200909212 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種熱收縮性聚烯烴系薄膜及其製 法，詳言之’係有關於一種適合標籤用途之熱收縮性聚嫌 烴系薄膜及其製法。 【先前技術】 近年來，在用以提升包裝品的外觀之外包裝、避免內 容物的直接碰撞之包裝、兼具玻璃瓶或塑膠瓶的保護及商 品標示之標籤包裝等用途，由各種樹脂所構成的熱收縮塑 膠薄膜被廣泛地使用。在該等的熱收縮塑膠薄膜內’由聚 氯乙烯系樹脂、聚苯乙烯系樹脂、聚酯系樹脂、聚烯烴系 樹脂等所構成的拉伸薄膜，在聚對酞酸乙二酯（pET)容器、 聚乙烯容器、玻璃容器等各種容器係使用作爲標籤或蓋部 密封或積體包裝之目的。 然而，雖然聚氯乙烯系薄膜具有優良的收縮特性，除 了耐熱性低以外，會有焚燒時產生氯化氫氣體、或成爲戴 奧辛的原因之問題。又，將聚氯乙烯系樹脂薄膜使用作爲 P E T容器等的收縮標籤時，亦會有在回收利用容器時必須 分離標籤與與容器之問題。另一方面，雖然聚乙烯系薄膜 收縮後的完成外觀性良好，但是因爲耐溶劑性差，會有在 印刷時必須使用特殊組成的印墨之不良。又，聚苯乙稀系 薄膜除了必須在高溫焚燒以外，會有在焚燒時伴隨著異味 而產生大量黑煙之問題。 因此，以往耐熱性高、焚燒容易且耐溶劑性優良的聚 200909212 酯系薄膜或聚烯烴系薄膜逐漸地被廣泛利用作爲收縮標 籤，隨著P E T容器的流通量增大，使用量有增加的傾向。 又，通常的熱收縮性聚酯系薄膜或熱收縮性聚烯烴系薄膜 係廣泛地利用在寬度方向高倍率拉伸並在寬度方向大幅度 地收縮之物（亦即，主收縮方向爲寬度方向者）（專利文獻1)。 [專利文獻1]特開2004-74426平號公報 【發明內容】 [發明所欲解決之課題] 但是，上述在寬度方向拉伸後的熱收縮性聚酯系薄膜 或熱收縮性聚烯烴系薄膜，沿著與主收縮方向正交之孔狀 接縫撕裂時，會有撕裂性（亦即孔狀接縫（Perforation)撕封 性）差之不良。又，上述在寬度方向拉伸後的熱收縮性聚烯 烴系薄膜在作爲標籤時，使用溶劑黏著時的黏著力（溶劑黏 著強度）未必可說是充分，且使熱收縮後時亦會有剝落掉之 情形。 而且，在寬度方向熱收縮之熱收縮性薄膜在作爲標籤 而安裝於瓶子時，係以寬度方向成爲瓶子的周方向之方式 來形成筒狀體後，因爲該筒狀體必須每規定長度切斷並安 裝在瓶子而使其熱收縮，所以難以高速地安裝於瓶子。而 且，近年來，開發了一種新穎的包裝方法，係藉由使用帶 狀的薄膜覆蓋飯盒等合成樹脂製之一面敞開容器的周圍 (開口部）來將容器保持在封閉的狀態，但是上述在寬度方 向收縮的薄膜，對於此種用途的使用方便性差。 本發明的目的係爲了消除上述先前的熱收縮性聚酯系 200909212 薄膜或熱收縮性聚烯烴系薄膜所存在的問題點，提供一種 實用的熱收縮性聚烯烴系薄膜，其在主收縮方向之長度方 向的收縮性良好’且收縮完成性、孔狀接縫撕封性、溶劑 黏著性良好，且能夠以主收縮方向爲瓶子的周方向之方式 自薄膜捲物直接安裝於瓶子的周圍，且對於上述新穎的包 裝用途之使用方便性良好。 [解決課題之手段] 本發明之中，如申請專利範圍第1項之發明其特徵係 層積以環狀的聚烯烴系樹脂作爲主成分之皮層；及以非環 狀的烯烴系樹脂作爲主成分之芯層，來形成規定寬度的長 條狀’且主收縮方向爲長度方向之熱收縮性聚烯烴系薄 膜，其中滿足以下必要條件（1 )〜（5 )者， (1)薄膜全體的厚度爲9微米以上、100微米以下， 同時皮層厚度爲1微米以上、60微米以下，且芯層的厚度 爲8微米以上、99微米以下， (2 )相對於薄膜全體的厚度，皮層厚度比率係在〇 . 〇 i 〜0.6的範圍， (3 )在8 0 °C的溫水中在長度方向使其1 〇 %收縮後之每 單位厚度之寬度方向的直角撕裂強度爲50N/mm以上、 200N/mm 以下’ (4)在9 0 °C的溫水中處理1 0秒後時，長度方向的溫 水熱收縮率爲2 0 °/〇以上、6 0 %以下， (5 )在9 0 °C的溫水中處理1 0秒後時，與長度方向正 交之方向的溫水熱收縮率爲0 %以上、1 5 %以下。 200909212 本發明之中，如申請專利範圍第2項之發明其特 層積以環狀的聚烯烴系樹脂作爲主成分之皮層；及以 狀的烯烴系樹脂作爲主成分之芯層，來形成一定寬度 條狀’同時主收縮方向爲長度方向之熱收縮性聚烯烴 膜，其中滿足以下必要條件（1)〜（5 )者， (1)薄膜全體的厚度爲9微米以上、1〇〇微米以 同時皮層厚度爲1微米以上、60微米以下，且芯層的 爲8微米以上、99微米以下， f (2)相對於薄膜全體的厚度，皮層厚度比率係在 〜0.6的範圍， (3 )在8 0 C的溫水中在長度方向使其丨〇 %收縮後 單位厚度之寬度方向的直角撕裂強度爲5 〇N/mm以 200N/mm 以下， (4 )在9 0 °C的溫水中處理1 〇秒後時，長度方向 水熱收縮率爲2 0 %以上、6 0 %以下， (5 )在規疋溫度的溫水中處理1 〇秒後，測定寬度 W 的溫水熱收縮率時，在處理溫度爲70〜9〇t時之溫水 縮率爲0 %以下。 而且’處理溫度爲7 0〜9 0 °C時之溫^水熱收縮率怎 以下，係意味著在經調節在7 0 °C〜9 0 t的範圍內之任 度的溫水中’處理1 0秒後’測定寬度方向的溫水熱 時，處理之溫水溫度爲任何溫度時，處理後之溫水 率都是〇 °/〇以下（亦即’未收縮）。又，-(負）的溫水熱 係意味著薄膜係伸長。又，必要條件（2)所稱「皮層 徵係 非環 的長 系薄 下， 厚度 0.0 1 之每 上、 的溫 方向 熱收 I 0% 一溫 縮率 收縮 縮率 :度」 200909212 係意味著合算表背各皮層厚度而成的層之皮層厚度（2種2 層結構時係較薄層的厚度）。 如申請專利範圍第3項之發明，係在如申請專利範圍 第1或2項之發明，其中環狀聚烯烴樹脂係降萡嫌系聚合 物及/或四環十二嫌系聚合物。 如申請專利範圍第4項之發明，係在如申請專利範圍 第1至3項中任一項之發明，其係在前述皮層中添加抗黏 結劑及/或防靜電劑。 如申請專利範圍第5項之發明，其特徵係製造如申請專 利範圍第1至4項中任一項之熱收縮性聚烯烴系薄膜之製 法，其中在拉幅器內藉由夾子把持未拉伸薄膜之寬度方向 的兩端時之狀態，以7 0°C以上、1 4 0°C以下的溫度在寬度 方向以2.5倍以上、8.0倍以下的倍率拉伸，以1 0 0 °C以上、 1 4 0 °C以下的溫度，進行熱鬆弛處理1 . 〇秒以上、5 0.0秒以 下的時間，如此進行後，切斷除去薄膜的寬度方向的兩端 緣之夾子把持部分後，以7 0°C以上、1 4 0°C以下的溫度在 長度方向拉伸2 . 〇倍以上、8.0倍以下。 如申請專利範圍第6項之發明，係在如申請專利範圍 5項之發明’其中長度方向的拉伸係在經加熱的低速輥及 高速輥之間進行，且將在該等2個輥間的拉伸間隙與拉伸 前的薄膜寬度之比調整爲0.10以上、0.50以下。 [發明之效果] 本發明的熱收縮性聚烯烴系薄膜係除了在主收縮方向 之長度方向的收縮性高以外，與主收縮方向直交之方向的 -10- 200909212 孔狀接縫撕封性良好。因而，能夠適合使用作爲瓶子等容 器的標籤，並且能夠在短時間內效率非常良好地安裝於容 器’且安裝而使其熱收縮時，熱收縮所引起皺紋或收縮不 足非常少而能夠呈現良好的完成性。同時能夠顯現非常良 好的孔狀接縫撕封性。而且’使用作爲瓶子等容器的標籤 時，溶劑黏著性良好，使其熱收縮時不會產生剝落掉之情 形。而且亦對上述新穎的包裝用途之使用方便性亦良好。 又’依照本發明的熱收縮性聚烯烴系薄膜之製法，能 ί 夠價廉且容易地製造如上述之在長度方向的收縮性高、收 縮完成性、孔狀接縫撕封性及溶劑黏著性良好之熱收縮性 聚烯烴系薄膜。 【實施方式】 在本發明所稱之環狀聚烯烴係指通常的總稱，具體上 係包含（1)將環狀烯烴的開環共聚物按照必要加氫而成之 聚合物；（2)環狀烯烴的加成（共）聚物；及（3)環狀烯烴與乙 烯、丙烯等α-烯烴之無規共聚物。此外亦包含（4)將述（1) I 〜（3 )改性成爲不飽和羧酸或其衍生物而成之接枝改性體 等。 此種環狀聚烯烴具體上可舉出以降萡烯爲主結構者及 其衍生物、或是以四環十二稀（四環-3 -十二烷）爲主結構者 及其衍生物等。又，降范嫌的衍生物可舉出二環庚-稀（2_ 降萡烯）及其衍生物、6 -甲基降萡烯、6 -乙基降萡烯、5 -丙 基降萡烯、6 -正丁基降萡烯、1_甲基降范嫌、7_甲基降萡烯、 5,6-二甲基降萡烯、5_苯基降范嫌及节基降萡烯等。又’降 -11- 200909212 萡烯樹脂能夠使用 POLYPLASTICS(股）製 TOPAS(註冊商 標）等。另一方面’四環十二烯的衍生物可舉出8-甲基四環 -3 -十二烯、8 -乙基四環-3-十二烯及5, 10 -二甲基四環-3-十 二烯等。又，四環十二烯系樹脂能夠適合使用三井化學（股） 製APEL(註冊商標）' JSR(股）製ARTON(註冊商標）或日本 ΖΕΟΝ(股）製ZEONOR(註冊商標）及ZEONEX(註冊商標）等。 該環狀烯烴系樹脂的比重通常爲1 . 0 0〜1 . 0 5。又，環 狀烯烴系樹脂之玻璃轉移溫度（Tg)係以5 5〜1 〇(TC爲佳，以 6 0〜9 0 °C爲更佳。T g小於5 5 °C時，在6 0 °C X 1 〇秒之主拉伸 方向的熱收縮率有變爲太大之傾向，Tg大於1 〇〇°c時，在 7 0〜9 0 °c之主拉伸方向的熱收縮率有變爲太小之傾向。 又，形成芯層之聚烯烴系樹脂能夠適合使用丙烯與其 他的α -烯烴之共聚物。使用於丙烯與其他的α -烯烴係以 碳數爲2〜8的α -烯烴、例如乙烯、丙烯-1等爲佳，亦能 夠使用戊烯-1、己烯-1、4 -甲基-1-戊烯等。又，共聚物係 以使上述所例示α -烯烴之1種或2種以上聚合而得到的無 規或嵌段共聚物爲佳。而且，該等共聚物之中’使用將丙 烯與乙烯共聚合而成且乙烯的量爲2.0質量％以上、ι〇·〇 質量％以下者；使丙烯與丁烯共聚合而成且丁烯的量爲15.0 質量％以上、35.0質量％以下者；及使丙烯與乙烯與丁烯共 聚合而成且乙烯及丁烯的量爲3.0質量％以上、1 5.0質量％ 以下者時，因爲能夠使用良好的收縮性，乃是特佳。 又，共聚物之熔融流速（MFR)以0.1〜100克/1〇分鐘的 範圍內爲佳，以0.5〜2 0克/1 0分鐘的範圍內爲更佳’以1 · 0 200909212 〜1 5克/1 0分鐘的範圍內爲特佳（又’熔融流速能夠依照 JIS-K-7210之方法來測定）。 在本發明’在所使用的樹脂，能夠按照必要在不損害 特性的範圍’添加各種添加材、塡料、例如熱安定劑、抗 氧化劑、光安定劑、防靜電劑、滑劑、核劑、難燃劑、顏 料、染料、碳酸鈣、硫酸鋇、氫氧化鎂、雲母、滑石、黏 土、氧化鋅、氧化鎂、氧化鋁、抗菌劑、防霧劑及賦予自 然分解性之塡料等。特別是從處理性方面，及賦予滑性、 防靜電劑及耐熱黏結性之意義，較佳是添加以脂肪酸醯胺 爲代表之有機系滑劑；或以脂肪酸烷基胺、脂肪酸烷基胺 酯、脂肪酸一甘油爲代表之界面活性劑；及以二氧化矽、 ΡΜΜΑ爲代表之抗黏結劑。而且，亦可在不損害本發明的 薄膜之特性的範圍，添加其他的熱塑性樹脂、熱塑性彈性 體、橡膠類、烴樹脂及石油樹脂等。 而且，本發明的薄膜在不阻礙其特性之範圍，與可在 表面層積同種的聚丙烯系樹脂層及其他的樹脂層、例如乙 烯-乙酸乙烯酯共聚物皂化物、聚乙烯醇等氣體阻障性樹脂 層。 在本發明的薄膜’按照必要在不阻礙本發明的特性之 範圍，可進行表面處理。表面處理之方法可例示電暈放電 處理、電漿處理、火焰處理及酸處理，沒有特別限制。可 連續處理，以在該薄膜的製造過程之卷取製程前能夠容易 地實施之電暈放電處理、電漿處理、火焰處理爲佳，作爲 提升熱熔接層表面的潤濕張力之手段，以電暈放電處理爲 200909212 特佳。 而且，本發明的熱收縮性聚烯烴系薄膜係以由環狀的 聚烯烴系樹脂作爲主成分之皮層與以非環狀的烯烴系樹脂 作爲主成分之芯層所構成的積層薄膜爲佳。亦即，本發明 的熱收縮性聚烯烴系薄膜以具有A/B (二種二層）、A/B/A(二 種三層）、A/B/C(三種三層）或A/B/C/B/A(三種五層）等的構 成爲佳。從卷曲而言，以對稱層構成之A/B/A構成爲佳。 又，在本發明，構成積層薄膜之各層內，將未在最外側位 置之中心部的層（亦即，A/B/A、或A/B/C的層構成時係B 層等）及二種二層構成時之較厚的層（亦即，較薄的A層與 較厚的B層之A/B層的層構成時係B層）稱爲芯層。又， 將在最外側位置之層（亦即，A/B的層構成時係A、B層， A/B/A或A/B/C的層構成時係A、C層等）及二種二層構成 時之較薄的層（亦即，較薄的A層與較厚的B層之A/B層 的層構成時係A層）稱爲皮層。又，層積皮層與芯層之方法 可舉出多層共擠壓法或乾式層壓法等。 U 而且，本發明之熱收縮性聚烯烴系薄膜厚度以9微米 以上、1 〇 〇微米以下的範圍爲佳’薄膜厚度以3 0微米以上、 8 0微米以下的範圍內爲更佳。並且’皮層厚度以1微米以 上、6 0微米以下爲佳，以3微米以上、2 0微米以下的範圍 內爲更佳。並且，皮層厚度的下限値以3微米以上爲佳’ 以5微米以上爲較佳，以1 0微米以上爲更佳，以1 5微米 以上爲又更佳。又’皮層厚度的上限値以6 0微米以下爲 佳，以4 5微米以下爲較佳，以3 0微米以下爲更佳’以2 5 -14- 200909212 微米以下爲又更佳，以20微米以下爲特佳。另一方面，芯 層厚度以§微米以上、9 9微米以下爲佳。心層厚度的下限 値以1 〇微米以上較佳，以1 5微米以上爲更佳’以2 0微米 以上爲特佳，以25/zm以上爲又更佳。又’芯層厚度的上 限値以8 0微米以下較佳，以70微米以下爲更佳’以5 0微 米以下爲特佳，以4 0以下爲又更佳° 並且，本發明之熱收縮性聚烯烴系薄膜係相對於本發 明之薄膜全體厚度，皮層（表層）的厚度比（以下’稱爲皮-〔 全體比）以〇.〇1以上、0.6以下的範圍內爲佳。該皮-全體比 以0 · 1以上、0.4以下的範圍內爲更佳。皮-全體比小於〇 . 〇 1 時，因爲將皮層使用作爲溶劑黏著層使用時無法得到充分 的溶劑黏著性，乃是不佳。相反地，皮-全體比大於〇 . 6時’ 因爲耐溶劑穿透性（在薄膜上滴加溶劑時之穿透容易性）變 爲不良’乃是不佳。 又。本發明的熱收縮性聚烯烴系薄膜使用作爲標籤時 用以使其黏著之溶劑，能夠使用1 , 3 -二氧雜戊環、苯、甲 u 苯、二甲苯、三甲基苯等的芳香族烴；二氯甲烷、氯仿等 的鹵化烴；苯酚等的苯酚類；四氫呋喃等的呋喃類等或該 等的混合溶劑；使用四氫呋喃作爲黏著劑的溶劑時，因爲 能夠顯現更高的溶劑黏著強度，乃是較佳。 又’本發明的熱收縮性聚烯烴系薄膜在9 〇 r的溫水以 無負荷狀態處理1 0秒後時，依照下式1從收縮前後的長度 所算出的薄膜長度方向的熱收縮率（亦即，9 0乞的熱水收縮 率）以2 0 %以上、6 0 %以下爲佳。 200909212 熱收縮率={(收縮前的長度-收縮後的長度）/收縮前的 長度} X 100(%) . . ·式 1 在9 0 °C之長度方向的溫水熱收縮率小於2 0 %時，因爲 收縮量小所以在熱收縮後的標籤產生皺紋或鬆弛，乃是不 佳。又，在9 0 °C之長度方向的溫水熱收縮率的下限値以2 2 % 以上爲佳，以2 4 %以上爲更佳，以2 6 %以上爲特佳。又， 考慮由皮層主原料之環狀的聚烯烴系樹脂及芯層主原料之 丙烯-α -烯烴共聚物所構成的積層薄膜之本質上的特性 時，在9 0 °C之長度方向的溫水熱收縮率的上限値爲6 0 %左 右。 又，本發明之第1發明的熱收縮性聚烯烴系薄膜在9 0 °C的溫水中以無負荷狀態處理1 0秒後時，從收縮前後的長 度依照上式1所算出之薄膜的寬度方向的溫水熱收縮率以 〇 %以上1 5 %以下爲佳。 在9 0 °C之寬度方向的溫水熱收縮率大於1 5 %時，因爲 使用作爲標籤時容易產生縱向縮孔狀凹斑，乃是不佳。又， 在90°C時之寬度方向的溫水熱收縮率的上限値以13%以下 爲佳，以1 1 %以下爲更佳，以9%以下爲特佳。而且，考慮 由皮層主原料之環狀的聚烯烴系樹脂及芯層主原料之丙烯 -α -烯烴共聚物所構成的積層薄膜之本質上的特性時，在 9〇t之寬度方向的溫水熱收縮率的下限値爲0%左右。 又，本發明的第2發明之熱收縮性聚烯烴系薄膜在規 定溫度的溫水中處理1 0秒後測定寬度方向的溫水熱收縮 率時，處理溫度爲7 0 °C〜9 0 °C時之溫水熱收縮率以0 %以 200909212 下爲佳（又，如上述，「處理溫度爲70〜90T：時之溫水熱 縮率爲0 %以下」’係意味著在經調節在7 〇 t〜9 〇 t的範 內之任一溫度的溫水中處理1 0秒後，測定寬度方向的溫 熱收縮率時’處理之溫水溫度爲任何溫度時，處理後之 水熱收縮率都是0 %以下（亦即，未收縮）。在處理溫度爲 °C〜9 0 °C時之溫水熱收縮率大於〇 %時，因爲使用作爲標 時在熱收縮時容易產生縱向縮孔狀凹斑，乃是不佳。又 在9 0 °C時之寬度方向的溫水熱收縮率小於_ 3 〇 %時，使用 ^ 爲標籤時會產生對瓶子的黏附不良，乃是不佳。 又’本發明的熱收縮性聚烯烴系薄膜在8 〇它的溫水 在長度方向收縮1 0%後，依照以下方法求取每單位厚度 寬度方向的直角撕裂強度時’其寬度方向的直角撕裂強 以5 0N/mm以上、2 0 0N/mm以下爲佳。 [直角撕裂強度的測定方法] 在已調整至8 0 °C之溫水中，使薄膜在長度方向收縮 10%後，依照JIS-K-7 128以規定大小的試驗片之方式進 I。 取樣。隨後，使用萬能拉伸試驗機夾住試驗片兩端，並 拉伸速度爲2 0 0毫米/分鐘的條件，進行測定在薄膜的寬 方向之拉張破壞時的強度。又，對在8(TC未收縮10%之 膜，係使其在8 0°C的溫水浸漬約5秒鐘並進行測定使能 收縮的程度收縮後之在薄膜寬度方向之拉張破壞時的 度。而且’使用下式2來算出單位厚度的直角撕裂強度 直角撕裂強度=拉伸破壞時的強度+厚度· ••式2 收 圍 水 溫 70 籤 作 中 之 度 後 行 以 度 薄 夠 強 -17- 200909212 於8 0 °C的溫水中在長度方向收縮後丨0 %後的直角撕裂 強度爲小於5 0 N/mm時，作爲標籤使用時會有因在搬運中 落下等的衝擊而簡單地破壞掉的情形之可能性，乃是不 佳。相反地’直角撕裂強度大於20 ON/mm時，因爲在將標 籤撕裂時之初期階段之切斷性（撕裂容易性）不良，乃是不 佳。而且，直角撕裂強度的下限値以70N/mm以上爲佳， 以90N/mm以上爲更佳，以ii〇N/mm以上爲特佳。又，直 角撕裂強度的上限値以180N/mm以下爲佳，以l6〇N/mm 以下爲更佳，以1 4 0 N / m m以下爲特佳。 關於在孔狀接縫部分將標籤撕裂之切斷性，認爲如上 述之縫紉機之最初部分標籤的上端或下端的部分）的撕裂 容易性（切入缺口之容易性）；及在沿著孔狀接縫傾斜偏移 的途中’翼片不會斷裂且藉由輕力即能夠以在孔狀接縫方 向撕裂至最後的撕裂容易性（孔狀接縫方向與直角方向的 撕裂容易性之平衡）之雙方，都有助於實際上以手剝下標籤 時的作業之容易性’後者係藉由改良孔狀接縫的間距，多 少能夠改善’又’認爲前者之孔狀接縫的最初部分的撕裂 容易性，係更能夠對應實際上以手撕裂標籤時之官能評 價，乃更重要的特性。因而，本發明的熱收縮性聚烯烴系 薄膜以具有上述範圍的直角撕裂強度爲佳。但是，使後者 之孔狀接縫方向與直角方向的撕裂容易性之平衡在特定範 圍，能夠更提高本發明的熱收縮性聚烯烴系薄膜的孔狀接 縫撕封性’乃是較佳。具體上，本發明的熱收縮性聚烯烴 系薄膜係在8 0 °C的溫水中使其在長度方向收縮1 0 %後，依 200909212 照以下方法求取長度方向及寬度方向的愛爾曼多夫撕裂負 荷時1該等的愛爾曼多夫撕裂負荷的比之的愛爾曼多夫比 以〇 · 5以上、2.0下爲佳。 [愛爾曼多夫比的測定方法] 在具有規定長度之矩狀的框將薄膜以預先鬆弛後的狀 態安裝（亦即，使用框把持薄膜的兩端）。而且，鬆弛後的 薄膜係在框內至成爲緊張狀態爲止（至鬆弛消失爲止），並 藉由浸漬在 8 0 r的溫水約5秒鐘使其在長度方向收縮 °如此進行後，依照JIS-K-7128，進行測定薄膜的長 度方向及寬度方向之愛爾曼多夫撕裂負荷，並使用下式3 算出愛爾曼多夫比。又，對在8 0 °C未收縮1 〇 %之薄膜，係 使其在8 0 °C的溫水浸漬約5秒鐘並進行測定使能夠收縮的 程度收縮後之在薄膜的長度方向及寬度方向之愛爾曼多夫 撕裂負荷。 愛爾曼多夫比二長度方向的愛爾曼多夫撕裂負荷+寬度 方向的愛爾曼多夫撕裂負荷·••式3 愛爾曼多夫比小於0.5時，使用作爲標籤時，沿著孔 狀接縫難以筆直地撕裂，乃是不佳。相反地，愛爾曼多夫 比大於2 · 0時’容易在與孔狀接縫偏移的位置撕裂，乃是 不佳。又’愛爾曼多夫比的下限値以〇 7以上爲佳，以〇 . 9 以上爲更佳，以1 . 1以上爲特佳。又，愛爾曼多夫比的上 限値以1 . 8以下爲佳，以丨.6以下爲更佳，以1 · 4以下爲特 佳。 上述熱收縮薄膜的熱收縮率、直角撕裂強度及愛爾曼 -19- 200909212 多夫比，能夠藉由使用較佳的薄膜組成’並組合後述較佳 的製造方法來達成。 並且，本發明的熱收縮性聚烯烴系薄膜係以溶劑黏著 強度爲4 (N /1 5 m m)以上的方式調整爲佳。溶劑黏著強度小 於4(N/15mm)時，因爲例如使標籤熱收縮時，溶劑黏著部 分會有剝離掉的可能性，乃是不佳。 又，本發明的熱收縮性聚烯烴系薄膜能夠藉由擠壓機 將上述的聚烯烴系樹脂原料熔融擠出來形成未拉伸薄膜， 並將該未拉伸薄膜依照以下所示方法，雙軸拉伸並熱處理 來得到。 將原料樹脂溶融擠出時，以使用料斗乾燥機、漿式乾 燥機等乾燥機、或是真空乾燥機來乾燥爲佳。如此，使聚 烯烴系樹脂原料乾燥後，利用擠壓機並在2 0 0〜3 0 0 °C的溫 度熔融且薄膜狀地擠出。在該擠出時，能夠採用T模頭法、 管狀法等原有之任意方法。 而且，藉由將擠壓後之薄片狀的熔融樹脂急速冷卻， 能夠得到未拉伸薄膜。又，急速冷卻熔融樹脂之方法，能 夠適合採用藉由噴嘴將熔融樹脂鑄塑於旋轉滾筒來得到實 質上未配向的樹脂薄片。 而且’藉由將所得到的未拉伸薄膜，如後述，依照規 定條件在寬度方向拉伸後，一次熱處理，隨後，依照規定 條件在長度方向拉伸，且急速冷卻該縱向拉伸後的薄膜， 能夠得到本發明的熱收縮性聚烯烴系薄膜。又，縱向拉伸 時’藉由適當地調整拉伸間隙（從縱向拉伸時之低速輥與薄 -20 - 200909212 膜的切點至高速輥與薄膜的切點之距離）及薄膜寬度，能夠 將間隙比率（拉伸間隙/薄膜寬度）調整在0 · 0 1〜0 · 1 0的範 圍。 以下’對用以得到本發明的熱收縮性聚烯烴系薄膜之 較佳的雙軸拉伸、熱處理方法，邊考慮與先前的熱收縮性 聚烯烴系薄膜之雙軸拉伸、熱處理方法之差異，邊詳細地 說明。 [熱收縮性聚烯烴系薄膜之較佳的製膜方法] 如上述’單純地在寬度方向拉伸而成的熱收縮性薄膜 會有與主收縮方向正交之方向之孔狀接縫撕封性差之不 良。另一方面’雖然以往對在長度方向收縮之熱收縮薄膜 的要求高，但是將未拉伸薄膜單純地在長度方向延伸時， 因爲無法製造寬度較寬廣的薄膜，除了生產性差以外且亦 無法製造厚度不均良好的薄膜。又，採用預先在寬度方向 拉伸後’在長度方向拉伸之方法時，會有在長度方向的收 縮量不充分、或是在寬度方向進行不必要地收縮之情形。 本發明者等對在寬度方向的拉伸後，在長度方向拉伸 之方法（以下稱爲橫向-縱向拉伸法），依照在各拉伸製程之 條件，薄膜的長度方向的溫水熱收縮率、孔狀接縫撕封性 係如何地變化進行專心硏討。結果查明依照橫向-縱向拉伸 法製造薄膜時，藉由採取以下的手段，能夠穩定地製造長 度方向的收縮量高且正交方向的孔狀接縫撕封性良好的薄 膜。而且’本發明者等基於該等見識而硏究出本發明。 (1)在寬度方向拉伸後進行中間熱鬆弛處理 200909212 (2) 在長度方向拉伸前對薄膜端部進行修剪 (3) 調整拉伸間隙 以下，依照順序說明上述的各手段 (1 )在寬度方向拉伸後進行中間熱鬆驰處理 依照本發明的橫向-縱向拉伸法製造薄膜，在寬度方向 拉伸未拉伸薄膜後，以在1 〇 〇 °C以上、1 4 0 °C以下的溫度熱 處理（以下，稱爲中間熱鬆弛處理）1 · 0秒以上、5 0.0秒以下 爲佳。藉由進行此種中間熱鬆弛處理，作爲標籤時能夠得 到孔狀接縫撕封性良好且不會產生收縮不均的薄膜。如 此，藉由在橫向拉伸後施加特定的中間熱鬆弛處理，能夠 得到孔狀接縫撕封性良好且不會產生收縮不均的薄膜之理 由並不清楚，認爲可能夠藉由施行特定的中間熱鬆弛處 理，在使寬度方向殘留某種程度的分子配向之同時，能夠 使寬度方向的收縮應力降低之緣故。又，中間熱處理的溫 度大於1 4 0 °C時，在縱向拉伸時會產生層間剝離，乃是不 佳。相反地，中間熱處理的溫度小1 〇 〇 °C時，無法控制薄 膜寬度方向最後的熱收縮率，乃是不佳。又，熱鬆弛處理 的溫度之下限以11 〇 °C以上爲佳，以1 1 5 °c以上爲更佳。另 一方面，熱鬆弛處理的溫度之上限以1 3 5 t以下爲佳，以 1 3 0 °C以下爲更佳。另一方面，熱鬆弛處理的時間以按照原 料組成適當地調整在1 . 〇秒以上、5 0.0秒以下爲佳。 又，未拉伸薄膜在寬度方向的拉伸係以在拉幅器內藉 由夾子把持寬度方向的兩端緣之狀態，於70 °C以上、140 °C以下的溫度且以2.5倍以上、8.0倍以下的倍率的方式進 -22 - 200909212 行爲佳。拉伸溫度小於7 0 °C時，因爲在拉伸時容易產生斷 裂，乃是不佳，相反地，大於140 °C時，寬度方向的厚度 不均變差，乃是不佳。又，橫向拉伸的溫度之下限以7 5 °C 以上爲佳，以8 0°C以上更佳。又，橫向拉伸的溫度之上限 以1 3 5 °C以下爲佳，以1 3 0 °C以下更佳。另一方面，寬度方 向的拉伸倍率小於2 · 5倍時，不只是生產性變差而且寬度 方向的厚度亦變差，乃是不佳，相反地，大於8.0時，在 拉伸時容易產生斷裂，乃是不佳，而且使其熱鬆弛時必須 ： 很大的能量及大規模的裝置且生產性變差，乃是不佳。又， 橫向拉伸的倍率之下限以3 . 0倍以上爲佳，以3 . 5倍以上爲 更佳。又，橫向拉伸的倍率之上限以7. 5倍以下爲佳，以 7 · 〇倍以下爲更佳。 (2)在長度方向拉伸前對薄膜端部進行修剪 依照本發明的橫向-縱向拉伸法製造薄膜，在將施行過 中間熱鬆弛處理的薄膜於長度方向拉伸之前，以修剪薄膜 端緣之未充分地被橫向拉伸之較高厚度部分（主要是橫向 1'拉伸時之夾子把持部分）爲佳。更具體地，係使用切割刀等 工具對在薄膜左右的端緣位置之厚度爲中央部分的厚度的 約1 . 1〜1 . 3倍的部分，切斷薄膜端緣之較高厚度部分’且 以邊除去較高厚度部分邊只使剩餘的部分在長度方向拉伸 爲佳。又，在修如上述的薄膜端部時，以進行冷卻來使修 剪前的薄膜表面溫度爲5 (TC以下爲佳。如此’藉由冷卻薄 膜，能夠不弄亂切斷面而進行修剪。又’薄膜端部的修剪’ 能夠使用通常的切割刀來進行，但是使用具有周狀刀鋒之 -23 - 200909212 圓刀鋒時，因爲不會產生局部性刀鋒鈍化之情形’能夠長 期間銳利地連續切斷薄膜的端部’且在長度方向拉伸時不 會有引起斷裂之情形，乃是較佳。 如此，藉由在長度方向拉伸前對薄膜端部進行修剪’ 能夠將一次熱鬆弛處理後的薄膜均勻地在長度方向拉伸’ 如此才能夠連續製造未斷裂且安定的薄膜。除此以外’亦 能夠得長度方向（主收縮方向）的收縮量大的薄膜。而且， 因爲能夠使薄膜均勻地在長度方向拉伸’能夠得到長度方 f 向的厚度不均小的薄膜。而且，藉由修剪薄膜的端部’能 夠避免在長度方向拉伸時之彎曲’能夠得到左右物性差異 小的薄膜。 (3)調整拉伸間隙 依本發明橫向-縱向拉伸法之薄膜的製造，係將上述中 間熱鬆弛處理後在長度方向的拉伸，在經加熱的低速輥與 高速輥進行，且該等2個輥間的拉伸間隙與拉伸前的薄膜 寬度之比（以下，稱爲拉伸間隙比率）係以調整在0 · 1 0以 i 上、0.5 0以下爲佳。如此，藉由將拉伸間隙比率調整在〇 . j 〇 以上' 〇 · 5 0以下，因爲作爲標籤而安裝於瓶子時，能夠得 到在與主收縮方向正交之方向不會產生收縮，不會產生所 謂“縱向縮孔狀凹斑”且收縮完成性良好，而且孔狀接縫 撕封性、耐熱黏結性任一者都良好之熱收縮性薄膜。拉伸 間隙比率小於〇 · 1 〇，安裝於瓶子作爲標籤時容易產生縱向 縮孔狀凹斑，乃是不佳，相反地，拉伸間隙比率大於0.5 0 時，因爲產生拉伸不均致使厚度不均變差，乃是不佳。 -24 - 200909212 而且，依照本發明的橫向-縱向拉伸法製造薄膜，如上 述，在橫向拉伸後施行中間熱鬆弛處理後在長度方向拉伸 後，亦可在拉幅器內使用夾子把持寬度方向的兩端緣之狀 態，於8(TC以上、1〇〇 °C以下的溫度熱處理1.0秒以上、1〇.〇 秒以下的時間（以下，稱爲最後熱處理）。藉由進行此種的 最後熱處理，能夠精確度良好地調整薄膜的最後收縮率。 又，只有上述（1)〜（3 )的手段內之特定任一者，對於薄 膜在長度方向之熱收縮性、孔狀接縫撕封性、穩定的製膜 性無法有效地幫助，認爲藉由組合使用（1)與（2)、或（1)〜 (3)的手段，能夠使用長度方向之熱收縮性、孔狀接縫撕封 性、穩定的製膜性非常有效率地顯現。 [薄膜製造的各製程對賦予薄膜特性之影響] 在本發明的熱收縮性聚烯烴系薄膜，長度方向的溫水 熱收縮率、寬度方向的溫水熱收縮率、長度方向的直角撕 裂強度及愛爾曼多夫比等特性，能夠藉由薄膜製造時之橫 向拉伸製程、中間熱鬆驰處理製程、縱向拉伸製程及最後 熱處理製程的條件來控制。亦即，增加中間熱鬆驰處理的 溫度時，長度方向的溫水熱收縮率增加，且寬度方向的溫 水熱收縮率減少。又，增加縱向拉伸倍率時，長度方向及 寬度方向的溫水熱收縮率增加。而且，增加縱向拉伸倍率 時，直角撕裂強度增加、長度方向的愛爾曼多夫撕裂負荷 減少，且寬度方向的愛爾曼多夫撕裂負荷增加。另一方面， 增加縱向拉伸時之拉伸溫度時，長度方向的溫水熱收縮率 減少，且寬度方向的溫水熱收縮率增加。而且，增加縱向 -25 - 200909212 拉伸之拉伸溫度時，直角撕裂強度降低’長度方向的愛爾 曼多夫撕裂負荷增加，寬度方向的愛爾曼多夫撕裂負荷減 少。但是，在製造本發明的熱收縮性聚烯烴系薄膜’只有 橫向拉伸製程、中間熱鬆弛處理製程、縱向拉伸製程中任 一製程，單獨時並無法使薄膜特性變爲良好，認爲藉由將 橫向拉伸製程、中間熱鬆驰處理製程、縱向拉伸製程之全 部依照上述的規定條件，能夠非常有效率地使薄膜特性變 爲良好。 [實施例] 以下，藉由實施例更詳言地說明本發明，但是本發明 完全未限定於此等實施例，在未脫離本發明的宗旨之範 圍，能夠適當地變更。在實施例、比較例所使用的原料之 性狀、組成：及在實施例 '比較例之薄膜的製造條件（拉伸、 鬆驰處理條件等）係各自如表1、表2、表4及表5所示。 又，在表1及表4之樹脂原料a〜F係如以下。 .樹脂原料A :聚丙烯-乙烯無規共聚物（住友化學股份公 司製S131乙烯=5.5質量％、^^11=1.2克/10分鐘、熔 點 1 3 5。(：） •樹脂原料B :聚丙烯-乙烯、丁烯無規共聚物（住友化學 股份公司製？8又66£8乙烯=2.5質量％、丁烯=6.9質量 %、MFR = 3_0克/10分鐘、溶點134。匚） •樹脂原料C :聚丙烯-乙烯無規共聚物（住友化學股份公 司製 FS2011DG3 乙烯= 〇·6 質量 ％、MFR = 2.5 克 /10 分 鐘、熔點1 5 8 °C )、在9 4質量％中添加6質量％硬脂酸一 -26- 200909212 甘油酯（防靜電劑理硏V I T A Μ I N股份公司製 s-ioo)而成者 •樹脂原料D :聚丙烯-乙烯無規共聚物（住友 司製 FS2011DG3 乙烯 鐘、熔點1 5 8 °c )、在94質量％中添加6質量 甘油酯（防靜電劑 理硏 VITAMIN 股 RIKEMAL S- 1 00)而成者 •樹脂原料E :聚丙烯-乙烯無規共聚物（住友 司製 FS2011DG3 乙烯=0.6 質量 ％、M F R = 2 鐘、熔點1 5 8 t )、在8 0質量％中添加2 0質 合物微粒子（住友化學股份公司製CS30平均 微米）而成者 •樹脂原料F :環狀聚烯烴（三井化學股份公 8008T MFR=15 克 /10 分鐘、T g = 7 0 °C ) 又，薄膜的評價方法如下述。 [Tm(熔點）] I 使用SEIKO電子工業股份公司製之差示掃 (型式：DSC220)，並採取未拉伸薄膜5毫克’ 升溫速度1 〇 t: /分鐘升溫後時的吸熱曲線的# _ [乙烯、丁烯含量] 丙烯-乙烯共聚物、丙烯-丁烯共聚物' Θ嫌 共聚物中的乙烯或丙烯的含量係依照高分' 5 (1 9 9 5年、紀伊國屋書店發行）的第6 1 5〜6 1 7頁 法、依照13C-NMR光譜法來決定。