201209118 - 六、發明說明: 【發明所屬之技術領域】 本發明係關於黏著性組合物、黏著性組合物之製造方 法、黏著劑(使黏著性組合物架橋之材料)及黏著板片,特 別是關於可良好地使用於偏光板等的光學構件用的黏著性 組合物、黏著性組合物之製造方法、黏著劑及黏著板片。 【先前技術】 一般而言,在於液晶面板,將偏光板或位相差板接著 於玻璃基板等多使用由黏著劑組合物所形成之黏著劑層。 但疋’由於偏光板或位相差板等的光學構件容易因熱等而 収縮,因熱履歷而發生収縮,結果,層積於該光學構件之 黏著劑層無法追隨其収縮,而有在界面發生剝落(所謂起 泡、剝落),及起因於光學構件収縮時的應力而使光學構件 的光軸偏移產生漏光(所謂白點)等的間題。 防止該等之方法’可舉(1)藉由將黏著力高,且形態安 疋性優良的黏著劑層黏貼於偏光板等的光學構件光學構件 抑制収縮本身之方法;或(2)使用光學構件収縮時之應力小 的黏著劑層之方法。(1)之方法,如專利文獻1所示使用貯 藏彈性係數高的黏著劑層為有効。另一方面,(2)之方法, 使用可柔軟地對應光學構件的變形之應力緩和性優良的黏 著劑層為有効。但是’先前欲形成如此之應力緩和性優良 的黏著劑層_,需要將該黏著劑層中的架橋密度設計較 低。如此則黏著劑層本身的強度降低,而有使耐久性惡化 201209118 之問題。 因此,於專利文 度,藉由將可塑劑、流動石臘、氨酯彈性體等添加於丙烯 酸系黏著劑,適度地使所得之黏著劑組合物變的柔軟,_ 予黏著劑層應力緩和性,而欲藉此得到耐漏光性 [先行技術文獻] ^ [專利文獻] [專利文獻1]日本特開2006-235568號公報 [專利文獻2]曰本特開平5_45517號公報 [專利文獻3]曰本特開平9_137143號公報 [專利文獻4]日本特開2〇〇5_194366號公報 【發明内容】 [發明所欲解決的課題] 但是,添加可塑劑或流動石服之黏著劑組合物 之黏著劑層,有因經時釋屮π猢淑丨七、、ώ & &成 塑劑或流動石臘之難點。缺 後,藉此,成為被荖鲈 …、 的問題。此外,添加& 各式各樣 ,、、力虱酉曰彈性體之黏著劑組合物, 相溶性則氨酯彈性體沾$ 欲.准持 W 生體的添加量的上限有所限制 和性的改善並不充分。 應力緩 再者,為提升應力緩和性 — 酯彈性體的添加量, 而^加氰 u 則與丙烯酸系黏著劑之相溶性降批 而會產生白濁等的問丨降低, 1喊。如此地,以先前的枯 構件用黏著劑組合物 知’由光學 耐漏光性及耐久性。 、根本改善其 201209118 本發明’係有鑑於如此之實狀而完成者,以提供使用 於偏光板等的光學構件時,而才漏光性與耐久性的雙方均優 良的黏著性組合物,該當黏著性組合物之製造方法、點著 劑及黏著板片為目標。 [用以解決課題的手段] 為達成上述目第卜本發明提供一種黏著性組合 物’其特徵在於:包含:重量平均分子量為7。萬〜25〇萬 之第U甲基)丙烯酸酯聚合物(八);重量平均分子量為 8000〜25萬之第2(甲基)丙稀酸酿聚合物(b);及架橋劑 (C)’上述第2(曱基)丙烯酸酯聚合物(B)對上述第丨(曱基) 丙烯酸酯聚合物(A)100質量部之比例為5〜4〇質量部,上 述第2(甲基)丙烤酸醋聚合物⑻,含有可與上述架橋劑⑹ 反應之官能基(bl)之單體作為構成成分,並且,具有上述 官能基(bi)之單體之比例’係於該當帛2(甲基)丙烯酸醋 聚合物(B)中超過工質量%,且未滿5〇質量%,上述第2(甲 基^丙稀酸醋聚合物(B)所含有之可與上述架橋劑(c)反應 之官能基,大體上只有上述官能基(bl),上述第丨(甲基) 丙烯:_合物(A)不含有可與上述架橋劑⑹反應之官能 基之單體作為構成成分,或含有與上述架橋劑(c)之反應性 車乂上述第2(甲基)丙烯酸酯聚合物(β)之上述官能基(bl)低 之官能基(al)之單體為構成成分(發明1)β 第2,本發明提供一種黏著性組合物其特徵在於: is .重里平均分子量為7〇萬〜250萬之第ι(甲基)丙烯酸 酉曰聚合物(Α);重量平均分子量為8〇〇〇〜25萬之第2(甲基) 201209118 丙烯酸酯聚合物(B);及架橋劑(C),上述第2(曱基)丙烯 酸酯聚合物(B)對上述第丨(甲基)丙烯酸酯聚合物(Α)ι〇〇 質量部之比例為5〜40質量部,上述第2(曱基)丙烯酸酯聚 合物(B)含有以具有與上述架橋劑(c)之反應性滿足下式(ι) 之官能基(bl)之單體為構成成分,並且,具有上述官能基 (bl)之單體之比例,在於該當第2(曱基)丙烯酸酯聚合物 (B)中超過1質量%,且未滿5〇質量%,且上述第2(曱基) 丙烯酸酯聚合物(B)’含有以具有上述官能基(bl)之單體之 含量的1/5以下的量(質量比),具有與上述架橋劑(c)之反 應性滿足下式(I)之官能基(1)2)之單體為構成成分,上述第 1(曱基)丙烯酸酯聚合物(A),不含有可與上述架橋劑(c) 反應之g忐基之單體為構成成分,或含有以具有與上述架 橋劑(c)之反應性較上述第2(甲基)丙烯酸酯聚合物(8)之 上述官能基(bl)低的官能基(al)之單體為構成成分(發明 2): 與架橋劑(c)之反應性:官能基(b2)〈官能基(M) (1) 在於使關於上述發明(發明丨、2)之黏著性組合物架橋 之黏著劑,於先前係以使用於可塑劑之低分子量聚合物(B) 之化學性架橋形成三次元網狀構造。然後,藉由對該三次 元網狀構造,插入複數高分子量的聚合物(A),將高分子量 的聚合物(A)相互拘束,於高分子量的聚合物(〇之間形成 假性的架橋構造。藉此,所得之黏著劑可發揮適切的團聚 力與優良的應力緩和性。藉由使用具有該優良的應力緩和 性之黏著劑,適用於偏光板等的光學構件時,可得耐漏光 6 201209118 性與耐久性的雙方均優良的黏著板片。 X在於上述發明(發明1、2),上述第1(甲基)丙稀酸酉旨 聚。物(A) ’於構成成分不包含具有可與上述架橋劑(〇反 應之官能基之單體為佳(發明3)。 在方、上述發明(發明1、3) ’在於上述第1(甲基)丙烯 酉文知聚0物(A)之上述官能基(al)以羧基,在於上述第曱 基)丙烯酸醋聚合物(B)之上述官能基(bi)以羥基,上述架 橋劑(C)以異氰酸酯類架橋劑為佳(發明。 在於上述發明(發明2、3),在於上述第1(甲基)丙烯 酸醋聚合物(A)之上述官能基(al)讀基,在於上述第2(曱 =)丙烯酸酯聚合物(B)之上述官能基(bi)以羥基,上述官 月匕基(b2)以緩基’上述架橋劑⑹以異氰酸醋類架橋劑為佳 (發明5)。 在於上述發明(發明4、5) ’上述第1 (曱基)丙烯酸酯 聚合物(A)含有〇〜^ U 15貝置%含有羧基之單體作為構成該當 聚合物之單體單位為佳(發明6)。 在於上述發明(發明“),上述第2(曱基)丙烯酸酯聚 口物(Β) 3有3〜40質量%含有羥基之單體作為構成該當聚 合物之單體單位為佳(發明7 )。 在於上述發明(發明4〜7),上述異氰酸酯類架橋劑的 含量’以該當異氰酸酯類架橋劑之異氰酸酯基對在於上述 第2(甲基)丙稀酸醋聚合物⑻之上述官能基⑽之量,成 〇.卜3· 5當量之量為佳(發明8)。 第3本發明提供一種黏著劑組合物之製造方法,其 201209118 明卜8)之方法,其特徵在於 係製造上述黏著劑組合物(發 將上述第ι(甲基)丙烯酸酯聚合物⑷,與上述第2(甲幻 丙烯酸S旨聚合物⑻混合,並且練意階段添加上述架橋劑 (C)(發明 9)。 第4,本發明提供一種黏著劑,係係將上述黏著性組 合物(發明卜8)架橋而成(發明1〇)。 第5,本發明提供一種黏著板片,其特徵在於:包含: 基材;及黏著劑層,且上述黏著劑層係由上述黏著劑(發明 1 〇)所構成(發明11)。 11),上述基材以光學構件為佳(發 在於上述發明(發明 明 12) 〇 第6’本發明提供一種黏著板片,其特徵在於:包含: 2片剝離板片;及黏著劑層,其係與上述2片剝離板片的 剝離面接觸地挾持於上述剝離板片,上述黏著劑層,係由 上述黏著劑(發明10)所構成(發明13)。 ’、 [發明效果] 在於使關於本發 诞考劑,先 前係以作為可塑劑使狀低分子量之聚合物#成化學性的 架橋之三次元網狀構造。然後,藉由對該三次元網狀構造, 插入複數高分子量的聚合物’將高分子量的聚合物相互拘 束,於高分子量的聚合物之間形成假性的架橋構造。藉此, 所得黏著劑可發揮適切的團聚力與優良的應力緩和性。藉 由使用具有該優良的應力緩和性之黏著劑,適用於偏光^ 等的光學構件時,可得耐漏光性與耐久性的雔 又々巧優良的 201209118 黏著板片。 【實施方式】 以下,說明本發明之實施形態。 〔黏著性組合物〕 關於本實施形態之黏著性組合物,包含:重量平均分 子量為70萬〜250萬之第1(甲基)丙烯酸酯聚合物(A);重 里平均分子量為8000〜25萬之第2(曱基)两稀酸g旨聚合物 (B);及架橋劑(C),且最好進一步含有偶合劑(D)。再者, 在於本說明書,所謂(甲基)丙烯酸酯,係指丙稀酸醋及甲 基丙烯酸酯之雙方之意思。其他的類似用語亦相同。此外, 於「聚合物」亦包含「共聚物」的概念。 第2 (甲基)丙烯酸酯聚合物(B),係 (1) 以具有可與架橋劑(C)反應之官能基(bl)之單體為 構成成分,該當聚合物(B)所含有之可與架橋劑(C)反應之 官能基大體上只有官能基(bl ),或 (2) 以具有與架橋劑(C)之反應性滿足下式(I)之官能 基(bl)之單體,及具有與架橋劑(C)之反應性滿足下式(I) 之官能基(b2)之單體為構成成分。 與架橋劑(C)之反應性:官能基(b2)〈官能基 (bl)…⑴, 即,在於(2)之聚合物(B),所謂與官能基(bl)之架橋 劑(C)之反應性,較與官能基(b2)之架橋劑(C)之反應性高。 在於上述(1)及(2)之任一之聚合物(B),具有官能基 201209118 (bl)之單體在於聚合物(b)之構成比例超過1質量%,且未 =50質量%。此外’上述⑴之聚合物(b),係以具有上述 官能基(bl)之單體含量之1/5 α下的量(質量比)含有具有 上述官能基(b2)之單體作為構成成分。 再者,在於上述(1)之聚合物(8)之「大體上官能基(bi) 」,係指可容許以不妨礙官能基(bl)與架橋劑(c)之反應性 之耘度包含與架橋劑(C)反應之其他的官能基者。因此,少 量匕3上述g旎基(b2)者亦包含於上述(丨)之聚合物(B), 此時(1)的聚合物(B)與(2)的聚合物(B)重複者。 另一方面,第1 (甲基)丙烯酸酯聚合物(A),係於構成 單位不含具有可與架橋劑(C)反應之官能基之單體,或者, 於構成單位包含與架橋劑(c)之反應性較第2(甲基)丙烯酸 酉曰聚合物(B)之上述官能基(bi)低的官能基(al)之單體。 上述(甲基)丙烯酸酯聚合物(。或(B),以酯部分之烷 基之碳數為卜20之(曱基)丙烯酸酯,具有與架橋劑(C)反 應之官能基之單體(含有反應性官能基之單體),及根據所 期望使用之其他的單體之共聚物為佳。再者,第丨(甲基) 丙烯酸酯聚合物(A)’作為構成單位以不包含上述含有反應 性官能基之單體者亦佳。 酯的部分的烷基之碳數為卜2〇之(甲基)丙烯酸酯,可 舉例如(甲基)丙烯酸曱酯、(甲基)丙烯酸乙酯、(曱基)丙 烯酸丙酯、(曱基)丙烯酸正丁酯、(曱基)丙烯酸正戊酯、(曱 基)丙烯酸正己酯、(曱基)丙烯酸環己酯、(甲基)丙烯酸 2-乙基己酯、(甲基)丙烯酸異辛酯、(曱基)丙烯酸正癸酯、 10 201209118 (曱基)丙稀酸正十二烧酉旨、(甲甘、 ^甲基)丙烯酸肉豆蔻酯、(甲基) 丙烯酸棕櫚酉旨、(甲基)丙,嫌_」 、T丞J内埤酸十八烷酯等。該等可以單獨 使用,亦可組合2種以上使用。 另一方面,含有反應性官能基之單體,可舉以於分子 内具有經基之單體(含有經基之單體)、於分子内具有叛基 之單體(含有叛基之單體)、於分子内具有胺基之單體(含有 胺基之單體)等為佳。 含有羥基之單體,可舉例如、(甲基)丙烯酸2 —羥基乙 酉曰、(曱基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3_羥基丙 酉曰、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3 —羥基丁 醋、(甲基)丙稀酸4-經基丁醋等的(甲幻丙稀暖M基烧基 酉旨等。該等可以單獨使用,亦可組合2種以上使用。 含有缓基之單體,可舉例如、丙稀酸、甲基丙稀酸、 巴丑I、馬來酸、衣康酸、檸康酸等的乙烯性不飽和羧酸。 該等可以單獨使用,亦可組合2種以上使用。 含有胺基之單體,可舉例如 '(甲基)丙烯酸胺基乙酷、 (曱基)丙烯酸正丁基胺基乙酯等。該等可以單獨使用,亦 可組合2種以上使用。 再者,上述其他的單體,可舉例如(甲基)丙烯酸環己 酯等的具有脂肪族環之(曱基)丙烯酸酯;(曱基)丙烯酸笨 基8曰等的具有芳香族環之(曱基)丙烯酸酯;丙烯醯胺、甲 基丙烯醯胺等的非架橋性之丙烯醯胺;(甲基)丙烯酸N,N_ 一曱基胺基乙酯、(曱基)丙烯酸N, N_二甲基胺基丙酯等的 具有非架橋性3級胺基之(甲基)丙烯酸酯;醋酸乙烯酯、 201209118 苯乙烯等。該等可以單獨使用,亦可組合2種以上使用。 再者、使用於第1(甲基)丙烯酸酯聚合物(〇之含有反 應性官能基(al )之單體以及使用於第2 (曱基)丙烯酸酯聚 合物(B)之含有反應性官能基(bl)之單體及含有反應性官 旎基(b2)之單體之選擇,係以與使用之架橋劑(c)之反應性 之關係決定。細節將於後述。 在此,第2(甲基)丙烯酸酯聚合物(β)包含超過1質量 %上述含有反應性官能基(bl)之單體,其上限為未滿5〇質 量%。包含上述含有反應性官能基(bl)之單體3〜4〇質量% 為佳,包含5〜25質量%特別佳。藉由以上述範圍包含含有 反應性官能基(bl)之單體,第2(曱基)丙烯酸酯聚合物(B) 之架橋程度變佳,在與第1(曱基)丙烯酸酯聚合物之組 合’所得之黏著劑之應力緩和性變優良者。此外、含有反 應性官能基(M)之單體之含量在1質量%以下,則第2(甲 基)丙烯酸醋聚合物(B)之架橋並不充分,因此而降低耐久 性。另一方面、含有反應性官能基(bl)之單體之含量為5〇 質量%以上,則第2(甲基)丙烯酸醋聚合物(B)之架橋變的 過度’有因而降低對被著體之黏貼性之虞。再者,藉由使 含有反應性官能基(M )之單體之含量的上限為4〇質量%, 可使所得黏著板片的耐久性更優良。 此外、第2(曱基)丙烯酸酯聚合物(B),雖然於構成成 分不包含.具有與架橋劑(c)之反應性較上述官能美(匕1) 低的官能基(b2)之單體(含有反應性官能基(b2)之單體)特 別佳’惟包含含有反應性官能基(b2)之單體作為構成成八 12 201209118 時,以質量比包含含有反應性官能基(bl)之單體之含量之 1/5以下之量,特別是以1/1()以下的量為佳。 第2(甲基)丙烯酸酯聚合物(B),以質量比包含超過含 有反應性官能基(bi)之單體之含量之1/5之量之含有反應 性官能基(b2)之單體,則所得黏著劑層之耐久性會降低。 第2(曱基)丙烯酸酯聚合物(B)中的反應性官能基(b2)過 夕,則可推測在藉此形成之三次元網狀構造體内亦殘存多 篁的反應性官能基(b2),使該當三次元網狀構造體與第 1 (甲基)丙烯酸酯聚合物(A)之相溶性產生變化。結果,有 務度值上升之情形。此外,殘存多量反應性官能基(b2)之 二次疋網狀構造體,則可推測將過度限制插入於該當三次 元網狀構造體之第1 (曱基)丙烯酸酯聚合物(A)之可動性。 結果,有耐久性惡化之情形。 再者,關於本實施形態之黏著性組合物含有矽烷偶合 劑(D)時,矽烷偶合劑(D) ’將與第丨(曱基)丙烯酸酯聚合 物(A)之反應性官能基(al)(特別是羧基)反應,與高分子量 的第1 (曱基)丙烯酸酯聚合物(幻鍵結,在於所得黏著劑與 被著體之玻璃基板等的密著性成較優良者,惟第2(甲基) 丙烯酸酯聚合物(B)過剩包含含有反應性官能基(b2)之單 體,則可推測矽烷偶合劑(D)之烷氧基矽基等,亦與第2(曱 基)丙烯酸酯聚合物(B)之反應性官能基(b2)(特別是羧基) 反應,與低分子量的第2(甲基)丙烯酸酯聚合物(B)鍵結。 結果,所得之黏著劑與被著體之玻璃基板等之密著性變 差’因此降低黏著劑層之耐久性。 13 201209118 在此,酯部分的烷基之碳數為1〜20之(甲基)丙稀酸 酷’與具有與架橋劑(C)反應之官能基之單體,聚合而得之 第2(甲基)丙烯酸酯聚合物(B)之聚合態樣,可為隨機共聚 物,亦可為嵌段共聚物。特別是’若第2(曱基)丙烯酸酯 聚合物(B)為嵌段共聚物’則可控制三次元網狀構造之網狀 的大小’故第2 (甲基)丙稀酸酯聚合物(b ),以嵌段共聚物 為佳。具體而言,於第2(甲基)丙烯酸酯聚合物(B),亦可 良好的舉出以於兩末端具有反應性官能基(bl)之單體,與 碳數為1〜20之(曱基)丙烯酸酯嵌段地共聚合之態樣。 在於本實施形態’上述第2 (曱基)丙烯酸酯類聚合物 (B ),可單獨使用1種,亦可組合2種以上使用。 第2(甲基)丙烯酸酯聚合物(B)之重量平均分子量為 8〇〇〇〜25萬’以2萬~15萬為佳。即,第2(曱基)丙烯酸酿 聚合物(B),係成低分子量高分子成分。再者,在於本說明 2之重量平均分子量,係以凝膠滲透層析(Gpc)法測定以聚 笨乙烯換算之值。 藉由使第2(曱基)丙烯酸酯聚合物(B)之重量平均分子 里在於上述範圍内,於關於本實施形態之黏著性組合物形 成特有的二次元網狀構造,賦予優良的應力緩和性。即, 第2(甲基)丙烯酸酯聚合物(8)之重量平均分子量未滿 8000,則無法得到良好的三次元網狀構造。另一方面,第 2(甲基)丙烯酸酯聚合物(B)之重量平均分子量超過Μ _ 、丨相’谷丨生降低,聚合物(A)對聚合物(B)所形成之三次 兀網狀構造體中的插入變的不充分’而耐久性及重製性變 14 201209118 差0 第1 (甲基)丙稀酸醋聚合物(A),係於構成成分不包含 具有與架橋劑(C)反應之官能基之單體,或於構成成分包含 具有與架橋劑(C)之反應性較第2(甲基)丙烯酸酯聚合物 之上述g忐基(b 1 )低的官能基(a 1)之單體,然後較佳的 是,於構成成分不包含具有與架橋劑(c)之反應性較上述官 能基(bl)高的官能基之單體。 第1 (甲基)丙烯酸酯聚合物(A),雖可不包含與架橋劑 (c)反應之官能基之單體,惟包含具有反應性較第2(甲基) 丙烯酸酯聚合物(B)之反應性官能基(bl)低的反應性官能 基(al)之單體(含有反應性官能基(al)之單體),有可促進 第2(曱基)丙烯酸酯聚合物與架橋劑之反應,或者 使用矽烷偶合劑(D)時,第丨(甲基)丙烯酸酯聚合物以)之 反應性官能基(al)與該當矽烷偶合劑(…之烷氧基矽基等 反應,可调整第1(曱基)丙烯酸酯聚合物(A)之團聚程度, 可得所期望的接著性而佳之情形。 第U甲基)丙烯酸酯聚合物(A)包含上述含有反應性官 月b基(al)之單體時,其含量通常為質量%以下,以π質 量%以下為佳,以1 〇質量%以下特別佳。 含有反應性官能基(al)之單體之含量超過20質量%, 則第1 (曱基)丙烯酸酯聚合物(A)過度團聚,而有無法得到 所期望的應力緩和性之虞。再者,由賦予重製性之觀點, a有反應性官能基(al)之單體之含量以15質量%以下 佳。 ’ 15 201209118 此外,相較於與第2(甲基)丙烯酸酯聚合物(B)所包含 之含有反應性官能基(bl)之單體,在於第丨(甲基)丙稀酸 酯聚合物(A)所包含之含有反應性官能基(al)之單體之該 當第1 (曱基)丙烯酸酯聚合物(A)中的比例,較在於第2(曱 基)丙烯酸酯聚合物(B)所包含之含有反應性官能基(bi)之 單體之該當第2(甲基)丙烯酸酯聚合物(B)中的比例小為 佳。藉此,可抑制第丨(甲基)丙烯酸酯聚合物(4)所包含之 反應性官能基(al)與架橋劑(c)之反應,可使第2(甲基)丙 烯酸酯聚合物(B)所包含之反應性官能基(bl)與架橋劑 確實反應。 第1(甲基)丙烯酸酯聚合物以),雖不包含於分子内具 有與架橋劑(C)之反應性與第2(甲基)丙烯酸醋聚合物(B) 之反應性官能基(bl)同等以上的官能基之單體較佳,惟假 如包含時,於分子内具有該當官能基之單體之含量,於聚 合物(A)中以1質量%以下為佳,以0.5質量%以下特別為 佳α該當單體之含量超過i質量%,則有阻礙應優先反應之 第2(甲基)丙烯酸《合物(B)與架橋劑⑹之反應之虞。 在此,使醋部分之院基之碳數為卜20之(曱基)丙烯酸 醋’與含有反應性官能基之單體聚合而得之帛i(甲基)丙 烯酸醋聚合物⑴之聚合態樣,可為隨機共聚物,亦可為嵌 段共聚物。 在於本實施形態,上述帛1 (甲基)丙稀酸8旨聚合物 (A) ’可單獨使用1種’亦可組合2種以上使用。 第1(甲基)丙稀酸酉旨聚合物(A)之重量平均分子量為 16 201209118 70萬〜250萬,以10〇萬〜200萬為佳。即’第1(曱基)丙烯 酸酯聚合物(A),成高分子量高分子成分。 藉由第1(甲基)丙烯酸酯聚合物(A)之重量平均分子量 在於上述範圍内,可推測該當第1 (甲基)丙烯酸酯聚合物 (A)可良好地插入第2(甲基)丙烯酸酯聚合物所形成之 一人元..周狀構造,2分子以上經由該當聚合物(a )假性的架 橋構造,將聚合物(A),以具有某種程度的自由度的狀態被 拘束藉此,形成之黏著劑,成一併具有適當的團聚力與 優良的應力緩和性,結果,耐漏光性優良,此外,於高溫. 濕熱條件下接著耐久性變充分,而可防止浮起或剝落等。 在此,第1(甲基)丙烯酸酯聚合物(A)之重量平均分子 量未滿70萬,貝彳(A)成分的團聚力降低,耐久性及重製性 有變差之虞。此外,第丨(甲基)丙烯酸酯聚合物(A)之重量 平均分子量㈣250萬,則有與第2(甲基)丙稀酸醋聚: 物(B)等之相溶性惡化,使霧度值上升,或無法得到所期望 的應力緩和性之虞。 第2(甲基)丙烯酸醋聚合物(B)對於第i(甲基)丙烯酸 酯聚合物(A)100質量部之比例為5〜4〇質量部,以 質量部為佳。 在由以上述比例含有第1(甲基)丙烯酸g旨聚合物⑴及 第曱基)丙烯酸sl聚合物⑻之㈣性組合物所得之黏著 劑’可推測第2(甲基)丙稀酸醋聚合物⑻(低分子量高分 子)經由架橋劑(c)形成三次元網狀構造,藉由2分子以上 的第1(曱基)丙烯酸酯聚合物(A)(高分古 刀于里向分子)插入該 201209118 成三次元網狀構造之構造,聚合物⑴形成招互 程度的自由度的狀離祜杓由Μ, 八有某種 日 “破拘束的假性的架橋構造。藉此,所 付之黏著劑,具有適當的團 ,,m , j發輝優良的應力緩和 性。因此,所得之黏著劑成耐久性及耐漏光性優良者。 架橋劑(c)可良好的舉出異氰酸酯類架橋劑、環氧 架橋劑、環乙亞胺系架橋劑、金屬螯合系架橋劑等。、 異氰酸醋類架橋劑’係至少包含聚異氰酸醋化合物 者。聚異氰酸醋化合物,可與办丨 τ舉例如、甲苯基二異氰酸酯、 二笨基曱烧二異氰酸§旨、二甲笨基二異氰酸自旨等的芳香族 聚異氮酸醋、六亞甲基二異氛酸醋等的脂肪族聚異氮酸 醋、異佛爾嗣二異氮酸酿、力口氣二苯基甲烧二異氛酸醋等 的脂環式聚異氰㈣等、及該等的雙縮尿體、三聚氰酸體, 以及乙二醇、丙二醇、新々一 新戍—轉、六羥甲基丙烷、蓖麻油 等的含有低分子活性氫之化合物之反應物之加成體等。 環氧系架橋劑,可舉例如、以七^卜二縮水甘油 基胺基甲基)環己m r,r -四縮水甘油基間二甲苯基 二胺、乙二醇二縮水甘油醚、u—己二醇二縮水甘油醚、 六羥曱基丙烷二縮水甘油醚、二縮水甘油基笨胺、二縮水 甘油基胺等。 環乙亞胺系架橋劑,可舉例如,二苯基曱烷4, 4, _雙 (卜環乙亞胺羧醯胺)、六羥甲基丙烷三氮丙啶基丙酸 酯、四羥曱基曱烷二冷-氮丙啶基丙酸酯、甲苯_2, 4_雙(卜 %乙亞胺羧醯胺)、二乙烯密胺、雙間苯二醯_(2_曱基 %乙亞胺)、三-1-(2-甲基環乙亞胺)膦、六羥甲基丙烷三 18 201209118 冷_(2-’基環乙亞胺)丙酸酯等。 於金屬螯合系架橋劑, 鐵、錫等的f合化合物,由性能之⑨子為紹、錯、欽、鋅、 紹螯合化合物,可舉例如:广紹螯合化合物為佳。 皁異丙氧基鋁雙油醇乙酸酯、單異 〇 基乙醯乙酸s旨、二里丙氧 、减料油酸醋車乙 丙氧基叙單硬脂基乙醯二桂基乙醯乙酸醋、二異 θ 土 酉文酯、二異丙氧基鋁單異硬脂基 乙醯乙酸酯等。 架橋劑(C)的含I,### ^ ~虽架橋劑(C)之架橋性基(例 、異氰酸S旨基)對第2(甲基)丙歸酸醋聚合物⑻之反應 性官能基(bl)(例如、經基)之量,通常係成0.05〜5當量5 之量,以成G.卜3.5當量之量為佳,以成0.2].8當量之 量特別佳。只要上述架橋性基之量在q i當量以上,所得 之黏著劑之凝膠分率成術,可發揮充分的團聚力, 要在0. 2當I以上,則可使所得黏著劑之耐久性更優良 者。另一方面,只要上述架橋基的量在3. 5當量以下則 可使所得黏著劑之重製性優良,再者,只要在18當量以 下,則可將所得黏著劑之霧度值抑制較低。 此外,在於本實施形態,架橋劑(C),只要是與反應性 官能基(bl)及反應性官能基(al)的雙方的反應性關係一致 之種類之架橋劑,亦可併用複數種類。由容易控制第2 (曱 基)丙稀酸醋聚合物(B)所形成之三次元網狀構造之觀點’ 例如僅使用異氰酸酯類架橋劑,僅使用1種架橋劑為佳, 再者,僅使用1種架橋劑特別佳。 19 201209118 另—方面,作為其他的態樣,架橋劑(C),以1種架橋 劑為佳,特別是使用1種架橋劑’並且與反應性官能基(bl ) 及反應性官能基(al)的雙方的反應性的關係與架橋劑(c) 相反的其他的架橋劑(CR),以與架橋劑(C)之質量比,以 1 /20以下為佳,以1 /3〇以下的量使用特別佳。可舉例如, 以異I酸酯類架橋劑作為架橋劑(C),以環氧系架橋劑作為 其他的架橋劑(CR)少量使用的態樣。如此之其他的架橋劑 之添加’對聚合物(A)並未充分地插入聚合物(B)所構成之 三次元網狀構造,而團聚力不足時很有效。再者,上述其 他的架橋劑(CR),並不包含於架橋劑(C),於上述量的關係 由架橋劑(C)去除。 在此,架橋劑(C),與(甲基)丙烯酸酯聚合物(〇及(8) 之各個含有反應性官能基之單體之組合,架橋劑(c)為異氰 酸酯類架橋劑時,聚合物(A)之含有反應性官能基(al)之單 體,可良好地選擇含有羧基之單體,聚合物(B)之含有反應 性官能基(bl)之單體以含有羥基之單體或含有胺基之單 體,聚合物(B)之含有反應性官能基(b2)之單體以含有羧基 之單體。 