201005066 六、發明說明 【發明所屬之技術領域】 本發明係關於黏著薄膜。 【先前技術】 一般而言，黏著薄膜係由具有黏著性之黏著層與支撐 此之基材層的至少2層所構成。此黏著薄膜中，用以使丙 〇 烯酸板或聚碳酸酯板等的樹脂板、鋁板或不鏽鋼板等金屬 板不會產生損傷而被覆者，稱爲表面保護薄膜，此爲黏著 薄膜的重要用途之一。以黏著薄膜所被覆之樹脂板或金屬 板，至出貨爲止前，會在倉庫或工廠等保管數天至半年。 因此，對於表面保護薄膜，係要求即使在倉庫保管，黏著 力亦無變化，且至出貨爲止前經過長期保管，即使表面保 護薄膜剝離，樹脂板或金屬板亦不會產生膠糊殘留之特性 。尤其當將表面保護薄膜使用於液晶面板的製造中所使用 Ο 之偏光板或相位差板，或是層合這些之橢圓偏光板等的光 學構件時，係強烈要求上述特性。 因此’日本特開平5-163468號公報中，係記載一種 表面保護薄膜用黏著劑’其係在黏著層的成分中含有具備 特定的組成及彈性率之丙烯酸系聚合物。 【發明內容】 然而，此在黏著層中含有丙烯酸系聚合物之表面保護 薄膜，其性能仍不夠充分。 201005066 本發明之目的，係提供一種相較於以往的黏著薄膜， 其初期黏著力充分，不易產生因時間經過或熱處理所導致 之黏著力的變動，且在藉由被黏著體將黏著薄膜剝離後不 易產生膠糊殘留之黏著薄膜。 亦即，本發明係提供一種層合有黏著層與基材層之黏 著薄膜。在此，黏著層係由含有7〇〜99重量份的成分（A )與30〜1重量份的成分（B)之樹脂組成物（以成分（A )與成分（B)的合計爲1〇〇重量份）所形成； φ 成分（A)係從滿足條件（a-Ι )及’（a-2 )之乙烯-乙 烯系不飽和酯共聚物（A1 )與滿足條件（a-1 ) 、（a-2) 及（a-3 )之乙烯-α ·烯烴共聚物（A2 )所成群中所選出之 至少一種； 條件： (a-1 ) : 23。(：之 tan <5 爲 〇·〇 1 以上； (a-2 ):熔流速率（MFR )爲1〜50g/10分； (a-3 ):庚烷萃取量爲1 .〇wt%以下； Θ 成分（B )爲滿足條件（b-1 ) 、（ b-2 )及（b-3 )之 乙烯-α -烯烴共聚物； 條件： (b-Ι):熔流速率（MFR)爲3g以上/10分； (b-2):庚烷萃取量爲1.5wt%以上7.0wt%以下； (b-3 ) ••密度 910kg/m3 以下。 此外，本發明係提供一種具備具有雙面之基材層、以 及於基材層的至少一面上具有黏著層之黏著薄膜。在此’ -6 - 201005066 黏著層係含有70~99重量份的成分（A)與3 0〜1重量份的 成分（B)之樹脂組成物（以成分（A)與成分（B)的合 計爲1 0 0重量份）； 成分（A )係從滿足前述條件（a-Ι )及（a-2 )之乙 烯-乙烯系不飽和酯共聚物（A1)與滿足條件（a-1)、( a-2)及（a-3)之乙烯-a-烯烴共聚物（A2)所成群中所 選出之至少一種； 〇 成分（B )爲滿足前述條件（b-1 ) 、（b-2)及（b-3 )之乙烯-α -烯烴共聚物。 根據本發明，係提供一種初期黏著力充分，不易產生 因時間經過或熱處理所導致之黏著力的變動，且在藉由被 黏著體將黏著薄膜剝離後不易產生膠糊殘留之黏著薄膜。 【實施方式】 本發明之黏著薄膜係層合有黏著層與基材層。黏著層 φ 係由含有成分（Α)與成分（Β)之樹脂組成物所形成°成 分（Α)爲滿足條件（a-1)及（a-2)之乙烯-乙烯系不飽 和酯共聚物（A1)，與滿足條件（a-1 ) 、（ a-2 )及（a-3 )之乙烯- α-烯烴共聚物（A2)，或是這些共聚物的組合 〇 (a-1 ) : 23°C 之 tan (5 爲 〇.〇1 以上 (a-2):熔流速率（MFR)爲1〜50g/10分 (a-3):庚院萃取量爲l.Owt%以下 成分（B)爲滿足條件（b-1) 、（b-2)及（b_3)之 201005066 乙烯-α -烯烴共聚物° (b-l):熔流速率（MFR)爲3g以上/10分 (b-2 ):庚烷萃取量爲1 .5wt%以上7.0wt%以下 (b-3 ):密度 910kg/m3 以下 成分（A)爲乙烯-乙烯系不飽和酯共聚物（A1)與乙 烯-α-烯烴共聚物（A2)。這些共聚物可單獨或組合使用 。乙烯-乙烯系不飽和酯共聚物（A1)(以下稱爲共聚物 (A1 ))，例如有乙烯-醋酸乙烯酯共聚物、乙烯-丙酸乙 @ 烯酯共聚物等之乙烯-乙烯酯共聚物；乙烯-甲基丙烯酸甲 酯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸乙酯共 聚物、乙烯-丙烯酸丁酯共聚物等之不飽和羧酸烷基酯乙 烯-共聚物；較理想爲乙烯·醋酸乙烯酯共聚物、乙烯-甲基 丙烯酸甲酯共聚物’更理想爲乙烯-甲基丙烯酸甲酯共聚 物。 共聚物（A1)，就初期黏著力的觀點來看，23 °C之 tan (5爲0.01以上，較理想爲0.05以上，更理想爲0·07 φ 以上。另一方面，23 °C之tan 5 —般爲0.2以下，較理想 爲0.18以下，更理想爲0.17以下。 tan 5係藉由下列方法所測定。首先將樹脂模壓加工 而製作寬度3mm、厚度〇.3mm的測定用薄片。使用Seiko 電子工業股份公司製的黏彈性測定裝置DMS200，以夾頭 間距離20mm、升溫速度5t： /min、頻率5Hz的條件對測 定用薄片進行測定，並讀取23 °C的測定値。 共聚物（A1)，其依據乙烯之構造單位的含量，一般 -8 - 201005066 爲50重量％以上，較理想爲60~99重量％，更理想爲 70〜97重量％，尤其理想爲75~95重量％ ’最理想爲75~80 重量％。此係以共聚物（A1)中之全構造單位的含量爲 100重量％。依據乙烯之構造單位的含量’係藉由紅外線 分光法所測定。 共聚物（A1)之23t：的tan<5，係與乙烯系不飽和酯 的種類或含量相依。例如，當乙烯系不飽和酯爲醋酸乙烯 φ 酯時，乙烯-醋酸乙烯酯共聚物中所含之來自醋酸乙烯酯 的單體單位的含量爲5重量％、26重量％、20重量％時， 乙烯-醋酸乙烯酯共聚物的tan <5，分別約爲0.13、0.05、 0.17。 當乙烯系不飽和酯爲甲基丙烯酸甲酯時，乙烯-甲基 丙烯酸甲酯共聚物中所含之來自甲基丙烯酸甲酯的單體單 位的含量爲5重量％、30重量％、20重量％時，乙烯-甲基 丙烯酸甲酯共聚物的tan<5 ，分別約爲 〇.〇1、0.05、0.17 ❹ 共聚物（A1 )之熔流速率（MFR )爲1〜50g/10分， 較理想爲3〜20 g/ΙΟ分，更理想爲5〜15 g/l〇分。具有前 述範圔的MFR之乙烯-乙烯系不飽和酯共聚物，其加工性 優良。MFR 係依循 JIS K721 0 ( 1995)，在荷重 21.1 8N、 溫度1 90 °C的條件下進行測定。 共聚物（A 1 )，例如可使用高壓自由基聚合法、溶液 聚合法、或乳化聚合法等，對乙烯系不飽和酯化合物與乙 烯進行共聚合而藉此製造。 -9- 201005066 乙烯-α-烯烴共聚物（A2)(以下稱爲共聚物（A2) )中的α-烯烴，例如有丙烯、丁烯-1、戊烯-1、4_甲基戊 煤-1、己嫌_1、辛燒-1、癸嫌_1’就便宜性之觀點來看’ 較理想爲丙烯、丁烯-1、己烯-1、辛烯-1，更理想爲丁烯-1、己烯-1、辛烯-1。 共聚物（Α2)，例如有乙烯-丙烯共聚物、乙烯-丁 烯-1共聚物、乙烯-4-甲基戊烯-1共聚物、乙烯-己烯-1共 聚物、乙燃-辛嫌-1共聚物、乙嫌_丙嫌-丁稀共聚物等 ，較理想爲乙烯-丙烯共聚物、乙烯-丁烯-1共聚物、乙 烯-己烯-1共聚物、乙烯-辛烯-1共聚物’更理想爲乙烯-丁烯-I共聚物、乙烯-己烯-1共聚物、乙嫌_辛稀_1共聚物 〇 共聚物（Α2)，就初期黏著力的觀點來看，23 °C之 tan <5爲0.01以上，較理想爲〇.05以上’更理想爲〇.07 以上。另一方面，23°C之tan<5 —般爲〇_2以下’較理想 爲0.1 8以下，更理想爲0.1 7以下。1 an 5的測定方法係與 (A 1 )相同。 共聚物（A2)之熔流速率（MFR)爲1〜50g/l〇分’ 較理想爲3~20 g/ΙΟ分，更理想爲5~15 g/10分。具有前 述範圍的MFR之乙烯-α-烯烴共聚物’其加工性優良。 MFR 係依循 JISK7210 ( 1995)，在荷重 21·18Ν、溫度 190°C的條件下進行測定。 共聚物（A2)之庚烷萃取量爲以下，就將黏 著薄膜從被黏著體剝離時之膠糊殘留的觀點來看’較理想 201005066 爲0.8 wt%以下。庚烷萃取量，可將測定試樣的小球100g ，於30°C浸漬於250cc的庚烷9小時後，以玻璃濾器予以 抽氣過濾，並測定庚烷溶液中所萃取的量而藉此求取。 共聚物（A2)的密度，就初期黏著力的觀點來看，較 理想爲920kg/m3以下，更理想爲915kg/m3以下，最理想 爲910kg/m3以下。另一方面，就乙烯-α -烯烴共聚物小球 的互相黏著等之處理的觀點來看，密度較理想爲860kg/m3 ❿ 以上。 共聚物（A2)，就抑制將黏著薄膜從被黏著體剝離時 之膠糊殘留的觀點來看，較理想爲藉由均一系觸媒所聚合 之共聚物。均一系觸媒，爲含有過渡金屬化合物，亦即所 謂的金屬芳香系化合物之觸媒，該過渡金屬化合物係具備 具有環戊二烯形陰離子骨幹之基。較理想的金屬芳香系化 合物，爲一般式MLcXn_c (式中，：Μ爲元素週期表的第4 族或鑭族元素系列的過渡金屬原子。L爲具有環戊二烯形 ❹ 陰離子骨幹之基或含有雜原子之基，至少一個爲具有環戊 二烯形陰離子骨幹之基。複數個L可互爲交聯。X爲鹵素 原子、氫或碳原子數1~20的烴基。η爲相當於過渡金屬原 子的原子價之數，c爲0<cSn之整數）所表示之化合物 。過渡金屬化合物可單獨使用或倂用2種以上。 含有過渡金屬化合物之觸媒，一般係包含組合有三乙 基鋁、三異丁基鋁等之有機鋁化合物；甲基鋁氧烷等之鋁 氧院化合物；及/或三苯甲基四（五氟苯基）硼酸鹽、 N，N-二甲基苯胺鹽四（五氟苯基）硼酸鹽等之離子性化合 -11 - 201005066 物作爲過渡金屬化合物者。此外，含有過渡金屬化合物之 觸媒，亦可爲將有機鋁化合物、鋁氧烷化合物、及/或離 子性化合物等，撐持於Si〇2、Ah〇3等之粒子狀無機撐體 、聚乙烯、聚苯乙烯等之粒子狀有機撐體之觸媒。 共聚物（A2)的聚合方法，例如有溶液聚合法、獎液 聚合法、高壓離子聚合法、氣相聚合法，較理想爲氣相聚 合法、高壓離子聚合法。 成分（A)爲乙烯-乙烯系不飽和酯共聚物（A1)及/ 或乙烯-α-烯烴共聚物（A2)。成分（A)可爲乙烯-乙烯 系不飽和酯共聚物（Α1)的1種或2種以上，或是乙烯_ α-烯烴共聚物（Α2)的1種或2種以上。此外，成分（Α )可爲（Α1)與（Α2)的混合物。當混合兩者時，該重 量比可任意選擇’一般而言，成分（Α1) /成分（Α2)爲 95/5〜5/95，較理想爲90/1 0〜10/90，更理想爲80/20〜20/80 〇 成分（Β)爲乙烯-α-烯烴共聚物。成分（Β)的α-烯烴爲碳原子數爲3以上之α-烯烴’例如有丙烯、丁烯-1 、戊烯-1、4-甲基戊烯-1、己烯-1、辛烯-1、癸烯-1，較 理想爲丙烯、丁烯-1'己烯-1、辛烯_1 ’更理想爲丁烯-1 、己稀-1。 成分（Β)，例如有乙烯-丙烯共聚物、乙烯-丁烯-1 共聚物、乙烯-4-甲基戊烯-1共聚物、乙烯-己烯-1共聚物 、乙烯·辛烯-1共聚物、乙烯-丙烯-丁烯_1共聚物等’較 理想爲乙烯-丙烯共聚物 '乙烯·丁烯-1共聚物、乙儲-己 -12- 201005066 稀-1共聚物、乙嫌-辛嫌-1共聚物’更理想爲乙嫌-丁稀_1 共聚物、乙烯-己烯-1共聚物。 成分（B)之熔流速率（MFR)爲3g以上/10分，較 理想爲4〜20 g/ΙΟ分，更理想爲5〜10g/l〇分。具有前述範 圍的MFR之成分（B )，其加工性優良。MFR係依循JIS K7210 ( 1995)，在溫度190°C、荷重21.18N的條件下進 行測定。 響 成分（B)之庚烷萃取量爲l」wt%以上7.0wt%以下。 當成分（B)之庚烷萃取量爲1.5 wt%以上時，黏著薄膜不 易產生因時間經過或熱處理所導致之黏著力的變動。當成 分（B)之庚烷萃取量爲7.Owt%以下時，在藉由被黏著體 將黏著薄膜剝離後不易產生膠糊殘留。成分（B)之庚烷 萃取量可藉由與成分（A2)同樣的方法求取。 成分（B)的密度爲910kg/m3以下。具有含有此成分 (B)之黏著層的黏著薄膜，不易產生因時間經過或熱處 Ο 理所導致之黏著力的變動。成分（B)的密度，較理想爲 907kg/m3以下，更理想爲905kg/m3以下。 成分（B)，就黏著薄膜不易產生因時間經過或熱處 理所導致之黏著力的變動，較理想爲藉由不均一系觸媒所 聚合之共聚物。不均一系觸媒，一般爲戚格勒-納他觸媒 (Ziegler-Natta Catalyst)，係由駄與鹵素所形成，可由 與一般的氯化物更適合之鎂所形成。戚格勒-納他觸媒係 具有可爲3價及/或4價之鈦化合物，以及作爲助觸媒之 有機鋁化合物。戚格勒-納他觸媒，可使用一般所知的觸 -13- 201005066 媒。 成分（B)的分子量分佈，較理想爲3以上，更理想 爲4以上。含有具備此分子量分佈之成分（B)的黏著薄 膜，不易產生因時間經過或熱處理所導致之黏著力的變動 〇 成分（B)的聚合方法，例如有溶液聚合法、漿液聚 合法、高壓聚合法、氣相聚合法，較理想爲氣相聚合法、 高壓離子聚合法。 φ 如上述般，黏著層係由含有由共聚物（A1)及/或共 聚物（A2)所構成之成分（A)，與含有成分（B)之樹 脂組成物所形成。成分（A )與成分（B )之比例，以成分 (A)與成分（B)的合計爲1〇〇重量份時，成分（A)爲 70〜99重量份，成分（B )爲30~1重量份，較理想爲成分 (入）爲80〜9 7重量份，成分（8)爲20~3重量份，更理 想爲成分（A)爲85〜95重量份，成分（B)爲15〜5重量 份。具備由具有前述範圍的成分（A)含量及成分（B)含 _ 量之樹脂組成物所形成之黏著層的黏著薄膜，不易產生因 時間經過或熱處理所導致之黏著力的變動，且在將黏著薄 膜剝離後不易產生膠糊殘留。 形成黏著層之樹脂組成物，除了成分（A)、成分（B )之外，尙可含有除此之外的聚烯烴系樹脂或改質聚烯烴 系樹脂、松香系樹脂、聚萜系樹脂、合成石油樹脂、色烷 系樹脂、酚系樹脂、二甲苯系樹脂、苯乙烯系樹脂、異戊 二烯系樹脂等之其他樹脂。 -14- 201005066 聚烯烴系樹脂，例如有同排聚丙烯、對排聚丙烯、包 含共單體之雜亂形式聚丙烯、依據多段聚合所形成之團聯 形式聚丙烯等之聚丙烯、低密度聚乙烯（LdPE)。 改質聚烯烴系樹脂，例如有藉由順丁烯二酸酐、順丁 烯—酸一甲酯、順丁烯二酸二乙酯、丙烯酸、甲基丙烯酸 、四氫鄰苯二甲酸、甲基丙烯酸縮水甘油酯、甲基丙烯酸 羥乙酯等之改質用化合物所改質之聚烯烴。改質之聚烯烴 G 系樹脂’例如有低密度聚乙烯（LDPE )或線狀低密度聚 乙烯（LLDPE)、高密度聚乙烯（HDPE)等之乙烯系樹 脂、同排聚丙烯、對排聚丙烯 '包含共單體之雜亂形式聚 丙烯、依據多段聚合所形成之團聯形式聚丙烯、聚（4_甲 基-1-戊烯）、聚（1-丁烯）。 松香系樹脂’例如有天然松香、聚合松香、部分加氫 松香、完全加氫松香、這些松香的酯化物（例如甘油酯、 新戊四醇酯、乙一醇酯、甲基酯）、松香衍生物（例如非 • 均化松香、富馬酸化松眷、石灰化松香）。 聚萜系樹脂’例如有α-璇稀、蕕稀、雙戊稀等之 環狀萜的單獨聚合物、上述環狀萜的共聚物、上述環狀萜 與酷、雙酣等的酚系化合物之共聚物（例如α-蒎烯-酚樹 脂、雙戊嫌-酚樹脂、萜-雙酣樹脂等之蔽-酣系樹脂）、上 述環狀萜與芳香族單體之共聚物的芳香族改質蔽樹脂。 合成石油樹脂’例如有輕油分解油的c5餾分、 C 6〜C! i餾分及其他烯烴系餾分的單獨聚合物或共聚物、這 些單獨聚合物或共聚物的加氫物之脂肪族系石油樹脂、芳 -15- 201005066 香族系石油樹脂、脂環式系石油樹脂、脂肪族-脂環式共 聚物。合成石油樹脂’除了前述以外，亦可爲輕油分解油 與萜之共聚物'共聚物的加氫物之共聚合系石油樹脂。 輕油分解油之較佳的c5餾分，例如有異戊二烯、環 戊二烯、1，3-戊二烯、2-甲基-1-丁烯、2-甲基-2-丁烯等之 甲基丁烯類；卜戊烯、2-戊烯等之戊烯類；二環戊二烯等 。（:6〜Cn餾分’較理想爲茚、苯乙烯、鄰乙烯甲苯、間乙 烯甲苯、對乙烯甲苯、甲基苯乙烯、冷-甲基苯乙烯等 φ 之甲基苯乙烯類；甲基茚、乙基茚、乙烯二甲苯、丙烯基 苯等。其他烯烴系餾分，較理想爲丁烯、己烯、庚烯、辛 烯、丁二烯、辛二烯。 色烷系樹脂，例如有色烷的單獨聚合物或色烷與茚之 共聚物。 酚系樹脂，例如有烷基酚樹脂、烷基酚與炔類之縮合 所形成之烷基酚-炔類樹脂及這些樹脂的改質物。