1301147 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（甲基）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 1301147 所公開的偏光板黏著劑係為可跟隨偏光板的尺寸變化，因 此在液晶元件上不容易產生色彩不均勻和白斑現象。但在 日本專利特開平 1 0 - 2 7 9 9 0 7號公報所公開的偏光板黏著 劑，係因為與多官能性化合物三維交聯的高分子量（曱基） 丙烯酸系共聚合體中存在著不易交聯或不交聯的低分子量 (曱基）丙烯酸系（共）聚合物，所以能顯示出應力緩和性， 而改善色彩不均勻和白斑現象，但有低分子量（曱基）丙烯 酸系聚合物很容易滲漏，而殘留有被黏著物受到污染的問 題。 又，於日本專利特開2 0 0 2 - 1 2 1 5 2 1號公報中，該文獻記 載有所公開之偏光板用黏著組合物，係同時具備不易產生 色彩不均勻和白斑現象的性能與低分子量丙烯酸系聚合物 不易發生滲漏的性能，但在更為苛刻的環境下之液晶顯示 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，其係即使在熱 或濕熱條件下也不產生黏著劑層發泡和偏光板剝離等現 象、使因偏光板伸縮等而產生的應力集中現象得到緩和， 而使液晶顯示裝置上不產生色彩不均勻和白斑等現象，而 且能夠減少重新黏貼偏光板時產生的被黏物污染和混濁等 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子量共聚合 體（A)、及在該共聚合體（A)存在下，帶有羧基的單體與其 他單體透過自由基共聚合反應所獲得的低分子量共聚合體 8 326\專利說明書(補件)\93-07\93110078 1301147 又，就單體（a)和單體（b)而言，可以適宜地使用（甲基）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（甲基）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-(甲基）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、1〇-(曱基）丙烯酸羥基癸酯、12-(曱基）丙烯酸 羥基月桂酯、曱基丙烯酸（4 -羥基曱基己基）酯、氯代-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（甲基）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 酸胺基甲酯、（甲基）丙烯酸二曱基胺基甲酯、（甲基）丙烯 酸二曱基胺基乙酯、（甲基）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 1301147 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 珀醯亞胺等。 帶有環氧基的單體（a)的具體實例，可以列舉（曱基）丙 烯酸縮水甘油醋等。 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）丙烯酸甲酯、（曱基）丙烯酸乙酯、（曱基）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、（曱基）丙烯酸正辛酯、（曱基）丙 烯酸異辛酯、（曱基）丙烯酸月桂酯、（甲基）丙烯酸十八烷 酯、（曱基）丙烯酸異壬酯、（甲基）丙烯酸環己酯、（曱基） 丙烯酸苄酯、（曱基）丙烯酸曱氧基乙酯、（甲基）丙烯酸乙 氧基乙酯、（曱基）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 1301147 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 -三曱基己醯基）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1 2 0萬以上1 8 0萬以下。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 1301147 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ί 處於2 0〜1 0 0重量份的範圍。 共聚合體（Β)以透過溶液聚合法來合成為佳， 共聚合體（Α)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（Β)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H 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 t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 1301147 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σ定系化合物等。特別以異氰酸酯系化合物、 環氧系化合物、氮丙啶系化合物較佳。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 1301147 就異氰酸酯系化合物的實例而言，可以列舉曱苯二 酸酯、六亞曱基二異氰酸酯、異佛爾酮二異氰酸酯、 苯二異氰酸酯、氫化二曱苯二異氰酸酯、二苯基甲烷 氰酸酯、氫化二苯基曱烷二異氰酸酯、四曱基二甲苯 氰酸酯、萘二異氰酸酯、三苯基甲烷三異氰酸酯、多 基多苯基異氰酸酯等多異氰酸酯化合物，以及這些多 酸酯化合物與三羥曱基丙烷等多元醇化合物的加成產 這些多異氰酸酯化合物的縮二脲產物和異氰脲酸酯 等，進一步可以列舉這些多異氰酸酯化合物與已知的 多元醇和聚酯多元醇、丙烯酸類多元醇、聚丁二烯多元 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，可以列舉雙酚 A 氣醇型之環氧系樹脂、乙二醇二縮水甘油醚、聚乙二 縮水甘油喊、甘油二縮水甘油醚、甘油三縮水甘油、 己二醇二縮水甘油醚、三經甲基丙烧三縮水甘油喊、 水甘油基苯胺、Ν,Ν,Ν’，Ν’-四縮水甘油基-m -二曱苯二 1，3-雙（N，Ν’-二縮水甘油基胺基曱基）環己烷、Ν,Ν, Ν’ 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 Ν，Ν ’ -二 曱烷- 4,4’-雙（1-氮丙啶羰基化物）、Ν, Ν’-曱苯-2, 4-售 氮丙啶羰基化物）、雙間苯二醯-；! - ( 2 -曱基氮丙啶）、三 氮丙啶基氧化膦、Ν，Ν’ -六亞曱基-1,6 -雙（1-氮丙啶羰 物）、三羥曱基丙烷三-β -氮丙啶基丙酸酯、四羥甲基 - β-氮丙σ定基丙酸酯、三-2，4，6-(1-氮丙σ定基）-1，3, 326\專利說明書(補件)\93-07\93110078 18 異氰 二曱 二異 二異 亞曱 異氰 物， 產物 聚醚 醇、 一表 醇二 1，6-二縮 胺、 ，Ν，- 苯基 i (1-.-1-基化 甲烷 5-三 1301147 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1 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，可以列舉乙烯基三甲氧基矽烷、乙烯基三乙輩 曱基丙烯氧基丙基三甲氧基矽烷、γ-甲基丙烯氧 基二甲氧基矽烷、γ_環氧丙氧丙基三甲氧基矽烷 丙氧丙基甲基二甲氧基矽烷、γ -環氧丙氧丙基甲 基矽烷、2 -（ 3，4 -環氧基環己基）乙基三曱氧基矽 基丙基三曱氧基矽烷、γ -胺基丙基三乙氧基矽烷 丙基甲基甲氧基石夕烧 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 酼基丙基三甲氧基矽烷、γ -鲼基丙基三乙氧基矽 丁基三曱氧基矽烷γ-巯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 ，基矽烷、 基丙基甲 、γ-環氧 基二乙氧 烷、γ-胺 、γ-胺基 基甲氧基 石夕烧、γ-烧、Μ基 等0 1301147 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 50〜90 %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 1301147 如表1所示，除了改變具有反應性官能基和乙 和雙鍵結的單體（a )、可與（a )發生共聚合反應的 乙烯性不飽和雙鍵結的單體（b )、具有羧基和乙稀 雙鍵結的單體（c)的種類和用量以外，依照與合成 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 份、4 -丙烯酸羥基丁酯1 . 0份、乙酸乙酯1 6 3 · 0 偶氮二異丁腈〇 . 〇 6份，在將該反應容器内的空氣 氣之後，在攪拌的同時於氮氣環境下，將該反應 到8 0 °C ，使其反應4小時。反應結束後，添加曱 和丙烯酸 0.25份和 2, 2’-偶氮二（2, 4-二曱基j 份，升溫到7 5 °C，反應6小時。反應後，添加甲 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 份、2 -丙烯酸乙基己酯 37.0份、4 -丙烯酸羥基 份、丙酮1 5 0 · 0份、2，2 ’ -偶氮二異丁腈0 . 0 6份 反應容器内的空氣置換為氮氣之後，在攪拌的同 環境下，將該反應溶液升溫到6 0 °C，使其反應5 應結束後，添加乙酸乙酯6 5. 0份和丙烯酸0. 2 8啦 偶氮二異丁腈〇. 〇 6份，升溫到6 0 °C ，反應8小 後，添加甲苯1 8 3份，冷卻至室溫，獲得固形分 聚合體溶液K。 326\專利說明書(補件)\93-07\93110078 23 烤性不飽 具有其他 性不飽和 例1相同 丁酯 9 9 . 0 份、2，2，-置換為氮 溶液升溫 苯1 7 6份 戈腈）0 · 5 0 苯57份， 〇 丁酯 6 0 . 0 丁酯 3. 0 ，在將該 時於氮氣 小時。反 Η口 2，2，- 時。反應 -2 0 . 0 % 的 1301147 (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，添加曱苯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相同的反應裝置卡，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1 0小時。反應結束後，添加曱苯1 9 8份和丙 烯酸0 · 0 8份和2，2 ’ -偶氮二（2，4 -二曱基戊腈）0 · 1 6份，升 溫到7 0 °C ，反應6小時。反應後，添加曱苯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。