201245378 六、發明說明： 【發明所屬之技術領域】 本發明係關於液晶顯示器的製造步驟中所利用的表面 保濩膜。更具體而言，本發明係關於為了保護構成液晶 顯示器的偏光板、相位差板等的光學構件的表面而使用 之表面保護膜用黏著劑組成物，以及使用其之表面保護 臈。 【先前技術】 一直以來，在作為構成液晶顯示器的構件之偏光板、 相位差板等光學構件的製造步驟中，4了暫時保護光學 構件的表面賴附表面保護^這樣的表面保護膜僅在 製造光學構件的㈣巾被❹，在將光學構件組裝入液 晶顯示器時’將其從光學構件剝離而除去。此種為了保 護光學構件表面的表面保護膜僅在製造步驟中使用。因 此’一般也被稱為步驟膜。 4造光學構件的步驟中使用的表面保護膜，係 在具有光學透明性的聚對苯二甲酸乙ΚΡΕτ)樹脂膜 的單面形成黏著劑層。表面佯， 、 ^ 自保5蒦膜直至貼合於光學構件 為止’為了保護其黏著劑 層的㈣離處理之剝離膜係貼 δ於黏者劑層之上。 人，由於偏光板、相位罢 * ^ 等々光予構件係在貼合有 表面保護膜的狀態下，進 虿 丁伴有液日日顯示板的顯示能 301110081 3 201245378 力、色度、對比度、雜質混入等光學評價的製品檢查， 因此作為對於表面保護膜的要求性能，係要求在黏著 劑層中不附著氣泡或雜質。 又近年來，將表面保護膜從偏光板、相位差板等的 光學構件剝離時，伴隨著從被黏體剝離黏著劑層時產生 的靜電而產生剝離帶電’擔心液晶顯示器的電氣控制電 路故1¥文到影響。因此，黏著劑層必須具有優異的抗靜 電性能。 又，在使表面保護臈貼合於偏光板、相位差板等光學 構件時，由於各種原因，有暫時聽表面保護膜並重新 點貼表面保護膜的情況’這時要求容諸被黏體的光學 構件剝離（返工性（rew〇rkabiHty))。 ;八料從偏光板、相位差板等光學構件剝離表面 濩膜時，要求可快速地剝離。即，為了利用高速剝離 可快速地剝離’要求黏著力隨著剝離速度的變化是少的 此近年來，作為對於構成表面保護膜的黏著劑^ 的要求性能’要求⑴取得低速剝離區域和高速剝離區太 中的點著力的平衡、⑺防止黏著劑殘留的發生、⑺具$ 優異的抗靜電性能、和(4)具有返工性能。表面保護㈣ 由具有這樣的性能而變得容易使用。 但是，雖訪滿足對於構成表面保護膜㈣著劑層^ 要求性能，亦即⑴〜(4)各自、每一個的要求性能，但同 >〇111〇〇81 4 201245378 時滿足對表面保護膜的黏著劑層要求的（υ〜(4)全部要求 性月t*疋非常困難的0 例如’關於（1)取得低速剝離區域和高速剝離區域中的 黏著力的平衡和（2)防止黏著劑殘留的發生，已知有以下 的提案。 以具有碳數在7以下的烷基的（曱基）丙烯酸烷基酯與 含有缓基的共聚合性化合物之共聚合體為主要成分，用 交聯劑對其交聯處理製成的丙烯酸系黏著劑層，在經過 長時間黏附的情況，具有黏著劑向被黏體一側移動而附 著’並且對被黏體的附著力經時大幅上升的問題。為了 避免該問題，已知提出一種設置有黏著劑層之物品，該 黏著劑層係使用具有碳數為8〜10的烷基的（曱基）丙烯酸 烷基酯與具有醇性羥基的共聚合性化合物之共聚合體， 用交聯劑對其交聯處理而得到（專利文獻丨）。 並且提出一種設置有黏著劑層之物品，該黏著劑層係 在上述同樣的共聚合體中少量混合（甲基）丙烯酸烷基酯 與含有羧基的共聚合性化合物之共聚合體，用交聯劑將 其交聯處理而得到。但是，當將其用於表面張力低且表 面光滑的塑膠板等之表面保護時，具有由於加工時或保 存時的加熱而產生浮起等剝離現象的問題、或經手工高 速剝離時再剝離性差的問題。 為了解決這些問題，提出一種黏著劑組成物，該黏著 101110081 c 201245378 劑組成物係藉由於_〇重量份之以具有碳數為8〜1〇的 烷基的（甲基）丙烯酸烧基醋4主要成分之（甲基）丙稀酸 烧基醋中’加入b)1〜15重量份之含有幾基的共聚合性化 合物與〇3〜100重量份之碳數為卜5的脂肪族羧酸的乙 稀基醋而得到單體混合物的共聚合體，並於該共聚合體 中混合入相對於上述b)成分的緩基為當量以上的交聯劑 而得（專利文獻2)。 專利文獻2中記載的黏著劑組成物，沒有產生在加工 時或保存時等中的浮㈣的剝離現象，並且附著力也沒 有經時大幅上升，因此再剝離性優異。而且，即使是長 期保存、特別是高溫環境下的長期保存，也可以小的力 再剝離，這時，在被黏體上不會產生黏著劑殘留，且在 進行向速剝離時也可以小的力再剝離。 又，關於(3)優異的抗靜電性能，作為賦予表面保護膜 抗靜電性的方法，已例示有對基材膜混練入抗靜電劑的 方法等。作為抗靜電劑，例如公開有（a)具有4級銨鹽、 比定嗡鹽、第1〜3級胺基等陽離子性基的各種陽離子性 抗靜電劑，（b)具有磺酸鹽基、硫酸酯鹽基、磷酸酯鹽基、 膦酸鹽基等陰離子性基的陰離子性抗靜f劑；⑷胺基酸 類、胺基硫酸酯類等的兩性抗靜電劑；（d)胺基醇系、甘 油系、眾乙一醇系等的非離子性抗靜電劑；（e)將如上述 的抗靜電劑高分子量化所得到的高分子型抗靜電劑等 J011I0081 6 201245378 (專利文獻3)。 又’近年來，不只提出將這樣的抗靜電劑包含在基材 膜裡或塗布於基材膜表面’還提出直接使黏著劑層含有 抗靜電劑。 又，關於（4)返工性能，例如提出有一種黏著劑組成物， 該黏著劑組成物係藉由於丙烯酸系樹脂中，對丙烯酸樹 脂100重量份以〇·〇〇〇 1〜1 〇重量份混合異氰酸酯系化合物 的硬化劑和特定的矽酸鹽寡聚物而得（專利文獻4)。 在專利文獻4中’以院基的碳數為2〜12左右的丙烯酸 烷基酯或烷基的碳數為4〜12左右的曱基丙烯酸烷基酯等 為主單體成分，並可包含例如含有敌基的單體等之含有 其他官能團的單體成分。一般而言，較佳係含有5〇重量 %以上的上述主單體，又，較佳係含有官能團的單體成分 的含量為0.001〜50重量％、更佳〇.〇〇丨〜25重量％、最佳 〇·〇1〜25重量％。由於此種專利文獻4中記載的黏著劑組 成物即使在高溫下或者高溫高濕下，凝聚力和附著力的 經時變化也是小的，且曲面黏附力也顯示優異的效果， 因此具有返工性。 一般而言，如果將黏著劑層製成柔軟性狀，則黏著劑 殘留變得容易發生，返工性也容易降低。即，容易變得 錯誤地貼合時剝離困難、重新貼合困難。因此，為了使 其具有返工性，需要將具有羧基等官能團的單體交聯於 101110081 201245378 主劑上，將黏著劑層製成—定的硬度。 [先行技術文獻] (專利文獻） (專利文獻1)曰本專利特開昭63_225677號公報 (專利文獻2)日本專利特開平U_2561U號公報 (專利文獻3)日本專利特開平11〇7〇629號公報 (專利文獻4)日本專利特開平8_19913〇號 【發明内容】 (發明所欲解決之問題） 在習知技術中，作為對於構成表面保護膜的黏著劑声 =要純能，要求⑴取得低速剝離區域和高迷剝離區域 的黏著力的平衡；（2)防止發生點著劑殘留 異的抗靜電性能；和⑷具有返工性。但是，相 ^⑷的各個、每個料求性能，但是_滿足表面保 4膜的黏著劑層中要求的⑴〜(4)的全部要求性能是困難 的，還不可實現。 :發明係有鑑於上述情況而完成。本發明的課題在於 供可同時滿足⑴取得低速剝離區域和高速剝離區域中 里黏者力的平衡、⑺防止黏著劑殘留的發生、⑺且有優 :的抗靜電性能、和⑷具有返工性之全部要求性能的黏 考劑組成物以及表面保護膜。 (解决問題之手段） !〇Π1〇〇8ι 201245378 為了解決上述問題，本發明提供一種黏著劑組成物， 其由含有（A)烷基碳數為C4〜cl〇的（曱基）丙烯酸酯單體、 (B)含有羥基的可共聚合單體、和（c)含有羧基的可共聚合 單體的共聚合體所構成，進—步含有（D)3官能以上的異 氰酸酯化合物、（E)交聯延遲劑、（F)交聯觸媒、（g)抗靜 電劑、（H)聚醚改質矽氧烷化合物。 上述(B)含有羥基的可共聚合單體係選自（甲基）丙烯酸 8-經基辛醋、（甲基）丙烯酸6_輕基己醋、（甲基）丙稀酸4_ I基丁 S曰、（甲基）丙烯酸2_羥基乙酯、N_羥基（甲基）丙烯 醯胺、N-經甲基（甲基）丙稀酸胺、Ν·經乙基（甲基）丙稀醯 胺所組成化合物群中的至少一種以上；較佳係相對於⑽ 重置份的上述（Α)烷基碳數為C4〜Ci〇的（甲基）丙烯酸酯 單體’含有G.1〜5.G重量份的上述(B)含有經基的可共聚 合單體，又，上述(B)含有羥基的可共聚合單體中，（甲基） 丙烯酸8-羥基辛酯、（曱基）丙烯酸6_羥基己酯、（甲基） 丙烯酸4-羥基丁酯的合計量為〇〜〇.9重量份。 上述（C)含有羧基的可共聚合單體係選自（甲基）丙烯 酸、羧乙基（甲基）丙烯酸酯、羧戊基（甲基）丙烯酸酯所組 成化合物群中的至少一種以上，較佳係相對於1〇〇重量 份的上述(A)烷基的碳數為C4〜cl〇的（甲基）丙烯酸酯單 體，含有0.35〜1.0重量份的上述（c)含有羧基的可共聚合 單體。 口 101110081 9 201245378 上述（D)3官能以上的異氰酸酯化合物係選自六亞甲基 一異氰酸酯化合物的三聚異氰酸酯體、異佛爾酮二異氰 酸酯化合物的三聚異氰酸酯體、六亞甲基二異氰酸酯化 合物的加成物體 '異佛爾酮二異氰酸酯化合物的加成物 體所組成化合物群中的至少一種以上，較佳係相對於J 〇〇 重量份的上述共聚合體，含有θ 5〜5 θ重量份的上述(D)3 B月包以上的異氰酸酉旨化合物。 上述（G)抗靜電劑較佳係為相對於1〇〇重量份的上述共 聚合體含有量為0.5〜5.0重量份且熔點為30〜80〇c的離子 型化合物，或在上述共聚合體中以1〇〜5〇重量％共聚合 且熔點為30〜80°C的4級銨鹽型丙烯酸系單體。 上述（H)聚醚改質矽氧烷化合物較佳係HLB值為7〜12 的聚醚改質矽氧烷化合物，相對於1〇〇重量份的上述共 聚合體，含有0.01〜0.5重量份的上述(11)聚醚改質矽氧烷 化合物。 上述（E)交聯延遲劑較佳係酮烯醇互變異構化合物，相 對於100重量份的上述共聚合體，含有1〇〜5 〇重量份的 上述（E)交聯延遲劑。 上述（F)觸媒較佳係有機錫化合物，相對於1〇〇重量份 的上述共聚合體，含有0.01〜0.5重量份的上述(F)觸媒Y 較佳係使上述黏著劑組成物交聯而成的黏著劑層在低 速剝離區域〇.3m/min的黏著力為〇.05〜〇 1N/25mm，在言 101110081 10 201245378 速剝離區域3Gm/min的黏著力為l.GN/25mm以下。 車又佳係使上述點著劑組成物交聯而成的黏著劑層的表 面電阻率在5.αχ1〇+1()Ω/□以下，剝離帶電壓為±G〜lkv。 又，本發明提供使上述黏著劑组成物交聯而成的黏著 劑層形成於樹脂膜的單面或雙面之黏著膜。 又’本發明提供使上述黏著劑組成物交聯而成的黏著 劑層形成於樹脂膜的單面之表面保護膜，用原子筆介隔 者上述黏著劑層在表面保護膜上描繪後，沒有向被黏體 轉移污染。 上述表面保護膜可作為偏光板用表面保護膜使用。 較佳係在上述樹脂膜形成有上述黏著劑層侧的相反 面，進行抗靜電和防污處理。 (發明效果） 根據本《明可提供可同時滿足⑴取得低速剝離區域和 高速剝離區域中的黏著力的平衡、⑺防止黏著劑殘留的 發生、（3)具有優異的抗靜電性能、和(4)具有返工性能之 全部要求性能的黏著劑組成物以及表面保護膜。 【實施方式】 以下，基於較佳的實施形態說明本發明。 本發明的黏著劑經成物，其主劑是由含有⑷院基碳數 為c^cio的（曱基）丙稀酸醋單體、⑻含有經基的可共 聚合早體、和(C)含有縣的可共聚合單體的共聚合體所 101110081 201245378 構成，並進-步含有⑼3官能以上的異氰酸醋化合物、 (E)交聯延遲劑、（F)交聯觸媒、（G)抗靜電劑、（h)聚醚改 質石夕氧烧化合物。 作為（A)烷基碳數為C4〜C10的（甲基）丙烯酸酯單體， 可舉出（甲基）丙烯酸丁酯、（曱基）丙烯酸異丁酯、（曱基) 丙烯酸戊酯、（曱基）丙烯酸己酯、（曱基）丙烯酸庚酯、（甲 基）丙烯酸辛酯、（甲基）丙烯酸異辛酯、（甲基）丙烯酸2_ 乙基己酯、（曱基）丙烯酸壬酯、（曱基）丙烯酸異壬酯、（甲 基）丙烯酸癸酯等。 作為（B)含有羥基的可共聚合單體，可舉出（曱基）丙烯 酸8-羥基辛酯、（甲基）丙烯酸6-羥基己酯、（甲基）丙烯酸 4-羥基丁酯、（曱基）丙烯酸2-羥基乙酯等的（甲基）丙烯酸 經基烧基酉旨類’ N·經基（曱基）丙稀醯胺、ν·經甲基（曱基） 丙稀醯胺、N-經乙基（甲基）丙烯醯胺等的含有經基的（曱 基）丙烯醢胺類等。 較佳係選自（甲基）丙烯酸8-羥基辛酯、（甲基）丙烯酸6_ 羥基己酯、（甲基）丙烯酸4-羥基丁酯、（曱基）丙烯酸2-羥基乙酯、N-羥基（甲基）丙烯醯胺、N-羥甲基（甲基）丙稀 醯胺、N_羥乙基（甲基）丙烯醯胺所組成化合物群中的至少 一種以上。 相對於100重量份的上述(A)烷基碳數為C4〜C10的（甲 基）丙烯酸酯單體，較佳係含有0.1〜5.0重量份的上述(B) 101110081 12 201245378 含有羥基的可共聚合單體。 並且’在（B)含有羥基的可共聚合單體中，（曱基）丙稀 酸8-羥基辛酯、（曱基）丙烯酸6_羥基己酯、（曱基）丙烯酸 4 -經基丁自旨的合計I較佳係未滿1重量份（亦允許不含有 的情況），較佳為0〜0.9重量份。 (C) 含有叛基的可共聚合單體較佳係選自（曱基）丙稀 酸、羧乙基（甲基）丙烯酸酯、羧戊基（曱基）丙烯酸酯所組 成化合物群中的至少一種以上。 相對於100重量份的（A)烧基的碳數為C4〜C10的（曱基) 丙烯酸酯單體，較佳係含有0.354.0重量份的（c)含有羧 基的可共聚合單體。 作為（D)3官能以上的異氰酸酯化合物，只要是i分子 中具有至少3個以上異氰酸酯（NC〇)基的多異氰酸酯 化合物即可，可以舉出六亞甲基二異氰酸酯、異佛爾酮 二異氰酸S旨、二苯基甲烧二異氰酸g旨、f代亞苯基二異 氰酉欠Sa、伸茬基二異氰酸酯等的二異氰酸酯類（1分子中 具有2個NCO基的化合物）的縮二腺改質體或三聚異氛 酸醋改質體、三羥甲基丙烧或甘油等3 it以上的多元醇 (1分子中具有至少3個以上的〇H基的化合物）的加成物 體（多元醇改質體）等。 (D) 3官能以上的異氰酸酯化合物是i分子中至少具有 3個以上的異氰酸_C0)基的多異氰酸醋化合物，特佳 101110081 13 201245378 係選自六亞曱基二異氰酸酯化合物的三聚異氰酸酯體、 異佛爾酮二異氰酸酯化合物的三聚異氰酸酯體（三聚 體）、六亞曱基二異氰酸酯化合物的加成物體、異佛爾酮 二異氰酸酯化合物的加成物體、六亞甲基二異氰酸酯化 合物的縮二脲體、異佛爾酮二異氰酸酯化合物的縮二脲 體所組成化合物群中的至少一種以上。相對於1 〇〇重量 伤的共聚合體，較佳係含有0.5〜5.0重量份的（£>)3官能以 上的異氰酸酯化合物。 本發明的黏著劑組成物可以進一步含有（E)交聯延遲 劑。 作為（E)交聯延遲劑，可以舉出：乙醯乙酸甲酯、乙醯 乙酸乙酯、乙醯乙酸辛酯、乙醯乙酸油基酯、乙醯乙酸 月桂酯、乙醯乙酸硬脂酯等的β_酮酯，或乙醯丙酮、2,4_ 己一酮、苯曱酼丙酮等的卜二酮。此等為酮烯醇互變異 構化合物，在以多異氰酸酯化合物為交聯劑的黏著劑組 成物中，藉由將交聯劑所具有的異氰酸酯基封閉，可抑 制交聯劑混合後黏著劑組成物的過度黏度上升或凝膠 化’延長黏著劑組成物的使用期限（potlife)。 (E)交聯延遲劑較佳為酮烯醇互變異構化合物，特佳為 選自乙醯丙酮、乙醯乙酸乙酯所組成化合物群中的至少 一種以上。 相對於100重量份的共聚合體，較佳係含有1〇〜5 〇重 101110081 14 201245378 量份的（E)交聯延遲劑。 本發明的黏著劑組成物可以進一步含有（F)交聯觸媒。 在以多異氰酸_化合物為交聯劑的情況中，（F)交聯觸媒 只要是對於上述共聚合體和交聯劑的反應（交聯反應）作 為觸媒而發揮功能的物質即可，可以舉出三級胺等的胺 類化合物及有機錫化合物、有機鉛化合物、有機鋅化合 物等的有機金屬化合物等。 作為三級胺可以舉出三烷基胺、N，N，N，，N，_四烷基二 胺、N，N-二烷基胺基醇、三亞乙基二胺、咮啉衍生物、 哌啡衍生物等。 作為有機錫化合物，可以舉出二烷基錫氧化物、二烷 基錫的脂肪酸鹽、亞錫的脂肪酸鹽等。 (F)父聯觸媒較佳係有機錫化合物，特佳係選自氧化二 辛基錫、二月桂酸二辛基錫所組成化合物群中的至少一 種以上。 相對於100重量份的共聚合體，較佳係含有〇〇1〜〇5 重量份的（F)交聯觸媒。 ⑹抗靜㈣較㈣常溫（勤3代）τ為關的物質， 更具體而言’較佳係相對於100重量份的上述共聚合體， 含有量為0.5〜5.0重量份且炼點為3Q〜8(rc的離子型化人 物’或在上述共聚合體中以重量％共聚合且㈣ 為30〜80t：的4級録鹽型丙稀酸系單體。本發明中，作為 101110081 15 201245378 ⑹抗靜電劑，係於共聚合體中添加⑹）㈣為％铺 的離子型化合物，或將⑹)炼點為3〇销的*級鍵趟型 丙稀酸系單體共聚合於共聚合體中。由於這些⑹抗;電 劑的熔點低，且且右具絲岭甘 ，、有長鏈烷基，因此推測其與丙烯酸乒 聚合體的親和性高。 ' 作為（GW點為3G〜8Gt的離子魏合物，係具有陽離 子和陰離子的離子型化合物，可以舉“下化合物：陽 離子為°比㈣陽離子、心鐳陽離子、射鏘陽離子、 口比_陽離子、料鑌陽離子、絲陽離子等的含氮錯 陽離子，或雜陽離子、硫鏘陽離子等的化合物；陰離 子為六氟化餐鹽（PIV)、硫氰酸鹽（隐）、烧基苯 石只酸鹽（rc6h4so3·)、過氯酸鹽（CKV)、四氟化石朋酸鹽 (bf4·)等的無機或有機陰離子的化合物。藉由烧基的鏈 長或取代基的位置、個數等的選擇，可得到熔點為 30〜80 C的物質。陽離子較佳係4級含氮錯陽離子，可舉 出1-烧基。比。定。翁(2〜6位的碳原子有取代基也可以，無取 代也可以）等的4級°tb°定01陽離子、1，3·二烧基咪嗤鏽(2、 4、5位的碳原子有取代基也可以，絲代也可以）等的4 級味唾錯陽離子、四烷基銨基等的4級銨陽離子等。 作為（G2)熔點為30〜8〇°c的4級銨鹽型丙烯酸系單體， 為具有陽離子和陰離子的離子型化合物，可舉出以下化 合物：陽離子為（曱基）丙烯醯氧基烷基三烷基銨 101110081 201245378 (R3N+-CnH2n-OCOCQ=CH2，其中，Q=H 或 CH3、R=現基） 等的含丙烯酿基（aery 1)的4級銨化合物，陰離子為六氣化 磷酸鹽(PF〇、硫氰酸鹽（SCN_)、有機磺酸鹽（Rs〇3-)、過 氣酸鹽（Cl〇4·)、四氟化硼酸鹽（BF4·)等的無機或有機陰離 子的化合物。 作為（G)抗静電劑的具體例’没有特别地限定，但是可 舉出1-辛基吡啶鏽六氟化磷酸鹽、丨·壬基吡啶鏽六氟化 磷酸鹽、2-曱基-1-十二烷基吡啶鏽六氟磷酸鹽、卜辛基 0比咬鏽十二院基苯確酸鹽、1 _十二院基σ比咬鏽硫氰酸鹽、 1 -十二烧基°比咬鏽十二烧基苯績酸鹽、4-曱基_ 1 _辛基0比 啶鏽六氟化磷酸鹽、丙烯酸二曱胺基甲酯六氟化磷酸曱 基鹽（(CH3)3N+CH2OCOCH=CH2 · PF6 )等。 (Η)聚喊改質石夕氧烧化合物是具有聚醚基的石夕氧烧化 &物，除了一般的石夕氧烧單元(_SiR^-0-)，還有帶聚喊基 的矽氧烷單元此處，Ri表示1 種或2種以上的烧基或芳基’r2和r3表示1種或2種以 上的伸烷基、R4表示1種或2種以上的烷基、醯基等（末 端基）。