201041947 六、發明說明： 【發明所屬之技術領域】 本發明係關於表面保護用聚丙烯系樹脂膜及表面保護 膜者，詳而言之，係關於髙溫時的熱變形耐性或平面性高’ 例如在黏著加工等的加工適性優異，且添加劑的移行性 少，進而適合作爲魚眼少的各種用途，特別是適合作爲各 . 種物品的表面保護用之表面保護用聚丙烯系樹脂膜、及使 • 用該表面保護用聚丙烯系樹脂膜之表面保護膜者。 Ο 【先前技術】 聚丙烯系無延伸薄膜由於透明性良好且便宜，所以被 廣泛地使用於以食品包裝等各種的包裝材料及各種物品的 表面保護爲目的之表面保護膜的基材。 此外，被使用作爲用於保護金屬板、化妝板、樹脂板、 玻璃板等、液晶面板與偏光板等的相關材料等的電子精密 製品、零件及相關構件、汽車的塗膜用的表面保護膜，又 被使用作爲爲了保護用以部分電鑛可撓性·印刷基板的連 〇 接端子部等用的光阻膜或抗鈾刻膜之表面保護膜，及被使 用作爲經由將薄膜積層於半導體元件沒有電路之面上而用 以保護半導體元件表面用的表面保護膜。 隨著近年用途的擴大對於品質與成本減低的要求也隨 之增強，除了貼合於被保護體的加工適性之外，還要求加 工黏著劑的容易度方面優異之表面保護用薄膜。 特別是基於提昇黏著加工的加工速度等的目的，亦要 求加工溫度的高溫化提昇，即使在高溫下加工黏著劑，該 201041947 加工溫度之熱變形小且加工時的尺寸安定性良好（亦僅稱 爲耐熱尺寸安定性）。 關於聚丙烯系薄膜，已揭示有一些作爲使上述的耐熱 尺寸安定性提昇的技術（例如，參照專利文獻1 ~ 4} 然而，專利文獻1中所揭示的熱封性聚丙烯薄膜係剛 . 性不充分，而專利文獻2中所揭示的透明聚丙烯薄片則貼 '合有困難。 ’又，專利文獻3及專利文獻4中記載的表面保護用聚 〇 丙烯薄膜係剛性也很大，貼合加工適性方面差。 此外，將薄膜卷繞於軋輥上時，會有所謂皺折或波紋 容易產生的問題。 又，在塗布黏著劑時，會有所謂薄膜變形的問題。 先行技術文獻 專利文獻 專利文獻1 特開平09-12657號公報 專利文獻2 特開2003- 170485號公報 〇 專利文獻 3 W02006/057294 專利文獻4 特開2007-270005號公報 【發明內容】 發明所欲解決之課題 本發明係提供一種耐熱尺寸安定性與平面性優異、耐 衝撃性與貼合加工性優異、魚眼少、進而卷繞於軋輥上時 沒有鈹折或波紋，例如適合作爲保護膜的基材薄膜之表面 保護用聚丙烯系樹脂膜，及將黏著層設置於該表面保護用 201041947 聚丙烯系樹脂膜上而成之保護膜。 【實施方式】 解決課題之手段 本發明者等係爲了解決上述的課題而反覆專心檢討的 結果，終於完成本發明。 . 亦即’本發明係關於一種表面保護用聚丙稀系樹脂 膜，係實質上以聚丙烯系樹脂爲主成分之聚丙嫌系樹脂 膜，其特徵在於：其係20°C二甲苯可溶部量超過9%、低 〇 於16%，結晶核劑的含有率爲lOOppm以下，薄膜的寬度 方向的厚度變動率爲1 %以上、10%以下，動摩擦係數爲 1.0以下，拉伸彈性模數爲500MPa以上、900MPa以下 之表面保護用聚丙烯系樹脂膜。 在該情形中，薄膜中的防黏連劑的含量爲50 ppm以 下，抗黏連性爲l〇mN以下爲佳》 又，在該情形中，薄膜中的最大直徑爲0.2mm以上的 魚眼爲〇個/ m2,且最大直徑爲低於0.2mm的魚眼爲100 W 個/ m2以下爲佳。 又再者，在該情形中，薄膜在23 °C中的縱向方向的楊 氏模數爲500Mpa以上爲佳。 又再者，在該情形中，薄膜在23 °C中的衝擊強度爲 0.3J以上爲佳。 又再者，在該情形中，含有至少丙烯酸酯系抗氧化劑， 且含有由磷系抗氧化劑及酚系抗氧化劑之中所選出的至少 1種抗氧化劑爲佳。 .201041947 又再者，在該情形中，上述薄膜的2 0 t：二甲苯可溶部 量的變動幅爲2 %低於爲佳。 又再者’本發明係在上述的表面保護用聚丙烯系樹脂 膜之至少單面上，設置有黏著劑層而形成的表面保護膜。 發明的效果 . 本發明係耐熱尺寸安定性與平面性優異，耐衝撃性、 貼合加工性與白化防止效果優異，魚眼少，進而卷繞於軋 ‘輥上時沒有皺折或波紋，適合作爲例如保護膜的基材薄膜。 〇 本發明的表面保護用聚丙烯系樹脂膜由於耐熱尺寸安 定性優異，所以例如，黏著加工等的二次加工適合性優異， 特別是由於即使在130 °C附近的高溫中進行乾燥等的處 理’熱皺與薄膜鬆弛的發生受到抑制，所以能夠抑制因爲 該二次加工的生產性提昇、熱皺、薄膜鬆弛爲起因的不良 品的發生。 又，本發明的聚丙烯系樹脂膜實質上不含有防黏連劑 爲佳’例如由於可迴避在使含有防黏連劑之薄膜行進的情 ^ 形中，因磨耗等而引起防黏連劑脫落的課題，所以因該脫 落物所致的污染與障礙發生等受到了抑制。 又，本發明實質上不含有滑劑與防黏連劑也沒有關 係’由於表面粗糙度適當，薄膜的光滑性與抗黏連性良好， 且剛性優異，所以薄膜的操作性優異。 又，由於透明性優異，所以被保護體的視認性優異。 又，因爲薄膜有強度，所以操作性優異。 .又，雖然上述的耐熱尺寸安定性提昇了，卻衝擊強度 201041947 優異，藉由從嵌段聚丙烯系樹脂所形成而附加之耐衝撃性 的好處受到維持，在作爲保護膜而使用的情形中可靠性高。 實施發明的最佳形態 本發明的聚丙烯系樹脂膜係以聚丙烯系樹脂爲主成 分，較佳係在薄膜中含有7 〇重量％以上的聚丙烯系樹脂爲 佳，而且含有8 0重量％以上爲佳。 •在本發明中所使用的聚丙烯系樹脂係可藉由混合由同 '元聚丙烯樹脂、共聚合乙烯與其他的α-烯烴之無規共聚合 Ο 聚丙烯樹脂、嵌段共聚合聚丙烯樹脂中的1種至3種而使 用。 從透明性的點而言，主要使用同元聚丙烯樹脂、或共 聚合乙烯與其他的 α -烯烴之無規共聚合聚丙烯樹脂爲 佳，使衝撃性與光滑性、特別是使抗黏連性提昇之情形係 主要使用嵌段共聚合聚丙烯樹脂爲佳。混合比係可任意地 調整。 關於上述聚丙烯系樹脂的組成係沒有特別地限定，若 〇 爲無規共聚合聚丙烯樹脂，從耐熱尺寸安定性的面而言以 α -烯烴含量爲5%以下爲佳。又，若爲嵌段共聚合聚丙烯 樹脂，從耐熱尺寸安定性與光滑性、抗黏連性的面而言， 以20°C二甲苯可溶部量爲3~50%爲佳，較佳爲5~30%的 範圍。 上述聚丙烯系樹脂全體的極限黏度爲1.5~4.0、20°C 二甲苯可溶部的極限黏度爲1.0~4.0、20°(：二甲苯不溶部 的極限黏度爲1.0~4.0者爲佳。又，本發明所使用之聚丙 201041947 烯系樹脂的熔融流速係在230°C中爲2~20g/10分者爲佳。 作爲在本發明中所使用的α -烯烴無規共聚物彈性 體，係可使用乙烯-丙烯、乙烯-丁烯或丙烯-丁烯的二元 系、乙烯-丙烯-丁烯的三元系共聚物或彼等的混合物。又， 在不損及其特性之範圍內，亦可使用進一步共聚合其他單 體之共聚物。特別是使用上述二元系共聚物爲佳。又，從 .可賦予積層體良好的彈性力之點而言，使用維卡軟化點爲 • 60 °C以下，且表面硬度爲8 0°以下者爲佳。 〇 在本發明中，特別是含有嵌段共聚合聚丙烯樹脂者， 以耐熱性與光滑性之點而言爲佳。 又，亦可根據各種的目的，而添加其他少量的α -烯烴 無規共聚合彈性體與多離子聚合物、其他母料類。 本發明的聚丙烯樹脂膜係必須2 0 °c二甲苯可溶部量 超過9%、低於16%。 如果爲9 %以下’則在高溫加工時薄膜容易塑性變形， 且薄膜的貼合適性與白化防止效果變差。 Ο 若爲1 6%以上’由於薄膜太容易拉伸，黏著劑塗布加 工適性變差而爲不佳。又，20 °C二甲苯可溶部量係其下限 從薄膜彎曲之際的白化防止之點而言1 0%以上爲較佳，又 從薄膜的抗黏連特性的面而言1 4%以下爲較佳。 在本發明中，如上述般沒有在一般聚丙烯系樹脂膜中 所實施的滑劑與防黏連劑的配合者爲佳，該情形係有抑制 薄膜的光滑性與黏連性的惡化之必要。該對應係藉由前述 之樹脂組成、特別是藉由來自嵌段共聚合樹脂與乙烯系共 201041947 聚合彈性體之海/島構造所致的薄膜表面突起而進行爲佳。 此時’作爲本發明薄膜的光滑特性，以後述之評價， 係有動摩擦係數爲1.0以下之必要。又，〇·9以下爲更佳， 0.8以下爲最佳。 動摩擦係數在該範圍外時，當將薄膜卷繞於乳輥上 時、薄膜間的空氣逸散時，薄膜彼此的黏性容易產生，且 • 成爲皺折或波紋產生的要因之一。 • 又，作爲本發明的薄膜的抗黏連特性，利用後述之評 Ο 價，以l~l〇mN以下爲佳。l~7mN以下爲更佳。 另一方面，來自該嵌段共聚合樹脂之海/島構造所致的 薄膜表面突起的形成由於會引起薄膜的透明性降低，所以 在該方法中，所謂因形成表面突起之光滑性與抗黏連性的 改善效果和透明性的確保，係爲自相矛盾現象。因此，薄 膜的霧度値係成爲重要的要因。 因此，在本發明中，薄膜的霧度値爲40%以下係爲重 要的。35%以下爲佳，30%以下爲較佳。藉由使霧度値爲 ^ 40%以下，被包裝物與被保護體的視認性係爲提昇，在作 爲包裝袋材料使用之情形中，被包裝物的内容確認係爲容 易。又，在作爲表面保護膜用材料使用之情形中，係可在 貼附表面保護膜之後，立即進行例如被保護體的檢査等。 相反地，霧度値超過40%的情形，由於透明性惡化，且被 包裝物與被保護體的視認性降低而爲不佳。另一方面，霧 度値的下限爲低的話由於透明性提昇而爲佳，但在與利用 上述方法而賦予光滑性之點的關連中，以5%以上爲佳， -10- 201041947 1 ο %以上爲較佳。 脂膜係在薄膜中 t量爲50ppm以 ，較佳，特佳係利 險測極限以下爲 此處，所謂的實 情形有相同的意 次加工步驟中因 抑制，所以因該 制。 係薄膜中的聚乙 酸醯胺等的滑劑 含量爲lOppm以 的通常定量方法 有滑劑爲佳。此 積極地添加滑劑 滑劑，由於包含 而微量混入之情 態樣。藉由該對 的方法中，所發 的或因朝被保護 且被保護體的澄 又，本發明的表面保護用聚丙烯系樹> 的無機及/或有機微粒子等的防黏連劑的专 下爲佳。防黏連劑的含量係1 〇 P P m以下爲 用灰分與元素分析等的通常定量方法爲 佳。亦即，實質上不含有防黏連劑爲佳。 . 質上不含有防黏連劑，係與上述的滑劑的 •思。藉由該對應，由於在薄膜的製造及二 〇 薄膜的磨耗所致之防黏連劑的脫落受到了 脫落物所致的污染與障礙發生等受到了抑 本發明的表面保護用聚丙烯系樹脂膜 烯蠟、硬脂酸鈣、芥酸醯胺、伸乙基雙芥 的含量爲50ppm以下爲重要的。滑劑的1 下爲較佳，特佳係以元素分析與抽出法等 爲檢測極限以下爲佳。亦即，實質上不含 處，所謂的實質上不含有滑劑，係意旨不 〇 而進行製膜。上述範圍即使不積極地添加 在原料聚合物與薄膜製造時因品牌替換等 形，所以實質上不含有滑劑爲較佳的實施 應，在配合該滑劑而使薄膜的光滑性提昇 生的該滑劑朝薄膜表面的遷移及繼續發生 體移行所致的被保護體的污染受到阻止 清度係爲保持。 在本發明中，拉伸彈性模數必須爲5 Ο Ο M Pa以上、 201041947 900MPa以下。 拉伸彈性模數過小時，在將薄膜軋輥纏繞之際，薄膜 變形1其結果應力殘留在軋輥上，而形成皺折或波紋產生 的問題。相反地，拉伸彈性模數過大時，黏著劑塗布後的 薄膜貼合變得困難。 _ 本發明的表面保.護用聚丙烯系樹脂膜，係由後述之測 • 定方法所致的薄膜的結晶化度爲3 4 ~ 6 5 %爲佳。結晶化度 • 低於34%的話，由於難以發現耐熱尺寸安定性，且在後步 〇 驟中實施加工之際容易發生薄膜的波紋與拉伸，平面性不 良之故而爲不佳。另一方面，結晶化度超過6 5%的情形， 由於薄膜的透明性顯著地劣化而爲不佳。又，結晶化度超 過6 5%的情形，楊氏模數變大，貼合加工適性變差。 薄膜的結晶化度的下限係40%以上爲較佳，從耐熱尺 寸安定性之觀點而言，50%以上爲最佳。另一方面，薄膜 的結晶化度的上限爲60%以下，從透明性的觀點而言爲佳。 又，本發明的表面保護用聚丙烯系樹脂膜亦可爲：利 〇 用實質上不含有結晶核劑之製造方法而達成所期望的結晶 化度（34 ~ 6 5%)之聚丙烯系樹脂膜。作爲製造方法，可使拉 伸·冷却固化熔融樹脂之際的冷却軋輥溫度高溫化，又可利 用熱處理（退火）而達成。 本發明的表面保護用聚丙烯系樹脂膜，若結晶核劑爲 lOOppm以下的範圍的話可以添加。藉由添加結晶核劑， 能夠提昇薄膜的耐熱尺寸安定性。另一方面，添加結晶核 劑超過lOOppm時，即使以樹脂的熔融壓出條件，亦會發 -12- 201041947 生有薄膜中的魚眼增加的傾向而成爲問題 除去樹脂中的異物爲目的，由於會因配置 器堵塞而進行昇壓等的使生產性下降等的 佳。 該結晶核劑係可予以限定，可舉例如 . 鹽爲主成分之結晶核劑、山梨糖醇系的結 ‘ 族有機磷酸酯金屬鹽所形成之結晶核劑等 '又，本發明的表面保護用聚丙烯系樹 Ο 射率（Δη)爲 〇_4xl〇-3~2.5xl〇-3。雙折射】 的情形，則各向異變得過大，而容易成爲 因。 另一方面，雙折射率低於0.4 X 1 0 -3的 拉伸容易產生，平面性不良且耐熱尺寸安 佳。從維持耐熱尺寸安定性與平面性的觀 射率爲Q.6X10-3以上爲佳，又爲0.8x10 另一方面，從防止薄膜的皺折或波紋的觀 C\ w 射率爲2.3 χ 1 0-3以下爲佳，又爲2 ·2 χ 1 0 在本發明中，本發明的表面保護用聚 薄膜在2 3 °C的衝擊強度爲0.3 J以上爲佳 佳。一般當提昇上述的剛性與耐熱尺寸安 度係朝向降低的方向。該衝擊強度降低時 袋與保護膜等使用之情形對於使用時的耐 降低，所以除了賦予前述之特性之外，能滿 上限係根據與其他特性的平衡，0.8 J左ΐ 的情形。又，以 有壓出機之過濾 問題發生而爲不 以松香類的金屬 晶核劑及由芳香 〇 脂膜較佳係雙折 率超過2.5x10-3 皺折或波紋的要 話，由於薄膜的 定性變差而爲不 點，薄膜的雙折 •3以上爲較佳。 點，薄膜的雙折 _3以下爲較佳。 丙烯系樹脂膜係 。0.5 J以上爲較 定性時，衝擊強 ，由於作爲包裝 衝撃性之可靠性 i足本特性爲佳。 ί爲佳。 -13- 201041947 賦予上述衝擊強度的方法雖然沒有限定’但是受到上 述之乙烯含量很大的影響。較佳係達成含有該乙嫌含量之 本說明書中記述的較佳實施態樣的總合效果。 在本發明中，本發明的表面保護用聚丙烯系樹脂膜係 薄膜中的最大直徑爲Q.2mm以上的魚眼爲〇個/ m2爲佳。 此外，最大直徑低於〇.2111111的魚眼爲100個/ m2以下爲 .佳。最大直徑低於Q.2 m m的魚眼爲0個/ m 2以下爲最佳’ •基於經濟性與市場的要求度等，較佳在上述範圍內。2~80 〇 個/ m2以下爲較佳，2~60個/ m2以下爲更佳。此外，可目 視判定之魚眼的最小直徑係爲 〇.〇3 ~ 0.0 5 mm。藉由該對 應，在外觀不良、與例如在作爲保護膜的基材薄膜使用之 情形中，可抑制因前述之黏著不良所致的電鍍液對保護部 分的浸透所引起的障礙發生等。 " 達成上述特性的手段雖然沒有限定，但是最佳可如後 述般進行抗氧化劑的配合9 本發明所謂的丙烯酸酯系抗氧化劑，係分子内具有含 〇 丙烯酸酯殘基之苯酚衍生物的抗氧化劑。作爲丙烯酸酯化 合物’可舉出例如2,4-二-第三戊基_6-[1-(3,5 -二-第三戊 基-2 -羥苯基）乙基]苯基丙烯酸酯、2,4_二-第三戊基 -6-[l-(3,5 -二-第三戊基-2-羥苯基）丁基丨苯基丙烯酸酯、 2,4-二-第三戊基-6-[1-(3,5-二-第三戊基-2-羥苯基）丙基] 苯基丙烯酸酯、2-第三丁基-6-(3_第三丁基-2_羥基-5_甲 苄基）-4-甲基苯基丙烯酸酯等。 較佳係2,4-二-第三戊基- 6- [l-(3,5 -二-第三戊基- 2- -14- 201041947 羥苯基）乙基】苯基丙烯酸酯及2-第三丁基- 6-(3-第三丁基 -2-羥基-5-甲苄基）-4-甲基苯基丙烯酸酯。 作爲上述丙烯酸酯化合物，可由市售品中適宜選擇而 使用。可舉出例如2 -第三丁基- 6- (3 -第三丁基-2-羥基- 5-甲苄基）-4-甲基苯基丙烯酸酯之住友化學（股）製 Sumilizer GM(註冊商標）、2,4-二-第三戊基-6-[l-(3,5-* 二-第三戊基-2-羥苯基）乙基]苯基丙烯酸酯之住友化學（股） ’ 製Sumilizer GS(註冊商標）等。特別是，Sumilizer GS(註 〇 冊商標）的使用爲佳。 在本發明中上述丙烯酸酯系抗氧化劑的配合量係沒有 限定，惟相對於上述之全聚丙烯系樹脂組成物，在 100~10〇Qppm的範圍爲佳。在200~800ppm爲較佳，在 3〇〇~70〇ppm爲更佳。超過lOOOppm的情形，在製膜步 驟中，由於冷却軋輥的污染增大而爲不佳。薄膜也因爲會 染成抗氧化劑特有的淡黃色而爲不佳。相反地，低於 10 Oppm的話，由於後述之倂用效果減低而爲不佳。僅將 Θ 上述丙烯酸酯系抗氧化劑降低的比上述之2種抗氧化劑的 配合量上限要低爲佳，推測其成因是因爲該丙烯酸酯系抗 氧化劑與其他的抗氧化劑相比，聚丙烯系樹脂對於橡膠成 分的溶解性高，所以會朝薄膜中的橡膠成分被大量分配， 且由於該橡膠成分部分與原料樹脂相比會更因冷却軋輥而 使得結晶化速度較慢，在與冷却軋輥接觸之情形中，分配 於該橡膠成分之上述的丙烯酸酯系抗氧化劑由於會容易往 冷却軋輥移行而提高冷却軋輥的污染度。 -15- .201041947 例如，在使用前述專利文獻2 3等所揭示之同元聚丙烯 樹脂的製膜中不會發生本發明中發生的特有現象。 作爲上述的磷系抗氧化劑的具體例，可舉出例如分子 中含有3價的磷原子，其磷原子係至少1個具有P-0-C鍵 的熱安定劑。例如，亞磷酸三丁基酯、亞磷酸三辛基酯、 亞磷酸三月桂基酯、亞磷酸三硬脂基酯、亞磷酸三癸基酯、 亞磷酸三甲苯基酯、亞磷酸三環己基酯、亞磷酸三苯基酯、 亞磷酸三月桂硫基酯、參（2 -乙基己基）亞磷酸酯、參（異癸 〇 基）亞磷酸酯、參（三癸基）亞磷酸酯、參（2,4 -二-第三丁基 苯基）亞磷酸酯、參（丁氧基乙基）亞磷酸酯、參（壬基苯基） 亞磷酸酯、參（3,5 -二-第三丁基-4-羥苯基）亞磷酸酯、參 [4,4' -異亞丙基雙（2 -第三丁基酚）]亞磷酸酯、參（1,3 -二-硬脂醯氧基異丙基）亞磷酸酯、亞磷酸2 -乙基己基二苯基 酯、亞磷酸癸基二苯基酯、亞磷酸苯基二-2-乙基己基酯、 亞磷酸苯基二癸基酯、亞磷酸苯基二異癸基酯、苯基二（三 癸基）亞磷酸酯、亞磷酸二苯基壬基酯、亞磷酸二苯基異辛 ^ 基酯、亞磷酸二苯基異癸基酯、二苯基單（三癸基）亞磷酸 酯、亞磷酸二丁基氫酯、4，^Γ -異亞丙基二酚烷基（C12~C15) 亞磷酸酯、4,4'-亞丁基雙（3-甲基-6-第三丁基苯基）二-三 癸基亞磷酸酯、2,2 -亞甲基雙（4,6-二-第三丁基苯基）辛基 亞磷酸酯、2,2'-亞乙基雙（4,6-二-第三丁基酚）氟亞磷酸 酯、雙（2,4-二-第三丁基-6-甲基苯基）.乙基亞磷酸酯、 4,4·-異亞丙基雙（2-第三丁基酚）.二（壬基苯基）亞磷酸 酯、二硬脂基季戊四醇二亞磷酸酯、二（壬基苯基）季戊四 -16 - 201041947 醇二亞磷酸酯、二苯基季戊四醇二亞磷酸酯、苯基.4,4'-異亞丙基二酚.季戊四醇二亞磷酸酯、雙（4,6-二-第三丁基 苯基）季戊四醇二亞磷酸酯、雙（2,6-二-第三丁基-4-甲基苯 基）季戊四醇二亞磷酸酯、苯基-雙酚A季戊四醇二亞磷酸 酯、四苯基二丙二醇二亞磷酸酯、四（三癸基）-1,1,3-參（2-甲基-5 -第三丁基-4 -羥基苯基）丁烷二亞磷酸酯、四 (C12-C15混合烷基）-4,4丨-異亞丙基二苯基二亞磷酸酯、 四（三癸基）-4,4'-亞丁基雙（3-甲基-6-第三丁基酚）二亞磷 〇 酸酯、肆（4,6 -二-第三丁基苯基）-4,4'-伸聯苯基二膦酸 酯、肆（2 -甲基-4,6 -二-第三丁基苯基）-4,4'-伸聯苯基二膦 酸酯、雙（辛基苯基）·雙[4,41-亞丁基雙（3-甲基-6-第三丁 基酚）].1，6 -己二醇二亞磷酸酯、氫化-4,4'-異亞丙基二酚 聚亞磷酸酯、9、10 -二氫-9-氧雜-9-氧雜-10 -磷雜菲-10-氧化物、2-[{2,4,8，1〇-肆（1,1-二甲基乙基）二苯并 (E>，F)(1，3,2)-二噁磷環庚烷，6-基}氧基]-N，N-雙 〔2-[{2,4,8,10-肆（1，卜二甲基乙基）二苯并（D，F)(1，3,2)· Ο 二噁磷環庚烷-6-基}氧基]乙基〕乙烷胺、H3-參（2_甲基 -4-二-三癸基亞磷酸酯-5-第三丁基苯基）丁烷、3,4,5,6_ 四苯并-1,2-氧代憐酸甘油酯-2-氧化物等。 較佳係不具有季戊四醇骨架者，參（2,4 -二-第三丁基 苯基）亞磷酸酯、參（3,5 -二-第三丁基-4_羥基苯基）亞磷酸 酯、雙（2,4-二-第三丁基-6-甲基苯基）_乙基亞磷酸酯 '肆 (2-甲基-4,6-二-第三丁基苯基卜4,4ι_伸聯苯基二膦酸酯。 作爲在本發明所使用的磷系抗氧化劑，亦可使用市售 -17- 201041947 品，可舉出例如 IRGAFOS 168(Ciba Specialty Chemicals 公司製）、IRGAFOS 3 8 ( C i b a Specialty Chemicals公司製）、GSY-P101(吉富精密化學公司製）、 Ultranox 641(GE Specialty Chemiclas 公司製）等。 在本發明中上述磷系抗氧化劑的配合量係沒有限定， 惟相對於上述之全聚丙烯系樹脂組成物，在 500~5000ppm 的範圍爲佳 ° 10QO~4000ppm 爲較佳， 1500~3000ppm爲更佳。低於500ppm的話，由於倂用後 〇 述之抗氧化劑的效果減少而爲不佳。相反地，超過 5000ppm的情形，由於倂用後述之抗氧化劑的效果飽和， 且會引起因該抗氧化劑朝薄膜表面移行所引起的薄膜白化 與污染在製膜步驟的冷却軋輥等而爲不佳。 在本發明中所使用的酚系抗氧化劑，係在分子内具有 苯酚衍生物的抗氧化劑，可舉出例如2,6-二-第三丁基_4-甲基酚、2,6-二-第三丁基-4-乙基酚、2,6-二環己基-4-甲 基酚、2,6-二-第三戊基-4-甲基酚、2,6-二-t-辛基-4-n-O 丙基酚、2，6-二環己基- 4-n-辛基酚、2-異丙基-4-甲基- 6-第三丁基酚、2-第三丁基-2-乙基-6-1-辛基酚、2-異丁基 -4-乙基-6-t-己基酚、2-環己基-4-n-丁基-6-異丙基酚、 dl-iz-生育酚、第三丁基氫醌、2,2'-亞甲基雙（4-甲基- 6-第三丁基酚）、4,4'-亞丁基雙（3-甲基-6-第三丁基酚）、4,4·-硫代雙（3 -甲基-6-第三丁基酚）、2,2-硫代雙（4 -甲基-6-第 三丁基酚）、4,4'-亞甲基雙（2，6-二-第三丁基酚）、2,2'-亞 甲基雙[6-(1-甲基環己基）-p_甲酚]、2,2'-亞乙基雙（4,6- -18- 201041947 二-第三丁基酚）、2,2'-亞丁基雙（2-第三丁基-4-甲基酚）、 2-第三丁基- 6-(3-第三丁基-2-羥基-5-甲苄基）-4 -甲基苯 基丙烯酸酯、2-[1-(2-羥基- 3,5-二-t-戊基苯基）乙基]-4,6-二-t-戊基苯基丙烯酸酯、1,1,3-參（2 -甲基-4-羥基-5-第三 丁基苯基）丁院、三甘醇-雙[3_(3_第三丁基_5_甲基·4 -羥苯 基）丙酸酯】、1,6 -己二醇-雙[3-(3,5_二-第三丁基_4 -羥苯 基）丙酸酯]、2,2-硫二伸乙基雙丨3_(3,5_二-第三丁基-4 -經 本基）丙酸酯]、Ν，Ν’-六亞甲基雙（3,5-二-第三丁基_4_羥基 〇 -氫桂皮醯胺）' 3,5-二-第三丁基-I羥基苄基磷酸酯-二乙 基醋、參（2,6-二甲基經基-4_第三丁基节基）異三聚氰酸 醋、參（3,5 -二-第三丁基_4_羥基苄基）異三聚氰酸酯、參 [(3,5 -二-第三丁基羥苯基）丙醯氧基乙基]異三聚氰酸 酯、參（4-第三丁基-2,6_二甲基_3_羥基苄基）異三聚氰酸 酯、2,4-雙（η-辛硫基卜6_(4_經基-3,5-二-第三丁基苯胺 基）-1，3,5-三阱、肆[亞甲基_3_(3,5_二-第三丁基-4-羥苯 基）丙酸酯]甲院、2,21-亞甲基雙（4 -甲基-6-第三丁基酣）對 Θ 苯二甲酸酯、1，3,5-三甲基_2,4,6_參（3,5-二-第三丁基- 4-羥基苄基）苯、3,9-雙以，卜二甲基_2-{/3-(3-第三丁基- 4-經基-5-甲基苯基）丙醯氧基}乙基卜2,4，8,10 -四氧雜螺 [5,5]十一碳烷、2,2_雙[4_(2_(3,5_二-第三丁基-4-羥基氫 桂皮醯氧基））乙氧基苯基]丙烷、0-(3,5-二-第三丁基- 4-羥苯基）丙酸硬脂基醋等。 較佳係冷-(3,5-二-第三丁基-4-羥苯基）丙酸硬脂基 酯、肆[亞甲基-3-(3，5_二-第三丁基—4-羥苯基）丙酸酯]甲 -19- 201041947 烷、參（3,5-二-第三丁基-4-羥基苄基）異三聚氰酸酯、 1，3,5-三甲基-2,4,6-參（3,5-二-第三丁基-4-羥基苄基） 苯、dl-α-生育酚、參（2,6-二甲基-3-羥基-4-第三丁基苄 基）異三聚氰酸酯、參[(3,5-二-第三丁基-4-羥苯基）丙醯氧 基乙基]異三聚氰酸酯、3,9-雙[1,1-二甲基-2-{冷-(3-第三 丁基-4-羥基-5-甲基苯基）丙醯氧基}乙基]-2,4,8,10-四氧 雜螺[5,5]十一碳烷。 作爲在本發明中所使用的酚系抗氧化劑，亦可使用市 〇 售品，可舉出例如 IRGANQX l〇l〇(Ciba Specialty Chemicals 公司製）、IRGANOX 1 〇76(Ciba Specialty Chemicals 公司製）、IROANOX 1 3 3 0 ( C i b a Specialty Chemicals 公司製}、IRGANOX 3114(Ciba Specialty Chemicals 公司製）、IRGANOX 1425WL(Ciba Specialty Chemicals公司製）等。 在本發明中上述酚系抗氧化劑的配合量係沒有限定， 惟相對於上述之全聚丙烯系樹脂組成物，在 〇 500~5000ppm 的範圍爲佳。1000~4000ppm 爲較佳， 1500~3000ppm爲更佳。低於500ppm的話，由於倂用後 述抗氧化劑的效果減少而爲不佳。相反地，超過5000ppm 的情形，由於倂用後述之抗氧化劑的效果飽和，且會引起 因該抗氧化劑朝薄膜表面移行所引起的薄膜白化與污染在 製膜步驟的冷却軋輥等而爲不佳。 在本發明中，如前述般含有從丙烯酸酯系抗氧化劑、 與由磷系抗氧化劑及酚系抗氧化劑之中所選出的至少1種 -20- 201041947 中所選出的至少2種抗氧化劑者爲佳，惟倂用丙稀酸 抗氧化劑、磷系抗氧化劑及酚系抗氧化劑3種者爲較 施態樣。 上述3種的抗氧化劑係在個別每1種的倂用上沒 定。可倂用各種類之中的2種以上，除了上述3種的 化劑以外，亦可更倂用例如硫系抗氧化劑等的其他構 抗氧化劑。 藉由倂用上述複數種的抗氧化劑，可發現以往眾 Ο 知的抗氧化劑的組合所不能得到的高度魚眼之混入抑 效果。 酚系抗氧化劑及磷系抗氧化劑對於上述原料樹脂 物的各成分之抗氧化效果的選擇性少，丙烯酸酯系抗 劑已知與聚丙烯系嵌段共聚物的橡膠部的親和性強且 先抑制橡膠部劣化的傾向。另一方面，關於魚眼的生 對於橡膠部的劣化影響很大。爲此，藉由倂用上述複 的抗氧化劑，推測是與魚眼的大幅低減有關者。 〇 又，本發明的表面保護用聚丙烯系樹脂膜係薄膜 度方向的厚度變動率在1〜10 %的範圍爲佳。厚度變動 於1 %的情形，雖然在品質面沒有發生問題，但是由於 調整時所需要的時間變得膨大，所以會有經濟性顯著 而不符合現實。另一方面，厚度變動率超過1 0 %的情 由於薄膜的平面性（波紋縐折或卷曲）惡化，又卷繞於 上時會產生鈹折或波紋而爲不佳。厚度變動率在 Ι.ί 爲較佳，2 ~ 5 %的範圍爲最佳。 酯系 佳實 有限 抗氧 造的 所周 制的 組成 氧化 有優 成， 數種 的寬 率低 厚度 降低 形， 軋輥 i ~ 8 % -21- 201041947 配合在本發明中所使用之上述抗氧化劑的聚丙烯系樹 脂組成物的調製方法係沒有特別地限制，可舉例眾所周知 的方法。例如，可舉出使用捏和機、班伯里混煉機、軋輥 等的混練機進行加熱熔融混練的方法，使用單軸或雙軸壓 出機等進行加熱熔融混練的方法等。又，亦可乾摻和各種 的樹脂膠粒。在該組成物的調製方法中，該抗氧化劑係可 直接添加各粉末，也可以預先做成混合至上述聚丙烯系樹 脂中的母料而添加。作爲母料而添加之情形亦可另外調製 〇 添加劑’亦可混合2種以上而調製。又，亦可組合使上述 添加劑配合之市售樹脂而實施。又，上述組成物係可預先 調製供給至製膜步驟之組成物再供給至製膜用的擠壓機 內，也可以將構成該組成物的成分供給至該製膜用的擠壓 機內而進行調製、製膜。 又’使上述薄膜的20°C二甲苯可溶部量的變動幅爲 2 %以下’對於塗布黏著劑時防止薄膜變形係爲重要。較佳 係1 %以下。 〇 w 抑制該變動率在上述範圍内的方法，可舉出例如各少 量混合原料而隨時投入壓出機的方法、使料斗的形狀成爲 接近筒狀而不使其偏析的方法、於料斗内部設置攪拌裝置 而防止偏析的方法等，惟從生產安定性、粉麈發生防止等 的點而言’較佳係在料斗内設置偏析防止裝置間隔物的方 法 開纟α之所以會產生偏析是由於經混合之原料樹脂的 —部份’滑落料斗下部傾斜之内壁的速度大小不—樣，例 如慘和如彈性體般緩緩滑落的不利原料的情形，沿著内壁 -22- 201041947 落下的原料、與落在中央附近的原料，係在配合比方面產 生變動。 