200527011 九、發明說明： 【發明所屬之技術領域】 本發明關於黏著劑組成物、使用其的黏著性光學機 能構件及液晶顯示元件。 更詳而言之，本發明關於黏著劑組成物，其即使在 高溫高濕條件下也能與被附體有優良的密接性及黏著耐 久性’同時對於被附體的伸縮有適應性；及關於在偏光 板等上設置有該黏著劑組成物層的黏著性光學機能構 件；以及關於經由該黏著劑組成物層，在液晶胞的兩面 上配設有偏光板等的光學機能構件所成的液晶顯示元 件。 【先前技術】 向來，在被附體彼此之間經由黏著劑層而貼附的物 品，於高溫高濕條件下，由於黏著劑的黏著耐久性不足， 故被附體有在端部剝離的問題。 爲了解決該問題，迄今已有採用提高構成黏著劑的 樹脂成分之分子量或提高交聯度等手段。然而，於如此 的黏著劑中，雖然黏著耐久性被提高了，但是於使用在 伸縮大的被附體之情況中，黏著劑不能適應該被附體的 伸縮，而成爲各種困擾發生的原因。 另一方面，液晶顯示元件之構造通常係爲：配置一 形成有配向層的2片透明電極基板，該配向層係經由間 隔物以預定的間隙隔著而在內側，其之周邊被密封而形 成液晶胞，同時在該電極基板間之間隙夾有液晶材料， 200527011 再者，於2片電極基板的外側表面上，各經由黏著劑層 而配設偏光板等的光學機能構件。 使用於該液晶顯示元件中的光學機能構件，於高溫 高濕條件下係容易伸縮，但是黏著劑層對於該光學機能 構件的伸縮係無法充分適應，而容易發生各種問題。例 如，在光學機能構件爲偏光板的情況中，由於偏光板所 產生的內部應力而使得偏光板周緣部位的吸收軸發生歪 斜，造成透光過率的變化，而容易發生所謂的「泛白」 現象。 爲了解決該問題，以往係藉由在黏著劑中加入可塑 劑或流動石蠘，使適度地軟化，以給予應力緩和性〔例 如，參照日本特許公開平成5年（1993年）第45517號公 報及日本特許公開平成9年（ 1 997年）第1 37 143號公報〕。 然而，就這些含有可塑劑或流動石蠘的黏著劑而 言，可能發生可塑劑或流動石鱲的滲出，或者在剝離偏 光板時滲出可塑劑或流動石蠘而污染液晶顯示元件等的 被附體之問題。 發明目的 本發明之目的爲在該狀況下，提供黏著劑組成物， 其即使在高溫高濕條件下也能與被附體有優良的密接性 及黏著耐久性，同時對於被附體的伸縮有適應性；及提 供在偏光板等上設置有該黏著劑組成物層的黏著性光學 機能構件；以及提供經由該黏著劑組成物層，在液晶胞 的兩面上配設有偏光板等的光學機能構件所成的液晶顯 -6- 200527011 示元件。 【發明內容】 發明槪述 本案發明者爲了達成上述目的，而重複精心地硏 究，結果發現以在丙烯酸系黏著劑中加入特定比例的胺 甲酸酯彈性體而成的黏著劑組成物，係可得到該目的。 本發明係爲以該知識爲基礎而完成者。 即，本發明提供： (1) 一種黏著劑組成物，其包含丙烯酸系黏著劑及相對於 每100重量份的該丙烯酸系黏著劑而言0.005〜20重量 份的胺甲酸酯彈性體； (2) 如上述（1)之黏著劑組成物，其中胺甲酸酯彈性體的 100%模數係1〜6MPa ; (3) 如上述（1)或（2)之黏著劑組成物，其中丙烯酸系黏著劑 係重量平均分子量50萬〜20〇萬的（甲基）丙嫌酸酯均聚 物或共聚物； (4) 如上述（1)或（2)之黏著劑組成物，其中丙烯酸系黏著劑 係由具有交聯點的重量平均分子量50萬〜200萬的（甲 基）丙烯酸酯共聚物與交聯劑所構成者； (5 ) —種黏著性光學機能構件，其特徵爲在光學機能構件 的一面或兩面上設置有由上述（1)〜（4)中任一項之黏著 劑組成物所成的層； (6 )如上述（5 )之黏著性光學機能構件，其中光學機能構件 係偏光板。及 -7- 200527011 (7) —種液晶顯示元件，其係由在液晶胞的兩面上隔著上 述（1)〜（4)中任一項之黏著劑組成物所成的層而配設光 學機能構件而成者。 發明的詳細説明 於本發明的黏著劑組成物中，丙烯酸系黏著劑較佳 爲使用（甲基）丙烯酸酯均聚物或共聚物。 爲了得到必要的密接性或黏著耐久性，該等（甲基） 丙烯酸酯均聚物或共聚物的重量平均分子量較佳爲50萬 以上’而爲了得到對於必要的被附體之伸縮的適應性， 其較佳爲200萬以下。即，（甲基）丙烯酸酯均聚物或共聚 物的重量平均分子量較佳係在50萬〜200萬的範圍內， 特佳爲在80萬〜180萬的範圍內。 再者’上述重量平均分子量係爲使用聚苯乙烯當作 標準物質，以凝膠滲透析術（GPC)所測定之値。 上記（甲基）丙烯酸酯均聚物所使用的單體，或是作爲 (甲基）丙烯酸酯共聚物之主成分而使用的單體，較佳係爲 形成酯的醇成分之烷基的碳數爲1〜20的（甲基）丙烯酸 烷酯，例如（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基） 丙烯酸丙酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸異丁 酯、（甲基）丙烯酸戊酯、（甲基）丙烯酸己酯、（甲基）丙烯 酸環己酯、（甲基）丙烯酸2—乙基己酯、（甲基）丙烯酸異 辛酯、（甲基）丙烯酸癸酯、（甲基）丙烯酸十一碳酯、（甲基） 丙烯酸肉豆蔻酯、（甲基）丙烯酸棕櫚酯、（甲基）丙烯酸硬 脂基酯等。這些單體可被單獨使用或可以二種以上的組 200527011 合來使用。 另一方面，作爲（甲基）丙烯酸酯共聚物所用的共聚單 體，例如有（甲基）丙烯酸2 -羥乙酯、（甲基）丙烯酸2 -羥丙 酯、（甲基）丙烯酸3-羥丙酯、（甲基）丙烯酸2-羥丁酯、（甲 基）丙烯酸3-羥丁酯、（曱基）丙烯酸4-羥丁酯等的（甲基） 丙烯酸羥烷酯類；丙烯醯胺、甲基丙烯醯胺、N-甲基丙 烯醯胺、N-甲基甲基丙烯醯胺、N-羥甲基丙烯醯胺、N-羥甲基甲基丙烯醯胺等的丙烯醯胺；（甲基）丙烯酸單甲基 胺基乙酯、（甲基）丙烯酸單乙基胺基乙酯、（甲基）丙烯酸 單甲基胺基丙酯、（甲基）丙烯酸單乙基胺基丙酯等的（甲 基）丙烯酸單烷基胺基烷酯；（甲基）丙烯酸二烷基胺基烷 酯；丙烯酸、甲基丙烯酸、巴豆酸、馬來酸、伊康酸、 檸康酸、馬來酸酐等的乙烯性不飽和羧酸或其之酸酐； 醋酸乙烯酯、丙酸乙烯酯等的乙烯基酯；乙烯、丙烯、 異丁烯等的烯烴；氯乙烯、偏二氯乙烯等的鹵化烯；苯 乙烯、α-甲基苯乙烯等的苯乙烯系單體；丁二烯、異戊二 烯、氯丁二烯等的二烯系單體；丙烯腈、甲基丙烯腈等 的腈系單體；N，N-二甲基丙烯醯胺、N，N-二甲基甲基丙 烯醯胺等的N，N-二烷基取代的丙烯醯胺等。 這些共聚單體可被單獨使用或可以二種以上的組合 來使用。 於（甲基）丙烯酸酯共聚物中，衍生自上述共聚單體的 單元之含量通常爲選自於0·1〜20重量％的範圍，較佳爲 選自於0.5〜1 0重量％的範圍。 200527011 於本發明的黏著劑組成物中，使用具有交聯性官能 基的共聚單體當作共聚合成分的（甲基）丙烯酸酯共聚 物，則由於含有交聯劑，而可提高凝集力及提高與被附 體的密接性及黏著耐久性。 作爲該情況之具有交聯性官能基的共聚單體，上述 共聚單體內的（甲基）丙烯酸羥基烷酯、丙烯醯胺、（甲基） 丙烯酸單烷基胺基烷酯及乙烯性不飽和羧酸或其之酸酐 係較宜的。 另一方面，作爲交聯劑，例如可爲多異氰酸酯化合 物、環氧化合物、金屬螯合化合物、金屬烷氧化物、金 屬鹽、胺化合物、肼化合物、醛化合物。 作爲多異氰酸酯化合物，例如可爲伸甲苯二異氰酸 酯、二苯基甲烷二異氰酸酯、伸二甲苯二異氰酸酯等的 芳香族多異氰酸酯、六亞甲基二異氰酸酯等的脂肪族多 異氰酸酯、異佛爾二異氰酸酯、加氫二苯基甲烷二異氰 酸酯等的脂環族多異氰酸酯；作爲環氧化合物，例如可 爲山梨糖醇聚縮水甘油醚、聚甘油聚縮水甘油醚、異戊 四醇聚縮水甘油醚、二甘油聚縮水甘油醚、甘油聚縮水 甘油醚、三羥甲基丙烷聚縮水甘油醚、間苯二酚二縮水 甘油醚、新戊二醇二縮水甘油醚、1，6-己二醇二縮水甘油 醚、氫化雙酚A二縮水甘油醚、聚乙二醇二縮水甘油醚、 聚丙二醇二縮水甘油醚等。 作爲本發明的黏著劑組成物中之胺甲酸酯彈性體， 例如可爲胺甲酸酯彈性體及改質胺甲酸酯彈性體等。作 -10- 200527011 爲改質胺甲酸酯彈性體，較佳爲含有在當作構成成分的 聚胺基化合物中以邁克爾附加不飽和化合物而導入各種 官能基的構造之邁克爾加成型胺甲酸酯尿素樹脂。 胺甲酸酯彈性體係爲由以高分子多元醇當作主成分 的軟鏈段及以二異氰酸酯等的多異氰酸酯當作鏈延長劑 所成的硬鏈段而構成者。胺甲酸酯彈性體的種類例如爲 高分子多元醇與伸甲苯二異氰酸酯（TDI)、4,4’-二苯基甲 烷二異氰酸酯（MDI)等的二異氰酸酯等多異氰酸酯被高 分子化而得到的熱可塑性胺甲酸酯彈性體被有機溶劑所 稀釋而成的一液型者，或是多異氰酸酯於其它系統中， 於塗佈前再添加而硬化的二液型者。另外，亦可爲藉由 空氣中的濕氣與異氰酸酯反應的濕氣硬化型、熱熔融壓 出型的熱熔型胺甲酸酯彈性體。 從對於被附劑有適度黏著力且於剝離時被附體的損 傷、汚染之觀點看，胺甲酸酯彈性體的1 00%模數較佳爲 1 MPa以上，對於被附劑之適度的黏著力及對於被附體 貼附性的觀點，胺甲酸酯彈性體的100 %模數較佳爲6MPa 以下。 