200914563 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種黏著劑及使用其之表面保護黏著 片，更詳細而言，本發明係關於一種可形成貼附於對象物 j時無氣泡進入，且剝離時無黏著劑殘留之黏著劑層之黏 著劑，以及含有該黏著劑所構成之適於光罩等之表面保護 的表面保護黏著片。 5 【先前技術】 光罩係用以將光阻劑印刻於基板上者。此處所使用之 表面保護黏著片，係用以防止於印刻之曝光中光阻材料盘 光罩直接接觸。 ^ ^近年來，在電視、個人電腦之許多電氣機器中，與先 月ίι相比正在謀求小型化、輕質化 t 间功旎化。為了實現該 專性m基板已變得更小’從而可封裝更多半導體。 因此’電路基板上之電路寬度已變得更細。先前線與間隙 (L/S )為 1 # m/'l 00 " m，目前則、壷 , 〆m目刖則達到25 // m/25以m。 於光罩表面印刻有電路圖荦。# 闽系尤罩其自身為銀鹽膜， 因此銀結晶會沿荖圖崇耳X隹 ^ 者圖案聚集，發生聚集之部位形成凸狀， 不發生聚集之部位形成凹狀。 為了清晰地轉印電路圖牵，矣 一 圆茶表面保濩片必須儘量地BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive and a surface protective adhesive sheet using the same, and more particularly, the present invention relates to a bubble which can be formed when attached to an object j. An adhesive which adheres to the adhesive layer which is not adhered to the adhesive when peeling off, and a surface protective adhesive sheet which is formed of the adhesive and which is suitable for surface protection of a mask or the like. 5 [Prior Art] A photomask is used to imprint a photoresist on a substrate. The surface protection adhesive sheets used herein are intended to prevent direct contact of the photoresist of the photoresist material during exposure. ^ ^ In recent years, in many electric machines such as televisions and personal computers, miniaturization and light weight have been achieved compared with the first month. In order to achieve this obligate m substrate has become smaller' so that more semiconductors can be packaged. Therefore, the circuit width on the circuit substrate has become finer. The previous line and gap (L/S) is 1 # m/'l 00 " m, currently, 壷, 〆m 刖 达到 reaches 25 // m/25 in m. A circuit diagram is printed on the surface of the mask. # 闽 尤 尤 其 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 尤 银 银 银 银 银 银 银 银 银 银 银 银 银 银 银 银 银 银 银 银 银 银 银 银 银 银 银 银In order to clearly transfer the circuit diagram, a round tea surface protection sheet must be as much as possible
溥。其原因在於，若表面俘螬H 卸保D蔓片較厚，則曝光發生擴散， 因此圖案會顯得模糊不清。 个/月進而，在將表面保護片進行黏 合時會有氣泡進入，從而產吐/中A ' 而產生在電路圖案上不能通電之缺 200914563 點。 因此，最新之表面保護片係基材膜自身較薄並 劑層U亦較薄者，並且業者正積極開發不影響圖案之: 凸、氣泡不進入之表面保護片。 片：其使用的由黏著劑所構成之表面保護 ^上剝離時，黏著劑往往會殘留於光罩上。 進而’亦期望在剛黏合後盔氣 經n# D 然氣泡會在 于又才间傻變小不久便消奂f σ 外），#銶你1更4失（口口貝差的表面保護膜除 } 仁就作業性及品質營理古而品丄 就無氣泡存在。 方面^ ’期望在剛黏合後 為著決此種問題點，在專利讀"揭示有-種| 其中敍述以溶劑可溶部分較 於此種黏著劑中會因交聯過 分之上限為4。重量,者較:專;Γ其：’以溶咖 構之部分較多者較佳。總之 其中㈣述以具交聯結 少，即凝膠分率較高者較佳 但是，由研究結果可知 多而無法消除氣泡。 [專利文獻1]日本專利特開2_·313282號公報 【發明内容】 劑層於提供—種黏著劑，其所形成之㈣ 留，以及提供一 2時無軋泡進入，且剝離時無黏著劑残 面保護的表面含有該黏著劑所構成之適於光罩等之表 π表面保護黏著片。 200914563 本發明者為達成上述目的而反覆進行努力研究，結果 發現：於含有丙烯酸酯系樹脂及交聯劑而成之黏著劑中， 上述丙烯酸酯系樹脂’係以丙烯酸酯系樹脂總量為基準， 含有特定量之含交聯性官能基的（甲基）丙烯酸酯成分者，且 丙烯酸酯系樹脂之重量平均分子量與黏著劑之凝膠分率的 關係係在適g範圍内，在此範圍内可解決如前述之氣泡及 霉著齊丨殘留（再剝離性）之問題。即，本發明者發現，藉 由製成如下黏著劑，其所形成之黏著劑層貼附於對象物上 時無氣泡進入，且剝離時無黏著劑殘留。即，上述丙烯酸 酯系樹脂以丙烯酸酯系樹脂總量為基準，含有〇.〇1〜5重量 %之含交聯性宫能基的（甲基）丙烯酸醋成分，且含有利用 C法測得之作為聚苯乙烯換算分子量的重量平均分子量 為萬1 00帛之丙稀酸醋系樹脂、及交聯劑而成之凝膠 分率為30〜90重量％的黏著劑。 又，本發明者發現，藉由在含有具特定重量平均分子 量之丙烯酸，系樹脂、交聯劑以及塑化劑而成之黏著劑 使’、凝膠刀率為7〇〜100重量。，則可形成貼附於對象 寺…'氣泡進入，且剝離時無黏著劑殘留之黏著劑層。 〜本t月者對4等發現進—步進行反覆研究，從而最終 完成本發明。 發明，可提供一種黏著劑，其 為聚苯乙烯換算分子量的重量 之丙烯酸酯系樹脂、以及交聯 即，根據本發明之第— 係含有利用GPC法測得之作 平均分子量為50萬〜10〇萬 劑而成者；其特徵在於： 200914563 在上述丙烯酸醋系樹脂中，以丙烯酸酯系樹脂總量為 基準，含有0.01〜5重量％之含交聯性官能基的（甲基）丙烯 酸酯成分，並且 在23°C將黏著劑於乙酸乙酯中浸潰24小時後，自乙酸 乙酿中取出，並於not:乾燥丨小時，此時下述式所示之= 膠分率（Y)為30〜90重量。/〇。 Y= 100XW2/W1 (式中，W1意指乾燥前之黏著劑之重量 燥後之黏著劑之重量） 思4曰乾 ^又，根據本發明之第二發明，可提供一種點英劍，1 得之作為聚苯乙歸換算分子量的重量 -刀子置為50 4〜1〇〇萬之丙烯酸酯 U ί&Ά JIU t @月曰 '交聯劍以 及塑化劑而成者；其特徵在於： 乂聯劑乂 忒塑化劑，係以黏著劑總量為基準， %，並且， 3有1〜40重量 在抑將黏著劑於乙酸乙醋中浸潰 乙醋中取出，並於"吖乾燥i小時，此時下：:4,自乙酸 膠分率（Y…。〜100重量％。 下迷式所示之凝 Y== 100xW2/Wl 二式中’ W1意指不計塑化劑重量之 一意指乾燥後之黏著劑之重量）、黏著劑之重 根據本發明之第三發明’可提供 第一發明之黏 8 200914563 著劑，其中在上述丙烯酸酯系樹脂中’以丙烯酸顆系樹脂 總量為基準’含有〇_〇2〜3重量％之含交聯性官能基的（甲基 丙稀酸醋成分。 進而，根據本發明之第四發明，可提供如第—發明之 黏著劑’其中上述交聯性官能基為羥基。 又，根據本發明之第五發明，可提供如第一發明之黏 著劑’其中在上述丙烯酸醋系樹脂中，以丙烯酸酿系樹脂 總量為基準，含有10〜95重量％之含碳數8〜18之烷基的 (曱基）丙稀酸酯成分。 —進而，根據本發明之第六發明，可提供如第五發明之 黏著d，其中上述（甲基）丙烯酸酯成分為丙烯酸乙基己 酉旨。 土 又，根據本發明之第七發明，可提供如第一發明或第 二發明之黏著劑’以上述交聯劑為異氰酸醋系交聯劑。 進而，根據本發明之第八發明，可提供如第一發明或 第二發明之黏著劑’其中上述丙烯酸醋系樹脂含有含碳數-4 〜12之炫基的（甲基）丙烯酸酯成分。 另一方面，根據本發明之第九發明，可提供一種表面 保護黏著片’其特徵在於：係於由合成樹 域層而成有由第-發明或第二發明之黏著劑所 著劑層。 ^又，根據本發明之第十發明，τ提供如第九發明之表 面保漠黏著片，其中上述黏著劑層之厚度為2〜20 // m。 進而’根據本發明之第十一發明，可提供如第九發明 200914563 之表面保護黏著片，其中p批主 板之製造中所使用之光罩的表面表:保護㈣係 70旱的表面加以保護者。 一根據本發明之勒著劑及使用其之表面保護黏著片，於 第-發明中，上述黏著劑係含有利用Gpc法測得之作為聚 本乙烯換|分子量的重量平均分子量為5〇萬〜⑽萬之丙 細酸酯系樹脂、及交聯劑而成者；其特徵在於：上 酸醋系樹脂以丙埽酸酿系樹脂總量為基準，含有〇〇ι =之含交聯性官能基的(甲基)丙歸酸醋成分 ⑺為3。〜90重量％;因此具有可形成使用該黏著劑J 成之黏者劑層貼附於對象物上時 " 時無黏著劑殘留之黏著劑層之效果、…入、進而在剝離 又，於本發明之第二發明中，黏著劑係含有 法測得之作為聚苯乙烯換算分子量的重量平均分子量為5〇 萬〜1〇0萬之丙烯酸酯系樹脂、交聯劑以及塑化劑而成者. 7成使用該黏著劑所形成之黏著劑層貼附於對象Μ …、孔泡進入、且在剝離時無黏著劑殘留之黏著劑層之效果。 樹脂明之第三發明中，特別規定在上述丙歸酸醋系 曰、3 # 0·02〜3重量％之含交聯性官能基的(曱基)丙烯 is曰成分’因而可更經濟有效地發揮上述第—發明之土效果。 本發明之第四發明中’特別規定上述交聯性官 :土 ‘、、經土’因而可更經濟有效地發揮上述第-發明之效 進而’於本發明之第五發明中’特別規定上述丙稀酸 200914563 酯系樹脂以丙烯酸酯系樹脂總體為基準，含有丨〇〜95重量 %之含碳數8〜18之院基的（甲基）丙烯酸醋成分，因而特別 八有使用該黏著劑所形成之黏著劑層貼附於對象物上時無 氣泡進入之效果。 又，於本發明之第六發明中，特別規定上述（甲基）丙烯 酸醋成分為丙烯酸_2•乙基以旨，㈣特別具有使用該黏著 劑所形成之黏著劑層貼附於對象物上時無氣泡進入之顯著 效果。 马異氰酸醋系交聯劊，IJI & 1 a /…士丄 又劑因而可更經濟有效地發揮上述第一 發明或第二發明之效果。 系：於本發明之第八發明中，特別規定上述丙烯酸酯 糸樹脂含有含碳數4〜丨2 之烷基的（甲基）丙烯酸酯成分，因 而特別具有使用該黏著惑# ’ 斤形成之黏者劑層貼附於對象物 上時热氣泡進入之效果。 之特徵在:面1於本發明之第九發明中’表面保護黏著片 成之黏係將由第一發明或第二發明之黏著劑所構 战之黏者劑層積層於由合忐 m , a ^ σ成树月曰所構成之基材上而成者， 匕具有即便該表面保護黏著 劑等的表面上時氣泡不‘』：較4，在貼附於光阻 表面伴蠖片制離日“ 2為了再利用光罩等而將 保4片剝離時黏著劑亦不會殘留之效果。 又，於本發明之第十發明中， 片中！_、+-## 士， W⑴观疋表面保護黏荖 A中上述黏奢劑層之厚度為2 釋者 地發揮上述效果。進—牛因而可更經濟有效 進步，可使黏著劑層變薄，且 200914563 光學特性優異，並有助於提昇配線圖案之可靠性之效果。 進而於本發明之第十—發明中，特別規定上述表面 保護黏著片係、保護電路基板之製造中所使用之光罩的表面 者，因此具有在保護電路基板之製造中所使用之光罩的表 面時，即便表面保護黏著片厚度較薄，在貼附於光罩之表 面時氣:包不會殘留，且為了再利用光罩而將表面保護片剝 離時黏著劑亦不會殘留之效果。 【實施方式】 以下，京尤本發明之黏著劑及使用其之表面保護黏著片 加以詳細說明。 1·黏著劑 本發明之第—發明之黏著劑，係含有利用CJPC法測得 之作為聚本乙烯換算分子量的重量平均分子量$ %萬〜 1〇〇萬之丙烯酸l系樹脂、及交聯劑而成者；其特徵在於: 上=烯酸酯系樹脂以丙烯酸酯系樹脂總量為基準，含有 特疋里之含交聯性官能基的（甲基）丙烯酸醋成分，並且將丙 重量平均分子量與黏著劑之凝膠分率的關 ”。正’’、、田範圍，藉此解決如前述之氣泡及黏著劑殘留 (再剝離性）之問題。 θ 本叙明之第一發明之黏著劑，係含有利用GPC法 」;于之作為聚笨乙烯換算分子量的重量平均分子量為萬 | 00萬之丙烯酸酯系樹脂、交聯劑以及塑化劑而成者；其 U在於.將丙烯酸酯系樹脂之重量平均分子量與黏著劑 12 200914563 藉此解決如前述之氣 之凝膠分率的關係調整為適當範圍， 泡及黏著劑殘留（再剝離性）之問題 (1)丙烯酸酯系樹脂 作為構成上述黏著劑之丙烯酸酯系樹脂，利用GPC法 測得之作為聚苯乙稀換算分子量的重量平均分子量必須為 5〇萬〜100萬’可舉出：使一種或二種以上的（▼基）丙稀酸 醋單體進行聚合或者共聚合而成之（甲基）丙稀酸醋樹脂、或 (甲基）丙烯酸醋#體與可和其發生共聚合的其I乙婦型單 體，共聚物；就調整黏著力、或與交聯劑反應之理由而言， 較佳為（甲基）丙烯酸酯單體與可和其發生共聚合的其他乙 稀型單體之共聚物。再者，於本發明中，所謂「（甲基）丙焊 心」意指「甲基丙烯酸或丙稀酸」。 、’·盧而作為上述（甲基）丙烯酸酯單體，並無特別限定， 但於第一發明中，較佳為藉由烷基之碳數為1〜12的一級 或二級醇與（甲基）丙烯酸之酯化反應而獲得者；具體可舉 出：（甲基）丙烯酸乙醋、（曱基）丙烯酸丁醋、（甲基）丙烯酸 -2-乙基己酯等；均聚物之Tg在丙烯酸酯類中為最低因而較 為柔軟’就有利於消除氣泡之理由而言，較佳為丙烯酸_2_ 乙基己醋。 再者’上述（甲基）丙烯酸酯單體既可單獨使用，亦可將 二種以上併用。 又，作為上述（甲基）丙烯酸酯單體，以丙浠酸酯系樹脂 總量為基準’含有10〜95重量％之含碳數8〜18之烷基的 (曱基）丙烯酸醋成分’因可有效地消除氣泡故較佳。具體而 13 200914563 °較佳為·丙稀酸_2-乙基己酯（2-ethyl hexyl acrylate )、 丙烯敲異辛酯、丙烯酸十二烷酯、丙烯酸十八烷酯。 進而’除上述丙烯酸_2_乙基己酯成分外，含有其他丙 烯曰單體（（曱基）丙烯酸酯單體），具體而言為丙烯酸異 辛S曰、丙烯酸十二烷酯、丙烯酸十八烷酯等而成之丙烯酸 酯系樹脂，因可更有效地消除氣泡，故較佳。 又’若上述丙烯酸酯系樹脂中之丙烯酸-2-乙基己酯成 刀之3里較少，則所形成之黏著劑層於貼附於被黏附體即 光罩上時，不會充分變形，因而氣泡易於殘留。若丙烯酸·2- 乙基己酯成分之含量較多，則凝集力會下降從而使黏著力 下降。 因此，於聚合或共聚合時，丙烯酸_2_乙基己酯成分之 3量以丙烯酸酯系樹脂總量為基準，較佳為配合丨〇〜％重 量°/° ’更佳為配合1 〇〜9 〇重量％。 又’於第二發明中，作為上述（甲基）丙烯酸酯單體，較 k為藉由烧基之碳數為4〜12的一級或二級醇與（甲基）丙 烯酸之酯化反應而獲得者；具體而言，較佳為：（曱基）丙烯 酸丁酯、（甲基）丙烯酸_2_乙基己酯、丙烯酸_2_乙基己酯 (2-ethyl hexyl acryiate)、丙烯酸異辛酯、丙烯酸十二烷 醋。 進而’上述（甲基）丙烯酸酯單體係含有含碳數4〜12之 烧基的（甲基）丙烯酸酯成分而成，因可有效地消除氣泡，故 較佳。 再者，上述（甲基）丙烯酸酯單體既可單獨使用，亦可將 14 200914563 二種以上併用。 蹄°〜上述（甲基）丙烯酸酯單體共聚合的其他乙烯型單 係為了對(曱基)丙烯酸酯單體與可和其發生共聚合的其 他乙烯i單體之共聚物進行改質，而提高所得黏著劑之凝 集力而添加者，例如可使用：使丙烯酸酯系樹脂之玻璃轉 移溫度（Tg) U γ| ^ . 升者、有助於在丙烯酸酯系樹脂之主鏈間 形成交聯結構者等。 為了不損害再剝離性，其他乙烯型單體成分之含量以 丙烯酸I系樹脂總體為基準，較佳為配合〇1〜1〇重量。/" 又，作為提高丙烯酸酯系樹脂之凝集力的乙烯型單 體，並無特別限S，例如可舉出：（甲基）丙稀酸、丁稀酸、 馬來酸、伊康酸（itaconicacid)料㈣之單體，N_經甲 基丙烯醯胺等含㈣之單體，馬來酸酐、乙酸乙烯醋、苯 乙烯等；較佳為丙烯酸。該等可提高丙烯酸_2•乙基己酯等 丙烯酸Ϊ旨系樹脂之凝集力，從而可提高接著力。 繼而，作為有助於在上述丙烯酸酯系樹脂之主鏈間形 成交聯結構之乙烯型單體，並無特別限定，例如可舉出：（甲 基）丙烯酸-2-羥基乙酯、（甲基）丙烯酸縮水甘油酯、丙烯基 縮水甘油醚等。於使用異氰酸醋化合物作為交聯劑時，ς 佳為（甲基）丙烯酸-2-羥基乙酯。 又，該等單體之中含有羥基 者，亦可提高丙烯酸酯系樹脂之凝集力，因而較佳 若以丙烯酸羥基乙酯或甲基丙烯酸羥基乙醋為代表之 含交聯性官能基的（甲基）丙烯酸酯成分較少，則交聯會過 少，因此即便使用交聯劑亦無法獲得所期望之凝勝分率， 15 200914563 攸而黏著劑殘留變差。若含交聯性官能基的（曱基）丙烯酸酯 成分過多，則即便因交聯單體自身之凝集力而使凝膠分率 處於所期望之範圍，但除氣泡效果亦會變差。因此，以丙 烯i酯系樹脂總量為基準，較佳為配合〇〇丨〜5重量。/❶、更 佳為配合〇.〇2〜3重量。/。、最佳為配合〇 〇5〜j重量％之上 述含父聯性官能基的（甲基）丙烯酸酯成分。 繼而，為了獲得上述丙烯酸酯系樹脂，使（甲基）丙烯酸 西曰單體與視需要之可和（甲基）丙烯酸酯單體發生共聚合的 其他乙埽型單體共同於聚合起始劑存在下進行自由基反應 即可。再者，作為聚合方法，可採用先前公知之方法，例 如可舉出：溶液聚合、乳化聚合、懸浮聚合、整體聚合等。 作為上述聚合起始劑，並無特別限定，例如可舉出： -（過氧化第二己基）三曱基環己院、過氧化特戊酸第三己 酯、過氧化特戊酸第三丁酯、2,5•二甲基_2,5_雙（過氧化2_ 乙基己S&基）己烧 '過氧化2_乙基己酸第三己醋、過氧化 乙基己酸m氧化異丁酸第三丁醋、過氧化3,5,5_ 三甲基己酸第三丁醋、過氧化十二烷酸第三丁酯等；因根 據10 j時半衰期溫度所顯不之活性較高，故較佳為過氧化 特戊酸第三己冑，作為市售者’較佳為曰本油脂股份有限 公司製造之「PERHEXYL (註冊商標）pv」等。再者，上 述聚合起始劑既可單獨使用，亦可將二種以上併用。 (2 )交聯劑 劑，從而在構成黏著劑 為上述交聯劑，並無特 於本發明之黏著劑中添加交聯 之樹脂的主鏈間形成交聯結構。作 16 200914563 別，疋’例如可舉出：異氰酸醋系交聯劑、氮丙咬（aziddine ) 系乂%•齊丨ί衣氧系交聯劑、金屬螯合型交聯劑等。該等之 中，就可使該黏著劑所形成之黏著劑層不易被伴隨被黏附 :旦變形所產生之剝離應力而被剝離的觀點而言，較佳為異 氰酉夂酉曰系父聯劑。異氰酸醋化合物之反應性高，若與蒸汽 接觸則會有危險，因此較佳為使用蒸汽壓低且安全性高之 改質異氛酸醋，·作為市售者，較佳為使用_二:二 Μ，股份有限公司製造者、或曰本聚胺醋工業股份有 限公司製造之「c_nate (註冊商標）l_45」。再者， 交聯劑既可單獨使用，亦可將二種以上併用。配合交聯劑 而將凝膠分率調整為所期望之範圍。 (3 )塑化劑 -般而言，凝膠分率較高之黏著劑雖無黏著劑， 但在層壓時會有氣泡殘留。於本發明中特別是於第二發明 之門=認為塑化劑係將黏著劑中特定的丙烯酸醋系樹脂 曰’隙加以擴大，並賦予流動性從而幫助黏著劑密 上。其結果’根據本發明，即便凝膠分率較高亦 發生黏著劑殘留的情況下解決氣泡之問題。 明中，可利用：鄰苯二甲酸二辛醋、鄰 ::叫、鄰苯二甲酸二異癸醋、鄰苯二甲酸二丁能、 甲：酸—辛醋、己二酸二異壬醋、偏笨三甲酸醋、偏：二 甲-文二辛酯、聚酯、磷酸酯、磷酸三甲笨酯 — 乙醯檸檬酸二丁酯、 T松酸酯、 二_、二：氧化亞麻仁油、癸 壬-酸酉曰、馬來酸醋、苯甲酸酸等塑化劑。