TW201038637A - Hard coat film for molding - Google Patents

Hard coat film for molding Download PDF

Info

Publication number
TW201038637A
TW201038637A TW099104065A TW99104065A TW201038637A TW 201038637 A TW201038637 A TW 201038637A TW 099104065 A TW099104065 A TW 099104065A TW 99104065 A TW99104065 A TW 99104065A TW 201038637 A TW201038637 A TW 201038637A
Authority
TW
Taiwan
Prior art keywords
film
molding
mass
hard coating
coating film
Prior art date
Application number
TW099104065A
Other languages
Chinese (zh)
Other versions
TWI437034B (en
Inventor
Katsufumi Kumano
Kaoru Sawada
Kenichi Mori
Mikiya Hayashibara
Yuki Haraguchi
Original Assignee
Toyo Boseki
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Boseki filed Critical Toyo Boseki
Publication of TW201038637A publication Critical patent/TW201038637A/en
Application granted granted Critical
Publication of TWI437034B publication Critical patent/TWI437034B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention provides a hard coat film for molding having excellent surface hardness and scratch resistance, it also has an excellent molding ability and solvent resistance under low temperature and low pressure. The hard coat film for molding has a substrate film and a hard layer, wherein the substrate film consists of a biaxially oriented polyester film containing a copolymerized polyester and the hard layer is formed by coating a coating solution then hardening. The coating solution comprises an ionizing radiation-hardening compound having at least 3 or more functional groups, and an ionizing radiation-hardening compound having 1 and/or 2 functional groups. The amount of the ionizing radiation-hardening compound having 1 and/or 2 functional groups of the ionizing radiation-hardening compound contained in the coating solution ranges from 5 mass% or more to 95 mass% or less; and the substrate film satisfies the following requirements (1) to (3): (1) the 100% stretching stresses in both the longitudinal direction and the width direction are 40 to 300 MPa at 25 DEG C and 1 to 100 MPa at 100 DEG C; (2) the melting temperature is 200 to 245 DEG C; and (3) the surface orientation ranges from 0.01 or more to less than 0.11.