酚系樹 脂’亦可爲藉由酸觸媒將酚予以羥甲化之酚醛型樹脂或是 ❹ 以鹸觸媒予以羥甲化之可溶酚醛型樹脂。 二甲苯系樹脂，例如有由間二甲苯與甲醛所構成之二 甲苯·甲醛樹脂、或是將第3成分添加於此並進行反應之 改質樹脂。 苯乙烯系樹脂，例如有苯乙烯的低分子量單體、α-甲基苯乙烯與乙烯甲苯之共聚物、苯乙烯與丙烯腈與茚之 共聚物、苯乙烯與丁二嫌之共聚物、苯乙烯與乙烯丁烯之 共聚物。 -16- 201005066 異戊二烯系樹脂，例如可將異戊二烯的二聚物之c10 脂環式化合物與C1Q鏈狀化合物與以共聚合而製得。 形成黏著層之樹脂組成物，尙可含有防氧化劑、抗結 塊劑、潤滑劑、防帶電劑、耐氣候安定劑、顏料、加工性 改良劑、金屬皂等之添加劑。添加劑可單獨或組合使用。 此外，基材層亦可含有此添加劑》 成分（A)與成分（B )之樹脂組成物，例如可藉由將 φ 成分（A )與成分（B )以及因應必要所添加之添加劑等的 其他成分予以乾式摻合或熔融摻合之方法而製造出。乾式 摻合可使用亨舍爾摻合機、滾筒摻合機等之各種摻合機。 熔融摻合可使用單軸擠壓機、雙軸擠壓機、班布里摻合機 、熱軋輥等之各種摻合機。 基材層一般係具有雙面（例如界面、表面）。基材層 較理想爲由樹脂所形成，主成分較理想爲烯烴系聚合物。 烯烴系聚合物’例如有乙烯系樹脂、丙烯系樹脂、改質聚 © 烯烴系樹脂。 乙烯系樹脂’例如有高密度聚乙烯、中密度聚乙烯、 低密度聚乙烯、直鏈狀低密度聚乙烯等之聚乙烯系樹脂； 乙嫌-丙烯共聚物樹脂、乙烯-丁烯共聚物樹脂、乙烯-戊烯 共聚物樹脂、乙烯-己烯共聚物樹脂、乙烯-辛烯共聚物樹 脂等之乙烯-α-烯烴共聚物；乙烯-苯乙烯共聚物樹脂、乙 稀-環狀烯烴共聚物樹脂。丙烯系樹脂，例如有丙烯單獨 聚口物或是丙稀與少量的α -嫌烴及/或乙稀之雜亂或團聯 共聚物。改質聚稀烴系樹脂’例如有藉由順丁烯二酸酐、 -17- 201005066 順』烯一酸二甲酯、順丁烯二酸二乙酯、丙烯酸、甲基丙 嫌酸、四氫鄰苯：甲帛、甲基丙烯酸縮水甘油酯、甲基丙 缔酸經乙醋等之改質用化合物所改質之聚烯烴。聚烯烴系 樹脂’例如有乙烯系樹脂、同排聚丙烯、對排聚丙烯、包 含共單體之雜亂形式聚丙烯、依據多段聚合所形成之團聯 形式聚丙靖、聚（4 -甲基-1-戊烯）、聚（1-丁烯），較理 想爲乙烯系樹脂、丙烯系樹脂。201005066 VI. Description of the Invention [Technical Field of the Invention] The present invention relates to an adhesive film. [Prior Art] Generally, an adhesive film is composed of at least two layers of an adhesive layer and an adhesive layer supporting the substrate. In the adhesive film, a metal plate such as a resin plate such as a acrylic acid plate or a polycarbonate plate, or a metal plate such as an aluminum plate or a stainless steel plate is not damaged, and is called a surface protective film, which is important for the adhesive film. One of the uses. The resin sheet or metal sheet covered with the adhesive film will be stored in warehouses or factories for several days to half a year until shipment. Therefore, in the case of the surface protective film, it is required that the adhesive strength does not change even when stored in a warehouse, and the resin sheet or the metal sheet does not have a residual adhesive property even after the surface protective film is peeled off for long-term storage. . In particular, when the surface protective film is used for a polarizing plate or a phase difference plate used in the production of a liquid crystal panel, or an optical member such as an elliptically polarizing plate in which these are laminated, the above characteristics are strongly required. In the Japanese Patent Application Laid-Open No. Hei 5-163468, an adhesive for a surface protective film is described as an acrylic polymer having a specific composition and an elastic modulus in a component of the adhesive layer. SUMMARY OF THE INVENTION However, the surface protective film containing an acrylic polymer in the adhesive layer is still insufficient in performance. 201005066 The object of the present invention is to provide an adhesive film having a sufficient initial adhesion compared with the conventional adhesive film, which is less likely to cause a change in adhesion due to passage of time or heat treatment, and after the adhesive film is peeled off by the adherend Adhesive film that is not easy to produce adhesive residue. That is, the present invention provides an adhesive film in which an adhesive layer and a substrate layer are laminated. Here, the adhesive layer is a resin composition containing 7 to 99 parts by weight of the component (A) and 30 to 1 part by weight of the component (B) (the total of the component (A) and the component (B) is 1〇. φ Component (A) is obtained from the ethylene-ethylene unsaturated ester copolymer (A1) satisfying the conditions (a-Ι) and '(a-2) and satisfying the condition (a-1), At least one selected from the group consisting of (a-2) and (a-3) of the ethylene-α·olefin copolymer (A2); Condition: (a-1): 23. (:tan <5 is 〇·〇1 or more; (a-2): melt flow rate (MFR) is 1~50g/10 minutes; (a-3): heptane extraction amount is 1. 〇wt% The following components: (B) are ethylene-α-olefin copolymers satisfying conditions (b-1), (b-2), and (b-3); Conditions: (b-Ι): Melt flow rate (MFR) (b-2): the heptane extraction amount is 1.5 wt% or more and 7.0 wt% or less; (b-3) • the density is 910 kg/m 3 or less. Further, the present invention provides a double having a double The base layer of the surface and the adhesive film having an adhesive layer on at least one side of the base material layer. Here, the adhesive layer contains 70 to 99 parts by weight of the component (A) and 30 to 1 part by weight. The resin composition of the component (B) (the total of the component (A) and the component (B) is 100 parts by weight); the component (A) is from the above conditions (a-Ι) and (a-2). The ethylene-ethylene unsaturated ester copolymer (A1) is selected from the group consisting of ethylene-a-olefin copolymers (A2) satisfying the conditions (a-1), (a-2) and (a-3). At least one of the components; (B) is an ethylene-α satisfying the aforementioned conditions (b-1), (b-2) and (b-3) -Olefin Copolymer. According to the present invention, it is provided that the initial adhesion is sufficient, the change in adhesion due to passage of time or heat treatment is not easily caused, and the adhesive residue is not easily generated after the adhesive film is peeled off by the adherend. [Adhesive film] The adhesive film of the present invention is formed by laminating an adhesive layer and a base material layer, and the adhesive layer φ is formed of a resin composition containing a component (Α) and a component (Β). The ethylene-ethylene unsaturated ester copolymer (A1) satisfying the conditions (a-1) and (a-2), and the ethylene satisfying the conditions (a-1), (a-2) and (a-3) Α-olefin copolymer (A2), or a combination of these copolymers 〇(a-1) : tan at 23 ° C (5 is 〇.〇1 or more (a-2): melt flow rate (MFR) is 1 ~50g/10 points (a-3): Gengyuan extraction amount is 1.0% by weight or less (B) is 201005066 ethylene-α-olefin satisfying conditions (b-1), (b-2) and (b_3) Copolymer ° (bl): melt flow rate (MFR) of 3 g or more / 10 min (b-2): heptane extraction amount of 1.5 wt% or more and 7.0 wt% or less (b-3): density of 910 kg/m3 or less Ingredient (A) is ethylene-ethylene unsaturated Ester copolymer (A1) and ethylene-α-olefin copolymer (A2). These copolymers may be used singly or in combination. Ethylene-ethylene unsaturated ester copolymer (A1) (hereinafter referred to as copolymer (A1)), For example, an ethylene-vinyl acetate copolymer such as an ethylene-vinyl acetate copolymer or an ethylene-propionate copolymer; an ethylene-methyl methacrylate copolymer, an ethylene-methyl acrylate copolymer, and an ethylene-acrylic acid; An ethyl acrylate copolymer, an ethylene butyl acrylate copolymer or the like, an unsaturated carboxylic acid alkyl ester ethylene-copolymer; more preferably an ethylene vinyl acetate copolymer or an ethylene methyl methacrylate copolymer Ethylene-methyl methacrylate copolymer. The copolymer (A1) has a tan at 23 °C from the viewpoint of initial adhesion (5 is 0.01 or more, preferably 0.05 or more, more preferably 0. 