又’亦可依200909212 IX. Description of the Invention: [Technical Field] The present invention relates to a heat-shrinkable polyolefin-based film and a process for producing the same, and more particularly to a heat-shrinkable poly (hydrocarbon) film suitable for label use And its method of production. [Prior Art] In recent years, it has been used for packaging such as packaging for avoiding the appearance of packaging products, avoiding direct collision of contents, packaging for protection of glass bottles or plastic bottles, and label packaging for product labeling. The heat shrinkable plastic film is widely used. In these heat-shrinkable plastic films, a stretched film composed of a polyvinyl chloride resin, a polystyrene resin, a polyester resin, a polyolefin resin, or the like, in polyethylene terephthalate (pET) Various containers such as containers, polyethylene containers, and glass containers are used for the purpose of labeling or cap sealing or integrator packaging. However, although the polyvinyl chloride-based film has excellent shrinkage characteristics, in addition to low heat resistance, there is a problem that hydrogen chloride gas is generated during incineration or dioxin is caused. Further, when a polyvinyl chloride resin film is used as a shrink label for a P E T container or the like, there is a problem that the label and the container must be separated when the container is recycled. On the other hand, although the polyethylene-based film has a good appearance after shrinkage, it is inferior in solvent resistance, and it is necessary to use a printing ink of a special composition at the time of printing. Further, in addition to being incinerated at a high temperature, the polystyrene film may have a problem of a large amount of black smoke accompanying an odor during incineration. Therefore, the poly 200909212 ester film or the polyolefin film which is excellent in heat resistance, easy to incinerate, and excellent in solvent resistance has been widely used as a shrink label, and the amount of use of the PET container tends to increase as the amount of the PET container increases. . In addition, a general heat-shrinkable polyester film or a heat-shrinkable polyolefin film is widely used as a material which is stretched at a high magnification in the width direction and which shrinks greatly in the width direction (that is, the main shrinkage direction is the width direction). (Patent Document 1). [Problem to be Solved by the Invention] However, the heat-shrinkable polyester film or the heat-shrinkable polyolefin film which has been stretched in the width direction described above. When it is torn along the hole-shaped seam orthogonal to the main shrinking direction, there is a problem that the tearing property (that is, the perforation tearing property) is poor. Further, when the heat-shrinkable polyolefin-based film which has been stretched in the width direction is used as a label, the adhesive force (solvent strength) when the solvent is adhered is not necessarily sufficient, and peeling occurs even after heat shrinkage. The situation of falling. In addition, when the heat-shrinkable film which is heat-shrinked in the width direction is attached to the bottle as a label, the cylindrical body is formed so that the width direction becomes the circumferential direction of the bottle, and the cylindrical body must be cut every predetermined length. It is installed in the bottle to be heat-shrinked, so it is difficult to mount the bottle at a high speed. Further, in recent years, a novel packaging method has been developed in which a container is kept in a closed state by covering a periphery (opening) of a one-side open container made of a synthetic resin such as a lunch box, but the above-mentioned width is Films that shrink in direction have poor ease of use for such applications. The object of the present invention is to provide a practical heat-shrinkable polyolefin-based film in the main shrinkage direction in order to eliminate the problems of the above-mentioned heat-shrinkable polyester-based 200909212 film or heat-shrinkable polyolefin-based film. The shrinkage property in the longitudinal direction is good, and the shrinkage completion property, the hole-shaped seam tearability, and the solvent adhesiveness are good, and the film shrinkage can be directly attached to the periphery of the bottle so that the main shrinkage direction is the circumferential direction of the bottle, and It is convenient to use for the above novel packaging applications. [Means for Solving the Problem] In the invention of the first aspect of the invention, the invention is characterized in that a skin layer having a cyclic polyolefin resin as a main component is laminated; and an acyclic olefin resin is mainly used. A heat-shrinkable polyolefin-based film having a long strip shape of a predetermined width and a longitudinal direction in the main shrinkage direction, wherein the following requirements (1) to (5) are satisfied, (1) the entire film The thickness is 9 micrometers or more and 100 micrometers or less, and the thickness of the skin layer is 1 micrometer or more and 60 micrometers or less, and the thickness of the core layer is 8 micrometers or more and 99 micrometers or less, and (2) the thickness ratio of the skin layer is relative to the thickness of the entire film. In 〇 . 〇 i ~0. The range of 6 (3) in the warm water of 80 °C, the right-angle tearing strength per unit thickness in the longitudinal direction after shrinking by 1 〇% is 50 N/mm or more and 200 N/mm or less ' (4 ) After 10 seconds of treatment in warm water at 90 °C, the thermal shrinkage rate of the warm water in the longitudinal direction is 20 ° / 〇 or more, 60 % or less, (5) treated in warm water at 90 ° C 1 After 0 seconds, the thermal water shrinkage rate in the direction orthogonal to the longitudinal direction was 0% or more and 15% or less. In the invention of the second aspect of the invention, the skin layer having a cyclic polyolefin resin as a main component and a core layer containing a olefin resin as a main component are formed in a special layer. a heat-shrinkable polyolefin film having a width strip shape and a main shrinkage direction in the longitudinal direction, wherein the following requirements (1) to (5) are satisfied, (1) the thickness of the entire film is 9 μm or more and 1 μm. At the same time, the thickness of the skin layer is 1 micrometer or more and 60 micrometers or less, and the core layer is 8 micrometers or more and 99 micrometers or less, and f (2) is thicker than the entire thickness of the film, and the skin layer thickness ratio is ～0. The range of 6 (3) in the warm water of 80 ° C in the longitudinal direction, the 直% shrinkage, the right-angle tear strength in the width direction of the unit thickness is 5 〇N/mm to 200 N/mm or less, (4) When treated in warm water at 90 °C for 1 〇 second, the hydrothermal shrinkage rate in the longitudinal direction is 20% or more and 60% or less. (5) After treating for 1 〇 second in the warm water of the standard temperature, the width W is measured. The warm water shrinkage rate of the warm water is 0% or less at a treatment temperature of 70 to 9 Torr. Moreover, 'when the treatment temperature is 70 to 90 °C, the temperature/water heat shrinkage rate is below, which means that the treatment is carried out in the warm water adjusted to the range of 70 ° C to 90 °. After 0 seconds, when measuring the warm water in the width direction, when the temperature of the warm water to be treated is any temperature, the temperature of the treated water is below 〇 ° / 〇 (that is, 'unshrinked'). Further, - (negative) warm water heat means that the film is elongated. Also, the necessary condition (2) is called "the cortical sign is a non-circular long thin, thickness 0. The temperature in the temperature direction of each of 0 1 is 0 0. The shrinkage rate of the temperature shrinkage rate: degree" 200909212 means the thickness of the layer of the layer formed by the thickness of each skin layer on the back of the table (two types of two-layer structure) The thickness of the thin layer). The invention of claim 3 is the invention of claim 1, wherein the cyclic polyolefin resin is a ruthenium polymer and/or a tetracyclic stimulating polymer. The invention of claim 4 is the invention of any one of claims 1 to 3, wherein an anti-adhesive and/or an antistatic agent is added to the skin layer. The invention of claim 5, wherein the invention is the method for producing a heat-shrinkable polyolefin film according to any one of claims 1 to 4, wherein the holder is held by a clip in the tenter When the both ends of the film are stretched in the width direction, the temperature is in the width direction at a temperature of 70 ° C or more and 140 ° C or less. 5 times or more, 8. Tensile stretching at a magnification of 0 times or less, and thermal relaxation treatment at a temperature of 100 ° C or higher and 140 ° C or lower. More than leap seconds, 5 0. After the time of 0 seconds or less, the clip holding portion of the both end edges in the width direction of the film is cut and removed, and then stretched in the longitudinal direction at a temperature of 70 ° C or higher and 140 ° C or lower. More than 〇, 8. 0 times or less. The invention of claim 6 is the invention of claim 5, wherein the lengthwise stretching is performed between the heated low speed roller and the high speed roller, and between the two rollers The ratio of the stretch gap to the film width before stretching is adjusted to 0. 10 or more, 0. 50 or less. [Effects of the Invention] The heat-shrinkable polyolefin-based film of the present invention has a high shrinkage property in the longitudinal direction of the main shrinkage direction, and a hole-to-hole joint in the direction perpendicular to the main shrinkage direction of -10-200909212. . Therefore, it is possible to suitably use a label as a container such as a bottle, and it is possible to mount the container in a very good manner in a short time, and when it is mounted and heat-shrinked, the wrinkles or shrinkage caused by heat shrinkage are insufficient and can be excellent. Completeness. At the same time, it is possible to show a very good hole-like seam tearing property. Further, when a label as a container such as a bottle is used, the solvent adhesion is good, so that it does not peel off when it is thermally shrunk. Moreover, the ease of use of the above novel packaging applications is also good. Further, according to the method for producing a heat-shrinkable polyolefin-based film of the present invention, the shrinkage property in the longitudinal direction, the shrinkage completion property, the hole-like seam tearing property, and the solvent adhesion can be easily and inexpensively manufactured as described above. A heat-shrinkable polyolefin film having good properties. [Embodiment] The term "cyclic polyolefin" as used in the present invention means a general term, and specifically includes (1) a polymer obtained by hydrogenating a ring-opening copolymer of a cyclic olefin as necessary; An addition (co)polymer of an olefin; and (3) a random copolymer of a cyclic olefin and an α-olefin such as ethylene or propylene. Further, (4) a graft modified product obtained by modifying (1) I to (3) into an unsaturated carboxylic acid or a derivative thereof is also contained. Specific examples of such a cyclic polyolefin include those having a decene-based structure and a derivative thereof, or a tetracyclodene (tetracyclo-3 -dodecane)-based structure and a derivative thereof. . Further, the derivatives of the antibiotics can be exemplified by bicycloheptyl-diluted (2_norbornene) and its derivatives, 6-methylnordecene, 6-ethylnorbornene, 5-propylnorpredene , 6-n-butylnordecene, 1_methyl-norbornene, 7-methylnordecene, 5,6-dimethylnordecene, 5-phenylene-lowering and decyl-decene Wait. Further, -11-200909212 terpene resin can be used by POLYPLASTICS (trademark) TOPAS (registered trademark). On the other hand, the derivatives of tetracyclododecene include 8-methyltetracyclo-3-dodecene, 8-ethyltetracyclo-3-dodecene and 5,10-dimethyltetracyclohexane. -3-dodecene and the like. In addition, the tetracyclic dodecene-based resin can be suitably used in the APEL (registered trademark) JSR (shared trademark) ARTON (registered trademark) or ZEONOR (registered trademark) and ZEONEX (registered trademark) manufactured by Mitsui Chemicals Co., Ltd. Trademarks) and so on. The cyclic olefin resin generally has a specific gravity of 1. 0 0~1. 0 5. Further, the glass transition temperature (Tg) of the cyclic olefin resin is preferably 5 5 to 1 Torr (TC is more preferably 60 to 90 ° C. When T g is less than 5 5 ° C, at 60 °CX 1 The thermal contraction rate in the main tensile direction of the leap second tends to be too large. When the Tg is greater than 1 〇〇 °c, the thermal shrinkage rate in the main tensile direction of 70 ° to 90 ° C has changed. Further, the polyolefin-based resin forming the core layer can suitably be a copolymer of propylene and another α-olefin, and is used for propylene and other α-olefins having α-carbon number of 2 to 8 An olefin such as ethylene or propylene-1 is preferred, and pentene-1, hexene-1, 4-methyl-1-pentene or the like can also be used. Further, the copolymer is such that the above-exemplified α-olefin is used. A random or block copolymer obtained by polymerizing one or more kinds is preferable. Further, among the copolymers, 'the copolymerization of propylene and ethylene is used and the amount of ethylene is 2. 0% by mass or more, ι〇·〇% by mass or less; propylene and butene are copolymerized and the amount of butene is 15. 0% by mass or more, 35. 0% by mass or less; and propylene and ethylene and butene are copolymerized and the amount of ethylene and butene is 3. 0% by mass or more, 1 5. When it is 0 mass% or less, it is particularly preferable because good shrinkability can be used. Further, the melt flow rate (MFR) of the copolymer is 0. 1 to 100 g / 1 〇 minutes is better, to 0. 