如是作爲偏析防止方法係如先前所舉例的，可舉例 如：1)在偏析產生之前將原料投入壓出機的方法、亦即各 少量混合原料而隨時投入壓出機的方法。2)滑落料斗内壁 的速度係在原料間沒有產生差異的方法、亦即使料斗的形 狀接近筒狀的方法。3)原料雖然偏析，但是從料斗被排出 之際不會偏析的混合裝置，例如於垂直方向***螺旋漿使 Ο 其回轉的方法。4)設置全部的原料沿著壁落下的步驟，使 原料不會偏析地落在料斗内的方法、亦即於料斗内設置偏 析防止間隔物的方法等。此等方法之中，1)與2 )係由於混 合結束的原料量少’而會在混合裝置產生問題的情形，由 於原料要立即切完，所以在生產性方面會有問題。3)的方 法係由於繼續混合原料，所以會有原料切削而容易產生粉 塵的問題。因此，工業上4)的方法最爲有用。 以下’具體地顯示用以達成上述4)的偏析防止方法之 〇 裝置的形狀，惟在適合得到本發明趣旨的範圍內，加入適 宜變更而實施係爲可能的，彼等係均包含在本發明的技術 的範圍內。 本裝置的特徴係在原料料斗、與其下部傾斜的内壁之 間’使爲了作出多少比原料樹脂的尺寸要廣的隙間所設置 的漏斗顛倒之形狀的間隔物，以原料落下之際實質上不振 動的方式，固定料斗的蓋部分而懸掛的部分所構成的。其 隙間的寬係爲使用之原料樹脂的最大長度的1 · 5倍~ 7倍， -23- 201041947 較佳係2倍~ 5倍。該隙間如果爲7倍以上，偏析防止效果 變小，如果爲1 · 5倍以下則會有原料樹脂堆積的危險。再 者，在該裝置下部的料斗容積’係原料通過的時間爲5分 以下爲佳。爲5分以上的通過時間時，會有原料樹脂通過 該隙間之後引起偏析的危險。 而且’該隙間的原料降落方向的長度沒有特別地規 定’惟由於最狹窄的部分爲短的一方且難以妨礙原料的下 降’所以最大爲1 〇 C m以下爲佳。又，即使該隙間在料斗 Ο 的上下方向設置2處以上也沒有關係，惟在1處則偏析防 止效果充分，且構造簡略而爲佳。此外，懸掛之零件的傘 部分裙角的角度係相對於水平方向爲40度以上，50度以 上爲較佳。低於4 〇度時，由於原料樹脂的流動變差且偏析 防止效果減弱而爲不佳。又，接近傘部分裙角的前端的原 料料斗傾斜之内壁的角度，係相對於水平方向亦爲4 0度以 上爲佳，50度以上爲最佳。該角度低於40度時由於原料 樹脂的流動依然會變差且偏析防止效果減弱而爲不佳。 C) w 將基於上述方法所得到的、構成樹脂混合比均一的組 成物之成分，供給至該製膜用的擠壓機以進行製造薄膜。 本發明的表面保護用聚丙烯系樹脂膜之製造方法的特 徴係在於： (1)在熔融樹脂的冷却條件控制中結晶化度的調整 (2 )熔融樹脂的拉伸·冷却固化時的拉伸比控制 (3)熔融樹脂的拉伸.冷却固化時的薄膜寬度方向厚度 控制。 -24- 201041947 〔在冷却條件控制中結晶化度的調整〕 本發明的壓出薄膜係利用T模頭法所製膜之未延伸薄 膜，薄膜的厚度雖然沒有特別地限定，但一般爲 l~50Q；wm，較佳的厚度係可按照需要而選擇。 作爲用以將本發明的聚丙烯樹脂組成物壓出薄膜而利 用的製膜條件，在擠壓模溫度2 0 0 °C〜2 5 0 °C、冷却軋輥溫 度4 〇 ~ 6 5 °C中進行爲佳。4 5 ~ 6 0°C爲較佳。冷却軋輥溫度 低於4 (TC的話，由於在耐熱尺寸安定性方面得不到充分的 〇 結晶化度而爲不佳。相反地，超過6 5 t的情形，由於產生 冷却軋輥的接觸輥壓痕而爲不佳，又透明性也會極端地降 低。又，關於冷却時間係沒有特別地限定，惟0.5秒以上 的範圍爲佳。冷却時間低於0.5秒的話，由於冷却效果不 充分，產生冷却軋輥的接觸輥壓痕而爲不佳。另一方面， 冷却時間的上限，從薄膜的結晶化度之觀點而言，沒有特 別地限制，從經濟性·生產性的觀點係5秒以下爲較佳，2 秒以上爲佳。又，將溫度設定稍低時，亦可爲3秒以上。 〇 倂用結晶核劑作爲任意地調整結晶化度的手段之情 形’如目II述般由於會擔心薄膜的魚眼增加，所以1 0 0 p p m 以下的添加係爲必要的。因此發現利用冷却條件之熔融樹 脂的冷却條件控制以調整結晶化度。 〔拉伸比的控制〕 本發明的壓出薄膜係藉由將熔融壓出後的拉伸步驟中 的拉伸比調整於〇.4~3.0的範圍內，可使薄膜的雙折射率 達到既定的範圍內。拉伸比一般已知利用以下的製膜條件 -25- 201041947 而算出。 拉伸比=(薄膜拉伸速度/擠壓模出口熔融 空隙 所謂的空隙係指從擠壓模出口使熔融樹脂 (冷却）軋輥爲止的距離（c m )。 拉伸比低於0.4的情形，由於薄膜的厚度 黏著加工之際薄膜的平面性降低而爲不佳。又 過3 · 0之情形，由於會有雙折射率超過所定的 〇 撃性顯著地降低，且薄膜本身的力學特性降低 不佳。 [薄膜寬度方向厚度控制] 作爲薄膜寬度方向厚度的控制方法，可舉 或自動調整模頭的模唇間隙的方法。作爲以更 小厚度變動的方法，以機械的或加熱電壓方式 模唇間隙的方法爲佳。又，除此之外，調整氣 在用以抑制寬度方向的厚度變動在1 0 %以下爲 ^ 室係爲對著落地於冷却軋輥之樹脂膜吹拂空氣 却軋輥之裝置，在吹拂空氣之際從氣動阻尼器 軋輥之隙間所漏出的空氣增加時，因爲所漏出 得接觸冷却軋輥之前的樹脂膜引起了波紋縐折 膜寬度方向的厚度變動了。爲此，使氣室内的 方向爲固定的同時，使風壓的絶對値不會提昇 係爲必要。氣室的風壓根據薄膜的拉伸速度爲 下爲佳。 樹脂速度）+ 連接至拉伸 斑增大，於 ，拉伸比超 範圍、耐衝 的問題而爲 例如以手動 短的時間縮 自動地調整 室的條件係 必要的。氣 且黏附於冷 上部與冷却 之空氣而使 '而使得薄 風壓在寬度 至必要以上 20mmHg 以 -26- 201041947 亦可藉由通常工業上所採用的方法，對本發明的壓出 薄膜實施電暈放電處理、或火焰處理等的表面處理。 在本發明中，在上述之表面保護用聚丙烯系樹脂膜的 至少單面上，設置有黏著劑層而成之表面保護膜係爲重要 的。藉由該對應，可有效地恢復上述之本發明聚丙烯系樹 脂膜的特徴，作爲保護膜在廣泛領域中的適用性係爲提 昇。特別是例如防止在液晶面板與偏光板等的相關材料等 的電子、精密製品、零件及相關構件的加工與組裝時的損 傷或灰塵附著、污染等的用途或作爲部分電鍍可撓性.印刷 基板的連接端子部等的方法、於非電鍍部貼附黏著薄膜形 成遮罩、然後進行電鍍之方法或保護在影孔板製造時的蝕 刻步驟中設置於非蝕刻面上的光阻膜或抗蝕刻膜的方法等 的在電鍍與蝕刻處理中使用、藉由在半導體元件沒有電路 的面上積層薄膜以保護半導體元件的表面，而在組裝半導 體裝置的情形中謀求製程簡略化的方法等的特別是污染與 缺點的抑制要求強烈的各種精密製品、零件的保護及該製 品、零件的加工、組裝步驟中，可適合作爲保護膜使用。 又’本發明的聚丙烯系樹脂膜係耐熱尺寸安定性優異，在 上述黏著加工中，例如由於提高乾燥步驟的乾燥溫度亦可 抑制熱敏與薄膜鬆弛的發生，所以提高該黏著加工的生產 性係爲可能的。又，可抑制熱皴與薄膜鬆弛起因的不良品 的發生。 上述黏著劑層的種類、厚度及黏著力等係沒有限定。 亦可根據市場要求而適宜選擇。又，該黏著劑層的積層方 -27- 201041947 法也沒有限定。可進行塗布法及擠壓積層法之中任一者。 實施例 以下’列舉實施例更具體地說明本發明，惟本發明原 本即不必受下述實施例所限制，在能適當得到本發明趣旨 之範圍內加入適宜變更而實施亦爲可能的，且彼等亦均包 含於本發明的技術範圍內。 1 _熔融流速[M F R ] 依照JIS Κ7210，以條件-14的方法（負荷2.16kg、 Ο 溫度2 3 0°c來測定。 2. 乙烯含量 根據高分子手冊（1995年、紀伊國屋書店發行）的616 頁中所記載的方法，以1 3 C - N M R法來測定。 3. 在2 0°C中二甲苯可溶部的比率（％} 將試料5g完全熔融於沸騰的二甲苯500 ml中之後， 降溫至2 0 °C，放置4小時以上。然後，分別過濾出析出物 與溶液，乾燥且硬化過瀘液，並使其於減壓下7 0 °C乾燥。 〇 由所得之乾燥物的質量測定20°c二甲苯可溶部量，以求得 其之比率。 4 .薄膜的結晶化度 使用廣角X射線回析透過法（RIGAKU RINT2500)來測 定。 5.動摩擦係數 使薄膜的密封層面之間合在一起，並依照 J I S - K 7 2 1 5 - 1 9 8 7來測定光滑性。 -28- 201041947 6.厚度變動率 依照JIS K7 130，使用崎製作所製線規（line gauge) 型號SIS-6’於寬度方向3cm節距測定lm寬的薄膜試樣 1片，以求出平均厚度。接著’使用在所測定之薄膜試樣 之中的最大値或最小値之中與平均厚度的差異大的任一 者，並用以下的計算式來算出。 厚度變動率（％) =丨（平均厚度）一（最大値或最小 値）丨/(平均厚度卜100 Ο 7.楊氏模數 依照JIS K7 127，試樣形狀係使用遵照i號形試驗片 而準備者（試樣長度200mm、試樣寬15mm、夾盤間距離 100mm)，以直角機頭速度500mm /分的條件針對MD方 向（薄膜長邊方向），在23°C來測定。 8.雙折射率（△ η) 使用阿貝折射計，測定薄膜流動方向的折射率Νχ、薄 膜流動方向與直行方向的折射率Ny，並使用下記式來計[Technical Field] The present invention relates to a polypropylene resin film for surface protection and a surface protective film, and more specifically, relates to heat deformation resistance or flatness at the time of enthalpy. For example, it is excellent in workability such as adhesion processing, and has less migration property of an additive, and is suitable as various uses for fish eyes, and is particularly suitable as each. A polypropylene resin film for surface protection for surface protection of articles and a surface protection film for a polypropylene resin film for surface protection.先前 [Prior Art] Since the polypropylene-based non-stretched film is excellent in transparency and is inexpensive, it is widely used as a substrate for a surface protective film for the purpose of protecting various packaging materials such as food packaging and surface protection of various articles. In addition, it is used as an electronic precision product, a component, and a related member for protecting a metal plate, a cosmetic board, a resin board, a glass plate, and the like, a liquid crystal panel, a polarizing plate, etc., and a surface protective film for a coating film of an automobile. Further, it is used as a surface protective film for a photoresist film or an anti-uranium engraved film for protecting a terminal portion for a part of an electric ore flexible/printed substrate, and is used as a thin film laminated on a semiconductor. The element has no surface on the circuit to protect the surface protection film for the surface of the semiconductor element. With the expansion of the use in recent years, the demand for quality and cost reduction has also increased. In addition to the processing suitability of the coated body, it is also required to apply a film for surface protection which is excellent in the ease of application of the adhesive. In particular, based on the purpose of improving the processing speed of the adhesive processing, etc., it is also required to increase the processing temperature. Even if the adhesive is processed at a high temperature, the thermal deformation of the processing temperature of 201041947 is small and the dimensional stability during processing is good (also called For heat resistant dimensional stability). As for the polypropylene-based film, some techniques for improving the heat-resistant dimensional stability described above have been disclosed (for example, refer to Patent Documents 1 to 4). However, the heat-sealable polypropylene film disclosed in Patent Document 1 is just. The properties are insufficient, and the transparent polypropylene sheet disclosed in Patent Document 2 is difficult to attach. Further, the surface-protected polypropylene film described in Patent Document 3 and Patent Document 4 has a large rigidity and is inferior in bonding workability. Further, when the film is wound on a roll, there is a problem that wrinkles or corrugations are likely to occur. Further, when the adhesive is applied, there is a problem that the film is deformed. CITATION LIST Patent Literature Patent Literature No. JP-A-2009-170485, JP-A-2003-170485, JP-A-2003-170485, JP-A-2007-057294 SUMMARY OF THE INVENTION The present invention provides a heat-resistant dimensional stability and flatness, excellent in impact resistance and bonding workability, and less fisheyes, and is not entangled or corrugated when wound on a roll, and is suitable, for example, as a protective film. A polypropylene resin film for surface protection of a material film, and a protective film obtained by providing an adhesive layer on the surface protective 201041947 polypropylene resin film. [Embodiment] The means for solving the problem The present inventors have finally completed the present invention by repeating the results of the intensive review in order to solve the above problems. . In other words, the present invention relates to a polypropylene resin film for surface protection, which is a polypropylene-based resin film containing a polypropylene resin as a main component, and is characterized in that it is a 20 ° C xylene soluble portion. More than 9%, less than 16%, the content of the crystal nucleating agent is 100 ppm or less, and the thickness variation rate in the width direction of the film is 1% or more and 10% or less, and the dynamic friction coefficient is 1. 0 or less, a polypropylene resin film for surface protection having a tensile modulus of 500 MPa or more and 900 MPa or less. In this case, the content of the anti-blocking agent in the film is 50 ppm or less, and the blocking resistance is preferably 1 〇 mN or less. Further, in this case, the maximum diameter in the film is 0. The fisheye of 2mm or more is 〇/m2, and the maximum diameter is less than 0. The 2mm fisheye is preferably 100 W/m2 or less. Further, in this case, it is preferable that the Young's modulus of the film in the longitudinal direction at 23 ° C is 500 MPa or more. Again, in this case, the impact strength of the film at 23 ° C is 0. 3J or more is better. Further, in this case, it is preferred to contain at least one acrylate-based antioxidant and at least one antioxidant selected from the group consisting of a phosphorus-based antioxidant and a phenol-based antioxidant. . Further, in this case, it is preferable that the variation range of the 20 t: xylene soluble portion of the film is less than 2%. Further, the present invention is a surface protective film formed by providing an adhesive layer on at least one surface of the above-mentioned surface protective polypropylene resin film. Effect of the invention. The present invention is excellent in heat-resistant dimensional stability and flatness, and is excellent in impact resistance, bonding workability, and whitening prevention effect, and has few fish eyes, and is not wrinkled or corrugated when wound on a roll, and is suitable as, for example, a protective film. Substrate film. The polypropylene resin film for surface protection of the present invention is excellent in heat resistance dimensional stability, and therefore, it is excellent in secondary processing suitability such as adhesion processing, and is particularly effective in drying at a high temperature in the vicinity of 130 ° C. Since the occurrence of hot wrinkles and film slack is suppressed, it is possible to suppress the occurrence of defective products due to the productivity improvement of the secondary processing, hot wrinkles, and film slack. Moreover, it is preferable that the polypropylene-based resin film of the present invention does not substantially contain an anti-blocking agent. For example, in the case where the film containing the anti-blocking agent is prevented from traveling, the anti-blocking agent is caused by abrasion or the like. Since the problem of falling off is caused, the occurrence of contamination and obstacles due to the falling off material is suppressed. Further, the present invention does not substantially contain a lubricant and an anti-adhesion agent. The film has good surface roughness, and the film has good smoothness and blocking resistance, and is excellent in rigidity. Therefore, the film has excellent handleability. Moreover, since it is excellent in transparency, it is excellent in the visibility of a to-be-protected body. Moreover, since the film has strength, it is excellent in workability. . In addition, although the above-mentioned heat-resistant dimensional stability is improved, the impact strength is excellent in 201041947, and the advantage of the punching resistance added by the formation of the block polypropylene-based resin is maintained, and it is reliable in the case of being used as a protective film. High sex. BEST MODE FOR CARRYING OUT THE INVENTION The polypropylene resin film of the present invention contains a polypropylene resin as a main component, and preferably a polypropylene resin containing 7 〇 by weight or more in the film, and preferably contains 80% by weight. The above is better. • The polypropylene-based resin used in the present invention can be obtained by mixing a homopolypropylene resin, a copolymerized ethylene and other α-olefins, a random copolymerized polypropylene resin, and a block copolymerized polypropylene. One to three kinds of resins are used. From the viewpoint of transparency, it is preferred to use a homopolypropylene resin or a random copolymerized polypropylene resin copolymerized with ethylene and other α-olefins, so that the punching property and the smoothness, particularly the anti-blocking property. In the case of improvement, it is preferred to use a block copolymerized polypropylene resin. The mixing ratio can be adjusted arbitrarily. The composition of the polypropylene-based resin is not particularly limited, and if the 〇 is a random copolymerized polypropylene resin, the α-olefin content is preferably 5% or less from the surface of the heat-resistant dimensional stability. Further, in the case of a block copolymerized polypropylene resin, it is preferred that the amount of xylene soluble portion at 20 ° C is from 3 to 50% from the surface of heat resistance dimensional stability, smoothness, and blocking resistance. It is in the range of 5 to 30%. The ultimate viscosity of the above polypropylene resin is 1. 