07 φ or more. On the other hand, tan at 23 °C 5 is generally 0.2 or less, preferably 0.18 or less, more preferably 0.17 or less. Tan 5 is measured by the following method. First, a resin is press-molded to prepare a sheet for measurement having a width of 3 mm and a thickness of 〇3 mm. The viscoelasticity measuring apparatus DMS200 manufactured by the Electronics Industry Co., Ltd. measured the sheet for measurement with a distance between the chucks of 20 mm, a temperature rising rate of 5 t: /min, and a frequency of 5 Hz, and read the measurement enthalpy at 23 ° C. A1), which is based on the content of structural units of ethylene, generally -8 - 201005066 is 50% by weight or more, more preferably 60 to 99% by weight, still more preferably 70 to 97% by weight, and particularly preferably 75 to 95% by weight. It is most preferably 75 to 80% by weight. The content of the total structural unit in the copolymer (A1) is 100% by weight. The content of the structural unit based on ethylene is determined by infrared spectroscopy. Copolymer (A1) ) 23t: tan<5, with B The type or content of the ethylenically unsaturated ester is dependent. For example, when the ethylenically unsaturated ester is vinyl acetate φ ester, the content of the monomer unit derived from vinyl acetate contained in the ethylene-vinyl acetate copolymer is 5 weight. When %, 26% by weight, and 20% by weight, the tan-lt;5 of the ethylene-vinyl acetate copolymer is about 0.13, 0.05, and 0.17, respectively. When the ethylenically unsaturated ester is methyl methacrylate, ethylene-A When the content of the monomer unit derived from methyl methacrylate contained in the methyl acrylate copolymer is 5% by weight, 30% by weight, or 20% by weight, the tan-lt;5 of the ethylene-methyl methacrylate copolymer The melt flow rate (MFR) of the copolymers (A1) is preferably from 1 to 50 g/10 minutes, more preferably from 3 to 20 g/min, more preferably from 5 to 15 g. The ethylene-ethylene unsaturated ester copolymer having the MFR of the above-mentioned formula has excellent processability. The MFR is in accordance with JIS K721 0 (1995) under the conditions of a load of 21.1 8 N and a temperature of 1 90 °C. The measurement is carried out. For the copolymer (A 1 ), for example, a high pressure radical polymerization method or a solution can be used. It is produced by copolymerizing an ethylene-based unsaturated ester compound and ethylene by a legal or emulsion polymerization method, etc. -9- 201005066 Ethylene-α-olefin copolymer (A2) (hereinafter referred to as copolymer (A2)) From the point of view of the cheapness of α-olefins such as propylene, butene-1, pentene-1, 4-methylpenta-1, suspicion _1, xin sing-1, 癸 _1 Preferably, it is propylene, butene-1, hexene-1, and octene-1, and more preferably butene-1, hexene-1, and octene-1. Copolymer (Α2), for example, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-4-methylpentene-1 copolymer, ethylene-hexene-1 copolymer, ethylene-cepene -1 copolymer, B-propylene-butylene copolymer, etc., preferably ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-hexene-1 copolymer, ethylene-octene-1 The copolymer is more preferably an ethylene-butene-I copolymer, an ethylene-hexene-1 copolymer, or a bismuth-_1 copolymer ruthenium copolymer (Α2), from the viewpoint of initial adhesion, 23 The tan <5 of °C is 0.01 or more, and more preferably 〇.05 or more, and more preferably 〇.07 or more. On the other hand, tan<5 at 23 °C is generally 〇_2 or less' is preferably 0.18 or less, more preferably 0.17 or less. The measurement method of 1 an 5 is the same as (A 1 ). The melt flow rate (MFR) of the copolymer (A2) is 1 to 50 g/l ’, which is preferably 3 to 20 g/min, more preferably 5 to 15 g/10. The ethylene-α-olefin copolymer having the MFR of the above range is excellent in processability. The MFR was measured in accordance with JIS K7210 (1995) under the conditions of a load of 21.18 Torr and a temperature of 190 °C. The heptane extraction amount of the copolymer (A2) is as follows, and it is more preferably 0.8 wt% or less from the viewpoint of the adhesive residue when the adhesive film is peeled off from the adherend. The heptane extraction amount can be 100 g of the pellet of the measurement sample, immersed in 250 cc of heptane at 30 ° C for 9 hours, and then suction-filtered with a glass filter, and the amount extracted in the heptane solution is measured. Seek. The density of the copolymer (A2) is preferably 920 kg/m3 or less, more preferably 915 kg/m3 or less, and most preferably 910 kg/m3 or less from the viewpoint of initial adhesion. On the other hand, from the viewpoint of the treatment of adhesion of the ethylene-α-olefin copolymer beads, etc., the density is preferably 860 kg/m3 ❿ or more. The copolymer (A2) is preferably a copolymer which is polymerized by a uniform catalyst from the viewpoint of suppressing the residual of the adhesive when the adhesive film is peeled off from the adherend. The homogeneous catalyst is a catalyst containing a transition metal compound, that is, a metal aromatic compound, and the transition metal compound has a group having a cyclopentadiene anion backbone. The preferred metal aromatic compound is a general formula MLcXn_c (wherein: Μ is a transition metal atom of the group 4 or lanthanide series of the periodic table. L is a group having a cyclopentadiene ❹ anion backbone or The group containing a hetero atom, at least one of which is a group having a cyclopentadiene-shaped anion backbone. The plurality of L may be cross-linked to each other. X is a halogen atom, hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. η is equivalent to a transition A compound represented by the number of valences of metal atoms, c is an integer of 0 <cSn. The transition metal compound may be used singly or in combination of two or more. The catalyst containing a transition metal compound generally comprises an organoaluminum compound in combination with triethylaluminum, triisobutylaluminum or the like; an aluminoxy compound such as methylaluminoxane; and/or trityltetramine (five) An ionic compound of fluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate or the like -11 - 201005066 as a transition metal compound. Further, the catalyst containing a transition metal compound may be a particulate inorganic support such as an organoaluminum compound, an aluminoxane compound, and/or an ionic compound supported on Si〇2, Ah〇3, or the like, or polyethylene. A catalyst for a particulate organic support such as polystyrene. The polymerization method of the copolymer (A2) is, for example, a solution polymerization method, a liquid polymerization method, a high pressure ion polymerization method or a gas phase polymerization method, and is preferably a gas phase polymerization method or a high pressure ion polymerization method. The component (A) is an ethylene-ethylene unsaturated ester copolymer (A1) and/or an ethylene-α-olefin copolymer (A2). The component (A) may be one type or two or more types of the ethylene-ethylene-based unsaturated ester copolymer (Α1), or one or two or more types of the ethylene-α-olefin copolymer (Α2). Further, the component (Α) may be a mixture of (Α1) and (Α2). When mixing the two, the weight ratio can be arbitrarily selected 'generally, the composition (Α1) / component (Α2) is 95/5 to 5/95, more preferably 90/1 0 to 10/90, more preferably 80/20~20/80 The 〇 component (Β) is an ethylene-α-olefin copolymer. The α-olefin of the component (Β) is an α-olefin having 3 or more carbon atoms, such as propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene. -1, decene-1, more preferably propylene, butene-1 'hexene-1, octene_1' is more preferably butene-1, hex-1. Ingredients (Β), for example, an ethylene-propylene copolymer, an ethylene-butene-1 copolymer, an ethylene-4-methylpentene-1 copolymer, an ethylene-hexene-1 copolymer, an ethylene octene-1 Copolymer, ethylene-propylene-butene-1 copolymer, etc. 