201247818 六、發明說明： 【發明所屬之技術領域3 發明領域 本發明係有關於一種黏著劑組成物及使用其之表面保 3蒦膜。更S羊§之，本發明係有關種能夠形成耐被黏物 污染性及透明性優良的黏著層之黏著劑組成物、以及耐被 黏物污染性及透明性優良之表面保護膜。 C先前技術3 發明背景 液晶顯示器面板和電漿顯示器面板等的平面顯示器面 板，係通常透過黏著層而積層偏光板、相位差板、防反射 薄膜等各種光學薄膜。x，在流通、製造過程將防止損傷 或污染設作目的’此種光學薄難貼合有脫模薄膜和表面 保護膜。 例如，在將平面顯示器面板組裝在電視接收機和行動 電^機的⑨體之步驟和將配線安裝在平面顯示器面板之步 驟為了保遵已貼合於平面顯示器面板之偏光板，表面保 護膜係透職著層㈣貼合在偏光板等。 但疋，因為平面顯示器面板的檢查係越過表面保護臈 而進仃’ 4在表硫護膜的料層存在有氣泡時，本來應 達到。格水準的平面顯示^面板，有被判定為未達合格水 準的不良品之可能性。因此，通常黏著劑組成物係經施行 脫泡處理後而塗布在保護膜，但是即便如此處理之後，亦 有在點著層存在氣泡之情形。因此，平面顯示器面板的表 201247818 面保護膜係被要求透明且不存在氣泡而且耐被黏物污染性 優良。除了上述以外’因為平面顯示器面板的表面保護膜 至檢查後出貨為止，係被配置在平面顯示器面板上，所以 即便長期保管後亦有必要能夠容易地被剝離。 另一方面，在專利文獻1 ’係揭示—種黏著劑組成物’ 其係含有：將丙烯酸烷酯單體作為主成分及能夠與異氰酸 酯基反應的乙烯性不飽和單體之共聚合組成物；以及含有 異氰酸酯基之碳二醯亞胺化合物。依照上述專利文獻i，係 s己載刖述能夠與異氰酸酯基反應的乙烯性不飽和單體，以 共聚合組成物作為基準，係由（1)2〜6重量％之（甲基）丙烯酸 羥基烷酯單體、及(11)0.5〜1重量％之含羧基的單體所構成。 上述專利文獻1的黏著劑組成物，因為交聯速度快且具有高 凝集力及強接著力’適合於黏貼玻璃、陶瓷器、地磚等的 無機材質，而且具有凝集力會迅速地開始且在常態的接著 力、耐水性、耐濕性優良，並且在高溫不會產生膨脹和浮 起之耐熱性、以及從被黏物剝離時不會產生殘糊之優點。 先前技術文獻 專利文獻 [專利文獻1]日本專利特許第4067173號說明書 t發明内容3 發明概要 發明欲解決之課題 但是，如在專利文獻1所記載，使用上述黏著劑組成物 所形成之黏著層，因為耐被黏物污染性和黏著層的透明性 201247818 差’上述在專利文獻1所記載之黏著劑組成物，有不適人於 被配置在如上述的平面顯示器面板的偏光板表面之表面保 護膜之問題。 μ 本發明係鑒於上述情形而進行，且將提供一種能夠抑 制被黏物污染性(耐被黏物污染性優良）、黏著層的透明性優 良之黏著劑組成物設作目的。 又，本發明之其他目的，係提供一種金屬腐蝕抑制· 防止性、低溫安定性、高壓釜適合性優良之黏著劑組成物。 本發明之另外目的，係提供一種能夠抑制高壓釜處理 時的發泡且被黏物污染性和黏著層的透明性優良之表面保 護膜，特別是提供一種光學構件用的表面保護膜。 用以解決課題之手段 為了解決上述問題，本發明者等進行精心研究。其結 果，發現使用黏著劑組成物（其使用將含羧基的單體控制在 特定量以下之（甲基）丙烯酸系共聚物)所形成之黏著層，能 夠抑制被黏物污染性（耐被黏物污染性優良）且透明性優 良。基於上述知識而完成了本發明。 亦即，上述目的係藉由提供一種黏著劑組成物來達 成，該黏著劑組成物含有100質量份（甲基）丙烯酸系共聚物 及0.1〜5質量份之碳二醯亞胺系交聯劑，該（甲基）丙烯酸系 共聚物係由〇質量份以上且小於0.5質量份之含羧基的單 體、0.6〜9質量份之含羥基的（甲基）丙烯酸系單體及 99.4〜90.5質量份之（曱基）丙烯酸酯單體所構成，且重量平 均分子量為10萬以上且小於1〇〇萬。 201247818 發明效果 使用本發明的黏著劑組成物而形成之黏著層，对被黏 物污染性、透明性、金屬腐餘抑制.防止性、低溫安定性 及高壓爸適合性優良。因此，本發明的黏著劑組成物作為 各種塑膠㈣等的被黏物之接著係有效的，特別是能夠適 合使用作為液晶顯示器面板和錢顯示器面板等的平面顯 示器面板之表面保護膜的黏著層。 L· ^ 用以實施發明之形態 本發明係有關於一種黏著劑組成物，其含有刚質量份 (甲基）丙稀酸系共聚物及(^質量份之碳二酿亞胺系交聯 劑；該（甲基）丙稀酸系共聚物係由〇質量份以上且小於05質 量狀含的單體、G.6〜9f量份之含經基的（甲基）丙稀 鲅系單體及99.4〜9〇_5質量份之(甲基)丙稀酸酯單體所構 成，重量平均分子量為1〇萬以上、且於100萬。 本發明的特徵在於：使構成（甲基）丙烯酸系絲物之含 緩基的單體的量，相對於該共聚物的單體總量為小於〇.5質 量％。如此’藉由控制含絲的單體的量，不會過度地提 高黏著力而能夠適當地調節成為容易剝離的程度又剝 離時黏著劑組成物係幾乎或完全沒有殘留在被黏物❹又， 藉由上述量，即便長期保管之後，能夠抑制.防止黏著力 過度地上升，能夠容易地從偏光板等的被黏物剝下，此時， 在剝離時黏著劑組成物係幾乎或完全沒有殘留在被黏物。 又，本發明的特徵在於：使用碳二醯亞胺系交聯劑作 201247818 j上述Ha成的（甲基)丙騎系共聚物的交聯劑。藉此， 月匕夠對黏著層提供—種可追隨高壓爸處理時㈣力及溫度 引I的收縮之父聯結構。因此，使用本發明的黏著劑组成 物而形成之黏著層，係即便在高溫.高祕件下（高壓爸處 夺)亦1夠抑制m發泡且耐被黏物污染性優良，又， 透明性亦優良。因此，仙將本發_黏著劑組成物而形 ^黏著層配置在保護_成之表面减膜，因為即便在 :壓· 1¾溫條件下錢乎不會產生發泡，即便使用作為液 B曰顯不$面板和電聚顯示器面板等的平面顯示器面板（例 如偏光板)之表面保護膜，亦幾乎或完全不會對該等的品質 檢查時之判定造成影響。除了上述優點以外，使用本發明 的黏著劑組成物而形成之黏著層，係具有適當的黏著力和 對基材的密著性且金屬腐蝕耐蝕性和低溫安定性亦優良。 又，在本說明書’所謂「耐被黏物污染性優良」或「優良 的耐被黏物污染性」，係意味著將具有使用本發明的黏著劑 組成物而形成的黏著層之表面保護膜，從被黏物剝下之前 後的接觸角的變化為3。以下，具體上，係使用在下述實施 例所記載之評價方法。又，在本說明書，所謂「透明性優 良J或「優良的透明性」係意味著在使用本發明的黏著劑 組成物而形成的黏著層，目視係無法觀察到白濁，具體上， 係依照在下述實施例所記載之評價方法。又，在本說明書， 所謂「金屬腐蝕抑制.防止性」、「黏著力」、「對基材的密 著性J、「被黏物污染性（耐被黏物污染性）」、「低温安定性」、 「透明性」及「高溫·高壓條件下（高壓釜處理時)之發泡存 201247818 在(在本說明書係稱為「高壓爸適合性」）係依照在下述實施 例所S己載之方法而進行評價。 因此’本發明的黏著劑組成物對於各種塑膠薄膜等的 被黏物之接㈣有效的，特別是適合個作躲晶顯示器 面板牙電A顯7F H面板等的平面顯示^面板⑽如偏光板) 的表面保護膜之黏著層。 以下，說明本發明的實施形態。又，在本說明書，（曱 基）丙烯酸等包含（甲基)之化合物，係意味著名稱中有「甲 基」的化合物及不具有「甲基」的化合物之總稱 。因此， 所明（甲基)丙稀基」係、包含丙稀基及曱基丙烯基雙方，「所 口月（甲基)丙稀酸醋」係包含丙稀酸酷及曱基丙稀酸醋雙方， 所謂「（甲基）丙贼」係包含丙騎及甲基丙烯酸雙方。 (A)(曱基）丙烯酸系共聚物 構成本發明的黏著劑組成物之（甲基）丙賴系共聚物 係將㈣〇質量份以上、小於咐量份之含羧基的單體、 (a-2)0.6〜9質量份之含經基的（甲基）丙稀酸系單體及 (a-3)99.4〜90.5質量份之（曱基）丙烯酸醋單體設作必要成分 而含有。 又’本發明之（甲基）丙稀酸系共聚物的重量平均分子量 (MW)係1G萬以上、小於1⑻萬H90萬為佳。在此，^ 量平均分子量係小於10萬時，形成黏著層係困難的，即便 能夠形成黏著層’黏著層的黏著力和對基材(被黏物)的 性係非常差。另-方面，重量平均分子量為⑽萬以上時， 製造步驟變為複雜，在成本面係不利。又，黏著層的黏著 8 201247818 力和對基材(被制_密紐過度上升，在㈣材剝離之 後著層的-部分有殘留在基材之情形。相反地，此種 =子量範圍時’能夠簡便μ短時間價廉地製造（曱基)丙稀 s夂系共聚物。又’因為此種分子量範圍的（甲基）丙稀酸系共 聚物的溶液係黏度低，塗布在保護膜等的基材時，能夠容 易且簡便地進行塗布，能夠容易地抑難著層的膜厚度。 (a-l)含羧基的單體 & 本發明之含躲料體，係在分子巾至少具#1健基 之不飽和單體。料含麟的單體之具體_，係不被以下 限制’可舉出（甲基）丙稀酸 '順丁稀二酸、順丁稀二_、 反丁烯二酸、反丁烯二酸酐、巴豆酸、伊康酸、伊康酸酐、 肉且蔻油酸酯（myristoleic acid)、棕櫚油酸及油酸等。兮等 可單獨使用亦可組合2種以上而使用。該尊 而一 Λ寻之中，以（曱基） 内烯I、順丁烯二酸、順丁烯二酸酐、反丁烯二萨反丁 烯二酸酐、巴豆酸、伊康酸、伊康酸酐為佳 ^主U(甲基）丙稀 馱為更佳。上述含羧基的單體係可單獨使用亦可以2種以上 的混合物之形態使用。 在本發明，含叛基的單體之使用量，係相斜於總單體 的合計量為100質量份，為0質量份以上、小於〇5質旦^ 在此’含羧基的單體之量為0.5質量份以上時，龜著為 太高致使難以從偏光板等的基材(被黏物）剝下，又 .、'、 之後’黏著層會殘留在基材上。 > (a-2)含羥基的（甲基）丙烯酸系單體 在本發明之含羥基的（甲基）丙烯酸系單體，係在八子中 201247818 具有羥基之丙烯酸系單體。作為此種含羥基的（甲基）丙烯酸 系單體之具體例，係不被以下限制，可舉出（甲基）丙烯酸2_ 羥基乙酯、（甲基）丙烯酸4-羥基丁酯、16_己二醇一（甲基） 丙烯酸酯、新戊四醇三（甲基）丙烯酸酯、二新戊四醇五（甲 基）丙烯酸酯、新戊二醇一（甲基）丙烯酸酯、三羥甲基丙烷 二（甲基）丙烯酸酯、三羥甲基乙烷二（甲基）丙烯酸酯、（甲基） 丙烯酸2-羥基丙酯、（甲基）丙烯酸2-羥基丁酯、（甲基）丙烯 酸2-羥基-3-苯氧基苯酯、（曱基）丙烯酸4-羥基環己酯、2-羥基乙基（曱基）丙烯醯胺、環己烷二甲醇一丙烯酸酯等，而 且，可舉出藉由烷基環氧丙基醚、烯丙基環氧丙基醚、（甲 基）丙烯酸環氧丙酯等含有環氧丙基的化合物與（曱基）丙烯 酸加成反應所得到之化合物等。該等係以（甲基）丙烯酸2-羥基乙酯、（曱基）丙烯酸4-羥基丁酯、2-羥基乙基（甲基）丙 烯醯胺、環己烷二曱醇一丙烯酸酯為佳，以（曱基）丙烯酸2-羥基乙酯、（甲基）丙烯酸4-羥基丁酯、2-羥基乙基（甲基）丙 烯醯胺為更佳，以丙烯酸2-羥基乙酯、丙烯酸4-羥基丁酯、 2-羥基乙基丙烯醯胺為特佳。上述含羥基的（甲基）丙烯酸系 單體係可單獨使用亦可以2種以上的混合物之形態使用。 在本發明，含羥基的（曱基）丙烯酸系單體之使用量係相 對於總單體之合計量100質量份，為0.6〜9質量份。在此， 含羥基的（甲基）丙烯酸系單體的使用量小於0.6質量份時’ 含羥基的（曱基）丙烯酸系單體之羥基與碳二醯亞胺系交聯 劑反應而得到的交聯點太少，而無法達成充分的黏著力。 又，相反地，含羥基的（甲基）丙烯酸系單體的使用量大於9 10 201247818 ^量份時，含減的（f基幽㈣、單體之減與碳二酿亞 胺系交聯劑反應而得到的交聯點變為太多，致使黏著力變 大，又，黏著層無法發揮充分的透明性。 (a-3)(甲基）丙烯酸酯單體 在本發明之（曱基）丙烯_單體係在分子中不具有幾 基之（曱基)丙稀㈣Sg。作為此種（甲基)丙烯酸醋單體之具 體例，係不被以下限制’可舉出（甲基)丙騎甲@旨、（甲基) 丙稀酸乙醋、（曱基)丙烯酸丙酷、（甲基)丙稀酸異丙醋、（甲 基）丙稀酸正丁醋、（甲基）丙稀酸異(曱基）丙稀酸第三 丁醋、（甲基)丙稀酸異戊醋'(甲基)丙稀酸正己醋、（甲基) 丙烯酸正庚醋'(甲基)丙烯酸正辛酿、(甲基)丙烯酸第三辛 醋、（甲基）丙稀酸2-乙基己醋、（甲基）丙稀酸癸醋、（甲基) 丙稀酸異癸醋、（曱基）丙烯酸十三醋、（甲基）丙稀酸硬脂 醋、（曱基）丙稀酸異硬月旨醋、（曱基）丙稀酸苯醋、（甲基）丙 稀酸节醋、（曱基)丙烯酸十：自旨、（甲基)丙稀酸四氮糖醋、 (甲基）丙烯酸環己酯 ' (曱基）丙烯酸4_正丁基環己酯、2_乙 基己基二甘醇（甲基）丙烯酸酯、（曱基）丙烯酸丁氧基乙酯、 (甲基）丙烯酸丁氧基甲酯、（甲基）丙烯酸3_曱氧基丁酯、（曱 基）丙烯酸2-(2-甲氧基乙氧基）乙酯、（甲基）丙烯酸2_(2_丁氧 基乙氧基）乙酯、（曱基）丙烯酸4-丁基笨酯、（曱基）丙烯酸笨 酯、（曱基）丙烯酸2,4,5-四甲基苯酯、（曱基）丙烯酸苯氧基 甲酯、（甲基）丙烯酸苯氧基乙酯、聚環氧乙烷一烷基醚（甲 基）丙烯酸酯、聚環氧丙烷一烷基醚（曱基）丙烯酸酯、（甲基) 丙烯酸三氟乙酯、（甲基）丙烯酸十五氟羥基乙酯、（曱基）丙 11 201247818 烯酸2-氯乙酯、（曱基）丙烯酸2,3_二溴丙酯、（甲基）丙烯酸 二溴苯酯等。上述（甲基）丙烯酸酯單體之中，以甲基丙烯酸 甲酉曰、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸 異丁酯、甲基丙烯酸第三丁酯、曱基丙烯酸2_乙基己酯為 佳，以丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸 2-乙基己酯為更佳，以丙烯酸曱酯、丙稀酸正丁酯、丙稀 酸2-乙基己酯為特佳。又，上述（甲基）丙烯酸酯單體係可單 獨使用亦可以2種以上的混合物之形態使用。 在本發明，（曱基）丙烯酸酯系單體的使用量係相對於總 單體之合計量100質量份，為99.4〜90·5質量份。 (a-4)其他單體 本發明之（曱基）丙烯酸系共聚物，係能夠將上述(&_υ 含羧基的單體、（a-2)含羥基的（甲基）丙烯酸系單體及 (a-3)(甲基）丙烯酸酯單體設作必要成分而進行共聚合來製 造’以只有將上述(a-1)、（a-2)及(a-3)設作單體成分而進行 共聚合來製造為佳，亦即本發明之（甲基）丙烯酸共聚物係以 只有由源自（a-Ι)含羧基的單體之構成單元、源自（a_2)含羥 基的（甲基）丙烯酸系單體之構成單元及源自（a-3)(曱基）丙 烯酸酯單體之構成單元所構成為佳。又，此時，上述(a_l) 含羧基的單體、（a-2)含羥基的（甲基）丙烯酸系單體及 (a-3)(甲基）丙烯酸酯單體之合計量為1〇〇質量份。 但是，本發明之（甲基）丙烯酸系單體係除了上述源自 (a-l)~(a-3)的構成單元以外，亦可具有源自其他單體的構成 0〇 一 單70。 12 201247818 在此’作為此夠使用之其他單體，係只要能夠與 (a-l)~(a-3)的單體共聚合，沒有特別限制。具體上可舉出（曱 基）丙烯酸環氧丙酯、（甲基）丙烯酸甲基環氧丙酯等具有環 氧基之丙烯酸系單體；（甲基）丙烯酸二曱胺基乙酯、（甲基） 丙烯酸二乙胺基乙酯、（曱基）丙烯酸N-第三丁基胺基乙酯、 (曱基）丙烯酸氣化甲基丙稀醯氧基乙基三甲録等具有胺基 之丙烯酸系單體；（曱基）丙烯醯胺、N-羥甲基（甲基）丙烯醯 胺、N-甲氧基甲基（曱基）丙烯醯胺、N，N-亞甲雙（曱基）丙烯 醯胺等具有醯胺基之丙烯酸系單體；磷酸2-甲基丙稀醯氧 基乙基二苯酯（甲基）丙烯酸酯、磷酸三甲基丙烯醯氧基乙酯 (曱基）丙烯酸酯、構酸三丙烯醯氧基乙酯（曱基）丙烯酸酯等 具有填酸基之丙烯酸系單體；（曱基）丙稀酸續酸基丙基納、 (甲基）丙稀酸2-績酸基乙基納、2-丙稀酿胺_2_甲基丙續酸納 等具有磺酸基之丙烯酸系單體；胺甲酸酯（甲基）丙烯酸酯等 具有胺曱酸酯基之丙烯酸系單體；（曱基）丙烯酸對第三丁基 苯酯、（甲基）丙烯酸鄰聯苯酯等具有笨基之丙烯酸系乙烯基 單體；（甲基）丙烯酸2-乙醯基乙醯氧基乙酯、乙烯基三曱氧 基矽烷、乙烯基三乙氧基矽烷、乙烯基參（yS_甲氧基乙基) 石夕烷、乙烯基三乙醯基矽烷、甲基丙烯醯氧基丙基三甲氧 基石夕烷等具有矽烷基之乙烯基單體；苯乙稀、氯苯乙烯、 曱基苯乙烯、乙烯基曱苯、氯乙烯、乙酸乙烯酯、丙酸 乙烯酯、丙烯腈、乙烯基〇比啶等。上述其他的單體之中， 以（甲基）丙烯醯胺、（甲基）丙烯酸環氧丙酯、（甲基）丙烯酸 二甲胺基乙酯、（曱基）丙烯酸2-乙醯基乙醯氧基乙酯為佳， 13 201247818 以丙烯醯胺、（甲基）丙烯酸二曱胺基乙酯、（曱基）丙烯酸2-乙醯基乙醯氧基乙酯為更佳。又，上述其他的單體係可單 獨使用亦可以2種以上的混合物之形態使用。 又，使用上述其他單體時之其他單體的使用量，係只 要不阻礙上述(a-l)〜(a-3)的單體之特性的程度之量，沒有特 別限制。上述其他單體的使用量係相對於(a-l)〜(a-3)的單體 之合計量100質量份，以〇.1~1〇質量份為佳，以0.2〜5質量份 為較佳，以0.3〜2質量份為更佳。 本發明之（曱基）丙烯酸系共聚物的製造方法，係沒有特 別限制，能夠使用下列眾所周知的方法：使用聚合起始劑 之溶液聚合法、乳化聚合法、懸浮聚合法、逆相懸浮聚合 法、薄膜聚合法、喷霧聚合法等。作為聚合控制的方法， 可舉出絕熱聚合法、溫度控制聚合法、等溫聚合法等。又， 除了利用聚合起始劑來使聚合開始方法以外，亦能夠採用 照射放射線、電子射線、紫外線等來使聚合開始之方法。 其中，因為容易調節分子量且不純物亦較少，以使用聚合 起始劑之溶液聚合法為佳。例能夠藉由使用乙酸乙酯、甲 苯、曱基乙基酮等作為溶劑，且相對於單體的合計量100質 量份，以添加0.01~0.50質量份之聚合起始劑為佳，而且在 氮氣環境下例如於反應溫度60〜90°C使其反應3~10小時來 得到。作為前述聚合起始劑，例如可舉出偶氮雙異丁腈 (AIBN)、2,2’-偶氮雙(2-甲基異丁腈）、偶氮雙氰基戊酸等的 偶氮化合物；過氧化三甲基乙酸第三丁酯、過氧化苯曱酸 第三丁酯、過氧化2-乙基己酸第三丁酯、過氧化二-第三丁 14 201247818 酉旨、異丙苯過氧化氫、過氧化苯甲醯、第三丁基過氧化氫 等的有機過氧化物；過氧化氫、過硫酸錄、過硫酸钟、過 硫酸納等的無機過氧化物。該等係可單獨使用亦可併用2種 以上。 如上述藉由將上述（a-Ι)〜(a_3)的單體及按照必要之 (a_4)的其他單體共聚合而得到之（甲基)丙烯酸系共聚物，其 重里平均刀子里（Mw)係10萬以上、小於1〇〇萬，以2〇~9〇萬 為佳。在此’重量平均分子量小於10萬時，難以形成黏著 層’即便關形絲著層，料層_著力和對基材(被黏 物）的密者性係非常差。另一方面，重量平均分子量為1〇〇 萬以上時I程變為複雜’且在成本方面不利。又，黏著 層的黏著力和對基材(被黏物）的密著性過度上升，在從基材 剝離之後’黏著層的—部分有殘留在基材之情形。相反地， 此種分子量範圍時，能夠簡便且以短時間價廉地製造（甲基) 丙稀酸系共聚物^又，因為此種分子量範圍的（甲基)丙烯酸 系共聚物的溶液係黏度低，塗布在保護膜等的基材時，能 夠4易且簡便地進行塗布’ χ ’能夠容易地抑制黏著層的 犋厚度。而且，在本發明，重量平均分子量係採用在實施 例記載的方法所測定之換算聚笨乙稀之值。 又，本發明的黏著劑組成物係可單獨含有或是以2種以 上的混合物的方式含有上述（甲基）丙稀酸系共聚物。 (Β)碳二醯亞胺系交聯劑 除了含有上述（甲基）丙烯酸系共聚物以外，本發明的黏 考劑組成物係含有碳二醯亞«交Μ。碳二醯亞胺系交 15 201247818 聯劑係與上述的（曱基）丙烯酸系共聚物之單體中的羥基或 缓基、特別是經基反應.鍵結來形成交聯結構。 在本發明所使用之碳二醯亞胺系交聯劑係沒有特別限 制。具體上，例如在分子内具有2個以上的碳二醯亞胺基 (_N=C=N-)之化合物係能夠適合使用’且能夠使用眾所周知 的聚碳二酿亞胺。 又，作為碳二醯亞胺化合物，亦能夠使用在碳二醯亞 胺化催化劑的存在下使二異氰酸酯脫碳酸縮合反應所生成 之高分子量聚碳二酿亞胺。 作為此種化合物，可舉出使以下的二異氰酸醋脫碳酸 縮合反應而成之聚碳二醯亞胺。 作為二異氰酸酯，能夠使用4,4’-二苯基曱烷二異氰酸 酯、3,3’-二甲氧基-4,4’-二苯基甲烷二異氰酸酯、3,3’-二甲 基-4,4’-二苯基曱烷二異氰酸酯、4,4’-二苯基醚二異氰酸 酯、3,3’-二曱基_4,4，，二苯基醚二異氰酸酯、2,4-甲苯二異 氰酸酯、2,6-曱苯二異氰酸酯、1-甲氧基苯基2,4-二異氰酸 酯、異佛爾酮二異氰酸酯、4,4’-二環己基甲烷二異氰酸酯、 四曱基笨二甲基二異氰酸酯之中的一種、或該等的混合物。 作為碳二醯亞胺化催化劑，能夠利用1-苯基-2-環磷稀 -1-氧化物、3-甲基-2-環填烯-1-氧化物、1-乙基-3-曱基_2-環磷烯-1-氧化物、1-乙基-2-環磷烯_1_氧化物或該等的3·環 磷烯異構物等的環磷烯氧化物。 又，本發明之碳二醯亞胺係可以合成亦可以使用市售 品。作為此種高分子量聚碳二醯亞胺，不被以下限制，例 16 201247818 如可舉出日清紡CHEMICAL股份公司製的CARBODILITE (註冊商標）系列，其中CARBODILITE(註冊商標）V-01、 V-03、V-05、V-07、V-09係與有機溶劑的相溶性優良，乃 是較佳。 在本發明，碳二醯亞胺系交聯劑的調配量係相對於100 質量份之（曱基）丙烯酸系共聚物，為〇.1~5質量份。在此， (Β)碳二醯亞胺系交聯劑的調配量小於0.1質量份時，無法對 黏著層賦予充分的交聯結構，而無法達成充分的黏著力。 又，碳二醯亞胺系交聯劑的調配量太少時，耐被黏物污染 性和透明性差，又，在高溫·高壓條件下（高壓釜處理時) 產生發泡。相反地，（Β)碳二醯亞胺系交聯劑的調配量超過 5質量份時，黏著層的透明性會過度地低落。 又，本發明的黏著劑組成物係可單獨或是以2種以上的 混合物的方式含有上述碳二醯亞胺系交聯劑。 (C)異氰酸酯系交聯劑 本發明的黏著劑組成物係必須含有上述（曱基）丙烯酸 系共聚物及碳二醯亞胺系交聯劑，但是亦可更含有異氰酸 酯系交聯劑。異氰酸酯系交聯劑係與構成上述（甲基）丙烯酸 系共聚物之單體的經基或竣基、特別是經基反應·鍵結來 形成交聯結構。藉由更調配異氰酸酯系交聯劑，能夠提升 使用黏著劑組成物而形成之黏著層的耐久性。 在本發明所使用之異氰酸酯系交聯劑係沒有特別限 制，能夠使用眾所周知之異氰酸酯系交聯劑。具體上，例 如可舉出異氰酸三烯丙酯、二聚酸二異氰酸酯、2,4-曱苯二 17 201247818 異氰酸酯（2,4-TDI)、2,6-甲笨二異氰酸酯（2,6-TDI)、4,4，-二苯基曱烧二異氰酸酯(4,4’-MDI)、2,4，-二笨基曱院二異氰 酸酯（2,4’-MDI)、1，4-苯二異氰酸酯、二曱苯二異氰酸酯 (XDI)、四甲基二甲苯二異氰酸酯（TMXDI)、曱苯胺二異氰 酸酯（TODI)、1，5-萘二異氰酸酯（NDI)等的芳香族二異氰酸 酯類；六亞甲基二異氰酸酯（HDI)、三曱基六亞曱基二異氰 酸酯（TMHDI)、離胺酸二異氰酸酯、降莰烷二異氰酸酯 (NBDI)等的脂肪族二異氰酸酯類；反式環己炫_M_二異氰 酸酯、異佛爾酮二異氰酸酯（IPDI)、H6-XDI(氫化XDI)、 H12-MDI(氫化MDI)等的脂環式二異氰酸酯類；上述二異氰 酸酯的碳二醯亞胺改性二異氰酸酯類；或是該等的異三聚 氛酸S旨改性·一異氰酸S旨類等。