於本發明的黏著劑組成物中，胺甲酸酯彈性體的配 合量，就相對於每1 〇〇重量份的丙烯酸系黏著劑而言， 必須在〇·〇〇5〜20重量份的範圍，若低於0.005重量份， 則不能得到必要的對於被附體之伸縮的適應性，若超過 2〇重量份，則由黏著劑組成物的相溶性問題，而成爲黏 著劑變白化的原因。胺甲酸酯彈性體的較佳配合量之範 -11- 200527011 圍係隨著丙烯酸系黏著劑的種類，即（甲基）丙烯酸酯聚合 物爲均聚物或共聚物，官能基的種類，交聯劑的有無等 而不同’不能一槪而定，但是較佳爲相對於每100重量 份的丙烯酸系黏著劑，在〇.〇1〜15重量份的範圍內。 於本發明的黏著劑組成物中，在不損害本發明目的 之範圍內’可依照希望而適當地含有已知的各種添加 劑’例如賦黏劑、可塑劑、抗氧化劑、紫外線吸收劑、 耐熱安定劑、塡充劑、矽烷偶合劑等。 其次’本發明的黏著性光學機能構件係可爲在光學 機能構件的兩面或一面上設置有本發明的黏著劑組成物 所成之層（以下簡稱黏著劑層）者。 黏著劑層可藉由將黏著劑組成物塗佈在光學機能構 件的兩面或一面上而形成者，亦可將黏著劑組成物塗佈 在經剝離處理的剝離片之剝離處理面上，接合於光學機 能構件的兩面或一面而形成。 塗佈的黏著劑組成物（以下簡稱黏著劑液）係可爲有 機溶劑系、乳液系、無溶劑系中任一種。 作爲有機溶劑系的黏著劑液所使用的有機溶劑，例 如甲苯、二甲苯、甲醇、乙醇、異丁醇、正丁醇、丙酮、 甲基乙基酮、醋酸乙酯、四氫呋喃等。它們可被可被單 獨使用一種或可以二種以上的組合來使用。 黏著劑液就塗佈上的便利而言，較佳爲使用該些有 機溶劑，使固體成份濃度成爲在1 0〜5 0重量％的範圍內 以調製者。 -12- 200527011 黏著劑的塗佈例如可藉由硬塗覆法、輥塗法、刀片 塗覆法、輥刀塗覆法法、口模式塗覆法、凹槽輥塗覆法、 空氣刀塗覆法、刮刀塗覆法等習知的塗佈方法來進行。 該黏著劑層的厚度通常較佳爲在5〜150μπι的範圍 內，尤其在10〜ΙΟΟμιη的範圍內。 作爲本發明的黏著性光學機能構件所使用的光學機 能構件，例如可爲偏光板、抗反射板、相位差板、視野 角擴大膜等，其中特別適合的爲偏光板。 作爲上述偏光板，可使用一般透明高分子薄膜經一 軸方向所配向，於配向分子間隙吸附碘及/或二色性染料 等而配向成偏光膜之兩面覆蓋保護膜而成者。上述透明 高分子薄膜現在幾乎都使用聚乙烯醇薄膜，而且保護膜 大多使用三乙醯纖維素膜。 於該偏光板中，偏光膜例如係使用碘系偏光膜、染 料系偏光膜、彩色偏光膜、聚乙烯系偏光膜、紅外偏光 膜、紫外偏光膜等，但是於本發明中並沒有特別的限制， 可以使用任一者。 又，該偏光板在用途的分別上，可用於液晶顯示元 件用（數位鐘錶、電子計算機、計測器系顯示器、壁掛型 電視、光學缺陷檢測器用等）、反射光的去除用（遮陽鏡、 照相軟片用等）、光量調整用（照相用濾光鏡、濃度可變濾 片用等）、避光之應用（汽車頭燈的防眩用、防透視用等）、 偏光千渉利用裝置用（歪斜檢査器、舞台照明、廣告用顯 示器用等）等任何用途的偏光板。於此等用途中，較宜使 -13- 200527011 用爲液晶顯示元件用的偏光板。 本發明的液晶顯示元件係爲在液晶胞的兩面上隔著 上述本發明的黏著劑組成物層，而配設有光學機能構件 者。 作爲光學機能構件，例如可爲上述黏著性光學機能 構件所用的光學機能構件，其中偏光板係特別適合者。 於液晶胞的面上配設有數個光學機能構件者，係皆 爲可經由本發明之黏著劑組成物層所進行接合的光學機 能構件。當然，未必要所有的光學機能構件皆經由本發 明的黏著劑組成物層來接合，但是較佳爲至少偏光板的 接合係經由本發明的黏著劑組成物層來進行。 例如，於在液晶胞與偏光板之間設置有補償雙折射 用的相位差板之情況中，較佳爲至少相位差板與偏光板 的接合係經由本發明的黏著劑組成物層來進行，再者視 需要亦可使用於液晶胞與相位差板的接合。 其次，藉由實施例來更詳細說明本發明，惟本發明 不受該些實施例所限定。 實施例1 100重量份由99重量％的丙烯酸丁酯單元與1重量％ 的丙儲酸4 -羥基丁基單元所構成的重量平均分子量爲 170萬的丙烯酸酯共聚物、10重量份的重量平均分子量 爲10萬且100%模數2MPa的胺甲酸酯彈性體（東洋油墨 製造社製，商品名：HP-H)及〇·2重量份的多異氰酸酯化合 物所成的交聯劑（總硏化學公司製，商品名：TD-7 5 )溶解 200527011 於甲基乙基酮中，以成爲固體成份含量爲30重量％的黏 著劑溶液。 藉由刀片塗覆器，將該黏著劑溶液塗佈在一面經矽 酮系所剝離處理的聚對酞酸乙二酯剝離片（Lintec公司 製，商品名：SP-PET381 1)的剝離處理面，於90°C乾燥1分 鐘，以形成厚度25 μπι的黏著劑層。 然後，將偏光板[乙醯纖維薄膜/聚乙烯醇薄膜/三乙 醯纖維素薄膜（含視野角擴大機能）的3層積層體，厚度 2〇〇μιη]積層在上述黏著劑層上，以得到附有黏著劑層的 偏光板。 實施例2 除了將黏著劑溶液中的胺甲酸酯彈性體之配合量由 1 〇重量份改爲1重量份（黏著劑溶液的固體成份含量爲30 重量％)以外，與實施例1同樣地實施，而得到附有黏著 劑層的偏光板。 實施例3 除了將黏著劑溶液中的胺甲酸酯彈性體之配合量由 10重量份改爲0.05重量份（黏著劑溶液的固體成份含量 爲30重量％)以外，與實施例1同様地實施，而得到附有 黏著劑層的偏光板。 比較例1 除了將黏著劑溶液中的胺甲酸酯彈性體之配合量由 10重量份改爲50重量份（黏著劑溶液的固體成份含量爲 30重量％)以外，與實施例1同樣地實施，而得到附有黏 200527011 著劑層的偏光板。 比較例2 除了將黏著劑溶液中的胺甲酸酯彈性體之配合量由 10重量份改爲0.0005重量份（黏著劑溶液的固體成份含 量爲30重量％)以外，與實施例1同樣地實施，而得到附 有黏著劑層的偏光板。 比較例3 除了於黏著劑溶液中不配合胺甲酸酯彈性體（黏著劑 溶液的固體成份含量爲3 0重量％)以外，與實施例1同樣 地實施，而得到附有黏著劑層的偏光板。 就實施例1〜3及比較例1〜3所得到之附有黏著劑 層的偏光板，依以下方法測量耐久性及明亮度差AL*，結 果示於表1中。 (1) 耐久性 將剝離片由15吋（23 3 mmx3 09 mm)之附有黏著劑層的 偏光板處剝離，將該偏光板貼附於玻璃板上，於80°C乾 燥或於60°C90%RH的環境條件下放置120小時後，目視 觀察外觀，依以下基準來評估。 〇：沒有浮起剝落 X :有浮起剝落 (2) 明度差異AL* 於無鹼玻璃板的兩面上以正交尼斗爾方式將剝離片 由15吋（23 3mmx309mm)之附有黏著劑層的偏光板處剝 離，將該偏光板貼附於玻璃板上，於8〇t乾燥環境條件 下放置1 20小時後，測量周緣部之各邊中央端起i cm之 -16- 200527011 箪B圍內的明売度以中央的明売度，求得各邊的明亮度之 平均値與偏光板中央的明亮度値之差異。 明亮度係使用大塚電子公司製的測定裝置 (MCPD-2 000)，在 23 °C 65 % RH 的條件下測量。 明亮度差異AL*愈大，則顯示黏著劑層的適應性愈 差。 表1 耐久性（120小時） 明亮度差異（AL*) 8〇°C乾燥 60〇C90%RH 8〇°C乾燥120小時 實施例1 〇 〇 0.34 實施例2 〇 〇 0.56 實施例3 〇 〇 2.89 比較例1 X X 0.24 比較例2 〇 〇 5.83 比較例3 〇 〇 6.09 發明的效果 本發明的黏著劑組成物即使在高溫高濕條件下也能 與被附體有優良的密接性及黏著耐久性，同時對於被附 體的伸縮有適應性，特別適用於在液晶胞表面上貼附偏 光板等的光學機能構件。 使用該黏著劑組成物在液晶胞表面上配設光學機能 構件而形成的本發明之液晶顯示元件，即使在高溫高濕 條件下也能與液晶胞有優良的密接性，而且黏著耐久性 -17- 200527011 亦優良，同時具有對於光學機能構件之伸縮的適應性， 而難以發生各種問題，例如難以在偏光板中發生所謂的 「泛白」現象。 【圖式簡單說明】 Μ 。