TW201008991A - Hard-coated film for forming - Google Patents

Hard-coated film for forming Download PDF

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Publication number
TW201008991A
TW201008991A TW098120011A TW98120011A TW201008991A TW 201008991 A TW201008991 A TW 201008991A TW 098120011 A TW098120011 A TW 098120011A TW 98120011 A TW98120011 A TW 98120011A TW 201008991 A TW201008991 A TW 201008991A
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Taiwan
Prior art keywords
hard coating
film
mass
molding
coating liquid
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TW098120011A
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Chinese (zh)
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TWI400284B (en
Inventor
Kaoru Sawada
Kenichi Mori
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Toyo Boseki
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Publication of TWI400284B publication Critical patent/TWI400284B/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B32B2038/0028—Stretching, elongating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Paints Or Removers (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention provides a hard coat film for molding, which has high surface hardness and high molding property. The hard coat film for molding has a hard coat layer on at least one side of its substrate film, and the hard coat layer is formed by applying and curing a coating solution. The coating solution comprises at least (1) an ionizing radiation curing type compound having 3 or more functional groups; and (2) an ionizing radiation curing type compound having 1 and/or 2 functional groups. The amount of the ionizing radiation curing type compound having 1 and/or 2 functional groups in the coating solution is more then 5 %, and less then 95 %.

Description