作為聚醚基可以舉出聚氧化伸乙基（(C2H4〇)n)或 t氧化伸丙基（(C3H60)n)等的聚氧化伸烧基。 (H)聚醚改質矽氧烷化合物係hlb值為7〜12的聚醚改 質矽氧烷化合物’相對於1〇〇重量份的上述共聚合體， 較佳係含有〇.〇1〜〇·5重量份的上述(H)聚醚改質矽氧烷化 10I1I0081 17 201245378 合物。更佳係為0.1〜0.5重量份。 所謂HLB係例如jIS K32U (界面活性劑用語）等令規 定的親水親油平衡（親水性與親油性的比）。 聚醚改貝石夕氧院化合物係可例如對於具有矽院基的聚 有機石夕氧Μ鏈，藉由氫化我化反應將具有不餘和鍵 和聚氧化伸烷基的有機化合物接枝而得到。具體而言可 以舉出二曱基石夕氧烧.曱基（聚氧化伸乙基）石夕氧烧共聚合 體、二甲基矽氧烷.甲基（聚氧化伸乙基）矽氧烷.甲基（聚氧 化伸丙基）石夕氧院共聚合體、二曱基矽氧烷.曱基（聚氧化 伸丙基）矽氧烷共聚合體等。 藉由將（Η)聚醚改質矽氧烷化合物混合入黏著劑組成 物’可改善黏著劑的黏著力和返工性能。 再者，作為其他的成分，可適當地混合含有伸烷氧化 物的可共聚合（曱基）丙烯酸系單體、（甲基）丙烯醯胺單 體、二烷基取代丙烯醯胺單體、界面活性劑、硬化促進 劑、可塑劑、填充劑 '硬化延遲劑、加工助劑、抗老化 劑、抗氧化劑等的公知添加劑。這些可以單獨或2種以 上合併使用。 本發明的黏著劑組成物中使用之主劑的共聚合體可藉 由使(Α)烷基碳數為C4〜C10的（曱基）丙烯酸酯單體、（Β) 含有羥基的可共聚合單體、和（c)含有羧基的可共聚合單 體進行聚合而合成。共聚合體的聚合方法沒有特別的限 101110081 18 201245378 定，可以使用溶液聚合、乳化聚合等適當的聚合方法。 作為（G)抗靜電劑，使用（G2)的4級銨鹽型丙烯酸系單 體的情況下，在本發明的黏著劑組成物中使用之主劑的 共聚合體可藉由使(A)烷基碳數為C4〜ci〇的（曱基）丙烯 酸酯單體、（B)含有羥基的可共聚合單體、（(：)含有羧基 的可共聚合單體、和（G2)的4級銨鹽型丙烯酸系單體進 行聚合而合成。 藉由在上述共聚合體中混合（D)3官能以上的異氰酸 酯化合物、（E)交聯延遲劑、交聯觸媒、抗靜電劑、 (H)聚醚改質石夕氧烧化合物、進—步適當任意的添加劑， 可製造本發明的黏著劑組成物。另外，將（G2)熔點為 30〜80°C的4級銨鹽型丙烯酸系單體聚合於主劑的共聚合 體中的情況下’對於共聚合體無論是否進—步添加⑹抗 靜電劑都沒有關係。 較佳係使上述黏著劑組成物交聯而成的黏著劑層在低 速剝離區域G.3m/min的黏著力為G.G5〜G.lN/25mm，在高 速剝離區域3Gm/min的黏著力為1厕25_以下。由 了待到黏著力著剝離速度變化少的性能，即使是 經高速剝離，亦可進行迅速的剝離。X，為了重新貼合， 暫時剝離表面保護膜時，不需要過大的力，可容易從被 黏體剝離。 車乂佳係使上述黏著劑組成物交聯而成的黏著劑層之表 101110081 201245378 面電阻率在5.〇χ1〇+ι〇Ω/□以下，剝離帶電壓為印〜化乂。 另外’在本發明中，上述「±0〜lkv」意思是〇〜·lkv和 0〜+lkV，亦即-1〜+ikV。由於表面電阻率大時，放掉剝 離時因帶電所產生的靜電之性能差，因此，藉由使表面 電阻率充分減小，可降低伴隨從被黏體剝離黏著劑層時 產生的靜電所生成之剝離帶電壓，抑制對被黏體的電氣 控制電路等的影響。 將本發明的黏著劑組成物交聯而成的黏著劑層（交聯 後的黏著劑）的凝膠分率較佳係95〜100%。如此，由於凝 膠分率向’可使低速剝離區域中的黏著力不變得過大， 降低從共聚合體的未聚合單體或寡聚物的溶出，改善返 工性、尚溫向濕中的财久性’抑制被黏體的污染。 本發明的黏著膜係使本發明的黏著劑組成物交聯而成 之黏著劑層形成於樹脂膜的單面或雙面。而且，本發明 的表面保護膜係將交聯本發明的黏著劑組成物所成的黏 著劑層形成於樹脂膜單面之表面保護膜。本發明的黏著 劑組成物由於使上述（A)〜(H)的各個成分以良好平衡混 6 了同時滿足（1)取得在低速剝離區域和高速剝離區域 中的黏著力的平衡、（2)防止黏著劑殘留的發生、（3)具有 優異的抗靜電性能、和（4)具有返工性能（用原子筆介隔著 itU著劑層在表面保濩膜上描繪後，不會向被黏體轉 移污染）之全部要求性能。因此，可在偏光板的表面保護 101110081 201245378 膜的用途中適當地使用。 作為黏著劑層的基材膜或保護黏合面的剝離膜（隔 片）’係可使用聚酯膜等的樹脂膜等。 在基材膜中，在樹脂膜形成有黏著劑層侧的相反面， 可實施利用聚矽氧系、氟系的脫模劑或塗層劑、二氧化 矽微粒等的防污處理；利用抗靜電劑的塗布或混入等的 抗靜電處理。 在剝離膜中’在黏著劑層與黏合面黏合之側的面上， 藉由聚矽氧系、氟系的脫模劑等實施脫模處理。 [實施例] 以下’基於實施例，具體說明本發明。 <丙烯酸共聚合體的製造> [實施例1] 於配備有攪拌器、溫度計、回流冷凝器和氮導入管的 反應裝置中導入氮氣，將反應裝置内的空氣用氮氣置 換。然後’於反應裝置中加入丙烯酸2-乙基己酯100重 量份、丙烯酸8-羥基辛酯〇.9重量份、丙烯酸0.5重量份、 和溶劑（乙酸乙酯）60份。然後，花費2小時滴入作為聚 合引發劑的偶氮二異丁腈〇.丨重量份，於65°C使其反應6 小時’得到重量平均分子量為5〇萬的實施例1中使用的 丙烯酸共聚合體溶液1。 [實施例2〜9和比較例1〜9] 101110081 21 201245378 單體的組成分別按照表1的（A)〜(C)所記載般設定，除 此以外，與上述實施例1中使用的丙烯酸共聚合體溶液！ 同樣地’得到實施例2〜9和比較例i〜9中使用的丙烯酸 共聚合體溶液。 <黏著劑组成物和表面保護膜的製造> [實施例1] 如上述般，於所製造的丙烯酸共聚合體溶液1(其中丙 烯酸共聚合體為100重量份）中加入丨·辛基吼啶鏽六氟化 磷酸鹽1.5重量份、KF_351A(HLB=12的聚醚改質矽氧烷 化合物）0.1重量份、乙醯丙酮2.5重量份並攪拌後，加入 CORONATE HX(六亞曱基二異氰酸酯化合物的三聚異氰 酸酯體）1.5重量份、二月桂酸二辛基錫〇 〇2重量份後， 攪拌混合，得到實施例1的黏著劑組成物。將該黏著劑 組成物塗布於經聚矽氧樹脂塗層的聚對苯二曱酸乙二酯 (PET)膜所構成的剝離膜上後，於9〇它下乾燥而除去溶 劑’得到黏著劑層的厚度為25μιη的黏著片。 然後’將黏著片轉移至單面經抗靜電和防污處理的聚 對苯二曱酸乙二酯（ΡΕΤ)膜經抗靜電和防污處理面的反 面’得到具有「經抗靜電和防污處理的PET膜/黏著劑層 /剝離膜（聚矽氧樹脂塗層的ΡΕΊΓ膜）」的積層結構之實施 例1的表面保護膜。 [實施例2〜9和比較例1〜9] 101110081 22 201245378 添加劑的組成各如表1的（D)〜(Η)所記載般設定，除此 以外，與上述實施例1的表面保護膜同樣地得到實施例 2〜9和比較1〜9的表面保護膜。 表1中，各成分的混合比係用括弧圈起表示以（Α)群的 合計為100重量份所求出之重量份的數值。又，表2中 顯示表1中使用的各成分代號之化合物名。另外， CORONATE (註冊商標）HX 和 HL 是日本 POLYURETHANE工業股份有限公司的商品名， 丁AKENATE(註冊商標）D-140N是三井化學股份有限公司 的商品名，KF-351A、KF-352A、KF-353、KF-640 和 X-22-6191是信越化學股份有限公司的商品名。201245378 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a surface protective film used in a manufacturing step of a liquid crystal display. More specifically, the present invention relates to an adhesive composition for a surface protective film used for protecting the surface of an optical member constituting a polarizing plate or a phase difference plate of a liquid crystal display, and a surface protective layer using the same. [Prior Art] In the manufacturing steps of an optical member such as a polarizing plate or a phase difference plate which constitute a member of a liquid crystal display, the surface protection film for temporarily protecting the surface of the optical member is only manufactured. The (four) towel of the optical member is removed, and when the optical member is assembled in the liquid crystal display, it is removed from the optical member. Such a surface protective film for protecting the surface of the optical member is used only in the manufacturing steps. Therefore, 'generally, it is also called a step film. The surface protective film used in the step of producing an optical member is formed by forming an adhesive layer on one side of a polyethylene terephthalate resin film having optical transparency. The surface 佯, , ^ self-protected 5 蒦 film until it is bonded to the optical member ′ in order to protect the adhesive layer (4) from the treated release film δ on the adhesive layer. Person, due to the polarizing plate, phase, etc., the member is attached to the surface protective film, and the display of the liquid and the daily display panel is 301110081 3 201245378 Force, Chromaticity, Contrast, Impurity Incorporation of an optical evaluation product inspection is required, and therefore, as a required performance for the surface protective film, it is required that no bubbles or impurities adhere to the adhesive layer. In recent years, when the surface protective film is peeled off from an optical member such as a polarizing plate or a retardation plate, peeling electrification occurs due to static electricity generated when the adhesive layer is peeled off from the adherend, and the electrical control circuit of the liquid crystal display is worried. ¥ text to influence. Therefore, the adhesive layer must have excellent antistatic properties. In addition, when the surface protection 臈 is bonded to an optical member such as a polarizing plate or a retardation plate, for some reason, there is a case where the surface protective film is temporarily listened to and the surface protective film is re-applied. In this case, it is required to accommodate the optical body of the adherend. Component peeling (reworkability (rew〇rkabiHty)). Eight materials are peeled off from the surface of the optical member such as a polarizing plate or a phase difference plate. In other words, in order to quickly peel off by the high-speed peeling, the adhesive force is required to be small as the peeling speed is small. In recent years, as a required performance for the adhesive constituting the surface protective film, (1) a low-speed peeling region and a high-speed peeling are obtained. The zone has a balance of effort, (7) prevents the occurrence of adhesive residue, (7) has excellent antistatic properties, and (4) has reworkability. Surface protection (4) is easy to use by having such properties. However, although the interview satisfies the required performance for the constituent layers of the surface protective film (4), that is, the required performance of each of (1) to (4), but the same as > 〇111〇〇81 4 201245378 The adhesive layer required (υ~(4) all required month t*疋 very difficult 0 such as 'About (1) achieving the balance of adhesion in the low-speed peeling zone and the high-speed peeling zone and (2) preventing the adhesive The following proposal is known for the occurrence of the residue. The copolymer of a (mercapto)acrylic acid alkyl ester having an alkyl group having 7 or less carbon atoms and a copolymerizable compound containing a slow group is used as a main component, and a crosslinking agent is used. When the acrylic pressure-sensitive adhesive layer produced by the crosslinking treatment is adhered for a long period of time, the adhesive adheres to the adherend side and adheres to it, and the adhesion to the adherend is greatly increased over time. In order to avoid this problem, it is known to provide an article provided with an adhesive layer which is a copolymer of an alkyl group having a carbon number of 8 to 10 and an alkyl group having an alcoholic hydroxyl group. Compound The polymer is obtained by crosslinking treatment with a crosslinking agent (Patent Document No.), and an article provided with an adhesive layer in which a small amount of (meth)acrylic acid is