯乙醯基之聚乙烯醇系樹脂與具有羥 -6 - 200923444 甲基之化合物以特定配合比混合者、配合含有羥甲基之化 合物並調整pH者、或配合乙二醛樹脂者、或配合金屬烷 氧化物而成之接著劑’據此可獲得耐水性高之偏光板。 該等之中，專利文獻4揭示於聚乙烯醇系樹脂所形成 之偏光膜之一面，隔介含有聚酯系離子聚合物型胺基甲酸 酯樹脂與具有環氧丙氧基之化合物的水系第1接著劑積層 環烯烴系樹脂膜，並於另一面，隔介具有與上述第1接著 劑不同組成之水系第2接著劑，例如隔介聚乙烯醇系樹脂 之水溶液，積層乙酸纖維素系膜而作成偏光板。又，專利 文獻2及3分別於實施例2記載於聚乙烯醇系樹脂所形成 之偏光膜之一面，將環烯烴系樹脂膜之一種的降冰片烯樹 脂膜，並於另一面’將三乙醯基纖維素膜，分別隔介胺基 甲酸酯系接著劑加以貼合，而製作偏光板。 日本特開2005-3520 1 1號公報（專利文獻8)亦揭示 於偏光膜之單面積層環烯烴系樹脂膜，於相反側之面積層 乙酸纖維素系膜之偏光板。 【發明內容】 [發明欲解決的課題] 本發明之目的係於聚乙烯醇系樹脂所形成之偏光膜之 至少單面隔介接著劑層積層保護膜而成之偏光板中，提供 藉由改良接著劑層而提升偏光膜與保護膜間之接著性及耐 溫水性的偏光板。 本發明之目的係提供使用實質上不含有機溶劑的之水 200923444 系接著劑，可使聚乙烯醇系樹脂所形成之偏光膜與保護膜 牢固接著之偏光板的製造方法。 [解決課題用之手段] 本發明者等抱持上述目的深入進行硏究之結果，發現 藉由使用配合特定成分之水系混合物作爲偏光膜與保護膜 黏合用的接著劑，使偏光板與保護膜的接著速度變快，而 可獲得貼合後之接著性及耐水性優越的偏光板，而達成本 發明。亦即本發明係如下述。 本發明之偏光板係於聚乙烯醇系樹脂所形成之偏光膜 之至少單面隔介聚乙烯醇系接著劑層積層保護膜而成者， 其特徵爲前述接著劑層係使用含有聚乙烯醇系樹脂與氧錯 鹽，且聚乙烯醇系樹脂與氧銷鹽之固形物重量比爲100: 1 0至1 0000的接著劑組成物所形成者。 本發明之偏光板中，接著劑組成物中所含之聚乙烯醇 系樹脂以選自經乙醯乙醯基改質之聚乙烯醇系樹脂、經陽 離子改質之聚乙烯醇系樹脂及經陰離子改質之聚乙烯醇系 樹脂之至少一種爲佳。 本發明之偏光板中，接著劑組成物中所含之氧锆鹽， 以選自硝酸氧銷（Ziconium oxynitrate)及乙酸氧銷之至 少一種爲佳。 本發明之偏光板，其保護膜以乙酸纖維素系樹脂或環 稀烴系樹脂所構成者爲佳，以於偏光膜之一面積層由乙酸 纖維素系樹脂所構成之保護膜，而於偏光膜之另一面積層 -8- 200923444 由環烯烴系樹脂所構成之保護膜者更佳。 本發明提供於聚乙烯醇系樹脂所形成之偏光膜之至少 單面，隔介含有聚乙烯醇系樹脂與氧銷鹽，且聚乙烯醇系 樹脂與氧鉻鹽之固形物重量比爲100: 10至1 0000的接著 劑組成物，積層保護膜而成之偏光板的製造方法。 於本發明之偏光板的製造方法中，接著劑組成物中所 含之聚乙烯醇系樹脂係以選自經乙醯乙醯基改質之聚乙烯 醇系樹脂、經陽離子改質之聚乙烯醇系樹脂及經陰離子改 質之聚乙烯醇系樹脂之至少一種爲佳。 於本發明之偏光板的製造方法中，接著劑組成物中所 含之氧锆鹽，以選自硝酸氧銷及乙酸氧锆之至少一種爲佳 發明之效果 依據本發明，可製造偏光膜與保護膜之接著性優越， 耐溫水性遠較以往產品優越的偏光板。又依據本發明，由 於製造偏光板時不需使用有機溶劑，因而對環境方面、安 全衛生方面均優越，使用與以往由保護膜/偏光膜製成偏 光板之相同設備即可製造，無需投資更大的設備。 【實施方式】 實施發明用之最佳型態 本發明之偏光板’基本上具備於聚乙烯醇系樹脂所形 成之偏光膜之至少單面隔介聚乙烯醇系接著劑層積層保護 -9- 200923444 膜而構成者。以下詳細說明本發明偏光板的各構成。 〈偏光膜〉 構成偏光膜之聚乙烯醇系樹脂係使聚乙酸乙烯酯系樹 脂驗化即可獲得。聚乙酸乙烯酯系樹脂除乙酸乙烯酯之單 聚物聚乙酸乙烯酯之外，亦可例示如乙酸乙烯酯與可與其 共聚之其他單體共聚而得之共聚物等。可與乙酸乙烯酯共 聚之其他單體可例舉如不飽和羧酸類、不飽和磺酸類、烯 烴類、乙烯醚類、具有銨基之丙烯醯胺類等。聚乙烯醇系 樹脂之鹼化度一般爲85至1〇〇莫耳％，較佳爲98莫耳％ 以上。該聚乙烯醇系樹脂亦可進一步加以改質，例如可使 用以醛類加以改質的聚乙烯聚合物、聚乙烯縮醛等。又， 構成偏光膜之聚乙烯醇系樹脂之平均聚合度一般爲10 00 至10000，較佳爲1500至5000。 將上述聚乙烯醇系樹脂製膜而成之膜狀物（聚乙烯醇 系樹脂膜）可作爲偏光膜之原材料膜使用。將聚乙烯醇系 樹脂製膜之方法並無特別限定，可使用週知方法製膜。聚 乙烯醇系樹脂膜之膜厚並無特別限定，惟例如爲1 〇至 1 5 0 μιη ° 偏光膜一般係經由下述步驟製造：使此種聚乙烯醇系 樹脂膜進行一軸延伸之步驟、將聚乙烯醇系樹脂膜以二色 性色素染色使吸著二色性色素之步驟、將已吸著二色性色 素之聚乙烯醇系樹脂膜以硼酸水溶液處理之步驟、以及經 硼酸水溶液處理後水洗之步驟。 -10- 200923444 一軸延伸可於染色前進行’亦可於染色時同時進行’ 亦可於染色後進行。於染色後進行一軸延伸時’該一軸延 伸可於硼酸處理前進行’亦可於硼酸處理中進行。當然’ 於該等複數個階段中亦均可進行一軸延伸。一軸延伸可於 周速不同之輥間於一軸進行延伸’亦可使用熱輥於一軸進 行延伸。又，可爲於大氣中進行延伸等之乾式延伸’亦可 爲於溶劑中以膨潤狀態進行延伸之濕式延伸。延伸倍率一 般爲3至8倍。 將聚乙烯醇系樹脂膜以二色性色素進行染色’例如可 將聚乙烯醇系樹脂膜浸漬於含有二色性色素之水溶液中。 二色性色素具體而言可使用碘、二色性染料。聚乙烯醇系 樹脂膜較佳係於染色處理之前以水施予浸漬處理。 使用碘作爲二色性色素時，一般採用將聚乙烯醇系樹 脂膜浸漬於含有碘及碘化鉀之水溶液中使染色之方法。 該水溶液中，對每100重量份水，碘之含量一般爲 0.01至1重量份，對每100重量份水，碘化鉀之含量一般 爲0.5至20重量份。染色用水溶液之溫度，一般爲20至 4 0。(：，對該水溶液之浸漬時間（染色時間）一般爲20至 1 8 0 0 秒。 一方面，使用二色性染料作爲二色性色素時’ 一般採 用將聚乙烯醇系樹脂膜浸漬於含有水溶性二色性染料之水 溶液中使染色之方法。該水溶液中，對每1 0 0重量份水， 二色性染料之含量—般爲1χ1〇 —4至10重量份，以1χ1(Γ3 至1重量份爲佳。該水溶液中亦可含有硫酸鈉等無機鹽作 -11 - 200923444 爲染色助劑。染色用之染料水溶液之溫度，一般爲20至 8 〇 °C，對該水溶液之浸漬時間（染色時間）一般爲1 〇至 1 8 0 0 秒 ° 經二色性色素染色後之硼酸處理，係藉由將經染色之 聚乙烯醇系樹脂浸漬於含有硼酸之水溶液中而進行。 含硼酸之水溶液中，對每100重量份水，硼酸之含量 一般爲2至1 5重量份，以5至12重量份爲佳。使用碘作 爲二色性色素時，該含硼酸之水溶液中以含有碘化鉀爲佳 。含硼酸之水溶液中，對每1〇〇重量份水，碘化鉀之含量 一般爲0.1至15重量份，以5至12重量份爲佳。對含硼 酸之水溶液之浸漬時間一般爲60至1 200秒，以150至 6〇〇秒爲佳，200至400秒更佳。含硼酸之水溶液之溫度 ’一般爲50°C以上，以50至85°C爲佳，60至80°C更佳 〇 經硼酸處理後之聚乙烯醇系樹脂膜，一般進行水洗處 理。水洗處理係例如，將經硼酸水溶液處理後之聚乙烯醇 系樹脂膜浸漬於水中而進行。水洗處理之水溫一般爲5至 40 °C，浸漬時間一般爲1至12〇秒。水洗後施予乾燥處理 即獲得偏光膜。 乾燥處理一般使用熱風乾燥機、遠紅外線加熱器進行 。乾燥處理之溫度，一般爲30至100 °C，以50至80 °C爲 佳。乾燥處理之時間一般爲60至600秒，以120至600 秒爲佳。 如此操作，對聚乙烯醇系樹脂膜施予一軸延伸、以二 -12- 200923444 色性色素染色及硼酸處理，即獲得偏光膜。該偏光膜之厚 度一般爲5至40 μπι之範圍內，以10至35 μιη之範圍內爲 佳。 〈接著劑層〉 本發明之偏光板，其特徵爲：介入於前述偏光膜與積 層於該偏光膜之至少單面的保護膜之間的接著劑層，係使 用含有聚乙烯醇系樹脂與氧鉻鹽，且聚乙烯醇系樹脂與氧 銷鹽之固形物重量比爲100: 10至1 0000的接著劑組成物 而形成者。此種本發明之接著劑層不會引發對環境上、作 業員之健康上之障礙，雖係以實質上不含有機溶劑之水系 接著劑組成物所形成的接著劑層，卻爲可使聚乙烯醇系樹 脂所形成之偏光膜與保護膜牢固接著之物。 本發明中用於形成接著劑層之接著劑組成物中所含之 聚乙烯醇系樹脂，與上述用於偏光膜之聚乙烯醇系樹脂同 樣地，使聚乙酸乙烯酯系樹脂鹼化即可獲得者，聚乙酸乙 烯酯系樹脂除了乙酸乙烯酯之單聚物聚乙酸乙烯酯外，亦 可例示如乙酸乙烯酯與可與其共聚之其他單體共聚而得之 共聚物等。與乙酸乙烯酯共聚之其他單體可例舉如不飽和 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。此種接著劑組成物中所含之聚乙烯醇系樹 脂以具有適當聚合度爲佳，例如作成4重量％濃度之水溶 液時，以黏度於4至50mPa· sec範圍內較佳，6至30mPa • sec範圍內更佳。 -13- 200923444 本發明之偏光板中接著劑層所用之接著劑組成物中所 含之聚乙烯醇系樹脂的鹼化度並無特別限制，以7 4莫耳％ 以上爲佳’ 8 0莫耳％以上更佳。接著劑組成物中所含之聚 乙烯醇系樹脂的鹼化度若低，則有接著性不足之傾向。 接著劑組成物中所含之聚乙烯醇系樹脂以經改質者爲 佳。此種改質聚乙烯醇系樹脂較佳者可列舉如選自經乙醯 乙醯基改質之聚乙烯醇系樹脂、經陽離子改質之聚乙烯醇 系樹脂及經陰離子改質之聚乙烯醇系樹脂之至少一種。使 用此種經改質之聚乙烯醇系樹脂時，由於具有提高接著劑 層耐水性之優點而佳。 本發明之偏光板中接著劑層所用之接著劑組成物，當 然亦可含有2種以上之上述經改質之聚乙烯醇系樹脂，又 ，亦可含有未經改質之聚乙烯醇系樹脂（具體而言，聚乙 酸乙烯酯之完全或部分鹼化物）及上述經改質之聚乙烯醇 系樹脂二者。 上述接著劑組成物可適當使用市售之聚乙烯醇系樹脂 ，具體而言’ Gohsefimer-Z系列、WO-239 (以上’日本 合成化學工業（股）製）、PVA-403、PVA-105、KL-318 、KL-506、KM-118、KM-618、C-506 (以上，Kuraray ( 股）製）等。 本發明中所用接著劑組成物中之上述聚乙烯醇系樹脂 之濃度並無特別限制，惟對水100重量份以1至1 0重量 份範圍內較佳，以1至5重量份範圍內更佳。若聚乙烯醇 系樹脂之濃度對水10 0重量份未達1重量份時’接著性有 -14- 200923444 降低之傾向，又，若聚乙烯醇系樹脂之濃度對水1 00重量 份超過1 0重量份時，所得偏光板之光學特性有容易降低 之傾向。本發明中接著劑組成物中所使用之水可爲純水、 超純水、自來水等，並無特別限制，惟就所形成接著劑層 之較佳均一性，及保持透明性之觀點而言，以純水或超純 水爲佳。 本發明中所用之接著劑組成物，除上述聚乙烯醇系樹 脂之外，可含有氧鉻鹽。此處，「氧锆鹽」係指含有以 ZrO所表示之正2價基（亦稱爲氧化锆）之鹽，例如硝酸 氧锆（Zr0(N03)2)、乙酸氧锆（Zr0(C2H302) 2)、 氯氧鉻（ZrOCl2 )、 硫酸氧錯（ZrOS〇4)、 碳酸氧銷（Zr0C03 )、 碳酸氧锆銨（（NH4 ) 2ZrO ( C03 ) 2 )、辛酸氧錆（ Zr0(C8H15 02 ) 2)、氫氧化氧锆（ZrO(OH)2)、氫氧 化氯氧銷（ZrO ( OH ) C1 )、碳酸氧銷鉀（K2[ZrO ( C〇3 )2])等。此等中，就密著性、密著速度、耐水性之觀點 而言，以選自硝酸氧锆及乙酸氧锆之至少一種爲佳。 上述氧錯鹽可適當使用市售品，例如Zirconia Sol ZN (ZrO ( N03 ) 2 · nH20 ) 、Zirconia Sol AC-7 ( ( NH4 ) 2ZrO ( C03 ) 2)、氯氧锆、Zirconia Sol ZC ( ZrOC12 )、 Zirconia Sol ZC-2( ZrO (OH) Cl. nH20)、硫酸氧銷、 Zirconia Sol ZA ( ZrO ( C2H3O2) 2) 、Zirconia Sol ZA-30 、Zirconia Sol ZA-20 ' Zirconia Sol ZK (碳酸銷鉀）-i〇 -15 - 200923444 、辛酸氧鉻、碳酸氧锆、氫氧化锆、R氫氧化鉻、NN氫 氧化鉻（以上，任一者均爲日本第一稀元素化學工業（股 )製）等。 本發明中所用之接著劑組成物，係上述聚乙烯醇系樹 脂與氧銷鹽之固形物重量比爲100: 10至1 0000者。相對 於聚乙烯醇系樹脂100，氧锆鹽之固形物重量比未達10時 ’有不能充分表現耐水性之不妥情況，又，相對於聚乙烯 醇系樹脂100，氧銷鹽之固形物重量比超過1 0000時，有 所得偏光板之光學特性下降之不妥情況，又，使用硝酸氧 銷等酸性氧銷鹽時，因其pH低導致金屬腐蝕性變高。就 耐水性與光學特性之觀點而言，本發明所用之接著劑組成 物中之聚乙烯醇系樹脂與氧鍩鹽之固形物重量比以1 00 : 5 0至1 〇 〇爲佳。 上述聚乙烯醇系樹脂與氧錆鹽之特佳組合，可例舉如 使用 Gohsefimer Z-100 (日本合成化學工業（股）製）作 爲聚乙烯醇系樹脂、使用Zirconia Sol ZN (日本第一稀元 素化學工業（股）製）作爲氧锆鹽之情況；使用 Gohsefimer Z-2 00 (日本合成化學工業（股）製）作爲聚 乙烯醇系樹脂、使用Zirconia Sol ZA-20 (日本第一稀元 素化學工業（股）製）作爲氧锆鹽之情況；使用KL3 1 8 ( 日本 Kuraray (股）製）作爲聚乙烯醇系樹脂、使用 Zirconia Sol A C-7 (日本第一稀元素化學工業（股）製） 作爲氧锆鹽之情況等。藉由此種組合，接著劑組成物之可 使用時間（pot life )延長，且密著性、耐水性提高。 -16- 200923444 本發明之接著劑層，其厚度並無特別限制，一般爲 0.001 至 5μιη，以 0.01 至 2μιη 爲佳，0.05 至 Ιμιη 更佳。接 著劑層之厚度超過5μπι時，偏光板之外觀容易變得不良。 本發明之接著劑層，亦可使用於上述接著劑組成物中 ，在不妨礙本發明效果之範圍內，添加例如交聯劑、可塑 劑、矽烷偶合劑、抗靜電劑、微粒子等習知的適當添加劑 而形成者。 〈保護膜〉 本發明之偏光板，係於上述偏光膜之至少單面，隔介 上述接著劑層積層保護膜而成。本發明之偏光板之保護膜 ，可使用例如乙酸纖維素系樹脂、環烯烴系樹脂、聚烯烴 系樹脂、丙烯酸系樹脂、聚醯亞胺系樹脂、聚碳酸酯系樹 脂、聚酯系樹脂等該領域自以往即廣泛用於作爲保護膜形 成材料的適當材料構成之保護膜，並無特別限制。就量產 性及接著性之觀點而言，上述中以具備由乙酸纖維素系樹 脂或環烯烴系樹脂所構成之保護膜爲佳。又，就設立表面 處理層的容易性及光學特性的觀點而言，本發明之偏光板 ，亦可製作成於偏光膜一側之單面積層由乙酸纖維素系樹 脂所構成之保護膜，而於偏光膜另一側之單面積層由環稀 烴系樹脂所構成之保護膜的構造。 本發明之保護膜中可使用之環烯烴系樹脂，係指例如 具有降冰片烯、多環降冰片烯系單體類之環狀烯烴（環稀 烴）所成之單體單元的熱塑性樹脂（亦稱爲熱塑性環烴 -17- 200923444 系樹脂）。該環烯烴系樹脂可爲上述環烯烴之開環聚合物 、使用2種以上環烯烴之開環共聚物的氫化物’亦可爲環 烯烴與鏈狀烯烴、具有乙烯基之芳族化合物等之加成聚合 物。又，導入極性基者亦有效。 使用環烯烴與鏈狀烯烴、具有乙烯基之芳族化合物之 共聚物構成保護膜時’鏈狀烯烴可例舉如乙烯、丙烯等’ 具有乙烯基之芳族化合物可例舉如’苯乙烯、α -甲基苯 乙烯、核烷基取代之苯乙烯等。於該等共聚物中’由環烯 烴所成之單體單元可爲50莫耳％以下（較佳爲15至50莫 耳％)。特別是使用環烯烴與鏈狀烯烴與具有乙烯基之芳 族化合物之三元共聚物構成保護膜時，由環烯烴所成之單 體單元，可爲較上述之量少。於該三元共聚物中’由鏈狀 烯烴所成之單體單元，一般爲5至80莫耳％，由具有乙烯 基之芳族化合物所成之單體單兀’ 一般爲5至80莫耳％。 環烯烴系樹脂可適當使用適宜之市售品’例如TP〇as (Ticona公司製）、ART0N(JSR (股）製）、季歐諾耳 (ZEONOR )(日本 ΖΕΟΝ (股）製）、季歐聶斯（ ΖΕΟΝΕΧ)(日本ΖΕΟΝ (股）製）、Ap e 11 e (日本三井化 學（股）製）等。將此種環烯烴系樹脂製膜作成薄膜時， 可適當使用溶劑澆鑄（east )法、熔融擠壓法等周知方法 。又，亦可使用例如愛司析那（音譯）（日本積水化學工 業（股）製）、SCA40 (日本積水化學工業（股）製）、 Zeonorfilm ( OPTES (股）製）等預先製膜之環烯烴系樹 脂所製之膜的市售品作爲保護膜。 -18- 200923444 以環烯烴系樹脂所構成之保護膜，可爲經一軸延伸或 二軸延伸者。此種情況之延伸倍率，一般爲1 . 1至5倍， 以1.1至3倍爲佳。 本發明之保護膜中適宜使用之乙酸纖維素系樹脂，可 例舉如纖維素部分或全部乙酸酯化之物，例如三乙醯基纖 維素膜、二乙醯基纖維素膜等。 此種乙酸纖維素系樹脂，可適當使用適宜之市售品， 例如富士達（FUJITAC ) TD80 (富 士膠捲（Fuji Photo Film ))(股）製）、富士達TD80UF (富士膠捲（股） 製）、富士達TD80UZ (富士膠捲（股）製）、KC8UX2M (Konica Minolta Opt (股）製）、KC8UY ( Konica Minolta Opt (股）製）等乙酸纖維素系樹脂製之薄膜。 本發明之偏光板中所用之保護膜，其厚度以較小者爲 佳，惟若過薄則強度降低，加工性有劣化傾向，又，若過 厚，則透明性降低，且偏光板之重量有增加之傾向。就此 觀點而言，本發明之偏光板中所用保護膜之厚度，於使用 環烯烴系樹脂所構成之保護膜之情況，一般爲5至200μηι ，以10至150μπι爲佳，20至ΙΟΟμπι更佳，又，於使用乙 酸纖維素系樹脂所構成之保護膜之情況，一般爲20至 200μηι，以 30 至 150μηι 爲佳，40 至 ΙΟΟμπι 更佳。 本發明偏光板中之保護膜，亦可爲於貼合偏光膜之面 與相反側之面施予防眩處理、硬塗層（hard coat )處理、 抗靜電處理、抗反射處理等表面處理者。又，於保護膜貼 合偏光膜之面與相反側之面，亦可形成由液晶性化合物、 -19- 200923444 其高分子量化合物等所成之塗層（coat layer )。 本發明偏光板中之保護膜，於貼著偏光膜之面與相反 側之面’亦可隔介黏著劑層，貼合光學機能性膜。黏著劑 係指，僅藉由按押即可接著於其他物質表面，且將其自被 接著面撕開時，只要被著物有強度即可幾乎不留痕跡去除 的彈性體，亦有稱爲感壓接著劑之情形。光學機能性膜可 例舉如於基材表面塗布液晶性化合物之定向光學補償膜、 透過某種偏光並將呈現與其相反性質之偏光加以反射的反 射型偏光分離膜、由聚碳酸酯系樹脂所成之相位差膜、由 環狀聚烯烴系樹脂所成之相位差膜、表面具有凹凸形狀的 附有防炫機能的膜、經表面抗反射處理之膜、表面具有反 射機能的反射膜、兼具反射機能及透過機能的半透過反射 膜等。 於基材表面塗布液晶性化合物之定向光學補償膜，其 相當之市售品可例舉如，WV膜（富士膠捲（股）製）、 NH膜（新曰本石油（股）製）、NR膜（新日本石油（股 )製）等。又，透過某種偏光，而將呈現與其相反性質之 偏光加以反射的反射型偏光分離膜’其相當之市售品可例 舉如，DBEF (住友3M (股）製）等。 又，由環狀聚烯烴系樹脂所成之相位差膜，其相當之 市售品可例舉如，ART ON (JSR (股）製）、愛司析那（ 日本積水化學工業（股）製）、Zeonorfilm ( OPTES (股 )製）等。 -20- 200923444 〈偏光板之製造方法〉 本發明亦提供偏光板之製造方法，其係於聚乙烯醇系 樹脂所形成之偏光膜之至少單面，隔介含有聚乙烯醇系樹 脂與氧鍩鹽’且聚乙稀醇系樹脂與氧銷鹽之固形物重量比 爲1 0 0 : 1 0至1 0 0 0 0的接著劑組成物，積層保護膜而製造 偏光板之方法。上述本發明之偏光板，其製造方法並無特 別限制’並不限定爲此種依據本發明之偏光板之製造方法 所製造者’可依據本發明之偏光板之製造方法適當的製造 〇 本發明之偏光板之製造方法，首先，將上述聚乙烯醇 系樹脂與氧鉻鹽以特定範圍內之固形物重量比配合於水中 ，調製接著劑組成物。此時，藉由聚乙烯醇系樹脂之配合 量即可調控接著劑組成物之黏度。於本發明之偏光板之製 造方法中，如上述，接著劑組成物中所含之聚乙烯醇系樹 脂，以選自經乙醯乙醯基改質之聚乙烯醇系樹脂、經陽離 子改質之聚乙烯醇系樹脂及經陰離子改質之聚乙烯醇系樹 脂之至少一種爲佳。