又，上述異氮酸醋化合物與 三經甲基丙炫•等多元醇化合物的加成體、該等異氰酸酯化 合物的縮二脲體和異三聚氰酸酯體亦適合使用。 上述異氰酸酯系交聯劑係可以合成亦可以使用市售 品。作為異氰酸酯系交聯劑的市售品，例如可舉出 CORONATE(註冊商標）L、CORONATE(註冊商標）HL、 CORONATE(註冊商標)HX、CORONATE(註冊商標）2030、 CORONATE(註冊商標）2031(以上、日本POLYURETHANE 工業股份公司製）、ΤΑΚΕΝΑΤΕ(註冊商標）D-102、 TAKEN ATE(註冊商標）D-11 ON、TAKENATE(註冊商 標）D-200、TAKENATE(註冊商標）D-202(以上'三井化學 POLYURETHANE 股份公司製）、DURANATE(商 標)24A-100、DURANATE(商標)TPA-100、DURANATE(商 18 201247818 標)TKA-100、DURANATE(商標)P301-75E、DURANATE(商 標)E402-90T、DURANATE(商標）E405-80T、DURANATE(商 標）TSE-100、DURANATE(商標）D-101、DURANATE(商 標)D-201(以上、旭化成CHEMICALS股份公司製）等。 該等異氰酸酯系交聯劑中，係以CORONATE(註冊商 標）L、CORONATE(註冊商標）HL、CORO NATE(註冊商 標)HX、ΤΑΚΕΝΑΤΕ(註冊商標)D- 110N、DURANATE(商 標）24A-100為佳，以CORONATE(註冊商標）L、 CORONATE(註冊商標)HX、ΤΑΚΕΝΑΤΕ(註冊商標)D-110N 為更佳，以CORO NATE(註冊商標)L及CORO ΝΑΤΕ(註冊商 標)ΗΧ為特佳。 在本發明’異氰酸酯系交聯劑的調配量係沒有特別限 制’能夠考慮上述（甲基）丙烯酸系共聚物的組成、上述碳二 醯亞胺系交聯劑的種類和調配量等而適當地選擇。調配異 氰酸酯系交聯劑時之異氰酸酯系交聯劑的調配量，係相對 於100質量份之（甲基）丙烯酸系共聚物為0.05〜3質量份，以 〇.1~2質量份為較佳。如此的調配量時，能夠提升使用黏著 劑組成物而形成之黏著層的耐久性。 而且’本發明的黏著劑組成物係可單獨含有或是以2種 以上的混合物的方式含有上述異氰酸酯系交聯劑。 在本發明，藉由上述碳二醯亞胺系交聯劑及必要時之 上述異氰酸酯系交聯劑，能夠與構成上述（甲基）丙烯酸系共 聚物之單體的·基、特別是祕反應.鍵結來形成 交聯結構，此時的交聯度係沒有特別限制。考慮黏著層形 19 201247818 成時之黏著層的黏著力、對基材之密著性、而推黏物污染 !·生低恤女疋f生、透明性、在局溫高壓條件下的發泡（高 壓爸適合性）及強度等，黏著劑組成物的㈣分率係以 8〇〜職為佳’㈣〜麵為更佳。在本制書，「凝膠分 率」係表利甲基)丙騎系共聚物料聯度之指標 ，且係依 照在下述實施例所記載之方法所測定的值。 (D)其他的調配成分 除了含有上述(C)異氰酸醋系交聯劑以外、或是代替上 述(C)異級“㈣劑，本發_料劑組祕亦可含有 如硬化促進劑、離子性液體、㈣、無機填料、軟化劑、 抗氧化劑、防老劑、安定劑、黏著賦予樹脂、改質樹脂（多 元醇樹脂、酚樹脂、丙烯酸樹脂、聚酯樹脂、聚烯烴樹脂、 環氧知、％<氧化聚丁二稀樹脂等）、調平劑、消泡劑、可 塑劑、染料、顏料(著色顏料、填充顏料等）、處理劑、紫外 線隔離劑、螢光增白劑、分散劑、熱安定劑、光安定劑、 1外線吸收劑、抗靜電劑、滑劑及溶劑之添加劑。該等之 中’作為硬化促進劑，例如可舉出二月桂酸二丁基錫、 JCS-50(城北化學工業公司製）' format TK-1 (三井化學 POLYURETHANE公司製）等。 又，作為離子性液體，例如可舉出具有鱗離子、。比0定 鏽離子、吡咯啶鏽離子、咪唑鑌離子、胍鏽離子、銨離子、 異腺錄離子（isouronium ion)、硫腺鐵離子（thiuronium ion)、 哌咬鏽離子、°比唑鏽離子、锍離子等的陽離子成分、及作 為陰離子成分可舉出鹵素離子、硝酸離子、硫酸離子、鱗 20 201247818 酸離子、聽_子、絲_子、魏贿離子、亞硫 酸離子錄子、^魏齡子、甲酸離子、 草酸離子、乙酸離子、=7^ 一氟乙馱離子、烷基磺酸離子等的 陰離子成分之物質。201247818 VI. Description of the Invention: [Technical Field 3 of the Invention] Field of the Invention The present invention relates to an adhesive composition and a surface-protecting film using the same. Further, the present invention relates to an adhesive composition capable of forming an adhesive layer excellent in adhesion resistance and transparency, and a surface protective film excellent in adhesion resistance and transparency. C. Prior Art 3 Background of the Invention A flat display panel such as a liquid crystal display panel or a plasma display panel is generally provided with various optical films such as a polarizing plate, a phase difference plate, and an antireflection film through an adhesive layer. x, in the circulation and manufacturing process, it is intended to prevent damage or contamination. This type of optical thin film is difficult to bond with a release film and a surface protective film. For example, in the step of assembling the flat panel display panel to the body of the television receiver and the mobile computer, and the step of mounting the wiring on the flat panel display panel, in order to ensure that the polarizing plate has been attached to the flat panel display panel, the surface protective film system The top layer (4) is attached to the polarizing plate. However, since the inspection of the flat panel display panel is over the surface protection 臈, it is supposed to be achieved when there is a bubble in the layer of the sulphur film. The level of the flat panel display panel has the possibility of being judged as a defective product that does not meet the qualified level. Therefore, usually, the adhesive composition is applied to the protective film after being subjected to a defoaming treatment, but even after such treatment, there is a case where bubbles are present in the layer. Therefore, the surface of the flat panel display panel 201247818 is required to be transparent, free of bubbles, and excellent in contamination resistance. In addition to the above, since the surface protective film of the flat display panel is placed on the flat display panel until it is shipped after inspection, it is necessary to be easily peeled off even after long-term storage. On the other hand, Patent Document 1 ' discloses an adhesive composition' which comprises a copolymerization composition comprising an alkyl acrylate monomer as a main component and an ethylenically unsaturated monomer capable of reacting with an isocyanate group; And a carbodiimide compound containing an isocyanate group. According to the above Patent Document i, the ethylenically unsaturated monomer capable of reacting with an isocyanate group is described as a reference, and the (1) 2 to 6 wt% of (meth)acrylic acid hydroxyl group is used as a reference. The alkyl ester monomer and (11) are 0.5 to 1% by weight of a carboxyl group-containing monomer. The adhesive composition of the above-mentioned Patent Document 1 has a high cross-linking speed and a high cohesive force and a strong adhesive force, which is suitable for an inorganic material which adheres to glass, ceramics, floor tiles, etc., and has a cohesive force which starts rapidly and is in a normal state. It has excellent adhesion, water resistance, and moisture resistance, and does not cause heat resistance of expansion and floating at high temperatures, and has no advantage of causing residual paste when peeled off from the adherend. [Patent Document 1] Japanese Patent Laid-Open No. 4,067,173, the disclosure of the present invention, the third aspect of the invention, and the object of the invention. However, as described in Patent Document 1, the adhesive layer formed by the above-mentioned adhesive composition is used. Because of the adhesion resistance to the adherend and the transparency of the adhesive layer, the adhesive composition described in Patent Document 1 is unsuitable for the surface protective film disposed on the surface of the polarizing plate of the flat display panel as described above. The problem. The present invention has been made in view of the above circumstances, and an adhesive composition capable of suppressing the contamination of the adherend (excellent resistance to adherend) and having excellent transparency of the adhesive layer is provided. Further, another object of the present invention is to provide an adhesive composition which is excellent in metal corrosion suppression and prevention, low-temperature stability, and autoclave suitability. Another object of the present invention is to provide a surface protective film which is capable of suppressing foaming at the time of autoclave treatment and which is excellent in viscosity of an adherend and transparency of an adhesive layer, and more particularly to provide a surface protective film for an optical member. Means for Solving the Problems In order to solve the above problems, the inventors of the present invention have conducted intensive studies. As a result, it has been found that the use of an adhesive composition (which uses a (meth)acrylic copolymer having a carboxyl group-containing monomer controlled to a specific amount or less) can suppress the contamination of the adherend (resistance to stickiness) It has excellent contamination properties and is excellent in transparency. The present invention has been completed based on the above knowledge. That is, the above object is attained by providing an adhesive composition containing 100 parts by mass of a (meth)acrylic copolymer and 0.1 to 5 parts by mass of a carbodiimide crosslinking agent. The (meth)acrylic copolymer is a carboxyl group-containing monomer having a mass of not less than 0.5 part by mass, 0.6 to 9 parts by mass of a hydroxyl group-containing (meth)acrylic monomer, and a mass of 99.4 to 90.5. The composition is a (mercapto) acrylate monomer, and has a weight average molecular weight of 100,000 or more and less than 1,000,000. 201247818 EFFECT OF THE INVENTION The adhesive layer formed by using the adhesive composition of the present invention is excellent in adhesion resistance, transparency, and metal corrosion resistance, prevention property, low-temperature stability, and high-pressure dad suitability. Therefore, the adhesive composition of the present invention is effective as a binder of various plastics (four) and the like, and in particular, it can be suitably used as an adhesive layer of a surface protective film of a flat display panel such as a liquid crystal display panel or a money display panel. The present invention relates to an adhesive composition comprising a rigid component (meth)acrylic acid copolymer and (a part by mass of a carbon di-ruthenium-based crosslinking agent). The (meth)acrylic acid-based copolymer is a monomer containing a mercapto group or more and a content of less than 05 mass, and a G.6 to 9f-containing (meth)acrylic monomer. And 99.4 to 9 〇 5 parts by mass of a (meth) acrylate monomer, the weight average molecular weight is 100,000 or more, and is 1,000,000. The present invention is characterized in that the composition (meth)acrylic acid is used. The amount of the slow-containing monomer of the filament is less than 0.5% by mass relative to the total amount of the monomer of the copolymer. Thus, by controlling the amount of the monomer containing the silk, the adhesion is not excessively increased. The force can be appropriately adjusted to the extent that it is easily peeled off, and the adhesive composition is almost or completely left in the adherend when peeled off. With the above amount, even after long-term storage, it can be suppressed. The adhesion is prevented from rising excessively. , can be easily peeled off from the adherend such as a polarizing plate, at this time, sticking at the time