TW201239016A - Mold release film - Google Patents

Abstract

The present invention provides a mold release film that has excellent releasability from a mold or a molded article, is excellent in followability to a mold for transferring mold shape to a molded article in accordance with designed size, obtains high surface smoothness of molded article and has high thermal resistance in an operating temperature of around 180 DEG C. The mold release film of this invention is formed by using ionizing radiation to irradiate a film only containing polyurethane-based elastomer having JIS A hardness of 70 or more and Vicat softening temperature of 100 to 180 DEG C or a film of thermoplastic elastomer composition containing polyurethane-based elastomer as a main component.

Description

201239016 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種光半導體元件或半導體元件之樹脂鑄 模成形時，尤其是LED(Light Emitting Diode，發光二極 體）透鏡之樹脂鑄模成形時所使用之離型用膜。 【先前技術】 例如’ LED、光電耦合器（Phot〇_is〇Ut〇r)、光電晶體 (Phototransistor)、光電二極體（Phot〇di〇de)、CCD(Charge Coupled Device，電荷耦合器件）、CM〇s(c〇mplementary Metal Oxide Semiconductor，互補金屬氧化物半導體）等光 半導體元件、或電晶體（Transistor)、ic(integrated201239016 VI. TECHNOLOGICAL FIELD OF THE INVENTION The present invention relates to a resin mold for forming an optical semiconductor element or a semiconductor element, in particular, a resin mold for forming an LED (Light Emitting Diode) lens. Release film for use. [Prior Art] For example, 'LED, photocoupler (Phot〇_is〇Ut〇r), phototransistor, photodiode (Phot〇di〇de), CCD (Charge Coupled Device) , such as CM〇s (c〇mplementary Metal Oxide Semiconductor), or a transistor (Transistor), ic (integrated)