另一方面,架橋劑(C)為環氧系架橋劑、環乙亞胺系架201209118 - VI. Description of the Invention: [Technical Field] The present invention relates to an adhesive composition, a method for producing an adhesive composition, an adhesive (a material for bridging an adhesive composition), and an adhesive sheet, in particular An adhesive composition for an optical member which can be suitably used for a polarizing plate or the like, a method for producing an adhesive composition, an adhesive, and an adhesive sheet. [Prior Art] In general, in a liquid crystal panel, an adhesive layer formed of an adhesive composition is often used in a polarizing plate or a phase difference plate followed by a glass substrate. However, the optical member such as a polarizing plate or a phase difference plate is likely to shrink due to heat or the like, and shrinks due to the heat history. As a result, the adhesive layer laminated on the optical member cannot follow the shrinkage, but occurs at the interface. Peeling (so-called foaming, peeling), and the stress caused by the contraction of the optical member causes the optical axis of the optical member to shift to cause light leakage (so-called white point). The method of preventing such a method is as follows: (1) a method of suppressing shrinkage by adhering an adhesive layer having high adhesion and excellent form retention property to an optical member optical member such as a polarizing plate; or (2) using optical A method of applying an adhesive layer with a small stress when the member is contracted. The method of (1) is effective as described in Patent Document 1, using an adhesive layer having a high storage modulus. On the other hand, in the method of (2), it is effective to use an adhesive layer which is soft and elastically compatible with the deformation of the optical member. However, it has been desired to form such an adhesive layer having excellent stress relaxation properties, which requires a low bridging density design in the adhesive layer. Thus, the strength of the adhesive layer itself is lowered, and there is a problem that the durability is deteriorated 201209118. Therefore, in the patent document, by adding a plasticizer, a fluid paraffin, a urethane elastomer or the like to an acrylic adhesive, the resulting adhesive composition is moderately softened, and the adhesive layer is subjected to stress relaxation. In order to obtain the light leakage resistance of the prior art, the prior art is disclosed in the prior art. [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. [Patent Document 4] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. 5-194366. [Problems to be Solved by the Invention] However, an adhesive layer of a plasticizer or a flowing stone adhesive composition is added. There are difficulties in the release of π 猢 丨 、 、, ώ && plasticizer or mobile paraffin. After the absence, it becomes a problem of being .... In addition, adding & various types of adhesive compositions for elastomers, compatibility, urethane elastomers, and the upper limit of the amount of W. The improvement is not sufficient. In addition, in order to improve stress relaxation, the amount of ester elastomer added is increased, and the compatibility of the addition of cyanide with the acrylic adhesive is reduced, and white turbidity is lowered. As described above, the adhesive composition for the conventional dry member is known to have optical light leakage resistance and durability. According to the present invention, in order to provide an optical member for use in a polarizing plate or the like, an adhesive composition which is excellent in both light leakage property and durability is adhered to the present invention. The method for producing a composition, a dispensing agent, and an adhesive sheet are targeted. [Means for Solving the Problem] In order to achieve the above object, the present invention provides an adhesive composition characterized by comprising: a weight average molecular weight of 7. 10,000 to 250,000 U-methyl acrylate polymer (VIII); 2nd (meth)acrylic acid styrene (b) having a weight average molecular weight of 8,000 to 250,000; and bridging agent (C) The ratio of the second (fluorenyl) acrylate polymer (B) to the mass portion of the first fluorenyl acrylate polymer (A) is 5 to 4 Å by mass, and the second (meth) The acrylic acid vinegar polymer (8) contains a monomer having a functional group (bl) reactive with the above-mentioned bridging agent (6) as a constituent component, and the ratio of the monomer having the above functional group (bi) is determined to be 帛2 ( The methyl methacrylate polymer (B) exceeds the working mass % and is less than 5% by mass, and the second (methyl acrylate vinegar polymer (B) contains the above-mentioned bridging agent (c) The functional group of the reaction is substantially only the above functional group (bl), and the above-mentioned third (meth) propylene:- (A) does not contain a monomer which can react with the above-mentioned bridging agent (6) as a constituent component. Or a functional group having a lower functional group (bl) than the above-mentioned second (meth) acrylate polymer (β) of the above-mentioned bridging agent (c) The monomer of the base (al) is a constituent component (Invention 1) β. The second invention provides an adhesive composition characterized by: is. ι (meth)acrylic acid having an average molecular weight of 70,000 to 2.5 million酉曰Polymer (Α); 2nd (meth) 201209118 acrylate polymer (B) having a weight average molecular weight of 8〇〇〇 to 250,000; and bridging agent (C), the above 2nd (fluorenyl) acrylic acid The ratio of the ester polymer (B) to the mass portion of the second (meth) acrylate polymer (Α) ι is 5 to 40 parts by mass, and the second (fluorenyl) acrylate polymer (B) contains The monomer having a functional group (bl) satisfying the following formula (1) with the reactivity of the bridging agent (c) is a constituent component, and the ratio of the monomer having the above functional group (bl) is the second More than 1% by mass in the (fluorenyl) acrylate polymer (B), and less than 5% by mass, and the above (2) fluorenyl acrylate polymer (B)' is contained to have the above functional group (bl) The amount (mass ratio) of 1/5 or less of the content of the monomer, and the reactivity with the above-mentioned bridging agent (c) satisfying the function of the following formula (I) The monomer of (1) 2) is a constituent component, and the first (fluorenyl) acrylate polymer (A) does not contain a monomer which can react with the bridging agent (c) as a constituent component, or a monomer having a functional group (al) having a lower reactivity with the above-mentioned second (meth) acrylate polymer (8) than the above-mentioned second (meth) acrylate polymer (8) as a constituent component (inventive) 2): Reactivity with the bridging agent (c): functional group (b2) <functional group (M) (1) is an adhesive for bridging the adhesive composition of the above invention (invention 丨, 2) A three-dimensional network structure is formed by chemical bridging of a low molecular weight polymer (B) used for a plasticizer. Then, by inserting a plurality of high molecular weight polymers (A) into the three-dimensional network structure, the high molecular weight polymers (A) are restrained from each other, and a false bridge is formed between the high molecular weight polymers (〇). Therefore, the obtained adhesive can exert an appropriate agglomeration force and excellent stress relaxation property. By using an adhesive having such excellent stress relaxation property, it can be used for an optical member such as a polarizing plate to obtain light leakage resistance. 6 201209118 Adhesive sheets excellent in both properties and durability. X is in the above invention (Inventions 1 and 2), and the first (meth) succinate is intended to be aggregated. (A) 'The constituents do not include It is preferable that the monomer having a functional group reactive with the above-mentioned bridging agent (the invention) is invented (Invention 3). The above invention (Inventions 1, 3) 'is in the above-mentioned first (meth)acryloyl hydrazine poly() A) the functional group (al) is a carboxyl group, the functional group (bi) of the above-mentioned fluorenyl acrylate polymer (B) is a hydroxyl group, and the bridging agent (C) is preferably an isocyanate bridging agent (invention) In the above invention (Inventions 2, 3), The functional group (al) read group of the first (meth)acrylic acid vinegar polymer (A) is characterized in that the functional group (bi) of the second (曱=) acrylate polymer (B) has a hydroxyl group, It is preferable that the above-mentioned bridging agent (6) is an isocyanate-based bridging agent (Invention 5). In the above invention (Invention 4, 5) 'The above-mentioned 1 (mercapto) acrylate polymerization The object (A) contains a monomer having a carboxyl group as a monomer having a carboxyl group as the monomer unit constituting the polymer (Invention 6). In the above invention (Invention), the above-mentioned second (fluorenyl) acrylic acid The ester agglomerate (Β) 3 has 3 to 40% by mass of a monomer having a hydroxyl group as a monomer unit constituting the polymer (Invention 7). In the above invention (Inventions 4 to 7), the above isocyanate-based bridging agent The content of the isocyanate group of the isocyanate bridging agent is preferably in the amount of the above functional group (10) of the second (meth)acrylic acid vinegar polymer (8). 8) The third invention provides a method for producing an adhesive composition, which is characterized by the method of 201209118, and 8) The above-mentioned adhesive composition is produced (the above-mentioned (meth) acrylate polymer (4) is mixed with the above-mentioned 2nd (methyst acrylic acid S-polymer (8), and the above-mentioned bridging agent (C) is added in a practice stage. (Invention 9). Fourth, the present invention provides an adhesive which is obtained by bridging the above adhesive composition (Invention 8). (Invention 1) The present invention provides an adhesive sheet characterized by The invention comprises: a substrate; and an adhesive layer, wherein the adhesive layer is composed of the above-mentioned adhesive (Invention 1). 