'ideally ethylene-propylene copolymer' ethylene-butene-1 copolymer, B-hex-12-201005066 dilute-1 copolymer, B- The bismuth-1 copolymer is more preferably a B-butylene-1 copolymer or an ethylene-hexene-1 copolymer. The melt flow rate (MFR) of the component (B) is 3 g or more and 10 minutes, more preferably 4 to 20 g/min, more preferably 5 to 10 g/l. The component (B) having the MFR of the aforementioned range is excellent in workability. The MFR was measured in accordance with JIS K7210 (1995) under the conditions of a temperature of 190 ° C and a load of 21.18 N. The heptane extraction amount of the component (B) is 1" wt% or more and 7.0 wt% or less. When the heptane extraction amount of the component (B) is 1.5 wt% or more, the adhesive film is less likely to cause a change in adhesion due to passage of time or heat treatment. When the heptane extraction amount of the component (B) is 7% by weight or less, the adhesive residue is less likely to be generated after the adhesive film is peeled off by the adherend. The heptane extraction amount of the component (B) can be determined by the same method as the component (A2). The density of the component (B) is 910 kg/m3 or less. An adhesive film having an adhesive layer containing the component (B) is less likely to cause a change in adhesion due to passage of time or heat treatment. The density of the component (B) is preferably 907 kg/m3 or less, more preferably 905 kg/m3 or less. In the component (B), the adhesive film is less likely to cause a change in adhesion due to passage of time or heat treatment, and is preferably a copolymer polymerized by a heterogeneous catalyst. The heterogeneous catalyst, generally Ziegler-Natta Catalyst, is formed of bismuth and halogen and can be formed from magnesium which is more suitable for general chlorides. The 戚Gle-Natta catalyst has a titanium compound which can be a trivalent and/or tetravalent, and an organoaluminum compound which acts as a cocatalyst.戚格勒-纳他触媒, can use the commonly known touch -13- 201005066 media. The molecular weight distribution of the component (B) is preferably 3 or more, more preferably 4 or more. An adhesive film containing the component (B) having such a molecular weight distribution, which is less likely to cause a change in adhesion due to passage of time or heat treatment, and a polymerization method of the component (B), for example, a solution polymerization method, a slurry polymerization method, or a high pressure polymerization method. The gas phase polymerization method is preferably a gas phase polymerization method or a high pressure ion polymerization method. φ As described above, the adhesive layer is formed of a resin composition containing the component (A) composed of the copolymer (A1) and/or the copolymer (A2) and the component (B). When the ratio of the component (A) to the component (B) is 1 part by weight based on the total of the component (A) and the component (B), the component (A) is 70 to 99 parts by weight, and the component (B) is 30 to 30. 1 part by weight, preferably the component (in) is 80 to 9 7 parts by weight, the component (8) is 20 to 3 parts by weight, more preferably the component (A) is 85 to 95 parts by weight, and the component (B) is 15 parts. ~ 5 parts by weight. An adhesive film having an adhesive layer formed of a resin composition having a content of the component (A) in the above range and a resin composition containing a component (B) is less likely to cause a change in adhesion due to passage of time or heat treatment, and After the adhesive film is peeled off, it is not easy to cause adhesive residue. The resin composition forming the adhesive layer may contain, in addition to the component (A) and the component (B), a polyolefin-based resin or a modified polyolefin-based resin, a rosin-based resin, a polyfluorene-based resin, or the like. Other resins such as a synthetic petroleum resin, a chromene resin, a phenol resin, a xylene resin, a styrene resin, and an isoprene resin. -14- 201005066 Polyolefin resin, for example, polypropylene in the same row, polypropylene in the same row, polypropylene in a disordered form containing a comonomer, polypropylene in agglomerated form of polypropylene formed by multistage polymerization, low density poly Ethylene (LdPE). Modified polyolefin resin, for example, by maleic anhydride, methyl methacrylate, diethyl maleate, acrylic acid, methacrylic acid, tetrahydrophthalic acid, methyl A polyolefin modified with a modifying compound such as glycidyl acrylate or hydroxyethyl methacrylate. The modified polyolefin G-based resin is, for example, a low-density polyethylene (LDPE) or a linear low-density polyethylene (LLDPE), a high-density polyethylene (HDPE), or the like, a vinyl resin, a polypropylene in the same row, and a pair of polypropylene. Propylene' comprises a comonomer in the form of a polypropylene, agglomerated form of polypropylene formed according to multistage polymerization, poly(4-methyl-1-pentene), poly(1-butene). The rosin-based resin is, for example, natural rosin, polymerized rosin, partially hydrogenated rosin, fully hydrogenated rosin, esterified of these rosins (for example, glyceride, neopentyl ester, ethyl alcohol ester, methyl ester), rosin derivative (eg non-homogeneous rosin, fumarate pine, calcified rosin). The polyfluorene-based resin is, for example, a single polymer of a cyclic oxime such as α-anthracene, lanthanum or dipentamethylene, a copolymer of the above cyclic oxime, a phenolic compound such as the above-mentioned cyclic oxime, and a bismuth or a bismuth compound. Copolymer (for example, α-pinene-phenol resin, bismuth-phenol resin, bismuth-bismuth resin, etc.), aromatic modification of the above-mentioned copolymer of cyclic oxime and aromatic monomer Resin resin. Synthetic petroleum resins such as c5 fractions of light oil decomposing oil, individual polymers or copolymers of C 6 to C! i fractions and other olefinic fractions, and aliphatic petroleums of hydrogenated products of these individual polymers or copolymers Resin, 芳-15- 201005066 Aromatic petroleum resin, alicyclic petroleum resin, aliphatic-alicyclic copolymer. In addition to the above, the synthetic petroleum