mixed in the same copolymer as described above is proposed. a copolymer of an alkyl ester and a carboxyl group-containing copolymerizable compound, which is obtained by crosslinking a crosslinking agent, but when used for surface protection of a plastic sheet having a low surface tension and a smooth surface, A problem of peeling phenomenon such as floating due to heating during processing or storage, or a problem of poor removability by manual high-speed peeling. To solve these problems, an adhesive composition is proposed, which is 101110081 c 201245378 composition By adding (b) 1 to (meth)acrylic acid vinegar as the main component of (meth)acrylic acid vinegar 4 having an alkyl group having a carbon number of 8 to 1 Å by weight 15 parts by weight of a copolymerizable compound containing a plurality of groups and 3 to 100 parts by weight of a vinyl ketone of an aliphatic carboxylic acid having a carbon number of 5, to obtain a copolymer of a monomer mixture, and Mixing body with respect to the slow group b) above is not less than the equivalent of the component obtained by the crosslinking agent (Patent Document 2). The adhesive composition described in Patent Document 2 does not cause a peeling phenomenon of floating (four) during processing or storage, and the adhesion does not increase significantly over time, so that the removability is excellent. Moreover, even if it is stored for a long period of time, especially in a high-temperature environment, it can be peeled off with a small force. In this case, no adhesive remains on the adherend, and a small force can be applied to the quick-release peeling. Strip again. In addition, (3) excellent antistatic performance, as a method of imparting antistatic property to the surface protective film, a method of kneading an antistatic agent to a base film, and the like are exemplified. Examples of the antistatic agent include (a) various cationic antistatic agents having a cationic group such as a quaternary ammonium salt, a specific sulfonium salt, and a first to third amino group, and (b) a sulfonate group. An anionic antistatic agent such as an anionic group such as a sulfate group, a phosphate group or a phosphonate group; (4) an amphoteric antistatic agent such as an amino acid or an amine sulfate; (d) an amino alcohol A nonionic antistatic agent such as a glycerin system or a acetyl alcohol group; (e) a polymer type antistatic agent obtained by polymerizing an antistatic agent as described above, and the like, J011I0081 6 201245378 (Patent Document 3). Further, in recent years, it has been proposed not only to include such an antistatic agent in a substrate film or to apply it to a surface of a substrate film, but also to directly form an adhesive agent layer with an antistatic agent. Further, regarding (4) reworkability, for example, an adhesive composition is proposed which is obtained by mixing an acrylic resin with 100 parts by weight of an acrylic resin in an amount of 〇·〇〇〇1 to 1 〇 by weight. A curing agent for an isocyanate compound and a specific phthalate oligomer (Patent Document 4). In Patent Document 4, an alkyl acrylate having a carbon number of about 2 to 12 in a yard group or an alkyl thioacrylate having an alkyl group having a carbon number of about 4 to 12 is mainly a monomer component, and may include For example, a monomer component containing an other functional group such as an enemy group-containing monomer. In general, it is preferable to contain 5% by weight or more of the above-mentioned main monomer, and it is preferable that the content of the monomer component containing a functional group is 0.001 to 50% by weight, more preferably 〇. The best 〇·〇1~25% by weight. Since the adhesive composition described in Patent Document 4 has a small change in cohesive force and adhesion over time even under high temperature or high temperature and high humidity, and the curved surface adhesion force exhibits an excellent effect, it has reworkability. In general, when the adhesive layer is made into a soft property, the adhesive residue tends to occur, and the reworkability is also liable to lower. In other words, it is easy to peel off when it is erroneously bonded, and it is difficult to reattach it. Therefore, in order to impart reworkability, it is necessary to crosslink a monomer having a functional group such as a carboxyl group to a principal agent of 101110081 201245378, and to form the adhesive layer to a predetermined hardness. [Patent Document 1] Patent Document 1 (Patent Document 1) Japanese Patent Laid-Open Publication No. Hei No. U_2561U (Patent Document 3) Japanese Patent Laid-Open No. 11〇7〇629 [Patent Document 4] Japanese Patent Laid-Open No. Hei 8_19913 No. [Draft of the Invention] (Problems to be Solved by the Invention) In the prior art, as an adhesive for a surface protective film, it is required to obtain a low speed. The balance of adhesion between the peeling area and the high peeling area; (2) preventing the antistatic property of the residue from occurring; and (4) having reworkability. However, the performance of each of the phases (4) and the properties of each material are required, but it is difficult and impossible to achieve all the required performances of (1) to (4) required in the adhesive layer of the surface protective film. : The invention was completed in view of the above situation. An object of the present invention is to simultaneously satisfy (1) obtaining a balance of viscous force in a low-speed peeling region and a high-speed peeling region, (7) preventing occurrence of adhesive residue, (7) having excellent antistatic performance, and (4) having reworkability. Adhesive composition and surface protective film that require performance. (Means for Solving the Problem) 〇Π1〇〇8ι 201245378 In order to solve the above problems, the present invention provides an adhesive composition comprising a (fluorenyl) acrylate single containing (A) an alkyl group having a carbon number of C4 to cl〇 (B) a copolymer of a hydroxyl group-containing copolymerizable monomer and (c) a carboxyl group-containing copolymerizable monomer, further comprising (D) a trifunctional or higher isocyanate compound, (E) a retardation agent, (F) a crosslinking catalyst, (g) an antistatic agent, and (H) a polyether modified siloxane compound. The above (B) hydroxyl group-containing copolymerizable single system is selected from the group consisting of (meth)acrylic acid 8-based octyl vinegar, (meth)acrylic acid 6-light hexyl vinegar, and (meth) acrylic acid 4 _ butyl butyl S曰, 2-hydroxyethyl (meth)acrylate, N-hydroxy(meth)acrylamide, N-methyl (meth) acrylate, Ν·ethyl (meth) propylene At least one or more of the compound group consisting of guanamine; preferably, the (meth) acrylate monomer having a C4 to Ci 上述 (C) is contained in the (10) replacement portion, and contains G.1~ 5. parts by weight of the above (B) copolymerizable monomer having a trans group, and (B) a hydroxyl group-containing copolymerizable monomer, (meth)acrylic acid 8-hydroxyoctyl ester, (fluorenyl) The total amount of 6-hydroxyhexyl acrylate and 4-hydroxybutyl (meth) acrylate is 〇~〇.9 parts by weight. The (C) carboxyl group-containing copolymerizable single system is at least one selected from the group consisting of (meth)acrylic acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth) acrylate. Preferably, the (meth) acrylate monomer having a carbon number of C4 to cl 上述 of the (A) alkyl group is contained in an amount of 0.35 to 1.0 part by weight, based on 1 part by weight, of the above (c) carboxyl group-containing compound. Copolymerization of monomers. Mouth 101110081 9 201245378 The above (D) trifunctional or higher isocyanate compound is selected from the group consisting of a trimeric isocyanate of a hexamethylene monoisocyanate compound, a isocyanurate of an isophorone diisocyanate compound, and a hexamethylene diisocyanate compound. At least one or more of the compound group of the addition object of the addition of the isophorone diisocyanate compound is preferably θ 5 to 5 θ by weight with respect to the above-mentioned copolymer of J 〇〇 parts by weight. The above-mentioned (D) 3 B-pack or higher isocyanate compound. The (G) antistatic agent is preferably an ionic compound having a content of the above-mentioned copolymer of 0.5 to 5.0 parts by weight and a melting point of 30 to 80 〇c with respect to 1 part by weight, or in the above copolymer. 