TW201109404A

TW201109404A - Polarizing plate and photo-curable adhesive for formation of polarizing plate

Info

Publication number: TW201109404A
Application number: TW099112470A
Authority: TW
Inventors: Satoko Kagiyama; Shinji Ishizaki; Hidekazu Ikeda
Original assignee: Toyo Ink Mfg Co
Priority date: 2009-09-04
Filing date: 2010-04-21
Publication date: 2011-03-16
Also published as: JP5459128B2; CN102012535B; KR101010574B1; JP2011076067A; TWI404784B; JP2011076058A; CN102012535A; JP4561936B1

Abstract

The present invention provides a polarizing plate constituted by covering both surfaces of a polyvinyl alcohol polarizer with a protective film respectively via an adhesive layer formed by curing a photo-curable adhesive containing a radical polymerizable compound (a): 60 to 99.8% by mass, a cation polymerizable compound (c) having cation polymerizable functional group but not having (meth) acryloyl group: 0.02 to 40% by mass, a photo radical polymerization initiator (d) and a photo cation polymerization initiator (e).

Description

201109404 , 六、發明說明：【發明所屬之技術領域】，本發明係有關液晶顯示I置等使用之偏光板及該偏光板形成用之光硬化性接著齊,j。【先前技術】在鐘錶、手機、個人用攜帶型終端機（舰，亦即個人數位助理）、筆§己型電腦、個人電腦用顯示器、數位光碟剛播放器、電視⑽等方面，液晶顯示裝置係在市場急速擴張。液晶顯示裝置為緩由液晶之切換㈤他⑽) 而使偏光狀態可視化者，從麵示原理而言，係使用偏光 :。尤其是在電視等之用途，越來越要求高亮度、高對比、廣視野角，在偏光板亦越來越要求高透過率、高偏光度、向色澤再顯性等。液S曰.4不關連領域等使用之偏光件，通常係由將在聚烯醇yPVA)巾吸附碟或染料者進行_軸延伸*製造。該聚乙稀醇系偏光件係因熱或水分而收縮，導致偏光性能降低此處將在PVA系偏光件的表面黏貼保護薄膜者作為偏光板使用。作為用於在偏光件黏貼保護薄膜的接著劑，以往廣泛使用聚乙稀醇系樹脂的水溶液（PVA系接著劑）（參照專利文獻卜2)。於專利文獻3揭示使用水性胺醋（urethane)系接著劑而形成的偏光板。不過，尤其是以電視為代表，近年來隨著畫像顯示裘 322005 3 201109404 置之大晝面化的進展，連帶地對於偏光板亦提高要求大型化，成為重要的課題。惟，使用上述水系接著劑的偏光板，由於背光的熱而使偏光板的尺寸產生變化’且肇因於該尺寸變化的變形係局部存在於晝面的一部分，結果’本來晝面全體應顯示全黑時，光會部分性地洩露’有所謂的光洩露（顏色不勻）變顯著的問題。根據如上述的理由，有使用陽離子聚合性紫外線硬化型接著劑來取代水系接著劑的提案（參照專利文獻4)。惟’使用陽離子聚合性紫外線硬化型接著劑時，由於在备、外線照射後會產生暗反應（後聚合），故在將長狀的硬化物作成捲筒狀時，有在保管時容易產生捲褶的問題。並且，陽離子聚合性紫外線硬化型接著劑容易受到硬化時濕度的影響，有硬化狀態容易有變異的問題。於是，為了表 ^岣一的硬化狀態，不只是環境濕度，pVA系偏光件的含水率亦需要嚴格管理。自由基聚合性紫外線硬化型接著劑有該等問題較少的不過狀B曰顯示裝置隨著其用途之擴大，而逐漸可 ==使用’而對於構成液晶顯示裝置的偏光板要高耐=:為代表的移動用途之液晶顯示裝置係要如上所述’自由基聚合性紫外線硬㈣接劑相較於陽 322005 4 201109404 .離子=合性硬化型接著劑，於種種特點上較優越。 . 惟’使用自由基聚合姓妙认we , 時間暴露在濕熱環境下，則偏光性能容易端部用峨或染料著色的偏光件容易發接著劑時，若長降低，有在切割色的問題。 …*比濕熱環境下更嚴苛的條件（例如浸潰於6〇°C 的酿水）時，偏光件的脫色顯著發生。 /亦即，在偏光板之使用環境更嚴苛的今曰，實情為期待比以往偏光板更具有耐濕熱性的偏光板。再者，為了簡便地將偏光板聚乙烯系薄膜與塑膠薄膜以充分的強度接著，提案將（曱基）丙烯酸系之自由基聚合卜生化合物與陽離子聚合性化合物併用的接著性組成物（專利文獻5)。惟’該技術更要求改善穿孔加工性。 [先前技術文獻] [專利文獻1]日本特開平09—258023號公報 [專利文獻2]日本特開2005-208456號公報 [專利文獻3]日本特開2004-37841號公報 [專利文獻4]日本特開2008-233874號公報 [專利文獻5]日本特開2008-260879號公報【發明内容】本發明係以提供將聚乙烯醇系偏光件與保護薄膜作為構成層，且保護薄祺與偏光件的接著性及穿孔加工性優越，並且耐水性亦優越的偏光板為目的。本發明人等為了解決上述課題，經過不斷的冰入研究，結果發現根據以下表示的偏光板可達成上述的目标 322005 5 201109404 因而完成本發明。亦即，本發明係有關一種偏光板，其係含有聚乙烯醇系偏光件、將光硬化性接著劑硬化而成之接著層、及保護薄膜，且分別藉由保護薄膜隔著上述接著層被覆上述偏光件之兩面而成的偏光板；其特徵為：上述光硬化性接著劑含有由自由基聚合性化合物及陽離子聚合性化合物所構成的主劑、光自由基聚合啟始劑、及光陽離子聚合啟始劑；就上述自由基聚合性化合物而言，形成玻璃轉移溫度為-80°C至0°C之均聚物的自由基聚合性化合物（a)在上述主劑中含有60至99. 8質量％ ; 就上述陽離子聚合性化合物而言，未具有（曱基）丙烯醯基之陽離子聚合性化合物（c)在上述主劑中含有0. 02至 40質量％ ; 相對於上述主劑100質量份，分別含有上述光自由基聚合啟始劑1至10質量份、上述光陽離子聚合啟始劑0. 5 至5質量份。又，本發明係有關一種偏光板形成用光硬化性接著劑，其含有由自由基聚合性化合物及陽離子聚合性化合物所構成之主劑、光自由基聚合啟始劑及光陽離子聚合啟始劑；就上述自由基聚合性化合物而言，形成玻璃轉移溫度為-80°C至0°C之均聚物的自由基聚合性化合物（a)在上述主劑中含有60至99. 8質量％ ; 6 322005 201109404 ，就上述陽離子聚合性化合物而言，未具有（曱基）丙烯醯基之^離子聚合性化合物（c)在上述主劑中含有〇· 〇2至 40質量％; * 相對於上述主劑100質量份，分別含有上述光自由基聚合啟始劑1至10質量份、上述光陽離子聚合啟始劑〇 5 至5質量份。【實施方式】以下’對於本發明之較佳實施形態加以說明。根據本發明’可提供將聚乙烯醇系偏光件及保護薄膜作為構成層之偏光板，其為接著性、穿孔加工性及耐水性優越之偏光板。 [接著層] 力以說月又个％月偏光板的接著層C或接著劑層）性接化合物)及陽離基聚合性成分(自由基聚合性自由基聚人^ 成分（陽離子聚合性化合物）。續之㈣辑料度為斯物自_合性化合物;= 為广可含有可形“移:t 之均聚物的自由基聚合性化合物（b)(以 322〇〇5 7 201109404 下，亦稱為「自由基聚合性化合物（b)」或「高Tg自由基聚合性化合物（b)」）。亦即，就自由基聚合性成分而言，係含有其均聚物的玻璃轉移溫度為-80°C至0。(：之自由基聚合性化合物（a) ’且任意地含有其均聚物的玻璃轉移溫度為60°C至250。(：之自由基聚合性化合物（b)。低Tg自由基聚合性化合物（a)中，單官能者可列舉例如：丙烯酸2-羥基乙酯（均聚物之Tg:-9°C，以下亦相同）、丙烯酸2-羥基丙酯（-7t：)及丙烯酸4-羥基丁酯（-55。(：）所代表之（曱基）丙烯酸羥基末端烷酯；丙烯酸2-曱氧基乙酯（-43°C)、丙烯酸3-曱氧基丁酯（-47°C)、丙烯酸十三烷酯（-65°C)及曱基丙烯酸十三烷酯（-37°C) 所代表之（曱基）丙烯酸烷基末端烷酯；二乙二醇單乙醚丙稀酸酯（-54°C)、乙氧基二乙二醇丙烯酸酯（_51°C)、曱氧基聚乙二醇（n=9)丙烯酸酯（-71°C)及甲氧基三縮三丙二醇丙烯酸酯（-75°C ) 所代表之烷基末端（聚）烷二醇系（曱基）丙烯酸酯；丙烯酸苯氧基乙醋（-15°C)、丙烯酸三氟乙酯（-10°C)、羧基-聚己内酯丙烯酸酯（_46°C)等。 8 322005 201109404 I 又’低Tg自由基聚合性化合物⑷中’多官能者可列举如· 聚乙二醇（獅）二⑽酸g旨（-28。〇、聚乙二醇（600)二丙烯酸酯（-42。〇、三乙二醇二甲基丙烯酸酯（-5。〇、乙氧化⑼一經甲基兩燒三丙稀酸醋（-19t：)等。本發明之光硬化性接著劑可將該等材料適當組合使用0 低Tg自由基聚合性化合物⑷較好為單官能者。即使為低Tg自由基聚合性化合物（a)，若只使用多官能者，則在後述之切割試驗性能之觀點上有不佳的情形。因此，為了作成該切割試驗性能亦良好者，在併用多官能者作為低 Tg自由基聚合性化合物（a)時，在低Tg自由基聚合性化合物（a)(作為丨〇〇質量％)中係控制在未達質量％的程度，較好係控制在未達10質量％的程度。又’使用後述之南Tg自由基聚合性化合物（b)時，該 :Tg自由基聚合性化合物（b)之較好例不是多官能而是單吕此°換言之，當使用多官能自由基聚合性化合物作為自由基聚合性化合物（（a)或（a) + (b))時，該比例在主劑（作為 100質量％)中係未達4〇質量％的程度，較好為未達1〇皙 %的程度。或者是，自由基聚合性化合物中之單官能自由基聚合性化合物（單官能之自由基聚合性化合物（a)、或單官能之自由基聚合性化合物（a)及（b)之合計）的比例較好在6〇質 9 322005 201109404 量％以上’更好在70質量％以上，最好在90質量％以上。該自由基聚合性化合物（a)更好為均聚物的玻璃轉移溫度為-60°C至-2(TC者，最好為均聚物的玻璃轉移溫度為 -60°C 至-40°C 者》該等低Tg自由基聚合性化合物（a)中，從提昇與pva 系偏光件之接著性之觀點而言，較好為（曱基）丙烯酸羥基烧醋等具有經基者，其中較好為丙烯酸4-經基丁酯。從硬化物的Tg不易變低之觀點而言，即使為具有羥基者，亦以不使用丙烯酸2-羥基乙酯、丙烯酸2-羥基丙酯為佳。亦即，（曱基）丙烯酸羥基烷酯之烷基之碳原子數較好為約4 至40。從使硬化後之接著劑層的凝集力提高且提昇接著力之銳點而§，低Tg自由基聚合性化合物（a)係以使用ω_繞基-聚己内酯單（曱基）丙烯酸酯更佳。惟，ω_羧基-聚己内酉曰早（曱基）丙烤酸g旨之硬化性不佳’故可經由適當選擇自由基聚合啟始劑之種類或量、適當選擇紫外線照射裝置之燈、適當選擇照射強度或曝光量等硬化條件、適當選擇保 »蒦薄膜之種類或厚度專’而彌補硬化性。Μ _竣基-聚己内酉曰單（甲基）丙烯酸酯之己内酯聚合度（η)並無特別限制，較好為η=2至20之程度。例如，以主劑合計當作1〇〇質量％時為6〇至99 8質量 %之自由基聚合性化合物（a)，較好係將丙烯酸4_羥基丁酯等（甲基）丙烯酸羥基烷酯在10至99. 8質量％、ω_羧基— 聚己内酯單（甲基）丙埽酸酯在〇至5〇質量％之各範圍中加 322005 10 201109404 以組合。 « 又，調配ω-羧基-聚己内酯單（甲基）丙烯酸酯時，更好係將（曱基）丙烯酸羥基烷酯在10至99.7質量％、ω-羧基-聚己内酯單（曱基）丙烯酸酯在0. 01至50質量％的範圍中使用。任意調配之高Tg自由基聚合性化合物（b)較好係使用例如：曱基丙烯酸二環戊烯酯（均聚物之Tg: 180°C，以下亦相同）、曱基丙烯酸三氟乙酯（81°C)、曱基丙烯酸第三丁酯（113°C)、曱基丙烯酸乙酯（65°C)、甲基丙烯酸四氫糠酯（68°C)、丙烯酸異冰片酯（85°C)及丙烯醯基嗎啉（106°C)等。其中，從耐熱性之觀點而言，較好係使用丙烯酸異冰片酯、丙烯醯基嗎啉。該自由基聚合性化合物（b)以均聚物的玻璃轉移溫度為60°C至200°C者較佳，以均聚物的玻璃轉移溫度為80°C 至150°C者更佳。本發明之光硬化性接著劑可將該等材料適當組合使用。可由上述之低Tg自由基聚合性化合物（a)、高Tg自由基聚合性化合物（b)所形成之各均聚物之Tg係依以下的操作求得之值。 11 322005 201109404 將各化合物及啟始劑放入適當容量之塑膠製容器中，將照射紫外線而硬化者10mg作為測定用試料，使用示差掃瞄熱量計（DSC)，以10°C/分鐘或20°C/分鐘的昇溫速度測定。未具有（甲基）丙烯酿基之陽離子聚合性化合物（c)(以下，將此稱為「陽離子聚合性化合物（c)」）為具有陽離子聚合性官能基且未具有（曱基）丙烯醯基之化合物，列舉例如3, 4-環氧基環己烷羧酸3, 4-環氧基環己基曱酯、 2-(3, 4 -環氧基環己基-5, 5 -螺-3, 4 -環氧基）環己院-間-二口琴烷、雙（3, 4-環氧基環己基曱基）己二酸酯、雙（3, 4-環氧基-6-曱基環己基甲基）己二酸酯、乙烯基環己烯一氧化物、1,2-環氧基-4-乙烯基環己烷等1分子中具有1個以上脂環式環氧基之化合物或具有氧雜環丁基之化合物。陽離子聚合性化合物（c)擔任提昇經硬化之接著層之耐水性的任務。具有脂環式環氧基之化合物中，從反應性之觀點而言，較好係使用3, 4-環氧基環己基曱基-3, 4-環氧基環己烷羧酸酯。於本發明，從確保接著力及穿孔加工性良好之觀點而言，陽離子聚合性化合物（c)較好係選擇未具有（曱基）丙烯醯基者。雖可將具有（甲基）丙烯醯基之陽離子聚合性化合物與上述（c)併用，惟，此時之具有（甲基）丙烯醯基之陽離子聚合性化合物之調配量在主劑100質量％中，必需控制在未達20質量％之程度，較好為控制在未達10質量％之程度。 12 322005 201109404 或是，在陽離子聚合性化合物全體中，未具有（甲基）丙烯醯基之陽離子聚合性化合物（C)占有之比例較好在50 質量％以上，更好在75質量％以上。光硬化性接著劑的主劑係含有自由基聚合性化合物 (a)60至99. 9質量％、陽離子聚合性化合物（c)0. 02至40 質量％，較好係自由基聚合性化合物（a) : 60至99質量°/〇、陽離子聚合性化合物（c) : 1至40質量％，更好係自由基聚合性化合物（a): 90至99質量％、陽離子聚合性化合物（c): 1至10質量％。低Tg自由基聚合性化合物（a)若少於60質量％，則形成之接著層太硬，不僅不能確保接著力，還會導致穿孔加工性惡化。另一方面，低Tg自由基聚合性化合物（a)若比99. 8 質量％多，亦即幾乎不含有陽離子聚合性化合物（c)時，所形成之接著層的耐水性惡化，若將偏光板浸潰在溫水中，則PVA偏光件的顏色會脫落。若使用三乙醯纖維素等乙醯纖維素系樹脂薄膜作為保護薄膜時，高Tg自由基聚合性化合物（b)有助於提昇接著力。使用高Tg自由基聚合性化合物（b)時，較好係低Tg 自由基聚合性化合物（a) : 60至75質量％、高Tg自由基聚合性化合物（b) : 0. 01至39. 98質量％、陽離子聚合性化合物（c) : 0. 02至24. 99質量％，更好係低Tg自由基聚合性化合物（a) : 60至70質量％、高Tg自由基聚合性化合物 13 322005 201109404 (b) : 10至35質量％、陽離子聚合性化合物（c) ·· 5至2〇質量％。或者是，較佳之一實施形態之光硬化性接著劑中，作為主劑者係含有形成玻璃轉移溫度為-80°C至0。(：之均聚物的單官能自由基聚合性化合物（a) : 60至99. 8質量％、幵>成玻璃轉移溫度為60°C至250°C之均聚物的單官能自由基聚合性化合物（b) : 〇至39. 98質量％、及具有陽離子聚合性官能基且未具有（甲基）丙烯醯基之陽離子聚合性化合物（c) ·· 〇. 〇2至40質量％(惟，上述（a) 至（c)合計為1〇〇質量％)，作為聚合啟始劑者係含有光自由基聚合啟始劑（d) : i 至10質量份（相對於上述（a)至（c)合計1〇〇質量份）及光陽離子聚合啟始劑（e) : 0. 5至5質量份（相對於上述（a)至（c)合計1〇〇質量份）。更好係含有低Tg自由基聚合性化合物（a):⑼至99 質量％、高Tg自由基聚合性化合物（b) : 〇至39質量％及陽離子聚合性化合物（c) : 1至40質量％。本發明之光硬化性接著劑中，除了低Tg自由基聚合性化合物（a)或高Tg自由基聚合性化合物（b)之外，亦可添加其他的自由基聚合性化合物。其他之自由基聚合性化合物可列舉如胺酯丙烯酸酯、環氧基丙烯酸酯、聚酯丙烯酸酯、聚醚丙烯酸酯。惟，如上所述，自由基聚合性化合物較好係在限定的調配範圍使用。本發明之光硬化性接著劑中，必要時可添加適當的添 14 322005 201109404 ，加劑。從可敎與保護薄膜的接著力、可抑制偏光板的收縮之觀點而言，添加劑較好為矽烷偶合劑。矽烷偶合劑較好為具有丙烯醯基者。 σ 本發明之光硬化性接著劑含有光自由基聚合啟始劑 ⑷。光自由基聚合啟始劑（d)並無特別限制，列舉例如依卡求亞（IRGACURE)-184、907、65卜 Π00、1800、819、369、 261 ; DAROCUR-TPO(汽巴精化公司製造）、塔羅求亞 (DAROCUR)-1173(默克（Merck)公司製造）、耶薩求亞 (EsaCure)-KIP150、TZT(日本謝貝海克那公司製造）、卡亞求亞（KAYACURE)BMS、卡亞求亞DMBI(日本化藥公司製造）等。該等中，在提高光硬化後之接著劑層的透明性之觀點，較好係使用光致漂白（Photobleach)之DAROCUR-TPO。光自由基聚合啟始劑（d)之調配比率，相對於上述自由基聚合性化合物（a)、（b)及陽離子聚合性化合物（c)之合計 100質量份，為1至10質量份，較好為1至5質量份。本發明之光硬化性接著劑含有光陽離子聚合啟始劑 (e) 〇光陽離子聚合啟始劑（e)可列舉例如UVACURE1590C大協·賽提克（daice卜cytec)公司製造）、CPI-110P(桑阿普洛 (San-apro)公司製造)等毓鹽或IRGACURE250(汽巴精化公司製造）、WPI-113C和光純藥公司製造）、RP-2074(羅迪亞. 