5~4. 0, 20 ° C The viscosity of the xylene soluble part of the limit is 1. 0~4. 0, 20 ° (: the ultimate viscosity of the xylene insoluble portion is 1. 0~4. 0 is better. Further, the melt flow rate of the polyacrylonitrile 201041947 olefin resin used in the present invention is preferably 2 to 20 g/10 min at 230 °C. As the α-olefin random copolymer elastomer used in the present invention, a ternary copolymer of ethylene-propylene, ethylene-butene or propylene-butene, and ethylene-propylene-butene can be used. Or a mixture of them. Further, it is also possible to use a copolymer which further copolymerizes other monomers within a range which does not impair the properties thereof. In particular, it is preferred to use the above binary copolymer. Again, from . It is preferable to use a Vicat softening point of 60 ° C or less and a surface hardness of 80 ° or less at a point which gives a good elastic force to the laminated body. 〇 In the present invention, in particular, those containing a block copolymerized polypropylene resin are preferred in terms of heat resistance and smoothness. Further, other small amounts of α-olefin random copolymerized elastomer, polyionic polymer, and other master batches may be added for various purposes. The polypropylene resin film of the present invention must have a xylene soluble portion of 20 ° C and more than 9% and less than 16%. If it is 9% or less, the film is easily plastically deformed at the time of high-temperature processing, and the film suitability and whitening prevention effect are deteriorated. Ο If it is more than 1 6%, the film is too easy to stretch, and the application of the adhesive coating is poor. Further, the lower limit of the soluble fraction of xylene at 20 ° C is preferably 10% or more from the point of prevention of whitening when the film is bent, and is less than 14% from the surface of the film which is resistant to blocking. It is better. In the present invention, as described above, it is preferable that the lubricant and the anti-blocking agent are not used in the general polypropylene-based resin film, and this is necessary to suppress the deterioration of the smoothness and the adhesion of the film. . This correspondence is preferably carried out by the above-described resin composition, particularly by the surface protrusion of the film from the sea/island structure of the polymerized elastomer of the block copolymerization resin and the ethylene-based 201041947 polymer. At this time, as the smoothing property of the film of the present invention, as will be described later, the coefficient of dynamic friction was 1. 0 or less is necessary. Also, 〇·9 or less is better, 0. 8 or less is the best. When the coefficient of dynamic friction is outside this range, when the film is wound on the latex roll and the air between the films is dissipated, the adhesion of the films to each other is liable to occur, and • one of the causes of wrinkles or ripples. Further, as the anti-blocking property of the film of the present invention, it is preferable to use the evaluation price described later, preferably 1 to 10 nm or less. Below l~7mN is better. On the other hand, since the formation of the surface protrusion of the film due to the sea/island structure of the block copolymer resin causes a decrease in the transparency of the film, in this method, the smoothness and anti-adhesion due to the formation of the surface protrusion are caused. The improvement effect of continuity and the guarantee of transparency are self-contradictory phenomena. Therefore, the haze of the film becomes an important factor. Therefore, in the present invention, it is important that the haze of the film is 40% or less. 35% or less is preferred, and 30% or less is preferred. By setting the haze to 40% or less, the visibility of the packaged object and the object to be protected is improved, and in the case of use as a packaging material, the contents of the packaged object are confirmed to be easy. Further, in the case of use as a material for a surface protective film, for example, inspection of a protected body or the like can be performed immediately after the surface protective film is attached. On the other hand, in the case where the haze is more than 40%, the transparency is deteriorated, and the visibility of the packaged object and the object to be protected is lowered. On the other hand, when the lower limit of haze 为 is low, transparency is improved, but in connection with the point of imparting smoothness by the above method, it is preferably 5% or more, -10- 201041947 1 ο % The above is preferred. In the film, the amount of t in the film is 50 ppm, preferably, and the above-mentioned limit is below. The so-called actual case has the same suppression in the processing step, so the system is used. A general quantitative method in which the amount of the slip agent such as polyethyl amide or the like in the film is 10 ppm is preferably a slip agent. This positively adds a slip agent, which is a mixture of inclusions due to inclusion. In the method of the pair, the anti-adhesion agent such as inorganic and/or organic fine particles of the surface-protecting polypropylene-based tree of the present invention is applied to or protected by the protected body. Specialized is better. The content of the anti-blocking agent is preferably 1 P P m or less, and is usually a quantitative method using ash and elemental analysis. That is, it is preferable that the anti-blocking agent is not substantially contained. . It does not contain anti-adhesion agent, and it is related to the above-mentioned slip agent. By this correspondence, the anti-adhesion agent which is caused by the manufacture of the film and the abrasion of the second film is contaminated by the detachment and the occurrence of the obstacle, and the like, the polypropylene resin for surface protection of the present invention is inhibited. It is important that the content of the filmene wax, calcium stearate, erucic acid amide, and ethyl erion are 50 ppm or less. It is preferable to use one of the lubricants, and it is preferable to use the elemental analysis and the extraction method as the detection limit or less. That is, it does not substantially contain a portion, and the so-called substantially no slip agent is used for film formation. When the above range is not actively added to the raw material polymer and the film is replaced by a brand, it is preferable that the lubricant is not contained, and the smoothness of the film is improved by blending the lubricant. The migration of the lubricant to the surface of the film and the contamination of the protected body due to the continued migration of the body are prevented from being maintained by the cleanliness. In the present invention, the tensile elastic modulus must be 5 Ο Ο M Pa or more and 201041947 900 MPa or less. When the tensile modulus of elasticity is too small, when the film roll is wound, the film is deformed by 1 and the stress remains on the roll to cause wrinkles or waviness. On the contrary, when the tensile elastic modulus is too large, the film bonding after the application of the adhesive becomes difficult. _ The surface protection of the invention. The polypropylene resin film for protection is preferably a film having a degree of crystallization of from 34 to 65 % by a measurement method described later. Crystallinity: When the temperature is less than 34%, it is difficult to find the heat-resistant dimensional stability, and when the processing is carried out in the subsequent step, the film is easily corrugated and stretched, and the planarity is not good. On the other hand, in the case where the degree of crystallization exceeds 65%, the transparency of the film is remarkably deteriorated, which is not preferable. Further, when the degree of crystallization exceeds 65%, the Young's modulus becomes large, and the fit processing property is deteriorated. The lower limit of the degree of crystallization of the film is preferably 40% or more, and from the viewpoint of heat-resistant dimensional stability, 50% or more is preferable. On the other hand, the upper limit of the degree of crystallization of the film is 60% or less, which is preferable from the viewpoint of transparency. Further, the polypropylene resin film for surface protection of the present invention may be a polypropylene resin which has a desired degree of crystallization (34 to 65%) by a production method which does not substantially contain a crystal nucleating agent. membrane. As a manufacturing method, the temperature of the cooling roll at the time of stretching, cooling and solidifying the molten resin can be increased, and heat treatment (annealing) can be used. The polypropylene resin film for surface protection of the present invention can be added if the crystal nucleating agent is in the range of 100 ppm or less. By adding a crystal nucleating agent, the heat-resistant dimensional stability of the film can be improved. On the other hand, when the addition of the crystal nucleating agent exceeds 100 ppm, even if the resin is subjected to the melt-extrusion condition, the fish eye in the film tends to increase, which is a problem, and the foreign matter in the resin is removed. It is preferable to increase the productivity, such as boosting due to clogging of the aligner. The crystal nucleating agent can be defined, for example. A crystal nucleating agent containing a salt as a main component, a crystal nucleating agent formed by a sorbitol-based chelating organophosphate metal salt, and the like, and the fluorination rate (Δη) of the surface-protecting polypropylene tree of the present invention is 〇 _4xl〇-3~2. 5xl〇-3. In the case of birefringence, the divergence becomes too large and is easy to cause. On the other hand, the birefringence is below zero. 4 X 1 0 -3 is easy to produce, has poor planarity and is excellent in heat resistance. From the viewpoint of maintaining heat resistance dimensional stability and planarity, the observation rate is Q. 6X10-3 is better than 0. 8x10 On the other hand, from the viewpoint of preventing the wrinkles or waviness of the film, the C\w rate is 2. 3 χ 1 0-3 or less is preferably 2 · 2 χ 1 0 In the present invention, the surface protective poly film of the present invention has an impact strength at 23 ° C of 0. 3 J or more is a good one. Generally, when the above-mentioned rigidity and heat-resistant dimensional safety are raised, the direction is lowered. When the impact strength is lowered, the use of the bag, the protective film, or the like is less than the resistance at the time of use. Therefore, in addition to the above-mentioned characteristics, the upper limit can be balanced according to other characteristics. 8 J left ΐ situation. Further, in the case of the filtration problem of the extruder, the metal nucleating agent of the rosin type and the aromatic bismuth film are preferably more than 2. If the 5x10-3 wrinkles or corrugations are not correct due to the qualitative deterioration of the film, the double fold of the film is preferably 3 or more. Point, the film double fold _3 or less is preferred. A propylene resin film system. 