resin may be a copolymerized petroleum resin of a hydrogenated product of a copolymer of a light oil-decomposing oil and ruthenium copolymer. Preferred c5 fractions of light oil decomposing oils, such as isoprene, cyclopentadiene, 1,3-pentadiene, 2-methyl-1-butene, 2-methyl-2-butene And other methylbutenes; pentenes such as pentene, 2-pentene, etc.; dicyclopentadiene. (6: Cn fraction is preferably 茚, styrene, o-ethylene toluene, m-vinyl toluene, p-vinyl toluene, methyl styrene, cold-methyl styrene, etc. φ methyl styrene; methyl hydrazine; , ethyl hydrazine, ethylene xylene, propylene benzene, etc. Other olefinic fractions are preferably butene, hexene, heptene, octene, butadiene, octadiene. a single polymer or a copolymer of a chromene and hydrazine. A phenolic resin, for example, an alkylphenol-alkyne resin formed by condensation of an alkylphenol resin, an alkylphenol and an acetylene, and a modified product of these resins. The resin ' can also be a phenolic resin which is hydroxylated by a acid catalyst or a resol type resin which is hydroformylated by a ruthenium catalyst. A xylene resin, for example, from metaxylene a xylene/formaldehyde resin composed of formaldehyde or a modified resin obtained by adding a third component thereto. A styrene resin such as a low molecular weight monomer having styrene or α-methylstyrene Copolymer of vinyl toluene, copolymerization of styrene and acrylonitrile with hydrazine Copolymer of styrene and styrene, copolymer of styrene and ethylene butene. -16- 201005066 Isoprene resin, for example, c10 alicyclic compound of dimer of isoprene It is obtained by copolymerization with a C1Q chain compound and a resin composition for forming an adhesive layer, which may contain an antioxidant, an anti-caking agent, a lubricant, an antistatic agent, a weather stabilizer, a pigment, and a processability improver. Additives such as metal soap, etc. The additives may be used singly or in combination. Further, the base material layer may also contain the resin composition of the additive (A) and the component (B), for example, by the φ component (A) and The component (B) and other components such as additives added as necessary are produced by dry blending or melt blending. The dry blending may be carried out by various blends of a Henschel blender, a drum blender, or the like. For the melt blending, various blenders such as a single-axis extruder, a twin-screw extruder, a Banbury blender, a hot roll, etc. may be used. The substrate layer generally has a double-sided (e.g., interface, surface). The substrate layer is preferably made of resin The olefin-based polymer is preferably an olefin-based polymer. The olefin-based polymer is, for example, an ethylene-based resin, a propylene-based resin, or a modified poly-olefin-based resin. The vinyl-based resin is, for example, a high-density polyethylene or a medium-density polyethylene. Polyethylene resin such as low density polyethylene or linear low density polyethylene; propylene-propylene copolymer resin, ethylene-butene copolymer resin, ethylene-pentene copolymer resin, ethylene-hexene copolymer An ethylene-α-olefin copolymer such as a resin or an ethylene-octene copolymer resin; an ethylene-styrene copolymer resin; an ethylene-cyclic olefin copolymer resin; and a propylene-based resin such as a propylene alone polymer or Propylene and a small amount of α-anhydrocarbon and/or ethylene chaotic or agglomerated copolymer. Modified poly-hydrocarbon resin 'for example, with maleic anhydride, -17-201005066 cis-ene carboxylic acid II Methyl ester, diethyl maleate, acrylic acid, methyl propylene acid, tetrahydroortylene: methyl hydrazine, glycidyl methacrylate, methyl propyl acrylate, acetonitrile, etc. Modified polyolefin. The polyolefin-based resin is, for example, a vinyl resin, a polypropylene in the same row, a polypropylene in a row, a polypropylene in a disordered form containing a comonomer, a polycondensed form formed according to a multistage polymerization, and a poly(4-methyl group). 1-pentene) and poly(1-butene) are preferably an ethylene resin or a propylene resin.
基材層的厚度，可在不損及黏著性等之範圍內適當地 選擇’一般爲3〜500 μπι，較理想爲5〜200μιη。黏著層的厚 度’可在不損及黏著性等之範圍內適當地選擇，一般爲 1〜ΙΟΟμιη，較理想爲 3〜50μιη，更理想爲 5〜30μπι。基材層 的厚度位於前述範圍之黏著薄膜，在貼合於被黏著體時不 易產生皺折等’且黏著薄膜的處理性良好。 黏著層的厚度一般爲5〜ΙΟΟμηι，較理想爲10~50μιη， 更理想爲1〇〜20μιη。The thickness of the base material layer can be appropriately selected from the range of 3 to 500 μm, preferably 5 to 200 μm, insofar as the thickness is not impaired. The thickness of the adhesive layer can be appropriately selected within the range of not impairing adhesion, etc., and is usually 1 to ΙΟΟμιη, more preferably 3 to 50 μm, more preferably 5 to 30 μm. When the thickness of the base material layer is in the above range, the adhesive film is less likely to wrinkle when attached to the adherend, and the handleability of the adhesive film is good. The thickness of the adhesive layer is generally 5 to ΙΟΟμηι, more preferably 10 to 50 μm, and more preferably 1 to 20 μm.
對於基材層，亦可因應必要，例如施以防污處理、酸 處理、鹼處理、底漆處理、定錨塗佈處理、電暈處理、電 漿處理、紫外線處理、防靜電處理。 黏著薄膜係含有至少1層的基材層及至少1層的黏著 層。黏著薄膜，只要其一方的表層爲由含有特定量的成分 (Α)與成分（Β)之樹脂組成物所形成的黏著層即可，其 他的層構成或層合數，並無特別限定。層合數例如可爲 2〜7層。黏著薄膜的層構成，例如爲基材層/黏著層、基材 層/黏接層/基材層/黏著層、基材層/黏著層/基材層/黏著層 -18- 201005066 黏著薄膜的製造方法，例如爲共擠壓成形法或疊合成 形法。共擠壓成形法，例如可藉由T模具成形法或充氣成 形法等之一般所知的方法，在熔融狀態下將基材層及黏著 層擠壓出，層合後再藉由冷卻軋輥等冷卻手段進行冷卻之 方法。疊合成形法，例如藉由擠壓成形法預先製作基材層 ，於其上方，例如在熔融狀態下將黏著層擠壓出並層合後 Φ ，再藉由冷卻軋輥等冷卻手段進行冷卻之方法。就製品設 計種類的多樣性之觀點來看，較理想爲共擠壓成形法。黏 著薄膜可於至少單軸方向進行拉伸。 當藉由擠壓成形來製造黏著薄膜時，擠壓機出口的樹 脂溫度，可因應成形機的種類、或各層所使用之樹脂的種 類或分子量來適當地選擇，一般爲100°C〜3 50°c，較理想 爲150〜300 °C。所使用之擠壓機、模具，可使用一般所知 者，並無特別限定》 # 黏著薄膜乃適合用作爲表面保護薄膜。當將黏著薄膜 用作爲表面保護薄膜時，被黏著體例如爲合成樹脂板、不 鏽鋼板（例如建築資材用）、鋁板、化粧合板、鋼板、玻 璃板、家電製品、精密機械、以及於製造時之汽車車體或 是液晶顯不器等的平面顯不器中所使用之偏光板、相位差 板、視角擴大板及亮度提升板等之光學構件，較理想爲偏 光板或相位差板。偏光板、相位差板、視角擴大板、亮度 提升板，分別含有偏光薄膜、相位差薄膜、視角擴大薄膜 、亮度提升薄膜。由於黏著薄膜的透明性亦優良，容易在 -19- 201005066 貼合於被黏著體之狀態下進行缺陷檢查，因此特別適合用 作爲光學構件用表面保護薄膜。 實施例 以下係藉由實施例來更具體地說明本發明。物性測定 係以下列所述內容來進行。 黏著層中所含有之成分（A)的tan «5，係將成分（A )模壓加工而製作寬度3mm、厚度0.3mm的測定用薄片 。使用 Seiko電子工業股份公司製的黏彈性測定裝置 DMS200，以夾頭間距離20mm、升溫速度5 t /min、頻率 5 HZ的條件進行測定，並讀取23 °C的測定値。 (2) 熔流速率（單位：g/10分） 成分（A)與成分（B)的熔流速率，係依循 JIS K7210，在溫度190°C、試驗荷重21.18N的條件下進行測 φ 定。 (3) 庚烷萃取量（單位：wt%) 成分（A)的乙烯-α-烯烴共聚物與成分（B)之庚烷 萃取量，係將小球l〇〇g於30°C浸漬於250cc的庚烷9小 時後，以玻璃濾器予以抽氣過濾，並測定庚烷溶液中所萃 取的量而藉此求取。 (4 )密度（單位：kg/m3 ) 成分（A)的乙烯-α-烯烴共聚物與成分（B)之密度 -20- 201005066 ’係依循JIS K7U 2- 1 980中之A法所規定的方法進行測 定。測定試樣片’係依循JIS K676 0- 1 995中所記載之低密 度聚乙烯的方法進行退火並使用於測定。 (5 )分子量分佈 成分（B)之分子量分佈’係使用凝膠滲透層析（ GPC )法，藉由下列條件進行測定以求取。 裝置：Waters 公司製 150C ALC/GPC 〇 管柱：昭和電工公司製 Shodex Packed Column A- 8 0M 2 根 溫度：1 4 0 °C 溶劑：鄰二氯苯 溶出溶劑流速：1.0ml/分 試樣濃度：lmg/ml 測定注入量：400μ1 分子量標準物質：標準聚苯乙烯 © 檢測器：差示折射 (6)成分（Α1)之來自乙烯系不飽和酯的單體單位 的含量 <來自甲基丙烯酸甲酯的單體單位的含量時> 裝置係使用日本分光股份公司製的FT/IR-7300，依據 厚度0.3mm的薄片之紅外線吸收光譜分析法，藉由下列式 1來求取。 MMA={4.1xlog ( I〇/I ) /t}-5.3 式 1 -21 - 201005066 式1中，MM A爲甲基丙烯酸甲酯的單體單位的含量 (重量％) ，I爲頻率3448 cm·1之透射光強度，1〇爲頻率 3 448cm·1之入射光強度，t爲測定試樣薄片厚度（cm)。 求取U時之基線爲3510~3 310 cnT1。 <來自醋酸乙烯酯的單體單位的含量時> 係依循ns K6730-1981進行測定。 (7 )初期黏著力（單位：N/25mm寬度） 依據JIS-K-Z0237，在23°C的恆溫室中，將層合有基 材層/黏著層之黏著薄膜裁切爲長條狀（寬25mm、長 150mm)，在裁切爲寬50mm、長150mm的大小之偏光板 上，以貼合速度3 00mm/分使貼合軋輥進行1次來回而壓 接，並於23 °C將此放置30分鐘。