曰本公司製造）等錤鹽等。 15 322005 201109404 光陽離子聚合啟私基聚合性化合物（a)、= (e)之調配比率，相對於上述自由 100質量份，為〇 5至,及陽離子聚合性化合物（c)之合計光硬化性接著轉^量份，較好為Q·5至5質量份。要時，在報礙本發心上述主劑及聚合啟始劑之外，必聚合引發助劑、紫外雄果的範圍内可含有聚合抑制劑、劑、消泡劑、可塑劑t收劑、增塑劑、著色劑、抗氧化 [偏光件] _各種公知的添加劑。圖之聚乙烯醇系娜可列舉聚乙稀醇作為偏光件基材的聚乙烯醇系樹脂而言，較好為乙Ή ^歸醇共聚物等’從财水性之觀親基有數+¾殘存的部分=共聚物。聚乙稀醇可列舉如乙® 全_^_、===醇韻基未殘細惟，並無特·定。聚之改性聚乙稀醇等’ 亦可將2種社個。㈣㈣脂可單獨㈣1種，或 ^述聚乙烯醇的具體例可列舉克拉雷（kray)(股） ^司製造的RS聚合物之RS〜U〇(專化度=99% ，聚合度 ^ 〇〇〇)、同公司製造的克拉雷普巴魯LM20SO(息化度 -4(U，聚合度=2, 〇〇〇)、日本合成化學工業（股）公司製造的勾協諾魯簡-14(皂化度=99%，聚合度=ι，4〇〇)等。聚乙烯醇可藉由例如將乙酸乙烯酯、丙酸乙烯酯、三曱基乙酸乙烯酯等脂肪酸乙烯酯的聚合物使用鹼觸媒等進行皂化而獲 16 322005 201109404 得。上述乙烯·乙烯醇共聚物為將乙烯及乙酸乙烯酯之共聚物之皂化物，亦即乙烯、乙酸乙烯酯無規共聚物予以皂化而獲仔者’包含從乙酸基有數十莫耳％殘存的部分皂化物到乙酉文基僅數莫耳％殘存或乙酸基未殘存之完全皂化物，並無特別限制。 … ^偏光件係藉由依照公知的方法將上述之聚乙烯醇系樹曰以鑄塑成形法等方法予以薄膜化，並使碘或二色染料（二色丨生色素）吸附定向而獲得。上述偏光件亦可為經由硼酸等進行父聯或經延伸者。進行延伸時，可在染色前/與染色同時/染色後之任何一個階段進行。偏光件的形狀並無特別限制，可列舉例如薄膜等。又，於本說明書，「薄膜（film)」、了尽度小者（厚度未達者）之夕卜，亦包含厚片（sheet) (例如厚度為1至5mm者）。偏光件的厚度並無特別限制，車父好為例如約10至。 [保護薄膜] 對於本發明偏光板使用的保護薄膜（第1、2圖中的符鱿1、5)加以說明。保護薄膜並無特別限制，具體而言’可使用現在作為偏光板的保護薄膜最廣泛使用的三乙酿纖维素（MC)等乙隨纖維素系樹脂薄犋、或透濕度比三乙醯纖維素低的透明樹脂薄膜。構成透濕度比三乙醯纖雉素低的保護薄膜的材料，係使用例如透明性、機械強度、熱安定性、水分遮斷性、各 322005 17 201109404 向同性等優越的熱可塑性樹脂。該等熱可塑性樹脂的具體例可列舉環煙稀系樹脂、丙稀酸系樹脂。環烯烴系樹脂為將環狀烯烴作為聚合單位並進行聚合而成的樹脂的總稱。具體例可列舉環狀烴烯之開環（共）聚物、環狀烯烴之加成聚合物、環狀烯烴與乙烯、丙烯等α_ 烯烴之共聚物（具代表性者為無規共聚物）、及將該等以不飽和叛酸或其衍生物改性之接枝共聚物及該等之氫化物等’較好為降冰片烯（n〇rb〇rnene)系樹脂。降冰片烯系樹脂薄膜可經由日本特開2005-164632號公報、日本特開 2006-201736號公報、日本特開2〇〇8_233279號公報等記載的公知方法獲得。環稀烴系樹脂有種種市售製品。具體例可列舉日本傑旺（ΖΕΟΝ)(股）公司製造之商品名「傑歐諾亞（ZE〇N〇R)」、 JSR(股）公司製造之商品名「亞楝（ART〇N)」、TIC〇M公司製造之商品名「特巴斯（T0PAS)」、三井化學（股）公司製造之商品名「APEL」。丙稀酸系樹脂以聚曱基丙烯酸甲酯為代表，為將曱基丙稀酸甲醋或甲基丙烯酸丁酯等烷基酯類之（曱基）丙烯酸酉旨作為主成分之樹脂（=共聚物）。根據場合，與其他的樹脂捧合、薄膜化。丙烯酸系薄膜可經由日本特開2〇〇2_361712 號公報等記載的公知方法獲得。丙稀酸系薄骐有種種市售製品。具體例列舉三菱嫘營 A司製ie之商品名「阿克利普連（Acrypien)」或卡聶卡 (Kaneka)公司製造之商品名「桑迪連（Sunduren)」。 18 322005 201109404 本發明之偏光板使用的保護薄膜（1)、（5)的兩樹脂薄膜，⑸使用丙雜系樹脂薄膜亦沒有任何問題〜保護薄膜的厚度可適當決定，通常從強度、摔。作業性、薄層性等之觀點而言，為約i至5心 1 二:：更:為5至2°°，保輪⑴及⑻二又，於偏光件之兩似董倾_時，其裏外由问-聚合物材料所構成的保護_ 用合物材料等所構成的保護薄臈。例如，在由不同聚用兩烯酸系薄膜時，丙烯酸系聚合物的種類可互使调配的添加劑亦可互相不同，並無任何限制。 5 ’ 本發明的偏光板可經由以下的操作獲得。亦即，較佳係經由下述操作而製造：在第1保護薄膜⑴之-面塗覆第丨光硬化性训，形成第1硬化性接著劑層（2,）；在第2保護薄臈（5)之一面塗形成第2硬化性接著劑層（4，）； _先硬化性接著劑，著咖光件⑶的各㈣1硬化性接疊()及第2硬化性接著劑層(4，)同時/或依序重從第2保護薄膜⑸側照射活性接著_及第2硬化性接著劑層上述硬化性接著劑層（2’）及…、保護薄膜⑴及（5) 322005 19 201109404 · 各自可相同或不同。亦即，硬化性接著劑層（2,）及硬化性接著劑層（4,）（換言之’為第1光硬化性接著劑及第2光硬化性接著劑）可為相同的組成，亦可為不同的組成❶形成的接著劑層（2)及（4)的厚度可相同或不同’並無特別限制，通常較好為0.1#m至50/zin，更好為〇 5#m至2〇#m。以下，以第2圖為基礎，對每個步驟加以說明。 [步驟（a)] 步驟（a)係如第2圖之（a)所示，在保護薄膜（丨）及（5) 之各個單面塗覆接著劑層形成用的光硬化性接著劑，必要時進行乾燥等，獲得具備硬化性接著劑層（2’）、（4,）之層壓體（1’）、（5’）的步驟。光硬化性接著劑的塗覆方法並無特別限制，可列舉例如模頭塗覆法（die coating)、滾筒塗覆法、凹版塗覆法、旋轉塗覆法等。 [步驟（b)] 步驟（b)係如第2圖之（b)所示，在聚乙烯醇系偏光件 (3)之一面（在圖中為上面）將具備保護薄膜及硬化性接著劑層（2’）之層壓體（Γ )疊合，並在聚乙烯醇系偏光件（3)之另一面（在圖中為下面）將具備保護薄膜（5)及硬化性接著劑層（4,）之層壓體（5,）疊合的步驟。 [步驟（c)] 步驟（c)係如第2圖之（c)所示，經由照射活性能量線 (6) ’使被保護薄膜（1)、（5)及聚乙烯醇系偏光件（3)所挾 20 322005 201109404 κ ，住之硬化性接著劑層（2,）、（4,）硬化，形成接著劑層⑵、 (4)的步驟。於圖中雖表不從保護薄膜(5)側照射活性能量線〇)的清开7准’亦可從保護薄膜⑴側照射活性能量線（6)，亦可從兩側同時或從兩侧依序照射活性能量線⑻。活性能量線的照射量並無特別限制，較好係將波長 200至450nm、照度1至500mW/cm2的光以使照射量成為 10至500〇mJ/cro2之方式進行照射而進行曝光。照射量若比lOnJ/cm2低，則不能促進紫外線硬化性組成物的硬化，不能發揮所希望的性能’照射量若比测以‘高，則 π射時間變非常長’有生產性的問題。照射之活性能量線的種類可列舉如可見光、紫外線、^線、m線、^ 線等以i外線較佳。光的照射裝置較好係使用例如高壓水銀燈、低壓水銀燈、鹵化金屬燈、準分子燈（Excimeriamp) 等。照射活性能量線（6)後’亦可在室溫進行約丨週的老化 (aging) 〇經由步驟（c) ’使硬化性接著劑層（2,）、（4,）硬化而製成接著劑層（2)、（4)，並完成使偏光件（3)、保護薄膜（1) 及（5)藉由接著劑層（2)、（4)而接著成的偏光板（參照第1 圖、第2圖中的（d))。本發明的偏光板亦可藉由下述操作而製造：在聚乙烯醇系偏光件（3)之一面塗抹光硬化性接著劑而形成第i硬化丨生接著劑層（2 )’並將形成的第1硬化性接著劑層（2 ’） 322005 21 201109404 · 的表面用第i保護薄膜⑴被覆，其次，在聚乙稀醇系偏光 $⑶之另-面塗抹光硬化性接著劑而形成第2硬化性接著劑層（4 )’並將形成的第2硬化性接著劑層（4,）的表面用第2保護薄膜⑸被覆，然後，從第2保護薄膜⑸側照射活性能篁線，使第1硬化性接著劑層（2,）及第2硬化性接著劑層（4,）硬化。偏光板係如上所述，為含有偏光件、接著層及保護薄膜作為必需構成者，但亦可含有其他之任意構成。例如在任意位置，必要時可含有反射層、抗反射層、硬塗膜層、防/亏層、防霧層、防黏附（anti_sticking)層等。 (實施例） [聚乙稀醇糸偏光件]的製造例將硼酸20質量份、碘0.2質量份、碘化鉀0.5質量份溶解於水480質量份，調製染色液。將pVA薄膜（維尼綸 (vinylon)薄膜#40，愛謝羅（aiceLLO)公司製造）浸潰在該染色液30秒後，將薄膜朝一方向延伸2倍，使其乾燥，獲得臈厚30 am的PVA偏光件。 [實施例1] 保護薄膜（1)係使用三菱嫘縈（股）公司製造的含有紫外線吸收劑之丙烯酸系薄膜：HBD_〇〇2(5〇//m)，保護薄膜 (5)係使用曰本傑旺公司製造的未含有紫外線吸收劑之環烯烴薄膜、傑歐諾亞薄膜「ZF-14」（lOOym)，對各自的表面以300W ·分鐘/见2的袜電n行電暈處理。在表面處理後1小時以内，對保護薄膜（1)及（5)分別使用線棒塗覆機 22 322005 201109404 m二表不的光聚合組成物’形成硬化性接著劑層、）’在該硬化性接著劑廣（2，）與（4，）之間挾住上述PVA偏光件，獲得由保護薄膜⑴/硬化性接著劑層（2，） /PVA系偏光件（3)/硬化性接著劑層（4,保護薄膜（5) 所構成的層壓體。以使保護薄膜（1)相接於馬口鐵板（tinplate)之方式，將S亥層壓體之四方用玻璃膠帶固定，固定於馬口鐵板上。用UV照射裝置（東芝公司製造’咼壓水銀燈）從保護薄膜（5)側照射最大照度500mW/cm2、積分光量800 m J / cm2的紫外線，製作偏光板。形成之各接著劑層的厚度為3至4 # m。 [實施例2至8、比較例1至7] 除了將光硬化性聚合組成物變更為如表1及表2所示者以外，經由與實施例1相同的操作而製作偏光板，並根據後述的方法評估其性能。 [實施例9及1〇] 除了在實施例9中之保護薄膜（1)改用富士薄膜（股）公司製造的含有紫外線吸收劑之三乙醯纖維素系薄膜：商品台「富士達克」（80 ym)，在實施例10中之保護薄膜（1) 改用日本傑旺公司製造的未含有紫外線吸收劑之環烯烴薄膜、傑歐諾亞薄膜「ZF-14」（10〇 # m)以外’進行與實施例 3相同的操作而獲得偏光板’並進行相同之έ平估。 [實施例11] 除了保護薄膜（1)改用富士薄膜（股）公司製造的含有 23 322005 201109404 紫外線吸收劑之三乙醯纖維素系薄膜：商品名「富士達克」 (80#m) ’且保護薄膜（5)改用未含有紫外線吸收劑之三乙醯纖維素系薄膜：商品名「TACPHAN N828GL」（80/zm)以外，進行與實施例3相同的操作而獲得偏光板，並進行相同之評估。 [實施例12] 保護薄膜（1)、（5)係與實施例11相同，並使用如表j 表示之含有尚Tg自由基聚合性化合物（b)之光硬化性接著劑，進行與實施例3相同的操作而獲得偏光板，並進行相同之評估。 [實施例13] 除了保護薄膜（1)、（5)使用日本傑旺公司製造的未含有紫外線吸收劑之環烯烴薄膜、傑歐諾亞薄膜「ZF_14」（1 /im)以外，使用與實施例丨2相同的光硬化性接著劑，獲得偏光板，進行相同的評估。 [實施例14及15] 保護薄膜（1)、（5)係與實施例13相同，並使用如表夏表示之含有多官能丙烯酸酯（b)或具有丙烯醯基之陽離子聚合性化合物⑴的光硬化性接著劑，進行與實施例^相同的操作，獲得偏光板，進行相同之評估。 [比較例8至11] 保護薄膜（1)、⑸係使用日本傑旺公司製造的未紫外線吸收劑之環烯烴薄膜、傑歐諾亞薄膜「邡—Μ ，）’並使用表2記載的光硬化性接著劑，獲得偏丄板100 322005 24 201109404 . 進行相同之評估。 * <接著力（剝離強度）> 將獲得的偏光板用切割機切成25mmxl5〇mnl的大小，作為試樣。將試樣以雙面黏著膠帶（東洋油墨製造（股）公司製造之DF8712S)貼附在金屬板上。對於試樣（偏光板），在保護薄膜與偏光件之間預先設置剝離的記號，於23°c、50%RH 環境下，以剝離速度：300mm/分鐘測定接著力。表中的接著力係根據以下的基準評估。 2. 5(N/25mm)以上·. · ◎ 1. 5(N/25mm)以上至未達 2. 5(N/25mm)...〇 1· 0(N/25mm)以上至未達 1. 5(N/25mm). . 未達 1.0(Ν/25ππη)·.·χ <切割試驗（密著力試驗）> 在獲得的偏光板之保護薄膜與偏光件之間劃入切割機的刀刃，將刀刃推進時’刀刃的進入形式用以下的基準進行評估。切割機的刀刃不容易進入薄膜間...◎ 將切割機的刀刀推進時，刀刃在進入薄膜間4至5mm 處停止· · ·〇切割機的刀刃順利地進入薄膜間·. .X <穿孔加工性> 使用菪貝魯（Dumbbel)公司製造的lOOmmxlOOmin的刀，從保護薄膜（1)側將製作的偏光板穿孔。用目視觀察經穿孔的偏光板周邊的剝離狀態。 25 322005 201109404 相對於偏光板的面積（100cm2)，剝離面積的比例（％) 未達0至1%者為◎，未達1至2%者為〇，未達2至3%者為△，剝離面積在3%以上者為X。 <溫水浸潰試驗（耐水性）> 將獲得的偏光板用切割機切成25mmx5Omm的大小，作為試樣，將該試樣在恆溫水（60°C)中分別浸潰24小時及 72小時後，用目視觀察試樣（偏光板）的脫色程度。相對於偏光板的面積，脫色面積的比例（％)未達0至 10%者為◎，未達10至30%者為〇，在30%以上者為X。評估結果表示於表1及表2。使用之化合物及保護薄膜係詳細記載於表1的下面。 26 322005 201109404 ^ [表 1] 播 lloll I 寸产一 s n—iz s 001 001[Technical Field] The present invention relates to a polarizing plate used for liquid crystal display I or the like and a photocurability for forming the polarizing plate, j. [Prior Art] In the watch, mobile phone, personal portable terminal (ship, that is, personal digital assistant), pen § computer, personal computer display, digital CD player, TV (10), etc., liquid crystal display device It is rapidly expanding in the market. The liquid crystal display device visualizes the polarization state by switching the liquid crystal (5) (10)), and uses the polarized light from the principle of surface display. In particular, in the use of televisions and the like, high brightness, high contrast, and wide viewing angle are increasingly required, and high transmittance, high polarization, and color reproducibility are increasingly required in polarizing plates. Liquid S曰. 4 Polarizers that are not used in fields or the like are usually manufactured by stretching the disc or dye on the polyolefin yPVA). The polyethylene-based polarizer shrinks due to heat or moisture, resulting in a decrease in polarizing performance. Here, a protective film is adhered to the surface of the PVA-based polarizer as a polarizing plate. As an adhesive for adhering a protective film to a polarizing material, an aqueous solution (PVA-based adhesive) of a polyvinyl alcohol-based resin has been widely used (see Patent Document 2). Patent Document 3 discloses a polarizing plate formed using an aqueous urethane-based adhesive. However, in particular, it has been represented by television. In recent years, with the progress of the portrait display 裘 322005 3 201109404, it has become an important issue to increase the size of the polarizing plate. However, the polarizing plate using the water-based adhesive has a change in the size of the polarizing plate due to the heat of the backlight, and the deformation due to the dimensional change partially exists in a part of the kneading surface. As a result, the original kneading surface should be displayed. When it is completely black, the light leaks partially. 