Description

201038637 六、發明說明： 【發明所屬之技術領域】 本發明與一種成型用硬被覆膜有關。詳言之，與表面 硬度及耐擦傷性優異，且在低溫度及低壓力下之成型性及 耐溶劑性優異之一種成型用硬被覆膜有關。另外，亦與具 有適合使用於屋外用途之耐光性成型用硬被覆膜有關。 【先前技術】 成型用片材向來以聚氯乙烯樹脂薄膜具代表性，由加 工性等之觀點而被喜好使用。另一方面，該薄膜因火災等 而燃燒時有發生有毒氣體之問題及增塑劑滲出之問題等， 由於近年來耐環境性之需要，故需求環境負擔小之新原料。 爲滿足上述要求，由非氯系原料之聚酯、聚碳酸酯、 及丙烯酸系樹脂所組成之未拉伸片材在廣泛領域使用。尤 其由聚酯系樹脂所組成之未拉伸片材，因其機械特性及透 明性良好且經濟性優異而備受注目。例如已有文獻1〜5記 載將聚對酞酸乙二酯中之約30莫耳％乙二醇成分以1，4-環己烷二甲醇取代之實質上非結晶之聚酯系樹脂爲構成成 分之未拉伸聚酯系片材（如參照專利文獻1〜5)。 上述未拉伸聚酯系片材在關於成型性或積層適合性方 面雖能滿足市場需求’但由於屬未拉伸片材，故耐熱性及 耐溶劑性不充分而未達成滿足市場之高度需求。 爲解決上述課題，有提出使用雙軸拉伸聚對酞酸乙二 酯薄膜之方法（如參照專利文獻6〜9)。 但上述方法雖能改善耐熱性及耐溶劑性，但成型性則 201038637 不充分’由總合性品質均衡之觀點而言未能滿足市場需 求。又在使用於屋外用途方面，因日光照射而引起印刷層 或樹脂容易進行變性 '變質，產生不耐長期使用之課題。 另一方面’將成型用薄膜安裝在與外部接觸位置時， 爲防止受傷，以補強成型用薄膜之表面硬度及提升耐擦傷 性爲目的，在其表面設置硬化層。 在成型用薄膜設置硬化層之方法，一般以氣壓成型法 _ 或真空成型法進行成型後，利用浸漬法、噴霧法等後加工 〇 方法，將硬化層進行積層。但此種方法係以枚葉式（cluster type)加工進行硬化層之積層，故除提升生產速度有限外， 品質之安定性亦有問題。因此，現近需求以卷對卷方式（roll to roll type)加工將硬化層設置在成型前之薄膜上後再進行 成型以製得成型體。 在成型前積層硬化層之方式而言，其硬化層所希求之 特性，除須要具有與以成型後之後加工方法設置硬化層之 〇 方法相同程度之表面硬度及耐擦傷性外，同時亦須要伴隨 成型發生變形時能夠追隨之成型性。但一般之硬化層樹 脂，爲滿足表面硬度而使硬化層過硬而無成型性，故因成 型加工時發生變形而有硬化層發生紋裂（硬化層之破裂）之 問題。 因此，有先前技術提出將硬化後具有一定程度表面硬 度但仍有柔軟性之樹脂進行積層而提升成型性之硬被覆 膜，或將具有柔軟性之層與具有強表面硬度之層在基材上 201038637 多數積層，以製得具有強表面硬度及彎曲性之硬被覆膜（參 照專利文獻10〜13)。 (專利文獻1)特開平9 — 1 56267號公報 (專利文獻2)特開200 1 — 7 1 669號公報 (專利文獻3)特開200 1 — 8025 1號公報 (專利文獻4)特開200 1 — 1 2995 1號公報 (專利文獻5)特開2002 — 24965 2號公報 (專利文獻6)特開平9一 1 87 903號公報 (專利文獻7)特開平1 0 - 296937號公報 (專利文獻8)特開平1 1 一 10816號公報 (專利文獻9)特開平11 一 2682 1 5號公報 (專利文獻10)特開2005 — 3053 83號公報 (專利文獻11)特開2007 - 284626號公報 (專利文獻12)特開2007 — 3 1 3728號公報 (專利文獻13)國際公開第2008/029666號說明小册 【發明內容】 「發明欲解決之課題」 但，專利文獻10、11所提出之硬被覆膜，雖具有適當 之表面硬度，但關於其成型性則僅具有彎曲性及打孔加工 之限定性加工特性；而專利文獻1 2所提出之硬被覆膜’雖 具有拉伸性，但表面硬度則不能滿足。又，專利文獻1 3所 提出之硬被覆膜，雖試圖使表面硬度與成型性並存’但在 需要更高度成型性或更高度表面硬度之領域’有時無法發 201038637 揮充分之性能。亦即，上述專利文獻在不損害具有成型性 及耐溶劑性優異特性之成型用聚酯薄膜之特性下，無法提 供同時滿足高表面硬度與高成型性雙方特性之成型用硬被 覆膜。 本發明之目的乃爲解決上述課題，亦即對於在低溫度 下及低壓力下之成型性及耐溶劑性優異之成型用薄膜，在 其成型前階段將硬化層加工、積層在成型用薄膜上，能夠 對提升生產性、品質安定性有所貢獻，且兼備表面硬度、 Ο 耐擦傷性及伴隨成型發生變形時之隨動成型性雙方特性之 成型用硬被覆膜。 「解決課題之方法」 能夠解決上述課題之本發明之成型用聚酯薄膜由下述 各項構成。 本發明之第1項發明爲具有由含共聚聚酯之雙軸定向 聚酯薄膜所構成之基材薄膜及塗布塗布液硬化而成之硬化 Q 層之一種成型用硬被覆膜， 上述塗布液至少含有具3以上之官能基之游離放射線 硬化型化合物、及1及/或2官能基之游離放射線硬化型化 合物， 上述塗布液所含游離放射線硬化型化合物中之1及/或 2官能基之游離放射線硬化型化合物含量爲5質量％以上、 9 5質量％以下， 上述基材薄膜滿足下列（1)〜（3)之必要條件： 201038637 (1) 薄膜之長度方向及寬度方向拉伸100 %時之應力均 爲在25°C下爲40〜300MPa及100°C下爲1〜lOOMPa; (2) 熔點爲200〜245 °C ; (3) 平面定向度爲0.01以上、0.095以下。 第2項發明爲上述塗布液所含游離放射線硬化型化合 物中之至少1種爲具胺基之游離放射線硬化型化合物之上 述成型用硬被覆膜。 第3項發明爲上述硬化層中含有平均粒徑10nm以上、 300nm以下之粒子，且硬化層中之該粒子含量爲5質量％以 上、70質量％以下之上述成型用硬被覆膜。 第4項發明爲上述共聚聚酯爲（a)由芳香族二羧酸成 分、乙二醇、及含有支鏈狀脂肪族二醇或脂環族二醇之二 醇成分所構成之共聚聚酯；或（b)由含有對酞酸及異對酞酸 之芳香族二羧酸成分及含有乙二醇之二醇成分所構成之共 聚聚酯之上述成型用硬被覆膜。 第5項發明爲上述構成該雙軸定向聚酯薄膜之聚酯， 其二醇成分含有1,3-丙二醇單位或1,4- 丁二醇單位之上 述成型用硬被覆膜。 第6項發明爲上述雙軸定向聚酯薄膜含有紫外線吸收 劑，其在波長370nm下之光線透射率爲50 %以下之上述成 型用硬被覆膜。 第7項發明爲應用上述成型用硬被覆膜以真空成型、 氣壓成型及模具成型之任一方法進行成型之成型體。 201038637 發明效果 本發明之成型用硬被覆膜具有在低溫度下及低壓力下 加熱成型時之成型性優異，且具有良好之耐溶劑性。再加 上本發明之成型用硬被覆膜具有表面硬度與耐擦傷性及能 夠追隨成型時變形之隨動成型性之雙方特性。本申請發明 之成型用硬被覆膜因具備高表面硬度及優異拉伸性，故其 實施方式可適合使用於如銘板用或建材用部品。又，於本 申請發明之適當實施方式，使用具有胺基之游離放射線硬 ❹ 化型樹脂及/或粒子時，能夠使表面硬度與成型性之雙方特 性更高度並存，適合使用於如箱體等之部品。再者，本發 明不需要成型後之硬被覆膜加工，在成型加工製造上對於 生產性及品質安定性有所貢獻。 又，於本發明之適當實施方式，在薄膜中含有紫外線 吸收劑以減低紫外線範圍之透射率結果，能夠賦予耐光 性，特別適合當做使用於屋外用途之成型材料。 〇 【實施方式】 關於實施本發明之方式，首先說明本發明之基材薄膜 物性之技術性意義。其次說明本發明之基材薄膜之製造方 法。並再說明本發明之硬化層。 (基材薄膜） 於本發明，所謂100%拉伸時之應力（F100)爲與薄膜之 成型性有密接相關之尺度。F100與薄膜之成型性具有密接 相關之理由爲例如以真空成型法將雙軸定向聚酯薄膜成型 201038637 時，薄膜在模具之角落附近有時局部性拉伸100%以上。就 F1 00高之薄膜而言，認爲在此種局部性拉伸部位產生部分 性之極高應力，因該應力之集中使薄膜斷裂而導致成型性 減低。反之，在F 1 00過小之薄膜而言，則認爲成型性雖變 良好，但在如模具平面部均勻拉伸之部位僅產生極弱之張 力，結果薄膜在該部位似無法獲得均勻之拉伸。 在本發明，關於對應成型時之溫度而與成型性有相關 之物性採用在100°C下拉伸100%時之應力（F10(h。。）。又， 關於使用有凹凸或窪陷之模具進行成型時，預先將成型前 薄膜與此種模具輕輕隨動成型而與成型性有相關之物性採 用在25°C下拉伸100%時之應力（F10〇25)。 本發明之薄膜，在25°C下拉伸100%時之應力（F10〇25) 無論薄膜之長度方向及寬度方向均爲40〜300MPa。 薄膜之長度方向及寬度方向之F10〇25均爲40〜3 00MPa 時，其下限値以50MPa爲宜，並以60MPa較佳、超過70MPa 更佳。而上限値以250MPa爲宜，並以200MPa較佳、180MPa 更佳。如F10〇25未達40MPa，則將輥狀薄膜牽引退卷（開卷） 時，因薄膜伸長或破裂使操作性不良。反之，如F 1 0〇25超 過3OOMPa，則使成型性不良。尤其使用有凹凸或窪陷之模 具進行成型時，可能預先將成型前薄膜與此種模具隨動成 型。此時薄膜不易附著於模具，使成品之設計性不良。 又，本發明之薄膜，在100°C下拉伸 100%時之應力 (F10〇l()〇無論薄膜之長度方向及寬度方向均爲1〜lOOMPa -10- 201038637 爲重要。 由成型性 佳。另一 形態安定 更佳、超 方向之熱 下限値以 收縮率上 算製造在 I 0.01%之 見顯著差 熱收縮率 方向及寬 鍍或印刷 進行後加 (thickness ，成型體 基材薄膜 0.5 %以上 薄膜之長度方向及寬度方向F10〇1()D之上限， 之觀點以90MPa爲較佳、80MPa更佳、70MPa特 方面，F100!。。之下限，由使用成型品時之彈性及 性之觀點，以5MPa爲佳、lOMPa較佳、20 MPa 過3 5 Μ P a特佳。 本發明之薄膜，在150 °C下之長度方向及寬度 收縮率以〇.〇1〜5.0 %爲宜。在150 °C之熱收縮率 ❹ 0.1 %爲宜，並以0.5 %較佳。另一方面，I50°c之熱 限蟫以4·5%爲宜，並以4.1%較佳、3.2%更佳。就 150°C之長度方向及寬度方向之薄膜熱收縮率未達 成型用雙軸拉伸聚酯薄膜，其在實用上之效果未 異，並由於生產性極度減低，故沒有使在150°C之 未達0.01 %之必然性。另一方面，在150 °C之長度 度方向之薄膜熱收縮率超過5.0%時，在蒸鏟、濺 Q 等需要熱之後處理步驟容易使薄膜變形，有時使 工後之薄膜外觀或設計性不良。 又，本發明之基材薄膜之厚薄不均 unevenness)以5%以下爲宜。厚薄不均超過5%時 表面之平面性惡化，可能使成型體之強度減低。 之厚薄不均以較小較好，但由生產性之觀點，以 爲佳。 又於本發明’薄膜之霧度爲0.1〜3.0 %爲宜。霧度之下 201038637 限値以0_3%較佳、〇_5%更佳。另—方面，霧度之上限値以 2.5 %較佳、2.0%更佳。霧度未達〇1%之薄膜由於滑動性差 故以一般之生產性工業規模進行生產困難。另一方面，薄 膜之霧度超過3.0%時，由薄膜背面看金屬等之蒸鍍或濺鍍 面或印刷面等時’金屬或印刷面看起來不鮮明，使設計性 差劣。 在本發明’薄膜之平面定向度（△ p)亦爲與成型性有相 關之物性’平面定向度愈高分子鏈愈向平面方向定向，使 成型性減低。在本發明，薄膜之平面定向度爲未達〇.n。 平面定向度之上限以0.095以下較佳、0.090更佳。又，平 面定向度愈小則成型性愈好’但薄膜之強度、耐藥劑性易 減低。因此，平面定向度之下限爲〇.〇1以上，並以〇.〇2較 佳、0.03更佳、0.04特佳。 (基材薄膜之製造方法） 本發明之成型用聚酯薄膜，使用共聚聚酯當做原料。 共聚聚酯以（a)由芳香族二羧酸成分、乙二醇、及含有支鏈 狀脂肪族二醇或脂環族二醇之二醇成分所構成之共聚聚 酯；或（b)由含有對酞酸及異對酞酸之芳香族二羧酸成分及 含有乙二醇之二醇成分所構成之共聚聚酯爲適合。又，構 成雙軸定向聚酯薄膜之聚酯，其二醇成分如再含有1,3 -丙 二醇單位或1,4 - 丁二醇單位，由進一步提升成型性之觀點 爲較佳。 在本發明，薄膜原料以單獨之共聚聚酯、摻混丨種以 -12- .201038637 上之均聚聚酯或共聚聚酯、或組合均聚聚酯與共聚聚酯等 任何方法均爲可能。其中以摻混法在抑制熔點減低之觀點 爲適合。 至於上述共聚聚酯，如使用由芳香族二羧酸成分、乙 二醇、及含有支鏈狀脂肪族二醇或脂環族二醇之二醇成分 所構成之共聚聚酯時，芳香族二羧酸成分以對酞酸、異酞 酸、萘二甲酸或此等之酯形成性衍生物較適合，相對於二 羧酸成分之對酞酸及/或萘二甲酸成分量，以70莫耳％以上 爲宜，並以8 5莫耳％以上較佳、9 5莫耳％以上更佳、1 〇〇 莫耳％特佳。 又，支鏈狀脂肪族二醇可例示如新戊二醇、1，2 -丙二 醇、1，3 -丙二醇、1，4 - 丁二醇等。脂肪族二醇可例示如 1，4-環己二甲醇、二羥甲基三環癸烷等。 其中，以新戊二醇及1，4-環己二甲醇特別適合。再 者’於本發明，除上述二醇成分外再將1,3 -丙二醇及1，4_ 〇 丁二醇當做共聚成分爲更適合之實施方式。使用此等二醇 當做共聚成分時，在賦予上述特性上爲適宜，且透明性及 耐熱性優異’並由提升與附著性改質層之附著性之觀點亦 適合。 又’上述共聚聚酯’如使用由含對酞酸及異酞酸之芳 香族二羧酸成分及含乙二醇之二醇成分所構成之共聚聚酯 時’相對於總二醇成分量，乙二醇以7 0莫耳％以上爲宜， 並以85莫耳％以上較佳、95莫耳％以上更佳、1 00莫耳％特 -13- 201038637 佳。乙二醇以外之二醇成分以上述支鏈狀脂肪族二 環族二醇或二乙二醇較適合。 上述共聚聚酯’由成型性、附著性、製膜安定 點’其固有黏度（intrinsic viscosity)爲 0.50dl/g 以上 〇.55dl/g以上更佳、0.60 dl/g以上特佳。固有黏 0.50dl/g時有成型性減低之趨勢。又在熔融線（inelt (或熔融途中）爲除去異物而設置過濾器時，由擠出 脂時排出安定性之觀點’固有黏度之上限以設定爲 較宜。 在本發明’使用1種以上之均聚聚酯或共聚聚 薄膜原料，並將此等摻混以製造薄膜結果，在維持 用共聚聚酯同等之柔軟性下能夠實現透明性與高爽 熱性）。又相對於僅使用高熔點均聚聚酯（如對酞酸 酯）’在維持高透明性下能夠實現柔軟性及實用上不 之熔點（耐熱性）。再者，基材薄膜具有2層以上之 構時，各層之共聚成分量雖然可相同或相異，但以 種以上共聚成分量不同之聚酯樹脂亦爲本發明之較 方式。 又，將上述共聚聚酯與聚對駄酸乙二酯以外之 種以上之均聚聚酯（如聚對酞酸四亞甲（又伸丁二）酯 酞酸丁二酯）摻混而當做本發明之成型用聚酯薄膜 使用時，由成型性之觀點爲更佳。 上述聚酯薄膜之熔點，由耐熱性及成型性之觀 醇及脂 性之觀 較佳、 度未達 line)上 熔融樹 1 .Odl/g 酯當做 與僅使 穿點（耐 聚乙二 成問題 多層結 使用2 佳實施 至少1 及聚對 之原料 點，以 -14 - 201038637 200〜24 5 °C爲要。控制所使用聚合物種類及組成，並將製 膜條件控制在上述熔點範圍內之結果，取得成型性與完成 性之均衡’能夠以經濟性生產高品位之成型品。 在此所謂熔點，即指以示差掃瞄式熱量測定法（DSC、 Differential Scanning Calorimetry)之 1 次升溫時所檢測熔 解時之吸熱波峰溫度。該熔點使用示差掃瞄式熱量計（如 Max Science公司製、DSC3100S)，以升溫速度20。(：/分進行 測定求得。熔點之下限値以210°C更佳、230°C特佳。熔點 未達200°C時’耐熱性有惡化之趨勢。因此成型時或使用成 型品時如曝露於高溫有可能發生問題。又，不具有熔點之 非晶質聚酯則在機械性強度及耐藥劑性方面有可能發生問 題。 又，基材薄膜在波長370nm下之光線透射率以50%以 下爲佳、40%以下更佳、30%以下特佳。將成型用聚酯薄膜 在波長370nm下之光線透射率控制在50%以下之結果，如 該薄膜實施印刷時能夠提升印刷層之耐光性，此爲本發明 之較佳實施方式。 上述將波長370nm下之光線透射率控制在50%以下之 方法，使用配合紫外線吸收劑於基材薄膜構成層之任一層 中之方法。紫外線吸收劑只要能夠賦予上述特性者，則無 機系或有機系均可。有機系紫外線吸收劑如苯并三唑系、 二苯甲酮系、環狀亞胺酯系等及其組合。由耐熱性之觀點 以苯并三唑系及環狀亞胺酯系較適合。倂用2種以上之紫 -15- 201038637 外線吸收劑時，由於能夠同時吸收各不同波長之紫外線， 可進一步改善紫外線吸收效果。 苯并三唑系紫外線吸收劑可舉例如·· 2 - [2,-羥基_ 5’ -(甲基丙烯醯氧甲基）苯基]—2H -苯并三唑、2 — [2，— 經基-5’-(甲基丙烯醢氧乙基）苯基]—2H-苯并三唑、2_ [2’-徑基-5’-(甲基丙烯醯氧丙基）苯基]-2H-苯并三 唑、2 - [2’-羥基-5’-(甲基丙烯醯氧己基）苯基]-2H-苯并三唑、2 - [2，-羥基-3’-三級丁基-5，-(甲基丙烯醯 氧乙基）苯基]-2H -苯并三唑、2 - [2，-羥基-5’-三級丁 基-3’-(甲基丙烯醯氧乙基）苯基]-2H -苯并三唑、2-[2’-羥基-5’-(甲基丙烯醯氧乙基）苯基]-5 -氯-2H-苯并三唑、2 - [2’-羥基-5’-（甲基丙烯醯氧乙基）苯基]-5 -甲氧基-2H -苯并三唑、2 - [2’ -羥基-5’-(甲基丙烯 醯氧乙基）苯基]-5 -氣基-2H -苯并三哇、2 - [2,-羥 基-5’-(甲基丙烯醯氧乙基）苯基]-5 -三級丁基-2H-苯并三唑、2 - [2’-羥基-5’ -（甲基丙烯醯氧乙基）苯基]_ 5 -硝基-2H -苯并三唑等’但不特別限定於此等。 環狀亞胺酯系紫外線吸收劑可舉例如：2，2 ’ —（1，4 -伸 苯基）雙（4H - 3,1-苯并噚畊-4 -酮）、2 -甲基-3,1-苯 并曙畊酮、2_ 丁基_3，1-苯并曙阱_4 -酮、2 -苯 基-3,1-苯并晤畊-4 -酮、2 - (1或2 -萘基）-3，1-苯 并噚阱_ 4_酮、2_ (4_聯苯基）- 3，1_苯并噚畊_ 4-酮、對硝苯基-3,1-苯并曙阱-4_酮、2 —間硝苯基_ 16 - 201038637 3,1-苯并噚哄-4 -酮、2 -對苯醯苯基-3,1-苯并曙阱-4 -酮、2 -對甲氧苯基- 3,1-苯并曙阱-4-酮、2 -鄰甲 氧苯基-3,1-苯并曙阱-4 -酮、2 -環己基-3,1-苯并噚 阱-4 -酮、2 -對（或間）酞醯亞胺苯基-3，1 -苯并曙阱-4 -酮、2,2’ - (1，4 -伸苯基）雙（4H - 3，1 -苯并噚阱-4 -酮） 2,2’-雙（3,1-苯并噚阱-4 -酮）、2,2’ -伸乙基雙（3,1-苯 并噚阱-4 -酮）、2,2四亞甲（或伸丁）基雙（3，1-苯并曙阱-4 -酮）、2,2’-十亞甲基雙（3，1_苯并噚阱-4 -酮）、2,2’- 〇 對伸苯基雙（3，1 -苯并噚畊-4 -酮）、2,2’ -間伸苯基雙 (3，1_ 苯并噚阱-4 -酮）、2,2’ -（4,4’-二伸苯基）雙（3，1-苯并噚阱-4 -酮）、2,2’- (2,6 -或1,5 -萘）雙（3,1-苯并 噚畊-4 -酮）、2,2’- (2 -甲基-對伸苯基）雙（3,1-苯并噚 阱-4 -酮）、2,2’ - (2 -硝基-對伸苯基）雙（3,1 -苯并噚 畊-4 -酮）、2,2’- (2 -氯-對伸苯基）雙（3,1-苯并曙哄-4 -酮）、2,2’_ (1,4 -環己烯）雙（3,1-苯并噚阱-4-Q 酮）1，3,5 -三（3，1-苯并噚哄-4 -酮-2 -基）苯、1，3,5 -三 (3,1-苯并噚畊-4 -嗣-2 -基）萘及2,4,6 -三（3，1_苯并 曙阱-4 -酮-2 -基）萘、2,8 -二甲基-4H,6H -苯并 (1，2 - d; 5,4 - d’）雙（1,3) -噚畊-4,6 -二酮、2,7 -二甲基-4H，9H-苯并（1,2- d;5,4- d’）雙（1,3)-噚阱-4,9-二酮、 2,8- 二苯基-4H，8H-苯并（1，2- d;5,4- d’）雙（1,3)-噚 阱- 4,6 - 二酮、2,7 -二苯基-4H，9H -苯并（1，2 - d;5,4 - d’） 雙（1，3)-曙阱-4,6 -二酮、6,6’-雙（2 -甲基-4H，3，1- -17- 201038637 苯并噚畊-4 -酮）、6,6’-雙（2 -乙基-4H，3，1-苯并腭 阱-4 -酮）、6,6’_雙（2 -苯基-4H，3,1-苯并噚阱-4-酮）、6,6’_亞甲基雙（2 -甲基-4H, 3,1-苯并噚阱- 4-酮）、6,6’ -亞甲基雙（2 -苯基-4H, 3,1-苯并噚畊-4-酮）、6,6’-伸乙基雙（2 -甲基-4H, 3,1-苯并曙畊-4_ 酮）、6,6’_伸乙基雙（2 -苯基-4H, 3,1-苯并噚畊-4-酮）、 6,6’_ 伸 丁基雙 （2- 甲基 - 4H, 3,1- 苯 并曙阱 - 4-酮）、6,6’_伸丁基雙（2 -苯基-4H，3,1-苯并噚阱-4-酮）、6,6’ -氧基雙（2 -甲基-4H，3，1 -苯并噚哄-4 _ 酮）、6,6’-氧基雙（2 -苯基-4H，3,1-苯并噚阱-4-酮）、6,6’ -磺醯基雙（2 -甲基-4H，3，1_苯并噚阱-4_ 酮）、6,6’ -磺醯基雙（2 -苯基-4H，3,1-苯并曙哄-4_ 酮）、6,6’-碳醯基雙（2 -甲基-4H，3，1-苯并曙畊-4-酮）、 6,6’_ 碳 醯基雙 （2- 苯基 - 4H， 3,1- 苯 并噚阱 - 4-酮）、7,7’_亞甲基雙（2 -甲基-4H，3，1_苯并噚阱-4-酮）、7,7’ -亞甲基雙（2 -苯基-4H, 3,1-苯并曙阱_ 4-酮）、7,7’_雙（2 -甲基-4H, 3,1-苯并曙阱-4 -酮）、 7,7’ -伸乙基雙（2 -甲基-4H，3,1-苯并噚畊- 4 -酮）、 7,7’-氧基雙（2 -甲基-4H，3,1-苯并噚阱-4_酮）、 7,7’_磺醯基雙（2 -甲基-4H, 3，1-苯并噚阱-4 -酮）、 7,7’_碳醯基雙（2 -甲基-4H, 3,1-苯并噚畊-4 -酮）、 6,7’_雙（2 -甲基-4H，3,1-苯并腭哄-4 -酮）、6,7’-雙 (2 -苯基-4H, 3,1-苯并噚阱-4 -酮）、6,7’ -亞甲基雙 -18- 201038637 (2 -甲基-4H，3,1-苯并噚畊-4 -酮）、及6,7’-亞甲基雙 (2 -苯基-4H，3,1-苯并噚阱-4 -酮）等。 配合上述有機系紫外線吸收劑於薄膜時，由於在擠出 步驟被曝露於高溫，故紫外線吸收劑如使用分解開始溫度 爲290°C以上之紫外線吸收劑，則在減少製膜時之製程污染 而言較適宜。如使用分解開始溫度爲290°C以下之紫外線吸 收劑，則紫外線吸收劑之分解物在製膜中附著於製造裝置 之輥群等，並進一步再附著於薄膜或損傷薄膜導致薄膜之 〇 光學性缺點故不宜。 無機系紫外線吸收劑可舉例如氧化铈、氧化鋅、氧化 鈦等金屬氧化物之超微粒子類。 又，爲改善薄膜之滑動性及卷取性等處理性，在薄膜 表面形成凹凸爲宜。在薄膜表面形成凹凸之方法，一般使 用在薄膜中含有粒子之方法。上述粒子如平均粒徑爲0.01 〜10//m之內部析出粒子，無機粒子及/或有機粒子等外部 〇 粒子。 又，粒子之平均粒徑係將至少200個以上粒子以電子 顯微鏡法照相攝影數枚後，將粒子輪廓示蹤在OHP底片， 再將該示蹤像以影像解析裝置換算成相當於圓之直徑求 出。 上述外部粒子可使用如濕式及乾式矽石、膠態矽石、 矽酸鋁、氧化鈦、碳酸鈣、磷酸鈣、硫酸鋇、氧化鋁、雲 母、高嶺石、黏土、氫氧磷灰石等無機粒子及以苯乙烯、 -19- 201038637 聚矽氧、丙烯酸類等爲構成成分之有機粒子等。其中，乾 式及濕式矽石、乾式膠態矽石、氧化鋁等無機粒子及以苯 乙烯、聚矽氧、丙烯酸、甲基丙烯酸、聚酯、二乙烯基苯 等爲構成成分之有機粒子等較適合使用。此等內部粒子、 無機粒子及/或有機粒子，在不損害本申請發明所規定特性 之範圍內可倂用2種以上。 再者，上述粒子在薄膜中之含量以0.001〜10質量％範 圍內爲宜。未達0.001質量％時薄膜之滑動性惡化或卷取困 難等而易減低處理性。另一方面，如超過10質量％時易成 爲形成粗大突起及製膜性或透明性惡化之原因。 但被含在薄膜中之粒子通常其析射率與聚酯不同，故 成爲減低薄膜透明性之主要原因。爲提高成型品之設計創 意性，薄膜成型前多在薄膜表面實施印刷。此種印刷層多 在成型用薄膜之背面實施，因此由印刷鮮明性之觀點，希 要薄膜之高透明性。 因此，爲欲保持薄膜之處理性下獲得高度透明性，具 有2層以上積層構造之基材薄膜，以使用具有主層之基材 薄膜中實質上不含粒子而僅表層含有粒子之積層構造之積 層薄膜能夠有效達成，此爲本發明之較佳實施方式。表層 厚度之上限値雖可依薄膜厚度而適當選擇，但以10/zm爲 佳，並以5/zm較佳、3/zm更佳、1/zm特佳。又表層厚度 之下限，由生產性之觀點以0 · 0 1 /i m爲宜。此時可使用如 上述例示之粒子。 -20- 201038637 又，要求高透明性時，本發明之基材薄膜之霧度以o.i 〜3.0%爲宜。獲得具有高透明性薄膜之方法爲在基材薄膜 中實質上不含粒子，而如後述在硬化層與基材薄膜之間設 置中間層且僅中間層含有粒子之積層構造，此亦爲本發明 之較佳實施方式。 又，上述所謂「在基材薄膜中實質上不含粒子」，如 以無機粒子而言，即指以螢光X射線分析定量無機元素時 爲檢測臨界以下之含量。此乃由於即使有意不添加粒子於 〇 基材薄膜，但仍有來自外來異物之污染成分可能混入之 故。又，欲獲得低霧度且高設計創意性之薄膜時，以在基 材薄膜中實質上不含粒子爲宜，但如30ppm以下則在基材 薄膜中添加粒子亦無妨。 本發明之基材薄膜，爲賦予其他機能，能夠使用不同 種類之聚酯以習知方法形成積層構造。此種積層薄膜形態 並無特別限定，如A/B之2種2層構造，B/A/B之2種3 〇 層構造’ C/A/B之3種3層構造等積層形態。如上述，在基 材薄膜中含有紫外線吸收劑時，如僅在中間層含有亦爲本 發明之較佳實施方式。 本發明之基材薄膜，以雙軸拉伸薄膜爲重要。在本發 明’由於雙軸拉伸之分子定向，能夠改善未拉伸片材之耐 溶劑性及尺寸安定性等缺點。亦即一面維持未拉伸片材之 良好成型性’一面改善未拉伸片材之耐溶劑性及尺寸安定 性等缺點，爲本發明之基材薄膜之—特色。 -21- 201038637 上述雙軸拉伸聚酯薄膜之製造方法並無特別限定，如 將聚酯樹脂依需要乾燥後供給習知之熔融擠壓機，由縫口 (又長條）狀模頭以片狀擠出，以外加靜電等方式附著於流 延滾筒，再冷卻硬化得未拉伸片材（原片材）後，將該未拉 伸片材進行雙軸拉伸之方法。 關於雙軸拉伸方法，採用將未拉伸片材向薄膜之長度 方向（MD)及寬度方向（TD)進行拉伸、熱處理，製得具有目 標平面定向度之雙軸拉伸薄膜之方法。在此方法中，由薄 膜品質之觀點，以向長度方向拉伸後再向寬度方向拉伸之 MD/TD法、及向寬度方向拉伸後再向長度方向拉伸之 TD/MD法等逐步雙軸拉伸方式，或向長度方向及寬度方向 大約同時拉伸之同步雙軸拉伸方式爲適宜。又，採用同步 雙軸拉伸法時，亦可使用以線性控制馬達驅動之拉幅機。 再者，亦可視需要，使用分成多階段進行同一方向拉伸之 多階拉伸法。 關於雙軸拉伸時之拉伸倍率，較佳爲長度方向與寬度 方向爲1.6~4.2倍’特佳爲1.7~4.0倍。於此情形，長度方 向與寬度方向的拉伸倍率哪一者大皆可，亦可爲相同倍 率。以長度方向的拉伸倍率爲2.8〜4.0倍、寬度方向的拉伸 倍率爲3.0-4.5倍進行較佳。 製造本發明之成型用聚酯薄膜時之拉伸條件，採用如 下述條件爲宜。 於縱向拉伸，爲使其後之橫向拉伸順利進行，設定拉 -22- 201038637 伸溫度爲50〜110 °C、拉伸倍率爲1.6〜4.0倍更適宜。 通常拉伸聚對酞酸乙二酯薄膜時，如拉伸溫度較低於 適當條件’則由於橫向拉伸開始初期之屈服應力（yield stress)急劇升高故不能拉伸。又，即使能夠拉伸但厚度或 拉伸倍率容易不均勻故不宜。 又’如拉伸溫度較高於適當條件，則橫向拉伸開始初 期之屈服應力雖低，但即使拉伸倍率升高應力亦不會升 高。因此，所形成之薄膜在25 °C拉伸100 %時之應力小。依 ❹ 此，採用最適拉伸溫度時，在確保拉伸性下能夠製得定向 度高之薄膜。 然而，如上述共聚聚酯含有1〜50莫耳％之共聚成分 時，欲漸次提高拉伸溫度以消除屈服應力，則拉伸應力急 劇減低。尤其在拉伸後半段拉伸應力亦不升高，故定向度 亦不提高，在25 °C拉伸100 %時之應力亦減低。 此種現象在薄膜厚度60〜500;zm時容易發生，尤其在 Q 厚度100〜3 00 /zm之薄膜特別顯著。因此，本發明之使用 共聚聚酯之薄膜，其橫向拉伸溫度設定爲以下條件爲宜。 首先，在薄膜材料以擠壓機擠出後之混合物（原片材） 之預熱處理，使用DSC測定時在其玻璃轉脆溫度+ l〇°C〜 + 50°C的範圍之預熱溫度進行。其次，在橫向拉伸前半段 其拉伸溫度設定爲較預熱溫度-20°C〜+ 15t爲宜。而在 橫向拉伸後半段其拉伸溫度設定爲較前半段拉伸溫度 〜一30°C較佳，而以較前半段拉伸溫度一 10°C--20°C之 -23- 201038637 範圍特佳。採用此種條件，則在橫向拉伸之前半段因屈服 應力小而容易拉伸’而在後半段則容易定向。又，橫向拉 伸倍率設定爲2.5〜5.0倍較適宜。其結果能夠製得滿足本 發明所規定之F100”或FlOOt。。之薄膜。 再者，雙軸拉伸後之熱處理（熱固定處理），以下限値 爲熔點一 l〇°C較佳及上限値爲熔點一 30°C較佳之熱固定溫 度進行。一般而言’減低平面定向度之方法己知有減低拉 伸倍率之方法及增加共聚成分配合量之方法，但前者之方 法使薄膜之厚薄不均惡化’而後者之方法使薄膜熔點減低 使耐熱性惡化故不宜。於本發明’欲減低雙軸定向聚酯薄 膜之平面定向度及在150°C下之熱收縮率，則以較通常高之 溫度進行熱固定。 (中間層） 本發明之成型用硬被覆膜，係由硬化層積層於基材薄 膜之一面而構成，但爲提升基材薄膜與硬化層之附著性爲 目的而設置中間層較佳。 上述中間層之構成樹脂，可舉如聚酯系樹脂、聚胺基 甲酸酯樹脂、聚酯型胺基甲酸酯樹脂、丙烯酸系樹脂、三 聚氰胺樹脂及此等之混合樹脂等，但以使基材薄膜與硬化 層之附著性良好來選擇爲重要，具體例如構成基材薄膜與 硬化層之樹脂爲丙烯酸系樹脂時，則由丙烯酸系、共聚聚 酯系、聚酯型胺基甲酸酯系等中至少選擇1種爲宜。 爲提升附著性、耐水性爲目的，在上述中間層中含有 • 24 - 201038637 交聯劑以形成交聯結構亦可。交聯劑如尿素系、環氧系、 三聚氰胺系、異氰酸酯系等。又，不使用交聯劑，而將具 有自交聯性之接枝共聚樹脂當作樹脂使用亦可。 在中間層，以形成硬化層前之基材薄膜表面形成凹凸 以改善滑動性爲目的，而可含有各種粒子。中間層所含有 之粒子，如矽石、高嶺石、滑石、碳酸鈣、沸石、礬土等 無機粒子，丙烯酸、PMM A、耐綸、苯乙烯、聚酯、胍胺/ 甲醛縮合物等有機粒子。又，由透明性之觀點，應選擇與 〇 所使用樹脂之折射率相近之粒子較佳。 設置中間層之方法以塗佈法較佳。塗佈法使用如凹版 塗佈法、滾壓塗佈法（Kiss coating)、浸漬塗佈法、噴霧塗 佈法、簾幕塗佈法、氣刀塗佈法、刮刀塗佈法、反向滾筒 塗佈法等習知塗佈法，並在基材薄膜之製造步驟中設置塗 佈層之倂線（或聯線）（i n-line)塗佈法，或製造基材薄膜後設 置塗佈層之離線（off-line)塗佈法設置中間層均可。此等方 Q 法中以倂線塗佈法不僅在成本上優越，且在中間層含有粒 子之結果，無必要在基材薄膜中含有粒子之故，能夠高度 改善透明性而較佳。 (硬化層） 本發明之成型用硬被覆膜，在基材薄膜之至少一面以 直接或透過中間層將硬化層積層。於本發明，所謂硬化層， 乃指爲補強由_材薄膜所構成基材之表面硬度並提升耐擦 傷性’而具有硬度較基材薄膜高之被膜（或層膜），且具有 -25- 201038637 對成型時之變形亦能夠隨動之優異成型性之層（膜）。更具 體而言，本申請發明之成型用硬被覆膜，其表面硬度至少 具有Η以上之鉛筆硬度，且依後述之評價法至少具有1〇% 以上之伸長率，故適合當作家電銘板用或建材用部品等使 用。 可使用於本發明之硬化層，必須以游離放射線硬化型 樹脂爲主要成分。如此則不必像熱硬化型樹脂硬化時需要 加熱處理，能夠減少因熱引起基材薄膜之熱收縮，故較適 合。於本發明，游離放射線硬化型化合物係以電子線、放 射線、紫外線之任一種照射結果引起聚合及/或反應之化合 物’此種化合物引起聚合及/或反應之結果構成硬化層。本 發明所使用之游離放射線硬化型化合物，如三聚氰胺系、 丙烯酸系、有機矽系之游離放射線硬化型化合物，其中由 能夠獲得高表面硬度之觀點，以丙烯酸酯系游離放射線硬 化型化合物較適合。 又於本發明，游離放射線硬化型化合物不僅限於單 體、先質’當然亦包含其等所聚合及/或反應之游離放射線 硬化型樹脂。如以上述丙烯酸酯系游離放射線硬化型化合 物爲例，可舉例如聚胺基甲酸酯丙烯酸酯、聚酯丙烯酸酯、 環氧丙烯酸酯、多元醇丙烯酸酯等但並無特别限定，可使 用任意之丙烯酸酯系游離放射線硬化型化合物。 本發明之硬化層，係將至少含有具3以上官能基之游 離放射線硬化型化合物、與丨及/或2官能基游離放射線硬 -26- 201038637 化型化合物之塗佈液塗佈在基材薄膜後，以電子線、放射 線、紫外線之任一種進行照射引起聚合及/或反應使其硬化 而成。 以丙烯酸酯系游離放射線硬化型化合物當作本發明之 游離放射線硬化型化合物使用時，本發明之1官能基（單官 能基）丙烯酸酯系游離放射線硬化型化合物，只要在分子中 至少含有1個（甲基）丙烯醯基之化合物則無特别限定。可 舉例如丙烯醯胺、（甲基）丙烯醯嗎啉、7-胺基-3,7 -二甲基 〇 辛基（甲基）丙烯酸酯、異丁氧基甲基（甲基）丙烯醯胺、異冰 片基氧乙基（甲基）丙烯酸酯、異冰片基（甲基）丙烯酸酯、2-乙己基（甲基）丙烯酸酯、乙基二伸乙甘醇（甲基）丙烯酸酯、 三級辛基（甲基）丙烯酸酯、雙丙酮（甲基）丙烯醯胺、二甲胺 乙基（甲基）丙烯酸酯、二乙胺乙基（甲基）丙烯酸酯、月桂基 (甲基）丙嫌酸酯、二環戊二嫌（dicyclopentadien)基（甲基）丙 烯酸酯、二環戊烯基（dicyclopentenyl)氧乙基（甲基）丙烯酸 Q 酯、二環戊烯基（甲基）丙烯酸酯、N，N-二甲基（甲基）丙烯 醯胺四氯苯基（甲基）丙烯酸酯、2 -四氯苯氧乙基（甲基）丙 烯酸酯、四氫糠基（甲基）丙烯酸酯、四溴苯基（甲基）丙烯酸 酯、2 -四溴苯氧乙基（甲基）丙烯酸酯、2 -三氯苯氧乙基（甲 基）丙烯酸酯、三溴苯基（甲基）丙烯酸酯、2 -三溴苯氧乙基 (甲基）丙烯酸酯、2 -羥乙基（甲基）丙烯酸酯、2 -羥丙基（甲 基）丙烯酸酯、乙烯基己內醯胺、N -乙烯吡咯酮、N -乙烯 甲醯胺、苯氧乙基（甲基）丙烯酸酯、丁氧乙基（甲基）丙烯酸 -27- 201038637 酯、五氯苯基（甲基）丙烯酸酯、五溴苯基（甲基）丙烯酸酯、 聚乙二醇單（甲基）丙烯酸酯、聚丙二醇單（甲基）丙烯酸酯、 冰片基（甲基）丙烯酸酯 '甲基三伸乙二甘醇（甲基）丙烯酸 酯、環己基（甲基）丙烯酸酯、壬苯基（甲基）丙烯酸酯、及其 己內醯胺轉化物等衍生物、丙烯酸等及此等之混合物等。 以丙烯酸酯系游離放射射線硬化型化合物當作游離放 射射線硬化型化合物使用時，本發明之2官能基丙烯酸酯 系游離放射射線硬化型化合物，可使用在1分子中具有2 個以上醇性羥基之多價醇中其羥基形成2個（甲基）丙烯酸 酯化物之化合物等。具體可舉例如（a)碳原子數2〜1 2之伸 烷基二醇之（甲基）丙烯酸二酯類：乙二醇二（甲基）丙烯酸 酯、丙二醇二（甲基）丙烯酸酯、丨，4 - 丁二醇二（甲基）丙烯 酸酯、新戊二醇二（甲基）丙烯酸酯、1，6 -己二醇二（甲基） 丙烯酸酯等；（b)聚氧伸烷基二醇之（甲基）丙烯酸二酯類： 二伸乙甘醇二（甲基）丙烯酸酯、三伸乙甘醇二（甲基）丙烯酸 酯、四伸乙二醇二（甲基）丙烯酸酯、二伸丙甘醇二（甲基） 丙烯酸酯、聚乙二醇二（甲基）丙烯酸酯、聚丙二醇二（甲基） 丙烯酸酯等；（c)多價醇之甲基丙烯酸二酯類’·新戊四醇二 (甲基）丙烯酸酯等；（d)雙酚A或雙酚A氫化物之環氧乙烷 及環氧丙烷加成物之（甲基）丙烯酸雙酯類：2,2’-雙（4-丙 嫌氧基乙氧基苯基）丙烷、2,2’-雙（4 -丙烯氧基丙氧基苯 基）丙院等；（e)將多價之異氰酸酯化合物與含2個以上醇性 S基之化合物預先進行反應所得末端含異氰酸酯基化合 -28- 201038637 物，再與含醇性羥基之（甲基）丙烯酸酯進行反應所得分子 中具有2個（甲基）丙烯醯氧基（acryloyloxy)之胺基甲酸酯 (甲基）丙烯酸酯類；（f)將丙烯酸或甲基丙烯酸與分子中具 有2個以上環氧基之化合物進行反應所得分子中具有2個 (甲基）丙烯醯氧基之環氧基（甲基）丙烯酸酯類等。 以丙烯酸酯系游離放射線硬化型化合物當作游離放射 線硬化型化合物使用時，本發明之具3官能基以上之丙烯 酸酯系游離放射線硬化型化合物，具體可使用（a)新戊四醇 ❹ 三（甲基）丙烯酸酯、新戊四醇四（甲基）丙烯酸酯、二新戊四 醇三（甲基）丙烯酸酯、二新戊四醇四（甲基）丙烯酸酯、二新 戊四醇五（甲基）丙烯酸酯、二新戊四醇六（甲基）丙烯酸酯、 三羥甲基丙烷三（甲基）丙烯酸酯等；（b)將多價異氰酸酯化 合物與含2個以上醇性羥基之化合物預先進行反應所得末 端含異氰酸酯基化合物，再與含醇性羥基之（甲基）丙烯酸 酯進行反應所得分子中具有3個以上（甲基）丙烯醯氧基之 Q 胺基甲酸酯（甲基）丙烯酸酯類；（c)將丙烯酸或甲基丙烯酸 與分子中具有3個以上環氧基之化合物進行反應所得分子 中具有3個以上（甲基）丙烯醯氧基之環氧基（甲基）丙烯酸 酯類等。 於本發明，在上述塗布液中所含游離放射線硬化型化 合物中，除含1或2官能基之游離放射線硬化型化合物以 外再含1種以上具3官能基以上之游離放射線硬化型化合 物爲重要。如此則在硬化後之硬化層中，交聯密度高之具 -29- 201038637 3官能基以上之游離放射線硬化型化合物成分以硬鏈段存 在，而1及/或2官能基之游離放射線硬化型化合物則以與 該硬鏈段結合方式進行反應使1及/或2官能基之游離放射 線硬化型化合物成分以軟鏈段存在。此種將2種以上不同 官能基數之游離放射線硬化型化合物調整在特定濃度範圍 之結果，可導入異交聯結構於硬化層，以硬鏈段賦予表面 硬度與耐擦傷性，並以軟鏈段之伸縮性賦予成型性，乃獲 得自相矛盾之特性並存之顯著效果。 於本發明，爲使高表面硬度與優異成型性並存，即具 體而言使Η以上之鉛筆硬度及10%以上之伸長率並存，在 上述塗布液中所含游離放射線硬化型化合物中之1及/或2 官能基之游離放射線硬化型化合物含量爲5質量％以上、95 質量％以下爲重要。上述含量如未達5質量％時，不僅被膜 (或層膜）之可撓性減低，成型時在硬化層發生紋裂故不 宜。又，上述含量如超過95質量％時，難以獲得具有充分 表面硬度與耐擦傷性之硬化被膜。上述含量之下限以10質 量％以上較佳，20質量％以上更佳。又，上述含量之上限以 90質量％以下較佳，80質量％以下更佳，70質量％以下最 佳。如游離放射線硬化型化合物中之1及/或2官能基之游 離放射線硬化型化合物含量爲20質量％以上、80質量％以 下時，能夠謀求更高度之表面硬度與成型性之並存，具體 而言能夠使2Η以上鉛筆硬度與20 %以上伸長率並存，適合 於如汽車等銘板用或隨身攜帶機器等之箱體等同時要求高 -30- 201038637 硬度與高加工性之成型用硬被覆膜。 再者，本發明者等除上述實施方式外，再加上以具有 胺基之游離放射線硬化型化合物當作游離放射線硬化型化 合物使用結果，發現能夠使表面硬度與成型性更高度並 存。亦即，在上述塗布液中所含之至少1種游離放射線硬 化型化合物具有胺基較宜。使用具有胺基之化合物當作游 離放射線硬化型化合物之結果引起之上述作用推想如下。 硬化層之硬度分布如有局部性差異，則拉伸硬化層時容易 〇 產生局部性破裂（紋裂）。此種局部性硬度分布差異之原 因，有因氧引起之游離放射線硬化樹脂之聚合抑制作用（氧 化抑制）。在此，如使用具有胺基之化合物當作游離放射線 硬化型化合物時，胺基可捕捉自由基氧，使影響硬化層表 層部硬化反應之氧化抑制減少，故能夠在硬化層全體進行 均勻之硬化反應。依此，成型時施加於硬化層之應力被分 散至該硬化層全體，故成型時發生裂紋亦被抑制。因此， Q 能夠謀求表面硬度與成型性之更高度並存。又，除上述效 果外，具有胺基之游離放射線硬化型樹脂由於塗膜速硬性 之效果，故如與不含胺基比較時，硬化層表面之硬化更加 被促進而能夠提升表面硬度。 在上述塗布液中所含游離放射線硬化型化合物中之具 有胺基之游離放射線硬化型化合物含量爲2.5質量％以 上、95質量％以下爲宜。在上述塗布液中所含游離放射線 硬化型化合物中之具有胺基之游離放射線硬化型化合物含 -31 - 201038637 量下限以5質量％以上較佳、10質量％以上更佳。又’上述 含量之上限以92.5質量％以下較佳、90質量％以下更佳、 50質量％以下最佳。在上述塗布液中所含游離放射線硬化 型化合物中之具有胺基之游離放射線硬化型化合物含量未 達2.5質量％時，硬化層全體較難均勻硬化，故較難獲得成 型時對紋裂之抗性。又，如具有胺基之游離放射線硬化型 化合物爲高濃度時，因胺基引起之硬化層黃變較強，故上 述含量如超過95質量％，則有時損害高透明性。例如在硬 化層之未積層面上實施印刷加工時，層膜之色調b以2以 下較佳，此時，上述具有胺基之游離放射線硬化型化合物 含量爲92.5質量％以下較佳。 於本發明之上述塗布液中，雖含有1及/或2官能基之 游離放射線硬化型化合物、及具3以上官能基之游離放射 線硬化型化合物，但於上述實施方式中，只要其中一部分 之游離放射線硬化型化合物具有胺基即可。又，1官能基 游離放射線硬化型化合物、或2官能基游離放射線硬化型 化合物、或具3以上官能基之游離放射線硬化型化合物中 之任一種爲具有胺基之游離放射線硬化型化合物亦爲較佳 實施方式。 以丙烯酸酯系游離放射線硬化型化合物當作具有胺基 之游離放射線硬化型化合物使用時，具有胺基之丙烯酸酯 系游離放射線硬化型化合物如丙烯醯胺、7-胺基-3,7 -二 甲辛基（甲基）丙烯酸酯、異丁氧甲基（甲基）丙烯醯胺、三級 -32- 201038637 辛基（甲基）丙烯醯胺、雙丙酮（甲基）丙烯醯胺、二甲胺乙基 (甲基）丙烯酸酯、二乙胺乙基（甲基）丙烯酸酯、N，N-二甲 基（甲基）丙烯醯胺四氯苯基（甲基）丙烯酸酯、N -乙烯甲醯 胺等。 又，本發明者等除上述實施方式外，再加上發現在硬 化層含有粒子時，能夠更提升成型性，並能夠使表面硬度 與成型性更高度並存。關於硬化層含有粒子之結果，能夠 更提升成型性之作用可做如下之推想。硬化層之硬度提升 〇 則成型時在硬度高之硬化層暫時發生強應力，導致硬化層 一下子發生破裂（紋裂）。在此，硬化層含有粒子之結果， 成型時施加於硬化層之內部應力在游離放射線硬化型化合 物與粒子之界面被緩和，除被抑制發生紋裂外，有在硬化 層先行發生不損害外觀程度、無法以目視確認之微小紋裂 之效果，延遲硬化層發生致命性破裂，結果表現提升成型 性之效果。 〇 至於硬化層含有之粒子，如非晶形矽石、結晶性矽石、 矽石-礬土複合氧化物、高嶺石、滑石、碳酸鈣（方解石型、 球霰石型）、沸石、礬土、氫氧磷灰石等無機粒子，交聯丙 烯酸酯粒子、交聯PMMA粒子、交聯聚苯乙烯粒子、耐綸 粒子、聚酯粒子、胍胺/甲醛縮合物粒子、胍胺/三聚氰胺/ 甲醛縮合物粒子、三聚氰胺/甲醛縮合物粒子等耐熱性高分 子粒子，及如矽石/丙烯酸複合化合物之有機/無機混種微粒 等，但於本發明，粒子之種類並無特別限定。 -33- 201038637 粒子之形狀，如球狀、塊狀、板狀、纖維狀、薄片狀 等，但無特別限定，其中由分散性及與其他部品接觸時粒 子脫落之觀點，以球狀較佳。 於本發明，粒子之平均粒徑以l〇nm以上、3〇〇nm以下 爲宜，再者下限爲40nm以上、上限爲200nm以下較佳，尤 其下限爲50nm以上、上限爲lOOnm以下更佳。粒子之平均 粒徑小於1 0 n m時，因平均粒徑過小，有時使上述因添加粒 子之表面硬度、耐擦傷性、成型性之提升效果減少全部或 某一部分。又，超過30nm時，硬化層可能變脆弱，成型性 減低。又，上述平均粒徑係使用庫爾特計數器（Coulter counter)(Beckman Coulter 公司製、MULTISIZER - II 型）’ 將粒子分散於不使粒子膨潤之溶劑中進行測定所得平均粒 徑。 於本發明，硬化層所含有之粒子含量以硬化層中之固 體成分計算爲5質量％以上、70質量％以下較佳，尤其，前 述含量下限爲15質量％以上、上限爲50質量％以下特佳。 粒子含量小於5質量％時，有時使上述因添加粒子之表面硬 度、耐擦傷性、成型性之提升效果減少全部或某一部分。 另一方面，如粒子含量超過70質量％，則成型時發生多量 前述微小紋裂，使霧度上升（泛白）導致損害成型體之透明 性。 於本發明，因應如上述之成型用硬被覆膜用途’以適 當選擇或組合上述之游離放射射線硬化型化合物使用具有 -34- 201038637 胺基之化合物及添加粒子於硬化層等爲較理想。特別適合 之方式爲此等之組合。依此，能夠使硬化層之表面硬度與 成型性以極高度並存，具體而言，可獲得具有表面硬度2H 以上且伸長率20%以上、甚至表面硬度2H以上且伸長率 3 0%以上之成型用硬被覆膜，適合使用於汽車等之覆蓋部品 或深底之箱體、容器等。 於本發明，將上述塗布液進行聚合及/或反應之方法如 照射電子線、放射線、紫外線之方法，但如照射紫外線時 〇 在上述塗布液中添加光聚合引發劑較理想。 光聚合引發劑之具體例，如苯乙酮、2,2 -二乙氧基苯 乙酮、對二甲基苯乙酮、對二甲胺基苯丙酮、二苯甲酮、2-氯二苯甲酮、4,4’ -二氯二苯甲酮、4,4’-雙二乙胺基二苯 甲酮、米其勒酮（Michler’ s ketone)、节基、苯偶姻、苯偶 姻甲醚、苯偶姻乙醚、苯偶姻異丙醚、苯甲醯甲酸甲酯、 對異丙基-α -羥基苯異丁酮、α -羥基苯異丁酮、2,2-Q 二甲氧基-2-苯基苯乙酮、1-羥基環己基苯基酮等羰基 化合物，硫化四甲基胺硫甲醯基（tetramethylthiuram monosulfide)、二硫化四甲基胺硫甲酿基、硫卩山哩 (thioxanthene)、2 -氯硫妯嗶、2 -甲基硫卩山噃等硫化合物， 過氧化苯甲醯基、二（三級丁基）過氧化物等過氧化物化合 物等。此等光聚合引發劑可舉出三級丁基過氧化物等過氧 化物化合物。此等光聚合引發劑單獨使用或2種以上組合 使用均可。光聚合引發劑之添加量爲上述塗布液中所含每 -35- 201038637 100質量份游離放射線硬化型化合物之0.01質量份以上、 1 5質量份以下較適當，使用量少時不僅反應慢、生產性不 良，且因未反應物殘存而不能獲得充分之表面硬度及耐擦 傷性。反’之，如添加量過多時，則有硬化層因聚合引發劑 而黃變之問題發生。 於本發明，爲防止製造時之熱聚合或貯存時之暗反 應，在上述塗布液中添加氫醌、氫醌一甲醚、2,5-三級丁 基氫醌等習知熱聚合抑制劑爲宜。熱聚合抑制劑之添加量 以上述塗布液中所含每1 00質量份游離放射射線硬化型化 合物之0.005質量份以上、0.05質量份以下較佳。 於本發明，在上述塗布液中，以提升塗布時之作業性、 控制塗布時之塗膜厚度爲目的，在不損害本發明之目的範 圍內，可配合有機溶劑。 關於有機溶劑，其沸點以50°C以上、150°C以下較佳。 具體例如甲醇、乙醇、異丙醇等醇系溶劑，乙酸甲酯、乙 酸乙酯、乙酸丁酯等乙酸酯系溶劑，丙酮、甲基乙基酮等 酮系溶劑，甲苯等芳香族系溶劑，二曙烷等環狀醚系溶劑 等。此等溶劑可單獨或2種以上混合使用。 於本發明，在上述塗布液中，以減低塗布液之表面張 力，改善硬化層之塗布外觀（尤其因微小泡沫引起之缺失、 異物附著引起之凹陷、乾燥步驟時之撥拒）爲目的，可含有 界面活性劑。 界面活性劑可適當使用習知之陽離子系、陰離子系、 -36- 201038637 非離子系’但由上述塗布液之變質或硬化層對基材薄膜之 附著性不良等問題’以不具有極性基之非離子系較佳，而 以界面活性能優異之有機矽系界面活性劑或氟系界面活性 劑更佳。 關於有機矽系界面活性劑，可舉例如二甲基矽、胺基 砂院、丙嫌基砂院、乙嫌节基政院（vinylbenzylsilane)、乙 稀节胺基砍院（vinylbenzylaminosilane)、去水甘油砂院 (glycidesilane)、锍基矽烷、二甲基矽烷、聚二甲基矽氧烷、 〇 聚院氧基砂氧院、氫二嫌（hydrodiene)改性砂氧院、乙嫌基 改性矽氧烷、羥基改性矽氧烷、胺基改性矽氧烷、羧基改 性矽氧烷、鹵化改性矽氧烷、環氧基改性矽氧烷、甲基丙 烯醯氧基改性矽氧烷、锍基改性矽氧烷、氟改性矽氧烷、 烷基改性矽氧烷、苯基改性矽氧烷、烯化氧改性矽氧烷等。 至於氟系界面活性劑，可舉例如四氟化乙烯、全氟烷 基敍鹽、全氟烷基烷磺醯胺、全氟烷基烷磺酸鈉、全氟烷 〇 基鉀鹽、全氟烷基碳酸鹽、全氟烷基磺酸鹽、全氟烷基環 氧乙烷加成物、全氟烷基三甲基銨鹽、全氟烷基胺磺酸鹽、 全氟烷基磷酸酯、全氟烷基烷化合物、全氟烷基烷基甜菜 鹼、全氟烷基鹵化物等。 由提升塗布外觀及滑動性之觀點，對構成硬化層之塗 布液而言，界面活性劑含量爲0.0 1質量％以上較佳。另一 方面，由於界面活性劑滲出硬化層表面而污染接觸硬化層 者，故界面活性劑含量爲2.00質量％以下較佳。 -37- 201038637 又，所使用界面活性劑以HLB爲2以上、1 2以 使用HLB爲2以上之界面活性劑時，能夠以界面: 升塗平性。界面活性劑之HLB以3以上更佳、4以 另一方面，使用HLB爲12以下之界面活性劑時 制滑動性之惡化。 又，所謂HLB係由美國Atlas Powder公司之W. 命名之H y d r 〇 p h i 1 L y 〇 p h i 1 B a 1 a n c e之縮寫字，爲界 分子中所含親水基與親油基之平衡當作特性値而 値。意指HLB値愈低則親油性愈高，反之HLB値 水性愈高。 本發明之硬化層可因應須要配合各種添加劑 予拒水性之氟系或有機矽系化合物，爲提升塗布 之消泡劑，以及防靜電劑或著色用染料及顏料等 於本發明，硬化層以在有機溶劑中含有游離 化型化合物、粒子、光聚合引發劑、界面活性劑 塗布於基材薄膜上乾燥後硬化而形成較佳。 積層硬化層之方法可舉習知方法，但以將上 塗布在基材薄膜上乾燥後硬化之方法較適合。塗 例如凹版塗布法、滾塗法（Kiss coating)、浸塗法、 簾幕塗佈法、氣刀塗布法、刮刀塗布法、反向滾筒 棒塗法、唇塗法（Lip coating)等習知塗布方法。其 以卷對卷方式均勻塗布之凹版塗布法、尤其反向 法較佳。 下較佳。 活性能提 上特佳。 ，能夠抑 C.Griffin 面活性劑 指標化之 愈高則親 。如爲賦 性或外觀 〇 放射線硬 之塗布液 述塗布液 布法可舉 噴塗法、 '塗布法、 中，能夠 凹版塗布 -38- 201038637 上述塗布液所含游離放射線硬化型化合物、粒子、光 聚合引發劑等溶解或分散於有機溶劑中之方法，以在加溫 下將此等攪拌、分散之方法較適合。將塗布液加溫時，能 夠提升游離放射線硬化型化合物、粒子、光聚合引發劑之 溶解性。因此，能夠抑制因未溶解物導致之塗布外觀惡化。 分散機可使用習知機器。具體例如球磨機、砂磨機、 攪拌磨機（Attritor)、輥磨機、攪拌機、膠體磨機、超音波 均質機、乳化機、珠磨機、濕式噴射硏磨機、塗料搖動機、 〇 ^ 蝶形混合機、行星式混合機、韓蘇混合機（Henschel mixer) 等。 上述塗布液所含游離輻射線硬化型化合物、粒子、光 聚合引發劑等之固體成分濃度以5質量％以上、70質量％ 較佳。塗布液之固體成分濃度調整爲5質量％以上時，能夠 抑制塗布後乾燥時間拉長導致之生產性減低。另一方面， 塗布液之固體成分濃度調整爲70質量％以下時，能夠防止 Q 塗布液黏度上升引起之塗平性惡化及拌隨其而導致之塗布 外觀惡化。又，由塗布外觀之觀點，隨塗布液之固體成分 濃度、或有機溶劑種類、界面活性劑種類調整配合量，使 塗布液黏度爲0.5cps以下、300cps以下較宜。 塗布並硬化後之硬化層厚度，依成型時之伸長程度而 定’但使成型後之硬化層厚度爲0.5 v m以上、50从m以下 較佳。具體而言，成型前之硬化層厚度下限以〇.6ym以上 較佳、1.0//m以上更佳。又，成型前之硬化層厚度上限以 -39- 201038637 100 /z m以下較佳、80 // m以下更佳、60 /2 m以下特佳、20 /zm以下最佳。如硬化層厚度較0.6/zm薄時難以獲得硬化 性，反之如超過100#m時，表現硬化層硬化不良或因硬化 收縮引起卷邊不良等之傾向。 如塗布液配合有機溶劑等而須要預乾燥時，塗布在基 材薄膜上並乾燥之方法，如習知之熱風乾燥、紅外線加熱 器等，但以乾燥速度快之熱風乾燥較理想。 塗布後之乾燥以40t以上、120°C以下之溫度條件進行 較佳，尤其以下限451以上、上限80°C以下更佳。未達40 °(：時，除塗布液所含有機溶劑不能充分去除外，有時發生 泛白等問題。反之超過120 °C之溫度時，易發生來自泡沬之 微小塗布缺失、微小撥拒、紋裂等塗膜之微小缺點，可能 使外觀不良。再者，基材薄膜因熱而強烈收縮，熱縐紋使 基材薄膜之平面性惡化，故成型時不能獲得均勻之伸長， 或發生局部性伸長，導致基材薄膜斷裂等使成型性不良。 乾燥中施加於基材薄膜之張力以5 0N/m以上、300N/m 以下較佳，尤其下限爲100N/m以上、上限爲250N/m以下 較佳。基材薄膜張力未達50N/m時，在行進中之基材薄膜 會蛇行，故無法塗布塗布液。反之超過3 0 0 N / m時，基材薄 膜發生縐紋，使平面性惡化或使卷取之基材薄膜外觀不 良。再者，基材薄膜之低溫成型性良好時，乾燥中之基材 薄膜向前進方向拉伸但寬方向則收縮，最壞情況下引起斷 裂等使生產性發生問題。 -40- 201038637 於本發明，在不設置硬化層之一面，以不阻礙本發明 效果之範圍內可賦予硬化層、防靜電層、易黏接層、黏合 層、易滑動層、電磁波吸收層、含染料或顏料等色素之樹 脂層等其他功能。 於本發明，將紫外線照射在塗布液以形成硬化層。照 射之累計光量以50mJ/cm2以上、1000mJ/cm2以下爲宜，尤 其下限爲30〇111}/(：1112以上、上限爲70〇111】/(：1112以下更佳。又， 在氮氣環境下進行照射時，能夠減少氧化抑制，提升耐擦 〇 傷性而較理想。累計光量未達50m〗/cm2時，不能促進游離 反射線硬化型化合物之聚合反應，使硬化層之表面硬度顯 著減低。累計光量超過1000m〗/cm2時，因受熱之影響可能 使基材薄膜變形。又，本發明之累計光量能夠利用TOPCON 製「UVR- T35」測定。 又，以電子線硬化塗布液時，照射線量爲5kGy以上、 lOOkGy以下較佳，尤其上限爲30kGy以上、下限爲70kGy Q 以下更佳。未達5kGy時，不能促進游離反射線硬化型化合 物之聚合反應，使硬化層之表面硬度顯著減低。超過lOOkGy 時，電子線照射管之壽命顯著減低，在生產成本上不利。 (成型用硬被覆膜） 本發明之成型用硬被覆膜爲表面硬度優異之薄膜。本 發明之成型用硬被覆膜，除表現良好成型性，同時由於使 用具有機械特性良好之特定特性之基材薄膜，能夠發揮更 良好之表面硬度。此乃由於基材薄膜之強度（硬度）有助於 -41- 201038637 硬化層表面硬度之故。具體而言，本發明之成型用硬被覆 膜，其鉛筆硬度測定値以Η以上較佳、2H以上特佳。在此， 鉛筆硬度之評價以JIS — Κ5600爲依據進行。 調整表面硬度之方法，可利用形成硬化層之塗布液所 含游離反射線硬化型化合物中之1或2官能基游離輻射線 硬化型化合物含量或具有胺基之游離反射線硬化型化合物 含量、硬化層中之粒子存在量、硬化層之厚度等進行改變。 本發明之成型用硬被覆膜爲耐擦傷性優異之薄膜。具 體而言，依據JIS — Κ5 600，用# 0000之鋼絲棉以500gf負 載在表面來回20次，以目視觀察有無發生擦傷及其程度結 果，以深度擦傷1 0條以下之少量擦傷較佳，並以完全無深 度擦傷特佳。 調整耐擦傷性之方法，可利用形成硬化層之塗布液所 含游離反射線硬化型化合物中之1或2官能基游離反射線 硬化型化合物含量或具有胺基之游離反射線硬化型化合物 含量、硬化層中之粒子存在量等進行改變。 本發明之成型用硬被覆膜爲成型性優異之薄膜。具體 而言，在室溫及薄膜實際溫度16〇°C時之伸長率均爲10% 以上較佳、20%以上更佳、30%以上特佳。在此所謂伸長率， 係由成型用硬被覆膜切取長度l〇mm、寬度150mm之細長 方形，於薄膜實際溫度160°C下各自拉伸時硬化層發生紋裂 或泛白時之拉伸率當作伸長率（％)。 調整成型性（伸長率）之方法，可利用形成硬化層之塗 -42- 201038637 布液所含游離反射線硬化型化合物中之1或2 反射線硬化型化合物含量或具有胺基之游離反 化合物含量、硬化層中之粒子存在量等進行改 本發明之成型用硬被覆膜，在不積層硬化 施印刷加工時，以無著色較佳。具體而言，色 爲2.0以下較佳。調整色調b*之方法，可利用 之塗布液所含游離反射線硬化型化合物中之具 離反射線硬化型化合物含量或光聚合引發劑添 ❹ 變。在此，色調b*係利用色差計（日本電色工 ZE- 20 00)，以C光源、視角2度測定色調b， 値之平均求得之値。 (成型用硬被覆膜輥） 本發明之成型用硬被覆膜輥，係將長條之 覆膜經連續卷取於圓柱形卷芯成輥狀之步驟而 成型用硬被覆膜輥時，能夠提升加工時之生產 Q 於成型體品質之安定性。長條之成型用硬被覆 於圓柱形卷芯成輥狀之成型用硬被覆膜輥之長 無特別限定，但以50m以上、5000m以下較佳， 3000m以下更佳。卷取長度短時，如在後製程 加工時因成型用硬被覆膜輥之更換頻率高而 化。反之，卷取長度長時，成型用硬被覆膜因 度而膨脹及收縮，發生卷緊使卷芯部外觀不良 成型用硬被覆膜輥之寬度依用途而異， 官能基游離 射線硬化型 變0 層之一面實 調b *之値 形成硬化層 有胺基之游 加量進行改 業公司製、 以5次測定 成型用硬被 製得。使用 性，並有助 膜連續卷取 度依用途而 1 00m以上、 實施印刷層 使作業性惡 外部環境溫 〇 並無特別限 -43- 201038637 疋’但由加工性之觀點以IQOmm以上、2000mm以下較佳， 500mm以上、1500mm以下更佳。 卷取成型用硬被覆膜之圓柱形卷芯以塑膠製卷芯較 宜。如使用一般所使用紙製卷芯時，發生紙粉等附著於硬 化層而易成爲不良品。塑膠製卷芯以習知者適合使用，但 由強度之觀點以聚丙烯製卷芯或FRP製卷芯較佳。圓柱形 卷芯之尺寸以直徑3英寸以上、6英寸以下較佳。使用直 徑小之圓柱形卷芯時，卷芯部發生卷取癖性，使後製程時 之操作性不良。另一方面，直徑大時使輥之直徑亦大，處 理性不良。 將成型用硬被覆膜卷繞在圓柱形卷芯時，藉雙面膠帶 將成型用硬被覆膜固定在卷芯後開始卷取較佳。不使用雙 面膠帶時，則在卷取中或搬運時容易發生卷膜偏移。雙面 膠帶可使用習知者，但由發生紙粉或強度之觀點，以塑膠 膜兩面具有黏合層者較佳。雙面膠帶厚度爲5//m以上、50 Mm以下較佳。較薄時強度減低使作業性不良，同時膜之 固定力亦減低。反之較厚時’因膠帶之高低差使卷芯部之 成型用硬被覆膜之平面性不良。 於本發明，在成型用硬被覆膜之寬方向兩端賦予凹凸 (壓紋）較佳。賦予凹凸時在卷芯部不易附著因雙面膠帶引 起之痕跡，同時使硬化層與其相反面之基材薄膜表面接觸 部分，或與積層在基材薄膜上之如前述賦予機能性層膜之 接觸部分降低’使輥形態之保存安定性良好。凹凸高度之 -44 - 201038637 下限以l〇em較佳、15/zm更佳。反之，凹凸高度之上限 以40//m較佳、35em更佳。凹凸高度過低時，因凹凸改 善輥形態之保存安定性之效果小。另一方面，凹凸高度過 高時，搬運時容易發生卷膜偏移。賦予凹凸之方法，可使 用習知方法。具體如以表面有突起之金屬輥壓緊而賦予凹 凸之方法。又，凹凸加工以在基材薄膜上形成硬化層前， 預先在基材薄膜進行凹凸加工較佳。 (成型體） 〇 本發明之成型用硬被覆膜，適合當作以真空成型、氣 壓成型、模具成型、模壓成型、積層成型、模具內（in-mold) 成型、壓伸成型、折彎成型、拉伸成型等成型方法所成型 之成型用材料。使用本發明之成型用硬被覆膜成型時，硬 化層不隨成型時之變形而發生紋裂，且能夠維持表面硬 度、耐擦傷性。 上述由成型用硬被覆膜所成型而成之成型體之硬化層 Q 厚度，以5/zm以上、50ym以下較佳，0.5em以上、1〇 以下特佳。成型體硬化層之厚度較〇.5ym薄時，不能 獲得硬化性，由耐熱性觀點如加熱於成型體時不能追隨基 材薄膜之收縮使硬化層表面引起波浪而損害外觀。反之超 過50 時，並不優於50 Am厚度硬化層之表面硬度，品 質上之優點少。 如此成型之成型體，因具有硬化層以補強表面硬度， 可適合當作安裝於與外部接觸位置且要求耐擦傷性之家電 -45- 201038637 用銘板、汽車用銘板、空罐、建材、化粧板、化粧鋼板、 轉印片材等成型部品使用。 實施例 玆以下述實施例詳細說明本發明。又，各實施例製得 之薄膜之特性，以下述方法進行測定、評價。 (1) 樹脂之固有黏度 ’ 精確秤取樹脂片樣品O.lg，溶解於25ml苯酚/四氯乙 烷=60/40(質量比）之混合溶劑中，使用奧氏黏度計 (OstwalcT s viscometer)在30°C進行測定。又，測定實施3 次，求其平均値。 (2) 原料（對象物）之熔點（Tm) 使用示差掃猫式熱量測定計（Differential Scanning Calorimeter、Max Science 公司製、DSC3100S)，以各實施 例之條件擠出之原料約7mg裝入樣品盤並加蓋，在氮氣環 境下由室溫至300°C以20°C /分鐘之升溫速度進行升溫並測 定。熔點以第9· 1項所定義之熔解波峰溫度（Tpm)求得。 基材薄膜之熔點亦同樣進行測定，求得熔解波峰溫度 (Tpm)。 (3) 基材薄膜之厚度不均 由製得之基材薄膜採取橫向拉伸方向之長度3m、縱向 拉伸方向之寬度5cm之薄膜，並卷取成連續帶狀樣品，使 用薄膜厚度連續測定機（安立（ANRITSU)股份公司製）測定 薄膜厚度並記錄於記錄器。由記錄圖求取厚度之最大値 -46 - 201038637 (Tmax)、最小値（Tmin)、平均値（Tav)，以下式計算厚度不 均（％)。又，測定實施3次，求其平均値。另，橫向拉伸方 向之長度不足3 m時經連接後實施。又連接部位之測定値則 刪除不計。 厚度不均（％) = [(Tmax — Tmin)/Tav]xl00 (4) 基材薄膜之厚度 製得之基材薄膜使用millitron進行測定，每1枚5點， 共3枚15點，求其平均値。 (5) 基材薄膜之1〇〇%伸長時應力、斷裂伸長率 由製得之基材薄膜以單面刀片切取長度方向之長 1 8 0mm、寬度方向之寬10mm之細長方形狀試樣。其次，使 用拉伸試驗機（東洋精機股份公司製）拉伸上述細長方形狀 試樣，由所得負荷一變形曲線求得各方向之1〇〇%伸長時應 力（MPa)及斷裂伸長率（％)。 又，測定在溫度25 °C下，以初期長度40mm(即抗拉試 驗之標點間距離）、夾頭間距離100mm、十字頭速度 100mm/min、記錄器之記錄圖速度200mm/min、測力器25kgf 之條件進行測定。又，測定實施1 〇次，求其平均値。 又，在溫度1 0 0 °C下，亦以與上述相同之條件下進行拉 伸測定。此時，試樣在溫度l〇〇°C下保持30秒後進行測定。 又，測定實施10次，求其平均値。 (6) 基材薄膜之150°C下之熱收縮率 由製得之基材薄膜切取長度方向之長15〇mm、寬度方 -47- 201038637 向之寬20mm之細長方形狀試樣。在各試樣之長度方向以 1 00mm間隔打上2個記號，先在無負荷下測定2個記號間 之間隔A。其次，在無負荷下，將各細長方形狀試樣之一 側以夾子吊掛於籃子，放入150°C環境下之陳化烘箱（geer oven)中並開始計時。經30分鐘後由陳化烘箱中取出籃子， 在室溫下放置3 0分鐘。其次，在無負荷下測定2個記號間 之間隔B。以量測所得間隔A與間隔B，由下式計算150 °C下之熱收縮率。 熱收縮率（％)= [(A — Β)/Α]χ100 (7) 基材薄膜之耐溶劑性 將試樣浸漬在調溫爲2 5 °C之甲苯中30分鐘，就浸漬前 後之外觀改變以下列基準進行判定，並以〇爲及格。又， 霧度値以下述方法測定（見第9項）。 〇：外觀幾無改變，霧度値之改變未達1 % X :可辨認外觀改變，或霧度値之改變1 %以上 (8) 平面定向度（△ P) 就製得之成型用硬被覆膜，以鈉D線（波長5 89nm)爲光 源，由硬化層對側進行觀察，使用阿貝（Abbe)折射計測定 薄膜長度方向之折射率（Nx)、寬度方向之折射率（Ny)、厚 度方向之折射率（Nz)，由下式計算平面定向度（ΔΡ)。 Δ P = [(Nx + Ny)/2] - Nz (9) 成型用硬被覆膜之霧度 就製得之成型用硬被覆膜，依據IIS — K7 1 3 6 — 2000， -48- 201038637 使用霧度計（日本電色工業股份公司製' 3 00 A)測定薄膜之 霧度。又，測定實施2次，求其平均値。 (10) 成型用硬被覆膜在波長370nm下之光線透射率 就製得之成型用硬被覆膜，使用分光光度計（島津製作 所股份公司製、UV— 1 200)，測定波長370nm紫外線下薄膜 之光線透射率。 (11) 成型用硬被覆膜之耐光性 將實施膠版印刷之印刷樣品以印刷面爲裡側，放置在 0 暗箱中日光燈（松下電器股份公司製' U型日光燈FUL9EX) 之直下3cm位置。接著進行連續2000小時之日光燈照射， 就光照射前後印刷面側之顏色（a *、b *、L * )，依據JIS -Z - 87 30測定色差（△ E値）。色差（△ E値）愈小則光照射 前後之顏色改變愈小，即耐光性優異。耐光性之及格標準 爲色差（△ E値）0.5以下。又，色差（A E値）由下式計算求得。 AE=v^(Aa2+ Ab2+L2A) Ο (12)成型用硬被覆膜之成型性 薄膜實施5mm四方之格線印刷（grid printing)，再以加 熱爲500°C之紅外線加熱器將此薄膜加熱10〜15秒後，以 模具溫度30〜100 °C進行真空成型。又，各薄膜之加熱條件 由上述範圍中選擇最適合條件。所使用模具形狀爲杯形， 開口部直徑50mm，底部直徑45mm，深5mm，所有角落均 製成直徑0.5mm之彎曲。 在最適合條件下進行真空成型製得5個成型品，評價 -49- 201038637 其成型性及完成性’以下列基準進行等級排序。又，◎及 〇爲及格，X爲不及格。 ◎ : (1)成型品無破裂、 (ii) 成型品的角之曲率半徑爲1mm以下，且印刷偏 離爲O.linm以下、 (iii) 並無相當於X之外觀不良； 〇：（i)成型品無破裂、 (ii) 成型品的角之曲率半徑超過1111111但丨.5111111以 下，或印刷偏離超過0.1mm但0.2mm以下'、 (iii) 並無相當於X之外觀不良，實用上無問題$ 水準之成型品； X: (i)成型品有破裂或雖無破裂但相當於下列（i)〜（lv) 各項之任一項： (i) 成型品的角之曲率半徑超過1.5mm、 (ii) 出現大皺紋而外觀不良、 (iii) 薄膜泛白而透明性減低、 (i v)印刷偏離超過0.2 m m。 (13)成型用硬被覆膜之印刷等級 將印刷前之硬被覆膜以90°C進行熱處理30分鐘後，在 硬化層之反面實施4色網版印刷。 此設置印刷層之硬被覆膜以8 0 °C乾燥3 0分鐘。印刷等 級之評價以下述透明感、印刷適合性、印刷偏離等印刷外 觀，非由印刷面而由印刷面之反面通過硬被覆膜以目視判 -50- 201038637 定。判定基準爲〇：所有項目均無問題、△:至少有1項 有問題、X : 2項以上有問題。 a. 透明感：印刷之圖案不被基材薄膜或塗布層遮蔽而 鮮明。 b. 印刷適合性：不發生因印刷墨水轉移不良引起之顏 色不均或漏失。 c. 印刷偏離：無法以目視判定印刷偏離。 (14) 硬化層之伸長率 〇 爲判定硬化層之伸長率，以前述方法進行評價。在此， 伸長率10%以上判定爲成型性優良，伸長率30%以上判定 爲成型性特優。 (15) 硬化層之鉛筆硬度 爲判定硬化層之表面硬度，以前述方法進行評價。在 此，鉛筆硬度爲Η以上判定爲具有優良表面硬度，2H以上 判定爲具有特優表面硬度。 Q (16)硬化層之耐擦傷性 爲判定硬化層之耐擦傷性，以前述方法進行評價，依 下述判定基準判定等級。耐擦傷性等級爲C以上時判定有 耐擦傷性，等級爲Β以上時判定耐擦傷性良好。 Α:無擦傷發生’或觀察到少量程度之淺傷痕； Β:觀察到淺傷痕，但無深傷痕； C :觀察到淺傷痕，並觀察到少量程度之深傷痕； D:觀察到多量深傷痕。 -51- 201038637 (17) 成型用硬被覆膜之色調b* 爲評價硬化層之著色（黃變）程度，以前述方法進行評 價。b *値爲2 · 0以下即判定良好，超過2 · 0則硬化層之黃 變大而判定爲不良。 (18) 成型後之鉛筆硬度、硬化層厚度 於前述之伸長率評價時，在發生紋裂直前停止拉伸’ 將此時之鉛筆硬度與前述評價方法相同進行評價。又’此 時之硬化層厚度以分光光度計（島津製作所製、UV- 3150 型）測定求得分光反射率，由波長400nm以上、600nm以下 之波形以峰谷（peak valley)法計算硬化層厚度。此時所須要 之折射率，係製作硬化層之單層膜，利用阿貝（Abbe)折射 計（ATAGO公司製、NAR- IT SOLID)測定求得折射率。 (19) 塗布硬化層用塗布液時有無發生縐紋 爲判定硬化層用塗布液塗布後乾燥時之乾燥溫度及薄 膜張力是否適當，而評價有無發生縐紋。將寬度700mm之 基材薄膜塗布1 〇〇m時，如不發生縐紋則判定爲良好（〇）， 如發生縐紋則判定爲不良（X)。 (20) 硬化層之塗布外觀 爲判定硬化層用塗布液塗布後乾燥時之乾燥溫度是否 適當，而評價塗布外觀。將寬度1 06 0mm之基材薄膜塗布 1 00m時，硬化後之硬化層如完全無泛白、塗布缺失、或撥 拒等缺陷則判定爲良好（〇）’如有缺陷則判定爲不良（X)。 (21) 塗布硬化層時之寬方向收縮率 -52- 201038637 爲判定硬化層用塗布液塗布後乾燥時之乾燥溫度及薄 膜張力是否適當，而評價寬方向收縮率。將寬度7 0 0mm之 基材薄膜塗布l〇〇m時，測定塗布前後基材薄膜之寬方向收 縮率。此收縮率如爲1.5 %以下時判定爲良好，超過1.5 %時 判定爲不良。 (實施例1) (調製塗布液） 依常法進行酯交換反應及縮聚反應，調製水分散性含 〇 磺酸金屬鹽基之共聚聚酯樹脂；其組成爲含對酞酸46莫耳 % (相對於總二羧酸成分、以下同）、異對酞酸4 6莫耳％、及 5 -磺酸根基（sulfonato)異酞酸鈉8莫耳％當做二羧酸成 分’乙二醇50莫耳％ (相對於總二醇成分、以下同）、及新 戊二醇50莫耳％當做二醇成分。其次，將水51.4重量份、 異丙醇38重量份、正丁基賽璐素5重量份、非離子系界面 活性劑0.06重量份混合後加熱攪拌，當到達77χ：時對此加 Q 入上述水分散性含磺酸金屬鹽基之共聚聚酯樹脂5重量 份，繼續攪拌至無樹脂塊存在後，將此樹脂水分散液冷卻 至常溫，得固體成分濃度5.0重量％之均勻水分散性共聚聚 酯樹脂液。另取聚集體矽石粒子（FU〗I - SILYSIA股份公司 製、SYLYSIA 310)3重量份分散於水50重量份後，將此 SYLYSIA 310之水分散液0.54重量份加入上述分散性共聚 聚酯樹脂液99.46重量份中，再一面攪拌一面加入水2〇重 量份，即得塗布液。 -53- 201038637 (調製基材薄膜） 將共聚聚酯（構成成分爲對酞酸單位100莫耳％當做芳 香族二羧酸成分，乙二醇單位40莫耳％及新戊二醇單位60 莫耳％當做二醇成分，固有黏度爲〇.69dl/g)之樹脂片（A)及 聚對酞酸乙二酯（固有黏度爲〇.69dl/g，含有平均粒徑（SEM 法）1.5从m之無定形矽石〇.〇4質量％及苯并三唑系紫外線吸 收劑（NKCIBA SPECIALITY CHEMICALS 股份公司製、 TINUVIN326)0.6質量％)之樹脂片（B)分別乾燥後，樹脂片（A) 與樹脂片（B)以25 : 7 5之質量比混合。其次，此等樹脂片 混合物由擠壓機之T模頭縫口以270 °C熔融擠出，在表面 溫度40°C之冷卻輥上急冷固化，同時使用靜電外加法使附 著於冷卻輥得無定形未拉伸片材。 上得未拉伸片材在加熱輥與冷卻輥之間以90°C縱向拉 伸3.3倍。 其次，在單軸拉伸薄膜之雙面塗布上述塗布液，以丨20 °C乾燥，設置固體成分濃度0.08g/m2之中間層（含有平均粒 徑0.2/Z m之矽石0.003質量％)。 其次，將單軸拉伸薄膜導入拉幅機，以120°C預熱10 秒鐘後，前半段以ll〇°C、後半段以100°C橫向拉伸3.9倍。 再以熱處理向橫方向進行7 %之鬆驰處理下以23 5°C實施熱 固定處理，得厚度1〇〇 之基材薄膜。 (製作硬被覆膜） 使用刮刷器將下列塗布液A塗布在上得基材薄膜使乾 -54- 201038637 燥後之塗膜厚度爲2/z m後，以溫度801之熱風乾燥60秒， 並在輸出功率120W/cm之高壓水銀燈下20cm位置以 10m/min速度通過，製得成型用硬被覆膜。 (硬被覆塗布液A) 將下列材料以下述質量比混合，並攪拌30分鐘以上使 之溶解。其次，使用標稱過濾精密度l^m之過濾器濾除未 溶解物，製成塗布液A。 * 甲基乙基酮 64.48質量％ 〇 肇新戊四醇三丙烯酸酯 11.45質量％ (新中村化學公司製、NK ESTER A - TMM - 3LM - N、 官能基數3) 鲁三伸丙二醇二丙烯酸酯 5.73質量％ (新中村化學公司製、NK ESTER APG - 200、官能基數2) •二甲基胺乙基甲基丙烯酸酯 5.72質量％ (共榮社化學公司製、LIGHT ESTER DM、官能基數1) Q •矽石微粒 11.45質量％ (日產化學工業公司製、MEK - ST-L、固體成分率： 30%、平均粒徑：50nm) «光聚合引發劑 1.14質量％ (CIBA SPECIALITY CHEMICALS 公司製、IRGACURE 184) *有機矽系界面活性劑 0.03質量％ (DOW CORNING TORAY 公司製、DC57) 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 -55- 201038637 傷性、著色程度均良好，當作成型用硬被覆膜良好。又， 使用製得之成型用硬被覆膜成型之成型體，其表面硬度亦 良好。所得結果不如第1表。 (實施例2) 於實施例1，除將形成硬化層之塗布液變更爲下述之 塗布液B以外’其他與實施例1相同，得成型用硬被覆膜。 (塗布液B) ♦甲基乙基酮 64.48質量％ •新戊四醇三丙烯酸酯 17.18質量％ (新中村化學公司製、NK ESTER A - TMM - 3LM - N、 官能基數3) *三伸丙二醇二丙烯酸酯 2.86質量％ (新中村化學公司製、NK ESTER APG - 200、官能基數2) *二甲基胺乙基甲基丙烯酸酯 2.86質量％ (共榮社化學公司製、LIGHT ESTER DM、官能基數1) *矽石微粒 11.45質量％ (曰產化學工業公司製、MEK -ST-L、固體成分率： 30%、平均粒徑：50nm) *光聚合引發劑 1.14質量％ (CIBA SPECIALITY CHEMICALS 公司製、IRGACURE 184) *有機矽系界面活性劑 0.03質量％ (DOW CORNING TQRAY 公司製、DC57) 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 -56- 201038637 傷性、著色程度均良好，當作成型用硬被覆膜良好。又， 使用製得之成型用硬被覆膜成型之成型體，其表面硬度亦 良好。所得結果示如第1表。 (實施例3) 於實施例1，除將形成硬化層之塗布液變更爲下述之 塗布液C以外’其他與實施例1相同，得成型用硬被覆膜。 (塗布液C) 鲁甲基乙基酮 64.48質量％ 〇 ^ •新戊四醇三丙烯酸酯 8.02質量％ (新中村化學公司製、NK ESTER A - TMM - 3LM - N、 官能基數3) 參三伸丙二醇二丙烯酸酯 7.44質量％ (新中村化學公司製、NK ESTER APG - 200、官能基數2) • 二甲基胺乙基甲基丙嫌酸酯 7.44質量％ (共榮社化學公司製、LIGHT ESTER DM、官能基數1) Q * 矽石微粒 11.45質量％ (日產化學工業公司製、MEK - ST - L、固體成分率： 3〇%、平均粒徑：50nm) *光聚合引發劑 1.14質量％ (CIBA SPECIALITY CHEMICALS 公司製、IRGACURE 184) *有機矽系界面活性劑 0.0 3質量％ (DOW CORNING TORAY 公司製、DC57) 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 -57- 201038637 傷性、著色程度均良好，當作成型用硬被覆膜良好。又， 使用製得之成型用硬被覆膜成型之成型體，其表面硬度亦 良好。所得結果示如第1表。 (實施例4) 於實施例1，除將形成硬化層之塗布液變更爲下述之 塗布液D以外，其他與實施例1相同，得成型用硬被覆膜。 (塗布液D) ♦ 甲基乙基酮 64.48質量％ 秦新戊四醇三丙烯酸酯 21.75質量％ (新中村化學公司製、NK ESTER A - TMM - 3LM - N、 官能基數3) * 三伸丙二醇二丙烯酸酯 0.58質量％ (新中村化學公司製、NK ESTER APG - 200、官能基數2) • 二甲基胺乙基甲基丙烯酸酯 0.57質量％ (共榮社化學公司製、LIGHT ESTER DM、官能基數1) 鲁矽石微粒 1 1.4 5質量％ (曰產化學工業公司製、MEK - ST - L、固體成分率： 3 0 %、平均粒徑：5 0 n m) *光聚合引發劑 1.1 4質量％ (CIBA SPECIALITY CHEMICALS 公司製、IRGACURE 184) *有機矽系界面活性劑 0.0 3質量％ (DOW CORNING TORAY 公司製、DC57) 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 -58- 201038637 傷性、著色程度均良好，當作成型用硬被覆膜良好。又’ 使用製得之成型用硬被覆膜成型之成型體，其表面硬度亦 良好。所得結果示如第1表。 (實施例5) 於實施例1，除將形成硬化層之塗布液變更爲下述之 塗布液E以外，其他與實施例1相同，得成型用硬被覆膜。 (塗布液E) * 甲基乙基酮 64.48質量％ 〇 _新戊四醇三丙烯酸酯 1.1 5質量％ (新中村化學公司製、NK ESTER A - TMM - 3LM - N、 官能基數3) * 三伸丙二醇二丙烯酸酯 0.58質量％ (新中村化學公司製、NK ESTER APG - 200、官能基數2) * 二甲基胺乙基甲基丙烯酸酯 21.17質量％ (共榮社化學公司製、LIGHT ESTER DM、官能基數1) Q ·矽石微粒 11.45質量％ (曰產化學工業公司製、MEK - ST - L、固體成分率： 30%、平均粒徑：50nm) * 光聚合引發劑 1.14質量％ (CIBA SPECIALITY CHEMICALS 公司製、IRGACURE 184) *有機矽系界面活性劑 0.0 3質量％ (DOW CORNING TORAY 公司製、DC57) 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 -59- 201038637 傷性、著色程度均良好，當作成型用硬被覆膜良好。又， 使用製得之成型用硬被覆膜成型之成型體，其表面硬度亦 良好。所得結果示如第1表。 (實施例6) 於實施例1，除將形成硬化層之塗布液變更爲下述之 塗布液F以外，其他與實施例1相同，得成型用硬被覆膜。 (塗布液F) 籲甲基乙基酮 64.48質量％ *新戊四醇三丙烯酸酯 21.75質量％ (新中村化學公司製、NK ESTER A - TMM - 3LM - N、 官能基數3) *三伸丙二醇二丙烯酸酯 1.15質量％ (新中村化學公司製、NK ESTER APG - 200、官能基數2) * 矽石微粒 11.45質量％ (日產化學工業公司製、MEK - ST-L、固體成分率： 30%、平均粒徑：50nm) *光聚合引發劑 1.14質量％ (CIBA SPECIALITY CHEMICALS 公司製、IRGACURE 184) * 有機矽系界面活性劑 0.03質量％ (DOW CORNING TORAY 公司製、DC57) 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 傷性、著色程度均良好，當作成型用硬被覆膜良好。又’ 使用製得之成型用硬被覆膜成型之成型體，其表面硬度亦 -60- .201038637 良好。所得結果示如第1表。 (實施例7) 於實施例1，除將形成硬化層之塗布液變更爲下述之 塗布液G以外，其他與實施例i相同，得成型用硬被覆膜。 (塗布液G) *甲基乙基酮 64.48質量％ *新戊四醇三丙烯酸酯 1.15質量％ (新中村化學公司製' NK ESTER A - TMM - 3LM - N、 Ο 官能基數3) *三伸丙二醇二丙烯酸酯 21.75質量％ (新中村化學公司製、NK ESTER APG - 200、官能基數2) *矽石微粒 11.45質量％ (日產化學工業公司製、MEK - ST - L、固體成分率： 30%、平均粒徑：50nm) *光聚合引發劑 1.1 4質量％ 〇 (CIBA SPECIALITY CHEMICALS 公司製、IRGACURE 184) *有機矽系界面活性劑 0.03質量％ (DOW CORNING TORAY 公司製、DC57) 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 傷性、著色程度均良好，當作成型用硬被覆膜良好。又， 使用製得之成型用硬被覆膜成型之成型體，其表面硬度亦 良好。所得結果示如第1表。 (實施例8) -61- 201038637 於實施例1，除將形成硬化層之塗布液變更爲下述之 塗布液Η以外’其他與實施例1相同’得成型用硬被覆膜。 (塗布液Η) * 甲基乙基酮 64.48質量％ 籲新戊四醇三丙烯酸酯 1.15質量％ (新中村化學公司製、NK ESTER A - ΤΜΜ - 3LM - Ν、 官能基數3) •二甲基胺乙基甲基丙烯酸酯 21.75質量％ (共榮社化學公司製、LIGHT ESTER DM、官能基數1) * 矽石微粒 11.45質量％ (日產化學工業公司製、MEK- ST - L、固體成分率： 3 0%、平均粒徑：50nm) ♦光聚合引發劑 1.14質量％ (CIBA SPECIALITY CHEMICALS 公司製、IRGACURE 184) *有機矽系界面活性劑 0.03質量％ (DOW CORNING TORAY 公司製、DC57) 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 傷性、著色程度均良好，當作成型用硬被覆膜良好。又， 使用製得之成型用硬被覆膜成型之成型體，其表面硬度亦 良好。所得結果示如第1表。 (實施例9) 於實施例1，除將形成硬化層之塗布液變更爲下述之 塗布液I以外，其他與實施例1相同，得成型用硬被覆膜。 -62- 201038637 (塗布液I) * 甲基乙基酮 64.48質量％ •新戊四醇三丙烯酸酯 11.45質暈％ (新中村化學公司製、NK ESTER A - ΤΜΜ - 3LM - Ν、 官能基數3) 參三伸丙二醇二丙烯酸酯 5.73質量％ (新中村化學公司製、NK ESTER APG - 200、官能基數2) • 二乙基胺乙基甲基丙烯酸酯 5.72質量％ Ο ο (共榮社化學公司製、LIGHT ESTER DE、官能基數1) ♦矽石微粒 11.45質量％ (曰產化學工業公司製、MEK- ST - L、固體成分率： 30%、平均粒徑：50nm) *光聚合引發劑 1.14質量％ (CIBA SPECIALITY CHEMICALS 公司製、IRGACURE 184) ♦有機矽系界面活性劑 0.03質量％ (DOW CORNING TORAY 公司製、DC57) 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 傷性、著色程度均良好，當作成型用硬被覆膜良好。又， 使用製得之成型用硬被覆膜成型之成型體，其表面硬度亦 良好。所得結果示如第1表。 (實施例10) 於實施例1，除將形成硬化層之塗布液變更爲下述之 塗布液J以外，其他與實施例1相同，得成型用硬被覆膜。 -63- 201038637 (塗布液υ * 甲基乙基酮 64.48質量％ •新戊四醇三丙烯酸酯 11.45質量％ (新中村化學公司製、NK ESTER A - TMM - 3LM - N、 官能基數3) 鲁三伸丙二醇二丙烯酸酯 5.73質量％ (新中村化學公司製、NK ESTER APG - 200、官能基數2) * N-乙烯基甲醯胺 5.72質量％ (荒川化學工業公司製、BEAMSET 770、官能基數1) '」 參矽石微粒 1 1.45質量％ (日產化學工業公司製、MEK - ST - L、固體成分率： 30%、平均粒徑：50nm) 修光聚合引發劑 1.14質量％ (CIBA SPECIALITY CHEMICALS 公司製、IRGACURE 184) * 有機矽系界面活性劑 0.03質量％ (DOW CORNING TORAY 公司製、DC57) £ . 1,1 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 傷性、著色程度均良好，當作成型用硬被覆膜良好。又， 使用製得之成型用硬被覆膜成型之成型體，其表面硬度亦 良好。所得結果示如第1表。 (實施例1 1) 於實施例1，除將形成硬化層之塗布液變更爲下述之 塗布液K以外，其他與實施例1相同，得成型用硬被覆膜。 -64 - 201038637 (硬被覆塗布液κ) • 甲基乙基酮 67.93質量％ 籲新戊四醇三丙烯酸酯 11.58質量％ (新中村化學公司製、NK ESTER A - ΤΜΜ - 3LM - Ν、 官能基數3) •三伸丙二醇二丙烯酸酯 5.79質量％ (新中村化學公司製、NK ESTER APG - 200、官能基數2) *二甲基胺乙基甲基丙烯酸酯 5.79質量％ 〇 (共榮社化學公司製、LIGHT ESTER DM、官能基數1) * 矽石微粒 7.72質量％ (日產化學工業公司製、MEK - ST - L、固體成分率： 30%、平均粒徑：50nm) _光聚合引發劑 1.16質量％ (CIBA SPECIALITY CHEMICALS 公司製、IRGACURE 184) 鲁有機矽系界面活性劑 0.03質量％ Q (DOW CORNING TORAY 公司製、DC57) 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 傷性、著色程度均良好，當作成型用硬被覆膜良好。又， 使用製得之成型用硬被覆膜成型之成型體，其表面硬度亦 良好。所得結果不如第1表。 (實施例12) 於實施例1’除將形成硬化層之塗布液變更爲下述之 塗布液L以外’其他與實施例1相同，得成型用硬被覆膜。 -65 - 201038637 (塗布液L) 鲁甲基乙基酮 4.24質量％ 鲁新戊四醇三丙烯酸酯 6.22質量％ (新中村化學公司製、NK ESTER A - TMM - 3LM - N、 官能基數3) *三伸丙二醇二丙烯酸酯 3.12質量％ (新中村化學公司製、NK ESTER APG - 200、官能基數 2) ♦二甲基胺乙基甲基丙烯酸酯 3.12質量％ (共榮社化學公司製、LIGHT ESTER DM、官能基數1) *矽石微粒 82.73質量％ (日產化學工業公司製、MEK - ST - L、固體成分率： 30%、平均粒徑：50nm) * 光聚合引發劑 0.55質量％ (CIBA SPECIALITY CHEMICALS 公司製 ' IRGACURE 184) •有機矽系界面活性劑 0.02質量％ (DOW CORNING TORAY 公司製、DC57) 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 傷性、著色程度均良好，當作成型用硬被覆膜良好。又， 使用製得之成型用硬被覆膜成型之成型體，其表面硬度亦 良好。所得結果不如第1表。 (實施例13) 於實施例1’除將形成硬化層之塗布液變更爲下述之 -66- 201038637 塗布液Μ以外，其他與實施例1相同，得成型用硬被覆膜。 (塗布液Μ) 籲甲基乙基酮 71.46質量％ •新戊四醇三丙烯酸酯 11.72質量％ (新中村化學公司製、NK ESTER Α - ΤΜΜ - 3LM - Ν、 官能基數3) 參三伸丙二醇二丙烯酸酯 5,86質量％ (新中村化學公司製、NK ESTER APG - 200、官能基數2) 〇 *二甲基胺乙基甲基丙烯酸酯 5.86質量％ (共榮社化學公司製、LIGHT ESTER DM、官能基數1) *矽石微粒 3.90質量％ (曰產化學工業公司製、MEK - ST - L、固體成分率： 30%、平均粒徑：50nm) 鲁光聚合引發劑 1.17質量％201038637 VI. Description of the Invention: [Technical Field to Which the Invention Is Alonged] The present invention relates to a hard coating film for molding. In particular, it is related to a hard coating film for molding which is excellent in surface hardness and scratch resistance and excellent in moldability and solvent resistance at low temperature and low pressure. In addition, it is also related to a hard coating film for light-resistant molding suitable for use in outdoor applications. [Prior Art] The sheet for molding has been conventionally represented by a polyvinyl chloride resin film, and is preferably used from the viewpoint of workability and the like. On the other hand, when the film is burned by a fire or the like, there is a problem of generation of a toxic gas and a problem of bleed out of the plasticizer. Since the environmental resistance is required in recent years, a new raw material having a small environmental burden is required. In order to satisfy the above requirements, an unstretched sheet composed of a polyester, a polycarbonate, and an acrylic resin of a non-chlorinated raw material is used in a wide range of fields. In particular, an unstretched sheet composed of a polyester resin is attracting attention because of its excellent mechanical properties, transparency, and economy. For example, in the prior art documents 1 to 5, a substantially amorphous polyester resin in which about 30 mol% of an ethylene glycol component in polyethylene terephthalate is substituted with 1,4-cyclohexane dimethanol is used. The unstretched polyester sheet of the component (see Patent Documents 1 to 5). The unstretched polyester-based sheet satisfies the market demand in terms of moldability or build-up suitability. However, since it is an unstretched sheet, heat resistance and solvent resistance are insufficient, and the market demand is not satisfied. . In order to solve the above problems, a method of biaxially stretching a polyethylene terephthalate film has been proposed (see, for example, Patent Documents 6 to 9). However, although the above method can improve heat resistance and solvent resistance, the moldability is not sufficient in 201038637, and the market demand cannot be satisfied from the viewpoint of uniformity of quality. Further, when it is used for outdoor use, the printed layer or the resin is easily denatured by sunlight, and it is deteriorated, which causes a problem that it is not resistant to long-term use. On the other hand, in order to prevent the injury when the film for molding is attached to the external contact position, a hardened layer is provided on the surface for the purpose of reinforcing the surface hardness of the film for molding and improving the scratch resistance. The method of providing a hardened layer in a film for molding is generally carried out by a pneumatic molding method or a vacuum molding method, and then the hardened layer is laminated by a post-processing method such as a dipping method or a spray method. However, in this method, the layering of the hardened layer is performed by a cluster type processing, so that the stability of the quality is also problematic in addition to the limited production speed. Therefore, it is now required to form a hardened layer on a film before molding by a roll to roll type process and then molding it to obtain a molded body. In the manner of laminating the hardened layer before molding, the properties sought by the hardened layer need to be accompanied by the same degree of surface hardness and scratch resistance as the method of setting the hardened layer after the post-forming method. Formability can be traced when the molding is deformed. However, in general, the hardened layer resin has a problem that the hardened layer is too hard and has no formability in order to satisfy the surface hardness, so that the hardened layer is cracked (the crack of the hardened layer) due to deformation during the forming process. Therefore, there has been a prior art which proposes a hard coating film which laminates a resin having a certain degree of surface hardness after hardening but which is still soft, or which improves the moldability, or a layer having flexibility and a layer having a strong surface hardness on the substrate. In 201038637, a plurality of layers are laminated to obtain a hard coating film having strong surface hardness and flexibility (see Patent Documents 10 to 13). (Patent Document 1) Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 9] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 2007-284626 (Patent Document No. Hei. [Patent Document 12] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2008-029666 (Patent Document 13) International Publication No. 2008/029666, the contents of the disclosure of the present invention. Although the coating film has an appropriate surface hardness, it has only the bending property and the limited processing property of the punching process, and the hard coating film proposed in Patent Document 12 has stretchability. However, the surface hardness cannot be satisfied. Further, the hard coating film proposed in Patent Document 13 attempts to coexist with surface hardness and moldability, but in the field where higher moldability or higher surface hardness is required, it is sometimes impossible to perform the full performance of 201038637. In other words, the above-mentioned patent document cannot provide a hard coating film for molding which satisfies both the characteristics of high surface hardness and high moldability without impairing the properties of the polyester film for molding which is excellent in moldability and solvent resistance. An object of the present invention is to solve the above problems, that is, a film for molding which is excellent in moldability and solvent resistance at a low temperature and a low pressure, and a hardened layer is processed and laminated on a film for forming before the molding. It is a hard coating film for molding that contributes to the improvement of productivity and quality stability, and has both surface hardness, scratch resistance, and follow-up moldability when deformation occurs during molding. "Means for Solving the Problem" The polyester film for molding of the present invention which can solve the above problems is composed of the following items. According to a first aspect of the invention, there is provided a hard coating film for forming a base film comprising a biaxially oriented polyester film containing a copolymerized polyester and a hardened Q layer obtained by curing a coating liquid, wherein the coating liquid The free radiation curable compound having at least 3 functional groups and the free radiation curable compound having 1 and/or 2 functional groups, and the 1 and/or 2 functional groups of the free radiation curable compound contained in the coating liquid The content of the radical radiation-curable compound is 5% by mass or more and 5% by mass or less, and the base film satisfies the following requirements (1) to (3): 201038637 (1) The film is stretched 100% in the longitudinal direction and the width direction. The stress at each time is 40 to 300 MPa at 25 ° C and 1 to 100 MPa at 100 ° C; (2) the melting point is 200 to 245 ° C; (3) the plane orientation is 0. 01 or more, 0. Below 095. According to a second aspect of the invention, at least one of the free-radiation-curable compounds contained in the coating liquid is a hard coating film for forming an epitaxial radiation-curable compound having an amine group. According to a third aspect of the invention, the hardened layer contains the particles having an average particle diameter of 10 nm or more and 300 nm or less, and the content of the particles in the hardened layer is 5% by mass or more and 70% by mass or less of the hard coating film for molding. According to a fourth aspect of the invention, the copolyester is (a) a copolyester composed of an aromatic dicarboxylic acid component, ethylene glycol, and a diol component containing a branched aliphatic diol or an alicyclic diol. Or (b) the above-mentioned hard coating film for molding comprising a copolymerized polyester comprising an aromatic dicarboxylic acid component of citric acid and an isocyanic acid and a glycol component containing ethylene glycol. According to a fifth aspect of the invention, the polyester comprising the biaxially oriented polyester film has a diol component containing 1,3-propanediol unit or 1,4-butanediol unit, and a hard coating film for molding. According to a sixth aspect of the invention, the biaxially oriented polyester film contains an ultraviolet absorber having a light transmittance of 50% or less at a wavelength of 370 nm. The seventh invention is a molded body obtained by applying any of the above-described hard coating films for molding by vacuum molding, pneumatic molding, and mold molding. 201038637 EFFECT OF THE INVENTION The hard coating film for molding of the present invention has excellent moldability at the time of heat molding at a low temperature and a low pressure, and has excellent solvent resistance. Further, the hard coating film for molding of the present invention has both surface hardness and scratch resistance and followability moldability which can follow the deformation at the time of molding. Since the hard coating film for molding of the present invention has high surface hardness and excellent stretchability, the embodiment can be suitably used for parts such as nameplates or building materials. Further, in the embodiment of the present invention, when the free radical hardening resin and/or particles having an amine group are used, both the surface hardness and the moldability can be more highly coherent, and it is suitably used in, for example, a case. Parts. Further, the present invention does not require hard coating processing after molding, and contributes to productivity and quality stability in molding processing. Further, in a preferred embodiment of the present invention, the film contains an ultraviolet absorber to reduce the transmittance in the ultraviolet range, and is capable of imparting light resistance, and is particularly suitable as a molding material for use in outdoor applications. EMBODIMENT OF THE INVENTION The mode of carrying out the present invention first describes the technical significance of the physical properties of the substrate film of the present invention. Next, a method of producing the base film of the present invention will be described. The hardened layer of the present invention will be further described. (Substrate film) In the present invention, the stress (F100) at the time of 100% stretching is a measure relating to the close contact with the moldability of the film. The reason why the F100 is in close contact with the moldability of the film is that, for example, when the biaxially oriented polyester film is molded by a vacuum molding method, 201038637, the film may be locally stretched by 100% or more in the vicinity of the corner of the mold. In the case of a film having a high F1 00, it is considered that a part of the extremely high stress is generated in such a local stretching portion, and the concentration of the stress causes the film to be broken to cause a decrease in moldability. On the other hand, in the film in which F 1 00 is too small, it is considered that although the moldability is good, only a weak tension is generated in a portion which is uniformly stretched at the plane of the mold, and as a result, the film does not seem to be uniformly pulled at the portion. Stretch. In the present invention, the physical property relating to moldability in accordance with the temperature at the time of molding is a stress (F10 (h.)) when 100% is stretched at 100 ° C. Further, regarding the use of a mold having irregularities or depressions In the case of molding, the film before molding and the mold are gently formed in advance, and the physical properties relating to moldability are measured by stress (F10 〇 25) at 100 ° C at 25 ° C. The film of the present invention, When the tensile strength is 100% at 25 ° C (F10 〇 25), the length direction and the width direction of the film are 40 to 300 MPa. When the length direction and the width direction of the film are 40 to 300 MPa, The lower limit is preferably 50 MPa, more preferably 60 MPa, more preferably more than 70 MPa, and the upper limit is preferably 250 MPa, more preferably 200 MPa, and more preferably 180 MPa. If F10 〇 25 is less than 40 MPa, the roll film is used. When pulling and unwinding (unwinding), the workability is poor due to elongation or rupture of the film. Conversely, if F 1 0〇25 exceeds 300 MPa, the moldability is poor. Especially when molding with a concave or convex mold, it may be advanced. The film before molding is formed along with the mold. It is not easy to adhere to the mold, and the design of the finished product is poor. Moreover, the stress of the film of the present invention when stretched at 100 ° C for 100% (F10〇l()〇 regardless of the length direction and the width direction of the film are 1~ lOOMPa -10- 201038637 is important. It is better in formability. The other form is better in stability, and the lower limit of heat in the super direction is calculated at the shrinkage rate. 01% sees a significant difference in heat shrinkage rate and width plating or printing after the addition (thickness, molded body substrate film 0. 