201008991 六、發明說明： 【發明所屬之技術領域】 本發明是關於表面硬度及耐擦傷性優異，且成型性 亦優異之成型用硬被覆膜。 【先前技術】 成型用膜向來以聚氯化乙烯樹脂膜爲代表，但近年 來因耐環境性之需要，使用對環境負擔較小之由聚酯樹 脂、聚碳酸酯樹脂、及丙烯酸系樹脂構成之未拉伸膜，以 及耐熱性或耐溶劑性優異之雙軸定向拉伸聚酯樹脂膜等。 (例如參照專利文獻1〜1 0) ^ 例如，於家電或汽車之銘板用或建材用構件等，將成 型用膜安裝在與外部接觸位置時，爲防止受傷，以補強成 型用膜之表面硬度及提升耐擦傷性爲目的，在其表面設置 硬被覆層。 在成型用膜設置硬被覆層之方法，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 方法，將硬被覆層進行積層。但此種方法係以枚葉式 (cluster type)加工進行硬被覆層之積層，故除提升生產速度 有限外，品質之安定性亦有問題。因此，目前需求以卷對 卷方式（roll to roll type)加工將硬被覆層設置在成型前之膜 上後再進行成型以製得成型體。 在成型前積層硬被覆層之方式，其硬被覆層所希求之 特性，除須要具有與以成型後之後加工方法設置硬被覆層 之方法相同程度之表面硬度及耐擦傷性外，同時亦須要伴 -4- 201008991 隨成型發生變形時能夠追隨之成型性。但，一般之硬被覆 層樹脂，爲滿足表面硬度而使硬被覆層過硬而無成型性， 而有因成型加工時發生變形使硬被覆層發生龜裂（硬被覆 層之破裂）之問題。 因此’有許多先前技術提案將硬化後具有一定程度之 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，或將多數具有柔軟性之層與具有強表面硬度之層 在基材上積層，以製得具有強表面硬度及彎曲性之硬被覆 W 膜（參照專利文獻11〜14)。 (專利文獻1)特開平9一 156267號公報 (專利文獻2)特開平9 - 1 87903號公報 (專利文獻3)特開平10 - 296937號公報 (專利文獻4)特開平11— 268215號公報 (專利文獻5)特開200 1 — 1 2995 1號公報 (專利文獻6)特開200 1 - 2 1 2868號公報 @ (專利文獻7)特開2002 - 249652號公報 (專利文獻8)特開2003 - 2 1 1 606號公報 (專利文獻9)特開2004 — 075713號公報 (專利文獻10)特開2005 - 290354號公報 (專利文獻11)特開2005 - 3053 83號公報 (專利文獻12)特開2007 - 284626號公報 (專利文獻13)特開2007 - 3 1 3728號公報 (專利文獻14)國際公開第2008/029666號說明小册 【發明內容】 201008991 「發明欲解決之課題」 但，專利文獻11、13所提示之硬被覆膜，雖具有適當 之表面硬度，至於其成型性則僅具彎曲性及打孔加工之限 定性加工特性；而專利文獻1 2所提案之硬被覆膜，雖具有 拉伸性，但表面硬度則不能滿足。又，專利文獻14所提案 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，有時無法發揮充 分之性能。亦即，上述專利文獻不能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，亦即提供在成型前 將硬被覆層加工、積層在成型用膜上，能夠對提升生產性、 品質安定性有所貢獻，且兼備表面硬度、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」 φ 本發明者等爲解決上述課題而悉心硏究結果，終於完 成本發明。亦即，本發明如下述。 第1項發明爲具有在基材膜之至少一面上塗布塗布液 使其硬化而成硬被覆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輻射線硬化型化合 物、及1及/或2官能基之游離輻射線硬化型化合物，上述 塗布液所含游離輻射線硬化型化合物中之1及/或2官能基 之游離輻射線硬化型化合物含量爲5質量％以上、95質量％ 以下。 201008991 第2項發明爲上述成型用硬被覆膜中，該基材膜爲含 有共聚合聚酯之雙軸定向聚酯膜。 第3項發明爲上述成型用硬被覆膜中，該塗布液所含 游離輻射線硬化型化合物中之至少1種爲具有胺基之游離 輻射線硬化型化合物。 第4項發明爲上述成型用硬被覆膜中，該硬被覆層中 含有平均粒徑l〇nm以上、300nm以下之粒子，且硬被覆層 中之該粒子含量爲5質量％以上、70質量％以下。 第5項發明爲上述成型用硬被覆膜中，該硬被覆層中 含有游離輻射線硬化型有機矽樹脂，硬被覆層中之該游離 輻射線硬化型有機矽樹脂含量，相對於上述游離輻射線硬 化型化合物100質量份爲0.15質量份以上、15質量份以下。 第6項發明爲將上述成型用硬被覆膜進行成型而形成 之一種成型體。 第7項發明爲上述成型體中，硬被覆層之厚度爲0.5 以上、50//m以下。 第8項發明爲一種成型用硬被覆膜輥之製造方法，係 具有在基材膜之至少一面上塗布塗布液使其硬化而成之硬 被覆層之成型用硬被覆膜之輥之製造方法，其特徵爲上述 塗布液至少含有有機溶劑、具3以上之官能基之游離輻射 線硬化型化合物、及1及/或2官能基之游離輻射線硬化型 化合物，上述塗布液所含游離輻射線硬化型化合物中之丄 及/或2官能基之游離輻射線硬化型化合物含量爲5質量％ 以上、95質量％以下，在塗布上述塗布液後，以薄膜張力 201008991 5 0N/m以上、3 00N/m以下及溫度40°C以上、120°C以下之 條件進行乾燥並硬化而設置硬被覆層。 