11) The substrate is preferably an optical member (in the above invention) (Embodiment 12) The present invention provides an adhesive sheet comprising: two peeling sheets; and an adhesive layer which is held in contact with the peeling surface of the two peeling sheets In the above-mentioned release sheet, the above-mentioned adhesive layer is composed of the above-mentioned adhesive (Invention 10) (Invention 13). The effect of the invention is that the first embodiment of the present invention is a three-dimensional network structure in which a low molecular weight polymer is used as a plasticizer to form a chemical bridge. Then, by inserting a plurality of high molecular weight polymers into the three-dimensional network structure, the high molecular weight polymers are mutually restrained to form a pseudo bridge structure between the high molecular weight polymers. Thereby, the obtained adhesive can exert an appropriate agglomeration force and excellent stress relaxation. By using an adhesive having such excellent stress relaxation properties, when it is applied to an optical member such as a polarizing film, it is possible to obtain a light-resistant and durable light-resistant 201209118 adhesive sheet. [Embodiment] Hereinafter, embodiments of the present invention will be described. [Adhesive Composition] The adhesive composition of the present embodiment comprises a first (meth) acrylate polymer (A) having a weight average molecular weight of 700,000 to 2.5 million; and an average molecular weight of 8,000 to 250,000. The second (indenyl) diacid acid g polymer (B); and the bridging agent (C), and preferably further contains a coupling agent (D). In the present specification, the term "(meth)acrylate" means both acrylic acid acrylate and methacrylate. Other similar terms are the same. In addition, the concept of "copolymer" is also included in "polymer". The second (meth) acrylate polymer (B) is a component having a functional group (bl) reactive with the bridging agent (C) as a constituent component, and the polymer (B) is contained therein. The functional group reactive with the bridging agent (C) is substantially only a functional group (bl), or (2) a monomer having a reactivity with the bridging agent (C) that satisfies the functional group (bl) of the following formula (I) And a monomer having a functional group (b2) satisfying the reactivity of the bridging agent (C) and satisfying the following formula (I) is a constituent component. Reactivity with bridging agent (C): functional group (b2) <functional group (bl) (1), that is, polymer (B) in (2), so-called bridging agent (C) with functional group (bl) The reactivity is higher than that of the bridging agent (C) of the functional group (b2). In the polymer (B) according to any one of the above (1) and (2), the monomer having a functional group of 201209118 (bl) is such that the composition ratio of the polymer (b) exceeds 1% by mass and is not = 50% by mass. Further, the polymer (b) of the above (1) contains, as a constituent component, a monomer having the above functional group (b2) in an amount (mass ratio) at a ratio of 1/5 α of the monomer content of the functional group (bl). . Further, the "substantially functional group (bi)" of the polymer (8) of the above (1) means that it can be contained so as not to interfere with the reactivity of the functional group (bl) and the bridging agent (c). Other functional groups that react with the bridging agent (C). Therefore, a small amount of 匕3 of the above g 旎 group (b2) is also included in the above (丨) polymer (B), at this time (1) polymer (B) and (2) polymer (B) repeater . On the other hand, the first (meth) acrylate polymer (A) is a monomer which does not contain a functional group capable of reacting with the bridging agent (C) in a constituent unit, or contains a bridging agent in a constituent unit ( c) a monomer having a lower functional group (al) than the above functional group (bi) of the second (meth)acrylic acid ruthenium polymer (B). The above (meth) acrylate polymer (. or (B), the carbon number of the alkyl group of the ester moiety is a (mercapto) acrylate having a functional group which reacts with the bridging agent (C) (Polymer containing a reactive functional group), and a copolymer of another monomer which is preferably used. Further, the fluorene (meth) acrylate polymer (A)' is not included in the constituent unit. The above-mentioned monomer having a reactive functional group is also preferred. The carbon number of the alkyl group of the ester portion is a (meth) acrylate, and examples thereof include decyl (meth)acrylate and (meth)acrylic acid. Ethyl ester, propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, (methyl) 2-ethylhexyl acrylate, isooctyl (meth)acrylate, n-decyl (meth) acrylate, 10 201209118 (fluorenyl) acrylic acid, 12 decyl, (methyl ketone, ^ methyl) Myristyl acrylate, palmitious (meth) acrylate, (methyl) propyl, _ T 丞 J internal octadecyl decanoate, etc. These may be used alone or in combination of two or more. On the other hand, the monomer having a reactive functional group may have a single group in the molecule. Preferably, the monomer (containing a monomer of a radical), a monomer having a rebel group in the molecule (a monomer containing a rebel group), a monomer having an amine group in the molecule (a monomer having an amine group), and the like. The monomer of the hydroxyl group may, for example, be 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl methacrylate, or 2-(meth) acrylate. Hydroxybutyl ester, (meth)acrylic acid 3-hydroxybutyl vinegar, (meth) acrylic acid 4-pyridyl vinegar, etc. (M-Phase M-based base, etc. These may be used alone, Two or more types may be used in combination. Examples of the monomer containing a slow group include ethylenic unsaturated, such as acrylic acid, methyl acrylic acid, Ba ug I, maleic acid, itaconic acid, and citraconic acid. The carboxylic acid may be used singly or in combination of two or more. The monomer containing an amine group may, for example, be '(meth) propylene. Ethyl acetyl, n-butylaminoethyl acrylate, etc. These may be used alone or in combination of two or more. Further, the other monomer may, for example, be (meth)acrylic acid. (Alkyl) acrylate having an aliphatic ring such as cyclohexyl ester; (fluorenyl) acrylate having an aromatic ring such as (mercapto)acrylic acid; acrylamide, methacrylamide, etc. Non-branching acrylamide; N,N_-mercaptoaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, etc. (meth) acrylate, vinyl acetate, 201209118 styrene, etc. These may be used alone or in combination of two or more. Further, it is used in the first (meth) acrylate polymer (〇 a monomer having a reactive functional group (al), a monomer containing a reactive functional group (bl) used in the second (fluorenyl) acrylate polymer (B), and a reactive sulfhydryl group (b2) The choice of monomer is determined by the reactivity with the bridging agent (c) used. Details will be described later. Here, the second (meth) acrylate polymer (β) contains more than 1% by mass of the above-mentioned monomer having a reactive functional group (bl), and the upper limit thereof is less than 5% by mass. The monomer containing the reactive functional group (bl) is preferably 3 to 4% by mass, particularly preferably 5 to 25% by mass. By including the monomer having a reactive functional group (bl) in the above range, the degree of bridging of the second (fluorenyl) acrylate polymer (B) is improved, and in combination with the first (fluorenyl) acrylate polymer The combination of the resulting adhesive has excellent stress relaxation properties. Further, when the content of the monomer having a reactive functional group (M) is at most 1% by mass, the bridging of the second (meth)acrylic acid vinegar polymer (B) is insufficient, and thus the durability is lowered. On the other hand, when the content of the monomer having a reactive functional group (bl) is 5% by mass or more, the bridging of the second (meth)acrylic acid vinegar polymer (B) becomes excessive. The adhesion of the body. Further, by setting the upper limit of the content of the monomer containing the reactive functional group (M) to 4% by mass, the durability of the obtained adhesive sheet can be further improved. Further, the second (fluorenyl) acrylate polymer (B) is not contained in the constituent component, and has a functional group (b2) having a lower reactivity with the bridging agent (c) than the functional group (匕1). The body (monomer containing a reactive functional group (b2)) is particularly preferred, and includes a monomer having a reactive functional group (b2) as a constituent 八12 201209118, and contains a reactive functional group (bl) in a mass ratio. The amount of the monomer content of 1/5 or less is particularly preferably 1/1 () or less. The second (meth) acrylate polymer (B) contains a monomer having a reactive functional group (b2) in an amount exceeding 1/5 of the content of the monomer containing the reactive functional group (bi) by mass. The durability of the resulting adhesive layer is lowered. In the case of the reactive functional group (b2) in the second (fluorenyl) acrylate polymer (B), it is presumed that a reactive functional group remains in the ternary network structure formed thereby ( B2) The compatibility of the three-dimensional network structure and the first (meth) acrylate polymer (A) is changed. As a result, there is a case where the value of the transaction rises. Further, it is presumed that the secondary ruthenium network structure in which a large amount of the reactive functional group (b2) remains remains inserted into the first (fluorenyl) acrylate polymer (A) of the three-dimensional network structure. Mobility. As a result, there is a case where the durability is deteriorated. Further, when the adhesive composition of the present embodiment contains the decane coupling agent (D), the decane coupling agent (D) 'will react with the functional group of the fluorene (meth) acrylate polymer (A) (al) (especially a carboxyl group) reacts with a high molecular weight first (fluorenyl) acrylate polymer (a phantom bond, in which the adhesion between the obtained adhesive and the glass substrate to be coated is superior, but only When the (meth) acrylate polymer (B) contains a monomer having a reactive functional group (b2) excessively, it is presumed that the alkoxy fluorenyl group of the decane coupling agent (D) is also the second group The reactive functional group (b2) (particularly a carboxyl group) of the acrylate polymer (B) is reacted with a low molecular weight second (meth) acrylate polymer (B). As a result, the resulting adhesive is The adhesion of the glass substrate to the body is deteriorated, and thus the durability of the adhesive layer is lowered. 13 201209118 Here, the carbon number of the alkyl group of the ester moiety is 1 to 20 (meth) acrylic acid cool' a second (meth) acrylate obtained by polymerization with a monomer having a functional group reactive with the bridging agent (C) The polymerized form of the compound (B) may be a random copolymer or a block copolymer, especially if the second (fluorenyl) acrylate polymer (B) is a block copolymer The size of the network of the three-dimensional network structure is such that the second (meth) acrylate polymer (b) is preferably a block copolymer. Specifically, the second (meth) acrylate is polymerized. The substance (B) can also be preferably a copolymerized monomer having a reactive functional group (bl) at both terminals and a block copolymerized with a (fluorenyl) acrylate having 1 to 20 carbon atoms. In the present embodiment, the second (fluorenyl) acrylate polymer (B) may be used singly or in combination of two or more. The weight of the second (meth) acrylate polymer (B) The average molecular weight is from 8 〇〇〇 to 250,000 Å, preferably from 20,000 to 150,000. That is, the second (mercapto) acrylic styrene (B) is a low molecular weight polymer component. The weight average molecular weight of 2 is measured by a gel permeation chromatography (Gpc) method in terms of polystyrene. By polymerizing the 2nd (fluorenyl) acrylate The weight average molecular weight of the substance (B) is within the above range, and the adhesive composition of the present embodiment forms a unique secondary network structure, and imparts excellent stress relaxation properties. That is, the second (meth) acrylate When the weight average molecular weight of the polymer (8) is less than 8,000, a good three-dimensional network structure cannot be obtained. On the other hand, the weight average molecular weight of the second (meth) acrylate polymer (B) exceeds Μ _, 丨The phase 'gluten is reduced, and the polymer (A) is insufficiently inserted into the tertiary ruthenium structure formed by the polymer (B), and the durability and the reworkability are changed. 