又，接著劑組成物中所含之氧锆鹽， 以選自硝酸氧锆及乙酸氧銷之至少一種爲佳。 使用此種接著劑組成物之偏光膜與保護膜之接合，可 依習知之適當方法進行，可例舉如以鑄造（cast )法、美 亞棒塗布（Meyer Bar coat)法、凹版塗布（gravure coat )法、模具塗布（d i e c o a t )法、浸漬法、噴霧法等，於 偏光膜及/或保護膜之接著面塗布接著劑組成物，將2者 重合之方法。鑄造法係指一邊將偏光板或保護膜等被塗布 -21 - 200923444 物，以大致垂直方向、大致水平方向或二者間傾斜之方向 移動’一邊於其表面流下接著劑組成物並使擴布之方法。 塗布接著劑組成物後，以夾輥（Nip roll )夾住偏光板或 保護膜使貼合。 爲了提高接著性，於偏光板或保護膜之表面亦可適當 施予等離子（plasma )處理、電暈處理、紫外線照射處理 、火焰（flame )處理、鹼化處理等表面處理。鹼化處理 可例舉如浸漬於氫氧化鈉、氫氧化鉀等鹼之水溶液中的方 法。 將偏光板與保護膜積層後，施予乾燥處理。乾燥處理 可藉由例如噴出熱風而進行，此時之溫度可於40至1〇〇它 ，較佳於60至100 °C之範圍適當加以選擇。乾燥時間一般 爲2 0至1 2 0 0秒。 下文列舉實施例及比較例更詳細說明本發明，惟本發 明並非受限於該等實施例者。例中之含有量或使用量以％ 及份表示，若無特別記述均爲重量基準。 〈實施例1〉 將厚度75 μιη之聚乙烯醇系樹脂膜（平均聚合度： 1 7 0 0，鹼化度：9 9 _ 9莫耳％以上）以延伸倍率5倍施予單 軸延伸，於保持緊張狀態之同時，於含碗及拂化鉀之水溶 液（碘：碘化鉀：水=〇.〇5 : 5 : 100 (重量比））中浸漬 6 0秒。繼之’於含碘化鉀及硼酸之6 5 °C水溶液（碘化鉀 :硼酸：水=2.5 : 7·5 : 1〇〇 (重量比））中浸漬3〇〇秒。 -22- 200923444 以2 5 °C之純水水洗2 0秒後，於5 0 °C乾燥’即可獲得由聚 乙烯醇系樹脂所形成之偏光膜。 將乙醯乙醯基改質聚乙烯醇系樹脂（Gohsefimer-Z100系列，日本化學工業（股）製，鹼化度：98.5莫耳％ 以上）溶解於純水中，調製5 %濃度之水溶液。另外’取 得硝酸氧锆之48%濃度水溶液（Zirconia Sol ZN，日本 第一稀元素化學工業（股）製）。將上述聚乙烯醇系樹脂 水溶液與硝酸氧锆水溶液，與乙醯乙醯基改質聚乙烯醇系 樹脂水溶液與硝酸氧鉻水溶液，以乙醯乙醯基改質聚乙烯 醇系樹脂：硝酸氧锆之固形物重量比成爲1 : 1之方式混 合，再以純水稀釋成對水1 〇 〇份而言，聚乙烯醇系樹脂之 固形物重量比爲1 . 5 0，而調製接著劑組成物。該組成物之 黏度爲 3.5mPa· sec。 於23 °C之氛圍下，於偏光膜之兩面塗布該接著劑組 成物，於其中一面，貼合表面經施予鹼化處理之三乙醯基 纖維素所構成之厚度80μιη的保護膜A，於另一面貼合由 環狀聚烯烴系樹脂延伸而得之厚度7 0 μιη的保護膜B。貼 合後將其於8 0 °C以3 0秒及5分鐘，2種時間進行乾燥而 製作偏光板（接著劑層之厚度：約〇. 1 μηι)。 〈實施例2〉 除了使用以乙醯乙醯基改質聚乙烯醇系樹脂：硝酸氧 鉻=1: 100 (固形物重量比）之比率配合，再以純水稀釋 成對水1 0 0份而言，聚乙烯醇系樹脂之固形物重量比爲 -23- 200923444 0. 1 0，而調製的接著劑組成物之外，與實施例1同樣操作 而製作偏光板。 〈實施例3〉 除了使用以乙醯乙醯基改質聚乙烯醇系樹脂：硝酸氧 锆=1 : 1 (固形物重量比）之比率配合，再以純水稀釋成 對水1〇〇份而言，聚乙烯醇系樹脂之固形物重量比爲0.50 ，而調製的接著劑組成物之外，與實施例1同樣操作而製 作偏光板。 〈實施例4〉 除了使用以乙醯乙醯基改質聚乙烯醇系樹脂：硝酸氧 銷=2 : 1 (固形物重量比）之比率配合，再以純水稀釋成 對水1 〇〇份’聚乙烯醇系樹脂之固形物重量比爲1 . 5 0，而 調製的接著劑組成物之外，與實施例1同樣操作而製作偏 光板。 〈實施例5〉 除了使用以乙醯乙醯基改質聚乙烯醇系樹脂：硝酸氧 锆=3 : 1 (固形物重量比）之比率配合，再以純水稀釋成 對水1 0 0份，聚乙烯醇系樹脂之固形物重量比爲1 . 5 〇，而 調製的接著劑組成物之外，與實施例同樣操作而製作偏光 板0 -24- 200923444 〈實施例6〉 除了使用以乙醯乙醯基改質聚乙烯醇系樹脂：硝酸氧 銷=20:3(固形物重暈比卜卜宠配么 _ r r ^ ^ T J里里CC ) Z比伞配口，再以純水稀釋成 對水1 〇〇份，聚乙烯醇系樹脂之固形物重量比爲丨·5〇 ,而 調製的接著劑組成物之外，與實施例i同樣操作而製作偏 光板。 〈實施例7〉 將經竣基改質之聚乙烯醇系樹脂（Kuraray Poval ([Technical Field] The present invention relates to a polarizing plate in which a protective film is laminated on at least one of the polarizing films formed of a polyvinyl alcohol-based resin, and a method for producing the same. [Prior Art] The polarizing plate is generally formed by laminating at least one surface or both surfaces of a polarizing film formed of a polyvinyl alcohol-based resin which is subjected to dichroic dye adsorption, and a protective film is laminated via an adhesive layer. The polarizing plate is used as a constituent member of the liquid crystal display device, and may be laminated to a liquid crystal cell with an adhesive, if necessary, via another optical film. The liquid crystal display device is required to be used in various environments as its use is expanded. Therefore, a high environmental resistance is required for the components constituting the liquid crystal display device. For example, a portable liquid crystal display device represented by a mobile phone is required to be used even under moist heat, and a polarizing plate used therein is required to have a high degree of resistance to moist heat durability. However, in the conventional polarizing plate, particularly when exposed to a hot and humid environment for a long period of time, the polarizing performance is liable to be lowered, and the interface between the polarizing film and the protective film is easily peeled off. In response to such a problem, it has been proposed to use a thermoplastic cycloolefin resin as a protective film for a polarizing film. For example, Japanese Laid-Open Patent Publication No. Hei-5-2 2 2 8 8 (Patent Document 1) discloses that at least one side of a polyvinyl alcohol-based sheet is an acrylic-based pressure-sensitive adhesive layer laminated thermoplastic saturated norbornene-based resin sheet, and is heated. Press-5-200923444 to create a polarizing plate (composite) technology. However, an acrylic-based adhesive (also referred to as a pressure-sensitive adhesive) has a thickness of 10 to 5 Å μm, and thus the liquid crystal display device has to be thick. Further, an adhesive for a dry laminate, a styrene butadiene rubber-based adhesive, an epoxy-based two-liquid-curing adhesive, or the like contains an organic solvent, and has environmental and industrial health problems. In addition, when such an organic solvent-containing adhesive is used in a polarizing plate manufacturing apparatus that does not use an organic solvent in the past, complicated troubles such as newly-installed explosion-proof equipment and equipment modification are required. Further, a polarizing film interlayer adhesive formed of a polyvinyl alcohol-based resin is known to be bonded to a cycloolefin-based resin film. For example, Japanese Laid-Open Patent Publication No. 2005-7014 (Patent Document 2), JP-A-2000 - 1 8 1 8 1 7 (Patent Document 3) and JP-A-2005-208456 (Patent Document 4) are disclosed as a polarizing film urethane resin formed of a polyvinyl alcohol resin. 'In particular, it is a water-based adhesive containing a polyester-based ionic polymer urethane resin, and a cyclic olefin-based resin film is laminated. According to this, a cycloolefin-based protective film can be directly laminated on the polarizing film formed of the polyvinyl alcohol-based resin by a roll to roll method. Japanese Patent Publication No. Hei 9-318814 (Patent Document 5), Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. It is proposed to use a transparent resin film formed of a cellulose resin typified by triethylenesulfonyl cellulose as a protective film for a polarizing plate, and a polarizing film for bonding the protective film to a polyvinyl alcohol resin. Various adhesives. Here, it is described that the adhesive agent applied between the films is a mixture of a polyvinyl alcohol-based resin containing an ethyl acetonitrile group and a compound having a hydroxy-6 - 200923444 methyl group in a specific mixing ratio, and a compound containing a methylol group. A polarizer having high water resistance can be obtained by adjusting the pH or the binder of the glyoxal resin or the metal alkoxide. Among these, Patent Document 4 discloses a water system in which a polyester-based ionic polymer type urethane resin and a compound having a glycidoxy group are interposed, on one side of a polarizing film formed of a polyvinyl alcohol-based resin. The first adhesive layer is laminated with a cycloolefin-based resin film, and on the other surface, a water-based second adhesive having a composition different from that of the first adhesive is interposed, for example, an aqueous solution of a polyvinyl alcohol-based resin, and a cellulose acetate-based layer is laminated. A film was used to form a polarizing plate. Further, in Patent Document 2 and 3, respectively, in the case of one of the polarizing films formed of the polyvinyl alcohol-based resin, the norbornene resin film of one of the cycloolefin-based resin films is formed on the other side. The fluorene-based cellulose film was bonded to each other with a urethane-based adhesive to prepare a polarizing plate. Japanese Laid-Open Patent Publication No. 2005-3520 No. 1 (Patent Document 8) also discloses a polarizing plate of a cellulose acetate film which is a single-layered layer olefin-based resin film of a polarizing film and an area layer on the opposite side. [Problem to be Solved by the Invention] The object of the present invention is to provide a polarizing plate in which at least one surface of a polarizing film formed of a polyvinyl alcohol-based resin is laminated with a protective film. The adhesive layer is then used to enhance the adhesion between the polarizing film and the protective film and the temperature-resistant polarizing plate. An object of the present invention is to provide a method for producing a polarizing plate in which a polarizing film formed of a polyvinyl alcohol-based resin and a protective film are firmly adhered to each other by using a water which is substantially free of an organic solvent, 200923444, an adhesive. [Means for Solving the Problem] As a result of intensive research on the above-mentioned objects, the present inventors have found that a polarizing plate and a protective film are obtained by using an aqueous mixture containing a specific component as an adhesive for bonding a polarizing film and a protective film. The subsequent step is faster, and a polarizing plate excellent in adhesion after bonding and water resistance can be obtained, and the present invention is achieved. That is, the present invention is as follows. The polarizing plate of the present invention is obtained by disposing a protective film of a polyvinyl alcohol-based adhesive layer on at least one side of a polarizing