0. When the above is more than 5 J, the impact is strong, and the reliability is good as a package. ί is better. -13- 201041947 Although the method of imparting the above impact strength is not limited, it is affected by the above-mentioned ethylene content. Preferably, the total effect of the preferred embodiment described in the present specification containing the content of the B is achieved. In the present invention, the maximum diameter in the polypropylene resin film-based film for surface protection of the present invention is Q. More than 2mm fish eyes are better / m2 is better. In addition, the maximum diameter is lower than 〇. The fisheye of 2111111 is 100/m2 or less. good. The maximum diameter is lower than Q. The fisheye of 2 m m is preferably 0/m 2 or less. □ It is preferably within the above range based on economical and market requirements. 2~80 //m2 or less is preferable, and 2~60/m2 or less is more preferable. In addition, the minimum diameter of the fisheye that can be visually determined is 〇. 〇3 ~ 0. 0 5 mm. In this case, in the case where the appearance is poor and the substrate film is used as a protective film, for example, it is possible to suppress the occurrence of an obstacle caused by the penetration of the plating solution by the plating solution due to the above-described adhesion failure. " The means for achieving the above characteristics is not limited, but it is preferable to carry out the compounding of the antioxidant as described later. 9 The acrylate-based antioxidant of the present invention is an anti-oxidation of a phenol derivative having a hydrazine-containing acrylate residue in the molecule. Oxidizer. As the acrylate compound, for example, 2,4-di-third amyl-6-[1-(3,5-di-tripentyl-2-hydroxyphenyl)ethyl]phenyl acrylate can be mentioned. 2,4-di-p-pentyl-6-[l-(3,5-di-tripentyl-2-hydroxyphenyl)butylphosphonium phenyl acrylate, 2,4-di- Tripentyl-6-[1-(3,5-di-third-pentyl-2-hydroxyphenyl)propyl]phenyl acrylate, 2-tert-butyl-6-(3_Third Base-2_hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, and the like. Preferred is 2,4-di-triptylamyl-6-[l-(3,5-di-p-pentyl-2-day-2010-201041947 hydroxyphenyl)ethyl]phenyl acrylate and 2 - Ternyl-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate. The acrylate compound can be suitably selected from commercially available products. Sumitomo Chemical Co., Ltd., Sumitomo Chemical Co., Ltd., which is, for example, 2-tert-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate Sumitomo Chemical Co., Ltd., 2,4-di-p-pentyl-6-[l-(3,5-*-di-p-pentyl-2-hydroxyphenyl)ethyl]phenyl acrylate Share) 'Sumilizer GS (registered trademark) and so on. In particular, the use of Sumilizer GS (registered trademark) is preferred. In the present invention, the amount of the acrylate-based antioxidant is not particularly limited, and is preferably in the range of 100 to 10 Torr Qppm with respect to the above-mentioned all-polypropylene resin composition. It is preferably 200 to 800 ppm, more preferably 3 to 70 pm. In the case of more than 1000 ppm, it is not preferable in the film forming step due to an increase in contamination of the cooling rolls. The film is also poor because it is dyed to the yellowish color that is characteristic of the antioxidant. On the other hand, when it is less than 10 Oppm, it is not preferable because the effect of the later use is reduced. It is preferable that the above acrylate-based antioxidant is lower than the upper limit of the amount of the above two kinds of antioxidants, and it is presumed that the acrylate-based antioxidant is a polypropylene-based resin as compared with other antioxidants. Since the solubility of the rubber component is high, the rubber component in the film is largely distributed, and since the rubber component portion is more cooled than the raw material resin, the crystallization speed is slower, and it is in contact with the cooling roller. In the case, the above-described acrylate-based antioxidant which is distributed to the rubber component is likely to migrate to the cooling roll to increase the degree of contamination of the cooling roll. -15- . For example, the peculiar phenomenon occurring in the present invention does not occur in the film formation using the homo-polypropylene resin disclosed in the aforementioned Patent Document No. 2 or the like. Specific examples of the phosphorus-based antioxidant include a trivalent phosphorus atom in the molecule, and a phosphorus atom having at least one thermal stabilizer having a P-0-C bond. For example, tributyl phosphite, trioctyl phosphite, trilauryl phosphite, tristearyl phosphite, tridecyl phosphite, tricresyl phosphite, tricyclohexyl phosphite Ester, triphenyl phosphite, trilauryl phosphite, cis (2-ethylhexyl) phosphite, cis (isodecyl) phosphite, ginseng (tridecyl) phosphite, Reference (2,4-di-tert-butylphenyl) phosphite, cis (butoxyethyl) phosphite, ginseng (nonylphenyl) phosphite, ginseng (3,5-di- Third butyl-4-hydroxyphenyl)phosphite, ginseng [4,4'-isopropylidene bis(2-tert-butylphenol)] phosphite, ginseng (1,3 -di-hard Lipidoxy isopropyl) phosphite, 2-ethylhexyl diphenyl phosphite, decyl diphenyl phosphite, phenyl di-2-ethylhexyl phosphite, phenyl phosphite Dimercapto ester, phenyl diisononyl phosphite, phenyl bis(trimethyl) phosphite, diphenyl decyl phosphite, diphenyl isooctyl phosphite, phosphorous acid Phenyl isodecyl ester, diphenyl mono(trimethylene) Phosphite, dibutyl hydrogen phosphite, 4, Γ-isopropylidene diphenol alkyl (C12~C15) phosphite, 4,4'-butylene bis(3-methyl-6 -T-butylphenyl)di-tridecylphosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite, 2,2'- Ethylene bis(4,6-di-t-butylphenol) fluorophosphite, bis(2,4-di-t-butyl-6-methylphenyl). Ethyl phosphite, 4,4·-isopropylidene bis(2-tert-butylphenol). Bis(nonylphenyl)phosphite, distearyl pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol-4-16 - 201041947 alcohol diphosphite, diphenyl pentaerythritol diphosphite, Phenyl. 4,4'-isopropylidenediphenol. Pentaerythritol diphosphite, bis(4,6-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol di Phosphate ester, phenyl-bisphenol A pentaerythritol diphosphite, tetraphenyl dipropylene glycol diphosphite, tetrakis(trimethyl)-1,1,3-para (2-methyl-5-tributyl) 4--4-hydroxyphenyl)butane diphosphite, tetra(C12-C15 mixed alkyl)-4,4丨-isopropylidene diphenyl diphosphite, tetrakis(trimethyl)-4 , 4'-butylidene bis(3-methyl-6-tert-butylphenol) diphosphite, ruthenium (4,6-di-t-butylphenyl)-4,4'- Biphenyl diphosphonate, bismuth (2-methyl-4,6-di-t-butylphenyl)-4,4'-extended biphenyl diphosphonate, bis(octylphenyl) · bis [4,41-butylene bis(3-methyl-6-tert-butylphenol)]. 1,6-hexanediol diphosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, 9,10-dihydro-9-oxa-9-oxa-10-phosphorus Phenanthrene-10-oxide, 2-[{2,4,8,1〇-肆(1,1-dimethylethyl)dibenzo(E>,F)(1,3,2)- Dioxaphosphocycloheptane, 6-yl}oxy]-N,N-bis[2-[{2,4,8,10-fluorene (1,b dimethylethyl)dibenzo (D, F) (1,3,2)· Ο diphosphorylcycloheptane-6-yl}oxy]ethyl]ethaneamine, H3-para (2-methyl-4-di-tridecylphosphite) Ester-5-t-butylphenyl)butane, 3,4,5,6-tetrabenzo-1,2-oxo-glycolic acid glyceride-2-oxide, and the like. Preferably, it does not have a pentaerythritol skeleton, ginseng (2,4-di-tert-butylphenyl) phosphite, ginseng (3,5-di-t-butyl-4-hydroxyphenyl) phosphite , bis(2,4-di-t-butyl-6-methylphenyl)-ethyl phosphite '肆(2-methyl-4,6-di-t-butylphenyl) 4, For the phosphorus-based antioxidant to be used in the present invention, a commercially available product of -17 to 201041947 may be used, and for example, IRGAFOS 168 (manufactured by Ciba Specialty Chemicals Co., Ltd.), IRGAFOS 3 may be used. 8 (manufactured by Ciba Specialty Chemicals Co., Ltd.), GSY-P101 (manufactured by Jifu Precision Chemical Co., Ltd.), Ultranox 641 (manufactured by GE Specialty Chemiclas Co., Ltd.), etc. In the present invention, the amount of the phosphorus-based antioxidant is not limited, but is relatively limited. The above all-polypropylene resin composition is preferably in the range of 500 to 5000 ppm, preferably 10 QO to 4000 ppm, more preferably 1,500 to 3,000 ppm, and less than 500 ppm, because of the effect of the antioxidant described later. The reduction is not good. On the contrary, in the case of more than 5000 ppm, since the effect of the antioxidant described later is saturated, The film whitening and contamination caused by the migration of the antioxidant toward the surface of the film may be poor in the cooling roll of the film forming step, etc. The phenolic antioxidant used in the present invention has a phenol derivative in the molecule. The antioxidant may, for example, be 2,6-di-t-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-dicyclohexyl- 4-methylphenol, 2,6-di-third amyl-4-methylphenol, 2,6-di-t-octyl-4-nOpropylphenol, 2,6-dicyclohexyl-4 -n-octylphenol, 2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-2-ethyl-6-1-octylphenol, 2-isobutyl 4-ethyl-6-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, dl-iz-tocopherol, tert-butylhydroquinone, 2,2 '-Methylene bis(4-methyl-6-tert-butylphenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 4,4·-sulfur Bis(3-methyl-6-tert-butylphenol), 2,2-thiobis(4-methyl-6-tert-butylphenol), 4,4'-methylenebis (2) ,6-di-t-butylphenol), 2,2'-methylenebis[6-(1-methylcyclohexyl)-p-cresol], 2,2'-ethylenebis (4 ,6- -18- 201041947 Di-tert-butylphenol), 2,2'-butylene bis(2-tert-butyl-4-methylphenol), 2-tert-butyl-6-(3-tert-butyl- 2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6 -di-t-pentyl phenyl acrylate, 1,1,3-glycol (2-methyl-4-hydroxy-5-t-butylphenyl) butyl, triethylene glycol-bis [3_(3 _T-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxybenzene) Propionate], 2,2-thiodiethylidene 3_(3,5-di-t-butyl-4-propenyl)propionate], hydrazine, Ν'-hexamethylene Bis(3,5-di-t-butyl-4-ylhydroxyindole-hydrocinnamate) 3,5-di-t-butyl-I-hydroxybenzyl phosphate-diethyl vinegar, ginseng (2 ,6-dimethylmethyl-based-4_t-butyl benzyl) iso-cyanuric acid vinegar, ginseng (3,5-di-tert-butyl-4-hydroxybenzyl)isomeric cyanurate , [(3,5-di-t-butylhydroxyphenyl)propenyloxyethyl]isocyanate, ginseng (4-tert-butyl-2,6-dimethyl_3 _hydroxybenzyl)isocyanate, 2,4-bis(η- Thiobu 6_(4_ mercapto-3,5-di-t-butylanilino)-1,3,5-tri-trap, 肆[methylene_3_(3,5_di-third 4-hydroxyphenyl)propionate] A, 2,21-methylenebis(4-methyl-6-tert-butylfluorene)-p-phthalate, 1,3,5 -trimethyl-2,4,6-glycol (3,5-di-t-butyl-4-hydroxybenzyl)benzene, 3,9-bis to, bis-dimethyl-2-{/3- (3-tert-butyl-4-transyl-5-methylphenyl)propanoxy}ethyl b 2,4,8,10-tetraoxaspiro[5,5]undecane, 2,2_bis[4_(2_(3,5-di-t-butyl-4-hydroxyhydrocinnamate))ethoxyphenyl]propane, 0-(3,5-di-third Butyl 4-hydroxyphenyl) propionate stearyl vinegar and the like. Preferred is stearyl-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, hydrazine [methylene-3-(3,5-di-t-butyl-) 4-hydroxyphenyl)propionate]methyl-19- 201041947 alkane, ginseng (3,5-di-t-butyl-4-hydroxybenzyl)isocyanate, 1,3,5-three Methyl-2,4,6-gin (3,5-di-t-butyl-4-hydroxybenzyl)benzene, dl-α-tocopherol, ginseng (2,6-dimethyl-3-hydroxyl) -4-t-butylbenzyl)isocyanate, gin[(3,5-di-tert-butyl-4-hydroxyphenyl)propenyloxyethyl]isocyanate ,3,9-bis[1,1-dimethyl-2-{cold-(3-t-butyl-4-hydroxy-5-methylphenyl)propanoxy}ethyl]-2, 4,8,10-Tetraoxaspiro[5,5]undecane. As a phenolic antioxidant used in the present invention, a commercially available product may be used, and examples thereof include IRGANQX l〇l〇 (manufactured by Ciba Specialty Chemicals Co., Ltd.) and IRGANOX 1 〇76 (manufactured by Ciba Specialty Chemicals Co., Ltd.). IROANOX 1 3 3 0 (manufactured by Ciba Specialty Chemicals Co., Ltd.), IRGANOX 3114 (manufactured by Ciba Specialty Chemicals Co., Ltd.), IRGANOX 1425WL (manufactured by Ciba Specialty Chemicals Co., Ltd.), etc. In the present invention, the amount of the phenolic antioxidant is not limited. The total polypropylene resin composition is preferably in the range of 500 to 5000 ppm, preferably 1000 to 4000 ppm, more preferably 1500 to 3000 ppm, and less than 500 ppm, because the antioxidant is used later. The effect is reduced and is not good. Conversely, in the case of more than 5000 ppm, the effect of the antioxidant described later is saturated, and the film whitening and contamination caused by the migration of the antioxidant toward the surface of the film are caused to be cooled in the film forming step. In the present invention, the acrylate-based antioxidant, the phosphorus-based antioxidant, and the phenol are contained as described above. It is preferred to use at least one of the antioxidants selected from at least one of the