特別 17 200914563 是就成本、相逾;,从+ i 岭11方面而言，較佳為鄰苯二甲酸酯。但是， ^化^亦係環境荷爾蒙，因此有時亦適合使用己二酸二 辛酯等由其他酸所構成之酯。 以黏著劑總量為基準，必須含有1〜40重量❶/。之塑化 齊丨J 〇 再者，t卜卩主 、 θ f之塑化劑以及黏著劑之重量均為乾燥前之 重里右塑化劑之配合量過多，則不僅黏著劑殘留變差， 而且有％會發生塑化劑自黏著劑中滲出之現象。另一方 面右塑化劑之配合量較少，則無法獲得改善氣泡之效果。 (4)丙烯酸酯系樹脂之重量平均分子量 本心明之黏著劑中丙烯酸酯系樹脂之利用GPC法測得 之作為聚本乙烯換算分子量的重量平均分子量必須為50萬 100萬。丙烯酸酯系樹脂可藉由調整聚合起始劑、聚合溶 J單體/辰度、鏈轉移劑量、聚合溫度，而獲得較理想之 分子量。 於本發明中，丙烯酸酯系樹脂之重量平均分子量係利 =GPC法測侍之作為聚苯乙烯換算分子量的重量平均分子 量。 具體而言’利用四氫吱喃（THF)將丙婦酸醋系樹脂稀 釋50倍，再用過遽器將所得稀釋液進行過滤，基於所獲得 之濾液’利用凝膠滲透層析儀測定丙烯酸酯系樹脂之聚苯 乙稀換算分子4，藉此可獲得丙烯酸S旨系樹脂之重量平均 分子量。作為上述凝膠滲透層析儀，例如可使用自^⑽ 公司靖得之商品名$「2690 Sepami〇n胸址」之商品等。 於丙婦酸I系樹脂之重量平均分子量與黏著剩之凝勝 200914563 分率的關係中，名：售· I j bv 重千φ刀子置較小，則所形成之黏著 切曰於再剥離時易發生黏著劑殘留，若重量平均分子量較 大’則除泡性會變差，因此重 〜 ϋ置Ϊ千均为子置被限定於50萬 萬，較佳為60萬〜_萬，更佳為60萬〜90萬。 此時’若黏著劑之凝膠分率鲂离 上剝離，因…… 自被黏附體 離因而再剝離時之黏著劑雖會殘留消失，但另一方 =黏合黏著劑時會有氣泡殘留。反之，若凝膠分率較低， 丙：：雖不會進入，但於再剝離時會有黏著劑殘留。因此， 二旨系樹脂之重量平均分子量為5〇萬〜1〇〇萬時於 較佳為Γ〜if重著 稀酸…上曹 本發明之第—發明中，於丙 夂α曰糸樹脂之重量平均分子量盥 係中，必項曰.”黏者劑之凝膠分率的關 、疋.丙稀酸醋系樹脂之重量平均分子量為5〇萬 0萬、較佳為60萬〜100萬，#曰 為30〜90舌4並且黏者劑之凝膠分率 9〇重罝％、較佳為化〜乃重量％。 又於本發明之第二發明中，黏著 定於70〜1ΛΛ丄 ⑷ < 錢勝分率被限 〇 100重量％，較佳為75〜90重量。/。ρ 明之第—發明中，於含有 Ρ於本發 化劑而成之苑菩❹ _曰糸樹月曰、父聯劑以及塑 ，、黏者劑之凝膠分率的 量 重量平均八；θ炎 乂肩疋丙烯酸酯系樹脂之 十々刀子450萬〜100萬、較佳為6〇萬〜9 黏著劑之凝膠分率為70〜100重量％ 重量％。 較佳為75〜90 劑 在如此之丙烯酸醋系樹脂之重量平均分子量與黏著 19 200914563 之凝膠分率的關係中之適當範圍$，可解決如前述之氣泡 及黏著劑殘留（再剝離性）之問題。 / (5 )黏著劑之製造 於以上述方式製備之丙烯酸酯系樹脂溶液中添加交聯 州藉此可衣造黏著劑溶液。又，製造黏著劑溶液時，視 而要亦可加入塑化劑、光聚合起始劑、增黏劑、穩定劑、 I外線吸收劑之添加劑。較佳為在不損害透光率、色相等 光學特性之範圍内配合該等添加劑。 (6 )黏著劑之凝膠分率 ^於本發明中，以上述方式製備之黏著劑的凝膠分率必 須為特定值。具體而言，於第一發明巾，上述重量平均分 子里為50萬〜1〇〇萬時’黏著劑之凝膠分率必須為〜％ 重里％、較佳為45〜75重量％。又，於第二發明中，上述 重量平均为子罝為50萬〜丨00萬時，黏著劑之凝膠分率必 頊為70〜1〇〇重量％、較佳為乃〜9〇重量％。於黏著劑中， 為了獲得上述範圍之凝膠分率，如前所述，藉由調整製造 丙烯酸酯系樹脂溶液時之分子量、交聯性（甲基）丙烯酸酯單 體量以及交聯劑量等來進行。於超過該範圍時，如前所述 有產生各自的問題之虞，因而欠佳。 此處，作為上述黏著劑之凝膠分率之測定方法，係將 黏著劑塗佈於脫模膜上於1〇(rc乾燥3分鐘，而獲得m 厚度之黏著劑層，再於其上覆蓋脫模膜，於23工、5〇%rh 環境中硬化一週。對該黏著劑進行取樣，在23。〇將其於乙 酸乙酯中浸潰24小時，然後自乙酸乙酯中取出，並於11〇 20 200914563 c之條件下& p ， 量，利用下:燦1小時。然後，測定乾燥後之試驗片之重 〜用下述式算出凝膠分率。 凝膠分率（重量。/。）=1〇〇xW2/Wi 重量）（W1 :㈣劑之重量’ W2 :浸潰、乾燥後之黏著劑之 再者&第二發明中，W1為不計塑化 黏著劑之會县 4里置〈燥前 所謂塑化劑重量，係指根據塑化劑含# f 分率而計算之塑化劑重量。 W含有百 2.表面保護黏著片 (工）表面保護黏著片之構成 繼而’就於基材之單面上積層而成有 構成之黏著劑層的表面保護黏著片加以說明。1者劑所 表面保遵黏著片係在基材之單面 劑所構成之黏墓如a 償增有由上迷黏著 +或之“劑層，進而，通常為了防止在使 濩黏者片之前黏著劑層貼 呆 於黏著劑，上^… 稱件上，或者塵埃附著 上，而於黏者劑層之表面以可剥 層脫模臈。 和雕之方式來積 進而，視需要亦可設置具有以下作用之抗靜電· 用以提高各層之密著力等而設置的中間層杨著 W上靜電而吸引空氣中之灰塵等。 一者 (2 )基材 作為上述基材，可使用由合成樹脂所構 別限定，例如可舉出.聚乙烯腺印品路 者，並無特 举出·聚乙烯膜、聚丙烯膜等聚烯烴 21 200914563 脂膜’聚對苯二？酸乙二酯膜等聚酿系樹脂膜，乙 乙=共聚物臈’聚氯乙婦系樹脂膜，聚胺 -夂 季父佳為聚酯系樹脂膜。 日膘荨’ 繼而，若上述基材之厚度較薄，則強产 或者使用變困難；另一方面，若又而易破壞 基材之強度過強而對段差的跟隨性變差材=較厚，則 光學特性'€、化’因而上述基材之厚度較 曝t = 佳為5〜12"m。 15em，更 (3 )黏著劑層 上述黏著劑層之厚度較佳為2〜2()_ 心。若黏著劑層之厚度小於以 、二二1。 夕ft . w 4 j另座生乳泡的問顏 虞’右黏者劑層之厚度大於 面產生問題之虞，因而欠佳。_則有會在光學特性方 (4) 脫模膜 作為上述脫模膜，可使用與上述基 為對與黏著劑層相接Μ & # ，之膜，較佳 著y層相接觸的面實施脫模處理者。 (5) 表面保護黏著片之製造方法 繼而’就表面保護黏著片之製造 表面俘嘈Η *丨 I坆方法加以說明。作為 H ° 製造方法，例如可舉出如下方法：製備黏著 心谷液，再㈣㈣劑溶液塗佈於脫 劑 液中的溶劑完全乾燥除去而形成黏著劑層，4 = =之黏耆劑層上；繼而利用橡膠輪等對上述積層 -進仃加壓，藉此獲得於基材之 在豆下而拉既 平调上形成黏著劑層，並 積層有脫模狀表面保護㈣片。又，亦可舉出 22 200914563 將構成黏著劑層之黏著 材的組成物進行_出“構成由合成樹脂所構成之基 …矣擠出，4此進行積層-體化之方法。 ()表面保護黏著片之用途 乂上述方式所獲得之本發明夕本二/ τ ^ r- 發月之表面保護黏著片具有以 下放果.即便厚度較薄， 、有μ 氣泡不會殘留，彳隹品Α 之表面時 ^ ^ 為了再利用光罩等對象物而將表面伴 〜片剝離時黏著劑亦不會殘留。 面保 女丄又肖由本發明之黏著劑可使黏著劑層變薄，因而星 #有助於“配線圖案的可靠性之效果。 進而’在保護電路基板等之贺谇 品晚+θ 寻之裊每中所使用之光罩的表 寺亦有以下效果：即便厚声齡壤 日车齑& 、 又，，在貼附於光罩表面 g* ^ . 先罩而將表面保護片剝 離和·黏著劑亦不會殘留。 :此’本發明之表面保護黏著片可較佳地用作保護電 路基板之製造中所使用之光罩的表面之表面保護黏著片。 [實施例] Μ Γ竿出賞施例 r奴π又態樣，但本 考X明並非僅限定於該等實施例。再者 、 丁只丨彳丹有’貫施例中所使用之 測定方法或評價方法示於如下。 1 ·測定方法或評價方法 (1)重量平均分子量 用四氫呋喃（THF)將丙烯酸酯系樹脂稀釋5〇倍，以 過濾器將所獲得之稀釋液進行過濾，基於所獲得之濾液， 利用凝膠滲透層析儀測定丙烯酸酯系樹脂之聚苯乙烯換算 23 200914563 分子量。此時，作為凝膠滲透層析儀，係使用自Water公司 購付之商品名為「2690 Separation Module」之商品。 (2)凝膠分率 將黏著劑塗佈於脫模膜上，於100°c乾燥3分鐘，而# 得4/z m厚度之黏著劑層，於其上覆蓋脫模膜，於23它^ 50%RH環境中硬化一週，繼而對該黏著劑進行取樣，將其 在23 C於乙酸乙酯中浸潰24小時，然後將黏著劑自乙酸乙 6旨中取出，並於110t：之條件下乾燥！小時。繼而，測定乾 燥後試驗片之重量，利用下述式算出凝膠分率。 凝膠分率（重量％) =l〇〇xW2/Wl …：黏著劑之重量，W2:浸潰、乾燥後之黏著劑之 重量） 再者，於實施例11〜18、比較例8〜12中，W1 塑化劑重量之乾燥前黏著劑之重量 -° 4〈垔置所谓塑化劑重量係指 I Κ據2化劑含有百分率而計算之塑化劑重量。 (3 )氣泡殘留評價 :::面保護片裁剪成5。_寬之帶狀。繼而，將表面保 於預先具有5。心間隔的梯形圖案之試驗用光罩 (Kodak公司製造之s〇_4〇4)上。此 ±θ /Λ-, 猎由使2 kg之橡 膝秦b作一次往返，而將表面 德，以矣， 則呆遵片與光罩牢固地黏合。其 表1所示之1 〇分法對該試脍M 殘留狀能a— h式驗樣品的剛黏合後之空氣Hey. The reason is that if the surface captive H unloads the D vine sheet to be thick, the exposure spreads, so the pattern may appear blurred. In addition, when the surface protection sheet is bonded, air bubbles enter, and the vomiting/middle A' causes a shortage of power supply in the circuit pattern. Therefore, the latest surface protection sheet base film itself is thinner and the layer U is also thinner, and the manufacturer is actively developing a surface protection sheet which does not affect the pattern: convex or bubble does not enter. Sheet: The surface protection used by the adhesive is used. When peeling off, the adhesive tends to remain on the mask. In addition, it is also expected that after the self-adhesive, the helmet will pass through the n# D, but the bubble will lie in the shortness of the squid, and then it will be dissipated by f σ.) #銶你1更四失(The surface protective film of the mouth is poor } In terms of workability and quality, there is no bubble in the management of the ancient product. Aspect ^ 'Expected to justify this problem after just bonding, in the patent read " reveals a kind of | In part, the upper limit of crosslinking due to this adhesive is 4. The weight is better than that of the special one; Γ: 'It is better to have more parts of the solvate. In short, (4) In other words, it is preferable that the gel fraction is high, but it is known that the bubble is not eliminated. [Patent Document 1] Japanese Patent Laid-Open No. Hei 2-313282 (Invention) The agent layer provides an adhesive. The formed (4) is left, and the surface is provided with no blistering at 2 o'clock, and the surface without the adhesive residue protection at the time of peeling contains the surface π surface protective adhesive sheet which is formed by the adhesive and is suitable for a reticle, etc. 200914563 The inventors repeatedly conducted diligent research to achieve the above objectives, and found that In the adhesive containing an acrylate resin and a crosslinking agent, the acrylate resin contains a specific amount of a (meth)acrylic acid having a crosslinkable functional group based on the total amount of the acrylate resin. In the ester component, the relationship between the weight average molecular weight of the acrylate resin and the gel fraction of the adhesive is in the range of g, and in this range, the bubble and the mildew residue (repeelability) as described above can be solved. The present inventors have found that the adhesive layer formed by adhering to the object is free from air bubbles when it is attached to the object, and no adhesive remains after peeling off, that is, the above acrylate. The resin contains a (meth)acrylic acid component containing 1 to 5 wt% of a crosslinkable holenyl group based on the total amount of the acrylate resin, and contains a polystyrene as measured by the C method. An adhesive having a gel fraction of 30 to 90% by weight, which has a weight average molecular weight of 10,000 Å, and a crosslinking agent having a molecular weight of 30 to 90% by weight. Further, the inventors have found that Contains a specific weight The average molecular weight of acrylic acid, resin, cross-linking agent and plasticizer is used as an adhesive to make ', the gel knife rate is 7〇~100 weight. It can be attached to the target temple...'bubble enters and peels off When there is no adhesive layer remaining in the adhesive agent, the present invention is finally completed by repeating the research on the fourth step, etc. The invention provides an adhesive which is a weight of polystyrene-converted molecular weight. The acrylate-based resin and the cross-linking, that is, the first aspect of the present invention, which comprises an average molecular weight of 500,000 to 100,000 by the GPC method, and is characterized in that: the above-mentioned acrylic vinegar resin The (meth) acrylate component having a crosslinkable functional group is contained in an amount of 0.01 to 5% by weight based on the total amount of the acrylate resin, and the adhesive is immersed in ethyl acetate at 23 ° C. After the lapse of time, it was taken out from the acetic acid, and was not dried for a few hours, at which time the gel fraction (Y) shown in the following formula was 30 to 90% by weight. /〇. Y= 100XW2/W1 (wherein, W1 means the weight of the adhesive after drying the weight of the adhesive before drying) 思4曰干^ Further, according to the second invention of the present invention, a point sword can be provided, 1 The weight of the polystyrene-converted molecular weight - the knife is set to 50 4 ~ 1 million acrylate U ί & Ά JIU t @月曰 'cross-linked sword and plasticizer; characterized by: The bismuth agent 乂忒 plasticizer is based on the total amount of the adhesive, %, and 3 has a weight of 1 to 40, and the adhesive is taken out in the ethyl acetate to be taken out in the vinegar, and is taken in "吖Drying for 1 hour, at this time: ::4, self-acetic acid gel fraction (Y...