5~2 0g / 1 0 minutes in the range of better '1' 0 200909212 ~ 1 5g / 1 0 minutes is particularly good (also 'melt flow rate can be in accordance with JIS-K-7210 method Determination). In the present invention, various additives, materials, such as heat stabilizers, antioxidants, light stabilizers, antistatic agents, slip agents, nucleating agents, can be added to the resin to be used as needed without impairing the properties. Flame retardant, pigment, dye, calcium carbonate, barium sulfate, magnesium hydroxide, mica, talc, clay, zinc oxide, magnesium oxide, aluminum oxide, antibacterial agent, antifogging agent, and natural decomposing materials. In particular, in terms of handleability, and imparting impartability to slipperiness, antistatic agent, and heat-resistant adhesiveness, it is preferred to add an organic slip agent represented by a fatty acid guanamine; or a fatty acid alkylamine or a fatty acid alkylamine ester. , a surfactant represented by fatty acid monoglycerin; and an anti-adhesive agent represented by cerium oxide and cerium. Further, other thermoplastic resins, thermoplastic elastomers, rubbers, hydrocarbon resins, petroleum resins, and the like may be added to the extent that the properties of the film of the present invention are not impaired. Further, the film of the present invention has a polypropylene resin layer and other resin layers which can be laminated on the surface in a range which does not inhibit the properties thereof, for example, a gas barrier such as ethylene-vinyl acetate copolymer saponified product or polyvinyl alcohol. A barrier resin layer. The film of the present invention can be subjected to surface treatment as long as it does not hinder the characteristics of the present invention. The surface treatment method can be exemplified by corona discharge treatment, plasma treatment, flame treatment, and acid treatment, and is not particularly limited. It can be continuously processed to corona discharge treatment, plasma treatment and flame treatment which can be easily performed before the winding process of the film manufacturing process, and is used as a means for improving the wetting tension of the surface of the heat fusion layer. The halo discharge treatment is particularly good for 200909212. Further, the heat-shrinkable polyolefin-based film of the present invention is preferably a laminated film comprising a skin layer containing a cyclic polyolefin resin as a main component and a core layer containing a non-cyclic olefin resin as a main component. That is, the heat-shrinkable polyolefin-based film of the present invention has A/B (two kinds of two layers), A/B/A (two kinds of three layers), A/B/C (three kinds of three layers) or A/ The composition of B/C/B/A (three types of five layers) is preferable. From the viewpoint of curling, it is preferable to constitute A/B/A which is composed of a symmetrical layer. Further, in the present invention, in each layer constituting the laminated film, a layer which is not at the center of the outermost position (that is, a layer of A/B/A or a layer of A/B/C, etc.) A thicker layer in the case of two two-layer structures (i.e., a thinner layer A and a thicker layer B layer of the A/B layer) is referred to as a core layer. Further, the layer at the outermost position (that is, the layer A, the layer of A/B, the layer of A/B/A or A/B/C, the layer A, the layer C, etc.) and the second layer A thinner layer in the case of a two-layer structure (that is, a thin layer A layer and a thicker layer B layer A/B layer layer) is called a skin layer. Further, a method of laminating the skin layer and the core layer may be a multilayer coextrusion method or a dry lamination method. Further, the thickness of the heat-shrinkable polyolefin-based film of the present invention is preferably 9 μm or more and 1 〇 〇 micron or less. The film thickness is preferably in the range of 30 μm or more and 80 μm or less. Further, the thickness of the skin layer is preferably 1 μm or more and 60 μm or less, and more preferably 3 μm or more and 20 μm or less. Further, the lower limit of the thickness of the skin layer is preferably 3 μm or more, preferably 5 μm or more, more preferably 10 μm or more, and still more preferably 15 μm or more. Further, the upper limit of the thickness of the skin layer is preferably 60 μm or less, preferably 45 μm or less, more preferably 30 μm or less, and more preferably 2 5 -14 to 200909212 μm or less, 20 μm or less. The following is especially good. On the other hand, the thickness of the core layer is preferably § micrometers or more and 9 9 micrometers or less. The lower limit of the thickness of the core layer is preferably 1 〇 micrometer or more, more preferably 15 μm or more, and particularly preferably 20 μm or more, and more preferably 25/zm or more. Further, the upper limit of the thickness of the core layer is preferably 80 μm or less, more preferably 70 μm or less, and particularly preferably 50 μm or less, and more preferably 40 or less. Further, the heat shrinkability of the present invention. The ratio of the thickness of the polyolefin film to the entire thickness of the film of the present invention and the skin layer (surface layer) is hereinafter referred to as the skin-to-all ratio. 〇1 or more, 0. It is better in the range of 6 or less. The skin-total ratio is 0·1 or more, 0. 4 is better in the range below. The skin-to-all ratio is less than 〇. When 〇 1, it is not preferable because the skin layer is used as a solvent adhesion layer, and sufficient solvent adhesion cannot be obtained. Conversely, the skin-to-total ratio is greater than 〇. At 6 o'clock, it is not preferable because the solvent penetration resistance (the ease of penetration when the solvent is dropped on the film) becomes poor. also. In the heat-shrinkable polyolefin-based film of the present invention, a solvent for adhering as a label can be used, and aroma of 1,3-dioxolane, benzene, methylbenzene, xylene, trimethylbenzene or the like can be used. a hydrocarbon; a halogenated hydrocarbon such as dichloromethane or chloroform; a phenol such as phenol; a furan such as tetrahydrofuran; or a mixed solvent thereof; and a solvent having a tetrahydrofuran as an adhesive because a higher solvent adhesion strength can be exhibited. Is better. In the case where the heat-shrinkable polyolefin-based film of the present invention is treated in a no-load state for 10 seconds in warm water of 9 Torr, the heat shrinkage ratio in the longitudinal direction of the film is calculated from the length before and after shrinking according to the following formula 1 ( That is, the hot water shrinkage rate of 90 ) is preferably 20% or more and 60% or less. 200909212 Heat shrinkage rate = {(length before shrinkage - length after shrinkage) / length before shrinkage} X 100 (%) . . - Formula 1 When the thermal water shrinkage rate in the longitudinal direction of 90 °C is less than 20%, it is not preferable because wrinkles or slacks occur in the label after heat shrinkage because the shrinkage amount is small. Further, the lower limit of the hot water heat shrinkage ratio in the longitudinal direction of 90 ° C is preferably 2 2 % or more, more preferably 24% or more, and particularly preferably 2 6 % or more. Further, in consideration of the essential characteristics of the laminated film composed of the cyclic polyolefin resin of the main raw material of the skin layer and the propylene-α-olefin copolymer of the core raw material, the temperature in the longitudinal direction of 90 ° C The upper limit of the hydrothermal shrinkage rate is about 60%. In the heat-shrinkable polyolefin-based film of the first invention of the present invention, the film is processed in a no-load state in a temperature of 90 ° C for 10 seconds, and the width of the film is calculated from the length before and after shrinking according to the above formula 1. The warm water shrinkage rate in the direction is preferably 〇% or more and 15% or less. When the warm water heat shrinkage rate in the width direction of 90 °C is more than 15%, it is not preferable because the longitudinal shrinkage-like pits are easily generated when used as a label. Further, the upper limit of the hot water heat shrinkage ratio in the width direction at 90 °C is preferably 13% or less, more preferably 11% or less, and particularly preferably 9% or less. Further, in consideration of the essential characteristics of the laminated film composed of the cyclic polyolefin resin of the main raw material of the skin layer and the propylene-α-olefin copolymer of the core material main raw material, the warm water in the width direction of 9 〇t The lower limit of the heat shrinkage ratio is about 0%. Moreover, when the heat-shrinkable polyolefin film of the second aspect of the present invention is treated in warm water of a predetermined temperature for 10 seconds, and then the hot water heat shrinkage ratio in the width direction is measured, the treatment temperature is 70 ° C to 90 ° C. At the time, the thermal water shrinkage rate is preferably 0% to 200909212 (again, as described above, "the treatment temperature is 70~90T: the warm water heat shrinkage rate is below 0%" means that it is adjusted at 7处理t~9 〇t is the temperature of any temperature in the temperature of 10 seconds, after measuring the warming shrinkage rate in the width direction, when the temperature of the treated warm water is any temperature, the heat shrinkage rate after the treatment is It is 0% or less (that is, it is not shrinkage). When the heat-shrinkage rate of warm water is higher than 〇% at a treatment temperature of °C to 90 °C, it is easy to produce longitudinal shrinkage at the time of heat shrinkage. The dent is not good. When the hot water heat shrinkage rate in the width direction at 90 °C is less than _ 3 〇%, it is not good to use the label as the label, which is poor adhesion to the bottle. 'The heat-shrinkable polyolefin-based film of the present invention is used after 8 〇 of its warm water shrinks by 10% in the longitudinal direction. When the right angle tear strength per unit thickness width direction is obtained, the right angle tear in the width direction is preferably 50 N/mm or more and 200 N/mm or less. [Method for Measuring Right Angle Tear Strength] After adjusting to 80 ° C in warm water, the film was shrunk by 10% in the longitudinal direction, and then subjected to a test piece of a predetermined size in accordance with JIS-K-7 128. Sampling. Subsequently, it was clamped using a universal tensile tester. At both ends of the test piece and at a tensile speed of 200 mm/min, the strength at the time of tensile failure in the width direction of the film was measured, and the film was made at 8 (TC not shrinking 10%). It was immersed in warm water of 80 ° C for about 5 seconds, and the degree of shrinkage after shrinkage was measured to reduce the degree of tensile failure in the film width direction. Moreover, 'the right angle tear of the unit thickness was calculated using the following formula 2 Crack strength Right angle tear strength = strength at the time of tensile failure + thickness ·•• Equation 2 The temperature of the water is 70. The degree of the sign is thin and strong enough -17- 200909212 In the warm water of 80 °C When the right angle tear strength after 丨0% in the longitudinal direction is less than 50 N/mm, When the label is used, there is a possibility that it is simply broken due to an impact such as falling during handling, but it is not preferable. When the right angle tear strength is greater than 20 ON/mm, because the label is torn In the initial stage, the cutting property (easiness of tearing) is poor, and the lower limit of the right-angled tearing strength is preferably 70 N/mm or more, more preferably 90 N/mm or more, and ii〇N. Further, the upper limit of the right-angle tearing strength is preferably 180 N/mm or less, more preferably l6 〇N/mm or less, and particularly preferably 14,000 N / mm or less. Regarding the cutting property of tearing the label at the seam portion, it is considered that the portion of the upper end or the lower end of the label of the first part of the sewing machine as described above is easy to tear (the ease of cutting into the notch); On the way to the oblique offset of the hole-shaped seam, the fins will not break and can be torn in the direction of the hole-like seam to the final tearing ease by light force (the tearing of the hole-like seam direction and the right-angle direction) Both sides of the ease of use contribute to the ease of work when actually peeling the label by hand. 'The latter is improved by the spacing of the hole-shaped joints. The ease of tearing of the initial portion of the seam is more compatible with the functional evaluation of the actual tearing of the label by hand, and is a more important property. Therefore, the heat-shrinkable polyolefin-based film of the present invention preferably has a right-angled tear strength in the above range. However, it is preferable that the balance between the hole-like seam direction of the latter and the easiness of tearing in the right-angle direction is within a specific range, and the hole-like seam tearing property of the heat-shrinkable polyolefin-based film of the present invention can be further improved. . Specifically, the heat-shrinkable polyolefin-based film of the present invention is obtained by shrinking 10% in the longitudinal direction in warm water of 80 ° C, and then obtaining the length direction and the width direction of Elmando according to the following method according to the following method: When the tearing load is 1 such a ratio of the Hermanndorf tear load, the ratio of Elmandorf is 〇·5 or more. 0 is better. [Measurement method of the Ellerdorf ratio] The film is attached in a state of being loosened in advance in a frame having a rectangular shape of a predetermined length (that is, both ends of the film are held by the frame). Further, the film after the relaxation is in the frame until it is in a state of tension (to the disappearance of the relaxation), and is immersed in warm water of 80 rpm for about 5 seconds to shrink in the longitudinal direction. -K-7128, the Elmandorf tearing load in the longitudinal direction and the width direction of the film was measured, and the Ehrmandorf ratio was calculated using the following formula 3. Further, the film which was not shrunk at 80 ° C for 1 〇% was immersed in warm water at 80 ° C for about 5 seconds and measured to shrink the degree of shrinkage to the length and width of the film. The direction of the Manchestern tear load. Elmandorf is less than 0 in the length direction of the Elmandorf tear load + width direction of the Elmandorf tear load ·•• 3 At 5 o'clock, when it is used as a label, it is difficult to tear straight along the hole-like seam, which is not preferable. Conversely, when the Ehrmandorf ratio is greater than 2 · 0, it is not easy to tear at a position offset from the hole-like seam. Also, the lower limit of the 'Ellmandorf ratio is better than 〇7 or more. 9 or more is better, to 1 . 