201136951 六、發明說明： 【發明所屬之技術領域】 本發明係關於使用在光學製品 保護薄膜。詳言之，本發明係關於點著特性、透：表面 性優異，對被黏著體等之污染少，膜 月生、耐熱 護薄膜。為「轉出性」）優異之表面保 【先前技術】 口表ΓΓΓ膜主要係貼附於建材用或光學用途之樹脂製 口口金屬製品、玻填製品等的 蓉之於样#… 攸邾者體而使用，具有防止該 專之輸…呆官或加工時的刮傷或異物混 =膜一般係由不具黏著性之表面層與用以與= 之黏著層所構成。表面層通常係由聚乙稀或聚丙 婦專之^^稀煙、或聚掛贫一 等之乙旨等之㈣、聚氣乙稀 寺之乙烯糸聚合體所形成。 '年來I用於液晶顯示器、電漿顯示器或背投影 p。細叫顯不器等構件(所謂的光學製品)之開發持 '、亍對於用以保護該等光學製品之表面保護薄膜，不僅 '*丨傷與異物混人，亦希望可在貼附表面保護薄膜之 〜下進仃SU。檢查之程度的透雜，或是即便在高溫狀態 下貼附亦可表現適絲著力等之黏著特性。 又，將表面保護薄膜使用於建材或汽車零件用途之情況， 100103883 3 201136951 係有在貼附表面保護薄 在古、、田狀離下熱成形之情況，要求 在_狀態下亦可作為表面保護賴使用 要欠 又，黏著力較高的矣而位崎— 又t熱性。 故係作成對黏著層貼合離型薄膜並予 的轉出性’ «^體進行_時再將該_薄_下而使^=采2 種手段’由於會產生大4_㈣膜作為廢棄物， 使不使用__係具有充分的轉之表面保護薄膜 專利文獻1中係揭示以聚乙烯成分為主體之表面保 膜。然而，該公報之保護薄膜雖可應用於—部分的用途 材，但黏著力低且透明性亦不充分，於被黏著體之用逯方構 有限制》 、面 [專利文獻] 專利文獻1 :日本專利特開2006_116769號公報 【發明内容】 (發明所欲解決之問題） 本發明之課題在於提供一種表面保護薄臈，其在光學製 οσ、建材製品或Η車零件之保管、輸送、加工、檢杳時在 作為用以保δ蒦該專之表面保護薄膜所要求之特性方面尤其 是黏著特性、透明性、在高溫狀態下仍可作為表面保護薄膜 使用的程度之耐熱性及轉出性方面優異。 (解決問題之手段） 本發明人等有鑒於上述問題，經過深入檢討，結果發現 100103883 4 201136951 經由具有由某特定之樹餘成物所構成的表面層之表 護薄膜，可解決上述問題，.遂完成本發明。 亦即，本發明係由表面層㈧及黏著層（χ)之至少2層所構 成之表面㈣賴，其絲面層⑷係由叫系（共）聚合體 ⑷〇〜98重量％及以碳數4以上之_烴作為主成分之稀煙 (共）聚合體(b)2〜100重量％(不論何種情況，為了說明⑷與⑼ 之間的比率，均僅將該等（a)及(b)之合計定為1〇〇重量％)所 構成，黏著層（X)係由烯烴系彈性體〇〜8〇重量％及笨乙烯· 異丁烯共聚合體20〜100重量％(不論何種情況，為了說明烯 烴系彈性體及苯乙烯•異丁烯共聚合體之間的比率，均僅將 该等之合計定為100重量％)所形成的表面保護薄膜。 此外，本發明之上述表面保護薄膜中的較佳態樣，係以碳 數4以上之〜烯烴作為主成分之烯烴（共）聚合體(1))為4_曱 基戊烯-1系聚合體的表面保護薄膜，且係相對於壓克力板 的黏著力為5〜40N/50mm之範圍的表面保護薄膜。 (發明效果） 本發明之表面保護賴之黏著特性、透明性、從捲取為親 狀之狀態的轉出性及即便在高溫狀態下仍可作為表面保護 薄膜使用之程度的耐熱性優異，不僅光學用途，亦適合作為 建材用途、汽車零件用途之表面保護薄膜。 【實施方式】 接著’詳細說明本發明。 100103883 5 201136951 本發明之表面保護薄膜係由表面層（A)及黏著層（X)之至 少2層所構成。 表面層（A)係由丙烯系（共）聚合體(a)及以碳數4以上之α-烯烴作為主成分之烯烴（共）聚合體(b)所構成之組成物所形 成。 作為丙烯系（共）聚合體(a)，例如可舉出丙烯均聚物、丙烯 與乙烯及/或碳數4〜20之α-烯烴的無規或嵌段共聚合體。另 外，丙烯系（共）聚合體之表示方式係表示包含丙烯之聚合 體、及丙烯與其他單體所構成之共聚合體兩者的表示方式。 作為使用於上述無規或嵌段共聚合體之碳數4〜20之α-烯 烴，可舉出1-丁烯、4-甲基戊烯-1、1-己烯、1-辛烯等。作 為此種共聚合體，可舉出丙烯•乙烯共聚合體、丙烯·1-丁烯共聚合體、丙烯•乙烯· 1-丁烯共聚合體等。 丙烯系（共）聚合體(a)從提升耐熱性之觀點而言，熔點較佳 為50〜170°C，更佳為70〜170°C，更佳為100〜165°C，其中 又以130〜165°C為最佳。在此，熔點係利用示差掃瞄熱量計 (DSC) ’以升溫及降溫速度10°C/min所測定之值。 又，丙烯系（共）聚合體(a)以230°C測定之熔融流動速率（以 下簡記為MFR)較佳為0.01〜500g/10分鐘，更佳為 0.1〜100g/10分鐘，再更佳為0.3〜50g/10分鐘之範圍。 上述丙烯系（共）聚合體(a)，不僅是以固體狀鈦化合物及烷 基鋁化合物作為主成分之固體狀鈦觸媒，亦可在以茂金屬化 100103883 6 201136951 合物作為主成分之茂金屬觸媒、甚至是幾何拘束觸媒等之存 在下，藉由丙烯之均聚合或將丙烯與乙烯或碳數4〜20之α-烯烴進行共聚合而獲得。 又，烯烴（共）聚合體(b)中，碳數4以上之α-烯烴較佳係含 有5〜100莫耳％，更佳為60〜100莫耳，再更佳為70〜100莫 耳％。作為碳數4以上之烯烴，可舉出1-丁烯、4-曱基戊 烯-1、1-己烯、1-辛烯、1-癸烯、1-十二烯等，較佳為4-曱 基戊烯-1。另外，烯烴（共）聚合體之表示方式係表示包含1 種烯烴之聚合體、及2種以上烯烴之共聚合體兩者的表示方 式。 作為從表面保護薄膜之耐熱性的觀點而言特佳的烯烴（共) 聚合體(b)，係有4-曱基戊烯-1系聚合體，亦即含有50〜100 莫耳％、較佳為60〜100莫耳％、更佳為70〜100莫耳％之4-曱基戊烯-1的聚合體。作為該等之例，可舉出4-曱基戊烯-1 均聚物、4-曱基戊烯-1與碳數6〜20之ce-烯烴之共聚合體。 藉由使用4-曱基戊烯-1均聚物、4-甲基戊烯-1與碳數6〜20 之α-烯烴之共聚合體作為烯烴（共）聚合體(b)，即便在高溫條 件下，仍不發生黏著性或薄膜之變形，可獲得作為表面保護 薄膜而發揮功用之程度的耐熱性特別優異之表面保護薄 膜。又，作為烯烴(共）聚合體(b)，4-曱基戊烯-1均聚物、4-曱基戊烯-1與碳數6〜20之α-烯烴之共聚合體相較於泛用的 烯烴樹脂（例如聚丙烯均聚物）係具有高熔點，故不僅表面 100103883 7 201136951 層對於包含點著層之表面保護薄膜整體於高溫條件下之使 用丨生月b有所幫助。另外，作為碳數6〜2〇之％烯煙，例如有 己稀、1_辛烯、丨_癸烯及丨十二烯等。 從獲得良好成形性及耐熱性優異之表面保護薄膜的觀點 而舌’烯烴（共）聚合體(b)之熔點較佳為150〜300¾，更佳為 180〜2801，再更佳為2〇〇〜25〇。(：之範圍。 又，從加工性之觀點而言，烯烴（共）聚合體(b)於23(TC下 疋之MFR較佳為〇丨〜5⑽分鐘，更佳為〇 5〜加他/1〇 刀在里，再更佳為分鐘之範圍。 本發明之表面保護薄膜之表面層(A)係由上述丙稀系（共） 聚D體⑷及烯經(共)聚合體(b)、以及進—步視需要之其他成 分所構成的組成物所形成。 十對該、，且成物中之丙稀系（共)聚合體⑷與稀煙(共)聚合名 ⑻之比率進行說明，丙烯系（共）聚合_之比例較^ 98重里％ ’更佳為〇〜95重量％，再吏佳為重量％ 八中又以1〇〜9〇重量％為特佳，婦烴(共)聚合體⑼之比例專 佳為2〜議重量％ ’更佳為5〜刚重量。/〇，再更佳為10〜9 重謂不論何種情況，為了說明⑷與(b)之間的比率 將該等（a)及(b)之合計定為1〇〇重量％)。 該組成物+，在對本發明之表面簡薄颜予抗靜電性; 耐候性、提升透雜或提❹卜觀之目的下，料添加抗靜: 劑、離型劑、抗氧化劑、耐候劑、結晶核劑等之各種添加劑 100103883 201136951 力聚乙烯或聚丁烯等之其他結 烯烴、 胺:彈，之樹脂改質劑。 1 一田j而要與上述丙烯系（共）聚合體(a)和烯烴（共）聚合體(b) '、、力ϋ劑或改質劑之情況，例如可在添加添加劑等之 早輪或雙軸擠出機或進料控制機(feeder_ruder)等 混練後，谁一 ^ 17 ^ + 一^加工為薄膜狀，亦可直接放入兼具擠出機之 \成开^機，製成本發明之表面保護薄膜的表面層（A)。 本毛明表面保護薄臈之黏著層（X)係由烯烴系彈性體、笨 =·異丁缔共聚合體及視需要之其他成分所構成，若針對 二^ θ令之烯烴系彈性體與苯乙烯·異丁烯共聚合體之比 :,、行°兒明，係由烯烴系彈性體〇〜80重量％及苯乙烯•異 ' 丁稀共聚合體20〜1GG重量％所構成。較佳係烯烴系彈性體 • 〇〜％ 4#%及苯乙稀•異丁烯共聚合體25〜1〇〇重量％，更 ，為稀^彈性體5〜75重量％及苯乙稀•異丁稀共聚合體 、 重量/(>(不論何種情況，為了說明婦烴系彈性體與苯乙 烯異丁稀共聚合體之間的比率，均僅將該等之合叶定 100 重量 ％) ° ’·’、 作為_系彈性體，巍係DSC測定（以升溫及降溫速度 測定)之雜在0〜·。c的範圍内無法觀測到的非 :蜂性體，或可觀測到在G〜2(m：之範_所觀測之溶點 =的溶解熱量為10J/g以下的波峰之微結晶性彈性體，更 糸上述非晶性彈性體姐‘时峰找軸量為聊以下 100103883 201136951 的微結晶性彈性體。 作為上述烯烴系彈性體，係有碳數2〜20之α-烯烴聚合體 或共聚合體，或者乙烯與不飽和羧酸或不飽和羧酸酯之共聚 合體。具體而言，可舉出乙烯•丙烯共聚合體、乙烯· 1-丁烯共聚合體、乙烯.1-己烯共聚合體、乙烯· 4-曱基戊烯 -1共聚合體、乙烯· 1-辛烯共聚合體、丙烯均聚物、丙烯· 乙烯共聚合體、丙烯•乙烯· 1-丁烯共聚合體、1-丁烯均聚 物、1-丁烯•乙烯共聚合體、1-丁烯•丙烯共聚合體、4-曱 基戊烯-1均聚物、4-甲基戊烯-1 ·丙烯共聚合體、4-曱基戊 烯-1 · 1-丁烯共聚合體、4-甲基戊烯-1 ·丙烯· 1-丁烯共聚 合體、丙烯•卜丁烯共聚合體、乙烯•醋酸乙烯酯共聚合 體、乙烯•曱基丙烯酸共聚合體、乙烯•甲基丙烯酸曱酯共 聚合體等。