1 〇 to 5 〇% by weight of a 4-stage ammonium salt type acrylic monomer copolymerized and having a melting point of 30 to 80 °C. The (H) polyether modified siloxane compound is preferably a polyether modified siloxane compound having an HLB value of 7 to 12, and is contained in an amount of 0.01 to 0.5 part by weight based on 1 part by weight of the above copolymer. The above (11) polyether modified oxoxane compound. The (E) crosslinking retarder is preferably a ketoenol tautomer compound, and the above (E) crosslinking retarder is contained in an amount of from 1 to 5 parts by weight based on 100 parts by weight of the above copolymer. The (F) catalyst is preferably an organotin compound, and 0.01 to 0.5 part by weight of the above (F) catalyst Y is preferably used to crosslink the above-mentioned adhesive composition with respect to 1 part by weight of the above copolymer. The adhesion layer of the adhesive layer in the low-speed peeling zone is 〇.05~〇1N/25mm in the low-speed peeling zone, and the adhesion force of 3Gm/min in the 101110081 10 201245378 speed peeling zone is below 1.GN/25mm. The surface resistivity of the adhesive layer obtained by crosslinking the above-mentioned dot composition is 5.αχ1〇+1()Ω/□ or less, and the peeling tape voltage is ±G~lkv. Further, the present invention provides an adhesive film in which the adhesive layer obtained by crosslinking the above-mentioned adhesive composition is formed on one surface or both surfaces of the resin film. Further, the present invention provides a surface protective film in which an adhesive layer obtained by crosslinking the above-mentioned adhesive composition is formed on one surface of a resin film, and the above-mentioned adhesive layer is drawn on the surface protective film by a pen holder. Transfer pollution to the adherend. The above surface protective film can be used as a surface protective film for a polarizing plate. It is preferable to carry out antistatic and antifouling treatment on the opposite side of the above-mentioned resin film on the side of the above-mentioned adhesive layer. (Effect of the Invention) According to the present invention, it is possible to simultaneously satisfy (1) the balance of adhesion in the low-speed peeling region and the high-speed peeling region, (7) prevention of occurrence of adhesive residue, (3) excellent antistatic property, and (4) An adhesive composition and a surface protective film having all the required properties of reworkability. [Embodiment] Hereinafter, the present invention will be described based on preferred embodiments. The adhesive agent of the present invention is mainly composed of (4) (mercapto) acrylic acid vinegar monomer having a carbon number of c^cio, (8) a copolymerizable early body containing a trans group, and (C) a copolymer comprising a copolymerizable monomer of a county, 101110081 201245378, and further comprising (9) a trifunctional or higher isocyanate compound, (E) a crosslinking retarder, (F) a crosslinking catalyst, (G) Antistatic agent, (h) polyether modified stone oxide compound. Examples of the (meth) acrylate monomer having (A) an alkyl group having a carbon number of C4 to C10 include butyl (meth) acrylate, isobutyl (meth) acrylate, and (mercapto) pentyl acrylate. (mercapto) hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, bismuth (mercapto) acrylate Ester, isodecyl (meth) acrylate, decyl (meth) acrylate, and the like. Examples of the (B) hydroxyl group-containing copolymerizable monomer include 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. (Meth)acrylic acid, such as 2-hydroxyethyl acrylate, such as (meth)acrylic acid, is based on the group of 'N·transyl (mercapto) acrylamide, ν·methyl (indenyl) acrylamide N-ethyl (meth) acrylamide or the like containing a mercapto group (fluorenyl) acrylamide. Preferably, it is selected from the group consisting of 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N- At least one or more of the group consisting of hydroxy (meth) acrylamide, N-methylol (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide. The above (B) 101110081 12 201245378 having a hydroxyl group is preferably contained in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the (A) alkyl group having a C4 to C10 alkyl group. Polymerization of monomers. And 'in (B) a hydroxyl group-containing copolymerizable monomer, (mercapto)acrylic acid 8-hydroxyoctyl ester, (mercapto)acrylic acid 6-hydroxyhexyl ester, (mercapto)acrylic acid 4-meridine The total of I is preferably less than 1 part by weight (and may not be contained), preferably 0 to 0.9 parts by weight. (C) the tether-containing copolymerizable monomer is preferably selected from the group consisting of (mercapto)acrylic acid, carboxyethyl (meth) acrylate, and carboxypentyl (mercapto) acrylate. At least one or more. It is preferable to contain 0.354.0 parts by weight of (c) a carboxyl group-containing copolymerizable monomer with respect to 100 parts by weight of the (A) alkyl group having a carbon number of C4 to C10 (fluorenyl) acrylate monomer. The (D) trifunctional or higher isocyanate compound may be a polyisocyanate compound having at least three or more isocyanate (NC〇) groups in the i molecule, and examples thereof include hexamethylene diisocyanate and isophorone diiso isomer. A diisocyanate such as cyanic acid, diphenylmethane diisocyanate, f-phenylene diisocyanide, Sa or decyl diisocyanate (a compound having two NCO groups in one molecule) a dimeric gland or a trimeric acetoacetate modified substance, a trimethylolpropane or a glycerol or the like having 3 or more polyols (a compound having at least 3 or more 〇H groups in one molecule) Additives (polyol modified bodies) and the like. (D) The trifunctional or higher isocyanate compound is a polyisocyanate compound having at least three or more isocyanate groups in the i molecule, and particularly preferably 101110081 13 201245378 is selected from a hexamethylene diisocyanate compound. Trimeric isocyanate, isomeric isocyanate (trimer) of isophorone diisocyanate compound, addition object of hexamethylene diisocyanate compound, addition object of isophorone diisocyanate compound, hexamethylene At least one or more of the compound groups of the biuret of the bis-isocyanate compound and the biuret of the isophorone diisocyanate compound. The isocyanate compound is preferably contained in an amount of from 0.5 to 5.0 parts by weight based on 1 part by weight of the total weight of the isocyanate compound. The adhesive composition of the present invention may further contain (E) a crosslinking delaying agent. Examples of the (E) crosslinking retarding agent include methyl ethyl acetate, ethyl acetate, octyl acetate, oleyl acetate, lauryl acetate, and stearyl acetate. Or a β-ketoester, or a diketone such as acetamidine, 2,4-hexanone or phenylhydrazine. These are ketoenol tautomer compounds, and in the adhesive composition using a polyisocyanate compound as a crosslinking agent, by blocking the isocyanate group of the crosslinking agent, the composition of the adhesive after the crosslinking agent is mixed can be suppressed. The excessive viscosity or gelation of the material 'extends the pot life of the adhesive composition. (E) The crosslinking retardation agent is preferably a ketoenol tautomer compound, and particularly preferably at least one selected from the group consisting of acetamidineacetone and ethyl acetate. It is preferred to contain (E) a crosslinking retarder in an amount of from 1 Torr to 5 Torr to 101110081 