'There is a problem that the so-called light leakage (uneven color) becomes significant. For the reason described above, there is a proposal to use a cationically polymerizable ultraviolet curable adhesive instead of a water-based adhesive (see Patent Document 4). However, when a cationically polymerizable ultraviolet-curable adhesive is used, a dark reaction (post-polymerization) occurs after irradiation of the external and external rays. Therefore, when the long-shaped cured product is formed into a roll shape, the roll tends to be generated during storage. The problem of pleats. Further, the cationically polymerizable ultraviolet curable adhesive is likely to be affected by the humidity at the time of curing, and there is a problem that the cured state is likely to be mutated. Therefore, in order to show the hardened state of the surface, not only the environmental humidity, but also the water content of the pVA-based polarizer needs to be strictly managed. The radically polymerizable ultraviolet-curable adhesive has such a problem that the B-shaped display device can be gradually replaced with the use of the liquid crystal display device with a large increase in resistance =: The representative liquid crystal display device for mobile use is as described above. 'Free radically polymerizable ultraviolet hard (four) solder is compared with Yang 322005 4 201109404. Ion = sclerosing type of adhesive, superior in various characteristics. . However, when the free radical polymerization is used, the time is exposed to the hot and humid environment, and the polarizing property is easy. When the polarizer which is colored with the enamel or the dye at the end is easy to be used, if the length is lowered, there is a problem of cutting the color. ...* Decolorization of the polarizer occurs significantly under more severe conditions in a hot and humid environment (for example, water immersed in 6 ° C). In other words, in the future where the use of polarizing plates is more stringent, it is expected that polarizers with more heat and humidity resistance than the polarizing plates of the past are expected. In addition, in order to easily carry out the polarizing plate polyethylene film and the plastic film with sufficient strength, an adhesive composition in which a (meth)acrylic radical polymerizable compound and a cationic polymerizable compound are used together is proposed (patent Document 5). However, this technology is more demanding to improve the piercing processability. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. [Invention] The present invention provides a polyvinyl alcohol-based polarizing member and a protective film as a constituent layer, and protects the thin raft and the polarizing member. A polarizer having excellent adhesion and perforation processability and excellent water resistance is also intended. In order to solve the above problems, the inventors of the present invention have conducted continuous ice-injection studies and found that the above-described object can be achieved by the polarizing plate shown below. 322005 5 201109404 Thus, the present invention has been completed. That is, the present invention relates to a polarizing plate comprising a polyvinyl alcohol-based polarizing member, an adhesive layer obtained by curing a photocurable adhesive, and a protective film, and each of which is covered by the protective film via the above-mentioned adhesive layer A polarizing plate comprising the polarizing member; the photocurable adhesive comprising a radically polymerizable compound and a cationically polymerizable compound, a photoradical polymerization initiator, and a photocation a radical polymerization agent (a) which forms a homopolymer of a glass transition temperature of -80 ° C to 0 ° C in the above radical polymerizable compound, and contains 60 to 99 in the above-mentioned main component. . In the above cationically polymerizable compound, the cationically polymerizable compound (c) having no (indenyl) acrylonitrile group contains 0. 02 to 40% by mass; with respect to 100 parts by mass of the above-mentioned main agent, respectively, 1 to 10 parts by mass of the above photoradical polymerization initiator, and the above photocationic polymerization initiator 0. 5 to 5 parts by mass. Moreover, the present invention relates to a photocurable adhesive for forming a polarizing plate, which comprises a main component comprising a radical polymerizable compound and a cationically polymerizable compound, a photoradical polymerization initiator, and a photocationic polymerization initiator. The radically polymerizable compound (a) which forms a homopolymer of a glass transition temperature of -80 ° C to 0 ° C in the above-mentioned radical contains 60 to 99 in the above-mentioned main agent. 6 。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。 * 1 to 10 parts by mass of the photoradical polymerization initiator and 5 to 5 parts by mass of the photocationic polymerization initiator, respectively, per 100 parts by mass of the above-mentioned main component. [Embodiment] Hereinafter, preferred embodiments of the present invention will be described. According to the present invention, a polarizing plate having a polyvinyl alcohol-based polarizing member and a protective film as a constituent layer can be provided, which is a polarizing plate excellent in adhesion, piercing processability, and water resistance. [Next layer] force to say that the layer B or the adhesive layer of the polarizing plate of the month and the adhesive layer) and the cationic polymerizable component (radical polymerizable radical polymerization component (cationic polymerizable compound) Continued (4) The aggregate degree is a self-consistent compound; = a radically polymerizable compound (b) which can contain a conformable "shift: t homopolymer (by 322〇〇5 7 201109404 Also known as "radical polymerizable compound (b)" or "high Tg radical polymerizable compound (b)"), that is, in the case of a radical polymerizable component, a glass transition containing a homopolymer thereof The temperature is -80 ° C to 0. (: the radical polymerizable compound (a) ' and optionally contains a homopolymer thereof, and the glass transition temperature is from 60 ° C to 250. (: a radical polymerizable compound (b) In the low Tg radical polymerizable compound (a), for example, a monofunctional one may be exemplified by 2-hydroxyethyl acrylate (Tg of a homopolymer: -9 ° C, the same applies hereinafter), 2-hydroxypropyl acrylate (-7t:) and 4-hydroxybutyl acrylate (-55. (:) represented by (fluorenyl) hydroxy terminal alkyl acrylate; 2-methoxyethyl acrylate (-43 ° C), 3-decyl butyl acrylate (-47 ° C), tridecyl acrylate (-65 ° C) and tridecyl decyl acrylate ( -37 ° C) represented by (alkyl) acrylate alkyl terminal alkyl ester; diethylene glycol monoethyl ether acrylate (-54 ° C), ethoxy diethylene glycol acrylate (_51 ° C) , alkyl-terminated (poly)alkanediol represented by decyloxy polyethylene glycol (n=9) acrylate (-71 ° C) and methoxytripropylene glycol acrylate (-75 ° C) (fluorenyl) acrylate; phenoxyacetic acid acrylate (-15 ° C), trifluoroethyl acrylate (-10 ° C), carboxy-polycaprolactone acrylate (_46 ° C), etc. 8 322005 201109404 In the 'low Tg radical polymerizable compound (4), 'polyfunctional group' can be exemplified by polyethylene glycol (Lion) bis(10) acid g (-28. 