Circuit，集成電路）、LSI(Large Scale Integration ,大型積 體電路）、超LSI等半導體元件係以聚矽氧樹脂組合物或環 氧樹脂組合物為密封材料，藉由樹脂鑄模成形而密封。 上述光半導體兀件或半導體元件之密封係使用鑄模成形 裝置，將包含聚矽氧樹脂組合物或環氧樹脂組合物之密封 材料作為鑄模樹脂注入至鑄模模具中而成形。 作為對鑄模模具與成形品進行離型之方法，例如已實用 化有於鑄模模具與鑄模樹脂之間***離型用膜之方法（例 如參照專利文獻1)。離型用膜係於鑄模成形裝置内藉由連 續捲繞（Roll to Roll)而供給，送入調溫至成形加工溫度之 鑄核模具中’以真空吸引而密接於鑄模模具上，其後，填 充鑄模樹脂。於一定時間後鑄模樹脂硬化後打開鑄模模 具’於離型用膜吸附於鑄模模具之狀態了，直接將成形品 159436.doc 201239016 自離型用膜剥離。該離型用膜係使用例如包含熱塑性氟樹 脂之四氟乙烯-乙烯共聚合樹脂（ETFE(Ethy丨咖 Tetrafluoroethylene)樹脂）或四氟乙烯_六氟丙烯共聚合樹 月a (FEP(Fluorinated Ethylene Propylene)樹脂）之單層之膜 (例如參照專利文獻2) » 然而，若將此種離型用膜用於以聚矽氧樹脂組合物為鑄 模樹脂之LED透鏡之成形，則例如對於底面為mm左 右、高度為4 mm左右之砲彈型透鏡形狀，即便以真空吸引 離型用膜亦存在並不延伸之現象，而且存在即便延伸亦不 社、接於鑄模模具上，從而無法獲得按照設計尺寸之LED透 鏡之異常。又，若使離型用膜之厚度變薄而改善延伸，則 於以真空吸引時存在於鑄模模具之邊緣離型用膜破裂之異 常。 又，已知有使用包含含有結晶性芳香族聚酯（所述結晶 性芳香族聚醋於結晶成分中含有對笨二曱酸丁二醋）之樹 脂組合物的膜作為離型用膜之方法（例如參照專利文獻3)。 然而，作為離型用膜，如專利文獻3所示那樣，若將包 含含有結晶性芳香族聚酯（所述結晶性芳香族聚酯包含對 苯二曱酸丁二酯）之樹脂組合物的膜用於led透鏡之成形， 則若以真空吸引離型用膜則密接於鑄模模具上，但由於是 超過斷裂點而延伸’因此存在離型用膜部分性變薄，於成 形之LED透鏡表面產生凹凸或㈣之異f。因& ,實際情 況是於LED透鏡之樹脂鑄模成形中，尚無可較佳地用作離 型用膜之膜。 159436.doc 201239016 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特開平8-142105號公報 [專利文獻2]曰本專利特開2001-3 10336號公報 [專利文獻3]日本專利特開2007-224311號公報 【發明内容】 [發明所欲解決之問題] 本發明係鑒於上述而成者，其目的在於提供—種與鑄模 模具或成形品之剝離性優異，並且，將鑄模模具之形狀按 照設計尺寸轉印至成形品之模具形狀轉印性優異，並立獲 得成形品之表面平滑性，進而亦具有14(rc左右之使用溫 度下之耐熱性之離型用膜。 [解決問題之技術手段] 此種目的係藉由下述（1)〜（1 2)之發明而達成。 (1) 一種離型用膜，其特徵在於：其係對單獨包含 JIS(Japanese Industrial Standards > 日本工業標準硬度為 70以上且維卡軟化溫度為1 〇〇〜1 g〇°c之聚胺基曱酸自旨系彈 性體或者包含以該聚胺基曱酸酯系彈性體為主成分之熱塑 性彈性體組合物之膜照射電離放射線而成。 (2) 如（1)之離型用膜，其中’聚胺基曱酸酯系彈性體係 藉由聚異氰酸酯、多元醇及鏈延長劑這3種成分之反應而 獲得之熱塑性聚胺基甲酸酯系彈性體。 (3) 如（2)之離型用膜，其中’多元醇係選自屬於由聚酯 多元醇、聚酯醯胺多元醇、聚碳酸酯多元醇、聚醚多元 159436.doc 201239016 醇、聚醚酯多兀醇、及聚烯烴多元醇所組成之群之數量平 均分子量為500〜10000之高分子多元醇中的丨種或複數種。 (4) 如（2)或（3)之離型用膜，其中，鏈延長劑係選自屬於 低分子多7G醇類、低分子多元胺類、及低分子胺基醇類之 數量平均分子量未達500之含活性氫之化合物。 (5) 如（1)至（4)中任一項之離型用膜，其中，熱塑性彈性 體組合物係相對於上述聚胺基甲酸酯系彈性體丨〇〇質量份 而含有0.05〜5.0質量份之範圍之氟系界面活性劑之組合 物。 (6) 如(5)之離型用膜’其中，i系界面活性劑係熔點為 250°C以下且分解溫度為3G(rc以上之全氟烧基續酸衍生物 化合物。 (7) 如⑴至(6)中任一項之剝離膜，其中，熱塑性彈性體 組合物進而包Μ種或複數種屬於调滑劑、抗結塊劑、抗 氧化劑、及磷系抗氧化劑之添加劑。 (8) 如⑴至⑺中任—項之離型用膜’其中，上述電離放 射線之照射係使用選自由α射線、Ρ射線、電子束、中子射 線、X射線、銘60輕射源之γ射線所組成之群中之】種以 5 0〜500 kGy之劑量進行。 (9) 如⑴至(8)中任一項之離型用膜’其中，膜之拉伸彈 性模數於膜縱方向（助）及膜橫方向（TD)上肖為10〜500 N/mm2之範圍。 (10) 如⑴至（9)中任—項之離型用膜，其中膜之潤莫數 (5〇% M°)之膜縱方向_)與膜橫方向（TD)之比（MD)/(TD) 159436.doc 201239016 為0.9〜1.2之範圍。 (11) 如（1)至（10)中任一項之離型用膜，其中膜之50〇/〇模 數（50% Mo)與 100%模數（100% Mo)之比（100% M〇)/(50% Mo)於膜縱方向（MD)及膜橫方向（TD)上均為u〜丨.6之範 圍。 (12) 如（1)至（11)中任一項之離型用膜，其中膜之拉伸伸 長率於膜縱方向（MD)及膜橫方向（TD)上均超過350%。 【實施方式】 本發明者等人為達成上述目的而進行各種研究，結果查 明對單獨包含於聚胺基曱酸酯系彈性體中JIS a硬度為70 以上、比重為1·〇5〜1.30及維卡軟化溫度為i〇〇〜18〇〇c之聚 胺基甲酸酯系彈性體或包含以該聚胺基甲酸酯系彈性體為 主成分之熱塑性彈性體組合物之膜照射電離放射線而成之 離型用膜與籍模模具或成形品之剝離性優異，並且，將鑄 模模具之形狀按照設計尺寸轉印至成形品之模具形狀轉印 性優異’並且獲得成形品之表面平滑性，進而亦具有耐熱 性0 進一步進行研究，結果查明藉由將熱塑性彈性體組合物 設為相對於聚胺基曱酸酯系彈性體丨〇〇質量份而含有 〇·〇5〜5.0質量份之範圍之氟系界面活性劑之組合物，變得 更有效果，從而完成本發明。 本發明中之聚胺基甲酸酯系彈性體係藉由聚異氰酸酯、 多70醇及鏈延長劑這3種成分之反應而獲得之熱塑性聚胺 基甲酸酯系彈性體。 159436.doc 201239016 作為上述聚異氰酸醋’例如可列舉：2,4·甲 :、2,6-甲苯二異氛酸自旨、二甲笨·1，4-二異氛酸酿、、二 本-一異氰酸醋、4,4，·二笨基甲烷二異氰酸自旨、二 苯基甲院二異氛酸酿、2,2，-二苯基甲烧二異氛酸醋、’4: 二笨_二異氰酸醋、2_硝基二苯基_4,4,_二異氰酸自旨、22,_ 一苯基丙烧-4,4，-二異氰酸酿、3,3,_二甲基二笨基甲院-4,4’_二異氰酸酯、4,4，_二苯基丙烷二異氰酸酯、間苯：異 氛酸醋、對苯：異氰酸8旨、伸萘基·Μ·二異氰_、伸萘 基·1，5-二異氰酸酯、3,3，_二甲氧基苯基_4,4，_二異氰酸酯等 芳香族二異氛酸醋類；四亞甲基二異氮酸自旨、六亞甲基二 異氰酸醋、十二烷二異氰酸醋、i甲基六亞甲基二異氰： 酯、離胺酸二異氰酸酯等脂肪族二異氰酸酯類；環己烷二 異氰酸醋、二環己基甲烷二異氰酸醋、異佛_二異二: S旨' 氫化甲苯二異氰酸酯、氫化二曱苯二異氰酸酯、氫化 二苯基曱烷二異氰酸酯、四甲基二曱苯二異氰酸酯、降冰 片烷二異氰酸曱酯等酯環族二異氰酸酯類；上述異氰酸酯 之縮二脲體、二聚物體、三聚物體、二聚物_三聚物體、 碳二醯亞胺體、脲酮亞胺體、由2官能以上之多元醇等與 上述異氰酸酯之反應獲得之加合物體等。又，亦可列舉： 利用曱醇、正丁醇、苯曱醇、乙醯乙酸乙酯、ε_己内醯 月女、甲基乙基酮肟、苯酚、甲酚等分子内具有1個活性氫 之封端劑使異氰酸酯基之一部分穩定化而成之聚異氰酸 S旨。該等可使用1種或將2種以上混合使用。 上述多元醇係數量平均分子量為50040000之高分子多 159436.doc 201239016 元醇，該等中存在有聚酯多元醇、聚酯醯胺多元醇、聚碳 酸酯多元醇、聚醚多元醇、聚醚酯多元醇、聚烯烴多元醇 等。該等高分子多元醇可使用1種或將2種以上混合使用。 作為聚酯多元醇、聚酯醯胺多元醇，可列舉：由多羧酸 與多元醇’視情況併用二胺或胺基醇，藉由縮合反應而獲 得者。 作為該多羧酸’例如有：琥珀酸、己二酸、癸二酸、二 聚酸、氫化二聚酸、鄰苯二甲酸、鄰苯二甲酸烷基酯類、 偏苯三甲酸、順丁烯二酸、反丁烯二酸、衣康酸等。又， 亦可列舉：藉由丁内酯、戊内酯、己内酯等環狀酯類之開 環聚合而獲得者。 作為該多元醇，例如可列舉：乙二醇、1，2-丙二醇、 1，3-丙二醇、丨，2_丁二醇、丨，3_丁二醇、丨，心丁二醇、n 戍基·1，5 —戊二醇、3-甲基-以-戊二醇、^-己 醇3-甲基-i，5_戊二醇、新戍二醇、^8•辛二醇、I』·壬 二醇、2,2-二乙基十3_丙二醇、2_正丁基_2_乙基十丙二 醇、2,2,4-三甲基十3_戊二醇、2_乙基妙己二醇、二 十六燒乙二醇、正二十烧乙二醇、2_正二十八 烧-1，2-乙二醇、二 醇、或雙…;氧二、二丙二醇、環己烧二尹 A、3_經基-^氧乙院或環氧丙院加成物、氣化雙紛 f基丙基-3_羥基-2,2-二甲基丙酸酯、三 ^ 油、季戊四料低分子多元醇類。作為Γ 胺或胺基醇’例如 乍為〜 異佛爾酮二胺等低 _ —、己二胺、苯二甲胺、 低刀子多兀胺類，單乙醇胺、二乙醇胺、 159436.doc 201239016 三乙醇胺等低分子胺基醇類。又’可列舉：以低分子多元 醇、低分子多元胺、低分子胺基醇為起始劑，藉由ε_己内 酯、γ-戊内酯等環狀酯（内酯）單體之開環聚合而獲得之内 酯系聚酯多元醇。 作為聚碳酸酯多元醇，可列舉：藉由上述聚酯多元醇之 合成所使用之低分子多元醇、與碳酸二乙二酯、碳酸二曱 酯、碳酸二乙酯、碳酸二苯酯等之脫醇反應、脫酚反應等 而獲得者。 作為聚鍵多元醇，可列舉 —^ jx yu r/| m ^ 低分子多元醇、低分子多元胺、低分子胺基醇為起始劑， 使環氧乙烷 '環氧丙烷、四氫呋喃等進行開環聚合而成之 聚乙二醇、聚丙二醇、聚四氫吱喃等、及使該等進行共聚 合而成之聚醚多元醇、進而以上述聚醋多元醇、聚碳酸醋 多元醇為起始劑之聚酯醚多元醇。 作為聚㈣多元醇’可列舉：除於獲得上述聚醋多元醇 時之縮合反應中所使用的多元醇之一部分或全部中使用聚 _外’以與㈣多元醇相同之方式而獲得者。 作為聚職多元醇，可轉：含祕之聚丁二烯、經氮 化之含羥基之聚丁二烯、 里基之聚異戊二烯、經氫化之 含赵基之聚異戊二烯、含 化聚乙烯等。 基之氣化聚丙烯、含經基之氯 上述鏈延長劑係數量平於八 日 勺刀子I未達500之含活性氫之 ^物，例如可列舉：上述低分子多元醇類、上述低分子 多錢類、上述低分子胺基醇類等。 159436.doc 201239016 聚胺基甲酸酯系彈性體之製造可採用公知之製造方法， 例如：單觸發法、預聚物法、分批反應法、連續反應法、 利用捏合機之方法、利用擠出機之方法等方法。 本發明所使用之聚胺基甲酸酯系彈性體之硬度係藉由 JIS K 7311之試驗法測定之JIS A硬度為7〇以上。進而，於 JIS A硬度為100以上之情形時，較佳為應用d硬度，以〇硬 度之70以下為上限。該JIS a硬度較佳為8〇以上更佳為 9〇以上。若JIS A硬度未達60,則橡膠性變強，因此於鑄 模成形裝置内之離型用膜之傳送時，存在膜延伸而傳送不 穩定之異常。另一方面，於〇硬度超過7〇之情形時，於擠 出成形時存在產生源自原料聚異氰酸酯、多元醇及鏈延長 劑這3種成分之凝膠之異常。 本發明所使用之聚胺基甲酸酯系彈性體之維卡軟化溫度 係藉由JIS K 7206之試驗法測定，為1〇〇〜18〇π之範圍。該 維卡軟化溫度較佳為l10〜180〇c，更佳為12〇〜18(rc，進而 較佳為130〜180°C之範圍。若維卡軟化溫度未達1〇〇。(：，則 即便照射電離放射線，離型用膜於使用時亦存在熔融之異 吊。亦即，無法獲得耐熱性。另一方面，維卡軟化溫度之 上限為180°C，但尚未獲得具有超過丨8〇〇c之維卡軟化溫度 之聚胺基甲酸酯系彈性體。 本發明中之所謂氟系界面活性劑係指全氟烷基磺酸衍生 物。作為全氣烧基確酸衍生物之具體例，可列舉：三氣甲 基續酸鉀（CFsSCbK)、三氟甲基磺酸鈉（CF3S〇3Na)、三氟 曱基磺酸鋰（CFJC^Li)、五氟乙基磺酸鉀（C2f5s〇3K) '五 159436.doc 201239016 氟乙基磺酸鈉（C2F5S03Na)、五氟乙基磺酸鋰 (C2F5S03Li)、七氟丙基磺酸鉀（C3F7S03K)、七氟丙基磺酸 鈉（C3F7S03Na)、七氟丙基磺酸鋰（C3F7S03Li)、九氟丁基 磺酸鉀（C4F9S03K)、九氟丁基磺酸鈉（C4F9S03Na)、九氟丁 基磺酸鋰（C4F9S03Li)等全氟烷基磺酸鹽。 又，可列舉：雙（三氟曱基磺醯基）醯亞胺鉀鹽 ((CF3S02)2NK)、雙（三氟曱基磺醯基）醯亞胺鈉鹽 ((CF3S02)2NNa)、雙（三氟甲基磺醯基）醯亞胺銨鹽 ((CF3S02)2NNH4)、雙（三氟曱基磺醯基）醯亞胺鋰鹽 ((CF3S02)2NLi)、雙（五氟乙基磺醯基）醯亞胺鉀鹽 ((C2F5S〇2)2NK)、雙（五敗乙基續酿基）醯亞胺鈉鹽 ((CjsSO^NNa)、雙（五氟乙基磺醢基）醯亞胺銨鹽 ((C2F5S02)2NNH4)、雙（五氟乙基磺醯基）醯亞胺鋰鹽 ((C^FsSOANLi)、雙（七氟丙基績酿基）酿亞胺钟鹽 ((C3F7S〇2)2NK)、雙（七氣丙基磧酿基）醢亞胺鈉鹽 ((C3F7S〇2)2NNa)、雙（九I 丁基項酿基）酿亞胺卸鹽 ((C4F9S02)2NK)、雙（九氟丁基磺醯基）亞胺鈉鹽 ((C4F9S02)2NNa)、環-六氟丙烷-1，3-雙（磺醯基）醯亞胺鉀鹽 (CF2(CF2S02)2NK)、環-六氟丙烷-1，3-雙（磺醯基）醯亞胺納 鹽（CF2(CF2S02)2NNa)等全氟烷基磺醯亞胺鹽。 進而’亦可列舉：以全氟烷基磺酸為陰離子種之離子液 體、以雙（全氟烷基磺醯基）醯亞胺為陰離子種之離子液 體、以雙（氟磺醯基）醯亞胺為陰離子種之離子液體、以環 六氟丙烷-1，3-雙（磺醯基）醯亞胺為陰離子種之離子液體 12 159436.doc 201239016 等。 於上述全氟烷基磺酸衍生物中亦可較佳地使用溶點為 250C以下且分解溫度為300C以上之化合物。作為該等之 具體例，可列舉：三氟甲基磺酸鉀（CFsSOsK)或雙（三就甲 基磺醯基）醯亞胺鉀鹽（(CF3S02)2NK)。 氟系界面活性劑係以賦予離型用膜滑性為目的而混合於 聚胺基甲酸酯系彈性體中。藉由氟系界面活性劑之混合而 賦予膜表面滑性，因此可獲得如下效果：使鑄模成形裝置 内之離型用膜之傳送變得順利之效果、於與鑄模模具相接 觸時防止離型用膜之褶皺之效果、提高與用作鑄模樹脂之 聚矽氧系樹脂組合物之剝離性之效果。其混合量係相對於 聚胺基曱酸醋系彈性體100質量份而言，將氟系界面活性 劑設為0_05〜5.0質量份之範圍。若混合量未達〇 〇5質量 份，則不會表現混合之效果。另一方面，即便超過5.0質 量份而混合’效果亦不會增大，又，存在如下之異常：敦 系界面活性劑滲出至膜表面或於膜表面起霜，於使用時污 染成形品之表面。 於本發明之熱塑性彈性體組合物中可視需要混合含多官 能不飽和基之交聯劑，例如：二丙二醇二丙烯酸酯、三丙 二醇二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、二-三羥甲 基丙烷四丙烯酸酯、乙二醇二曱基丙烯酸酯、二乙二醇二 甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、甘油二甲基丙 烯酸酯、三羥曱基丙烷三曱基丙烯酸酯、異三聚氰酸三烯 丙酯等。言亥等交聯劑相對於胺基曱酸酯系彈性體1〇〇質量 159436.doc 201239016 份而言較佳為1〜10質量份β 於本發明之熱塑性彈性體組合物中，可於不損及本發明 之特性的範圍内混合其他熱塑性彈性體。作為熱塑性彈性 體例如可列舉：聚酯系彈性體、聚醯胺系彈性體、聚氣 乙烯系彈性體、苯乙烯系彈性體及烯烴系彈性體等。亦可A semiconductor element such as a circuit, an integrated circuit, or a LSI (Large Scale Integration) or a super LSI is sealed by a resin molding using a polyoxyxylene resin composition or an epoxy resin composition as a sealing material. The sealing of the above-mentioned photo-semiconductor element or semiconductor element is carried out by injecting a sealing material containing a polyoxynoxy resin composition or an epoxy resin composition into a mold as a mold resin using a mold forming apparatus. As a method of releasing the mold and the molded article, for example, a method of inserting a film for release film between the mold and the mold resin has been put to practical use (for example, see Patent Document 1). The release film is supplied by a roll to roll in a mold forming apparatus, and is fed into a casting mold which is tempered to a forming processing temperature, and is vacuum-adsorbed and adhered to the mold, and thereafter, Fill the mold resin. After a certain period of time, the mold resin is hardened and the mold is opened, and the film for release film is adsorbed to the mold, and the molded article is directly peeled off from the release film of 159436.doc 201239016. The film for release film is, for example, a tetrafluoroethylene-ethylene copolymer resin (ETFE (Ethy丨Te Tetrafluoroethylene) resin) containing thermoplastic fluororesin or a tetrafluoroethylene-hexafluoropropylene copolymerized tree a (FEP (Fluorinated Ethylene Propylene) a film of a single layer of a resin (for example, refer to Patent Document 2). However, if such a film for release film is used for forming an LED lens in which a polyoxyxylene resin composition is a mold resin, for example, the bottom surface is mm. The shape of the cannonball lens with a height of about 4 mm on the left and right sides, even if it is vacuum-extracted, the film is not extended, and even if it is extended, it is not attached to the mold, so that it cannot be obtained according to the design size. Abnormal LED lens. Further, when the thickness of the release film is made thinner and the elongation is improved, the film for release film which is present at the edge of the mold is broken when vacuum is sucked. Further, a method of using a film containing a resin composition containing a crystalline aromatic polyester (the crystalline aromatic condensate containing a bismuth succinic acid in a crystal component) as a release film is known. (For example, refer to Patent Document 3). However, as a film for release film, as shown in Patent Document 3, a resin composition containing a crystalline aromatic polyester (the crystalline aromatic polyester containing butylene terephthalate) is contained. When the film is used for the formation of a led lens, if the film for vacuum release is adhered to the mold, but it extends beyond the break point, the film for the release film is partially thinned, and the surface of the formed LED lens is formed. Produces bumps or (four) different f. Since &, the actual situation is that in the resin molding of the LED lens, there is no film which can be preferably used as a film for release film. [Patent Document 1] [Patent Document 1] Japanese Patent Laying-Open No. Hei 8-142105 (Patent Document 2) Japanese Patent Laid-Open No. Hei. [Problem to be Solved by the Invention] The present invention has been made in view of the above-described advantages, and an object thereof is to provide a mold which is excellent in peelability from a mold or a molded article, and which is to be molded. The shape of the mold is transferred to the molded article in accordance with the design size, and the shape is excellent in transferability, and the surface smoothness of the molded article is obtained, and the release film having a heat resistance at a use temperature of about 14 rc is also obtained. The technical means of the problem is achieved by the inventions of the following (1) to (1). (1) A film for release molding, characterized in that the pair includes JIS (Japanese Industrial Standards > Japanese industrial standard hardness of 70 or more and Vicat softening temperature of 1 〇〇~1 g〇 °c of polyamine phthalic acid from the purpose of elastomer or containing the polyamine phthalate elastomer as the main component Thermoplastic elastomer The film of the composition is irradiated with ionizing radiation. (2) The film for release film of (1), wherein the 'polyamine phthalate-based elastic system is composed of three components of a polyisocyanate, a polyol, and a chain extender. A thermoplastic polyurethane elastomer obtained by the reaction. (3) The release film according to (2), wherein the 'polyol is selected from the group consisting of polyester polyol, polyester decylamine polyol, and poly Carbonate polyol, polyether multi-component 159436.doc 201239016 Alcohol, polyether ester polyterpene alcohol, and polyolefin polyols of the group consisting of a plurality of high molecular weight polyols having a molecular weight average of 500 to 10,000 (4) The release film according to (2) or (3), wherein the chain extender is selected from the group consisting of low molecular weight 7G alcohols, low molecular weight amines, and low molecular weight amine alcohols. The release-type film of any one of (1) to (4), wherein the thermoplastic elastomer composition is relative to the above-mentioned polyurethane system a combination of a fluorine-based surfactant in an amount of 0.05 to 5.0 parts by mass based on the mass of the elastomer (6) The film for release film of (5) wherein the i-type surfactant is a perfluoroalkyl acid derivative compound having a melting point of 250 ° C or lower and a decomposition temperature of 3 G (rc or more). The release film according to any one of (1) to (6), wherein the thermoplastic elastomer composition further comprises an additive or a plurality of additives which are a slip agent, an anti-caking agent, an antioxidant, and a phosphorus-based antioxidant. 