200427804 玖、發明說明： 【發明所屬之技術領域】 本發明係關於在液晶顯示裝置之液晶單元等光學元件 上，黏貼偏光板和相位差板等光學元件所用之黏著劑及使 用該黏著劑之光學元件。 【先前技術】 於液晶顯示裝置之液晶單元等光學元件上，黏貼偏光板 及偏光板與相位差板之層積體。該偏光板，一般具有以三 乙醯纖維素系保護膜從兩面將聚乙烯醇系偏光鏡夾起之多 層結構，並且在此偏光板一面或兩面的三乙醯纖維素系保 護膜上形成黏著劑層。偏光板係作為透過此黏著劑層而黏 貼在液晶單元等光學元件上之液晶顯示裝置來使用。近年 來，液晶顯示裝置從以個人電腦之顯示器、液晶電視為首 之屋内用途開始，擴展到汽車導航用顯示器等車輛搭載用 途上亦被廣泛地使用，其使用環境變得越來越苛刻。 液晶顯示裝置上所使用的偏光板，因其材料特性所致， 其尺寸安定性不佳，在熱或濕熱條件下發生伸縮，因尺寸 的變化很大，故在如此般之條件下，容易產生黏著劑層發 泡以及從偏光板之液晶單元中浮起剝離等問題。 作為為解決這些問題之黏著劑，知道有由烷基碳數為 1〜12 之（曱基）丙烯酸之烷酯為主要成分的丙烯酸系聚合 物所組成之感壓性黏著劑，該感壓性黏著劑係含有重量平 均分子量1 0萬以下之聚合物成分1 5重量％以下，及含有重 量平均分子量1 0 0萬以上之聚合物成分1 0重量％以上之丙 6 326\專利說明書(補件)\93-07\93110078 200427804 烯酸系聚合物所組成之感壓性黏著劑。（例如，參照日本專 利特開平1 - 6 6 2 8 3號公報）。 經由使用上述感壓性黏著劑，能夠抑制黏著劑層之發泡 及從偏光板之液晶單元中浮起剝離的現象，但是無法吸 收、緩和由偏光板之尺寸變化而產生的應力，因應力集中 在偏光板的邊緣部上，所以液晶顯示裝置的邊緣部與中央 部的明亮程度是不同的，因此存有在液晶顯示裝置表面上 產生色彩不均勻及白斑之問題。 作為為消除此液晶顯示裝置表面上的色彩不均勻及白 斑現象之黏著劑，知道有由重量平均分子量1 0 0萬以上的 高分子量（曱基）丙烯酸系共聚合體100重量份、與重量平 均分子量 3萬以下的低分子量（曱基）丙烯酸系共聚合體 2 0〜2 0 0重量份、與多官能性化合物0 . 0 0 5〜5重量份所形成 之偏光板用黏著劑（例如，參照日本專利特開平1 0 - 2 7 9 9 0 7 號公報）。 又，知道有由具有反應性官能基的重量平均分子量1 0 0 萬〜2 5 0萬的高分子量丙烯酸系聚合物與玻璃化轉移點為0 °C〜-8 0 °C的重量平均分子量3萬〜1 0萬的低分子量丙烯酸 系聚合物與具有可以形成交聯結構的官能基的多官能性化 合物所形成的偏光膜用黏著劑組合物（例如，參照日本專利 特開2 0 0 2 - 1 2 1 5 2 1號公報）。 【發明内容】 (發明所欲解決之問題） 在曰本專利特開平1 0 - 2 7 9 9 0 7號公報中，該文獻記載有 326\專利說明書(補件)\93-07\93110078 7 200427804 所公開的偏光板黏著劑係為可跟隨偏光板的尺 此在液晶元件上不容易產生色彩不均勻和白斑 曰本專利特開平 1 0 - 2 7 9 9 0 7號公報所公開的 劑，係因為與多官能性化合物三維交聯的高分 丙烯酸系共聚合體中存在著不易交聯或不交聯 (曱基）丙烯酸系（共）聚合物，所以能顯示出應 而改善色彩不均勻和白斑現象，但有低分子量 酸系聚合物很容易滲漏，而殘留有被黏著物受 題。 又，於日本專利特開2 0 0 2 - 1 2 1 5 2 1號公報中 載有所公開之偏光板用黏著組合物，係同時具 色彩不均勻和白斑現象的性能與低分子量丙烯 不易發生渗漏的性能，但在更為苛刻的環境下 裝置的使用，很難發揮性能平衡。 因此，本發明之目的是提供一種黏著劑，其 或濕熱條件下也不產生黏著劑層發泡和偏光 象、使因偏光板伸縮等而產生的應力集中現象 而使液晶顯示裝置上不產生色彩不均勻和白斑 且能夠減少重新黏貼偏光板時產生的被黏物污 問題。 (解決問題之手段） 本發明的黏著劑因為含有特定比例的高分 體（A)、及在該共聚合體（A)存在下，帶有羧基 他單體透過自由基共聚合反應所獲得的低分子 326\專利說明書(補件)\93-07\93110078 8 寸變化，因 現象。但在 偏光板黏著 子量（曱基） 的低分子量 力缓和性， (曱基）丙烯 到污染的問 ，該文獻記 備不易產生 酸系聚合物 之液晶顯不 係即使在熱 板剝離等現 得到緩和， 等現象，而 染和混濁等 子量共聚合 的單體與其 量共聚合體 200427804 (B )及多官能性化合物（C )，所以同時具有使因偏光板尺寸 變化而產生的色彩不均勻和白斑等現象緩和的性質，及在 熱或濕熱條件下能夠抑制發泡和剝離等現象的性質。 即，本發明之黏著劑是由利用下述單體（a )及（b )透過自 由基共聚合反應而形成其重量平均分子量為 1 0 0萬以上 200萬以下之共聚合體（A)、及相對於該共聚合體（A)100 重量份，在上述共聚合體（A)存在下由下述單體（c)及（d) 透過自由基共聚合反應而形成其重量平均分子量1萬以上 10萬以下之共聚合體（B)20〜100重量份，及可與上述共聚 合體（A)及/或上述共聚合體（B)發生反應之至少有兩個反 應性官能基之多官能性化合物（C ) 0 . 0 0 3〜3重量份所組成 之黏著劑。 (a )具有反應性官能基及乙烯性不飽和雙鍵結之單體， (b)與上述共聚合體（a)可共聚合下，與上述共聚合體（a) 相異之乙烯性不飽和雙鍵結之單體， (c )具有羧基及乙烯性不飽和雙鍵結之單體， (d)與上述共聚合體（c)可共聚合下，與上述共聚合體（c) 相異之乙烯性不飽和雙鍵結之單體。 在上述黏著劑中，構成共聚合體（A)的單體（a)的共聚合 比例較佳為 0 . 1〜1 5重量％，單體（b )的共聚合比例較佳為 8 5〜9 9 · 9重量％。 還有，本發明中黏著劑的製造方法是包含下述步驟 (1 )〜（3 )的黏著劑製造方法： (1 )具有反應性官能基及乙烯性不飽和雙鍵結之單體（a) 9 326\專利說明書(補件)\93-07\93110078 200427804 及與上述共聚合體（a)可共聚合下，與上述共聚合體（a)相 異之乙烯性不飽和雙鍵結之單體（b )依轉化率 5 0〜9 0 %發生 自由基共聚合反應以聚合共聚合體（A )的步驟。 (2) 聚合共聚合體（A)時殘留的單體及具有羧基及乙烯 性不飽和雙鍵結之單體（c )，在共聚合體（A )存在下，發生 自由基共聚合反應以聚合共聚合體（B)的步驟。 (3) 添加可與共聚合體（A)及/或共聚合體（B)發生反應 之至少有兩個反應性官能基之多官能性化合物（C)的步驟。 在上述步驟（2)中，聚合共聚合體（A)時殘留的單體及具 有羧基及乙烯性不飽和雙鍵結之單體（c)依轉化率 70〜100 %發生自由基共聚合反應以聚合共聚合體（B)為佳。 還有，本發明的黏著劑是按照上述方法製造的黏著劑。 還有，本發明的光學元件是以由上述任一黏著劑所組成 之黏著劑層形成於光學元件之至少一面處為特徵的光學元 件。 【實施方式】 首先，針對本發明的黏著劑進行說明。 黏著劑中所含的共聚合體（A )係具有反應性官能基及乙 烯性不飽和雙鍵結之單體（a)及與上述共聚合體（a)可共聚 合下，與上述共聚合體（a)相異之乙烯性不飽和雙鍵結之單 體（b)[即，具有與（a )可共聚合之其他乙烯性不飽和雙鍵結 之單體（b )]發生自由基共聚合反應所得到之共聚合體。作 為反應性官能基，可以列舉羧基、羥基、胺基、醯胺基、 馬來醯亞胺基、衣康醯亞胺基、琥珀醯亞胺基、環氧基等。 10 326\專利說明書(補件)\93·07\93110078 200427804 又，就單體（a)和單體（b)而言，可以適宜地使用（曱基）丙 烯酸系單體、乙烯基系單體。 帶有羧基的單體（a)的具體實例，可以列舉（曱基）丙烯 酸、β -丙烯酸羧基乙酯、衣康酸、巴豆酸、富馬酸、富馬 酸酐、馬來酸、馬來酸酐、馬來酸丁酯等。 帶有羥基的單體（a )的具體實例，可以列舉 2 -(曱基）丙 烯酸羥基乙酯、2-(曱基）丙烯酸羥基丙酯、4-(曱基）丙烯 酸羥基丁酯、6 -(曱基）丙烯酸羥基己酯、8 -(曱基）丙烯酸 羥基辛酯、1 0 -(曱基）丙烯酸羥基癸酯、1 2 -(曱基）丙烯酸 羥基月桂酯、曱基丙烯酸（4 -羥基曱基己基）酯、氣代-2 -（曱 基）丙烯酸羥基丙酯、二乙二醇單（曱基）丙烯酸酯、己内酯 改質（曱基）丙烯酸酯類、聚乙二醇（曱基）丙烯酸酯類、聚 丙二醇（曱基）丙烯酸酯類等。 帶有胺基的單體（a)的具體實例，可以列舉（曱基）丙烯 酸胺基曱酯、（曱基）丙烯酸二甲基胺基曱酯、（曱基）丙烯 酸二曱基胺基乙酯、（曱基）丙烯酸二曱基胺基丙酯等。 帶有醯胺基的單體（a)的具體實例，可以列舉（曱基）丙 烯醯胺、N -丙烯醯嗎啉、N -取代（曱基）丙烯醯胺、N -乙烯 基咄咯烷酮等。 帶有馬來醯亞胺基的單體（a)的具體實例，可以列舉 N -環己基馬來醯亞胺、N -異丙基馬來醯亞胺、N -月桂基馬來 醯亞胺、N -苯基馬來醯亞胺等。 帶有衣康醯亞胺基的單體（a)的具體實例，可以列舉 N -曱基衣康醯亞胺、N -乙基衣康醯亞胺、N - 丁基衣康醯亞胺、 11 326\專利說明書(補件)\93-07\93110078 200427804 N-辛基衣康醯亞胺、N-2 -乙基己基衣康醯亞胺、N-環己基 衣康醯亞胺、N -月桂基衣康醯亞胺等。 帶有琥珀醯亞胺基的單體（a )的具體實例，可以列舉 N-(甲基）丙烯醯氧亞曱基琥珀醯亞胺、N-(甲基）丙烯醯_6-氧六亞甲基琥珀醯亞胺、N-(甲基）丙烯醯-8-氧八亞曱基琥 ί白醢亞胺等。 帶有環氧基的單體（a)的具體實例，可以列舉（曱基）丙 稀酸縮水甘油酯等。 這些單體可以單獨或多個組合一起使用。 構成共聚合體（A )的單體（a )的共聚合比例，以單體的總 量為基準，0 . 1〜1 5重量％為佳。其共聚合比例低於0 . 1重 量％時，黏著劑的凝聚力降低，在加熱環境下會產生黏著劑 發泡和剝離等現象。還有，超過1 5重量％時，黏著劑的黏 接力降低，很難顯現充分吸收、緩和因偏光板伸縮而引起 的應力集中現象的性能。 還有，單體（b )的具體實例，可以列舉（甲基）丙烯酸酯， 例如（曱基）丙烯酸曱酯、（曱基）丙烯酸乙酯、（甲基）丙烯 酸丙酯、（曱基）丙烯酸正丁酯、（甲基）丙烯酸異丁酯、（曱 基）丙烯酸 2 -乙基己酯、（甲基）丙烯酸正辛酯、（曱基）丙 烯酸異辛酯、（曱基）丙烯酸月桂酯、（曱基）丙烯酸十八烷 酯、（曱基）丙烯酸異壬酯、（甲基）丙烯酸環己酯、（甲基） 丙烯酸苄酯、（曱基）丙烯酸甲氧基乙酯、（曱基）丙烯酸乙 氧基乙酯、（甲基）丙烯酸苯氧基乙酯等。還有，可以列舉 苯乙烯、曱基苯乙烯、乙烯基曱苯等芳香族乙烯基單體、 12 326\專利說明書(補件)\93-07\93110078 200427804 乙酸乙烯酯、（曱基）丙烯腈等。 構成共聚合體（A )的單體（b )之共聚比例，以單體的總量 為基準，8 5〜9 9 . 9重量％為佳。其共聚合比例低於8 5重量％ 時，偏光板與光學元件的密著性下降。還有，超過 9 9. 9 重量％時，帶有反應性官能基的單體（a)的含量變少，黏著 劑的凝聚力降低，在加熱環境下會產生黏著劑發泡和剝離 等現象。 共聚合體（A )能由已知的任何方法製造。 例如，合成共聚合體（A )時，相對於單體總量 1 0 0重量 份，可以使用0 . 0 0 1〜1重量份的聚合起始劑，可透過塊狀 聚合、溶液聚合等方法進行，較佳為溶液聚合法。就聚合 起始劑而言，可以使用偶氮系化合物、有機過氧化物，併 用兩種以上之聚合起始劑亦可。還有，溶液聚合時，就聚 合溶劑而言，可以使用乙酸乙酯、乙酸正丁酯、乙酸異丁 酯、曱苯、丙酮、己烷、甲基乙基酮等。混合使用兩種以 上聚合溶劑亦可。 就聚合起始劑中的偶氮系化合物而言，可以列舉例如 2，2 ’ -偶氮二異丁腈、2，2 ’ -偶氮二（2 -曱基丁腈）、1，1 ’ - 偶氮二（環己烷-1-腈）、2,2’-偶氮二（2,4-二曱基戊腈）、 2, 2’ -偶氮二（2, 4 -二曱基-4-曱氧基戊腈）、二曱基 2, 2’ -偶氮二（2 -曱基丙酸酯）、4, 4’ -偶氮二（4 -氰基戊 酸）、2, 2’ -偶氮二（2 -羥基曱基丙腈）、2,2’ -偶氮雙 [2 - ( 2 -咪唑啉-2 -基）丙烷]等。 還有，就有機過氧化物而言，可以列舉例如過氧化苯甲 13 326\專利說明書(補件)\93-07\93110078 200427804 醯、第三丁基過苯曱酸酯、氫過氧化枯烯、二異丙基過氧 化二碳酸酯、二正丙基過氧化二碳酸酯、二（2 -乙氧基乙基） 過氧化二碳酸酯、第三丁基過氧化新癸酸酯、第三丁基過 氧化新戊酸酯、（3，5，5 -三甲基己醯基）過氧化物、二丙醯 基過氧化物、二乙醯基過氧化物等。 共聚合體（A )的重量平均分子量必須為 1 0 0萬以上 2 0 0 萬以下，較佳為120萬以上180萬以下。共聚合體（A)的重 量平均分子量比1 0 0萬小時，即使交聯後再使用，黏著劑 的凝聚力也不足，會產生發泡和剝離等現象。還有，重量 平均分子量超過2 0 0萬時，黏著劑的黏度變大，使塗佈等 操作性能變差。而且，共聚合體（A)的重量平均分子量是在 共聚合體（B)開始聚合之上透過從反應溶液中取樣，利用凝 膠滲透色譜法（G P C )測定而計算出來的。 黏著劑中所含的共聚合體（B )係帶有羧基和乙烯性不飽 和雙鍵結的單體（c)與帶有可和（c )共聚合的其他乙烯性不 飽和雙鍵結的單體（d)，在上述共聚合體（A)存在下，透過 自由基共聚合反應而形成重量平均分子量1萬以上10萬以 下的共聚合體。透過在共聚合體（A)存在下使單體（c)及單 體（d)透過自由基共聚合反應而獲得之較共聚合體（A)低分 子量之共聚合體（B)包含在黏著劑中，即使在熱或濕熱條件 下也不會產生黏著劑發泡和剝離等現象、使因偏光板伸縮 而產生的應力集中得到緩和，因而使液晶元件上不會產生 色彩不均勻和白斑現象。 就單體（c)和單體（d)而言，可適宜地使用（曱基）丙烯酸 14 326\專利說明書(補件)\93-07\93110078 200427804 系單體、乙烯基系單體。單體（c)的具體實例，可以列舉（曱 基）丙烯酸、β -羧基乙基丙烯酸酯、衣康酸、巴豆酸、富 馬酸、富馬酸酐、馬來酸、馬來酸酐、馬來酸丁酯等。這 些單體可以單獨或多個組合一起使用。 構成共聚合體（Β )的單體（c )的共聚合比例，以單體（c ) 和單體（d )的總計量為基準，0 · 1〜5 0重量％為佳，0 · 5〜3 0 重量％更佳。 作為單體（d)，可以使用與在構成共聚合體（A)的單體（a) 中，與帶有羧基以外的反應性官能基的單體（a)相同的單 體，以及與單體（b)相同的單體。 共聚合體（B)可以是帶有羧基和乙烯性不飽和雙鍵結的 單體（c)及可與上述共聚合體（c)共聚合且帶有與上述共聚 合體（c)不同的乙烯性不飽和雙鍵結的單體（d )[即，帶有可 與（c)發生共聚合反應的其他乙烯性不飽和雙鍵結的單體 (d)]，在共聚合體（A)存在下，依照與共聚合體（A)相同的 方法，透過自由基共聚合反應製造的。共聚合體（B)係使單 體（a )和單體（b )依照轉化率 5 0〜9 0 % (較佳 7 0〜8 0 % )透過自 由基共聚合反應而聚合共聚合體（A)之後，使殘留的單體與 單體（c)在共聚合體（A)存在下，進行自由基共聚合反應而 製造者為佳。 還有，共聚合體（A)聚合時，殘留的單體與單體（c)係依 轉化率 7 0〜1 0 0 %進行自由基共聚合反應為佳。此處之轉化 率係單體聚合而獲得的共聚合體的重量除以作為原料的單 體的總重量所得到的值。 15 326\專利說明書(補件)\93-07\93110078 200427804 透過在上述轉化率下，使共聚合體（A)和共聚^ 合，相對於共聚合體（A ) 1 0 0重量份，很容易使共I 處於2 0〜1 0 0重量份的範圍。 共聚合體（B)以透過溶液聚合法來合成為佳， 共聚合體（A)時之5〜50重量倍左右的聚合起始劑 於單體總量1 0 0重量份，使用0 . 0 0 5〜5 0重量份的 劑為佳。還有，合成共聚合體（B )時，使用月桂基 十二烷基硫醇等硫醇類、α -甲基苯乙烯二聚合體 等鏈轉移劑亦可。 共聚合體（Β )的重量平均分子量必須1萬以上 下，以2萬以上5萬以下較佳。使用重量平均分 萬小的共聚合體（Β)時，因為凝聚力不足，容易產 剝離等現象。還有，使用重量平均分子量超過1 0 合體（Β)時，難以顯現充分吸收、緩和因偏光板伸 的應力集中現象的性質。其中，共聚合體（Β )的重 子量是透過 GPC法測定共聚合體（Α)和共聚合磨 物，從所獲得的 GPC譜與上述方法測定的共聚名 GPC譜的差示譜計算而得。 相對於共聚合體（A) 1 0 0重量份，黏著劑中所含 體（B )的含有量是2 0〜1 0 0重量份，較佳為2 0〜5 0 共聚合體（B)的含有量低於2 0重量份時，難以顯 吸收、緩和因偏光板伸縮而引起的應力集中現象 還有，共聚合體（B)含量超過100重量份時，因為 凝聚力不足，容易產生發泡和剝離等現象。 326\專利說明書(補件)\93-07\93110078 16 ‘體（B)聚 i合體（B) 使用合成 ，即相對 聚合起始 硫醇、正 、萜二烯 10萬以 子量比1 生發泡和 萬的共聚 縮而引起 量平均分 (B)混合 -體（A)的 的共聚合 重量份。 現其充分 的性質。 黏著劑的 200427804 共聚合體（A)和共聚合體（B)的重量比是透過以下方法 求得的。即，首先將在共聚合體（B )聚合開始前，取樣一定 量之溶液，添加到重量已知的容器中，加以精確稱量，將 該精確稱量的溶液加熱乾燥，使共聚合體以外的成分揮 發，將只殘留有共聚合體（A )的容器精確稱量，計算出該一 定量溶液中所含的共聚合體（A)的重量。然後在共聚合體（B) 聚合結束後，取樣於含有共聚合體（A )和共聚合體（B )的溶 液，使用與計算共聚合體（A )重量時相同的方法，計算出一 定量溶液中所含的共聚合體（A )和共聚合體（B )的重量。然 後將一定量溶液中所含的共聚合體（A)及共聚合體（A)與共 聚合體（B )之混合物的重量換算成同量溶液中所含的共聚 合體（A )以及共聚合體（A )和共聚合體（B )混合物的重量，從 共聚合體（A)和共聚合體（B)混合物的重量中扣除掉共聚合 體（A)，藉此計算出共聚合體（B)的重量。 含有至少兩個可與黏著劑中所含的共聚合體（A )及/或 共聚合體（B )發生反應之反應性官能基的多官能性化合物 (C )，係具有至少兩個、較佳為2〜4個可以與共聚合體（A ) 具有的反應性官能基及/或共聚合體（B)具有的羧基以及除 羧基以外的反應性官能基等發生反應的反應性官能基的化 合物。作為這種多官能性化合物的實例，可以列舉異氰酸 酯系化合物、環氧系化合物、胺系化合物、金屬螯合物系 化合物、氮丙啶系化合物等。特別以異氰酸酯系化合物、 環氧系化合物、氮丙唆系化合物較佳。多官能性化合物可 以單獨使用或者多種組合在一起使用。 17 326\專利說明書(補件)\93-07\93110078 200427804 就異氰酸酯系化合物的實例而言，可以列舉曱苯二異氰 酸酯、六亞曱基二異氰酸酯、異佛爾酮二異氰酸酯、二曱 苯二異氰酸酯、氫化二曱苯二異氰酸酯、二苯基曱烷二異 氰酸酯、氫化二苯基曱烷二異氰酸酯、四甲基二曱苯二異 氰酸酯、萘二異氰酸酯、三苯基曱烷三異氰酸酯、多亞曱 基多苯基異氰酸酯等多異氰酸酯化合物，以及這些多異氰 酸酯化合物與三經曱基丙烧等多元醇化合物的加成產物， 這些多異氰酸酯化合物的縮二脲產物和異氰脲酸酯產物 等，進一步可以列舉這些多異氰酸酯化合物與已知的聚醚 多元醇和聚酯多元醇、丙烯酸類多元醇、聚丁二烯多元醇、 聚異戊二烯多元醇等的加成產物等。 