〇, polyethylene glycol (600) diacrylate (- 42. Anthracene, triethylene glycol dimethacrylate (-5. oxime, ethoxylated (9)-methyl-di-burned triacetic acid vinegar (-19t:), etc. The photocurable adhesive of the present invention can Use appropriate materials such as 0 low Tg radical polymerization The compound (4) is preferably monofunctional. Even if it is a low Tg radically polymerizable compound (a), if only a polyfunctional group is used, it may be inferior in terms of the cutting test performance described later. In the case where the low-Tg radically polymerizable compound (a) is used in combination with a polyfunctional person, the low-Tg radical polymerizable compound (a) (as a mass%) is controlled in the absence of the cutting test performance. The degree of the mass % is preferably controlled to a level of less than 10% by mass. Further, when the south Tg radical polymerizable compound (b) described later is used, the Tg radical polymerizable compound (b) is preferred. In other words, when a polyfunctional radical polymerizable compound is used as the radical polymerizable compound ((a) or (a) + (b)), the ratio is in the main component (as 100 mass). %) The degree of the middle system is less than 4% by mass, preferably less than 1% by weight. Or a monofunctional radically polymerizable compound (monofunctional radically polymerizable compound (a) or monofunctional radically polymerizable compound (a) and (b) in a radically polymerizable compound) The ratio is better at 6 〇 9 322005 201109404 5% or more 'better than 70% by mass, preferably 90% by mass or more. The radical polymerizable compound (a) is more preferably a homopolymer having a glass transition temperature of -60 ° C to -2 (TC, preferably a homopolymer glass transition temperature of -60 ° C to -40 °) In the low-Tg radical polymerizable compound (a), from the viewpoint of improving the adhesion to the pva-based polarizer, it is preferably a thiol-acrylic hydroxy vinegar or the like having a base. The 4-butyl butyl acrylate is preferred. From the viewpoint that the Tg of the cured product is not easily lowered, it is preferred to use 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate even if it has a hydroxyl group. That is, the alkyl group of the (hydroxy) hydroxyalkyl acrylate preferably has a carbon number of about 4 to 40. The cohesive force of the adhesive layer after hardening is increased and the sharp point of the adhesion is increased. §, low Tg The radically polymerizable compound (a) is preferably a ω-cyclohexyl-polycaprolactone mono(indenyl) acrylate. However, ω-carboxy-polycaprolactone (mercapto)propanol acid g In order to achieve poor hardenability, it is possible to appropriately select the type of ultraviolet radical irradiation device by appropriately selecting the type or amount of the radical polymerization initiator. When the hardening conditions such as the irradiation intensity or the exposure amount are selected, and the type or thickness of the film is appropriately selected, the hardenability is compensated for. Μ 竣 - - - - - - - - 聚合聚合聚合聚合聚合The degree (η) is not particularly limited, and is preferably a degree of η = 2 to 20. For example, a radically polymerizable compound (a) of 6 to 99% by mass in a total amount of the main component is 1% by mass. It is preferred to use a hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl acrylate at 10 to 99. 8 mass%, ω_carboxyl-polycaprolactone mono(methyl)propionate was added in each range of 〇 to 5% by mass to 322005 10 201109404 to be combined. « Also, when ω-carboxy-polycaprolactone mono(meth)acrylate is formulated, it is preferred to use a hydroxyalkyl (meth) acrylate at 10 to 99. 7 mass%, ω-carboxy-polycaprolactone mono(indenyl) acrylate at 0. Used in the range of 01 to 50% by mass. The arbitrarily formulated high Tg radical polymerizable compound (b) is preferably, for example, dicyclopentenyl decyl acrylate (Tg of homopolymer: 180 ° C, the same applies hereinafter), trifluoroethyl methacrylate (81 ° C), tert-butyl methacrylate (113 ° C), ethyl methacrylate (65 ° C), tetrahydrofurfuryl methacrylate (68 ° C), isobornyl acrylate (85 ° C) and acryloylmorpholine (106 ° C) and the like. Among them, isobornyl acrylate and acryloyl morpholine are preferably used from the viewpoint of heat resistance. The radical polymerizable compound (b) is preferably a glass transition temperature of the homopolymer of from 60 ° C to 200 ° C, more preferably a glass transition temperature of the homopolymer of from 80 ° C to 150 ° C. The photocurable adhesive of the present invention can be used in an appropriate combination of these materials. The Tg of each of the homopolymers formed from the low Tg radical polymerizable compound (a) and the high Tg free radical polymerizable compound (b) described above can be obtained by the following operation. 11 322005 201109404 Each compound and starter are placed in a plastic container of appropriate capacity, and 10 mg of the cured material is irradiated with ultraviolet rays as a sample for measurement, and a differential scanning calorimeter (DSC) is used at 10 ° C / min or 20 The rate of temperature rise was measured at ° C/min. The cationically polymerizable compound (c) having no (meth)acrylic group (hereinafter referred to as "cationic polymerizable compound (c)") has a cationically polymerizable functional group and does not have (mercapto) acrylonitrile. The compound of the group includes, for example, 3,4-epoxycyclohexyldecyl 3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3 , 4 -epoxy)cyclohexyl-m-dicycloparin, bis(3,4-epoxycyclohexyldecyl) adipate, bis(3,4-epoxy-6-fluorenyl) a compound having one or more alicyclic epoxy groups in one molecule such as cyclohexylmethyl) adipate, vinylcyclohexene monooxide or 1,2-epoxy-4-vinylcyclohexane Or a compound having an oxetanyl group. The cationic polymerizable compound (c) serves as a task for improving the water resistance of the hardened adhesive layer. Among the compounds having an alicyclic epoxy group, 3,4-epoxycyclohexyldecyl-3,4-epoxycyclohexanecarboxylate is preferably used from the viewpoint of reactivity. In the present invention, the cationically polymerizable compound (c) is preferably selected from those having no (fluorenyl) acrylonitrile group from the viewpoint of ensuring good adhesion and puncturing workability. The cationically polymerizable compound having a (meth) acrylonitrile group may be used in combination with the above (c), but the amount of the cationically polymerizable compound having a (meth) acrylonitrile group at this time is 100% by mass of the main component. In the case, it is necessary to control the degree to less than 20% by mass, preferably to the extent of not more than 10% by mass. In the total amount of the cationically polymerizable compound, the proportion of the cationically polymerizable compound (C) having no (meth) acrylonitrile group is preferably 50% by mass or more, more preferably 75% by mass or more. The main agent of the photocurable adhesive contains a radical polymerizable compound (a) 60 to 99. 9% by mass, cationically polymerizable compound (c) 0. 02 to 40% by mass, preferably a radical polymerizable compound (a): 60 to 99 mass% / 〇, cationically polymerizable compound (c): 1 to 40% by mass, more preferably a radical polymerizable compound (a) ): 90 to 99% by mass of the cationically polymerizable compound (c): 1 to 10% by mass. When the amount of the low Tg radical polymerizable compound (a) is less than 60% by mass, the formed back layer is too hard, and not only the adhesion is not ensured, but also the punching workability is deteriorated. On the other hand, the low Tg radical polymerizable compound (a) is more than 99. When the amount of the polymerizable compound (c) is almost no more than 8% by mass, the water resistance of the formed adhesive layer is deteriorated, and when the polarizing plate is impregnated in warm water, the color of the PVA polarizer is dropped. When an acetonitrile cellulose resin film such as triacetonitrile cellulose is used as the protective film, the high Tg radical polymerizable compound (b) contributes to the improvement of the adhesion. When the high Tg radical polymerizable compound (b) is used, it is preferably a low Tg radical polymerizable compound (a): 60 to 75% by mass, and a high Tg radical polymerizable compound (b): 0. 01 to 39. 98% by mass, cationically polymerizable compound (c): 0. 02 to 24. 