12 201209118 Poor 0 1 (methyl) The acrylic acid vinegar polymer (A) is a monomer which does not contain a functional group having a reaction with the bridging agent (C), or contains a reactivity with the bridging agent (C) in the constituent component. a monomer of the (meth) acrylate polymer having a lower functional group (a 1) of the above fluorenyl group (b 1 ), and then preferably, the constituent component does not contain reactivity with the bridging agent (c) a monomer having a higher functional group than the above functional group (bl). The first (meth) acrylate polymer (A) may contain a reactive (2) (meth) acrylate polymer (B), although it may not contain a monomer having a functional group reactive with the bridging agent (c). a monomer having a reactive functional group (bl) having a low reactive functional group (al) (a monomer having a reactive functional group (al)), which promotes a second (fluorenyl) acrylate polymer and a bridging agent In the reaction, or when the decane coupling agent (D) is used, the reactive functional group (al) of the ruthenium (meth) acrylate polymer reacts with the oxane coupling agent (the alkoxy thiol group of the oxime coupling agent, etc.) The degree of agglomeration of the first (fluorenyl) acrylate polymer (A) is adjusted to obtain a desired adhesion. The U-methyl acrylate polymer (A) contains the above-mentioned reactive sulphur-containing b group. When the monomer (al) is used, the content thereof is usually 5% by mass or less, preferably π% by mass or less, and particularly preferably 1% by mass or less. When the content of the monomer having a reactive functional group (al) exceeds 20% by mass, the first (fluorenyl) acrylate polymer (A) is excessively agglomerated, and the desired stress relaxation property cannot be obtained. Further, from the viewpoint of imparting remanufacturability, the content of the monomer having a reactive functional group (al) is preferably 15% by mass or less. ' 15 201209118 Further, compared to the monomer containing a reactive functional group (bl) contained in the second (meth) acrylate polymer (B), the ruthenium (meth) acrylate polymer is (A) The proportion of the first (fluorenyl) acrylate polymer (A) of the monomer containing the reactive functional group (al) contained in the second (fluorenyl) acrylate polymer (B) The ratio of the monomer containing the reactive functional group (bi) to the second (meth) acrylate polymer (B) is preferably small. Thereby, the reaction of the reactive functional group (al) contained in the fluorene (meth) acrylate polymer (4) with the bridging agent (c) can be suppressed, and the second (meth) acrylate polymer can be obtained ( B) The reactive functional group (bl) contained therein does react with the bridging agent. The first (meth) acrylate polymer does not contain a reactivity with the bridging agent (C) in the molecule and a reactive functional group of the second (meth) acrylate polymer (B) (bl The monomer having the same functional group or more is preferably a content of the monomer having the functional group in the molecule, and is preferably 1% by mass or less, and 0.5% by mass or less based on the polymer (A). In particular, when the content of the monomer exceeds i% by mass, there is a possibility that the reaction of the second (meth)acrylic acid compound (B) and the bridging agent (6) which should be preferentially reacted is inhibited. Here, the polymerization state of the 帛i(meth)acrylic acid vinegar polymer (1) obtained by polymerizing the carbon number of the vinegar portion into the phenolic vinegar of the phenolic group and the monomer having the reactive functional group For example, it may be a random copolymer or a block copolymer. In the present embodiment, the above-mentioned hydrazine 1 (meth) acrylic acid 8 polymer (A) ' may be used singly or in combination of two or more. The weight average molecular weight of the first (meth) acrylate polymer (A) is 16 201209118 700,000 to 2.5 million, preferably 100,000 to 2,000,000. Namely, the 'first (fluorenyl) acrylate polymer (A) is a high molecular weight polymer component. When the weight average molecular weight of the first (meth) acrylate polymer (A) is within the above range, it is presumed that the first (meth) acrylate polymer (A) can be favorably inserted into the second (meth) group. The acrylate polymer is formed by a human element: a circumferential structure, and two or more molecules are restrained by a pseudo-branched structure of the polymer (a), and the polymer (A) is restrained to a certain degree of freedom. Thereby, the formed adhesive has an appropriate agglomeration force and excellent stress relaxation property, and as a result, the light leakage resistance is excellent, and further, at a high temperature, the durability is sufficiently maintained under the moist heat condition, and the floating or peeling can be prevented. Wait. Here, the weight average molecular weight of the first (meth) acrylate polymer (A) is less than 700,000, and the agglomeration power of the shellfish (A) component is lowered, and the durability and the reworkability are deteriorated. Further, the weight average molecular weight (four) of the second (meth) acrylate polymer (A) is 2.5 million, and the compatibility with the second (meth) acrylic acid vinegar polymer (B) is deteriorated to cause haze. The value rises or the desired stress relaxation is not obtained. The ratio of the second (meth)acrylic acid vinegar polymer (B) to 100 parts by mass of the i-th (meth)acrylate polymer (A) is 5 to 4 parts by mass, preferably in the mass portion. The second (meth)acrylic acid vinegar is presumed to be an adhesive obtained from the (four) composition containing the first (meth)acrylic acid-based polymer (1) and the fluorenyl-acrylic acid sl polymer (8) in the above ratio. The polymer (8) (low molecular weight polymer) forms a three-dimensional network structure via the bridging agent (c), and is composed of two or more molecules of the first (fluorenyl) acrylate polymer (A) (high-resolution ancient knives in the inner molecule) Inserting the structure of the 201209118 into a three-dimensional network structure, the polymer (1) forms a degree of freedom of the degree of mutuality, and there is a certain kind of "bridged pseudo-bridge structure." The adhesive has an appropriate mass, and m, j is excellent in stress relaxation. Therefore, the obtained adhesive is excellent in durability and light leakage resistance. The bridging agent (c) can well be cited as an isocyanate bridge. Agent, epoxy bridging agent, ethyleneimine bridging agent, metal chelate bridging agent, etc., isocyanate vinery bridging agent' is at least polyisocyanate compound. Polyisocyanate compound, For example, toluene diisocyanate, diphenyl hydrazine An aliphatic polyisocyanuric acid such as an aromatic polyisocyanate or a hexamethylene diiso-succinic acid vinegar or the like, which is a diisocyanate or a dimethicone diisocyanate An alicyclic polyisocyanate (tetra), etc., and a diuret, a cyanuric acid, and an ethylene glycol, and the like, and an alicyclic polyisocyanate (tetra), etc. An adduct of a reactant of a compound containing a low molecular weight active hydrogen such as propylene glycol, neodymium neodymium-transfer, hexamethylolpropane or castor oil. The epoxy-based bridging agent may, for example, be seven Glycidylaminomethyl)cyclohexane mr,r-tetraglycidyl-xylylenediamine, ethylene glycol diglycidyl ether, u-hexanediol diglycidyl ether, hexahydroxypyranyl propane condensed water Glycidyl ether, diglycidyl succinylamine, diglycidylamine, etc. Cycloethylenimine-based bridging agent, for example, diphenyl decane 4, 4, bis (b-ethylenimine carboxamide) , hexamethylolpropane triaziridine propionate, tetrahydrocarbyl decane di-cold-aziridine propionate, toluene-2, 4_bis (b-ethylimine carboxamide), two Imiamine, bis-m-benzoquinone_(2_mercapto-ethylenimine), tri-1-(2-methylcycloethylimine)phosphine, hexamethylolpropane tri- 18 201209118 cold _(2- 'Like-ethylenimine) propionate, etc. In the metal chelate bridging agent, iron, tin and other f-compound compounds, the performance of the 9 sub-sham, sham, chin, zinc, schel compound, can be exemplified Such as: Guangshao chelating compound is preferred. Soap isopropoxide aluminum bis- oleyl acetate, monoisodecyl acetonitrile acetic acid s, two propylene oxide, reduced oleic acid vinegar car Ethoxypropyl Stearic acid ethyl phthalocyanate, vinegar, diiso-theta, tert-butyl ester, diisopropoxy aluminum monoisostearylacetate, etc. The bridging agent (C) contains I,## # ^ ~Although the bridging agent (C) bridging group (for example, isocyanate S) is a reactive functional group (bl) for the 2 (meth) a carboxylic acid polymer (8) (for example, a trans-base) The amount is usually 0.05 to 5 equivalents of 5, preferably in an amount of 3.5 equivalents, preferably in an amount of 0.2 to 0.8 equivalents. As long as the amount of the above-mentioned bridging group is more than qi equivalent, the gel fraction of the obtained adhesive agent can be fully agglomerated, and the durability of the obtained adhesive can be further improved at 0.2 or more. Excellent. On the other hand, as long as the amount of the bridging group is 3.5 equivalents or less, the obtained adhesive can be excellent in reworkability, and if it is 18 equivalents or less, the haze value of the obtained adhesive can be suppressed to be low. . Further, in the present embodiment, the bridging agent (C) may be a plurality of types of bridging agents in accordance with the reactivity relationship between the reactive functional group (bl) and the reactive functional group (al). From the viewpoint of easy control of the three-dimensional network structure formed by the second (mercapto) acrylonitrile polymer (B), for example, only an isocyanate bridging agent is used, and only one type of bridging agent is preferably used. It is especially preferred to use one type of bridging agent. 19 201209118 On the other hand, as another aspect, the bridging agent (C) is preferably one type of bridging agent, especially one type of bridging agent' and with a reactive functional group (bl) and a reactive functional group (al) The reactivity relationship between the two sides is the same as the other bridging agent (CR) of the bridging agent (c), and the mass ratio of the bridging agent (C) is preferably 1 / 20 or less, and 1 / 3 or less. The amount is especially good. For example, an iso-acid ester bridging agent is used as the bridging agent (C), and an epoxy-based bridging agent is used as a small amount of another bridging agent (CR). Such addition of other bridging agents is not effective in the three-dimensional network structure in which the polymer (A) is not sufficiently inserted into the polymer (B), and the agglomeration power is insufficient. Further, the above-mentioned other bridging agent (CR) is not included in the bridging agent (C), and the relationship of the above amount is removed by the bridging agent (C). Here, when the bridging agent (C) is combined with a (meth) acrylate polymer (a monomer containing a reactive functional group of hydrazine and (8), and the bridging agent (c) is an isocyanate bridging agent, polymerization is carried out. The monomer having a reactive functional group (al) of the substance (A) is preferably a monomer having a carboxyl group, and the monomer having a reactive functional group (bl) of the polymer (B) is a monomer having a hydroxyl group. Or a monomer containing an amine group, the monomer containing the reactive functional group (b2) of the polymer (B) is a monomer having a carboxyl group. On the other hand, the bridging agent (C) is an epoxy bridging agent, and the ring B Imine frame