5 % or more The upper limit of the length direction and the width direction of the film F10 〇 1 () D is 90 MPa, more preferably 80 MPa, and 70 MPa, F100! . The lower limit is preferably 5 MPa, preferably 10 MPa, and 20 MPa over 35 Μ P a from the viewpoint of elasticity and properties when the molded article is used. The film of the present invention has a shrinkage ratio in the length direction and width at 150 ° C. 〇1~5. 0% is appropriate. Thermal shrinkage at 150 °C ❹ 0. 1% is appropriate and 0. 5% is preferred. On the other hand, the thermal limit of I50 °c is preferably 4.5%, and is 4. 1% is better, 3. 2% is better. The biaxially stretched polyester film having a heat shrinkage ratio of the film in the longitudinal direction and the width direction of 150 ° C has not been achieved, and its practical effect is not different, and since the productivity is extremely lowered, it is not made at 150 ° C. It has not reached 0. 01% inevitability. On the other hand, the film shrinkage rate in the direction of the length of 150 °C exceeds 5. At 0%, the processing step is likely to cause the film to be deformed after the steaming shovel or splashing Q is required to be heated, and the film may be poor in appearance or design after work. Further, the base film of the present invention preferably has a thickness unevenness of 5% or less. When the thickness unevenness exceeds 5%, the planarity of the surface deteriorates, which may reduce the strength of the molded body. The thickness unevenness is preferably small, but it is preferable from the viewpoint of productivity. Further, in the present invention, the film has a haze of 0. 1~3. 0% is appropriate. Below the haze 201038637 Limited to 0_3% better, 〇 _5% better. On the other hand, the upper limit of haze is 2. 5 % is better, 2. 0% is better. Films having a haze of less than 1% are difficult to produce on a general production scale due to poor slidability. On the other hand, the haze of the film exceeds 3. At 0%, when the vapor deposition or the sputtering surface or the printing surface of the metal or the like is observed from the back side of the film, the metal or the printed surface does not appear to be inconspicuous, and the design is inferior. In the present invention, the degree of planar orientation (?p) of the film is also related to the formability of the formability. The degree of planar orientation is such that the polymer chain is oriented in the direction of the plane to reduce the formability. In the present invention, the plane orientation of the film is less than 〇. n. The upper limit of the plane orientation is 0. 095 or less is better, 0. 090 is better. Further, the smaller the orientation degree is, the better the moldability is. However, the strength of the film and the chemical resistance are liable to be lowered. Therefore, the lower limit of the plane orientation is 〇. 〇 1 or more, and 〇. 〇 2 is better, 0. 03 is better, 0. 04 is particularly good. (Method for Producing Base Film) The polyester film for molding of the present invention uses a copolymerized polyester as a raw material. The copolyester is (a) a copolymerized polyester composed of an aromatic dicarboxylic acid component, ethylene glycol, and a diol component containing a branched aliphatic diol or an alicyclic diol; or (b) A copolymerized polyester comprising an aromatic dicarboxylic acid component of citric acid and isomeric decanoic acid and a diol component containing ethylene glycol is suitable. Further, the polyester constituting the biaxially oriented polyester film preferably has a diol component such as 1,3-propanediol unit or 1,4-butanediol unit, and is preferable from the viewpoint of further improving moldability. In the present invention, the film raw material is a single copolymerized polyester, and the mixed seed is -12-. Any method such as homopolyester or copolyester on 201038637, or a combination of homopolyester and copolyester is possible. Among them, the blending method is suitable from the viewpoint of suppressing the decrease in the melting point. As the above copolymerized polyester, when a copolymerized polyester composed of an aromatic dicarboxylic acid component, ethylene glycol, and a diol component containing a branched aliphatic diol or an alicyclic diol is used, the aromatic diol is used. The carboxylic acid component is preferably p-citric acid, isophthalic acid, naphthalene dicarboxylic acid or an ester-forming derivative thereof, and is 70 mol relative to the amount of the citric acid and/or naphthalene dicarboxylic acid component of the dicarboxylic acid component. More than % is preferable, and it is preferably more than 8 5 mol%, more preferably 95 mol% or more, and 1 mol%. Further, as the branched aliphatic diol, for example, neopentyl glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol or the like can be exemplified. The aliphatic diol may, for example, be 1,4-cyclohexanedimethanol or dimethyloltricyclodecane. Among them, neopentyl glycol and 1,4-cyclohexanedimethanol are particularly suitable. Further, in the present invention, it is more suitable to use 1,3 -propanediol and 1,4-butanediol as a copolymerization component in addition to the above diol component. When such a diol is used as a copolymerization component, it is suitable for imparting the above properties, and it is excellent in transparency and heat resistance, and is also suitable from the viewpoint of improving the adhesion to the adhesion-modifying layer. Further, when the above-mentioned copolyester is a copolymerized polyester composed of an aromatic dicarboxylic acid component containing a tereic acid and an isophthalic acid and a glycol component containing ethylene glycol, the amount of the total diol component is relative to the total diol component. The ethylene glycol is preferably 70% by mole or more, more preferably 85% by mole or more, more preferably 95% by mole or more, and 100% by mole of the total -13 to 201038637. The diol component other than ethylene glycol is preferably the above-mentioned branched aliphatic dicyclo diol or diethylene glycol. The above copolyester 'haves an intrinsic viscosity of 0 from moldability, adhesion, and film forming stability point. 50dl/g or more 〇. More preferably 55dl/g or more, 0. More than 60 dl / g or more. Intrinsic viscosity At 50 dl/g, there is a tendency for moldability to decrease. In addition, when the filter is provided in the melt line (or in the middle of the melting), it is preferable to set the upper limit of the intrinsic viscosity from the viewpoint of discharging the stability when extruding the grease. In the present invention, one type or more is used. The homopolyester or the copolypolymer film raw material is blended to produce a film, and transparency and high heat resistance can be achieved while maintaining the same flexibility as the copolyester. Further, it is possible to achieve flexibility and practically no melting point (heat resistance) with respect to the use of only a high melting point homopolyester (e.g., phthalic acid ester) while maintaining high transparency. Further, when the base film has two or more layers, the amount of the copolymerization component of each layer may be the same or different, but a polyester resin having a different amount of the copolymer component or more is also a comparative embodiment of the present invention. Further, the above-mentioned copolymerized polyester is blended with a homopolyester other than polyethylene terephthalate (for example, polyparaphthalic acid tetramethylene (tetrabutyl) butyl phthalate) When the polyester film for molding of the present invention is used, it is more preferable from the viewpoint of moldability. The melting point of the above-mentioned polyester film is better from the viewpoint of heat resistance and moldability, and the degree of the oil and the fatity is not reached. The Odl/g ester is used as the raw material point for the multi-layered knot to be used only for the multi-layered joints, and at least 1 and the pair of raw materials are used. The polymerization is controlled by -14 - 201038637 200~24 5 °C. The type and composition of the substance, and the result of controlling the film forming conditions within the above-mentioned melting point range, and achieving a balance between moldability and completeness' can economically produce a high-grade molded article. Here, the melting point means that the scanning is performed by differential scanning. The endothermic peak temperature at the time of melting is detected at the time of one temperature rise in the heat measurement method (DSC, Differential Scanning Calorimetry), and the melting point is a temperature-increasing speed of 20 using a differential scanning calorimeter (for example, DSC3100S manufactured by Max Science Co., Ltd.). The lower limit of the melting point is preferably 210 ° C and 230 ° C. When the melting point is less than 200 ° C, the heat resistance tends to deteriorate. Therefore, when molding or when using a molded article, such as exposure There is a possibility of problems at high temperatures. In addition, amorphous polyesters having no melting point may have problems in terms of mechanical strength and chemical resistance. Further, the light transmittance of the substrate film at a wavelength of 370 nm 50% or less is preferable, 40% or less is more preferable, and 30% or less is more preferable. The light transmittance of the molding polyester film at a wavelength of 370 nm is controlled to 50% or less, and the printing layer can be lifted when the film is printed. The light resistance is a preferred embodiment of the present invention. The method of controlling the light transmittance at a wavelength of 370 nm to 50% or less is to use a method in which a UV absorber is blended in any one of the base film constituent layers. The absorbent may be inorganic or organic, as long as it can impart the above characteristics. Organic ultraviolet absorbers such as benzotriazole, benzophenone, cyclic imine, and the like, and combinations thereof. From the viewpoints of benzotriazole-based and cyclic imine esters, when two or more kinds of violet-expressing agents are used, the ultraviolet absorbing effect can be further improved by simultaneously absorbing ultraviolet rays of different wavelengths at the same time. The benzotriazole-based ultraviolet absorber may, for example, be -2 -[2,-hydroxy-5'-(methacrylomethoxymethyl)phenyl]-2H-benzotriazole, 2 - [2, — Jingji-5'-(methacrylofluorene) Ethyl)phenyl]-2H-benzotriazole, 2_[2'-diabase-5'-(methacryloxypropyl)phenyl]-2H-benzotriazole, 2 - [2' -hydroxy-5'-(methacrylofluorenyl)phenyl]-2H-benzotriazole, 2 - [2,-hydroxy-3'-tertiary butyl-5,-(methacrylofluorene) Ethyl)phenyl]-2H-benzotriazole, 2-[2,-hydroxy-5'-tertiary butyl-3'-(methacrylomethoxyethyl)phenyl]-2H-benzo Triazole, 2-[2'-hydroxy-5'-(methacrylomethoxyethyl)phenyl]-5-chloro-2H-benzotriazole, 2-[2'-hydroxy-5'-( Methyl propylene oxiranyl) phenyl]-5-methoxy-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloxyethyl)phenyl]-5 - gas-based-2H-benzotrim, 2-[2,-hydroxy-5'-(methacrylomethoxyethyl)phenyl]-5-tertiary butyl-2H-benzotriazole, 2 - [2'-hydroxy-5'-(methacrylomethoxyethyl)phenyl]-5-nitro-2H-benzotriazole or the like 'but is not particularly limited thereto. The cyclic imide-based ultraviolet absorber may, for example, be 2,2 '-(1,4-phenylene)bis(4H-3,1-benzoxanth-4-one), 2-methyl- 3,1-benzoxanthine, 2_butyl_3,1-benzopyrene _4-ketone, 2-phenyl-3,1-benzoindole-4-one, 2- (1 or 2-naphthyl)-3,1-benzopyrene _ 4 ketone, 2_(4-diphenyl)-3,1-benzoindole _ 4-ketone, p-nitrophenyl-3,1- Benzopyrene-4-one, 2-n-nitrophenyl_ 16 - 201038637 3,1-benzopyrene-4-one, 2-p-benzoquinone-3,1-benzopyrene-4 -ketone, 2-p-methoxyphenyl-3,1-benzoxanthene-4-one, 2-methoxymethoxy-3,1-benzoxanthene-4-one, 2-cyclohexyl- 3,1-benzoxanthene-4-one, 2-(p-()-(p-imide)phenyl-3,1-benzoindole-4-one, 2,2' - (1,4 - Phenyl)bis(4H-3,1-benzoindole-4-one) 2,2'-bis(3,1-benzoindole-4-one), 2,2'-extended ethyl Bis(3,1-benzoxanthene-4-one), 2,2 tetramethylene (or butyl) bis (3,1-benzoxanthene-4-one), 2,2'-ten Methylene bis(3,1_benzoxanthene-4-one), 2,2'-fluorene-p-phenylene (3,1 - And tillage-4-keto), 2,2'-meta-phenylene (3,1_benzoindole-4-one), 2,2'-(4,4'-diphenyl) double (3,1-benzoxanthene-4-one), 2,2'-(2,6- or 1,5-naphthalene)bis(3,1-benzoindole-4-one), 2, 2'-(2-Methyl-p-phenylene)bis(3,1-benzoindole-4-one), 2,2'-(2-nitro-p-phenylene) bis (3, 1 -benzoindole-4 -one), 2,2'-(2-chloro-p-phenylene)bis(3,1-benzopyrene-4-one), 2,2'_ (1 , 4 -cyclohexene) bis (3,1-benzopyrene-trap-4-Q ketone) 1,3,5-tris(3,1-benzoxanth-4 -one-2-yl)benzene, 1,3,5-tris(3,1-benzoxamicin-4 -indol-2-yl)naphthalene and 2,4,6-tris(3,1-benzoindole-4-one-2 - Naphthalene, 2,8-dimethyl-4H,6H-benzo(1,2-d; 5,4 - d') bis(1,3)-indole-4,6-dione, 2 ,7-Dimethyl-4H,9H-benzo(1,2-d;5,4-d')bis(1,3)-anthracene-4,9-dione, 2,8-diphenyl -4H,8H-benzo(1,2-d;5,4-d')bis(1,3)-fluorene- 4,6-diketone, 2,7-diphenyl-4H,9H -Benzo(1,2 - d;5,4 - d') bis(1,3)-fluorene trap-4,6-dione, 6,6 - bis(2-methyl-4H,3,1- -17- 201038637 benzoindole-4-one), 6,6'-bis(2-ethyl-4H,3,1-benzopyrene -4 -keto), 6,6'-bis(2-phenyl-4H,3,1-benzoindole-4-one), 6,6'-methylenebis(2-methyl-4H) , 3,1-benzopyrene--4-one), 6,6'-methylenebis(2-phenyl-4H, 3,1-benzoindole-4-one), 6,6' -Extended ethyl bis(2-methyl-4H, 3,1-benzoindole-4_one), 6,6'-extended ethyl bis(2-phenyl-4H, 3,1-benzopyrene Till-4-ketone), 6,6'_ butyl bis(2-methyl-4H, 3,1-benzoxanthene-4-one), 6,6'-butylbutylene (2- Phenyl-4H,3,1-benzoindole-4-one), 6,6'-oxybis(2-methyl-4H,3,1-benzoindole-4-one), 6 , 6'-oxybis(2-phenyl-4H,3,1-benzoindole-4-one), 6,6'-sulfonyl bis(2-methyl-4H,3,1_ Benzopyrene-4-ketone), 6,6'-sulfonylbis(2-phenyl-4H,3,1-benzoindole-4-one), 6,6'-carbon fluorenyl double (2) -Methyl-4H,3,1-benzoxanthene-4-one), 6,6'_Carbendyl bis(2-phenyl-4H, 3,1-benzoindole t- 4-one) 7,7'_ Methylene bis(2-methyl-4H,3,1-benzoindole-4-one), 7,7'-methylenebis(2-phenyl-4H, 3,1-benzopyrene Well _ 4-keto), 7,7'-bis(2-methyl-4H, 3,1-benzoindole-4-one), 7,7'-extended ethyl bis(2-methyl- 4H,3,1-Benzoindole 4- 4-one), 7,7'-oxybis(2-methyl-4H,3,1-benzoindole-4-one), 7,7' _sulfonyl bis(2-methyl-4H, 3,1-benzoindole-4-one), 7,7'-carbon bis (2-methyl-4H, 3,1-benzo)噚耕-4-keto), 6,7'-bis(2-methyl-4H,3,1-benzoindole-4-one), 6,7'-bis(2-phenyl-4H, 3,1-benzoxanthene-4-one), 6,7'-methylenebis-18- 201038637 (2-methyl-4H,3,1-benzoindole-4-one), and 6,7'-methylenebis(2-phenyl-4H,3,1-benzoindole-4-one) and the like. When the organic ultraviolet absorber is blended in the film, since it is exposed to a high temperature in the extrusion step, if the ultraviolet absorber is used as a UV absorber having a decomposition start temperature of 290 ° C or higher, the process contamination at the time of film formation is reduced. The words are more appropriate. When an ultraviolet absorber having a decomposition starting temperature of 290 ° C or less is used, the decomposition product of the ultraviolet absorber adheres to a roll group of a manufacturing apparatus in the film formation, and further adheres to the film or the damaged film to cause optical flexibility of the film. The disadvantage is not suitable. The inorganic ultraviolet absorber may, for example, be an ultrafine particle of a metal oxide such as cerium oxide, zinc oxide or titanium oxide. Further, in order to improve handleability such as slidability and take-up property of the film, it is preferable to form irregularities on the surface of the film. A method of forming irregularities on the surface of a film generally employs a method of containing particles in the film. The above particles have an average particle diameter of 0. 01 to 10//m of internal precipitated particles, inorganic particles and/or external particles such as organic particles. Further, the average particle diameter of the particles is obtained by photographing at least 200 or more particles by electron microscopy, and then the particle profile is traced on the OHP film, and the trace image is converted into a diameter equivalent to a circle by an image analysis device. Find out. The above external particles may be used, for example, wet and dry vermiculite, colloidal vermiculite, aluminum niobate, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, alumina, mica, kaolinite, clay, hydroxyapatite, etc. Inorganic particles and organic particles containing styrene, -19-201038637 polyfluorene, acrylic, etc. as constituents. Among them, dry and wet vermiculite, dry colloidal vermiculite, alumina and other inorganic particles, and organic particles such as styrene, polyoxymethylene, acrylic acid, methacrylic acid, polyester, divinylbenzene, etc. More suitable for use. These internal particles, inorganic particles, and/or organic particles may be used in combination of two or more kinds within the range not impairing the characteristics specified by the present invention. Furthermore, the content of the above particles in the film is 0. 001 to 10% by mass is suitable. Not up to 0. When the 001% by mass is deteriorated in the slidability of the film or the winding is difficult, the handleability is easily lowered. On the other hand, when it exceeds 10% by mass, it tends to cause formation of coarse protrusions and deterioration of film formability or transparency. However, since the particles contained in the film usually have a different precipitation rate than the polyester, they are the main reason for reducing the transparency of the film. In order to improve the design creativity of the molded article, the film is printed on the surface of the film before molding. Since such a printing layer is often applied to the back surface of the film for molding, it is desirable from the viewpoint of printing sharpness that the film has high transparency. Therefore, in order to obtain high transparency in order to maintain the film, a base film having a laminated structure of two or more layers is formed by using a laminate structure in which a base film having a main layer contains substantially no particles and only a surface layer contains particles. The laminated film can be effectively achieved, which is a preferred embodiment of the present invention. The upper limit of the thickness of the surface layer may be appropriately selected depending on the thickness of the film, but it is preferably 10/zm, more preferably 5/zm, more preferably 3/zm, and particularly preferably 1/zm. Further, the lower limit of the thickness of the surface layer is preferably 0 · 0 1 /i m from the viewpoint of productivity. At this time, particles as exemplified above can be used. -20- 201038637 Further, when high transparency is required, the haze of the substrate film of the present invention is o. i ~3. 0% is appropriate. The method for obtaining a film having high transparency is that the substrate film is substantially free of particles, and a layered structure in which an intermediate layer is provided between the hardened layer and the base film and only the intermediate layer contains particles as described later is also the present invention. A preferred embodiment. Further, the above-mentioned "substantially free of particles in the base film", such as inorganic particles, means that the content of the inorganic element is determined by fluorescent X-ray analysis to be a critical value or less. This is because even if the particles are not intentionally added to the base film, there is a possibility that contaminated components from foreign matter may be mixed. Further, in order to obtain a film having a low haze and high design creativity, it is preferable that the substrate film contains substantially no particles, but if it is 30 ppm or less, it is also possible to add particles to the substrate film. The base film of the present invention can be formed into a laminated structure by a conventional method by using a different type of polyester in order to impart other functions. The form of the laminated film is not particularly limited, and is a two-layer structure of two types of A/B, two types of three 〇 layer structures of B/A/B, and three types of three-layer structures of C/A/B. As described above, when the base material film contains the ultraviolet absorber, it is also a preferred embodiment of the present invention if it is contained only in the intermediate layer. The base film of the present invention is mainly a biaxially stretched film. In the present invention, the molecular orientation of biaxial stretching can improve the solvent resistance and dimensional stability of the unstretched sheet. That is, while maintaining the good moldability of the unstretched sheet while improving the solvent resistance and dimensional stability of the unstretched sheet, it is a feature of the base film of the present invention. -21- 201038637 The method for producing the above biaxially stretched polyester film is not particularly limited, and if the polyester resin is dried as needed, it is supplied to a conventional melt extruder, and a slit (and a long strip) is used as a sheet. The unstretched sheet is subjected to biaxial stretching by adhering to a casting drum, adding static electricity or the like, and then cooling and hardening the unstretched sheet (original sheet). The biaxial stretching method is a method of stretching and heat-treating an unstretched sheet in the longitudinal direction (MD) and the width direction (TD) of the film to obtain a biaxially stretched film having a target plane orientation. In this method, from the viewpoint of film quality, the MD/TD method of stretching in the longitudinal direction and then stretching in the width direction, and the TD/MD method of stretching in the width direction and then stretching in the longitudinal direction are gradually performed. The biaxial stretching method or the simultaneous biaxial stretching method in which the stretching is performed at the same time in the longitudinal direction and the width direction is suitable. Further, when the synchronous biaxial stretching method is employed, a tenter driven by a linear control motor can also be used. Further, a multi-step stretching method in which the stretching in the same direction is carried out in multiple stages can be used as needed. Regarding the stretching ratio in the biaxial stretching, it is preferred that the length direction and the width direction are 1. 6~4. 2 times 'very good is 1. 7~4. 0 times. In this case, the stretching ratio in the length direction and the width direction may be either the same or the same magnification. The stretching ratio in the longitudinal direction is 2. 8~4. 0 times, the stretching ratio in the width direction is 3. 0-4. 5 times is preferred. The stretching conditions in the production of the polyester film for molding of the present invention are preferably as follows. Stretching in the longitudinal direction, in order to make the subsequent transverse stretching smooth, set the pull -22-201038637 stretch temperature is 50~110 °C, the draw ratio is 1. 6~4. 0 times more suitable. When the polyethylene terephthalate film is usually stretched, if the stretching temperature is lower than the appropriate condition, the yield stress in the initial stage of the transverse stretching is sharply increased, so that the stretching cannot be performed. Further, even if it is stretchable, the thickness or the stretching ratio is likely to be uneven, which is not preferable. Further, if the stretching temperature is higher than the appropriate condition, the yield stress at the beginning of the transverse stretching is low, but the stress does not rise even if the stretching ratio is increased. Therefore, the formed film has a small stress at 100% stretching at 25 °C. According to this, when the optimum stretching temperature is employed, a film having a high degree of orientation can be obtained while ensuring stretchability. However, when the above copolymerized polyester contains 1 to 50 mol% of a copolymerization component, the tensile stress is drastically reduced as the stretching temperature is gradually increased to eliminate the yield stress. In particular, the tensile stress does not increase during the second half of the drawing, so the orientation is not improved, and the stress is also reduced when the tensile force is 100% at 25 °C. This phenomenon is likely to occur when the film thickness is 60 to 500; zm, especially in the case of a film having a thickness of 100 to 300 Å / zm. Therefore, in the film of the copolymerized polyester of the present invention, the transverse stretching temperature is preferably set to the following conditions. First, in the preheating treatment of the mixture (original sheet) of the film material extruded by an extruder, the preheating temperature in the range of the glass turning brittle temperature + l〇 ° C to + 50 ° C when measured by DSC get on. Secondly, the stretching temperature in the first half of the transverse stretching is set to be -20 ° C to + 15 t more than the preheating temperature. In the second half of the transverse stretching, the stretching temperature is set to be better than the first half stretching temperature ~ 30 ° C, and the first half stretching temperature is 10 ° C - -20 ° C -23 - 201038637 range Very good. With such a condition, it is easy to stretch due to a small yield stress in the first half of the transverse stretching and easy to be oriented in the latter half. Also, the lateral stretch magnification is set to 2. 5~5. 0 times is more suitable. As a result, it is possible to obtain a film which satisfies the requirements of the present invention, F100" or F100. Further, the heat treatment after the biaxial stretching (heat setting treatment), the following limit is the melting point - l 〇 ° C preferred and upper limit The crucible is preferably a heat-fixing temperature of 30 ° C. Generally speaking, the method of reducing the plane orientation degree has a method of reducing the draw ratio and a method of increasing the blending amount of the copolymer component, but the former method makes the thickness of the film thin. In the latter method, the method of reducing the melting point of the film to deteriorate the heat resistance is not suitable. In the present invention, the degree of planar orientation of the biaxially oriented polyester film and the heat shrinkage at 150 ° C are more common. (The intermediate layer) The hard coating film for molding of the present invention is formed by laminating a hard layer on one surface of a base film, but for the purpose of improving the adhesion between the base film and the hardened layer. The intermediate layer is preferably a polyester resin, a polyurethane resin, a polyester urethane resin, an acrylic resin, a melamine resin, and the like. It is important to select a mixed resin or the like in order to improve the adhesion between the base film and the cured layer. For example, when the resin constituting the base film and the cured layer is an acrylic resin, the acrylic or copolymerized polyester is used. At least one of the polyester urethane type and the like is preferably selected. For the purpose of improving adhesion and water resistance, the intermediate layer may contain a crosslinker to form a crosslinked structure. The crosslinking agent is, for example, urea, epoxy, melamine or isocyanate. Further, a crosslinking copolymer having self-crosslinking property may be used as the resin without using a crosslinking agent. The surface of the base film before the formation of the hardened layer is formed with irregularities to improve the slidability, and may contain various particles. The particles contained in the intermediate layer, such as vermiculite, kaolinite, talc, calcium carbonate, zeolite, alumina and the like , organic particles such as acrylic acid, PMM A, nylon, styrene, polyester, decylamine/formaldehyde condensate. Also, from the viewpoint of transparency, the particles with a refractive index similar to that of the resin used in bismuth should be selected. Preferably, the method of providing the intermediate layer is preferably a coating method using, for example, a gravure coating method, a kiss coating method, a dip coating method, a spray coating method, a curtain coating method, A conventional coating method such as an air knife coating method, a knife coating method, a reverse roll coating method, or the like, and a twist line (or a line) of a coating layer is provided in a manufacturing step of a base film (i n-line) The coating method, or the off-line coating method in which the coating layer is formed after the production of the substrate film, may be provided with an intermediate layer. In the square Q method, the twist coating method is not only superior in cost, but also As a result of containing the particles in the intermediate layer, it is not necessary to contain the particles in the base film, and it is preferable to improve the transparency. (The hardened layer) The hard coating film for molding of the present invention is on at least one side of the base film. The hardened layer is laminated directly or through the intermediate layer. In the present invention, the term "hardened layer" refers to a film (or film) having a hardness higher than that of the substrate film to reinforce the surface hardness of the substrate composed of the film of the material and to improve the scratch resistance, and has a -25- 201038637 A layer (film) that is excellent in moldability as it is deformed during molding. More specifically, the hard coating film for molding of the present invention has a surface hardness of at least 铅笔 铅笔 pencil hardness, and has an elongation of at least 1% by weight according to the evaluation method described later, so that it is suitable for use as a nameplate for home appliances. Or use for parts such as building materials. The hardened layer used in the present invention must have a free radiation curable resin as a main component. In this case, it is not necessary to heat-treat as the thermosetting resin is cured, and it is possible to reduce the heat shrinkage of the substrate film due to heat, which is suitable. In the present invention, the free-radiation-curable compound is a compound which causes polymerization and/or reaction as a result of irradiation with either electron beam, radiation or ultraviolet ray. The compound causes polymerization and/or reaction to form a hardened layer. The free-radiation-curable compound to be used in the present invention is, for example, a melamine-based, acrylic-based or organic-based free-radiation-type compound, and an acrylate-based free-radiation-hardening compound is preferable from the viewpoint of obtaining high surface hardness. Further, in the present invention, the free-radiation-curable compound is not limited to a monomer or a precursor, and of course, an free radiation-curable resin which is polymerized and/or reacted. For example, the acrylate-based free-radiation-type compound may, for example, be a polyurethane acrylate, a polyester acrylate, an epoxy acrylate or a polyol acrylate, and is not particularly limited, and any of them may be used. The acrylate-based free radiation-curable compound. The hardened layer of the present invention is obtained by coating a coating liquid containing at least three or more functional groups of an exogenous radiation-curable compound and a ruthenium and/or a bifunctional free radiation hard -26-201038637 compound. Then, it is irradiated by any one of electron beam, radiation, and ultraviolet light to cause polymerization and/or reaction to be hardened. When the acrylate-based free-radiation-type compound is used as the free-radiation-curable compound of the present invention, the monofunctional (monofunctional) acrylate-based free-radiation-type compound of the present invention contains at least one molecule in the molecule. The compound of the (meth)acrylonitrile group is not particularly limited. For example, acrylamide, (meth) propylene morpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) propylene oxime Amine, isobornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl diethylene glycol (meth) acrylate, Tertiary octyl (meth) acrylate, diacetone (meth) acrylamide, dimethylamine ethyl (meth) acrylate, diethylamine ethyl (meth) acrylate, lauryl (methyl a propylene acrylate, a dicyclopentadienyl (meth) acrylate, a dicyclopentenyl oxyethyl (meth) acrylate Q ester, a dicyclopentenyl (methyl) Acrylate, N,N-dimethyl(meth)acrylamide, tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydroindenyl (methyl) Acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (A) Acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (methyl) Acrylate, vinyl caprolactam, N-vinylpyrrolidone, N-vinylformamide, phenoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate -27- 201038637 ester, Pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, borneol (methyl) Acrylates such as methyl dimethyl ethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, decyl phenyl (meth) acrylate, and its caprolactam conversion, acrylic acid Wait for such a mixture and the like. When the acrylate-based free radiation ray-curable compound is used as the radical radiation ray-curable compound, the bifunctional acrylate-based free radiation-ray-curable compound of the present invention can have two or more alcoholic hydroxyl groups in one molecule. The compound in which the hydroxyl group forms two (meth) acrylate compounds in the polyvalent alcohol. Specific examples thereof include (a) (meth)acrylic acid diesters of alkylene glycol having 2 to 12 carbon atoms: ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate,丨, 4-butanediol di(meth) acrylate, neopentyl glycol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, etc.; (b) polyoxyalkylene (meth)acrylic acid diesters: diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate Ester, dipropylene glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, polypropylene glycol di(meth) acrylate, etc.; (c) methacrylic acid diester of polyvalent alcohol (') pentaerythritol di(meth)acrylate, etc.; (d) bisphenol A or bisphenol A hydride of ethylene oxide and propylene oxide adducts (meth)acrylic acid diesters: 2,2'-bis(4-propionyloxyethoxyphenyl)propane, 2,2'-bis(4-propoxypropyloxyphenyl)propene, etc.; (e) multivalent Isocyanate compound The reaction is carried out in advance with a compound containing two or more alcoholic S groups to obtain an isocyanate group-containing compound -28-201038637, and then reacted with an alcoholic hydroxyl group-containing (meth) acrylate to obtain two molecules (methyl group). a acryloyloxy urethane (meth) acrylate; (f) a propylene or methacrylic acid having a reaction with a compound having two or more epoxy groups in the molecule An epoxy group (meth) acrylate such as (meth) propylene fluorenyl. When the acrylate-based free-radiation-type compound is used as the free-radiation-type compound, the acrylate-based free-radiation-curable compound having a trifunctional or higher functional group of the present invention can be specifically used (a) pentaerythritol ❹ three ( Methyl) acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, etc.; (b) polyvalent isocyanate compound and two or more alcoholic hydroxyl groups The compound obtained by reacting the compound in advance contains an isocyanate group-containing compound, and further reacts with an alcoholic hydroxyl group-containing (meth) acrylate to obtain a Q urethane having 3 or more (meth) acryloxy groups in the molecule ( (c) a compound obtained by reacting acrylic acid or methacrylic acid with a compound having three or more epoxy groups in the molecule, and having three or more (meth) acryloxy groups in the molecule. Oxy (meth) acrylate and the like. In the present invention, it is important that the free radiation curable compound contained in the coating liquid contains one or more kinds of free radiation curable compounds having three or more functional groups in addition to the free radiation curable compound having one or two functional groups. . Thus, in the hardened layer after hardening, the free radiation hardening type compound having a high crosslink density of -29-201038637 3 functional groups or more is present as a hard segment, and the free radiation hardening type of 1 and/or 2 functional groups is present. The compound is reacted in such a manner as to bond with the hard segment to allow the free radiation curable compound component of the 1 and/or 2 functional groups to exist as a soft segment. As a result of adjusting the free radiation curable compound of two or more different functional groups to a specific concentration range, a hetero crosslinked structure can be introduced into the hardened layer to impart surface hardness and scratch resistance to the hard segment, and a soft segment is used. The stretchability imparts formability, and it is a remarkable effect of obtaining contradictory characteristics. In the present invention, in order to coexist with high surface hardness and excellent moldability, that is, specifically, a pencil hardness of more than Η and an elongation of 10% or more, one of the free radiation curing compounds contained in the coating liquid The content of the free radiation curable compound of the functional group is preferably 5% by mass or more and 95% by mass or less. When the content is less than 5% by mass, not only the flexibility of the film (or film) is lowered, but also the cracking of the hardened layer during molding is not preferable. Further, when the content is more than 95% by mass, it is difficult to obtain a cured film having sufficient surface hardness and scratch resistance. The lower limit of the above content is preferably 10% by mass or more, more preferably 20% by mass or more. Further, the upper limit of the above content is preferably 90% by mass or less, more preferably 80% by mass or less, and most preferably 70% by mass or less. When the content of the free radiation curable compound of the 1 and/or 2 functional groups in the free radiation curable compound is 20% by mass or more and 80% by mass or less, it is possible to achieve a higher degree of surface hardness and moldability, specifically It is possible to coexist with a pencil hardness of 2 Η or more and an elongation of 20 % or more. It is suitable for a hard coating film for molding that requires a high hardness of -30 to 201038637 and a high workability, such as a nameplate for a car or a case for a portable device. In addition to the above-described embodiment, the inventors of the present invention have found that the free radiation curable compound having an amine group can be used as a free radiation curable compound, and it has been found that surface hardness and moldability can be made higher. In other words, it is preferred that at least one of the free radiation hardening compounds contained in the coating liquid has an amine group. The above effects caused by the use of a compound having an amine group as a result of a radioactive hardening type compound are as follows. If the hardness distribution of the hardened layer is locally different, it is easy to cause local cracking (grain cracking) when the hardened layer is stretched. The reason for this difference in local hardness distribution is the polymerization inhibition (oxidation inhibition) of the free radiation hardening resin by oxygen. Here, when a compound having an amine group is used as the radical radiation-curable compound, the amine group can capture radical oxygen, and the oxidation inhibition which affects the surface layer hardening reaction of the hardened layer is reduced, so that uniform hardening can be performed in the entire hardened layer. reaction. As a result, the stress applied to the hardened layer during molding is dispersed to the entire hardened layer, so that cracking during molding is also suppressed. Therefore, Q can achieve a higher degree of surface hardness and moldability. Further, in addition to the above effects, the radical-curable resin having an amine group has an effect of being fast on the coating film. Therefore, when compared with the case where no amine group is contained, the hardening of the surface of the hardened layer is further promoted, and the surface hardness can be improved. The content of the free radiation hardening type compound having an amine group in the free radiation curable compound contained in the above coating liquid is 2. More than 5 mass% and 95 mass% or less are preferred. The radically curable compound having an amine group in the free radiation-curable compound contained in the coating liquid contains -31 - 201038637, and the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more. Further, the upper limit of the above content is 92. It is preferably 5 mass% or less, more preferably 90 mass% or less, and most preferably 50 mass% or less. The content of the free radiation hardening type compound having an amine group in the free radiation hardening type compound contained in the above coating liquid is less than 2. When the amount is 5 mass%, it is difficult to uniformly harden the entire hardened layer, so that it is difficult to obtain resistance to cracking during molding. Further, when the free radiation curable compound having an amine group has a high concentration, the hardened layer is yellowish due to the amine group. Therefore, if the content exceeds 95% by mass, the high transparency may be impaired. For example, when the printing process is carried out on the uncovered layer of the hardened layer, the color tone b of the film is preferably 2 or less. In this case, the content of the above-mentioned free radical hardening compound having an amine group is 92. It is preferably 5 mass% or less. In the coating liquid of the present invention, the free radiation curable compound having 1 and/or 2 functional groups and the free radiation curable compound having 3 or more functional groups are used, but in the above embodiment, as long as a part of them is free The radiation hardening type compound may have an amine group. Further, any of the monofunctional radical radiation-curable compound, the bifunctional radical radiation-curable compound, or the free radiation-curable compound having three or more functional groups is an free-radiation-curable compound having an amine group. Good implementation. When an acrylate-based free radiation-curable compound is used as an epitaxial radiation-curable compound having an amine group, an acrylate-based free radiation-curable compound having an amine group such as acrylamide, 7-amino-3,7-di Methyl octyl (meth) acrylate, isobutyloxymethyl (meth) acrylamide, tertiary - 32 - 201038637 octyl (meth) acrylamide, diacetone (meth) acrylamide, two Methylaminoethyl (meth) acrylate, diethylamine ethyl (meth) acrylate, N, N-dimethyl (meth) acrylamide tetrachlorophenyl (meth) acrylate, N - Ethylene carbenamide and the like. Further, in addition to the above-described embodiments, the inventors of the present invention have found that when the hard layer contains particles, the moldability can be further improved, and the surface hardness and the moldability can be made higher. As a result of the fact that the hardened layer contains particles, the effect of further improving moldability can be as follows. The hardness of the hardened layer is increased. 〇 The strong stress temporarily occurs in the hardened layer with high hardness during molding, which causes the hardened layer to crack (grain) at once. Here, as a result of the particles contained in the hardened layer, the internal stress applied to the hardened layer during molding is moderated at the interface between the radical radiation-curable compound and the particles, and in addition to being inhibited from occurring in the hardened layer, there is a degree of appearance in the hardened layer without impairing the appearance. It is impossible to visually confirm the effect of the micro-cracking, and the delayed hardening layer is fatally cracked, and the effect of improving the moldability is exhibited. The particles contained in the hardened layer, such as amorphous vermiculite, crystalline vermiculite, vermiculite-alumina composite oxide, kaolinite, talc, calcium carbonate (calcite type, vaterite type), zeolite, alumina, hydrogen Inorganic particles such as oxyapatite, crosslinked acrylate particles, crosslinked PMMA particles, crosslinked polystyrene particles, nylon particles, polyester particles, guanamine/formaldehyde condensate particles, guanamine/melamine/formaldehyde condensate The heat-resistant polymer particles such as particles, melamine/formaldehyde condensate particles, and organic/inorganic hybrid fine particles such as a vermiculite/acrylic composite compound are not particularly limited in the present invention. -33- 201038637 The shape of the particles, such as a spherical shape, a block shape, a plate shape, a fiber shape, a flake shape, etc., is not particularly limited, and it is preferably spherical in view of dispersibility and particle peeling when it comes into contact with other parts. . In the present invention, the average particle diameter of the particles is preferably 10 nm or more and 3 Å or less, and further preferably 40 nm or more and the upper limit is 200 nm or less, and particularly preferably 50 nm or more and the upper limit is 100 nm or less. When the average particle diameter of the particles is less than 10 n m, the average particle diameter is too small, and the effect of improving the surface hardness, the scratch resistance, and the moldability of the added particles may be reduced to all or a part. Further, when it exceeds 30 nm, the hardened layer may become brittle and the moldability may be lowered. In addition, the average particle diameter is obtained by dispersing particles in a solvent which does not swell the particles using a Coulter counter (manufactured by Beckman Coulter, Inc., MULTISIZER-II type). In the present invention, the content of the particles contained in the hardened layer is preferably 5% by mass or more and 70% by mass or less based on the solid content in the hardened layer. In particular, the lower limit of the content is 15% by mass or more, and the upper limit is 50% by mass or less. good. When the particle content is less than 5% by mass, the surface hardness, scratch resistance, and moldability of the above-mentioned added particles may be reduced by all or a part. On the other hand, when the content of the particles exceeds 70% by mass, a large amount of the aforementioned minute cracks occur during molding, and the haze is increased (whitening) to impair the transparency of the molded body. In the present invention, it is preferable to use a compound having an amine group of -34 to 201038637 and an additive particle in a hardened layer or the like in order to appropriately select or combine the above-mentioned free radiation ray-curable compound. A particularly suitable method for this combination. According to this, it is possible to coexist the surface hardness and the moldability of the hardened layer with an extremely high degree. Specifically, it is possible to obtain a molding having a surface hardness of 2H or more and an elongation of 20% or more, or even a surface hardness of 2H or more and an elongation of 30% or more. The hard coating film is suitable for use in a cover member such as an automobile or a case or container having a deep bottom. In the present invention, the method of polymerizing and/or reacting the above coating liquid is a method of irradiating electron beams, radiation, or ultraviolet rays, but it is preferable to add a photopolymerization initiator to the coating liquid when irradiated with ultraviolet rays. Specific examples of the photopolymerization initiator, such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorodi Benzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzene Alanine methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methyl benzoic acid methyl ester, p-isopropyl-α-hydroxyphenylisobutyl ketone, α-hydroxyphenylisobutyl ketone, 2,2-Q a carbonyl compound such as dimethoxy-2-phenylacetophenone or 1-hydroxycyclohexyl phenyl ketone, tetramethylthiuram monosulfide, tetramethylamine thiosulfate disulfide, Sulfur compounds such as thioxanthene, 2-chlorothiazide, 2-methylsulfonium, and peroxide compounds such as benzammonium peroxide and di(tertiary butyl) peroxide . Such a photopolymerization initiator may, for example, be a peroxy compound such as a tertiary butyl peroxide. These photopolymerization initiators may be used singly or in combination of two or more kinds. The photopolymerization initiator is added in an amount of from -35 to 201038637 per 100 parts by mass of the free radiation curable compound contained in the above coating liquid. 01 parts by mass or more and 15 parts by mass or less are suitable, and when the amount of use is small, not only the reaction is slow, the productivity is poor, and sufficient surface hardness and scratch resistance cannot be obtained due to the remaining unreacted material. In contrast, if the amount of addition is too large, there is a problem that the hardened layer is yellowed by the polymerization initiator. In the present invention, in order to prevent thermal reaction during production or dark reaction during storage, a conventional thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether or 2,5-tributylhydroquinone is added to the above coating liquid. It is appropriate. The amount of the thermal polymerization inhibitor added is 0.1% by mass of the free radiation ray hardening type compound contained in the above coating liquid. 