99% by mass, more preferably low Tg radical polymerizable compound (a): 60 to 70% by mass, high Tg radical polymerizable compound 13 322005 201109404 (b) : 10 to 35 mass%, cationically polymerizable compound (c ) ·· 5 to 2〇% by mass. Alternatively, in the photocurable adhesive according to a preferred embodiment, the main component contains a glass transition temperature of -80 ° C to 0. (: a monofunctional radical polymerizable compound of the homopolymer (a): 60 to 99. 8% by mass, 幵> a monofunctional radically polymerizable compound (b) which is a homopolymer of a glass transition temperature of 60 ° C to 250 ° C : 〇 to 39. 98% by mass, and a cationically polymerizable compound (c) having a cationically polymerizable functional group and having no (meth)acryl fluorenyl group. 〇2 to 40% by mass (except that (a) to (c) above is 1% by mass in total), and as a polymerization initiator, a photoradical polymerization initiator (d) is contained: i to 10 parts by mass (1 part by mass relative to the above (a) to (c)) and a photocationic polymerization initiator (e): 0. 5 to 5 parts by mass (1 part by mass relative to the above (a) to (c)). More preferably, it contains a low Tg radical polymerizable compound (a): (9) to 99% by mass, a high Tg radical polymerizable compound (b): 〇 to 39% by mass and a cationically polymerizable compound (c): 1 to 40 mass %. In the photocurable adhesive of the present invention, in addition to the low Tg radical polymerizable compound (a) or the high Tg radical polymerizable compound (b), other radical polymerizable compounds may be added. Other radical polymerizable compounds include, for example, an amine ester acrylate, an epoxy acrylate, a polyester acrylate, and a polyether acrylate. However, as described above, the radically polymerizable compound is preferably used in a defined blending range. In the photocurable adhesive of the present invention, an appropriate additive may be added as needed. The additive is preferably a decane coupling agent from the viewpoint of the adhesion of the protective film to the protective film and the suppression of shrinkage of the polarizing plate. The decane coupling agent is preferably one having an acrylonitrile group. σ The photocurable adhesive of the present invention contains a photoradical polymerization initiator (4). The photoradical polymerization initiator (d) is not particularly limited, and examples thereof include IRGACURE-184, 907, 65, Π 00, 1800, 819, 369, 261; DAROCUR-TPO (Ciba Specialty Chemicals Co., Ltd. Manufacturing), DAROCUR-1173 (Merck), EsaCure-KIP150, TZT (made by Japan Sheikhecken), KAYACURE BMS Kayaqia DMBI (manufactured by Nippon Kayaku Co., Ltd.). Among these, in order to improve the transparency of the adhesive layer after photohardening, photobleaching of DAROCUR-TPO is preferably used. The blending ratio of the photoradical polymerization initiator (d) is 1 to 10 parts by mass based on 100 parts by mass of the total of the radical polymerizable compounds (a) and (b) and the cationically polymerizable compound (c). It is preferably from 1 to 5 parts by mass. The photocurable adhesive of the present invention contains a photocationic polymerization initiator (e). The photocatalytic polymerization initiator (e) is exemplified by, for example, UVACURE 1590C, Daice Bucy Co., Ltd., CPI-110P. (made by San-apro), such as strontium salt or IRGACURE 250 (manufactured by Ciba Specialty Chemicals Co., Ltd., WPI-113C and Wako Pure Chemical Industries, Ltd.), RP-2074 (Rhodia. 曰I made by the company), etc. 15 32 。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。 Then, the amount is transferred, preferably from 5 to 5 parts by mass. When necessary, in addition to the above-mentioned main agent and polymerization initiator, the polymerization initiator, ultraviolet male fruit may contain a polymerization inhibitor, a defoaming agent, a plasticizer t-receiving agent, Plasticizers, colorants, antioxidants [polarizers] _ various known additives. In the case of the polyvinyl alcohol-based resin in which the polyvinyl alcohol is used as the base material of the polarizer, it is preferred that the polyvinyl alcohol-based resin has a residual number of +3⁄4 from the water-based side. Part = copolymer. Polyethylene glycol can be enumerated, for example, B. All _^_, === alcohol base is not fine, and there is no special. Poly-modified polyethylene, etc. can also be used in two kinds. (4) (4) The lipid may be used alone (4), or the specific example of the polyvinyl alcohol may be RS to U 〇 of the RS polymer manufactured by Kray (s). (Specialization degree = 99%, polymerization degree ^ 〇〇〇), Claret Baru LM20SO manufactured by the same company (U, degree of polymerization = 2, 〇〇〇), Japan Synthetic Chemical Industry Co., Ltd. (saponification degree = 99%, degree of polymerization = ι, 4 Å), etc. Polyvinyl alcohol can be used, for example, by using a base of a polymer of a fatty acid vinyl ester such as vinyl acetate, vinyl propionate or tridecyl vinyl acetate. The saponification of a catalyst or the like is carried out in 16 322005 201109404. The above ethylene-vinyl alcohol copolymer is obtained by saponifying a saponified product of a copolymer of ethylene and vinyl acetate, that is, a random copolymer of ethylene and vinyl acetate. 'There is no particular limitation on a partial saponified product containing tens of moles of residual acetate from the acetic acid group to only a few moles of acetaminophen or a residual saponification of the acetoxy group. ... ^ Polarizing member is known by The above-mentioned polyvinyl alcohol-based tree stalk is thinned by a casting method or the like. The film is obtained by absorbing orienting iodine or a dichroic dye (bichrome pigment). The polarizer may be a parent or a stretcher via boric acid or the like. At the same time, it is carried out at any stage after the dyeing. The shape of the polarizer is not particularly limited, and examples thereof include a film, etc. Further, in the present specification, "film" and the smallest one (thickness is not reached) Further, the sheet also includes a sheet (for example, a thickness of 1 to 5 mm). The thickness of the polarizing member is not particularly limited, and the carrier is preferably, for example, about 10 to. [Protective film] Protective film for the polarizing plate of the present invention (The symbols 1 and 5 in the first and second figures are explained.) The protective film is not particularly limited, and specifically, "the most widely used triethyl cellulose (MC) which can be used as a protective film for a polarizing plate can be used. A transparent resin film which is thinner than a cellulose resin or has a lower moisture permeability than triethyl hydrazine cellulose. A material which constitutes a protective film having a lower moisture permeability than triethylene cerium fibrin, for example, transparency and mechanical strength are used. , thermal stability, The water-blocking property is excellent in the thermoplastic resin such as 322005 17 201109404. The specific examples of the thermoplastic resin include a ring-shaped thin resin and an acrylic resin. The cyclic olefin resin is a cyclic olefin. A general term for a resin obtained by polymerizing a unit and polymerizing it. Specific examples thereof include a ring-opening (co)polymer of a cyclic hydrocarbon, an addition polymer of a cyclic olefin, and copolymerization of a cyclic olefin with an α-olefin such as ethylene or propylene. a material (representatively a random copolymer), and a graft copolymer modified with an unsaturated tauric acid or a derivative thereof, and the like, preferably a norbornene (n〇 The rb〇rnene) resin is obtained by a known method described in JP-A-2005-164632, JP-A-2006-201736, JP-A-2002-201727, and the like. The cycloaliphatic resin has various commercially available products. Specific examples include the brand name "ZE〇N〇R" manufactured by JEW (Japan) Co., Ltd., and