8) The film for release film according to any one of (1) to (7) wherein the irradiation of the ionizing radiation is performed by using γ selected from the group consisting of α-ray, X-ray, electron beam, neutron beam, X-ray, and Ming 60 light source. The species in the group consisting of rays is carried out at a dose of 50 to 500 kGy. (9) The film for release film according to any one of (1) to (8) wherein the tensile modulus of the film is 10 to 500 N in the longitudinal direction of the film (assisted) and the transverse direction of the film (TD). The range of mm2. (10) The film for release film according to any one of (1) to (9), wherein the ratio of the film longitudinal direction of the film (5〇% M°) to the film transverse direction (TD) (MD) /(TD) 159436.doc 201239016 is a range of 0.9 to 1.2. (11) The release film according to any one of (1) to (10), wherein a ratio of a 50 〇/〇 modulus (50% Mo) of the film to a 100% modulus (100% Mo) (100%) M〇)/(50% Mo) is in the range of u~丨.6 in the longitudinal direction (MD) of the film and the transverse direction (TD) of the film. (12) The release film according to any one of (1) to (11), wherein the film has a tensile elongation of more than 350% in both the film longitudinal direction (MD) and the film transverse direction (TD). [Embodiment] The inventors of the present invention conducted various studies to achieve the above object, and as a result, it was found that the JIS a hardness of the polyamine phthalate-based elastomer alone is 70 or more, and the specific gravity is 1·〇5 to 1.30. A film having a Vicat softening temperature of i〇〇~18〇〇c or a film comprising a thermoplastic elastomer composition containing the polyurethane elastomer as a main component, irradiating ionizing radiation The film for release film is excellent in releasability from a mold or a molded article, and the shape of the mold is transferred to the mold of the molded article in accordance with the design size, and the transfer property is excellent, and the surface smoothness of the molded article is obtained. Further, the heat resistance is further studied. As a result, it has been found that the thermoplastic elastomer composition is contained in an amount of 〜·〇5 to 5.0 parts by mass based on the mass% of the polyamino phthalate elastomer. The composition of the fluorine-based surfactant in the range is more effective, and the present invention has been completed. The polyurethane-based elastomer in the present invention is a thermoplastic polyurethane-based elastomer obtained by a reaction of three components of a polyisocyanate, a polyhydric alcohol, and a chain extender. 159436.doc 201239016 The above-mentioned polyisocyanuric acid vinegar is, for example, 2,4·A:, 2,6-toluenediiso-acid, dimethyl 1,4-diiso-acid, Two-one isocyanic acid vinegar, 4,4, · di-peptidyl methane diisocyanate, diphenyl ketone diiso-acid acid brewing, 2,2,-diphenyl carbaryl diiso-acid Vinegar, '4: two stupid_diisocyanate, 2_nitrodiphenyl_4,4,_diisocyanate, 22,_ phenylpropanol-4,4,-di Cyanate, 3,3,_dimethyl dimethyl phenyl group-4,4'-diisocyanate, 4,4,-diphenylpropane diisocyanate, m-benzene: isophthalic acid vinegar, p-benzene: different Cyanate 8 , anthracene such as naphthyl, anthracene diisocyanide, anthranyl group 1,5-diisocyanate, 3,3,-dimethoxyphenyl 4,4,-diisocyanate Anisophthalic acid vinegar; tetramethylene diisoxamic acid, hexamethylene diisocyanate, dodecane diisocyanate, i methyl hexamethylene diisocyanate: ester, away Aliphatic diisocyanates such as amino acid diisocyanate; cyclohexane diisocyanate vinegar, dicyclohexylmethane diisocyanate vinegar, isophora _ diiso are: S: 'hydrogenated toluene diiso An ester cyclic diisocyanate such as an acid ester, hydrogenated diphenylene diisocyanate, hydrogenated diphenyldecane diisocyanate, tetramethyldiphenylene diisocyanate or norbornane diisocyanate; and the above isocyanate a urea body, a dimer, a trimer, a dimer_trimer, a carbodiimide, a uretonimine, an adduct obtained by reacting a difunctional or higher polyhydric alcohol with the above isocyanate Wait. Further, it is also possible to use one activity in the molecule such as decyl alcohol, n-butanol, benzofuranol, ethyl acetate, ε_hexene oxime, methyl ethyl ketone oxime, phenol or cresol. A hydrogen isocyanate is a polyisocyanate obtained by stabilizing one of the isocyanate groups. These may be used alone or in combination of two or more. The above polyol having a molecular weight average molecular weight of 500,400,000 is more than 159,436.doc 201239016, and there are polyester polyol, polyester decylamine polyol, polycarbonate polyol, polyether polyol, polyether. Ester polyol, polyolefin polyol, and the like. These polymer polyols may be used alone or in combination of two or more. Examples of the polyester polyol and the polyester decylamine polyol include those obtained by a condensation reaction using a polycarboxylic acid and a polyhydric alcohol as the case may be a diamine or an amino alcohol. Examples of the polycarboxylic acid include succinic acid, adipic acid, sebacic acid, dimer acid, hydrogenated dimer acid, phthalic acid, alkyl phthalate, trimellitic acid, and cis. Aenedioic acid, fumaric acid, itaconic acid, and the like. Further, it is also obtained by ring-opening polymerization of a cyclic ester such as butyrolactone, valerolactone or caprolactone. Examples of the polyhydric alcohol include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, anthracene, 2-butanediol, anthracene, 3-butanediol, anthracene, butanediol, and n-butylene. 1,5-pentanediol, 3-methyl-p-pentanediol, 2-hexanol 3-methyl-i, 5-pentanediol, neodecanediol, ^8-octanediol, I 』 壬 diol, 2,2-diethyl decylene propylene glycol, 2-n-butyl -2-ethyl propylene glycol, 2,2,4-trimethyl decyl pentanediol, 2 _ Ethyl hexane diol, hexadecane sulphuric acid glycol, hexahydrate sulphuric acid glycol, 2 yttrium octadecyl-1,2-ethanediol, diol, or double... Oxygen II, II Propylene glycol, cyclohexanol yin A, 3 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ , three oil, pentaerythrine low-molecular polyols. As a guanamine or an amino alcohol, for example, hydrazine is a low _, hexamethylenediamine, xylylenediamine, a low knives polyamine, monoethanolamine, diethanolamine, 159436.doc 201239016 Low molecular weight amino alcohols such as ethanolamine. Further, it can be exemplified by a low molecular weight polyol, a low molecular weight polyamine, and a low molecular weight amino alcohol as a starting agent, and a cyclic ester (lactone) monomer such as ε_caprolactone or γ-valerolactone. A lactone-based polyester polyol obtained by ring-opening polymerization. Examples of the polycarbonate polyol include a low molecular polyol used for the synthesis of the above polyester polyol, and diethyldicarbonate, dinonyl carbonate, diethyl carbonate, diphenyl carbonate, and the like. Obtained by a dealcoholization reaction, a dephenolization reaction, and the like. Examples of the poly-bonded polyol include -^jx yu r/| m ^ low molecular weight polyol, low molecular weight polyamine, and low molecular weight amino alcohol as initiators, and ethylene oxide 'propylene oxide, tetrahydrofuran, etc. a polyethylene glycol, a polypropylene glycol, a polytetrahydrofuran, etc., which are obtained by ring-opening polymerization, and a polyether polyol obtained by copolymerizing the same, and further comprising the above-mentioned polyester polyol or polycarbonate polyol Starting agent polyester ether polyol. The poly(tetra)polyol' is exemplified by the use of poly-exo group in part or all of the polyol used in the condensation reaction in obtaining the above-mentioned polyglycol polyol, in the same manner as the (iv) polyol. As a poly-polyol, it can be transferred: polybutadiene containing a secret, hydroxy-containing polybutadiene, a polyisoprene of a rivet, and a polyisoprene containing a hydrogenated Zhao group. , containing polyethylene and so on. The gasified polypropylene and the chain-containing chlorine-containing chain extender coefficient are equal to the active hydrogen containing the knife of the knife I of the eight-day spoon, and examples thereof include the above-mentioned low molecular polyols and the above low molecular weight. More money, the above low molecular weight amino alcohols, and the like. 159436.doc 201239016 The manufacture of polyurethane elastomers can be carried out by a known manufacturing method, for example, a single trigger method, a prepolymer method, a batch reaction method, a continuous reaction method, a method using a kneader, and a squeeze. Method of exiting the machine. The hardness of the polyurethane-based elastomer used in the present invention is JIS A hardness of 7 Å or more as measured by the test method of JIS K 7311. Further, in the case where the JIS A hardness is 100 or more, it is preferable to apply the d hardness, and the upper limit of the hardness of 70 or less is used. The JIS a hardness is preferably 8 Å or more, more preferably 9 Å or more. When the JIS A hardness is less than 60, the rubber property is increased. Therefore, when the release film is conveyed in the mold forming apparatus, there is an abnormality that the film is stretched and the conveyance is unstable. On the other hand, when the hardness of the crucible exceeds 7 Å, there is an abnormality in the gel generated from the three components of the raw material polyisocyanate, the polyol, and the chain extender at the time of extrusion molding. The Vicat softening temperature of the polyurethane-based elastomer used in the present invention is measured by the test method of JIS K 7206 and is in the range of 1 〇〇 18 〇 π. The Vicat softening temperature is preferably from 10 to 180 〇c, more preferably from 12 to 18 (rc, further preferably from 130 to 180 ° C. If the Vicat softening temperature is less than 1 〇〇. (:, Even if the ionizing radiation is irradiated, the release film may be melted when it is used. That is, heat resistance cannot be obtained. On the other hand, the upper limit of the Vicat softening temperature is 180 ° C, but it has not been obtained with more than 丨8 The polycarbamate-based elastomer of the Vicat softening temperature of 〇〇c. The fluorine-based surfactant in the present invention refers to a perfluoroalkylsulfonic acid derivative, which is an all-gas-based acid derivative. Specific examples include potassium trimethyl phthalate (CFsSCbK), sodium trifluoromethanesulfonate (CF3S〇3Na), lithium trifluoromethanesulfonate (CFJC^Li), and potassium pentafluoroethylsulfonate. (C2f5s〇3K) 'Five 159436.doc 201239016 Sodium fluoroethyl sulfonate (C2F5S03Na), lithium pentafluoroethyl sulfonate (C2F5S03Li), potassium heptafluoropropyl sulfonate (C3F7S03K), sodium heptafluoropropyl sulfonate (C3F7S03Na), lithium heptafluoropropyl sulfonate (C3F7S03Li), potassium nonafluorobutyl sulfonate (C4F9S03K), sodium nonafluorobutyl sulfonate (C4F9S03Na), nonafluoro A perfluoroalkyl sulfonate such as lithium sulfonate (C4F9S03Li). Further, bis(trifluoromethylsulfonylsulfonyl) quinone imide potassium salt ((CF3S02)2NK), bis(trifluoromethylsulfonate) Sodium sulfhydryl sodium salt ((CF3S02) 2NNa), bis(trifluoromethylsulfonyl) sulfoximine ammonium salt ((CF3S02) 2NNH4), bis(trifluoromethylsulfonyl) fluorene imine Lithium salt ((CF3S02)2NLi), bis(pentafluoroethylsulfonyl) sulfinium imide potassium salt ((C2F5S〇2) 2NK), bis(five-ethylethyl) succinimide sodium salt (( CjsSO^NNa), bis(pentafluoroethylsulfonyl) sulfoximine ammonium salt ((C2F5S02) 2NNH4), bis(pentafluoroethylsulfonyl) quinone imide lithium salt ((C^FsSOANLi), double (Sevoflurane-based brewing base) Brewed imine clock salt ((C3F7S〇2) 2NK), bis (seven-propyl propyl aryl) sodium sulfoxide sodium salt ((C3F7S〇2) 2NNa), double (nine I butyl aryl hydride ((C4F9S02)2NK), bis(nonafluorobutylsulfonyl)imide sodium salt ((C4F9S02)2NNa), cyclo-hexafluoropropane-1,3- Perfluorocarbons such as bis(sulfonyl) fluorene imide potassium salt (CF2(CF2S02)2NK), cyclo-hexafluoropropane-1,3-bis(sulfonyl) sulfinium imide (CF2(CF2S02)2NNa) alkyl Sulfonimide salt. Further, an ionic liquid in which perfluoroalkyl sulfonic acid is an anion species, an ionic liquid in which bis(perfluoroalkylsulfonyl) quinone imine is an anion species, and a double Fluorosulfonyl) ruthenium imide is an ionic liquid of anionic species, and ionic liquid with cyclohexafluoropropane-1,3-bis(sulfonyl) quinone imine as an anion species 12 159436.doc 201239016 and the like. Further, a compound having a melting point of 250 C or less and a decomposition temperature of 300 C or more can be preferably used in the above perfluoroalkylsulfonic acid derivative. Specific examples of these include potassium trifluoromethanesulfonate (CFsSOsK) or bis(trimethylsulfonylsulfonyl)phosphonium imide potassium salt ((CF3S02)2NK). The fluorine-based surfactant is mixed in the polyurethane elastomer for the purpose of imparting film slip properties for release. By blending the fluorine-based surfactant to impart smoothness to the surface of the film, it is possible to obtain an effect of smoothing the transfer of the release film in the mold forming apparatus, and preventing the release when it comes into contact with the mold. The effect of the wrinkles of the film is used to improve the peeling property of the polyoxynenoid resin composition used as the mold resin. The amount of the fluorine-based surfactant is in the range of from 0.05 to 5.0 parts by mass based on 100 parts by mass of the polyamino phthalic acid-based elastomer. If the blending amount is less than 质量 5 parts by mass, the effect of mixing will not be exhibited. On the other hand, even if it exceeds 5.0 parts by mass, the effect of mixing does not increase, and there is an abnormality that the surfactant acts on the surface of the film or blooms on the surface of the film, and the surface of the molded article is contaminated during use. . The polyfunctional unsaturated group-containing crosslinking agent may be mixed in the thermoplastic elastomer composition of the present invention as needed, for example, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, di-three Hydroxymethylpropane tetraacrylate, ethylene glycol dimercapto acrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, glycerol dimethacrylate, trishydroxypropyl propane Mercapto acrylate, triallyl cyanurate, and the like. The crosslinking agent such as Yanhai is preferably 1 to 10 parts by mass based on the mass of the amino phthalate elastomer 1 436 159 436.doc 201239016. In the thermoplastic elastomer composition of the present invention, Other thermoplastic elastomers are mixed within the range that detracts from the characteristics of the present invention. Examples of the thermoplastic elastomer include a polyester elastomer, a polyamide-based elastomer, a polyethylene-based elastomer, a styrene-based elastomer, and an olefin-based elastomer. Can also