14 201245378, based on 100 parts by weight of the copolymer. The adhesive composition of the present invention may further contain (F) a crosslinking catalyst. In the case where the polyisocyanate compound is used as a crosslinking agent, the (F) crosslinking catalyst may be a substance that functions as a catalyst for the reaction (crosslinking reaction) of the copolymer and the crosslinking agent. Examples thereof include amine compounds such as tertiary amines, and organometallic compounds such as organotin compounds, organic lead compounds, and organozinc compounds. Examples of the tertiary amine include a trialkylamine, N,N,N,N,4-tetraalkyldiamine, N,N-dialkylamino alcohol, triethylenediamine, and a porphyrin derivative. Piperne derivatives and the like. Examples of the organotin compound include a dialkyl tin oxide, a fatty acid salt of a dialkyl tin, a fatty acid salt of stannous, and the like. (F) The parent-contact catalyst is preferably an organotin compound, and is particularly preferably at least one selected from the group consisting of dioctyltin oxide and dioctyltin dilaurate. It is preferred to contain (F) a crosslinking catalyst in an amount of from 1 to 5 parts by weight based on 100 parts by weight of the copolymer. (6) Anti-static (4) Compared with (4) normal temperature (3 generations), τ is off, more specifically 'preferably relative to 100 parts by weight of the above copolymer, the content is 0.5 to 5.0 parts by weight and the refining point is 3Q~ 8 (Ionicized character of rc) or a 4-stage salt type acrylic monomer which is copolymerized by weight % in the above copolymer and (4) is 30 to 80 t: In the present invention, as 101110081 15 201245378 (6) The electrostatic agent is obtained by adding (6)) to the copolymer (4) as an ionic compound in %, or copolymerizing (6) a *-bonded fluorene-based monomer having a 3 fluorene-doped amount into the copolymer. Since these (6) anti-resistances have a low melting point and a right-handed spirulina having a long-chain alkyl group, it is presumed to have high affinity with the acrylic pingbatch polymer. 'As an ionic compound having a GW point of 3 G to 8 Gt, which is an ionic compound having a cation and an anion, "lower compound: cation is a ratio of (iv) cation, cardiac radium cation, cation cation, ratio cation a nitrogen-containing cation such as a ruthenium cation or a silk cation, or a compound such as a hetero cation or a sulfonium cation; the anion is a hexafluoride salt (PIV), a thiocyanate (hidden), or a benzoate-only acid. a compound of an inorganic or organic anion such as a salt (rc6h4so3·), a perchlorate (CKV) or a tetrafluoride salt (bf4·), such as the chain length of the alkyl group or the position or number of the substituent. Alternatively, a substance having a melting point of 30 to 80 C can be obtained. The cation is preferably a 4-stage nitrogen-containing cation, and a 1-alkyl group is mentioned. The ratio is fixed. The carbon atom having a substituent at the 2 to 6 position may also be used. , without substitution, etc., etc., 4 grades, tb°, 01 cations, 1,3·dialkyl amides (2, 4, 5 carbon atoms may have substituents, silk may also be used), etc. a 4-stage ammonium cation such as a 4-stage sulfonium cation, a tetraalkylammonium group, etc. as a (G2) melting point The 4-stage ammonium salt type acrylic monomer of 30 to 8 ° C is an ionic compound having a cation and an anion, and the following compounds are mentioned: the cation is (mercapto) propylene decyloxyalkyltrialkylammonium 101110081 201245378 (R3N+-CnH2n-OCOCQ=CH2, where Q=H or CH3, R=now base), etc., a 4-grade ammonium compound containing a styrene (aery 1), an anion of hexamed phosphate (PF 〇, a compound of an inorganic or organic anion such as thiocyanate (SCN_), an organic sulfonate (Rs〇3-), a peroxyacid salt (Cl〇4·), or a tetrafluoride borate (BF4·). G) Specific examples of the antistatic agent are not particularly limited, but examples thereof include 1-octylpyridine rust hexafluorophosphate, ruthenium decyl pyridine hexafluoride phosphate, and 2-mercapto-1- Dodecylpyridinium hexafluorophosphate, octyl ketone 0 than biting rust 12 yard benzoate, 1 _ 12 yards σ than bite rust thiocyanate, 1 - 12 base ratio Biting rust 12-alkyl benzoate, 4-mercapto _ 1 _ octyl 0 pyridine hexafluoride phosphate, bis-amino acrylate hexafluoride ruthenium phosphate ((CH3) 3N+ CH2OCOCH=CH2 · PF6 ). (Η) The shouting modified Shixi oxygen burning compound is a polyether-based Shihe oxygen burning & substance, in addition to the general Shixi oxygen burning unit (_SiR^-0-), there is also a gathering Here, Ri represents one or two or more kinds of alkyl or aryl groups. 'r2 and r3 represent one or two or more kinds of alkylene groups, and R4 represents one or two or more types of alkyl groups. And a fluorenyl group or the like (terminal group). Examples of the polyether group include a polyoxyalkylene group such as a polyoxyalkylene group ((C2H4〇)n) or a t-oxidized propyl group ((C3H60)n). (H) a polyether modified oxoxane compound is a polyether modified siloxane compound having a hlb value of 7 to 12', and preferably contains 〇.〇1~〇 with respect to 1 〇〇 part by weight of the above copolymer. 5 parts by weight of the above (H) polyether modified oxirane 10I1I0081 17 201245378. More preferably, it is 0.1 to 0.5 part by weight. The HLB system is, for example, a hydrophilic-lipophilic balance (ratio of hydrophilicity to lipophilicity) such as jIS K32U (termactivator of surfactant). The polyether-recycling compound can be grafted, for example, to a polyorganophosphonium chain having a brothel group, by grafting an organic compound having a bond and a polyoxyalkylene group by a hydrogenation reaction. get. Specifically, it can be exemplified by a ruthenium oxyfluoride, a fluorenyl group (polyoxylated ethyl group), an oxirane-oxygenated copolymer, a dimethyl methoxyoxane, a methyl group (polyoxyethylidene), a decane. A (polyoxylated propyl) osmium oxide copolymer, a dimercapto oxane, a fluorenyl (polyoxylated propyl) oxirane copolymer, and the like. The adhesion and reworkability of the adhesive can be improved by mixing the (Η) polyether modified oxoxane compound into the adhesive composition. Further, as another component, a copolymerizable (fluorenyl) acrylic monomer containing a alkylene oxide, a (meth)acrylamide monomer, a dialkyl-substituted acrylamide monomer, or the like may be appropriately mixed. A well-known additive such as a surfactant, a hardening accelerator, a plasticizer, a filler 'hardening retarder, a processing aid, an anti-aging agent, an antioxidant, and the like. These may be used alone or in combination of two or more. The copolymer of the main component used in the adhesive composition of the present invention can be obtained by copolymerizing a (fluorenyl) acrylate monomer having a (C) alkyl carbon number of C4 to C10, and (Β) a hydroxyl group-containing copolymerizable monomer. The body and (c) a carboxyl group-containing copolymerizable monomer are polymerized and synthesized. The polymerization method of the copolymer is not particularly limited. 