film formed of a polyvinyl alcohol-based resin, and is characterized in that the adhesive layer is made of polyvinyl alcohol. A resin and an oxygen barrier salt, and a solid content ratio of the polyvinyl alcohol resin to the oxygen salt salt is formed by an adhesive composition of 100:10 to 100,000. In the polarizing plate of the present invention, the polyvinyl alcohol-based resin contained in the adhesive composition is a polyvinyl alcohol-based resin modified from an ethylene sulfonate group, a cationically modified polyvinyl alcohol-based resin, and a At least one of the anion-modified polyvinyl alcohol-based resins is preferred. In the polarizing plate of the present invention, the oxyzirconium salt contained in the adhesive composition is preferably at least one selected from the group consisting of a Ziconium oxynitrate and an oxyhydrin pin. In the polarizing plate of the present invention, the protective film is preferably composed of a cellulose acetate resin or a cycloaliphatic resin, and a protective film composed of a cellulose acetate resin in one area of the polarizing film, and a polarizing film. The other layer -8-200923444 is preferably a protective film composed of a cycloolefin resin. The present invention provides at least one side of a polarizing film formed of a polyvinyl alcohol-based resin, which comprises a polyvinyl alcohol-based resin and an oxygen-sodium salt, and a solid-weight ratio of the polyvinyl alcohol-based resin to the oxychromium salt is 100: A method for producing a polarizing plate comprising a laminate composition of 10 to 100,000 and a protective film. In the method for producing a polarizing plate of the present invention, the polyvinyl alcohol-based resin contained in the adhesive composition is a polyethylene modified by a polyvinyl alcohol-based resin modified by an ethylene sulfonate group. At least one of an alcohol resin and an anionically modified polyvinyl alcohol resin is preferred. In the method for producing a polarizing plate of the present invention, the oxyzirconium salt contained in the adhesive composition is preferably obtained from at least one selected from the group consisting of a nitric oxide pin and a zirconyl acetate. According to the present invention, a polarizing film can be produced. The protective film is superior in adhesion, and the temperature-resistant water is far superior to the polarizing plate of the prior art. According to the present invention, since the organic solvent is not required when manufacturing the polarizing plate, it is superior in terms of environment, safety, and hygiene, and can be manufactured by using the same equipment as the polarizing plate which has been conventionally made of a protective film/polarizing film, without further investment. Large equipment. [Embodiment] The best mode for carrying out the invention The polarizing plate of the present invention basically comprises at least one side of a polarizing film formed of a polyvinyl alcohol-based resin, which is protected by a layer of a polyvinyl alcohol-based adhesive layer. 200923444 The film is composed. The respective configurations of the polarizing plate of the present invention will be described in detail below. <Polarizing film> The polyvinyl alcohol-based resin constituting the polarizing film is obtained by testing a polyvinyl acetate-based resin. The polyvinyl acetate-based resin may be, for example, a copolymer of vinyl acetate and another monomer copolymerizable therewith, in addition to the polyvinyl acetate of the vinyl acetate. Other monomers which can be copolymerized with vinyl acetate may, for example, be unsaturated carboxylic acids, unsaturated sulfonic acids, olefins, vinyl ethers, acrylamides having an ammonium group, and the like. The degree of alkalinity of the polyvinyl alcohol-based resin is generally from 85 to 1 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be further modified, for example, a polyethylene polymer or a polyvinyl acetal which is modified with an aldehyde. Further, the average degree of polymerization of the polyvinyl alcohol-based resin constituting the polarizing film is generally from 10 to 10,000, preferably from 1,500 to 5,000. A film-formed product (polyvinyl alcohol-based resin film) obtained by forming the above polyvinyl alcohol-based resin can be used as a raw material film of a polarizing film. The method of forming the film of the polyvinyl alcohol-based resin is not particularly limited, and a film can be formed by a known method. The film thickness of the polyvinyl alcohol-based resin film is not particularly limited, and for example, a polarizing film of from 1 Å to 10.5 μm is generally produced by the following steps: a step of stretching the polyvinyl alcohol-based resin film by one axis, The polyvinyl alcohol-based resin film is dyed with a dichroic dye to adsorb a dichroic dye, the polyvinyl alcohol-based resin film having a dichroic dye is treated with a boric acid aqueous solution, and the boric acid aqueous solution is treated. After the step of washing. -10- 200923444 One-axis extension can be carried out before dyeing, or can be carried out simultaneously during dyeing, or after dyeing. When the one-axis extension is performed after dyeing, the one-axis extension can be carried out before the boric acid treatment, and can also be carried out in the boric acid treatment. Of course, one-axis extension can also be performed in these multiple stages. One-axis extension can be extended on one axis between rolls having different circumferential speeds. It can also be extended on one axis using a heat roller. Further, it may be a dry stretching such as stretching in the atmosphere, or may be a wet stretching in which a solvent is stretched in a swollen state. The stretching ratio is generally 3 to 8 times. The polyvinyl alcohol-based resin film is dyed with a dichroic dye. For example, the polyvinyl alcohol-based resin film can be immersed in an aqueous solution containing a dichroic dye. Specifically, an iodine or a dichroic dye can be used as the dichroic dye. The polyvinyl alcohol-based resin film is preferably subjected to an immersion treatment with water before the dyeing treatment. When iodine is used as the dichroic dye, a method in which a polyvinyl alcohol-based resin film is immersed in an aqueous solution containing iodine and potassium iodide for dyeing is generally used. In the aqueous solution, the iodine content is usually 0.01 to 1 part by weight per 100 parts by weight of water, and the potassium iodide content is usually 0.5 to 20 parts by weight per 100 parts by weight of water. The temperature of the aqueous solution for dyeing is generally from 20 to 40. (: The immersion time (dyeing time) of the aqueous solution is generally 20 to 180 seconds. On the one hand, when a dichroic dye is used as the dichroic dye, the polyvinyl alcohol resin film is generally impregnated in the containing a method of dyeing in an aqueous solution of a water-soluble dichroic dye. In the aqueous solution, the content of the dichroic dye is generally 1χ1〇-4 to 10 parts by weight per 1 part by weight of water, and is 1χ1 (Γ3 to 1 part by weight is preferred. The aqueous solution may also contain an inorganic salt such as sodium sulfate as -11 - 200923444 as a dyeing aid. The temperature of the dye aqueous solution for dyeing is generally 20 to 8 〇 ° C, and the immersion time of the aqueous solution (Dyeing time) is generally from 1 Torr to 1880 seconds. Boric acid treatment after dyeing with dichroic dye is carried out by immersing the dyed polyvinyl alcohol-based resin in an aqueous solution containing boric acid. In the aqueous solution, the content of boric acid is generally 2 to 15 parts by weight, preferably 5 to 12 parts by weight per 100 parts by weight of water. When iodine is used as the dichroic dye, the aqueous solution containing boric acid contains potassium iodide. Better. Containing boric acid In the aqueous solution, the content of potassium iodide is generally 0.1 to 15 parts by weight, preferably 5 to 12 parts by weight per 1 part by weight of water, and the immersion time for the aqueous solution containing boric acid is generally 60 to 1 200 seconds to 150. It is preferably 6 seconds, more preferably 200 to 400 seconds. The temperature of the aqueous solution containing boric acid is generally 50 ° C or higher, preferably 50 to 85 ° C, and 60 to 80 ° C is better after boric acid treatment. The polyvinyl alcohol-based resin film is generally subjected to a water washing treatment, and the water-washing treatment is carried out, for example, by immersing the polyvinyl alcohol-based resin film treated with an aqueous solution of boric acid in water, and the water temperature of the water washing treatment is generally 5 to 40 ° C. The immersion time