還有，作為環氧系化合物的實例，可以列舉雙齡 A 一表 氯醇型之環氧系樹脂、乙二醇二縮水甘油醚、聚乙二醇二 縮水甘油醚、甘油二縮水甘油喊、甘油三縮水甘油醚、1，6 -己二醇二縮水甘油醚、三經甲基丙烧三縮水甘油醚、二縮 水甘油基苯胺、N，N , N ’，N ’ -四縮水甘油基-m -二曱苯二胺、 1，3 -雙（N，N ’ -二縮水甘油基胺基曱基）環己烷、N，N , N ’，N ’ -四縮水甘油基胺基苯基曱烷、三縮水甘油基等。 還有，作為氮丙啶化合物的實例可以列舉 N，N ’ -二苯基 曱烷- 4,4’-雙（1-氮丙啶羰基化物）、N，N’-曱苯- 2,4 -雙（卜 氮丙啶羰基化物）、雙間苯二醯-1 - ( 2 -曱基氮丙啶）、三-；1 -氮丙啶基氧化膦、Ν，Ν’ -六亞曱基_1，6 -雙（1-氮丙啶羰基化 物）、三經曱基丙烧三-β -氮丙σ定基丙酸酯、四經曱基曱烧 -β-氮丙啶基丙酸酯、三-2, 4, 6-(1-氮丙啶基）-1,3，5 -三 18 326\專利說明書(補件)\93-07\93110078 200427804 嗉等。 多官能性化合物（c)的官能基，可根據具有上 體（A )及/或上述共聚合體（B)的反應性官能基的 適當地選擇。例如，具有上述共聚合體（A)及/或 合體（B )的反應性官能基是羥基時，多官能性化d 具有異氰酸酯基作為官能基，具有上述共聚合體 上述共聚合體（B )的反應性官能基是羧基時，多官 物（C )具有環氧基或氮丙啶基作為官能基為佳。 相對於上述共聚合體（A ) 1 0 0重量份，多官能性 的含量是0 . 0 0 3〜3重量份。多官能性化合物（C )的 到0 . 0 0 3重量份時，著色劑的凝聚力不足，容易 和剝離等現象。還有，超過3重量份時，難以顯 吸收、緩和因偏光板伸縮而引起的應力集中現象 黏著劑中組合使用矽烷偶合劑是較佳的。作為 劑，可以列舉乙烯基三曱氧基矽烷、乙烯基三乙辈 曱基丙烯氧基丙基三甲氧基矽烷、γ -甲基丙烯氧 基二曱氧基矽烷、γ-環氧丙氧丙基三曱氧基矽烷 丙氧丙基甲基二曱氧基矽烷、γ -環氧丙氧丙基甲 基矽烷、2 - ( 3，4 -環氧基環己基）乙基三甲氧基矽 基丙基三曱氧基矽烷、γ -胺基丙基三乙氧基矽烷 丙基曱基甲氧基矽烷 Ν-(2-胺基乙基）3 -胺基丙 石夕烧、Ν-(2 -胺基乙基）3 -胺基丙基曱基二甲氧基 敏基丙基三曱氧基石夕院、γ -魏基丙基三乙氧基石夕 丁基三甲氧基矽烷γ-酼基丙基甲基二曱氧基矽烷 326\專利說明書(補件)\93-07\93110078 19 述共聚合 種類進行 上述共聚 卜物（C )可 (Α)及/或 能性化合 化合物（C) 含量未達 產生發泡 現其充分 的性質。 矽烷偶合 4基矽烷、 基丙基甲 、γ-環氧 基二乙氧 烧、γ -胺 、γ-胺基 基甲氧基 石夕烧、γ-烧、巯基 等。 200427804 相對於共聚合體（A ) 1 0 0重量份，黏著劑中矽烷偶合劑的 含量是0 . 0 1〜2重量份為佳。比0 . 0 1重量份少時，改善物 理性能的效果不足，超過2重量份時，不僅黏著劑成本高 而且會產生剝離現象。 還有，黏著劑中組合使用紫外線吸收劑、抗氧化劑、增 黏樹脂、可塑劑、消泡劑、平整劑也是可以的。 本發明的黏著劑可以 (1) 上述共聚合體（Α)和共聚合體（Β)與 (2 )多官能性化合物（C ) 的雙液型黏著劑的形態利用之。 該黏著劑可透過下述步驟（1 )〜（3 )進行製造。 (1 )使帶有反應性官能基和乙烯性不飽和雙鍵結的單體 (a)和可與（a)發生共聚合反應且帶有其他乙烯性不飽和雙 鍵結的單體（b )依轉化率 5 0〜9 0 %發生自由基共聚合反應而 聚合共聚合體（A)的步驟。 (2) 使共聚合體（A)聚合時殘留的單體與帶有羧基和乙 烯性不飽和雙鍵結的單體（c )，在共聚合體（A)存在下，依 轉化率 70〜100 %發生自由基共聚合反應而聚合共聚合體（B) 的步驟。 (3) 添加可與共聚合體（A)和/或共聚合體（B)發生反應 的具有至少兩個反應性官能基的多官能性化合物（C )的步 驟。 在透過上述製造方法獲得的黏著劑中，上述共聚合體（B) 含有來自於單體（c )的羧基，所以本發明所獲得的黏著劑， 20 326\專利說明書(補件)\93-07\93110078 200427804 在黏著界面上表現出優異的物理性能，不容易產生浮起和 剝離等現象。而且，單體（a )在步驟（1 )中完全消耗掉，沒 有殘留，所以即使上述步驟（1 )中所用的單體（a)含有作為 反應性官能基的羧基時，也有必要透過在步驟（2 )中添加含 有叛基的單體（c)，而在共聚合體（B)中引入叛基。還有， 如果上述步驟（1)中所用的單體（b)未在上述步驟（1)中完 全消耗而是殘留下來，那麼在步驟（2 )中就沒有必要添加單 體（d ) 〇 透過控制它們在進行共聚合反應時，所使用的聚合起始 劑的種類和使用量，能夠適當控制共聚合體（A )和共聚合體 (B )各自的重量平均分子量。例如，在上述步驟（1 )中，使 用偶氮二異丁腈在反應溫度約 5 0〜7 0 °C下調製共聚合體 (A )，接著以溶劑（例如曱苯）將上述步驟（1 )的生成物進行 稀釋，然後在上述步驟（2 )中，使用偶氮二異戊腈在反應溫 度約6 0〜8 0 °C下調製共聚合體（B )，即可形成重量平均分子 量和重量比於目標範圍内之共聚合體（A)和共聚合體（B)的 組合物。 即，在上述步驟（2)所生成的共聚合體（A)和共聚合體（B) 的組合物中，實質上沒有殘留未反應的單體，因此無須經 過特別的精製步驟，而是直接能夠使其與多官能性化合物 (C )發生反應。 接下來針對本發明的光學元件進行說明。 本發明的光學元件是透過在光學元件的至少一個面上 形成由本發明黏著劑形成的黏著劑層之光學元件。 21 326\專利說明書(補件)\93-07\93110078 200427804 作為形成黏著劑層之光學元件，可以列舉偏光 差膜、橢圓偏光膜、防反射膜、亮度增強膜等。 黏著劑之形成，可以用通常使用的塗佈裝置進 塗佈裝置，例如可以列舉輥上刮板塗佈機、模壓 輥塗佈機、繞線棒塗佈機、凹印輥塗佈機、逆轉報 浸塗機、刮刀塗佈機等。 還有，從對於吸收、緩和因偏光板伸縮而引起 中現象適當的膜厚及經濟性考慮之，黏著劑層之 以5〜ΙΟΟμιη為佳。 (實施例） 以下使用實施例對本發明進行更詳細的說明， 並不限於這些。而且，在以下說明中，份及％分別 份和重量％。 (合成例1 ) 於配備有攪拌器、溫度計、回流冷凝器、滴加 氮氣導入管的反應容器中，添加丙稀酸正丁酯99 丙烯酸羥基丁酯1 . 0份、丙酮1 5 0 . 0份、2，2 ’ -偶 腈0 . 0 6份，以氮氣置換該反應容器内的空氣後， 同時於氮氣環境下，將該反應溶液升溫到6 0 °C， 5小時。反應結束後，添加曱苯1 9 0份和丙烯酸（ 2，2 ’ -偶氮二（2，4 -二曱基戊腈）0 · 5 0份，升溫到 應6小時。反應之後，添加曱苯5 5份，冷卻至室 固形份2 0 . 0 %的聚合體溶液A。 (合成例2〜9 ) 326\專利說明書(補件)\93·07\93110078 22 膜、相位 行。作為 塗佈機、 塗佈機、 的應力集 乾燥膜厚 但本發明 表示重量 裝置、和 • 0 份、4-氮二異丁 在授摔的 使其反應 ).2 5份和 7 0〇C，反 溫，獲得 200427804 如表1所示，除了改變具有反應性官能基和乙烯性不飽 和雙鍵結的單體（a )、可與（a )發生共聚合反應的具有其他 乙烯性不飽和雙鍵結的單體（b )、具有羧基和乙烯性不飽和 雙鍵結的單體（c)的種類和用量以外，依照與合成例1相同 的方式，獲得聚合體溶液B〜I。 (合成例1 0 ) 在與合成例1相同的反應裝置中，添加丙烯酸丁酯9 9 . 0 份、4 -丙烯酸羥基丁酯1 · 0份、乙酸乙酯1 6 3 · 0份、2，2 ’ -偶氮二異丁腈0 . 0 6份，在將該反應容器内的空氣置換為氮 氣之後，在攪拌的同時於氮氣環境下，將該反應溶液升溫 到8 0 °C ，使其反應4小時。反應結束後，添加曱苯1 7 6份 和丙烯酸 0.25份和 2, 2’-偶氮二（2,4-二曱基戊腈）0.50 份，升溫到7 5 °C，反應6小時。反應後，添加曱苯5 7份， 冷卻至室溫，獲得固形分2 0 . 0 %的聚合體溶液J。 (合成例1 1 ) 在與合成例1相同的反應裝置中，添加丙烯酸丁酯6 0 . 0 份、2 -丙烯酸乙基己酯 37.0份、4 -丙烯酸羥基丁酯 3.0 份、丙酮1 5 0 . 0份、2，2 ’ -偶氮二異丁腈0 . 0 6份，在將該 反應容器内的空氣置換為氮氣之後，在攪拌的同時於氮氣 環境下，將該反應溶液升溫到6 0 °C，使其反應5小時。反 應結束後，添加乙酸乙酯6 5 · 0份和丙烯酸0. 2 8份和2，2 ’ -偶氮二異丁腈〇. 〇 6份，升溫到6 0 °C ，反應8小時。反應 後，添加曱苯1 8 3份，冷卻至室溫，獲得固形分2 0 . 0 %的 聚合體溶液K。 23 326\專利說明書(補件)\93-07\93110078 200427804 (合成例1 2 ) 在與合成例1相同的反應裝置中，添加丙烯酸丁酯9 9 . 0 份、4 -丙烯酸羥基丁酯1 . 0份、丙酮1 5 0 · 0份、2，2 ’ -偶氮 二異丁腈0 . 0 6份，在將該反應容器内的空氣置換為氮氣之 後，在攪拌的同時於氮氣環境下，將該反應溶液升溫到6 0 °C ，使其反應3小時。反應結束後，添加甲苯1 . 1份和丙 烯酸0 · 5 5份和2，2 ’ -偶氮二（2，4 -二曱基戊腈）1 · 1份，升 溫到7 0 °C ，反應7小時。反應後，添加甲苯2 3 6份，冷卻 至室溫，獲得固形分2 0 . 0 %的聚合體溶液L。 (合成例1 3 ) 在與合成例1相同的反應裝置中，添加丙烯酸丁酯9 9. 0 份、4 -丙烯酸羥基丁酯1 . 0份、丙酮1 5 0 . 0份、2，2 ’ -偶氮 二異丁腈0.06份，在將該反應容器内的空氣置換為氮氣之 後，在攪拌的同時於氮氣環境下，將該反應溶液升溫到6 0 °C，使其反應1 0小時。反應結束後，添加曱苯1 9 8份和丙 烯酸0.08份和2, 2’-偶氮二（2, 4 -二甲基戊腈）0.16份，升 溫到7 0 °C ，反應6小時。反應後，添加甲苯51份，冷卻 至室溫，獲得固形分2 0 . 0 %的聚合體溶液Μ。 (合成例1 4 ) 在與合成例 1相同的反應容器中，添加丙烯酸正丁酯 9 9 · 0份、4 -丙烯酸羥基丁酯1 . 0份、丙酮1 5 0 . 0份、2，2 ’ -偶氮二異丁腈〇 . 〇 6份，在將該反應容器内的空氣置換為氮 氣之後，在攪拌的同時於氮氣環境下，將該反應溶液升溫 到6 0 °C ，使其反應5小時。反應後，添加曱苯1 5 0份，冷 24 326\專利說明書(補件)\93-07\93110078 200427804 卻至室溫，獲得固形分2 0 . 0 %的聚合體溶液N。聚合體的重 量平均分子量為161萬，Mw/Mn為4.8。 (合成例1 5 ) 在與合成例 1相同的反應容器中，添加丙烯酸正丁酯 99.0份、4 -丙烯酸羥基丁酯1.0份、丙酮 150.0份、α-曱基苯乙烯二聚合體1份和2, 2’-偶氮二異丁腈2份，在 將該反應容器内的空氣置換為氮氣之後，在攪拌的同時於 氮氣環境下，將該反應溶液升溫到7 0 °C，使其反應6小時。 反應後，添加曱苯1 5 0份，冷卻至室溫，獲得固形分4 0 . 0 °/〇 的聚合體溶液0。聚合體的重量平均分子量為2. 4萬，Mw/Mn 為 2. 8。 針對合成例 1〜1 3獲得的聚合體溶液，按照先前所述的 方法計算出共聚合體（A)的重量平均分子量（Mw)、共聚合體 (A)合成時的轉化率、共聚合體（B)的重量平均分子量 (Mw)、共聚合體（B)合成時的轉化率、以及相對於共聚合體 (A ) 1 0 0份，共聚合體（B )的比例。結果見表1。 25 326\專利說明書(補件)\93-07\93110078 200427804 表1 (B) 重量份 32.0 38.5 26.2 24.0 32.3 35.5 32.6 32.3 25.9 CD 完· 38.1 114.8 CO od 共聚合雜(B) 轉化率 (%) 95.0 96.0 92.0 94.0 96.0 95.0 〇 96.0 CD 5S 94.0 97.0 93.0 95.0 Mw (xlO4) UO 〇〇 CNI 〇5 CO CO csi CO — cn 03 CNJ 卜 (>i 00 OJ CO 03 27.6 c<5 卜 oi 單體(c) 重量份 0.25 0.84 0.22 0.40 0.25 0.27 0.52 0.25 0.22 0.25 0.28 0.55 0.08 5 1 5 1 4-HBA 5 5 共聚合艘(A) 轉化率 (%) 75.0 72.0 78.0 80.0 75.0 73.0 74.0 75.0 78.0 75.0 72.0 45.0 92.0 Mw (xl〇4) § g g § LO CO § S g g CO LO r-H g 單體(b) 1 <=> LO 20.0 28.0 2EHA 37.0 37.0 99.0 60.0 96.0 70.0 75.0 93.0 98.0 99.0 96.0 99.0 60.0 99.0 99.0 單體(a) 1 1 〇 c<i 〇 isi 4-HBA CZ5 〇 CO Ο csi Ο ◦ 〇 —· 〇 CO CD —· 〇 聚合體溶液A 聚合想溶液B 聚合競容液C 聚合想溶液D 聚合^液E 聚合想溶液F 聚合體溶液G 聚純容液Η 聚合德容液I 聚合想溶液J 聚合齡容液K 聚合撤容液L 聚合能容液M 合成例1 合成例2 合成例3 合成例4 合成例5 合成例6 合成例7 合成例8 合成例9 合成例10 合成例11 合成例12 合成例13200427804 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to an optical element such as a polarizing plate and a retardation plate, and an optical element using the adhesive on an optical element such as a liquid crystal cell of a liquid crystal display device. element. [Prior art] A polarizing plate and a laminated body of a polarizing plate and a retardation plate are adhered to optical elements such as a liquid crystal cell of a liquid crystal display device. The polarizing plate generally has a multilayer structure in which a polyvinyl alcohol-based polarizer is sandwiched on both sides with a triethyl cellulose-based protective film, and adhesion is formed on the triethyl cellulose-based protective film on one or both sides of the polarizing plate.剂 层。 The agent layer. The polarizing plate is used as a liquid crystal display device that is adhered to an optical element such as a liquid crystal cell through this adhesive layer. In recent years, liquid crystal display devices have been widely used in vehicles, such as display monitors for personal computers and indoor TVs, and have been used in vehicles such as car navigation displays. The use environment has become increasingly demanding. The polarizing plate used in the liquid crystal display device is due to its material characteristics, its dimension stability is not good, it expands and contracts under hot or humid heat conditions, and because the size changes greatly, it is easy to produce under such conditions. Problems such as foaming of the adhesive layer and floating peeling from the liquid crystal cell of the polarizing plate. As a pressure-sensitive adhesive for solving these problems, a pressure-sensitive pressure-sensitive adhesive composed of an acrylic polymer whose main component is an alkyl alkyl group of (fluorenyl) acrylic acid having 1 to 12 alkyl carbons is known. Adhesives are C 6 326 containing a polymer component with a weight average molecular weight of 100,000 or less and 10 weight% or more with a polymer component with a weight average molecular weight of 1 million or more. ) \ 93-07 \ 93110078 200427804 Pressure-sensitive adhesive composed of enoic acid polymer. (For example, refer to Japanese Patent Laid-Open Publication No. 1-6 6 2 8 3). By using the pressure-sensitive adhesive described above, it is possible to suppress the foaming of the adhesive layer and the phenomenon of floating and peeling from the liquid crystal cell of the polarizing plate, but it is unable to absorb and alleviate the stress caused by the dimensional change of the polarizing plate, due to stress concentration. At the edge portion of the polarizing plate, the brightness of the edge portion and the central portion of the liquid crystal display device is different, and therefore there is a problem that color unevenness and white spots are generated on the surface of the liquid crystal display device. As an adhesive for eliminating color unevenness and white spots on the surface of this liquid crystal display device, it is known that there are 100 parts by weight of a high molecular weight (fluorenyl) acrylic copolymer based on a weight average molecular weight of 1 million or more, and Low molecular weight (fluorenyl) acrylic copolymer of 30,000 or less, 20 to 200 parts by weight, and polyfunctional compound 0. 