反應後，添加曱苯1 5 0份，冷 24 326\專利說明書(補件)\93-07\93110078 1301147 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 9 9 · 0份、4 -丙烯酸羥基丁酯1 · 0份、丙酮 1 5 0 · 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 1301147 表1 〇 m CO Ο CO to CO CO 05 CO 114.8 CO CQ Φ1 oi CO CO 03 芬· LO CO 03 CO oi CO CO* 00 轉化率 (%) 95.0 96.0 92.0 94.0 96.0 95.0 91.0 96.0 ◦ 53 94.0 97.0 93.0 95.0 ¥ Mw (xl〇4) LO oi oo 03 CO CO c<i CO 一 03 oi 寸 CO 卜 〇〇 CO oa 27.6 oi 卜 c<i tM LO 03 LO C<I 8S TO 2 Alh.i c=> o <=> CD 〇· 。· ◦· o ◦· ◦· <=> ◦· ◦· 越 ϊή- i 5 5 1 % 5 5 1 墀 4-HBA 5 5 5 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 1# (xlO4) g S g § g 0¾ <NI § CO in g Μ 5 20.0 單體⑹ 28.0 雪 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 1 〇 c<i | 1 C3 oi 3 〇 — 〇 in 4-HBA 〇 〇 CO 〇 oi 〇 ◦ Ο 〇 CO ◦ 〇 < I i OQ 雇 1 i 1 s ω 1 bu i i i i ! 1 1 ί 1 se 1 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13 26 326\專利說明書(補件)\93-07\93110078 1301147 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 Η E A ·· 2 -丙烯酸羥基乙酯 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 :丙烯酸乙酯 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 )1301147 A pressure-sensitive adhesive composed of an olefinic polymer. (For example, refer to Japanese Patent Laid-Open 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 not possible to absorb and relax the stress caused by the dimensional change of the polarizing plate due to stress concentration. Since the edge portion of the liquid crystal display device and the central portion are different in brightness at the edge portion of the polarizing plate, 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 the liquid crystal display device, 100 parts by weight of a high molecular weight (fluorenyl) acrylic copolymer having a weight average molecular weight of 1,000,000 or more and a weight average molecular weight are known. Adhesive for polarizing plate formed by a low molecular weight (meth)acrylic copolymer of 30,000 or less and 20 parts by weight of a polyfunctional compound of 0.05 to 5 parts by weight (for example, refer to Japan Patent Unexamined Patent Publication No. 1 0 - 2 7 9 9 0 7). Further, it is known that a high molecular weight acrylic polymer having a weight average molecular weight of from 1,000,000 to 250,000 having a reactive functional group and a weight average molecular weight of from 0 ° C to -8 ° C of a glass transition point of 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. 2000- 1 2 1 5 2 Bulletin 1). SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) In the publication of Japanese Patent Laid-Open No. Hei No. 0 0-279-9077, the document describes 326\Patent Specification (supplement)\93-07\93110078 1301147 The disclosed polarizing plate adhesive is a size change that can follow the polarizing plate, so that color unevenness and white spot phenomenon are less likely to occur on the liquid crystal element. However, the polarizing plate adhesive disclosed in Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei. No. Hei. No. Hei. A low molecular weight (fluorenyl) acrylic (co)polymer that is crosslinked or not crosslinked, so it can exhibit stress relaxation and improve color unevenness and white spot phenomenon, but has a low molecular weight (fluorenyl) acrylic polymer. It is easy to leak, and there is a problem of contamination of the adherend. Further, in Japanese Laid-Open Patent Publication No. 2000-221, which discloses a disclosed adhesive composition for a polarizing plate, it has a property of not easily causing color unevenness and white spot phenomenon. Low molecular weight acrylic polymers are less prone to leakage, but the use of liquid crystal display devices in more demanding environments is difficult to balance performance. Accordingly, an object of the present invention is to provide an adhesive which does not cause foaming of an adhesive layer and peeling of a polarizing plate even under heat or humid heat conditions, and which alleviates stress concentration due to stretching of a polarizing plate or the like. Therefore, the liquid crystal display device does not cause color unevenness and white spots, and the like, and it is possible to reduce the problem of contamination and turbidity caused by adhering to the polarizing plate. (Means for Solving the Problem) The adhesive of the present invention contains a specific ratio of the high molecular weight copolymer (A), and in the presence of the copolymer (A), the carboxyl group-containing monomer and other monomers are subjected to radical copolymerization. Low molecular weight copolymer obtained by the reaction 8 326\patent specification (supplement)\93-07\93110078 1301147 Further, as the monomer (a) and the monomer (b), (meth)acrylic acid can be suitably used. It is a monomer or a vinyl monomer. Specific examples of the monomer (a) having a carboxyl group include (meth)acrylic acid, carboxyethyl β-acrylate, itaconic acid, crotonic acid, fumaric