is generally 1 to 12 sec. After the washing, the drying treatment is performed to obtain a polarizing film. The drying treatment is generally carried out using a hot air dryer or a far infrared ray heater, and the drying treatment temperature is generally 30 to 100 ° C to 50. It is preferably at 80 ° C. The drying treatment time is generally 60 to 600 seconds, preferably 120 to 600 seconds. In this operation, the polyvinyl alcohol-based resin film is subjected to a one-axis extension, and the two--12-200923444 coloring pigment Dyeing and boric acid treatment The thickness of the polarizing film is generally in the range of 5 to 40 μm, preferably in the range of 10 to 35 μm. <Adhesive layer> The polarizing plate of the present invention is characterized in that it is interposed in the polarizing film and the laminate. The adhesive layer between the protective film on at least one side of the polarizing film is made of a polyvinyl alcohol-based resin and an oxygen chromium salt, and the solid weight ratio of the polyvinyl alcohol-based resin to the oxygen-sodium salt is 100: 10 The adhesive composition of the present invention is formed by the adhesive composition of the present invention. The adhesive layer of the present invention does not cause environmental and worker health problems, and is a water-based adhesive composition substantially free of an organic solvent. The adhesive layer formed is a material in which the polarizing film formed of the polyvinyl alcohol-based resin and the protective film are firmly adhered to each other. In the polyvinyl alcohol-based resin contained in the adhesive composition for forming the adhesive layer in the present invention, the polyvinyl acetate-based resin can be alkalized in the same manner as the polyvinyl alcohol-based resin used for the polarizing film. The obtained polyvinyl acetate-based resin may be, for example, a copolymer of vinyl acetate and another monomer copolymerizable therewith, in addition to the polyvinyl acetate of the vinyl acetate. The other monomer copolymerized with the vinyl acetate may, for example, be an unsaturated carboxylic acid, an unsaturated sulfonic acid, an olefin, a vinyl ether or a acrylamide having an ammonium group. The polyvinyl alcohol-based resin contained in such an adhesive composition preferably has a suitable degree of polymerization, for example, an aqueous solution having a concentration of 4% by weight, preferably in a range of 4 to 50 mPa·sec, and 6 to 30 mPa. Better in the sec range. -13- 200923444 The degree of alkalinity of the polyvinyl alcohol-based resin contained in the adhesive composition for the adhesive layer in the polarizing plate of the present invention is not particularly limited, and is preferably 7 4 mol% or more. More than the ear is better. When the degree of alkalization of the polyvinyl alcohol-based resin contained in the composition of the second embodiment is low, the adhesion tends to be insufficient. The polyvinyl alcohol-based resin contained in the subsequent composition is preferably a modified one. Preferred examples of such a modified polyvinyl alcohol-based resin include a polyvinyl alcohol-based resin selected from the group consisting of ethylene sulfonate-modified, a cationically modified polyvinyl alcohol-based resin, and an anion-modified polyethylene. At least one of an alcohol resin. When such a modified polyvinyl alcohol-based resin is used, it is advantageous in that it has an advantage of improving the water resistance of the adhesive layer. The adhesive composition used for the adhesive layer in the polarizing plate of the present invention may of course contain two or more kinds of the modified polyvinyl alcohol-based resins, and may also contain unmodified polyvinyl alcohol-based resin. (specifically, all or part of the alkalinity of polyvinyl acetate) and the above modified polyvinyl alcohol-based resin. As the above-mentioned adhesive composition, a commercially available polyvinyl alcohol-based resin can be suitably used, specifically, 'Gohsefimer-Z series, WO-239 (above 'Nippon Synthetic Chemical Industry Co., Ltd.), PVA-403, PVA-105, KL-318, KL-506, KM-118, KM-618, C-506 (above, Kuraray). The concentration of the above polyvinyl alcohol-based resin in the adhesive composition used in the present invention is not particularly limited, but is preferably in the range of 1 to 10 parts by weight, and in the range of 1 to 5 parts by weight, based on 100 parts by weight of water. good. When the concentration of the polyvinyl alcohol-based resin is less than 1 part by weight to 10 parts by weight of water, the adhesiveness tends to decrease from -14 to 200923444, and if the concentration of the polyvinyl alcohol-based resin exceeds 100 parts by weight of water, When the amount is 0 parts by weight, the optical characteristics of the obtained polarizing plate tend to be lowered. The water used in the adhesive composition of the present invention may be pure water, ultrapure water, tap water or the like, and is not particularly limited, but in terms of the preferable uniformity of the formed adhesive layer and the viewpoint of maintaining transparency It is better to use pure water or ultrapure water. The adhesive composition used in the present invention may contain an oxygen chromium salt in addition to the above polyvinyl alcohol-based resin. Here, "oxyzirconium salt" means a salt containing a positive divalent group (also referred to as zirconium oxide) represented by ZrO, such as zirconyl nitrate (Zr0(N03)2), zirconyl acetate (Zr0 (C2H302)) 2), chromium oxychloride (ZrOCl2), oxysulfate (ZrOS〇4), oxycarbonate (Zr0C03), zirconium oxycarbonate ((NH4) 2ZrO (C03) 2 ), octanoate (Zr0 (C8H15 02) 2) Zirconium hydroxide (ZrO(OH)2), oxyhydroxide (ZrO(OH)C1), potassium carbonate (K2[ZrO(C〇3)2)). Among these, at least one selected from the group consisting of zirconyl nitrate and zirconyl acetate is preferred from the viewpoints of adhesion, adhesion speed, and water resistance. Commercially available products such as Zirconia Sol ZN (ZrO (N03) 2 · nH20 ), Zirconia Sol AC-7 ((NH4 ) 2ZrO (C03 ) 2), zirconium oxychloride, Zirconia Sol ZC (ZrOC12) can be suitably used. ), Zirconia Sol ZC-2 (ZrO (OH) Cl. nH20), Sulfuric Acid Oxygen, Zirconia Sol ZA (ZrO (C2H3O2) 2), Zirconia Sol ZA-30, Zirconia Sol ZA-20 ' Zirconia Sol ZK Potassium)-i〇-15 - 200923444, chromic oxychromate, zirconyl carbonate, zirconium hydroxide, R chrome hydroxide, NN chrome hydroxide (all of which are made by Japan's first rare element chemical industry) )Wait. The adhesive composition used in the present invention is a solid weight ratio of the above polyvinyl alcohol-based resin to the oxygen-salt salt of from 100:10 to 10,000. When the weight ratio of the solid content of the oxyzirconium salt is less than 10 to the polyvinyl alcohol-based resin 100, it is difficult to sufficiently express the water resistance, and the solid content of the oxygen-salt salt is compared with the polyvinyl alcohol-based resin 100. When the weight ratio exceeds 1,000,000, the optical characteristics of the obtained polarizing plate are lowered, and when an acidic oxygen salt such as a nitric oxide pin is used, the metal corrosion property is high due to the low pH. From the viewpoint of water resistance and optical properties, the weight ratio of the polyvinyl alcohol-based resin to the oxonium salt in the adhesive composition used in the present invention is preferably from 100:50 to 1 Torr. A particularly preferable combination of the above polyvinyl alcohol-based resin and an oxonium salt is, for example, a Gohsefimer Z-100 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) as a polyvinyl alcohol-based resin, and a Zirconia Sol ZN (Japan's first rare). Elemental Chemical Industry Co., Ltd.) as a zirconia salt; using Gohsefimer Z-2 00 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) as a polyvinyl alcohol resin, using Zirconia Sol ZA-20 (Japan's first rare element) Chemical Industry Co., Ltd.) as a zirconium oxychloride salt; KL3 18 (manufactured by Kuraray Co., Ltd.) is used as a polyvinyl alcohol resin, and Zirconia Sol A C-7 (Japan's first rare element chemical industry) ))) as a case of oxyzirconium salt. By such a combination, the pot life of the adhesive composition is prolonged, and the adhesion and water resistance are improved. -16- 200923444 The thickness of the adhesive layer of the present invention is not particularly limited, and is generally 0.001 to 5 μm, preferably 0.01 to 2 μηη, and more preferably 0.05 to Ιμηη. When the thickness of the adhesive layer exceeds 5 μm, the appearance of the polarizing plate tends to be poor. The adhesive layer of the present invention may be used in the above-mentioned adhesive composition, and a conventional agent such as a crosslinking agent, a plasticizer, a