of peeling The agent composition has little or no residue in the adherend. Further, the present invention is characterized in that a carbodiimide-based crosslinking agent is used as the above-mentioned Ha-formed (meth)-propene copolymer of 201247818 j. The cross-linking agent can thereby provide the adhesive layer of the adhesive layer which can follow the contraction of the high-pressure dad (four) force and the temperature index I. Therefore, the adhesive layer formed by using the adhesive composition of the invention Even in the high temperature. High secrets (high pressure dad), 1 is enough to suppress m foaming and is excellent in adhesion to sticky substances, and also excellent in transparency. Therefore, the essence of the hair _ adhesive composition The shape of the adhesive layer is placed on the surface of the protective film to reduce the film, because even under the pressure of 13⁄4, the money does not cause foaming, even if it is used as a liquid B, the panel and the electro-polymer display panel are not used. The surface protective film of the flat display panel (for example, a polarizing plate) also has little or no influence on the judgment of the quality inspection. In addition to the above advantages, the adhesive layer formed by using the adhesive composition of the present invention, With proper adhesion It is also excellent in adhesion to the substrate, corrosion resistance to metal corrosion, and low-temperature stability. In addition, in this specification, "the so-called "good resistance to adherend contamination" or "excellent resistance to adherence" means The change in the contact angle of the surface protective film having the adhesive layer formed using the adhesive composition of the present invention before and after being peeled off from the adherend is 3. Hereinafter, specifically, the following examples are used. In the present specification, the term "excellent transparency J" or "excellent transparency" means an adhesive layer formed by using the adhesive composition of the present invention, and white turbidity cannot be observed by visual observation. Specifically, According to the evaluation method described in the following examples, the term "metal corrosion suppression, prevention", "adhesion", "adhesiveness to the substrate", "contamination of the adherend" "Resistance to sticky materials", "low temperature stability", "transparency" and "foaming under high temperature and high pressure conditions (at the time of autoclave treatment) 201247818 (in this specification, it is called "High Pressure Dad" ") Is in accordance with an embodiment described below and were evaluated by the methods already contained in S. Therefore, the adhesive composition of the present invention is effective for the adhesion of various plastic films and the like (four), and is particularly suitable for a flat display panel (10) such as a polarizing plate for a hidden display panel, a dental A-type 7F H panel, and the like. ) The adhesive layer of the surface protective film. Hereinafter, embodiments of the present invention will be described. Further, in the present specification, a compound containing a (meth) group such as (meth)acrylic acid means a general term for a compound having a "methyl group" and a compound having no "methyl group". Therefore, it is known that both (meth)acrylic groups, including both acryl and decyl propylene groups, contain "acrylic acid and thioglycolic acid". Both sides of the vinegar, the so-called "(meth) thief" contains both C-ridden and methacrylic acid. (A) (fluorenyl) acryl-based copolymer The (meth) propylene-based copolymer constituting the adhesive composition of the present invention is a carboxy group-containing monomer having (4) 〇 by mass or more and less than 咐 by weight, (a) -2) 0.6 to 9 parts by mass of a transalkyl group-containing (meth)acrylic acid-based monomer and (a-3) 99.4 to 90.5 parts by mass of a (mercapto)acrylic acid vinegar monomer are contained as essential components. Further, the weight average molecular weight (MW) of the (meth)acrylic acid-based copolymer of the present invention is preferably 1 G 10,000 or more and less than 1 (8) 10,000 H 900,000. Here, when the average molecular weight is less than 100,000, it is difficult to form an adhesive layer, and the adhesion of the adhesive layer and the adhesion to the substrate (adhesive) are extremely poor. On the other hand, when the weight average molecular weight is (10) or more, the manufacturing steps become complicated, and the cost is disadvantageous. Moreover, the adhesion of the adhesive layer 8 201247818 force and the substrate (the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 'It is easy to manufacture (fluorenyl) propylene s-based copolymer in a short time and cheaply. 'Because the solution of this molecular weight range (meth) acrylic acid copolymer has low viscosity, it is coated on the protective film. When the base material is used, the coating can be easily and easily carried out, and the film thickness of the layer can be easily suppressed. (al) Carboxyl group-containing monomer & The present invention contains a hiding body, which is at least a molecular towel. 1 The unsaturated monomer of the base. The specific content of the monomer containing the lining is not limited by the following 'may be given (methyl) acrylic acid 'succinic acid, cis-butadiene _, anti-butyl Adipic acid, fumaric anhydride, crotonic acid, itaconic acid, itaconic anhydride, myristoleic acid, palmitoleic acid, oleic acid, etc., etc. may be used alone or in combination. Used above. The esteem is a quest for the (indenyl) ene 1, maleic acid, maleic acid Preferably, the anti-butenyl bis-succinic anhydride, crotonic acid, itaconic acid, and itaconic anhydride are preferably the main U (methyl) acrylonitrile. The above-mentioned single system containing a carboxyl group may be used alone or in combination. In the form of a mixture of two or more kinds of the mixture, in the present invention, the amount of the monomer containing the thiol group is 100 parts by mass in total of the total monomer, and is 0 parts by mass or more and less than 〇5. When the amount of the monomer having a carboxyl group is 0.5 parts by mass or more, the turtle is too high to be peeled off from the substrate (adhered matter) such as a polarizing plate, and the adhesive layer remains after On the substrate. (a-2) Hydroxyl-containing (meth)acrylic monomer The hydroxyl group-containing (meth)acrylic monomer of the present invention is a sulphuric acrylic single in 201247818. Specific examples of such a hydroxyl group-containing (meth)acrylic monomer are not limited to the following, and examples thereof include 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate. 16_hexanediol mono(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (Meth) acrylate, neopentyl glycol mono(meth) acrylate, trimethylolpropane di(meth) acrylate, trimethylolethane di(meth) acrylate, (methyl) 2-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxyphenyl (meth)acrylate, 4-hydroxycyclohexyl (decyl)acrylate, 2-hydroxyl Ethyl (fluorenyl) acrylamide, cyclohexane dimethanol monoacrylate, etc., and examples thereof include alkyl epoxy propyl ether, allyl epoxy propyl ether, and (meth)acrylic acid ring. a compound obtained by an addition reaction of a compound containing a glycidyl group such as oxypropyl ester with (meth)acrylic acid, etc. These are 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate. Ester, 2-hydroxyethyl (meth) acrylamide, cyclohexanedimethanol monoacrylate, preferably 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, More preferably 2-hydroxyethyl (meth) acrylamide, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl propyl The eneamine is particularly preferred. The above-mentioned hydroxyl group-containing (meth)acrylic single system may be used singly or in the form of a mixture of two or more kinds. In the present invention, the hydroxyl group-containing (fluorenyl) acrylic monomer is used in an amount of from 0.6 to 9 parts by mass based on 100 parts by mass based on the total amount of the total monomers. Here, when the amount of the hydroxyl group-containing (meth)acrylic monomer used is less than 0.6 parts by mass, the hydroxyl group of the hydroxyl group-containing (fluorenyl) acrylic monomer is reacted with a carbodiimide crosslinking agent. There are too few cross-linking points to achieve sufficient adhesion. Further, conversely, when the hydroxyl group-containing (meth)acrylic monomer is used in an amount greater than 9 10 201247818 ^ parts by weight, the reduction (f-based (tetra), monomer reduction, and carbon di-ruthenium crosslinking) The cross-linking point obtained by the reaction of the agent becomes too much, so that the adhesive force becomes large, and the adhesive layer cannot exhibit sufficient transparency. (a-3) (Meth) acrylate monomer in the present invention The propylene-single system does not have a certain number of (mercapto) propylene (tetra) Sg in the molecule. Specific examples of such a (meth)acrylic acid vine monomer are not limited to the following (exemplified by (methyl)丙骑甲@旨, (methyl) acetic acid ethyl vinegar, (mercapto) acrylic acid, (meth) isopropyl isopropyl vinegar, (methyl) acrylic acid n-butyl vinegar, (methyl) Acetic acid iso(indenyl)acrylic acid tert-butyl vinegar, (meth)acrylic acid isovaleric acid '(meth)acrylic acid n-hexanoic acid, (meth)acrylic acid n-heptavine' (methyl) Acrylic acid, third octyl vinegar (meth) acrylate, 2-ethyl hexanoic acid (meth) acrylate, bismuth vinegar (meth) acrylate, (meth) isopropyl acetonate (曱基) acrylic acid vinegar (Methyl) benzoic