從黏著力之經時安定性的觀點而言，較佳為丙烯 均聚物、丙烯•乙烯共聚合體、丙烯· 1-丁烯共聚合體、丙 稀•乙烯· 1-丁烯共聚合體。 作為苯乙烯•異丁烯共聚合體，係有苯乙烯•異丁烯•苯 乙烯三嵌段共聚合體或苯乙烯•異丁烯二嵌段共聚合體。苯 乙烯•異丁烯共聚合體以膠體滲透色層分析（GPC)所測定 之重量平均分子量(Mw)較佳為10,000〜300,000之範圍，更 佳為15,000〜250,000之範圍，再更佳為20,000〜200,000之 範圍。若Mw小於10,000或大於300,000，則有表面保護薄 膜之生產性差的問題。 100103883 10 201136951 藉由將上述烯烴系彈性體及/或苯乙烯•異丁烯共聚八體 單獨或摻合各自相異之組成成分’可形成本發明表面保*蔓薄 膜之黏著層（X)。又，本發明中，在控制黏著力之目的下\ 可進一步在不損及本發明效果之範圍内含有聚乙稀或聚内 烯等之聚烯烴、酸改質聚烯烴、聚酯、聚醯胺等之樹腊改質 劑，或抗靜電劑、結晶核劑、抗氧化劑等之各種添加劑，作 為構成黏著層（X)之素材。 上述由烯烴系彈性體及/或苯乙烯•異丁稀共聚合體、以 及視需要所添加之樹脂改質劑或添加劑所構成之勘著芦 (X) ’係藉由與上述表面層（A)積層，而可獲得本發明之表面 保護薄膜。 . 對於積層表面層（A)與黏著層（X)之方法並無特別限制，可 舉出於預先形成以T字模成形或充氣成形所得之表面層的 薄膜上，利用擠出層疊、擠出塗佈等之公知積層法積層黏著 層之方法，或將形成表面層及黏著層之薄膜各自獨立形成為 薄膜後’將各薄蘭用乾式層疊予以積層之方法等，從生產 效率之觀點而言，較佳係將表面層、黏著層之各成分供至多 層擠出機而進行共擠出成形之方法。 本發明中’亦可在表面層⑷與黏著層（X)之間設置至少！ 層的中間層。又’當與表面層(A)及黏著層(X)之接著力不足 的情況’作為巾間層亦可使賴㈣或接著層。 作為中間層並無特別限制，一般可使用溶點綱^以上之 100103883 11 201136951 聚丙烯或聚乙烯等之結晶性聚烯烴，或聚酯、聚醯胺、聚烯 烴系彈性體等。將中間層使用作為接著層之情況，可使用改 質聚烯烴或聚烯烴系彈性體、苯乙烯系彈性體、聚酯彈性體 等。該等之中，從生產性及透明性之觀點而言，較佳係使用 聚丙烯或聚烯烴彈性體作為中間層。 又，當表面層（A)及黏著層（X)之接著力不足的情況，中間 層亦可將用以使接著劑或表面層（A)與黏著層（X)接合的薄 膜等之素材作為接著層而構成。 本發明表面保護薄膜之表面層（A)的厚度通常為 0.05〜200/xm，較佳為〇.5〜ΙΟΟμπι，更佳為，再更佳 為1〜lS/rni。黏著層（X)之厚度通常為〇〇5〜5〇/mi，較佳為 0.3〜40/xm，更佳為 〇.5〜30μιη。 因此，本發明之表面保護薄膜的厚度，包含視需要所設置 之中間層，通常為0.1〜5〇〇Mm，較佳為〇 5〜4〇〇^m，更佳為 3〜300μηι。 藉由使用上述較佳形態之表面層⑷、黏著層⑻及中間 層，可獲得回捲性優異之表面保護薄膜，尤其可適合利用於 光學用途。 本發明之表面保護薄膜相對於壓克力之黏著力較佳為 5〜40N/50mm之範圍，更佳為5〜雇5〇麵之範圍，再更佳 為6 30N/50mm之範圍。若黏著力低於谓5〇麵，則常有 對被黏著體之黏著性不充分之情況，若超過撕㈣賴則常 100103883 12 201136951 有轉出性降低之情況。 本發明表面保護薄膜之回捲力（亦即從將表面保護薄祺锩 成輥狀之狀態將上述薄膜以一定速度轉出時之剝離強度)係 為轉出性的指標。當本發明之表面保護薄膜的回捲力為 2.5N/50mm以下、較佳為0.01〜2.0N/50mm之範圍時，可獲 得優異的轉出性。 作為本發明表面保護薄膜之透明性，以JISK7105為基 準，以50μπι的總厚度測定之霧值較佳為80%以下，更佳為 75%以下，再更佳為70%以下。 [實施例] 以下，利用實施例詳細說明本發明，但本發明並不限定於 該等實施例。 [評估法] 黏著力··於氣溫23°C±2°C、濕度50%±10%之條件下，將 壓克力板裁斷為寬50mm、長125mm，將薄膜樣品載置於上 述壓克力板表面，以2kg之橡膠|昆的自身重量按壓該樣品薄 膜之整體，藉此貼附於壓克力板。接著，測定以300mm/分 鐘之速度剝離（180度剝離）時的剝離力，以每50mm寬之剝 離力作為黏著力（N/50mm)。 回捲力：使用輥狀樣品，測定以300mm/分鐘之速度從輕 剝除時之剝離力（N/50mm)，作為回捲力。 霧值：以JIS K7105為基準，以總厚度50/zm之薄膜進行 100103883 13 201136951 測定。 [實施例1] 對兼具表面層及黏著層用為30mm0之單轴擠出機、中間 層為4Omm0單軸擠出機的模頭寬5〇〇mm之3種3層τ字 模成形機’供給以下原料’獲得表面層（A)厚度1 〇焊、黏著 層（X)厚度ΙΟμιη、中間層厚度30μιη、總厚度50/xm的本發 明表面保護薄膜。將所得之薄膜的各評估結果示於表1。 表面層： 均聚丙嫦（型號名：F107BV，熔點=16〇°C，MFR=7g/10 分鐘，Prime Polymer公司製）70重量％、 4-曱基戊烯-1系聚合體（商品名：TPX，型號名：RT18， 溶點=237 C，MFR=26g/10分鐘，三井化學公司製)3〇重量 % 中間層： 均聚丙烯(熔點= 160°C，MFR=7g/10分鐘）1〇〇重量％ 黏著層： 丙烯•乙烯· 1-丁烯共聚合體(0〜200°c之範圍内觀測到 熔解熱量4J/g之炫點波峰，MFR=7gA0分鐘)6〇重量％ 笨乙烯•異丁烯共聚合體（苯乙烯·異丁烯•苯乙烯三嵌 段共聚合體，SIBSTAR072T(Kaneka公司製))4〇重量％ [貫施例2〜8、比較例1〜2] 除了將各種層之樹脂組成改變為表1記載之樹脂組成以 100103883 14 201136951 外，與實施例1同樣地獲得表面保護薄膜。將所得之薄膜的 評估結果示於表1。 100103883 15 201136951 【11 比較例2 R ^ 8 O 1 o VO 1 寸 ^ ^ ro — 比較例1 § 〇 〇 8 Ο Ο 1 v〇寸 1 姐 W ^ -ΖΓ» 〇 rS 1 — 實施例8 ^ R 8 1 i … α I (N 1 〇〇 寸· m —(N — 實施例7 ^ R S 1 § 1 —，ro (N 〇4 ' 實施例6 ^ R 8 Ο Ο 1 OO CN 1 vn — 2 |實施例5 | Ο Ο 〇 S *—H O O I vo寸 1 卜 —in 實施例4 ^ ^ 8 ♦—1 O O I v〇寸 1 卜〜· cn 1 —一 實施例3 R ^ 8 *—* O O I 寸v〇 1 m O ——CN 實施例2 8 O O I VO寸丨 卜2 2 實施例1 .R ^ 8 Ο Ο I ν〇寸丨 〜2另 樹脂組成 表面層 h-PP (重量 ％) PB (重量％) TPX (重量％) 中間層 h-PP (重量 ％) 玄玄玄 id ㈣ Φ4 φ4 _ ‘如 s^/ .¾ 1 g I 砌S S κ 'ΓχΓ 黏著力 （N/50mm) 回捲力 （N/50nmm) 霧值 （％)201136951 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a protective film for use in an optical article. More specifically, the present invention relates to a spot-like property, a transparency, an excellent surface property, a small amount of contamination to an adherend, and the like, and a film-like, heat-resistant protective film. Excellent surface protection for the "transfer" (previous technique) The enamel film is mainly attached to the resin-made mouth metal products, glass-filled products, etc. for building materials or optical applications. It is used to prevent the scratch or the foreign matter from being mixed. The film is generally composed of a non-adhesive surface layer and an adhesive layer for use with =. The surface layer is usually formed by a polyethylene ruthenium polymer of polyethylene or polypropylene, or a mixture of ethylene and cesium. 