decane coupling agent, an antistatic agent, or a fine particle may be added to the extent that the effects of the present invention are not impaired. Formed with appropriate additives. <Protective film> The polarizing plate of the present invention is formed by laminating at least one surface of the polarizing film and interposing the protective film on the adhesive layer. For the protective film of the polarizing plate of the present invention, for example, a cellulose acetate resin, a cycloolefin resin, a polyolefin resin, an acrylic resin, a polyimide resin, a polycarbonate resin, a polyester resin, or the like can be used. The field is widely used as a protective film made of a suitable material for a protective film forming material, and is not particularly limited. From the viewpoint of mass productivity and adhesion, it is preferable to provide a protective film composed of a cellulose acetate resin or a cycloolefin resin. Moreover, the polarizing plate of the present invention can be formed as a protective film made of a cellulose acetate resin in a single-area layer on the side of the polarizing film, from the viewpoint of easiness and optical characteristics of the surface treatment layer. The structure of the protective film composed of a ring-diffuse-type resin in the single-area layer on the other side of the polarizing film. The cycloolefin-based resin which can be used in the protective film of the present invention is, for example, a thermoplastic resin having a monomer unit of a cyclic olefin (cycloaliphatic hydrocarbon) having a norbornene or a polycyclic norbornene-based monomer ( Also known as thermoplastic cyclic hydrocarbon-17-200923444 resin). The cycloolefin resin may be a ring-opening polymer of the above cyclic olefin, or a hydrogenated product of a ring-opening copolymer using two or more kinds of cyclic olefins, and may be a cyclic olefin, a chain olefin, or an aromatic compound having a vinyl group. Addition polymer. Also, it is effective to introduce a polar base. When a copolymer of a cyclic olefin and a chain olefin or a copolymer of a vinyl compound is used to form a protective film, the 'chain olefin may, for example, be ethylene, propylene or the like.' The aromatic compound having a vinyl group may, for example, be 'styrene, Α-methylstyrene, aryl substituted styrene, and the like. The monomer unit formed from the cycloolefin in the copolymer may be 50 mol% or less (preferably 15 to 50 mol%). In particular, when a protective film is formed using a cyclic olefin and a terpolymer of a chain olefin and an aromatic compound having a vinyl group, the monomer unit derived from the cyclic olefin may be less than the above amount. In the terpolymer, the monomer unit formed by the chain olefin is generally 5 to 80 mol%, and the monomer monoterpene formed by the aromatic compound having a vinyl group is generally 5 to 80 mol. ear%. As the cycloolefin resin, a commercially available product such as TP〇as (manufactured by Ticona Co., Ltd.), ART0N (manufactured by JSR Co., Ltd.), ZEONOR (manufactured by Nippon Co., Ltd.), and quaternary euro can be suitably used. Nie Si (ΖΕΟΝΕΧ) (Japanese ΖΕΟΝ (share) system), Ap e 11 e (Japan Mitsui Chemical Co., Ltd.) and so on. When the film of the cycloolefin resin is formed into a film, a known method such as a solvent casting method or a melt extrusion method can be suitably used. In addition, it is also possible to use, for example, a ring of pre-formed films such as Espresso (produced by Japan Sekisui Chemical Co., Ltd.), SCA40 (made by Nippon Sekisui Chemical Co., Ltd.), and Zeonorfilm (made by OPTES). A commercially available product of a film made of an olefin resin is used as a protective film. -18- 200923444 A protective film composed of a cycloolefin resin may be one-axis extension or biaxial extension. The stretching ratio of this case is generally 1.1 to 5 times, preferably 1.1 to 3 times. The cellulose acetate-based resin suitably used in the protective film of the present invention may, for example, be a cellulose partially or wholly acetated product, for example, a triethylenesulfonyl cellulose film or a diethyl cellulose film. For the cellulose acetate-based resin, a commercially available product such as FUJITAC TD80 (Fuji Photo Film) or Fujitec TD80UF (Fuji Film Co., Ltd.) can be suitably used. A film made of a cellulose acetate resin such as Fujitec TD80UZ (made by Fujifilm Co., Ltd.), KC8UX2M (made by Konica Minolta Opt Co., Ltd.), or KC8UY (made by Konica Minolta Opt Co., Ltd.). The protective film used in the polarizing plate of the present invention preferably has a smaller thickness, but if it is too thin, the strength is lowered, the workability tends to be deteriorated, and if it is too thick, the transparency is lowered, and the weight of the polarizing plate is lowered. There is a tendency to increase. In this regard, the thickness of the protective film used in the polarizing plate of the present invention is generally 5 to 200 μm in the case of using a protective film composed of a cycloolefin resin, preferably 10 to 150 μm, and more preferably 20 to ΙΟΟμπι. Further, in the case of using a protective film composed of a cellulose acetate resin, it is generally 20 to 200 μm, preferably 30 to 150 μm, and more preferably 40 to ΙΟΟμπ. The protective film in the polarizing plate of the present invention may be subjected to surface treatment such as antiglare treatment, hard coat treatment, antistatic treatment, and antireflection treatment on the surface on the opposite side and the opposite side of the polarizing film. Further, a coating layer made of a liquid crystal compound, a high molecular weight compound of -19-200923444, or the like may be formed on the surface of the protective film which is bonded to the surface of the polarizing film and the surface on the opposite side. In the protective film of the polarizing plate of the present invention, the surface of the polarizing film and the surface opposite to the polarizing film may be interposed with an adhesive layer to bond the optical functional film. Adhesive refers to an elastomer that can be removed from the surface of another substance by merely pressing it, and the elastic body can be removed with almost no trace as long as the object has strength. The case of a pressure-sensitive adhesive. The optically functional film may, for example, be a directional optical compensation film coated with a liquid crystal compound on the surface of a substrate, a reflective polarized separation film that transmits a polarized light and reflects a polarized light having an opposite property, and is made of a polycarbonate resin. a retardation film made of a retardation film, a retardation film made of a cyclic polyolefin resin, a film having an anti-glare function having a concave-convex shape on the surface, a film subjected to surface anti-reflection treatment, a reflection film having a reflection function on the surface, and Semi-transmissive reflective film with reflective function and transmission function. A directional optical compensation film which is coated with a liquid crystal compound on the surface of the substrate, and a commercially available product such as a WV film (manufactured by Fujifilm Co., Ltd.), an NH film (manufactured by Shin Sakamoto Co., Ltd.), and NR are used. Membrane (Nippon Oil Co., Ltd.) and the like. In addition, a commercially available product of a reflective polarizing separation film which exhibits a polarized light having a reversed nature and which is reflected by a polarized light is exemplified by DBEF (manufactured by Sumitomo 3M Co., Ltd.). In addition, a commercially available product of a retardation film made of a cyclic polyolefin resin, for example, ART ON (JSR (share) system), Ai Siyan (Japan Sekisui Chemical Industry Co., Ltd.) ), Zeonorfilm (OPTES (share) system) and so on. -20-200923444 <Method for Producing Polarizing Plate> The present invention also provides a method for producing a polarizing plate which is based on at least one side of a polarizing film formed of a polyvinyl alcohol-based resin, and contains a polyvinyl alcohol-based resin and an oxygen oxime. A method of producing a polarizing plate by laminating a protective film with a weight ratio of a solid content of a salt-polyvinyl alcohol-based resin and an oxygen-selling salt of from 1 to 10:1 to 0. The method for producing the polarizing plate of the present invention is not particularly limited. It is not limited to the manufacturer of the polarizing plate according to the present invention. The present invention can be suitably produced according to the method for producing a polarizing plate of the present invention. In the method for producing a polarizing plate, first, the polyvinyl alcohol-based resin and the oxychromic salt