~100% by weight. Condensed Y== 100xW2/Wl in the formula) W1 means no plasticizer weight One of the weights of the adhesive after drying, and the weight of the adhesive according to the third invention of the present invention can provide the adhesive of the first invention, wherein the acrylic resin is used in the above acrylate resin. The total amount is based on the content of the '_〇2 to 3% by weight of the cross-linkable functional group (methyl acetoacetate component. According to a fourth invention of the present invention, there is provided an adhesive according to the first invention, wherein the crosslinkable functional group is a hydroxyl group. Further, according to the fifth invention of the present invention, the adhesive of the first invention can be provided. The acrylic vinegar-based resin contains 10 to 95% by weight of a (fluorenyl) acrylate component having an alkyl group having 8 to 18 carbon atoms, based on the total amount of the acrylic styrene resin. According to a sixth invention of the present invention, there is provided an adhesive d according to the fifth invention, wherein the (meth) acrylate component is ethyl hexyl acrylate. Further, according to the seventh invention of the present invention, the first invention can be provided. Or the adhesive agent of the second invention, wherein the crosslinking agent is an isocyanate-based crosslinking agent. Further, according to the eighth invention of the present invention, the adhesive of the first invention or the second invention may be provided, wherein the acrylic acid The vinegar-based resin contains a (meth) acrylate component having a condensing group having a carbon number of -4 to 12. On the other hand, according to the ninth invention of the present invention, a surface protective adhesive sheet can be provided, which is characterized in that Synthetic tree The layer is formed by the adhesive of the first invention or the second invention. Further, according to the tenth invention of the present invention, the τ provides the surface-protecting adhesive sheet according to the ninth invention, wherein the adhesive layer is The thickness is 2 to 20 // m. Further, according to the eleventh invention of the present invention, the surface protective adhesive sheet of the ninth invention 200914563 can be provided, wherein the surface of the photomask used in the manufacture of the p-batch main board: protection (4) A surface protected by a dry surface of 70. A lacquer according to the present invention and a surface protective adhesive sheet using the same, in the first invention, the adhesive contains a polyethylene exchange measured by the Gpc method | The weight average molecular weight of the molecular weight is from 50,000 to 10,000 per million of the fine ester resin and the crosslinking agent; and the upper vinegar resin is based on the total amount of the acrylic acid resin. The (meth) acrylate component (7) having a crosslinkable functional group of 〇〇ι = 3 is 3. ～90% by weight; therefore, it has the effect of forming an adhesive layer which is adhered to the object when the adhesive layer formed by using the adhesive J is adhered to the object, and is in the form of an adhesive layer remaining in the adhesive, In the second invention of the present invention, the adhesive is a acrylate resin, a crosslinking agent, and a plasticizer having a weight average molecular weight of 50,000 to 10,000 in terms of molecular weight measured in terms of polystyrene as measured by a method. The adhesive layer formed by using the adhesive is applied to the target layer, the bubble enters, and the adhesive layer remaining without the adhesive at the time of peeling. In the third invention of Resin Ming, the above-mentioned acridine vinegar-based bismuth, 3 #0·02 to 3% by weight of a (fluorenyl) propylene-containing fluorene-containing component containing a crosslinkable functional group is specified, and thus it is more economical and effective. The soil effect of the above-mentioned first invention is exerted. In the fourth invention of the present invention, the above-mentioned cross-linking officer: soil, and soil-based soil can be used to more effectively and effectively exert the effects of the above-described first invention, and in the fifth invention of the present invention, Acrylic acid 200914563 The ester resin contains (~95% by weight of a (meth)acrylic acid component containing a hospital base of 8 to 18% by weight based on the total of the acrylate resin, and thus the adhesive is particularly useful. When the formed adhesive layer is attached to the object, there is no effect of bubble entry. Further, in the sixth invention of the present invention, the (meth)acrylic acid vinegar component is specifically made of acrylic acid _2 ethyl group, and (4) the adhesive layer formed using the adhesive is attached to the object. There is no significant effect of bubble entry. The horse isocyanate vinegar cross-linking, IJI & 1 a /... gem-based agent can thereby exert the effects of the first invention or the second invention more economically and efficiently. In the eighth invention of the present invention, it is specifically provided that the acrylate oxime resin contains a (meth) acrylate component having an alkyl group having a carbon number of 4 to 2, and thus is particularly formed by using the adhesive. The effect of the thermal bubbles entering when the adhesive layer is attached to the object. The invention is characterized in that: in the ninth invention of the present invention, the adhesive layer formed by the surface protective adhesive sheet is laminated on the adhesive agent which is composed of the adhesive of the first invention or the second invention. ^ σ 成 树 树 曰 曰 曰 基材 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 气泡 气泡 气泡 气泡 气泡 气泡 气泡 气泡 气泡 气泡 气泡 气泡 气泡 气泡"2. In order to reuse the mask or the like, the adhesive does not remain when peeling off the four sheets. Further, in the tenth invention of the present invention, in the sheet!_, +-##士, W(1) Guanlan surface The thickness of the above-mentioned layer of the viscous layer in the protective viscous A is 2 to exert the above effects. The ox can thus be more economically and effectively improved, and the adhesive layer can be thinned, and the optical properties of 200914563 are excellent and contribute to the improvement. Further, in the tenth invention of the present invention, the surface protection adhesive sheet and the surface of the photomask used for the production of the protective circuit substrate are specified, and therefore, the protective circuit substrate is provided. When manufacturing the surface of the reticle used in the manufacture, ie The thickness of the surface protective adhesive sheet is thin, and when the surface is attached to the surface of the photomask, the air does not remain, and the adhesive does not remain when the surface protective sheet is peeled off by using the photomask. In the following, the adhesive of the invention and the surface protective adhesive sheet using the same are described in detail. 1. Adhesive The adhesive of the invention of the present invention contains the molecular weight as measured by the CJPC method. The acrylic acid-based resin and the cross-linking agent having a weight average molecular weight of from 10,000 to 10,000 are characterized in that the upper-olefinic resin contains Tetrali based on the total amount of the acrylate resin. The (meth)acrylic acid component containing a crosslinkable functional group, and the weight average molecular weight of the C is related to the gel fraction of the adhesive. The problem of the bubble and the adhesive residue (re-peelability) as described above is solved by the positive range. θ The adhesive of the first invention of the present invention contains a GPC method, and is an acrylate resin, a crosslinking agent, and a plasticizer having a weight average molecular weight of 10,000 mg as a molecular weight in terms of polystyrene. U is based on the weight average molecular weight of the acrylate resin and the adhesive 12 200914563, thereby adjusting the relationship between the gel fraction of the gas as described above to an appropriate range, and the foam and adhesive residue (re-peelability). (1) Acrylate-based resin As the acrylate-based resin constituting the above-mentioned adhesive, the weight average molecular weight of the molecular weight in terms of polystyrene measured by the GPC method must be 50,000 to 1,000,000'. (meth)acrylic acid vinegar resin or (meth)acrylic acid vinegar obtained