acid stearin, (mercapto) acrylic acid iso-hard vinegar, (mercapto) acrylic acid benzene vinegar, (meth) acrylic acid vinegar, (mercapto) acrylic acid :Simple, (meth)acrylic acid tetrakis succinate, cyclohexyl (meth) acrylate 4 (n-butylcyclohexyl acrylate), 2-ethylhexyl diglycol (methyl Acrylate, butoxyethyl (meth)acrylate, butoxymethyl (meth)acrylate, 3-methoxypropenyl (meth)acrylate, 2-(2-methyl)(mercapto)acrylate Oxyethoxyethyl)ethyl ester, 2-(2-butoxyethoxy)ethyl (meth)acrylate, 4-butylalkyl (meth)acrylate, and (meth)acrylic acid, (曱2,4,5-tetramethylphenyl acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene oxide monoalkyl ether (methyl) Acrylate, polypropylene oxide monoalkyl ether (mercapto) acrylate, trifluoroethyl (meth)acrylate, pentafluorohydroxyethyl (meth)acrylate, (mercapto) propene 11 201247818 olefinic acid 2 -chloroethyl ester 2,3-dibromopropyl acrylate, dibromophenyl (meth) acrylate, etc. Among the above (meth) acrylate monomers, methyl methacrylate, ethyl methacrylate, methyl N-butyl acrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, preferably methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethyl acrylate More preferably, the hexyl acrylate is preferably decyl acrylate, n-butyl acrylate or 2-ethylhexyl acrylate. Further, the above (meth) acrylate single system may be used alone or in combination. In the present invention, the amount of the (fluorenyl) acrylate monomer used is from 99.4 to 90. 5 parts by mass based on 100 parts by mass of the total of the total monomers. (a-4) Other monomer The (mercapto)acrylic copolymer of the present invention is capable of using the above (&_carboxy group-containing monomer, (a-2) hydroxyl group-containing (meth)acrylic monomer And (a-3) a (meth) acrylate monomer is copolymerized as an essential component to produce 'to make only the above (a-1), (a-2) and (a-3) as monomers It is preferred that the component is copolymerized to produce, that is, the (meth)acrylic copolymer of the present invention is derived from (a_2) a hydroxyl group-containing monomer only from a constituent unit derived from a (a-fluorene) carboxyl group-containing monomer. It is preferable that the constituent unit of the (meth)acrylic monomer and the constituent unit derived from the (a-3) (fluorenyl) acrylate monomer are formed. Further, in this case, the (a-1) carboxyl group-containing monomer, (a-2) The total amount of the hydroxyl group-containing (meth)acrylic monomer and the (a-3) (meth)acrylate monomer is 1 part by mass. However, the (meth)acrylic acid of the present invention In addition to the above-described constituent units derived from (al) to (a-3), the system may have a composition derived from other monomers, such as a single unit 70. 12 201247818 Here, as another sufficient use of this single body The copolymer is not particularly limited as long as it can be copolymerized with the monomer (al) to (a-3), and specific examples thereof include (meth)acrylic acid propyl acrylate and (meth)acrylic acid methyl methacrylate. An acrylic monomer having an epoxy group; diammonium ethyl (meth)acrylate; diethylaminoethyl (meth)acrylate; N-tert-butylaminoethyl (meth)acrylate; (fluorenyl) acrylic acid vaporized methyl propylene oxiranyl ethyl methacrylate or the like having an amine group; (mercapto) acrylamide, N-hydroxymethyl (meth) acrylamide, N - methoxymethyl (fluorenyl) acrylamide, N, N-methylene bis(indenyl) acrylamide, etc., acrylic monomer having a guanamine group; 2-methyl propyl sulfoxide Acidic acid-containing acrylic acid, such as diphenyl ester (meth) acrylate, trimethyl propylene methoxyethyl acrylate (mercapto) acrylate, tridecyl methoxyethyl ester (mercapto) acrylate Monomer; (fluorenyl) acrylic acid propyl propyl, (methyl) acrylic acid 2-picionic acid ethyl, 2-propanolamine 2 - methyl propionate sodium, etc. With Acrylic monomer of sulfonic acid group; acrylic monomer having amine phthalate group such as urethane (meth) acrylate; p-tert-butylphenyl (meth) acrylate Acrylic vinyl monomer having a stupid base such as o-biphenyl ester; 2-ethylindenyl ethyl oxyethyl (meth)acrylate, vinyl trimethoxy decane, vinyl triethoxy decane, ethylene a vinyl monomer having a mercaptoalkyl group such as a ginseng (yS_methoxyethyl) azacene, a vinyltriethoxydecane, a methacryloxypropyltrimethoxy oxane or the like; Chlorostyrene, mercaptostyrene, vinyl anthracene, vinyl chloride, vinyl acetate, vinyl propionate, acrylonitrile, vinyl pyridinium, and the like. Among the other monomers mentioned above, (meth) acrylamide, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 2-ethyl fluorenyl (meth) acrylate Preferably, decyloxyethyl ester is used, and 13 201247818 is more preferably acrylamide, dimethylaminoethyl (meth)acrylate or 2-ethyl decyl ethoxyethyl (meth) acrylate. Further, the above other single system may be used singly or in the form of a mixture of two or more kinds. Further, the amount of the other monomer used in the case of using the above other monomer is not particularly limited as long as it does not inhibit the characteristics of the monomer of the above (a-1) to (a-3). The amount of the other monomer to be used is preferably 100 parts by mass or more, and preferably 0.2 to 5 parts by mass, based on 100 parts by mass of the total of the monomers (al) to (a-3). It is more preferably 0.3 to 2 parts by mass. The method for producing the (fluorenyl) acrylic copolymer of the present invention is not particularly limited, and the following well-known methods can be used: a solution polymerization method using a polymerization initiator, an emulsion polymerization method, a suspension polymerization method, and a reverse phase suspension polymerization method. , film polymerization method, spray polymerization method, and the like. Examples of the method for controlling the polymerization include an adiabatic polymerization method, a temperature-controlled polymerization method, and an isothermal polymerization method. Further, in addition to the polymerization initiation method, a method of starting the polymerization by irradiation with radiation, electron rays, ultraviolet rays or the like can be employed. Among them, since the molecular weight is easily adjusted and the amount of impurities is small, a solution polymerization method using a polymerization initiator is preferred. For example, it is preferable to use 0.01 to 0.50 parts by mass of a polymerization initiator, and nitrogen gas, by using ethyl acetate, toluene, mercaptoethyl ketone or the like as a solvent and 100 parts by mass based on the total amount of the monomers. The reaction is carried out, for example, at a reaction temperature of 60 to 90 ° C for 3 to 10 hours. Examples of the polymerization initiator include azo such as azobisisobutyronitrile (AIBN), 2,2'-azobis(2-methylisobutyronitrile), and azobiscyanovaleric acid. Compound; tert-butyl peroxytriacetate, tert-butyl peroxybenzoate, tert-butyl peroxy 2-ethylhexanoate, di-tertiary peroxidation 14 201247818 An organic peroxide such as benzene hydrogen peroxide, benzamidine peroxide or t-butyl hydroperoxide; an inorganic peroxide such as hydrogen peroxide, persulfate, persulfate, or sodium persulfate. These may be used alone or in combination of two or more. The (meth)acrylic copolymer obtained by copolymerizing the monomer of the above (a-Ι) to (a_3) and other monomers (a_4) as necessary, and the average knife (Mw) ) is more than 100,000 and less than 1 million, preferably 2 to 9 million. When the weight average molecular weight is less than 100,000, it is difficult to form an adhesive layer. Even if the wire is layered, the thickness of the layer and the adhesion to the substrate (adhesive) are very poor. On the other hand, when the weight average molecular weight is 100,000 or more, the I-pass becomes complicated' and it is disadvantageous in terms of cost. Further, the adhesion of the adhesive layer and the adhesion to the substrate (adhered matter) excessively rise, and the portion of the adhesive layer remains in the substrate after being peeled off from the substrate. Conversely, in the molecular weight range, the (meth)acrylic acid copolymer can be produced simply and inexpensively in a short time, because the solution viscosity of the (meth)acrylic copolymer of such molecular weight range is When it is applied to a substrate such as a protective film, it is possible to easily and easily apply the coating 'χ' to easily suppress the thickness of the adhesive layer. Further, in the present invention, the weight average molecular weight is a value calculated by the method described in the examples. Further, the adhesive composition of the present invention may contain the above (meth)acrylic acid copolymer alone or in a mixture of two or more. (Β)Carboquinone-based crosslinking agent In addition to the above (meth)acryl-based copolymer, the adhesive composition of the present invention contains a carbon dioxide. The carbodiimide crosslinking 15 201247818 The crosslinking agent is bonded to a hydroxyl group or a slow group in the monomer of the above (fluorenyl) acrylic copolymer, in particular, via a base to form a crosslinked structure. The carbodiimide crosslinking agent used in the present invention is not particularly limited. Specifically, for example, a compound having two or more carbodiimide groups (_N = C = N-) in the molecule can be suitably used, and a well-known polycarbodiimide can be used. Further, as the carbodiimide compound, a high molecular weight polycarbodiimide which is produced by decarbonation condensation reaction of a diisocyanate in the presence of a carbodiimide catalyst can also be used. Examples of such