acid, fumaric anhydride, maleic acid, and maleic anhydride. , maleic acid butyl ester and the like. Specific examples of the monomer (a) having a hydroxyl group include hydroxyethyl 2-(mercapto)acrylate, hydroxypropyl 2-(meth)acrylate, hydroxybutyl 4-(decyl)acrylate, 6 _ (fluorenyl) hydroxyhexyl acrylate, hydroxyoctyl 8-(indenyl) acrylate, hydroxy decyl chloroformate, hydroxylauryl 12-(mercapto) acrylate, methacrylic acid (4-hydroxyl) Mercaptohexyl) ester, hydroxypropyl chloro-2-(indenyl) acrylate, diethylene glycol mono(indenyl) acrylate, caprolactone modified (mercapto) acrylate, polyethylene glycol ( Mercapto) acrylates, polypropylene glycol (meth) acrylates, and the like. Specific examples of the amine group-containing monomer (a) include (mercapto)acrylic acid aminomethyl ester, (meth)acrylic acid didecylaminomethyl ester, and (meth)acrylic acid didecylamino group B. Ester, dimethylaminopropyl (meth)acrylate, and the like. Specific examples of the monomer (a) having a guanamine group include (fluorenyl) acrylamide, N-propylene morpholine, N-substituted (fluorenyl) acrylamide, and N-vinyl arrotaxane. Ketones, etc. Specific examples of the monomer (a) having a maleidino group include N-cyclohexylmaleimide, N-isopropylmaleimide, N-lauryl maleimide, N-phenyl maleimide and the like. Specific examples of the monomer (a) having a ketimine group include N-mercaptoconazole, N-ethyl itaconimine, N-butyl itaconimine, 11 326\Patent specification (supplement)\93-07\93110078 1301147 N-octyl ketimine, N-2 -ethylhexyl ketimine, N-cyclohexyl ketimine, N - Lauryl kiln, and the like. Specific examples of the monomer (a) having an amber quinone imine group may, for example, be N-(methyl) propylene sulfonium sulfenyl succinimide, N-(methyl) propylene fluorene-6-oxyhexa Methyl amber quinone imine, N-(meth) propylene 醯-8-oxo octadecyl succinimide, and the like. Specific examples of the epoxy group-containing monomer (a) include (mercapto)acrylic acid glycidic vinegar and the like. These monomers may be used alone or in combination of plural kinds. The copolymerization ratio of the monomer (a) constituting the copolymer (A) is preferably from 0.1 to 15% by weight based on the total amount of the monomers. When the copolymerization ratio is less than 0.1% by weight, the cohesive force of the adhesive is lowered, and the foaming and peeling of the adhesive occur in a heated environment. On the other hand, when the amount is more than 15% by weight, the adhesive strength of the adhesive is lowered, and it is difficult to exhibit sufficient absorption and relaxation of the stress concentration phenomenon caused by the expansion and contraction of the polarizing plate. Further, specific examples of the monomer (b) include (meth) acrylates such as methyl (mercapto) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (fluorenyl). N-butyl acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (decyl) acrylate, isooctyl (decyl) acrylate, lauric (meth) acrylate Ester, octadecyl (meth) acrylate, isodecyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, decyl acrylate (mercapto) acrylate, ( Ethoxyethyl methacrylate, phenoxyethyl (meth) acrylate, and the like. Further, examples thereof include aromatic vinyl monomers such as styrene, mercaptostyrene, and vinyl fluorene, and 12 326\patent specification (supplement)\93-07\93110078 1301147 醯, tert-butylperbenzoquinone Acid ester, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, bis(2-ethoxyethyl)peroxydicarbonate, tert-butyl Oxidized neodecanoate, tert-butyl peroxypivalate, (3,5,5-tridecylhexyl) peroxide, dipropyl hydrazine peroxide, diethyl hydrazine peroxide Wait. The weight average molecular weight of the copolymer (A) must be 1,000,000 or more and 2,000,000 or less, preferably 12,000 or more and 18,000 or less. The weight average molecular weight of the copolymer (A) is more than 1,000,000 hours, and even if it is used after crosslinking, the cohesive force of the adhesive is insufficient, and foaming and peeling occur. Further, when the weight average molecular weight exceeds 200,000, the viscosity of the adhesive becomes large, and the handling properties such as coating are deteriorated. Further, the weight average molecular weight of the copolymer (A) was calculated by gel permeation chromatography (G P C ) by sampling from the reaction solution above the polymerization of the copolymer (B). The copolymer (B) contained in the adhesive is a monomer having a carboxyl group and an ethylenically unsaturated double bond (c) and a single monomer having an ethylenically unsaturated double bond copolymerizable with (c). The body (d) is a copolymer of a weight average molecular weight of 10,000 or more and 100,000 or less by a radical copolymerization reaction in the presence of the above-mentioned copolymer (A). The lower molecular weight copolymer (B) obtained by permeating the monomer (c) and the monomer (d) by radical copolymerization in the presence of the copolymer (A) is contained in the adhesive, Even under hot or humid heat conditions, the phenomenon of foaming and peeling of the adhesive does not occur, and stress concentration due to expansion and contraction of the polarizing plate is alleviated, so that color unevenness and white spots do not occur on the liquid crystal element. For the monomer (c) and the monomer (d), the (mercapto)acrylic acid 14 326\patent specification (supplement)\93-07\93110078 1301147 can be suitably used to pass the copolymer at the above conversion rate. The combination of (A) and copolymerization # is easily in the range of 20 to 100 parts by weight based on 100 parts by weight of the copolymer (A). It is preferred that the copolymer (Β) is synthesized by a solution polymerization method, and a polymerization initiator of about 5 to 50 times by weight in the case of the copolymer (in terms of hydrazine) is used in a total amount of 100 parts by weight of the monomer, and 0·0 0 5 is used. Preferably, 50 parts by weight of the agent is used. Further, in the case of synthesizing a copolymer (Β), a chain transfer agent such as a mercaptan such as lauryl lauryl mercaptan or an α-methylstyrene dimer may be used. The weight average molecular weight of the copolymer (Β) must be 10,000 or more, preferably 20,000 or more and 50,000 or less. When a copolymer having a weight average of 10,000 is used, since the cohesive force is insufficient, peeling or the like is likely to occur. Further, when the weight average molecular weight exceeds 10% (Β), it is difficult to exhibit the property of sufficiently absorbing and alleviating the stress concentration phenomenon due to the extension of the polarizing plate. Here, the barium amount of the copolymer (Β) is obtained by measuring the copolymer (Α) and the copolymerized H by a GPC method, and calculating from the obtained GPC spectrum and the difference spectrum of the copolymerization name GPC spectrum measured by the above method. The content of the body (B) contained in the adhesive is 20 to 100 parts by weight, preferably 20 to 5 0, of the copolymer (B), based on 100 parts by weight of the copolymer (A). When the amount is less than 20 parts by weight, it is difficult to absorb and relax the stress concentration caused by the expansion and contraction of the polarizing plate. When the content of the copolymer (B) exceeds 100 parts by weight, the cohesive force is insufficient, and foaming and peeling are likely to occur. phenomenon. 326\Patent specification (supplement)\93-07\93110078 16 'Body (B) poly t-complex (B) Synthetic, that is, relative polymerization starting thiol, n-, decadiene 100,000 to 1 The copolymerization of the foam and the 10,000 is caused by the average amount. (B) The copolymerized parts by weight of the mixture-body (A). Now its full nature. The weight ratio of the 1301147 copolymer (A) to the copolymer (B) of the adhesive was obtained by the following method. That is, first, before the start of polymerization of the copolymer (B), a certain amount of the 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. Volatile, the container in which only the copolymer (A) remains is accurately weighed, and the weight of the copolymer (A) contained in the solution is calculated. 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 method as in calculating the weight of the copolymer (A) is used to calculate a certain amount of the solution. The weight of the copolymer (A) and the copolymer (B). Then, the weight of the mixture of the copolymer (A) and the copolymer (A) and the copolymer (B) contained in a certain amount of the solution is converted into the copolymer (A) and the copolymer (A) contained in the same amount of the solution. The weight of the mixture of the copolymer (B) is subtracted from the weight of the mixture of the copolymer (A) and the copolymer (B), whereby the weight of the copolymer (B) is calculated. The polyfunctional compound (C) containing at least two reactive functional groups reactive with the copolymer (A) and/or the copolymer (B) contained in the adhesive has at least two, preferably at least two, preferably 2 to 4 compounds which can react with a reactive functional group of the copolymer (A) and/or a carboxyl group which the copolymer (B) has, and a reactive functional group which reacts with a reactive functional group other than a carboxyl group. Examples of such a polyfunctional compound include an isocyanate compound, an epoxy compound, an amine compound, a metal chelate compound, and an aziridine compound. Particularly, an isocyanate compound, an epoxy compound, or an aziridine compound is preferable. The polyfunctional compounds may be used singly or in combination of plural kinds. 