藉由對此種其他熱塑性彈性體進行共擠壓而製成接著積層 膜。 S 本發明之熱塑性彈性體組合物中，可於不損及本發明之 特性的範圍内混合例如醯胺系蠟或硬脂酸鈣等潤滑劑、矽 石等抗結塊劑、作為自由基補充劑*發揮功能之齡系抗氧 化劑、作為過氧化物分解劑而發揮功能之磷系抗氧化劑、 甘油月曰肪酸酯、聚甘油脂肪酸酯、山梨糖醇酐脂肪酸酯、 聚氧乙婦炫基醚等抗靜電劑。 本心明之離型用膜係對包含上述熱塑性彈性體組合物之 膜（以下稱為未照射膜）照射電離放射線，使胺基甲酸酯系 彈性體交聯，藉此提高作為離型用膜之丨8〇β(：前後之高溫 下之機械強度，即耐熱強度。作為電離放射線，可列舉： α射線β射線、電子束、中子射線、χ射線、錯的輕射源 之γ射線等，通常使用電子束與γ射線。電離放射線可以公 知之方法照射。例如’於本發明之一實施形態中，利用分 批式以成為特定劑量之方式對捲取之未照射膜照射丫射 線。 電離放射線之劑量為5〇〜5〇〇 kGy，較佳為1〇〇〜5〇〇 kGy，更佳為200〜500 kGy。若電離放射線之劑量未達5〇 159436.doc 201239016 kGy，則劑量不足而交聯變得不充分，無法獲得離型用膜 所必需之耐熱強度。另一方面，於電離放射線之劑量超過 500 kGy之情形時，胺基曱酸酯系彈性體之分子鏈切割超 過父聯反應，因此產生劣化，從而造成離型用膜之拉伸伸 長率降低。 本發明中之離型用膜係依據JIS Z 1702於溫度為23°C、 拉伸速度為100 mm/min下測定之膜之拉伸彈性模數於膜縱 方向（MD)及膜橫方向（TD)上均為1〇.〇〜5〇〇 N/mm2之範圍。 該拉伸彈性模數較佳為2〇.〇~4〇〇 N/mm2之範圍，更佳為 30.0〜300 N/mm2之範圍。若拉伸彈性模數未達1〇 〇 N/mm2，則存在如下之異常：於在鑄模成形裝置内自捲繞 體抽出離型用膜時，膜之張力較弱而產生鬆弛。另一方 面’於拉伸彈性模數超過5〇〇 N/mm2之情形時，存在如下 之異常.於在鑄模模具内以真空吸引離型用膜時，膜不延 伸而不密接於鑄模模具。 本發明中之離型用膜係依據jIS z 1702，於溫度為 23C、拉伸速度為100 mm/min下測定之膜之5〇%模數（5〇% Mo)之膜縱方向（MD)與膜橫方向（TD)之比（md)/(td)為 0.90〜1.20之範圍。該（MD)/(TD)較佳為〇 95〜12〇之範圍。 若為藉由擠出成形法而成形之膜’則無（MD)/(TD)成為未 達〇.90之現象。另一方面，於（MD)/(TD)超過1.20之情形 時’存在如下之異常：於在鑄模成形裝置内將離型用膜向 鑄模模具供給時，膜產生褶皺。 本發明中之離型用膜係依據JIS Z 1702，於溫度為 159436.doc •15- 201239016 23°C、拉伸速度為100 mm/min下測定之膜之50%模數（50% Mo)與 100%模數（100°/。Mo)之比（100% Mo)/(5 0% Mo)於膜 縱方向（MD)及膜橫方向（TD)上均為1·〇〇〜1.60之範圍。該 (100% Mo)/(50% Mo)較佳為 1.00〜1.50之範圍。若（100〇/〇A laminate film is formed by co-extruding such other thermoplastic elastomers. In the thermoplastic elastomer composition of the present invention, a lubricant such as a guanamine wax or calcium stearate, an anti-caking agent such as vermiculite, or the like may be mixed as a free radical in a range that does not impair the characteristics of the present invention. Agent* is an antioxidant that functions as a antioxidant, a phosphorus-based antioxidant that functions as a peroxide decomposer, a glycerol lauric acid ester, a polyglycerin fatty acid ester, a sorbitan fatty acid ester, and a polyoxymethylene Antistatic agent such as daidyl ether. In the film for release film of the present invention, the film containing the thermoplastic elastomer composition (hereinafter referred to as a non-irradiated film) is irradiated with ionizing radiation to crosslink the urethane-based elastomer, thereby improving the film for release film.丨8〇β (: mechanical strength at high temperatures before and after, that is, heat resistance. As ionizing radiation, examples include: α-ray β-ray, electron beam, neutron beam, x-ray, wrong gamma-ray source, etc. The electron beam and the gamma ray are usually used. The ionizing radiation can be irradiated by a known method. For example, in one embodiment of the present invention, the unirradiated film which is wound up is irradiated with xenon rays by a batch method in a specific dose. The dose of radiation is 5〇~5〇〇kGy, preferably 1〇〇~5〇〇kGy, more preferably 200~500 kGy. If the dose of ionizing radiation is less than 5〇159436.doc 201239016 kGy, the dose is insufficient. However, the crosslinking becomes insufficient, and the heat resistance strength necessary for the film for release film cannot be obtained. On the other hand, when the dose of ionizing radiation exceeds 500 kGy, the molecular chain cutting of the amine phthalate elastomer is super The reaction of the parent is degraded, thereby causing a decrease in the tensile elongation of the film for release. The film for release film according to the present invention is based on JIS Z 1702 at a temperature of 23 ° C and a tensile speed of 100 mm / min. The tensile modulus of the film to be measured is in the range of 1 〇.〇5〇〇N/mm2 in the longitudinal direction (MD) of the film and the transverse direction (TD) of the film. The tensile modulus of elasticity is preferably 2 〇.〇~4〇〇N/mm2 range, more preferably in the range of 30.0~300 N/mm2. If the tensile modulus is less than 1〇〇N/mm2, there is an abnormality as follows: When the film for release film is taken out from the wound body in the apparatus, the tension of the film is weak and slack. On the other hand, when the tensile modulus exceeds 5 〇〇N/mm2, the following abnormality exists. When the film for release film is suctioned by vacuum in the mold, the film does not extend without being in close contact with the mold. The release film of the present invention is based on JIS z 1702 at a temperature of 23 C and a tensile speed of 100 mm/min. The ratio (md)/(td) of the film longitudinal direction (MD) to the film transverse direction (TD) of the 5〇% modulus (5〇% Mo) of the film to be measured is in the range of 0.90 to 1.20. D)/(TD) is preferably in the range of 〜95 to 12 。. If the film is formed by extrusion molding, then (MD)/(TD) becomes a phenomenon that does not reach 〇.90. In the case where (MD)/(TD) exceeds 1.20, there is an abnormality in that the film is wrinkled when the release film is supplied to the mold in the mold forming apparatus. The release film in the present invention According to JIS Z 1702, the 50% modulus (50% Mo) and 100% modulus (100°) of the film measured at a temperature of 159436.doc •15-201239016 23°C and a tensile speed of 100 mm/min. /. The ratio of Mo) (100% Mo) / (50% Mo) is in the range of 1·〇〇 to 1.60 in the longitudinal direction (MD) of the film and the transverse direction (TD) of the film. The (100% Mo) / (50% Mo) is preferably in the range of 1.00 to 1.50. If (100〇/〇