1 or more is especially good. Also, the upper limit of Elmandorf is 1 . 8 is better than below. 6 or less is more preferable, and 1 or less of the following is preferable. The heat shrinkage ratio, the right-angle tear strength, and the Olman-19-200909212 Doffer ratio of the above-mentioned heat-shrinkable film can be achieved by using a preferable film composition' in combination with a preferred production method described later. Further, the heat-shrinkable polyolefin-based film of the present invention is preferably adjusted so that the solvent adhesive strength is 4 (N / 15 m m) or more. When the solvent adhesion strength is less than 4 (N/15 mm), the solvent adhesion portion may be peeled off, for example, when the label is thermally shrunk, which is not preferable. Further, the heat-shrinkable polyolefin-based film of the present invention can be obtained by melt-extruding the above polyolefin-based resin material by an extruder to form an unstretched film, and the unstretched film is biaxially oriented according to the method shown below. It is obtained by stretching and heat treatment. When the raw material resin is melted and extruded, it is preferably dried by using a dryer such as a hopper dryer or a paddle dryer or a vacuum dryer. After drying the raw material of the polyolefin resin, it was melted at a temperature of 200 to 300 ° C by an extruder and extruded in the form of a film. At the time of this extrusion, any conventional method such as a T-die method or a tubular method can be employed. Further, the unstretched film can be obtained by rapidly cooling the extruded sheet-shaped molten resin. Further, the method of rapidly cooling the molten resin can be suitably carried out by casting a molten resin onto a rotating drum by a nozzle to obtain a substantially unaligned resin sheet. Further, the obtained unstretched film is subjected to primary heat treatment by stretching in the width direction in accordance with predetermined conditions, as will be described later, and then stretched in the longitudinal direction in accordance with predetermined conditions, and rapidly cooled the longitudinally stretched film. The heat-shrinkable polyolefin-based film of the present invention can be obtained. Further, in the longitudinal stretching, the gap can be adjusted by appropriately adjusting the stretching gap (the distance between the low speed roller and the thin -20 - 200909212 film to the tangent point of the high speed roller and the film) and the film width. The ratio (stretching gap/film width) is adjusted in the range of 0 · 0 1 to 0 · 1 0. In the following, the difference between the biaxial stretching and the heat treatment method of the heat-shrinkable polyolefin-based film of the present invention is considered, and the difference between the biaxial stretching and the heat treatment method of the conventional heat-shrinkable polyolefin-based film is considered. , explain in detail. [Preferred film forming method of heat-shrinkable polyolefin-based film] The heat-shrinkable film which is simply stretched in the width direction has a hole-shaped seam in a direction orthogonal to the main shrinkage direction. Poor sex. On the other hand, although the heat shrinkable film which shrinks in the longitudinal direction is high in the past, when the unstretched film is simply stretched in the longitudinal direction, it is impossible to manufacture a film having a wide width, and it cannot be manufactured except for poor productivity. A film having a poor thickness. Further, when the method of stretching in the longitudinal direction after stretching in the width direction is used, the amount of shrinkage in the longitudinal direction may be insufficient or may be unnecessarily contracted in the width direction. The method of stretching in the longitudinal direction after stretching in the width direction (hereinafter referred to as transverse-longitudinal stretching method), the inventors of the present invention heat-shrink the warm water in the longitudinal direction of the film in accordance with the conditions of each stretching process. The rate and the seam-like seam tearing system are changed to concentrate on begging. As a result, when the film is produced by the transverse-longitudinal stretching method, it is possible to stably produce a film having a high shrinkage amount in the longitudinal direction and a good hole-to-hole joint tearability in the orthogonal direction by the following means. Further, the present inventors have studied the present invention based on such findings. (1) Intermediate thermal relaxation treatment after stretching in the width direction 200909212 (2) Trimming the film end portion before stretching in the longitudinal direction (3) Adjusting the stretching gap or less, and explaining the above-mentioned respective means (1) in order Intermediate thermal relaxation treatment after stretching in the width direction. The film is produced by the transverse-longitudinal stretching method according to the present invention, and after stretching the unstretched film in the width direction, it is 1 〇〇 ° C or more and 140 ° C or less. Temperature heat treatment (hereinafter, referred to as intermediate thermal relaxation treatment) 1 · 0 seconds or more, 5 0. 0 seconds or less is preferred. By performing such an intermediate thermal relaxation treatment, it is possible to obtain a film which is excellent in tear-sealing property of the hole-shaped joint and which does not cause shrinkage unevenness as a label. Thus, the reason why a film having a good hole-sealing tearability and a shrinkage unevenness is not obtained by applying a specific intermediate thermal relaxation treatment after the transverse stretching is not clear, and it is considered that it is possible to perform a specific The intermediate thermal relaxation treatment can reduce the contraction stress in the width direction while leaving a certain degree of molecular alignment in the width direction. Further, when the temperature of the intermediate heat treatment is more than 140 ° C, interlayer peeling occurs in the longitudinal stretching, which is not preferable. On the contrary, when the temperature of the intermediate heat treatment is as small as 1 〇 〇 °C, the final heat shrinkage rate in the width direction of the film cannot be controlled, which is not preferable. Further, the lower limit of the temperature of the thermal relaxation treatment is preferably 11 〇 ° C or more, more preferably 1 15 ° C or more. On the other hand, the upper limit of the temperature of the thermal relaxation treatment is preferably 1 3 5 t or less, more preferably 130 ° C or less. On the other hand, the time of the thermal relaxation treatment is appropriately adjusted at 1 according to the composition of the raw material. More than leap seconds, 5 0. Below 0 seconds is preferred. Further, the stretching of the unstretched film in the width direction is performed at a temperature of 70 ° C or more and 140 ° C or less by a state in which both ends of the width direction of the clip are held by the clip in the tenter. 5 times or more, 8. The method of multiplying the magnification of 0 times or less is -22 - 200909212. When the stretching temperature is less than 70 °C, it is not preferable because cracking is likely to occur during stretching. Conversely, when the temperature is more than 140 °C, the thickness unevenness in the width direction is deteriorated, which is not preferable. Further, the lower limit of the temperature for the transverse stretching is preferably 75 ° C or more, more preferably 80 ° C or more. Further, the upper limit of the temperature of the transverse stretching is preferably 135 ° C or less, more preferably 1300 ° C or less. On the other hand, when the stretching ratio in the width direction is less than 2 · 5 times, not only the productivity is deteriorated but also the thickness in the width direction is deteriorated, which is not preferable, and conversely, more than 8. When it is 0, it is easy to cause breakage during stretching, and it is not preferable, and it is necessary to make it thermally slack: It is not preferable because of large energy and large-scale apparatus and poor productivity. Also, the lower limit of the lateral stretching magnification is 3 . 0 times or more is better, to 3 . More than 5 times is better. Moreover, the upper limit of the lateral stretching magnification is 7. It is preferably 5 times or less, and more preferably 7 〇 or less. (2) Trimming the end of the film before stretching in the longitudinal direction According to the transverse-longitudinal stretching method of the present invention, a film is produced, and the film edge is trimmed before stretching the film subjected to the intermediate thermal relaxation treatment in the longitudinal direction. It is preferred that the portion of the higher thickness that is not sufficiently stretched laterally (mainly the grip portion that is stretched in the lateral direction 1'). More specifically, the thickness of the edge portion at the left and right ends of the film is about 1 of the thickness of the central portion using a cutter or the like. 1~1. The three-fold portion cuts the higher-thickness portion of the film edge, and it is preferable to stretch the remaining portion in the longitudinal direction while removing the higher-thickness portion. Further, when the film end portion is repaired as described above, the surface temperature of the film before trimming is preferably 5 (TC or less) by cooling. Thus, by cooling the film, it is possible to trim without cutting the cut surface. 'The trimming of the end of the film' can be performed using a normal cutter, but when using a round blade with a peripheral blade -23 - 200909212, since there is no local blade passivation, it can be cut sharply and continuously for a long period of time. It is preferable that the end portion of the film does not cause breakage when stretched in the longitudinal direction. Thus, the end portion of the film is trimmed before stretching in the longitudinal direction. The film is uniformly stretched in the longitudinal direction. Thus, it is possible to continuously produce a film which is not broken and stabilized. In addition, a film having a large amount of shrinkage in the longitudinal direction (main shrinkage direction) can be obtained. Moreover, since the film can be uniformly formed Stretching in the longitudinal direction can provide a film having a small thickness unevenness in the length f direction. Moreover, by trimming the end portion of the film, it is possible to avoid stretching in the longitudinal direction. Bending 'can obtain a film having a small difference in physical properties. (3) Adjusting the stretching gap According to the transverse-longitudinal stretching method of the present invention, the film is stretched in the longitudinal direction after the intermediate heat relaxation treatment, and is heated. The low speed roller and the high speed roller are performed, and the ratio of the stretching gap between the two rollers to the film width before stretching (hereinafter referred to as the stretching gap ratio) is adjusted at 0 · 1 0 by i. 0. Below 5 0 is preferred. Thus, by adjusting the stretch gap ratio to 〇. j 〇 or more ' 〇 · 5 0 or less, when it is attached to a bottle as a label, it is possible to obtain shrinkage in a direction orthogonal to the main shrinkage direction, and no so-called "longitudinal shrinkage dent" is formed and shrinkage is completed. A heat-shrinkable film which is good in any of the pore-sealing joints and heat-resistant adhesiveness. The stretch gap ratio is less than 〇 · 1 〇. It is not easy to produce a longitudinal shrinkage dent in the bottle as a label. On the contrary, the stretch gap ratio is greater than 0. At 50°, uneven thickness is caused by uneven stretching, which is not preferable. -24 - 200909212 Moreover, the film is produced by the transverse-longitudinal stretching method according to the present invention, as described above, after stretching in the longitudinal direction after performing the intermediate thermal relaxation treatment after the transverse stretching, and also using the clip holder in the tenter. The state of both end edges in the width direction is heat-treated at a temperature of 8 (TC or more, 1 〇〇 ° C or less. 0 seconds or more, 1〇. The time below 〇 seconds (hereinafter referred to as the final heat treatment). By performing such final heat treatment, the final shrinkage of the film can be adjusted with high precision. Further, only the specific one of the means (1) to (3) above does not effectively contribute to the heat shrinkability of the film in the longitudinal direction, the tear seam sealing property, and the stable film forming property. By using the combination of (1) and (2), or (1) to (3), the heat shrinkability in the longitudinal direction, the tear seam sealing property, and the stable film forming property can be expressed very efficiently. . [Effect of each process of film production on imparting film properties] The heat-shrinkable polyolefin film of the present invention has a hot water heat shrinkage ratio in the longitudinal direction, a warm water heat shrinkage ratio in the width direction, and a right angle tear strength in the longitudinal direction. And the characteristics of the Hermanndorf ratio can be controlled by the conditions of the transverse stretching process, the intermediate thermal relaxation process, the longitudinal stretching process and the final heat treatment process in the film manufacturing. That is, when the