by polymerizing or copolymerizing one or more kinds of (▼-based) acrylic acid vinegar monomers and copolymerizing therewith Its I-type monomer, copolymer; in terms of adjusting the adhesion or reacting with the crosslinking agent, it is preferred that the (meth) acrylate monomer and other ethylene which can be copolymerized with it Type of monomer Thereof. Further, in the present invention, the term "(meth)acrylic solder" means "methacrylic acid or acrylic acid". The above-mentioned (meth) acrylate monomer is not particularly limited, but in the first invention, it is preferably a primary or secondary alcohol having an alkyl group having a carbon number of 1 to 12 ( Obtained by esterification reaction of methyl)acrylic acid; specific examples thereof include ethyl (meth)acrylate, butyl acrylate (meth)acrylate, 2-ethylhexyl (meth)acrylate, and the like; homopolymer The reason why the Tg is the lowest in the acrylate and is relatively soft is preferable to the elimination of the bubbles, and is preferably 2-ethylhexyl acrylate. Further, the above (meth) acrylate monomers may be used singly or in combination of two or more. Further, the (meth) acrylate monomer is a (mercapto) acrylic acid vinegar component containing 10 to 95% by weight of an alkyl group having 8 to 18 carbon atoms based on the total amount of the acrylate resin. It is preferred because it can effectively eliminate bubbles. Specifically, 13 200914563 ° is preferably 2-ethyl hexyl acrylate, hexyl isooctyl acrylate, dodecyl acrylate or octadecyl acrylate. Further, in addition to the above 2-ethylhexyl acrylate component, it contains other propylene fluorene monomer ((mercapto) acrylate monomer), specifically, isooctyl acrylate, dodecyl acrylate, acrylic acid An acrylate-based resin such as octadecyl ester is preferred because it can more effectively eliminate bubbles. Further, if the 2-ethylhexyl acrylate in the acrylate-based resin is less than 3 in the knives, the formed adhesive layer is not sufficiently deformed when attached to the viscous body, that is, the reticle. Therefore, the bubbles are liable to remain. When the content of the ethyl 2-ethylhexyl acrylate component is large, the cohesive force is lowered to lower the adhesive strength. Therefore, in the case of polymerization or copolymerization, the amount of the 2-ethylhexyl acrylate component is based on the total amount of the acrylate resin, preferably 丨〇~% by weight/°', more preferably 1 〇. ~9 〇% by weight. Further, in the second invention, as the (meth) acrylate monomer, k is an esterification reaction of a primary or secondary alcohol having a carbon number of 4 to 12 with a (meth)acrylic acid by a calcination group. Obtained; specifically, preferably: (mercapto) butyl acrylate, (meth)acrylic acid 2-ethylhexyl acrylate, 2-ethyl hexyl acryiate, acrylic acid Octyl ester, dodecyl acrylate. Further, the (meth) acrylate single system contains a (meth) acrylate component having a carbon group of 4 to 12, which is preferable because it can effectively eliminate bubbles. Further, the above (meth) acrylate monomer may be used singly or in combination of two or more of 2009-14563. Other vinyl type monopolymers copolymerized with the above (meth) acrylate monomer are modified to copolymerize a (mercapto) acrylate monomer with another ethylene i monomer copolymerizable therewith, In order to increase the cohesive force of the obtained adhesive, for example, a glass transition temperature (Tg) of the acrylate resin (Tg) U γ| ^ . can be used to help form a cross between the main chains of the acrylate resin. Associated structure, etc. In order not to impair the re-peelability, the content of the other vinyl monomer component is preferably based on the total weight of the acrylic I-based resin, preferably 〇1 to 1 〇. Further, the vinyl monomer which improves the cohesive force of the acrylate resin is not particularly limited to S, and examples thereof include (meth)acrylic acid, butyric acid, maleic acid, and itaconic acid. (itaconic acid) a monomer of the material (IV), a monomer containing (4) such as methacrylamide or the like, maleic anhydride, vinyl acetate, styrene or the like; preferably acrylic acid. These can increase the cohesive force of the acrylic acid-based resin such as acrylic acid 2-ethylhexyl ester, thereby improving the adhesion. Further, the vinyl monomer which contributes to the formation of a crosslinked structure between the main chains of the acrylate-based resin is not particularly limited, and examples thereof include 2-hydroxyethyl (meth)acrylate and (A). Glycidyl acrylate, propylene glycidyl ether, and the like. When an isocyanate compound is used as the crosslinking agent, ruthenium is preferably 2-hydroxyethyl (meth)acrylate. Further, since the hydroxyl group is contained in the monomers, the cohesive force of the acrylate resin can be increased. Therefore, it is preferred to use a crosslinkable functional group represented by hydroxyethyl acrylate or hydroxyethyl methacrylate ( When the amount of the methyl acrylate component is small, the crosslinking is too small, so that even if a crosslinking agent is used, the desired condensing fraction cannot be obtained, and the adhesive residue is deteriorated. When the amount of the (fluorenyl) acrylate component having a crosslinkable functional group is too large, even if the gel fraction is in a desired range due to the cohesive force of the crosslinking monomer itself, the bubble removing effect is also deteriorated. Therefore, it is preferable to blend 〇〇丨~5 by weight based on the total amount of the propylene i-ester resin. /❶, better for 〇.〇 2~3 weight. /. Preferably, the (meth) acrylate component having a parental functional group is contained in an amount of 5 to j% by weight. Then, in order to obtain the above acrylate-based resin, another oxime-type monomer which copolymerizes a (meth)acrylic acid oxime monomer and, if necessary, a (meth) acrylate monomer may be used together with a polymerization initiator. The radical reaction can be carried out in the presence of it. Further, as the polymerization method, a conventionally known method can be employed, and examples thereof include solution polymerization, emulsion polymerization, suspension polymerization, and overall polymerization. The polymerization initiator is not particularly limited, and examples thereof include: - (peroxidized second hexyl) trimethyl cycline, third hexyl peroxypivalate, and third butyl peroxypivalate Ester, 2,5• dimethyl-2,5_bis (peroxide 2-ethylhexyl S& base) hexane-peroxide 2-ethylhexanoic acid third vinegar, peroxyethylhexanoate m oxidation Isobutyric acid, third butyl vinegar, 3,5,5-trimethylhexanoic acid, third butyl vinegar, tert-butyl peroxydodecanoate, etc.; due to the activity according to the half-life temperature at 10 j It is preferably PERHEXYL (registered trademark) pv manufactured by Sakamoto Oil Co., Ltd. as a commercial product. Further, the above polymerization initiator may be used singly or in combination of two or more. (2) A crosslinking agent, whereby a crosslinking structure is formed between the main chains in which the crosslinking agent is added to the adhesive of the present invention in which the adhesive is the above-mentioned crosslinking agent. 16 200914563 疋 疋 例如 例如 例如 例如 例如 例如 例如 例如 例如 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 。 。 。 。 。 。 Among these, the adhesive layer formed by the adhesive is less likely to be peeled off due to the peeling stress caused by the deformation of the adhesive, and is preferably an isocyanide-based parent. Agent. The isocyanate compound has high reactivity and may be dangerous if it is in contact with steam. Therefore, it is preferred to use a modified sulphuric acid vinegar having a low vapor pressure and high safety, and is preferably used as a commercially available product. : "C_nate (registered trademark) l_45" manufactured by Ershi, Co., Ltd., or 曰本聚胺醋工业股份有限公司. Further, the crosslinking agent may be used singly or in combination of two or more. The gel fraction was adjusted to the desired range in combination with the crosslinking agent. (3) Plasticizers - Generally, although the adhesive having a higher gel fraction has no adhesive, there is a residual air bubble during lamination. In the present invention, in particular, the door of the second invention is considered to be that the plasticizer expands the specific acrylic vinegar resin 曰' gap in the adhesive and imparts fluidity to help the adhesive to adhere. As a result, according to the present invention, even if the gel fraction is high, the problem of the bubble is solved in the case where the adhesive remains. Mingzhong, can be used: phthalic acid dioctyl vinegar, o::, phthalic acid diisoindole vinegar, dibutyl