005 parts by mass or more, 0. It is preferably 05 parts by mass or less. In the above-mentioned coating liquid, for the purpose of improving the workability at the time of coating and controlling the thickness of the coating film at the time of coating, an organic solvent can be blended without impairing the object of the present invention. The organic solvent preferably has a boiling point of 50 ° C or more and 150 ° C or less. Specific examples include alcohol solvents such as methanol, ethanol, and isopropyl alcohol; acetate solvents such as methyl acetate, ethyl acetate, and butyl acetate; ketone solvents such as acetone and methyl ethyl ketone; and aromatic solvents such as toluene. a cyclic ether solvent such as dioxane. These solvents may be used alone or in combination of two or more. In the above coating liquid, in order to reduce the surface tension of the coating liquid and to improve the coating appearance of the hardened layer (especially due to the loss caused by the micro foam, the depression caused by the adhesion of the foreign matter, and the rejection during the drying step), Contains a surfactant. As the surfactant, a conventional cationic or anionic system, -36-201038637 nonionic system can be suitably used, but the problem of poor adhesion of the coating liquid or the adhesion of the hardened layer to the base film is not to have a polar group. The ion system is preferred, and the organic lanthanide surfactant or the fluorine-based surfactant which is excellent in interfacial activity is more preferable. The organic lanthanide surfactant may, for example, be dimethyl hydrazine, an amine based sand house, a propyl sulphate garden, a vinylbenzylsilane, a vinyl benzylaminosilane, or a dehydrated water. Glycidesilane, decyl decane, dimethyl decane, polydimethyl methoxy oxane, cerium polyoxyxide, hydrodiene modified sand oxy-yard, B-modified Alkoxysilane, hydroxyl modified alkane, amine modified alkane, carboxyl modified alkane, halogenated modified alkane, epoxy modified alkane, methacryloxy group A siloxane, a thiol-modified siloxane, a fluorine-modified siloxane, an alkyl-modified siloxane, a phenyl-modified siloxane, an alkylene oxide-modified oxirane, or the like. Examples of the fluorine-based surfactant include tetrafluoroethylene, perfluoroalkyl salt, perfluoroalkyl alkanesulfonamide, sodium perfluoroalkyl alkane sulfonate, perfluoroalkyl sulfonium potassium salt, and perfluorocarbon. Alkyl carbonate, perfluoroalkyl sulfonate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl trimethyl ammonium salt, perfluoroalkyl amine sulfonate, perfluoroalkyl phosphate , a perfluoroalkyl alkane compound, a perfluoroalkyl alkyl betaine, a perfluoroalkyl halide, and the like. From the viewpoint of improving the appearance of the coating and the slidability, the surfactant content of the coating liquid constituting the hardened layer is 0. 0 1% by mass or more is preferred. On the other hand, since the surfactant bleeds out of the surface of the hardened layer and contaminates the contact hardened layer, the surfactant content is 2. 00% by mass or less is preferred. Further, when the surfactant used is an HLB of 2 or more and 1 2, when the surfactant having an HLB of 2 or more is used, the interface can be flattened by the interface. The HLB of the surfactant is preferably 3 or more, and on the other hand, when the surfactant having an HLB of 12 or less is used, the slidability is deteriorated. Also, the so-called HLB is made by W. Atlas Powder of the United States.  The abbreviated name of H y d r 〇 p h i 1 L y 〇 p h i 1 B a 1 a n c e is the balance between the hydrophilic group and the lipophilic group contained in the boundary molecule as a property 値. It means that the lower the HLB, the higher the lipophilicity, and the higher the HLB. The hardened layer of the present invention can be used in combination with various additives to impart water repellency to fluorine-based or organic lanthanide compounds, to enhance coating of defoaming agents, and to antistatic agents or dyeing dyes and pigments equal to the present invention, the hardened layer is organic The solvent contains a free-form compound, particles, a photopolymerization initiator, and a surfactant, and is applied to a base film to be dried, and then cured. The method of laminating the hardened layer may be a conventional method, but a method of applying the upper layer to the substrate film after drying and hardening is suitable. Coating such as gravure coating, kiss coating, dip coating, curtain coating, air knife coating, knife coating, reverse roller coating, lip coating, etc. Coating method. It is preferred that the gravure coating method, particularly the reverse method, is uniformly applied in a roll-to-roll manner. The next is better. The activity can be especially good. Can suppress C. The higher the Griffin surfactant, the higher the index. For example, the coating liquid coating method is a coating method, a coating method, a 'coating method, and a gravure coating method-38-201038637. The above-mentioned coating liquid contains free radiation-curable compounds, particles, and photopolymerization. A method in which an initiator or the like is dissolved or dispersed in an organic solvent is preferably a method of stirring and dispersing the mixture under heating. When the coating liquid is heated, the solubility of the radical radiation-curable compound, the particles, and the photopolymerization initiator can be improved. Therefore, deterioration of the coating appearance due to undissolved matter can be suppressed. A conventional machine can be used for the disperser. Specific examples include ball mills, sand mills, Attritors, roller mills, mixers, colloid mills, ultrasonic homogenizers, emulsifiers, bead mills, wet jet honing machines, paint shakers, 〇^ Butterfly mixer, planetary mixer, Hanschel mixer, etc. The solid content concentration of the radiation-hardening type compound, the particles, and the photopolymerization initiator contained in the coating liquid is preferably 5% by mass or more and 70% by mass. When the solid content concentration of the coating liquid is adjusted to 5% by mass or more, the productivity can be suppressed from being deteriorated by the drying time after coating. On the other hand, when the solid content concentration of the coating liquid is adjusted to 70% by mass or less, it is possible to prevent the deterioration of the coating property due to the increase in the viscosity of the Q coating liquid and the deterioration of the coating appearance due to the mixing. Further, from the viewpoint of the coating appearance, the solid content of the coating liquid, the type of the organic solvent, and the type of the surfactant are adjusted so that the viscosity of the coating liquid is 0. Below 5cps, below 300cps is more suitable. The thickness of the hardened layer after coating and hardening depends on the degree of elongation during molding, but the thickness of the hardened layer after molding is 0. 5 v m or more and 50 m or less are preferred. Specifically, the lower limit of the thickness of the hardened layer before molding is 〇. 6ym or more is better, 1. More preferably 0//m or more. Further, the upper limit of the thickness of the hardened layer before molding is preferably -39 to 201038637 100 /z m or less, more preferably 80 // m or less, more preferably 60 /2 m or less, and most preferably 20 / zm or less. Such as the thickness of the hardened layer is greater than 0. When 6/zm is thin, it is difficult to obtain hardenability. On the other hand, when it exceeds 100#m, it tends to cause hardening of the hardened layer or poor curling due to hardening shrinkage. When the coating liquid is pre-dried in combination with an organic solvent or the like, it is applied to a substrate film and dried, such as a conventional hot air drying, an infrared heater, etc., but it is preferably dried by hot air at a fast drying speed. The drying after application is preferably carried out at a temperature of 40 t or more and 120 ° C or less, and more preferably 451 or more and more preferably 80 ° C or less. When it is less than 40 ° (:, in addition to the machine solvent contained in the coating liquid can not be sufficiently removed, sometimes whitening and other problems occur. On the contrary, when the temperature exceeds 120 °C, the micro coating loss from the foam is likely to occur, and the micro-rejection is likely to occur. Small defects such as cracks and coatings may cause poor appearance. Furthermore, the base film shrinks strongly due to heat, and the hot crepe makes the planarity of the base film deteriorate, so that uniform elongation cannot be obtained during molding, or occurs. Local elongation causes poor moldability due to breakage of the base film, etc. The tension applied to the base film during drying is preferably 50 N/m or more and 300 N/m or less, and particularly, the lower limit is 100 N/m or more, and the upper limit is 250 N/ Preferably, m is less than or equal to 50. When the substrate film tension is less than 50 N/m, the substrate film on the traveling is serpentine, so that the coating liquid cannot be applied. On the contrary, when the film thickness exceeds 300 N / m, the base film is creped. The planarity is deteriorated or the appearance of the base film to be wound is poor. Further, when the low-temperature moldability of the base film is good, the base film during drying is stretched in the advancing direction, but shrinks in the width direction, and fractures in the worst case. Wait for productivity to occur -40- 201038637 In the present invention, a hardened layer, an antistatic layer, an easy-adhesion layer, an adhesive layer, an easy-slip layer, and electromagnetic wave absorption can be imparted to the surface of the hardened layer without impeding the effects of the present invention. Other functions such as a layer, a resin layer containing a dye such as a dye or a pigment, etc. In the present invention, ultraviolet rays are applied to the coating liquid to form a hardened layer. The total amount of light to be irradiated is preferably 50 mJ/cm 2 or more and 1000 mJ/cm 2 or less, and particularly, the lower limit is 30〇111}/(: 1112 or more, upper limit is 70〇111)/(: 1112 or less is more preferable. Further, when irradiated in a nitrogen atmosphere, it is preferable to reduce oxidation inhibition and improve scratch resistance. When the amount of light is less than 50 m/cm2, the polymerization reaction of the free reflection line-curing compound cannot be promoted, and the surface hardness of the hardened layer is remarkably reduced. When the cumulative amount of light exceeds 1000 m/cm2, the base film may be deformed by the influence of heat. Further, the integrated light amount of the present invention can be measured by "TOPR" "UVR-T35". When the coating liquid is cured by electron beam, the irradiation amount is preferably 5 kGy or more, preferably 100 kGy or less, especially It is more preferably 30 kGy or more and a lower limit of 70 kGy Q or less. When the temperature is less than 5 kGy, the polymerization reaction of the free reflection line hardening type compound is not promoted, and the surface hardness of the hardened layer is remarkably reduced. When the temperature exceeds 100 kGy, the life of the electron beam irradiation tube is remarkably reduced. (The hard coating film for molding) The hard coating film for molding of the present invention is a film having excellent surface hardness. The hard coating film for molding of the present invention exhibits good moldability and is also used. A substrate film having a specific property having good mechanical properties can exhibit a better surface hardness because the strength (hardness) of the substrate film contributes to the surface hardness of the hardened layer of -41 to 201038637. Specifically, in the hard coating film for molding of the present invention, the pencil hardness is preferably Η or more, more preferably 2H or more. Here, the pencil hardness was evaluated based on JIS - Κ 5600. The method of adjusting the surface hardness may be a content of a 1 or 2 functionalized radical radiation-hardening compound or a content of a free-reflective-hardening type compound having an amine group in a free reflection-line-hardening compound contained in a coating liquid for forming a hardened layer, and hardening The amount of particles present in the layer, the thickness of the hardened layer, and the like are changed. The hard coating film for molding of the present invention is a film excellent in scratch resistance. Specifically, according to JIS — Κ 5 600, the steel wool of # 0000 is loaded on the surface 20 times with a load of 500 gf to visually observe the occurrence of scratches and the degree of scratching, and it is preferable to deeply scratch a small amount of scratches of 10 or less. It is especially good for no deep abrasion. The method of adjusting the scratch resistance by using the content of the 1 or 2 functional group of the free reflection line hardening type compound in the coating liquid for forming the hardened layer or the content of the free reflection line hardening type compound having an amine group, The amount of particles present in the hardened layer is changed. The hard coating film for molding of the present invention is a film excellent in moldability. Specifically, the elongation at room temperature and the actual film temperature of 16 ° C is preferably 10% or more, more preferably 20% or more, and particularly preferably 30% or more. Here, the elongation is a fine rectangular shape having a length of l〇mm and a width of 150 mm, which is formed by a hard coating film for molding, and is stretched when the hardened layer is stretched or whitened at a film actual temperature of 160 ° C. The rate is taken as the elongation (%). The method of adjusting the moldability (elongation) can be carried out by using a hard-cured layer-coated coating of the free-reflecting-curing compound containing 1 or 2 of the line-hardening type compound or a free anti-compound having an amine group. The hard coating film for molding of the present invention is modified in the content and the amount of particles present in the hardened layer, and is preferably colored without coloring. Specifically, the color is 2. 0 or less is preferred. The method of adjusting the hue b* can be carried out by using a composition of a reflection-reducing type compound or a photopolymerization initiator in a free-reflecting-curable compound contained in the coating liquid. Here, the hue b* is obtained by using a color difference meter (Nippon Denshoku ZE-2000), and measuring the hue b by a C light source and a viewing angle of 2 degrees. (hard coating roll for molding) The hard coating roll for molding of the present invention is a step of forming a long film by continuously winding a cylindrical roll into a roll shape to form a hard coated roll. It can improve the stability of the production Q in the processing of the molded body. The length of the hard coated film roll for forming a rectangular roll in a roll shape is not particularly limited, but is preferably 50 m or more and 5000 m or less, more preferably 3,000 m or less. When the winding length is short, the replacement frequency of the hard coating roller for forming is high during the post-process processing. On the other hand, when the length of the winding is long, the hard coating film for molding expands and contracts due to the degree, and the width of the hard coating film for forming the core portion is poorly formed depending on the application, and the functional group is free-ray curing type. On the one side of the 0 layer, the b* is formed, and the hardening layer has an amine group. The amount of the amine is added to the company. Usability, and the continuous take-up of the film is more than 100m depending on the application. The printing layer is used to make the work environment. The external environment is not particularly limited. -43- 201038637 但'But from the viewpoint of workability, IQOmm or more, 2000mm Preferably, the following is more preferably 500 mm or more and 1500 mm or less. The cylindrical core of the hard coating film for coil forming is preferably made of a plastic core. When a paper core used in general is used, paper powder or the like adheres to the hard layer and is liable to be a defective product. The plastic core is suitable for use by a conventional one, but it is preferably a polypropylene core or an FRP core from the viewpoint of strength. The size of the cylindrical core is preferably 3 inches or more and 6 inches or less in diameter. When a cylindrical core having a small diameter is used, the winding core is wound and the operability at the time of the post-process is poor. On the other hand, when the diameter is large, the diameter of the roller is also large, and the treatment is poor. When the hard coating film for molding is wound around a cylindrical core, it is preferable to fix the hard coating film for molding to the core after double-sided tape. When the double-sided tape is not used, the film roll is likely to occur during winding or handling. The double-sided tape can be used by a conventional one, but it is preferable that the plastic film has an adhesive layer on both sides from the viewpoint of occurrence of paper powder or strength. The thickness of the double-sided tape is preferably 5/m or more and 50 Mm or less. When the thickness is thin, the strength is lowered to make the workability poor, and the fixing force of the film is also reduced. On the other hand, when it is thick, the flatness of the hard coating film for forming the core portion is poor due to the difference in height of the tape. In the present invention, it is preferable to provide irregularities (embossing) at both ends in the width direction of the hard coating film for molding. When the unevenness is applied, the mark caused by the double-sided tape is less likely to adhere to the core portion, and the hardened layer is brought into contact with the surface of the base film opposite to the surface of the substrate, or the contact with the functional layer film as described above is laminated on the base film. Partially reduced's good preservation of the roll form. The height of the bump is -44 - 201038637 The lower limit is preferably l〇em, and 15/zm is better. On the other hand, the upper limit of the height of the concavities and convexities is preferably 40//m and more preferably 35 em. When the height of the unevenness is too low, the effect of improving the stability of the roll shape due to the unevenness is small. On the other hand, when the unevenness height is too high, the film roll is likely to occur during transportation. A conventional method can be used for the method of imparting irregularities. Specifically, it is a method of imparting a concave convex by pressing a metal roll having a protrusion on the surface. Further, before the uneven processing is performed to form a hardened layer on the base film, it is preferable to perform the uneven processing on the base film in advance. (Molded body) The hard coating film for molding of the present invention is suitable for vacuum molding, air pressure molding, mold molding, press molding, laminate molding, in-mold molding, extrusion molding, and bending molding. A molding material formed by a molding method such as stretch molding. When the hard coating film for molding of the present invention is used for molding, the hardened layer is not cracked by deformation at the time of molding, and surface hardness and scratch resistance can be maintained. The thickness of the hardened layer Q of the molded body formed by the hard coating film for forming is preferably 5/zm or more and 50ym or less, and is 0. 5em or more and 1〇 or less. The thickness of the hardened layer of the molded body is relatively thin. When the thickness is 5 μm, the hardenability cannot be obtained, and from the viewpoint of heat resistance, such as heating to the molded body, the shrinkage of the substrate film cannot be caused, and the surface of the hardened layer causes waves to impair the appearance. On the other hand, when it exceeds 50, it is not superior to the surface hardness of the 50 Am thick hardened layer, and the quality is less. The molded body thus formed has a hardened layer to reinforce the surface hardness, and can be suitably used as a home appliance that is attached to an external contact position and is required to have scratch resistance. 45-201038637 Nameplate, automobile nameplate, empty can, building material, cosmetic board , molded parts such as cosmetic steel sheets and transfer sheets are used. EXAMPLES The invention is illustrated in detail by the following examples. Further, the properties of the films obtained in the respective examples were measured and evaluated by the following methods. (1) Intrinsic viscosity of resin ’ Precision weighing of resin sheet sample O. Lg was dissolved in a mixed solvent of 25 ml of phenol/tetrachloroethane = 60/40 (mass ratio), and measured at 30 ° C using an Oswald viscometer (OstwalcT s viscometer). Further, the measurement was carried out three times, and the average enthalpy was obtained. (2) Melting point (Tm) of the raw material (object) Using a differential scanning calorimeter (Differential Scanning Calorimeter, manufactured by Max Science Co., Ltd., DSC3100S), about 7 mg of the raw material extruded under the conditions of each example was placed in the sample tray. The mixture was capped and heated in a nitrogen atmosphere at room temperature to 300 ° C at a temperature elevation rate of 20 ° C /min. The melting point is determined by the melting peak temperature (Tpm) as defined in item 9.1. The melting point of the base film was also measured in the same manner to determine the melting peak temperature (Tpm). (3) The thickness of the base film is uneven. The obtained base film is a film having a length of 3 m in the transverse direction and a width of 5 cm in the longitudinal direction, and is taken up into a continuous strip sample, and the film thickness is continuously measured. The machine (manufactured by ANRITSU AG) measures the film thickness and records it on a recorder. The thickness 之 -46 - 201038637 (Tmax), the minimum 値 (Tmin), and the average 値 (Tav) are obtained from the recorded map, and the thickness unevenness (%) is calculated by the following formula. Further, the measurement was carried out three times, and the average enthalpy was determined. Further, when the length of the transverse stretching direction is less than 3 m, it is carried out after the connection. The measurement of the joints is not removed. Thickness unevenness (%) = [(Tmax - Tmin) / Tav] xl00 (4) The base film obtained by the thickness of the base film was measured using a millitron, and each of 5 points was 3 points and 15 points in total. Average 値. (5) Stress and elongation at break at 1% elongation of the base film The base film obtained was cut into a rectangular shape sample having a length of 180 mm in the longitudinal direction and a width of 10 mm in the width direction by a single-sided blade. Next, the above-mentioned elongated square-shaped sample was stretched using a tensile tester (manufactured by Toyo Seiki Co., Ltd.), and the stress (MPa) and elongation at break (%) at 1% elongation in each direction were obtained from the obtained load-deformation curve. ). Further, the measurement was carried out at a temperature of 25 ° C, with an initial length of 40 mm (ie, the distance between the punctuation points of the tensile test), a distance between the chucks of 100 mm, a crosshead speed of 100 mm/min, a recording speed of the recorder of 200 mm/min, and a force measurement. The measurement was carried out under the conditions of 25 kgf. In addition, the measurement was carried out 1 time, and the average enthalpy was obtained. Further, at a temperature of 100 ° C, the tensile measurement was also carried out under the same conditions as above. At this time, the sample was measured at a temperature of 10 ° C for 30 seconds. Further, the measurement was carried out 10 times, and the average enthalpy was determined. (6) Thermal shrinkage at 150 °C of the base film The base film obtained was cut into a rectangular shape sample having a length of 15 mm in the longitudinal direction and a width of -47 to 201038637 to a width of 20 mm. Two marks were placed at intervals of 100 mm in the longitudinal direction of each sample, and the interval A between the two marks was first measured under no load. Next, under no load, one side of each of the elongated square-shaped samples was hung in a basket with a clip, placed in a geer oven at 150 ° C and started to be timed. After 30 minutes, the basket was taken out of the aged oven and allowed to stand at room temperature for 30 minutes. Next, the interval B between the two marks is measured under no load. The heat shrinkage ratio at 150 ° C was calculated from the following equation by measuring the interval A and the interval B. Heat shrinkage ratio (%) = [(A - Β) / Α] χ 100 (7) Solvent resistance of the base film The sample was immersed in toluene at a temperature of 25 ° C for 30 minutes, and the appearance before and after the immersion The change is judged on the basis of the following criteria, and is passed as a pass. Further, the haze was measured by the following method (see item 9). 〇: The appearance is almost unchanged, and the change in haze is less than 1%. X: The identifiable appearance changes, or the haze change is more than 1%. (8) The plane orientation degree (Δ P) is obtained by forming a hard quilt. The film was observed with a sodium D line (wavelength of 5 89 nm) as the light source, and the opposite side of the hardened layer was observed. The refractive index (Nx) in the longitudinal direction of the film and the refractive index (Ny) in the width direction were measured using an Abbe refractometer. The refractive index (Nz) in the thickness direction is calculated by the following equation (ΔΡ). Δ P = [(Nx + Ny)/2] - Nz (9) The hard coating film for molding obtained by the haze of the hard coating for molding, according to IIS - K7 1 3 6 - 2000, -48- 201038637 The haze of the film was measured using a haze meter ("300 A" manufactured by Nippon Denshoku Industries Co., Ltd.). Further, the measurement was carried out twice, and the average enthalpy was determined. (10) A hard coating film for forming a hard coating film for molding at a wavelength of 370 nm, which is obtained by using a spectrophotometer (UV-1200 manufactured by Shimadzu Corporation) and measuring ultraviolet rays at a wavelength of 370 nm. The light transmittance of the film. (11) Light resistance of the hard coating film for forming The printing sample on which the offset printing was applied was placed on the back side of the printing surface, and placed in a straight position of 3 cm below the fluorescent lamp (U-shaped fluorescent lamp FUL9EX manufactured by Matsushita Electric Co., Ltd.) in a 0 black box. Subsequently, the fluorescent lamp was irradiated for 2,000 hours, and the color (a*, b*, L*) on the printing surface side before and after the light irradiation was measured, and the color difference (ΔE値) was measured in accordance with JIS-Z-87 30. The smaller the color difference (ΔE値), the smaller the color change before and after the light irradiation, that is, the light resistance is excellent. The pass standard for light fastness is the color difference (△ E値)0. 5 or less. Further, the chromatic aberration (A E 値) is obtained by the following formula. AE=v^(Aa2+Ab2+L2A) Ο (12) The film of the hard coating film for molding is subjected to 5 mm square grid printing, and then the film is heated by an infrared heater heated at 500 °C. After heating for 10 to 15 seconds, vacuum molding was carried out at a mold temperature of 30 to 100 °C. Further, the heating conditions of the respective films are selected from the above ranges. The shape of the mold used was cup-shaped, the diameter of the opening was 50 mm, the diameter of the bottom was 45 mm, and the depth was 5 mm. All the corners were made to have a diameter of 0. 5mm bending. Five molded articles were obtained by vacuum molding under the most suitable conditions, and the evaluation of -49-201038637's moldability and completeness was ranked by the following criteria. Also, ◎ and 〇 are passing, and X is failing. ◎ : (1) The molded article has no crack, and (ii) the radius of curvature of the corner of the molded article is 1 mm or less, and the printing deviation is O. Below linm, (iii) there is no appearance defect corresponding to X; 〇: (i) the molded article is not broken, and (ii) the radius of curvature of the corner of the molded article exceeds 1111111. Below 5111111, or the printing deviation exceeds 0. 1mm but 0. 2mm or less', (iii) There is no appearance defect equivalent to X, and there is no problem in practical use. The molded product of X level; X: (i) The molded article is cracked or not broken but is equivalent to the following (i) to (lv) Any one of the items: (i) The radius of curvature of the corner of the molded article exceeds 1. 5mm, (ii) large wrinkles and poor appearance, (iii) film whitening and reduced transparency, (i v) printing deviation exceeds 0. 2 m m. (13) Printing grade of hard coating film for molding The hard coating film before printing was heat-treated at 90 ° C for 30 minutes, and then 4-color screen printing was performed on the reverse side of the hardened layer. The hard coating of this printed layer was dried at 80 ° C for 30 minutes. The evaluation of the printing level is based on the printing appearance such as the following transparency, printing suitability, and printing deviation, and is determined by the hard surface of the printing surface from the opposite side of the printing surface by the printed surface -50-201038637. The judgment criterion is 〇: all items have no problem, △: at least one item has a problem, and X: two or more items have a problem. a.  Transparency: The printed pattern is not obscured by the substrate film or the coating layer. b.  Printing suitability: There is no uneven color or loss due to poor transfer of printing ink. c.  Printing deviation: The printing deviation cannot be determined visually. (14) Elongation of hardened layer 〇 In order to determine the elongation of the hardened layer, it was evaluated by the aforementioned method. Here, the elongation is 10% or more, and it is judged that the moldability is excellent, and the elongation is 30% or more, and it is judged that the moldability is excellent. (15) Pencil hardness of the hardened layer In order to judge the surface hardness of the hardened layer, it was evaluated by the aforementioned method. Here, it is judged that the pencil hardness is Η or more to have an excellent surface hardness, and it is judged that it has a superior surface hardness of 2H or more. Q (16) Scratch resistance of the hardened layer In order to judge the scratch resistance of the hardened layer, it was evaluated by the above method, and the grade was determined according to the following criteria. When the scratch resistance level is C or more, it is judged to have scratch resistance, and when the grade is Β or more, it is judged that the scratch resistance is good. Α: no scratches occurred or a small amount of shallow scars were observed; Β: shallow scratches were observed, but no deep scars were observed; C: shallow scratches were observed, and a small amount of deep scars were observed; D: a large number of deep scars were observed . -51- 201038637 (17) The hue b* of the hard coating film for molding was evaluated by the above method in order to evaluate the degree of coloring (yellowing) of the hardened layer. When b * 値 is 2 · 0 or less, the judgment is good, and when it exceeds 2 · 0, the yellow of the hardened layer becomes large and it is judged to be defective. (18) Pencil hardness and hardened layer thickness after molding In the evaluation of the elongation described above, the stretching was stopped immediately before the occurrence of cleavage. The pencil hardness at this time was evaluated in the same manner as in the above evaluation method. In addition, the thickness of the hardened layer at this time is measured by a spectrophotometer (manufactured by Shimadzu Corporation, UV- 3150 type) to obtain a fractional light reflectance, and the thickness of the hardened layer is calculated by a peak valley method using a waveform having a wavelength of 400 nm or more and 600 nm or less. . The refractive index required at this time was a single layer film of a hardened layer, and the refractive index was measured by an Abbe refractometer (manufactured by ATAGO Co., Ltd., NAR-IT SOLID). (19) The presence or absence of crepe in the application of the coating liquid for the hardened layer. The drying temperature and the film tension at the time of drying after application of the coating liquid for the hardened layer were evaluated to determine whether or not crepe was generated. When a base film having a width of 700 mm was applied at 1 〇〇m, it was judged to be good if no crepe was generated, and it was judged to be defective (X) when crepe was generated. (20) Appearance of the hardened layer The coating appearance was evaluated by determining whether or not the drying temperature at the time of drying after application of the coating liquid for a hardened layer was appropriate. When the base film having a width of 6,000 mm is applied to 100 m, the hardened layer after hardening is judged to be good if it is completely free of whitening, missing coating, or rejected, and is judged to be defective if it is defective (X ). (21) Shrinkage in the width direction when the hardened layer is applied -52 to 201038637 The width shrinkage ratio is evaluated in order to determine whether the drying temperature and the film tension during drying after application of the coating liquid for a hardened layer are appropriate. When the base film having a width of 700 mm was coated at 10 μm, the shrinkage ratio in the width direction of the base film before and after coating was measured. This shrinkage rate is 1. When it is less than 5%, it is judged to be good, and it is more than 1. When it is 5 %, it is judged to be bad. (Example 1) (Preparation of coating liquid) A transesterification reaction and a polycondensation reaction were carried out according to a usual method to prepare a water-dispersible copolymerized polyester resin containing a sulfonic acid metal salt group; the composition was 46% by mole of bismuth citrate ( Relative to the total dicarboxylic acid component, the same as below), 45% molar % of isotonic acid, and 8 mole % of sodium sulfonato sulfonate as the dicarboxylic acid component 'ethylene glycol 50 Ear % (relative to the total diol component, the same below), and neopentyl glycol 50 mole % are used as the diol component. Secondly, the water will be 51. 4 parts by weight, 38 parts by weight of isopropyl alcohol, 5 parts by weight of n-butyl sialoside, and a nonionic surfactant. 06 parts by weight of the mixture was heated and stirred, and when it reached 77 χ:, 5 parts by weight of the above-mentioned water-dispersible sulfonic acid metal salt-containing copolymerized polyester resin was added, and stirring was continued until the resin-free block was present, and the resin water was added. The dispersion was cooled to room temperature to obtain a solid concentration of 5. 0% by weight of a homogeneous water-dispersible copolymerized polyester resin liquid. Further, 3 parts by weight of aggregated vermiculite particles (FU, I-SILYSIA AG, SYLYSIA 310) were dispersed in 50 parts by weight of water, and the aqueous dispersion of SYLYSIA 310 was 0. 54 parts by weight of the above dispersible copolymerized polyester resin liquid was added. In 46 parts by weight, a weight of 2 parts of water was further added while stirring to obtain a coating liquid. -53- 201038637 (Preparation of base film) Copolyester (constituent component is 100% by mole of citric acid unit as aromatic dicarboxylic acid component, ethylene glycol unit 40 mol% and neopentyl glycol unit 60 Mo The ear % is used as the diol component and the intrinsic viscosity is 〇. 69dl/g) resin sheet (A) and polyethylene terephthalate (inherent viscosity is 〇. 69dl/g, containing average particle size (SEM method) 1. 5 from the amorphous amethyst of m. 〇4% by mass and benzotriazole-based ultraviolet absorber (NKCIBA SPECIALITY CHEMICALS AG, TINUVIN326) 0. After the resin sheets (B) of 6 mass%) were respectively dried, the resin sheet (A) and the resin sheet (B) were mixed at a mass ratio of 25:75. Next, the resin sheet mixture was melt extruded at 270 ° C from the T die slit of the extruder, and rapidly solidified on a cooling roll having a surface temperature of 40 ° C, while using an electrostatic external addition method to adhere to the cooling roll. Shape the unstretched sheet. The unstretched sheet is stretched longitudinally at a temperature of 90 ° C between the heating roll and the chill roll. 3 times. Next, the above coating liquid was applied to both sides of the uniaxially stretched film, and dried at 丨20 ° C to set a solid concentration of 0. The middle layer of 08g/m2 (containing an average particle diameter of 0. 2/Z m of the meteorite 0. 003 mass%). Next, the uniaxially stretched film was introduced into a tenter, and after preheating at 120 ° C for 10 seconds, the first half was stretched at 100 ° C in the first half at ll 〇 ° C and the second half at 100 ° C. 9 times. Further, heat treatment was carried out at 23 ° C under a 7% relaxation treatment in the transverse direction by heat treatment to obtain a substrate film having a thickness of 1 Å. (Making a hard coating film) The following coating liquid A was applied to the obtained substrate film using a wiper to dry the film to a thickness of 2/zm after drying at -54 to 201038637, and then dried by hot air at a temperature of 801 for 60 seconds. The hard coating film for molding was obtained by passing at a speed of 10 m/min at a position of 20 cm under a high-pressure mercury lamp having an output of 120 W/cm. (Hard coating coating liquid A) The following materials were mixed in the following mass ratio and stirred for 30 minutes or more to dissolve. Next, the undissolved matter was filtered off using a filter having a nominal filtration precision of 1 μm to prepare a coating liquid A. * Methyl ethyl ketone 64. 48% by mass 〇 肇 neopentyl alcohol triacrylate 11. 45% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, functional group number 3) Lusan propylene glycol diacrylate 5. 73% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group 2) • Dimethylamine ethyl methacrylate 5. 72% by mass (made by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1) Q • Vermiculite particles 11. 45% by mass (MEK-ST-L, solid content: 30%, average particle size: 50 nm) «Photopolymerization initiator 1. 14% by mass (manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184) *Organic lanthanide surfactant 0. 03% by mass (DOW CORNING TORAY CO., LTD., DC57) The hard coating film for molding has good moldability, surface hardness, and scratch resistance. -55-201038637 Good damage and coloration, and it is used as a hard coating for molding. The film is good. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are not as good as in Table 1. (Example 2) In the same manner as in Example 1, except that the coating liquid for forming the hardened layer was changed to the coating liquid B described below, the hard coating film for molding was obtained. (coating solution B) ♦ methyl ethyl ketone 64. 48% by mass • Neopentyl alcohol triacrylate. 18% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, functional group number 3) * Tri-propylene glycol diacrylate 2. 86% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group 2) * Dimethylamine ethyl methacrylate 2. 86% by mass (made by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1) * Vermiculite particles 11. 45% by mass (manufactured by Seiko Chemical Industry Co., Ltd., MEK-ST-L, solid content ratio: 30%, average particle diameter: 50 nm) * Photopolymerization initiator 1. 14% by mass (manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184) *Organic lanthanide surfactant 0. 03% by mass (DOW CORNING TQRAY Co., Ltd., DC57) The hard coating film for molding has good moldability, surface hardness, and abrasion resistance. -56-201038637 Good damage and coloration, and it is used as a hard coating for molding. The film is good. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1. (Example 3) The hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hardened layer was changed to the coating liquid C described below. (Coating liquid C) Lu Methyl ethyl ketone 64. 48% by mass 〇 ^ • Pentaerythritol triacrylate 8. 02% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, functional group number 3) ginseng propylene glycol diacrylate 7. 44% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group 2) • Dimethylamine ethyl methyl propyl acrylate 7. 44% by mass (made by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1) Q * Vermiculite particles 11. 45% by mass (manufactured by Nissan Chemical Industries, Ltd., MEK-ST-L, solid content ratio: 3〇%, average particle diameter: 50 nm) * Photopolymerization initiator 1. 14% by mass (manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184) *Organic lanthanide surfactant 0. 0 3 mass% (DOW CORNING TORAY CO., LTD., DC57) A hard coating film for molding, which has good moldability, surface hardness, and scratch resistance. -57-201038637 Good damage and coloration. The film is good. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1. (Example 4) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hardened layer was changed to the coating liquid D described below. (Coating liquid D) ♦ Methyl ethyl ketone 64. 48% by mass Qinxin pentaerythritol triacrylate 21. 75 mass% (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, functional group number 3) * Tri-propylene glycol diacrylate 0. 58% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group 2) • Dimethylamine ethyl methacrylate 0. 57% by mass (made by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1) Rough Stone Particles 1 1. 4 5 mass% (manufactured by Seiko Chemical Industry Co., Ltd., MEK-ST-L, solid content ratio: 30%, average particle diameter: 50 n m) * Photopolymerization initiator 1. 1 4% by mass (manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184) *Organic lanthanide surfactant 0. 0 3 mass% (DOW CORNING TORAY CO., LTD., DC57) A hard coating film for molding, which has good moldability, surface hardness, and scratch resistance. -58-201038637 Good damage and coloration. The film is good. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1. (Example 5) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the cured layer was changed to the coating liquid E described below. (Coating liquid E) * Methyl ethyl ketone 64. 48% by mass 〇 _ pentaerythritol triacrylate 15% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, functional group number 3) * Tri-propylene glycol diacrylate 0. 58% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG - 200, functional group 2) * Dimethylamine ethyl methacrylate 21. 17% by mass (made by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1) Q · Vermiculite particles 11. 45% by mass (manufactured by Seiko Chemical Industry Co., Ltd., MEK-ST-L, solid content ratio: 30%, average particle diameter: 50 nm) * Photopolymerization initiator 1. 14% by mass (manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184) *Organic lanthanide surfactant 0. 0 3 mass% (DOW CORNING TORAY CO., LTD., DC57) A hard coating film for molding, which has good moldability, surface hardness, and scratch resistance. 59-201038637 Good damage and coloration. The film is good. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1. (Example 6) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hardened layer was changed to the coating liquid F described below. (Coating liquid F) Methyl ethyl ketone 64. 48% by mass * pentaerythritol triacrylate 21. 75 mass% (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, functional group number 3) * Tri-propylene glycol diacrylate 1. 15% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG - 200, functional base 2) * Vermiculite particles 11. 45% by mass (manufactured by Nissan Chemical Industries, Ltd., MEK-ST-L, solid content ratio: 30%, average particle diameter: 50 nm) * Photopolymerization initiator 1. 14% by mass (manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184) * Organic lanthanide surfactant 0. 03% by mass (DOW CORNING TORAY CO., LTD., DC57) The hard coating film for molding has good moldability, surface hardness, scratch resistance, and coloration, and is excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a surface hardness of -60-. 201038637 Good. The results obtained are shown in Table 1. (Example 7) A hard coating film for molding was obtained in the same manner as in Example i except that the coating liquid for forming the hardened layer was changed to the coating liquid G described below. (Coating liquid G) *Methyl ethyl ketone 64. 48% by mass * pentaerythritol triacrylate 15% by mass (made by Shin-Nakamura Chemical Co., Ltd. ' NK ESTER A - TMM - 3LM - N, Ο Functional Group 3) * Tri-propylene glycol diacrylate 21. 75 mass% (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional base 2) * Vermiculite particles 11. 45% by mass (manufactured by Nissan Chemical Industries, Ltd., MEK-ST-L, solid content ratio: 30%, average particle diameter: 50 nm) * Photopolymerization initiator 1. 1 4% by mass 〇 (manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184) *Organic lanthanide surfactant 0. 03% by mass (DOW CORNING TORAY CO., LTD., DC57) The hard coating film for molding has good moldability, surface hardness, scratch resistance, and coloration, and is excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1. (Example 8) -61-201038637 The hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hardened layer was changed to the coating liquid layer described below. (coating liquid Η) * methyl ethyl ketone 64. 48% by mass of pentaerythritol triacrylate 15% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - ΤΜΜ - 3LM - Ν, functional group 3) • Dimethylamine ethyl methacrylate 21. 75 mass% (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1) * Vermiculite particles 11. 45% by mass (manufactured by Nissan Chemical Industries, Ltd., MEK-ST-L, solid content ratio: 30%, average particle diameter: 50 nm) ♦ Photopolymerization initiator 1. 14% by mass (manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184) *Organic lanthanide surfactant 0. 03% by mass (DOW CORNING TORAY CO., LTD., DC57) The hard coating film for molding has good moldability, surface hardness, scratch resistance, and coloration, and is excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1. (Example 9) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hardened layer was changed to the coating liquid I described below. -62- 201038637 (coating solution I) * methyl ethyl ketone 64. 48% by mass • Pentaerythritol triacrylate 11. 45 halo% (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - ΤΜΜ - 3LM - Ν, functional group number 3) ginseng propylene glycol diacrylate 5. 73% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group 2) • Diethylamine ethyl methacrylate 5. 72% by mass Ο ο (made by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DE, functional base 1) ♦ Vermiculite particles 11. 45% by mass (MEK-ST-L, solid content rate: 30%, average particle diameter: 50 nm) * Photopolymerization initiator 1. 14% by mass (manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184) ♦ Organic lanthanide surfactant 0. 03% by mass (DOW CORNING TORAY CO., LTD., DC57) The hard coating film for molding has good moldability, surface hardness, scratch resistance, and coloration, and is excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1. (Example 10) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hardened layer was changed to the coating liquid J described below. -63- 201038637 (coating liquid υ * methyl ethyl ketone 64. 48% by mass • Pentaerythritol triacrylate 11. 45% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, functional group number 3) Lusan propylene glycol diacrylate 5. 73% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group 2) * N-vinylformamide 5. 72% by mass (made by Arakawa Chemical Industry Co., Ltd., BEAMSET 770, functional group number 1) '" 矽石石颗粒 1 1. 45% by mass (manufactured by Nissan Chemical Industries, Ltd., MEK-ST-L, solid content ratio: 30%, average particle diameter: 50 nm) Photopolymerization initiator 1. 14% by mass (manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184) * Organic lanthanide surfactant 0. 03% by mass (DOW CORNING TORAY, DC57) £ .  The hard coating film for molding obtained in 1,1 has good moldability, surface hardness, scratch resistance, and coloration degree, and is excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1. (Example 1 1) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hardened layer was changed to the coating liquid K described below. -64 - 201038637 (hard coating liquid κ) • methyl ethyl ketone 67. 93% by mass of pentaerythritol triacrylate 11. 58% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - ΤΜΜ - 3LM - Ν, functional group 3) • Tri-propylene glycol diacrylate 5. 79% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group number 2) * Dimethylamine ethyl methacrylate 5. 79% by mass 〇 (made by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1) * Vermiculite particles 7. 72% by mass (manufactured by Nissan Chemical Industries, Ltd., MEK-ST-L, solid content ratio: 30%, average particle diameter: 50 nm) _Photopolymerization initiator 1. 16% by mass (manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184) Lu organic surfactant surfactant 0. 03% by mass Q (Dow CORNING TORAY CO., LTD., DC57) The hard coating film for molding has good moldability, surface hardness, scratch resistance, and coloration, and is excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are not as good as in Table 1. (Example 12) The hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hardened layer was changed to the coating liquid L described below. -65 - 201038637 (coating liquid L) ruthenium methyl ketone 4. 24% by mass of ruthenium pentaerythritol triacrylate 6. 22% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, functional group number 3) * Tri-propylene glycol diacrylate 3. 12% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group 2) ♦ Dimethylamine ethyl methacrylate 3. 12% by mass (made by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1) * Vermiculite particles 82. 73% by mass (manufactured by Nissan Chemical Industries, Ltd., MEK-ST-L, solid content ratio: 30%, average particle diameter: 50 nm) * Photopolymerization initiator 0. 55% by mass (IRGACURE 184, manufactured by CIBA SPECIALITY CHEMICALS) • Organic lanthanide surfactants 02% by mass (DOW CORNING TORAY CO., LTD., DC57) The hard coating film for molding has good moldability, surface hardness, scratch resistance, and coloration, and is excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are not as good as in Table 1. (Example 13) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hardened layer was changed to the following -66-201038637 coating liquid. (coating liquid Μ) Methyl ethyl ketone 71. 46% by mass • Neopentyl alcohol triacrylate 11. 72% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER Α - ΤΜΜ - 3LM - Ν, functional group number 3) ginseng propylene glycol diacrylate 5,86 mass% (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional Base 2) 〇* dimethylamine ethyl methacrylate 5. 86% by mass (made by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1) * Vermiculite particles 3. 90% by mass (MEK-ST-L, solid content rate: 30%, average particle size: 50 nm) Luguang polymerization initiator 1. 17% by mass