'Year I used for liquid crystal display, plasma display or rear projection p. The development of the components such as the display device (so-called optical products), and the surface protection film used to protect these optical products, not only '* bruises and foreign objects, but also hope to be attached to the surface protection The film is lowered into the 仃SU. The degree of inspection is thorough, or it can be attached to a high temperature state to exhibit adhesion characteristics such as sturdiness. Moreover, when the surface protective film is used for the use of building materials or automobile parts, 100103883 3 201136951 is a case where the surface protection is thin and hot-formed in the ancient and field-like manner, and it is required to be used as a surface protection in the _ state. Lai is used to owe it, and the adhesion is high, and the position is good - and t-heat. Therefore, the adhesive layer is bonded to the release film and the transferability is ''When the body is _, then _thin_lower and ^=take two means' because a large 4_(four) film is produced as waste, A surface protective film having a sufficient conversion is not disclosed in Patent Document 1. A surface film mainly composed of a polyethylene component is disclosed. However, although the protective film of the publication can be applied to a part of the use material, the adhesion is low and the transparency is insufficient, and the structure for the adherend is limited. [Patent Document] Patent Document 1: Japanese Patent JP-A-2006_116769 SUMMARY OF INVENTION [Problem to be Solved by the Invention] An object of the present invention is to provide a surface protection sheet which is stored, conveyed, processed, and inspected in an optical system, a building material, or a brake component. In the case of the properties required for the surface protective film to maintain δ, the adhesive properties, transparency, and heat resistance and transferability which are used as the surface protective film in a high temperature state are excellent. (Means for Solving the Problem) The present inventors have intensively reviewed in view of the above problems, and as a result, found that 100103883 4 201136951 can solve the above problem via a surface protective film having a surface layer composed of a specific tree residue.遂Complete the invention. That is, the present invention is a surface (4) composed of at least two layers of a surface layer (8) and an adhesive layer (χ), and the silk layer (4) is composed of a polymer (4) 〇 98% by weight and carbon. (b) 2 to 100% by weight of the dilute (co)polymer (b) having a hydrocarbon content of 4 or more (in any case, in order to explain the ratio between (4) and (9), only (a) and (b) is a total of 1% by weight), and the adhesive layer (X) is composed of an olefin-based elastomer 〇 8 8% by weight and a stupid ethylene/isobutylene copolymer 20 to 100% by weight (in any case). In order to explain the ratio between the olefin-based elastomer and the styrene-isobutylene copolymer, only the total amount of the surface protective film is 100% by weight. Further, in a preferred aspect of the above surface protective film of the present invention, an olefin (co)polymer (1) having a carbon number of 4 or more and an olefin as a main component is a 4-decylpentene-1 polymerization. The surface protective film of the body is a surface protective film having an adhesion to the acrylic plate in the range of 5 to 40 N/50 mm. (Effect of the Invention) The surface protection of the present invention is excellent in heat resistance and the like, and the heat transfer property to the extent that it can be used as a surface protective film even in a high temperature state. For optical applications, it is also suitable as a surface protection film for building materials and automotive parts. [Embodiment] Next, the present invention will be described in detail. 