phthalate, a: acid-octyl vinegar, adipic acid diisoindole vinegar , stupid tricarboxylic acid vinegar, partial: dimethyl-dioctyl octyl ester, polyester, phosphate ester, trimethyl phosphate ester - acetonitrile dibutyl citrate, T-terate, bis, two: oxidized linseed oil , plasticizers such as bismuth-acid strontium, maleic acid vinegar, and benzoic acid. Special 17 200914563 is in terms of cost, more than; from the aspect of + i ling 11, it is preferably phthalate. However, since it is also an environmental hormone, it is sometimes suitable to use an ester composed of other acids such as dioctyl adipate. It must contain 1 to 40 parts by weight based on the total amount of the adhesive. In addition, the weight of the plasticizer and the adhesive of the θ 卩 main, θ f, and the weight of the adhesive before the drying are excessive, so that not only the adhesive residue is deteriorated, but also There is a % of plasticizer oozing out of the adhesive. On the other hand, if the amount of the right plasticizer is small, the effect of improving the bubbles cannot be obtained. (4) Weight average molecular weight of the acrylate resin The acrylate resin in the adhesive of the present invention has a weight average molecular weight of 500,000 million as measured by a GPC method. The acrylate resin can obtain a desired molecular weight by adjusting the polymerization initiator, the polymerization solvent/density, the chain transfer amount, and the polymerization temperature. In the present invention, the weight average molecular weight of the acrylate resin is the weight average molecular weight measured by the GPC method as a molecular weight in terms of polystyrene. Specifically, 'the vinegar vinegar-based resin was diluted 50-fold with tetrahydrofuran (THF), and the obtained diluted solution was filtered with a buffer to determine acrylic acid by gel permeation chromatography based on the obtained filtrate. The polystyrene-converted molecule 4 of the ester resin can thereby obtain the weight average molecular weight of the acrylic S-based resin. As the above-mentioned gel permeation chromatograph, for example, a product of "2690 Sepami〇n Chest Site" of the company name of "(10) Company" can be used. In the relationship between the weight average molecular weight of the propylene glycol acid I resin and the adhesion of the remaining stagnation 200914563, the name: sale · I j bv is a small φ knife set smaller, then the formed bond is cut and then peeled off. Adhesive residue is prone to occur, and if the weight average molecular weight is larger, the defoaming property will be deteriorated. Therefore, the weight is less than 500,000, preferably 600,000 to 10,000. It is 600,000 to 900,000. At this time, if the gel fraction of the adhesive is peeled off, the adhesive remains after disappearing from the adhered body, but the other side = bubbles remain when the adhesive is adhered. On the other hand, if the gel fraction is low, C:: will not enter, but there will be adhesive residue when peeling again. Therefore, the weight average molecular weight of the second-purpose resin is from 50,000 to 10,000, preferably in the form of Γ~if heavy dilute acid. In the invention of the invention, in the case of propylene carbonate In the weight average molecular weight system, the gel fraction of the adhesive agent is 疋. The weight average molecular weight of the acrylic acid vinegar resin is 50,000, preferably 600,000 to 1,000,000. #曰 is 30~90 tongue 4 and the gel fraction of the adhesive agent is 9〇%, preferably 〜% by weight. Also in the second invention of the present invention, the adhesion is set at 70~1ΛΛ丄(4) < The winning percentage is limited to 100% by weight, preferably 75 to 90% by weight. / ρ 明第第—Inventive, in the case of containing the 发 本 本 苑 苑 苑 曰糸 曰糸 曰糸 曰糸 曰糸 曰糸 曰糸The ratio of the gel fraction of the parent-linked agent and the plastic, and the adhesive agent is eight; the θ 乂 乂 乂 疋 疋 疋 疋 疋 450 450 450 450 450 450 450 450 450 450 450 450 450 450 450 450 450 450 450 450 450 450 450 450 450 The gel fraction of the agent is 70 to 100% by weight. Preferably, the weight average molecular weight and adhesion of the acrylic vinegar resin are 75 to 90. An appropriate range of the relationship of the gel fraction of 63 can solve the problem of the bubble and the adhesive residue (re-peelability) as described above. / (5) The adhesive is produced by the acrylate resin prepared in the above manner. The cross-linking state is added to the solution to make the adhesive solution. In addition, when the adhesive solution is prepared, it is also possible to add a plasticizer, a photopolymerization initiator, a tackifier, a stabilizer, and an external absorbent. Preferably, the additives are blended in a range that does not impair the light transmittance and the optical properties of the color. (6) Gel fraction of the adhesive ^ In the present invention, the gelation of the adhesive prepared in the above manner The gel fraction must be a specific value. Specifically, in the first invention towel, the weight average molecular weight is 500,000 to 1 million, and the gel fraction of the adhesive must be 5% by weight, preferably Further, in the second invention, when the weight average is from 500,000 to 10,000, the gel fraction of the adhesive must be 70 to 1% by weight, preferably It is ~9〇% by weight. In the adhesive, in order to obtain the above range of condensation As described above, the gel fraction is adjusted by adjusting the molecular weight, the crosslinkable (meth) acrylate monomer amount, the amount of the crosslinking agent, and the like in the production of the acrylate resin solution. The method of measuring the gel fraction of the above-mentioned adhesive is to apply an adhesive to the release film at 1 Torr (rc drying for 3 minutes, as described above). The adhesive layer of m thickness was obtained, and the release film was covered thereon, and hardened in a 23-mesh, 5 〇% rh environment for one week. The adhesive was sampled at 23. The sputum was immersed in ethyl acetate. The mixture was decomposed for 24 hours, and then taken out from the ethyl acetate, and under the conditions of 11〇20 200914563 c & p, the amount was utilized: 1 hour. Then, the weight of the test piece after drying was measured, and the gel fraction was calculated by the following formula. Gel fraction (weight: /)) = 1 〇〇 x W2 / Wi weight) (W1: weight of the (four) agent 'W2: after the dipping, drying of the adhesive & second invention, W1 is not counted The plasticizing adhesive is located in Huixian County. The so-called plasticizer weight refers to the weight of the plasticizer calculated according to the plasticizer containing the #f fraction. W contains 100. Surface protection adhesive sheet (work) The surface protective adhesive sheet is then composed of a surface protective adhesive sheet which is laminated on the single side of the substrate to form an adhesive layer. The surface of the adhesive is adhered to the single side of the substrate. The composition of the sticky tomb, such as a replenishment, has a layer of adhesion + or "the agent layer, and, in order, usually to prevent the adhesive layer from sticking to the adhesive before the adhesive sheet is placed on the adhesive, or The dust adheres to the surface of the adhesive layer, and is peeled off from the surface of the adhesive layer. In addition to the engraving, it is also possible to provide an antistatic having the following effects, and to set the adhesion of each layer. The middle layer of Yang holds the static electricity on the W to attract dust in the air, etc. One (2) substrate as the upper The base material may be defined by a synthetic resin, and for example, a polyethylene gland printing road may be mentioned, and a polyolefin film such as a polyethylene film or a polypropylene film is not specifically mentioned. A polyethylene resin film such as a diethylene glycol film, a polyethylene ethyl ester = copolymer 臈 'polychloroethylene resin film, and a polyamine- 夂 父 佳 is a polyester resin film. If the thickness of the substrate is thin, it is difficult to produce or use; on the other hand, if the strength of the substrate is too strong and the followability of the step is too thick, the optical property is ', Therefore, the thickness of the above substrate is more than the exposure t = preferably 5 to 12 " m. 15em, more (3) the thickness of the adhesive layer of the adhesive layer is preferably 2 to 2 () _ heart. If the adhesive layer The thickness is less than that of 222. 