temperature of the intermediate thermal relaxation treatment is increased, the thermal shrinkage rate of the warm water in the longitudinal direction is increased, and the thermal shrinkage ratio of the warm water in the width direction is decreased. Further, when the longitudinal stretching ratio is increased, the warm water heat shrinkage rate in the longitudinal direction and the width direction increases. Moreover, when the longitudinal stretching ratio is increased, the right-angle tearing strength is increased, the length of the Aimandorf tearing load is decreased, and the width direction of the Ermandorf tearing load is increased. On the other hand, when the stretching temperature in the longitudinal stretching is increased, the warm water shrinkage ratio in the longitudinal direction is decreased, and the warm water shrinkage ratio in the width direction is increased. Moreover, when the stretching temperature of the longitudinal -25 - 200909212 stretching is increased, the right-angled tearing strength is decreased. The length of the Ermandorf tear load is increased, and the width direction of the Elmandorf tearing load is reduced. However, in the production of the heat-shrinkable polyolefin-based film of the present invention, only one of the transverse stretching process, the intermediate thermal relaxation treatment process, and the longitudinal stretching process can not make the film properties good, and it is considered that All of the transverse stretching process, the intermediate thermal relaxation process, and the longitudinal drawing process can be made to have good film characteristics very efficiently in accordance with the above-described predetermined conditions. [Examples] Hereinafter, the present invention will be described in more detail by way of Examples. However, the present invention is not limited thereto, and may be appropriately modified without departing from the spirit and scope of the invention. The properties and composition of the raw materials used in the examples and comparative examples and the production conditions (stretching, relaxation treatment conditions, etc.) of the films of the comparative examples are as shown in Table 1, Table 2, Table 4, and Table. 5 is shown. Further, the resin materials a to F in Tables 1 and 4 are as follows. . Resin raw material A: Polypropylene-ethylene random copolymer (S131 ethylene = 5. Sumitomo Chemical Co., Ltd.) 5 mass%, ^^11=1. 2 g/10 min, melting point 1 3 5 . (:) • Resin raw material B: Polypropylene-ethylene, butene random copolymer (manufactured by Sumitomo Chemical Co., Ltd.? 8 and 66 £8 ethylene = 2. 5 mass%, butene = 6. 9 mass %, MFR = 3_0 g/10 min, melting point 134.匚) • Resin raw material C: Polypropylene-ethylene random copolymer (FS2011DG3 manufactured by Sumitomo Chemical Co., Ltd. Ethylene = 〇·6 mass %, MFR = 2. 5 g/10 min, melting point 1 5 8 ° C), and 6% by mass of stearic acid -26-200909212 glyceride (antistatic agent 硏 ITA VITA Μ IN company s-ioo) Founder • Resin raw material D: polypropylene-ethylene random copolymer (FS2011DG3 vinyl clock, melting point 1 5 8 °c), adding 6 masses of glyceride in 94% by mass (antistatic agent, VITAMIN shares) RIKEMAL S- 1 00) The original • Resin raw material E: Polypropylene-ethylene random copolymer (Sumitomo Division FS2011DG3 ethylene=0. 6% by mass, MFR = 2 minutes, melting point: 158 °), and 20% by mass of fine particles (the average micron size of CS30 manufactured by Sumitomo Chemical Co., Ltd.) are added to 80% by mass. • Resin raw material F: cyclic poly Olefin (Mitsui Chemical Co., Ltd. 8008T MFR = 15 g/10 min, T g = 70 ° C) Further, the evaluation method of the film is as follows. [Tm (melting point)] I Using the differential sweep (type: DSC220) manufactured by SEIKO Electronics Industries Co., Ltd., and taking the unheated film 5 mg' heating rate 1 〇t: / minute after the endothermic curve # _ [Ethylene, butene content] Propylene-ethylene copolymer, propylene-butene copolymer' The content of ethylene or propylene in the copolymer is based on the high score '5 (1959, issued by Kiiiyaya Bookstore) 6 1 5~6 1 7-page method, determined according to 13C-NMR spectroscopy. Also
RIKEMAL 化學股份公 .5克/1 0分 %硬脂酸一 份公司製 化學股份公 .5克/10分 量％有機聚 粒徑爲3 . 5 司製 APEL 描型熱量計 從自室溫以 t求取。 -乙烯-丁烯 F分析手冊 所記載之方 照同書的第 -27 - 200909212 256頁[(i)無規共聚物]的項目所記載之方法、依照ir光譜 法來決定。 [熱收縮率（溫水熱收縮率）] 將薄膜裁斷成10公分xlO公分的正方形，並在規定溫 度（7 0 C、7 5 °C、8 0 °C、8 5 °C、9 0。(：）土 0 · 5 °C 的溫水中，於無 負荷狀態處理1 0秒鐘來使其熱收縮後，測定薄膜的縱向及 橫向的尺寸’並依照上式1，來求取各自的熱收縮率。將 該熱收縮率較大的方向（長度方向）作爲主收縮方向。 [直角撕裂強度] 將切斷成規定大小的矩形（長度方向X寬度方向=1 5 0毫 米X150毫米）之薄膜’使用調整爲8(TC之溫水中使其在主 收縮方向收縮1 0 %。又’對在8 0 °C未收縮1 0 %之薄膜，係 使其在8 0°C的溫水浸漬約5秒鐘來使能夠收縮的程度收 縮。如此進行後，依照JI S - K - 7 1 2 8，取樣如第1圖所示的 形狀來製造試驗片（又，取樣係以試驗片的長度方向作爲薄 膜的主收縮方向）。如此進行後，使用萬能拉伸試驗機（島 津製作所製AUTO GRAPH)夾住試的兩端，並以拉伸速度爲 2 00毫米/分鐘的條件，進行測定在薄膜的寬度方向之拉伸 破壞時的強度，並使用上式2來算出每單位厚度之直角撕 裂強度。 [愛爾曼多夫比] 在矩狀的框將所得到的薄膜以預先鬆弛後的狀態安裝 (亦即，使用框把持薄膜的兩端）。而且，鬆弛後的薄膜係 在框內至成爲緊張狀態爲止（鬆弛消失爲止），並藉由浸漬 -28 - 200909212 在8(TC的溫水約5秒鐘使薄膜在主收縮方向收縮1 0%(以 下，稱爲收縮）。又’對在8 0 °c未收縮1 0 %之薄膜’係使其 在8 0 °C的溫水浸漬約5秒鐘來使使能夠收縮的程度收縮。 如此進行後，依照JIS - K -7 1 2 8，切取主收縮方向X正交方向 =63毫米X75毫米的尺寸，並藉由從長條的端緣（沿著正交 方向之端緣）的中央以與該端緣正交的方式切下20毫米的 狹縫（切口）來製造試驗片。然後使用所製造的試驗片進行 測定主收縮方向之愛爾曼多夫撕裂負荷。又’使用與上述 〔 方法同樣的方法使薄膜在主收縮方向預收縮後’將薄膜的 主收縮方向與正交方向更換來製造試驗片’並進行測定正 交方向的愛爾曼多夫撕裂負荷。然後從所得到主收縮方向 及與主收縮方向正交之方向的愛爾曼多夫撕裂負荷使用上 述3來算出愛爾曼多夫比。 [溶劑黏著強度] 在拉伸後的薄膜使用四氫呋喃來施行密封（以塗布量 爲5.0克/平方公尺的方式將四氫呋喃塗布在薄膜表面後， 迅速地在該薄膜表面上黏著另外的薄膜（表面））。於薄膜的 主拉伸方向切取密封部1 5毫米的寬度，並將其安裝於 BALDWIN(股）公司製萬能拉伸試驗機 STM-50，在 180°剝 離試驗係以拉伸速度爲2 00毫米/分鐘來測定。 [收縮完成性] 對主收縮方向爲長度方向之薄膜捲物，係將所得到的 薄膜捲物切割成約1 2 0毫米的寬度後，分割成規定長度並 卷取來製造小型的切條捲物，並在該切條捲物預先使用東 -29 - 200909212 洋油墨製造（股）的草綠色、金色、白色印墨，重複施行標 籤用的印刷（3色印刷）。又，在全部各標籤用印刷’於與薄 膜捲物的長度方向正交之方向，在薄膜總寬度範圍以約2 2 毫米的間隔形成2條平行的孔狀接縫（以約1毫米間隔且約 1毫米直徑的圓連續之孔狀接縫）。然後，將經施行標籤用 印之捲物狀的薄膜之一側的端部，藉由重疊於在3 5 0毫升 的四方型熱用PET瓶（已塡充有內容物者）外周的一部分所 塗布的黏著劑上而黏著，且在此狀態，將捲物狀的薄膜以 規定長度引出，且使其纏繞於PET瓶的外周。如此進行後’ 使在PET瓶的外周疊合的熱收縮性薄膜藉由上述的黏著劑 邊貼合邊使用切割刀在垂直方向切割外側的薄膜’而使標 籤被覆P E T瓶的外周。 另一方面，關於主收縮方向爲寬度方向之薄膜捲物’ 係在該收縮性薄膜預先使用東洋油墨製造（股）的草綠色' 金色、白色印墨施行3色印刷。然後，使用白光股份公司 製、白光密封器（型式：N 〇 . 3 1 0 -1)將印刷後的薄的兩端部密 封，來製造圓筒狀的標籤。如此進行後，將所製造的標籤 安裝於PET瓶的周圍。 然後，使用 Fuji Astec公司製蒸氣險道（型式； S Η - 1 5 0 0 - L )，並使被覆標籤後P E T瓶（由長度方向爲主收縮 方向之薄膜所構成的標籤所被覆而成的PET瓶、及由寬度 方向爲主收縮方向之薄膜所構成的標籤所被覆而成的PET 瓶）以通過時間爲1 〇秒、區域溫度爲80°C的條件使其通 過，藉由使在 PET瓶外周之標籤熱收縮而完成標籤的安 -30 - 200909212 裝。又’在安裝時，在頸部係以直徑4 0毫米 籤的一側端部之方式調整。目視進行收縮 價，其基準係如下述。 ◎:未產生敲紋、跳起、收縮不足之任一者 顏色不均 〇：無法確認有皺紋、跳起或收縮不足之任 夠觀察到若色顏色不均 △:未產生跳起、收縮不足之任一者，但是 不均 X :產生皺紋、跳起、收縮不足 [孔狀接縫撕封性] 將預先在與主收縮方向正交之方向施加 籤’使用與上述收縮完成性的測定條件之同 PET瓶。但是，孔狀接縫係藉由以1毫米間 毫米的孔眼來形成，且在標籤的縱向（高度^ 毫米、寬度1 2 0毫米的範圍設置2條。隨後 °C冷藏，在剛從冰箱取出後以指尖撕裂瓶子 接縫，計算能夠沿著從縱向完整地撕列且能 子剝下的條數，來算出相對於總試樣5 0條之 的部分成爲標 後的完成性評 ，且未觀察到 一者，但是能 觀察到頸部的 孔狀接縫之標 一條件安裝在 隔施加長度1 ?向）在長度 1 ，將該瓶以5 之標籤的孔狀 夠將標籤從瓶 .比率。 200909212 [表i] 樹脂原料的組成(質量％) 皮層 芯層 乙烯量(％) 丁烯量(％) 實施例1 E/F=l/99 A=100 3.67 實施例2 E/F=l/99 A=100 3.67 實施例3 E/F=l/99 A=100 3.67 實施例4 E/F=l/99 B = 100 1.67 4.6 實施例5 E/F=l/99 A=100 3.67 實施例6 E/F=l/99 A=100 3.67 實施例7 E/F=l/99 A=100 3.67 比較例1 E/F=l/99 A=100 3.67 比較例2 A/D/E=90/8/2 F=100 3.33 比較例3 C/D/E=90/8/2 C=100 0.6 比較例4 C/D/E=90/8/2 C=100 0.6 比較例5 E/F=l/99 A=100 3.67 比較例6 E/F=l/99 A=100 3.67 •樹脂原料A :聚丙烯-乙烯無規共聚物（乙烯=5 . 5質量％ ) •樹脂原料B :聚丙烯-乙烯、丁烯無規共聚物（乙烯=2.5 質量％、丁烯=6 _ 9質量％) •樹脂原料C :聚丙烯-乙烯無規共聚物（乙烯=0.6質量％) •樹脂原料D :在9 4質量％聚丙烯-乙烯無規共聚物（乙烯 = 0.6質量％)中添加6質量％硬脂酸一甘油酯而成者 •樹脂原料E :在8 0質量％聚丙烯-乙烯無規共聚物（乙烯 = 0.6質量％)中添加20質量％有機聚合物微粒子而成者 •樹脂原料F :環狀聚烯烴 32- 200909212 [表2]RIKEMAL Chemical Co., Ltd. 5g / 10%% stearic acid, a company-made chemical company. 5g/10% by weight organic poly particle size is 3.5. The system APEL calorimeter is obtained from room temperature take. - Ethylene-butene F analysis manual The method described in the item -27 - 200909212 256 [(i) Random copolymer] of the same book is determined according to the ir spectroscopy method. [Heat shrinkage rate (warm water heat shrinkage rate)] The film was cut into a square of 10 cm x 10 cm and at a predetermined temperature (70 C, 75 ° C, 80 ° C, 85 ° C, 90). (:) In warm water of 0 ° 5 °C, after 10 seconds of no-load condition to heat-shrink, measure the longitudinal and lateral dimensions of the film' and determine the heat according to the above formula 1. Shrinkage ratio: The direction (longitudinal direction) in which the heat shrinkage ratio is large is taken as the main shrinkage direction. [Right-angle tear strength] A rectangle having a predetermined size (length direction X width direction = 150 mm X 150 mm) The film's use was adjusted to 8 (the warm water of TC shrinks by 10% in the main shrinkage direction. Also, the film which is not shrinkage at 80 °C and 10% is made to be impregnated in warm water at 80 °C. After about 5 seconds, the degree of shrinkage was contracted. After this, the test piece was sampled according to the shape shown in Fig. 1 in accordance with JIS-K-7 1 2 8 (again, the length of the test piece was measured. The direction is the main shrinkage direction of the film.) After this, it is clamped using a universal tensile tester (AUTO GRAPH manufactured by Shimadzu Corporation). The strength at the time of tensile failure in the width direction of the film was measured at both ends of the film at a tensile speed of 200 mm/min, and the right-angle tear strength per unit thickness was calculated using the above formula 2. Elmandorf ratio] The obtained film is attached in a state of being loosened in advance in a rectangular frame (that is, both ends of the film are held by the frame). Moreover, the relaxed film is in the frame until it becomes tense. Until the state (relaxation disappears), and by dipping -28 - 200909212 in 8 (TC of warm water for about 5 seconds, the film shrinks by 10% in the main shrinkage direction (hereinafter, referred to as shrinkage). Again 'on the 8 The 0 °c uncontracted 10% film was immersed in warm water at 80 ° C for about 5 seconds to shrink the degree of shrinkage. After this, according to JIS - K -7 1 2 8, Cut the main contraction direction X orthogonal direction = 63 mm X 75 mm, and cut 20 mm from the center of the end edge of the strip (the edge along the orthogonal direction) orthogonal to the end edge The slit (cut) is used to manufacture the test piece, and then the test piece is used to measure the main sample. In the direction of the teardown of the Ermandorf tear load, 'using the same method as the above method, the film is pre-shrinked in the main shrinkage direction, 'the main shrinkage direction of the film is replaced with the orthogonal direction to produce a test piece' and The Ehrmandorf tear load in the orthogonal direction is measured. Then, from the obtained main contraction direction and the direction of the main contraction direction, the Elmandorf tear load is calculated using the above 3 to calculate the Ehrmandorf ratio. [Solvent Adhesive Strength] The film after stretching was sealed using tetrahydrofuran (after applying tetrahydrofuran to the surface of the film in a coating amount of 5.0 g/m 2 , another film was quickly adhered to the surface of the film ( surface)). The width of the sealing portion was cut into a width of 15 mm in the main drawing direction of the film, and it was mounted on a universal tensile testing machine STM-50 manufactured by BALDWIN Co., Ltd., and the tensile speed was 200 mm at a 180° peeling test system. /min to determine. [Shrinkage Completion] A film roll in which the main shrinkage direction is the longitudinal direction is obtained by cutting the obtained film roll into a width of about 120 mm, and then dividing it into a predetermined length and winding it to produce a small slit roll. In the cut strip, the green, gold, and white inks of the East -29 - 200909212 foreign ink manufacturing (stock) were used in advance, and the printing for the label was repeated (three-color printing). Further, in all the labels, the printing is performed in a direction orthogonal to the longitudinal direction of the film roll, and two parallel hole-shaped seams are formed at intervals of about 2 2 mm in the total width of the film (at intervals of about 1 mm and A continuous hole-shaped seam of approximately 1 mm in diameter). Then, the end portion on the side of the film-formed film which is subjected to the label printing is applied by being superposed on a portion of the outer circumference of a 350 ml square hot PET bottle (which has been filled with the contents). The adhesive adheres to the adhesive, and in this state, the roll-shaped film is taken out in a predetermined length and wound around the outer circumference of the PET bottle. After the above, the heat-shrinkable film laminated on the outer periphery of the PET bottle was subjected to the above-mentioned adhesive while being bonded, and the outer film was cut in the vertical direction using a dicing blade, and the label was coated on the outer periphery of the P E T bottle. On the other hand, the film roll of the width direction of the main shrinkage direction is subjected to three-color printing in which the shrinkable film is previously prepared using the grass green 'gold and white ink of Toyo Ink Co., Ltd. Then, the printed thin end portions were sealed with a white light sealer (type: N 〇 . 3 1 0 -1) manufactured by Baiguang Co., Ltd. to manufacture a cylindrical label. After doing so, the manufactured label was mounted around the PET bottle. Then, using a steam barrier manufactured by Fuji Astec Co., Ltd. (type: S Η - 1 500-L), and coating the labelled PET bottle (a label composed of a film whose length direction is the main contraction direction) A PET bottle coated with a PET bottle and a label consisting of a film whose width direction is the main shrinkage direction is passed through with a pass time of 1 sec and a zone temperature of 80 ° C. The label of the outer circumference of the bottle is heat-shrinked and the label is completed in An-30 - 200909212. Further, at the time of installation, the neck portion was adjusted so as to end on one side of the diameter of 40 mm. The shrinkage price is visually observed, and the basis is as follows. ◎: No color unevenness caused by knocking, jumping, or insufficient shrinkage 〇: It is impossible to confirm that there are wrinkles, jumps, or insufficient shrinkage. It is observed that the color of the color is uneven △: no jump, insufficient shrinkage Any of them, but unevenness X: wrinkles, jumps, and insufficient shrinkage [hole-like joint tear-off property] A test condition in which the sign is used in the direction orthogonal to the main shrinkage direction and the shrinkage completion property described above is used. The same PET bottle. However, the hole-shaped seam is formed by an eyelet having a millimeter of 1 mm, and two in the longitudinal direction of the label (height ^ mm, width of 120 mm), then refrigerated at ° C, just taken out of the refrigerator After tearing the seam of the bottle with the fingertip, calculating the number of strips that can be completely torn from the longitudinal direction and capable of being peeled off, to calculate the completion score of the part relative to the total sample of 50 pieces. And one was not observed, but it can be observed that the condition of the hole-shaped joint of the neck is installed at the interval of the application length 1 ?) at the length of 1, and the bottle is shaped like a hole of 5 to the label from the bottle. .ratio. 