100103883 5 201136951 The surface protective film of the present invention comprises at least two layers of a surface layer (A) and an adhesive layer (X). The surface layer (A) is formed of a composition composed of a propylene (co)polymer (a) and an olefin (co)polymer (b) having a carbon number of 4 or more α-olefin as a main component. The propylene-based (co)polymer (a) may, for example, be a propylene homopolymer, a random or block copolymer of propylene and ethylene and/or an α-olefin having 4 to 20 carbon atoms. Further, the expression of the propylene-based (co)polymer means a representation of both a polymer comprising propylene and a copolymer composed of propylene and another monomer. Examples of the α-olefin having 4 to 20 carbon atoms used in the above-mentioned random or block copolymer include 1-butene, 4-methylpentene-1, 1-hexene, 1-octene and the like. Examples of such a copolymer include a propylene/ethylene copolymer, a propylene/1-butene copolymer, and a propylene/ethylene/1-butene copolymer. The propylene-based (co)polymer (a) has a melting point of preferably from 50 to 170 ° C, more preferably from 70 to 170 ° C, still more preferably from 100 to 165 ° C, from the viewpoint of improving heat resistance. 130~165°C is the best. Here, the melting point is a value measured by a differential scanning calorimeter (DSC) ' at a temperature rise and a temperature drop rate of 10 ° C / min. Further, the melt flow rate (hereinafter abbreviated as MFR) measured at 230 ° C of the propylene-based (co)polymer (a) is preferably from 0.01 to 500 g/10 min, more preferably from 0.1 to 100 g/10 min, still more preferably It is in the range of 0.3 to 50 g/10 minutes. The propylene-based (co)polymer (a) is not only a solid titanium catalyst containing a solid titanium compound or an alkyl aluminum compound as a main component, but also a metallocene 100103883 6 201136951 compound as a main component. In the presence of a metallocene catalyst, or even a geometrically bound catalyst, it is obtained by homopolymerization of propylene or copolymerization of propylene with ethylene or an α-olefin having 4 to 20 carbon atoms. Further, in the olefin (co)polymer (b), the α-olefin having 4 or more carbon atoms is preferably contained in an amount of 5 to 100 mol%, more preferably 60 to 100 mol, and still more preferably 70 to 100 mol. %. Examples of the olefin having 4 or more carbon atoms include 1-butene, 4-decylpentene-1, 1-hexene, 1-octene, 1-decene, 1-dodecene, etc., preferably 4-decylpentene-1. Further, the expression of the olefin (co)polymer means a method of expressing both a polymer comprising one olefin and a copolymer of two or more olefins. The olefin (co)polymer (b) which is particularly preferable from the viewpoint of heat resistance of the surface protective film is a 4-nonylpentene-1 polymer, that is, 50 to 100 mol%, more preferably Preferably, it is a polymer of 60 to 100 mol%, more preferably 70 to 100 mol% of 4-decylpentene-1. Examples of such a compound include a 4-mercaptopentene-1 homopolymer, a copolymer of 4-decylpentene-1 and a ce-olefin having 6 to 20 carbon atoms. By using a 4-decylpentene-1 homopolymer, a copolymer of 4-methylpentene-1 and an α-olefin having 6 to 20 carbon atoms as the olefin (co)polymer (b), even at a high temperature Under the circumstance, the surface protective film which is particularly excellent in heat resistance as a surface protective film and which exhibits a function as a surface protective film does not occur. Further, as the olefin (co)polymer (b), a copolymer of 4-decylpentene-1 homopolymer, 4-decylpentene-1 and an α-olefin having 6 to 20 carbon atoms is compared with a pan. The olefin resin (for example, a polypropylene homopolymer) used has a high melting point, so that not only the surface 100103883 7 201136951 layer contributes to the use of the surface protective film containing the delamination layer under high temperature conditions. Further, examples of the olefinic tobacco having a carbon number of 6 to 2% include hexamethylene, 1-octene, decene-decene and decadecane. The melting point of the tongue 'olefin (co)polymer (b) is preferably from 150 to 3003⁄4, more preferably from 180 to 2801, more preferably from 2 to 2, from the viewpoint of obtaining a surface protective film excellent in moldability and heat resistance. ~25〇. Further, from the viewpoint of workability, the olefin (co)polymer (b) is preferably 〇丨 5 (10) minutes at 23 TC, and more preferably 〇 5 to plus / 1 〇 在 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , And the formation of a composition consisting of other components as needed. The ratio of the propylene (co)polymer (4) to the dilute (co)polymer name (8) is described in the same. , the ratio of propylene (co)polymerization _ is more than 98% by weight. 