are blended in water in a specific weight ratio in a specific range to prepare an adhesive composition. At this time, the viscosity of the adhesive composition can be adjusted by the amount of the polyvinyl alcohol-based resin. In the method for producing a polarizing plate of the present invention, as described above, the polyvinyl alcohol-based resin contained in the adhesive composition is cation-modified by a polyvinyl alcohol-based resin selected from the group consisting of ethylene sulfonate-modified. At least one of a polyvinyl alcohol-based resin and an anion-modified polyvinyl alcohol-based resin is preferred. Further, the oxyzirconium salt contained in the adhesive composition is preferably at least one selected from the group consisting of zirconyl nitrate and an oxyhydrin pin. The bonding of the polarizing film and the protective film using such an adhesive composition can be carried out by a suitable method, and examples thereof include a casting method, a Meyer Bar coating method, and a gravure coating. A method in which a binder composition, a die coating method, a dipping method, a spray method, or the like is applied to the adhesive film and/or the adhesive film, and the adhesive composition is applied to the adhesive film. The casting method refers to a method in which a polarizing plate or a protective film or the like is coated in a direction of a substantially vertical direction, a substantially horizontal direction, or a direction in which the polarizing plate or the protective film is applied, and the adhesive composition is spread on the surface thereof and spread. The method. After the adhesive composition was applied, the polarizing plate or the protective film was sandwiched by a Nip roll to bond. In order to improve the adhesion, surface treatment such as plasma treatment, corona treatment, ultraviolet irradiation treatment, flame treatment, or alkalization treatment may be appropriately applied to the surface of the polarizing plate or the protective film. The alkalization treatment may, for example, be a method of immersing in an aqueous solution of a base such as sodium hydroxide or potassium hydroxide. After the polarizing plate and the protective film are laminated, the drying treatment is applied. The drying treatment can be carried out, for example, by spraying hot air, and the temperature can be appropriately selected in the range of 40 to 1 Torr, preferably 60 to 100 °C. The drying time is generally from 20 to 1,200 seconds. The invention is illustrated in more detail in the following examples and comparative examples, but the invention is not limited by the examples. The content or the amount used in the examples are expressed in % and parts, and unless otherwise stated, they are all based on the weight basis. <Example 1> A polyvinyl alcohol-based resin film having a thickness of 75 μm (average degree of polymerization: 17,000, degree of alkalinity: 9 9 -9 mol% or more) was uniaxially stretched at a stretching ratio of 5 times. While maintaining the tension, it was immersed in an aqueous solution containing potassium and potassium telluride (iodine: potassium iodide: water = 〇. 〇 5 : 5 : 100 (weight ratio)) for 60 seconds. Subsequently, it was immersed in an aqueous solution of potassium iodide and boric acid at 65 ° C (potassium iodide: boric acid: water = 2.5: 7.5 : 1 Torr (weight ratio)) for 3 sec. -22- 200923444 After washing with pure water at 25 °C for 20 seconds, it is dried at 50 °C to obtain a polarizing film formed of a polyvinyl alcohol-based resin. Ethyl acetonitrile-modified polyvinyl alcohol-based resin (Gohsefimer-Z100 series, manufactured by Nippon Chemical Industry Co., Ltd., alkalinity: 98.5 mol% or more) was dissolved in pure water to prepare an aqueous solution having a concentration of 5%. Further, a 48% aqueous solution of zirconyl nitrate (Zirconia Sol ZN, manufactured by Japan First Least Element Chemical Industry Co., Ltd.) was obtained. The polyvinyl alcohol-based resin aqueous solution and the aqueous solution of zirconium nitrate and the aqueous solution of the modified polyvinyl alcohol-based resin and the aqueous solution of chromium nitrate are modified with an ethylene glycol-based polyvinyl alcohol resin: oxygen nitrate. The zirconium solids are mixed in a weight ratio of 1:1, and then diluted with pure water to a water content of 1 part by weight. The solid weight ratio of the polyvinyl alcohol-based resin is 1.50, and the composition of the adhesive is adjusted. Things. The composition had a viscosity of 3.5 mPa·sec. Applying the adhesive composition on both sides of the polarizing film in an atmosphere of 23 ° C, and bonding a protective film A having a thickness of 80 μm composed of triethyl fluorenated cellulose having an alkalized treatment on one surface thereof, On the other surface, a protective film B having a thickness of 70 μm stretched from a cyclic polyolefin resin was bonded. After bonding, it was dried at 80 ° C for 30 seconds and 5 minutes for 2 hours to prepare a polarizing plate (thickness of the adhesive layer: about 1. 1 μηι). <Example 2> In addition to the use of an ethylene ethoxylate-modified polyvinyl alcohol-based resin: chromium oxynitride = 1:100 (solids weight ratio), and then diluted with pure water to 100 parts of water In the same manner as in Example 1, except that the weight ratio of the solid content of the polyvinyl alcohol-based resin was -23 to 200923444 to 0.10, a polarizing plate was produced in the same manner as in Example 1. <Example 3> In addition to the use of a modified polyvinyl alcohol-based resin: zirconia nitrate = 1: 1 (solids weight ratio), it was diluted with pure water to a ratio of 1 part by weight to water. In the same manner as in Example 1, except that the weight ratio of the solid content of the polyvinyl alcohol-based resin was 0.50, a polarizing plate was produced in the same manner as in Example 1. <Example 4> In addition to the use of a modified polyvinyl alcohol-based resin: oxynitride pin = 2:1 (solids weight ratio), it was diluted with pure water to a ratio of 1 part by weight. A polarizing plate was produced in the same manner as in Example 1 except that the weight ratio of the solid content of the polyvinyl alcohol-based resin was 1.50, and the composition of the adhesive was prepared. <Example 5> In addition to the use of an ethylene ethoxylate-modified polyvinyl alcohol-based resin: zirconyl nitrate = 3:1 (solids weight ratio), and then diluted with pure water to 100 parts of water The weight ratio of the solid content of the polyvinyl alcohol-based resin was 1.5 〇, and the polarizing plate was produced in the same manner as in the example except the prepared adhesive composition. 0 - 24 - 200923444 <Example 6> Except that the use of B醯 醯 改 改 改 聚乙烯 聚乙烯 : : : : : 硝酸 硝酸 = = = = = = = = = = 硝酸 硝酸 硝酸 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 A polarizing plate was produced in the same manner as in Example i except that the weight ratio of the solid content of the polyvinyl alcohol-based resin was 丨·5 〇, and the composition of the adhesive was adjusted. <Example 7> A thiol-modified polyvinyl alcohol-based resin (Kuraray Poval (
Polyvinyl Alcohol，P0VAL) KL 318 (股）Kuraray 製’鹼 化度：8 5 - 9 G莫耳。以上）溶解於純水中，調製5 %濃度之 水溶液。另外’取得碳酸氧锆銨之1 3 %濃度水溶液（ Zircoma Sol AC-7’日本第一稀元素化學工業（股）製 )。將上述之聚乙烯醇系樹脂水溶液與碳酸氧锆銨水溶液 ’以乙醯乙醯基改質聚乙烯醇系樹脂：碳酸氧锆銨之固形 物重量比成爲1: 1之方式混合，再以純水稀釋成對水100 份’聚乙烯醇系樹脂之固形物重量比爲1.50，而調製接著 劑組成物。該組成物之黏度爲4.5 mP a · sec。除使用該接 著劑組成物之外’與實施例1同樣操作而製作偏光板。 〈實施例8〉 除了使用以羧基改質聚乙烯醇系樹脂：碳酸氧锆銨=1 :1 0 0 (固形物重量比）之比率配合，再以純水稀釋成對 水1〇〇份’聚乙烯醇系樹脂之固形物重量比爲0.10，而調 -25- 200923444 製的接著劑組成物之外，與實施例7同樣操作而製作偏光 板。 〈實施例9〉 取得氫氧化氯氧锆之49%濃度水溶液（Zirconia Sol ZC-2，曰本第一稀元素化學工業（股）製）。將該氫氧化 氯氧锆之49%水溶液，與實施例1調製之乙醯乙醯基改質 聚乙烯醇系樹脂（〇〇)136：{'丨11^]"-2100)之5%水溶液，以乙 醯乙醯基改質聚乙烯醇系樹脂：氫氧化氯氧錆之固形物重 量比成爲1 : 1之方式配合，再以純水稀釋成對水1 〇〇份 ，聚乙烯醇系樹脂之固形物重量比爲1 . 5 0，而調製接著劑 組成物。該組成物之黏度爲3.5mPa· sec。除使用該接著 劑組成物之外，與實施例1同樣操作而製作偏光板。 〈實施例1 0〉 除了使用以乙醯乙醯基改質聚乙烯醇系樹脂：氫氧化 氯氧锆=1 : 1 00 (固形物重量比）之比率配合，再以純水 稀釋成對水1 00份，聚乙烯醇系樹脂之固形物重量比爲 〇 · 1 〇，而調製的接著劑組成物之外，與實施例9同樣操作 而製作偏光板。 〈實施例11〉 取得乙酸氧锆之20%濃度水溶液（Zirconia Sol ZA- 20，日本第一稀元素化學工業（股）製）。將該乙酸氧锆 -26- 200923444 之20 %水溶液，與實施例1調製之乙醯乙醯 醇系樹脂（〇〇1^6^11^1'-2100)之5%水溶液 基改質聚乙烯醇系樹脂：乙酸氧锆之固形物 :1之方式配合’調製接著劑組成物。該組 3.5mPa · sec。除使用該接著劑組成物之外 同樣操作而製作偏光板。 〈實施例1 2 > 除了使用以乙醯乙醯基改質聚乙烯醇系 锆=1: 100(固形物重量比）之比率配合， 成對水100份，聚乙烯醇系樹脂之固形物重 而調製的接著劑組成物之外，與實施例11 作偏光板。 〈比較例1〉 除了使用以乙醯乙醯基改質聚乙烯醇系 锆=20 : 1 (固形物重量比），再以純水稀釋j ，聚乙烯醇系樹脂之固形物重量比爲1.50, 劑組成物之外，與實施例1同樣操作而製作1 〈比較例2〉 除了使用以羧基改質聚乙烯醇系樹脂 =20 ·· 1 (固形物重量比），再以純水稀釋成 聚乙烯醇系樹脂之固形物重量比爲1 .50，而 基改質聚乙烯 ，以乙醯乙醯 重量比成爲1 成物之黏度爲 ，與實施例1 樹脂：乙酸氧 再以純水稀釋 量比爲0.1 0， 同樣操作而製 樹脂：氧硝酸 或對水1 0 0份 而調製的接著 扁光板。 :碳酸氧鉻銨 討水100份， 調製的接著劑 -27- 200923444 組成物之外’與實施例7同樣操作而製作偏光板。 〈比較例3〉 依據日本特開平9-3 18814號公報（專利文獻5 )實施 例2之記載’首先於溶解槽內，將聚乙烯醇系樹脂（ Gohsenol AH17，日本化學工業（股）製，鹼化度：97_ 98.5莫耳％ ) 1〇〇份溶解於水1 900份中，調製聚乙烯醇系 樹脂之水溶液。