the product name "ART〇N" manufactured by JSR Co., Ltd. The trade name "APEL" manufactured by Mitsui Chemicals Co., Ltd., manufactured by TIC〇M, is the trade name "APEL" manufactured by Mitsui Chemicals Co., Ltd. The acrylic resin is represented by polymethyl methacrylate, and is a resin having a molecular component of an alkyl ester such as mercaptopropyl methacrylate or butyl methacrylate. Copolymer). Depending on the occasion, it is combined with other resins and thinned. The acrylic film can be obtained by a known method described in JP-A No. 2,361,712 or the like. There are various commercially available products of acrylic acid thin. For the specific example, the trade name "Acrypien" or the brand name "Sunduren" manufactured by Kaneka Co., Ltd. is used. 18 322005 201109404 The protective film (1) and (5) of the polarizing plate of the present invention are used, and (5) the acrylic resin film is used without any problem. The thickness of the protective film can be appropriately determined, and it is usually from strength to strength. From the point of view of workability, thin layer, etc., it is about i to 5 hearts 1 2:: more: 5 to 2 ° °, and the wheel (1) and (8) are two, when the two polarizers are like DON, It is protected by a protective material composed of a polymer material and a protective material. For example, when the two-acid-based film is used in a different manner, the types of the acrylic polymer may be different from each other without any limitation. 5' The polarizing plate of the present invention can be obtained by the following operations. In other words, it is preferably produced by applying a first light-curing adhesive layer to the surface of the first protective film (1) to form a first curable adhesive layer (2); and a second protective thin layer. (5) One surface is coated with a second curable adhesive layer (4,); _ a first hardenable adhesive, each of the (4) 1 curable stack () and the second curable adhesive layer (4) of the coffee member (3) ,) at the same time, or sequentially, from the second protective film (5) side, the activity is followed by _ and the second curable adhesive layer, the above-mentioned curable adhesive layer (2') and ..., protective film (1) and (5) 322005 19 201109404 · Each can be the same or different. In other words, the curable adhesive layer (2) and the curable adhesive layer (4) (in other words, the first photocurable adhesive and the second photocurable adhesive) may have the same composition, or may be the same composition. The thicknesses of the adhesive layers (2) and (4) formed for different compositions are the same or different, and are not particularly limited, and are usually preferably 0. 1#m to 50/zin, better 〇 5#m to 2〇#m. Hereinafter, each step will be described based on Fig. 2 . [Step (a)] Step (a) is a photocurable adhesive for forming an adhesive layer on one surface of each of the protective films (丨) and (5) as shown in Fig. 2(a). If necessary, drying or the like is carried out to obtain a laminate (1') and (5') having the curable adhesive layers (2') and (4). The coating method of the photocurable adhesive is not particularly limited, and examples thereof include a die coating method, a roll coating method, a gravure coating method, a spin coating method, and the like. [Step (b)] The step (b) is as shown in Fig. 2(b), and a protective film and a curable adhesive are provided on one surface (upper side in the figure) of the polyvinyl alcohol-based polarizing member (3). The laminate of the layer (2') is laminated, and the protective film (5) and the curable adhesive layer are provided on the other side of the polyvinyl alcohol-based polarizing member (3) (below in the drawing). 4,) laminate (5,) the step of lamination. [Step (c)] Step (c) is as shown in Fig. 2(c), and the protected film (1), (5) and the polyvinyl alcohol-based polarizer are irradiated by irradiation of the active energy ray (6). 3) Step 20 322005 201109404 κ , the hardening adhesive layer (2,), (4,) is cured to form the adhesive layers (2), (4). In the figure, although the active energy ray is not irradiated from the side of the protective film (5), the active energy ray (6) may be irradiated from the side of the protective film (1), or both sides may be simultaneously or from both sides. The active energy rays (8) are sequentially irradiated. The amount of irradiation of the active energy ray is not particularly limited, and it is preferred to irradiate light having a wavelength of 200 to 450 nm and an illuminance of 1 to 500 mW/cm 2 so that the irradiation amount is 10 to 500 〇 mJ/cro 2 . When the irradiation amount is lower than lOnJ/cm2, the curing of the ultraviolet curable composition cannot be promoted, and the desired performance cannot be exhibited. When the irradiation amount is "high, the π-ray time becomes very long" has a problem of productivity. The type of the active energy ray to be irradiated is preferably a visible light, an ultraviolet ray, a ^ line, an m line, a ^ line, or the like, and is preferably an outer line. The light irradiation device is preferably, for example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an excimer lamp or the like. After illuminating the active energy ray (6), aging can also be performed at room temperature for about aging. 步骤 The step (c) is used to cure the hardenable adhesive layers (2,) and (4,). The agent layers (2) and (4) complete the polarizing plate in which the polarizer (3) and the protective films (1) and (5) are formed by the adhesive layers (2) and (4) (refer to the first Figure, (d) in Figure 2). The polarizing plate of the present invention can also be produced by applying a photocurable adhesive to one side of a polyvinyl alcohol-based polarizing member (3) to form an ith hardened adhesive layer (2)' and forming The first sclerosing adhesive layer (2') 322005 21 201109404 · The surface is covered with the ith protective film (1), and secondly, the photocurable adhesive is applied to the other side of the polyvinyl alcohol-based polarizing $(3). (2) The surface of the second curable adhesive layer (4) is covered with the second protective film (5), and then the active energy entangled line is irradiated from the side of the second protective film (5). The first curable adhesive layer (2) and the second curable adhesive layer (4,) are cured. As described above, the polarizing plate is an essential component including a polarizing material, an adhesive layer, and a protective film, but may have any other configuration. For example, at any position, if necessary, a reflective layer, an antireflection layer, a hard coat layer, an anti-depletion layer, an anti-fog layer, an anti-sticking layer, or the like may be contained. (Example) [Production Example of Polyvinyl Ethylene Polarizer] 20 parts by mass of boric acid and iodine 0. 2 parts by mass, potassium iodide 0. 5 parts by mass was dissolved in 480 parts by mass of water to prepare a dyeing solution. After p24 film (vinylon film #40, manufactured by Ace LLO) was immersed in the dyeing solution for 30 seconds, the film was stretched twice in one direction and dried to obtain a thickness of 30 am. PVA polarizer. [Example 1] The protective film (1) was an acrylic film containing an ultraviolet absorber manufactured by Mitsubishi Rayon Co., Ltd.: HBD_〇〇2 (5 〇//m), and a protective film (5) was used. A cycloolefin film made of 紫外线本杰旺, which does not contain a UV absorber, and a Zeono film "ZF-14" (100 μm), which are treated with a corona wire of 300 W · min / see 2 for each surface. . Within 1 hour after the surface treatment, the protective film (1) and (5) were respectively subjected to a photopolymerization composition of a wire bar coater 22 322005 201109404 m to form a hardenable adhesive layer, The PVA polarizer is sandwiched between the wide (2,) and (4,) adhesives to obtain a protective film (1) / a curable adhesive layer (2,) / PVA polarizer (3) / a hardenable adhesive Layer (4, laminate of protective film (5). In order to connect the protective film (1) to the tinplate, the square of the S-wall laminate is fixed with glass tape and fixed to the tinplate. On the side of the protective film (5), a UV illuminating device (manufactured by Toshiba Corporation) was used to irradiate ultraviolet rays having a maximum illuminance of 500 mW/cm 2 and an integrated light amount of 800 m J / cm 2 to prepare a polarizing plate. The thickness is 3 to 4 #m. [Examples 2 to 8 and Comparative Examples 1 to 7] The same procedures as in Example 1 were carried out except that the photocurable polymer composition was changed as shown in Tables 1 and 2. A polarizing plate was produced by operation, and its performance was evaluated according to the method described later. 