Mo)/(50% Mo)未達1.00，則存在如下之異常：不會隨著膜 之延伸之增加而產生應力之增加，因此無法獲得均勻的膜 之延伸，於在鑄模模具内以真空吸引離型用膜時產生褶 皺。另一方面，於（100。/。Mo)/(5〇% M〇)超過j 6〇之情形 時，存在如下之異常：隨著膜之延伸之增加的應力之增加 較大，膜不能完全延伸至使離型用膜密接於鑄模模具内表 面。 本發明之離型用膜係依據JIS z 17〇2 ’於溫度為23t、 拉伸速度為100 mm/min下測定之膜之拉伸伸長率於膜縱方 向（MD)及膜橫方向（TD)上均為35〇%以上。該拉伸伸長率 較佳為4〇〇/0以上。若拉伸伸長率未達⑽％，則存在如下 之異㊉.於在鑄模模具内以真空吸引離型用膜時，於鑄模 模具之邊緣破裂。 述L 3熱塑性彈性體組合物之未照射·膜可藉由例如* 融擠出法或熔融㈣法等先前公知之方法而成形。於以_ ，列舉藉由使πτ模之熔融擠出法而成形未照射膜; 万法。 使種方法獲得之未照射膜係藉由如下步驟而獲得： 體！：：擠出機或雙轴擠出機等擠出機，根據熱塑性彈性 σ物之特性， 、氮氧置換存在於擠出機内及成形材 J 59436.doc -16 - 201239016 料間之間隙之空氣的氣體環境下，對熱塑性彈性體組合物 之成形材料進行溶融混練，將自配置於擠出機前端之τ模 前端之模唇部熔融擠出的未照射膜直接夾於牽拉機内之壓 接輥與冷卻輥之間進行冷卻，或自壓接輥側與冷卻輥側之 兩側或一側***分隔件來夾持而進行冷卻，繼而利用捲取 機依序捲取於捲取管。 圆Ή糸表示利用上述方 概略之構成圖。又，圖4係圖3所示之膜製造裝置之材料投 入料斗之周邊之剖面圖。於圖3中，膜製造裝置係大致包 括材料投入料斗2、擠出機卜Τ模7、牵拉機U、捲取機15 而構成。材料投入料斗2係用以投入成形材料，如圖4所 示’於材料投入料斗2與擠出⑹連接之途中，經由間隔物 3a***有氮氣供給用導管3。又，氮氣供 :料投入口™心轴之方式彎曲，其前二= 出機1内之擠出螺桿1&之外周附近。自材料投入料斗2投 入之成形材料中或播出機1内所含之氧氣係於利用擠出m 之擠出螺桿u對絲㈣進行混合'㈣時 氣供給用導管3之氮氣所置換。 “至氣 2出機1係^擠出螺桿1靖成形材料進行混合、 缸見b内—面向箭頭^向傳送，並藉由内裝於擠出機!之料 =電熱機構’對成形材料進行加熱、溶融。以此種 給==送之成形材料係經由如圖3所示之連接管4送 慮機構5。繼而，藉由 材料分離，將熔融之心^ 將未炫融之成形 字嫁融之成形材料送給至齒輪以。於齒輪^ I59436.doc -17* 201239016 中 面提问熔融之成形材料之壓力，一面向T模7擠出熔 融成形材料。於了模7中，以特定壓力擠纽融成形材料， 自Τ模7之模唇部乃成形特定厚度、特定寬度之膜8。以此 種方式成形之未照射臈8係一面捲繞於牽拉機i i之冷卻輥 10之外周面上，—面利用壓接輥9調整為特定厚度，進而 進订冷部、g)化’利用傳送輥對12、13而傳送至捲取機 15 〇 於捲取機15令，未照射膜8係由引導報…、15卜仏引 導並藉由捲取官16捲取。再者，於傳送輥對U、Η與引導 輥15a之間配设有厚度測定器14，根據由厚度測定器μ測 定之厚度，調整、控制冷卻輥IQ之圓周速度以使其成為所 需之厚度。藉此形成上述未照射膜。 上述捲取於捲取管之未照射膜係藉由進行於8〇〜ιι〇亡之 溫度下靜置24小時以上之熟化而使各物性穩定後，照射特 定劑量之鈷60輻射源之γ射線，藉此形成離型用膜。 離型用膜只要係根據成形品所必需之表面形狀而形成膜 之表面形狀即可。例如，於LED等其表面成為鏡面之情形 時，使用使離型用膜之表面為鏡面之離型用膜。又，⑴或 LSI等係使其表面形成有微細之凹凸，因此使用於離型用 膜之表面形有微細之凹凸之離型用膜。 作為形成離㈣膜之表面形狀之方法，於使表面為鏡面 之情形時，存在有預先使上述之金屬製冷卻輥之表面為鏡 面，以壓接輥將處於熔融狀態之離型用膜壓接於該冷卻輥 上，將離型用膜之表面調整為鏡面之方法。又，於使用分 159436.doc -18- 201239016 抛光之 PET(polyethylene —醋）膜或 OPP(Oriented 為分隔件，而轉印其表 隔件之情形時，存在有使用鏡面 terephthalate，聚對笨二甲酸乙 polypropylene ’定向聚丙烯）膜作 面之方法。 於圖3中，於膜8之壓接輥9之側，自送出輥m將分隔件 W向箭頭之方向供給，於膜8之冷卻㈣之側，自送出輥 m將分隔件18b向箭頭之方向供給，藉此可由分隔件而轉 印膜8之表面形狀。將雙面積層有分隔件…、18b之膜8暫 :捲取後’將分隔件18a、18b剝離而捲取膜8，藉此可獲 斗于具有特定表面形狀之離型膜。 於在離型㈣之表面形成微細之凹凸之情形時，存在有 如下方法.預先於上述之金屬製冷卻輥之外周面形成微細 之凹凸’以壓接輥將處於溶融狀態之膜魔接於該冷卻親上 時，使形成於冷卻輥之外周面之微細之凹凸轉印至離型用 膜表面♦ X⑪使用分隔件之情形時，存在有使用對表面 進行了消光加工之PET膜或〇pp膜作為分隔件，而轉印其 表面之方法。 於使離型用膜之表面為鏡面之情形時，只要以其表面粗 度係依據JIS B0601-2001，於速度為〇6 mm/秒、截斷值為 0.8 mm、坪價長度為8 〇随下測定之輪扉算術平均偏差^ 為0.10以下，最大高度粗糙度Rz成為1〇〇以下之方式，適 當地形成表面即可。若輪廓算術平均偏差Ra為〇.1〇以下及 最大咼度粗糙度以為丨·^以下，則轉印有離型用膜之表面 的成形品之表面變得平滑。 159436.doc 19 201239016 於在離型用膜之表面形成微細之凹凸之情形時只要以 其表面粗度係與上述同樣地測定之輪廓算術平均偏差以為 0.5以上，最大高度粗糙度RZ成為5 〇〇以上之方式適當地 形成表面即可。 本發明之離型用膜之厚度為5 μΓη〜5〇〇 μιη之範圍，較佳 為10 μηι〜400 μιη之範圍，只要根據所使用之鑄模模具之形 狀適當地選擇即可。於將離型用膜之厚度設為未達5 μιη之 情形時，於在使用時追從鑄模模具時，存在離型用膜延伸 變薄而斷裂，或因鑄模樹脂之壓力而破損之異常，因此欠 佳。又，於超過500 μηι之情形時，離型用膜之厚度成為障 礙’從而存在變得無法追從具有微細之構造之铸模模具之 異常’或者變得無法將鑄模模具之複雜的形狀轉印至成形 品之異常，因此欠佳。 [實施例] 以下’使用表1〜3發明之離型用膜之實施例加以說明。 再者’本發明之離型用膜不受實施例1〜11限定。 此處’表1〜3中所示之胺基曱酸酯系彈性體i、氟系界面 活性劑1及氟系界面活性劑2係使用如下所示之材料。 (胺基甲酸酯系彈性體1)When Mo)/(50% Mo) is less than 1.00, there is an abnormality that an increase in stress does not occur as the elongation of the film increases, so that a uniform film extension cannot be obtained, and vacuum suction is performed in the mold. Wrinkles occur when the film is used for release. On the other hand, when (100%/Mo)/(5〇% M〇) exceeds j 6〇, there is an abnormality that the film cannot be completely increased as the increase in the stress of the extension of the film is large. The film is extended to adhere the release film to the inner surface of the mold. The release film of the present invention is obtained by measuring the tensile elongation of the film in the longitudinal direction (MD) of the film and the transverse direction of the film in accordance with JIS z 17〇2' at a temperature of 23 t and a tensile speed of 100 mm/min. ) are above 35〇%. The tensile elongation is preferably 4 Å/0 or more. If the tensile elongation is less than (10)%, there is the following difference. When the release film is vacuum-drawn in the mold, it is broken at the edge of the mold. The unirradiated film of the L 3 thermoplastic elastomer composition can be formed by a conventionally known method such as a melt extrusion method or a melt (four) method. In _, the unexposed film is formed by a melt extrusion method using a πτ mold; The unirradiated film obtained by the method is obtained by the following steps: Body! ::Extruder or extruder such as twin-screw extruder, according to the characteristics of thermoplastic elastomer σ, nitrogen-oxygen substitution in the air between the extruder and the material J 59436.doc -16 - 201239016 In the gas environment, the molding material of the thermoplastic elastomer composition is melted and kneaded, and the unirradiated film which is melt-extruded from the lip portion of the tip end of the τ mold disposed at the tip end of the extruder is directly clamped to the crimping machine in the drawing machine. Cooling is performed between the roller and the cooling roller, or a separator is inserted from both sides or one side of the pressure roller side and the cooling roller side to be cooled, and then sequentially taken up by the coiler by the coiler. The circle indicates the configuration diagram using the above summary. Further, Fig. 4 is a cross-sectional view showing the periphery of a material injection hopper of the film manufacturing apparatus shown in Fig. 3. In Fig. 3, the film manufacturing apparatus is roughly constituted by a material input hopper 2, an extruder die 7, a pulling machine U, and a coiler 15. The material input hopper 2 is for inserting a molding material, and as shown in Fig. 4, the nitrogen supply conduit 3 is inserted through the spacer 3a while the material input hopper 2 is connected to the extrusion (6). Further, the nitrogen gas is supplied so as to be bent by the material input port TM, and the first two are in the vicinity of the outer circumference of the extrusion screw 1 & The oxygen contained in the molding material injected from the material input hopper 2 or in the distributor 1 is replaced by nitrogen gas supplied from the gas supply conduit 3 when the yarn (4) is mixed by the extrusion screw u of the extrusion m. "To the gas 2 outlet 1 system ^ extrusion screw 1 molding material for mixing, cylinder see b - facing the arrow ^ direction, and by the built-in extruder = material = electric heating mechanism 'to the forming material Heating and melting. The forming material sent by this == is fed through the connecting pipe 4 as shown in Fig. 3. Then, by separating the materials, the molten heart is married to the unshaved forming word. The molten forming material is sent to the gear. In the gear ^ I59436.doc -17* 201239016, the pressure of the molten forming material is asked, and the molten forming material is extruded toward the T-die 7. In the mold 7, the specific pressure is applied. The squeezing forming material is formed by forming a film 8 of a specific thickness and a specific width from the lip portion of the dies 7. The unirradiated 臈8-line formed in this manner is wound around the outer circumference of the chill roll 10 of the stretching machine ii. On the surface, the surface is adjusted to a specific thickness by the pressure roller 9, and the cold portion is further fed, and the conveyance roller pair 12, 13 is conveyed to the winder 15 to the winder, and the film is not irradiated. The 8 series is guided by the guide...15, and is taken up by the take-up officer 16. Further, on the transport roller pair U, A thickness measuring device 14 is disposed between the guide roller 15a, and the circumferential speed of the cooling roller IQ is adjusted and controlled so as to have a desired thickness based on the thickness measured by the thickness measuring device μ. Thereby, the unirradiated film is formed. The unirradiated film taken up in the take-up tube is immersed for 24 hours or more at a temperature of 8 〇 to ι 〇 to stabilize the physical properties, and then irradiated with a specific dose of the gamma ray of the cobalt 60 radiation source. In this case, the release film can be formed into a surface shape of the film according to the surface shape necessary for the molded article. For example, when the surface of the LED or the like is mirror-finished, it is used for release. The surface of the film is a film for release film of a mirror surface. Further, (1) or LSI or the like has fine irregularities formed on the surface thereof, and thus is used for a release film having fine irregularities on the surface of the release film. (4) A method of forming a surface of a film, wherein when the surface is a mirror surface, the surface of the metal cooling roll is mirror-formed in advance, and the release film in a molten state is pressure-bonded to the cooling by a pressure roller. On the roll The method of adjusting the surface of the release film to a mirror surface. Further, using a PET (polyethylene-vinegar) film or OPP (Oriented as a separator), and transferring the surface spacer thereof, using 159436.doc -18-201239016 polishing. In the case of the case, there is a method of using a mirrored terephthalate, a polyethylene terephthalate polypropylene polypropylene (oriented polypropylene) film as a surface. In Fig. 3, on the side of the pressure roller 9 of the film 8, the self-feeding roller m will be a separator W is supplied in the direction of the arrow, and on the side of the cooling (4) of the film 8, the separator 18b is supplied from the feeding roller m in the direction of the arrow, whereby the surface shape of the film 8 can be transferred by the separator. The film 8 of the double-area layer having the separators..., 18b is temporarily: after the winding, the separators 18a, 18b are peeled off and the film 8 is taken up, whereby the release film having a specific surface shape can be obtained. In the case where fine irregularities are formed on the surface of the release type (4), there is a method in which fine irregularities are formed in advance on the outer peripheral surface of the metal cooling roll described above, and the film in a molten state is spliced by the pressure roller. When cooling, the fine unevenness formed on the outer peripheral surface of the cooling roll is transferred to the surface of the release film ♦ X11 When a separator is used, there is a PET film or a 〇pp film which is subjected to matting treatment on the surface. As a separator, a method of transferring the surface thereof. When the surface of the release film is mirror-finished, the surface roughness is based on JIS B0601-2001, the speed is 〇6 mm/sec, the cutoff value is 0.8 mm, and the ping price is 8 〇. The measured rim arithmetic mean deviation ^ is 0.10 or less, and the maximum height roughness Rz is 1 〇〇 or less, and the surface may be appropriately formed. When the contour arithmetic mean deviation Ra is 〇.1〇 or less and the maximum roughness roughness is 丨·^ or less, the surface of the molded article to which the surface of the release film is transferred is smooth. When a fine unevenness is formed on the surface of the release film, the arithmetic mean deviation of the profile measured in the same manner as described above is 0.5 or more, and the maximum height roughness RZ is 5 〇〇. The above method may suitably form the surface. The thickness of the film for release film of the present invention is in the range of 5 μΓη to 5 μm, preferably in the range of 10 μηη to 400 μηη, as long as it is appropriately selected depending on the shape of the mold to be used. When the thickness of the film for release film is less than 5 μm, when the mold is used in the mold, the film for the release film is thinned and broken, or the film is broken due to the pressure of the mold resin. Therefore, it is not good. In addition, when the thickness exceeds 500 μm, the thickness of the release film becomes an obstacle 'there is a failure to follow the abnormality of the mold having a fine structure' or the complicated shape of the mold cannot be transferred to The abnormality of the molded article is therefore not good. [Examples] Hereinafter, examples of the release film of the inventions shown in Tables 1 to 3 will be described. Further, the release film of the present invention is not limited to Examples 1 to 11. Here, the amine phthalate-based elastomer i, the fluorine-based surfactant 1 and the fluorine-based surfactant 2 shown in Tables 1 to 3 are the materials shown below. (urethane-based elastomer 1)