夕 ft. w 4 j The other part of the raw milk blister is the thickness of the right adhesive layer is larger than the surface problem, so it is not good. _ There will be optical properties (4) Release film As the above release film, a film which is in contact with the above-mentioned base and the adhesive layer may be used, preferably a y layer The surface to be contacted is subjected to mold release treatment. (5) The method of manufacturing the surface protective adhesive sheet is then described as 'the surface captive of the surface protective adhesive sheet. 丨I坆 method is explained. As the H ° manufacturing method, for example, The method is as follows: preparing a viscous heart solution, and then the solvent applied to the solution in the (iv) (four) solution is completely dried and removed to form an adhesive layer, 4 = = on the adhesive layer; and then the above layer is laminated by using a rubber wheel or the like - Pressing and pressing, thereby obtaining an adhesive layer on the substrate under the bean and pulling it flat, and laminating the surface of the adhesive layer (4). Also, 22 200914563 will constitute an adhesive layer The composition of the adhesive material is subjected to a method of forming a base composed of a synthetic resin, and extruding it. () Use of surface protective adhesive sheet The surface protective adhesive sheet of the present invention obtained in the above manner has the following results: even if the thickness is thin, the μ bubbles do not remain, 彳When the surface of the product is used, ^ ^ The adhesive does not remain when the surface is peeled off with the object such as a mask. The face protector and the adhesive of the present invention can make the adhesive layer thinner, and thus the star # contributes to the effect of the reliability of the wiring pattern. Further, in the protection circuit board, etc., the product is late + θ. The watch temple of the reticle used in the middle also has the following effects: even if it is thick and sturdy, it is attached to the surface of the reticle g* ^. The cover is peeled off and adhered. The surface protective adhesive sheet of the present invention can be preferably used as a surface protective adhesive sheet for protecting the surface of the photomask used in the manufacture of the circuit substrate. [Example] Μ Γ竿 Γ竿The example of the invention is not limited to the examples. Further, the measurement method or evaluation method used in the example of the method is shown below. - Measurement method or evaluation method (1) Weight average molecular weight The acrylate resin was diluted 5 times with tetrahydrofuran (THF), and the obtained diluent was filtered with a filter, and a gel permeation layer was used based on the obtained filtrate. Determination of polystyrene of acrylate resin by analyzer Ethylene conversion 23 200914563 Molecular weight. In this case, as a gel permeation chromatograph, a product sold under the trade name "2690 Separation Module" from Water Corporation was used. (2) Gel fraction The adhesive was applied to the release film and dried at 100 ° C for 3 minutes, and #4 / zm thickness of the adhesive layer was overlaid on the release film, at 23 it ^ After hardening for one week in a 50% RH environment, the adhesive was sampled, and it was immersed in 23 C in ethyl acetate for 24 hours, and then the adhesive was taken out from the acetic acid, and under conditions of 110 t: dry! hour. Then, the weight of the test piece after drying was measured, and the gel fraction was calculated by the following formula. Gel fraction (% by weight) = l〇〇xW2 / Wl ...: weight of the adhesive, W2: weight of the adhesive after dipping and drying) Further, in Examples 11 to 18, Comparative Examples 8 to 12 In the weight of the W1 plasticizer, the weight of the pre-drying adhesive is -4. The so-called plasticizer weight refers to the weight of the plasticizer calculated according to the percentage of the 2 chemical agent. (3) Evaluation of bubble residue ::: The face protection sheet was cut into 5. _ wide band shape. Then, the surface is guaranteed to have 5 in advance. The mask of the trapezoidal pattern of the heart interval was tested on a mask (s〇_4〇4 manufactured by Kodak Co., Ltd.). This ±θ /Λ-, hunting by making 2 kg of rubber knees b b a round trip, and the surface of the German, to 矣, then the film and the mask firmly bonded. The 1 〇 method shown in Table 1 is the air immediately after bonding the test sample M residual energy a-h test sample.
^ .. . ^ 伞汁價忒驗係於23°c、50G/ORH 之％纟兄中進行。 24 200914563 [表1] 有無氣泡 氣泡形狀 評價 分數 是否合格 益 圓形、橢圓形 ◎ 10 合格 微少 圓形、橢圓形 ◎ 9 合格 少 圓形、橢圓形 〇 8 合格 少 葫蘆形小 〇 7 合格 少 葫蘆形大 Δ 6 不合格 有 葫蘆形緊接 Δ 5 不合格 有 絲狀小 X 4 不合格 有 絲狀大 X 3 不合格 有 整面小 XX 2 不合格 有 整面大 XX 1 不合格 (4 )黏著劑殘留評價 用雙面膠帶將一日前黏合了表面保護片之光罩20cmx 20cm ( Kodak公司製造）固定於厚度為2mm之鋁板上。繼 而，用手將表面保護片以與光罩成近90度之角度垂直且儘 ( 量迅速地撕下。以表2所示之3分法來評價黏著劑殘留狀 態。再者，本評價試驗係於23 °C、50%RH之環境中進行。 [表2] 觀察 評價 分數 是否合格 無 〇 3 合格 極少有殘留 Δ 2 不合格 經常有殘留 X 1 不合格 25 200914563 [實施例1〜10、比較例1〜7] I黏著劑以及表面保護黏著片之製造 (丙歸酸酯系樹脂之製備） 準備具備溫度計、攪拌機、冷卻管之反應器，於該反 應态内加入表3所示之既定量之單體及乙酸乙酯，用一小 時自反應器底部投入Ns。其後，將液溫調整為7(rc。依照 表4之條件，用4小時向反應器中定量添加作為聚合起始 Γ 劑的過氧化特戊酸第三己酯（「PERHEXYL (註冊商標） P V」日本油脂股份有限公司製造），於N2環境氣氛中進行 永合。繼而，自聚合開始8小時後，用乙酸乙酯進行稀释 並冷卻反應器以終止聚合反應。獲得固體含量為3〇重量％ 之丙烯酸酯系樹脂溶液。 26 200914563 【£<】 聚合物 S 92.7 iy-> cn 〇 86萬 77.7 rn 〇 86萬 87.7 〇 CS cn d 〇 86萬 *—> 97.7 ΓΛ 〇 91萬 1—Η 47.7 CNJ CO o 〇 86萬 X 97.7 cn ο 〇 62萬 〇 5； <N 卜 〇 86萬 [Jh yri 〇\ CM m 〇 94萬 97.97 (N 0.03 〇 92萬 Q 00 ON 0.005 〇 89萬 〇 I 97.7 <N cn 〇 〇 88萬 CQ 97.7 CN cn d 〇 86萬 < 97.7 (N m o 〇 43萬 原材料 製造廠商 曰本觸媒 I 大阪有機化學 大阪有機化學 大阪有機化學 曰本觸媒 共榮社 日本油脂 和光純藥 曰本聚胺酯 重量平均分子量 内容 I 1單體 單體 單體 單體 厂 單體 鹪 單體 焕 交聯劑 名稱 2EHA (丙烯酸-2-乙基己酯） 丙烯酸異辛酯 丙稀酸十二烧δ旨 丙烯酸十八烧S旨 AAC (丙烯酸） HEA (丙稀酸經基乙酯） HEMA (曱基丙烯酸羥基乙酯） 乙酸乙酯 Coronate L-45 aoOOI 遛ro潜ο,&οε V3H ,&ΰο(Νυνν ,ΰοΑ 卜 6 vffis : ν#φ龄(苳 (如：与缽)餵 ο 韶toe黩缽客 ¥^oiw<??T<^-fi-lltr^矣* 200914563 [表4] 起始劑 投入量 第1階段 PERHEXYL PV 0.010 第2階段 PERHEXYLPV 0.020 第3階段 PERHEXYL PV 0.050 第4階段 PERHEXYL PV 0.100 用一小時定量投入 用一小時定量投入 用一小時定量投入 用一小時定量投入· *用乙酸乙酯將10倍量之起始劑（單位：g)稀釋成60 mb 並以1 ml/min進行滴加。^ .. . ^ Umbrella price test is carried out in the brothers of 23 ° C, 50 G / ORH. 24 200914563 [Table 1] Whether or not the bubble shape evaluation score is acceptable. Round or oval ◎ 10 Qualified slightly round, oval ◎ 9 Qualified less round, oval 〇 8 Qualified less cucurbit-shaped 〇 7 Qualified less cucurbit Large Δ 6 unqualified with gourd shape close to Δ 5 unqualified with filamentous small X 4 unqualified with filamentous large X 3 unqualified with whole surface small XX 2 unqualified with full surface large XX 1 unqualified (4) Evaluation of Adhesive Residues A 20 cm x 20 cm (manufactured by Kodak Co., Ltd.) photomask having a surface protective sheet adhered one day ago was attached to an aluminum plate having a thickness of 2 mm. Then, the surface protective sheet was rubbed by hand at an angle of nearly 90 degrees to the reticle by hand (the amount was quickly peeled off. The adhesive residue state was evaluated by the 3-point method shown in Table 2. Further, this evaluation test It is carried out in an environment of 23 ° C and 50% RH. [Table 2] Observe whether the evaluation score is acceptable or not. 3 Qualified rarely has residual Δ 2 Failed often has residual X 1 Failed 25 200914563 [Examples 1 to 10, Comparative Examples 1 to 7] Preparation of I-Adhesive and Surface-Protective Adhesive Sheet (Preparation of a Propionic Acid-Based Resin) A reactor equipped with a thermometer, a stirrer, and a cooling tube was prepared, and the predetermined conditions shown in Table 3 were added to the reaction state. The monomer and ethyl acetate were charged with Ns from the bottom of the reactor for one hour. Thereafter, the liquid temperature was adjusted to 7 (rc. According to the conditions of Table 4, the addition to the reactor was quantitatively added as a polymerization start in 4 hours. Tetrahexyl peroxypivalate ("PERHEXYL (registered trademark) PV" manufactured by Nippon Oil & Fats Co., Ltd.), which is a sputum agent, is aged in an N2 atmosphere. Then, after 8 hours from the start of the polymerization, ethyl acetate is used. Dilute and cool down The polymerization was terminated to obtain an acrylate resin solution having a solid content of 3% by weight. 26 200914563 [£<] Polymer S 92.7 iy-> cn 〇860000 77.7 rn 〇868,000 87.7 〇CS cn d 〇86 million*—> 97.7 ΓΛ 〇910,000 1—Η 47.7 CNJ CO o 〇86 million X 97.7 cn ο 〇 62 million 〇 5; <N 〇 〇 86 million [Jh yri 〇\ CM m 〇94 million 97.97 (N 0.03 〇920,000 Q 00 ON 0.005 〇89 million 〇I 97.7 <N cn 〇〇88 million CQ 97.7 CN cn d 〇86 million< 97.7 (N mo 〇430,000 raw material manufacturer 曰本触媒I Osaka Organic Chemistry Osaka Organic Chemistry Osaka Organic Chemistry Sakamoto Catalyst Kyoeisha Japanese Oils and Light Pure Chemicals Polyurethane Weight Average Molecular Weight Content I 1 Monomer Monomer Monomer Monomer Monomer Monomer Monofluoride Crosslink Name 2EHA ( 2-ethylhexyl acrylate) Isooctyl acrylate acrylate 12 oz. Acrylic octadecyl S. AAC (acrylic acid) HEA (acrylic acid ethyl ester) HEMA (methacrylic acid) Ethyl ethyl ester) ethyl acetate Coronate L-45 aoOOI 遛ro dive ο, & οε V3H , & ΰο (Νυνν , ΰοΑ 卜 6 vffis : ν# φ 苳 (苳:和和钵)送ο 韶toe黩¥客¥^oiw<??T<^-fi-lltr^矣* 200914563 [Table 4] Starting agent input amount Stage 1 PERHEXYL PV 0.010 Stage 2 PERHEXYLPV 0.020 Stage 3 PERHEXYL PV 0.050 Stage 4 PERHEXYL PV 0.100 Quantitative input with one hour Quantitative input with one hour Quantitative input with one hour Quantitative input with one hour · * 10 times the amount of initiator (unit: g) diluted to 60 mb with ethyl acetate and 1 ml/min Make a drop.