使用股份公司島津製作 所Autograph AGS-500D，測定出於23°C的氛圍環境中， 在剝離速度300mm/分的條件下藉由180°剝離法將黏著薄 膜從偏光板剝離所需之力，並以此爲初期黏著力。 (8)熱處理後的黏著力（單位：N/2 5 mm寬度） 依據JIS-K-Z0237，在23°C的恆溫室中，將層合有基 材層/黏著層之黏著薄膜裁切爲長條狀（寬25mm、長 150mm)，在裁切爲寬50mm、長150mm的大小之偏光板 上，以貼合速度300mm/分使貼合軋輥進行1次來回而壓 接，以80。(：對此進行3小時的熱處理’再於23 °C放置30 分鐘。使用股份公司島津製作所Aut〇graPh AGS-5 00D ’ 測定出於23t的氛圍環境中’在剝離速度300mm/分的條 201005066 件下藉由180°剝離法將黏著薄膜從偏光板剝離所需之力， 並以此爲熱處理後的黏著力。 (9)熱處理前後的黏著力變動 以初期黏著力與熱處理後的黏著力之値的（=熱處理 後的黏著力/初期黏著力）爲黏著力增進比。此値愈接近 於1，熱處理前後的黏著力變動愈小。 (1〇)熱處理後的膠糊殘留 Q 在23 °C的恆溫室中，將層合有基材層/黏著層之黏著 薄膜裁切爲長條狀（寬25mm、長150mm)，在裁切爲寬 50mm、長150mm的大小之偏光板上，以貼合速度300mm/ 分使貼合軋輥進行1次來回而壓接，以80°C對此進行3小 時的熱處理，再於23 °C放置30分鐘。以目視來觀察於23 °C的氛圍環境中，在剝離速度300mm/分的條件下藉由180 °剝離法將黏著薄膜從偏光板剝離後之樣本的偏光板表面 ，並以下列方式進行評估。 Q X:觀察到膠糊殘留 〇：未觀察到膠糊殘留 (11 )透明性（單位：％ ) 使用所製得之黏著薄膜，依循JIS K 7105來測定霧度 。此値愈小，其透明性愈高。 實施例1 黏著層的樹脂，係預先藉由單軸擠壓機，在230°C中 將成分（A)之95重量份的乙烯-甲基丙烯酸甲酯共聚物 -23- 201005066 (商品名稱：Acryft WH303、住友化學股份公司製、 MFR = 7g/10分、23°C之tan <5 =0.09、甲基丙烯酸甲酯單體 單位含量=18wt% )與成分（B)之5重量份的乙烯-丁烯-1 共聚物（商品名稱：Excellene VL VL700、住友化學股份 公司製、MFR=10g/10分、密度：905kg/m3、庚烷萃取量 =2.0 wt%、分子量分佈=4.6、不均一系觸媒）予以熔融捏 合，而製得成分（A)與成分（B)的混合物（A-B)。上 述（7) 、（8)及（9)的評估用黏著薄膜，係依循下列 方法所製作。 [黏著薄膜的製作] 基材層的樹脂係使用聚乙烯系樹脂（商品名稱：L211 、住友化學股份公司製、MFR = 2g/10分），黏著層的樹脂 係使用上述混合物（A-B)，並使用Tanabe Plastic股份 公司製的30ram φ之2種2層T模具薄膜成形機（T模具 寬度250mm、澆斗嘴開度〇.9mm)，在模具溫度190°C、 冷卻軋輥30°C、拉取速度6.0m/分下，製造出各層的厚度 分別爲黏著層ΙΟμπι，基材層50μιη，總薄膜厚度爲60μιη 之薄膜。 [黏著薄膜的評估] 將所製得之薄膜貼合於偏光板並進行評估。結果如表 1所示。 -24- 201005066 實施例2 除了將成分（A)變更爲90重量份，將成分（B)變 更爲10重量份之外’其他與實施例i相同而製作黏著薄 膜並進行評估。結果如表1所示。 實施例3 除了將成分（A)變更爲70重量份，將成分（B)變 〇 更爲3 0重量份之外，其他與實施例1相同而製作黏著薄 膜並進行評估。結果如表1所示。 實施例4 除了將成分（A)變更爲90重量份的乙烯-醋酸乙烯 酯共聚物（商品名稱：Evertate H301 1、住友化學股份公 司製、MFR = 7g/10分、23°C之tan (5 =0.15、醋酸乙烯酯單 體單位含量=15 wt%)之外，其他與實施例1相同而製作並 φ 進行評估。結果如表1所示。 實施例5 除了將成分（B)變更爲乙烯-丁烯-1共聚物（商品名 稱：Excellene VL EUL731、住友化學股份公司製、 MFR=l〇g/l〇 分、密度：895kg/m3、庚烷萃取量=6.1wt%、 分子量分佈=4.0、不均一系觸媒）之外，其他與實施例1 相同而製作並進行評估。結果如表1所示。 -25- 201005066 實施例6 除了將成分（A)變更爲90重量份的乙烯-己烯-1共 聚物（商品名稱：Excellene FX CX4008、住友化學股份公 司製、MFR=8g/10分、庚烷萃取量=〇.8wt%、密度： 880kg/m3、23 °C 之 tan 5 : 0.02、均一系觸媒）之外，其 他與實施例1相同而製作黏著薄膜並進行評估。結果如表 2所示。 實施例7 除了將成分（A)變更爲90重量份之藉由均一系觸媒 所聚合的乙烯-己烯-1共聚物（商品名稱：Excellene FX CX8008、住友化學股份公司製、MFR=14g/10分、庚烷萃 取量= 0.5wt%、密度：894kg/m3、23°C 之 tan<5 : 0.03、均 一系觸媒）之外’其他與實施例1相同而製作黏著薄膜並 進行評估。結果如表2所示。 比較例1 除了將成分（A)變更爲100重量份的乙烯-甲基丙烯 酸甲酯共聚物（商品名稱：Aery ft WH3 03、住友化學股份 公司製、MFR = 7g/l〇分、23°C之tan5=0.09、甲基丙烯酸 甲酯單體單位含量=1 8wt % )之外，其他與實施例1相同而 製作並進行評估。結果如表3所示。 比較例2 -26- 201005066 除了將成分（B)變更爲10〇重量份的乙烯-丁烯-1共 聚物（商品名稱：Excellene VL VL700、住友化學股份公 司製、MFR=10g/10分、密度：903kg/m3、庚烷萃取量 =2.Owt%、不均一系觸媒）之外，其他與實施例1相同而 製作並進行評估。結果如表3所示。 比較例3 〇 除了將成分（B)變更爲乙烯-丁烯-1共聚物（商品名 稱：Excellene VL VL200、住友化學股份公司製、 MFR = 2g/10 分、密度：900kg/m3、庚烷萃取量=2.5wt%、 不均一系觸媒）之外，其他與實施例1相同而製作並進行 評估。結果如表3所示。 比較例4 除了將成分（B)變更爲乙烯-己烯-1共聚物（商品名 φ 稱：Excellene FX CX4008、住友化學股份公司製、 MFR=8g/l〇 分、密度：880kg/m3、庚院萃取量=0_8wt%、 均一系觸媒）之外，其他與實施例1相同而製作並進行評 估。結果如表3所示。 -27- 201005066 表1 實施例 實施例 實施例 實施例 實施例 1 2 3 4 5 乙烯-乙 23 °C 之tan (5 0.09 0.09 0.09 0.15 0.09 成分 ㈧ 烯系不 飽和酯 乙烯系不飽和 酯單體單位含 量(wt%) 18 18 18 15 18 黏 共聚物 MFR(g/10 分） 7 7 7 7 7 密度(kg/m3) 905 905 905 905 895 著 MFR(g/10 分） 10 10 10 10 10 層 成分 (B) 庚烷萃取量 (wt%) 2.0 2.0 2.0 2.0 6.1 分子量分佈 4.6 4.6 4.6 4.6 4.0 觸媒 不均一系 成分(A)/成分(B)的重量比 95/5 90/10 70/30 90/10 90/10 基材層 聚乙烯系樹脂L211 黏著層/基材層厚度(μπι) 10/50 初期黏著力(N/25mm寬度） 5.4 6.9 7.0 6.8 7.6 熱處理後的黏著力(N/25mm寬度） 8.0 14 19 21 20 黏著力增進比 1.5 2.0 2.7 3.1 2.9 熱處理後的膠糊殘留 〇 〇 〇 〇 〇 透明性(％) 7.5 6.0 5.3 4.7 5.3 201005066 表2The base material layer may be subjected to, for example, antifouling treatment, acid treatment, alkali treatment, primer treatment, anchor coating treatment, corona treatment, plasma treatment, ultraviolet treatment, and antistatic treatment as necessary. The adhesive film contains at least one substrate layer and at least one adhesive layer. The adhesive film is not particularly limited as long as one of the surface layers is an adhesive layer formed of a resin composition containing a specific amount of a component (Α) and a component (Β). The other layer constitution or the number of laminations is not particularly limited. The number of laminations can be, for example, 2 to 7 layers. The layer structure of the adhesive film is, for example, a substrate layer/adhesive layer, a substrate layer/adhesive layer/substrate layer/adhesive layer, a substrate layer/adhesive layer/substrate layer/adhesive layer-18-201005066 The manufacturing method is, for example, a coextrusion molding method or a stack molding method. In the co-extrusion molding method, for example, the base material layer and the adhesive layer can be extruded in a molten state by a generally known method such as a T-die molding method or an inflation molding method, and after laminating, a cooling roll or the like can be used. A method of cooling by means of cooling. In the superposition method, for example, a substrate layer is preliminarily formed by extrusion molding, and an adhesive layer is extruded thereon and laminated, for example, in a molten state, and then cooled by a cooling means such as a cooling roll. method. From the viewpoint of the variety of product design types, a co-extrusion method is preferred. The adhesive film can be stretched in at least a uniaxial direction. When the adhesive film is produced by extrusion molding, the resin temperature at the exit of the extruder can be appropriately selected depending on the type of the molding machine or the kind or molecular weight of the resin used in each layer, and is generally 100 ° C to 3 50. °c, ideally 150~300 °C. The extruder and the mold to be used can be generally used, and there is no particular limitation. # Adhesive film is suitable as a surface protective film. When the adhesive film is used as a surface protective film, the adherend is, for example, a synthetic resin plate, a stainless steel plate (for example, for construction materials), an aluminum plate, a cosmetic plywood, a steel plate, a glass plate, home electric appliances, precision machinery, and at the time of manufacture. An optical member such as a polarizing plate, a phase difference plate, a viewing angle expansion plate, and a brightness enhancement plate used in a flat panel display such as an automobile body or a liquid crystal display device is preferably a polarizing plate or a phase difference plate. The polarizing plate, the phase difference plate, the viewing angle expansion plate, and the brightness enhancement plate respectively include a polarizing film, a retardation film, a viewing angle expansion film, and a brightness enhancement film. Since the adhesive film is excellent in transparency, it is easy to perform defect inspection in the state of being bonded to the adherend, and it is particularly suitable as a surface protective film for optical members. EXAMPLES Hereinafter, the present invention will be more specifically illustrated by the examples. The physical property measurement was carried out as follows. In the tan «5 of the component (A) contained in the adhesive layer, the component (A) was subjected to press molding to prepare