0 to 5 to 5 parts by weight of an adhesive for a polarizing plate (for example, refer to Japanese Patent Laid-Open Publication No. 10-2 7 9 9 0 7). In addition, it is known that a high molecular weight acrylic polymer having a weight average molecular weight of 1 million to 25,000 having a reactive functional group and a weight average molecular weight of 3 to 0 ° C and a glass transition point of the glass transition point are 3 An adhesive composition for a polarizing film formed of a low molecular weight acrylic polymer having a molecular weight of 10,000 to 100,000 and a polyfunctional compound having a functional group capable of forming a crosslinked structure (for example, refer to Japanese Patent Laid-Open No. 2 0 2- 1 2 1 5 2 1). [Summary of the Invention] (Problems to be Solved by the Invention) In Japanese Patent Laid-Open Publication No. 10-2 7 9 9 0 7, this document describes 326 \ Patent Specification (Supplement) \ 93-07 \ 93110078 7 The polarizing plate adhesive disclosed in 200427804 is a rule that can follow the rule of the polarizing plate, and it is not easy to generate color unevenness and white spots on the liquid crystal element. The agent disclosed in Japanese Patent Laid-Open No. 1-2 7 9 9 0 7 Because high-acrylic acrylic copolymers which are three-dimensionally cross-linked with polyfunctional compounds have difficult to cross-link or non-cross-linking (fluorenyl) acrylic (co) polymers, they can show improvement in color unevenness and White spot phenomenon, but there are low molecular weight acid polymers that are easy to leak, and there are problems caused by adherends. In addition, the adhesive composition for polarizing plates disclosed in Japanese Patent Laid-Open No. 2000-1-2 2 1 5 2 1 has properties of uneven color and white spots, and low-molecular-weight propylene is difficult to occur. Leakage performance, but the use of the device in more severe environments, it is difficult to achieve performance balance. Therefore, an object of the present invention is to provide an adhesive that does not generate foaming and polarizing images of the adhesive layer under humid or hot conditions, and causes stress concentration due to the expansion and contraction of the polarizing plate, so that no color is generated on the liquid crystal display device. The unevenness and white spots can reduce the problem of contamination caused by sticking when re-adhering the polarizing plate. (Means for Solving the Problem) The adhesive of the present invention contains a high proportion (A) of a specific fraction and a low content obtained by radical copolymerization reaction of a monomer having a carboxyl group in the presence of the copolymer (A). Molecule 326 \ Patent Specification (Supplement) \ 93-07 \ 93110078 8 inch change due to phenomenon. However, the low-molecular-weight force relaxation of the polarizer (fluorenyl) on the polarizer, and the problem of (fluorenyl) propylene to pollution, the document states that liquid crystals that are not prone to produce acid-based polymers are not present even when they are peeled off on hot plates The phenomenon of relaxation, etc. is obtained, and the monomers copolymerized in the same amount as the dye and turbidity are copolymerized with the amount copolymer 200427804 (B) and the polyfunctional compound (C). Therefore, the color unevenness due to the size change of the polarizing plate It is a property that mitigates phenomena such as white spots, and can suppress foaming and peeling under hot or humid conditions. That is, the adhesive of the present invention is formed by the following monomers (a) and (b) through a radical copolymerization reaction to form a copolymer (A) having a weight average molecular weight of 1 million to 2 million, and With respect to 100 parts by weight of the copolymer (A), in the presence of the copolymer (A), the following monomers (c) and (d) are subjected to a radical copolymerization reaction to form a weight average molecular weight of 10,000 to 100,000 20 to 100 parts by weight of the following copolymer (B) and a polyfunctional compound (C) having at least two reactive functional groups that can react with the above copolymer (A) and / or the above copolymer (B) 0. 0 0 3 to 3 parts by weight of an adhesive. (a) a monomer having a reactive functional group and an ethylenically unsaturated double bond, (b) an ethylenically unsaturated double copolymer different from the above-mentioned copolymer (a) in a copolymerizable manner with the above-mentioned copolymer (a) Bonded monomers, (c) monomers having a carboxyl group and an ethylenically unsaturated double bond, (d) copolymerizable with the above-mentioned copolymer (c), and different ethylene properties from the above-mentioned copolymer (c) Unsaturated double-bonded monomer. In the above-mentioned adhesive, the copolymerization ratio of the monomer (a) constituting the copolymer (A) is preferably 0. 1 to 15% by weight, and the copolymerization ratio of the monomer (b) is preferably 85 to 99. 9% by weight. The method for producing an adhesive in the present invention is the method for producing an adhesive including the following steps (1) to (3): (1) a monomer having a reactive functional group and an ethylenically unsaturated double bond (a ) 9 326 \ Patent Specification (Supplement) \ 93-07 \ 93110078 200427804 and monomers with ethylenically unsaturated double bonds which are different from the above copolymer (a) under copolymerization with the above copolymer (a) (B) a step of polymerizing the copolymer (A) by performing a radical copolymerization reaction at a conversion rate of 50 to 90%. (2) Residual monomers and monomers (c) having a carboxyl group and an ethylenically unsaturated double bond in the copolymer (A) are polymerized by radical copolymerization in the presence of the copolymer (A) Step of fitting (B). (3) A step of adding a polyfunctional compound (C) having at least two reactive functional groups capable of reacting with the copolymer (A) and / or the copolymer (B). In the above step (2), the monomers remaining during the polymerization of the copolymer (A) and the monomer having a carboxyl group and an ethylenically unsaturated double bond (c) undergo a radical copolymerization reaction at a conversion rate of 70 to 100% to The polymerized copolymer (B) is preferred. The adhesive of the present invention is an adhesive produced by the above method. The optical element of the present invention is an optical element characterized in that an adhesive layer composed of any of the above-mentioned adhesives is formed on at least one side of the optical element. [Embodiment] First, the adhesive of this invention is demonstrated. The copolymer (A) contained in the adhesive is a monomer (a) having a reactive functional group and an ethylenically unsaturated double bond, and copolymerizable with the copolymer (a), and the copolymer (a) ) Dissimilar ethylenically unsaturated double-bonded monomers (b) [that is, monomers (b) having other ethylenically unsaturated double bonds that are copolymerizable with (a)] undergo radical copolymerization The copolymer obtained. Examples of the reactive functional group include a carboxyl group, a hydroxyl group, an amine group, a sulfonium group, a maleimide group, an itacene group, an succinimide group, and an epoxy group. 