17 326\Patent specification (supplement)\93-07\93110078 1301147 Examples of the isocyanate compound may include terephthalate, hexamethylene diisocyanate, isophorone diisocyanate, phenyl diisocyanate. , hydrogenated diphenylene diisocyanate, diphenylmethane cyanate, hydrogenated diphenyldecane diisocyanate, tetradecyl xylene cyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, polyphenylene polyphenyl A polyisocyanate compound such as an isocyanate, and a polyhydric alcohol compound such as a polyhydroxyl compound, and a polyhydric alcohol compound such as trihydroxy hydrazine propane, and a biuret product and an isocyanurate of these polyisocyanate compounds, etc., and further, these polyisocyanate compounds are mentioned. Addition products such as known polyols and polyester polyols, acrylic polyols, polybutadiene polyisoprene polyols, and the like. Further, examples of the epoxy compound include bisphenol A gas alcohol type epoxy resin, ethylene glycol diglycidyl ether, polyethylene diglycidyl glycerin, glycerol diglycidyl ether, and glycerol triglycidyl. , hexanediol diglycidyl ether, trimethyl methacrylate triglycidide shout, water glyceryl aniline, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl-m-diphenylene benzene Bis(N,Ν'-diglycidylamino)cyclohexane, hydrazine, hydrazine, Ν'tetraglycidylaminophenyl decane, triglycidyl and the like. Further, examples of the aziridine compound include hydrazine, Ν '-dioxane-4,4'-bis(1-aziridine carbonyl), hydrazine, Ν'-nonphenyl-2, 4- Aziridine carbonyl), bis-m-benzoquinone-;! - (2-mercaptoaziridine), triaziridine phosphine oxide, hydrazine, Ν'-hexamethylene-1,6-double ( 1-Aziridine carbonyl), trihydroxymercaptopropane tris-β-aziridine propionate, tetramethylol-β-aza propionate propionate, tris-2,4,6-( 1-Aziridine sigma)-1,3, 326\Patent specification (supplement)\93-07\93110078 18 Isocyanide diisoisoindole isocyanide, product polyether alcohol, one alcohol 1,6-Diamine, hydrazine, -phenyl i (1-.-1-methylated methane 5-trisole 1301147 hydrazine, etc. The functional group of the polyfunctional compound (c) may have an upper body (A) And/or the reactive functional group of the above-mentioned copolymer (B) is appropriately selected. For example, when the reactive functional group having the above-mentioned copolymer (A) and/or the complex (B) is a hydroxyl group, the polyfunctionality is 1 Having an isocyanate group as a functional group and having the above copolymerized body as described above (B) When the reactive functional group is a carboxyl group, the polyorganic compound (C) preferably has an epoxy group or an aziridine group as a functional group. The polyfunctional content is 100 parts by weight based on the above copolymer (A). When it is 0. 0 0 3 parts by weight, when the polyfunctional compound (C) is 0.03 parts by weight, the cohesive force of the colorant is insufficient, and it is easy to peel off, etc. Further, when it exceeds 3 parts by weight, It is difficult to absorb and alleviate the stress concentration caused by the expansion and contraction of the polarizing plate. It is preferable to use a decane coupling agent in combination in the adhesive. Examples of the agent include vinyl trimethoxynonane and vinyl triethylene sulfonyloxy group. Propyltrimethoxydecane, γ-methylacryloxydimethoxydecane, γ-glycidoxypropyltrimethoxydecanepropoxypropylmethyldimethoxydecane, γ-glycidoxy Propylmethyldecane, 2-(3,4-epoxycyclohexyl)ethyltridecyloxymercaptopropyltrimethoxyoxydecane, γ-aminopropyltriethoxydecanepropylmethyl Methoxy 夕 夕 Ν-(2-aminoethyl) 3-aminopropyl ketone, Ν-(2-aminoethyl) 3-aminopropyl Nonyldimethoxydecylpropyltrimethoxydecane, γ-mercaptopropyltriethoxyphosphonium butyltrimethoxy decane γ-mercaptopropylmethyldimethoxy decane 326\Patent Specification Supplement) \93-07\93110078 19 The type of copolymerization is carried out by the above-mentioned copolymer (C), and the compound (C) is not sufficiently soluble in foaming. , decyl, propyl-propyl, γ-epoxydiethoxy oxane, γ-amine, γ-amino methoxy sulphur, γ-sinter, fluorenyl, etc. 0 1301147 relative to the copolymer (A) 100 parts by weight, the content of the decane coupling agent in the adhesive is preferably 0.01 parts by weight. When the amount is less than 0.1 part by weight, the effect of improving the physical properties is insufficient. When the amount is more than 2 parts by weight, not only the cost of the adhesive is high but also peeling occurs. Further, it is also possible to use an ultraviolet absorber, an antioxidant, a tackifying resin, a plasticizer, an antifoaming agent, and a leveling agent in combination with the adhesive. The adhesive of the present invention can be utilized in the form of a two-liquid type adhesive of (1) the above-mentioned copolymer (Α) and the copolymer (Β) and (2) the polyfunctional compound (C). The adhesive can be produced