antioxidants selected from the group consisting of oxidant antioxidants, phosphorus antioxidants and phenolic antioxidants. The above-mentioned three types of antioxidants are not determined for each of the above-mentioned types of antimony. Two or more kinds of various types can be used, and the above three kinds of chemicals can be used in addition to the above-mentioned three kinds of chemicals. For example, other antioxidants such as a sulfur-based antioxidant can be found by using a plurality of antioxidants as described above, and it is possible to find a highly fish-eye-inhibiting effect which cannot be obtained by a combination of conventionally known antioxidants. And the phosphorus-based antioxidant has little selectivity to the antioxidant effect of each component of the raw material resin material, and the acrylate-based antioxidant is known to have a strong affinity with the rubber portion of the polypropylene-based block copolymer and to suppress deterioration of the rubber portion first. On the other hand, the growth of the fisheye has a great influence on the deterioration of the rubber portion. Therefore, it is presumed that the above-mentioned complex antioxidant is associated with a large reduction in fisheye by the use of the above-mentioned complex antioxidant. Table The polypropylene resin film for surface protection has a thickness variation ratio in the film thickness direction of preferably 1 to 10%. When the thickness is changed to 1%, there is no problem in the quality surface, but the time required for the adjustment is required. It becomes inflated, so it is economically significant and not in line with reality. On the other hand, the case where the thickness variation rate exceeds 10% is caused by the deterioration of the planarity (corrugation or curling) of the film, and it is generated when it is wound up. It is not good if it is folded or corrugated. The rate of change in thickness is Ι. ί is better, and the range of 2 to 5% is optimal. The ester system is excellent in the composition of the oxidation of the system, and the width and the thickness of the composition are reduced. The roll i ~ 8 % -21 - 201041947 is blended with the above antioxidants used in the present invention. The preparation method of the polypropylene resin composition is not particularly limited, and a well-known method can be exemplified. For example, a method of heating and melting kneading using a kneader such as a kneader, a Banbury mixer, or a roll, and a method of heating and melting kneading using a uniaxial or biaxial extruder or the like can be mentioned. Further, various resin micelles may be blended. In the preparation method of the composition, the antioxidant may be added as it is, or may be added in advance to a master batch which is mixed into the polypropylene resin. In the case of being added as a master batch, it is also possible to prepare a 〇 additive ’ or a mixture of two or more kinds. Further, it may be carried out by combining a commercially available resin in which the above additives are blended. Further, the composition may be prepared by previously supplying the composition supplied to the film forming step to the extruder for film formation, or the component constituting the composition may be supplied to the extruder for film formation. Modulation and film formation. Further, the variation of the amount of the xylene-soluble portion of the film at 20 ° C is 2% or less. It is important to prevent deformation of the film when the adhesive is applied. Preferably, it is 1% or less. 〇w The method of suppressing the fluctuation rate in the above range is, for example, a method in which a small amount of a mixed raw material is introduced into the extruder at any time, a method in which the shape of the hopper is close to a cylindrical shape and is not segregated, and the inside of the hopper is provided. A method of preventing segregation by a stirring device, etc., but it is preferable to provide a segregation preventing device spacer in the hopper from the point of production stability, prevention of the occurrence of whitefly, etc. The raw material of the mixed raw material resin - the speed of the inner wall of the lower part of the sliding hopper is not the same, such as the case of unfavorable raw materials that are sluggishly falling off like an elastomer, the raw materials falling along the inner wall -22-201041947, and The raw materials that fall near the center are subject to change in the blending ratio. As the segregation prevention method, as exemplified above, for example, 1) a method in which a raw material is introduced into an extruder before segregation, that is, a method in which a small amount of a raw material is mixed and introduced into an extruder at any time. 2) The speed at which the inner wall of the hopper is slid is a method in which no difference occurs between the raw materials, and even if the shape of the hopper is close to the cylindrical shape. 3) A method in which the raw material is segregated, but the mixing device does not segregate from the time when the hopper is discharged, for example, a method in which the propeller is inserted in the vertical direction to rotate it. 4) A method in which all of the raw materials are dropped along the wall, a method in which the raw material falls into the hopper without segregation, that is, a method of providing a separation preventing spacer in the hopper. Among these methods, in the case where 1) and 2) are small in the amount of the raw material to be mixed, a problem occurs in the mixing device, and since the raw material is immediately cut, there is a problem in productivity. In the method of 3), since the raw materials are continuously mixed, there is a problem that the raw materials are cut and dust is easily generated. Therefore, the method of industry 4) is most useful. In the following, the shape of the apparatus for preventing the segregation prevention method for achieving the above-mentioned 4) is specifically shown, and it is possible to carry out appropriate modification and implementation within the scope which is suitable for the purpose of the present invention, and all of them are included in the present invention. Within the scope of the technology. The feature of the apparatus is that a spacer having a shape in which the funnel is reversed in order to make a gap larger than the size of the raw material resin is formed between the raw material hopper and the inner wall inclined to the lower portion thereof, and does not substantially vibrate when the raw material falls. The manner in which the cover portion of the hopper is fixed and suspended. The width between the gaps is 1-5 times to 7 times the maximum length of the raw material resin used, and -23-201041947 is preferably 2 times to 5 times. If the gap is 7 times or more, the segregation prevention effect becomes small, and if it is 1 · 5 times or less, there is a risk that the raw material resin is deposited. Further, the hopper volume in the lower portion of the apparatus is preferably 5 minutes or less. When the passage time is 5 minutes or more, there is a risk that the raw material resin will cause segregation after passing through the gap. Further, the length of the material in the falling direction of the gap is not particularly limited. However, since the narrowest portion is short and it is difficult to hinder the lowering of the raw material, it is preferably at most 1 〇 C m or less. Further, even if the gap is provided in two or more places in the vertical direction of the hopper ,, it is preferable that the segregation prevention effect is sufficient at one position, and the structure is simple and preferable. Further, the angle of the skirt portion of the umbrella portion of the suspended component is 40 degrees or more with respect to the horizontal direction, and preferably 50 degrees or more. When the temperature is lower than 4 Torr, the flow of the raw material resin is deteriorated and the segregation prevention effect is weakened, which is not preferable. Further, the angle of the inner wall of the original material hopper which is close to the front end of the skirt portion of the umbrella portion is preferably 40 degrees or more with respect to the horizontal direction, and is preferably 50 degrees or more. When the angle is less than 40 degrees, the flow of the raw material resin is still deteriorated and the segregation prevention effect is weakened, which is not preferable. C) w A component of the composition which is obtained by the above method and which has a uniform resin mixing ratio is supplied to the extruder for film formation to produce a film. The method for producing a polypropylene resin film for surface protection according to the present invention is characterized in that: (1) adjustment of the degree of crystallization in the control of the cooling condition of the molten resin (2) stretching at the time of stretching and cooling of the molten resin Ratio control (3) stretching of molten resin. Thickness control in the width direction of the film during cooling and solidification. -24- 201041947 [Adjustment of crystallinity in cooling condition control] The extruded film of the present invention is an unstretched film formed by a T-die method, and the thickness of the film is not particularly limited, but is generally l~ 50Q; wm, the preferred thickness can be selected as needed. The film forming conditions used for extruding the polypropylene resin composition of the present invention out of the film are at an extrusion die temperature of 2 0 0 ° C to 2 50 ° C and a cooling roll temperature of 4 〇 to 65 ° C. It is better to carry out. 4 5 ~ 60 ° C is preferred. When the cooling roll temperature is lower than 4 (TC, it is not preferable because sufficient crystallization degree of enthalpy is not obtained in terms of heat-resistant dimensional stability. Conversely, in the case of more than 65 ton, contact roll indentation due to generation of a cooling roll However, the transparency is also extremely reduced. In addition, the cooling time is not particularly limited, but 0. A range of 5 seconds or more is preferred. Cooling time is less than 0. In the case of 5 seconds, since the cooling effect is insufficient, the contact roll indentation of the cooling roll is generated, which is not preferable. On the other hand, the upper limit of the cooling time is not particularly limited from the viewpoint of the degree of crystallization of the film, and is preferably 5 seconds or less from the viewpoint of economy and productivity, and more preferably 2 seconds or longer. Further, when the temperature is set to be slightly lower, it may be 3 seconds or longer. 〇 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶Therefore, it was found that the cooling conditions of the molten resin using the cooling conditions were controlled to adjust the degree of crystallization. [Control of Stretch Ratio] The extruded film of the present invention is adjusted to have a draw ratio in the stretching step after melt extrusion. 