由架橋劑(C)與聚合物(B) •有羥基之單體,聚合物(B) 體以含有羧基之單體,聚合 )之單體以含有羥基之單體。 之間形成之鍵結柔軟性,及 20 201209118 架橋反應的緩和性’以及聚合物(A)之反應性基適當地與矽 院偶合劑(D)反應而貢獻於提升聚合物(八)之團聚力,使架 橋劑(C )為異氰酸醋類架橋劑’聚合物(A)之含有反應性官 能基(al)之單體以含有羧基之單體,聚合物(B)之含有反應 性官能基(bl)之單體以含有羥基之單體,聚合物(B)之含有 反應性官能基(b2)之單體以含有羧基之單體特別佳。 關於本實施形態之黏著性組合物,進一步包含矽烷偶 合劑(D)為佳。當包含該矽烷偶合劑(D),則於第丨(甲基) 丙烯酸醋聚合物(A)具有羧基時,矽烷偶合劑(1))之有機反 應性基等與第1(甲基)丙烯酸®旨聚合物(A)之缓基反應,在 另一方面矽烷偶合劑(D)的烷氧基矽基等將與玻璃基板等 的被著體面作用。因此,例如將偏光板黏貼於液晶玻璃胞 時,黏著劑與液晶玻璃胞之間的密著性更佳。 該石夕烧偶合劑⑻,係於分子内只少具有】個炫氧基石夕 基之有機矽化合物,與黏著劑成分之相溶性佳,且具有光 穿透性者,例如以實質上透明者為佳。如此之石夕烷偶合劑 ⑻之添加量,對帛K甲基)丙烯酸醋聚合物(A)10。質量 部’以〇.。卜。.5質量部為佳,以。.〇5~〇3質量部特別佳。 :燒偶合劑⑻之具體例,可舉乙稀基三甲氧綱、 土二乙氧基矽烷、甲基丙烯醯氧 的含有聚合性不飽和美μm T乳春7说寺 不釭和基之矽化合物、3-丙烯醯氧丙三甲氧 夕燒、2-(3,4 -環氣美援ρ其、7甘 有環盡I接 衣乳基衣己基)乙基三甲氧基矽烷等的具 有^基構造W化合物、㈣基 " 胺基丙基三甲氧基矽烷、N-(2-胺基乙 201209118 基)-3 -胺基丙基甲其^ —甲乳基石夕院等的胺基含有石夕化合 物' 3 -乳丙基三甲氧基石夕惊、q-思*说工曾— ★ 疋 3異鼠酸丙基二乙氧基碎燒 等該等’可以1種單獨使用,亦可組合2種以上使用。 於上述黏著性組合物,可根據所期望,添加通常使用 於丙烯酸系黏著劑之各種添加劑,例如黏著付與劑、氧化 防止劑、紫外線吸収劑、氺 ^ , hl九女疋劑、軟化劑、充填劑、帶 電防止劑、折射率調整劑等。 〔黏著性組合物之製造方法〕 上述黏著性組合物,可藉由將第丨(甲基)丙烯酸酯聚 合物(A),與第2(甲基)丙烯酸酯聚合物(B)混合的同時, 於任意階段將架橋劑(C)及根據所期望添加矽烷偶合劑(d) 而製造。 較佳的具體例,係將(甲基)丙烯酸酯聚合物(A)及 (B) ’分別個別地以通常的自由基聚合法調製。(甲基)丙雄 酸酯聚合物(A)及(B)之聚合,可根據所期望使用聚合起始 劑’以溶液聚合法等進行。聚合溶劑,可舉例如,醋酸乙 酯、醋酸正丁酯、醋酸異丁酯、曱苯、丙酮、己烷、曱乙 綱等,亦可併用2種類以上。 聚合起始劑,可舉重氮系化合物、有機過氧化物等, 亦可併用2種類以上。重氮系化合物’可舉例如、2 2,__ 重氮雙異丁腈、2, 2’-重氮雙(2-曱基丁腈)、u,—重氮錐 (環己烷1-羰腈)、2, 2,-重氮雙(2, 4-二曱基戍腈)、2, 2,— 重氮雙(2,4-二甲基4 -甲氧基戊腈)、二曱基2, 2’-重氣雔 (卜曱基丙酸酯:^心斗’-重氮雙^^-氰基戊酸)、〗?,— 22 201209118 2 ~重氮雙[2-(2-咪唑啉-2-基) 雙(2-羥基甲基丙腈) 丙烷]等。 有機過氧化物’可舉例如, __ 過氧化笨、過氧化本曱酸 第三丁酯、過氧化氫異丙笨、_ —吳丙基過氧碳酸酯、二正 丙基過氧碳酸酯、二(2-乙氧其 乳卷乙基)過氧碳酸酯、過氧化 新癸酸第三丁醋、過氧化戊酸第三丁醋、(3,5,5 —三甲基己 醯)過氧化物、過氧化二丙酿、過氧化二乙醯等。 其次’將所得聚合物(A )及r — ^夂C B )之洛液混合,加入稀釋 溶劑。 之後,將架橋劑(C )及;w 根據所期望添加石夕烧偶合劑 (D) ’充分混合’得到以溶劑 — 宵褅釋之黏者性組合物(塗佈溶 液)。 丙醇 醇、1-甲氧基-2-丙醇等的醇 稀釋黏著性組合物成塗佈溶液之稀釋溶劑,可使用例 :、己烷、庚烷、環己烷等的脂肪烴、甲笨、二甲苯等的 方香烴、二氣甲烷、二氣乙烷等的“烴、甲醇、乙醇、 丙酮、甲乙酮、2- 戊嗣、異佛_、環己酮等的酮、醋酸乙酉旨 '醋酸丁醋等 的酯、乙基溶纖劑等的溶纖劑系溶劑等。 —如此地調製之塗佈溶液之濃度.黏度,只要可塗層之 靶圍即可,並無特別限制’可按照情況適宜選定。例如, 將黏著性組合物之漢度稀釋成1〇〜4〇質量%。再者,在於得 =塗佈溶液時,稀釋溶㈣的添加並非必要條件只要= 著:組合物為可塗層之黏度等,可不添加稀釋溶劑。此時, 黏著性組合物直接成塗佈溶液。 23 201209118 〔黏著劑〕 關於本實施形態之黏著劑,係將上述黏著性組合物架 橋而成者。上述黏著性組合物之架橋,可藉由加熱處理進 订再者,違加熱處理,亦可兼作使黏著性 溶劑等揮發時之乾燥處理。 物之稀釋 、進行加熱處理時,加熱溫度以5〇〜15(rc為佳,特別是 以70:120t為佳。此外,加熱時間,以3〇秒〜3分為佳, 特別疋以50秒〜2分為佳。再者,加熱處理後,設置以常 溫(例如,23。(:,50_卜2週間程度的固化期間特別佳。 可推測以上述加熱處理(及固化),藉由架橋劑(c)使第 2(甲基)丙稀酸自旨聚合物⑻架橋,形成緻密的三次元網狀 構造。然I ’可推測於該三次元網狀構造中2分子以上的 第1(甲基)丙稀酸醋聚合㉗⑴不伴隨直接的化學鍵結,或 伴隨極少的化學鍵結而插人,使該#聚合物⑴被拘束,而 形成擬架橋構造°料’帛1(甲基)丙稀酸醋聚合物(A)具 有羧基時’第1(甲基)丙烯酸酯聚合物(A)與矽烷偶合劑(D) 反應’團聚特定程度。 以上所δ兑明之黏著劑,可良好地使用於光學構件用, 適於例如,偏光板與位相差板之接著’或者偏光板(偏光膜) 或位相差板(位相差膜)與玻璃基板之接著。以上述黏著劑 形成之黏著劑層,由於應力緩和性非常優良,故即使是被 著體的尺寸變化很大時,可藉由黏著劑層吸収.緩和因該 尺寸變化所產生的應力,因此可長期不容易由被著體剝 落,使用於如上所述之光學構件時,可有效地防止漏光。 24 201209118 即’關於本實施形態之黏著劑,係可並存耐漏光性與耐久 性之雙方者。 〔黏著板片〕 如圖1所示,關於第1實施形態之黏著板片1A,係由 下面依序,由剝離板片12 ;層積於剝離板片12之剝離面 之黏著劑層11 ;及層積於黏著劑層i i之基材i 3所構成。 此外,如圖2所示,關於第2實施形態之黏著板片ΐβ, 係由2片剝離板片12a、12b;及接於該等2片制離板片 12a、12b之剝離面而被該當2片剝離板片12&、工託夾 之黏著劑層U所構成。再者’在於本說明書之剝離板片之 剝離面,係指於剝離板片具有剝離性之面,施有剝離處理 之面及即使未施予剝離處理即顯示剥離性之面均包含。 在任—黏著板片1A、1B,黏著劑層u,係 黏著性、组合物而成之黏著劑所·组成。 〃 a 黏著劑層U之厚度,可按照黏著板片丨 目的適宜決定,通常為5〜1〇〇“ 之使用 佳,例如,夯Μ Μ处 10〜之範圍為 佳例如λ學構件,A monomer containing a hydroxyl group by a bridging agent (C) and a polymer (B), a monomer having a hydroxyl group, and a polymer (B) having a carboxyl group-containing monomer. The bond softness formed between the two, and the reactivity of the polymer of the polymer (A) and the reactive group of the polymer (A) are appropriately reacted with the broth coupling agent (D) to contribute to the agglomeration of the polymer (8). Force, the bridging agent (C) is an isocyanate-type bridging agent 'polymer (A) containing a reactive functional group (al) monomer containing a carboxyl group monomer, polymer (B) containing reactivity The monomer of the functional group (bl) is a monomer having a hydroxyl group, and the monomer containing the reactive functional group (b2) of the polymer (B) is particularly preferably a monomer having a carboxyl group. The adhesive composition of the present embodiment preferably further contains a decane coupling agent (D). When the decane coupling agent (D) is contained, the organic reactive group of the decane coupling agent (1) and the like (1) (meth)acrylic acid when the (meth)acrylic acid vinegar polymer (A) has a carboxyl group In the case of the slow-radical reaction of the polymer (A), on the other hand, the alkoxy fluorenyl group of the decane coupling agent (D) or the like acts on the surface of the glass substrate or the like. Therefore, for example, when the polarizing plate is adhered to the liquid crystal glass cell, the adhesion between the adhesive and the liquid crystal glass cell is better. The shovel coupling agent (8) is an organic ruthenium compound having only a few oxo oxo groups in the molecule, which is excellent in compatibility with the adhesive component and has light penetrability, for example, is substantially transparent. It is better. Such an amount of the talc coupling agent (8) is added to the 帛K methyl methacrylate polymer (A) 10. The quality department is 〇. Bu. .5 quality department is better. .〇5~〇3 Quality is especially good. : Specific examples of the smouldering agent (8) include ethylidene trimethoxy oxymethane, earth diethoxy decane, and methacryl oxime containing a polymerizable unsaturated US μm T 乳春 7 saying that the temple is not 釭 基a compound, 3-propenyloxypropoxytrioxane, 2-(3,4-cyclohexene conjugated ruthenium, 7-glycan-containing lactated hexyl) ethyltrimethoxydecane, etc. Base structure W compound, (tetra) group " alanine propyl trimethoxy decane, N-(2-aminoethyl 201209118 yl)-3 -aminopropylmethyl ketone Shi Xi compound ' 3 - propyl propyl trimethoxy stone Xi Jing, q - think * said that the work - ★ 疋 3 isoric acid propyl diethoxy sinter and so on 'can be used alone, can also be combined Two or more types are used. In the above adhesive composition, various additives generally used for an acrylic adhesive, such as an adhesive agent, an oxidation preventive agent, an ultraviolet absorber, a 氺^, a hl nine licking agent, a softener, or the like, may be added as desired. Filler, charge inhibitor, refractive index modifier, and the like. [Method for Producing Adhesive Composition] The above adhesive composition can be mixed with the second (meth)acrylate polymer (B) by mixing the second (meth)acrylate polymer (A) It is produced at any stage by adding a bridging agent (C) and adding a decane coupling agent (d) as desired. In a preferred embodiment, the (meth) acrylate polymers (A) and (B)' are individually prepared by a usual radical polymerization method. The polymerization of the (meth)propionate polymers (A) and (B) can be carried out by a solution polymerization method or the like using a polymerization initiator as desired. The polymerization solvent may, for example, be ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane or oxime. Alternatively, two or more types may be used in combination. The polymerization initiator may be a heavy nitrogen compound or an organic peroxide, and two or more types may be used in combination. The diazo compound 'for example, 2 2,__diazobisisobutyronitrile, 2,2'-diazobis(2-mercaptobutyronitrile), u,-diazonium cone (cyclohexane 1-carbonyl) Nitrile), 2, 2,-diazobis(2,4-dimercaptophthalonitrile), 2, 2,-diazobis(2,4-dimethyl-4-methoxyvaleronitrile), diterpenes Base 2, 2'-heavy gas 雔 (dipenyl propionate: ^ heart bucket '-diazobis^^-cyanovaleric acid), 〗? , — 22 201209118 2 ~ Diazobis[2-(2-imidazolin-2-yl) bis(2-hydroxymethylpropionitrile) propane]. The organic peroxide can be exemplified by, for example, __peroxidized stupid, peroxybenztal acid tert-butyl ester, hydrogen peroxide isopropyl, _-wupropyl peroxycarbonate, di-n-propyl peroxycarbonate, di ( 2-ethoxylated milk ethyl) peroxycarbonate, peroxy neodecanoic acid, third vinegar, peroxy valeric acid, third vinegar, (3,5,5-trimethylhexyl) peroxide , dipropylene peroxide, diethyl peroxide, etc. Next, the obtained polymer (A) and r-^夂C B are mixed and added to a diluent solvent. Thereafter, the bridging agent (C) and the ?w are sufficiently mixed according to the desired addition of the sulphur coupling agent (D) ' to obtain a viscous composition (coating solution) which is released as a solvent. An alcohol-diluting adhesive composition such as propanol or 1-methoxy-2-propanol is used as a diluent solvent for a coating solution, and examples thereof include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane. a ketone such as a hydrocarbon, methanol, ethanol, acetone, methyl ethyl ketone, 2-pentanyl, isophora, cyclohexanone or the like, such as aromatized or xylene, such as aromatized hydrocarbon, dioxane or dioxane. An ester such as butyl acetate or the like, a cellosolve such as ethyl cellosolve, or the like. - The concentration and viscosity of the coating solution thus prepared are not particularly limited as long as the target of the coating can be coated. It can be suitably selected according to the case. For example, the degree of the adhesive composition is diluted to 1 to 4% by mass. Further, when the coating solution is obtained, the addition of the diluted solution (4) is not a necessary condition as long as: The adhesive is not coatable, and the adhesive composition is directly added to the coating solution. 