(表面保護片之製造） 向以上述方式獲得之丙烯酸酯系樹脂溶液中，添加如 表5或表6所示之既定量的增黏樹脂、異氰酸酯系交聯劑 (「Coronate (註冊商標）L_45」日本聚胺酯工業股份有限 公司製造），並進行攪拌，藉此獲得固體含量為8重量％之 黏著劑溶液。 繼而將上述黏著劑溶液塗佈於成為脫模膜之厚度為 25^m的聚對苯二曱酸乙二g旨膜之脫模處理面的表面上，於 匕〇〇 C乾蚝3分鐘以除去黏著劑溶液中的乙酸乙酯，而形成 之黏著劑層，然後將成為基材之厚度為— ♦、本-曱酸乙二醋膜重疊於黏著 °C、5〇%RH之環境中硬化一週。 將〃於 其次，以上述要領測定以上述方式 樹脂之重量平均八+旦 ^ 獲得丙烯酸酯系 上述要領對氣泡殘留評價、黏著劑殘留評 定。評價結果示於表5或表6。 仏方面進仃測 28 200914563 k<】 實施例10 r- (N . (N CO c5 〇 r-H CN o 86萬 56% 0Q m 實施例9 (N cn o t-H (N 〇 86萬 57% 00 ΓΛ 實施例8 r- ο (N m o o (N 〇 86萬 56% 00 實施例7 ·—i Γ-； (N rn o (N 〇 91萬 62% 〇\ 實施例6 HH (N m o o (N 〇 86萬 59% QO 丨實施例5 ffi σί (N m o o 1—H r〇 〇 62萬 53% 00 rn 實施例4 ί-tH IT) Γ0 ro o T-H s d 94萬 57% rn 實施例3 97.97 <N S 〇 o r-H 92萬 52% 實施例2 u Γ-; (N rO 〇 o 1-H (N 〇 88萬 63% 卜 m 實施例1 CQ 卜 σί <N CO o o CN 〇 86萬 57% 聚合物編號 2EHA 丙烯酸異辛醋 丙稀酸十二焼J旨 丙稀酸十八院S旨 AAC HEA HEMA 聚合物 Coronate L-45 重量平均分子量 凝膠分率 SB戎 傲Φ 頊2 ㈣W 黏著劑殘留 (3分法） I? 。％ ¥ ¥ W 长友^齧 < 衅砩嫦鍥璨荽^&4xt'#s17-13-(->BUOJ03* 200914563 【9 1 比較例7 〇 (N 卜 〇 t—H s o 86萬 34% m j 比較例6 Q 97.995 (N 0.005 1 o o 89萬 23% ON CN 比較例5 CQ 卜 CN m c5 o Τ·"Η <N 86萬 91% 寸 rn 1 比較例4 ffl <N rn o S o 86萬 28% 〇 比較例3 < 卜 σί (N m ο o T-H (N 43萬 84% (N 比較例2 < ι> Os (N cn o CN 〇 43萬 55% 00 比較例1 < (N cn o s o 43萬 23% 〇 τ^Η 聚合物編號 2EHA 丙烯酸異辛酯 丙烯酸十二燒西旨 丙稀酸十八烧酯 AAC HEA HEMA 聚合物 Coronate L-45 重量平均分子量 凝膠分率 S 激Φ 頊2 黏著劑殘留 (3分法） 言啊賈結果 。0/0 ¥ ¥ W 长茫伞to®!-蛛^蝇 H 黧荽φ^^^ς 寸-一 3SUOJOU* 200914563 由表5及表6之結果可知，若將實施例卜1〇與比較 例1〜7加以對比，則未滿；^作為本發明第—發明之特定事 項的丙烯酸醋系樹脂以丙烯酸醋系樹脂總體為基準，含 有0 · 01〜5重量。/。之含交聪祕古甘 ，眭s此基的（曱基）丙烯酸酯成 分」之要件的比較例6及比較例7’係於氣泡殘留以及黏著 劑殘留之評價中並未同時滿足兩者。 同樣，未滿足作為本發明第一發明之特定事項的「丙 烯酸醋系樹脂之利用GPC法測得之作為聚苯乙稀換算分子 量的重量平均分子量為50萬〜⑽萬，且黏著劑之特徵在 於《分率為3G〜9()重4%」之要件中的前者之比較例^ 〜3,係分別於氣泡殘留以及黏著劑殘留之評價 滿足兩者。 个N听 又’同樣未滿；i後者之比較例！及比較例卜6，亦係 分別於氣泡殘留以及黏著劑殘留之評價中並未同時滿足兩 者。 與該等相比，同時滿足作為本發明第一發明之特定事 項的「丙燁酸I系樹脂以丙烯酸醋系樹脂總體為基準，含 有〇·〇ι〜5 f量。/。之含交聯性官能基的(甲基)丙烯酸輯： 分」以及「丙烯酸自旨系樹脂之利用GPC法測得之作 乙烯換算分子量的重量平均分子量為50萬〜100 U之凝膠分率為3G〜9G重量％」之要件的實施例 均係於氣泡殘留以及黏著劑殘留之評價中同時滿足兩者。 因此可知，實施例1〜10中所獲得之表面保護黏著帶， 與比較例1〜7中所獲得之表面保護黏著帶相比，更適合用 31 200914563 作表面保濩黏著帶’並可解也* 鮮决乳泡殘留及黏著劑殘留之問 題點’因此在用作光罩用表面 — 衣向保瘦黏著帶時具有優異性能。 [貫施例11〜18、比較例8〜12] 1.原材料 使用表7所不者’作為用 •、’用以製備丙稀酸酯系樹脂之原 材料。 [表7] ----- 名 稱 — 内 容 製造麻商 丙稀酸-2-乙基己@旨 單體 曰太觸梯 丙烯酸 曰本觸媒 HEA (丙浠酸羥基乙酯） 單體__ 日本油脂 乙酸乙酯 溶劑 Μ Coronate L-45 交聯#1 —--- ——- 曰本聚胺西曰 2.黏著劑之製造 (1 )丙烯酸酯系樹脂之製備 準備具備溫度計、擾拌機、冷卻管之反應器，向該反 應器内加入表8所示之既定量的單體及乙酸乙酯，用一小 ¥自反應器底部投入Ν2。其後，將液溫調整為7(Γ(：。依照 表9之條件，用4小時向反應器内定量添加作為聚合起始 劑的過氧化特戊酸第三己酯（「PERHEXYL (註冊商樑 PV」日本油脂股份有限公司製造），並於乂環境氣氛中進 行聚合。繼而，自聚合開始8小時後，用乙酸乙酯進行稀 釋並冷卻反應器以終止聚合反應。獲得固體含量為3〇重量 Μ之丙烯酸酯系樹脂溶液。 32 200914563 [表8] 聚合物編號 A B C D E 丙烯酸-2-乙基己酯 97.7 97.7 97.7 97.7 97.7 丙稀酸 2 2 2 2 2 HEA 0.3 0.3 0.3 0.3 0.3 乙酸乙酯 70 100 80 60 50 分子量 72萬 40萬 60萬 90萬 120萬 *向反應器中投入上述表之10倍量的單體及乙酸乙酯（單位：g) 例）聚合物 A : 2EHA 977 g、AAC 20 g、HEA 3 g、乙 酸乙酯70 g [表9] 起始劑 投入量 第1階段 PERHEXYLPV 0.010 第2階段 PERHEXYLPV 0.020 第3階段 PERHEXYL PV 0.050 第4階段 PERHEXYL PV 0.100 用一小時定量投入 用一小時定量投入 用一小時定量投入 用一小時定量投入 *用乙酸乙醋將10倍量之起始劑（g )稀釋成60 ml，並以1 ml/min 進行滴加。 (2 )黏著劑之製造 向以上述方式獲得之丙烯酸酯系樹脂溶液中，添加如 表1 0或表11所示之既定量之增黏樹脂、異氰酸酯系交聯 劑（「Coronate (註冊商標）L-45」日本聚胺酯工業股份有 限公司製造），並進行攪拌，藉此獲得固體含量為8重量％ 之黏著劑溶液。 33 200914563 3 ·表面保護黏著片之製造 將上述黏著劑溶液塗佈於成為脫模膜之厚度為25 m 。r馱乙—酯膜之脫模處理面的表面上，於100 二：？ 3分鐘以除去黏著劑溶液中的乙酸乙醋，而形成厚 又’.，、之黏著劑層，然後將成為基材之厚声 聚對苯二甲酸乙…/旱度為6心的 T醆乙—酯膜重疊於黏著劑層上。 50%RH 之掙译 士 工 23 C > 〈％<境中硬化一週。 繼而，胳L、+、, f上述方式獲得之丙烯酸酯系樹脂t # I 1 均分子量 Ί彳阳I垔里平 、黏者劑之凝膠分率、氣泡殘留評價以及 殘留評價之处 只Ζ及漆占耆劑 只 <結果不於表10及表11〇 34 200914563 01<】 實施例18 < 97.7 (Ν rn 72萬 〇 o 78% Ο c^i 實施例17 C 97.7 CN m 72萬 〇 m ο 78% 卜 cn 1 實施例16 < 1 97.7 (Ν cn 72萬 〇 ο (Ν 96% 卜 m 實施例15 < 97.7 (Ν m ο 72萬 〇 r—H Ο 91% οο m 實施例14 < 97.7 (Ν cn 72萬 Ο <r—f (Ν Ο 63% Ον cn 實施例13 Q 97.7 (Ν m O 90萬 o m ο 85% 00 cn 實施例12 < 97.7 CM m O 72萬 o ο 78% Os cn 實施例11 〇 97.7 (N 〇 60萬 o ιη 74% On ro 聚合物編號 丙烯酸-2-乙基己酯 丙稀酸 HEA (丙烯酸羥基乙酯） 重量平均分子量 聚合物 己二酸二辛酯（塑化劑） Coronate L-45 凝膠分率 氣泡殘留 (10分法） 黏著劑殘留 (3分法） 聚合物組成 I 黏著劑組成i 評價結果 。％ ¥ 侧 W 长^伞齧-铢^硪鹳璨#如鉍^'#ln寸·Ί 2BUOJOU* 200914563 【11<】 ra < 1 97.7 (Ν m 〇 72萬 〇 r-H yr) 〇 78% Ο CN 比較例11 C 97.7 (Ν rn 72萬 〇 〇 ο 78% 〇 < 97.7 (Ν m 72萬 〇 »—( 48% ο r-H i 比較例9 ω 97.7 1___________ (Ν m ο 120萬 〇 T11 Η ο 88% CO ! 比較例8 97.7 1_ (Ν <Τ) ο 40萬 〇 r—Η ο 71% ο r·^ 聚合物編號 丙烯酸-2-乙基己酯 丙稀酸 ΗΕΑ (丙烯酸羥基乙酯） 重量平均分子量 聚合物 己二酸二辛g旨（塑化劑） Coronate L-45 凝膠分率 氣泡殘留 (10分法） 黏著劑殘留 (3分法） 聚合物組成 黏著劑組成 評價結果 200914563 根據表1 〇及矣j + #田 表之結果，若將實施例11〜18與比較 例8〜12加以對比目丨去 較 對比則未滿足作為本發明第二發明之 事項的「黏著劑传人古4丨 、疋 算分子量=:S有利用GPC法測得之作為聚苯乙稀換 士 、置平均分子量為50萬〜10〇萬之丙烯酸 樹脂、交聯劑以及塑化劑而成者 * •曰’、 1 , y 者」之要件的比較例8、9及 1者係於氣泡殘留以及黏著劑殘留之評價中並未同時滿足 著：2滿足作為本發明第二發明之特定事項的「點 /之’/分率為7〇〜100重量％」之要件的比較例10, :於氣泡殘留以及黏著劑殘留之評價中並未同時滿足兩 又，未滿足作為本發明第二發明之特定 :劑總體為基準，含有1，重量%之塑化劑而成」之要： 比較例12’係於氣泡殘留以及黏著劑殘留之評 同時滿足兩者。 禾(Production of Surface Protective Sheet) To the acrylate-based resin solution obtained as described above, a predetermined amount of a tackifying resin or an isocyanate-based crosslinking agent as shown in Table 5 or Table 6 ("Coronate (registered trademark) L_45) was added. "Manufactured by Japan Polyurethane Industry Co., Ltd." and stirred, thereby obtaining an adhesive solution having a solid content of 8% by weight. Then, the above-mentioned adhesive solution was applied onto the surface of the release-treated surface of the polyethylene terephthalate film having a thickness of 25 μm as a release film, and dried on 匕〇〇C for 3 minutes. The ethyl acetate in the adhesive solution is removed to form an adhesive layer, and then the thickness of the substrate is - ♦, the bismuth phthalate film is superimposed on the adhesion °C, 5〇% RH in the environment to harden one week. Next, in the above manner, the average weight of the resin in the above manner was measured in the above manner to obtain an acrylate system. The above method was used to evaluate the bubble residue and the adhesion residue evaluation. The evaluation results are shown in Table 5 or Table 6.仏 仃 28 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施Example 8 r- ο (N moo (N 〇 86 million 56% 00 Example 7 · -i Γ-; (N rn o (N 〇 910,000 62% 〇 \ Example 6 HH (N moo (N 〇 860,000 59% QO 丨Example 5 ffi σί (N moo 1—H r〇〇62 million 53% 00 rn Example 4 ί-tH IT) Γ0 ro o TH sd 94 million 57% rn Example 3 97.97 <NS 〇 o rH 92 million 52% Example 2 u Γ-; (N rO 〇o 1-H (N 〇 880,000% 卜m Example 1 CQ 卜 ί ί; N CO oo CN 〇 86 million 57% polymer number 2EHA Acrylic isooctyl acrylate acetonate Twelve 焼 J-acrylic acid 18th S S AAC HEA HEMA Polymer Coronate L-45 Weight average molecular weight Gel fraction SB 戎 Φ 顼 2 (4) W Adhesive residue (3 points Method) I? %% ¥ ¥ 长友^拳<衅砩嫦锲璨荽^&4xt'#s17-13-(->BUOJ03* 200914563 [9 1 Comparative Example 7 〇(N 卜〇t —H so 86 million 34% mj Comparative example 6 Q 97.995 (N 0.005 1 oo 890,000 23% ON CN Comparative Example 5 CQ Bu CN m c5 o Τ·"Η <N 86 million 91% inch rn 1 Comparative Example 4 ffl <N rn o S o 86 10,000 28% 〇Comparative Example 3 < 卜σί (N m ο o TH (N 43 million 84% (N Comparative Example 2 <ι> Os (N cn o CN 〇435,000 55% 00 Comparative Example 1 < ( N cn oso 43 million 23% 〇τ^Η Polymer No. 2EHA Acrylic acid isooctyl acrylate 12-burning acrylic acid octadecyl ester AAC HEA HEMA Polymer Coronate L-45 Weight average molecular weight Gel fraction S Φ 顼 2 Adhesive residue (3 points method) 0/0 ¥ ¥ 茫 茫 to ! ! - - - - - - - ^ 一 一 一 一 一 一 一 一 一 一 一 一 一 一 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 1 to 7 is not satisfied, and the acrylic vinegar resin which is a specific matter of the first invention of the present invention contains 0. 