a compound include a polycarbodiimide obtained by subjecting the following diisocyanate condensate to a condensation reaction. As the diisocyanate, 4,4'-diphenyldecane diisocyanate, 3,3'-dimethoxy-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl- can be used. 4,4'-diphenyldecane diisocyanate, 4,4'-diphenyl ether diisocyanate, 3,3'-dimercapto-4,4, diphenyl ether diisocyanate, 2,4- Toluene diisocyanate, 2,6-nonyl diisocyanate, 1-methoxyphenyl 2,4-diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, tetradecyl One of dimethyl diisocyanate, or a mixture of such. As the carbondiamine imidization catalyst, 1-phenyl-2-cyclophosphazene-1-oxide, 3-methyl-2-cyclopentene-1-oxide, 1-ethyl-3- can be used. A cyclophosphene oxide such as decyl-2-cyclophosphene-1-oxide, 1-ethyl-2-cyclophosphene-1_oxide or such a 3·cyclophosphene isomer. Further, the carbodiimide of the present invention can be synthesized or used in a commercial product. The high-molecular-weight polycarbodiimide is not limited to the following. Example 16 201247818 The CARBODILITE (registered trademark) series manufactured by Nikko Textile Co., Ltd., including CARBODILITE (registered trademark) V-01, V-03 V-05, V-07, and V-09 are preferred because they have excellent compatibility with an organic solvent. In the present invention, the amount of the carbodiimide-based crosslinking agent is from 0.1 to 5 parts by mass based on 100 parts by mass of the (fluorenyl)acrylic copolymer. Here, when the amount of the bismuth carbodiimide crosslinking agent is less than 0.1 part by mass, a sufficient crosslinked structure cannot be provided to the adhesive layer, and sufficient adhesion cannot be achieved. Further, when the amount of the carbodiimide-based crosslinking agent is too small, the stain resistance and the transparency are poor, and foaming occurs under high-temperature and high-pressure conditions (at the time of autoclaving). On the other hand, when the amount of the (bi)carbodiimide crosslinking agent is more than 5 parts by mass, the transparency of the adhesive layer is excessively lowered. Further, the adhesive composition of the present invention may contain the above-described carbodiimide-based crosslinking agent alone or in a mixture of two or more kinds. (C) Isocyanate-based crosslinking agent The pressure-sensitive adhesive composition of the present invention must contain the above (mercapto)acrylic copolymer and the carbodiimide crosslinking agent, but may further contain an isocyanate crosslinking agent. The isocyanate crosslinking agent forms a crosslinked structure with a radical or a mercapto group of a monomer constituting the above (meth)acrylic copolymer, in particular, a radical reaction/bonding. By further blending the isocyanate crosslinking agent, the durability of the adhesive layer formed using the adhesive composition can be improved. The isocyanate crosslinking agent to be used in the invention is not particularly limited, and a known isocyanate crosslinking agent can be used. Specific examples thereof include triallyl isocyanate, dimer acid diisocyanate, 2,4-nonylbenzene 17 201247818 isocyanate (2,4-TDI), and 2,6-methylidene diisocyanate (2, 6-TDI), 4,4,-diphenylsulfonium diisocyanate (4,4'-MDI), 2,4,-diphenyl phthalocyanine diisocyanate (2,4'-MDI), 1,4 Aromatic diisocyanates such as phenyl diisocyanate, diphenylene diisocyanate (XDI), tetramethyl xylene diisocyanate (TMXDI), indole amide diisocyanate (TODI), and 1,5-naphthalene diisocyanate (NDI) ; an aliphatic diisocyanate such as hexamethylene diisocyanate (HDI), tridecyl hexamethylene diisocyanate (TMHDI), diazonic acid diisocyanate, norbornane diisocyanate (NBDI); trans-cyclohexane An alicyclic diisocyanate such as _M_diisocyanate, isophorone diisocyanate (IPDI), H6-XDI (hydrogenated XDI), H12-MDI (hydrogenated MDI); carbodiimide of the above diisocyanate Modified diisocyanates; or such isocyanuric acid S is modified, monoisocyanate S, and the like. Further, an adduct of the above-described isobornic acid hydrate compound and a polyhydric alcohol compound such as trimethyl methacrylate or the like, and a biuret and an isocyanurate of the isocyanate compound are also suitably used. The above isocyanate crosslinking agent may be synthesized or commercially available. The commercially available product of the isocyanate-based crosslinking agent is, for example, CORONATE (registered trademark) L, CORONATE (registered trademark) HL, CORONATE (registered trademark) HX, CORONATE (registered trademark) 2030, CORONATE (registered trademark) 2031 ( Above, Japan POLYURETHANE INDUSTRIAL CO., LTD.), ΤΑΚΕΝΑΤΕ (registered trademark) D-102, TAKEN ATE (registered trademark) D-11 ON, TAKENATE (registered trademark) D-200, TAKENATE (registered trademark) D-202 (above ' Mitsui Chemicals POLYURETHANE AG), DURANATE (trademark) 24A-100, DURANATE (trademark) TPA-100, DURANATE (Business 18 201247818) TKA-100, DURANATE (trademark) P301-75E, DURANATE (trademark) E402-90T , DURANATE (trademark) E405-80T, DURANATE (trademark) TSE-100, DURANATE (trademark) D-101, DURANATE (trademark) D-201 (above, manufactured by Asahi Kasei Chemical Co., Ltd.). Among these isocyanate-based crosslinking agents, CORONATE (registered trademark) L, CORONATE (registered trademark) HL, CORO NATE (registered trademark) HX, ΤΑΚΕΝΑΤΕ (registered trademark) D-110N, and DURANATE (trademark) 24A-100 are It is better to use CORONATE (registered trademark) L, CORONATE (registered trademark) HX, ΤΑΚΕΝΑΤΕ (registered trademark) D-110N, and CORO NATE (registered trademark) L and CORO ΝΑΤΕ (registered trademark) 特 is particularly good. In the present invention, the amount of the isocyanate-based crosslinking agent is not particularly limited, and the composition of the above (meth)acrylic copolymer, the type and amount of the above-described carbodiimide crosslinking agent, and the like can be appropriately considered. select. The blending amount of the isocyanate-based crosslinking agent in the case of blending the isocyanate-based crosslinking agent is 0.05 to 3 parts by mass based on 100 parts by mass of the (meth)acrylic copolymer, and preferably 0.1 to 2 parts by mass. . When such a blending amount is obtained, the durability of the adhesive layer formed using the adhesive composition can be improved. Further, the pressure-sensitive adhesive composition of the present invention may contain the above-mentioned isocyanate-based crosslinking agent alone or in a mixture of two or more kinds. In the present invention, the carbodiimide-based crosslinking agent and the above-mentioned isocyanate-based crosslinking agent can react with the monomer constituting the (meth)acryl-based copolymer, particularly the reaction. Bonding to form a crosslinked structure, and the degree of crosslinking at this time is not particularly limited. Considering the adhesion layer 19 201247818 Adhesive layer adhesion, adhesion to the substrate, and push-adhesive contamination! · Low-profile women's hair, transparency, foam under local high temperature conditions (High-pressure dad suitability) and strength, etc., the (four) rate of the adhesive composition is 8 〇 ~ job is better '(four) ~ face is better. In the present specification, the "gel fraction" is an index of the degree of association of the copolymer of the methyl group and the copolymer, and is measured according to the method described in the following examples. (D) Other compounding ingredients may contain, in addition to the above (C) isocyanate-based cross-linking agent, or in place of the above-mentioned (C) hetero-(4) agent, the present-agent group may also contain, for example, a hardening accelerator. , ionic liquid, (four), inorganic filler, softener, antioxidant, anti-aging agent, stabilizer, adhesion-imparting resin, modified resin (polyol resin, phenol resin, acrylic resin, polyester resin, polyolefin resin, epoxy Know, % <oxidized polybutylene resin, etc.), leveling agent, antifoaming agent, plasticizer, dye, pigment (coloring pigment, filler pigment, etc.), treating agent, ultraviolet blocking agent, fluorescent whitening agent, An additive for a dispersing agent, a heat stabilizer, a light stabilizer, an external absorbent, an antistatic agent, a lubricant, and a solvent. Among the hardening accelerators, for example, dibutyltin dilaurate and JCS-50 are mentioned. (City North Chemical Industry Co., Ltd.) 'format TK-1 (manufactured by Mitsui Chemicals POLYURETHANE Co., Ltd.), etc. Further, examples of the ionic liquid include scaly ions, specific rust ions, pyrrolidine rust ions, and imidazolium. Ion, rust ion A cation component such as an ammonium ion, an isononium ion, a thiurium ion ion, a piperidium rust ion, a pyrazole ion, a cesium ion, or the like, and an anion component may be a halogen ion or a nitric acid. Ion, sulfate ion, scale 20 201247818 acid ion, listen _ son, silk _ child, Wei bri ion, sulfite ion record, ^ Wei ling, formic acid ion, oxalate ion, acetic acid ion, = 7 ^ fluoroacetamidine A substance of an anion component such as an ion or an alkylsulfonic acid ion.