10 326 \ Patent Specification (Supplement) \ 93 · 07 \ 93110078 200427804 In addition, as for the monomer (a) and the monomer (b), (fluorenyl) acrylic monomers and vinyl monomers can be suitably used. body. Specific examples of the carboxyl group-containing monomer (a) include (fluorenyl) acrylic acid, β-acrylic carboxyethyl ester, itaconic acid, crotonic acid, fumaric acid, fumaric anhydride, maleic acid, and maleic anhydride. , Butyl maleate and so on. Specific examples of the hydroxy-containing monomer (a) include hydroxyethyl 2- (fluorenyl) acrylate, hydroxypropyl 2- (fluorenyl) acrylate, hydroxybutyl 4- (fluorenyl) acrylate, and 6- (Fluorenyl) hydroxyhexyl acrylate, 8- (fluorenyl) hydroxyoctyl acrylate, 1 0-(fluorenyl) hydroxydecyl acrylate, 1 2-(fluorenyl) hydroxylauryl acrylate, fluorenyl acrylic acid (4- Hydroxy fluorenylhexyl) ester, oxo-2-(fluorenyl) hydroxypropyl acrylate, diethylene glycol mono (fluorenyl) acrylate, caprolactone modified (fluorenyl) acrylate, polyethylene glycol (Fluorenyl) acrylates, polypropylene glycol (fluorenyl) acrylates, and the like. Specific examples of the amine-group-containing monomer (a) include fluorenyl (fluorenyl) methacrylate, dimethylamino fluorenyl (fluorenyl) methacrylate, and fluorenyl methacrylate (fluorenyl) acrylate Esters, difluorenyl aminopropyl (fluorenyl) acrylate, and the like. Specific examples of the fluorenylamino group-containing monomer (a) include (fluorenyl) acrylamide, N-acrylhydrazine, N-substituted (fluorenyl) acrylamide, and N-vinylpyrrolidine Ketones, etc. Specific examples of the maleimide-imide-containing monomer (a) include N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide and the like. Specific examples of the itacinimide-containing monomer (a) include N-fluorenyl itacimide, N-ethyl itacimide, N-butyl itacimide, 11 326 \ Patent Specification (Supplement) \ 93-07 \ 93110078 200427804 N-octyl itaconate imine, N-2 -ethylhexyl itaconate imine, N-cyclohexyl itaconate imine, N -Lauryl ketoconimine, etc. Specific examples of the monomer (a) having an succinimide group include N- (meth) acryl fluorenyloxysuccinimide, N- (meth) acryl hydrazone-6-oxohexamethylene Methyl succinimide, N- (meth) acryl hydrazone-8-oxoctamidinosuccinate, stilbene imine and the like. Specific examples of the epoxy-group-containing monomer (a) include (fluorenyl) glycidyl acrylate and the like. These monomers can be used alone or in combination. The copolymerization ratio of the monomers (a) constituting the copolymer (A) is based on the total amount of the monomers, 0. 1 to 15% by weight is preferred. Its copolymerization ratio is lower than 0. At 1% by weight, the cohesive force of the adhesive is reduced, and foaming and peeling of the adhesive may occur in a heated environment. In addition, if it exceeds 15% by weight, the adhesive force of the adhesive decreases, and it is difficult to exhibit the performance of sufficiently absorbing and mitigating the stress concentration phenomenon caused by the expansion and contraction of the polarizing plate. Specific examples of the monomer (b) include (meth) acrylates, such as (fluorenyl) fluorenyl acrylate, (fluorenyl) ethyl acrylate, propyl (meth) acrylate, and (fluorenyl) N-butyl acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (fluorenyl) acrylate, n-octyl (meth) acrylate, isooctyl (fluorenyl) acrylate, lauryl (fluorenyl) acrylate Ester, octadecyl (fluorenyl) acrylate, isononyl (fluorenyl) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, methoxyethyl (fluorenyl) acrylate, ( Fluorenyl) ethoxyethyl acrylate, phenoxyethyl (meth) acrylate, and the like. In addition, examples include aromatic vinyl monomers such as styrene, fluorenylstyrene, and vinyl benzene. 12 326 \ Patent Specification (Supplements) \ 93-07 \ 93110078 200427804 vinyl acetate, (fluorenyl) propylene. Nitrile and so on. The copolymerization ratio of the monomer (b) constituting the copolymer (A) is based on the total amount of the monomers, 8 5 to 9 9. 9% by weight is preferred. When the copolymerization ratio thereof is less than 85 wt%, the adhesion between the polarizing plate and the optical element is reduced. Also, more than 9 9. At 9% by weight, the content of the reactive functional group-containing monomer (a) decreases, the cohesive force of the adhesive decreases, and the phenomenon of foaming and peeling of the adhesive may occur in a heated environment. The copolymer (A) can be produced by any known method. For example, when synthesizing the copolymer (A), 100% by weight relative to the total amount of monomers may be used. 0 0 1 to 1 part by weight of the polymerization initiator can be carried out by methods such as block polymerization and solution polymerization, and is preferably a solution polymerization method. The polymerization initiator may be an azo compound or an organic peroxide, or two or more polymerization initiators may be used. For the solution polymerization, as the polymerization solvent, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, methyl ethyl ketone, and the like can be used. Two or more polymerization solvents may be used in combination. Examples of the azo compound in the polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-fluorenylbutyronitrile), and 1,1 ' -Azobis (cyclohexane-1-nitrile), 2,2'-Azobis (2,4-diamidinovaleronitrile), 2, 2'-Azobis (2, 4 -difluorenyl) -4-Methoxyvaleronitrile), difluorenyl 2, 2'-azobis (2-fluorenylpropionate), 4, 4'-azobis (4-cyanovaleric acid), 2, 2'-azobis (2-hydroxyfluorenylpropionitrile), 2,2'-azobis [2- (2-imidazolin-2-yl) propane], and the like. In addition, as for the organic peroxide, for example, benzyl peroxide 13 326 \ Patent Specification (Supplement) \ 93-07 \ 93110078 200427804 醯, third butyl perbenzoate, hydroperoxide Ene, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, bis (2-ethoxyethyl) peroxydicarbonate, third butylperoxyneodecanate, Tributylperoxypivalate, (3,5,5-trimethylhexyl) peroxide, dipropylfluorenyl peroxide, diethylfluorenyl peroxide, and the like. The weight average molecular weight of the copolymer (A) must be 1 million to 2 million, and preferably 1.2 million to 1.8 million. The copolymer (A) has a weight-average molecular weight ratio of 1 million hours. Even if it is used after crosslinking, the cohesive force of the adhesive is insufficient, and foaming and peeling may occur. In addition, when the weight average molecular weight exceeds 2 million, the viscosity of the adhesive becomes large, which deteriorates handling performance such as coating. The weight average molecular weight of the copolymer (A) was calculated by sampling the reaction solution from the start of the copolymer (B) and measuring it by gel permeation chromatography (GPPC). The copolymer (B) contained in the adhesive is a monomer having a carboxyl group and an ethylenically unsaturated double bond (c) and a monomer having another ethylenically unsaturated double bond copolymerizable with (c). The body (d) is a copolymer having a weight average molecular weight of 10,000 to 100,000 in the presence of the above-mentioned copolymer (A) through a radical copolymerization reaction. The copolymer (B) having a lower molecular weight than the copolymer (A) obtained by subjecting the monomer (c) and the monomer (d) to radical copolymerization in the presence of the copolymer (A) is contained in the adhesive, Even under hot or humid conditions, foaming and peeling of the adhesive do not occur, and stress concentration caused by the expansion and contraction of the polarizing plate is reduced, so that color unevenness and white spots do not occur on the liquid crystal element. As for the monomer (c) and the monomer (d), (fluorenyl) acrylic acid 14 326 \ Patent Specification (Supplement) \ 93-07 \ 93110078 200427804-based monomer and vinyl-based monomer can be suitably used. Specific examples of the monomer (c) include (fluorenyl) acrylic acid, β-carboxyethyl acrylate, itaconic acid, crotonic acid, fumaric acid, fumaric anhydride, maleic acid, maleic anhydride, and maleic acid. Butyl Ester etc. These monomers can be used alone or in combination. The copolymerization ratio of the monomer (c) constituting the copolymer (B) is based on the total measurement of the monomer (c) and the monomer (d), preferably from 0.1 to 50% by weight, and from 0.5 to 5 30% by weight is more preferred. As the monomer (d), the same monomer as the monomer (a) constituting the copolymer (A) and the monomer (a) having a reactive functional group other than a carboxyl group, and a monomer (B) The same monomer. The copolymer (B) may be a monomer (c) having a carboxyl group and an ethylenically unsaturated double bond, and may be copolymerized with the copolymer (c) and have an ethylenic property different from the copolymer (c). Saturated double-bonded monomer (d) [that is, another monomer (d) with ethylenically unsaturated double bonds that can copolymerize with (c)] in the presence of copolymer (A), It is produced by a radical copolymerization reaction by the same method as the copolymer (A). The copolymer (B) is a monomer (a) and a monomer (b) which polymerize the copolymer (A) through a radical copolymerization reaction at a conversion rate of 50 to 90% (preferably 70 to 80%). After that, it is preferred that the remaining monomer and the monomer (c) are subjected to a radical copolymerization reaction in the presence of the copolymer (A), and the manufacturer is preferred. When the copolymer (A) is polymerized, it is preferred that the remaining monomer and the monomer (c) undergo radical copolymerization at a conversion rate of 70 to 100%. The conversion here is a value obtained by dividing the weight of the copolymer obtained by polymerizing the monomers by the total weight of the monomers as raw materials. 