9 and 1] In addition to the protective film (1) in the ninth embodiment, a film containing a UV absorbing agent made of Fujifilm Co., Ltd. was used: "Fujidak" (80 ym) The protective film (1) in the example 10 was changed to a cycloolefin film which was not contained in the ultraviolet absorber and a "ZF-14" (10〇#m) manufactured by Japan Jiewang Co., Ltd. The same procedure as in Example 3 was carried out to obtain a polarizing plate' and the same evaluation was carried out. [Example 11] In addition to the protective film (1), the third film containing 23 322005 201109404 ultraviolet absorber manufactured by Fujifilm Co., Ltd. was used. Ethyl cellulose film: trade name "Fujidak" (80#m) 'and protective film (5) is changed to triethylene cellulose film without UV absorber: trade name "TACPHAN N828GL" (80 The same operation as in Example 3 was carried out to obtain a polarizing plate, and the same evaluation was carried out. [Example 12] The protective films (1) and (5) were the same as in Example 11, and were used as in Table j. Indicates that it contains a Tg radical polymerizable compound (b) The photocurable adhesive was subjected to the same operation as in Example 3 to obtain a polarizing plate, and the same evaluation was carried out. [Example 13] In addition to the protective film (1), (5), the product manufactured by Japan Jiewang Co., Ltd. was not contained. The polarizing plate was obtained using the same photocurable adhesive as in Example 2 except for the cycloolefin film of the absorbent and the Zeon Nooran film "ZF_14" (1 / im), and the same evaluation was carried out. [Example 14 and 15] The protective films (1) and (5) are the same as in Example 13, and a photocurable adhesive containing a polyfunctional acrylate (b) or a cationically polymerizable compound (1) having an acrylonitrile group as shown in Table Summer is used. The same operation as in Example ^ was carried out to obtain a polarizing plate, and the same evaluation was performed. [Comparative Examples 8 to 11] The protective films (1) and (5) were obtained by using a cycloolefin film of a non-ultraviolet absorber manufactured by JEW Corporation of Japan, a Geon Noah film "邡-Μ,", and using the light shown in Table 2 A hardening adhesive to obtain a bismuth plate 100 322005 24 201109404 . Make the same assessment. * <Adhesion force (peeling strength)> The obtained polarizing plate was cut into a size of 25 mm x 15 〇mn by a cutter to prepare a sample. The sample was attached to a metal plate with a double-sided adhesive tape (DF8712S manufactured by Toyo Ink Co., Ltd.). For the sample (polarizing plate), a peeling mark was previously provided between the protective film and the polarizing member, and the adhesion was measured at a peeling speed of 300 mm/min in an environment of 23 ° C and 50% RH. The adhesions in the table are evaluated against the following criteria. 2. 5 (N/25mm) or more · · · ◎ 1. 5 (N / 25mm) or more to less than 2. 5 (N / 25mm) ... 〇 1 · 0 (N / 25mm) or more to less than 1 . 5(N/25mm). . Not up to 1.0 (Ν/25ππη)···χ <Cutting test (adhesion test)> The blade of the cutter was placed between the protective film of the obtained polarizing plate and the polarizer, and the entry form of the blade was evaluated by the following criteria. The cutting edge of the cutting machine does not easily enter the film... ◎ When the cutter of the cutting machine is advanced, the cutting edge stops 4 to 5 mm between the film. · · · The cutting edge of the cutting machine smoothly enters the film. · X <Poreing Processability> The produced polarizing plate was perforated from the side of the protective film (1) using a knife of 100 mm x 100 min manufactured by Dumbbel Co., Ltd. The peeling state around the perforated polarizing plate was visually observed. 25 322005 201109404 Relative to the area of the polarizing plate (100cm2), the ratio (%) of the peeling area is less than 0% to 1%, ◎, less than 1% to 2% is 〇, and less than 2% to 3% is △, If the peeling area is 3% or more, it is X. <Warm water impregnation test (water resistance)> The obtained polarizing plate was cut into a size of 25 mm x 5 Omm by a cutter, and the sample was immersed in constant temperature water (60 ° C) for 24 hours as a sample. After 72 hours, the degree of decolorization of the sample (polarizing plate) was visually observed. The proportion (%) of the decolorizing area is less than 0 to 10% with respect to the area of the polarizing plate, ◎ is less than 10 to 30%, and X is 30% or more. The evaluation results are shown in Tables 1 and 2. The compound to be used and the protective film system are described in detail below in Table 1. 26 322005 201109404 ^ [Table 1] Broadcast lloll I inch production s n-iz s 001 001

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靼你«^-T-SXCMW l$il*;l»<ja>f、zlr-lxo,109 © 1相 0H owo 避 * 龙 £ 5 猫龙 •ΙΓ C 避 2： rO 1 3 « W m RT <•5 Μ 〇 LTi as 诩 0 *« « 想 S* 琎想眾 >1 〇甚 Ί 〇 fir << k 避 SQ ψ 进 * 〇猫 »1 /-Ν 0 讀 «ί 逋 1 CV3 *<·✓ '*1 避 tO 1 <0 U RT <ί <〇 Μ in CsJ CO » 珊 B- 硪 tO ΓΟ 想 tO «# «? Λ CO άΐ g 命 » 堋 S- 硪 tO «? Λ CO 龙 B- § ―η =ε /-S ΠΓ <•3 s &3 s_> 審 •O sr 1 ¢4 Ί 濾 s- >4 B- »1 i 〇 E- ΠΓ << Φ fc « CO & 键 Μ 取 ·>« 1 *<mt CJ> y ο S 班 * 女 W <•5 /-s 隹 S-/ '.·! S 〇 ό 3Q 2 〇 Β 波 κϋ 拥 m «Ε 女 < ΠΓ << m 4 m 呀 7 〇 00 « 玻〇 Έ «f u> 00 00 » Z S X < 〇 E- S =t S 琏浓 U Η V «f RT << η 狡 W I (a)可形成Tg:-80至Ot之硬化物的自由基聚合性化合物 (b)可形成Tg:60至250t之硬化物的單官电自由基聚合性化合物審 jJ 5 >QJI 仓0 ί W Ρ S CO § 5 十鳋 W 诹 « /"-s Β- 埤 4 4 5 ®- ffltc /-N Μ <〇书 Όϋ W 赵屮 Φ ω 保護薄祺（1)、（5) 27 322005 201109404[表2] u °s tn 001靼你«^-T-SXCMW l$il*;l»<ja>f,zlr-lxo,109 © 1 phase 0H owo evasion* dragon £5 cat dragon•ΙΓ C circum 2: rO 1 3 « W m RT <•5 Μ 〇LTi as 诩0 *« « Think S* 琎想众>1 〇 Ί 〇fir << k 避 SQ ψ入* 〇猫»1 /-Ν 0 read «ί 逋1 CV3 *<·✓ '*1 避 tO 1 <0 U RT < ί <〇Μ in CsJ CO » 珊B- 硪tO ΓΟ 想 tO «# «? Λ CO άΐ g 命» 堋S-硪tO «? Λ CO Dragon B- § ―η =ε /-S ΠΓ <•3 s &3 s_> Review •O sr 1 ¢4 Ί Filter s- >4 B- »1 i 〇E- ΠΓ << Φ fc « CO & key Μ 取 ·>« 1 *<mt CJ> y ο S class* Female W <•5 /-s 隹S-/ '.·! S 〇ό 3Q 2 〇Β波κϋ mm «Ε Female< ΠΓ << m 4 m 呀7 〇00 « Glass 〇Έ «f u> 00 00 » ZSX < 〇E- S =t S 琏U Η V «f RT < η 狡 WI (a) The radically polymerizable compound (b) which forms a hardened product of Tg: -80 to Ot can form a monovalent electroactive radical of a cured product of Tg: 60 to 250t Polymeric compound review jJ 5 >QJI warehouse 0 ί W Ρ S CO § 5 十鳋W 诹« /"-s Β- 埤4 4 5 ®- ffltc /-N Μ <〇书Όϋ W Zhao 屮Φ ω Protection thin 祺 (1), (5) 27 322005 201109404 [Table 2 ] u °s tn 001