200909212 [Table i] Composition of resin raw material (% by mass) Cortex core layer Amount of ethylene (%) Amount of butene (%) Example 1 E/F = l/99 A = 100 3.67 Example 2 E/F = l/ 99 A=100 3.67 Example 3 E/F=l/99 A=100 3.67 Example 4 E/F=l/99 B=100 1.67 4.6 Example 5 E/F=l/99 A=100 3.67 Example 6 E/F=l/99 A=100 3.67 Example 7 E/F=l/99 A=100 3.67 Comparative Example 1 E/F=l/99 A=100 3.67 Comparative Example 2 A/D/E=90 /8/2 F=100 3.33 Comparative Example 3 C/D/E=90/8/2 C=100 0.6 Comparative Example 4 C/D/E=90/8/2 C=100 0.6 Comparative Example 5 E/F =l/99 A=100 3.67 Comparative Example 6 E/F=l/99 A=100 3.67 • Resin raw material A: Polypropylene-ethylene random copolymer (ethylene = 5.9 mass%) • Resin raw material B: poly Propylene-ethylene, butene random copolymer (ethylene = 2.5% by mass, butene = 6 -9 % by mass) • Resin raw material C: polypropylene-ethylene random copolymer (ethylene = 0.6% by mass) • Resin raw material D : Adding 6% by mass of stearic acid monoglyceride to 94% by mass of polypropylene-ethylene random copolymer (ethylene = 0.6% by mass) • Resin raw material E: at 80% by mass of polypropylene-ethylene Synthetic copolymer Addition of 20% by mass of organic polymer microparticles in ethylene = 0.6% by mass) Resin raw material F: Cyclic polyolefin 32- 200909212 [Table 2]
溫度 J°C) 溫度 CC) 倍率 低逮輥速度 运^鏟) 高速輥速度 分鐘） 倍率 實施例l 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6 橫篆 橫| 橫-篆 橫孤 橫| 橫-藏· 橫來一 100 ——' 一 100 一 100 一 100 100 100 100 橫-I 橫-I〆 橫I 橫-I 橫一 100 100 165 100 100 6.5 6.5 6.5 6.5 6.5 6.5 4.5 6.5 6.5 6.5 6.5 6.5 130 130 130 130 130 130 130 75 130 130 160 130 43 80 43 43 43 43 43 43 43 43 43 43 43 43 90 85 100 100 100 140 1.0 --- 1.5 -—-— 1.0 — 2.0 ~~ -—. —一 ±0^_κο_ 1.0 3.0 3.0 3.0 6.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 2.0 3.0 3.0 3.0 2.0 3.0 3.0 3.0 3.0 3.0 [實施例1] 利用共擠出法，從2個擠壓機（第一、第二擠壓機）將 聚j：希煙系棱f脂熔融擠壓（在模頭內層積而擠出），藉由纏繞 M B # gp g 3 〇 °C之旋轉金屬滾筒而急速冷卻，來得到二種 Ξ ® g的未拉伸薄膜（聚烯烴系樹脂積層薄片）。此時之 未拉伸薄膜的拉伸速度（金屬輥的轉速）爲約6.8公尺/分 鐘。未延伸各層的形成方法（至熔融擠壓的步驟）係以下所 示。又，在以下的說明’依照從聚烯烴系樹脂積層薄片的 -33- 200909212 表層之順序，稱第一層、第二層、第三層（亦即， 表面係金屬輥接觸面）。又，在形成未拉伸薄膜之 機的吐出量係以第一層/第二層/第三層的厚度比怎 方式來調整。 •第一層及第三層（皮層）的形成 將乾燥後的上述原料樹脂E、F，使用定量螺 連續地各自供給至擠壓機（第一擠壓機）的料斗。 料樹脂F的供給量爲9 9質量％，且使原料樹脂e 爲1質量°/。。然後，將所供給的原料樹脂F、E在 合’並藉由單軸式第一擠壓於25〇r從T模頭熔_ •第二層（芯層）的形成 將乾燥後的上述原料樹脂A，使用定量螺桿 續地各自供給至擠壓機（第二擠壓機）的料斗。然 供給的原料樹脂A藉由單軸式第二濟壓於2 5 0 °C 熔融擠出。 如此進行後’將所得到的未拉伸薄膜，引導 設置有橫向拉伸區、中間區及中間熱鬆弛處理 益。又’在該拉幅器’在橫向拉伸區與中間熱鬆 之中間的位置之中間區的長度係設定爲約40公交 中間區，以在未使薄膜通過的狀態垂吊薄長方形 該紙片係完全地在垂直方向下垂之方式，隔離來 的熱風及來自熱處理區的熱風。 而且，將引導至拉幅器之未拉伸薄膜預加熱 度爲9 0 °C後，在橫向拉伸區於橫向以1 〇 〇 t拉伸 第三層的 第一擠壓 ^ 1/4/1 的 桿供料器 又，使原 的供給量 料斗內混 座擠出。 供料器連 後，將所 從T模頭 至連續地 區之拉幅 驰處理區 •。又，在 紙片時1 自拉伸區 至薄膜溫 6.5倍且 -34- 200909212 使其通過中間區後，藉由引導中間熱鬆驰處 t的溫度熱處理4 3秒鐘，得到厚度1 0 0微米 伸薄膜。如此進行後，利用設置於拉幅器的 對的修剪裝置（由具有周狀刀鋒之圓刀鋒構域 單軸拉伸薄膜的端緣（中央的薄膜厚度之約 分），並連續地除去在切斷部分的外側位置之 而且，藉由將如此地修剪端部而成的薄 = 5 00毫米）引導至連續地配置複數個輥群而 機，並在預熱輥上將薄膜溫度預加熱至9 (TC 度設定爲8 0 °C之低速拉伸輥與內部循環水白< 。(：之高速拉伸輥之間，拉伸3 .0倍。又，低矣 低速輥一同移動之薄膜速度）係調整爲1 .0公 輥的速度與高速輥一同移動之薄膜速度）係調 /分鐘。又，低速拉伸輥與高速拉伸輥之拉伸 3 0毫米（拉伸間隙比率=0.0 6)。 然後’藉由將如此縱向拉伸後的薄膜卷 來得到約4 〇微米之依規定長度捲繞的雙軸j 縮性聚烯烴薄膜）。而且，依照上述方法評價 特性。評價結果係如表3所示。 [實施例2 ] 除了將縱向拉伸之低速拉伸輥的溫度蠻 外’依照與實施例1同樣的方法進行，來得 性薄膜而成的薄膜捲物。而且，依照與實施 法評價。評價結果係如表3所示。 理區，在 1 3 0 的橫向單軸拉 後方之左右一 匕者）切斷橫向 1 . 2倍厚度部 薄膜的端部。 :膜（薄膜寬度 成的縱向拉伸 後，在表面溫 J溫度設定3 0 I輥的速度（與 尺/分鐘，高速 整爲3 · 0公尺 間隙係調整爲 取在紙管上， £伸薄膜（熱收 所得到薄膜的 $更爲90°C以 到捲繞熱收縮 例1同樣的方 200909212 [實施例3 ] 除了藉由將縱向拉伸之低速拉伸輥的溫度變更爲8 5 °C 且將低速輥的速度變更爲1 · 5公尺/分鐘來使縱向拉伸倍率 變更爲2倍以外，依照與實施例1同樣的方法進行，來得 到捲繞熱收縮性薄膜而成的薄膜捲物。而且，依照與實施 例1同樣的方法評價。評價結果係如表3所示。 [實施例4] 除了將形成芯層的原料樹脂變更爲原料樹脂B以外， 依照與實施例1同樣的方法進行，來得到捲繞熱收縮性薄 膜而成的薄膜捲物。而且，依照與實施例1同樣的方法評 價。評價結果係如表3所示。 [實施例5] 除了藉由將縱向拉伸之低速拉伸輥的速度變更爲2 . G 公尺/分鐘且將高速輥速度各自變更爲6 · 0公尺/分鐘，來使 縱向拉伸倍率變更爲3倍以外，依照與實施例1同樣的$ 法進行，來得到捲繞熱收縮性薄膜而成的薄膜捲物。而且， 依照與實施例1同樣的方法評價。評價結果係如表3所开；。 [實施例6] 除了將橫向拉伸之拉伸輥的溫度變更爲8 〇。<：以外，_ 照與實施例1同樣的方法進行，來得到捲繞熱收縮性薄_ 而成的薄膜捲物。而且，依照與實施例1同樣的方法評f賈。 評價結果係如表3所示。 [實施例7 ] 除了在形成未拉伸的樹脂薄片時’調整、變更吐出鼍， -36 - 200909212 來將橫向拉伸時之拉伸倍率變更爲4 · 5倍，且將縱向拉伸 時之低速輥的速度變更爲1 · 5公尺/分鐘，來使縱向拉伸倍 率變更爲2倍以外，依照與實施例1同樣的方法進行，來 得到卷取厚度6 0微米的熱收縮性薄膜而成的薄膜捲物。而 且’依照與實施例1同樣的方法評價。評價結果係如表3 所示。 [比較例1 ] 除了在形成未拉伸的樹脂薄片時，調整、變更擠出量 以外’藉由將與實施例1同樣地進行而得到的橫向拉伸， 在通過中間區後引導至中間熱鬆弛處理區，並在7 5 r的溫 度熱處理4 3秒鐘，且將該熱處理後的薄膜卷取於紙管，來 得到以規定長度卷取約60微米的橫向拉伸薄膜而成的薄 膜捲物。而且，依照上述的方法評價所得到的薄膜的特性。 又，因爲所得到的薄膜之薄膜寬度方向爲主收縮方向，所 以直角撕裂強度、愛爾曼多夫比、孔狀接縫撕封性的評價 係使薄膜試料的長度方向/寬度方向與其他的實施例、比較 例相反來進行評價。評價結果係如表3所示。 [比較例2 ] 除了在形成未拉伸的樹脂薄片時，將供給至第一擠壓 機及第二擠壓機之樹脂原料如表2所示變更以外，且將皮 層及芯層的厚度如表3變更以外’依照與實施例1同樣的 方法，來得到卷取熱收縮性薄膜而成的薄膜捲物。而且， 依照與實施例1同樣的方法來評價所得到薄膜的特性。評 價結果係如表3所示。 -37 - 200909212 [比較例3 ] 除了在形成未拉伸的樹脂薄片時，將供給至第一擠壓 機及第二擠壓機之樹脂原料如表1所示變更以外，欲依照 與實施例1同樣的方法來製造熱收縮性薄膜時，由於破裂 而無法製造薄膜。 [比較例4 ] 除了在形成未拉伸的樹脂薄片時，將供給至第一擠壓 機及第二擠壓機之樹脂原料如表2所示變更，且將在橫向 拉伸時之拉伸溫度（薄膜溫度）變更爲1 6 5 °C，將中間熱鬆弛 處理時之中間熱鬆弛處理區之溫度變更爲1 6 (TC，且將在 縱向拉伸時之縱向拉伸溫度（低速輥的溫度）變更爲1 4 0 °C 以外，依照與實施例1同樣的方法，來得到卷取厚度3 0微 米的熱收縮性薄膜而成的薄膜捲物。而且，依照與實施例 1同樣的方法來評價所得到薄膜的特性。評價結果係如表3 所示。 [比較例5 ] 除了將中間熱鬆弛處理時之熱處理溫度變更爲8 0 °C以 外，依照與實施例1同樣的方法進行，來得到捲繞熱收縮 性薄膜而成的薄膜捲物。而且，依照與實施例1同樣的方 法評價。評價結果係如表3所示。 [比較例6 ] 除了在形成未拉伸的樹脂薄片時，調整、變更吐出量， 而且將橫向拉伸時之拉伸倍率變更爲2.0倍以外，依照與 實施例1同樣的方法進行，來得到卷取厚度約6 0微米的熱 -38 - 200909212 收縮性薄膜而成的薄膜捲物。而且，依照與實施例1同樣 的方法評價。評價結果係如表3所示。 -39 - 2 1X29 ο09200 u漱〕 誕 & S m » m m 收縮 不均 〇 〇 ◎ 〇 〇 〇 ◎ ◎ ◎ 1 X X ◎ 孔眼撕 封性 (不良率） (%) 寸 寸 00 00 寸 1 1 寸 溶劑黏著 強度 (N/I5mm) 4.45 4.72 4.58 4.40 4.26 4.64 5.08 5.31 0.05 1 i 0.03 5.82 90°C溫水 熱收縮率(％) 正交 方向* 10.0 II.5 〇 \6 12.0 ll.5 (N ο 〇\ 1 00 〇 26.5 主收縮 方向 i 43.5 48.0 ; 38.0 45.5 45.5 40.5 20.0 39.0 1 〇 ro (N 寸 49.5 愛爾曼 多夫比 I 3 Ι·21 〇 <N ON 1.18 1.12 l.3l :0.22 ! 1.21 1 0.90 寸 0.49 4K I RE£ t?ly» U I 正交 方向* I I 163.3 176.2 258.3 152.3 191.5 188.9 289.2 464.1 158.3 1 48.0 157.3 323.8 主收縮 方向 202.5 I 213.1 310.8 181.5 226.4 2H.6 379.4 ιοι.ο 191.3 1 43.0 226.7 160.1 正交方向 的直角撕 裂強度 (N/mm) 141.5 144.0 rn 133.5 139.3 155.6 181.9 280.8 137.3 1 36.0 160.5 213.2 薄膜的 主收縮 方向 長度方向 長度方向 長度方向 長度方向 長度方向 長度方向 長度方向 寬度方向 長度方向 1 長度方向 1長度方向 長度方向 厚度構成 S | έ g ss -¾ s ^ 0.33 0.33 0.33 0.33 0.33 0.33 0.33 I 0.33 2.03 1 0.33 0.33 0.33 皮層 (微米） ^6 10.0 Ό 10.0 \〇 ^6 13,4 1 〇 IT) \〇 \6 芯層 (微米） 26.8 26.8 40.0 26.8 26.8 26.8 40.0 26.8 13.2 1 20.0 26.8 26.8 I 皮層 (微米） i- :ιο.ο \〇 'sO so 10.0 : \6 13.4 1 〇 (Ti Ό VO ^6 實施例I 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 比較例I 比較例2 比較例3 比較例4 比較例5 比較例6 —〇寸丨 200909212 從表3能夠清楚知道，實施例1〜7所得到的薄膜任一 者在主收縮方向之長度方向的收縮性高，且在與主收縮方 向正交之方向之寬度方向的收縮性非常低。又，實施例1 〜7所得到的薄膜，任一者都無收縮不均，且收縮完成性、 孔狀接縫撕封性、溶劑黏著性良好。亦即，實施例所得到 的熱收縮性聚烯烴系薄膜任一者作爲標籤時，都是品質高 且實用性非常高。 相對地，比較例1及比較例6所得到的熱收縮性薄膜 之孔狀接縫撕封性不良。又，比較例2所得到的熱收縮性 薄膜之溶劑黏著強度低。而且，比較例4所得到的薄膜之 長度方向的熱收縮率非常低，作爲標籤而使其安裝時的收 縮不均差。並且孔狀接縫撕封性、溶劑黏著強度亦不良。 比較例5所得到的薄膜作爲標籤而使其安裝時，產生了跳 起、顯著的縱向縮孔狀凹斑。 亦即’比較例所得到的熱收縮性聚烯烴系薄膜任一者 都是品質差且無實用性。 200909212 [表4] —- __. - 持f脂原料的組成(質量％) 皮層 芯層 乙烯量(％) 丁烯量(％) 實施例8 E/F=l/99 A 二 100 3.67 — 實施例9 E/F=l/99 A=l〇〇 3.67 — 實施例10 E/F=l/99 B=100 1.67 4.6 實施例11 E/F=l/99 A-100 3.67 一 實施例12 E/F=l/99 A-100 3.67 一 比較例7 E/F=l/99 A=100 3.67 _ 比較例8 C/D/E=90/8/2 C=l〇〇 0.6 _ 比較例9 C/D/E=90/8/2 C=l〇〇 0.6 一 比較例10 __ E/F=l/99 A=100 3.67 - 樹脂原料A :聚丙烯-乙烯無規共聚物（乙烯=5 · 5質量％) 棱f脂原料b :聚丙烯-乙烯、丁烯無規共聚物（乙烯= 2.5 質量％、丁烯=6 · 9質量。/。） 樹脂原料C :聚丙烯-乙烯無規共聚物（乙烯=0.6質量。/。） 植ί脂原料〇 :在94質量％聚丙烯-乙烯無規共聚物（乙烯 =0·6質量％)中添加6質量％硬脂酸一甘油酯而成者 樹脂原料Ε :在80質量％聚丙烯-乙烯無規共聚物（乙烯 一〇·6質毚％)中添加20質量％有機聚合物微粒子而成者 樹脂原料F :環狀聚烯烴 -42- 200909212 [表5] —--- 拉伸條伴 ~~~一 拉伸 方式 橫向拉伸 —— 中間熱桑 1弛處理 溫度 ΓΟ 倍率 溫度 CC) 時間 (秒） 溫度 (°〇 ---_ 恢丨口J 汉1甲 ^速輥速度 1 尺/分鐘） 高速輥速度 (公尺/分鐘） 倍率 實施例8 橫-縱 100 6.5 130 43 90 —_2.0 6.0 3.0 實施例9 橫-縱 100 6.5 130 43 —---- 90 ___ 3.0 9,0 3.0 實施例10 橫-縱 100 6.5 130 43 ----- 90 -__2.0 6.0 3.0 實施例11 橫-縱 80 6.5 130 43 —〜 一 90 2〇 Α Λ 實施例〗2 橫-縱 100 4.5 130 43 90 -—2.0 8.0 j . U 4.0 比較例7 縱 . —2.0 6.0 3.0 比較例8 橫-縱 100 6.5 130 43 90 2.0 6 0 ^ 〇 比較例8 橫-縱 160 6.5 130 43 90 2 0 6.0 · V/ 3.0 比較例10 橫-縱 100 2 130 43 90 _ 2.0 6.0 3.0 [實施例8] 利用共濟出法’從2個濟壓機（第一、第二擠壓機）將 聚烯烴系樹脂熔融擠壓（在模頭內層積而擠出），藉由纏繞 於已冷卻至3 0 °C之旋轉金屬滾筒而急速冷卻，來得到二種 三層構成的未拉伸薄膜（聚烯烴系樹脂積層薄片）。此時之 未拉伸薄膜的拉伸速度（金屬輥的轉速）爲約6.8公尺/分 鐘。未拉伸薄膜各層的形成方法（至熔融擠壓的步驟）係如 以下所示。又’在以下的說明，依照從聚烯烴系樹脂積層 薄片的表層之順序’稱第一層、第二層、第三層（亦即，第 三層的表面係金屬輥接觸面）。又，在形成未拉伸薄膜之第 一擠壓機的吐出量係以第一層/第二層/第三層的厚度比爲 1 / 4 /1的方式來調整。 200909212 •第一層及第三層（皮層）的形成 知乾燥後的上述原料樹脂e、F，使用定量螺桿供料器 連續地各自供給至擠壓機（第—擠壓機）的料斗。又，使原 料樹脂F的供給量爲9 9質量％，且使原料樹脂E的供給量 爲1質量％。然後，將所供給的原料樹脂F、E在料斗內混 合’並藉由單軸式第一擠壓於25(TC從T模頭熔融濟出。 •第二層（芯層）的形成 將乾燥後的上述原料樹脂A，使用定量螺桿供料器連 續地各自供給至擠壓機（第二擠壓機）的料斗。然後，將所 供給的原料樹脂A藉由單軸式第二擠壓於2 5 〇 從T模頭 熔融擠出。 如此進行後’將所得到的未拉伸薄膜，引導至連續地 設置有橫向拉伸區、中間區及中間熱鬆弛處理區之拉幅 器。又’在該拉幅器’在橫向拉伸區與中間熱鬆弛處理區 之中間的位置之中間區的長度係設定爲約4 0公分。又，在 中間區，以在未使薄膜通過的狀態懸吊薄長方形紙片時， 該紙片係完全地在垂直方向下垂之方式，隔離來自拉伸區 的熱風及來自熱處理區的熱風。 而且，將引導至拉幅器之未拉伸薄膜預加熱至薄膜溫 度爲9 5 °C後，在橫向拉伸區於橫向以1 0 0 °C拉伸6.5倍且 使其通過中間區後，藉由引導中間熱鬆弛處理區，在1 3 〇 °C的溫度熱處理4 3秒鐘，得到厚度1 0 0微米的橫向單軸拉 伸薄膜。如此進行後，利用設置於拉幅器的後方之左右一 對的修剪裝置（由具有周狀刀鋒之圓刀鋒構成者）切斷橫 -44- 200909212 向單軸拉伸薄膜的端緣（中央的薄膜厚度之約1 · 2倍厚度部 分），並連續地除去在切斷部分的外側位置之薄膜的端部。 而且’藉由將如此地修剪端部而成的薄膜（薄膜寬度 =5 0 0毫米）引導至連續地配置複數個輥群而成的縱向拉伸 機’並在預熱輥上將薄膜溫度預加熱至90。(：後’在表面溫 度設定爲9 0 °C之低速拉伸輥與內部循環水的溫度設定3 0 °C之高速拉伸輥之間，拉伸3 . 0倍。又，低速輥的速度（與 低速輥一同移動之薄膜速度）係調整爲2.0公尺/分鐘’高速 輥的速度與高速輥一同移動之薄膜速度）係調整爲6.0公尺 /分鐘。又，低速拉伸輥與高速拉伸輥之拉伸間隙（從低速 拉伸輥與薄膜的切點至高速拉伸輥與薄膜的切點之長度） 係調整爲1 1 6毫米。因而，拉伸間隙比率爲0.2 3。 然後’藉由將如此縱向拉伸後的薄膜卷取在紙管上， 來得到約46微米之依規定長度捲繞的雙軸拉伸薄膜（熱收 縮性聚烯烴薄膜）。而且，依照上述方法評價所得到薄膜的 特性。評價結果係如表6所示。 [實施例9] 除了將縱向拉伸時之低速輕的速度變更爲3.0公尺/分 鐘，且將高速輥的速度變更爲9.0公尺/分鐘（縱向拉伸倍率 =3 . 〇倍）以外’依照與實施例8同樣的方法進行，來得到捲 繞熱收縮性薄膜而成的薄膜捲物。而且，依照與實施例8 同樣的方法來評價所得到薄膜的特性。評價結果係如表6 所示。 [實施例1 〇 ] -45 - 200909212 除了將形成芯層之原料樹脂變更爲原料樹脂B以外， 依照與實施例8同樣的方法進行，來得到捲繞熱收縮性薄 膜而成的薄膜捲物。而且’依照與實施例8同樣的方法來 評價所得到薄膜的特性。評價結果係如表6所示。 [實施例1 1 ] 除了將橫向拉伸時之拉伸溫度變更爲80°C以外，依照 與實施例8同樣的方法進行’來得到捲繞熱收縮性薄膜而 成的薄膜捲物。而且’依照與實施例8同樣的方法來評價 所得到薄膜的特性。評價結果係如表6所示。 [實施例1 2 ] 除了將橫向拉伸時之拉伸倍率變更爲4.5倍，且進而 將縦向拉伸時之高速輥的速度變更爲8 · 0公尺/分鐘，來將 縱向拉伸倍率變更爲4倍以外，依照與實施例8同樣的方 法進行’來得到捲繞熱收縮性薄膜而成的薄膜捲物。而且， 依照與實施例8同樣的方法來評價所得到薄膜的特性。評 價結果係如表6所示。 [比較例7 ] 將與實施例8同樣地進行所得到的未拉伸薄膜，未進 行中間熱鬆弛處理、橫向拉伸，而使用與實施例8同樣的 條件縱向拉伸，同時藉由將該縱向拉伸薄膜以規定長度卷 取於紙管，來得到薄膜捲物。又，製造未拉伸薄膜時，係 藉由使第一擠壓機及第二擠壓機的吐出量比在實施例8之 吐出量少，以縱向拉伸薄膜的厚度爲約4 5微米的方式調 整。又’第一層〜第三層的厚度比係以與實施例8同樣的 -46- 200909212 來評價所得到薄膜的特性 方式調整。而且’依照上述方法 評價結果係如表6所示。 [比較例8 ] 在形成未拉伸薄膜日0 % π & 时供給至第一擠壓機及第二擠 壓機之樹脂原料如表4變w「t Βπ . 瘦吏（亦即’將乾燥後的原料樹脂 C、D、E各自以90質量％、8質量％及2質量％的比率供給 至第-擠壓機，並將乾燥後的原料樹月旨c供給至第二擠壓 機）。此外’依照與實施例8同樣的方法嘗試製造卷取熱收 縮性薄膜而成的薄膜捲物，但是無法得到能夠評價的薄膜。 [比較例9] 在形成未拉伸薄膜時 將供給至第一擠壓機及第二擠 乾燥後的原料樹脂 2質量％的比率供給 壓機之樹脂原料如表4變更（亦即，將 C、D、E各自以90質量％、8質量％及 供給至第二擠壓 至第一擠壓機’並將乾燥後的原料樹脂Temperature J ° C) Temperature CC) Low rate of capture speed shovel) High speed roller speed minutes) Magnification Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 横篆横| 横-篆横孤横 | 横-藏·横来一100 ——' 一100一100一100 100 100 100 横-I 横-I〆 Transverse I Transverse - I Transverse 100 100 165 100 100 6.5 6.5 6.5 6.5 6.5 6.5 4.5 6.5 6.5 6.5 6.5 6.5 130 130 130 130 130 130 130 75 130 130 160 130 43 80 43 43 43 43 43 43 43 43 43 43 43 43 90 85 100 100 100 140 1.0 --- 1.5 ---- 1.0 — 2.0 ~~ — — — —±0^_κο_ 1.0 3.0 3.0 3.0 6.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 [Example 1] The co-extrusion method was used to melt-extrude the poly-J: 烟 棱 f f fat from two extruders (first and second extruders) (layering in the die) And extrusion), by rapidly winding the rotating metal drum of MB #gp g 3 〇 °C to obtain two kinds of unstretched film of Ξ ® g (polyolefin resin laminated thin) ). The stretching speed (rotation speed of the metal roll) of the unstretched film at this time was about 6.8 m/min. The method of forming the unextended layers (the step to the melt extrusion) is as follows. In the following description, the first layer, the second layer, and the third layer (that is, the surface-based metal roll contact surface) are referred to in the order of the surface layer of the polyolefin-based resin laminated sheet from -33 to 200909212. Further, the discharge amount of the machine for forming the unstretched film was adjusted in accordance with the thickness ratio of the first layer/second layer/third layer. • Formation of the first layer and the third layer (skin layer) The raw material resins E and F after drying are continuously supplied to the hopper of the extruder (first extruder) using the quantitative screw. The feed amount of the resin F was 99% by mass, and the raw material resin e was 1 mass%. . Then, the raw materials P and E supplied are combined and melted from the T die by a single-axis first extrusion at 25 〇r. • The second layer (core layer) is formed by drying the above-mentioned raw materials. Resin A was continuously supplied to the hopper of the extruder (second extruder) using a metering screw. The supplied raw material resin A was melt extruded by a uniaxial second pressure at 250 °C. After this was carried out, the obtained unstretched film was guided with a transverse stretching zone, an intermediate zone, and an intermediate thermal relaxation treatment. Further, the length of the intermediate portion of the position of the tenter in the middle of the transverse stretch zone and the middle hot pine is set to about 40 bus intermediate zone to hang a thin rectangular shape in a state where the film is not passed. The method of sagging completely in the vertical direction, the isolated hot air and the hot air from the heat treatment zone. Moreover, after the pre-heating degree of the unstretched film guided to the tenter is 90 ° C, the first extrusion of the third layer is stretched by 1 〇〇t in the transverse direction in the transverse stretching zone. The rod feeder of 1 again causes the original supply hopper to be mixed out. After the feeder is connected, the stretched processing area from the T die to the continuous zone is •. Moreover, in the case of the paper sheet 1 from the stretching zone to the film temperature of 6.5 times and -34-200909212, after passing through the intermediate zone, the temperature is heat treated by guiding the intermediate heat relaxation point t for 4 3 seconds to obtain a thickness of 100 μm. Stretch the film. After doing so, the edge of the uniaxially stretched film (the thickness of the film at the center) of the uniaxially stretched film is formed by a pair of tenter blades having a circumferential blade edge, and is continuously removed. Further, the outer position of the broken portion is guided by the thinning of the end portion so as to be continuously arranged to a plurality of roller groups, and the film temperature is preheated to 9 on the preheating roller. (The low-speed stretching roll with the TC degree set to 80 °C and the internal circulating water white < (: between the high-speed stretching rolls, stretching 3.0 times. Also, the film speed of the low-low speed roller moving together) The system adjusts the speed of the 1.0 mm male roll to the speed of the film moving with the high speed roller. Further, the drawing of the low speed stretching roll and the high speed drawing roll was 30 mm (stretching gap ratio = 0.06). Then, by winding the film thus stretched in the longitudinal direction, a biaxially-shrinkable polyolefin film wound by a predetermined length of about 4 μm is obtained. Moreover, the characteristics were evaluated in accordance with the above method. The evaluation results are shown in Table 3. [Example 2] A film roll obtained by obtaining a film was carried out in the same manner as in Example 1 except that the temperature of the low-speed stretching roll which was longitudinally stretched was substantially the same. Moreover, it is evaluated in accordance with the implementation method. The evaluation results are shown in Table 3. The area is cut at the left and right sides of the horizontal uniaxial tension of 1 30.) Cut the lateral direction 1. 