15 326 \ Patent Specification (Supplement) \ 93-07 \ 93110078 200427804 By combining the copolymer (A) with the copolymer at the above conversion rate, it is easy to make the copolymer (A) 100 parts by weight. The total I is in the range of 20 to 100 parts by weight. The copolymer (B) is preferably synthesized by a solution polymerization method. The copolymerization initiator (A) is about 5 to 50 times the weight of the polymerization initiator. Based on 100 parts by weight of the total monomers, 0 is used. 0 0 5 to 50 parts by weight of the agent is preferred. When the copolymer (B) is synthesized, a thiol such as lauryl dodecyl mercaptan or a chain transfer agent such as α-methylstyrene dimer may be used. The weight average molecular weight of the copolymer (B) must be 10,000 or more, and preferably 20,000 or more and 50,000 or less. When the copolymer (B) having a weight average of 10,000 is used, the cohesive force is insufficient and the phenomenon such as peeling is liable to occur. In addition, when the weight average molecular weight exceeds 10 (B), it is difficult to exhibit a property of sufficiently absorbing and alleviating the stress concentration phenomenon due to the extension of the polarizing plate. Among them, the weight of the copolymer (B) was determined by measuring the copolymer (A) and the copolymer abrasive by the GPC method, and calculating from the difference spectrum of the obtained GPC spectrum and the copolymer name GPC spectrum determined by the above method. The content of the body (B) contained in the adhesive is 20 to 100 parts by weight, and preferably 20 to 50 parts of the copolymer (B) with respect to 100 parts by weight of the copolymer (A). When the amount is less than 20 parts by weight, it is difficult to significantly absorb and reduce stress concentration caused by the expansion and contraction of the polarizing plate. When the content of the copolymer (B) exceeds 100 parts by weight, foaming and peeling are likely to occur due to insufficient cohesion phenomenon. 326 \ Patent Specification (Supplement) \ 93-07 \ 93110078 16 'Body (B) Polymer (B) Use synthesis, that is, relative to the initial polymerization of mercaptan, n- and terpene diene at a ratio of 100,000 at a ratio of 100,000 The copolymerization and shrinkage of the foam and the 10,000 caused a weight average copolymerization (B) of the copolymerized body (A) by weight. Show its full nature. The weight ratio of 200427804 copolymer (A) and copolymer (B) of the adhesive was obtained by the following method. That is, before the copolymer (B) is polymerized, a certain amount of solution is sampled, added to a container of known weight, accurately weighed, and the accurately weighed solution is dried by heating to make components other than the copolymer Volatilize, weigh the container with only the copolymer (A) accurately, and calculate the weight of the copolymer (A) contained in the certain amount of solution. Then, after the polymerization of the copolymer (B) is completed, a solution containing the copolymer (A) and the copolymer (B) is sampled, and the same content as in the calculation of the weight of the copolymer (A) is used to calculate the content of the solution in a certain amount. The weight of the copolymer (A) and the copolymer (B). Then, the weight of the copolymer (A) and the mixture of the copolymer (A) and the copolymer (B) contained in a certain amount of solution is converted into the copolymer (A) and the copolymer (A) contained in the same amount of solution. The weight of the copolymer (B) is calculated by subtracting the copolymer (A) from the weight of the copolymer (A) and the copolymer (B). The polyfunctional compound (C) containing at least two reactive functional groups capable of reacting with the copolymer (A) and / or the copolymer (B) contained in the adhesive, has at least two, preferably 2 to 4 compounds capable of reacting with a reactive functional group such as the copolymer (A) and / or a carboxyl group contained in the copolymer (B) and a reactive functional group other than the carboxyl group. Examples of such a polyfunctional compound include an isocyanate-based compound, an epoxy-based compound, an amine-based compound, a metal chelate-based compound, and an aziridine-based compound. In particular, isocyanate-based compounds, epoxy-based compounds, and aziridine-based compounds are preferred. The polyfunctional compound may be used alone or in combination. 17 326 \ Patent Specification (Supplement) \ 93-07 \ 93110078 200427804 As examples of isocyanate-based compounds, benzenebenzene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and dibenzobenzenediene Isocyanate, hydrogenated diphenylbenzene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethyldimethanebenzene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, polyisocyanate Polyisocyanate compounds such as methyl polyphenyl isocyanate, and addition products of these polyisocyanate compounds with polyol compounds such as tris (fluorenyl propane), biuret products and isocyanurate products of these polyisocyanate compounds, etc., further Examples of the addition products of these polyisocyanate compounds include known polyether polyols and polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, and the like. In addition, as examples of the epoxy-based compound, a two-stage A-epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol diglycidyl, Glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylol triglycidyl ether, diglycidyl aniline, N, N, N ', N'-tetraglycidyl- m-Difluorenylphenylenediamine, 1,3-bis (N, N'-diglycidylaminofluorenyl) cyclohexane, N, N, N ', N'-tetraglycidylaminophenyl Pinane, triglycidyl, etc. Examples of the aziridine compound include N, N′-diphenylphosphorane-4,4′-bis (1-aziridinecarbonyl), and N, N′-fluorene-2,4. -Bis (aziridine carbonyl), bis-m-phenylenedihydrazone-1-(2-amidinoaziridine), tri-; 1-aziridinylphosphine oxide, N, N'-hexamethylene 1,6-bis (1-aziridine carbonyl), tris (fluorenylpropanyl) tri-β-aziridine stilbyl propionate, tetras (fluorenylpyridine) -β-aziridinylpropionate , Tri-2, 4, 6- (1-aziridinyl) -1,3,5 -tri 18 326 \ Patent Specification (Supplement) \ 93-07 \ 93110078 200427804 嗉 and so on. The functional group of the polyfunctional compound (c) can be appropriately selected according to a reactive functional group having an upper body (A) and / or the above-mentioned copolymer (B). For example, when the reactive functional group having the copolymer (A) and / or the complex (B) is a hydroxyl group, the polyfunctional d has an isocyanate group as a functional group and has the reactivity of the copolymer and the copolymer (B). When the functional group is a carboxyl group, it is preferable that the multifunctional substance (C) has an epoxy group or an aziridinyl group as the functional group. The content of polyfunctionality is 0. 100 parts by weight with respect to the copolymer (A). 