(CIBA SPECIALITY CHEMICALS 公司製、IRGACURE 〇 184) *有機矽系界面活性劑 0.03質量％ (D〇W CORNING TORAY 公司製、DC57) 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 傷性、著色程度均良好，當作成型用硬被覆膜良好。又， 使用製得之成型用硬被覆膜成型之成型體，其表面硬度亦 良好。所得結果示如第1表。 (實施例14) -67- 201038637 於實施例1，除將形成硬化層之塗布液變更爲下述之 塗布液N以外，其他與實施例1相同’得成型用硬被覆膜。 (塗布液N) 鲁新戊四醇三丙稀酸酯 5.28質量％ (新中村化學公司製、NK ESTER A - TMM - 3LM - N、 官能基數3) *三伸丙二醇二丙烯酸酯 2.64質量％ (新中村化學公司製、NK ESTER APG - 200、官能基數(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 〇184) *Organic lanthanide surfactant 0.03 mass% (D〇W CORNING TORAY CO., DC57) A hard coating for molding, which has moldability, surface hardness and resistance. The scratch resistance and the degree of coloration are good, and it is good as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1. (Example 14) -67-201038637 The hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hardened layer was changed to the coating liquid N described below. (coating liquid N) ruthenium pentaerythritol triacrylate 5.28% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, functional group number 3) * Tri-propylene glycol diacrylate 2.64% by mass ( New Nakamura Chemical Co., Ltd., NK ESTER APG - 200, functional base