23 201209118 [Adhesive] The adhesive of the present embodiment is formed by bridging the above adhesive composition. The bridge of the above adhesive composition can be heat treated In addition, the heat treatment may be used as a drying process for volatilizing an adhesive solvent, etc. When the material is diluted and heat-treated, the heating temperature is preferably 5 〇 15 (rc is preferred, especially 70: 120 t). In addition, the heating time is preferably divided into 3 sec to 3, especially 50 to 50 sec to 2 sec. Furthermore, after heat treatment, set to normal temperature (for example, 23 (:, 50_b 2 The curing period during the week is particularly good. It is presumed that the second (meth)acrylic acid is bridged by the bridging agent (c) by the bridging agent (c) to form a dense three-dimensional network by the above heat treatment (and curing). Structure I. It is presumed that the first (meth)acrylic acid vinegar polymerization 27(1) of two or more molecules in the three-dimensional network structure is not accompanied by direct chemical bonding, or is inserted with little chemical bonding, so that #polymer(1) is restrained, and forms a pseudo-bridge structure. The material ''1(meth)acrylate vinegar polymer (A) has a carboxyl group 'the 1st (meth) acrylate polymer (A) and a decane couple Mixture (D) reaction 'aggregation to a certain extent. The above-mentioned δ-defined adhesive can be well For use in optical members, for example, a polarizing plate and a phase difference plate are followed by either a polarizing plate (polarizing film) or a phase difference plate (phase difference film) and a glass substrate. The adhesive layer formed by the above adhesive is used. Since the stress relaxation property is very excellent, even if the size of the object is greatly changed, it can be absorbed by the adhesive layer to alleviate the stress caused by the dimensional change, so that it can be easily peeled off by the object for a long period of time. When it is used for the optical member as described above, it is possible to effectively prevent light leakage. 24 201209118 That is, the adhesive of the present embodiment can be used for both light leakage resistance and durability. [Adhesive sheet] The adhesive sheet 1A of the first embodiment is formed by peeling the sheet 12 in the following order, the adhesive layer 11 laminated on the peeling surface of the peeling sheet 12, and the laminated layer of the adhesive layer ii. The substrate i 3 is composed of. Further, as shown in Fig. 2, the adhesive sheet piece ΐβ of the second embodiment is composed of two peeling sheets 12a and 12b, and is attached to the peeling faces of the two pieces of the separating sheets 12a and 12b. Two peeling sheets 12 & and an adhesive layer U of the work clamp are formed. Further, the peeling surface of the peeling sheet of the present specification means a surface having a peeling property on the peeling sheet, a surface to which the peeling treatment is applied, and a surface which exhibits peeling property even if no peeling treatment is applied. In the adhesive sheet 1A, 1B, the adhesive layer u is composed of an adhesive and a composition. 〃 a The thickness of the adhesive layer U can be appropriately determined according to the purpose of the adhesive sheet, and is usually 5 to 1 〇〇, which is preferably used, for example, a range of 10 之 is preferably a λ-like member,
Bi ^ 1 n rn & F ^偏先板用黏著劑層 時為1〇〜5〇“,特別是以為佳。 基材13,並無特別限制,通常 材板片者均可使用。可舉例如,所期望基 使用螺營、屡克力、聚醋等的纖維之織布”之外, 紙、亮面紙、含浸紙、塗 、、或不織布,上質 愛層...氏等的紙類. 酸乙 洛,·氨酯發泡體、聚乙蝉發泡體 广銅專的金屬 缺^ 一醇酯、聚對笨_ p _ 、务冶體;聚對苯二f …丁二醇醋、聚蔡駿乙二醇醋等 25 201209118 的聚酯膜、聚氨酯腔、 ^ 、聚乙烯膜、聚丙烯膜、聚氯乙烯膜、 聚偏風乙稀膜、聚乙樣醉邮 H醇膜、乙稀-醋酸乙烯酯共聚物膜、 聚苯乙稀膜、聚碳酸胺 -曰瞑、丙烯酸樹脂膜、降冰片烯系樹 脂膜、環烯烴樹脂膜等 β塑膠膜,該等的2種以上的層積 體等。塑膠臈,可為單輛延伸或雙軸延伸者。 光學構件,可舉例如,偏光板(偏光膜),偏光片,位 相差板(位相差膜),α & 、 、視野角補償膜,亮度提升膜,對比提 升膜’液4分子膜等。其中偏光板(偏光膜),由於容易 縮而尺寸變化大,故由耐漏光性的觀點,可良好地作 為形成本實施形態之黏著劑(上述黏著劑層⑴之對象。 基材13之厚度’根據其種類而異,例如在光學構件之 情形,通常為W5〇Mm,以5〇^3〇Mm為佳。 剝離板片12、12a、12b,可使用例如,聚乙稀膜聚 丙烯膜、聚丁烯膜 '聚丁二烯膜、聚甲基戊缔膜、聚氯乙 烯膜、氣乙烯基共聚物膜、聚對苯二甲酸乙二醇酿膜、聚 萘酸乙二醇酯膜、聚對苯二甲酸丁二醇酿膜、聚氨酷膜、 乙烯醋酸乙烯醋膜、離聚樹脂膜、乙稀.(甲基)丙稀酸共 聚物膜、乙烯.(甲基)丙烯酸酯共聚物膜、聚苯乙烯膜、 聚碳酸酯膜、聚醯亞胺膜、氟樹脂膜等。此' '/J、便用 該等的架橋膜。再者’亦可為該等的層積膜。 與上述剝離板片之剝離面(特別是接於黏著劑層丨丨之 面),施以剝離處理為佳。使用於剝離處理之剝離齊j,可舉 例如,醇酸系,石夕膠系,氟系,;f飽和聚醋類,聚稀煙系, 服糸剝離劑。 7 26 201209118 關於剝離板片12、12a、12b之厚度,並I牲… . ,、将別限制, 通吊’為20〜150#m程度。 上述黏著板片1A之製造,係於剝離板片12之 、 、剩離面, 塗佈包含上述黏著劑組合物之溶液(塗佈溶液〜 運行加熱 處理形成黏著劑層11之後,於該黏著劑層11層積基材13。 再者’關於加熱處理之條件,如上所述。 此外,上述黏著板片1B之製造,係於另一剝離板片 12a(或12b)之剝離面,塗佈包含上述黏著劑組合物之塗佈 溶液^進行加熱處理形成黏著劑| 後,於該點著:層 11重疊另一剝離板片12b(或12a)之剝離面。 塗佈上述塗佈溶液之方法,例如棒塗佈法,刀塗佈法, 輥塗法,到刀塗佈法,模具塗佈法,凹版塗佈法等。 _在此’例如’於製造由液晶胞與偏練所構成之液晶 顯不裝置’使用偏光板作為黏著板片1A之基# W,將該 當黏著板片1A之剝離板片12剝離,將露出之黏著劑層“ 與液晶胞黏貼即可。 此外,例如,於製造在液晶胞與偏光板之間配置位相 差板之液晶顯示裝置’係將黏著板片IBt另一剝離板片 心(或12b)剝離,將露出之黏著劑層u與液晶胞黏貼, 接者將另一剝離板片]19 极乃Ub(或12a)剝離,將露出之黏著劑層 11與位相差板黏貼,再者 ^ 丹有將以偏光板作為基材13之黏 者板片1A之剝離柄Μ ΐ9Α,·ω- 1Α - 2剝離,將路出之黏著劑層丨丨與位 相差板黏貼即可。 根據以上的黏著枥h彳Λ 1D A ^ 板片ΙΑ、IB,由於黏著劑層u的應 27 201209118 力緩和性非常優良,故例如使用於偏光板之接著時,可以 黏著劑層1 1吸仅·緩和因偏光板之變形而產生之應力,推 測藉此’可發揮優良的耐漏光性及高的耐久性。 於以上所説明之實施形態,係為容易理解本發明而記 載者,並非限定本發明而記載者。因此,揭示於上述實施 形態之各要素,亦包含屬於本發明之技術範圍之所有的設 計變更或均等物。 例如,黏著板片i A之剝離板片J 2可省略,在於黏著 板片1B之剝離板片12a、12b之任一方亦可省略。 【實施例】 乂下以實施例等進一步具體說明本發明,惟本發明 之範圍並非受限於該等實施例等。 〔實施例1〕 1.聚合物(A)之調製 於具備攪拌機、溫度計、回流冷卻器、滴人裝置及氣 氣導入管之反應容器’放入丙稀酸正丁酷95〇質量部,丙 稀酸5·。質量部’醋酸乙醋2〇〇質量部,及2 2、重氣雙 異丁腈0. 08質量部,將上述及廐六 這反應夺益内的空氣以氮氣置 換。於該氮氣氣氛下邊糌拉 ’將反應溶液升溫至60°C,反 16小時後,冷卻至室溫。在 仕此將所得溶液之一部分以 後述之方法以GPC測定,確認生成 啤生成重里平均分子量150萬 之聚合物(A)。 2.聚合物(B)之調製 滴入裝置及氮 於具備攪拌機、溫度計、回流冷卻器 28 201209118 氣導入管之反應容琴, m r ? « ° 丙烯酸正丁鞄85. 0質量部,丙 烯酸2-¾基乙酯15 〇暂旦加 _〇f里部,醋酸乙醋200質量部,2,2,_ 重氮又異丁猜〇·16曾吾Λβ 4 ’及2 -狒基乙醇〇 3質量部, 將上述反應容器内的空氣以 買篁丨· 氮虱置換。於該氮氣氣氛下邊 攪半,將反應溶液升溫至7 〇 1 υ匕,反應δ小時後,冷卻至室 溫。在此,將所得溶液 °丨刀以後述之方法以GPC測定, 確5忍生成重量平均分早吾人 j刀于I 5萬之聚合物(Β)。 3.黏著性組合物之調製 將上述步驟⑴所得聚合物(Α) 1 〇〇質量部(固形份換算 值)’與上述步驟(2)所得聚合物(Β)2〇質量部(固形份換算 值)混合之後’添加聚合物⑻之羥基相當於〇8當量之量 之六羥甲基丙烷之甲苯基二異氰酸酯(TDI系)加成物(日本 聚氨酯公司製,商品名「c〇R〇NATE L」)作為架橋劑(c)。最 後,添加3-丙烯醯氧丙三甲氧基矽烷(信越化學公司製, 商品名ΓΚΒΜ403」)0. 2質量部作為矽烷偶合劑(D),藉由充 分授拌’得到黏著性組合物之稀釋溶液。 在此’於表1表示該當黏著性組合物之配方。再者, 記載於表1之簡號等的詳細如下。 [聚合物(A)及(B)] BA :丙烯酸正丁酯 AA :丙烯酸 HEA:丙烯酸2 -羥基乙酯 HBA :丙烯酸4 -羥基丁酯 HEMA:甲基丙烯酸2-羥基乙酯 29 201209118 [架橋劑(c)] •異氰酸酯類架橋劑 TDI系:六羥甲基丙烷之甲笨基二異氰酸酯加成物(曰 本聚氨醋公司製,商品名「c〇R〇NATE l」) 三聚氰酸系:六亞曱基二異氰酸酯之三聚氰酸體(日本 聚氨醋工業株式會社製,商品名「CORONATE HXR」) •其他的架橋劑(環氧系架橋劑) Ν’ Ν’ Ν’,Ν’ -四縮水甘油基間二曱苯基二胺(三菱瓦斯 化學公司製’商品名「TETRAD-X」) [矽烷偶合劑(D)] ΚΒΜ40 3 :3-丙烯醯氧丙三甲氧基矽烷(信越化學公司 製,商品名「KBM403」) KBE9007: 3-異氰酸丙基三乙氧基矽烷(信越化學公司 製,商品名「KBE9007」) KBE40 3:3-丙烯醯氧丙三乙氧基矽烷(信越化學公司 製’商品名「KBE403」) 將所得黏著性組合物之稀釋溶液,對聚對苯二甲酸乙 二醇雖膜之單面以矽膠系剝離劑剝離處理之剝離板片 (LINTEC公司製,SP-PET3811,厚度:38/zm)之剝離處理 面’以刀塗佈機塗佈成乾燥後之厚度為25//πι之後,以9〇 °C加熱處理1分鐘形成黏著劑層。 接著,將由具有圓盤型液晶層之偏光膜所組成,偏光 膜與視野角擴大膜一體化之偏光板,使黏著劑層接於圓盤 型液晶層地黏貼,以23°C,50%RH固化7天,得到具有黏 201209118 著劑層之偏光板。 〔實施例2〜32'比較例卜7〕 將構成黏著性組合物 早體之種類及比例,架橋劑 及石夕烧偶合劑之種類及 窃 及添加置,以及聚合物(A)及聚合物(B) 之配方比變更如矣1 — 外’以與實施例1同樣地製造具有 黏著劑層之偏光板。 〔4驗例1〕(黏著力測定—重製性評估) 由實施例或比較例所得之具有黏著劑層之偏光板,切 出寬25龍’長100_之樣品,將剝離板片剝離,經由露出 之黏著劑層黏貼於無驗玻璃(康寧公司製,⑹之 後於栗原製作所公司製高壓反應器,以〇. 5心,5(rc加 壓20刀鐘。之後,以23 c,50%RH之條件下放置24小時, 再使用拉張試験機(〇rientec公司製,tensil〇n),以剝離 速度300nnn/inin,剝離角度18〇度的條件測定黏著力 (N/25mm)。在此記載以外之條件遵照JISZ〇237: 2〇〇9進行 測定。 再者,以23C,50%RH之條件下放置14天,再以與上 述同樣地測定黏著力(黏貼14天後的黏著力;N/25mm)。再 者’較佳的黏著力範圍,係0. lN/25mm以上,未滿25N/25mm。 根據上述黏貼14天後的黏著力,以如下基準進行重製 性之評估。將結果示於表2。 黏貼14天後的黏著力在20N/25mm以下:◎, 黏貼 14天後的黏者力超過 2 0 N / 2 5 m m,未滿 25N/25mm:〇 201209118 黏貼14天後的黏著力為25N/25mm以上:χ 〔試驗例2〕(凝膠分率之測定) 取代用於實施例或比較例之具有黏著劑層之偏光板之 製作之偏光板,使用將聚對苯二甲酸乙二醇酯膜之單面以 石夕膠系剝離劑剝離處理之剝離板片(LiNteC公司製, SP PET3801,厚度:38/im),製作黏著板片。具體而言, 在由實施例或比較例之製造過程所得剥離板片/黏著劑層 (厚度:25# m)所組成之構成體之露出之黏著劑層上,使上 述剝離板片接於剝離處理面側而層積。藉此,製作由剝離 板片/黏著劑層/剝離板片之構成所組成之黏著板片。 將所得黏著板片’以23°C ’ 50%RH之條件下固化7天。 之後’將該¥黏著板片取樣為8〇 之尺寸,將該黏 著劑層包於聚酯製網目(網目尺寸2〇〇),將只有黏著劑之 質量以精密天平秤量。以此時之質量為M1。 使用索式萃取器(Soxh 1 et Extractor),將黏著劑的樣 品浸潰於醋酸乙酯溶劑,進行回流16小時。之後取出黏著 劑,於溫度23 C,相對濕度50%之環境下,風乾24小時, 進一步以80°C的烘箱乾燥12小時。將乾燥後之只有黏著 劑之質量,以精密天平秤量。此時之質量為M2。凝膠分率 (%) ’係以(M2/Ml)xl〇〇表示。將結果示於表2。 〔試験例3〕(光學性能之測定) 準備與用於凝膠分率之測定之黏著板片同樣的黏著板 片(以做7天的固化)作為測定樣品。對該當黏著板片之勘 著劑層,使用霧度計(日本電色工業公司製,NDH2〇〇〇),遵 32 201209118 照JISK7105測定霧度值(%) ,,A, ^ ^ 时結果不於表2。再者’較 佳的霧度值之範圍為〇〜5%。 〔試驗例4〕(耐久性評估) 將實施例或比較例所得 田接^+ ”有黏者劑層之偏光板,使 用裁切裝置(荻野製作所公司 J ^ SUPER CUTTER » PN1-600)Bi ^ 1 n rn & F ^ When the adhesive layer is used for the first layer, it is preferably 1〇~5〇", especially preferably. The substrate 13 is not particularly limited and can be used by any of the material sheets. For example, papers, glossy papers, impregnated papers, coated, or non-woven fabrics, papers of the upper quality layer, etc. are used in addition to the woven fabrics of fibers such as snails, hexagrams, and polyesters.酸乙洛,·························································· Vinegar, poly Caijun glycol vinegar, etc. 25 201209118 Polyester film, polyurethane cavity, ^, polyethylene film, polypropylene film, polyvinyl chloride film, polyhedral film, polyethyl-like drunken H film, B a β-plastic film such as a dilute-vinyl acetate copolymer film, a polystyrene film, a polycarbonate-ruthenium, an acrylic resin film, a norbornene-based resin film, or a cycloolefin resin film, or two or more layers thereof Integral and so on. Plastic cymbal, which can be a single extension or a biaxial extension. The optical member may, for example, be a polarizing plate (polarizing film), a polarizing plate, a phase difference plate (phase difference film), an α & , a viewing angle compensation film, a brightness enhancement film, a comparative lifting film, a liquid 4 molecular film or the like. Among them, the polarizing plate (polarizing film) has a large dimensional change due to the fact that it is easily shrunk. Therefore, the adhesive of the present embodiment can be favorably formed from the viewpoint of light leakage resistance (the object of the above-mentioned adhesive layer (1). The thickness of the substrate 13' Depending on the type thereof, for example, in the case of an optical member, it is usually W5 〇 Mm, preferably 5 〇 3 〇 Mm. For peeling the sheets 12, 12a, 12b, for example, a polyethylene film polypropylene film, Polybutene film 'polybutadiene film, polymethyl pentylene film, polyvinyl chloride film, gas vinyl copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, Polybutylene terephthalate granulated film, polyurethane film, ethylene vinyl acetate film, ionized resin film, ethylene (meth) acrylic acid copolymer film, ethylene. (meth) acrylate copolymer a film, a polystyrene film, a polycarbonate film, a polyimide film, a fluororesin film, etc. This ''/J, these bridged films are used. Further, 'the laminated film can also be used It is preferable to apply a peeling treatment to the peeling surface of the peeling sheet (particularly, the surface of the adhesive layer). The peeling treatment may be, for example, an alkyd type, a sulphur type, a fluorine type, a f-saturated vinegar type, a poly-smoke type, and a peeling agent. 