200527011 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to an adhesive composition, an adhesive optical function member using the same, and a liquid crystal display element. More specifically, the present invention relates to an adhesive composition, which can have excellent adhesion and adhesion durability with an adherend even under high-temperature and high-humidity conditions, and has adaptability to the expansion and contraction of the adherend; and An adhesive optical function member provided with the adhesive composition layer on a polarizing plate or the like; and an optical function member provided with a polarizing plate or the like on both sides of a liquid crystal cell via the adhesive composition layer Liquid crystal display element. [Prior art] In the past, under the condition of high temperature and high humidity, the articles adhered between the adherents through the adhesive layer have insufficient adhesion durability, so the adherends have a problem of peeling off at the ends. . In order to solve this problem, measures such as increasing the molecular weight of the resin component constituting the adhesive or increasing the degree of crosslinking have been used. However, in such an adhesive, although the adhesive durability is improved, when it is used in an adherend having a large elasticity, the adhesive cannot adapt to the expansion and contraction of the adherend, and thus causes various problems. On the other hand, the structure of a liquid crystal display element is generally configured by arranging two transparent electrode substrates formed with an alignment layer. The alignment layer is formed on the inner side with a predetermined gap therebetween via a spacer, and the periphery thereof is formed by sealing. The liquid crystal cell has a liquid crystal material interposed between the electrode substrates. 200527011 Furthermore, on the outer surface of the two electrode substrates, optical function members such as a polarizing plate are arranged through an adhesive layer. The optical function member used in the liquid crystal display element is easy to expand and contract under high temperature and high humidity conditions, but the adhesive layer cannot fully adapt to the expansion and contraction system of the optical function member, and various problems easily occur. For example, in the case where the optical function member is a polarizing plate, the absorption axis at the peripheral portion of the polarizing plate is skewed due to the internal stress generated by the polarizing plate, causing a change in the transmittance, and the so-called "whitening" is liable to occur. phenomenon. In order to solve this problem, conventionally, a plasticizer or a flowing ballast was added to an adhesive to soften it moderately to give stress relief [for example, refer to Japanese Patent Publication No. 45517 (1993) and Japanese Patent Publication No. 1 37 143 of Heisei 9 (997)]. However, with regard to these adhesives containing plasticizers or mobile ballasts, bleeding of the plasticizers or mobile ballasts may occur, or the plasticizers or mobile ballasts may leak when the polarizing plate is peeled off and contaminate the liquid crystal display elements. Physical problems. OBJECTS OF THE INVENTION An object of the present invention is to provide an adhesive composition under such a condition, which can have excellent adhesion and adhesion durability with an adherend even under high temperature and high humidity conditions, and at the same time has an expansion and contraction of the adherend. Adaptability; and providing an adhesive optical function member provided with the adhesive composition layer on a polarizing plate or the like; and providing optical functions such as a polarizing plate disposed on both sides of the liquid crystal cell via the adhesive composition layer The liquid crystal display-200527011 display element formed by the component. [Summary of the Invention] In order to achieve the above-mentioned object, the inventors of the present invention have repeatedly and carefully studied. As a result, they have discovered that an adhesive composition comprising a urethane elastomer in a specific proportion is added to an acrylic