0 0 3 to 3 parts by weight. Polyfunctional compounds (C) to 0. When the content is 0.3 parts by weight, the cohesive power of the colorant is insufficient, and the phenomenon such as easiness and peeling may occur. When it exceeds 3 parts by weight, it is difficult to significantly absorb and alleviate the stress concentration phenomenon caused by the expansion and contraction of the polarizing plate. It is preferable to use a silane coupling agent in combination in the adhesive. Examples of the agent include vinyltrimethoxysilane, vinyltriethylenefluorenylpropoxypropyltrimethoxysilane, γ-methacryloxydimethoxysilane, and γ-glycidoxypropane Trimethoxysilane, propoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethylsilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilyl Propyltrimethoxysilane, γ-aminopropyltriethoxysilane, propylfluorenylmethoxysilane N- (2-aminoethyl) 3-aminopropyllithium, N- (2 -Aminoethyl) 3 -Aminopropylfluorenyldimethoxysensitizylpropyltrioxolium, γ-Weipropylpropylethoxylbutylbutyltrimethoxysilane γ-fluorenyl Propylmethyldioxysilane 326 \ Patent Specification (Supplement) \ 93-07 \ 93110078 19 The above-mentioned copolymerization type (C) can be (A) and / or a functional compound (C) If the content is not reached, foaming occurs and its sufficient properties are obtained. Silane coupling 4-based silane, propyl methyl, γ-epoxy diethoxy, γ-amine, γ-amino methoxy stone sulfide, γ-thio, thiol, and the like. 200427804 The content of the silane coupling agent in the adhesive is 0 to 100 parts by weight of the copolymer (A). 0 1 to 2 parts by weight is preferred. Than 0. When the amount is less than 1 part by weight, the effect of improving physical properties is insufficient. When it exceeds 2 parts by weight, not only the cost of the adhesive is high, but peeling may occur. It is also possible to use a combination of an ultraviolet absorber, an antioxidant, a tackifier resin, a plasticizer, a defoamer, and a leveling agent in the adhesive. The adhesive of the present invention can be used in the form of (1) the two-component adhesive of the copolymer (A) and the copolymer (B) and (2) the polyfunctional compound (C). This adhesive can be manufactured through the following steps (1) to (3). (1) A monomer (a) having a reactive functional group and an ethylenically unsaturated double bond and a monomer (b) which can copolymerize with (a) and have other ethylenically unsaturated double bonds (b) ) A step of polymerizing the copolymer (A) by subjecting a radical copolymerization reaction to a conversion of 50 to 90%. (2) The monomer remaining during the polymerization of the copolymer (A) and the monomer (c) having a carboxyl group and an ethylenically unsaturated double bond, in the presence of the copolymer (A), the conversion rate is 70 to 100% A step of polymerizing the copolymer (B) by a radical copolymerization reaction. (3) A step of adding a polyfunctional compound (C) having at least two reactive functional groups capable of reacting with the copolymer (A) and / or the copolymer (B). In the adhesive obtained by the above-mentioned manufacturing method, the above-mentioned copolymer (B) contains a carboxyl group derived from the monomer (c), so the adhesive obtained by the present invention is 20 326 \ Patent Specification (Supplement) \ 93-07 \ 93110078 200427804 exhibits excellent physical properties on the adhesive interface, and is not prone to floating and peeling. In addition, the monomer (a) is completely consumed in step (1) and there is no residue, so even if the monomer (a) used in the above step (1) contains a carboxyl group as a reactive functional group, it is necessary to pass through the step (2) The monomer (c) containing a bad group is added, and the bad group is introduced into the copolymer (B). In addition, if the monomer (b) used in the step (1) is not completely consumed in the above step (1) but remains, then it is not necessary to add the monomer (d) in the step (2). By controlling the type and amount of the polymerization initiator used during the copolymerization reaction, the weight average molecular weight of each of the copolymer (A) and the copolymer (B) can be appropriately controlled. For example, in the above step (1), azobisisobutyronitrile is used to prepare the copolymer (A) at a reaction temperature of about 50 to 70 ° C, and then the above step (1) is performed with a solvent (such as toluene). The resulting product is diluted, and then in step (2) above, the copolymer (B) is prepared by using azobisisovaleronitrile at a reaction temperature of about 60 to 80 ° C to form a weight average molecular weight and weight ratio. A composition of the copolymer (A) and the copolymer (B) within the target range. That is, in the composition of the copolymer (A) and the copolymer (B) produced in the step (2), there is substantially no unreacted monomer remaining. Therefore, it is not necessary to go through a special purification step, and it is possible to directly make It reacts with a polyfunctional compound (C). Next, an optical element of the present invention will be described. The optical element of the present invention is an optical element which is formed by forming an adhesive layer formed of the adhesive of the present invention on at least one side of the optical element. 21 326 \ Patent Specification (Supplement) \ 93-07 \ 93110078 200427804 As the optical element forming the adhesive layer, a polarizing film, an elliptical polarizing film, an anti-reflection film, and a brightness enhancement film can be cited. The formation of the adhesive can be applied to the coating device using a commonly used coating device, for example, a roll-on-blade coater, a die roll coater, a winding bar coater, a gravure roll coater, a reverse Report dip coating machine, blade coating machine, etc. In addition, from the viewpoint of an appropriate film thickness and economy for absorbing and mitigating the phenomenon caused by the expansion and contraction of the polarizing plate, the thickness of the adhesive layer is preferably 5 to 100 μm. (Examples) The present invention will be described in more detail below using examples, but is not limited to these. In the following description, parts and% are parts and weight%, respectively. (Synthesis Example 1) To a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a drop-in nitrogen introduction tube, n-butyl acrylic acid 99 hydroxybutyl acrylate 1 was added. 0 parts, acetone 1 50. 0 parts, 2,2 ′ -even nitrile 0. After replacing the air in the reaction container with nitrogen gas, the reaction solution was heated to 60 ° C under a nitrogen environment for 5 hours. After the reaction, 190 parts of toluene and acrylic acid (2,2'-azobis (2,4-difluorenylvaleronitrile) 0.50 parts were added, and the temperature was raised to 6 hours. After the reaction, 曱 was added 5 5 parts of benzene, cooled to room solids 2 0. 0% Polymer Solution A. (Synthesis Examples 2 to 9) 326 \ Patent Specification (Supplement) \ 93 · 07 \ 93110078 22 Film, phase line. As the stress set of the coating machine, the coating machine, the dry film thickness, but the present invention means a weight device, and • 0 parts, 4-nitrodiisobutyl is allowed to react when falling). 25 parts and 700 ° C, inverse temperature, to obtain 200427804 As shown in Table 1, except that the monomer (a) having a reactive functional group and an ethylenically unsaturated double bond can be changed to copolymerize with (a) The monomers (b) having other ethylenically unsaturated double bonds and the monomers (c) having carboxyl groups and ethylenically unsaturated double bonds reacted were obtained in the same manner as in Synthesis Example 1 except for the types and amounts of the monomers (c) having carboxyl groups and ethylenically unsaturated double bonds. Polymer solution B ~ I. (Synthesis Example 10) In the same reaction apparatus as in Synthesis Example 1, butyl acrylate 9 9 was added. 0 parts, 4-hydroxybutyl acrylate 1.0 parts, ethyl acetate 16 3 · 0 parts, 2, 2'-azobisisobutyronitrile 0. After replacing the air in the reaction container with nitrogen gas, the reaction solution was heated to 80 ° C under a nitrogen atmosphere while stirring, and the reaction was allowed to proceed for 4 hours. After the reaction was completed, 176 parts of toluene and acrylic acid were added. 25 parts and 2, 2′-azobis (2,4-diamidinovaleronitrile) 0. 50 parts, heated to 7 5 ° C, and reacted for 6 hours. After the reaction, 57 parts of toluene were added and cooled to room temperature to obtain a solid content of 20%. 0% polymer solution J. (Synthesis Example 1 1) In the same reaction apparatus as in Synthesis Example 1, butyl acrylate 6 0 was added. 0 parts, 2-hexyl acrylate 37. 0 parts, 4-hydroxybutyl acrylate 3. 