101110081 18 201245378 A suitable polymerization method such as solution polymerization or emulsion polymerization can be used. In the case of using the (G2) fourth-order ammonium salt type acrylic monomer as the (G) antistatic agent, the copolymer of the main component used in the adhesive composition of the present invention can be obtained by using (A) an alkane a (meth) acrylate monomer having a carbon number of C4 to ci 、, (B) a copolymerizable monomer having a hydroxyl group, ((:) a copolymerizable monomer having a carboxyl group, and a grade 4 of (G2) The ammonium salt type acrylic monomer is polymerized and synthesized. (D) a trifunctional or higher isocyanate compound, (E) a crosslinking retarder, a crosslinking catalyst, an antistatic agent, (H) are mixed in the above copolymer. The adhesive composition of the present invention can be produced by using a polyether modified stone oxide compound and a suitable optional additive. Further, a (G2) 4-grade ammonium salt type acrylic single sheet having a melting point of 30 to 80 ° C In the case where the body is polymerized in the copolymer of the main component, it is irrelevant whether or not the (6) antistatic agent is added to the copolymer. It is preferred that the adhesive layer obtained by crosslinking the above adhesive composition is peeled off at a low speed. The adhesion of the area G.3m/min is G.G5~G.lN/25mm, and the high-speed peeling area is 3Gm/min. The adhesive force is 1 to 25 Å or less. The performance of the peeling speed change is small until the adhesive force is applied, and even if it is peeled off at a high speed, rapid peeling can be performed. X, when the surface protective film is temporarily peeled off for re-bonding, It does not require too much force and can be easily peeled off from the adherend. The adhesive layer of the adhesive composition is obtained by cross-linking the above adhesive composition. 101110081 201245378 The surface resistivity is 5.〇χ1〇+ι〇Ω/ □ In the following, the stripping voltage is printed to 乂. In the present invention, the above “±0 to lkv” means 〇~·lkv and 0 to +lkV, that is, -1 to + ikV. Due to surface resistivity When it is large, the performance of static electricity generated by charging at the time of peeling is poor. Therefore, by sufficiently reducing the surface resistivity, the peeling band voltage generated by the static electricity generated when the adhesive layer is peeled off from the adherend can be reduced. The influence on the electrical control circuit of the adherend or the like is suppressed. The adhesive layer (the crosslinked adhesive) obtained by crosslinking the adhesive composition of the present invention preferably has a gel fraction of 95 to 100%. Thus, the gel fraction can be stripped at a low speed. The adhesion in the domain does not become excessively large, and the elution of the unpolymerized monomer or oligomer from the copolymer is lowered, and the reworkability and the long-term durability to the wetness are suppressed, and the contamination of the adherend is suppressed. Adhesive film The adhesive layer obtained by crosslinking the adhesive composition of the present invention is formed on one side or both sides of the resin film. Further, the surface protective film of the present invention is crosslinked with the adhesive composition of the present invention. The adhesive layer is formed on the surface protective film on one side of the resin film. The adhesive composition of the present invention satisfies the components of the above (A) to (H) in a good balance and satisfies (1) at a low speed. Balance of adhesion in the peeling area and high-speed peeling area, (2) prevention of adhesive residue generation, (3) excellent antistatic performance, and (4) reworkability (using the atomic pen to isolate the itU agent) After the layer is drawn on the surface protective film, it does not transfer all the required properties to the adherend. Therefore, it can be suitably used in the application of the surface protection of the polarizing plate 101110081 201245378 film. A resin film such as a polyester film or the like can be used as the base film of the pressure-sensitive adhesive layer or the release film (separator) for protecting the adhesive surface. In the base film, the anti-fouling treatment using a polyfluorene-based or fluorine-based release agent, a coating agent, cerium oxide fine particles or the like can be performed on the opposite side of the resin film on the side of the adhesive layer; Antistatic treatment such as application or mixing of an electrostatic agent. In the release film, the mold release treatment is carried out by a polyfluorene-based or fluorine-based release agent on the surface on the side where the adhesive layer and the adhesive surface are bonded. [Examples] Hereinafter, the present invention will be specifically described based on examples. <Production of Acrylic Copolymer] [Example 1] Nitrogen gas was introduced into a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, and the air in the reaction apparatus was replaced with nitrogen. Then, 100 parts by weight of 2-ethylhexyl acrylate, 9 parts by weight of 8-hydroxyoctyl acrylate, 0.5 parts by weight of acrylic acid, and 60 parts of a solvent (ethyl acetate) were added to the reaction apparatus. Then, the azobisisobutyronitrile ruthenium ruthenium as a polymerization initiator was added dropwise for 2 hours, and reacted at 65 ° C for 6 hours to obtain an acrylic acid used in Example 1 having a weight average molecular weight of 50,000. Copolymer solution 1. [Examples 2 to 9 and Comparative Examples 1 to 9] 101110081 21 201245378 The composition of the monomer was set as described in (A) to (C) of Table 1, respectively, and the acrylic acid used in the above Example 1 was used. Copolymer solution! Similarly, the acrylic copolymer solutions used in Examples 2 to 9 and Comparative Examples i to 9 were obtained. <Production of Adhesive Composition and Surface Protective Film> [Example 1] As described above, ruthenium octyl acridine was added to the produced acrylic copolymer solution 1 (in which the acrylic copolymer was 100 parts by weight) 1.5 parts by weight of rust hexafluorophosphate, 0.1 parts by weight of KF_351A (polyether modified oxirane compound of HLB=12), and 2.5 parts by weight of acetamidine acetone, and stirred, and then added CORONATE HX (hexamethylene diisocyanate compound) After 1.5 parts by weight of dimeric isocyanate) and 2 parts by weight of dioctyltin laurate, the mixture was stirred and mixed to obtain an adhesive composition of Example 1. The adhesive composition is applied onto a release film composed of a polyoxyethylene resin coated polyethylene terephthalate (PET) film, and then dried under 9 Torr to remove the solvent to obtain an adhesive. The layer has a thickness of 25 μm of the adhesive sheet. Then 'transfer the adhesive sheet to the anti-static and anti-fouling treatment of the anti-static and anti-fouling treatment of the polyethylene terephthalate (ΡΕΤ) film on the opposite side of the antistatic and antifouling treatment surface to get "antistatic and antifouling" The surface protective film of Example 1 of the laminated structure of the treated PET film/adhesive layer/release film (polysilicone resin coated ruthenium film). [Examples 2 to 9 and Comparative Examples 1 to 9] 101110081 22 201245378 The composition of the additive was set as described in (D) to (Η) of Table 1, except for the surface protective film of Example 1 described above. Surface protective films of Examples 2 to 9 and Comparative Examples 1 to 9 were obtained. In Table 1, the mixing ratio of each component is a numerical value of the weight fraction obtained by adding the total of (Α) groups to 100 parts by weight in parentheses. Further, in Table 2, the compound names of the respective component numbers used in Table 1 are shown. In addition, CORONATE (registered trademark) HX and HL are trade names of Japan POLYURETHANE Industrial Co., Ltd., Ding AKENATE (registered trademark) D-140N is the trade name of Mitsui Chemicals Co., Ltd., KF-351A, KF-352A, KF- 353, KF-640 and X-22-6191 are trade names of Shin-Etsu Chemical Co., Ltd.