adhesive. This purpose is obtained. The present invention has been completed based on this knowledge. That is, the present invention provides: (1) an adhesive composition comprising an acrylic adhesive and 0.005 to 20 parts by weight of a urethane elastomer per 100 parts by weight of the acrylic adhesive; 2) The adhesive composition as described in (1) above, wherein the 100% modulus of the urethane elastomer is 1 to 6 MPa; (3) The adhesive composition as described in (1) or (2) above, wherein acrylic acid Adhesives are (meth) propionic acid homopolymers or copolymers with a weight average molecular weight of 500,000 to 200,000; (4) The adhesive composition according to (1) or (2) above, wherein acrylic The adhesive is composed of a (meth) acrylic acid ester copolymer having a weight average molecular weight of 500,000 to 2 million and a crosslinking agent having a crosslinking point; (5) An adhesive optical function member, which is characterized in optical A layer made of the adhesive composition of any one of (1) to (4) above is provided on one or both sides of the functional member; (6) The adhesive optical functional member according to (5) above, wherein the optical function The component is a polarizing plate. And -7-200527011 (7)-a liquid crystal display element, which is provided with optical layers formed on both sides of a liquid crystal cell with the adhesive composition of any one of (1) to (4) above Made of functional components. DETAILED DESCRIPTION OF THE INVENTION In the adhesive composition of the present invention, it is preferable to use a (meth) acrylate homopolymer or copolymer as the acrylic adhesive. In order to obtain the necessary adhesion or adhesion durability, the weight average molecular weight of the (meth) acrylate homopolymer or copolymer is preferably 500,000 or more ', and in order to obtain the adaptability to the necessary expansion and contraction of the attached body It is preferably below 2 million. That is, the weight average molecular weight of the (meth) acrylate homopolymer or copolymer is preferably in the range of 500,000 to 2 million, and particularly preferably in the range of 800,000 to 1.8 million. It is to be noted that the weight average molecular weight is measured by gel permeation analysis (GPC) using polystyrene as a standard material. The monomer used in the above (meth) acrylate homopolymer or the monomer used as the main component of the (meth) acrylate copolymer is preferably a carbon of an alkyl group forming an alcohol component of an ester. 1 to 20 alkyl (meth) acrylates, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, (formyl) Base) isobutyl acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid Octyl ester, decyl (meth) acrylate, undecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like. These monomers may be used alone or in a combination of two or more types 200527011. On the other hand, as the comonomer used for the (meth) acrylate copolymer, there are, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3- Hydroxypropyl (meth) acrylates, such as hydroxypropyl ester, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; acrylic fluorene Amine, methacrylamide, N-methacrylamide, N-methacrylamide, N-methylmethacrylamine, N-methylmethacrylamine, etc. ; Monomethylaminoethyl (meth) acrylate, Monoethylaminoethyl (meth) acrylate, Monomethylaminopropyl (meth) acrylate, Monoethylamino (meth) acrylate Monoalkylaminoalkyl (meth) acrylates such as propyl ester; dialkylaminoalkyl (meth) acrylates; acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid , Maleic anhydride and other ethylenically unsaturated carboxylic acids or their anhydrides; vinyl esters such as vinyl acetate and vinyl propionate; ethylene, propylene, isopropyl Olefins such as butene; halogenated olefins