繼之，以使四-正丙醇锆：乙醯丙酮=1: 2 (莫耳比）之比例，將四-正丙醇锆添加至乙醯丙酮中後 ，由於生成沉澱，僅取其上清液3份，於攪拌下滴加至上 述聚乙烯醇系樹脂之水溶液中，於室溫（23 °C )混合1小 時，而調製接著劑組成物。除了使用如此調製之接著劑組 成物之外，與實施例1同樣操作而製作偏光板。 〈比較例4〉 將乙醯乙醯基改質聚乙烯醇系樹脂（Gohsefimer Z· 200，日本合成化學工業（股）製，鹼化度：99莫耳％以 上）2.88份與羥甲基三聚氰胺1·24份（對聚乙烯醇系樹 脂100份，羥甲基三聚氰胺爲43份）於3 0°C之溫度條件 下，溶解於純水1 0 0份中，調製接著劑組成物。除了使用 該接著劑組成物之外’與實施例1同樣操作而製作偏光板 〈比較例5〉 -28- 200923444 除了使用將乙醯乙醯基改質聚乙烯醇系樹脂之量改爲 3.03份，羥甲基三聚氰胺之量改爲1.15份（對聚乙烯醇 系樹脂100份，羥甲基三聚氰胺爲36份）而調製的接著 劑組成物之外，與比較例4同樣操作而製作偏光板。 〈比較例6〉 將乙醯乙醯基改質聚乙烯醇系樹脂（Gohsefimer Z-200) 3·00份與羥甲基三聚氰胺1.05份（對聚乙烯醇系樹 脂100份，羥甲基三聚氰胺爲35份）於30°C之溫度條件 下，溶解於純水1 00份，於其中添加0.4%乙酸調製成 pH4.0之水溶液，除了使用該水溶液作爲接著劑組成物以 外，與比較例4同樣操作而製作偏光板。 〈比較例7〉 將乙醯乙醯基改質聚乙嫌醇系樹脂（Gohsefimer Z-200 ) 3.00份與羥甲基三聚氰胺1.05份（對聚乙烯醇系樹 脂100份，羥甲基三聚氰胺35份）於30 °c之溫度條件下 ，溶解於純水100份，於其中添加0.4%乙酸調製成PH3.0 之水溶液，除了使用該水溶液作爲接著劑組成物以外，與 比較例4同樣操作而製作偏光板。 〈比較例8〉 除了使用於毎1 00份純水分別含有聚乙烯醇系樹脂（ Kuraray Poval 117H，Kuraray (股）製，鹼化度：99.3 莫 -29- 200923444 耳％以上）2份與乙醯乙醯基改質聚乙烯醇系樹 Gohsenol Z100’日本化學工業（股）製，鹼化度： 莫耳％以上）2份之水溶液中，添加乙二醛〇. 4份（ 乙烯醇系樹脂及乙醯乙醯基改質聚乙烯醇系樹脂合 1 〇〇份，其量爲1 〇份）而調製的接著劑組成物之外， 施例1同樣操作而製作偏光板。 〈比較例9〉 除了使用將乙二醛之添加量改爲0.8份（對聚乙 系樹脂及乙醯乙醯基改質聚乙烯醇系樹脂合計每100 其量爲2 0份）而調製的接著劑組成物之外，與比較 同樣操作而製作偏光板。 〈評估試驗〉 對由實施例1至12、比較例1至9所分別得到的 板，進行下列評估試驗。結果示於表1。 脂（ 98.5 對聚 計每 與實 烯醇 份， 例8 偏光 •30- 200923444 總侵蝕長度（μ m) 乾燥5分 〇 350 450 450 850 350 300 580 750 〇 00 1500 1900 接著劑層溶解 1600 2500 1200 1300 1000 〇 00 乾燥30秒 I-— 400 380 450 450 600 1050 500 〇 450 450 〇 00 950 2200 2000 接著劑層溶解 接著劑層溶解 接著劑層溶解 接著劑層溶解 接著劑層溶解 1100 950 接著性 乾燥5分 < < < < < < < < < < < < < C U < < 〇 <3 < 乾燥30秒 < < < < < < CQ < < PQ CQ < CQ U U U U U U U OJ φ _ _ W Si 2 E ^ > 1.50 0.10 0.50 〇 yn 1.50 ”_ Η 1.50 0.10 〇 vn 0.10 <'< 0.10 1.50 1.50 5.26 2.88 3.03 3.00 3.00 4.00 4.00 氧錯鹽或其他添加劑 |對PVA100重量份之配合量 〇 ； 10000 〇 33.3 in i 4 〇 10000 Ο 10000 〇 10000 in P 4 5 m in 〇 y 4 〇 (N 種類 硝酸氧锆 碳酸氧锆銨 氣氧化氧銷 乙酸氧銷 硝酸氧锆 碳酸氧锆銨 四正丙醇锆 羥甲基三聚氰胺 羥甲基三聚氰胺 羥甲基三聚氰胺 11 / 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 實施例11 實施例12 比較例1 比較例2 比較例3 比較例4 比較例5 比較例ό 比較例7 比較例8 比較例9 -31 - 200923444 [1 ]接著性（切割刀（c u 11 e r )評估） 將各偏光板於常溫放置1小時後，於偏光板之各薄膜 間（偏光膜與保護膜A之間及偏光膜與保護膜B之間）放 入切割刀之刀刃，將刀刃押入時刀刃進入者依下列基準進 行評估。 A :切割刀之刀刃均不能進入任一膜與膜之間。 B:刀刃押入時，至少任一膜與膜之間刀刃進入達4 至5 mm爲止。 C:刀刃押入時，至少任一膜與膜之間刀刃輕易進入 (若任一膜與膜之間刀刃輕易進入，而另一方刀刃不能進 入，則進入達4至5mm爲止之情況亦包含在內）。 [2]耐水性 將各偏光板於23°C、相對溼度55%之環境下放置24 小時，進行下列耐溫水性試驗（溫水浸漬試驗），評估耐 水性。首先，以偏光板之吸收軸（延伸方向）作爲長邊， 將偏光板切成5cm X 2cm之短箋狀以製作試樣，正確測 量長邊方向之尺寸。此處’試樣因偏光膜所吸著之碘而全 面呈現均勻之特有顏色。於此，第1圖係表示耐水性評估 試驗方法之模式圖’第1圖（A)表示溫水浸漬前之試樣 1，第1圖（B )表示溫水浸漬後之試樣1。如第1圖（A )所示，以把持部5把持住試樣之一短邊側’將長邊方向 之約8成浸漬於60 °C之水槽中，保持4小時。然後，自水 槽取出試樣1，拭除水分。 -32- 200923444 由於溫水浸漬，偏光板之偏光膜4收縮。該偏光膜4 之收縮程度係藉由測定自試樣1短邊中央之試樣1邊緣1 a (保護膜之邊緣）至收縮之偏光膜4之邊緣的距離加以評 估，作爲收縮長度。又，如第1圖（B)所示，由於溫水 浸漬，位於偏光板正中之偏光膜4收縮，而於保護膜間形 成無偏光膜4存在之區域2。又，由於溫水浸漬，自接觸 溫水之偏光膜4之週邊部溶出碘，而於試樣1之週邊部產 生脫色部分3。該脫色程度係藉由測定自試樣1短邊中央 之收縮偏光膜4之邊緣至偏光板特有顏色仍殘留區域的距 離加以評估，作爲碘脫色長度。又，以上述收縮長度與碘 脫色長度之合計作爲總侵蝕長度X。亦即，總侵蝕長度X 係指自試樣1短邊中央之試樣1邊緣la (保護膜之邊緣） 至偏光板特有顏色仍殘留區域的距離。收縮長度、碘脫色 長度及總侵蝕長度X較小者，可判定在水存在下之接著性 (耐水性）高。 表1中，PVA表示聚乙烯醇系樹脂。由表1可知，本 發明之偏光板，即使乾燥時間短亦可顯示充分之接著性’ 且於溫水浸漬試驗中其自邊緣部之侵蝕亦小。 應認爲本次揭示之實施型態及實施例’非全部之例示 ，本發明並非受限於該等。本發明之範圍不僅限於上述之 說明，亦包括申請專利範圍，且應係包括與申請專利範圍 同等意義者以及在範圍內之所有變更。 【圖式簡單說明】 -33- 200923444 第1圖係表示耐水性評估方法之模式圖，第1圖（A )表示溫水浸漬前之試樣1，第1圖（B)表示溫水浸漬 後之試樣1。 【主要元件符號說明】 1 :試樣 2 :保護膜之間無偏光膜存在之區域 3:偏光板周圍部脫色之部分 4 :收縮之偏光膜 5 :把持部 -34 -Polyvinyl Alcohol, P0VAL) KL 318 (share) Kuraray system 'basic degree: 8 5 - 9 G mol. The above) was dissolved in pure water to prepare an aqueous solution having a concentration of 5%. Further, a 13% aqueous solution of zirconium oxycarbonate (Zircoma Sol AC-7' manufactured by Japan First Least Element Chemical Industry Co., Ltd.) was obtained. The polyvinyl alcohol-based resin aqueous solution and the aqueous solution of zirconium oxycarbonate are mixed in such a manner that the solid weight ratio of the ethylene glycol-based modified polyvinyl alcohol-based resin: zirconium oxycarbonate is 1:1, and then pure The water was diluted to 100 parts by weight of 'polyvinyl alcohol-based resin, and the solid weight ratio was 1.50, and the adhesive composition was prepared. The composition has a viscosity of 4.5 mP a · sec. A polarizing plate was produced in the same manner as in Example 1 except that the composition of the adhesive was used. <Example 8> In addition to the use of a carboxyl group-modified polyvinyl alcohol-based resin: zirconium oxycarbonate = 1:10 (solid weight ratio), and then diluted with pure water to a water of 1 part ' A polarizing plate was produced in the same manner as in Example 7 except that the weight ratio of the solid content of the polyvinyl alcohol-based resin was 0.10, and the composition of the adhesive was adjusted to 25-200923444. <Example 9> A 49%-concentration aqueous solution of zirconyl hydroxide (Zirconia Sol ZC-2, manufactured by Sakamoto Rare Element Chemical Industry Co., Ltd.) was obtained. 5% of the 49% aqueous solution of zirconium oxyhydroxide and the modified ethoxylated polyvinyl alcohol resin (〇〇) 136: {'丨11^]"-2100) prepared in Example 1. The aqueous solution is blended in such a manner that the weight ratio of the solid of the polyvinyl alcohol-based resin: oxyhydroxide hydroxide is 1:1, and then diluted with pure water to form 1 part of water, polyvinyl alcohol The weight ratio of the solid content of the resin was 1.50, and the composition of the adhesive was prepared. The composition had a viscosity of 3.5 mPa·sec. A polarizing plate was produced in the same manner as in Example 1 except that the composition of the adhesive was used. <Example 1 0> In addition to the use of an ethylene glycol-based modified polyvinyl alcohol-based resin: zirconyl hydroxide = 1:100 (solids weight ratio), and then diluted with pure water into water A polarizing plate was produced in the same manner as in Example 9 except that the weight ratio of the solid matter of the polyvinyl alcohol-based resin was 〇·1 1, and the composition of the adhesive was prepared. <Example 11> A 20% strength aqueous solution of zirconyl acetate (Zirconia Sol ZA-20, manufactured by Japan First Least Element Chemical Industry Co., Ltd.) was obtained. The 20% aqueous solution of zirconyl acetate-26-200923444 and the 5% aqueous solution-based modified polyethylene of the acetaminophen resin (〇〇1^6^11^1'-2100) prepared in Example 1 Alcohol-based resin: solid content of zirconyl acetate: a method of mixing the 'adhesive binder composition'. This group is 3.5mPa · sec. A polarizing plate was produced in the same manner except that the adhesive composition was used. <Example 1 2 > In addition to using a ratio of ethylene glycol-based modified polyvinyl alcohol-based zirconium = 1:100 (solid weight ratio), 100 parts of water was used, and the solid content of the polyvinyl alcohol-based resin In addition to the heavily prepared adhesive composition, a polarizing plate was used as in Example 11. <Comparative Example 1> The weight ratio of the solid content of the polyvinyl alcohol-based resin was 1.50, except that the polyvinyl alcohol-based zirconium modified by acetonitrile was used = 20:1 (solid weight ratio), and then diluted with pure water. In the same manner as in Example 1, except for the composition of the composition, 1 was produced. <Comparative Example 2> In addition to the use of a carboxyl group-modified polyvinyl alcohol-based resin = 20 ··1 (solid weight ratio), it was diluted with pure water. The weight ratio of the solid content of the polyvinyl alcohol-based resin is 1.50, and the viscosity of the base-modified polyethylene to the weight ratio of the acetaminophen is 1%, and the resin of the embodiment 1 is diluted with pure oxygen. The amount ratio was 0.10, and the same operation was carried out to prepare a resin: oxynitric acid or a slab of light smeared with water of 100 parts. : Ammonium oxycarbonate 100 parts of water, prepared adhesive -27- 200923444 Other than the composition A polarizing plate was produced in the same manner as in Example 7. <Comparative Example 3> According to the description of Example 2 of JP-A-9-3 18814 (Patent Document 5), a polyvinyl alcohol-based resin (Gohsenol AH17, manufactured by Nippon Chemical Industry Co., Ltd.) was first placed in a dissolution tank. Degree of alkalization: 97_98.5 mol%) One part was dissolved in 1900 parts of water to prepare an aqueous solution of a polyvinyl alcohol-based resin. Then, after adding zirconium tetra-n-propanolate to acetamidine acetone in a ratio of zirconium tetra-n-propoxide: acetamidine acetone = 1: 2 (mole ratio), only the upper portion is formed due to the formation of a precipitate. Three parts of the supernatant were added dropwise to the aqueous solution of the above polyvinyl alcohol-based resin under stirring, and the mixture was mixed at room temperature (23 ° C) for 1 hour to prepare an adhesive composition. A polarizing plate was produced in the same manner as in Example 1 except that the thus-formed adhesive composition was used. <Comparative Example 4> 2.88 parts of methyl acetonitrile-modified