'More preferably 〇~95% by weight, and then 吏 is preferably % by weight. 八中为1〇~9〇% by weight is particularly good, female hydrocarbons (total) The ratio of the polymer (9) is preferably 2 to about % by weight, more preferably 5 to just weight. / 〇, and even more preferably 10 to 9, whichever is the case, in order to explain the ratio between (4) and (b) The total of the above (a) and (b) is set to 1% by weight. The composition +, on the surface of the present invention, has an antistatic property; weather resistance, enhanced penetration or lifting Purpose Adding anti-static: various additives such as agent, release agent, antioxidant, weathering agent, crystal nucleating agent, etc. 100103883 201136951 Other olefins, amines, and other resin modifiers such as polyethylene or polybutene. 1 In the case of the above-mentioned propylene-based (co)polymer (a) and olefin (co)polymer (b) ', a force agent or a modifier, for example, an early round in which an additive or the like is added After mixing with a twin-screw extruder or a feeder control machine (feeder_ruder), whoever processes a film into a film shape can also be placed directly into the extruder and into a machine. The surface layer (A) of the surface protective film of the present invention. The adhesive layer (X) of the surface protective thin layer of the present invention is composed of an olefin-based elastomer, a stupid copolymer, an isobutyl conjugated copolymer, and other components as necessary. The ratio of the olefin-based elastomer to the styrene-isobutylene copolymer of the θ θ is: 、 儿 明, from the olefin-based elastomer 〇 80% by weight and the styrene-iso-butylene copolymer 20~ 1 GG% by weight. Preferred is an olefin-based elastomer. 〇~% 4#% and styrene-isobutylene The polymer is 25 to 1% by weight, more preferably 5 to 75% by weight of the dilute elastomer, and styrene-isobutylene copolymer, weight/(> (in any case, to illustrate the elasticity of the hydrocarbon system) The ratio between the body and the styrene isobutylene copolymer is only 100% by weight of the combined leaves, ° '·', as the _-based elastomer, and the oxime DSC measurement (measured by the temperature rise and the temperature drop) Non-observable non-bee body in the range of 0~·.c, or it can be observed that the dissolved heat of G~2 (m: the observed melting point = 10 J/g or less) The microcrystalline elastomer of the crest, and the microcrystalline elastomer of the above-mentioned amorphous elastomer Sister's time peak is 100103883 201136951. The olefin-based elastomer is a polymer or a copolymer of an α-olefin having 2 to 20 carbon atoms or a copolymer of ethylene and an unsaturated carboxylic acid or an unsaturated carboxylic acid ester. Specific examples thereof include an ethylene/propylene copolymer, an ethylene-1-butene copolymer, an ethylene.1-hexene copolymer, an ethylene-4-decylpentene-1 copolymer, and ethylene-1-octene. Copolymer, propylene homopolymer, propylene/ethylene copolymer, propylene/ethylene/1-butene copolymer, 1-butene homopolymer, 1-butene/ethylene copolymer, 1-butene/propylene copolymer , 4-decylpentene-1 homopolymer, 4-methylpentene-1·propylene copolymer, 4-decylpentene-1·1-butene copolymer, 4-methylpentene-1 • Propylene·1-butene copolymer, propylene/butene copolymer, ethylene/vinyl acetate copolymer, ethylene/mercaptoacrylic acid copolymer, ethylene/methacrylate methacrylate copolymer, etc. From the viewpoint of stability over time of the adhesion, a propylene homopolymer, a propylene/ethylene copolymer, a propylene·1-butene copolymer, and a propylene/ethylene·1-butene copolymer are preferable. As the styrene-isobutylene copolymer, there are a styrene-isobutylene-styrene triblock copolymer or a styrene-isobutylene diblock copolymer. The weight average molecular weight (Mw) of the styrene-isobutylene copolymer measured by colloidal permeation