2 times the thickness of the end of the film. : film (the film width is longitudinally stretched, the surface temperature J temperature is set to the speed of the 3 0 I roller (with the ruler / minute, the high speed is 3 · 0 m the gap is adjusted to take on the paper tube, Film (heated to obtain a film of more than 90 ° C to the same extent as the coil heat shrinkage example 1 200909212 [Example 3] except by changing the temperature of the longitudinally stretched low speed drawing roll to 85 ° C. A film obtained by winding a heat-shrinkable film was obtained in the same manner as in Example 1 except that the speed of the low-speed roll was changed to 1·5 m/min and the longitudinal stretching ratio was changed to twice. The evaluation was carried out in the same manner as in Example 1. The evaluation results are shown in Table 3. [Example 4] The same procedure as in Example 1 was carried out except that the raw material resin forming the core layer was changed to the raw material resin B. The method was carried out to obtain a film roll obtained by winding a heat-shrinkable film. The evaluation was carried out in the same manner as in Example 1. The evaluation results are shown in Table 3. [Example 5] The speed of the stretched low speed drawing roll is changed to 2. G meters / The heat-shrinkable film was obtained by winding the heat-shrinkable film in the same manner as in Example 1 except that the high-speed roll speed was changed to 6 × 10 m/min, and the longitudinal stretch ratio was changed to three times. The film roll was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3. [Example 6] The temperature of the stretching roll which was transversely stretched was changed to 8 Å. < In the same manner as in Example 1, a film roll obtained by winding a heat shrinkable film was obtained in the same manner as in Example 1. Further, FJ was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3. [Example 7] In the case of forming an unstretched resin sheet, 'adjusting and changing the discharge enthalpy, -36 - 200909212, the stretching ratio in the transverse stretching was changed to 4 · 5 times, and the longitudinal direction was pulled. The speed of the low-speed roll at the time of stretching was changed to 1 · 5 m / min, and the longitudinal stretching ratio was changed to 2 times, and the same method as in Example 1 was carried out to obtain a heat shrinkage of a winding thickness of 60 μm. Film roll made of a film, and 'according to Example 1 The evaluation results are shown in Table 3. [Comparative Example 1] The same procedure as in Example 1 was carried out except that the amount of extrusion was adjusted and changed in the case of forming an unstretched resin sheet. The transverse stretching is guided to the intermediate thermal relaxation treatment zone after passing through the intermediate zone, and heat treated at a temperature of 75 ° for 43 seconds, and the heat-treated film is taken up in a paper tube to obtain a roll of a prescribed length. A film roll of a transversely stretched film of about 60 μm was taken. Further, the characteristics of the obtained film were evaluated in accordance with the above method. Further, since the film width direction of the obtained film was mainly the contraction direction, the right angle tear The evaluation of the strength, the Hermanndorf ratio, and the hole-shaped seam tearability was evaluated by comparing the longitudinal direction/width direction of the film sample with the other examples and comparative examples. The evaluation results are shown in Table 3. [Comparative Example 2] In addition to the formation of the unstretched resin sheet, the resin raw materials supplied to the first extruder and the second extruder were changed as shown in Table 2, and the thickness of the skin layer and the core layer was as In addition to the change in Table 3, a film roll obtained by winding up a heat-shrinkable film was obtained in the same manner as in Example 1. Further, the properties of the obtained film were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3. -37 - 200909212 [Comparative Example 3] The resin raw materials supplied to the first extruder and the second extruder were changed as shown in Table 1 except for the formation of the unstretched resin sheet, and the examples were to be in accordance with the examples. When the heat-shrinkable film was produced in the same manner, the film could not be produced due to cracking. [Comparative Example 4] In addition to the formation of the unstretched resin sheet, the resin raw materials supplied to the first extruder and the second extruder were changed as shown in Table 2, and the stretching was performed in the transverse stretching. The temperature (film temperature) was changed to 165 ° C, and the temperature of the intermediate thermal relaxation treatment zone during the intermediate thermal relaxation treatment was changed to 16 (TC, and the longitudinal stretching temperature in the longitudinal stretching (low speed roller A film roll obtained by winding a heat-shrinkable film having a thickness of 30 μm was obtained in the same manner as in Example 1 except that the temperature was changed to 140 ° C. The same method as in Example 1 was carried out. The characteristics of the obtained film were evaluated. The evaluation results are shown in Table 3. [Comparative Example 5] The same procedure as in Example 1 was carried out except that the heat treatment temperature in the intermediate thermal relaxation treatment was changed to 80 °C. A film roll obtained by winding a heat-shrinkable film was obtained, and the evaluation was carried out in the same manner as in Example 1. The evaluation results are shown in Table 3. [Comparative Example 6] In addition to forming an unstretched resin sheet Adjust and change the amount of discharge, and A film roll obtained by winding a heat-38 - 200909212 shrinkable film having a thickness of about 60 μm was obtained in the same manner as in Example 1 except that the draw ratio at the time of the transverse stretching was changed to 2.0 times. The evaluation was carried out in the same manner as in Example 1. The evaluation results are shown in Table 3. -39 - 2 1X29 ο09200 u漱] Birthday & S m » mm Shrinkage unevenness 〇〇 ◎ ◎ ◎ ◎ ◎ 1 XX ◎ Eye tearing (non-performing rate) (%) Inch 00 00 inch 1 1 inch solvent adhesion strength (N/I5mm) 4.45 4.72 4.58 4.40 4.26 4.64 5.08 5.31 0.05 1 i 0.03 5.82 90 °C warm water heat shrinkage rate (% Orthogonal direction * 10.0 II.5 〇\6 12.0 ll.5 (N ο 〇\ 1 00 〇26.5 Main contraction direction i 43.5 48.0 ; 38.0 45.5 45.5 40.5 20.0 39.0 1 〇ro (N inch 49.5 Elmandorf Ratio I 3 Ι·21 〇<N ON 1.18 1.12 l.3l :0.22 ! 1.21 1 0.90 inch 0.49 4K I RE£ t?ly» UI Orthogonal Direction* II 163.3 176.2 258.3 152.3 191.5 188.9 289.2 464.1 158.3 1 48.0 157.3 323.8 Main contraction direction 202.5 I 213.1 310.8 181.5 226.4 2H.6 379.4 ιο Ι.ο 191.3 1 43.0 226.7 160.1 Right-angle tear strength in orthogonal direction (N/mm) 141.5 144.0 rn 133.5 139.3 155.6 181.9 280.8 137.3 1 36.0 160.5 213.2 Main shrinkage direction of film Length direction Length direction Length direction Length direction Length direction length Direction length direction Width direction Length direction 1 Length direction 1 Length direction Length direction thickness S | έ g ss -3⁄4 s ^ 0.33 0.33 0.33 0.33 0.33 0.33 0.33 I 0.33 2.03 1 0.33 0.33 0.33 Cortex (micron) ^6 10.0 Ό 10.0 \ 〇^6 13,4 1 〇IT) \〇\6 Core layer (micron) 26.8 26.8 40.0 26.8 26.8 26.8 40.0 26.8 13.2 1 20.0 26.8 26.8 I Cortex (micron) i- : ιο.ο \〇'sO so 10.0 : \6 13.4 1 〇 (Ti Ό VO ^6 Example I Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example I Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 - 〇 丨 200909212 It is clear from Table 3 that any of the films obtained in Examples 1 to 7 has high shrinkage in the longitudinal direction of the main shrinkage direction and is wide in the direction orthogonal to the main shrinkage direction. Shrinkage direction is very low. Further, in any of the films obtained in Examples 1 to 7, no shrinkage unevenness was obtained, and the shrinkage completion property, the pore-shaped seam tearing property, and the solvent adhesion were good. In other words, when any of the heat-shrinkable polyolefin-based films obtained in the examples is used as a label, the quality is high and the practicality is extremely high. On the other hand, the heat-shrinkable film obtained in Comparative Example 1 and Comparative Example 6 had poor hole-to-hole sealability. Further, the heat-shrinkable film obtained in Comparative Example 2 had a low solvent adhesion strength. Further, the film obtained in Comparative Example 4 had a very low heat shrinkage rate in the longitudinal direction, and the shrinkage unevenness at the time of mounting as a label was poor. Moreover, the hole-like seam tearing property and the solvent adhesion strength are also poor. When the film obtained in Comparative Example 5 was attached as a label, a jump and a remarkable longitudinal shrinkage cavity-like pit were generated. That is, either of the heat-shrinkable polyolefin-based films obtained in the comparative examples was inferior in quality and was not practical. 200909212 [Table 4] —- __. - Composition of the fat raw material (% by mass) Cortex core layer Amount of ethylene (%) Butene amount (%) Example 8 E/F=l/99 A II 100 3.67 - Implementation Example 9 E/F=l/99 A=l〇〇3.67 - Example 10 E/F=l/99 B=100 1.67 4.6 Example 11 E/F=l/99 A-100 3.67 An Example 12 E /F=l/99 A-100 3.67 A comparative example 7 E/F=l/99 A=100 3.67 _ Comparative Example 8 C/D/E=90/8/2 C=l〇〇0.6 _ Comparative Example 9 C/D/E=90/8/2 C=l〇〇0.6 A comparative example 10 __ E/F=l/99 A=100 3.67 - Resin raw material A: Polypropylene-ethylene random copolymer (ethylene = 5 · 5 mass%) rib fat raw material b: polypropylene-ethylene, butene random copolymer (ethylene = 2.5 mass%, butene = 6.9 mass. /.) Resin raw material C: polypropylene-ethylene random Copolymer (ethylene = 0.6 mass%). 植 脂 〇 〇 〇 〇 〇 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 Into the resin raw material Ε: 20% by mass of a polypropylene-ethylene random copolymer (ethylene 〇·6 毚%) is added with 20% by mass of organic polymer microparticles Resin raw material F: cyclic polyolefin-42- 200909212 [Table 5] —--- Stretching strip with ~~~ stretching method transverse stretching - intermediate heat sang 1 treatment temperature 倍 rate temperature CC) time ( Seconds) Temperature (°〇---_ Recovery port J Han 1 A) Speed roller speed 1 ft / min High speed roller speed (meter / minute) Magnification Example 8 Horizontal - vertical 100 6.5 130 43 90 —_2. 0 6.0 3.0 Example 9 Horizontal-Vertical 100 6.5 130 43 —---- 90 ___ 3.0 9,0 3.0 Example 10 Horizontal-Vertical 100 6.5 130 43 ----- 90 -__2.0 6.0 3.0 Example 11 Horizontal-vertical 80 6.5 130 43 —~ One 90 2〇Α 实施 Example 〖2 Horizontal-Vertical 100 4.5 130 43 90 --2.0 8.0 j . U 4.0 Comparative Example 7 Vertical. —2.0 6.0 3.0 Comparative Example 8 Horizontal-Vertical 100 6.5 130 43 90 2.0 6 0 ^ 〇Comparative Example 8 Transverse-vertical 160 6.5 130 43 90 2 0 6.0 · V/ 3.0 Comparative Example 10 Horizontal-Vertical 100 2 130 43 90 _ 2.0 6.0 3.0 [Example 8] The method of yielding 'extrudes the polyolefin resin from two presses (first and second extruders) (stacking and laminating in the die) by winding it to have cooled to 30 ° Rotation of C The metal roll was rapidly cooled to obtain two kinds of unstretched films (polyolefin-based resin laminated sheets) having three layers. The stretching speed (rotation speed of the metal roll) of the unstretched film at this time was about 6.8 m/min. The method of forming each layer of the unstretched film (the step to the melt extrusion) is as follows. Further, in the following description, the first layer, the second layer, and the third layer (i.e., the surface of the third layer of the metal roll contact surface) are referred to in the order of the surface layer of the polyolefin-based resin laminated sheet. Further, the discharge amount of the first extruder in which the unstretched film was formed was adjusted so that the thickness ratio of the first layer/second layer/third layer was 1 / 4 /1. 