2.6 4質量％ (共榮社化學公司製、LIGHT ESTER DM、官能基數1) 鲁矽石微粒 88.88質量％ (曰產化學工業公司製、MEK- ST - L、固體成分率： 30%、平均粒徑：50nm) 籲光聚合引發劑 0.55質量％2.6 4% by mass (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1) Rumex granules 88.88% by mass (manufactured by Suga Chemical Industry Co., Ltd., MEK-ST-L, solid content ratio: 30%, average granules) Diameter: 50 nm) Photopolymerization initiator 0.55 mass%

(CIBA SPECIALITY CHEMICALS 公司製、IRGACURE 184) *有機矽系界面活性劑 0.02質量％ (DOW CORNING TORAY 公司製、DC57) 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 傷性、著色程度均良好，當作成型用硬被覆膜良好。又， 使用製得之成型用硬被覆膜成型之成型體，其表面硬度亦 良好。所得結果示如第1表。 -68- .201038637 (實施例15) 於實施例1，除將形成硬化層之塗布液變更爲下述之 塗布液0以外，其他與實施例1相同，得成型用硬被覆膜。 (塗布液〇) • 甲基乙基酮 58.76質量％ ♦新戊四醇三丙烯酸酯 11.45質量％ (新中村化學公司製、NK ESTER A - TMM - 3LM - N、 官能基數3) 〇 鲁三伸丙二醇二丙烯酸酯 5.73質量％ (新中村化學公司製、NK ESTER APG - 200、官能基數 2) 參二甲基胺乙基甲基丙烯酸酯 5.72質量％ (共榮社化學公司製、LIGHT ESTER DM、官能基數1) 鲁矽石微粒 1 7 . 1 7質量％ (扶桑化學工業公司製、PL2L - MEK、固體成分率： Q 20%、平均粒徑：20nm) 籲光聚合引發劑 1.14質量％(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184) * Organic enamel-based surfactant 0.02% by mass (DOW CORNING TORAY, DC57), a hard coating film for molding, moldability, surface hardness, scratch resistance, The degree of coloration is good, and it is good as a hard coating for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1. -68-.201038637 (Example 15) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the cured layer was changed to the coating liquid 0 described below. (coating liquid 〇) • methyl ethyl ketone 58.76 mass% ♦ neopentyl alcohol triacrylate 11.45 mass% (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, functional group number 3) Propylene glycol diacrylate 5.73 mass% (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group number 2) 5.7% by mass of dimethylaminoethyl methacrylate (produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, Functional group number 1) Rough stone particles 17.7% by mass (manufactured by Fuso Chemical Industry Co., Ltd., PL2L-MEK, solid content ratio: Q 20%, average particle diameter: 20 nm) Photopolymerization initiator 1.14% by mass