4~3. Within the range of 0, the birefringence of the film can be brought to a predetermined range. The draw ratio is generally known to be calculated by the following film forming conditions -25 - 201041947. Stretch ratio = (film stretching speed / extrusion die exit melting void) The so-called void means the distance (c m ) from the extrusion die exit to the molten resin (cooling) roll. The draw ratio is less than 0. In the case of 4, the film is less favorable in film thickness due to the thickness of the film. In the case of 3 · 0, the birefringence exceeds a certain degree of enthalpy, and the mechanical properties of the film itself are not deteriorated. [Thin film width direction thickness control] As a method of controlling the thickness in the film width direction, a method of automatically adjusting the lip gap of the die can be mentioned. As a method of varying the thickness, it is preferable to mold the lip gap by mechanical or heating voltage. In addition, in addition to the above, the adjustment gas is used to suppress the thickness variation in the width direction of 10% or less as a means for blowing air against the resin film which is placed on the cooling roll, and the air is blown from the air. When the air leaking between the gaps of the pneumatic damper rolls is increased, the thickness of the corrugated film in the width direction of the corrugated film is changed due to leakage of the resin film before the contact with the cooling rolls. For this reason, it is necessary to make the direction of the air chamber constant while making the absolute pressure of the wind pressure not increase. The wind pressure of the gas chamber is preferably as follows depending on the stretching speed of the film. Resin speed) + is connected to the stretching spot, and the stretching ratio is over-range and the problem of the impact is necessary. For example, it is necessary to automatically adjust the condition of the chamber by a short time. Gas and adhere to the cold upper part and the cooling air to make the thin wind pressure to the width of 20mmHg or more to -26-201041947. The corrugated film of the present invention can also be corona by the method generally used in the industry. Surface treatment such as discharge treatment or flame treatment. In the present invention, it is important that a surface protective film in which an adhesive layer is provided on at least one surface of the above-mentioned surface protective polypropylene resin film. By this correspondence, the characteristics of the above-mentioned polypropylene-based resin film of the present invention can be effectively recovered, and the applicability as a protective film in a wide range of fields is improved. In particular, for example, it is used to prevent damage or dust adhesion, contamination, etc. during processing and assembly of electronic, precision products, parts, and related components such as liquid crystal panels and polarizing plates, or as part of plating flexibility. a method of connecting a terminal portion of a printed circuit board, a method of attaching an adhesive film to a non-plating portion to form a mask, and then performing a plating method or a photoresist film provided on an unetched surface in an etching step in the manufacture of a shadow plate or A method of etching a film, etc., which is used for plating and etching, a method of laminating a surface of a semiconductor element on a surface of a semiconductor element without a circuit to protect a surface of the semiconductor element, and a method of simplifying the process in the case of assembling a semiconductor device. In particular, it is suitable for use as a protective film in the protection of various precision products and parts, and the processing and assembly steps of the products and parts, which are required to suppress contamination and defects. Further, the polypropylene resin film of the present invention is excellent in heat resistance dimensional stability, and in the adhesion processing, for example, by increasing the drying temperature in the drying step, heat generation and film relaxation can be suppressed, so that the productivity of the adhesive processing is improved. It is possible. Further, it is possible to suppress the occurrence of defective products caused by heat enthalpy and film relaxation. The type, thickness, and adhesion of the above-mentioned adhesive layer are not limited. It can also be selected according to market requirements. Further, the method of laminating the adhesive layer is not limited to the method of -27-201041947. Any of the coating method and the extrusion lamination method can be carried out. The present invention is more specifically described by the following examples, but the present invention is not limited by the following examples, and it is possible to carry out appropriate modifications and implementations within the scope of appropriately departing from the scope of the present invention. And the like are also included in the technical scope of the present invention. 1 _ melt flow rate [M F R ] according to JIS Κ 7210, with the condition of-14 (load 2. The measurement was carried out at a temperature of 16 kg and Ο 2 3 0 °c. 2. Ethylene content The measurement was carried out by the 1 3 C - N M R method according to the method described in the pp. 616 of the Handbook of Polymers (1995, issued by Kiyoshiya Shoten). 3. Ratio of xylene soluble portion at 20 ° C (%} After completely melting the sample 5 g in 500 ml of boiling xylene, the temperature was lowered to 20 ° C and allowed to stand for 4 hours or more. Then, the precipitate was separately filtered. With the solution, the solution was dried and hardened, and dried under reduced pressure at 70 ° C. 〇 The amount of the 20 ° c xylene soluble portion was determined from the mass of the dried product obtained to obtain the ratio. . The degree of crystallization of the film was measured using a wide-angle X-ray crystallization method (RIGAKU RINT 2500). 5. The coefficient of dynamic friction is used to combine the sealing layers of the film and the smoothness is determined in accordance with J I S - K 7 2 1 5 - 1 9 8 7 . -28- 201041947 6. Thickness variation rate One film sample of lm width was measured in a width of 3 cm in the width direction using a line gauge model SIS-6' manufactured by Kawasaki Co., Ltd. in accordance with JIS K7 130 to obtain an average thickness. Then, any one of the maximum or minimum enthalpy among the measured film samples and the difference in average thickness was used, and was calculated by the following calculation formula. Thickness variation rate (%) = 丨 (average thickness) - (maximum 最小 or minimum 値) 丨 / (average thickness 100 100 Ο 7. The Young's modulus is in accordance with JIS K7 127, and the sample shape is prepared using a test piece conforming to the i-shaped test piece (sample length 200 mm, sample width 15 mm, chuck distance 100 mm), and a right-angle head speed of 500 mm/min. The conditions were measured at 23 ° C in the MD direction (film longitudinal direction). 8. Birefringence (Δ η) The refractive index Νχ of the film flow direction, the flow direction of the film, and the refractive index Ny in the straight direction are measured using an Abbe refractometer, and are calculated using the following formula.
Δη=| Nx-Ny| 8.在20 °C中二甲苯可溶部的變動幅（％) 在寬度方向及縱向方向3 cm節距取樣lm寬的薄膜試 樣1片，以上述記載之方法測定2 0。(：二甲苯可溶部量，以 求得由1 〇點數據的最大値減去最小値之數値。 9 ·熱變形耐性 將經成型之薄膜切出成於流動方向5cmx相對於流動 -29- 201041947 方向於橫向方向25cm，在模具框於使兩端部保持之狀態 下水平地將薄膜片在 120 °C的乾熱烘箱内加熱處理5分 鐘。加熱處理後立即從烘箱取出且於室溫下放置冷却30 分鐘後’用以下的範圍目視觀察因薄膜本身的重量所致的 垂伸（伸長）狀態。 〇：沒有垂伸、或幾乎沒有。 △:觀察到一點點的垂伸狀態。 X :觀察到垂伸狀態。 〇 1 〇 .皺折·波紋評價（1) 將經成型之薄膜卷曲以1300mm寬軋輥狀的切分卷取 機（（股）東伸製SXR-140型}卷取成薄膜長i00m的軋輥之 際，目視觀察皴折·波紋的發生狀況。 〇：在行進中及卷取時沒有皴折.波紋的發生。 △:稍微在行進中或卷取時觀察到皺折·波紋的發 生。 X :在行進中或卷取時明顯觀察到皴折·波紋的發 11.皺折·波紋評價（2) 在上述皺折·波紋評價（1)中卷取之薄膜軋輥在濕度 50RH%、溫度23°C中、保管30天之後，目視觀察皴折. 波紋的發生狀況。 〇：沒有皺折·波紋的發生。 △:觀察到皺折·波紋的發生。 X :明顯觀察到皺折·波紋的發生。 -30- 201041947 1 8 .黏著劑塗布後的歪斜 將曰本合成化學製「COPONYL 8694」使用邁耶棒塗 布成黏著劑的厚度爲3~5/zm後’在70°C乾燥5秒。將黏 著劑塗布後的薄膜在平坦的場所擴展，以目視確認歪斜的 有無。 〇：無歪斜 △:稍微有點歪斜 x :有歪斜 1 2 .薄膜白化 將薄片1 80°折彎且產生折痕之後，目視判定於展開時 的彎曲部白化的有無。 ◎:無白化。 〇：觀察到稍微有點白化。 △:觀察到白化。 X :明顯地觀察到白化。 13.霧度 〇 依照JIS-K-6714’使用東洋精機製作所製的「霧度檢 驗器J」來測定。 1 4 .抗黏連性 依照ATM-D1893-67，將90N的負荷蓋在A4尺寸的 面積上，於60°C環境下放置2小時後去掉負荷之後，以移 動速度100mm/分的條件測定由0 5的鋁棒所致的剝離抵 抗。 1 5 .衝擊強度 -31- 201041947 依照 ASTM D3420，試樣係於縱向方向切成 55~60cm、於橫向方向且成9~10cm。讀取在23°C的屋子 裡使用衝擊檢驗器進行沖壓時的強度値至小數點以下第1 位。重複該操作1 0次’求得其平均値。 16.魚眼 將經成型之薄膜於流動方向切取成33.3 cmx相對於流 動方向爲橫向方向切取成30cm’放置在從薄膜的下方照 射螢光燈之板上’以目視觀察透過光’計測0.1 m m以上的 〇 魚眼。接著，將經計算之魚眼浸入液體氮中，在硬化的狀 態下，以剃刀切成一半並以顯微鏡用5 0 ~3 0 0倍觀察該魚 眼的剖面，若沒有形成核的物質’例如若沒有以纖維素等 爲代表性的異物的話’彼等係判定爲未熔融的結塊、原料 的一部份因凝膠化而成之結塊、成形中因部分材料的劣化 所致的結塊等的凝膠起因的魚眼。有核的情形’判定爲異 物起因的魚眼則不算入計算中。 (實施例1) Θ 將包含由同元聚丙烯樹脂（MFR=7)69重量份、橡膠成 分量爲13.0% ·乙烯含量爲6.5%的嵌段共聚合聚丙烯樹脂 (MFR = 2)22重量份、含有三井化學（股）製彈性體（商品 名：Tafmer P0480)7重量份及丙儲酸酯系抗氧化劑之 Sumilizer GS(住友化學（股）公司製）5重量％之同元聚丙烯 樹脂（MFR = 7)所構成之丙烯酸酯系抗氧化劑的母料樹脂2 重量份，在掛有加熱電壓式之自動厚度控制機能的T模頭 製膜機中進行熔融壓出，以在冷却軋輥溫度60 °C中、冷却 -32- 201041947 時間2.0秒（製膜速度60m /分）、熔融樹脂的拉伸時的拉伸 比1.56(擠壓模模唇間隙：0.5mm、擠壓模模唇出口熔融樹 脂速度：4.8m/分、空隙：8cm)、氣室風壓lOmmHg的製膜 條件得到厚度40# m的未延伸薄膜。而且’將上述擠壓機 的供給區、混練區及計量區的各個樹脂溫度設爲230、240 及235 °C。其結果表示於表1。 本實施例所得之聚丙烯系樹脂膜係如表1所示的任一 特性均爲良好且爲高品質。 Ο (實施例2) 除了配合含有作爲磷系抗氧化劑之 IRGAFOS 1 6 8 ( C i b a Specialty Chemicals(股）公司製）0.15 質量％ 及作爲酚系抗氧化劑之IRGANOX 1010(Ciba Specialty Chemicals(股）公司製）0.18質量％之橡膠成分量爲13.0%、 乙烯含量爲6.5%的嵌段共聚合聚丙烯樹脂（]\4?1^ = 2)95重 量份、與乙烯含量 3.0%的無規共聚合聚丙烯樹脂 (MFR = 7)5重量份，且冷却軋輥溫度設爲45t以外，以與 ^ 實施例1同樣的方法，得到實施例2的聚丙烯系樹脂膜。 其結果表示於表1。 本實施例所得之聚丙烯系樹脂膜係如表1所示的任一 特性均爲良好且爲高品質。 (實施例3) 除了配合含有作爲磷系抗氧化劑之 IRGAFOS 1 68(Ciba Specialty Chemicals(股）公司製）0.15 質量。/。 及作爲酚系抗氧化劑之IRGANOX l〇l〇(Ciba Specialty -33- 201041947Δη=| Nx-Ny| 8. Variation range (%) of xylene soluble portion at 20 °C Sample one lm wide film sample at a pitch of 3 cm in the width direction and the longitudinal direction, by the method described above Determination 20. (: The amount of xylene soluble portion is obtained by subtracting the minimum enthalpy from the maximum enthalpy of 1 〇 point data. 9 · Thermal deformation resistance The formed film is cut into a flow direction of 5 cmx relative to flow -29 - 201041947 The direction was 25 cm in the transverse direction, and the film sheet was horizontally heated in a dry heat oven at 120 ° C for 5 minutes while the mold frame was held at both ends. Immediately after the heat treatment, the film was taken out from the oven at room temperature. After standing under cooling for 30 minutes, the state of elongation (elongation) due to the weight of the film itself was visually observed in the following range. 〇: No sag, or almost no. △: A slight degree of sag was observed. : The state of sag is observed. 〇1 〇. Wrinkle and corrugation evaluation (1) The formed film is crimped by a 1300 mm wide roll-shaped slitter reel (SXR-140 type) When the film was a roll of i00 m in length, the occurrence of collapse and waviness was visually observed. 〇: No breakage occurred during traveling and winding. Occurrence of ripples △: Wrinkles were observed slightly during traveling or during winding. · The occurrence of ripples. X: On the road or in the coil When the folds and corrugations were observed, the wrinkles and the corrugations were evaluated. (2) The film rolls taken up in the wrinkle/corrugation evaluation (1) were stored at a humidity of 50 RH% and a temperature of 23 ° C for 30 days. After that, the occurrence of the wrinkles was visually observed. 〇: No wrinkles and ripples occurred. △: Wrinkles and waviness were observed. X: Wrinkles and waviness were observed clearly. -30- 201041947 1 8. The skew after the application of the adhesive is applied to the synthetic chemical "COPONYL 8694" using a Meyer bar to a thickness of 3 to 5 / zm after the adhesive is dried at 70 ° C for 5 seconds. After the adhesive is coated The film is spread in a flat place to visually confirm the presence or absence of skew. 〇: no skew △: slightly skewed x: skewed 1 2 . film whitening, after the sheet is bent at 80° and creased, visually judged at the time of expansion ◎: No whitening. 〇: A little whitening was observed. △: Whitening was observed. X: Whitening was clearly observed. 13. Haze 东 东 精 〇 〇 〇 〇 〇 〇 〇 东 东 东 东 东 东 东 东 东The "haze tester J" manufactured by the system is measured. 1 4 . Adhesiveness According to ATM-D1893-67, the load of 90N was placed on the area of A4 size, and after being placed in a 60 °C environment for 2 hours, the load was removed, and the aluminum of 0 5 was measured at a moving speed of 100 mm/min. Peeling resistance by bar. 1 5. Impact strength -31- 201041947 According to ASTM D3420, the sample is cut into 55~60cm in the longitudinal direction and 9~10cm in the transverse direction. Read in the room at 23°C. The strength at the time of punching using the impact tester is 第 to the first decimal place. Repeat this operation 10 times to find the average 値. 16. The fisheye cuts the formed film in the direction of flow to 33.3 cmx and cuts it into a transverse direction with respect to the flow direction to 30 cm'. It is placed on the plate from the lower side of the film to illuminate the fluorescent lamp 'measured through the light' 0.1 mm. Above the squid eye. Next, the calculated fisheyes are immersed in liquid nitrogen, and in a hardened state, the razor is cut into half and the fisheye cross section is observed with a microscope at 50 to 300 times, if no nuclear substance is formed' If there is no foreign matter such as cellulose, 'they are judged to be unmelted agglomerates, a part of the raw material is agglomerated by gelation, and the knot is formed due to deterioration of some materials during forming. A fish eye caused by a gel such as a block. In the case of a nucleus, the fisheye determined to be the cause of the foreign matter is not included in the calculation. (Example 1) 嵌段 A block copolymerized polypropylene resin (MFR = 2) 22 weight containing 69 parts by weight of a homopolymer polypropylene resin (MFR = 7), a rubber component amount of 13.0%, and an ethylene content of 6.5%. 