such as vinyl chloride, vinylidene chloride; styrene-based monomers such as styrene, α-methylstyrene; butadiene, isoprene, chloroprene, etc. Diene monomers; nitrile monomers such as acrylonitrile and methacrylonitrile; N, N-dimethylacrylamide, N, N-dimethylacrylamide Alkyl substituted acrylamide and the like. These comonomers may be used alone or in a combination of two or more. In the (meth) acrylate copolymer, the content of the unit derived from the comonomer is usually selected from the range of 0.1 to 20% by weight, and preferably selected from the range of 0.5 to 10% by weight . 200527011 In the adhesive composition of the present invention, a (meth) acrylic acid ester copolymer using a comonomer having a crosslinkable functional group as a copolymerization component can improve the cohesive strength and Improve the adhesion and adhesion durability to the object. As the comonomer having a crosslinkable functional group in this case, hydroxyalkyl (meth) acrylate, acrylamide, monoalkylaminoalkyl (meth) acrylate, and ethylenic unsaturated in the comonomer are mentioned. Carboxylic acids or their anhydrides are preferred. On the other hand, examples of the crosslinking agent include polyisocyanate compounds, epoxy compounds, metal chelate compounds, metal alkoxides, metal salts, amine compounds, hydrazine compounds, and aldehyde compounds. Examples of the polyisocyanate compound include aromatic polyisocyanates such as xylene diisocyanate, diphenylmethane diisocyanate, and xylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; isophor diisocyanate; Cycloaliphatic polyisocyanates such as hydrogenated diphenylmethane diisocyanate; examples of the epoxy compound include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, isoprene tetraglycidyl polyglycidyl ether, and diglycerol Polyglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether , Hydrogenated bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and the like. Examples of the urethane elastomer in the adhesive composition of the present invention include a urethane elastomer and a modified urethane elastomer. Operation -10- 200527011 is a modified urethane elastomer, preferably a Michael addition molding carbamate containing a structure in which various functional groups are introduced into the polyamine compound as a constituent by adding Michael unsaturated compounds. Ester urea resin. The urethane elastic system is composed of a soft segment having a polymer polyol as a main component and a hard segment composed of a polyisocyanate such as a diisocyanate as a chain extender. The type of the urethane elastomer is, for example, a polymer polyol and a polyisocyanate such as a diisocyanate such as tolylene diisocyanate (TDI) or 4,4'-diphenylmethane diisocyanate (MDI). The one-liquid type of thermoplastic urethane elastomer diluted with organic solvents, or the two-liquid type of polyisocyanate in other systems, which is hardened by adding before coating. Alternatively, it may be a moisture-hardening type or a hot-melt extruding type urethane elastomer which reacts with moisture in the air and isocyanate. From the viewpoint of moderate adhesion to the adherent and damage and contamination of the adherend during peeling, the 100% modulus of the urethane elastomer is preferably 1 MPa or more. From the viewpoint of the adhesive force and the adherence of the adherend, the 100% modulus of the urethane elastomer is preferably 6 MPa or less. In the adhesive composition of the present invention, the compounding amount of the urethane elastomer must be in the range of 0.05 to 20 parts by weight per 1,000 parts by weight of the acrylic adhesive. If it is less than 0.005 parts by weight, the necessary adaptability to the expansion and contraction of the adherend cannot be obtained. If it