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X o-寸— oos?-l oos—2 iwii 3 ops ooISz pisi_f oow s wi -·「 sz,?2 _0,si"5v • 1ml— vxs (q) s~s ilqj-耷 __sir1" τ-!·&*¥¥§¥ (o) 3 (φ¥锏)女咖 szw-l •-3J :-"1:·5 •J·51!'1 ........... χιωα (❿) (3 <0«*¥ ί!Η4_5ί:执赵梅埘贫，f、zlr>xlol°ol<o. ¾砌雄 («l^i*) «5ί*ί«^ίι csl敝 ¢ 1· 28 322005 201109404 如表1所示，在任何一個實施例中，皆可形成接著性、寧穿孔加工性及耐水性優越的偏光件。實施例3及實施例6係任一例都為使用未含高Tg自由基聚合性化合物（b)，且低Tg自由基聚合性化合物（a)之含量為90質量％的光硬化性接著劑的情形，低Tg自由基聚合性化合物（a)除了丙烯酸4-羥基丁酯之外亦併用ω-羧基-聚己内酯丙烯酸酯的實施例3，係凝集力比實施例6高，在接著力之特點上為優越。實施例12為使用含有高Tg自由基聚合性化合物（b) 的光硬化性接著劑的情形，與未含有高Tg自由基聚合性化合物（b)之實施例11相比，由於對於保護薄膜之三乙醯纖維素系薄膜的接著性優越，所以在接著力及耐水性之特點上為優越。再者，實施例13在與實施例12相比時，為保護薄膜使用透濕性較低之環烯烴薄膜的情形，在对水性之特點上為更優越。另一方面，使用未含陽離子聚合性化合物（c)之光硬化性接著劑之比較例1，即使是24小時的耐水性亦不佳。又，低Tg自由基聚合性化合物（a)含量少之比較例2 至5及10係任一例之經硬化之接著層皆變得太硬，故接著力小，穿孔加工性亦不佳。並且，比較例6、7為低Tg自由基聚合性化合物（a) 之含量少，且使用3官能之自由基聚合性化合物替代單官能高Tg自由基聚合性化合物（b)，並使用具有陽離子聚合 29 322005 201109404 性官能基及（甲基）丙烯醯基之化合物替代陽離子合物（C)的情形，其接著力極小。比較例8及9為低Tg自由基聚合性化合物之含量不充分，且使用具有陽離子聚合性官能基及（曱基）丙^醯基之化合物替代陽離子聚合性化合物（c)的情形，其接著力極小。又，比較例4至9儘管接著力極小，但卻耐水性佳，認為切割試驗之黏合性良好係原因之一。【圖式簡單說明】第1圖為表示本發明偏光板之一例之剖面圖（示意圖）。第2圖（a)至（d)為表示本發明偏光板之製造方法之一例之流程圖（示意圖）。【主要元件符號說明】 1、5 保護薄膜 1 保護薄膜（1)與由硬化性組成物所構成之層（2,）的層壓體 2 第1接著劑層 2’ 第1硬化性接著劑層 3 ^^乙稀醇系偏光件 4 第2接著劑層 4’ 第2硬化性接著劑層 5 保護薄膜（5)與由硬化性組成物所構成之層（4,）的層壓體 6 活性能量線 30 322005X o-inch — oos?-l oos—2 iwii 3 ops ooISz pisi_f oow s wi -·” sz,?2 _0,si"5v • 1ml— vxs (q) s~s ilqj-耷__sir1" τ- !·&*¥¥§¥ (o) 3 (φ¥锏) female coffee szw-l •-3J :-"1:·5 •J·51!'1 ......... .. χιωα (❿) (3 <0«*¥ ί!Η4_5ί: 执赵梅埘穷,f,zlr>xlol°ol<o. 3⁄4 雄雄(«l^i*) «5ί*ί«^ίι csl敝¢ 1· 28 322005 201109404 As shown in Table 1, in any of the embodiments, a polarizer having excellent adhesion, puncture workability, and water resistance can be formed. Any of the examples 3 and 6 is When a photocurable adhesive having a high Tg radical polymerizable compound (b) and a low Tg radical polymerizable compound (a) content of 90% by mass is used, the low Tg radical polymerizable compound (a) is used. In Example 3, in which ω-carboxy-polycaprolactone acrylate was used in addition to 4-hydroxybutyl acrylate, the cohesive force was higher than that of Example 6, and it was superior in the characteristics of the adhesion force. a case of a photocurable adhesive of a high Tg radical polymerizable compound (b), and In comparison with Example 11 which does not contain a high Tg radical polymerizable compound (b), since the triacetylcellulose-based film of the protective film is superior in adhesion, it is superior in characteristics of adhesion and water resistance. In the case of using a cycloolefin film having a low moisture permeability as a protective film, the case of Example 13 is superior in water characterization. On the other hand, the use of non-cationic polymerizable property is used. In Comparative Example 1 of the photocurable adhesive of the compound (c), the water resistance was not good even for 24 hours. Further, Comparative Examples 2 to 5 and 10 of the low Tg radical polymerizable compound (a) were used. In one example, the hardened adhesive layer became too hard, so that the adhesive force was small and the punching workability was also poor. Further, Comparative Examples 6 and 7 showed that the content of the low Tg radical polymerizable compound (a) was small, and 3 was used. A functional radical polymerizable compound replaces the monofunctional high Tg radical polymerizable compound (b), and a compound having a cationic polymerization 29 322005 201109404 functional group and a (meth) acrylonitrile group is used instead of the cationic compound (C). situation, In the comparative examples 8 and 9, the content of the low Tg radical polymerizable compound is insufficient, and a compound having a cationically polymerizable functional group and a (fluorenyl) fluorenyl group is used instead of the cationically polymerizable compound (c). In the case, the force is minimal. Further, in Comparative Examples 4 to 9, although the adhesion was extremely small, the water resistance was good, and it was considered that the adhesion of the cutting test was good. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view (schematic diagram) showing an example of a polarizing plate of the present invention. Fig. 2 (a) to (d) are flowcharts (schematic diagrams) showing an example of a method of producing a polarizing plate of the present invention. [Description of main component symbols] 1. 5 Protective film 1 Laminate 2 of a protective film (1) and a layer (2) composed of a curable composition First adhesive layer 2' First hardenable adhesive layer 3 ^^ Ethyl alcohol-based polarizer 4 Second adhesive layer 4' Second hardenable adhesive layer 5 Laminate 6 of protective film (5) and layer (4,) composed of curable composition Energy line 30 322005

Claims

201109404 • VII. Patent application scope: , [Polarized plate] contains a polyethylene polarizing element, an adhesive layer which is cured by photohardening and then d, and a protective film, and is separated by a protective film. A polarizing plate in which the above-mentioned adhesive layer is coated on both surfaces of the polarizing member, wherein the photocurable adhesive contains a main component composed of a radical polymerizable compound and a cationically polymerizable compound, and photoradical polymerization starts. a radically polymerizable compound (a) which forms a homopolymer of a glass transition temperature of -80 ° C to 0 ° C in the above radical polymerizable compound, in the above-mentioned main component In the above cationically polymerizable compound, the cationically polymerizable compound (c) having no (meth) acrylonitrile group is contained in the above-mentioned main agent ♦ 02 to 40% by mass; 1 part by mass of the above-mentioned main component contains 1 to 1 g parts by mass of the photoradical polymerization initiator, and 5 to 5 parts by mass of the photocationic polymerization initiator. 2. The polarizing plate of claim 1, wherein the radical polymerizable compound (a) is monofunctional. 3. The polarizing plate of claim 1, wherein the photocurable second agent is a compound containing an alicyclic epoxy group as the cation polymerizable compound (c). (1) A polarizing plate according to item 2 of the full-time application, wherein the photocurable second agent contains acrylic acid 4 and butyl vinegar as the above-mentioned radical polymerization 31 322005 201109404 compound (a). 5. The polarizing plate of claim 4, wherein the photocurable second agent further contains a carboxyl group-polycaprolactone mono(meth)acrylate as the radical polymerizable compound (a). 6. The polarizing plate of claim 4 or 5, wherein the main agent contains 4-hydroxybutyl acrylate: 1 〇 to 99.8 % by mass and carboxy-polycaprolactone single (A) Acrylate: 〇 to 5% by mass as the above radical polymerizable compound (a). 7. The polarizing plate of claim 1, wherein the photocurable second agent further comprises a radically polymerizable compound (b) which forms a homopolymer having a glass transition temperature of 60 to 250 Å. 8. The polarizing plate of the first aspect of the invention, wherein the ratio of the cationically polymerizable compound (c) to the cationically polymerizable compound is 75 mass% or more. A photocurable adhesive for forming a polarizing plate, comprising a main component comprising a radically polymerizable compound and a cationically polymerizable compound, a photoradical polymerization initiator, and a photocationic polymerization initiator; In the above radical polymerizable compound, the radically polymerizable compound (a) which forms a homopolymer having a glass transition temperature of -80 ° C to Ot contains 6 Å to 99.8% by mass in the above-mentioned main component; In the polymerizable compound, the cationically polymerizable compound having no (fluorenyl) acrylonitrile group contains 2 to 40% by mass of the above-mentioned main component, and the above-mentioned light is contained in an amount of 1 part by mass based on the above-mentioned main component. Free 32 322005 201109404 base polymerization initiator 1 to 10 parts by mass, the above photocationic polymerization initiator 〇. 5 to 5 parts by mass. 10. The photocurable adhesive for forming a polarizing plate according to the ninth aspect of the invention, wherein the radical polymerizable compound (a) is monofunctional. 11. The photocurable adhesive for forming a polarizing plate according to the first aspect of the patent application, wherein 'the' contains 4-hydroxybutyl acrylate: 10 to 99.8 mass% and ω-carboxy-polycaprolactone mono (曱) Acrylate: 0 to 50% by mass The above radical polymerizable compound (a). 33 322005