7 26 201209118 About the peeling sheets 12, 12a , the thickness of 12b, and I sacrifice ...., will not limit, the hanging 'to 20~150#m degree. The above-mentioned adhesive sheet 1A is manufactured, which is attached to the peeling sheet 12, left, coated A solution containing the above-described adhesive composition (coating solution - after running the heat treatment to form the adhesive layer 11, the substrate 13 is laminated on the adhesive layer 11. Further, the conditions regarding the heat treatment are as described above. The adhesive sheet 1B is produced by peeling the peeling surface of the other peeling sheet 12a (or 12b), applying a coating solution containing the above-mentioned adhesive composition, heat-treating to form an adhesive, and then at that point. The layer 11 overlaps the peeling surface of the other peeling sheet 12b (or 12a). The method of applying the above coating solution, such as a bar coating method, a knife coating method, a roll coating method, a knife coating method, a mold coating method Cloth method, gravure coating method, etc. _ Here, 'for example, 'manufacturing by liquid crystal cell and partial training The liquid crystal display device 'uses a polarizing plate as the base #W of the adhesive sheet 1A, and peels off the peeling sheet 12 of the adhesive sheet 1A, and adheres the exposed adhesive layer to the liquid crystal cell. Further, for example, In the liquid crystal display device in which the phase difference plate is disposed between the liquid crystal cell and the polarizing plate, the adhesive sheet IBt is peeled off from the other peeling plate core (or 12b), and the exposed adhesive layer u is adhered to the liquid crystal cell. The other peeling sheet is peeled off from the 19-pole Ub (or 12a), and the exposed adhesive layer 11 is adhered to the phase difference plate. Further, there is a sticky sheet 1A which will use the polarizing plate as the substrate 13. The peeling handle Μ Α 9 Α, · ω - 1 Α - 2 peeling, the adhesive layer 路 of the road can be adhered to the phase difference plate. According to the above adhesion 枥h彳Λ 1D A ^ plate ΙΑ, IB, since the adhesive layer u is 27, 201209118, the force relaxation is very excellent, so that, for example, when used in the case of a polarizing plate, the adhesive layer 1 1 can be sucked only. - The stress generated by the deformation of the polarizing plate is alleviated, and it is presumed that it exhibits excellent light leakage resistance and high durability. The embodiments described above are described for easy understanding of the present invention, and are not intended to limit the present invention. Therefore, all the elements of the above-described embodiments are also included in the technical scope of the present invention. For example, the peeling sheet J 2 of the adhesive sheet i A may be omitted, and either one of the peeling sheets 12a and 12b of the adhesive sheet 1B may be omitted. [Embodiment] The present invention will be further described by way of Examples and the like, but the scope of the present invention is not limited to the embodiments and the like. [Example 1] 1. The polymer (A) was prepared in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a gas introduction tube. Dilute acid 5. The quality department 'acetic acid ethyl acetate 2 〇〇 mass part, and 2 2, heavy gas double isobutyronitrile 0. 08 mass parts, the above and the sixth six of the reaction benefit of the air is replaced with nitrogen. The reaction solution was heated to 60 ° C under a nitrogen atmosphere, and after 16 hours, it was cooled to room temperature. A part of the obtained solution was measured by GPC in the manner described later, and it was confirmed that the beer (A) having a beer having an average molecular weight of 1.5 million was produced. 2. Polymer (B) preparation drip device and nitrogen in a reactor with a mixer, thermometer, reflux cooler 28 201209118 gas introduction tube, mr ? « ° acrylonitrile n-butyl acrylate 85. 0 mass, acrylic 2- 3⁄4 ethyl ester 15 〇 旦 加 〇 里 里 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , In the section, the air in the reaction vessel is replaced with a nitrogen hydrazine. The mixture was stirred for half while under a nitrogen atmosphere, and the reaction solution was heated to 7 〇 1 Torr, and after reacting for δ hours, it was cooled to room temperature. Here, the obtained solution was measured by GPC, and the method of GPC was used to determine the weight average of the polymer (Β). 3. Preparation of Adhesive Composition The polymer (Α) 1 〇〇 mass portion (solid content converted value) ' obtained in the above step (1) and the polymer (Β) 2 〇 mass portion obtained in the above step (2) (solid content conversion) After mixing, the hydroxyl group of the polymer (8) is added to a toluene diisocyanate (TDI) adduct of hexamethylolpropane in an amount of 8 equivalents (manufactured by Nippon Polyurethane Co., Ltd., trade name "c〇R〇NATE" L") as a bridging agent (c). Finally, 3-propenyl methoxypropane trimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name ΓΚΒΜ403) was added as a decane coupling agent (D), and the mixture was sufficiently mixed to obtain a dilution of the adhesive composition. Solution. Herein, the formulation of the adhesive composition is shown in Table 1. The details of the simple numbers and the like described in Table 1 are as follows. [Polymer (A) and (B)] BA: n-butyl acrylate AA: Acrylic acid HEA: 2-hydroxyethyl acrylate HBA: 4-hydroxybutyl acrylate HEMA: 2-hydroxyethyl methacrylate 29 201209118 [Bridge (c)] • Isocyanate bridging agent TDI: hexamethylene diisocyanate adduct of hexamethylolpropane (manufactured by Sakamoto Polyurethane Co., Ltd., trade name "c〇R〇NATE l") melamine Acid system: cyanuric acid of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Co., Ltd., trade name "CORONATE HXR") • Other bridging agent (epoxy bridging agent) Ν' Ν' Ν' ,Ν'-tetraglycidyl-di-p-phenylenediamine (trade name "TETRAD-X", manufactured by Mitsubishi Gas Chemical Co., Ltd.) [decane coupling agent (D)] ΚΒΜ40 3 :3-propene oxirane trimethoxy矽 ( (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM403") KBE9007: 3-isocyanate propyl triethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBE9007") KBE40 3:3-Acetyloxypropane 3-B Oxydecane (trade name "KBE403" manufactured by Shin-Etsu Chemical Co., Ltd.) Release solution, a release sheet of a polyethylene terephthalate film which is peeled off by a silicone-based release agent (manufactured by LINTEC, SP-PET3811, thickness: 38/zm) The coater was applied to a thickness of 25//m after drying, and then heat-treated at 9 ° C for 1 minute to form an adhesive layer. Next, a polarizing plate composed of a polarizing film having a disc-shaped liquid crystal layer and a polarizing film integrated with a viewing angle expansion film is adhered to the disc-shaped liquid crystal layer at 23 ° C, 50% RH. After curing for 7 days, a polarizing plate having a binder layer of 201209118 was obtained. [Examples 2 to 32 'Comparative Example 7] The types and ratios of the early forms of the adhesive composition, the types of the bridging agent and the stagnation coupling agent, and the addition and the addition of the polymer (A) and the polymer In the same manner as in Example 1, a polarizing plate having an adhesive layer was produced in the same manner as in the modification of (B). [4 Test Example 1] (Adhesion measurement - Reproducibility evaluation) From the polarizing plate having the adhesive layer obtained in the examples or the comparative examples, a sample of a width of 25 long 'long 100_ was cut out, and the peeled sheet was peeled off. Adhesive layer is adhered to the non-test glass (made by Corning Co., Ltd., (6) after the high pressure reactor manufactured by Kurihara Co., Ltd., 〇. 5 hearts, 5 (rc presses 20 knives. After that, 23 c, 50%) After standing under the conditions of RH for 24 hours, the tensile strength (N/25 mm) was measured using a tensile tester (tensil〇n, manufactured by 〇rientec Co., Ltd.) at a peeling speed of 300 nnn/inin and a peeling angle of 18 〇. The conditions other than the measurement were measured in accordance with JIS Z 〇 237: 2〇〇9. Further, the adhesion was measured under the conditions of 23 C and 50% RH for 14 days, and the adhesion was measured in the same manner as described above (adhesive force after 14 days of adhesion; N/25mm). Further, the preferred range of adhesion is 0. lN/25mm or more, less than 25N/25mm. Based on the adhesion after 14 days of adhesion, the evaluation of remanufacturing is performed on the following basis. The results are shown in Table 2. The adhesion after 14 days of adhesion was below 20 N/25 mm: ◎, after 14 days of bonding Viscosity exceeds 20 N / 2 5 mm, less than 25N/25mm: 〇201209118 Adhesion for 14 days after bonding is 25N/25mm or more: χ [Test Example 2] (measurement of gel fraction) In the polarizing plate produced by the polarizing plate having the adhesive layer of the embodiment or the comparative example, a peeling sheet in which one side of the polyethylene terephthalate film is peeled off by a Shishi gum-based release agent is used (LiNteC Co., Ltd.) , SP PET3801, thickness: 38/im), to make an adhesive sheet. Specifically, it consists of a peeling sheet/adhesive layer (thickness: 25# m) obtained by the manufacturing process of the embodiment or the comparative example. On the adhesive layer exposed to the body, the release sheet is laminated on the side of the release-treated surface and laminated, thereby forming an adhesive sheet composed of a structure of a release sheet/adhesive layer/release sheet. The obtained adhesive sheet was cured under conditions of 23 ° C '50% RH for 7 days. Then the 'adhesive sheet was sampled to a size of 8 inches, and the adhesive layer was wrapped in a polyester mesh (mesh size 2) 〇〇), only the quality of the adhesive is weighed with a precision balance. The mass at this time is M1 Using a soxh extractor (Soxh 1 Extractor), the adhesive sample was immersed in ethyl acetate solvent and refluxed for 16 hours. Then the adhesive was taken out and air-dried at a temperature of 23 C and a relative humidity of 50%. 24 hours, further drying in an oven at 80 ° C for 12 hours. After drying, only the quality of the adhesive is weighed with a precision balance. The mass at this time is M2. The gel fraction (%) ' is (M2/Ml )xl〇〇 indicates. The results are shown in Table 2. [Test Example 3] (Measurement of optical properties) An adhesive sheet (for 7 days of curing) similar to the adhesive sheet used for the measurement of the gel fraction was prepared as a measurement sample. For the coating layer of the adhesive sheet, a haze meter (NDH2〇〇〇 manufactured by Nippon Denshoku Industries Co., Ltd.) was used, and the haze value (%) was measured according to JIS K7105 in accordance with 32 201209118, and A, ^ ^ was not obtained. In Table 2. Furthermore, the range of better haze values is 〇~5%. [Test Example 4] (Evaluation of Durability) The polarizing plate having the adhesive layer was obtained by the example or the comparative example, and the cutting device (J ^ SUPER CUTTER » PN1-600)