作為抗氧化劑，例如可舉出二丁基經基甲苯(Βητ)、 驅酬註冊商標则、IRG_x(註冊商標卿FF、 腸順註冊商標）撕（任—者均是CWY CHEMICALS公司製）等。 作為黏著辭_旨，例如可舉出香茅酸、聚合香茅酸 及香茅酸S旨等的松香類、㈣樹脂、㈣笨_脂、芳香 族烴樹脂、脂肪族飽和烴樹脂和石油樹脂等。 作為石夕烧偶合劑，例如可舉出曱基三甲氧基石夕烧、二 曱基二曱氧基矽烷、三甲基甲氧基矽烷、正丙基三甲氧基 石夕烧、乙基三甲氧基魏、二乙基二乙氧基碎院正丁基 二甲氧基矽烷、正己基三乙氧基矽烷、正辛基三甲氧基矽 烷、苯基三甲氧基矽烷、二苯基二甲氧基矽烷、環己基甲 基二甲氧基矽烷、乙烯基三氯矽烷、乙烯基三曱氧基矽烷、 乙烯基三乙氧基矽烷、乙烯基參（/8_甲氧基乙氧基)矽烷、 召_(3,4-環氧基環己基）乙基三甲氧基矽烷、τ環氧丙氧基 丙基三甲氧基矽烷' r-環氧丙氧基丙基三乙氧基矽烷、r -甲基丙烯醯氧基丙基甲基二甲氧基矽烷、r-甲基丙烯醯氧 基丙基三曱氧基矽烷、r_曱基丙烯醯氧基丙基曱基二乙氧 基石夕烷、7-甲基丙烯醯氧基丙基三乙氧基矽烷、丙烯醯 氧基丙基三乙氧基矽烷、N-yS-(胺乙基)-7^-胺丙基甲基二 21 201247818 甲氧基矽烷、N-/5-(胺乙基)-r-胺丙基三甲氧基矽烷、N-冷-(胺乙基)-r-胺丙基三乙氧基矽烷、r-胺丙基三曱氧基 矽烧、r-胺丙基三乙氧基矽烷、n-苯基-r-胺丙基三甲氧 基矽烷、r-氣丙基三甲氧基矽烷、r-氫硫基丙基三甲氧基 矽烷、τ-氩硫基丙基曱基二甲氧基矽烷、雙-(3-[三乙氧基 矽烷基]丙基）四硫醚、r-異氰酸酯丙基三乙氧基矽烷等。 而且，亦能夠使用將具有環氧基(環氧丙基）、胺基、氫硫基、 (甲基）丙烯醯基等的官能基之矽烷偶合劑、及含有具有能夠 與該等官能基反應的官能基之矽烷偶合劑、其他的石夕院偶 合劑、聚異氰酸酯等’以任意比例使各官能基反應而得到 之具有加水分解性矽烧基之化合物。上述矽炫偶合劑係可 以合成亦可以使用市售品。作為石夕炫1偶合劑的市售品，例 如可舉出 ΚΒΜ-303、ΚΒΜ-403、ΚΒΕ-402、KBM-403、 KBE-502、ΚΒΕ·503、KBM-5103、ΚΒΜ·573、KBM-802、 ΚΒΜ-803、ΚΒΕ-846、ΚΒΕ-9007(以上、信越化學工業股份 公司製）等。 使用上述的添加劑時，添加劑的使用量係沒有特_ 制，例如相對於上述(Α)(甲基）丙稀_單體及(Β)碳二酿亞、 胺系交聯.按照必要之(c)異氰酸系交聯劑的合計量 100質量份’為0·1〜20質量份。 本發明的點著劑組成物’係能夠藉由將上述各成分成 批地混α或將各成分依次混合、或將任意的複數成分現 合之後’齡難的成料而成柄自的混合物來製 以。更具體地，此夠藉由按照必要而加溫、例如加溫至队 22 201247818 °c的溫度錢㈣拌齡鐘〜5小時至均勻為 進調製。 本發明的黏著·成物係能触詩各種基材的貼 〇月匕夠適合使用於表面保護膜 '特別是光學構件用的表 面保護膜。因而，本發明係提供—種表聽賴，其具備 保護膜、及在前述保護_至少—面所形成的黏著層之表 面保4膜，其巾前雜著層係含有本發明的黏著劑組成物。 在本發明，作為保護膜係沒有特別限制，能夠將取所 周知的保護膜同樣地進行而制。例如能夠使用聚對酞酸 乙二酯、聚乙烯、聚丙烯、乙烯_乙酸乙烯酯共聚物、聚酯、 聚氣乙烯'聚碳酸s旨、聚酿胺、聚苯乙稀等的薄膜或該等 的複合薄膜等㈣脂薄膜，以聚對酜酸乙二s旨為佳。又， 保護膜係例如能夠使用具有15〜5〇μιη的厚度者。 又，在保護膜形成黏著層係能夠藉由在保護膜直接塗 布本發明的黏著劑組成物之方法；及將本發明的黏著劑組 成物暫時塗布在另外的基材（例如剝離襯裡等）而形成者進 行轉印之方法等。 黏著劑組成物的塗布方法係沒有特別限制，能夠使用 在製ia黏著膠帶所使用之眾所周知的方法。具體上，可舉 出自然塗布機(natural coater)、刮刀皮帶塗布機(knife bdt coater)、浮動到刀（fi〇ating knife)、輥塗布、空氣刮刀塗布、 輥式刮刀(knife over roll)、刮刀式毡塗布機、噴塗、浸潰、 接觸上膠輥(kiss roll)、擠壓輥、逆輥塗布、氣刀（airbiade)、 簾式流動塗布器、刮片、繞線棒、模頭塗布器、到刀式塗 23 201247818 布器（comma coater)、BAKER可調式塗膜器及凹版塗布器等 的裝置之各種塗布方法。該等之中，以使用親塗布、凹版 塗布、逆輥塗布、輥刷、喷塗、空氣刮刀塗布、模頭塗布 法為佳。 又，本發明的黏著劑組成物之塗布時的黏度係沒有特 別限制。但是，考慮塗布的容易性等時，於25t的黏度係 以500~6000mPa · s為佳，以 i〇〇〇~4000mPa · s為更佳。黏 度在如此的範圍時，在塗布面不會產生桔皮面和塗布條紋。 在保護膜上所形成之組成物的塗布厚度（黏著層的厚 度）係沒有特別限定，能夠依照所需要的用途而適當地選 擇。較佳疋在保s蔓膜上所形成之組成物的塗布厚度(黏著居 的厚度；乾燥後的厚度)S3~200ym，以1〇〜1〇〇〇y m為佳。 本發明的表面保護膜係能夠使用於保護貼合在液晶顯 示器面板和f軸面板等的平面顯㈤面板之光學構 件之用途。作為光學構件，係包含偏光板、相位差板、亮 度提升板或防眩片等者β又，光學構件係亦可以是將偏光 板與相位差板積層而成者、相位差板的積層體、偏光板與 亮度提升板或防眩片的積層體等將光學材料積層2層以上 者。 又，本發明的表面保護膜係不僅是光學構件單獨流通 時、且在光學構件係㈣合在平面顯示^面板的狀態流通 時亦能夠使用。 在本發明的表面保護膜，在保護膜所形成之黏著層（黏 著劑組成物）的黏著力係以002~02(N/25mm)左右為佳以 24 201247818 0.05~0_15(N/25mm)左右為更佳。如此的黏著力時，能夠比 較容易地將表面保護膜從偏光板等的光學構件剝離，例如 能夠以10m/分鐘左右的速度進行剝離。 又’在本說明書’所謂「黏著力」係依據JIS Z0237(2000 年)的黏著膠帶.黏著片試驗方法進行測定而求得，更具體 地，係依照在下述實施例所記載之方法進行測定。 由本發明的黏著劑組成物所得到之黏著層，係能夠使 用本發明黏著劑組成物而形成。如上述，本發明的黏著層 係具有適當的黏著力和對基材的密著性，且金屬腐蝕耐蝕 性、耐被黏物污染性、低溫安定性、透明性優良，又，能 夠抑制.防止發泡在高溫.高壓條件下（高壓爸處理時)的發 泡。 [實施例] 使用以下的實施例及比較例來說明本發明的效果。但 是本發明的技術範圍係不只有限制在以下的實施例。 又，黏著劑組成物溶解之溶液的固體成分及黏度、以 及丙烯酸系聚合物(A)的重量平均分子量之測定，係使用以 下的方法進行。 <固體成分> 在經精稱的玻璃皿，精稱約lg的聚合物溶液。於105°C 乾燥1小時之後，恢復至室溫且精稱玻璃孤與殘留固體成分 的合計質量。將玻璃·DDL的質量設作X，將乾燥前的玻璃孤與 聚合物溶液的合計質量設為Y，且將玻璃血與殘留固體成分 的合計質量設為Z，而從下式數式1算出固體成分。 25 201247818 [數1] 固體成分(％)=Examples of the antioxidant include dibutyl-based toluene (Βητ), a reprinted registered trademark, and IRG_x (registered trademark FF, Intestine-registered trademark), and all of them are all made by CWY CHEMICALS. Examples of the adhesiveness include rosin, citric acid, and citronellic acid, rosin, (iv) resin, (iv) stupid, aromatic hydrocarbon resin, aliphatic saturated hydrocarbon resin, and petroleum resin. Wait. Examples of the zebra calcining coupling agent include mercaptotrimethoxy sinter, dimercapto decyloxydecane, trimethyl methoxy decane, n-propyltrimethoxy sulphur, and ethyl trimethoxy. Wei, diethyl diethoxy oxalate n-butyl dimethoxy decane, n-hexyl triethoxy decane, n-octyl trimethoxy decane, phenyl trimethoxy decane, diphenyl dimethoxy Decane, cyclohexylmethyl dimethoxydecane, vinyl trichlorodecane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (/8-methoxyethoxy) decane, _(3,4-Epoxycyclohexyl)ethyltrimethoxydecane, τ-glycidoxypropyltrimethoxydecane' r-glycidoxypropyltriethoxydecane, r - Methyl propylene methoxy propyl methyl dimethoxy decane, r-methyl propylene methoxy propyl tri methoxy decane, r 曱 醯 propylene methoxy propyl fluorenyl diethoxy oxalate , 7-methacryloxypropyltriethoxydecane, propylene methoxypropyltriethoxydecane, N-yS-(aminoethyl)-7--aminopropylmethyldi 21 201247818 Methoxy Decane, N-/5-(aminoethyl)-r-aminopropyltrimethoxydecane, N-cold-(aminoethyl)-r-aminopropyltriethoxydecane, r-aminopropyltri曱 矽 矽, r-aminopropyl triethoxy decane, n-phenyl-r-aminopropyl trimethoxy decane, r-gas propyl trimethoxy decane, r- thiopropyl propyl trimethyl Oxydecane, τ-arylthiopropylmercaptodimethoxydecane, bis-(3-[triethoxydecyl]propyl)tetrasulfide, r-isocyanatepropyltriethoxydecane, etc. . Further, a decane coupling agent having a functional group having an epoxy group (epoxypropyl group), an amine group, a thiol group, a (meth) acryl fluorenyl group or the like, and a component having a reactivity capable of reacting with the functional group can also be used. A functional group-containing decane coupling agent, another lithene coupling agent, a polyisocyanate or the like, which has a hydrolyzable sulfonic acid group obtained by reacting each functional group at an arbitrary ratio. The above-mentioned oxime coupling agent can be synthesized or used as a commercially available product. As a commercial item of the Shi Xi Xuan 1 coupling agent, for example, ΚΒΜ-303, ΚΒΜ-403, ΚΒΕ-402, KBM-403, KBE-502, ΚΒΕ·503, KBM-5103, ΚΒΜ·573, KBM- 802, ΚΒΜ-803, ΚΒΕ-846, ΚΒΕ-9007 (above, Shin-Etsu Chemical Co., Ltd.). When the above-mentioned additives are used, the amount of the additive used is not particularly limited, for example, relative to the above (Α) (methyl) propylene monomer and (Β) carbon di-branched, amine-based cross-linking. c) The total amount of the isocyanic acid crosslinking agent is 100 parts by mass '0 to 1 to 20 parts by mass. The dot composition of the present invention can be obtained by mixing the above components in batches or by sequentially mixing the components, or by combining any of the plurality of components. To make it. More specifically, this can be achieved by warming up as necessary, for example, by warming up to the temperature of the team 22 201247818 °c (four) mixing time clock ~ 5 hours to uniform modulation. The adhesive/adhesive system of the present invention can be applied to a variety of substrates, and is suitable for use as a surface protective film, particularly a surface protective film for optical members. Accordingly, the present invention provides a protective film having a protective film and a film on the surface of the adhesive layer formed by the at least one surface, and the pre-clothing layer contains the adhesive of the present invention. Things. In the present invention, the protective film system is not particularly limited, and a known protective film can be produced in the same manner. For example, a film of polyethylene terephthalate, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyester, polyethylene ethylene carbonate, polyacrylamide, polystyrene or the like can be used. The (4) lipid film, such as a composite film, is preferably a polyethylene terephthalate. Further, the protective film can be, for example, a thickness of 15 to 5 μm. Further, the adhesive layer can be formed on the protective film by a method in which the adhesive composition of the present invention is directly applied to the protective film; and the adhesive composition of the present invention is temporarily applied to another substrate (for example, a release liner or the like). The method in which the formr performs the transfer or the like. The coating method of the adhesive composition is not particularly limited, and a well-known method for using an adhesive tape for ia can be used. Specifically, a natural coater, a knife bdt coater, a fl〇ating knife, a roll coating, an air knife coating, a knife over roll, and the like are mentioned. Scraper-type felt coater, spray coating, dipping, contact kiss roll, squeeze roll, reverse roll coating, airbiade, curtain flow applicator, doctor blade, wire rod, die coating Various methods of coating, such as stencil coating 23, 201247818 comma coater, BAKER adjustable applicator, and gravure coater. Among these, it is preferred to use a co-coating, a gravure coating, a reverse roll coating, a roll brush, a spray coating, an air knife coating, or a die coating method. Further, the viscosity at the time of application of the adhesive composition of the present invention is not particularly limited. However, in consideration of easiness of coating, etc., the viscosity at 25 t is preferably 500 to 6000 mPa·s, and more preferably i〇〇〇 to 4000 mPa·s. When the viscosity is in such a range, no orange peel and coating streaks are formed on the coated surface. The coating thickness (thickness of the adhesive layer) of the composition formed on the protective film is not particularly limited, and can be appropriately selected depending on the intended use. Preferably, the coating thickness (the thickness of the adherent; the thickness after drying) of the composition formed on the smear film is S3 to 200 μm, preferably 1 〇 to 1 〇〇〇 y m. The surface protective film of the present invention can be used for the purpose of protecting an optical member bonded to a flat display panel of a liquid crystal display panel or an f-axis panel. The optical member includes a polarizing plate, a phase difference plate, a brightness enhancement plate, or an anti-glare sheet, and the optical member may be a laminate of a polarizing plate and a phase difference plate, or a laminate of a phase difference plate. The optical material is laminated in two or more layers, such as a laminate of a polarizing plate and a brightness enhancement plate or an anti-glare sheet. Further, the surface protective film of the present invention can be used not only when the optical member is separately circulated, but also when the optical member (4) is placed in a state in which the flat display panel is disposed. In the surface protective film of the present invention, the adhesion of the adhesive layer (adhesive composition) formed on the protective film is preferably about 002 to 02 (N/25 mm) to 24 201247818 0.05 to 0_15 (N/25 