200909212 • Formation of the first layer and the third layer (cortex) The raw material resins e and F after drying were continuously supplied to the hopper of the extruder (first extruder) using a quantitative screw feeder. In addition, the supply amount of the raw material resin F was 99% by mass, and the supply amount of the raw material resin E was 1% by mass. Then, the supplied raw material resins F, E are mixed in the hopper' and are first pressed by a uniaxial type at 25 (TC is melted out from the T die. • The formation of the second layer (core layer) is dried. The above-mentioned raw material resin A is continuously supplied to the hopper of the extruder (second extruder) continuously using a quantitative screw feeder. Then, the supplied raw material resin A is pressed by the uniaxial second pressing 2 5 熔融 melt extrusion from the T die. After doing so, the obtained unstretched film is guided to a tenter which is continuously provided with a transverse stretching zone, an intermediate zone and an intermediate thermal relaxation treatment zone. The length of the intermediate portion of the tenter 'position between the transverse stretching zone and the intermediate thermal relaxation treatment zone is set to about 40 cm. Further, in the intermediate zone, the suspension is suspended in a state where the film is not passed. In the case of a thin rectangular sheet of paper, the sheet is sagged completely in the vertical direction to isolate hot air from the stretching zone and hot air from the heat treatment zone. Further, the unstretched film guided to the tenter is preheated to a film temperature of After 9 5 °C, in the transverse stretch zone After stretching at 6.5 ° C for 6.5 times and passing it through the intermediate zone, heat treatment at a temperature of 13 ° C for 4 3 seconds by guiding the intermediate thermal relaxation treatment zone to obtain a transverse single sheet having a thickness of 100 μm After the shaft is stretched, the uniaxially stretched film is cut by a pair of right and left trimming devices (constructed by a round blade having a peripheral blade edge) provided at the rear of the tenter. The end edge (about 1⁄2 times the thickness portion of the film thickness in the center), and continuously removes the end portion of the film at the outer position of the cut portion. Further, the film (the film is formed by trimming the end portion as such) Width = 500 mm) is guided to a longitudinal stretching machine in which a plurality of rolls are continuously arranged' and the film temperature is preheated to 90 on the preheating roll. (: After 'the surface temperature is set to 90 ° The low-speed drawing roll of C and the temperature of the internal circulating water are set to a high-speed drawing roll of 30 ° C, and the stretching speed is 3.0 times. Further, the speed of the low-speed roll (the film speed moving together with the low-speed roll) is adjusted. The speed of the high speed roller is 2.0 meters per minute. The film speed is adjusted to 6.0 m/min. Further, the stretching gap between the low-speed stretching roll and the high-speed drawing roll (from the cut point of the low-speed drawing roll to the film to the length of the cut point of the high-speed drawing roll and the film) Adjusted to 1 16 mm. Thus, the stretch gap ratio is 0.2 3. Then 'by taking the film thus stretched longitudinally onto a paper tube to obtain a biaxial winding of about 46 μm according to the specified length The film (the heat-shrinkable polyolefin film) was stretched. The properties of the obtained film were evaluated in accordance with the above method. The evaluation results are shown in Table 6. [Example 9] In addition to the speed change at a low speed in the longitudinal stretching In the same manner as in Example 8, except that the speed of the high speed roll was changed to 9.0 m/min (longitudinal stretching ratio = 3. 〇 times), the heat shrinkage of the winding was obtained at 3.0 m/min. Film roll made of film. Further, the properties of the obtained film were evaluated in the same manner as in Example 8. The evaluation results are shown in Table 6. [Example 1 〇] -45 - 200909212 A film roll obtained by winding a heat-shrinkable film was obtained in the same manner as in Example 8 except that the raw material resin forming the core layer was changed to the raw material resin B. Further, the characteristics of the obtained film were evaluated in the same manner as in Example 8. The evaluation results are shown in Table 6. [Example 1 1] A film roll obtained by winding a heat-shrinkable film was obtained in the same manner as in Example 8 except that the stretching temperature in the transverse stretching was changed to 80 °C. Further, the characteristics of the obtained film were evaluated in the same manner as in Example 8. The evaluation results are shown in Table 6. [Example 1 2] The longitudinal stretching ratio was changed by changing the stretching ratio in the transverse stretching to 4.5 times and further changing the speed of the high speed roller at the time of stretching to 8 · 0 m / min. A film roll obtained by winding a heat-shrinkable film was obtained in the same manner as in Example 8 except that the amount was changed to four times. Further, the properties of the obtained film were evaluated in the same manner as in Example 8. The evaluation results are shown in Table 6. [Comparative Example 7] The obtained unstretched film was subjected to longitudinal stretching in the same manner as in Example 8 except that the obtained unstretched film was subjected to the intermediate thermal relaxation treatment and the transverse stretching without using the same conditions as in Example 8. The longitudinally stretched film is taken up in a paper tube in a predetermined length to obtain a film roll. Further, when the unstretched film was produced, the discharge amount of the first extruder and the second extruder was made smaller than that in Example 8, and the thickness of the film was longitudinally stretched to about 45 μm. Way adjustment. Further, the thickness ratio of the first layer to the third layer was adjusted in the same manner as in Example 8 from -46 to 200909212. Further, the evaluation results according to the above method are shown in Table 6. [Comparative Example 8] The resin raw materials supplied to the first extruder and the second extruder at the time of forming the unstretched film day 0% π & as shown in Table 4, changed "t Β π. Thin (ie, 'will The raw material resins C, D, and E after drying are supplied to the first extruder at a ratio of 90% by mass, 8% by mass, and 2% by mass, and the dried raw material is supplied to the second extruder. In addition, in the same manner as in Example 8, a film roll obtained by winding up a heat-shrinkable film was attempted, but a film which can be evaluated was not obtained. [Comparative Example 9] When an unstretched film was formed, it was supplied to The resin raw material supplied to the press at a ratio of 2% by mass of the first extruder and the second extruded dry raw material resin is changed as shown in Table 4 (that is, each of C, D, and E is supplied at 90% by mass and 85% by mass). To the second extrusion to the first extruder' and dry the raw resin
機）。又，將在橫向拉伸之拉伸溫度（薄膜溫度）變更爲i 65 °C。除此以夕卜依照與實施仿"同樣的方法得到捲繞熱收 縮性薄膜而成的薄膜捲物。而且，依照上述方法來評價所 得到薄膜的特性。評價結果係如表6所示。 [比較例1 〇] 除了在形成未拉伸的樹脂薄片時’調整、變更吐出量， 而且將橫向拉伸時之拉伸倍率變更爲2 . 〇倍以外，依照與 實施例8同樣的方法進行，來得到捲繞熱收縮性薄膜而成 的薄膜捲物。又，製造未拉伸薄膜時，係藉由使第一濟壓 機及弟一擠壓機的吐出量比在實施例8之吐出量少，以縱 -47 - 200909212 向拉伸薄膜的厚度爲約4 5微米的方式調整。又，第一層〜 第三層的厚度比係以與實施例8同樣的方式調整。而且， 依照上述方法來評價所得到薄膜的特性。評價結果係如表 6所示。 -48 - 200909212 .\ 齄靼盈越漉担锴婪癒_I_；【9 £ 收縮 不均 ◎ ◎ ◎ 〇 〇 ◎ X ◎ 孔眼撕 封性 {不良率) (%) <Ν 寸 寸 00 o oo rn 1# Έ ϊ®乸| iri 00 Tf 寸 iri •η r- τί- oo \〇 ― d (N vi $ ά 键键 疏Ή 爷叇 ii ·· s W P 〇抑 州 州 P § Η p 寸· (N ο •/S <Ν »r> (N ο (Ν oo (N (N o yn 〆 +Η K Ο 姿 oo 5 Ο •n (N yr> oo CO 专 P un 〇〇 囚 oo Ο (N rn (Ν o OS 1 -21.0 m 〇 (N o 寸 ο oo W LT) Ο 寸 m ίΛι 〇 jn m rsi rs <Ν ίΛ o g Η 〇 oo ir> oo m vd o 卜·· 〇 Γ*~ι o 寸’ 州 o 'O ΓΛ y/Ί 'sd o oo m 00 »〇 m 00 On m 00 r- ΟΟ o m P in 〇 (N 〇 r<i rn 〇 v-j p o ΓΛ Ο oo cK 州 〇 \D (N 〇 ΙΛ) >/S m s rs ιη 00 P o Η 〇 vp iri ι/Ί 寸 00 寸 o in o Ο r~\ rn 4Η o r-i oo fS m ΓΛ cs IT) 对. oo Ο o (N 90°C溫水熱 收縮率 (%) 正交 方向φ o ^r (N o (N m (N o 寸· fN CO <N (N o ΙΤι Ο in 主收縮 方向 S o ? oo σ； 〇 OO rsi oo 5 oo fe(膣W也4K丑 \o o P> o 卜 o m 00 o 芝 o o 5: ο s C5 愛爾曼多夫 撕裂負荷 (mN) 1 1 正交1 方向 ♦ m 351.7 333.6 358.8 400.3 973.2 ο Μ 632.6 主收縮 方向 287.3 271.2 236.9 297.6 1 oo oo ο 128.4 正交方向 的直角撕 裂強度 (N/mm) 158.9 162.3 151.4 173.5 s 1 432.2 οό 358.2 1§8焉 長度 方向 長度 方向 長度 方向 長度 方向 長度 方向 長度 方向 長度 方向 長度 方向 厚度構成 s s ^ ώ g ㈣gg i S g 11 ™ ft ® S ^ m m o Γ〇 m ο Γ<Ί ΓΟ Ο m o m m c> m r〇 o rn 〇 m rn 〇 皮層 (m) Ό 00 '-O, Ό in 芯層 (μπι) oo \〇 ο m o o o o o m 1 1 皮層 (μπι) Ό 卜^ oo 'Ο 'sO V) * in 卜 實施例8 實施例9 實施例ίο 實施例11 實施例12 比較例7 比較例8 比較例9 比較例10 歴嫩面糜坦摧但葳蝱胡粼骤骤-frf:5iw:oos¥!s^厄枳^以囚厄柁躍婪州鄱：*叵枳βΗΓ _ 6寸— 200909212 從表6能夠清楚知道，實施例8〜1 2所得到的薄膜任 一者在主收縮方向之長度方向的收縮性高，且在與主收縮 方向正交之方向之寬度方向的收縮性非常低。又，實施例 8〜1 2所得到的薄膜，任一者都無收縮不均，且收縮完成 性、孔狀接縫撕封性、溶劑黏著性良好。亦即，實施例所 得到的熱收縮性聚烯烴系薄膜任一者作爲標籤時，都是品 質高且實用性非常高。 相對地，比較例7及比較例1 0所得到的熱收縮性薄膜 之孔狀接縫撕封性不良。又，比較例8的條件，無法得到 能夠評價的薄膜。而且，比較例9所得到的薄膜之長度方 向的熱收縮率非常低，作爲標籤而使其安裝時的收縮不均 差。並且溶劑黏著性亦不良。亦即，比較例所得到的熱收 縮性聚烯烴系薄膜任一者都是品質差，實用性低之物。 [產業上之利用可能性] 因爲本發明的熱收縮性聚烯烴系薄膜具有如上述優良 的加工特性’能夠適合使用於瓶子的標籤用途。 【圖式簡單說明】 第1圖係顯示測定直角撕裂強度時之試驗片的形狀之 說明圖（又，在圖中之試驗片的各部分長度之單位爲毫米）。 【主要元件符號說明】 F 薄膜 -50 -machine). Further, the stretching temperature (film temperature) in the transverse stretching was changed to i 65 °C. In addition, a film roll obtained by winding a heat-shrinkable film was obtained in the same manner as in the practice of "imitation". Further, the characteristics of the obtained film were evaluated in accordance with the above method. The evaluation results are shown in Table 6. [Comparative Example 1] In the same manner as in Example 8, except that the amount of discharge was adjusted and changed when the unstretched resin sheet was formed, and the stretching ratio in the transverse stretching was changed to 2. A film roll obtained by winding a heat-shrinkable film is obtained. Further, when the unstretched film was produced, the discharge amount of the first press machine and the presser was made smaller than that in the eighth embodiment, and the thickness of the stretched film was from -47 to 200909212. Adjusted in a way about 4 microns. Further, the thickness ratios of the first layer to the third layer were adjusted in the same manner as in the eighth embodiment. Further, the characteristics of the obtained film were evaluated in accordance with the above method. The evaluation results are shown in Table 6. -48 - 200909212 .\ 齄靼 漉 漉 _ _ _ _ _ _ _ _ _ _ _ _ _ _ ◎ ◎ ◎ ◎ X ◎ hole tearing {non-performing rate) (%) < Ν 寸 inch 00 o oo Rn 1# Έ ϊ®乸| iri 00 Tf inch iri •η r- τί- oo \〇― d (N vi $ ά key sparse 叇 叇 ii ·· s WP 州州州 P § Η p inch· (N ο •/S <Ν »r> (N ο (Ν oo (N (N o yn 〆+Η K Ο 姿 oo 5 Ο •n (N yr> oo CO P P oo oo Ο ( N rn (Ν o OS 1 -21.0 m 〇 (N o inch ο oo W LT) Ο inch m ίΛι 〇jn m rsi rs <Ν ίΛ og Η 〇oo ir> oo m vd o 卜·· 〇Γ*~ ι o 寸 ' 州 o 'O ΓΛ y / Ί 'sd o oo m 00 »〇m 00 On m 00 r- ΟΟ om P in 〇 (N 〇r<i rn 〇vj po ΓΛ Ο oo cK State 〇\D (N 〇ΙΛ) >/S ms rs ιη 00 P o Η 〇vp iri ι/Ί inch 00 inch o in o Ο r~\ rn 4Η o ri oo fS m ΓΛ cs IT) 对. oo Ο o (N 90°C warm water heat shrinkage rate (%) Orthogonal direction φ o ^r (N o (N m (N o · · fN CO < N (N o ΙΤι Ο in main contraction direction S o oo σ ; 〇 OO rsi oo 5 oo fe (膣W also 4K ugly \oo P> o Bu om 00 o Chi oo 5: ο s C5 Elmandorf tear load (mN) 1 1 Orthogonal 1 direction ♦ m 351.7 333.6 358.8 400.3 973.2 ο Μ 632.6 Main contraction direction 287.3 271.2 236.9 297.6 1 oo oo ο 128.4 Right angle tear strength in orthogonal direction (N/mm) 158.9 162.3 151.4 173.5 s 1 432.2 οό 358.2 1§8焉 Length direction length length Length direction direction Length direction Length direction Length direction Length direction thickness ss ^ ώ g (4) gg i S g 11 TM ft ® S ^ mmo Γ〇m ο Γ <Ί ΓΟ Ο momm c> mr〇o rn 〇m rn 〇 〇 m) 00 00 '-O, Ό in core layer (μπι) oo \〇ο mooooom 1 1 skin layer (μπι) 卜 ^ ^ oo 'Ο 'sO V) * in 卜 embodiment 8 embodiment 9 embodiment ίο embodiment 11 Example 12 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 歴 糜 糜 糜 葳蝱 葳蝱 葳蝱 - - - - - - - - - - fr fr fr fr fr fr fr fr fr fr fr fr fr fr fr fr fr fr 以 以 以 以 以 以 以 以 以 以 以 以: *叵枳βΗΓ _ 6 inch — 200909212 It can be clearly seen from Table 6 that Examples 8 to 12 are Any of the obtained films has high shrinkage in the longitudinal direction of the main shrinkage direction, and has very low shrinkage in the width direction in the direction orthogonal to the main shrinkage direction. Further, in any of the films obtained in Examples 8 to 12, there was no shrinkage unevenness, and the shrinkage completion property, the hole-like seam tearing property, and the solvent adhesion were good. In other words, when any of the heat-shrinkable polyolefin-based films obtained in the examples is used as a label, the quality is high and the practicality is extremely high. On the other hand, the heat-shrinkable film obtained in Comparative Example 7 and Comparative Example 10 had poor hole-to-hole sealability. Further, under the conditions of Comparative Example 8, a film which can be evaluated could not be obtained. Further, the film obtained in Comparative Example 9 had a very low heat shrinkage rate in the longitudinal direction and was inferior in shrinkage when mounted as a label. And the solvent adhesion is also poor. In other words, any of the heat-shrinkable polyolefin-based films obtained in the comparative examples was poor in quality and low in practicality. [Industrial Applicability] The heat-shrinkable polyolefin-based film of the present invention has a processing property as described above, which can be suitably used for labeling of bottles. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an explanatory view showing the shape of a test piece when measuring the right-angle tear strength (again, the unit of the length of each portion of the test piece in the drawing is mm). [Main component symbol description] F film -50 -