(CIBA SPECIALITY CHEMICALS 公司製、IRGACURE 184) *有機矽系界面活性劑 0.03質量％ (DOW CORNING TORAY 公司製、DC57) 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 傷性、著色程度均良好，當作成型用硬被覆膜良好。又， -69- 201038637 使用製得之成型用硬被覆膜成型之成型體，其表面硬度亦 良好。所得結果示如第1表。 (實施例16) 於實施例1，除將形成硬化層之塗布液變更爲下述之 塗布液P以外’其他與實施例1相同，得成型用硬被覆膜。 (塗布液P) 籲甲基乙基酮 58.76質量％ ♦新戊四醇三丙烯酸酯 11.45質量％ (新中村化學公司製、NK ESTER A - TMM - 3LM - N、 官能基數3) ♦三伸丙二醇二丙烯酸酯 5.73質量％ (新中村化學公司製、NK ESTER APG - 200、官能基數 2) *二甲基胺乙基甲基丙烯酸酯 5.72質量％ (共榮社化學公司製、LIGHT ESTER DM、官能基數1) *矽石微粒 1 7 .1 7質量％ (扶桑化學工業公司製、PL30L - MEK、固體成分率： 20%、平均粒徑：297nm) ♦光聚合引發劑 1.14質量％(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184) * 0.03 mass% of an organic lanthanide surfactant (manufactured by DOW CORNING TORAY, DC57), a hard coating film for molding, moldability, surface hardness, scratch resistance, The degree of coloration is good, and it is good as a hard coating for molding. Further, -69-201038637 The molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1. (Example 16) The hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hardened layer was changed to the coating liquid P described below. (Coating liquid P) Methyl ethyl ketone 58.76% by mass ♦ Neopentyl alcohol triacrylate 11.45% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, functional group number 3) ♦ Tri-propylene glycol 5.93 mass% of diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group number 2) * dimethylamine ethyl methacrylate 5.72% by mass (produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional Base 1) * Vermiculite particles 17.7 mass% (made by Fuso Chemical Industry Co., Ltd., PL30L - MEK, solid content ratio: 20%, average particle diameter: 297 nm) ♦ Photopolymerization initiator 1.14% by mass

(CIBA SPECIALITY CHEMICALS 公司製、IRGACURE 184) *有機矽系界面活性劑 0.03質量％ (DOW CORNING TORAY 公司製、DC57) -70- 201038637 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 傷性、著色程度均良好，當作成型用硬被覆膜良好。又， 使用製得之成型用硬被覆膜成型之成型體，其表面硬度亦 良好。所得結果示如第1表。 (實施例17) 於實施例1，除將形成硬化層之塗布液變更爲下述之 塗布液Q以外，其他與實施例1相同，得成型用硬被覆膜。 (塗布液Q) 〇 • 甲基乙基酮 5 8.7 6質量％ • 新戊四醇三丙烯酸酯 11.45質量％ (新中村化學公司製' NK ESTER A - TMM - 3LM - N、 官能基數3) 修三伸丙二醇二丙烯酸酯 5.73質量％ (新中村化學公司製、NK ESTER APG - 200、官能基數 2) Q · 二甲基胺乙基甲基丙烯酸酯 5.72質量％ (共榮社化學公司製、LIGHT ESTER DM、官能基數1) • 矽石微粒 1 7 . 1 7質量％ (日本觸媒公司製、SEAHOSTAR KE- E50、固體成分 率：20%、平均粒徑：511nm) 籲光聚合引發劑 1.14質量％(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184) * Organic lanthanide surfactant 0.03 mass% (manufactured by DOW CORNING TORAY, DC57) -70-201038637 A hard coating film for molding, which has moldability and surface hardness. The scratch resistance and the degree of coloration are good, and it is good as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1. (Example 17) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hardened layer was changed to the coating liquid Q described below. (coating liquid Q) 〇• methyl ethyl ketone 5 8.7 6 mass% • neopentyl alcohol triacrylate 11.45 mass% (Nippon Nakamura Chemical Co., Ltd. 'NK ESTER A - TMM - 3LM - N, functional group number 3) Propylene glycol diacrylate 5.73 mass% (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group number 2) Q · dimethylamine ethyl methacrylate 5.72% by mass (produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1) • Vermiculite particles 17.7% by mass (manufactured by Nippon Shokubai Co., Ltd., SEAHOSTAR KE-E50, solid content ratio: 20%, average particle diameter: 511 nm) Photopolymerization initiator 1.14% by mass

(CIBA SPECIALITY CHEMICALS 公司製、IRGACURE -71- 184) 201038637 *有機矽系界面活性劑 0.03質量％ (DOW CORNING TORAY 公司製、DC57) 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 傷性、著色程度均良好，當作成型用硬被覆膜良好。又， 使用製得之成型用硬被覆膜成型之成型體，其表面硬度亦 良好。所得結果示如第1表。 (實施例18) 於實施例1，除將形成硬化層之塗布液變更爲下述之 r% 塗布液R以外，其他與實施例1相同，得成型用硬被覆膜。 (塗布液R) • 甲基乙基酮 72.50質量％ • 新戊四醇三丙烯酸酯 11.45質量％ (新中村化學公司製、NK ESTER A - TMM - 3LM - N、 官能基數3) • 三伸丙二醇二丙烯酸酯 5.73質量％ (新中村化學公司製、NK ESTER APG - 200、官能基數 ，4 \,：β 2) • 二甲基胺乙基甲基丙烯酸酯 5.72質量％ (共榮社化學公司製、LIGHT ESTER DM、官能基數1) • 三聚氰胺/甲醛縮合物微粒 3.43質量％ (日本觸媒公司製、EPOSTARS、平均粒徑：196nm) *光聚合引發劑 1.14質量％(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE -71- 184) 201038637 *Organic lanthanide surfactant 0.03 mass% (DOW CORNING TORAY, DC57) Hardness coating for molding, moldability, surface hardness, The scratch resistance and the degree of coloration are good, and it is good as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1. (Example 18) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the cured layer was changed to the r% coating liquid R described below. (coating liquid R) • methyl ethyl ketone 72.50% by mass • neopentyl alcohol triacrylate 11.45 mass% (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, functional group number 3) • Tri-propylene glycol 5.93 mass% of diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group number, 4 \, :β 2) • dimethylaminoethyl methacrylate 5.72% by mass (manufactured by Kyoeisha Chemical Co., Ltd.) LIGHT ESTER DM, functional group number 1) • Melamine/formaldehyde condensate particles 3.43 mass% (manufactured by Nippon Shokubai Co., Ltd., EPOSTARS, average particle size: 196 nm) * Photopolymerization initiator 1.14% by mass

(CIBA SPECIALITY CHEMICALS 公司製、IRGACURE -72- 201038637 184) *有機矽系界面活性劑 0.03質量％ (DOW CORNING TORAY 公司製、DC57) 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 傷性、著色程度均良好’當作成型用硬被覆膜良好。又， 使用製得之成型用硬被覆膜成型之成型體，其表面硬度亦 良好。所得結果示如第1表。 (實施例19) 〇 於實施例1，除將形成硬化層之塗布液變更爲下述之 塗布液s以外，其他與實施例1相同，得成型用硬被覆膜。 (塗布液s) *甲基乙基酮 75.08質量％ *新戊四醇三丙烯酸酯 11.85質量％ (新中村化學公司製、NK ESTER A - TMM - 3LM - N、 官能基數3) Q *三伸丙二醇二丙烯酸酯 5.93質量％ (新中村化學公司製、NK ESTER APG - 200、官能基數 2) *二甲基胺乙基甲基丙烯酸酯 5.92質量％ (共榮社化學公司製、LIGHT ESTER DM、官能基數1) *光聚合引發劑 1.1 9質量％(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE -72-201038637 184) * Organic lanthanide surfactant 0.03 mass% (DOW CORNING TORAY, DC57) Hardness coating for molding, moldability, surface hardness, Good scratch resistance and coloration' is good as a hard coating for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1. (Example 19) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hardened layer was changed to the coating liquid s described below. (coating liquid s) * methyl ethyl ketone 75.08 mass% * pentaerythritol triacrylate 11.85 mass% (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, functional group number 3) Q * three-stretch Propylene glycol diacrylate 5.93 mass% (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group number 2) * dimethylamine ethyl methacrylate 5.92% by mass (produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, Functional group number 1) * Photopolymerization initiator 1.1 9 mass%

(CIBA SPECIALITY CHEMICALS 公司製、IRGACURE -73- 184) 201038637 *有機矽系界面活性劑 0.03質量％ (DOW CORNING TORAY 公司製、DC57) 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 傷性、著色程度均良好，當作成型用硬被覆膜良好。又’ 使用製得之成型用硬被覆膜成型之成型體，其表面硬度亦 良好。所得結果示如第1表。 (實施例20) 於實施例1，除塗布塗布液使硬化後形成之硬化層厚 度爲1 . 1 // m外，其他與實施例1相同，得成型用硬被覆膜。 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 傷性、著色程度均良好，當作成型用硬被覆膜良好。又， 使用製得之成型用硬被覆膜成型之成型體，其表面硬度亦 良好。所得結果示如第1表。 (實施例21) 於實施例1，除塗布塗布液使硬化後形成之硬化層厚 度爲50ym外，其他與實施例1相同，得成型用硬被覆膜。 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 傷性、著色程度均良好，當作成型用硬被覆膜良好。又， 使用製得之成型用硬被覆膜成型之成型體，其表面硬度亦 良好。所得結果不如第1表。 (實施例2 2) 於實施例1 ’除塗布塗布液使硬化後形成之硬化層厚 度爲0.5/zm外，其他與實施例1相同，得成型用硬被覆膜。 -74- 201038637 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 傷性、著色程度均良好，當作成型用硬被覆膜良好。又， 使用製得之成型用硬被覆膜成型之成型體，其表面硬度諸 多不良。此爲經由成型之硬被覆層度可維持表面硬度至範 圍以外而變薄的原因。所得結果示如第1表。 (實施例23) 於實施例1，除塗布塗布液使硬化後形成之硬化層厚 度爲60 "m外，其他與實施例1相同，得成型用硬被覆膜。 〇 製得之成型用硬被覆膜，其成型性、表面硬度、耐擦 傷性、著色程度均良好，當作成型用硬被覆膜良好。又， 使用製得之成型用硬被覆膜成型之成型體，其表面硬度亦 良好。所得結果示如第1表。 (比較例1) 於實施例1，除將形成硬化層之塗布液變更爲下述之 塗布液T以外’其他與實施例1相同，得成型用硬被覆膜。 Q (塗布液T) 參甲基乙基酮 .6 4.48質量％ *新戊四醇三丙烯酸酯 22.90質量％ (新中村化學公司製、NK ESTER A - TMM - 3LM - N、 官能基數3) 鲁矽石微粒 U.45質量％ (日產化學工業公司製、MEK - ST - L、固體成分率： 30%、平均粒徑：50nm) -75- 201038637 ♦光聚合引發劑 1.14質量％ (CIBA SPECIALITY CHEMICALS 公司製、IRGACURE 184) *有機矽系界面活性劑 0.03質量％ (DOW CORNING TORAY 公司製、DC57) 製得之成型用硬被覆膜，其表面硬度、耐擦傷性、著 色程度均良好但成型性不良，當作成型用硬被覆膜亦不 良。所得結果示如第1表。 (比較例2) 於實施例1，除將形成硬化層之塗布液變更爲下述之 塗布液U以外，其他與實施例1相同，得成型用硬被覆膜。 (塗布液U) 6 4.4 8質量％ • 甲基乙基酮 • 三伸丙二醇二丙烯酸酯 11.45質量％ (新中村化學公司製、NK ESTER APG - 200、官能基數2)(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE -73- 184) 201038637 *Organic lanthanide surfactant 0.03 mass% (DOW CORNING TORAY, DC57) Hardness coating for molding, moldability, surface hardness, The scratch resistance and the degree of coloration are good, and it is good as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1. (Example 20) A hard coating film for molding was obtained in the same manner as in Example 1 except that the thickness of the hardened layer formed by the coating liquid was 1. 1 // m. The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1. (Example 21) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid was applied to a hardened layer having a thickness of 50 μm. The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are not as good as in Table 1. (Example 2 2) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid was applied to a hardened layer having a thickness of 0.5/zm. -74- 201038637 The hard coating film for molding has good moldability, surface hardness, scratch resistance, and coloration degree, and is excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a poor surface hardness. This is the reason why the degree of hard coating layer can be maintained to be thinner than the range by the hard coating layer. The results obtained are shown in Table 1. (Example 23) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid was applied so that the thickness of the hardened layer formed after curing was 60 " m. The hard coating film for molding obtained from 〇 is excellent in moldability, surface hardness, scratch resistance, and coloration degree, and is excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1. (Comparative Example 1) The hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hardened layer was changed to the coating liquid T described below. Q (coating liquid T) ginsyl methyl ethyl ketone. 6 4.48% by mass * pentaerythritol triacrylate 22.90% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, functional group number 3) U.45 mass% of vermiculite particles (MEK-ST-L, solid content: 30%, average particle size: 50 nm) -75- 201038637 ♦ Photopolymerization initiator 1.14% by mass (CIBA SPECIALITY CHEMICALS Company, IRGACURE 184) *Organic lanthanide surfactant 0.03 mass% (DOW CORNING TORAY, DC57) The hard coating for molding has good surface hardness, scratch resistance and coloration but moldability Poor, it is also bad as a hard coating for molding. The results obtained are shown in Table 1. (Comparative Example 2) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hardened layer was changed to the coating liquid U described below. (coating liquid U) 6 4.4 8 mass% • methyl ethyl ketone • tri-propylene glycol diacrylate 11.45 mass% (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group number 2)

1 1 .4 5質量％ (共榮社化學公司製、LIGHT ESTER DM、官能基數1) *矽石微粒 11.45質量％ (日產化學工業公司製、MEK - ST - L、固體成分率： 30%、平均粒徑：50nm) 鲁光聚合引發劑 1 .1 4質量％ (CIBA SPECIALITY CHEMICALS 公司製、IRGACURE 184) *有機矽系界面活性劑 0.03質量％ -76- 201038637 (DOW CORNING TO RAY 公司製、DC57) 製得之成型用硬被覆膜，其成型性、著色程度均良好 但表面硬度、耐擦傷性不良，當作成型用硬被覆膜亦不良。 所得結果示如第1表。 (實施例24) 將寬度1000mm、長度200m之薄膜輥，以卷對卷方式 使用微凹版方法及下述塗佈液V進行塗布，使塗布硬化後 之硬化層厚度爲2；c/m後，在薄膜張力180N/m條件下以溫 度80°C熱風乾燥60秒，並在輸出功率160W/cm之高壓水 銀燈下20cm位置（累計光量300mJ/cm2)以10m/min速度通 過使之硬化，再將成型用硬被覆膜卷繞在直徑6英寸之聚 丙烯製圓柱形卷芯，製成寬度1000mm、長度200m之成型 用硬被覆膜輥。 (塗布液V) 將下述材料以下述質量比混合，並攪拌30分鐘以上使 Q 之溶解。其次，使用標稱過濾精密度1/zm之過濾器濾除未 溶解物，製成塗布液V。 鲁甲基乙基酮 28.24質量％ ♦ 甲苯 3 6.24質量％ ♦新戊四醇三丙烯酸酯 11.45質量％ (新中村化學公司製、NK ESTER A - TMM - 3LM - N、 官能基數3) *三伸丙二醇二丙烯酸酯 5.73質量％ -77- 201038637 (新中村化學公司製、NK ESTER APG _ 200 '官能基數2) *二甲基胺乙基甲基丙烯酸酯 5.72質量％ (共榮社化學公司製、LIGHT ESTER DM、官能基數1) *矽石微粒 11.45質量％ (曰產化學工業公司製、MEK - ST - L、固體成分率： 30%、平均粒徑·· 50nm) *光聚合引發劑 1.14質量％ (CIBA SPECIALITY CHEMICALS 公司製、IROACURE 184) *有機矽系界面活性劑 0.03質量％ (DOW CORNING TORAY 公司製、DC57) 在基材薄膜上進行塗布並硬化以形成硬化層時，行進 之薄膜未發生蛇行或縐紋，故生產性無問題而能夠製成硬 被覆膜。製得之成型用硬被覆膜，其塗布外觀良好，寬方 向收縮率亦良好。又，製得之成型用硬被覆膜，具有與實 施例1同等之成型性、表面硬度、耐擦傷性，其成型體之 表面硬度亦良好。所得結果示如第2表。 (實施例25) 於實施例24，除將乾燥溫度變更爲40°C外，其他與實 施例24相同，製得成型用硬被覆膜輥。 在基材薄膜上進行塗布、硬化以形成硬化層時，行進 之薄膜未發生蛇行或縐紋，故生產性無問題而能夠製成硬 被覆膜。製得之成型用硬被覆膜，其塗布外觀良好，寬方 向收縮率亦良好。又，製得之成型用硬被覆膜，具有與實 -78- 201038637 施例1同等之成型性、表面硬度、耐擦傷性，其成型體之 表面硬度亦良好。所得結果示如第2表。 (實施例26) 於實施例24，除將乾燥溫度變更爲i2〇°C外，其他與 實施例24相同，製得成型用硬被覆膜輥。 在基材薄膜上進行塗布、硬化以形成硬化層時，行進 之薄膜未發生蛇行或縐紋’故生產性無問題而能夠製成硬 被覆膜。製得之成型用硬被覆膜，其塗布外觀良好，寬方 〇 向收縮率亦良好。又，製得之成型用硬被覆膜，具有與實 施例1同等之成型性、表面硬度、耐擦傷性，其成型體之 表面硬度亦良好。所得結果示如第2表。 (實施例27) 於實施例24’除將薄膜張力變更爲5ON/m外，其他與 實施例24相同，製得成型用硬被覆膜輥。 在基材薄膜上進行塗布、硬化以形成硬化層時，行進 Q 之薄膜未發生蛇行或縐紋’故生產性無問題而能夠製成硬 被覆膜。製得之成型用硬被覆膜，其塗布外觀良好，寬方 向收縮率亦良好。又，製得之成型用硬被覆膜，具有與實 施例1同等之成型性、表面硬度、耐擦傷性，其成型體之 表面硬度亦良好。所得結果示如第2表。 (實施例28) 於實施例24’除將薄膜張力變更爲300N/m外，其他 與實施例24相同，製得成型用硬被覆膜輥。 -79- 201038637 在基材薄膜上進行塗布、硬化以形成硬化層時，行進 之薄膜未發生蛇行或縐紋，故生產性無問題而能夠製成硬 被覆膜。製得之成型用硬被覆膜，其塗布外觀良好，寬方 向收縮率亦良好。又，製得之成型用硬被覆膜，具有與實 施例1同等之成型性、表面硬度、耐擦傷性，其成型體之 表面硬度亦良好。所得結果示如第2表。 (比較例3) 於實施例24，除將乾燥溫度變更爲30°C外，其他與實 施例24相同，製得成型用硬被覆膜輥。 在基材薄膜上進行塗布、硬化以形成硬化層時，行進 之薄膜未發生蛇行或縐紋，故生產性無問題而能夠製成硬 被覆膜。製得之成型用硬被覆膜，其寬方向收縮率良好， 但塗布外觀發生泛白而不良。所得結果示如第2表。 (比較例4) 於實施例24，除將乾燥溫度變更爲14CTC外，其他與 實施例24相同，製得成型用硬被覆膜輥。 在基材薄膜上進行塗布、硬化以形成硬化層時，行進 之薄膜未發生蛇行但發生縐紋，故生產性不適合。製得之 成型用硬被覆膜，其塗布外觀有微小塗布缺失或撥拒而不 良，寬方向收縮率亦不良。所得結果示如第2表。 (比較例5) 於實施例24，除將薄膜張力變更爲40N/m外，其他與 實施例24相同，製得成型用硬被覆膜輥。 -80- 201038637 在基材薄膜上進行塗布、硬化以形成硬化層時，雖無 發生縐紋，但行進之薄膜發生蛇行，故生產性不適合。由 於行進之薄膜發生蛇行，故不能製得成型用硬被覆膜。 (比較例6) 於實施例24，除將薄膜張力變更爲320N/m外，其他 與實施例24相同，製得成型用硬被覆膜輥。 在基材薄膜上進行塗布、硬化以形成硬化層時，行進 之薄膜雖無發生蛇行，但發生縐紋，故生產性不適合。製 〇 得之成型用硬被覆膜，其塗布外觀良好，但寬方向收縮率 不良。所得結果示如第2表。 (比較例7) 於實施例1，除將熱固定溫度變更爲205 °C外，其他與 實施例1相同製作基材薄膜’製得成型用硬被覆膜。 (實施例29) 於實施例1，除樹脂片（B)變更爲不含紫外線吸收劑之 Q 聚對酞酸乙二酯之樹脂片（C)外’其他與實施例1相同’製 得成型用硬被覆膜。 (實施例30) 準備下列樹脂片（D)、（E)、（,F) ’當做實施例30之薄膜 原料。 樹脂片（D)之構成成分爲對駄酸單位100莫耳％當做芳 香族二羧酸成分，乙二醇單位70莫耳％及新戊二醇單位30 莫耳％當做二醇成分’含有苯并三哩系紫外線吸收劑 -81 - 201038637 (N)( CIBA SPECIALITY CHEMICALS 股份公司製、 TINUVIN326)0.5質量％，且固有黏度爲0.77dl/g之共聚聚 酯之樹脂片。 樹脂片（F)爲含有苯并三唑系紫外線吸收劑（N)( CIBA SPECIALITY CHEMICALS 股份公司製、TINUVIN326)0.67 質量％，且固有黏度爲0.77dl/g之聚對酞酸乙二酯之樹脂 片。 樹脂片（E)爲含有苯并三唑系紫外線吸收劑（N)( CIBA SPECIALITY CHEMICALS 股份公司製、TINUVIN326)0.67 質量％，且固有黏度爲0.7 5 dl/g之聚對酞酸丙二酯（PPT)之 樹脂片。 將上述樹脂片各別乾燥後，樹脂片（D)、樹脂片（F)及樹 脂片（Ε)以50 : 1 0 : 40之質量比混合。其次，此等樹脂片混 合物由擠壓機之Τ模頭縫口以270°C熔融擠出，在表面溫 度40°C之冷卻輥上急冷固化，同時使用靜電外加法使附著 於冷卻輥得無定形未拉伸片材。 上得未拉伸片材在加熱輥與冷卻輥之間以83 °C縱向拉 伸3.5倍。 其次，在單軸拉伸薄膜之單面以實施例1之塗布液與 實施例1相同方法塗布乾燥，設置中間層。其次，將設置 塗布層之單軸拉伸薄膜導入拉幅機，以95°C預熱10秒鐘 後，前半段以80°C、後半段以75°C橫向拉伸3.9倍。再一 面進行橫方向之7%鬆弛處理下以205 °C進行熱固定處理， -82- 201038637 得厚度50#m之基材薄膜。使用製得之基材薄膜’與實施 例1相同方法製得成型用硬被覆膜° (實施例31) 除將實施例30之原料構成當做芯層原料’樹脂片（D) 及樹脂片（F)以50 : 50之質量比混合之樹脂片當做表層原 料，將此混合樹脂片投入另一部擠壓機以280 °C瑢融後與芯 層原料以分流器（feedblock)接合使表層/芯層/表層= 10/80/10，再以270°C由T模頭擠出’並將橫向拉伸及熱固 〇 定處理變更爲如第6表所示以外，其他與實施例30相同方 法製作基材薄膜，製得成型用硬被覆膜。 (實施例32) 除上述樹脂片（F)外，準備下列樹脂片（H)及樹脂片 (I)，當做實施例32之薄膜原料。 樹脂片（H)之構成成分爲對酞酸單位60莫耳％及異對 駄酸單位40莫耳％當做芳香族二羧酸成分’乙二醇單位100 〇 莫 耳％當做二醇成分，且固有黏度爲〇.71dl/g之共聚聚酯之 樹脂片。 樹脂片（I)之構成成分爲對酞酸單位60莫耳％及萘二甲 酸單位40莫耳％當做芳香族二羧酸成分’乙二醇單位100 莫耳％當做二醇成分，且固有黏度爲0.71 dl/g之共聚聚酯之 樹脂片。 將樹脂片（F)及上述共聚聚酯之樹脂片（H)與聚對酞酸 乙二酯之樹脂片（I)以50 : 25 : 25之質量比混合並乾燥。其 -83- 201038637 次，此等樹脂片混合物由擠壓機之T模頭縫口以270 °C熔 融擠出，在表面溫度40°C之冷卻輥上急冷固化’同時使用 靜電外加法使附著於冷卻輥得無定形未拉伸片材。 上得未拉伸片材在加熱輥與冷卻輥之間以90°C縱向拉 伸3.5倍。其次，將單軸拉伸薄膜導入拉幅機，以120°C預 熱10秒鐘後，前半段以110°c、後半段以100°c橫向拉伸 3.9倍。再一面進行7%鬆弛處理下以23 8 °C進行熱固定處 理，得厚度100 Am之基材薄膜。使用製得之基材薄膜，與 實施例1相同方法製得成型用硬被覆膜。 (比較例8) 準備樹脂片（G)，當做比較例8之薄膜原料。樹脂片（G) 爲固有黏度0.64dl/g，且含有平均粒徑（SEM法）1.5" m之無 定形矽石0.08質量％之聚對酞酸乙二酯之樹脂片（G)。 將上述PET之樹脂片（G)在180°C真空乾燥4小時後供 給熔融擠壓機，由縫口狀模頭以片狀擠出，製成未拉伸片 材。此未拉伸片材首先以加熱成溫度105 °C之壓延輥向長度 方向拉伸3.0倍，再以拉伸溫度125 °C向寬度方向拉伸3.2 倍後，一面進行6 %之鬆弛處理下以1 9 5。(：進行熱固定處 理，得厚度100#m、平面定向度0.138之基材薄膜。使用 製得之基材薄膜，與實施例1相同方法製得成型用硬被覆 膜。 (比較例9) 除使用市售之A- PET未拉伸片材（東洋紡績股份公司 -84- 201038637 製、PETMAX® A5 60GE0R、厚度2〇〇v m)當做基材薄膜外， 其他與實施例1相同方法製得成型用硬被覆膜。 (比較例10) 除使用市售之聚碳酸酯未拉伸片材（帝人化成股份公 司製、PANLITE®SHEETPC2151、厚度200# m)當做基材薄 膜外，其他與實施例1相同方法製得成型用硬被覆膜。 (比較例11) 除使用市售之丙烯酸酯未拉伸片材（三菱化成#股份公 〇 司製、ACRYPLEN® HBS006、厚度125/z m)當做基材薄膜 外，其他與實施例1相同方法製得成型用硬被覆膜。 茲將所使用聚合物之原料組成及聚合物特性示如第1 表，薄膜之製造條件及特性示如第2〜5表，製得成型用硬 被覆膜之特性示如第6、8表，成型用硬被覆膜輥之特性示 如第7表。 第1表 聚酯之組成(莫耳％) 紫外線吸 收劑含量 (質量％) 粒子含量 固有黏度 酸成分 二醇成分 Si〇2 TPA IPA NDC EG NPG PD ppm dl/g A 共聚PEs⑴ 100 - - 40 60 - - - 0.69 B PET (1) 100 - - 100 • - 0.67 400 0.69 C PET⑵ 100 - - 100 • - - 400 0.69 D 共聚PEs (2) 100 - _ 70 30 - 0.5 - 0.77 E PPT 100 - - _ • 100 0.67 - 0.75 F PET⑶ 100 - - 100 - 0.67 - 0.69 G PET⑷ 100 - - 100 _ - - 800 0.65 Η 共聚PEs⑶ 60 40 - 100 • - - - 0.71 I 共聚PEs⑷ 60 - 40 100 - 響 - - 0.71 -85- 201038637 第2表 實肺"〜28 比較例1〜6 赚例7 實施例29 原料之質量比 A 共聚PEs⑴ 25 25 25 B PET (1) 75 75 - C PET⑵ - - 75 原片材 Tm(°C) 243 243 243 縱向拉伸 拉伸溫度（。〇 90 90 90 拉伸倍率㈠ 3.3 3.3 3.3 橫向拉伸 預熱溫度（Ό 120 120 120 預熱時間（秒） 10 10 10 拉伸溫度前半段（°C) 110 110 110 拉伸溫度後半段ΓΟ 100 100 100 拉伸倍率㈠ 3.9 3.9 3.9 熱處理 最高熱處理溫度（。〇 235 205 235 鬆弛率（%) 7 7 7 薄膜特性 厚度Um) 100 100 100 霧度（％) 3.5 3.5 3.5 平面定向度 0.078 0.11 0.078 F100 (MPa) MD/ΎΌ (25°〇 80/85 110/120 80/85 MDmD(uxrc) 30/30 70/75 30/30 熱收縮率（％) MD/TD (150°〇 1.5/0.6 2.3/1.2 1.5/0.6 厚度不均（％) 5.5 2.5 5.5 波長370nm下之光線透射率(％) 0 0 78 耐光性 〇 〇 X 成型性 〇 X 〇 耐溶劑性 〇 〇 〇 印刷等級 Δ Δ Δ -86- 201038637 第3表 實施例30 實施例31 D 共聚PEs⑵ 50 表層50/ 芯層50 原料之質量比 F PET (3) 10 表層50/ 芯層10 E PTT 40 表層0/ 芯層40 原片材 Tm(°C) 218 表層238/ 芯層218 縱向拉伸 拉伸溫度（°C) 83 83 拉伸倍率（一） 3.5 3.5 預熱溫度（。〇 95 95 預熱時間（秒） 10 10 橫向拉伸 拉伸溫度前半段（。〇 80 95 拉伸溫度後半段（°c) 75 90 拉伸倍率㈠ 3.9 3.9 熱處理 最高熱處理溫度（。〇 205 225 鬆弛率（％) 7 7 厚度（//m) 50 50 霧度（％) 0.8 0.6 平面定向度 0.035 0.068 F 100 MDATD (25°〇 80/85 90/95 (MPa) ΜΌίΐΌ (100°〇 30/30 60/65 薄膜特性 熱收縮率（％) ΜΌ/ΊΌ (150°〇 1.5/0.6 2.8/2.1 厚度不均（％) 3.6 3.9 波長370nm下之光線透射率(％) 0 0 耐光性 〇 〇 成型性 〇 〇 耐溶劑性 〇 〇 印刷等級 〇 〇 -87- 201038637 第4表1 1 4 5 % by mass (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1) * 11.45 mass% of vermiculite particles (MEK-ST-L, solid content rate: 30%, manufactured by Nissan Chemical Industries, Ltd.) Average particle size: 50 nm) Luguang polymerization initiator 1.1% by mass (manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184) * Organic lanthanide surfactant 0.03 mass% -76- 201038637 (DOW CORNING TO RAY, DC57) The hard coating film for molding obtained is excellent in moldability and coloration, but has poor surface hardness and scratch resistance, and is also inferior as a hard coating film for molding. The results obtained are shown in Table 1. (Example 24) A film roll having a width of 1000 mm and a length of 200 m was applied by a micro-gravure method and a coating liquid V described below in a roll-to-roll manner, and the thickness of the hardened layer after coating hardening was 2; c/m. It was dried by hot air at a temperature of 80 ° C for 60 seconds under a film tension of 180 N/m, and hardened at a speed of 10 m/min at a position of 20 cm under a high-pressure mercury lamp having an output of 160 W/cm (accumulated light amount: 300 mJ/cm 2 ). The hard coating film for molding was wound around a cylindrical core of polypropylene having a diameter of 6 inches to form a hard coating roll for molding having a width of 1000 mm and a length of 200 m. (Coating liquid V) The following materials were mixed in the following mass ratio, and stirred for 30 minutes or more to dissolve Q. Next, the undissolved matter was filtered off using a filter having a nominal filtration precision of 1/zm to prepare a coating liquid V. Lu Methyl ethyl ketone 28.24% by mass ♦ Toluene 3 6.24% by mass ♦ Neopentyl alcohol triacrylate 11.45% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, functional group number 3) *Three-stretch Propylene glycol diacrylate 5.73 mass% -77- 201038637 (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG _ 200 'functional group number 2) * dimethylamine ethyl methacrylate 5.72% by mass (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1) * 11.64 mass% of vermiculite particles (manufactured by Seiko Chemical Industry Co., Ltd., MEK - ST - L, solid content ratio: 30%, average particle diameter · 50 nm) * Photopolymerization initiator 1.14 mass % (manufactured by CIBA SPECIALITY CHEMICALS, IROACURE 184) * Organic lanthanide surfactant 0.03 mass% (manufactured by DOW CORNING TORAY, DC57) When the base film is coated and hardened to form a hardened layer, the traveling film does not occur. Snake or crepe, so it can be made into a hard coating without any problem. The hard coating film for molding obtained was excellent in coating appearance and good in wide width shrinkage. Further, the obtained hard coating film for molding had the same moldability, surface hardness, and scratch resistance as those of Example 1, and the surface hardness of the molded body was also good. The results obtained are shown in Table 2. (Example 25) A hard coating roll for molding was obtained in the same manner as in Example 24 except that the drying temperature was changed to 40 °C. When the base film is coated and hardened to form a hardened layer, the traveling film does not undergo meandering or crepe, so that the productivity can be made into a hard coating without any problem. The hard coating film for molding obtained was excellent in coating appearance and good in wide width shrinkage. Further, the obtained hard coating film for molding has the same moldability, surface hardness, and scratch resistance as those of Example 1 of the Japanese Patent Publication No. 78-201038637, and the surface hardness of the molded body is also good. The results obtained are shown in Table 2. (Example 26) A hard coating roll for molding was obtained in the same manner as in Example 24 except that the drying temperature was changed to i2 °C. When the base film is coated and hardened to form a hardened layer, the traveling film does not undergo meandering or crepe pattern, so that the productivity can be solved without problems, and a hard coating film can be obtained. The hard coating film for molding obtained was excellent in coating appearance and good in shrinkage in the width direction. Further, the obtained hard coating film for molding had the same moldability, surface hardness, and scratch resistance as those of Example 1, and the surface hardness of the molded body was also good. The results obtained are shown in Table 2. (Example 27) A hard coating roll for molding was obtained in the same manner as in Example 24 except that the film tension was changed to 5 ON/m in Example 24'. When the base film is coated and hardened to form a hardened layer, the film of the traveling Q does not undergo meandering or crepe pattern, so that the productivity can be made without problems, and a hard coating film can be obtained. The hard coating film for molding obtained was excellent in coating appearance and good in wide width shrinkage. Further, the obtained hard coating film for molding had the same moldability, surface hardness, and scratch resistance as those of Example 1, and the surface hardness of the molded body was also good. The results obtained are shown in Table 2. (Example 28) A hard coating roll for molding was obtained in the same manner as in Example 24 except that the film tension was changed to 300 N/m in Example 24'. -79-201038637 When the base film is coated and hardened to form a hardened layer, the traveling film does not wrap or crepe, so that the productivity can be made into a hard coating without any problem. The hard coating film for molding obtained was excellent in coating appearance and good in wide width shrinkage. Further, the obtained hard coating film for molding had the same moldability, surface hardness, and scratch resistance as those of Example 1, and the surface hardness of the molded body was also good. The results obtained are shown in Table 2. (Comparative Example 3) A hard coating roll for molding was obtained in the same manner as in Example 24 except that the drying temperature was changed to 30 °C. When the base film is coated and hardened to form a hardened layer, the traveling film does not undergo meandering or crepe, so that the productivity can be made into a hard coating without any problem. The obtained hard coating film for molding has a good shrinkage ratio in the width direction, but the coating appearance is whitened and poor. The results obtained are shown in Table 2. (Comparative Example 4) A hard coating roll for molding was obtained in the same manner as in Example 24 except that the drying temperature was changed to 14 CTC. When the base film is coated and hardened to form a hardened layer, the traveling film does not wrap and is creped, so that productivity is not suitable. The hard coating film for molding obtained has a coating appearance which is poor in micro coating loss or poorly rejected, and has a poor shrinkage in the width direction. The results obtained are shown in Table 2. (Comparative Example 5) A hard coating roll for molding was obtained in the same manner as in Example 24 except that the film tension was changed to 40 N/m. -80-201038637 When the base film is coated and hardened to form a hardened layer, no wrinkles occur, but the traveling film is meandering, so productivity is not suitable. Since the traveling film is meandered, a hard coating film for molding cannot be obtained. (Comparative Example 6) A hard coating roll for molding was obtained in the same manner as in Example 24 except that the film tension was changed to 320 N/m. When the base film is coated and hardened to form a hardened layer, the traveling film does not wander, but crepe is generated, so that productivity is not suitable. The hard coating film for molding obtained is excellent in coating appearance, but has poor shrinkage in the width direction. The results obtained are shown in Table 2. (Comparative Example 7) A hard coating film for molding was produced in the same manner as in Example 1 except that the heat-fixing temperature was changed to 205 °C. (Example 29) In the first embodiment, except that the resin sheet (B) was changed to a resin sheet (C) of Q-polyethylene terephthalate containing no ultraviolet absorber, "others were the same as in Example 1" to obtain a molding. Use a hard coating. (Example 30) The following resin sheets (D), (E), (, F) were prepared as the film raw materials of Example 30. The constituent component of the resin sheet (D) is 100% by mole of the citric acid unit as an aromatic dicarboxylic acid component, 70 parts by mole of the ethylene glycol unit, and 30% by mole of the neopentyl glycol unit as the diol component 'containing benzene Further, the triternetic ultraviolet absorber-81 - 201038637 (N) (manufactured by CIBA SPECIALITY CHEMICALS CO., LTD., TINUVIN 326) was a resin sheet of a copolyester having an intrinsic viscosity of 0.77 dl/g of 0.5% by mass. Resin sheet (F) is a resin containing polyethylene phthalate containing 0.63 mass% of a benzotriazole-based ultraviolet absorber (N) (manufactured by CIBA SPECIALITY CHEMICALS CO., LTD., TINUVIN 326) and having an intrinsic viscosity of 0.77 dl/g. sheet. The resin sheet (E) is a propylene terephthalate containing a benzotriazole-based ultraviolet absorber (N) (manufactured by CIBA SPECIALITY CHEMICALS CO., LTD., TINUVIN 326) of 0.67 mass% and an intrinsic viscosity of 0.75 dl/g. PPT) resin sheet. After the respective resin sheets were dried, the resin sheet (D), the resin sheet (F) and the resin sheet (Ε) were mixed at a mass ratio of 50:10:40. Next, the resin sheet mixture was melt-extruded at 270 ° C from the die slit of the extruder, and rapidly solidified on a cooling roll having a surface temperature of 40 ° C, while using an electrostatic external addition method to adhere to the cooling roll. Shape the unstretched sheet. The unstretched sheet was stretched 3.5 times in the longitudinal direction at 83 °C between the heating roll and the cooling roll. Then, the coating liquid of Example 1 was applied and dried on the single side of the uniaxially stretched film in the same manner as in Example 1 to provide an intermediate layer. Next, the uniaxially stretched film provided with the coating layer was introduced into a tenter, and after preheating at 95 ° C for 10 seconds, the first half was stretched 3.9 times at 80 ° C and the second half at 75 ° C in the transverse direction. Further, heat treatment was carried out at 205 °C under a 7% relaxation treatment in the transverse direction, and a substrate film having a thickness of 50 #m was obtained at -82-201038637. Using the obtained base film 'in the same manner as in Example 1 to obtain a hard coating film for molding ° (Example 31) except that the raw material of Example 30 was used as a core material "resin sheet (D) and a resin sheet ( F) A resin sheet mixed at a mass ratio of 50:50 is used as a surface material, and the mixed resin sheet is placed in another extruder to be melted at 280 ° C, and then joined to the core material by a feedblock to form a surface layer / The core layer/surface layer = 10/80/10, which was extruded from the T die at 270 ° C, and the transverse stretching and thermosetting measurement were changed to the same as shown in Table 6, and the others were the same as in Example 30. Method A substrate film was produced to obtain a hard coating film for molding. (Example 32) In addition to the above resin sheet (F), the following resin sheet (H) and resin sheet (I) were prepared as the film material of Example 32. The constituent component of the resin sheet (H) is 60 mol% of the tannic acid unit and 40 mol% of the isocyanic acid unit, and the aromatic dicarboxylic acid component 'ethylene glycol unit 100 〇 mol% is used as the diol component, and A resin sheet having a cohesive polyester having an intrinsic viscosity of 71.71 dl/g. The constituent component of the resin sheet (I) is 60 mol% of the tannic acid unit and 40 mol% of the naphthalene dicarboxylic acid unit, and the aromatic dicarboxylic acid component 'ethylene glycol unit 100 mol% is used as the diol component, and the intrinsic viscosity is A resin sheet of a copolyester of 0.71 dl/g. The resin sheet (F) and the resin sheet (H) of the above copolymerized polyester and the resin sheet (I) of polyethylene terephthalate were mixed at a mass ratio of 50:25:25 and dried. From -83 to 201038637 times, these resin sheet mixtures were melt extruded at 270 °C from the T die slit of the extruder, and rapidly solidified on a cooling roll having a surface temperature of 40 ° C while using electrostatic addition to make adhesion. An amorphous unstretched sheet was obtained on the chill roll. The unstretched sheet was stretched 3.5 times in the longitudinal direction at 90 ° C between the heating roll and the cooling roll. Next, the uniaxially stretched film was introduced into a tenter, and after preheating at 120 ° C for 10 seconds, the first half was stretched by 3.9 times at 110 ° C and the second half at 100 ° C in the transverse direction. Further, heat treatment was carried out at 23 ° C under a 7% relaxation treatment to obtain a substrate film having a thickness of 100 Am. Using the obtained base film, a hard coating film for molding was obtained in the same manner as in Example 1. (Comparative Example 8) A resin sheet (G) was prepared as the film material of Comparative Example 8. The resin sheet (G) is a resin sheet (G) having an intrinsic viscosity of 0.64 dl/g and containing polyethylene terephthalate (0.0) of an amorphous vermiculite having an average particle diameter (SEM method) of 1.5 " m. The PET resin sheet (G) was vacuum dried at 180 ° C for 4 hours, and then supplied to a melt extruder, and extruded into a sheet shape by a slit-like die to obtain an unstretched sheet. The unstretched sheet was first stretched 3.0 times in the longitudinal direction by a calender roll heated to a temperature of 105 ° C, and then stretched 3.2 times in the width direction at a stretching temperature of 125 ° C, and then subjected to a relaxation treatment of 6%. Take 1 9 5 . (: A heat-fixing treatment was carried out to obtain a base film having a thickness of 100 #m and a plane orientation of 0.138. Using the obtained base film, a hard coating film for molding was obtained in the same manner as in Example 1. (Comparative Example 9) The same procedure as in Example 1 was carried out except that a commercially available A-PET unstretched sheet (manufactured by Toyobo Co., Ltd. - 84-201038637, PETMAX® A5 60GE0R, thickness: 2 〇〇 vm) was used as the base film. Hard coating film for molding. (Comparative Example 10) Except for the use of a commercially available polycarbonate unstretched sheet (manufactured by Teijin Chemical Co., Ltd., PANLITE® SHEETPC 2151, thickness 200# m) as a base film, In the same manner as in Example 1, a hard coating film for molding was obtained. (Comparative Example 11) A commercially available acrylate unstretched sheet (manufactured by Mitsubishi Chemical Corporation, ACRYPLEN® HBS006, thickness: 125/zm) was used. A hard coating film for molding was obtained in the same manner as in Example 1 except for the base film. The raw material composition and polymer properties of the polymer used are shown in Table 1, and the production conditions and characteristics of the film are shown in Table 2. ~5 table, the characteristics of the hard coating film for molding are as follows Tables 6 and 8 show the characteristics of the hard coating roll for molding as shown in Table 7. Composition of the first table polyester (% by mole) Content of the ultraviolet absorber (% by mass) Particle content Intrinsic viscosity Acid component diol component Si〇2 TPA IPA NDC EG NPG PD ppm dl/g A Copolymer PEs(1) 100 - - 40 60 - - - 0.69 B PET (1) 100 - - 100 • - 0.67 400 0.69 C PET(2) 100 - - 100 • - - 400 0.69 D Copolymerized PEs (2) 100 - _ 70 30 - 0.5 - 0.77 E PPT 100 - - _ • 100 0.67 - 0.75 F PET(3) 100 - - 100 - 0.67 - 0.69 G PET(4) 100 - - 100 _ - - 800 0.65 Η Copolymerized PEs (3) 60 40 - 100 • - - - 0.71 I Copolymer PEs (4) 60 - 40 100 - Loud - - 0.71 -85- 201038637 2nd Table Real Lung "~28 Comparative Example 1~6 Earning Example 7 Example 29 Mass ratio of raw materials Copolymerized PEs (1) 25 25 25 B PET (1) 75 75 - C PET(2) - - 75 Original sheet Tm (°C) 243 243 243 Longitudinal tensile stretching temperature (. 〇90 90 90 Stretching ratio (1) 3.3 3.3 3.3 Lateral stretching preheating temperature (Ό 120 120 120 Preheating time (seconds) 10 10 10 The first half of stretching temperature (°C) 110 110 110 The second half of stretching temperature ΓΟ 100 100 100 draw ratio (1) 3.9 3.9 3.9 Heat treatment maximum heat treatment temperature (. 〇235 205 235 relaxation rate (%) 7 7 7 film characteristic thickness Um) 100 100 100 haze (%) 3.5 3.5 3.5 plane orientation degree 0.078 0.11 0.078 F100 (MPa) MD/ΎΌ (25°〇80/85 110/120 80/85 MDmD(uxrc) 30/30 70/75 30/30 Thermal shrinkage (%) MD/TD (150°〇1.5/0.6 2.3/ 1.2 1.5/0.6 Thickness unevenness (%) 5.5 2.5 5.5 Light transmittance at a wavelength of 370 nm (%) 0 0 78 Light resistance 〇〇X Formability 〇X 〇 Solvent resistance 〇〇〇Printing grade Δ Δ Δ -86- 201038637 Table 3 Example 30 Example 31 D Copolymerized PEs (2) 50 Surface layer 50 / core layer 50 Mass ratio of raw materials F PET (3) 10 Surface layer 50 / core layer 10 E PTT 40 Surface layer 0 / core layer 40 Original sheet Tm ( °C) 218 Surface layer 238 / core layer 218 Longitudinal tensile stretching temperature (°C) 83 83 Stretching ratio (1) 3.5 3.5 Hot temperature (.〇95 95 Preheating time (seconds) 10 10 The first half of the transverse stretching temperature (.〇80 95 The second half of the stretching temperature (°c) 75 90 The stretching ratio (I) 3.9 3.9 Heat treatment maximum heat treatment temperature ( 〇205 225 Relaxation rate (%) 7 7 Thickness (//m) 50 50 Haze (%) 0.8 0.6 Planar orientation 0.035 0.068 F 100 MDATD (25°〇80/85 90/95 (MPa) ΜΌίΐΌ (100 °〇30/30 60/65 Film characteristics Thermal shrinkage (%) ΜΌ/ΊΌ (150°〇1.5/0.6 2.8/2.1 Thickness unevenness (%) 3.6 3.9 Light transmittance at 370 nm (%) 0 0 Light resistance Sexual temperability, solvent resistance, printing grade 〇〇-87- 201038637