Miractran E598PNAT :商品名，日本聚胺酯工業公司製 造’ JIS A硬度為98，維卡軟化溫度為14TC (氟系界面活性劑1)Miractran E598PNAT: trade name, manufactured by Japan Polyurethane Industry Co., Ltd. ' JIS A hardness is 98, Vicat softening temperature is 14 TC (fluorine-based surfactant 1)

Eftop EF-N112 :商品名，三菱综合材料公司製造，雙 159436.doc -20- 201239016 (三氟甲基續醯基）醢亞胺钟鹽（(CF3S〇2)2NK)，溶點為 200°c (氟系界面活性劑2)Eftop EF-N112 : trade name, manufactured by Mitsubishi Materials Corporation, double 159436.doc -20- 201239016 (trifluoromethyl hydrazino) quinone imine clock salt ((CF3S〇2) 2NK), melting point 200° c (fluorine surfactant 2)

Eftop EF-12 :商品名’三菱综合材料公司製造，三氣甲 基磺酸鉀（CF3S03K)，熔點為233°C [表1] 項目 實施例1 實施例2 實施例3 實施例4 胺基曱酸酯系彈性體 種類 1 1 1 1 質量份 100 100 100 100 膜 氟系界面活性劑 種類 - - 質量份 - - - 厚度(μηι) 50 50 50 50 γ射線照射劑量(kGy) 150 250 350 450 拉伸彈性模數(N/mm2) 縱(MD) 78.9 79.7 77.3 83.7 橫(TD) 73.4 74.9 75.6 Γ79.6 50% 模數(50% Mo)(N/mm2) 縱(MD) 7.99 8.07 7.89 8.11 橫(TD) 7.57 7.72 7.66 7.89 離 50% 模數(MD)/(TD) 1.06 1.05 1.03 1.04 型 100% 模數(100% Mo)(N/mm2) 縱(MD) 11.0 11.1 10.8 10.9 膜 橫(TD) 10.8 10.6 10.4 10.1 物 性 (100% Mo)/(50% Mo) 縱(MD) 1.38 1.38 1.37 1.34 橫(TD) 1.43 1.37 1.36 1.28 拉伸伸長率(％) 縱(MD) 468 466 430 417 橫(TD) 453 448 426 412 E^Pa)(耐熱強度） 縱(MD) Ι.ΙχΙΟ6 2·6χ106 4.9χ106 7.1χ106 橫(TD) 9.9χ105 2.0χ106 4.1χ105 6.3χ105 耐熱性 0 0 0 〇 剝離性 0 0 0 Ο 5T 價 模具尺寸轉印性 0 Ο 0 Ο 表面平滑性 〇 〇 0 Ο 實際使用性 〇 〇 〇 〇 159436.doc -21 - 201239016 [表2] 項目 實施例5 實施例6 實施例7 實施例8 膜 胺基甲酸酯系彈性體 種類 1 1 1 1 質量份 100 100 100 100 氟系界面活性劑 種類 編 - - 1 質量份 - - 2 厚度〇im) 25 100 300 50 γ射線照射劑量(kGy) 250 250 250 250 離 型 膜 物 性 拉伸彈性模數(N/mm2) 縱(MD) 78.3 82.2 80.2 76.2 橫(TD) 77.4 74.1 76.0 74.2 50% 模數(50% Mo)(N/mm2) 縱(MD) 8.09 8.19 8.62 8.15 橫(TD) 7.97 8.18 7.97 7.74 50% 模數(MD)/(TD) 1.02 1.00 1.03 1.05 100% 模數(100% Mo)(N/mm2) 縱(MD) 10.7 10.5 10.9 10.4 橫(TD) 10.4 10.3 10.2 10.3 (100% Mo)/(50% Mo) 縱(MD) 1.32 1.28 1.26 1.28 橫(TD) 1.30 1.26 1.28 1.33 拉伸伸長率(％) 縱(MD) 451 476 481 459 橫(TD) 449 462 462 478 E’(Pa)(耐熱強度） 縱(MD) 2.1χ106 2.9xl06 3-lxlO6 2.8xl06 橫(TD) 1.8χ106 3.〇χ106 2.9χ106 2.1χ106 評 價 耐熱性 〇 〇 〇 〇 剝離性 〇 〇 〇 〇 模具尺寸轉印性 〇 0 〇 〇 表面平滑性 〇 〇 〇 〇 實際使用性 〇 〇 〇 〇 159436.doc 22- 201239016 [表3] 項目 實施例9 實施例10 實施例11 膜 胺基甲酸酯系彈性體 種類 1 1 1 質量份 100 100 100 氟系界面活性劑 種類 1 2 2 質量份 4 2 4 厚度(μτη) 50 50 50 γ射線照射劑量(kGy) 250 250 250 離 型 膜 物 性 拉伸彈性模數(N/mm2) 縱(MD) 78.2 82.2 80.2 橫(TD) 77.4 74.1 73.4 50% 模數(50〇/〇 Mo)(N/mm2) 縱(MD) 8.47 8.49 8.35 橫(TD) 8.33 8.44 8.10 50% 模數 _)/(TD) 1.02 1.01 1.03 100% 模數(100% Mo)(N/mm2) 縱(MD) 10.5 10.8 11.0 橫(TD) 10.5 10.5 10.3 (100% Mo)/(50% Mo) 縱(MD) 1.24 1.27 1.32 橫(TD) 1.26 1.24 1.27 拉伸伸長率(％) 縱(MD) 464 480 470 橫(TD) 449 436 466 E'(Pa)(耐熱強度） 縱(MD) 2.7χ106 2.4x106 2.5χ106 橫(TD) 2.〇χ1〇6 1·8χ106 2.2χ106 評 價 耐熱性 0 〇 〇 剝離性 〇 〇 〇 模具尺寸轉印性 〇 0 〇 表面平滑性 〇 〇 〇 實際使用性 〇 0 〇 159436.doc 23- 201239016 [表4]Eftop EF-12: trade name 'Mitsubishi Synthetic Material Co., Ltd., potassium trimethylsulfonate (CF3S03K), melting point 233 ° C [Table 1] Item Example 1 Example 2 Example 3 Example 4 Amino hydrazine Acid ester elastomer type 1 1 1 1 parts by mass 100 100 100 100 Membrane fluorine surfactant type - - Parts by mass - - - Thickness (μηι) 50 50 50 50 γ-ray irradiation dose (kGy) 150 250 350 450 Extensible modulus (N/mm2) Vertical (MD) 78.9 79.7 77.3 83.7 Transverse (TD) 73.4 74.9 75.6 Γ79.6 50% Modulus (50% Mo) (N/mm2) Vertical (MD) 7.99 8.07 7.89 8.11 Horizontal (TD) 7.57 7.72 7.66 7.89 From 50% Modulus (MD) / (TD) 1.06 1.05 1.03 Type 1.04 100% Modulus (100% Mo) (N/mm2) Vertical (MD) 11.0 11.1 10.8 10.9 Membrane (TD) 10.8 10.6 10.4 10.1 Physical Properties (100% Mo) / (50% Mo) Vertical (MD) 1.38 1.38 1.37 1.34 Cross (TD) 1.43 1.37 1.36 1.28 Tensile Elongation (%) Vertical (MD) 468 466 430 417 Horizontal ( TD) 453 448 426 412 E^Pa) (heat resistance) Longitudinal (MD) Ι.ΙχΙΟ6 2·6χ106 4.9χ106 7.1χ106 Transverse (TD) 9.9χ105 2.0χ106 4.1χ105 6.3χ105 Heat resistance 0 0 0 〇Removability 0 0 0 Ο 5T price mold size transferability 0 Ο 0 Ο Surface smoothness 〇〇 0 实际 Practical use 〇〇〇〇 159436.doc -21 - 201239016 [Table 2] Item Example 5 Example 6 Example 7 Example 8 Membrane urethane type elastomer type 1 1 1 1 parts by mass 100 100 100 100 Type of fluorine-based surfactant - - 1 part by mass - - 2 Thickness 〇im) 25 100 300 50 γ-ray irradiation dose (kGy ) 250 250 250 250 Release film physical tensile modulus (N/mm2) Vertical (MD) 78.3 82.2 80.2 76.2 Transverse (TD) 77.4 74.1 76.0 74.2 50% Modulus (50% Mo) (N/mm2) (MD) 8.09 8.19 8.62 8.15 Horizontal (TD) 7.97 8.18 7.97 7.74 50% Modulus (MD) / (TD) 1.02 1.00 1.03 1.05 100% Modulus (100% Mo) (N/mm2) Vertical (MD) 10.7 10.5 10.9 10.4 Horizontal (TD) 10.4 10.3 10.2 10.3 (100% Mo) / (50% Mo) Vertical (MD) 1.32 1.28 1.26 1.28 Horizontal (TD) 1.30 1.26 1.28 1.33 Tensile elongation (%) Vertical (MD) 451 476 481 459 Transverse (TD) 449 462 462 478 E'(Pa) (heat resistance) Longitudinal (MD) 2.1χ106 2.9xl06 3-lxlO6 2.8xl06 Transverse (TD) 1.8χ106 3.〇χ106 2.9χ106 2.1χ106 Evaluation of heat resistance 〇〇〇 peeling 〇〇〇〇 mold size transferability 〇 0 〇〇 surface smoothness 〇〇〇〇 actual usability 〇〇〇〇 159436.doc 22- 201239016 [Table 3] Item Example 9 Example 10 Implementation Example 11 Membrane urethane-based elastomer type 1 1 1 parts by mass 100 100 100 Fluoride-based surfactant type 1 2 2 parts by mass 4 2 4 Thickness (μτη) 50 50 50 γ-ray irradiation dose (kGy) 250 250 250 Release film physical tensile modulus (N/mm2) Vertical (MD) 78.2 82.2 80.2 Transverse (TD) 77.4 74.1 73.4 50% Modulus (50〇/〇Mo) (N/mm2) Vertical (MD) 8.47 8.49 8.35 Transverse (TD) 8.33 8.44 8.10 50% Modulus _)/(TD) 1.02 1.01 1.03 100% Modulus (100% Mo) (N/mm2) Longitudinal (MD) 10.5 10.8 11.0 Transverse (TD) 10.5 10.5 10.3 (100% Mo) / (50% Mo) Vertical (MD) 1.24 1.27 1.32 Horizontal (TD) 1.26 1.24 1.27 Tensile elongation (%) Vertical (MD) 464 480 470 Horizontal (TD) 449 436 466 E' (Pa ) (heat resistance) Longitudinal (MD) 2.7χ106 2.4x106 2.5χ106 Transverse (TD) 2.〇χ1〇6 1·8χ106 2.2χ106 Evaluation of heat resistance 0 〇〇Removability 〇〇〇Mold size Transferability 〇0 Surface smoothness square square square square practical use of 0 billion 159436.doc 23- 201239016 [Table 4]

項目 比較例1 比較例2 比較例3 比較例4 膜 胺基甲酸酯系彈性體 種類 1 1 1 ETra膜 Aflex 100KN-500NT 厚度為100 μηι 質量份 100 100 100 氟系界面活性劑 種類 - - 質量份 - - - 厚度(μηι) 50 50 50 γ射線照射劑量(kGy) 未照射 30 600 拉伸彈性模數(N/mm2) 縱(MD) 73.9 74.6 79.1 933 橫(TD) 69.5 70.9 75.6 929 50% 模數(50% Mo)(N/mm2) 縱(MD) 8.04 8.20 8.12 22.5 橫(TD) 7.74 7.97 7.99 21.2 50% 模數(MD)/(TD) 1.04 1.03 1.02 1.06 離 型 膜 物 性 100% 模舞(100% Mo) (N/mm2) 縱(MD) 10.4 10.6 10.7 25.4 橫(TD) 10.0 10.5 9.89 22.8 (100% Mo)/(50°/〇 Mo) 縱(MD) 1.29 1.29 1.32 1.13 橫(TD) 1.29 1.32 1.24 1.08 拉伸伸長率(％) 縱(MD) 479 469 336 332 橫〇Ό) 454 458 325 348 E’(Pa)(耐熱強度） 縱(MD) 3.〇χ105 2.9χ105 9.8χ106 3.〇χ107 橫(TD) 1.7x10s 1.7χ105 8.1χ106 3.〇χ107 評 價 对熱性 X X 〇 〇 剝離性 X X 〇 〇 模具尺寸轉印性 X X X X 表面平滑性 X X X 〇 實際使用性 X X X X 159436.doc 24- 201239016 [表5]Item Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Membrane urethane-based elastomer type 1 1 1 ETra film Aflex 100KN-500NT Thickness 100 μηι parts by mass 100 100 100 Fluoride-based surfactant type - - Quality Parts - - - Thickness (μηι) 50 50 50 γ-ray irradiation dose (kGy) No irradiation 30 600 Tensile elastic modulus (N/mm2) Vertical (MD) 73.9 74.6 79.1 933 Horizontal (TD) 69.5 70.9 75.6 929 50% Modulus (50% Mo) (N/mm2) Vertical (MD) 8.04 8.20 8.12 22.5 Transverse (TD) 7.74 7.97 7.99 21.2 50% Modulus (MD) / (TD) 1.04 1.03 1.02 1.06 Release film properties 100% mode Dance (100% Mo) (N/mm2) Vertical (MD) 10.4 10.6 10.7 25.4 Horizontal (TD) 10.0 10.5 9.89 22.8 (100% Mo) / (50 ° / 〇 Mo) Vertical (MD) 1.29 1.29 1.32 1.13 Horizontal ( TD) 1.29 1.32 1.24 1.08 Tensile elongation (%) Vertical (MD) 479 469 336 332 Horizontal 〇Ό 454 458 325 348 E' (Pa) (heat resistance) Longitudinal (MD) 3.〇χ105 2.9χ105 9.8χ106 3.〇χ107 Transverse (TD) 1.7x10s 1.7χ105 8.1χ106 3.〇χ107 Evaluation of thermal XX 〇〇 peelability XX 〇〇 Mold size transferability XXXX Surface smoothness XXX 〇 Actually Of X X X X 159436.doc 24- 201239016 [Table 5]