by the following steps (1) to (3). (1) a monomer (a) having a reactive functional group and an ethylenically unsaturated double bond, and a monomer which can be copolymerized with (a) and having other ethylenically unsaturated double bonds (b) The step of polymerizing the copolymer (A) by radical copolymerization at a conversion of 50 to 90%. (2) The monomer remaining in 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), a conversion ratio of 70 to 100% The step of polymerizing the copolymer (B) by radical copolymerization. (3) A step of adding a polyfunctional compound (C) having at least two reactive functional groups which can react with the copolymer (A) and/or the copolymer (B). In the adhesive obtained by the above production method, the above-mentioned copolymer (B) contains a carboxyl group derived from the monomer (c), so the adhesive obtained by the present invention, 20 326\patent specification (supplement)\93-07 \93110078 1301147 As shown in Table 1, except for the monomer (a) having a reactive functional group and a double bond and a double bond, an ethylenically unsaturated double bonded monomer which can undergo copolymerization with (a) b) In addition to the kind and amount of the monomer (c) having a carboxyl group and an ethylene double bond, the polymer solutions B to I are obtained in accordance with the synthesis. (Synthesis Example 10) In the same reaction apparatus as in Synthesis Example 1, an acrylic acid component, a 4-hydroxybutyl acrylate, 1.0 part, and an ethyl acetate 1 6 3 · 0 azobisisobutyronitrile ruthenium were added. After the air in the reaction vessel was placed, the reaction was allowed to proceed to 80 ° C under a nitrogen atmosphere while stirring, and allowed to react for 4 hours. After the completion of the reaction, 0.25 parts of hydrazine and acrylic acid and 2 parts of 2,2'-azobis(2,4-didecyl group) were added, and the temperature was raised to 75 ° C for 6 hours. After the reaction, the methyl group was cooled to room temperature. A polymer solution J having a solid content of 20.0% was obtained (Synthesis Example 1 1 ) In the same reaction apparatus as in Synthesis Example 1, an acrylic acid component, 37.0 parts of 2-ethyl hexyl acrylate, and a hydroxyl group of 4-acrylic acid were added. , acetone 1 5 0 · 0 parts, 2, 2 '-azobisisobutyronitrile 0. 0 6 parts of the air in the reaction vessel was replaced by nitrogen, and the reaction solution was heated to 60 in the same environment of stirring. °C, after the reaction 5 is finished, add ethyl acetate 6 5. 0 parts and acrylic acid 0. 2 8 azobisisobutyronitrile 〇. 6 parts, heat up to 60 ° C, after 8 hours of reaction Add 1 8 3 parts of toluene and cool to room temperature to obtain a solid polymer solution K. 326\Patent specification (supplement)\93-07\93110078 23 Roasting is not saturated with other unsaturation Example 1 same butyl ester 9 9 parts, 2, 2, - replaced with a nitrogen solution to raise benzene 176 parts of nicotinonitrile) 0 · 5 0 benzene 57 parts, butyrate 6 0. 0 butyl ester 3. 0, at this time Gas hour. When the mouth is 2, 2, -. Reaction - 20.0% of 1301147 (Synthesis Example 1 2) In the same reaction apparatus as in Synthesis Example 1, 9.0 parts of butyl acrylate, 1.0 part of 4-hydroxybutyl acrylate, and acetone 1 5 were added. 0 parts, 2,2 '-azobisisobutyronitrile 0. 0 6 parts, after replacing the air in the reaction vessel with nitrogen, the reaction solution is heated to a nitrogen atmosphere while stirring Allow to react at 60 ° C for 3 hours. After the reaction is completed, 1.1 parts of toluene and 0. 5 parts of acrylic acid and 1 · 1 part of 2,2 azobis(2,4-dimercapto valeronitrile) are added, and the temperature is raised to 70 ° C, and the reaction is carried out. hour. After the reaction, 2 36 parts of toluene was added, and the mixture was cooled to room temperature to obtain a polymer solution L of a solid content of 2.0%. (Synthesis Example 1 3) In the same reaction apparatus card as in Synthesis Example 1, 90 parts of butyl acrylate, 1.0 part of 4-hydroxybutyl acrylate, 1.0 part of acetone, 1 part of acetone, and 2, 2 ' of acetone were added. - azobisisobutyronitrile 0.6 parts, after replacing the air in the reaction vessel with nitrogen, the reaction solution is heated to 60 ° C under a nitrogen atmosphere while stirring, and the reaction is carried out. 0 hours. After the reaction was completed, 198 parts of toluene and 0. 0 parts of acrylic acid and 2,2 '-azobis(2,4-dimercapto valeronitrile) 0 · 16 parts were added, and the temperature was raised to 70 ° C. , the reaction was 6 hours. After the reaction, 51 parts of toluene was added, and the mixture was cooled to room temperature to obtain a solid solution of 20.0% of a polymer solution. (Synthesis Example 1 4) In the same reaction vessel as in Synthesis Example 1, 9 9 · 0 parts of n-butyl acrylate, 1.0 part by weight of hydroxybutyl 4-acrylate, and 1 part of acetone, 1 part, 2 parts, 2, 2 were added. '-Azobisisobutyronitrile 0. 