polyvinyl alcohol-based resin (Gohsefimer Z.200, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., alkalinity: 99 mol% or more) and methylol melamine 1 part of 24 parts (100 parts of polyvinyl alcohol-based resin and 43 parts of methylol melamine) were dissolved in 100 parts of pure water at a temperature of 30 ° C to prepare an adhesive composition. A polarizing plate was produced in the same manner as in Example 1 except that the composition of the adhesive was used. <Comparative Example 5> -28- 200923444 The amount of the modified polyvinyl alcohol-based resin was changed to 3.03 in addition to the use. A polarizing plate was produced in the same manner as in Comparative Example 4 except that the amount of the methylol melamine was changed to 1.15 parts (100 parts of a polyvinyl alcohol-based resin and 36 parts of methylol melamine). <Comparative Example 6> 3 parts of acetonitrile-modified polyvinyl alcohol-based resin (Gohsefimer Z-200) and 1.05 parts of methylol melamine (100 parts of polyvinyl alcohol-based resin, methylol melamine) 35 parts) was dissolved in 100 parts of pure water at a temperature of 30 ° C, and 0.4% acetic acid was added thereto to prepare an aqueous solution of pH 4.0, and the same as in Comparative Example 4 except that the aqueous solution was used as the adhesive composition. A polarizing plate is produced by operation. <Comparative Example 7> Ethyl acetonitrile modified poly(ethyl alcohol) resin (Gohsefimer Z-200) 3.00 parts and 1.05 parts of methylol melamine (100 parts for polyvinyl alcohol resin, 35 parts of methylol melamine) The solution was dissolved in 100 parts of pure water at a temperature of 30 ° C, and 0.4% acetic acid was added thereto to prepare an aqueous solution of pH 3.0, and the same procedure as in Comparative Example 4 was carried out except that the aqueous solution was used as an adhesive composition. Polarizer. <Comparative Example 8> In addition to the use of polyvinyl alcohol-based resin (Kuraray Poval 117H, Kuraray (manufactured by Kuraray Poval 117H, alkalizity: 99.3 Mo-29-200923444%) or more)醯 醯 改 改 聚乙烯 聚乙烯 G G G G G G G G G G G G G G G G G G G G G G G G G G G G G G G G G G G G G G G G G G G G G G G G G G A polarizing plate was produced in the same manner as in Example 1 except that the acetonitrile-modified polyvinyl alcohol-based resin was used in an amount of 1 part by weight in an amount of 1 part by weight. <Comparative Example 9> The preparation was carried out except that the amount of addition of glyoxal was changed to 0.8 part (the total amount of the polyethylene-based resin and the ethyl acetonitrile-modified polyvinyl alcohol-based resin was 20 parts per 100 parts). A polarizing plate was produced in the same manner as in the comparative example except for the composition of the composition. <Evaluation Test> The following evaluation tests were carried out on the panels obtained in each of Examples 1 to 12 and Comparative Examples 1 to 9. The results are shown in Table 1. Grease (98.5 pairs of poly-alcohols, Example 8 Polarization • 30- 200923444 Total erosion length (μ m) Drying 5 minutes 〇 350 450 450 850 350 300 580 750 〇 00 1500 1900 The next layer dissolves 1600 2500 1200 1300 1000 〇00 drying for 30 seconds I-—400 380 450 450 600 1050 500 〇450 450 〇00 950 2200 2000 The following layer dissolves the adhesive layer, dissolves the adhesive layer, dissolves the adhesive layer, dissolves the adhesive layer, dissolves 1100 950, and then drys. 5 points <<<<<<<<<<<<<<<<<<<3<<3< Drying for 30 seconds <<<<<<< CQ << PQ CQ < CQ UUUUUUU OJ φ _ _ W Si 2 E ^ > 1.50 0.10 0.50 〇yn 1.50 ” _ Η 1.50 0.10 〇vn 0.10 <'< 0.10 1.50 1.50 5.26 2.88 3.03 3.00 3.00 4.00 4.00 Oxygen salt or other additives | For the PVA 100 parts by weight 〇; 10000 〇 33.3 in i 4 〇 10000 Ο 10000 〇 10000 in P 4 5 m in 〇 y 4 〇 (N type zirconia carbonate Oxy zirconium ammonium oxide oxidizing oxygen pin acetic acid oxygen pin zirconyl nitrate zirconium oxynitrate ammonium tetrazoate Zirconium hydroxymethyl melamine hydroxymethyl melamine hydroxymethyl melamine 11 / Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example ό Comparative Example 7 Comparative Example 8 Comparative Example 9 - 31 - 200923444 [1] Adhesive (Cut knife (cu 11 er ) evaluation) After each polarizing plate is left at a normal temperature for one hour, the cutting blade is placed between the films of the polarizing plate (between the polarizing film and the protective film A and between the polarizing film and the protective film B), and the blade edge enters when the blade is pushed in. Evaluate according to the following criteria: A: The cutting edge of the cutting blade cannot enter between any film and film. B: When the blade is pushed in, at least one of the film and the film enters between 4 and 5 mm. C: When the blade is pushed in, the blade is easily inserted between at least one of the film and the film (if the blade is easily inserted between any film and the film, and the other blade cannot enter, the case of entering 4 to 5 mm is also included. ). [2] Water resistance Each of the polarizing plates was allowed to stand in an environment of 23 ° C and a relative humidity of 55% for 24 hours, and the following temperature resistance test (warm water immersion test) was carried out to evaluate the water resistance. First, the polarizing plate was cut into a short shape of 5 cm X 2 cm by using the absorption axis (extension direction) of the polarizing plate as a long side to prepare a sample, and the dimension in the longitudinal direction was accurately measured. Here, the sample is uniformly colored in its entirety due to the iodine absorbed by the polarizing film. Here, Fig. 1 is a schematic view showing a water resistance evaluation test method. Fig. 1(A) shows a sample before warm water immersion, and Fig. 1(B) shows sample 1 after warm water immersion. As shown in Fig. 1(A), the grasping portion 5 holds about one side of the short side of the sample and immerses about 80% of the longitudinal direction in a water bath of 60 ° C for 4 hours. Then, the sample 1 was taken out from the water tank to remove moisture. -32- 200923444 The polarizing film 4 of the polarizing plate shrinks due to warm water immersion. The degree of contraction of the polarizing film 4 was evaluated by measuring the distance from the edge 1 a of the sample 1 at the center of the short side of the sample 1 (the edge of the protective film) to the edge of the contracted polarizing film 4 as the contraction length. Further, as shown in Fig. 1(B), the polarizing film 4 located in the middle of the polarizing plate is shrunk by warm water immersion, and the region 2 where the non-polarizing film 4 exists is formed between the protective films. Further, due to the immersion in warm water, iodine is eluted from the peripheral portion of the polarizing film 4 which is in contact with the warm water, and the decolored portion 3 is formed in the peripheral portion of the sample 1. The degree of decolorization was evaluated by measuring the distance from the edge of the shrinking polarizing film 4 at the center of the short side of the sample 1 to the residual area of the polarizing plate characteristic color as the iodine bleaching length. Further, the total length of the shrinkage and the length of the iodine bleaching are taken as the total etching length X. That is, the total erosion length X refers to the distance from the edge 1 of the sample 1 at the center of the short side of the sample 1 (the edge of the protective film) to the area where the characteristic color of the polarizing plate remains. When the shrinkage length, the iodine decolorization length, and the total erosion length X are small, it is judged that the adhesion (water resistance) in the presence of water is high. In Table 1, PVA represents a polyvinyl alcohol-based resin. As is apparent from Table 1, the polarizing plate of the present invention exhibits sufficient adhesion even when the drying time is short, and the erosion from the edge portion is small in the warm water immersion test. It is to be understood that the present invention is not limited to the embodiments and the embodiments of the present disclosure. The scope of the present invention is not limited by the scope of the invention, and the scope of the invention is intended to be included in the scope of the claims. [Simple description of the drawing] -33- 200923444 Fig. 1 is a schematic view showing the water resistance evaluation method, Fig. 1 (A) shows sample 1 before warm water immersion, and Fig. 1 (B) shows after warm water immersion Sample 1. [Explanation of main component symbols] 1 : Sample 2 : Area where no polarizing film exists between protective films 3: Decolorized part around polarizing plate 4 : Shrinking polarizing film 5 : Holding part -34 -