5% by weight of homopolymer polypropylene resin containing 7 parts by weight of Mitsui Chemicals Co., Ltd. (trade name: Tafmer P0480) and Sumilizer GS (manufactured by Sumitomo Chemical Co., Ltd.) (MFR = 7) 2 parts by weight of the master batch resin of the acrylate-based antioxidant, which is melt-extruded in a T-die film forming machine with a heating voltage type automatic thickness control function to cool the roll temperature 60 °C, cooling -32-201041947 time 2.0 seconds (filming speed 60m / min), stretch ratio of molten resin when stretching 1.56 (extrusion die lip gap: 0.5mm, extrusion die lip outlet A filming condition of a molten resin speed: 4.8 m/min, a void: 8 cm) and a gas pressure of 10 mmHg was obtained as an unstretched film having a thickness of 40 #m. Further, the respective resin temperatures of the supply zone, the kneading zone and the metering zone of the above extruder were set to 230, 240 and 235 °C. The results are shown in Table 1. The polypropylene resin film obtained in the present Example was excellent in any of the properties shown in Table 1 and was of high quality.实施 (Example 2) In addition to containing IRGAFOS 1 6 8 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as a phosphorus-based antioxidant, 0.15 mass% of IRGANOX 1010 (Ciba Specialty Chemicals Co., Ltd.) as a phenolic antioxidant a random copolymerization of 0.18 mass% of a rubber component having a rubber content of 13.0% and an ethylene content of 6.5%, 95 parts by weight, and an ethylene content of 3.0% by weight of a block copolymerized polypropylene resin (=\4?1^ = 2) A polypropylene resin film of Example 2 was obtained in the same manner as in Example 1 except that the polypropylene resin (MFR = 7) was 5 parts by weight and the cooling roll temperature was 45 t. The results are shown in Table 1. The polypropylene resin film obtained in the present Example was excellent in any of the properties shown in Table 1 and was of high quality. (Example 3) In addition to containing IRGAFOS 1 68 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as a phosphorus-based antioxidant, 0.15 by mass. /. And as a phenolic antioxidant IRGANOX l〇l〇 (Ciba Specialty -33- 201041947
Chemicals(股）公司製）0.15質量。/〇之同元聚丙烯樹脂 (MFR = 7)85.5重量份、與三井化學（股）製彈性體（商品 名：Tafmer P〇480)l4.5重量份’且將冷却軋輥溫度設爲 50 °C、熔融樹脂的拉伸時的拉伸比設爲2.50(擠壓模模唇 間隙：0.8mm、擠壓模模唇出口熔融樹脂速度：3.〇m /分、 空隙：8 c m)以外，以與實施例1同樣的方法，得到實施例3 的聚丙烯系樹脂膜。其結果表示於表1。 本實施例所得之聚丙烯系樹脂膜係具有與實施例1所 得之聚丙烯系樹脂膜同等的特性且爲高品質。 (實施例4) 將包含同元聚丙烯樹脂（MFR = 7)73重量份、橡膠成分 量爲13.0%.乙烯含量爲6_5 %的嵌段共聚合聚丙烯樹脂 (MFR = 2) 23重量份、由含有三井化學（股）製彈性體（商品 名：Tafmer P0480)12重量份及丙烯酸酯系抗氧化劑之 Sumilizer GS(住友化學（股）公司製）5重量。/。之同元聚丙烯 樹脂（MFR=7)所構成之丙烯酸酯系抗氧化劑的母料樹脂2 重量份，從具備偏析防止裝置之原料料斗投入至壓出機並 熔融，在掛有加熱電壓式之自動厚度控制機能的T模頭製 膜機中進行熔融壓出，以冷却軋輥溫度6 0 °C且冷却時間 2.0秒（製膜速度60m/分）、熔融樹脂的拉伸時的拉伸比 1.56(擠壓模模唇間隙：0.5mm、擠壓模模唇出口熔融樹脂 速度：4.8m/分、空隙：8cm)氣室風壓 lOmmHg的製膜條 件，得到厚度40#m的未延伸薄膜。而且，將上述擠壓機 的供給區、混練區及計量區的各個樹脂溫度設爲230、240 -34- 201041947 及235 °C。又’進行寬度方向的厚度控制。其結果表示於 表 1。 本實施例所得之聚丙烯系樹脂膜係如表1所示的任一 特性均爲良好且爲高品質。 (實施例5) 除了配合含有作爲磷系抗氧化劑之 IRGAFOS 168(Ciba Specialty Chemicals(股）公司製）〇.15 質量 ％ 及作爲酣系抗氧化劑之IRGANOX l〇l〇(Ciba Specialty O chemicals(股）公司製）0.15質量。/。的同元聚丙烯樹脂 (MFR= 7)90重量份、與三井化學（股）製彈性體（商品 名：Tafmer P0480)10重量份，且將冷却軋輥溫度設爲 50 °C、熔融樹脂的拉伸時的拉伸比設爲2.50(擠壓模模唇 間隙：0.8mm、擠壓模模唇出口熔融樹脂速度：3.0m/分、 空隙：8cm)以外，以與實施例4同樣的方法，得到實施例2 的聚丙烯系樹脂膜。其結果表示於表1。 本實施例所得之聚丙烯系樹脂膜係具有與實施例4所 Θ 得之聚丙烯系樹脂膜同等的特性且爲高品質。 (實施例6> 除了從不具備偏析防止裝置之原料料斗投入壓出機、 使原料樹脂熔融以外，以與實施例4同樣的方法，得到實 施例6的聚丙烯系樹脂膜。其結果表示於表2。 (比較例1} 除了配合乙烯含量爲〇·5質量％的無規共聚合聚丙烯 樹脂（MFR = 7) 30重量份、及含有作爲磷系抗氧化劑之 -35- 201041947 IRGAFOS 168(Ciba Specialty Chemicals(股）公司 製）0.22 質量％及作爲酚系抗氧化劑之IRGANOX 1010(Ciba Specialty Chemicals(股）公司製）〇.28 質量 ％ 的橡膠成分量爲8.5%·乙烯含量爲5.0 %的嵌段共聚合聚 丙烯樹脂（MFR = 2)70重量份以外，以與實施例1同樣的方 法，得到比較例2的聚丙烯系樹脂膜。其結果表示於表2。 本比較例所得之聚丙烯系樹脂膜係在薄膜軋輥保管中 發生了皺折·波紋。 〇 (比較例2) 配合包含乙烯含量爲〇·5質量％的無規共聚合聚丙烯 樹脂（MFR = 7)98重量份、含有由作爲環狀有機磷酸酯化合 物之雙（2,2_-亞甲基-雙（4,6-二-第三丁基苯基）磷酸酯）-氫 氧化鋁鹽（旭電化工業（股）公司製、ADEKASTAB ΝΑ-21Π 重量％含同元聚丙烯樹脂（MFR = 7)所構成之結晶核劑的母 料樹脂（M-1)1重量份、含有由丙烯酸酯系抗氧化劑之 Sumilizer GS (住友化學（股）公司製）5重量％的同元聚丙烯 Ο 樹脂（MFR = 7)所構成之丙烯酸酯系抗氧化劑的母料樹脂1 重量份，在T模頭製膜機中進行熔融壓出’以冷却軋輥溫 度45 °C且冷却時間3·0秒（製膜速度40m/分）、熔融樹脂 的拉伸時的拉伸比1.60(擠壓模模唇間隙：〇.5mm、擠壓模 模唇出口熔融樹脂速度：8.〇m/分、空隙：8cm)的製膜條件， 得到厚度lOO/zm的未延伸薄膜。其結果表_示於表2。本 比較例所得之聚丙烯系樹脂膜也會在薄膜乳輥保管中發生 皺折·波紋。 -36- 201041947 (比較例3) 除了配合含有作爲磷系抗氧化劑之IRGAFOS 1 68 (Ciba Specialty Chemicals(股）公司製）0.15 質量 ％ 及作爲酣系抗氧化劑之 IRGANOX 1010(Ciba Specialty Chemicals(股）公司製）0.18質量％的橡膠成分量爲11.0%、 乙烯含量爲20%的嵌段共聚合聚丙烯樹脂（MFR = 2)100重 量份以外，以與實施例1同樣的方法，得到比較例3的聚 丙烯系樹脂膜。其結果表示於表2。 〇 本比較例所得之聚丙烯系樹脂膜係熱變形耐性不充 分。 (比較例4) 除了將氣室風壓設爲40 mHg以外，以與實施例1同 樣的方法，得到比較例4的聚丙烯系樹脂膜。其結果表示 於表2。 本比較例所得之聚丙烯系樹脂膜係在薄膜軋輥保管中 發生了皺折·波紋。 Ο (比較例5) 除了配合乙烯含量爲0.5質量％的無規共聚合聚丙烯 樹脂（MFR = 7) 9 7重量份、及包含由含有丙烯酸酯系抗氧化 劑之Sumilizer GS(住友化學（股）公司製）5重量。/〇的同元 聚丙烯樹脂（MFR = 7)所構成之丙烯酸酯系抗氧化劑的母料 樹脂1重量份、三井化學（股）製彈性體（商品名：Tafmer P0 4 8 0)2重量份以外，以與實施例4同樣的方法得到比較 例5的聚丙烯系樹脂膜。其結果表示於表2。 -37- 201041947 本比較例所得之聚丙烯系樹脂膜係薄膜容易白化、熱 變形耐性也變差之外，在薄膜軋輥保管中發生了皴折.波 紋。 (比較例6) 配合含有作爲磷系抗氧化劑之IRGAFOS 168(Ciba Specialty Chemicals(股）公司製）0.22質量％及作爲酚系 抗氧 化劑之 IRGANOX 10 10(Ciba Specialty Chemicals(股）公司製）0.28質量。/。的橡膠成分量爲13%. 〇 乙烯含量爲6.5%的嵌段共聚合聚丙烯樹脂（^^尺=7)22重 量份、包含由含有同元聚丙烯樹脂（MFR = 7)57重量份、三 井化學（股）製彈性體（商品名：Tafmer P0480)2重量份及丙 烯酸酯系抗氧化劑之 Sumilizer GS(住友化學（股）公司 製）5重量％的同元聚丙烯樹脂（MFR = 7)所構成之丙烯酸酯 系抗氧化劑的母料樹脂1重量份，以與實施例1同樣方式 從具備偏析防止裝置之原料料斗投入壓出機並熔融，在掛 有加熱電壓式之自動厚度控制機能的T模頭製膜機中進行 Ο 熔融壓出，以冷却軋輥溫度45°C且冷却時間3.0秒（製膜 速度40m/分）、熔融樹脂的拉伸時的拉伸比0.63(擠壓模 模唇間隙：0.5mm、擠壓模模唇出口熔融樹脂速度：8.〇m/ 分、空隙：8cm)的製膜條件，得到厚度100 /z m的未延伸薄 膜。其結果表示於表2。本比較例所得之聚丙烯系樹脂膜 係在黏著劑塗布後的薄膜有歪斜。 (比較例7) 除了不進行寬度方向的厚度控制以外，以與實施例4 -38- 201041947 同樣的方法，得到比較例7的聚丙烯系樹脂膜。其結果表 示於表2。 本比較例所得之聚丙烯系樹脂膜係在薄膜的行進中及 薄膜軋輥保管中發生了鈹折.波紋。 {參考例1) 在比較例1的方法中，除了添加含有結晶核劑之母料 樹脂（Μ- 1) 5重量份以外，以與比較例1同樣的方法，得到 參考例3的聚丙烯系樹脂膜。其結果表示於表3。 〇 本參考例所得之聚丙烯系樹脂膜係魚眼與比較例1所 得之聚丙烯系樹脂膜相比爲大幅增大且爲低品質。 將上述結果表示於表1、表2。 〇 -39- 201041947 ο ο I嗽 實施例6 VO v〇 1 CO 1-H in v〇 <N (N <N O 14.9 | 〇 v£> § 2.0 1.56 ο 寸 S 0.79 00 rH 4.4 Ο S 850 0.42 〇 〇 〇 〇 X 實施例5 〇 1 1 « 1 o o 10.0 | S o v〇 [2.0 2.50 ο 寸 (N 寸 0.93 CO 1 2.2 ?—1 LO 0.9 Ο ν〇 CN 700 0.49 〇 〇 〇 〇 〇 實施例4 66 t 1 CO «-Η in 'ό CN cs <N H o 14.9 〇 v〇 〇 v〇 2.0 1.56 ο 寸 寸 ΙΟ ! 0.79 rH oq 4.7 i-H ο ν〇 850 0.42 〇 ◎ 〇 〇 〇 實施例3 85.5 1 1 1 1 1 14.5 o 14.5 s 〇 \〇 2.0 2.50 ο i-H Ο 寸 0.85 ¢0 CN (N i 6.4 1 ο ν〇 <Ν 770 0.47 〇 〇 〇 〇 i 實施例2 ______ -_____J c〇 ΙΟ CO f-H l〇 lO σ> o o 12.35 l〇 寸 〇 VO 0 01 1.56 ο 寸 (N 00 Γ〇 0.95 in !>· 1—( CO ιό 1 ο 10 ν〇 600 0.69 〇 〇 〇 〇 1 實施例1 _71_, 1 1 CO i—H 6.5 CN (N o 9.9 ο 〇 v〇 2.0 1.56 ο 寸 0.82 o oq i-H 4.0 1 ο S 900 0.61 〇 ◎ 〇 〇 § _ Λπί Ρη S <Sn I in 账 1R E 咖 4α 涯 ΚΙ 募 An 嵌 * φ _ ilmil 闕 a <!□ I 4Π m 昵 m 著 Φ： m 151 擀 fi ll P 〇 cs 募 <n m 豳 M mM K) 豪 <ίπ m Φ _ 細 s 如 I _ ilmll PH t <n 藥 BibL ά Φ _ _ t ±i <□ 圇 m m mg 堞 全體的20%二甲苯可溶分:％ .ΰ u 頰 s ity； 脚 m m 酲 m s 变 拉伸比 __ __ m st m 脓 螂 < 驗 I 柱 iacL 挪 ?r ό «-Η X ft 褂 1 m it i20°C二甲苯可溶部暈變動率 β Μ β fi (Ν ό μ"1 β 、^ 圉 e 6 (Ν Ο g m 1 bjbL 录 S 缌 鏘 Itlwii 郷 薄膜白化 熱變形耐件 T-H & Μ 'k 篛 C? Μ έ 黏著劑塗布後的歪斜 1 聚合物原料 1 製膜條件 薄膜特性 劁 ¥¥]nHwl®Chemicals (stock) company) 0.15 quality. / 〇 同 聚丙烯 polypropylene resin (MFR = 7) 85.5 parts by weight, and Mitsui Chemicals (trade name: Tafmer P 480) 14.5 parts by weight 'and the cooling roll temperature is set to 50 ° C. The draw ratio at the time of stretching of the molten resin was set to 2.50 (extrusion die lip gap: 0.8 mm, extrusion die lip outlet melt resin speed: 3. 〇m / min, void: 8 cm), The polypropylene resin film of Example 3 was obtained in the same manner as in Example 1. The results are shown in Table 1. The polypropylene resin film obtained in the present example has the same characteristics as those of the polypropylene resin film obtained in Example 1, and is high in quality. (Example 4) 23 parts by weight of a block copolymerized polypropylene resin (MFR = 2) containing 73 parts by weight of a homopolymer polypropylene resin (MFR = 7), a rubber component amount of 13.0%, an ethylene content of 6 - 5 %, 5 parts by weight of Sumilizer GS (manufactured by Sumitomo Chemical Co., Ltd.) containing 12 parts by weight of an elastomer (trade name: Tafmer P0480) made of Mitsui Chemicals Co., Ltd. and an acrylate-based antioxidant. /. 2 parts by weight of the master batch resin of the acrylate-based antioxidant composed of the homopolypropylene resin (MFR=7), which is supplied from the raw material hopper having the segregation preventing device to the extruder and melted, and is heated with a heating voltage type Melt extrusion in the T-die film forming machine of the automatic thickness control function to cool the roll temperature of 60 ° C and the cooling time of 2.0 seconds (film forming speed of 60 m / min), and the draw ratio of the molten resin when stretched by 1.56 (Extrusion die lip gap: 0.5 mm, extrusion die lip outlet resin speed: 4.8 m/min, void: 8 cm) Film forming conditions of a gas chamber wind pressure of 10 mmHg, and an unstretched film having a thickness of 40 #m was obtained. Further, the respective resin temperatures of the supply zone, the kneading zone and the metering zone of the above extruder were set to 230, 240 - 34 - 201041947 and 235 °C. Further, thickness control in the width direction is performed. The results are shown in Table 1. The polypropylene resin film obtained in the present Example was excellent in any of the properties shown in Table 1 and was of high quality. (Example 5) In addition to containing IRGAFOS 168 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as a phosphorus-based antioxidant, 15 mass% and IRGANOX l〇l〇 (Ciba Specialty O chemicals) as a lanthanide antioxidant )Company system) 0.15 quality. /. 90 parts by weight of a homopolypropylene resin (MFR=7) and 10 parts by weight of an elastomer (trade name: Tafmer P0480) manufactured by Mitsui Chemical Co., Ltd., and the cooling roll temperature was set to 50 ° C, and the molten resin was pulled. The same method as in Example 4 was carried out except that the draw ratio at the time of stretching was set to 2.50 (extrusion die lip gap: 0.8 mm, extrusion die lip melt resin speed: 3.0 m/min, void: 8 cm). The polypropylene resin film of Example 2 was obtained. The results are shown in Table 1. The polypropylene resin film obtained in the present example has the same characteristics as those of the polypropylene resin film obtained in Example 4 and is high in quality. (Example 6) A polypropylene-based resin film of Example 6 was obtained in the same manner as in Example 4 except that the raw material hopper was placed in the raw material hopper without the segregation preventing device and the raw material resin was melted. Table 2 (Comparative Example 1) 30 parts by weight of a random copolymerized polypropylene resin (MFR = 7) having an ethylene content of 〇·5% by mass, and -35-201041947 IRGAFOS 168 (as a phosphorus-based antioxidant) 0.22% by mass and IRGANOX 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as a phenolic antioxidant, 2.88% by mass of the rubber component is 8.5%, and the ethylene content is 5.0%. A polypropylene-based resin film of Comparative Example 2 was obtained in the same manner as in Example 1 except that the block copolymerized polypropylene resin (MFR = 2) was 70 parts by weight. The results are shown in Table 2. The propylene-based resin film was wrinkled and corrugated during storage of the film roll. 〇 (Comparative Example 2) 98 parts by weight of a random copolymerized polypropylene resin (MFR = 7) containing an ethylene content of 〇·5% by mass, contain Bis(2,2--methylene-bis(4,6-di-t-butylphenyl)phosphate)-hydrogen aluminum hydroxide as a cyclic organophosphate compound (made by Asahi Kasei Kogyo Co., Ltd.) ADEKASTAB ΝΑ-21Π 1% by weight of a masterbatch resin (M-1) containing a crystal nucleating agent composed of a homopolypropylene resin (MFR = 7), containing Sumilizer GS (Sumitomo Chemical) (manufactured by the company) 1 part by weight of a masterbatch resin of an acrylate-based antioxidant composed of 5% by weight of a homopolypropylene resin (MFR = 7), and melt-pressed in a T-die film forming machine' The cooling roll temperature was 45 ° C and the cooling time was 3.0 seconds (film forming speed 40 m / min), and the stretching ratio of the molten resin was 1.60 (extrusion die lip gap: 〇.5 mm, extrusion die) The film forming conditions of the lip outlet molten resin speed: 8. 