exceeds 20 parts by weight, the compatibility of the adhesive composition is a problem and the adhesive becomes white. The range of the preferred blending amount of urethane elastomer-11- 200527011 The range is based on the type of acrylic adhesive, that is, the type of (meth) acrylate polymer is a homopolymer or copolymer, and the type of functional group. The presence or absence of a cross-linking agent varies depending on the conditions, but it is preferably within a range of 0.01 to 15 parts by weight per 100 parts by weight of the acrylic adhesive. In the adhesive composition of the present invention, as long as the object of the present invention is not impaired, various known additives may be appropriately contained, such as a tackifier, a plasticizer, an antioxidant, an ultraviolet absorber, and a heat-resistant stabilizer. Agents, tinctures, silane coupling agents, etc. Secondly, the adhesive optical function member of the present invention may be a layer (hereinafter referred to as an adhesive layer) formed by providing the adhesive composition of the present invention on both or one side of the optical function member. The adhesive layer can be formed by applying an adhesive composition on both or one side of an optical function member, or by applying the adhesive composition on the release-treated surface of a release-treated release sheet and bonding it to The optical function member is formed on both or one side. The applied adhesive composition (hereinafter referred to as an adhesive solution) may be any of an organic solvent system, an emulsion system, and a solventless system. Examples of the organic solvent used as the organic solvent-based adhesive solution include toluene, xylene, methanol, ethanol, isobutanol, n-butanol, acetone, methyl ethyl ketone, ethyl acetate, and tetrahydrofuran. They may be used singly or in a combination of two or more. For the convenience of application, the adhesive solution is preferably prepared by using these organic solvents so that the solid content concentration is in the range of 10 to 50% by weight. -12- 200527011 The adhesive can be applied by, for example, hard coating method, roll coating method, blade coating method, roll knife coating method, mouth pattern coating method, groove roll coating method, air knife coating, etc. It is performed by a known coating method such as a coating method and a doctor blade coating method. The thickness of the adhesive layer is usually preferably in a range of 5 to 150 μm, and particularly in a range of 10 to 100 μm. The optical function member used for the adhesive optical function member of the present invention may be, for example, a polarizing plate, an antireflection plate, a retardation plate, or a viewing angle widening film. Among them, a polarizing plate is particularly suitable. As the above-mentioned polarizing plate, a general transparent polymer film is aligned in one axis direction, and iodine and / or dichroic dye are adsorbed on the gap between the alignment molecules, and both sides of the polarizing film are covered with a protective film. Almost all of the above-mentioned transparent polymer films are polyvinyl alcohol films, and most of the protective films are triacetin cellulose films. In this polarizing plate, the polarizing film is, for example, an iodine-based polarizing film, a dye-based polarizing film, a color polarizing film, a polyethylene-based polarizing film, an infrared polarizing film, or an ultraviolet polarizing film, but it is not particularly limited in the present invention. You can use either. In addition, the polarizing plate can be used for liquid crystal display elements (digital clocks, electronic computers, monitors, wall-mounted televisions, optical defect detectors, etc.) and reflected light removal (shading mirrors, photography) For soft films, etc.), for light quantity adjustment (for photographic filters, variable density filters, etc.), for applications that avoid light (for anti-glare, anti-see-through, etc. for automotive headlights), for polarizing devices (for Polarizers for any purpose, such as skew checkers, stage lighting, and advertising displays. For these applications, -13-200527011 is preferably used as a polarizing plate for a liquid crystal display element. The liquid crystal display element of the present invention is one in which optical function members are provided on both sides of a liquid crystal cell with the above-mentioned adhesive composition layer of the present invention interposed therebetween. The optical function member may be, for example, an optical function member used for the above-mentioned adhesive optical function member, and among them, a polarizing plate is particularly suitable. Those having a plurality of optical function members arranged on the surface of the liquid crystal cell are all optical function members that can be joined via the adhesive composition layer of the present invention. Of course, it is not necessary that all of the optical function members are bonded via the adhesive composition layer of the present invention, but it is preferred that at least the bonding of the polarizing plate is performed via the adhesive composition layer of the present invention. For example, in the case where a retardation plate for compensating birefringence is provided between the liquid crystal cell and the polarizing plate, it is preferable that at least the joining of the retardation plate and the polarizing plate is performed through the adhesive composition layer of the present invention. Furthermore, if necessary, it can also be used for joining a liquid crystal cell and a retardation plate. Next, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples. Example 1 100 parts by weight of an acrylate copolymer having a weight average molecular weight of 1.7 million composed of 99% by weight of a butyl acrylate unit and 1% by weight of a 4-hydroxybutyl propionate unit, and a weight average of 10 parts by weight Crosslinking agent made of urethane elastomer (manufactured by Toyo Ink Manufacturing Co., Ltd .: HP-H) having a molecular weight of 100,000 and a 100% modulus of 2 MPa and a polyisocyanate compound of 0.2 parts by weight (total Manufactured by Chemical Co., Ltd., trade name: TD-7 5) 200527011 was dissolved in methyl ethyl ketone to make an adhesive solution having a solid content of 30% by weight. With a blade applicator, this adhesive solution was coated on a release-treated side of a polyethylene terephthalate release sheet (made by Lintec, trade name: SP-PET381 1) which had been peeled off by a silicone system. And dried at 90 ° C for 1 minute to form an adhesive layer with a thickness of 25 μm. Then, a three-layer laminated body of a polarizing plate [ethyl acetate fiber film / polyvinyl alcohol film / triethylacetate cellulose film (including viewing angle expansion function) with a thickness of 200 μm] was laminated on the above-mentioned adhesive layer to A polarizing plate with an adhesive layer was obtained. Example 2 The same as Example 1 except that the compounding amount of the urethane elastomer in the adhesive solution was changed from 10 parts by weight to 1 part by weight (the solid content of the adhesive solution was 30% by weight). It was implemented, and the polarizing plate with which the adhesive layer was attached was obtained. Example 3 The same procedure as in Example 1 was carried out except that the compounding amount of the urethane elastomer in the adhesive solution was changed from 10 parts by weight to 0.05 parts by weight (the solid content of the adhesive