「發明效果」 本發明之成型用硬被覆膜具有表面硬度、耐擦傷性與 能夠追隨成型時變形之成型性之兩方特性。本發明因具備 髙表面硬度及優異伸張性，故如以銘板用或建材用構件爲 適當實施形式時適合使用。又，以本發明之較佳實施態樣 而使用具胺基之游離輻射線硬化型樹脂及/或粒子時，表面 • 硬度與成型性之兩方特性能夠更高度並存，而適合使用於 如箱體等之構件。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，以本發明之較佳實施態樣當作成型用膜輥使用時，成 型體之品質安定性優異。 ' 【實施方式】 (基材膜） φ 在本發明，基材膜並無特別限定，但以具有成型性爲 其特徵。在此所謂成型性乃指能夠以模具成型或氣壓成 型、真空成型等成型加工法形成成型體。具體而言，因成 型而在局部被拉伸之部位發生部分高應力時，基材膜具有 不會斷裂而能夠形成成型體之膜應力特性。 此種基材膜，如聚酯系、丙烯酸系、纖維素系、聚乙 烯系、聚丙烯系、聚烯烴系、聚氯乙烯系、聚碳酸酯系、 苯酚系、聚胺基甲酸乙酯系等之塑膠膜或塑膠片及黏合此 等之任意2種以上者。其中以耐熱性及柔軟性之平衡良好 201008991 之聚酯系膜較佳。 基材膜以含有低溫下或低壓下加熱成型時成型性優異 之共聚合聚酯之聚酯膜較好。共聚合聚酯以（a)由含有芳香 族二羧酸成分、乙二醇、支鏈狀脂肪族二元醇或脂環族二 元醇之二元醇成分構成之共聚合聚酯；或（b)由含對苯二甲 酸或異對苯二甲酸芳香族二羧酸成分、及含乙二醇之二元 醇成分構成之共聚合聚酯較適合。 至於上述共聚合聚酯，使用由含有芳香族二羧酸成 分、乙二醇、支鏈狀脂肪族二元醇或脂環族二元醇之二元 醇成分構成之共聚合聚酯時，芳香族二羧酸成分以對苯二 甲酸、異對苯二甲酸、萘二甲酸或此等之酯形成性衍生物 較適合’相對於二羧酸成分全量之對苯二甲酸及/或萘二甲 酸成分的量’以70莫耳％以上爲宜，並以85莫耳％以上較 好、95莫耳％以上更好、1〇〇莫耳％最好。 在本發明’含有共聚合聚酯之聚酯膜，其膜構成成分 含有共聚合聚酯成分，其具體態樣如下：（1)基材膜全由共 聚合聚醋構成；（2)含有共聚合聚酯當作基材膜構成成分之 一部分（如混合共聚合聚酯與聚對苯二甲酸乙二醇酯或聚 萘二甲酸乙二醇醋等其他均聚酯構成之樹脂組成物）；（3) 基材膜由含共聚合聚酯之聚酯層與不含共聚合聚酯之聚酯 層之多層所構成。 上述基材膜’由耐熱性及耐溶劑性之觀點，以雙軸拉 伸膜特別適合。至於拉伸方法，可舉出如管式（tubular)拉伸 法、同時雙軸拉伸法、逐次雙軸拉伸法等，但由平面性、 201008991 尺寸安定性、厚度不均匀等之觀點，以逐次雙軸拉伸法較 佳。例如使用聚酯膜當作基材膜時之逐次雙軸拉伸法，於 50°C以上、110°C以下向長度方向以滾筒拉伸1.6倍以上、 4.0倍，接著使用拉幅供乾機（tenter)預熱後，在聚酯之玻 璃轉脆溫度一4(TC以上、+65°C以下可向寬度方向拉伸丄.2 倍以上、5·0倍以下。再者，於雙軸拉伸後，可在聚酯熔點 之一 40°C以上、一 10°C以下之溫度進行熱固定處理。 本發明所使用之基材膜，爲賦予操作性（如積層後之卷 取性），以膜中含有粒子而使膜表面形成突起較好。膜中所 含有的粒子，如矽石、高嶺石、滑石、碳酸鈣、沸石、礬 土等無機粒子，壓克力、PMMA、耐綸、聚苯乙烯、聚酯、 苯并狐胺（benzoguanamin)甲醒縮合物等耐熱性高分子粒 子。由透明性之觀點，膜中粒子之含量以少量爲宜，如1 ppm 以上、lOOOppm以下。再由透明性之觀點，以選擇與使用 樹脂之折射率相近之粒子爲宜。又，由於膜因應需要而賦 予各種功能，故可含有耐光劑（防紫外線劑）、色素、防靜 電劑等。 成型用硬被覆膜，如在其不積層硬被覆層之一面實施 印刷加工時，基材膜之總光線穿透率以80%以上，且霧度 以5 %以下爲宜。基材膜之透明性差，則由硬被覆層方看印 刷層時視認性減低。 本發明所使用之基材膜，以單層膜或以積層表面層與 中心層之2層以上之複合膜均可。複合膜有各別設計表面 層與中心層之功能之優點。例如一方面只在厚度較薄之表 -10- 201008991 面層含有粒子使表面形成凹凸以維持操作性，一方面在厚 度較厚之中心層實質上不含粒子，而能夠更加提升複合膜 全體之透明性。上述複合膜之製造方法並無特別限定，但 如考慮生產性，則將表面層與中心層之原料由各別之擠壓 機擠出後導入同一模頭製得未拉伸片後，以至少向單軸方 向定向之所謂共擠壓法進行積層爲宜。 本發明所使用基材膜之厚度因原料而異，使用聚酯膜 時其厚度下限以35/zm以上較好、50//m以上更好。另一 方面’其厚度上限以260 v m以下較好、200 M m以下更好。 厚度較薄時，不僅使操作性不良，另如將硬被覆層加熱乾 燥以減少其殘留溶劑時，膜容易產生熱皺紋而使平面性不 良。另一方面，膜之厚度較厚時，不僅成本上有問題，卷 取成輥狀保存時，因卷取癖性而容易發生平面性不良。 (中間層） 本發明之成型用硬被覆膜，由積層硬被覆層於基材膜 之一面而構成，但爲提升基材膜與硬被覆層之黏合性爲目 的而設置中間層較佳。又，爲提升基材膜之透明性而不在 其中含有粒子時，則在製造基材膜時同時設置含有粒子之 中間層，能夠對基材膜賦予操作性。 上述中間層之構成樹脂，可舉出如聚酯系樹脂、聚胺 甲酸乙酯樹脂、聚酯型聚胺甲酸乙酯樹脂、丙烯酸系樹脂、 三聚氰胺樹脂及此等之混合樹脂等，但以基材膜與硬被覆 層之黏合性良好而選擇爲重要，具體例如構成基材膜與硬 被覆層之樹脂爲丙烯酸系樹脂時，則由丙烯酸系、共聚合 -11- 201008991 聚酯系、聚酯型聚胺甲酸乙酯系等中至少選擇1種爲宜。 爲提升黏合性、耐水性爲目的，在上述中間層中含有 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。 中間層可含有各種粒子，其目的爲在形成硬被覆層前 之基材膜表面形成凹凸以改善滑動性。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’壓克力、PMM A、耐綸、聚苯乙烯、聚酯、苯并胍胺 (benzoguanamin) /甲醛縮合物等有機粒子。又，由透明性之 觀點，應選擇與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布法較佳。塗布法使用如凹版 塗布法、滾壓塗布法（Kiss coating)、浸漬塗布法、噴霧塗 布法、簾幕塗布法、氣刀塗布法、反向滾筒塗布法等習知 塗布法，並以製造基材膜時設置塗布層之倂線（或聯 g 線Kin-line)塗布法，或以製造基材膜後設置塗布層之離線 (off-line)塗布法設置中間層。此等方法中以倂線塗布法不 僅在成本上優越，且在中間層含有粒子之結果，勿須在基 材膜中含有粒子，能夠高度改善透明性而較佳。 (硬被覆層） 本發明之成型用硬被覆膜，在基材膜之至少一面以直 接或透過中間層將硬被覆層積層。於本發明，所謂硬被覆 層，乃爲補強由基材膜構成基材之表面硬度並提升耐擦傷 性，而具有較基材高硬度之薄膜，且具有對成型時之變形 -12- 201008991 亦能夠追隨之優異成型性之層。更具體而言，本發明之成 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10%以上之伸長率，故適合當 作家電等銘板用或建材用構件使用。 本發明所使用之硬被覆層，必須以游離輻射線硬化型 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，同時能夠減少因熱引起基材膜之熱收縮，故較 適合。於本發明，游離輻射線硬化型化合物係以電子線、 放射線、紫外線中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被覆 層。本發明所使用之游離輻射線硬化型化合物，如三聚氰 胺系、丙烯酸系、有機矽系之游離輻射線硬化型化合物， 其中由能夠獲得高表面硬度之觀點，以丙烯酸酯系游離輻 射線硬化型化合物較佳》 又於本發明，游離輻射線硬化型化合物不僅限於單 Φ 體、先質，當然亦包含其等所聚合及/或反應之游離輻射線 硬化型樹脂。如以上述丙烯酸酯系游離輻射線硬化型化合 物爲例’可舉例如聚胺甲酸乙酯丙烯酸酯、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輻射線硬化型化合物。 本發明之硬被覆層，係將至少含有具3以上官能基之 游離輻射線硬化型化合物、與1及/或2官能基游離輻射線 硬化型化合物之塗布液塗布在基材膜後，以電子線、放射 線 '紫外線中之任一種進行照射引起聚合及/或反應使其硬 -13- 201008991 化而成。 使用丙烯酸酯系游離輻射線硬化型化合物當作游離輻 射線硬化型化合物時，本發明之1官能基（單官能基）丙烯 酸酯系游離輻射線硬化型化合物，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）丙烯醯味嗎啉、7-胺基-3,7 -二甲基辛基（甲 基）丙烯酸酯、異丁氧甲基（甲基）丙烯醯胺、異萡基氧乙基 (甲基）丙烯酸酯、異萡基（甲基）丙烯酸酯、2 -乙基己基（甲 ❹ 基）丙烯酸酯、乙基二伸乙甘醇（甲基）丙烯酸酯、第三辛基 (甲基）丙烯酸酯、雙丙酮（甲基）丙烯醯胺、二甲胺基乙基（甲 基）丙烯酸酯、二乙胺基乙基（甲基）丙烯酸酯、月桂基（甲基） 丙烯酸酯、二環戊二烯基（甲基）丙烯酸酯、二環戊烯基氧 乙基（甲基）丙烯酸酯、二環戊烯基（甲基）丙烯酸酯、Ν,Ν-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、 Ν -乙烯吡咯酮、Ν -乙烯甲醯胺、苯氧乙基（甲基）丙烯酸 酯、丁氧基乙基（甲基）丙烯酸酯、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、萡基（甲基）丙烯酸酯、甲 基三伸二甘醇（甲基）丙烯酸酯、環己基（甲基）丙烯酸酯、壬 -14- 201008991 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。 