chromatography (GPC) is preferably in the range of 10,000 to 300,000, more preferably in the range of 15,000 to 250,000, still more preferably 20,000 to 200,000. range. If the Mw is less than 10,000 or more than 300,000, there is a problem that the productivity of the surface protective film is poor. 100103883 10 201136951 The adhesive layer (X) of the surface protective film of the present invention can be formed by separately or blending the above-mentioned olefin-based elastomer and/or styrene-isobutylene copolymer. Further, in the present invention, in the purpose of controlling the adhesion, the polyolefin, the acid-modified polyolefin, the polyester, the polyfluorene, which contains polyethylene or polyene, etc., may be further contained in the range which does not impair the effects of the present invention. A wax modifier, such as an amine, or an antistatic agent, a crystal nucleating agent, an antioxidant, or the like, as a material constituting the adhesive layer (X). The above-mentioned surface layer (A) is composed of an olefin-based elastomer and/or a styrene-isobutylene copolymer, and optionally a resin modifier or an additive. The surface protection film of the present invention can be obtained by laminating. The method for laminating the surface layer (A) and the adhesive layer (X) is not particularly limited, and may be carried out by extrusion lamination or extrusion coating on a film in which a surface layer obtained by T-die molding or aeroforming is formed in advance. A method of laminating an adhesive layer by a known lamination method, or a method of forming a film of a surface layer and an adhesive layer separately as a film, and a method of laminating each thin blue layer by dry lamination, from the viewpoint of production efficiency Preferably, the components of the surface layer and the adhesive layer are supplied to a multilayer extruder to perform coextrusion molding. In the present invention, it is also possible to provide at least between the surface layer (4) and the adhesive layer (X)! The middle layer of the layer. Further, the case where the adhesion to the surface layer (A) and the adhesive layer (X) is insufficient can be used as the inter-sheet layer to make the laminate (four) or the subsequent layer. The intermediate layer is not particularly limited, and generally, a crystalline polyolefin such as polypropylene or polyethylene, or a polyester, a polyamide or a polyolefin elastomer, or the like can be used as the above-mentioned 100103883 11 201136951. When the intermediate layer is used as the adhesive layer, a modified polyolefin or polyolefin elastomer, a styrene elastomer, a polyester elastomer or the like can be used. Among these, from the viewpoint of productivity and transparency, polypropylene or a polyolefin elastomer is preferably used as the intermediate layer. Further, when the adhesion between the surface layer (A) and the adhesive layer (X) is insufficient, the intermediate layer may also have a material such as a film for bonding the adhesive or the surface layer (A) and the adhesive layer (X). It is composed of layers. The surface layer (A) of the surface protective film of the present invention has a thickness of usually 0.05 to 200/xm, preferably 〇.5 to ΙΟΟμπι, more preferably, still more preferably 1 to 1 S/rni. The thickness of the adhesive layer (X) is usually 〇〇5 to 5 〇/mi, preferably 0.3 to 40/xm, more preferably 〇.5 to 30 μιη. Therefore, the thickness of the surface protective film of the present invention, including the intermediate layer provided as needed, is usually 0.1 to 5 Å Mm, preferably 〇 5 to 4 〇〇 ^ m, more preferably 3 to 300 μη. By using the surface layer (4), the adhesive layer (8) and the intermediate layer of the above preferred embodiment, a surface protective film excellent in rewindability can be obtained, and it is particularly suitable for use in optical applications. The adhesion of the surface protective film of the present invention to acryl is preferably in the range of 5 to 40 N/50 mm, more preferably 5 to 5 Å, and more preferably 6 30 N/50 mm. If the adhesion is lower than that of the surface, the