調整為233mmx309mm夕ρ斗 ϋ々A 之尺寸。將剝離板片剝離,經由露出 之黏著劑層黏貼於盔給诂 y .、,、鹼玻璃(康寧公司製,EAGLE: XG)之 後’以栗原製作所製之离厭后 口 土反應盗’以〇. 5MPa,50°C加壓 20分鐘。 之後’投入下述各耐久條株,+τ j人條仵之% i兄下,於5 〇 〇小時後 以10倍放大鏡進行觀窣。外顴燃 銳祭外觀變化以如下基準。將結果示 於表2。 ◎:於4邊’沒有缺點者 〇:於4邊,由外周端部至〇6關卩上的部位沒有缺點 者 X:在於4邊的至少1邊,由外周端部至0如以上的 部位,有浮起、剝落、發泡、條紋等的G1m以上的黏著 劑外觀異常缺點者 〈对久條件〉 .60°C ’相對濕度90% • 80°C dry 〔試験例5〕(漏光性試験) 實施例或比較例所得具有黏著劑層之偏光板,使用裁 切裝置(荻野製作所公司製SUPER CUTTER,PW_6〇〇)調整 33 201209118 為233mmx309mm之尺寸。將剝離板片剝離,經由露出之黏 著劑層黏貼於無鹼玻璃(康寧公司製,EAGLE XG)之後,以 栗原製作所製高壓反應器以〇. 5MPa,50°C,加壓20分鐘。 再者’上述黏貼’係使具有黏著劑層之偏光板的偏光軸在 無驗玻璃正反面呈正交偏振狀態(偏光軸:z 45。,幺丨35。) 地進行。以此狀態,於8(TC dry環境下放置500小時後, 以如下所示方法評估漏光性。將結果示於表2。 〈漏光性評估〉 使用大塚電子公司製之MCPD-2000,測定圖3所示各 區域之明亮度,將明亮度差△ L*,以式 △ L*=[(b+c + d + e)/4]-a (其中,a、b、c、d及e,分別係事先分別設定於A區 域、β區域、C區域、D區域及E區域之測定點(各區域之 中央部1處)之明亮度。)求得,作為漏光性。△ L*之值越 小表示漏光越少。 在此,上述之重量平均分子量,係使用凝膠滲透層析 (GPC)以如下條件測定(GPC測定)以聚苯乙烯換算之重量平 均分子量。 〈測定條件〉 .GPC測定裝置:T0S0公司製,hlc_8〇2〇 • GPC管柱(以如下順序通過):T〇s〇公司製 TSK guard column HXL-H TSK gel GMHXL (x2)Adjust to the size of 233mmx309mm ρ 斗 ϋ々A. The peeling sheet is peeled off, and the exposed adhesive layer is adhered to the helmet to the helmet, and the alkali glass (EAGLE: XG, manufactured by Corning Co., Ltd.) 5MPa, pressurized at 50 ° C for 20 minutes. After that, the following endurance strains were put in, and the +τ j person's sputum was taken down. After 5 〇 〇 hours, the spectacles were observed with a magnifying glass of 10 times. The appearance of the outer smoldering sharp sacrifice is based on the following criteria. The results are shown in Table 2. ◎: On the 4 sides, there is no defect. On the 4 sides, there is no defect in the part from the outer end to the 〇6. X: at least one side of the four sides, from the outer end to the zero. There are abnormalities in the appearance of G1m or more adhesives such as floating, peeling, foaming, streaking, etc. <Long-term conditions> .60°C 'Relative humidity 90% • 80°C dry [Test Example 5] (Light leakage test) The polarizing plate having the adhesive layer obtained in the examples or the comparative examples was adjusted to a size of 233 mm x 309 mm by using a cutting device (SUPER CUTTER, PW_6, manufactured by Takino Seisakusho Co., Ltd.). The peeled sheet was peeled off, and the exposed adhesive layer was adhered to an alkali-free glass (EAGLE XG, manufactured by Corning Co., Ltd.), and then pressurized in a high-pressure reactor manufactured by Kurihara Co., Ltd. at 50 MPa, 50 ° C for 20 minutes. Further, the above-mentioned "adhesive" is performed by causing the polarizing axis of the polarizing plate having the adhesive layer to be in an orthogonal polarization state (polarizing axis: z 45, 幺丨 35) on the front and back surfaces of the glass. In this state, after leaving it for 8 hours in a TC dry environment, the light leakage was evaluated by the method shown below. The results are shown in Table 2. <Light Leakage Evaluation> Using the MCPD-2000 manufactured by Otsuka Electronics Co., Ltd., Figure 3 was measured. The brightness of each area shown will be Δ L* in brightness, with the formula Δ L* = [(b + c + d + e) / 4] - a (where a, b, c, d and e, The brightness of each of the measurement points (one at the central portion of each region) of the A region, the β region, the C region, the D region, and the E region is set in advance as a light leakage. The value of Δ L* is higher. Here, the weight average molecular weight is measured by gel permeation chromatography (GPC) under the following conditions (GPC measurement) in terms of polystyrene-equivalent weight average molecular weight. <Measurement conditions> GPC measurement Device: T0S0 company, hlc_8〇2〇• GPC pipe column (passed in the following order): TSKs guard column HXL-H TSK gel GMHXL (x2)
TSK gel G2000HXL 34 201209118TSK gel G2000HXL 34 201209118
•測定溶劑:四氣。夫喃 •測定溫度:4 0 °C• Determination of solvent: four gases. Fulan • Measurement temperature: 40 °C
[表1[Table 1
S 聚合物(A) 聚合物(B) Mw(A)/(B) NCO系 架橋劑 [NCO]/[OH] 環氧系 架橋劑 矽烷偶合劑 組成 質 量 部 組成 質 量 部 質量 部 質量 部 實施例1 150萬/5萬 0.8 實施例2 80萬/5萬 0.8 實施例3 100萬/5萬 0.8 實施例4 20 200萬Λ萬 0.8 實施例5 0.5 實施例6 1.0 實施例7 BA/HEA=85/15 150萬/5萬 0.8 0.1 實施例8 5 0.8 實施例9 10 0.8 實施例10 30 0.8 KBM403 實施例11 BA/AA=95/5 100 150萬/1萬 0.8 實施例12 150萬/10萬 0.8 實施例13 150萬/20萬 TDI系 0.8 實施例14 BA/HEA=97/3 2.0 實施例15 BA/HEA=95/5 2.0 實施例16 BA/HEA=90/10 0.8 實施例17 BA/HEA=90/10 0.5 實施例18 BA/HEA=80/20 0.5 實施例19 BA/HEA=80/20 0.3 實施例20 BA/HEA=70/30 0.3 實施例21 BA/HEA=70/30 0.1 KBE9007 實施例22 BA=100 100 0.8 0.2 實施例23 BA/AA=99.5/0.5 100 0.8 KBN403 實施例24 BA/AA=97/3 100 0.8 實施例25 BA/AA=90/10 100 BA/HEA=85/15 20 150萬/5萬 0.5 實施例26 0.8 - KBE403 實施例27 BA/AA=95/5 100 三聚氰 酸系 0.8 實施例28 BA/HBA=85/15 0.8 實施例29 BA/HEMA=85/15 0.8 實施例30 BA/AA=80/20 100 BA/HEA=90/10 0.8 實施例31 BA/HEA=97/3 4.0 實施例32 BA/HEA=95/5 4.0 實施例33 BA/HEA/AA =84/15/1 0.8 KBM403 比較例1 BA/HEA=50/50 TDI系 0.1 比較例2 BA/HEA=90/10 50萬/5萬 0.8 比較例3 BA/AA=95/5 100 BA/HEA=99/1 150萬/5萬 0.8 比較例4 BA/HEA=90/10 150萬/5千 0.8 比較例5 BA/HEA=90/10 150萬/30萬 0.8 比較例6 BA/HEA=90/10 50 0.8 比較例7 BA/HEA=90/10 1 150萬/5萬 0.8 比較例8 BA/HEA/AA =84/15/4 20 0.8 35 201209118 [表2 ] 耐久性(500h) 耐漏光性 黏著力 重製性 凝膠分率 霧度 60°C90% 赃 (AI*) (N/25mm) (%) (%) 贲施例1 ◎ ◎ 0.8 8.0 ◎ 78 0.8 贲施例2 〇 〇 0.9 9.6 〇 53 0.8 實施例3 〇 ◎ 0.9 15.3 〇 70 0.8 實施例4 ◎ ◎ 1.4 10.7 〇 77 0.8 實施例5 〇 ◎ 1.5 5.7 ◎ 71 0.8 實施例6 ◎ ◎ 0.9 12.2 〇 82 0.8 實施例7 ◎ ◎ 0.8 3.4 ◎ 91 0.9 實施例8 ◎ 〇 1.5 10.3 〇 47 0.7 實施例9 ◎ ◎ 2.5 9.2 ◎ 68 0.8 實施例10 〇 ◎ 0.5 4.3 ◎ 79 1.0 實施例11 〇 〇 1.1 6.3 ◎ 64 0.8 實施例12 ◎ ◎ 0.9 9.5 ◎ 77 0.9 實施例13 ◎ ◎ 0.8 12.2 ◎ 76 1.0 實施例14 〇 〇 1.7 8.5 〇 78 3.2 實施例15 〇 〇 1.4 9.1 〇 82 3.8 實施例16 ◎ ◎ 2.9 6.2 ◎ 76 0.8 實施例17 ◎ ◎ 3.6 6.5 ◎ 69 0.8 實施例18 ◎ ◎ 1.5 5.1 ◎ 73 0.8 實施例19 ◎ ◎ 1.6 4.0 ◎ 54 0.7 實施例20 ◎ ◎ 1.2 4.2 ◎ 52 1.9 實施例21 〇 ◎ 1.0 3.7 ◎ 41 1.6 實施例22 〇 ◎ 1.1 2.2 〇 49 1.9 實施例23 〇 ◎ 1.3 3.9 〇 60 1.3 實施例24 〇 ◎ 1.2 4.5 ◎ 69 0.7 實施例25 ◎ ◎ 2.0 14.0 〇 86 0.7 實施例26 〇 ◎ 1.5 5.8 〇 75 0.8 實施例27 〇 〇 1.2 7.1 〇 80 0.8 實施例28 ◎ ◎ 1.5 4.9 〇 80 0.8 實施例29 ◎ ◎ 2.1 6.3 〇 78 0.9 實施例30 ◎ ◎ 2.7 29 X 89 0.7 贲施例31 〇 ◎ 1.6 18.1 X 87 5.2 實施例32 ◎ ◎ 1.4 21.0 X 89 4.8 實施例33 ◎ ◎ 1.1 9.3 〇 81 1.1 比較例1 X X 0.8 2.9 ◎ 52 2.9 比較例2 X X 0.8 14.4 X 48 0.7 比較例3 X X 0.5 13.1 〇 10 0.9 比較例4 X 〇 1.0 6.2 〇 33 0.6 比較例5 X X 1.3 15.1 X 69 1.4 比較例6 X X 1.6 9.3 〇 80 2.0 比較例7 X X 0.4 7.9 〇 11 0.7 比較例8 X ◎ 2.2 12.5 〇 84 1.8 36 201209118 由表 2可知,总· » /, 、、 貫施例所得具有黏著劑層之偏光板,耐 久性並’又有問題’耐漏光性亦優良。再者,關於實施例30, :於第1(甲基)丙烯酸醋聚合物⑴之羧基之含量比較佳的 量補微夕重t性較^。此外,關於實施例3^及實施例 32’異氰_員架橋劑之含量比較佳的量稍微多,故重製 性較差。 關於比較例卜在於第2(甲基)丙烯酸酿聚合物⑻之 紅基之含里過多’故耐久性較佳。關於比較例2,由於第 1(甲基)丙烯酸@旨聚合物(A)之重量平均分子量過小,故对 久性及重製性較差。關於比較例3,在於第2(甲基)丙烯酸 酉旨聚合物⑻之經基之含量過少,故凝膠分率(架橋程度) 低,耐久性較差。關於比較例4,由於第2(甲基)丙烯酸酯 聚合物(B)之重量平均分子量過小,故耐久性較^。關於比 較例5,由於第2(甲基)丙烯酸酯聚合物(B)之重量平均分 子量過大,故耐久性及重製性較差。關於比較例6,由於 第2(甲基)丙烯酸酯聚合物(β)之含量過多,耐久性較差。 關於比較例7,由於第2(曱基)丙烯酸酯聚合物之含量 過少’凝膠分率(架橋程度)較低,而耐久性較差。 [產業上的利用可能性] 本發明之黏著性組合物及黏著劑,適於光學構件,例 如偏光板或位相差板之接著,此外,本發明之黏著板片, 適於偏光板或位相差板等的光學構件用之黏著板片。 【圖式簡單說明】 37 201209118 圖1係關於本發明之第1實施形態之黏著板片之剖面 圖。 圖2係關於本發明之第2實施形態之黏著板片之剖面 圖。 圖3係表示在於附有黏著劑層之偏光板之漏光性試験 之測定區域之圖。 【主要元件符號說明】 ΙΑ、IB~黏者板片, 11~黏著劑層; 12、12a、12b〜離板片; 13~基材。 38S Polymer (A) Polymer (B) Mw (A) / (B) NCO bridging agent [NCO] / [OH] Epoxy bridging agent decane coupling agent composition mass part composition mass part mass part quality part example 1 1.5 million / 50,000 0.8 Example 2 800,000 / 50,000 0.8 Example 3 1 million / 50,000 0.8 Example 4 20 20 million 0.8 Example 5 0.5 Example 6 1.0 Example 7 BA / HEA = 85 /15 1.5 million / 50,000 0.8 0.1 Example 8 5 0.8 Example 9 10 0.8 Example 10 30 0.8 KBM 403 Example 11 BA / AA = 95 / 5 100 1.5 million / 10,000 0.8 Example 12 1.5 million / 100,000 0.8 Example 13 1.5 million/200,000 TDI series 0.8 Example 14 BA/HEA=97/3 2.0 Example 15 BA/HEA=95/5 2.0 Example 16 BA/HEA=90/10 0.8 Example 17 BA/ HEA=90/10 0.5 Example 18 BA/HEA=80/20 0.5 Example 19 BA/HEA=80/20 0.3 Example 20 BA/HEA=70/30 0.3 Example 21 BA/HEA=70/30 0.1 KBE9007 Example 22 BA = 100 100 0.8 0.2 Example 23 BA/AA = 99.5 /0.5 100 0.8 KBN403 Example 24 BA/AA=97/3 100 0.8 Example 25 BA/AA=90/10 100 BA/HEA=85/15 20 1.5 million/5 million 0.5 Example 26 0.8 - KBE403 Example 27 BA/AA=95/5 100 cyanuric acid system 0.8 Example 28 BA/HBA=85/15 0.8 Example 29 BA/HEMA=85/15 0.8 Example 30 BA/AA=80/20 100 BA/ HEA = 90/10 0.8 Example 31 BA/HEA = 97/3 4.0 Example 32 BA/HEA = 95/5 4.0 Example 33 BA/HEA/AA = 84/15/1 0.8 KBM403 Comparative Example 1 BA/HEA =50/50 TDI system 0.1 Comparative Example 2 BA/HEA=90/10 500,000/50,000 0.8 Comparative Example 3 BA/AA=95/5 100 BA/HEA=99/1 1.5 million/5 million 0.8 Comparative Example 4 BA/HEA=90/10 1.5 million/5 thousand 0.8 Comparative Example 5 BA/HEA=90/10 1.5 million/300,000 0.8 Comparative Example 6 BA/HEA=90/10 50 0.8 Comparative Example 7 BA/HEA=90/ 10 1 1.5 million / 50,000 0.8 Comparative Example 8 BA / HEA / AA = 84 / 15 / 4 20 0.8 35 201209118 [Table 2 ] Durability (500h) Light leakage resistance Reproducibility Gel fractional haze 60 °C90% 赃(AI*) (N/25mm) (%) (%) 贲Example 1 ◎ ◎ 0.8 8.0 ◎ 78 0.8 贲 Example 2 〇〇 0.9 9.6 〇 53 0.8 Example 3 〇 ◎ 0.9 15.3 〇 70 0.8 Example 4 ◎ ◎ 1.4 10.7 〇 77 0.8 Example 5 〇 ◎ 1.5 5.7 ◎ 71 0.8 Example 6 ◎ ◎ 0.9 12.2 〇82 0.8 Example 7 ◎ ◎ 0.8 3.4 ◎ 91 0.9 Example 8 ◎ 〇 1.5 10.3 〇 47 0.7 Example 9 ◎ ◎ 2.5 9.2 ◎ 68 0.8 Example 10 〇 ◎ 0.5 4.3 ◎ 79 1.0 Example 11 〇〇 1.1 6.3 ◎ 64 0.8 Example 12 ◎ ◎ 0.9 9.5 ◎ 77 0.9 Example 13 ◎ ◎ 0.8 12.2 ◎ 76 1.0 Example 14 〇〇 1.7 8.5 〇 78 3.2 Example 15 〇〇 1.4 9.1 〇 82 3.8 Example 16 ◎ ◎ 2.9 6.2 ◎ 76 0.8 Example 17 ◎ ◎ 3.6 6.5 ◎ 69 0.8 Example 18 ◎ ◎ 1.5 5.1 ◎ 73 0.8 Example 19 ◎ ◎ 1.6 4.0 ◎ 54 0.7 Example 20 ◎ ◎ 1.2 4.2 ◎ 52 1.9 Example 21 〇 ◎ 1.0 3.7 ◎ 41 1.6 Example 22 〇 ◎ 1.1 2.2 〇 49 1.9 Example 23 〇 ◎ 1.3 3.9 〇 60 1.3 Example 24 〇 ◎ 1.2 4.5 ◎ 69 0.7 Example 25 ◎ ◎ 2.0 14.0 〇 86 0.7 Example 26 〇 ◎ 1.5 5.8 75 0.8 Example 27 〇〇 1.2 7.1 〇 80 0.8 Example 28 ◎ ◎ 1.5 4.9 〇 80 0.8 Example 29 ◎ ◎ 2.1 6.3 〇 78 0.9 Example 30 ◎ ◎ 2.7 29 X 89 0.7 贲 Example 31 〇 ◎ 1.6 18.1 X 87 5.2 Example 32 ◎ ◎ 1.4 21.0 X 89 4.8 Example 33 ◎ ◎ 1.1 9.3 〇 81 1.1 Comparative Example 1 XX 0.8 2.9 ◎ 52 2.9 Comparative Example 2 XX 0.8 14.4 X 48 0.7 Comparative Example 3 XX 0.5 13.1 〇10 0.9 Comparative Example 4 X 〇 1.0 6.2 〇 33 0.6 Comparative Example 5 XX 1.3 15.1 X 69 1.4 Comparative Example 6 XX 1.6 9.3 〇 80 2.0 Comparative Example 7 XX 0.4 7.9 〇11 0.7 Comparative Example 8 X ◎ 2.2 12.5 〇84 1.8 36 201209118 As can be seen from Table 2, the polarizing plate having the adhesive layer obtained by the general example was excellent in durability and 'difficult to suffer from light leakage. Further, in Example 30, the amount of the carboxyl group in the first (meth)acrylic acid vinegar polymer (1) was relatively good. Further, the amount of the isocyanate-based bridging agent of Example 3 and Example 32' is preferably a small amount, so that the reworkability is inferior. The comparative example is that the red base of the second (meth)acrylic polymer (8) is excessively contained, so that the durability is preferable. In Comparative Example 2, since the weight average molecular weight of the first (meth)acrylic acid@polymer (A) was too small, the durability and the reproducibility were inferior. In Comparative Example 3, the content of the base group of the second (meth)acrylic acid-based polymer (8) was too small, so the gel fraction (degree of bridging) was low and the durability was poor. In Comparative Example 4, since the weight average molecular weight of the second (meth) acrylate polymer (B) was too small, the durability was improved. In Comparative Example 5, since the weight average molecular weight of the second (meth) acrylate polymer (B) was too large, durability and reworkability were inferior. In Comparative Example 6, the content of the second (meth) acrylate polymer (β) was too large, and the durability was inferior. In Comparative Example 7, the content of the second (fluorenyl) acrylate polymer was too small, and the gel fraction (degree of bridging) was low, and the durability was inferior. [Industrial Applicability] The adhesive composition and the adhesive of the present invention are suitable for an optical member such as a polarizing plate or a phase difference plate, and further, the adhesive sheet of the present invention is suitable for a polarizing plate or a phase difference An adhesive member for an optical member such as a board. BRIEF DESCRIPTION OF THE DRAWINGS 37 201209118 Fig. 1 is a cross-sectional view showing an adhesive sheet according to a first embodiment of the present invention. Fig. 2 is a cross-sectional view showing an adhesive sheet according to a second embodiment of the present invention. Fig. 3 is a view showing a measurement area of a light leakage test of a polarizing plate with an adhesive layer. [Main component symbol description] ΙΑ, IB~ sticky sheet, 11~ adhesive layer; 12, 12a, 12b~ off-plate; 13~ substrate. 38