mm). For better. When such an adhesive force is applied, the surface protective film can be easily peeled off from the optical member such as a polarizing plate, and can be peeled off at a speed of, for example, about 10 m/min. Further, the "adhesive force" in the present specification is determined in accordance with the adhesive tape test method of JIS Z0237 (2000), and more specifically, it is measured in accordance with the method described in the following examples. The adhesive layer obtained from the adhesive composition of the present invention can be formed by using the adhesive composition of the present invention. As described above, the adhesive layer of the present invention has an appropriate adhesive force and adhesion to a substrate, and is excellent in metal corrosion resistance, stain resistance, low temperature stability, and transparency, and can be suppressed. Foaming under high temperature and high pressure conditions (high pressure dad treatment). [Examples] The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following embodiments. Further, the solid content and viscosity of the solution in which the adhesive composition was dissolved, and the measurement of the weight average molecular weight of the acrylic polymer (A) were carried out by the following methods. <Solid content> In a well-called glass dish, a polymer solution of about lg was weighed. After drying at 105 ° C for 1 hour, it was returned to room temperature and finely referred to as the total mass of the glass orphan and the residual solid content. The mass of the glass and the DDL is set to X, and the total mass of the glass solitary polymer solution before drying is Y, and the total mass of the glass blood and the residual solid content is Z, and is calculated from the following formula Solid content. 25 201247818 [Number 1] Solid content (%) =
Z - X Y-X X 100 <黏度> 將放入玻璃瓶之聚合物溶液調溫至25°c且使用B型黏 度計測定。 <重量平均分子量> 依照下述表1的測定方法·測定條件進行測定。 [表1] 裝置：凝膠滲透層析法(GPC)(機器No. GPC-16) 檢測器：差示折射率檢測器RI(TOSOH股份公司製8020型敏感度32) 紫外吸收檢測器UV (Water公司製2487、波長215nm、敏感度 0.2AUFS) 管柱：TOSOH股份公司製 TSKgelGMHXL(2支）、G2500HXL(1 支） (S/N M0052、M0051、N0010、（D7.8mmx30cm) 溶劑：四氫呋喃（和光純藥工業股份公司製） 流速：1.0mL/min 管柱溫度：23°C 試料：[濃度]約0.2% [溶解]於室溫緩慢地攪拌。 [溶解性]溶解（目視確認） [過濾]使用0.45 μ m過濾器進行過濾。 注入量：0.200mL 標準試料：單分散苯乙烯 數據處理：GPC數據處理系統 [合成例1] 在具備回流器及攪拌機之燒瓶，投入40份丙烯酸正丁 酯（日本觸媒股份公司製）、59質量份丙烯酸2-乙基己酯、1 26 201247818 份丙烯酸2-羥基乙酯及150質量份乙酸乙酯。隨後，邊進行 氮取代邊加熱至65°C為止，且添加0.1質量份偶氮雙異丁腈 (AIBN)，而且在1小時後更添加0.05份AIBN，邊維持65°C 邊進行聚合6小時。聚合反應結束之後，添加36質量份乙酸 乙酯且冷卻至室溫而得到共聚合物(A-1)溶液。所得到的共 聚合物（A-1)溶液之固體成分係35%，黏度係3500mPa«s。 又，所得到的共聚合物(A-1)的平均重量分子量係80萬。又， 測定所得到的共聚合物(A-1)溶液之固體成分、黏度、重量 平均分子量且將其結果顯示下述在表2。 (合成例2〜19) 在合成例1，除了將單體成分的組成變更為如表2所表 示的組成以外，藉由與合成例1進行同樣的操作而得到共聚 物（A-2)~(A-19)的溶液。又，測定所得到的共聚物（A-2) 〜(A-19)溶液的固體成分、黏度及重量平均分子量。將其結 果顯示在表2。又，在下述表2,「BA」係丙烯酸丁酯；「2EHA」 係丙烯酸2-乙基己酯；「HEA」係丙烯酸2-羥基乙酯；「4HBA」 係丙烯酸4-羥基丁酯；「HEAA」係羥乙基丙烯醯胺；「AM」 係丙烯醯胺；及「AA」係丙烯酸。 27 201247818 αφZ - X Y-X X 100 <Viscosity> The polymer solution placed in a glass bottle was tempered to 25 ° C and measured using a B type viscometer. <Weight average molecular weight> The measurement was carried out in accordance with the measurement methods and measurement conditions in Table 1 below. [Table 1] Apparatus: Gel Permeation Chromatography (GPC) (Machine No. GPC-16) Detector: Differential refractive index detector RI (8020 type sensitivity 32 by TOSOH Co., Ltd.) Ultraviolet absorption detector UV ( Water Company 2487, wavelength 215nm, sensitivity 0.2AUFS) Pipe column: TSKgelGMHXL (2 pieces) made by TOSOH Co., Ltd., G2500HXL (1 piece) (S/N M0052, M0051, N0010, (D7.8mmx30cm) Solvent: Tetrahydrofuran ( Wako Pure Chemical Industries Co., Ltd.) Flow rate: 1.0 mL/min Column temperature: 23 ° C Sample: [concentration] about 0.2% [Dissolved] Stir slowly at room temperature [Solubility] Dissolved (visual confirmation) [Filter Filtration using a 0.45 μm filter Injection amount: 0.200 mL Standard sample: Monodisperse styrene Data processing: GPC data processing system [Synthesis Example 1] In a flask equipped with a refluxer and a stirrer, 40 parts of n-butyl acrylate was charged. (manufactured by Nippon Shokubai Co., Ltd.), 59 parts by mass of 2-ethylhexyl acrylate, 1 26 201247818 parts of 2-hydroxyethyl acrylate, and 150 parts by mass of ethyl acetate. Subsequently, the mixture was heated to 65 ° C while nitrogen substitution. Up to this, and adding 0.1 parts by mass of azobisisobutyronitrile (AIBN) Further, after adding 1 part of AIBN after 1 hour, polymerization was carried out for 6 hours while maintaining 65 ° C. After completion of the polymerization reaction, 36 parts by mass of ethyl acetate was added and cooled to room temperature to obtain a copolymer (A-1). The obtained copolymer (A-1) solution has a solid content of 35% and a viscosity of 3500 mPa «s. Further, the obtained copolymer (A-1) has an average weight molecular weight of 800,000. The solid content, viscosity, and weight average molecular weight of the obtained copolymer (A-1) solution were measured, and the results are shown in Table 2 below. (Synthesis Examples 2 to 19) In Synthesis Example 1, except for the monomer component The composition of the copolymers (A-2) to (A-19) was obtained by the same operation as in Synthesis Example 1 except that the composition was changed to the composition shown in Table 2. Further, the obtained copolymer was measured ( A-2) The solid content, viscosity, and weight average molecular weight of the solution (~-19). The results are shown in Table 2. In addition, in Table 2 below, "BA" is butyl acrylate; "2EHA" is acrylic acid 2 -ethylhexyl ester; "HEA" is 2-hydroxyethyl acrylate; "4HBA" is 4-hydroxybutyl acrylate; "HEAA" is hydroxyethyl Acrylamide; "AM" is acrylamide; and "AA" acrylic. 27 201247818 αφ
Os A-19 m o ο in Ο +〇£* f-» ，吨 oo A-18 yn 妄 d σ\ CN o ο m s 〇 *aff 卜 1*0· 卜 A-17 r- g V*J CN »〇 d o 2000 m ΓΛ Ο *λΓ 寸鄕 A-16 cn g vn 卜 d o *—H 2000 m m Ο w?* 寸w v~) A-15 CN ε； o 2000 CO 〇 AttC* 寸挪 对 A-14 〇 00 CN o 2000 l〇 cn 〇 4ftS* 寸视 m A-13 ο α\ ON 一 o 2000 »n Ο 4β£ CO興 CN A-12 o On 寸 ο VO o o 4000 «〇 Ο 4φΕ* OS W 二 1 < o ON 00 o 3500 cn Ο AftS* ν〇姆 Ο A-10 VO On 寸 d o ο tn vn cn 寸w σ\ CTN < 00 § o 1500 们 〇 Aftp ro W- 00 00 < 00 ON CM o 1500 们 CO 〇 4eS* 卜 r- < g 00 (N o 2500 u-> O *ftg* 仰 \〇 < (N ON σ\ v〇 d o 1000 »n C^) Ο 4〇Ρ m *〇 < »〇 (N On CO o 2000 «η O «bp 寸 ί*Β· 寸 寸 < o On 00 — o ο cn 〇 4ftC* 寸轉 cn < 00 g 00 CN d o 1000 V} cn 〇 AftP 1/-) ΐββ. (N fN < 00 ON <N o 1500 »n m Ο 4φ£· π ί»6· — 1 < o OS «Τ5 — o 3500 m CO Ο Aflff 〇〇 1®5. 聚合物(A)的組成 < PQ 2EHA HEA 4HBA HEAA s < < < 合計（質量份） 黏度(mPa*s) 固體成分(％) φή Η~* Ssa 龚牛 *4〇 φ*ι κν Jaj βΓ< T®1! sel·鋇噠令（》«Η傘） 甾锺装¢:sv 避卜砩墩-寸想敢《 : van寸 ISto-fo-fN^泼肊：νω(Ν 怒装¢: νν 鍩15泼«砩10頦：VV3H 溫10砩-:§!-3怒$«:¥«3: 15卜怒装肊：VCQ(坊 28 201247818 (實施例1) 實施例1係添加286質量份（以聚合物的固體成分計為 1〇〇質量份)在上述合成例1所得到的共聚物溶液、〇 5 份碳二醯亞胺系交聯劑（B)亦即碳二醯亞胺（註冊商 標）V-01(日清紡CHEMICAL股份公司製、表1中的試料名 B-1)、0.5份異氰酸酯系交聯劑(〇亦即c〇R〇NATE(註冊商 標）HX(六亞曱基二異氰酸酯、曰本POLYURETHANE工業 股份公司製、表1中的試料名：C-1)，於室溫(25。〇混合10 分鐘而以溶液形態得到黏著劑組成物。 將該黏著劑組成物溶液在剝離PET薄膜（三菱化學 POLYESTER HLM股份公司製、MRF38、厚度：38 y m)上， 以乾燥後的厚度為25#πι的方式塗布，且於90°C使其乾燥3 分鐘而形成黏著劑層之後，進而藉由將黏著層側貼合在PET 薄膜（TORAY股份公司製' 商品名Lumirror(註冊商 標）S10#25、厚度：23//m)來製造表面保護膜⑴。 (實施例2〜1 〇、比較例1 ~9) 在實施例1，除了以如下述表4所表示之組成比，且使 用在上述合成例所合成的聚合物、碳二醯亞胺系交聯劑及 異氰酸酯系交聯劑以外，與實施例1同樣地進行調製黏著劑 組成物溶解之溶液（黏著劑組成物溶液）及製作表面保護 膜，來得到表面保護膜(2 )〜(10)及比較例表面保護膜（1)〜(9) 又，碳二醯亞胺系交聯劑B-2及B-3的詳細係如下述表3。 [表3] •碳二醯亞胺系交聯劑(B) B-2 : CARBODILITE (註冊商標)V-09(日清紡CHEMICAL股份公司製） B-3 : CARBODILITE (註冊商標)V-05(日清紡CHEMICAL股份公司製） 29 201247818 針對如上述進行而在實施例1~1〇所得到的表面保護膜 (1)~(10)、及在比較例1〜9所得到的比較表面保護膜 (1)~(9)，依照下述方法而評價各性能，且將其結果顯示在 下述表4。 1. 金屬腐蝕抑制.防止性 將在23°C、50%RH的環境下放置7天後之表面保護薄膜 的黏著層面貼在鋁箔，且在60°C、90%RH的環境下放置2 天，觀察此時的腐蝕性。又，下述表4中，係各自如以丁表 示，「〇」係表示無變化，「X」係表示白化。 2. 高壓釜適合性 將在23°C、50%RH的環境下放置7天後之表面保護膜裁 斷成為25mm寬且將其貼合在偏光板，在5〇 ^、 0.49MPa(5kg/cm2)的條件下進行高壓釜處理，觀察此時的發 泡。又，下述表4中，係各自如以下表示，「〇」係表示未 觀察到發泡’「X」係表示觀察到發泡。 3. 黏著力 將在23°C、50%RH的環境下放置7天後之表面保護膜， 裁斷成為25mm寬度且貼合在偏光板且以5〇 t、 0.49MPa(5kg/cm2)的條件進行高壓釜處理2〇分鐘。使用拉伸 試驗機，在23°C、50%RH的環境下以剝離角18〇度、剝離速 度0.3m/分鐘，依據JIS Z2〇37(20〇〇年)所記載之黏著膠帶. 黏者薄片a式驗方法進行測定黏著力（ν/25πιπι) 〇 4. 對基材之密著性 在上述3.黏著力的測定時，評價對保護膜(基材)之密著 30 201247818 性。又，下述表4中，係各自如以下表示，「〇 _ 護膜剝 著劑完全未從保護義離，「X」係表示黏著劑從=表不黏 離。 >、 5.被黏物污染性 測定上述黏著力測定前後之偏光板面的接觸角。又， 接觸角的測定係依據在jIS们257(1"9年)所記載之基板玻 璃表面的濕潤性試驗方法而進行。下述表4中，係各=如以 下表示，「〇」係表示黏著力測定前後之偏光板面的接觸^ 為3。以下，「X」係表示黏著力測定前後之偏光板板面的接 觸角有變化。 6 ·低溫安定性 將在23°C、50%RH的環境下放置7天後之表面保護膜貼 合在偏光板，且以50〇C、0.49MPa(5kg/cm2)的條件進行高壓 釜處理20分鐘。隨後，觀察於_4(rc環境下放置12〇小時後 的外觀。下絲4巾，係各自如以下表*，「〇」係表示未 觀察到發泡、浮起、剝離、或析出物，「x」係表示觀察到 發泡、浮起、剝離、或析出物。 7 ·點著層的透明性 目視確認在23°C、50%RH的環境下放置7天後之表面保 護膜的黏著層。又’下述表4中，係各自如以下表示，「〇」 係表示透明性良好的情況，「X」係表示在黏著層觀察到白 濁的情況。 8.凝膠分率 使用經剝離處理之聚酯薄膜代替在各實施例、比較例 31 201247818 所製作之形成有黏著劑層的偏光板，在聚酯薄膜上形成黏 著層來測定在塗布7天後之凝膠分率（％)。凝膠分率係秤量 約O.lg之在23°C、50%RH的環境下放置後的黏著劑組成物 且測定重量WKg)。將其採取至試樣瓶且添加約30g乙酸乙 酯而放置24小時。使用200網目的不鏽鋼製金屬絲網（將金 屬絲網的重量設作W2)過濾經過預定時間後之該試樣瓶的 内容物，且測定使金屬絲網及殘留物於90°C乾燥1小時後之 整體的重量W3(g)。此時，凝膠分率係從該等的測定值且依 照下述數式2算出。 [數2] 凝膠分手 整理各評價結果且顯示在表4。又，因為表4中的比較 例6係在調配交聯劑後產生凝膠化而無法得到薄片，無法進 行各項評價。 32 201247818 【寸ϊ 比較例 ON A-18 o CN Ό σν 〇 (Ν 〇 X 〇 〇 〇 00 A-17 o ΟΝ 〇 (S 〇 X 〇 〇 〇 卜 A-17 o d \ο ΟΝ 〇 沄 d 〇 X 〇 〇 〇 \〇 A-16 o (N I 1 1 1 1 1 1 1 1〇 A-15 o 卜 寸 d ν〇 σ\ 〇 g d 〇 X 〇 X 〇 寸 A-14 o 寸 卜 d Ό ΟΝ 〇 <N d 〇 〇 〇 X 〇 cn A-13 o s d d 00 〇 沄 d 〇 X 〇 X X (N A-12 o — »〇 ΟΝ 〇 s d 〇 〇 〇 〇 X — A-ll o — ΟΝ 〇 g d 〇 〇 〇 〇 X 實施例 〇 A-10 o 一 OS 〇 CO d 〇 〇 〇 〇 〇 On ON < o f— CN d 裘 〇 d 〇 〇 〇 〇 〇 00 00 < o v) Ό ΟΝ 〇 o o 〇 〇 〇 〇 〇 卜 < o ΟΝ 〇 m d 〇 〇 〇 〇 〇 < o d 〇\ 〇 d 〇 〇 〇 〇 〇 »n < o 寸 <N ΟΝ 〇 CO d 〇 〇 〇 〇 〇 寸 寸 < o 00 d CN d ν〇 as 〇 CN d 〇 〇 〇 〇 〇 m C^l < o cn 〇〇 ΟΝ 〇 CN d 〇 〇 〇 〇 〇 <N CN < o r- d 00 d U-) σ\ 〇 d 〇 〇 〇 〇 〇 — 1 < o V-) d d 〇 o d 〇 〇 〇 〇 〇 組成(質量份） 1 _1 聚合物(A) 1 PQ (N ώ ώ ΰ 凝膠分率(％) 金屬腐餘抑制·防止性 黏著力（N/25mm) 對基材之密著性 被黏物污染性 低溫安定性 黏著層的透明性 高壓釜適合性 碳二醯亞胺系交聯 劑(B) 異氰酸酯系交聯劑 (C) (？ΙΕ?