0 6 parts, after replacing the air in the reaction vessel with nitrogen, the reaction solution was heated to 60 ° C under a nitrogen atmosphere while stirring, and reacted. 5 hours. After the reaction, 150 parts of toluene was added, and cold 24 326 \patent specification (supplement) \93-07\93110078 1301147 was taken to room temperature to obtain a polymer solution N having a solid content of 2.0%. The weight average molecular weight of the polymer was 1.61 million, and Mw/Mn was 4.8. (Synthesis Example 1 5) In the same reaction vessel as in Synthesis Example 1, 9 9 · 0 parts of n-butyl acrylate, 1 · 0 part of 4-hydroxy acrylate, 1 1 0 0 · 0 part of acetone, and α - 曱 were added. 1 part of styrene dimer and 2 parts of 2,2'-azobisisobutyronitrile, after the air in the reaction vessel is replaced with nitrogen, the reaction solution is heated under a nitrogen atmosphere while stirring. It was allowed to react at 70 ° C for 6 hours. After the reaction, 150 parts of toluene was added, and the mixture was cooled to room temperature to obtain a polymer solution 0 having a solid content of 40 ° / 〇. The weight average molecular weight of the polymer was 24,000, and the Mw/Mn was 2.8. With respect to the polymer solution obtained in Synthesis Examples 1 to 13, the weight average molecular weight (Mw) of the copolymer (A), the conversion ratio at the time of synthesis of the copolymer (A), and the copolymer (B) were calculated by the method described previously. The weight average molecular weight (Mw), the conversion ratio at the time of synthesis of the copolymer (B), and the ratio of the copolymer (B) to 100 parts of the copolymer (A). The results are shown in Table 1. 25 326\Patent specification (supplement)\93-07\93110078 1301147 Table 1 〇m CO Ο CO to CO CO 05 CO 114.8 CO CQ Φ1 oi CO CO 03 Fen· LO CO 03 CO oi CO CO* 00 Conversion rate ( %) 95.0 96.0 92.0 94.0 96.0 95.0 91.0 96.0 ◦ 53 94.0 97.0 93.0 95.0 ¥ Mw (xl〇4) LO oi oo 03 CO CO c<i CO a 03 oi inch CO 〇〇CO oa 27.6 oi 卜 c<i tM LO 03 LO C<I 8S TO 2 Alh.ic=> o <=> CD 〇· . · ◦· o ◦· ◦· <=> ◦· ◦· 越ϊή- i 5 5 1 % 5 5 1 墀4-HBA 5 5 5 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 1# (xlO4) g S g § g 03⁄4 <NI § CO in g Μ 5 20.0 monomer (6) 28.0 snow 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 1 〇c<i 1 C3 oi 3 〇—〇in 4-HBA 〇〇CO 〇oi 〇◦ Ο 〇CO ◦ 〇< I i OQ Employment 1 i 1 s ω 1 bu iiii ! 1 1 ί 1 se 1 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 26 326\Patent Specification (Supplement)\93-07\93110078 1301147 The abbreviations of the monomers in Table 1 are as follows: 4 - HBA: 4-hydroxybutyl acrylate AA: ruthenium acrylate EA · 2 - hydroxyethyl acrylate HEMA: 2 - hydroxyethyl methacrylate BA: butyl acrylate 2EHA : 2- Ethyl hexyl acrylate LA: Lauryl acrylate EA: Ethyl acrylate VAc: Vinyl acetate and the weight average molecular weight of the copolymer is measured by GPC, and the obtained weight average molecular weight in terms of polystyrene, GPC measurement conditions As follows: Device: Shodex GPC System-21 (manufactured by Showa Denko Co., Ltd.) Pipe column: 1 Shodex KF-602. 5, 2 Shodex KF-606M (manufactured by Showa Denko Co., Ltd.), 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 amount: 50 μl (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/TMPC二曱苯二異氰酸酯的三羥甲基丙烷加成產 物）0 · 0 5份和矽烷偶合劑（信越化學工業（股）製造[KBM 27 326\專利說明書(補件)\93·07\93110078 1301147 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 in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 1301147 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 比較例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 比車交例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 0.10 表2中的多官能性化合物和矽烷偶合劑的簡稱，如下所 示。 TAT:三- 2,4,6-(1-氮丙 °定基）_1，3，5-三啳 TGMXDA ： N，N，Ν’，Ν’ -四縮水甘油基-間二甲苯二胺 ΚΒΜ 9 0 3 ：信越化學工業（股）製造的矽烷偶合劑[ΚΒΜ 9 0 3 ] ΚΒΜ8 0 3 ：信越化學工業（股）製造的矽烷偶合劑[ΚΒΜ803] ΚΒΜ9 0 0 7 ：信越化學工業（股）製造的矽烷偶合劑[ΚΒΜ9007] 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 in in大小，然後 按照使偏光板的吸收轴垂直相交的方式，用積層機黏貼在 326\專利說明書(補件)\93-07\93110078 29 1301147 厚度為1 . 1 m m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 (TC 、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 in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。 ®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\93110078100 parts by weight of the polymer solution A obtained in Synthesis Example 1 with the addition of XDI/TMPC dinonylbenzene diisocyanate to the trimethylolpropane addition product) 0·0 5 parts and a decane coupling agent (Shin-Etsu Chemical Industry) (Stock) Manufacturing [KBM 27 326\Patent Specification (Supplement)\93·07\93110078 1301147 4 0 3 ] ) 0.1 part, fully stirred to obtain an adhesive. The adhesive is coated on the release-treated polyester film, and then dried, and a 25 μ in adhesive layer is disposed, and then transferred onto one surface of the polarizing film to perform adhesion treatment on the polarizing film. . The polarized film which had been subjected to the adhesion treatment was aged for 1 week under the conditions of a temperature of 2 3 ° C and a relative humidity of 50% to obtain a polarizing plate. (Examples 2 to 7 and Comparative Examples 1 to 7) The same procedure as in Example 1 was carried out except that the polymer solution of the kind and amount shown in Table 2, the polyfunctional compound (C) and the decane coupling agent were used. An adhesive is produced, and the adhesive-processed polarizing plate is produced using the obtained adhesive. (Comparative Example 8) The same procedure as in Example 1 except that the polymer solution N was used without using the polymer solution N: 100 parts and the polymer solution 0: 30 parts of the mixed polymer solution. Method An adhesive is produced, and an adhesive-processed polarizing plate is produced using the obtained adhesive. 28 326\Patent Specification (Supplement)\93-07\93110078 1301147 Table 2 Polymer Solution Polyfunctional Compound (C) Iridium Coupler Type Weight Parts Type Weight Parts Type 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 Comparison 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 Comparative Example 4 Polymer solution Κ 100.0 XDI/TMP 0.05 KBM403 0.10 Comparative Example 5 Polymer solution L 100.0 XDI/TMP 0.05 KBM403 0.10 than the car case 6 polymer solution Μ 100.0 XDI/TMP 0.05 KBM403 0.10 than the car case 7 polymer solution Ν 100.0 XDI/TMP 0 .05 KBM403 0.10 The abbreviation for the polyfunctional compound and the decane coupling agent in Table 2 is as follows. TAT: tris-2,4,6-(1-azapropionyl)_1,3,5-triterpene TGMXDA: N,N,Ν',Ν'-tetraglycidyl-m-xylylenediamine ΚΒΜ 9 0 3 : decane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. [ΚΒΜ 9 0 3 ] ΚΒΜ8 0 3 : decane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. [ΚΒΜ803] ΚΒΜ9 0 0 7: Shin-Etsu Chemical Co., Ltd. Decane coupling agent [ΚΒΜ9007] For the adhesives and the adhesive-processed polarizing plates obtained in the examples and the comparative examples, heat resistance, moist heat resistance, optical properties, and reworkability were evaluated in accordance with the following methods. The results are shown in Table 3. (1) Evaluation method of heat resistance, heat and humidity resistance, and optical characteristics (white spot) The adhesively processed polarizing plate is cut into a size of 150 mm X 8 in in, and then the perpendicularly intersecting the absorption axis of the polarizing plate Apply to the 326\patent specification (supplement)\93-07\93110078 29 1301147 on both sides of the float glass plate with a thickness of 1.1 mm. Then, the glass plate to which the polarizing plate was pasted was held in an autoclave at 50 ° C under 5 atmospheres for 20 minutes to bring the polarizing plate into close contact with the glass plate. Further, the composition of the polarizing plate and the glass plate was visually observed, and the degree of peeling (heat resistance) after leaving for 500 hours at 80 ° C, at 60 ° C, and relative humidity of 90%, placed 5 The degree of light leakage (moisture and heat resistance) after 0 0 hours and the degree of light leakage (white spot) when light passes through the components of the polarizing plate and the glass plate after being placed at 6 (TC, relative humidity of 90% for 500 hours) The evaluation is divided into three grades. 9 represents [no peeling and white spot phenomenon observed at all], 〇 represents [some peeling and white spot phenomenon is observed, but there is no practical problem], and △ represents [obvious peeling observed] White spot phenomenon, there are practical problems. (2) Evaluation method of heavy operation The polarized plate processed by the adhesive is cut into a size of 25 mm X 1 50 m in and pasted with a thickness of 1.1 mm using a laminator. On the float glass, keep it in the autoclave at 50 ° C and 5 atmospheres for 20 minutes, and put it on the glass plate. The test piece is at 23 ° C and the relative humidity is 50%. After 1 week of placement, perform a 180 ° peel test (peeling speed 300 mm) / mi η ), visually observe the degree of blurring of the glass after peeling, the evaluation is divided into two grades. ® indicates [there is no problem in actual use], and △ indicates [there is a problem in actual use]. (3) Optical properties (haze) Evaluation method The adhesive was applied onto the release-treated polyester film, and then dried, and an adhesive layer of 25 μm was placed, and then covered with a release-treated polyester film. The polyester film is sandwiched in the middle of the adhesive layer at a temperature of 2 3 30 326\patent specification (supplement)\93-07\93110078