solution was 30% by weight). To obtain a polarizing plate with an adhesive layer. Comparative Example 1 The same procedure as in Example 1 was carried out except that the compounding amount of the urethane elastomer in the adhesive solution was changed from 10 parts by weight to 50 parts by weight (the solid content of the adhesive solution was 30% by weight). , And a polarizing plate with a 2005200511 adhesive layer was obtained. Comparative Example 2 The same procedure as in Example 1 was carried out except that the compounding amount of the urethane elastomer in the adhesive solution was changed from 10 parts by weight to 0.0005 parts by weight (the solid content of the adhesive solution was 30% by weight). To obtain a polarizing plate with an adhesive layer. Comparative Example 3 A polarized light with an adhesive layer was obtained in the same manner as in Example 1 except that the urethane elastomer was not added to the adhesive solution (the solid content of the adhesive solution was 30% by weight). board. The polarizing plates with an adhesive layer obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were measured for durability and brightness difference AL * by the following methods. The results are shown in Table 1. (1) Durability The peeling sheet is peeled off from a 15-inch (23 3 mm x 3 09 mm) polarizer with an adhesive layer. The polarizer is attached to a glass plate and dried at 80 ° C or 60 ° After being left for 120 hours under an environmental condition of C90% RH, the appearance was visually observed and evaluated according to the following criteria. 〇: No lifting and peeling X: There is lifting and peeling (2) Brightness difference AL * On both sides of the alkali-free glass plate, the peeling sheet is made of 15 inches (23 3mmx309mm) with an adhesive layer The polarizing plate was peeled off, and the polarizing plate was attached to a glass plate. After being left for 120 hours under 80 ° t dry environment, the central end of each side of the peripheral part was measured to -16-200527011 箪 B The inner brightness is the brightness at the center, and the difference between the average brightness of each side and the brightness at the center of the polarizer is obtained. Brightness was measured at 23 ° C 65% RH using a measuring device (MCPD-2 000) manufactured by Otsuka Electronics Co., Ltd. The larger the brightness difference AL *, the worse the adaptability of the adhesive layer. Table 1 Durability (120 hours) Brightness difference (AL *) 80 ° C drying 60 ° C 90% RH 80 ° C drying 120 hours Example 1 0.000.34 Example 2 0.000.56 Example 3 0.002.89 Comparative Example 1 XX 0.24 Comparative Example 2 0.005.83 Comparative Example 3 6.06. Effect of the invention The adhesive composition of the present invention can have excellent adhesion and adhesion durability to an adherend even under high temperature and high humidity conditions, At the same time, it has adaptability to the expansion and contraction of the attached body, and is particularly suitable for attaching optical functional components such as polarizing plates on the surface of the liquid crystal cell. The liquid crystal display element of the present invention, which is formed by using the adhesive composition to dispose optical function members on the surface of a liquid crystal cell, can have excellent adhesion with the liquid crystal cell even under high temperature and high humidity conditions, and has excellent adhesion durability-17 -200527011 is also excellent. At the same time, it has adaptability to the expansion and contraction of optical functional components, and it is difficult to cause various problems, such as the so-called "whitening" phenomenon in polarizing plates. [Schematic description] Μ.
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