項目 比較例5 比較例6 膜 胺基曱酸酯系彈性體 種類 ETFE 膜 Aflex 25N-1250NT 厚度為25 pm Hytrel 5577膜 厚度為50 μιη 質量份 氟系界面活性劑 種類 質量份 厚度(μηι) γ射線照射劑量(kGy) 離 拉伸彈性模數(N/mm2) 縱(MD) 933 173 橫(TD) 929 169 50% 模數(50% Mo)(N/mm2) 縱(MD) 22.5 12.6 橫(TD) 21.2 11.8 50% 模數(MD)/(TD) 1.06 1.07 型 膜 物 性 1 〇〇% 模數(100% Mo)(N/mm2) 縱(MD) 25.4 12.7 橫(TD) 22.8 11.8 (100% Mo)/(50°/〇 Mo) fe(MD) 1.13 1.01 橫(TD) 1.08 1.00 拉伸伸長率(％) 縱(MD) 332 522 橫(TD) 348 550 E'(Pa)(耐熱強度） 縱(MD) 3.1χ107 1.7x106 橫(TD) 3.2x107 1.9x1 〇6 評 價 耐熱性 0 0 剝離性 0 〇 模具尺寸轉印性 〇 〇 表面平滑性 〇 X 實際使用性 X X 以下’基於表1〜3，對離型用膜之製作、剝離性、财熱 性、模具尺寸轉印性、表面平滑性及實際使用性加以詳 述。再者，該等成為於表4 ' 5較例1〜6亦同樣地適用之内 容。 159436.doc •25· 201239016 (離型用膜之製作） 將熱塑性彈性體組合物供給至#40 mm、L/D=25之單軸 擠出機（IKG公司製造），使用壓縮比為2 5之全螺紋擠出螺 桿，於料缸溫度為l8(TC〜21(rc之條件下，進行熔融混 練，於鑄模溫度為210°C〜22(TC之條件下自寬度為4〇() mm 之T模連續地擠出。該擠出之未照射膜係於牵拉機内，自 壓接輥側將消光加工PET膜作為分隔件而供給，自冷卻輥 側將鏡面加工PET膜作為分隔件而供給’將該等夾於壓接 輥冷卻輥之間進行冷卻。於捲取機内利用切刀將兩端部裁 斷，將未照射膜捲取至捲取管上，藉此製造表丨〜3中記載 之厚度、且寬度為250 mm、長度為50 m之未照射膜。對 將該等未照射膜於80°c之氣體環境下放置24小時進行熟化 後’一面將分隔件之消光加工PET膜及鏡面加工PET膜剝 離 面重新捲繞離型膜而獲得之評價用離型膜照射表 1〜3所記載之劑量之γ射線，製備離型用膜。 (耐熱強度） 耐熱強度係藉由離型用膜之動態黏彈性測定中之溫度 180 C下的膜縱方向（MD)及膜橫方向（TD)之儲存彈性模數 進行《平仏。具體而言係使用Rhe〇metrics公司製造之 SOLIDSA NALYZERRSAII(商品名），於頻率為} Hz、應變 為〇.1 /°、升溫速度為5/min之條件下測定之儲存彈性模 數E’。該儲存彈性模數E'必須於膜縱方向（MD)及膜橫方向 (TD)上均為5 〇xl〇5 pa以上。若儲存彈性模數p未達 5·〇Χΐ〇 Pa’則存在如下之異常：於在18〇t左右之溫度下 I59436.doc -26· 201239016 之實際使用中’因鑄模樹脂之璧力而造成離型用膜破損。 (評價之方法） 评價係使用具備圖1所示之透鏡形狀之圖2(a)、（b)所示 之構成之鑄模模具30，使離型用膜吸附於鑄模模具3〇後， 滴加聚矽氧樹脂組合物而進行熱壓成形，分別對剝離性、 耐熱性、模具尺寸轉印性、表面平滑性進行評價。 具體而言，以於鑄模模具30中離型用膜之消光面成為鑄 模模具30側，鏡面成為空氣側之方式張設離型用膜，以真 空吸引而使離型用膜吸附於鑄模模具3〇 ^繼而，於離型用 膜上滴加聚矽氧樹脂組合物RH〇D〇RSIL RTvi4i (BLUESTAR SILICONES公司製造），於該等上貼屋表面經 硬鉻電鍍之平板模具，由兩個模具夾持進行熱壓成形。對 成形之積層品的離型用膜與硬化之聚矽氧樹脂之剝離性、 離型用膜之耐熱性、硬化之聚矽氧樹脂進行模具尺寸轉印 性與表面平滑性評價。熱壓成形係於溫度為14〇<)(：、壓力 為1 〇 kg/cm2、5分鐘之條件下實施。 (剝離性） 剝離性之評價係將硬化之聚矽氧樹脂組合物可不殘留於 離型用膜上地剝離之情形表示為「Q」，將聚錢樹脂組合 物部分性地破斷而殘存於離型用膜上之情形表示為「χ」。 (耐熱性） 耐熱性之評價係以目視觀察剝離了硬化之聚矽氧樹脂組 合物之離型用膜，將無熔融、熔化地保持膜形狀之情形表 示為「〇」，將離型用膜存在熔融、熔化之情形表示為 159436.doc -27- 201239016 「X」。 (模具尺寸轉印性） 模具尺寸轉印性係測定硬化之聚矽氧樹脂組合物之尺寸 而進行6平如。將透鏡高度之評價基準設為自孔深4 mm減去 離用膜之厚度而得之尺寸進一步_〇1 以内之範圍， 亦即，設為（(4-離型用膜之厚度）_〇1)mm以上。將乃個透 鏡全部於基準以内之情形表示為「。」，將即便存在1個未 滿足基準之形狀之情形表示為「X」。 (表面平滑性） 表面平滑性係以目視對硬化之聚矽氧樹脂組合物之表面 狀J進行β平彳貝。將聚石夕氧樹脂之表面未產生凹凸或褶皺之 情形表不為「〇」，將產生凹凸或褶皺之情形表示為「X」。 (實際使用性） 關於實際使用性，係藉由於鎊模成形裝置内進行樹脂禱 模成形而進行確認、、評價。具體而言，於作為模塑裝置的 APIC YAMADA公司製造之铸模成形裝置g une邮㈣Item Comparative Example 5 Comparative Example 6 Membrane-based phthalate-based elastomer type ETFE film Aflex 25N-1250NT Thickness 25 pm Hytrel 5577 Film thickness 50 μη mass parts fluorine-based surfactant type mass part thickness (μηι) γ-ray Irradiation dose (kGy) Deviation elastic modulus (N/mm2) Longitudinal (MD) 933 173 Transverse (TD) 929 169 50% Modulus (50% Mo) (N/mm2) Longitudinal (MD) 22.5 12.6 Transverse ( TD) 21.2 11.8 50% Modulus (MD) / (TD) 1.06 Type 1.07 Membrane Properties 1 〇〇% Modulus (100% Mo) (N/mm2) Vertical (MD) 25.4 12.7 Transverse (TD) 22.8 11.8 (100 % Mo)/(50°/〇Mo) fe(MD) 1.13 1.01 Transverse (TD) 1.08 1.00 Tensile elongation (%) Longitudinal (MD) 332 522 Transverse (TD) 348 550 E'(Pa) (heat resistance) Longitudinal (MD) 3.1χ107 1.7x106 Horizontal (TD) 3.2x107 1.9x1 〇6 Evaluation of heat resistance 0 0 Peelability 0 〇 Mold size transferability 〇〇 Surface smoothness 〇 X Actual use XX The following 'based on Table 1~ 3. The production, release property, heat recovery, mold size transferability, surface smoothness, and practical use of the release film are described in detail. Further, these are the same as those applicable to Tables 1 '5 and Examples 1 to 6. 159436.doc •25· 201239016 (Production of release film) The thermoplastic elastomer composition was supplied to a single-axis extruder (manufactured by IKG Corporation) of #40 mm and L/D=25, and the compression ratio was 2 5 . The full-thread extrusion screw is melt-kneaded at a cylinder temperature of l8 (TC~21 (rc), and the mold temperature is 210 ° C to 22 (the width is 4 〇 () mm under the condition of TC The T-die is continuously extruded. The extruded unirradiated film is supplied to a pulling machine, and the matte-processed PET film is supplied as a separator from the side of the pressure-bonding roll, and the mirror-finished PET film is supplied as a separator from the side of the cooling roll. 'These are sandwiched between the pressure roller cooling rolls and cooled. The both ends are cut by a cutter in a coiler, and the unirradiated film is wound up on the take-up tube, thereby producing the description in Table 3-5. An unirradiated film having a thickness of 250 mm and a length of 50 m. After the unirradiated film is left to stand in a gas atmosphere of 80 ° C for 24 hours for aging, the matte film of the separator is polished on one side and The mirror-finished PET film peeling surface was re-wound the release film and the evaluation was obtained by using the release film irradiation in Tables 1 to 3. The dose of gamma rays is used to prepare a release film. (Heat resistance) The heat resistance is measured by the dynamic viscoelasticity of the film for release film. The film longitudinal direction (MD) and film transverse direction (TD) at 180 C. The storage elastic modulus is used for "flat". Specifically, SOLIDSA NALYZERRSAII (trade name) manufactured by Rhe〇metrics Co., Ltd. is used at a frequency of Hz, a strain of 〇.1 /°, and a heating rate of 5/min. The stored elastic modulus E' is measured. The storage elastic modulus E' must be 5 〇xl 〇 5 pa or more in the longitudinal direction (MD) and the transverse direction (TD) of the film. If the storage modulus p is not Up to 5·〇Χΐ〇Pa' has the following abnormality: In the actual use of I59436.doc -26· 201239016 at a temperature of about 18 〇t, the film for the release film is damaged due to the force of the mold resin. Method for Evaluation) The mold was molded by using a mold 30 having the configuration shown in Figs. 2(a) and 2(b) having the lens shape shown in Fig. 1, and the release film was adsorbed to the mold 3, and then dropped. The polyoxyxene resin composition is subjected to hot press forming, and the peelability, heat resistance, and mold size are respectively transferred. Specifically, the matte surface of the film for release mold in the mold 30 is placed on the side of the mold 30, and the film for the release is placed on the air side, and is evacuated by vacuum suction. The film for the type is adsorbed to the mold mold 3, and then the polyoxyphthalocene resin composition RH〇D〇RSIL RTvi4i (manufactured by BLUESTAR SILICONES Co., Ltd.) is dropped on the release film, and the surface of the house is hard chrome plated. The flat plate mold is thermoformed by sandwiching two molds. The release property of the formed release product film and the cured polyoxymethylene resin, the heat resistance of the release film, and the cured polyoxymethylene resin were evaluated for mold size transferability and surface smoothness. The hot press forming was carried out under the conditions of a temperature of 14 〇 () and a pressure of 1 〇 kg/cm 2 , 5 minutes. (Releasability) The peelability was evaluated by curing the cured polyoxyxene resin composition. The case where the release film is peeled off is shown as "Q", and the case where the polyacetal resin composition is partially broken and remains on the release film is "χ". (Heat resistance) Heat resistance In the evaluation, the film for release film from which the cured polyoxynene resin composition was peeled off was visually observed, and the case where the film shape was not melted and melted was expressed as "〇", and the film for release film was melted and melted. 159436.doc -27- 201239016 "X". (Mold size transferability) Mold size transferability is measured by measuring the size of the hardened polyoxyxene resin composition, and the evaluation of the lens height is set to The size obtained by subtracting the thickness of the release film from the hole depth of 4 mm is further _〇1 or less, that is, ((the thickness of the film for 4-release type) _〇1) mm or more. When the lens is all within the reference, it is expressed as ".", even if there is one The case where the shape of the reference is satisfied is expressed as "X". (Surface smoothness) The surface smoothness is obtained by visually observing the surface of the hardened polyoxyxene resin composition. The case where no unevenness or wrinkles are generated is not "〇", and the case where unevenness or wrinkles are generated is expressed as "X". (Practical usability) Regarding practical use, resin prayer molding is performed by means of a pound molding apparatus. In addition, it is confirmed and evaluated. Specifically, it is a mold forming device manufactured by APIC YAMADA Co., Ltd. as a molding device.