a sheet for measurement having a width of 3 mm and a thickness of 0.3 mm. The viscoelasticity measuring apparatus DMS200 manufactured by Seiko Electronics Co., Ltd. was used to measure the distance between the chucks of 20 mm, the temperature increase rate of 5 t /min, and the frequency of 5 HZ, and the measurement enthalpy at 23 ° C was read. (2) Melt flow rate (unit: g/10 min) The melt flow rate of the component (A) and the component (B) is measured according to JIS K7210 at a temperature of 190 ° C and a test load of 21.18 N. . (3) Heptane extraction amount (unit: wt%) The amount of heptane extracted from the ethylene-α-olefin copolymer of the component (A) and the component (B) is immersed in a pellet of 10 μg at 30 ° C After 9 hours of 250 cc of heptane, it was suction-filtered with a glass filter, and the amount extracted in the heptane solution was measured and thereby obtained. (4) Density (unit: kg/m3) The density of the ethylene-α-olefin copolymer of the component (A) and the component (B) -20- 201005066 'According to the A method specified in JIS K7U 2- 1 980 Method was performed. The measurement sample piece was annealed in accordance with the method of low density polyethylene described in JIS K676 0-995, and was used for measurement. (5) Molecular weight distribution The molecular weight distribution of the component (B) was determined by a gel permeation chromatography (GPC) method under the following conditions. Device: 150C ALC/GPC manufactured by Waters Co., Ltd.: Shodex Packed Column A- 8 0M manufactured by Showa Denko Co., Ltd. 2 Root temperature: 1 40 °C Solvent: o-dichlorobenzene solvent solvent flow rate: 1.0 ml/min sample concentration : lmg/ml Determination of injection amount: 400 μl Molecular weight Standard substance: Standard polystyrene © Detector: Differential refractive (6) component (Α1) Content of monomer unit derived from ethylenically unsaturated ester < From methacrylic acid In the case of the content of the monomer unit of the methyl ester, the apparatus was obtained by the following formula 1 using an infrared absorption spectrum analysis method of a sheet having a thickness of 0.3 mm using FT/IR-7300 manufactured by JASCO Corporation. MMA={4.1xlog ( I〇/I ) /t}-5.3 Formula 1 -21 - 201005066 In Formula 1, MM A is the content (% by weight) of the monomer unit of methyl methacrylate, and I is the frequency of 3448 cm. The transmitted light intensity of 1 is 1 〇 is the incident light intensity at a frequency of 3 448 cm·1, and t is the thickness (cm) of the measured sample sheet. The baseline for obtaining U is 3510~3 310 cnT1. <The content of the monomer unit derived from vinyl acetate> was measured in accordance with ns K6730-1981. (7) Initial adhesion (unit: N/25 mm width) According to JIS-K-Z0237, the adhesive film laminated with the substrate layer/adhesive layer was cut into strips in a constant temperature chamber at 23 °C ( The width is 25 mm and the length is 150 mm. The bonding rolls are crimped one at a time at a bonding speed of 300 mm/min on a polarizing plate having a width of 50 mm and a length of 150 mm, and this is crimped at 23 ° C. Leave for 30 minutes. Using the company's Shimadzu Corporation Autograph AGS-500D, the force required to peel the adhesive film from the polarizing plate by a 180° peeling method at a peeling speed of 300 mm/min was measured in an atmosphere of 23 ° C. This is the initial adhesion. (8) Adhesion after heat treatment (unit: N/2 5 mm width) According to JIS-K-Z0237, the adhesive film laminated with the substrate layer/adhesive layer was cut into a constant temperature chamber at 23 ° C. In the strip shape (width 25 mm, length 150 mm), the bonding roll was pressed back and forth at a bonding speed of 300 mm/min on a polarizing plate having a width of 50 mm and a length of 150 mm, and was crimped to 80. (: Heat treatment for 3 hours) and then place at 23 °C for 30 minutes. Use the joint stock company Shimadzu Corporation Aut〇graPh AGS-5 00D' to measure the strip at a stripping speed of 300mm/min in a 23t atmosphere 201005066 The force required to peel the adhesive film from the polarizing plate by the 180° peeling method is used as the adhesive force after the heat treatment. (9) The adhesive force change before and after the heat treatment is the initial adhesive force and the adhesive force after the heat treatment.値 (= adhesion after heat treatment / initial adhesion) is the adhesion enhancement ratio. This cure is close to 1, the change of adhesion before and after heat treatment is smaller. (1〇) The residual Q of the paste after heat treatment is 23 ° In the constant temperature chamber of C, the adhesive film laminated with the substrate layer/adhesive layer is cut into a strip shape (width 25 mm, length 150 mm), and is cut into a polarizing plate having a width of 50 mm and a length of 150 mm. The bonding speed was 300 mm/min, and the bonding rolls were pressed back and forth once, and heat-treated at 80 ° C for 3 hours, and then left at 23 ° C for 30 minutes. The atmosphere was observed visually at 23 ° C. In the case of a stripping speed of 300 mm/min, stripping by 180 ° The surface of the polarizing plate of the sample after peeling the adhesive film from the polarizing plate was evaluated in the following manner. QX: Residual adhesive residue was observed: no adhesive residue was observed (11) Transparency (unit: %) The obtained adhesive film was measured for haze according to JIS K 7105. The smaller the shrinkage, the higher the transparency. Example 1 The resin of the adhesive layer was previously passed through a single-axis extruder at 230 ° C. 95 parts by weight of ethylene-methyl methacrylate copolymer of component (A)-23- 201005066 (trade name: Acryft WH303, manufactured by Sumitomo Chemical Co., Ltd., MFR = 7g/10 minutes, tan < =0.09, methyl methacrylate monomer unit content = 18 wt%) and 5 parts by weight of the ethylene-butene-1 copolymer of the component (B) (trade name: Excellene VL VL700, manufactured by Sumitomo Chemical Co., Ltd., MFR = 10 g/10 min, density: 905 kg/m3, heptane extraction amount = 2.0 wt%, molecular weight distribution = 4.6, heterogeneous catalyst) melt-kneaded to obtain a mixture of the component (A) and the component (B) ( AB). The adhesive films for evaluation of (7), (8) and (9) above are based on the following [Production of the adhesive film] The resin of the base material layer is a polyethylene resin (trade name: L211, manufactured by Sumitomo Chemical Co., Ltd., MFR = 2 g/10 minutes), and the resin of the adhesive layer is the above mixture (AB). ), two types of two-layer T-die film forming machines of 30 ram φ manufactured by Tanabe Plastic Co., Ltd. (T-die width: 250 mm, bucket opening degree 〇.9 mm) were used, and the mold temperature was 190 ° C, and the cooling roll was 30 ° C. At a pulling speed of 6.0 m/min, a film having a thickness of the adhesive layer ΙΟμπι, a substrate layer of 50 μm, and a total film thickness of 60 μm was produced. [Evaluation of Adhesive Film] The obtained film