adhesion to the adherend is often insufficient. If the tear is exceeded, the 100103883 12 201136951 is often reduced. The rewinding force of the surface protective film of the present invention (i.e., the peel strength when the film is transferred at a constant speed from the state in which the surface is protected into a roll shape) is an index of the turn-off property. When the rewinding force of the surface protective film of the present invention is in the range of 2.5 N / 50 mm or less, preferably 0.01 to 2.0 N / 50 mm, excellent turn-out property can be obtained. The transparency of the surface protective film of the present invention is preferably 80% or less, more preferably 75% or less, still more preferably 70% or less, based on JIS K7105, measured at a total thickness of 50 μm. [Examples] Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited to the examples. [Evaluation method] Adhesive force · Under the conditions of temperature 23 ° C ± 2 ° C, humidity 50% ± 10%, the acrylic sheet is cut into a width of 50 mm and a length of 125 mm, and the film sample is placed on the above-mentioned pressure. On the surface of the force plate, the whole of the sample film was pressed with 2 kg of rubber|Kun's own weight, thereby being attached to the acrylic plate. Next, the peeling force at the time of peeling at 180 mm/min (180-degree peeling) was measured, and the peeling force per 50 mm width was used as the adhesive force (N/50 mm). Rewinding force: Using a roll sample, the peeling force (N/50 mm) at the time of light peeling at a speed of 300 mm/min was measured as a rewinding force. Haze value: 100103883 13 201136951 was measured on a film having a total thickness of 50/zm based on JIS K7105. [Example 1] Three kinds of three-layer τ-shaped molding machine having a width of 5 mm and a die width of 30 mm0 for a single-axis extruder having a surface layer and an adhesive layer of 30 mm0 and a die of a 4Omm0 single-axis extruder having an intermediate layer' The following raw materials were supplied to obtain a surface protective film of the present invention having a thickness of the surface layer (A) of 1 〇, a thickness of the adhesive layer (X), an intermediate layer thickness of 30 μm, and a total thickness of 50/xm. The evaluation results of the obtained film are shown in Table 1. Surface layer: homopolypropylene (model name: F107BV, melting point = 16 ° C, MFR = 7 g/10 min, manufactured by Prime Polymer Co., Ltd.) 70 wt%, 4-decylpentene-1 polymer (trade name: TPX, model name: RT18, melting point = 237 C, MFR = 26g / 10 minutes, manufactured by Mitsui Chemicals Co., Ltd.) 3 〇 wt% Intermediate layer: homopolypropylene (melting point = 160 ° C, MFR = 7 g / 10 min) 1 〇〇% by weight Adhesive layer: Propylene, ethylene, 1-butene copolymer (a peak of melting heat of 4 J/g is observed in the range of 0 to 200 ° C, MFR = 7 gA0 min) 6 〇 wt% Stupid vinyl • Isobutylene copolymer (styrene, isobutylene, styrene, triblock copolymer, SIBSTAR072T (manufactured by Kaneka)) 4% by weight [Comprehensive Examples 2 to 8, Comparative Examples 1 to 2] In addition to changing the resin composition of various layers A surface protective film was obtained in the same manner as in Example 1 except that the resin composition shown in Table 1 was 100103883 14 201136951. The evaluation results of the obtained film are shown in Table 1. 100103883 15 201136951 [11 Comparative Example 2 R ^ 8 O 1 o VO 1 inch ^ ^ ro - Comparative Example 1 § 〇〇8 Ο Ο 1 v〇 inch 1 sister W ^ -ΖΓ» 〇rS 1 - Example 8 ^ R 8 1 i ... α I (N 1 · m · (N - Example 7 ^ RS 1 § 1 -, ro (N 〇 4 ' Example 6 ^ R 8 Ο Ο 1 OO CN 1 vn — 2 | Example 5 | Ο Ο 〇 S * - HOOI vo inch 1 卜 - in Example 4 ^ ^ 8 ♦ -1 OOI v 〇 1 卜 ~ · cn 1 - an embodiment 3 R ^ 8 * - * OOI inch v 〇1 m O ——CN Example 2 8 OOI VO inch 2 2 2 Example 1 .R ^ 8 Ο Ο I 〇 〇 丨 〜 2 2 other resin composition surface layer h-PP (% by weight) PB (% by weight ) TPX (% by weight) Intermediate layer h-PP (% by weight) Xuanxuanxuan id (4) Φ4 φ4 _ 'such as s^/ .3⁄4 1 g I SS SS κ 'ΓχΓ Adhesion (N/50mm) Rewinding force (N /50nmm) Fog value (%)