實施例32 比較例8 F PET (3) 50 - 原料之質量比 Η 共聚PEs⑶ 25 - I 共聚PEs⑷ 25 - G PET (4) - 100 原片材 Tm(°C) 245 256 縱向拉伸 拉伸溫度（°C) 90 105 拉伸倍率（―） 3.3 3.0 預熱溫度（。〇 120 115 預熱時間（秒） 10 6 橫向拉伸 拉伸溫度前半段（°c) 110 125 拉伸溫度後半段rc) 100 125 拉伸倍率（―） 3.9 3.2 熱處理 最高熱處理溫度（。〇 238 195 鬆弛率（％) 7 6 厚度（jam) 100 100 霧度（％) 0.5 0.6 平面定向度 0.068 0.138 F100 ΜΌΠΌ (25°〇 90/95 125/135 (MPa) MD/TD (100°〇 40/45 75/75 薄膜特性 熱收縮率（％) MD/TD (150°〇 2.2/1.8 1.5/0.3 厚度不均（％) 4.2 14 波長370nm下之光線透射率(％) 0 78 耐光性 〇 X 成型性 〇 X 耐溶劑性 〇 〇 印刷等級 〇 X -88- 201038637Example 32 Comparative Example 8 F PET (3) 50 - mass ratio of raw materials 共聚 copolymerized PEs (3) 25 - I copolymerized PEs (4) 25 - G PET (4) - 100 original sheet Tm (°C) 245 256 longitudinal tensile stretching temperature (°C) 90 105 Stretching ratio (―) 3.3 3.0 Preheating temperature (.〇120 115 Preheating time (seconds) 10 6 Horizontal stretching stretching temperature first half (°c) 110 125 Stretching temperature second half rc 100 125 Stretching ratio (―) 3.9 3.2 Heat treatment maximum heat treatment temperature (.〇238 195 Relaxation rate (%) 7 6 Thickness (jam) 100 100 Haze (%) 0.5 0.6 Planar orientation 0.068 0.138 F100 ΜΌΠΌ (25° 〇90/95 125/135 (MPa) MD/TD (100°〇40/45 75/75 film characteristics heat shrinkage rate (%) MD/TD (150°〇2.2/1.8 1.5/0.3 thickness unevenness (%) 4.2 14 Transmittance of light at a wavelength of 370 nm (%) 0 78 Light resistance 〇X Formability 〇X Solvent resistance 〇〇Printing grade 〇X -88- 201038637

第5表 比較例9 比較例10 比較例11 厚度(Mm) 200 200 125 F100 MD/TD (25°〇 55/55 70/70 - (Mpa) MDATKlOOt：) 2/2 35/35 11/11 波長370nm下之光線透射率(％) 78 0 0 成型性 ◎ 〇 〇 耐溶劑性 X X X 印刷等級 X 〇 〇 -89- 201038637 成型後 硬化層 (Aim) VO cn oq <—Η OO 1—H 1 < 寸· 鉛筆硬度 cs K CS3 ffi cs X <N ffi K cs ffi S ffi (N 成型用硬被覆膜 色調b* i CN Os CO oo oq oq 寸· m ί t 耐擦傷性 1 CQ < < U 0Q u u PQ cri 1 鉛筆硬度 ffi CN ffi OJ 〇J ffi csi K ffi OJ CN CNl I 1 伸長率(％) 异 cs gN o o ss cn cn to cn -1 硬化層 ! ! 粒子含量 (質量％) cs to CN cs to 03 CN r-H 12.5 12.5 to 03 1 < 12.5 塗布液中之游離幅射線硬化型化合物 鍵Θ € m m μ •N » « ® ίϋί Μ ^ 概志；^ 如！$ <|π 25.0 oi 1 i 32.5 in oi 92.4 o o 95.0 25.0 25.0 ^ S' s g _ S 1 Ilii t g 1 ell ^ 1 25.0 65.0 95.0 [ i 95Ό 95.0 50.0 50.0 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10Table 5 Comparative Example 9 Comparative Example 10 Comparative Example 11 Thickness (Mm) 200 200 125 F100 MD/TD (25°〇55/55 70/70 - (Mpa) MDATKlOOt:) 2/2 35/35 11/11 Wavelength Light transmittance at 370 nm (%) 78 0 0 Formability ◎ 〇〇 Solvent resistance XXX Printing grade X 〇〇-89- 201038637 Hardened layer after molding (Aim) VO cn oq <—Η OO 1—H 1 &lt ; inch · pencil hardness cs K CS3 ffi cs X <N ffi K cs ffi S ffi (N forming hard film hue b* i CN Os CO oo oq oq inch · m ί t scratch resistance 1 CQ << U 0Q uu PQ cri 1 Pencil hardness ffi CN ffi OJ 〇J ffi csi K ffi OJ CN CNl I 1 Elongation (%) different cs gN oo ss cn cn to cn -1 Hardened layer! ! Particle content (% by mass Cs to CN cs to 03 CN rH 12.5 12.5 to 03 1 < 12.5 Free Radiation Hardening Compound Key in Coating Liquid Θ € mm μ •N » « ® ίϋί Μ ^ Overview; ^ 如!$ < |π 25.0 oi 1 i 32.5 in oi 92.4 oo 95.0 25.0 25.0 ^ S' sg _ S 1 Ilii tg 1 ell ^ 1 25.0 65.0 95.0 [i 95Ό 95.0 50.0 50.0 Example 1 Example 2 Example 3 Example 6 Example 7 Example 4 Example 5 Example 89 Example 10

II

201038637201038637

1 < »〇 r~H MD vn W-J i—( vq T—^ VO 1—H t—Ή t>； O) X 03 κ cs m CN X CN S K <N K C<1 S X <Ν K ffi cs s cs cn r-H CN cs CN T—H cn oo o O) oo o ON oo o 1—^ cn CQ CQ PQ CQ PQ PQ PQ PQ U PQ u < Q X CN ffi CsJ ffi CNJ S ffi cs K CN cs ffi CN K (N ffi ffi <N ffi s ffi cs Uh r ~H CO 03 CSJ 沄 cn wo CO 9 »—*H <N VO o r- cn 65.6 VO 70.6 vn csi 12.5 VTi oi l-H p 12.5 vn cs T—· 12.5 r—l v〇 cs r—H CS Ο CS 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 P 50.0 50.0 50.1 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 p 100.0 i H l—< cs y—( cn Γ—< v〇 v〇 r- oo t—H ON =7 CN ·=» 辑 镯 鍵 m 辑 辑 習 辑 握 辑 辑 揭 鎰 鎰 卹 u 卹 u K 鹣 u Ιϋ m IK IK n n 5 J-X 201038637 第7表 有無發生皺紋 塗布外觀 寬方向收縮率(％) 實施例24 〇 〇 0.0 實施例25 〇 〇 0.1 實施例26 〇 〇 1.3 實施例27 〇 〇 0.1 實施例28 〇 〇 0.3 比較例3 〇 X 0.0 比較例4 X X 2.4 比較例5 無法製作 比較例6 X 〇 1.6 -92- 201038637 c ο 嗽oo紙 成型後 硬化層 (卿） v〇 υη VO vq vq 寸· VO 鉛筆硬度 1 _ ffi <N ffi 05 ffi CN K cs <N ffi cn κ w X 成型用硬被覆膜 ! 色調b* i _1 CS3 1-( r-^ cn i-H CN (N CO 1 耐擦傷性 _^ TO PQ PQ PQ DQ PQ u 〇 u 鉛筆硬度 K CN X Cvl X cs K 03 X CNl X K K 伸長率(％) R cn On CM cn CO C7\ CN 硬化層 粒子含量 價量％) 12.5 VO T-^ 12.5 ^T) 12.5 12.5 v〇 c4 r—i 塗布液中之游離幅射線硬化型化合物 1¾如 龌蓉g S 15 μ S 1 ^ <Ιΰ 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 1- 25.0 !S _ 鍵4π ϋ ^ 雖翠綱 {ππ 到 » CSI ΛΡ w % m k ^ r-H 50.0 50.0 50.0 50.0 50.0 50.0 ! 50.0 Γ'— 50.0 I ' 1 ' 50.0 比較例7 實施例29 實施例30 實施例31 實施例32 比較例8 比較例9 比較例10 比較例11 — s- 201038637 [產業上之利用可能性] 本發明之成型用硬被覆膜由於在低溫度及低壓力下加 熱成型時成型性優異，故適合應用於廣泛之成型方法，且 以成型品在常溫環境下使用時，彈性及形態安定性（熱收縮 特性、厚斑）優異，再加上耐溶劑性、耐熱性優良，且有環 境負擔小之優點。再者，本發明之成型用硬被覆膜由於具 有硬化層而補強基材薄膜之表面硬度，故使用本發明之成 型用硬被覆膜成型而成之成型體，適合於要求耐擦傷性之 家電、汽車銘板用或建材用部品，行動電話手機、音響、 手提錄放音機、1C記錄器、汽車衛星導航器、PDA手機等 攜帶式機器或筆記型電腦等之外殼箱體。又，在成型加工 製造上，成型前將硬化層加工、積層於基材薄膜之結果， 能夠有助於提升生產性及品質安定性，對產業界之貢獻甚 大。 又，在薄膜中含有紫外線吸收劑使在紫外線下之光線 透射率減低結果’能夠賦予耐光性，尤其適合使用於屋外 用途（汽車外裝用或建材用部品）之成型材料。 【圖式簡單說明】 Μ 〇 /w\ 【主要元件符號說明】 -fnr 無。 -94·1 < »〇r~H MD vn WJ i—( vq T—^ VO 1—H t—Ή t>; O) X 03 κ cs m CN X CN SK <NK C<1 SX <Ν K Ffi cs s cs cn rH CN cs CN T—H cn oo o O) oo o ON oo o 1—^ cn CQ CQ PQ CQ PQ PQ PQ PQ U PQ u < QX CN ffi CsJ ffi CNJ S ffi cs K CN Cs ffi CN K (N ffi ffi <N ffi s ffi cs Uh r ~H CO 03 CSJ 沄cn wo CO 9 »—*H <N VO o r- cn 65.6 VO 70.6 vn csi 12.5 VTi oi lH p 12.5 Vn cs T—· 12.5 r—lv〇cs r—H CS Ο CS 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 P 50.0 50.0 50.1 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 p 100.0 i H l— < cs y—( cn Γ—< v〇v〇r- oo t—H ON =7 CN ·=» Bracelet key m Collection of the collection of the collection of the unbuttoned shirt u K 鹣u Ιϋ m IK IK nn 5 JX 201038637 Table 7 for presence or absence of wrinkle coating appearance Wide direction shrinkage (%) Example 24 〇〇0.0 Example 25 〇〇0.1 Example 26 〇〇1.3 Example 27 〇〇0.1 Example 28 〇 〇0.3 ratio Comparative Example 3 〇X 0.0 Comparative Example 4 XX 2.4 Comparative Example 5 Unable to make Comparative Example 6 X 〇1.6 -92- 201038637 c ο 嗽oo Paper forming hardened layer (Qing) v〇υη VO vq vq inch · VO Pencil hardness 1 _ ffi <N ffi 05 ffi CN K cs <N ffi cn κ w X Hard coating for molding! Hue b* i _1 CS3 1-( r-^ cn iH CN (N CO 1 abrasion resistance _^ TO PQ PQ PQ DQ PQ u 〇u Pencil hardness K CN X Cvl X cs K 03 X CNl XKK Elongation (%) R cn On CM cn CO C7\ CN Hardened layer particle content valence %) 12.5 VO T-^ 12.5 ^T) 12.5 12.5 v〇c4 r—i free radiation hardening compound in coating liquid 13⁄4 such as Cistanche g S 15 μ S 1 ^ <Ιΰ 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 1- 25.0 !S _ Key 4π ϋ ^ Although Jade class {ππ to » CSI ΛΡ w % mk ^ rH 50.0 50.0 50.0 50.0 50.0 50.0 ! 50.0 Γ ' - 50.0 I ' 1 ' 50.0 Comparative Example 7 Example 29 Example 30 Example 31 Example 32 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 - s- 201038637 [Industrial Applicability] The hard coating film for molding of the present invention is low in temperature and low in When it is heated under heat, it is excellent in moldability, so it is suitable for a wide range of molding methods. When the molded article is used in a normal temperature environment, it is excellent in elasticity and form stability (heat shrinkage characteristics, thick spots), and solvent resistance. It has excellent heat resistance and has the advantage of small environmental burden. Further, since the hard coating film for molding of the present invention has a hardened layer to reinforce the surface hardness of the base film, the molded body formed by using the hard coating film for molding of the present invention is suitable for scratch resistance. Housings for home appliances, car nameplates or building materials, mobile phone handsets, stereos, portable recorders, 1C recorders, car satellite navigators, PDA phones, and other portable devices such as laptops or notebook computers. Further, in the molding process, the hardened layer is processed and laminated on the base film before molding, which contributes to improvement in productivity and quality stability, and contributes greatly to the industry. In addition, the film contains an ultraviolet absorber to reduce the transmittance of light under ultraviolet light. As a result of imparting light resistance, it is particularly suitable for use as a molding material for outdoor applications (automobile exterior or building materials). [Simple description of the diagram] Μ 〇 /w\ [Description of main component symbols] -fnr None. -94·

Claims (1)

201038637 七、申請專利範圍·· 1. 一種成型用硬被覆膜，係具有由含共聚聚酯之雙軸定向 聚酯薄膜所構成之基材薄膜及塗布塗布液硬化而成之硬 化層的成型用硬被覆膜， 該塗布液至少含有具3以上之官能基之游離放射線硬 化型化合物、及1及/或2官能基之游離放射線硬化型化 合物， 該塗布液所含游離放射線硬化型化合物中之1及/或2 〇 官能基之游離放射線硬化型化合物含量爲5質量％以 上、9 5質量％以下， 該基材薄膜滿足下列（1)〜（3)之必要條件： (1) 薄膜之長度方向及寬度方向拉伸100 %時之應力均 爲在25°C下爲40〜300MPa及100°C下爲1〜lOOMPa; (2) 熔點爲200〜245°C ; (3) 平面定向度爲0.01以上、未達0.11。 Q 2.如申請專利範圍第1項之成型用硬被覆膜，其中該塗布 液所含游離放射線硬化型化合物中之至少1種爲具胺基 之游離放射線硬化型化合物。 3. 如申請專利範圍第1項之成型用硬被覆膜，其中該硬化 層中含有平均粒徑10nm以上、300nm以下之粒子，且硬 化層中之該粒子含量爲5質量％以上、70質量％以下。 4. 如申請專利範圍第1項之成型用硬被覆膜，其中該共聚 聚酯爲（a)由芳香族二羧酸成分、乙二醇、及含有支鏈狀 -95- 201038637 脂肪族二醇或脂環族二醇之二醇成分所構成之共聚聚 酯；或（b)由含有對酞酸及異對酞酸之芳香族二羧酸成分 及含有乙二醇之二醇成分所構成之共聚聚酯。 5_如申請專利範圍第4項之成型用硬被覆膜，其中構成該 雙軸定向聚酯薄膜之聚酯，其二醇成分含有1，3 -丙二醇 單位或1,4 - 丁二醇單位。 6. 如申請專利範圍第1項之成型用硬被覆膜，其中該雙軸 定向聚酯薄膜含有紫外線吸收劑，其在波長370nm下之 光線透射率爲50%以下。 7. —種成型體，其係將如申請專利範圍第1至6項中之任 —項成型用硬被覆膜以真空成型、氣壓成型及模興成型 之任一方法進行成型之成型體。 -96- 201038637 四、指定代表圖： (一） 本案指定代表圖為：無。 (二） 本代表圖之元件符號簡單說明: 無。201038637 VII. Patent application scope · 1. A hard coating film for molding, which is formed by a base film composed of a biaxially oriented polyester film containing a copolymerized polyester and a hardened layer formed by hardening a coating liquid. In the hard coating film, the coating liquid contains at least a radical radiation-curable compound having a functional group of 3 or more, and a free radiation-curable compound having 1 and/or 2 functional groups, and the coating liquid contains the free radiation-curable compound. The content of the free radiation curable compound of the 1 and/or 2 fluorene functional groups is 5% by mass or more and 95% by mass or less, and the base film satisfies the following requirements (1) to (3): (1) Film The stress at 100% elongation in the longitudinal direction and the width direction is 40 to 300 MPa at 25 ° C and 1 to 100 MPa at 100 ° C; (2) The melting point is 200 to 245 ° C; (3) Planar orientation It is 0.01 or more and less than 0.11. (2) The hard coating film for molding according to the first aspect of the invention, wherein at least one of the free radiation curable compounds contained in the coating liquid is an amine-based free radiation curing compound. 3. The hard coating film for molding according to the first aspect of the invention, wherein the hardened layer contains particles having an average particle diameter of 10 nm or more and 300 nm or less, and the content of the particles in the hardened layer is 5% by mass or more and 70 mass%. %the following. 4. The hard coating film for molding according to item 1 of the patent application, wherein the copolyester is (a) an aromatic dicarboxylic acid component, ethylene glycol, and a branched-95-201038637 aliphatic second a copolyester composed of a diol component of an alcohol or an alicyclic diol; or (b) comprising an aromatic dicarboxylic acid component containing a phthalic acid and an isocyanic acid and a diol component containing ethylene glycol. Copolyester. 5_ The hard coating film for molding according to item 4 of the patent application, wherein the polyester constituting the biaxially oriented polyester film has a diol component containing 1,3 -propylene glycol unit or 1,4-butanediol unit . 6. The hard coating film for molding according to the first aspect of the invention, wherein the biaxially oriented polyester film contains an ultraviolet absorber having a light transmittance of 50% or less at a wavelength of 370 nm. A molded article obtained by molding any of the hard coating films for molding of any of claims 1 to 6 by vacuum molding, pneumatic molding, and molding. -96- 201038637 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention:
TW099104065A 2009-02-12 2010-02-10 Hard coat film for molding TWI437034B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2009029656A JP4766122B2 (en) 2009-02-12 2009-02-12 Hard coat film for molding

Publications (2)

Publication Number Publication Date
TW201038637A true TW201038637A (en) 2010-11-01
TWI437034B TWI437034B (en) 2014-05-11

Family

ID=42561694

Family Applications (1)

Application Number Title Priority Date Filing Date
TW099104065A TWI437034B (en) 2009-02-12 2010-02-10 Hard coat film for molding

Country Status (3)

Country Link
JP (1) JP4766122B2 (en)
TW (1) TWI437034B (en)
WO (1) WO2010092847A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI673166B (en) * 2011-12-21 2019-10-01 日商東麗股份有限公司 Laminated film

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102149433B1 (en) * 2012-07-30 2020-10-14 도요보 가부시키가이샤 Liquid crystal display device, polarizing plates, and polarizer protection film
KR101713880B1 (en) * 2014-08-14 2017-03-22 주식회사 엘지화학 System for controlling tension of films and System for manufacturing a polarizing plate comprising the same
JPWO2018003516A1 (en) * 2016-06-29 2018-10-11 Dic株式会社 Resin composition, paint, and article coated with the paint

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4583699B2 (en) * 2002-08-09 2010-11-17 東洋紡績株式会社 Polyester film, polyester film for molding, and molded member using the same
JP2005290354A (en) * 2003-09-03 2005-10-20 Toyobo Co Ltd Polyester film for forming
DE102006002595A1 (en) * 2006-01-18 2007-07-19 Tesa Ag Process for the production of versatile plastic products with preferably abrasion-resistant surface
WO2008029666A1 (en) * 2006-09-06 2008-03-13 Toyo Boseki Kabushiki Kaisha Polyester film for molding
JP4968461B2 (en) * 2007-04-13 2012-07-04 住友ベークライト株式会社 HARD COAT FILM FOR INJECTION MOLDING AND METHOD FOR PRODUCING INJECTION MOLDING USING THE FILM
JP5527871B2 (en) * 2007-06-20 2014-06-25 日本化薬株式会社 UV curable hard coat resin composition
WO2009154042A1 (en) * 2008-06-18 2009-12-23 東洋紡績株式会社 Hardcoat film for molding

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI673166B (en) * 2011-12-21 2019-10-01 日商東麗股份有限公司 Laminated film

Also Published As

Publication number Publication date
TWI437034B (en) 2014-05-11
WO2010092847A1 (en) 2010-08-19
JP2010185000A (en) 2010-08-26
JP4766122B2 (en) 2011-09-07

Similar Documents

Publication Publication Date Title
TWI400284B (en) Hard-coated film for forming
TWI418578B (en) Polyester film for molding
JP5471419B2 (en) Hard coat film for molding with protective film
JP2011148301A (en) Mat hard coat film for molding
JP5428830B2 (en) Hard coat film for molding
JP6232702B2 (en) Liquid crystal display device, polarizing plate and polarizer protective film
JP5471077B2 (en) Polyester film for molding and hard coat film for molding
JP2011126165A (en) Hard coat film for molding
TWI437034B (en) Hard coat film for molding
JP2011131404A (en) Hard coat film for molding
JP2011131407A (en) Hard coat film for molding
JP2015136792A (en) Laminate
JP2011148964A (en) Hardcoat film for molding
JP2005068238A (en) Polyester film for molding and dummy container obtained from the same
JP2011131406A (en) Hard coat film for molding
JP5428829B2 (en) Hard coat film for molding
JP2011131408A (en) Hard coat film for molding
JP2011131403A (en) Hard coat film for molding
JP5304484B2 (en) Polyester film for molding and hard coat film for molding
JP5605489B2 (en) Hard coat film for molding with protective film
JP5428831B2 (en) Hard coat film for molding
JP5716810B2 (en) Hard coat film for molding with protective film
JP2011131405A (en) Hard coat film for molding