was attached to a polarizing plate and evaluated. The results are shown in Table 1. -24-201005066 Example 2 An adhesive film was prepared and evaluated in the same manner as in Example i except that the component (A) was changed to 90 parts by weight and the component (B) was changed to 10 parts by weight. The results are shown in Table 1. (Example 3) An adhesive film was prepared and evaluated in the same manner as in Example 1 except that the component (A) was changed to 70 parts by weight and the component (B) was changed to 30 parts by weight. The results are shown in Table 1. Example 4 In addition to the component (A), 90 parts by weight of an ethylene-vinyl acetate copolymer (trade name: Everate H301 1, manufactured by Sumitomo Chemical Co., Ltd., MFR = 7 g/10 min, 23 ° C tan (5) The results were as shown in Table 1 except that the content of the component (B) was changed to ethylene. -butene-1 copolymer (trade name: Excellene VL EUL731, manufactured by Sumitomo Chemical Co., Ltd., MFR = l〇g / l 〇, density: 895 kg / m3, heptane extraction amount = 6.1 wt%, molecular weight distribution = 4.0 The results were as follows and were evaluated in the same manner as in Example 1. The results are shown in Table 1. -25 - 201005066 Example 6 In addition to changing the component (A) to 90 parts by weight of ethylene - Hexene-1 copolymer (trade name: Excellene FX CX4008, manufactured by Sumitomo Chemical Co., Ltd., MFR = 8 g/10 min, heptane extraction amount = 〇. 8 wt%, density: 880 kg/m3, 23 °C tan 5 : An adhesive film was prepared and evaluated in the same manner as in Example 1 except for 0.02, homogenous catalyst. The results are shown in Table 2. Example 7 In addition to the component (A) was changed to 90 parts by weight of an ethylene-hexene-1 copolymer polymerized by a homogeneous catalyst (trade name: Excellene FX CX8008, Sumitomo Chemical Co., Ltd.) Company-made, MFR = 14g/10 minutes, heptane extraction amount = 0.5wt%, density: 894kg/m3, 23°C tan<5: 0.03, uniform catalyst) 'Others are the same as in Example 1 The adhesive film was prepared and evaluated. The results are shown in Table 2. Comparative Example 1 In addition to changing the component (A) to 100 parts by weight of an ethylene-methyl methacrylate copolymer (trade name: Aery ft WH3 03, Sumitomo Chemical Co., Ltd. The company made, evaluated, and evaluated the same results as in Example 1 except that the company had a MFR of 7 g/l, a tan5 of 0.2 at 23 ° C, and a monomer content of methyl methacrylate = 18 wt%. Table 3: Comparative Example 2 -26- 201005066 In addition to the component (B), the ethylene-butene-1 copolymer was changed to 10 parts by weight (trade name: Excellene VL VL700, manufactured by Sumitomo Chemical Co., Ltd., MFR = 10 g /10 points, density: 903kg/m3, heptane extraction amount = 2.Owt%, heterogeneous catalyst) Others were produced and evaluated in the same manner as in Example 1. The results are shown in Table 3. Comparative Example 3 The component (B) was changed to an ethylene-butene-1 copolymer (trade name: Excellene VL VL200, Sumitomo Chemical Co., Ltd.) The production was carried out and evaluated in the same manner as in Example 1 except that the company was manufactured by the company, MFR = 2 g/10 minutes, density: 900 kg/m3, heptane extraction amount = 2.5 wt%, and heterogeneous catalyst. The results are shown in Table 3. Comparative Example 4 The component (B) was changed to an ethylene-hexene-1 copolymer (trade name: φ: Excellene FX CX4008, manufactured by Sumitomo Chemical Co., Ltd., MFR = 8 g/l, density: 880 kg/m3, g Other than Example 1, the extraction amount was 0_8 wt%, and the homogeneous catalyst was produced and evaluated. The results are shown in Table 3. -27- 201005066 Table 1 Examples Examples Examples Examples 1 2 3 4 5 ethylene-ethyl 23 ° C tan (5 0.09 0.09 0.09 0.15 0.09 component (eight) ethylenically unsaturated ester ethylenically unsaturated ester monomer Unit content (wt%) 18 18 18 15 18 Viscosity copolymer MFR (g/10 points) 7 7 7 7 7 Density (kg/m3) 905 905 905 905 895 by MFR (g/10 points) 10 10 10 10 10 Layer composition (B) Heptane extraction amount (wt%) 2.0 2.0 2.0 2.0 6.1 Molecular weight distribution 4.6 4.6 4.6 4.6 4.0 Catalyst heterogeneous component (A) / component (B) weight ratio 95/5 90/10 70/ 30 90/10 90/10 Substrate layer polyethylene resin L211 Adhesive layer/substrate layer thickness (μπι) 10/50 Initial adhesion (N/25mm width) 5.4 6.9 7.0 6.8 7.6 Adhesion after heat treatment (N/ 25mm width) 8.0 14 19 21 20 Adhesion improvement ratio 1.5 2.0 2.7 3.1 2.9 Adhesive residue after heat treatment 〇〇〇〇〇 Transparency (%) 7.5 6.0 5.3 4.7 5.3 201005066 Table 2
實施例6 實施例7 黏 著 層 成分 (A) 乙烯-α-烯烴共聚物 MFR(g/10 分） 8 14 庚烷萃取量(wt%) 0.8 0.5 密度(kg/m3) 880 894 23°C2tan<5 0.02 0.03 觸媒 均一系 成分(B) 密度(kg/m3) 905 905 MFR(g/10 分） 10 10 庚烷萃取量(wt%) 2.0 2.0 分子量分佈 3.0 3.0 觸媒 不均一系 成分(A)/成分(B)的重量比 90/10 90/10 基材層 聚乙烯系樹脂L211 黏著層/基材層厚度(μιη) 10/50 初期黏著力(N/25mm寬度） 7.0 6.0 熱處理後的黏著力(N/25mm寬度） 12 6.5 黏著力增進比 1.7 1.1 熱處理後的膠糊殘留 〇 〇 透明性(％) 5.2 4.6Example 6 Example 7 Adhesive layer component (A) Ethylene-α-olefin copolymer MFR (g/10 min) 8 14 Heptane extraction amount (wt%) 0.8 0.5 Density (kg/m3) 880 894 23°C2 tan< 5 0.02 0.03 Catalyst homogeneous component (B) Density (kg/m3) 905 905 MFR (g/10 min) 10 10 Heptane extraction amount (wt%) 2.0 2.0 Molecular weight distribution 3.0 3.0 Catalyst heterogeneous component (A ) / Component (B) Weight ratio 90/10 90/10 Substrate layer Polyethylene resin L211 Adhesive layer / Substrate layer thickness (μιη) 10/50 Initial adhesion (N/25mm width) 7.0 6.0 After heat treatment Adhesion (N/25mm width) 12 6.5 Adhesion improvement ratio 1.7 1.1 Residual paste after heat treatment 〇〇 Transparency (%) 5.2 4.6
-29- 201005066 表3 比較例1 比較例2 比較例3 比較例4 黏 著 層 成分 (A) 乙烯-乙 烯系不 飽和酯 共聚物 23。。之 tan 5 0.09 — 0.09 0.09 乙烯系不飽和酯單 體單位含量(wt%) 18 — 18 18 MFR(g/10 分） 7 — 7 7 成分 (B) 密度(kg/m3) — 905 900 880 MFR(g/10 分） — 10 2 8 庚院萃取量(wt%) — 2.0 2.5 0.8 分子量分佈 ~~ 4.6 5.5 1.8 觸媒 — 不均 一系 均一系 成分(A)/成分(B)的重量比 100/0 0/100 90/10 90/10 基材層 聚乙烯系樹脂L211 黏著層/基材層厚度(μιη) 10/50 初期黏著力(N/25mm寬度） 9.1 5.4 8.9 7.1 熱處理後的黏著力(N/25mm寬度） 70 5.4 72 67 黏著力增進比 7.7 1.0 8.1 9.4 熱處理後的膠糊殘留 〇 X 〇 〇 透明性(％) 8.0 5.8 6.5 5.3-29-201005066 Table 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Adhesive layer Component (A) Ethylene-ethylenically unsaturated ester copolymer 23. . Tan 5 0.09 — 0.09 0.09 Ethylene Unsaturated Ester Monomer Unit Content (wt%) 18 — 18 18 MFR (g/10 min) 7 — 7 7 Ingredient (B) Density (kg/m3) — 905 900 880 MFR (g/10 points) — 10 2 8 Gengyuan extraction amount (wt%) — 2.0 2.5 0.8 Molecular weight distribution ~~ 4.6 5.5 1.8 Catalyst - Heterogeneous homogeneous component (A) / component (B) weight ratio 100 /0 0/100 90/10 90/10 Substrate layer polyethylene resin L211 Adhesive layer/substrate layer thickness (μιη) 10/50 Initial adhesion (N/25mm width) 9.1 5.4 8.9 7.1 Adhesion after heat treatment (N/25mm width) 70 5.4 72 67 Adhesion improvement ratio 7.7 1.0 8.1 9.4 Residue of paste after heat treatment 〇〇X 〇〇Transparency (%) 8.0 5.8 6.5 5.3