91S8S50I 201136951 h-PP : 均聚丙烯（熔點= 160°C，MFR=7g/10 分鐘，Prime Polymer 公司製） PB ： 均聚丁烯(熔點= 120°C，MFR=2g/10分鐘） TPX ： 4-甲基戊烯-1系聚合體（商品名：ΤΡΧ，型號名：RT18， 溶點=237°C，MFR=26g/10分鐘，三井化學公司製） PEBR ： 丙烯•乙烯· 1-丁烯共聚合體(於〇〜2〇〇°C之範圍内觀測 到熔解熱量4J/g之熔點波峰，MFR=7g/10分鐘） SIBS ： 苯乙烯•異丁烯共聚合體（苯乙烯·異丁烯•苯乙烯三嵌 段共聚合體，Mw=65,000 ，JIS-A 硬度=33 ， SIBSTAR072T(Kaneka 公司製）） HSBR ： 苯乙烯•丁二烯共聚合體氫化物（DYNARON1320P(JSR 公司製)） 實施例1〜4、6〜8之表面層係由h-PP(亦即丙烯系（共）聚合 體(a))70〜30重量％以及TPX(亦即烯烴（共)聚合體(b))30〜70 重量％所構成。又，黏著層係由PEBR(亦即烯烴系彈性 體）0〜80重量％以及SIBS(亦即笨乙烯•異丁烯共聚合 100103883 17 201136951 體)20〜100重量％所構成。黏著力係為$〜2iN/50mm，可知 具有作為表面保護薄膜為充分的黏著力。又，回捲力均為 2,4N/50mm，均具有優異的黏著力，且具備轉出性。 又，關於透明性，實施例1〜4之霧值均為70%以下，具 有適合作為表面保護薄膜的透明性。此外，當於表面層中使 用TPX之情況，表面保護薄膜之霧值為，可知透明性特 別優異。 另一方面，比較例1中，黏著層係PEBR60重量％、SIBS40 重量％，由於表面層僅由h-PP所構成，故表面層與黏著層 之間的黏著力變大至無法測定回捲力之程度。因此，比較例 1之薄膜不具有良好的轉出性，缺乏作為表面保護薄膜之實 用性。 又，比較例2中，表面層係由h-PP7〇重量％及τρχ30重 里％所構成’黏著層係由PEBR60重量。/0及HSBR40重量〇/〇 所構成。回捲力為3.6N/50mm，為非常大的值。因此，比較 例2之薄臈不具有良好的轉出性’缺乏作為表面保護薄膜之 實用性。 由上述實施例1〜8及比較例1、2可知，本發明之表面保 »蔓薄膜除了具有適合作為表面保護薄膜之透明性之外，不僅 具有充刀的對於被黏著體之黏著力，亦具有優異的轉出性。 (產業上之可利用性） 本發明之表面保護薄膜的黏著特性、透明性、回捲性及耐 100103883 201136951 熱性優異，作為光學用途、建材用途、汽車零件用途的保護 薄膜之產業上利用價值極高。 100103883 1991S8S50I 201136951 h-PP : homopolypropylene (melting point = 160 ° C, MFR = 7 g / 10 min, manufactured by Prime Polymer Co., Ltd.) PB : homopolybutene (melting point = 120 ° C, MFR = 2 g / 10 min) TPX : 4-methylpentene-1 polymer (trade name: ΤΡΧ, model name: RT18, melting point = 237 ° C, MFR = 26 g/10 min, manufactured by Mitsui Chemicals Co., Ltd.) PEBR : propylene, ethylene, 1-butyl Alkene copolymer (melting peak of melting heat 4J/g is observed in the range of 〇~2〇〇°C, MFR=7g/10min) SIBS : styrene·isobutylene copolymer (styrene·isobutylene•styrene III) Block copolymer, Mw=65,000, JIS-A hardness=33, SIBSTAR072T (Kaneka)) HSBR: styrene-butadiene copolymer hydride (DYNARON 1320P (manufactured by JSR)) Examples 1 to 4, 6 The surface layer of ～8 is composed of 70 to 30% by weight of h-PP (that is, propylene (co)polymer (a)) and 30 to 70% by weight of TPX (that is, olefin (co)polymer (b)). Composition. Further, the adhesive layer is composed of 0 to 80% by weight of PEBR (i.e., olefin-based elastomer) and 20 to 100% by weight of SIBS (i.e., stupid ethylene/isobutylene copolymer 100103883 17 201136951). The adhesive force was $2 to 2iN/50 mm, and it was found to have sufficient adhesion as a surface protective film. In addition, the rewinding force is 2, 4N/50mm, both of which have excellent adhesion and have a turn-off property. Further, regarding the transparency, the haze values of Examples 1 to 4 were all 70% or less, and the transparency was suitable as a surface protective film. Further, when TPX is used in the surface layer, the haze value of the surface protective film is particularly excellent in transparency. On the other hand, in Comparative Example 1, the adhesive layer was PEBR 60% by weight and SIBS 40% by weight, and since the surface layer was composed only of h-PP, the adhesion between the surface layer and the adhesive layer became large until the curling force could not be measured. The extent of it. Therefore, the film of Comparative Example 1 did not have good turn-out property and lacked practicality as a surface protective film. Further, in Comparative Example 2, the surface layer was composed of h-PP7〇% by weight and τρχ30% by weight. The adhesive layer was composed of PEBR60 by weight. /0 and HSBR40 weight 〇 / 〇 constitute. The rewinding force is 3.6 N/50 mm, which is a very large value. Therefore, the thin enamel of Comparative Example 2 did not have good roll-out property, and the utility as a surface protective film was lacking. It can be seen from the above Examples 1 to 8 and Comparative Examples 1 and 2 that the surface protective film of the present invention has not only the transparency of the surface protective film but also the adhesion of the filling blade to the adherend. Excellent turn-off. (Industrial Applicability) The surface protective film of the present invention has excellent thermal properties, transparency, rewindability, and resistance to 100103883 201136951, and is an industrial use value for protective films for optical applications, building materials, and automotive parts. high. 100103883 19