101110081 23 S 201245378 [表i] ㈧ (B) (C) (D) (H) (F) (G) (H) 實施例1 2EHA (1〇〇) 8H〇A(0.9) AAc (0.5) D-l (1.5) AA (2.5) DOTL (0.02) G-l(l.O) H-l (0.1) 實施例2 IOA(IOO) 6HHA(0.2) HEA(3.0) MAAc (0.35) D-2 (3.5) AA (4.5) DOTL (0.05) G-2(2.0) H-2(0.5) 實施例3 2EHA (9〇) BA (10) 4HBA(0.5) HEA(4.5) AAc (1.0) D-3 (2.5) EtAcAc (1.5) DOTL (0.2) G-3 (2.5) H-3(0.15) 實施例4 2EHA (100) HMAA (3.0) CEA(0.5) D-2 (1.5) D-3 (2.5) EtAcAc (3.5) DOTO (0.4) G-4(2.0) H-l (0.15) 實施例5 IOA(50) 2EHA (50) HEAA(4.5) CPA (0.35) D-2 (0.5) AA (1.5) DOTL (03) G-5(1.0) H-2(0.2) 實施例6 IOA(90) BA (10) HEA(l.O) HEAA(4.0) AAc (0.35) D-l (5.0) AA (2.0) DOTO (0.05) G-6(1.0) G-7(1.0) H-3 (0.2) 實施例^ 2EHA (100) 4HBA(0.5) HEMA (3.0) MAAc (0.9) D-2 (2.5) D-l (1.0) EtAcAc (3.5) DOTL (0.1) G-7(1.0) H-l (0.1) H-3 (0.2) 實施例8 IOA(IOO) 6HHA(0.2) HEAA(3.5) CEA(0.4) D-l (2.0) D-3 (0.5) AA (3.0) DOTL (0.15) G-8 (5.0) H-3 (0.1) 實施例9 2EHA (100) 4HBA(0.8) HEAA(3.0) AAc (0.4) D-4(3.0) AA (4.0) DOTO (0.15) G-l (1.0) G-8 (1.5) H-2(0.1) 比較例1 2EHA (100) 4HBA(1.5) AAc (0.5) D-2 (3.5) AA (4.5) DOTL (0.05) G-2(2.0) H-2(0.5) 比較例2 2EHA (90) BA (10) HEA(0.05) AAc (0.35) D-l (6.0) AA (2.0) DOTO (0.05) G-6(1.0) G-7(1.0) H-4(0.3) 比較例3 IOA(50) 2EHA (50) HEAA(6.0) CEA(1.5) D-2 (3.5) AA (1.5) DOTL (0.04) G-2(2.0) H-5 (0.3) 比較例4 IOA(90) BA (10) 6HHA(0.9) MAAc (0,05) D-3 (1.0) EtAcAc (2.0) DOTO (0.05) G-6(1.0) G-7(1.0) H-l (0.2) 比較例5 2EHA (100) 6HHA(2.5) AAc (0.4) D-2 (0.1) AA(3.0) DOTL (0.05) G-l (2.0) H-3 (0.2) 比較例6 IOA(IOO) HEA(1.5) CPA(0.35) D-l (4.5) — DOTL (0.8) G-3 (2.5) H-2(0.2) 比較例7 BA (80) MA(20) HEA(3.5) CEA(0.5) D-3 (4.0) AA(2.0) 一 G-2 (2.0) H-l (0.2) 比較例8 2EHA (100) HMAA (2.5) AAc (1.0) D-2 (1.0) AA(1.5) DOTO (0-5) G-4(0.2) — 比較例9 2EHA 0〇〇) HEA(2.0) MAAc (0.5) D-l (2.5) EtAcAc (2.5) DOTL (0.03) G-9(1.5) H-2(1.0) 24 101110081 201245378 [表2] 群 縮寫 化合物名稱 (A)群 2EHA 丙烤酸2-乙基己S旨 IOA 丙烯酸異辛酯 BA 丙烯酸丁酯 (B)群 8HOA 丙烯酸8-經基辛酯 6HHA 丙烯酸6-經基己酯 4HBA 丙烯酸4-經基丁酯 HEA 丙烯酸2-經基乙酯 HMAA N-羥曱基丙烯酿胺 HEAA N-羥乙基丙烯醯胺 (C)群 AAc 丙稀酸 MAAc 曱基丙烯酸 CEA 羧乙基丙烯酸酷 CPA 羧戊基丙烯酸醋 (D)群 D-l CORONATE HX (HDI三聚異氰酸酯體） D-2 CORONATE HL (HDI 加成物體） D-3 TAKENATED-140N (IPDI 加成物體） D-4 DURANATE 24A-100 _ 缩二脲體） HDI 六亞甲基二異氰酸酯化合物 IPDI 異佛爾酮二異氰酸酯化合物 (E)組 AA 乙酿丙酿] EtAcAc 乙S篮乙8变乙酯 (F)組 DOTO 氧化二辛基錫 DOTL 二月桂酸二辛基錫 (G)組 G-l 1-辛基吡。定鏽六氟化構酸鹽 G-2 1-壬基吡啶鑌六象/lb^酸鹽 G-3 2·甲基-1·十二烧基"比咬鐵六氟4滅酸鹽 G-4 1-辛基°比咬鑌十二烧基苯績酸鹽 G-5 1-十二院基》比咬鏽硫氰酸鹽 G-6 1·十二院基。比咬鏽十二院基苯續酸鹽 G-l ‘甲基-1-辛基'比咬鑌六wsm鹽 G-8 丙烯酸二甲胺基甲酯六氟化雄酸甲基鹽 G-9 3_甲基-1-辛基吡啶鏽六氟4城酸鹽 (H)組 H-l KF-351A (HLB=12的聚醚改質矽氧院化合物） H-2 KF-352A (HLB=7的聚醚改質矽氧炫化合物） H-3 KF-353 (HLB=10的聚醚改質矽氧烷化合物） H-4 X-22-6191 (HLB=2的聚醚改質矽氧烧化合物） H-5 KF-640 (HLB=14的聚醚改質矽氧烧化合物） 25 101110081 201245378 <試驗方法和評價〉101110081 23 S 201245378 [Table i] (8) (B) (C) (D) (H) (F) (G) (H) Example 1 2EHA (1〇〇) 8H〇A(0.9) AAc (0.5) Dl (1.5) AA (2.5) DOTL (0.02) Gl(lO) Hl (0.1) Example 2 IOA(IOO) 6HHA(0.2) HEA(3.0) MAAc (0.35) D-2 (3.5) AA (4.5) DOTL ( 0.05) G-2 (2.0) H-2 (0.5) Example 3 2EHA (9〇) BA (10) 4HBA(0.5) HEA(4.5) AAc (1.0) D-3 (2.5) EtAcAc (1.5) DOTL ( 0.2) G-3 (2.5) H-3 (0.15) Example 4 2EHA (100) HMAA (3.0) CEA (0.5) D-2 (1.5) D-3 (2.5) EtAcAc (3.5) DOTO (0.4) G -4 (2.0) Hl (0.15) Example 5 IOA (50) 2EHA (50) HEAA (4.5) CPA (0.35) D-2 (0.5) AA (1.5) DOTL (03) G-5 (1.0) H- 2(0.2) Example 6 IOA(90) BA (10) HEA(lO) HEAA(4.0) AAc (0.35) Dl (5.0) AA (2.0) DOTO (0.05) G-6(1.0) G-7(1.0 H-3 (0.2) Example ^ 2EHA (100) 4HBA (0.5) HEMA (3.0) MAAc (0.9) D-2 (2.5) Dl (1.0) EtAcAc (3.5) DOTL (0.1) G-7 (1.0) Hl (0.1) H-3 (0.2) Example 8 IOA (IOO) 6HHA (0.2) HEAA (3.5) CEA (0.4) Dl (2.0) D-3 (0.5) AA (3.0) DOTL (0.15) G-8 (5.0) H-3 (0.1) Example 9 2EHA (100) 4HBA (0.8) HEAA (3.0) AAc (0.4) D-4 (3.0 AA (4.0) DOTO (0.15) Gl (1.0) G-8 (1.5) H-2 (0.1) Comparative Example 1 2EHA (100) 4HBA(1.5) AAc (0.5) D-2 (3.5) AA (4.5) DOTL (0.05) G-2 (2.0) H-2 (0.5) Comparative Example 2 2EHA (90) BA (10) HEA (0.05) AAc (0.35) Dl (6.0) AA (2.0) DOTO (0.05) G-6 (1.0) G-7(1.0) H-4(0.3) Comparative Example 3 IOA(50) 2EHA (50) HEAA(6.0) CEA(1.5) D-2 (3.5) AA (1.5) DOTL (0.04) G- 2(2.0) H-5 (0.3) Comparative Example 4 IOA(90) BA (10) 6HHA(0.9) MAAc (0,05) D-3 (1.0) EtAcAc (2.0) DOTO (0.05) G-6 (1.0) G-7(1.0) Hl (0.2) Comparative Example 5 2EHA (100) 6HHA(2.5) AAc (0.4) D-2 (0.1) AA(3.0) DOTL (0.05) Gl (2.0) H-3 (0.2) Comparative Example 6 IOA (100O) HEA (1.5) CPA (0.35) Dl (4.5) - DOTL (0.8) G-3 (2.5) H-2 (0.2) Comparative Example 7 BA (80) MA (20) HEA (3.5 CEA(0.5) D-3 (4.0) AA(2.0) G-2 (2.0) Hl (0.2) Comparative Example 8 2EHA (100) HMAA (2.5) AAc (1.0) D-2 (1.0) AA (1.5) DOTO (0-5) G-4 (0.2) - Comparative Example 9 2EHA 0〇〇) HEA(2.0) MAAc (0.5) Dl (2.5) EtAcAc (2.5) DOTL (0.03) G-9(1.5) H- 2(1.0) 24 101110081 201245378 [Table 2] Group abbreviations Compound name (A) Group 2EHA Propane acid 2-B IO S IOA Isooctyl Acrylate BA Butyl Acrylate (B) Group 8HOA Acrylic Acid 8-Bisyl Ester 6HHA Acrylic Acid 6-Hexylhexyl Ester 4HBA Acrylic 4-Butyl Ester HEA Acrylic 2-Ethyl Ethyl Group HMAA N - Hydroxyalkyl acrylamide HEAA N-hydroxyethyl acrylamide (C) Group AAc Acrylic acid MAAc Mercaptoacrylic acid CEA Carboxyethyl acrylate Cool CPA Carboxylic acid vinegar (D) Group Dl CORONATE HX (HDI III Polyisocyanate) D-2 CORONATE HL (HDI Addition Object) D-3 TAKENATED-140N (IPDI Addition Object) D-4 DURANATE 24A-100 _ Biuret) HDI Hexamethylene Diisocyanate Compound IPDI Vorketone diisocyanate compound (E) group AA E-branched] EtAcAc E-S basket B 8 ethyl ester (F) group DOTO Oxidized dioctyltin DOTL Dioctyl tin dilaurate (G) group Gl 1- Octylpyrazine. Rust hexafluoride acid salt G-2 1-mercaptopyridinium hexafluoride / lb^ acid salt G-3 2·methyl-1·12 alkyl group" than biting iron hexafluoro 4 fenate G -4 1-octyl ° than biting 镔 12-base phenyl acid salt G-5 1- 12 yards than the bite rust thiocyanate G-6 1 · 12 yards. Than the bite rust 12 yards phenyl phthalate Gl 'methyl-1-octyl' than bite 镔 six wsm salt G-8 dimethyl amide methyl hexafluoride male acid methyl salt G-9 3_ Methyl-1-octylpyridine rust hexafluorotetramate (H) group Hl KF-351A (HLB=12 polyether modified oxime compound) H-2 KF-352A (HLB=7 polyether Modified oxime compound H-3 KF-353 (polyether modified oxirane compound of HLB=10) H-4 X-22-6191 (polyether modified oxime compound of HLB=2) H -5 KF-640 (polyether modified oxirane compound of HLB=14) 25 101110081 201245378 <Test method and evaluation>
將實施例1〜9和比較例1〜9的表面保護膜於23°C、50%RHThe surface protective films of Examples 1 to 9 and Comparative Examples 1 to 9 were at 23 ° C, 50% RH.
的環境下老化7天後，剝離剝離膜(經聚矽氧樹脂塗層的PET 膜）’暴路出勘著劑層，以此作為凝膠分率和表面電阻率的 測試樣品。 進而’介隔著黏著劑層將該暴露出黏著劑層的表面保護膜 貼合於黏貼在液晶盒上的偏光板的表面，放置1天後，經 50C、5個大氣壓、20分鐘的南壓爸處理，進一步於室溫下 放置12小時’將如此得到者作為黏著力、剝離帶電壓和耐 久性的測試樣品。 <凝膠分率> 老化結束後’正確地測定貼合於偏光板前的測試樣品的品 質，於曱苯中浸泡24小時後，通過200網目的金屬網過濾。 然後，以l〇〇°C乾燥過濾物1小時後，正確地測定殘留物的 品質’從下式計算出黏著劑層（交聯後的黏著劑）的凝膠分 率。 凝膠分率(％)=不溶物質量(g)/黏著劑質量(g)x 1 〇〇 <黏著力> 使用拉力試驗機以低速（0.3m/min)和高速（30m/min)於 180°方向剝離上述得到的測試樣品（在偏光板表面貼合 25mm寬的表面保護膜者），測定剝離強度，以下此作為黏 著力。 101110081 26 201245378 <表面電阻> 老化後，貼合於偏光板前，將剝離膜（聚矽氧樹脂塗層的 PET膜）剝離而暴露黏著劑層表面，使用電阻率計 UP-HT450(三菱化學ANALYTECH製）測定黏著劑層的表面 電阻。 <剝離帶電壓> 以30m/min的拉伸速度180。剝離上述般得到的測試樣品 時，使用高精度靜電感測器SK-035、SK-200(KEYENCE股 份有限公司製）側定偏光板帶電產生的電壓（帶電壓），以測定 值的最大值作為剥離帶電壓。 <返工性> 用原子筆在上述般得到的測試樣品之表面保護片上描繪 後’從偏光板剝離表面保護片，觀察偏光板之表面，確認沒 有對偏光板轉移污染。評價目標基準為沒有對偏光板轉移污 染的情況評價為「〇」，確認沿著原子筆描繪的軌跡向至少 一部分轉移污染的情況評價為「x」。 <耐久性> 在60°C、90%RH之環境下放置上述般得到的測試樣品250 小時後，在室溫將其取出，進一步放置12小時後，測定黏 著力，確認與最初的黏著力相比沒有明顯的增加。評價目標 基準為試驗後的黏著力是最初黏著力的丨·5倍以下的情況評 價為「〇」、超過1.5倍的情況評價為「x」。 101110081 27 201245378 評價結果示於表3中。另外，主 「 +n _ 表面電阻率係藉由將 mx10」不為「mE+n」的方或γ甘占 方式（其中’功為任意的實數， η為正整數)標記。 [表3]After aging for 7 days, the release film (PET film coated with polyoxymethylene resin) was peeled off to expose the layer of the coating as a test sample of gel fraction and surface resistivity. Further, the surface protective film exposed to the adhesive layer was adhered to the surface of the polarizing plate adhered to the liquid crystal cell via the adhesive layer, and left for 1 day, and then subjected to 50 C, 5 atm, and 20 minutes of south pressure. Dad treatment, further placed at room temperature for 12 hours, was used as a test sample for adhesion, stripping voltage and durability. <Gel fraction> After the aging was completed, the quality of the test sample before the polarizing plate was accurately measured, and after immersing in benzene for 24 hours, it was filtered through a 200 mesh metal mesh. Then, the filtrate was dried at 1 ° C for 1 hour, and the quality of the residue was accurately measured. The gel fraction of the adhesive layer (adhesive after crosslinking) was calculated from the following formula. Gel fraction (%) = insoluble mass (g) / adhesive mass (g) x 1 〇〇 <adhesion> Using a tensile tester at low speed (0.3 m/min) and high speed (30 m/min) The test sample obtained above was peeled off in the 180° direction (the surface protective film of 25 mm width was bonded to the surface of the polarizing plate), and the peeling strength was measured, and the adhesive force was used hereinafter. 