PreSS(商品名）中，使用 RHODORSIL RTV141(BLUESTAR SILICONES公司製造）作為聚矽氧樹脂組合物，藉由目視 確認實際使用性。 貫際使用性之評價係將如下狀態設為「〇」：於在铸模成 形裝置内傳送離型用膜時於不使膜鬆弛之狀態下供給，於 吸附時臈不產生㈣’熱壓成形後，離型用膜與聚矽氧樹 脂組合物之剝離性良好，且硬化之聚矽氧樹脂組合物之表 面無凹凸或褶敏而平滑，離型用膜無破損紐斷，無聚石夕 159436.doc -28- 201239016 氧樹脂組合物之殘留，鑄模模具無污垢；將或多或少存在 異常之情形表示為「X」。 如表4、5所示，於不對與實施例卜4中所使用者相同之 包含1種胺基曱酸酯系彈性體之厚度為50 μηι之臈照射之比 較例1、照射少量之30 kGy之γ射線之比較例2中’結果是 耐熱性、剝離性、模具尺寸轉印性、表面平滑性均較差， 未能獲得實際使用性。又，於對相同之膜照射大量之6〇〇 kGy之γ射線之比較例3中，結果是模具尺寸轉印性、表面 平滑性均較差，未能獲得實際使用性。於比較例4中，以 旭硝子公司製造之ETFE膜、Aflex(商品名）之厚度1〇〇 μιη 者為比較對象，模具尺寸轉印性較差，未能獲得實際使用 性。於比較例5中，以旭硝子公司製造ETFE膜、Afie<商 品名）之厚度25 μηι者為比較對象，於吸附至鑄模模具内時 膜破損，未能獲得實際使用性。於比較例6中，以 DuPont公司製造之Hytrel 5577(商品名），亦即包含聚醋聚 醚共聚物、D硬度為55且維卡軟化溫度為192它之熱塑性彈 性體組合物的厚度為5〇 μηι之離型用膜為比較對象。於包 含聚矽氧樹脂組合物之成形品之表面產生褶皺，表面平滑 性較差，未能獲得實際使用性。 相對於此，如表1〜3所示，可明確本發明之各實施例之 離型用膜，除了獲得剝離性以外，亦具有耐熱性，且模具 尺寸轉印性與表面平滑性優異，進而賦予有實際使用性。、 由此可知：藉由本發明可獲得具有如下性質之離型用膜： 與對鑄杈樹脂進行成形加工而獲得之成形品之剝離性優 159436.doc •29· 201239016 異’並且可獲得形狀與表面性優異之成形品β 以上，使用實施形態對本發明進行了說明，本發明之技 術範圍當然並不限定於上述實施形態所記載之範圍。業者 應明白可對上述實施形態加以多種變更或改良。又由申 請專利範圍之記載可明確加以此種變更或改良之形態亦可 包含於本發明之技術範圍内。 【圖式簡單說明】 圖1係本發明之實施形態之砲彈型LED透鏡之側視圖。 圖2 ( a)係本發明之實施形態之砲彈型L E D透鏡之鑄模模 具的俯視圖。圖2(b)係本發明之實施形態之砲彈型led透 鏡之鑄模模具的圖2(a)之A-A箭頭方向指向剖面圖。 圖3係表不本發明之實施形態之離型用膜膜製造裝置之 概略構成的圖。 圖4係表示本發明之實施形態的圖2所示之膜製造裝置之 材料投入料斗之周邊的剖面圖。 【主要元件符號說明】 1 擠出機 2 材料投入料斗 3 氮氣供給用導管 4 連接管 5 過濾器 6 齒輪泵 7 T模 7a 模唇部 159436.doc -30- 201239016 8 未照射膜 9 壓接輥 10 冷卻輥 11 牵拉機 12、13 傳送輥對 14 厚度測定器 16 捲取管 17a、17b 送出輥 18a' 18b 分隔件 20 砲彈型LED透鏡 21a、21b 導線 30 鑄模模具 31 透鏡成形凹部 159436.doc -31 ·In the PreSS (trade name), RHODORSIL RTV141 (manufactured by BLUESTAR SILICONES Co., Ltd.) was used as a polyoxyxylene resin composition, and the actual usability was visually confirmed. In the evaluation of the continuation of the use, the following state is set to "〇": when the film for release film is conveyed in the mold forming apparatus, the film is supplied without being loosened, and the film is not produced during the adsorption (4) after the hot press forming The release film and the polyoxymethylene resin composition have good peelability, and the surface of the cured polyoxymethylene resin composition has no unevenness or pleats and is smooth, and the release film has no breakage, and no polylithic eve 159436 .doc -28- 201239016 Residue of the oxygen resin composition, the mold of the mold is free of dirt; the case where there is more or less abnormality is expressed as "X". As shown in Tables 4 and 5, Comparative Example 1 in which the thickness of one of the amino phthalate-based elastomers having the same thickness as that of the user of Example 4 was 50 μηη was irradiated, and a small amount of 30 kGy was irradiated. In Comparative Example 2 of the gamma ray, the results were poor in heat resistance, peelability, mold size transferability, and surface smoothness, and practical use was not obtained. Further, in Comparative Example 3 in which a large amount of γ ray of 6 〇〇 kGy was irradiated to the same film, the mold size transfer property and the surface smoothness were both poor, and practical use was not obtained. In Comparative Example 4, the thickness of the ETFE film manufactured by Asahi Glass Co., Ltd. and the thickness of Aflex (trade name) of 1 〇〇 μηη were compared, and the mold size transferability was poor, and practical use was not obtained. In Comparative Example 5, the thickness of 25 μm of the ETFE film manufactured by Asahi Glass Co., Ltd. and the Afie<trade name) was compared, and when it was adsorbed into the mold, the film was broken, and practical use was not obtained. In Comparative Example 6, Hytrel 5577 (trade name) manufactured by DuPont Co., Ltd., which is a polyester elastomer composition having a D hardness of 55 and a Vicat softening temperature of 192, has a thickness of 5 The release film of 〇μηι was used as a comparison object. Wrinkles were formed on the surface of the molded article containing the polyoxyxylene resin composition, and the surface smoothness was poor, and practical use was not obtained. On the other hand, as shown in Tables 1 to 3, it is clarified that the release film of each of the examples of the present invention has heat resistance and is excellent in mold size transferability and surface smoothness, in addition to the release property. Give practical use. From this, it can be seen that the release film having the following properties can be obtained by the present invention: the peeling property of the molded article obtained by molding the cast resin is excellent 159436.doc •29·201239016 The molded article having excellent surface properties is described above. The present invention has been described using the embodiment, and the technical scope of the present invention is of course not limited to the range described in the above embodiment. It will be appreciated by those skilled in the art that various changes and modifications can be made in the embodiments described above. It is also possible to clarify that the form of the change or the improvement is also included in the technical scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a side view of a bullet-type LED lens according to an embodiment of the present invention. Fig. 2 (a) is a plan view showing a mold of a projectile type L E D lens according to an embodiment of the present invention. Fig. 2 (b) is a cross-sectional view taken along the line A-A of Fig. 2 (a) of the casting mold of the bullet-type led lens according to the embodiment of the present invention. Fig. 3 is a view showing a schematic configuration of a film forming apparatus for release film according to an embodiment of the present invention. Fig. 4 is a cross-sectional view showing the vicinity of a material input hopper of the film production apparatus shown in Fig. 2 according to an embodiment of the present invention. [Explanation of main components] 1 Extruder 2 Material input hopper 3 Nitrogen supply conduit 4 Connection pipe 5 Filter 6 Gear pump 7 T-die 7a Lip lip 159436.doc -30- 201239016 8 Uncoated film 9 Crimp roller 10 Cooling roller 11 Pulling machine 12, 13 Transfer roller pair 14 Thickness measuring device 16 Winding pipe 17a, 17b Feeding roller 18a' 18b Separator 20 Cannonball type LED lens 21a, 21b Wire 30 Molding mold 31 Lens forming recess 159436.doc -31 ·

Claims (1)

201239016 七、申請專利範圍： 1. 一種離型用膜，其特徵在於：其係對單獨包含JIS A硬度 為70以上且維卡軟化溫度為1〇〇〜180t之聚胺基甲酸酯 系彈性體或者包含以該聚胺基曱酸酯系彈性體為主成分 之熱塑性彈性體組合物之膜照射電離放射線而成。 2. 如請求項1之離型用膜，其中，上述聚胺基曱酸酯系彈 性體係錯由聚異氛酸醋、多元酵及鍵延長劑之3種成分 之反應而獲得之熱塑性聚胺基曱酸酯系彈性體。 3. 如請求項2之離型用膜，其中，上述多元醇係選自屬於 由聚酯多元醇、聚酯醯胺多元醇、聚碳酸酯多元醇、聚 醚多元醇、聚醚酯多元醇、及聚烯烴多元醇所組成之群 之數量平均分子量為5004 〇〇〇〇之高分子多元醇中的1種 或複數種。 4. 如請求項2之離型用膜，其中，上述鏈延長劑係選自屬 於低分子多元醇類、低分子多元胺類、及低分子胺基醇 類之數量平均分子量未達5〇〇之含活性氫之化合物。 5. 如請求項3之離型用膜’其中’上述鏈延長劑係選自屬 . 於低分子多元醇類、低分子多元胺類、及低分子胺基醇 類之數量平均分子量未達5〇〇之含活性氫之化合物。 .6·如請求項1至5令任-項之離型用膜，其中上述熱塑性彈 體’且口物係相對於上述聚胺基甲酸酯系彈性體_質 量份而含有0泰5.0質量份之範圍的Μ界面 組合物。 ^之 •、項6之離型用膜’其中上述氟系界面活性劑係熔 159436.doc 201239016 /皿度為300C以上之全氟烧基項酸 點為250°C以下且分解 衍生物化合物。 8. 9. 如請求項1至5中任—Jg 左 項之剝離膜，其中上述熱塑性彈性 體組合物進而包含丨# 1種或複數種屬於潤滑劑、抗結塊 劑、抗氧化劑、及磷系抗氧化劑之添加劑。 如請求項1至5中任—項 唄之離型用膜，其中上述電離放射 線之照射係使用選自由晴線、β射線、電子束、中子射 線X射，線ϋ 60輻射源之7射線所組成之群中之1種， 以50〜500 kGy之劑量進行。 10.如明求項1至5中任一項之雜刑田描 ，义離型用膜，其中膜之拉伸彈性 模數於膜縱方向（MD)及膜搭 v〜汉膜楨方向（td)上均為10〜500 N/mm2之範圍。 11. 如請求項1至5中任-項之離型㈣，其中膜之5_數 (5〇% Mo)之膜縱方向（MD)與膜橫方向（td)之比（md)/ (TD)為0.9〜1·2之範圍。 12. 如請求項！至5中任一項之離型用膜，其中膜之5〇%模數 (50% 厘〇)與100%模數（100% Μ〇)之比（1〇〇% μ〇)/(5〇% Mo)於膜縱方向（MD)及膜橫方向（TD)上均為i 〇〜丨6之範 圍。 13.如請求項1至5中任一項之離型用膜，其中膜之拉伸伸長 率於膜縱方向（MD)及膜橫方向（TD)上均超過35〇%。 159436.doc201239016 VII. Patent application scope: 1. A film for release film, characterized in that it is a polyurethane-based elastic layer containing JIS A hardness of 70 or more and Vicat softening temperature of 1 〇〇 to 180 t. The film or the film containing the thermoplastic elastomer composition containing the polyamino phthalate elastomer as a main component is irradiated with ionizing radiation. 2. The release film according to claim 1, wherein the polyamine phthalate-based elastic system is obtained by reacting three components of polyisoleic acid vinegar, multi-enzyme and a bond extender to obtain a thermoplastic polyamine. A bismuth phthalate elastomer. 3. The release film according to claim 2, wherein the polyol is selected from the group consisting of polyester polyols, polyester decylamine polyols, polycarbonate polyols, polyether polyols, polyether ester polyols And one or more of the polymer polyols having a number average molecular weight of 5004 Å, which is composed of a polyolefin polyol. 4. The release film according to claim 2, wherein the chain extender is selected from the group consisting of low molecular polyols, low molecular weight amines, and low molecular weight amines having an average molecular weight of less than 5 Å. A compound containing active hydrogen. 5. The release film according to claim 3, wherein the chain extender is selected from the group consisting of low molecular weight polyols, low molecular weight polyamines, and low molecular weight amine alcohols having a number average molecular weight of less than 5 A compound containing active hydrogen. The release film according to any one of claims 1 to 5, wherein the thermoplastic elastomer 'and the mouth material are 0 to 5.0 mass with respect to the mass of the polyurethane elastomer. A range of Μ interface compositions. The film for release film of the item 6 wherein the fluorine-based surfactant is melted 159436.doc 201239016 / the perfluoroalkyl group acid point having a degree of 300 C or more is 250 ° C or lower and the derivative compound is decomposed. 8. The release film according to any one of claims 1 to 5, wherein the thermoplastic elastomer composition further comprises 丨#1 or a plurality of lubricants, anti-caking agents, antioxidants, and phosphorus. It is an additive for antioxidants. The release film according to any one of claims 1 to 5, wherein the irradiation of the ionizing radiation is performed by using 7 rays selected from the group consisting of a clear line, a beta ray, an electron beam, a neutron ray X-ray, and a line ϋ 60 radiation source. One of the group consisting of is carried out at a dose of 50 to 500 kGy. 10. The method according to any one of claims 1 to 5, wherein the tensile modulus of the film is in the longitudinal direction of the film (MD) and the direction of the film v~ Han film ( Both td) are in the range of 10 to 500 N/mm2. 11. The release (4) of any one of claims 1 to 5, wherein the ratio of the longitudinal direction (MD) of the film to the transverse direction (td) of the film (5 〇 % Mo) is (md) / ( TD) is in the range of 0.9 to 1.2. 12. As requested! The film for release film according to any one of 5, wherein a ratio of a 〇% modulus (50% 〇) of the film to a 100% modulus (100% Μ〇) (1〇〇% μ〇) / (5) 〇% Mo) is in the range of i 〇 to 丨6 in the longitudinal direction (MD) of the film and the transverse direction (TD) of the film. The release film according to any one of claims 1 to 5, wherein the tensile elongation of the film exceeds 35 % in both the longitudinal direction (MD) of the film and the transverse direction (TD) of the film. 159436.doc