0 parts, acetone 1 50. 0 parts, 2,2'-azobisisobutyronitrile 0. After 0.6 parts of air was replaced with nitrogen in the reaction container, the reaction solution was heated to 60 ° C under a nitrogen environment while stirring, and reacted for 5 hours. After the reaction was completed, 65 parts of ethyl acetate and 0.1 parts of acrylic acid were added. 28 parts and 2,2'-azobisisobutyronitrile. 〇 6 parts, heated to 60 ° C, and reacted for 8 hours. After the reaction, 183 parts of toluene were added and cooled to room temperature to obtain a solid content of 20%. 0% Polymer Solution K. 23 326 \ Patent Specification (Supplement) \ 93-07 \ 93110078 200427804 (Synthesis Example 1 2) In the same reaction apparatus as in Synthesis Example 1, butyl acrylate 9 9 was added. 0 parts, hydroxybutyl 4-acrylate 1. 0 parts, acetone 15 0 · 0 parts, 2,2'-azobisisobutyronitrile 0. After 0.6 parts of air was replaced with nitrogen in the reaction container, the reaction solution was heated to 60 ° C under a nitrogen environment while stirring, and reacted for 3 hours. After the reaction was completed, toluene 1. 1 part and 0.55 parts of acrylic acid and 1.1 parts of 2,2'-azobis (2,4-difluorenylvaleronitrile) were heated to 70 ° C and reacted for 7 hours. After the reaction, 2 3 6 parts of toluene was added and cooled to room temperature to obtain a solid content of 20%. 0% polymer solution L. (Synthesis Example 1 3) In the same reaction apparatus as in Synthesis Example 1, butyl acrylate 99 was added. 0 parts, hydroxybutyl 4-acrylate 1. 0 parts, acetone 1 50. 0 份 、 2,2 ′ -azobisisobutyronitrile 0. In 06 parts, after the air in the reaction container was replaced with nitrogen, the reaction solution was heated to 60 ° C under a nitrogen environment while stirring, and reacted for 10 hours. After the reaction was completed, 198 parts of toluene and acrylic acid were added. 08 parts and 2, 2′-azobis (2, 4-dimethylvaleronitrile) 0. 16 parts, heated to 70 ° C, and reacted for 6 hours. After the reaction, 51 parts of toluene was added and cooled to room temperature to obtain a solid content of 20%. 0% polymer solution M. (Synthesis Example 1 4) In the same reaction vessel as in Synthesis Example 1, 99.0 parts of n-butyl acrylate and hydroxybutyl acrylate 1 were added. 0 parts, acetone 1 50. 0 parts, 2,2'-azobisisobutyronitrile. 〇6 parts. After replacing the air in the reaction container with nitrogen, the reaction solution was heated to 60 ° C under a nitrogen atmosphere while stirring, and reacted for 5 hours. After the reaction, 150 parts of toluene were added and cooled to 24 326 \ Patent Specification (Supplement) \ 93-07 \ 93110078 200427804 to room temperature to obtain a solid content of 20. 0% polymer solution N. The weight average molecular weight of the polymer was 1.61 million, and the Mw / Mn was 4. 8. (Synthesis Example 15) In the same reaction vessel as in Synthesis Example 1, n-butyl acrylate 99 was added. 0 parts, 4-hydroxybutyl acrylate 1. 0 parts, acetone 150. 0 parts, 1 part of α-fluorenyl styrene dimer and 2 parts of 2, 2'-azobisisobutyronitrile. After replacing the air in the reaction vessel with nitrogen, it was stirred under a nitrogen atmosphere. The reaction solution was heated to 70 ° C and allowed to react for 6 hours. After the reaction, 150 parts of toluene were added and cooled to room temperature to obtain a solid content of 40. 0 ° / 〇 polymer solution 0. The weight average molecular weight of the polymer was 2. 40,000, Mw / Mn is 2. 8. For the polymer solutions obtained in Synthesis Examples 1 to 13, the weight average molecular weight (Mw) of the copolymer (A), the conversion rate during the synthesis of the copolymer (A), and the copolymer (B) were calculated according to the methods described above. Weight average molecular weight (Mw), the conversion of the copolymer (B) during synthesis, and the proportion of the copolymer (B) relative to 100 parts of the copolymer (A). The results are shown in Table 1. 25 326 \ Patent Specification (Supplement) \ 93-07 \ 93110078 200427804 Table 1 (B) Parts by weight 32. 0 38. 5 26. 2 24. 0 32. 3 35. 5 32. 6 32. 3 25. 9 CD End38. 1 114. 8 CO od copolymer hetero (B) conversion (%) 95. 0 96. 0 92. 0 94. 0 96. 0 95. 0 〇 96. 0 CD 5S 94. 0 97. 0 93. 0 95. 0 Mw (xlO4) UO 〇〇 CNI 〇5 CO CO csi CO — cn 03 CNJ Bu (> i 00 OJ CO 03 27. 6 c < 5 Monomer (c) parts by weight 0.25 0.84 0.22 0.40 0.25 0.27 0.52 0.25 0.22 0.25 0.28 0.55 0.08 5 1 5 1 4-HBA 5 5 Copolymerization vessel (A) Conversion rate (%) 75.0 72.0 78.0 80.0 75.0 73.0 74.0 75.0 78.0 75.0 72.0 45.0 92.0 Mw (x104) § gg § LO CO § S gg CO LO rH g monomer (b) 1 < = > LO 20.0 28.0 2EHA 37.0 37.0 99.0 60.0 96.0 70.0 75.0 93.0 98.0 99.0 96.0 99.0 60.0 99.0 99.0 Monomer (a) 1 1 〇 c < i 〇isi 4-HBA CZ5 〇CO 〇 csi 〇 ◦ 〇— · 〇CO CD — · 〇 Polymer Solution A Polymerization Solution B Polymerization Solution C Polymerization Solution D Polymerization Solution E Polymerization Solution F Polymerization Body solution G Poly-pure volume 德 Polymer de-volume I Polymer-think solution J Polymer-age volume K K Polymer de-volume liquid L Polymer energy-capacity liquid M Synthesis example 1 Synthesis example 2 Synthesis example 3 Synthesis example 4 Synthesis example 5 Synthesis example 6 Synthesis example 7 Synthesis example 8 Synthesis example 9 Synthesis example 10 Synthesis example 11 Synthesis example 12 Synthesis example 13
326\專利說明書(補件)\93-07\93110078 26 200427804 表1中單體的簡稱如下所示： 4-HBA ： 4-丙烯酸羥基丁酯 AA :丙烯酸 HEA: 2 -丙烯酸羥基乙S旨 HEMA: 2 -曱基丙烯酸羥基乙酯 BA :丙烯酸丁酯 2EHA: 2 -丙烯酸乙基己酯 LA :丙烯酸月桂酯 EA :丙烯酸乙酉旨 VAc :乙酸乙烯酯 而且，共聚合體的重量平均分子量是以G P C測定，所求 得的聚苯乙烯換算之重量平均分子量，GPC測定條件如下： 裝置·· Shodex GPC System-21(昭和電工（股）製造） 管柱·· 1 根 Shodex KF-602.5、2 根 Shodex KF-606M(昭和 電工（股）製造），共計3根連結使用。 溶劑：四氫呋喃 流速：0 . 5 m 1 / m i η 溫度：4 0 °C 試樣濃度：0 . 1 w t % 試樣注入量：5 0 μ 1 (實施例1 )326 \ Patent Specification (Supplement) \ 93-07 \ 93110078 26 200427804 The abbreviations of the monomers in Table 1 are as follows: 4-HBA: 4-Hydroxybutyl Acrylate AA: HEA Acrylic Acid: 2-Hydroxyethyl Acrylic Acid : 2-Ethyl hydroxyethyl acrylate BA: Butyl acrylate 2EHA: 2-Ethylhexyl acrylate LA: Lauryl acrylate EA: Ethyl acrylate Vac: Vinyl acetate The weight average molecular weight of the copolymer is measured by GPC The weight-average molecular weight in terms of polystyrene obtained and GPC measurement conditions are as follows: Device: Shodex GPC System-21 (manufactured by Showa Denko Corporation) Columns: 1 Shodex KF-602.5, 2 Shodex KF -606M (manufactured by Showa Denko Co., Ltd.) for a total of 3 links. Solvent: tetrahydrofuran Flow rate: 0.5 m 1 / m i η Temperature: 40 ° C Sample concentration: 0.1 w t% Sample injection volume: 50 μ 1 (Example 1)
相對於1 0 0重量份之合成例1獲得的聚合物溶液A，添 加 XDI/TMP(二曱苯二異氰酸酯的三羥曱基丙烷加成產 物）0 · 0 5份和矽烷偶合劑（信越化學工業（股）製造[K BM 27XDI / TMP (trihydroxymethylpropane addition product of diphenylbenzene diisocyanate) was added to 0.5 to 5 parts by weight of polymer solution A obtained in Synthesis Example 1 and a silane coupling agent (Shin-Etsu Chemical Co., Ltd.) Industrial (stock) manufacturing [K BM 27
326\專利說明書(補件)\93-07\93110078 200427804 4 0 3 ] ) 0 . 1份，充分攪拌而獲得黏著劑。將該黏著劑塗佈在 經剝離處理過的聚酯膜上，然後乾燥，設置 2 5 μ m的黏著 劑層，然後將其轉印到偏光膜的一個面上，進行對偏光膜 的黏著加工。使該黏著加工過的偏光膜，於溫度2 3 °C、相 對濕度5 0 %的條件下，熟化1星期以獲得偏光板。 (實施例2〜7和比較例1〜7 ) 除了使用表2中所示種類和用量的聚合物溶液、多官能 性化合物（C )和矽烷偶合劑以外，依照與實施例1完全相同 的方法製造黏著劑，使用所獲得的黏著劑製造經黏著加工 過的偏光板。 (比較例8 ) 除了不使用聚合物溶液A，而使用聚合物溶液N : 1 0 0份 與聚合物溶液0 ·· 3 0份的所混合之聚合物溶液以外，按照 與實施例1完全相同的方法製造黏著劑，使用所獲得的黏 著劑製造經黏著加工過的偏光板。 28 326\專利說明書(補件)\93-07\93110078 200427804 表2 聚合體溶液 多官能性化合物(C) 矽烧偶合劑 種類 重量份 種類 重量份 種類 重量份 實施例1 聚合體溶液A 100.0 XDI/TMP 0. 05 KBM403 0.10 實施例2 聚合體溶液B 100.0 ΤΑΤ 0.10 KBM403 0.10 實施例3 聚合體溶液C 100.0 TGMXDA 0. 05 KBM903 0.20 實施例4 聚合體溶液D 100.0 XDI/TMP 0.10 KBM803 0.10 實施例5 聚合體溶液E 100.0 TGMXDA 0.05 KBM9007 0.10 實施例6 聚合體溶液F 100.0 TAT 0.05 KBM403 0.20 實施例7 聚合體溶液G 100.0 XDI/TMP 0.05 KBM403 0.10 比較例1 聚合體溶液Η 100.0 XDI/TMP 0. 05 KBM403 0.10 比較例2 聚合體溶液I 100.0 XDI/TMP 0. 05 KBM403 0.10 比較例3 聚合體溶液J 100.0 XDI/TMP 0. 05 KBM403 0.10 比車交例4 聚合體溶液Κ 100.0 XDI/TMP 0. 05 KBM403 0.10 比較例5 聚合體溶液L 100.0 XDI/TMP 0. 