〇m/min, void: 8 cm) were obtained, and an unstretched film having a thickness of 100/zm was obtained. The results are shown in Table 2. The polypropylene resin obtained in the present comparative example. The film also wrinkles and wrinkles during storage of the film roll. -36- 201041947 (Comparative Example 3) IRGAGOS 1 68 (manufactured by Ciba Specialty Chemicals Co., Ltd.) of the oxidizing agent, 0.15 mass%, and IRGANOX 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as a lanthanide antioxidant, the amount of the rubber component was 0.18% by mass, and the ethylene content was 11.0%. A polypropylene resin film of Comparative Example 3 was obtained in the same manner as in Example 1 except that the amount of the block copolymerized polypropylene resin (MFR = 2) was 20 parts by weight. The results are shown in Table 2.聚丙烯 The polypropylene resin film obtained in this comparative example is not sufficiently resistant to thermal deformation. (Comparative Example 4) A polypropylene-based resin film of Comparative Example 4 was obtained in the same manner as in Example 1 except that the gas pressure was 40 mHg. The results are shown in Table 2. The polypropylene resin film obtained in the comparative example was wrinkled and corrugated during storage of the film roll. Ο (Comparative Example 5) In addition to a 97% by weight of a random copolymerized polypropylene resin (MFR = 7) having an ethylene content of 0.5% by mass, and a Sumilizer GS containing Sucrose-containing oxidant (Sumitomo Chemical Co., Ltd.) Company system) 5 weight. 1 part by weight of a masterbatch resin of an acrylate-based antioxidant composed of a homopolymer polypropylene resin (MFR = 7), and 2 parts by weight of an elastomer manufactured by Mitsui Chemicals Co., Ltd. (trade name: Tafmer P0 4 8 0) A polypropylene resin film of Comparative Example 5 was obtained in the same manner as in Example 4 except for the above. The results are shown in Table 2. -37-201041947 The polypropylene resin film-based film obtained in the comparative example is easily whitened and the heat deformation resistance is also deteriorated, and the film roll is damaged during storage of the film roll. (Comparative Example 6) 0.2 g by mass of IRGAFOS 168 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as a phosphorus-based antioxidant and 0.28% by mass of IRGANOX 10 10 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as a phenolic antioxidant . /. The amount of the rubber component is 13%. The block copolymerized polypropylene resin having an ethylene content of 6.5% (manufactured by mass = 7) is 22 parts by weight, and contains 57 parts by weight of the homopolymer polypropylene resin (MFR = 7). 2 parts by weight of an elastomer (trade name: Tafmer P0480) manufactured by Mitsui Chemicals Co., Ltd. and a lactic acid antioxidant, Sumilizer GS (manufactured by Sumitomo Chemical Co., Ltd.), 5% by weight of the same polypropylene resin (MFR = 7) 1 part by weight of the master batch resin of the acrylate-based antioxidant, which was put into the extruder from the raw material hopper having the segregation prevention device and melted in the same manner as in the first embodiment, and the automatic thickness control function of the heating voltage type was attached. The T-die film forming machine performs 熔融 melt extrusion to cool the roll temperature of 45 ° C and a cooling time of 3.0 seconds (film forming speed of 40 m / min), and the draw ratio of the molten resin during drawing is 0.63 (extrusion die) Lip gap: 0.5 mm, extrusion die lip outlet resin speed: 8. 〇m / min, void: 8 cm) film forming conditions, to obtain a thickness of 100 / zm unstretched film. The results are shown in Table 2. The polypropylene resin film obtained in the comparative example was skewed by the film after the application of the adhesive. (Comparative Example 7) A polypropylene-based resin film of Comparative Example 7 was obtained in the same manner as in Example 4-38-201041947 except that the thickness control in the width direction was not performed. The results are shown in Table 2. The polypropylene resin film obtained in the comparative example was broken and corrugated during the progress of the film and during storage of the film roll. {Reference Example 1> In the method of Comparative Example 1, a polypropylene system of Reference Example 3 was obtained in the same manner as in Comparative Example 1, except that 5 parts by weight of a master batch resin (Μ-1) containing a crystal nucleating agent was added. Resin film. The results are shown in Table 3. The polypropylene resin film obtained from the reference example was significantly larger and lower in quality than the polypropylene resin film obtained in Comparative Example 1. The above results are shown in Tables 1 and 2. 〇-39- 201041947 ο ο I 嗽 Example 6 VO v〇1 CO 1-H in v〇<N (N <NO 14.9 | 〇v£> § 2.0 1.56 ο S S 0.79 00 rH 4.4 Ο S 850 0.42 〇〇〇〇X Example 5 〇1 1 « 1 oo 10.0 | S ov〇[2.0 2.50 ο inch (N inch 0.93 CO 1 2.2 ?-1 LO 0.9 Ο ν〇CN 700 0.49 〇〇〇〇〇 implementation Example 4 66 t 1 CO «-Η in 'ό CN cs <NH o 14.9 〇v〇〇v〇2.0 1.56 ο inch inch ΙΟ ! 0.79 rH oq 4.7 iH ο ν〇850 0.42 〇◎ 〇〇〇 Example 3 85.5 1 1 1 1 1 14.5 o 14.5 s 〇\〇2.0 2.50 ο iH Ο inch 0.85 ¢0 CN (N i 6.4 1 ο ν〇<Ν 770 0.47 〇〇〇〇i Example 2 ______ -_____J c〇ΙΟ CO fH l〇lO σ> oo 12.35 l〇 inch 〇 VO 0 01 1.56 ο inch (N 00 Γ〇0.95 in !>· 1—( CO ιό 1 ο 10 ν〇600 0.69 〇〇〇〇1 Example 1 _71_ , 1 1 CO i-H 6.5 CN (N o 9.9 ο 〇v〇2.0 1.56 ο inch 0.82 o oq iH 4.0 1 ο S 900 0.61 〇◎ 〇〇§ _ Λπί Ρη S <Sn I in account 1R E coffee 4α涯ΚΙ Recruitment An embedded * φ _ Ilmil 阙a <!□ I 4Π m 昵m with Φ: m 151 擀fi ll P 〇cs raise <nm 豳M mM K) 豪<ίπ m Φ _ fine s such as I _ ilmll PH t <n Medicine BibL ά Φ _ _ t ±i < □ mg mm mg 堞 all 20% xylene soluble fraction: % .ΰ u cheek s ity; foot mm 酲 ms variable stretch ratio __ __ m st m purulent < Test I column iacL move?r ό «-Η X ft 褂1 m it i20 °C xylene soluble halo variation rate β Μ β fi (Ν ό μ"1 β , ^ 圉e 6 (Ν Ο gm 1 bjbL Record S 缌锵Itlwii 郷 Film whitening heat deformation resistant parts TH & Μ 'k 篛C? Μ 歪 Viscosity after coating 1 Polymer raw material 1 Film forming conditions Film characteristics 劁¥¥]nHwl®
I 201041947 ο 參考例1 io d Ο CO 1__1 cs ro 〇 卜 O 0.05 1_„一1 〇 <〇 〇 v〇 2.0 | 1.56 | 〇 σ\ CO 〇\ v〇 ； 0.79 | ο Ο) rH 6.5 1 1 〇 ι-Η 187 810 1 0.65 1 X 〇 〇 < 比較例7 v〇 v〇 I CO rH I 6.5 ! <N <N ο 1___1 S S 2.0 「1.56 1 〇 寸 吳 CO LO | 0.80 1 00 rH 11.9 1 CO 〇 v£) i-H 850 1 0.40 | 〇 X X X 比較例6 58 1 Ο CO 1 6.5 (N (N § ο 1 22.9 1 〇 3.0 「0.63 ] Γ loo__ 00 co CO 「0.92 1 ΙΟ 1 0.6 1 4.9 1 <J\ d 〇 in 560 1 0.85 1 ◎ < 〇 〇 X 比較例5 1 N ο o o 〇 <N ο 12Ό__1 S 〇 2.0 I 1.56 1 〇 (N co 00 ID __1-14 1 卜 1-Η 3.8 1 0.2 〇 00 (N 760 1 0.52 1 X X 〇 X 〇 比較例4 0 i-H 卜 1 1 CO r-H 6.5丨 (N CN Ν 1^__1 〇 ν£) S 2.0 | 1.56 1 〇 另 | 0.88 | ο 00 »-Η 14.9 1 1 〇 \〇 I—( 900 1 0.61 | 〇 ◎ X X 比較例3 0 t ο | 20.0 | __lL〇_ 100 〇 Ο 1 20.0 1 § 〇 2.0 I 1.56 1 〇 S | 0.94 1 Οί 1 〇 (N CO __67P_ | 0.81 | ◎ < 〇 X 比較例2 2 ! in d 00 θ' o o o 〇 ο.οι 1 1 o.o i LO 寸 〇 寸 3.0 [0.63 | __1〇〇_ 1-H 00 寸 _L15_ 00 \〇 6 4.9 1 1 〇 in r-H 560 1 0.48 | X 〇 〇 X |〇 in d ο C0 1__1 CN CO o ο 14,7___I Ο 〇 2.0 I 1.56 | 〇 CO 00 in 10^1__ ο Ο] «-Η 1____ 1 〇 00 CN 1ISO__ | 0.42 | X 〇 〇 < 1 $ ιΗ <1mil Ρπ t <!□ in IS K iM 部 ΚΙ I 4π K % 摧 § _ Jmil Ρπ 禁 i m φ 键 t? 梢· B- ii P s <n Μ <tn K] <n m 豳 m § _ ihml Pit s 1 跋 m d 〇M _ 廳 m nmt 酰 Φ m κ hO φ _ ff 奪 OJ §1 < m Φ 锲 t? 擀 fi ll 容 § S m 〇ΰ m si 龜 Φ β « Jn/ 糊 m 1 酲 m 辑 1拉伸比 1 涵 it m 嫩 冢 m 臟 m =¥ mg m 職 ft 1 却 MJ 挪 CO^ j fe ¥ i m tt 20°C二甲苯可溶部量變動率 μ"· e '_ g B (N d 疵 oT* g 6 (N o % cu s M m- nr> i： 1 m litwi 戰 满膜白化 is 翁 m i-H 1 ite u s 輕 te 鐘 蕊 削 S m 槲 *5 聚合物原料 1 製膜條件 薄膜特性 蕊|§Ί ¥ II酿 afft,你^ -K褂 染舰郵概#1 a '*1 棄/¾ 201041947 產業上的利用可能性 本發明係耐熱尺寸安定性與平面性優異 貼合加工性優異，例如適合作爲保護膜的基 本發明的表面保護用聚丙烯系樹脂膜由 定性優異，例如在黏著加工等的二次加工適 別是由於即使在1 3 0 °C附近的高溫進行乾燥 可抑制熱皴與薄膜鬆弛的發生，所以可提昇 生產性、或可抑制熱皺與薄膜鬆弛起因的不 又本發明係厚度斑小。 ^ 又’本發明的聚丙烯系樹脂膜較佳係實 黏連劑，例如由於可迴避在使含防黏連劑之 形中，因磨耗等所引起的防黏連劑的脫落之 該脫落物所致的污染與障礙發生等受到了抑 又，本發明係實質上不含有滑劑與防黏 係’由於表面粗糙度適當，薄膜的光滑性與枉 且剛性優異，所以薄膜的操作性優異。 又，由於透明性優異，所以被包裝物與 Q 認性優異。 又，因爲薄膜有強度，所以操作性優異 又’雖然上述的耐熱尺寸安定性提昇了 優異’藉由從嵌段聚丙烯系樹脂所形成而附 的好處受到維持，在作爲保護膜而使用的情刃 【圖式簡單說明】 te 。 【主要元件符號說明】I 201041947 ο Reference example 1 io d Ο CO 1__1 cs ro 〇 O O 0.05 1_„一一 〇<〇〇v〇2.0 | 1.56 | 〇σ\ CO 〇\ v〇; 0.79 | ο Ο) rH 6.5 1 1 〇ι-Η 187 810 1 0.65 1 X 〇〇< Comparative Example 7 v〇v〇I CO rH I 6.5 ! <N <N ο 1___1 SS 2.0 "1.56 1 〇寸吴 CO LO | 0.80 1 00 rH 11.9 1 CO 〇v£) iH 850 1 0.40 | 〇XXX Comparative Example 6 58 1 Ο CO 1 6.5 (N (N § ο 1 22.9 1 〇 3.0 "0.63 ] Γ loo__ 00 co CO "0.92 1 ΙΟ 1 0.6 1 4.9 1 <J\ d 〇in 560 1 0.85 1 ◎ < 〇〇X Comparative Example 5 1 N ο oo 〇<N ο 12Ό__1 S 〇2.0 I 1.56 1 〇(N co 00 ID __1-14 1 卜 1- Η 3.8 1 0.2 〇00 (N 760 1 0.52 1 XX 〇X 〇Comparative example 4 0 iH Bu 1 1 CO rH 6.5丨(N CN Ν 1^__1 〇ν£) S 2.0 | 1.56 1 〇Other | 0.88 | ο 00 »-Η 14.9 1 1 〇\〇I—( 900 1 0.61 | 〇◎ XX Comparative Example 3 0 t ο | 20.0 | __lL〇_ 100 〇Ο 1 20.0 1 § 〇2.0 I 1.56 1 〇S | 0.94 1 Οί 1 〇(N CO __67P_ | 0.81 | ◎ < 〇X Comparative Example 2 2 ! in d 00 θ' o Oo 〇ο.οι 1 1 oo i LO inch inch 3.0 [0.63 | __1〇〇_ 1-H 00 inch_L15_ 00 \〇6 4.9 1 1 〇in rH 560 1 0.48 | X 〇〇X |〇in d ο C0 1__1 CN CO o ο 14,7___I Ο 〇2.0 I 1.56 | 〇CO 00 in 10^1__ ο Ο] «-Η 1____ 1 〇00 CN 1ISO__ | 0.42 | X 〇〇< 1 $ ιΗ <1mil Ρπ t <! □ in IS K iM ΚΙ I 4π K % § _ Jmil Ρ π 禁 im φ key t? tip · B- ii P s <n Μ <tn K] <nm 豳m § _ ihml Pit s 1 跋md 〇M _ Hall m nmt ac Φ m κ hO φ _ ff OJ §1 < m Φ 锲t? 擀fi ll 容 S m 〇ΰ m si Turtle Φ β « Jn/ paste m 1酲m series 1 stretch ratio 1 culvert it m tender 冢 m dirty m = ¥ mg m job ft 1 but MJ move CO^ j fe ¥ im tt 20 °C xylene soluble fraction change rate μ"· e '_ g B (N d 疵oT* g 6 (N o % cu s M m- nr> i: 1 m litwi war full film whitening is Weng m iH 1 ite us light te clock refine S m 槲*5 polymer raw material 1 film-forming conditions film characteristics core | § Ί ¥ II brewing afft, you ^ -K 褂 dye ship mail summary #1 a '*1 abandon / 3⁄4 201041947 production In the present invention, the heat-resistant dimensional stability and the planarity are excellent in the bonding workability. For example, the polypropylene resin film for surface protection which is suitable as a protective film is excellent in properties, for example, in adhesion processing. The secondary processing is suitable because the drying at a high temperature in the vicinity of 130 ° C can suppress the occurrence of heat enthalpy and film relaxation, so that the productivity can be improved, or the cause of thermal wrinkles and film relaxation can be suppressed. Small spots. Further, the polypropylene-based resin film of the present invention is preferably a solid adhesive, for example, because the anti-adherent agent can be prevented from falling off due to abrasion or the like in the form of the anti-adhesion agent. The resulting contamination and the occurrence of the barrier are suppressed. The present invention does not substantially contain a slip agent and an anti-adhesion system. Since the surface roughness is appropriate, the smoothness of the film and the rigidity of the film are excellent, so that the handleability of the film is excellent. Moreover, since it is excellent in transparency, it is excellent in the object to be packaged and Q. In addition, since the film has strength, it is excellent in workability, and the above-mentioned heat-resistant dimensional stability is improved. The advantage of being formed by the block-type polypropylene-based resin is maintained, and it is used as a protective film. Blade [simple description of the schema] te. [Main component symbol description]
Anr 無。 、耐衝撃性與 材薄膜。 於耐熱尺寸安 合性優異，特 等的處理，亦 該二次加工的 良品的發生。 質上不含有防 薄膜行進的情 課題，所以因 制。 連劑也沒有關 :黏連性良好， 被保護體的視 ，卻衝擊強度 加之耐衝撃性 >中可靠性高。 -42-Anr no. , resistance to punching and film. It is excellent in heat-resistant dimensional stability, and special treatment is also a good result of secondary processing. The quality does not contain the problem of preventing the film from traveling, so it is a cause. The agent is not closed: the adhesion is good, the appearance of the protected body, but the impact strength combined with the resistance to punching > high reliability. -42-