<·5φ^#τ3ζνΗ13ΗηΛΊ〇£ί4Β,^^®έΒ*Μ^&-54()ΧΗ(#^:#ί+®)31νζ〇Η〇υ:ιό (鉍 t?<<^inv3IS3a:3^他 Β)ςο-Λ (弊框-61m)3HnIaoaHVu: ε-« (鉍 w<<^inv3ISHHu^*B)60-> (弊框-&m)31nIa〇aHV3:z-H (鉍阳<<傘^lvuIS3Hu^*B)I0-> (!ll^t^)alnIa〇pqosvu:l-Da(s 33 201247818 從上述表4，得知相較於比較例1~9之表面保護膜 (1)~(9)，本發明的實施例1〜10之表面保護膜（1)~(10)，係耐 被黏物污染性、黏著劑層的透明性及高壓釜適合性優良。 I：圖式簡單說明3 (無） 【主要元件符號說明】 (無） 34Os A-19 mo ο in Ο +〇£* f-» , ton oo A-18 yn 妄d σ\ CN o ο ms 〇*aff Bu 1*0· Bu A-17 r- g V*J CN » 〇do 2000 m ΓΛ Ο *λΓ inch 鄕A-16 cn g vn 卜do *—H 2000 mm Ο w?* inch wv~) A-15 CN ε; o 2000 CO 〇AttC* inch to A-14 〇 00 CN o 2000 l〇cn 〇4ftS* inch view m A-13 ο α\ ON one o 2000 »n Ο 4β£ CO Xing CN A-12 o On inch ο VO oo 4000 «〇Ο 4φΕ* OS W II 1 < o ON 00 o 3500 cn Ο AftS* ν〇姆Ο A-10 VO On inch do ο tn vn cn inch w σ\ CTN < 00 § o 1500 〇 Aftp ro W- 00 00 < 00 ON CM o 1500 COCO 〇4eS* 卜r- < g 00 (N o 2500 u-> O *ftg* 仰 〇 〇 ( (N ON σ\ v〇do 1000 »n C^) Ο 4〇Ρ m *〇< »〇(N On CO o 2000 «η O «bp inch ί*Β·inch inch< o On 00 — o ο cn 〇4ftC* inch to cn < 00 g 00 CN do 1000 V} cn 〇 AftP 1/-) ΐββ. (N fN < 00 ON <N o 1500 »nm Ο 4φ£· π ί»6· — 1 < o O S «Τ5 — o 3500 m CO Ο Aflff 〇〇1®5. Composition of polymer (A) < PQ 2EHA HEA 4HBA HEAA s <<< Total (parts by mass) Viscosity (mPa*s) Solid content (%) φή Η~* Ssa Gongniu*4〇φ*ι κν Jaj βΓ< T®1! sel·钡哒令(》«Η伞) 甾锺装¢:sv 砩卜砩墩-寸想敢: van inch ISto-fo-fN^ splash: νω (Ν ¢ ¢: νν 鍩 15 splash «砩10颏: VV3H temperature 10砩-: §!-3 anger $«: ¥«3: 15 anger肊: VCQ (Fang 28 201247818 (Example 1) Example 1 was added 286 parts by mass (1 part by mass based on the solid content of the polymer). The copolymer solution obtained in the above Synthesis Example 1 and 5 parts of hydrazine were used. The carbodiimide crosslinking agent (B) is carbodiimide (registered trademark) V-01 (manufactured by Nisshinbo Chemical Co., Ltd., sample name B-1 in Table 1), and 0.5 part isocyanate crosslinked. (〇), ie, c〇R〇NATE (registered trademark) HX (hexamethylene diisocyanate, manufactured by POL本 POLYURETHANE INDUSTRIAL CO., LTD. The crucible was mixed for 10 minutes to obtain an adhesive composition in the form of a solution. The adhesive composition solution was applied to a PET film (Mitsubishi Chemical POLYESTER HLM Co., Ltd., MRF38, thickness: 38 μm), and dried to a thickness of 25 #πι, and dried at 90 ° C. After the adhesive layer was formed in 3 minutes, the surface of the adhesive layer was bonded to a PET film (trade name: Lumirror (registered trademark) S10 #25, thickness: 23/m). (1). (Examples 2 to 1 and Comparative Examples 1 to 9) In Example 1, except that the composition ratios shown in Table 4 below were used, and the polymer synthesized by the above synthesis example or the carbodiimide group was used. In the same manner as in Example 1, except that the crosslinking agent and the isocyanate-based crosslinking agent were prepared, a solution (adhesive composition solution) in which the adhesive composition was dissolved was prepared, and a surface protective film was prepared to obtain a surface protective film (2) to (10). Comparative Examples Surface Protective Films (1) to (9) Further, the details of the carbodiimide crosslinking agents B-2 and B-3 are shown in Table 3 below. [Table 3] • Carbon diimide-based cross-linking agent (B) B-2 : CARBODILITE (registered trademark) V-09 (manufactured by Nisshinbo Chemical Co., Ltd.) B-3 : CARBODILITE (registered trademark) V-05 (Nisshinbo) The product of the surface protective films (1) to (10) obtained in the above Examples 1 to 1 and the comparative surface protective films (1) obtained in Comparative Examples 1 to 9 were prepared as described above. ~(9), each performance was evaluated in accordance with the following method, and the results are shown in Table 4 below. 1. Metal corrosion inhibition. Preventability The adhesive layer of the surface protective film after being placed in an environment of 23 ° C and 50% RH for 7 days is attached to an aluminum foil and placed in an environment of 60 ° C and 90% RH for 2 days. Observe the corrosiveness at this time. Further, in the following Table 4, each of them is indicated by "d", "〇" means no change, and "X" means whitening. 2. Autoclave suitability The surface protective film after being placed in an environment of 23 ° C and 50% RH for 7 days was cut to a width of 25 mm and attached to a polarizing plate at 5 〇 ^, 0.49 MPa (5 kg / cm 2 ). The autoclave treatment was carried out under the conditions of this, and the foaming at this time was observed. Further, in the following Table 4, each of them is shown below, and "〇" means that no foaming was observed. "X" means that foaming was observed. 3. The surface protection film after 7 days of adhesion in a 23 ° C, 50% RH environment, cut to a width of 25 mm and attached to a polarizing plate at 5 〇 t, 0.49 MPa (5 kg / cm 2 ) Autoclave treatment was carried out for 2 minutes. Using a tensile tester, the peeling angle was 18 、 and the peeling speed was 0.3 m/min in an environment of 23 ° C and 50% RH, and the adhesive tape was described in accordance with JIS Z 2 〇 37 (20 〇〇). The sheet a test method was used to measure the adhesion (v/25 πιπι) 〇 4. The adhesion to the substrate was evaluated in the adhesion of the protective film (substrate) at the time of measuring the adhesion. Further, in the following Table 4, each of them is as follows, "" _ _ film peeling agent is not completely protected from the protection, and "X" means that the adhesive does not stick from the table. >, 5. Viscosity of the adherend The contact angle of the polarizing plate surface before and after the measurement of the above adhesive force was measured. Further, the measurement of the contact angle was carried out in accordance with the wettability test method of the surface of the substrate glass described in JIS 257 (1 "9 years). In the following Table 4, each of the following = "如" indicates that the contact of the polarizing plate surface before and after the adhesion measurement is 3. Hereinafter, "X" indicates that the contact angle of the surface of the polarizing plate before and after the measurement of the adhesion is changed. 6 · Low-temperature stability The surface protective film after being placed in an environment of 23 ° C and 50% RH for 7 days is attached to a polarizing plate, and autoclaved at 50 ° C, 0.49 MPa (5 kg / cm 2 ). 20 minutes. Subsequently, the appearance of _4 (12 hours after the rc environment was observed. The lower wire 4 towels were each as shown in the following table *, "〇" means that no foaming, floating, peeling, or precipitates were observed. "x" indicates that foaming, floating, peeling, or precipitation was observed. 7 - Transparency of the layer was visually confirmed to adhere to the surface protective film after being left for 7 days in an environment of 23 ° C and 50% RH. In the following Table 4, each of them is shown below, "〇" indicates a case where the transparency is good, and "X" indicates a case where white turbidity is observed in the adhesive layer. The treated polyester film was used instead of the polarizing plate on which the adhesive layer was formed in each of Examples and Comparative Examples 31 201247818, and an adhesive layer was formed on the polyester film to measure the gel fraction (%) after 7 days of coating. The gel fraction was obtained by weighing an adhesive composition of about 0.1 g in an environment of 23 ° C and 50% RH and measuring the weight WKg). This was taken to a sample vial and about 30 g of ethyl acetate was added and left for 24 hours. The content of the sample vial after a predetermined period of time was filtered using a 200 mesh stainless steel wire mesh (the weight of the wire mesh was set to W2), and the wire mesh and the residue were dried at 90 ° C for 1 hour. The overall weight is W3 (g). At this time, the gel fraction was calculated from the measured values and according to the following formula 2. [Number 2] Gel breakup Each evaluation result was sorted and shown in Table 4. Further, in Comparative Example 6 in Table 4, gelation occurred after the preparation of the crosslinking agent, and the sheet could not be obtained, and various evaluations could not be performed. 32 201247818 [inch ϊ comparative example ON A-18 o CN Ό σν 〇 (Ν 〇〇〇X 〇〇〇00 A-17 o ΟΝ 〇 (S 〇X 〇〇〇 A A-17 od \ο ΟΝ 〇沄d 〇X 〇〇〇\〇A-16 o (NI 1 1 1 1 1 1 1 1 〇A-15 o 卜 inch d ν〇σ\ 〇gd 〇X 〇X 〇 inch A-14 o inch b d Ό ΟΝ 〇< ;N d 〇〇〇X 〇cn A-13 osdd 00 〇沄d 〇X 〇XX (N A-12 o — »〇ΟΝ 〇sd 〇〇〇〇X — A-ll o — ΟΝ 〇gd 〇〇〇 〇X Example 〇A-10 o One OS 〇CO d 〇〇〇〇〇On ON < of- CN d 裘〇d 〇〇〇〇〇00 00 < ov) Ό ΟΝ 〇oo 〇〇〇〇〇卜< o ΟΝ 〇md 〇〇〇〇〇< od 〇\ 〇d 〇〇〇〇〇»n < o inch<N ΟΝ 〇CO d 〇〇〇〇〇 inch< o 00 d CN d 〇〇 〇CN d 〇〇〇〇〇m C^l < o cn 〇〇ΟΝ 〇CN d 〇〇〇〇〇<N CN < o r- d 00 d U-) σ\ 〇d 〇 〇〇〇 〇— 1 < o V-) dd 〇od 〇〇〇〇〇 Composition (parts by mass) 1 _1 Polymer (A) 1 PQ (N ώ ώ 凝胶 Gel fraction (%) Metal corrosion suppression and prevention Adhesive strength (N/25mm) Adhesion to the substrate Adhesive contamination Low-temperature stability Adhesive layer Transparent autoclave Suitable carbodiimide cross-linking agent (B) Isocyanate cross-linking agent (C) (?ΙΕ?<·5φ^#τ3ζνΗ13ΗηΛΊ〇£ί4Β,^^®έΒ*Μ^&-54()ΧΗ(#^:#ί+®)31νζ〇Η〇υ:ιό (铋t? <<^inv3IS3a:3^他Β)ςο-Λ (Big-61m) 3HnIaoaHVu: ε-« (铋w<<^inv3ISHHu^*B)60->(Big-&m) 31nIa〇aHV3:zH (铋阳<<Umbrella^lvuIS3Hu^*B)I0-> (!ll^t^)alnIa〇pqosvu:l-Da(s 33 201247818 From the above Table 4, it is known The surface protective films (1) to (9) of Comparative Examples 1 to 9 and the surface protective films (1) to (10) of Examples 1 to 10 of the present invention are resistant to adhesion of the adherend and the adhesive layer. The transparency and autoclave are excellent in suitability. I: Simple description of the diagram 3 (none) [Explanation of main component symbols] (none) 34