05 KBM403 0.10 比較例6 聚合體溶液Μ 100.0 XDI/TMP 0.05 KBM403 0.10 比車交例7 聚合體溶液Ν 100.0 XDI/TMP 0.05 KBM403 0.10326 \ Patent Specification (Supplement) \ 93-07 \ 93110078 200427804 4 0 3]) 0.1 parts, and stir well to obtain an adhesive. This adhesive was coated on a polyester film subjected to a peeling treatment, and then dried to provide an adhesive layer of 25 μm, and then transferred to one surface of a polarizing film to perform an adhesive processing on the polarizing film. . This adhesively processed polarizing film was aged at a temperature of 23 ° C and a relative humidity of 50% for 1 week to obtain a polarizing plate. (Examples 2 to 7 and Comparative Examples 1 to 7) Except that a polymer solution, a polyfunctional compound (C), and a silane coupling agent of the kinds and amounts shown in Table 2 were used, the method was completely the same as that of Example 1. An adhesive was manufactured, and the obtained polarizer was used to manufacture an adhesive-processed polarizing plate. (Comparative Example 8) Except that polymer solution A was not used, but polymer solution N: 100 parts and polymer solution 0 · 30 parts of the mixed polymer solution were used, the procedure was the same as in Example 1. The method is used to produce an adhesive, and the obtained adhesive is used to produce an adhesive-processed polarizing plate. 28 326 \ Patent Specification (Supplement) \ 93-07 \ 93110078 200427804 Table 2 Polymer solution polyfunctional compound (C) Type of silicon sintering coupler parts by weight kind by weight parts kind by weight part Example 1 Polymer solution A 100.0 XDI / TMP 0. 05 KBM403 0.10 Example 2 Polymer solution B 100.0 ΤΑΤ 0.10 KBM403 0.10 Example 3 Polymer solution C 100.0 TGMXDA 0.05 KBM903 0.20 Example 4 Polymer solution D 100.0 XDI / TMP 0.10 KBM803 0.10 Example 5 Polymer solution E 100.0 TGMXDA 0.05 KBM9007 0.10 Example 6 Polymer solution F 100.0 TAT 0.05 KBM403 0.20 Example 7 Polymer solution G 100.0 XDI / TMP 0.05 KBM403 0.10 Comparative Example 1 Polymer solution Η 100.0 XDI / TMP 0. 05 KBM403 0.10 Comparative Example 2 Polymer Solution I 100.0 XDI / TMP 0. 05 KBM403 0.10 Comparative Example 3 Polymer Solution J 100.0 XDI / TMP 0. 05 KBM403 0.10 Comparing Example 4 Polymer Solution K 100.0 XDI / TMP 0. 05 KBM403 0.10 Comparative Example 5 Polymer solution L 100.0 XDI / TMP 0. 05 KBM403 0.10 Comparative Example 6 Polymer solution M 100.0 XDI / TMP 0.05 KBM403 0.10 Than car example 7 Polymer solution N 100.0 XDI / TMP 0.05 KBM403 0.10
表2中的多官能性化合物和石夕烧偶合劑的簡稱，如下所 示。The abbreviations of the polyfunctional compound and the Shiyaki coupling agent in Table 2 are shown below.
TAT:三-2,4,6-(1-氮丙啶基）-1，3,5-三嗉 TGMXDA ： N，N，N’，N’-四縮水甘油基-間二曱苯二胺 KBM 9 0 3 ：信越化學工業（股）製造的矽烷偶合劑[KBM 9 0 3 ] KBM 8 0 3 ：信越化學工業（股）製造的矽烷偶合劑[KBM8 0 3 ] KBM 9 0 0 7 ：信越化學工業（股）製造的矽烷偶合劑[KBM 9 0 0 7 ] 針對實施例和比較例所獲得的黏著劑和經黏著加工的 偏光板，依照以下方法評價其耐熱性、耐濕熱性、光學特 性和重操作性。結果見表3。 (1 )耐熱性、耐濕熱性、光學特性（白斑）的評價方法 將經黏著加工的偏光板切割成 1 5 0 m m X 8 0 m m大小，然後 按照使偏光板的吸收軸垂直相交的方式，用積層機黏貼在 326\專利說明書(補件)\93-07\93110078 29 200427804 厚度為1 . 1 m in的浮法玻璃板的兩面上。然後，將黏貼了該 偏光板的玻璃板，在5 0 °C下、5個大氣壓條件下之高壓釜 内保持2 0分鐘，使偏光板與玻璃板貼緊。進一步地，目測 觀察此偏光板和玻璃板的構成物，在8 0 °C下放置5 0 0小時 後的剝離程度（耐熱性）、在6 0 °C 、相對濕度9 0 %下，放置 5 0 0小時後的剝離程度（耐濕熱性）以及在6 0 °C 、相對濕度 9 0 %下放置 5 0 0小時後之當光透過偏光板和玻璃板的構成 物時，產生的漏光程度（白斑），該評價分為三個等級。 ⑨代表[完全沒有觀察到剝離和白斑現象]，〇代表[觀察 到些許剝離和白斑現象，但無實用上問題]，△代表[觀察 到明顯的剝離和白斑現象，有實用上問題]。 (2 )重操作性的評價方法 將經黏著加工的偏光板切割成 2 5 m m X 1 5 0 m m大小，使用 積層機黏貼在厚度為1 . 1 m m的浮法玻璃上，在5 0 °C、5個 大氣壓條件下之高壓釜内保持2 0分鐘，使其貼緊在玻璃板 上。將該試驗片在2 3 °C、相對濕度5 0 %下放置1星期之後， 進行1 8 0 °剝離試驗（剝離速度3 0 0 m m / m i η )，目測觀察剝離 後玻璃的模糊程度，該評價分為兩個等級。 ⑨表示[實際使用完全沒有問題]，△表示[實際使用時有 問題]。 (3 )光學特性（霧度）的評價方法 將黏著劑塗佈在經剝離處理的聚酯膜上，然後乾燥，設 置2 5 μ m的黏著劑層，然後再覆蓋以經剝離處理的聚酯膜。 使被經剝離處理的聚酯膜夾在中間的黏著劑層，在溫度2 3 30 326\專利說明書(補件)\93-07\93110078 200427804 °C 、相對濕度5 0 %的條件下熟化1星期後，取下經剝離處 理的聚酯膜，使用NDH - 300Α(日本電色工業（股）公司製造） 測定黏著劑層單體的霧度。 表3 耐熱性 而才溼熱性 光學特性 重操作性 剝離 剝離 白斑 霧度 被黏著體污染 實施例1 ◎ ◎ 1.2 實施例2 ◎ ◎ ◎ 1.2 ◎ 實施例3 ◎ 〇 ◎ 1.3 ◎ 實施例4 〇 ◎ ◎ 1.3 ◎ 實施例5 ◎ 〇 ◎ 1.4 ◎ 實施例6 ◎ ◎ 〇 1.4 ◎ 實施例7 ◎ 〇 ◎ 1.2 ◎ 比較例1 〇 Δ ◎ 1.3 ◎ 比較例2 ◎ ◎ Δ 1.3 ◎ 比較例3 △ Δ ◎ 1.3 ◎ 比較例4 ◎ ◎ Δ 1.5 ◎ 比較例5 Δ Δ ◎ 1.3 Δ 比車交例6 ◎ ◎ Δ 1.2 ◎ 比較例7 ◎ ◎ Δ 1.2 ◎ 比較例8 ◎ ◎ 〇 1.7 Δ (發明效果） 透過使用本發明的黏著劑，就能夠提供即使在熱或濕熱 條件下，也不產生發泡和剝離等現象、透過使因偏光板伸 縮等而產生的應力集中現象得到緩和，而使液晶元件上不 產生色彩不均勻和白斑等現象的光學元件。 31 326\專利說明書(補件)\93-07\93110078TAT: tri-2,4,6- (1-aziridinyl) -1,3,5-triamidine TGMXDA: N, N, N ', N'-tetraglycidyl-m-phenylenediamine KBM 9 0 3: Silane coupling agent manufactured by Shin-Etsu Chemical Industry Co., Ltd. [KBM 9 0 3] KBM 8 0 3: Silane coupling agent manufactured by Shin-Etsu Chemical Industry Co., Ltd. [KBM8 0 3] KBM 9 0 0 7: Shin-Etsu Silane coupling agent manufactured by Chemical Industry Co., Ltd. [KBM 9 0 0 7] For the adhesives obtained in the examples and comparative examples and the polarized plates subjected to adhesion processing, the heat resistance, humidity and heat resistance, and optical characteristics were evaluated according to the following methods. And heavy operability. The results are shown in Table 3. (1) Evaluation method of heat resistance, humidity and heat resistance, and optical characteristics (white spots) The polarizing plate subjected to the adhesive processing is cut into a size of 150 mm X 80 mm, and then the absorption axes of the polarizing plates intersect perpendicularly. Use a laminating machine to stick to 326 \ Patent Specification (Supplement) \ 93-07 \ 93110078 29 200427804 on both sides of a float glass plate with a thickness of 1.1 mm. Then, the glass plate to which the polarizing plate was adhered was kept in an autoclave at 50 ° C and 5 atmospheres for 20 minutes to make the polarizing plate and the glass plate closely. Furthermore, the structure of the polarizing plate and the glass plate was visually observed, and the degree of peeling (heat resistance) after being left at 80 ° C for 500 hours, at 60 ° C and at a relative humidity of 90%, it was left at 5 Peeling degree (moisture and heat resistance) after 0 hours, and the degree of light leakage that occurs when light passes through the structure of the polarizing plate and glass plate after being left at 60 ° C and 90% relative humidity for 50 hours ( White spot), the evaluation is divided into three levels. ⑨ represents [no peeling and white spot phenomenon was observed at all], 〇 represents [some peeling and white spot phenomenon is observed but there is no practical problem], and △ represents [obvious peeling and white spot phenomenon are observed, and there are practical problems]. (2) Evaluation method of heavy operability The polarized plate processed by the adhesive was cut into a size of 25 mm X 150 mm, and was laminated on a float glass with a thickness of 1.1 mm using a laminating machine at 50 ° C. The autoclave at 5 atmospheres is kept for 20 minutes to make it close to the glass plate. After the test piece was left at 23 ° C and 50% relative humidity for 1 week, a 180 ° peeling test (peeling speed 300 mm / mi η) was performed, and the degree of blurring of the glass after peeling was visually observed. The evaluation is divided into two levels. ⑨ indicates [there is no problem in actual use], △ indicates [there is no problem in actual use]. (3) Evaluation method of optical characteristics (haze) The adhesive is coated on a polyester film subjected to a peeling treatment, and then dried to provide an adhesive layer of 25 μm, and then covered with a polyester subjected to the peeling treatment. membrane. The adhesive layer sandwiched between the peeled polyester film and aged at a temperature of 2 3 30 326 \ Patent Specification (Supplement) \ 93-07 \ 93110078 200427804 ° C and a relative humidity of 50% 1 After one week, the peeled polyester film was removed, and the haze of the adhesive layer monomer was measured using NDH-300A (manufactured by Nippon Denshoku Industries Co., Ltd.). Table 3 Heat resistance, wet heat, optical properties, heavy handling, peeling, peeling, white spot, haze, contaminated with adherends, Example 1 ◎ ◎ 1.2 Example 2 ◎ ◎ ◎ 1.2 ◎ Example 3 ◎ ○ 1.3 1.3 ◎ Example 4 ○ ◎ 1.3 ◎ Example 5 ◎ ○ ◎ 1.4 ◎ Example 6 ◎ ◎ 〇1.4 ◎ Example 7 ◎ ○ ◎ 1.2 ◎ Comparative Example 1 〇Δ ◎ 1.3 ◎ Comparative Example 2 ◎ Δ 1.3 1.3 ◎ Comparative Example 3 Δ Δ ◎ 1.3 ◎ Comparative Example 4 ◎ Δ 1.5 ◎ Comparative Example 5 Δ Δ 1.3 1.3 Δ Compared to Car Delivery Example 6 ◎ Δ 1.2 1.2 ◎ Comparative Example 7 ◎ ◎ Δ 1.2 ◎ Comparative Example 8 ◎ ◎ 1.7 (Inventive Effect) By using the present invention The adhesive can provide no foaming and peeling even under hot or humid conditions, and alleviate the stress concentration phenomenon caused by the expansion and contraction of the polarizing plate, so that no color loss occurs on the liquid crystal element. Optical elements with uniformity and white spots. 31 326 \ Patent Specification (Supplement) \ 93-07 \ 93110078