01 to 5 by weight based on the total of the acrylic vinegar resin. /. In Comparative Example 6 and Comparative Example 7', which are required for the (indenyl) acrylate component of this group, both of the bubbles remained and the evaluation of the adhesive residue did not satisfy both of them. In the same manner, the weight average molecular weight of the acrylic acid-based resin which is measured by the GPC method and measured as a polystyrene-reduced molecular weight is 500,000 to 100,000, and the adhesive is characterized in that the adhesive is not satisfied. The comparative examples ^3 of the former in the "3G to 9 (4%) weight requirement" satisfy both the bubble residue and the adhesive residue evaluation. N listens and 'also not satisfied; i the latter's comparative example! And Comparative Example 6, which also did not satisfy both of the bubble residue and the adhesive residue evaluation. In comparison with the above, the "propionate I-based resin which is a specific matter of the first invention of the present invention contains a cross-linking amount of 〇·〇ι~5f based on the total acrylic vinegar-based resin. The functional group-based (meth)acrylic acid: minute and the "acrylic acid-based resin" have a weight average molecular weight of 500,000 to 100 U as measured by the GPC method, and the gel fraction is 3 G to 9 G. The examples of the "% by weight" requirements are both in the evaluation of the bubble residue and the adhesion of the adhesive while satisfying both. Therefore, it can be seen that the surface protective adhesive tapes obtained in Examples 1 to 10 are more suitable for the surface protective adhesive tapes of 31 200914563 than the surface protective adhesive tapes obtained in Comparative Examples 1 to 7. * The problem of residual milk foam residue and adhesive residue is therefore 'excellent in the use of the surface for the mask - the garment to the thin adhesive tape. [Examples 11 to 18 and Comparative Examples 8 to 12] 1. Raw materials The raw materials of the acrylate resin were prepared by using "," as shown in Table 7. [Table 7] ----- Name - Contents of Mazhan Acrylic Acid-2-Ethyl@@单单曰Tail to the ladder Acrylic acid oxime HEA (hydroxyethyl propyl acrylate) Monomer __ Japanese fat ethyl acetate solvent Μ Coronate L-45 cross-linking #1 —--- ——- 曰 聚 polyamine 曰 2. Preparation of adhesive (1) preparation of acrylate resin prepared with thermometer, scrambler In the reactor for cooling the tubes, a predetermined amount of monomer and ethyl acetate shown in Table 8 were added to the reactor, and Ν2 was introduced from the bottom of the reactor with a small amount. Thereafter, the liquid temperature was adjusted to 7 (Γ.: According to the conditions of Table 9, a third hexyl peroxypivalate as a polymerization initiator was quantitatively added to the reactor over 4 hours ("PERHEXYL (Registrar) Beam PV" manufactured by Nippon Oil & Fat Co., Ltd.), and polymerization was carried out in an atmosphere of ruthenium. Then, 8 hours after the start of the polymerization, the reactor was diluted with ethyl acetate and the reactor was cooled to terminate the polymerization. Weight Μ acrylate resin solution 32 200914563 [Table 8] Polymer No. ABCDE 2-ethylhexyl acrylate 97.7 97.7 97.7 97.7 97.7 Acrylic acid 2 2 2 2 2 HEA 0.3 0.3 0.3 0.3 0.3 Ethyl acetate 70 100 80 60 50 Molecular weight: 7.2 million 4,060,900,200,000 *Into the reactor, 10 times the amount of monomer and ethyl acetate (unit: g) were put into the reactor. Example: Polymer A: 2EHA 977 g, AAC 20 g, HEA 3 g, ethyl acetate 70 g [Table 9] Starting agent input amount Stage 1 PERHEXYLPV 0.010 Stage 2 PERHEXYLPV 0.020 Stage 3 PERHEXYL PV 0.050 Stage 4 PERHEXYL PV 0.100 One-hour quantitative input Hourly The input was quantified with one hour and the input was quantified with one hour. * 10 times the amount of the starter (g) was diluted to 60 ml with ethyl acetate, and added dropwise at 1 ml/min. (2) Manufacturing of the adhesive To the acrylate-based resin solution obtained in the above manner, a predetermined amount of a tackifying resin or an isocyanate-based crosslinking agent ("Coronate (registered trademark) L-45" Japanese Polyurethane Industrial Co., Ltd. as shown in Table 10 or Table 11 is added. Co., Ltd.), and stirring, thereby obtaining an adhesive solution having a solid content of 8% by weight. 33 200914563 3 ·Manufacture of surface protective adhesive sheet The above adhesive solution is applied to a release film having a thickness of 25 m. The surface of the release surface of the r-b-ester film is removed at 100:3 for 3 minutes to remove the ethyl acetate from the adhesive solution to form a thick layer of adhesive, which will then become The thick acoustic polyethylene terephthalate of the substrate.../T-B-ester film with a dryness of 6 hearts is superimposed on the adhesive layer. 50% RH of the Shifter 23 C ><%< Harden for a week. Then, L, +,, f obtained acrylic in the above manner Ester resin t # I 1 average molecular weight Ί彳阳I垔里平, gel fraction of the adhesive, bubble residue evaluation and residue evaluation only 漆 漆 耆 耆 只 & & & & 结果 结果 结果 结果 结果 结果 结果 结果Table 11〇34 200914563 01<] Example 18 < 97.7 (Ν rn 720,000 〇 o 78% Ο c^i Example 17 C 97.7 CN m 720,000 〇 m ο 78% 卜 1 Example 16 < 1 97.7 (Ν cn 720,000 〇ο (Ν 96% 卜m Example 15 < 97.7 (Ν m ο 〇 〇 〇 — — — 实施 实施 实施 实施 实施 实施 实施 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 —f (Ν Ο 63% Ον cn Example 13 Q 97.7 (Ν m O 900,000 om ο 85% 00 cn Example 12 < 97.7 CM m O 720,000 o ο 78% Os cn Example 11 〇 97.7 (N 〇600,000 o ιη 74% On ro Polymer number 2-ethylhexyl acrylate acrylic acid HEA (hydroxyethyl acrylate) Weight average molecular weight polymer dioctyl adipate (plasticizer) Coronate L-45 Gel fraction bubble residue (10-point method) Adhesive residue (3-point method) Polymer composition I Adhesive composition i Evaluation results. % ¥ Side W Long ^ Umbrella-铢^硪鹳璨#如铋^'#lninch·Ί 2BUOJOU* 200914563 【11<】 ra < 1 97.7 (Ν m 〇720000〇rH yr) 〇78% Ο CN Comparative Example 11 C 97.7 (Ν rn 720,000〇〇ο 78% 〇< 97.7 (Νm 720,000〇»—(48% ο rH i Comparative Example 9 ω 97.7 1___________ (Ν m ο 1.2 million 〇T11 Η ο 88% CO ! Comparative Example 8 97.7 1_ (Ν <Τ) ο 400,000 〇r-Η ο 71% ο r·^ Polymer number 2-ethylhexyl acrylate acrylate (hydroxyethyl acrylate) Weight average molecular weight polymer dipic acid dioctyl g (plasticizer) Coronate L-45 gel fraction bubble residue (10 points method) Adhesive residue (3 points method) Polymer composition adhesive composition evaluation result 200914563 According to Table 1 〇 and 矣 j + #表表 results, if the examples 11 to 18 and the comparative examples 8 to 12 are compared, the comparison is not satisfied, and the "adhesive agent" is not satisfied as the second invention of the present invention. 4丨, calculated molecular weight =: S has been measured by GPC method as a polystyrene, the average molecular weight of 500,000 ~ 10 million The acid resin, the cross-linking agent, and the plasticizer are the same as those of the first, the ninth, the first, the first, the first, the :2Comparative Example 10 satisfying the requirement of "point/yield/partition rate of 7 〇 to 100% by weight" as a specific matter of the second invention of the present invention: not simultaneously in the evaluation of bubble residue and adhesive residue Satisfy both, not satisfying the specificity of the second invention of the present invention: the total amount of the agent is based on the total amount of the plasticizer: "Comparative Example 12' is based on the bubble residue and the adhesive residue. Satisfy both.
與該等相比，同時滿足作為本發明第：發明W 項的「黏著劑係含有利用GPC法測得之作為聚苯 分子量的重量平均分子量為5〇萬〜1〇。萬 ： 脂、交聯劑以及塑化劑而虚去 r# 樹 2化川而成者」、「以黏著劑總體為基準， 〜4G重量％之塑化劑而成」以及「㈣劑之凝膠分率 為70〜100重量％,(•生 夏/〇J之要件的實_ u〜18，均係於氣泡 殘留以及黏著劑殘留之評價中同時滿足兩者。 •因此可知，實施例U〜18中所獲得之表面保護黏著 f，與比較例8〜12中所僅p +主尤# 节所獲仔之表面保護黏著帶相比，更 37 200914563 適合用作表面保護黏著帶，並可解決氣泡殘留以及黏著劑 殘留之問題點’因此在用作光罩用表面保護黏著帶時具有 優異性能。 [產業上之可利用性] 本發明之黏著劑及使用其之表面保護黏著片，係形成 如上述之構成’其係可形成貼附㈣象物上時無氣泡進 入j且剥離時無1占著劑歹篆留之黏著劑層之黏著齋j，以及含 有：玄黏著劑所構成之表面保護黏著片，因此特別適於對光 罩等之表面加以保護的表面保護黏著片。 【圖式簡單說明】 (無） 【主要元件符號說明】 (無） 38In comparison with the above, the "adhesive agent containing the weight average molecular weight of the polyphenylene having a molecular weight measured by the GPC method is 50,000 to 1 〇. 10,000: fat, cross-linking The agent and the plasticizer are virgins to get the r# tree 2 and the chemistry of the chuanchuan", "based on the overall viscosity of the adhesive, ~4G% by weight of the plasticizer" and "(4) agent gel fraction is 70~ 100% by weight, (the actual _u~18 of the raw material of the summer/〇J, both of which are satisfied in the evaluation of the bubble residue and the adhesive residue.) Therefore, it can be seen that the obtained in Examples U to 18 The surface protection adhesion f is compared with the surface protection adhesive tape obtained only in the p + main special section of Comparative Examples 8 to 12, and 37 200914563 is suitable as a surface protection adhesive tape, and can solve the bubble residue and the adhesive. The problem of residuals is therefore excellent in performance as a surface protective adhesive tape for a photomask. [Industrial Applicability] The adhesive of the present invention and the surface protective adhesive sheet using the same are formed as described above. The system can form a sticker (4) when there is no bubble entering the object. And when peeling off, there is no adhesion layer of the adhesive layer which is retained by the agent, and a surface protective adhesive sheet comprising: a mysterious adhesive, so that it is particularly suitable for surface protection adhesion for protecting the surface of the mask or the like. [Simplified illustration] (none) [Explanation of main component symbols] (none) 38