101110081 26 201245378 <Surface resistance> After aging, before peeling off the polarizing plate, the release film (polyoxyphthalic resin coated PET film) was peeled off to expose the surface of the adhesive layer, using a resistivity meter UP-HT450 (Mitsubishi Chemical) ANALYTECH) The surface resistance of the adhesive layer was measured. <Peeling tape voltage> A tensile speed of 180 at 30 m/min. When the test sample obtained as described above was peeled off, the voltage (band voltage) generated by the polarizing plate of the high-precision electrostatic sensor SK-035 and SK-200 (manufactured by KEYENCE Co., Ltd.) was used, and the maximum value of the measured value was used as the maximum value of the measured value. Stripping the voltage. <Reworkability> After the surface protection sheet of the test sample obtained above was drawn with a ballpoint pen, the surface protection sheet was peeled off from the polarizing plate, and the surface of the polarizing plate was observed to confirm that no contamination was transferred to the polarizing plate. The evaluation target criterion was evaluated as "〇" in the case where no contamination was transferred to the polarizing plate, and it was confirmed that the contamination was transferred to at least a part of the trajectory drawn by the atomic pen as "x". <Durability> The test sample obtained above was placed in an environment of 60 ° C and 90% RH for 250 hours, and then taken out at room temperature. After further standing for 12 hours, the adhesion was measured to confirm the initial adhesion. There is no significant increase in force. Evaluation target The evaluation is that the adhesion after the test is 5 times or less of the initial adhesion, and the evaluation is "〇". If it is more than 1.5 times, it is evaluated as "x". 101110081 27 201245378 The results of the evaluation are shown in Table 3. Further, the main "+n _ surface resistivity is marked by a mode in which mx10" is not "mE+n" or a gamma-sweet mode (where 'the work is an arbitrary real number, and η is a positive integer). [table 3]
- | w I yy 實施例1〜9的表面保護膜在低速剝離區域〇 3m/min的黏 著力是0.05〜0.1N/25mm，在高速剝離區域3〇m/min的黏著 力是1.0N/25mm以下。又，表面電阻率為5 〇xl〇+i〇Q/□以 下，剝離帶電壓為±〇〜lkV。並且，用原子筆介隔著黏著劑 層在表面保護片上描繪後不會對被黏體污染轉移，6〇t、 90%RH的環境下放置250小時的耐久性也是優異的。 101110081 28 201245378 :，同時滿足⑴取得低速剝離區域和高速_區域中的 黏著力的平衡、（2)防止黏著劑殘留的發生、（3)具有優: 抗靜電性能、和(4)具有返工性能之全部要求性能。異的 比較例1的表面保護膜可能由於(B)含有經基的單體過 多，得到了低速剝離區域〇.3m/min的黏著力低的結果。 比較例2的表面保護膜中，可能由於(B)含有經基的單體 過少、（D)異氰酸酯化合物過多、（H)聚醚改質矽氧烷化合物 的HLB值過小，因此低速剝離區域〇.3in/min的黏著力和言 速剝離區域30m/min的黏著力變得過大、剝離帶電麗變古 返工性和财久性變差、凝膠分率變低。 比較例3的表面保護膜中，可能由於(B)含有羥基的單體 過多、（C)含酸單體過多、（H)聚醚改質矽氧烷化合物的hLb 值過大，因此低速剝離區域0.3m/min的黏著力低、表面電 阻率高、剝離帶電壓高、返工性和耐久性差。 比較例4的表面保護膜中，可能由於(C)含有酸的單體過 少，因此低速剝離區域〇.3m/mm的黏著力低，耐久性差。 比較例5的表面保護膜中，可能由於(B)含有羥基的單體 過多、（D)異氰酸酯化合物過少，因此低速剝離區域0.3m/min 的黏著力和高速剝離區域30m/min的黏著力變得過大、剝 離帶電壓變高、返工性和耐久性變差、凝膠分率變低。 比較例6的表面保護膜可能是由於沒有混合(E)交聯延遲 劑、（F)交聯觸媒過多’因此使用期限變得過短’在塗布前 101110081 29 201245378 進行了交聯，而無法進行塗層。 比較例7的表面保護膜可能是由於含有在(A)具有烷基的 (甲基）丙烯酸酯單體中具有C1烷基的MA、沒有混合(F)交 聯觸媒，因此低速剝離區域0.3m/min的黏著力和高速剝離 區域30m/min的黏著力過大、表面電阻率高、剝離帶電壓 高、返工性和财久性差。 比較例8的表面保護膜中，可能由於(G)抗靜電劑過少、 沒有混合（H)聚醚改質矽氧烷化合物，因此低速剝離區域 0.3m/min的黏著力和高速剝離區域30m/min的黏著力過 大、表面電阻率高、剝離帶電壓高、返工性差。 比較例9的表面保護膜中，可能由於(G)抗靜電劑的熔點 未滿30°C(常溫下為液體）、（H)聚醚改質矽氧烷化合物過 多，因此低速剝離區域0.3m/min的黏著力低、剝離帶電壓 高、耐久性差。 如此，在比較例1〜9的表面保護膜中，無法同時滿足（1) 取得低速剝離區域和高速剝離區域中的黏著力的平衡、（2) 防止黏著劑殘留的發生、（3)具有優異的抗靜電性能、和(4) 具有返工性能之全部要求性能。 101110081 30- | w I yy The surface protective film of Examples 1 to 9 has an adhesive force of 〜3 m/min in the low-speed peeling region of 0.05 to 0.1 N/25 mm, and an adhesive force of 3 〇m/min in the high-speed peeling region is 1.0 N/25 mm. the following. Further, the surface resistivity is 5 〇 xl 〇 + i 〇 Q / □ or less, and the peeling strip voltage is ± 〇 to lkV. Further, it is excellent in durability after being placed in a surface of a 6 〇t, 90% RH atmosphere for 250 hours by using a ball pen to form an adhesive layer on the surface protective sheet after being drawn on the surface protective sheet. 101110081 28 201245378 :: At the same time, it satisfies (1) achieving the balance of adhesion in the low-speed peeling area and the high-speed area, (2) preventing the occurrence of adhesive residue, (3) having excellent: antistatic performance, and (4) having reworkability. All required performance. The surface protective film of Comparative Example 1 may have a low adhesion at a low-speed peeling region of 〇3 m/min due to excessive (B) a monomer having a radical group. In the surface protective film of Comparative Example 2, since (B) the monomer having a radical group is too small, (D) the isocyanate compound is excessive, and the HLB value of the (H) polyether modified siloxane compound is too small, the low-speed peeling region 〇 The adhesive force of .3in/min and the adhesive force of 30m/min in the stripping area of the speech speed become too large, the peeling electrification, the reworkability and the long-term deterioration of the economy, and the gel fraction are low. In the surface protective film of Comparative Example 3, there may be a case where (B) a hydroxyl group-containing monomer is excessive, (C) an acid-containing monomer is excessive, and (H) a polyether-modified oxirane compound has an excessive hLb value, so that the low-speed peeling region is excessive. Low adhesion at 0.3m/min, high surface resistivity, high stripping voltage, poor reworkability and durability. In the surface protective film of Comparative Example 4, since the (C) acid-containing monomer was too small, the adhesion at a low-speed peeling region of 〇3 m/mm was low, and durability was poor. In the surface protective film of Comparative Example 5, since (B) the monomer having a hydroxyl group is excessive and (D) the isocyanate compound is too small, the adhesion at a low-speed peeling region of 0.3 m/min and the adhesive force at a high-speed peeling region of 30 m/min may be changed. If it is too large, the peeling tape voltage becomes high, the reworkability and durability are deteriorated, and the gel fraction is lowered. The surface protective film of Comparative Example 6 may be crosslinked due to the absence of mixing (E) crosslinking retarder and (F) too much cross-linking catalyst, so that the use period is too short 'before coating, 101110081 29 201245378 Coating. The surface protective film of Comparative Example 7 may have a low-speed peeling region of 0.3 because it contains MA having a C1 alkyl group in (A) a (meth) acrylate monomer having an alkyl group, and no mixed (F) crosslinking catalyst. The adhesion of m/min and the high-speed peeling area of 30m/min have excessive adhesion, high surface resistivity, high stripping voltage, poor reworkability and longevity. In the surface protective film of Comparative Example 8, the (G) antistatic agent was too small and the (H) polyether modified oxoxane compound was not mixed, so the adhesion at a low-speed peeling region of 0.3 m/min and the high-speed peeling region of 30 m/ The adhesion of min is too large, the surface resistivity is high, the stripping voltage is high, and the reworkability is poor. In the surface protective film of Comparative Example 9, the (G) antistatic agent may have a melting point of less than 30 ° C (liquid at normal temperature) and (H) polyether modified oxoxane compound, so the low-speed peeling region is 0.3 m. /min has low adhesion, high stripping voltage and poor durability. As described above, in the surface protective films of Comparative Examples 1 to 9, it is impossible to simultaneously satisfy (1) the balance of the adhesive force in the low-speed peeling region and the high-speed peeling region, (2) prevention of the occurrence of the adhesive residue, and (3) excellent Antistatic properties, and (4) all required performance with reworkability. 101110081 30