使用丙烯酸酯系游離輻射線硬化型化合物當作游離輻 射線硬化型化合物時，本發明之2官能基丙烯酸酯系游離 輻射線硬化型化合物，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2〜12之伸烷基二元 醇之（甲基）丙烯酸二酯類：如乙二醇二（甲基）丙烯酸酯、丙 β 二醇二（甲基）丙烯酸酯、L4 - 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)聚氧伸烷基二元醇之（甲基）丙烯酸二酯類：如二 _ 伸乙甘醇二（甲基）丙烯酸酯、三伸甘醇二（甲基）丙烯酸酯、 四乙二醇二（甲基）丙烯酸酯、二丙烯甘醇二（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)多元醇之甲基丙烯酸二酯類：如新戊四醇二（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：如2,2’-雙（4-丙烯氧 基乙氧苯基）丙烷、2,2’-雙（4 -丙烯氧基丙氧苯基）丙烷 等；（e)先將多價之異氰酸酯化合物與含2個以上醇性羥基 之化合物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2個 (甲基）丙烯醯氧基之胺甲酸乙酯（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 -15- 201008991 (甲基）丙烯酸酯類等。 使用丙烯酸酯系游離輻射線硬化型化合物當作游離|g 射線硬化型化合物時，本發明之具3官能基以上之丙烯酸 酯系游離輻射線硬化型化合物，具體可使用U)新戊四醇三 (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)先將多價異氰酸酯化 合物與含2個以上醇性羥基之化合物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）丙烯醯氧基之胺甲 酸乙酯（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，上述塗布液中所含游離輻射線硬化型化合 物中，除含1或2官能基之游離輻射線硬化型化合物以外 再含1種以上具3官能基以上之游離輻射線硬化型化合物 爲重要。如此則在硬化後之硬被覆層中，交聯密度高之具 3官能基以上之游離輻射線硬化型化合物成分以硬鏈段存 在，而1及/或2官能基之游離輻射線硬化型化合物與此等 連結方式進行反應使1及/或2官能基之游離輻射線硬化型 化合物成分以軟鏈段存在。此種將2種以上不同官能基數 之游離輻射線硬化型化合物調整在特定濃度範圍之結果， -16- 201008991 與 相 具 在 2 95 覆 度 上 量 游 線 能 夠 車 與 具 化 I - 少 線 可導入異交聯結構於硬被覆層，以硬鏈段賦予表面硬度 耐擦傷性，並以軟鏈段之伸縮性賦予成型性，乃獲得自 矛盾之特性並存之顯著效果。 於本發明，爲使髙表面硬度與優異成型性並存，即 體而言使Η以上之鉛筆硬度及1〇%以上之伸長率並存， 上述塗布液中所含游離輻射線硬化型化合物中之1及/或 官能基之游離輻射線硬化型化合物含量爲5質量％以上、 質量％以下爲重要。上述含量如未達5質量％時，不僅被 膜之可撓性減低，成型時在硬被覆層發生紋裂故不宜。又 上述含量如超過95質量％時，難以獲得具有充分表面硬 與耐擦傷性之硬化薄膜。上述含量之下限以10質量％以 較好，20質量％以上更好。又，上述含量之上限以90質 %以下較好，80質量％以下更好，70質量％以下最好。如 離輻射線硬化型化合物中之1及/或2官能基之游離輻射 硬化型化合物含量爲20質量％以上、80質量％以下時， 夠謀求更高度之表面硬度與成型性之並存，具體而言能 使2Η以上鉛筆硬度與20%以上伸長率並存，適合於如汽 等銘板用或隨身攜帶機器等之外殼等，同時要求高硬度 高加工性之成型用膜。 再者，本發明者等除上述實施態樣外，再加上使用 胺基之游離輻射線硬化型化合物當作游離輻射線硬化型 合物時，發現能夠使表面硬度與成型性更高度並存。亦艮Ρ 在上述塗布液中所含之游離輻射線硬化型化合物其中至 1種具有胺基較好。使用具胺基之化合物當作游離輻射 -17- 201008991 硬化型化合物之結果引起之上述作用可思考如下。硬被覆 層之硬度分布如有局部性差異，則拉伸硬被覆層時容易產 生局部性破裂（紋裂）。此種局部性硬度分布差異之原因， 有因氧引起之游離輻射線硬化樹脂之聚合抑制作用（氧化 抑制）。在此，如使用具胺基之化合物當作游離輻射線硬化 型化合物時，胺基可捕捉自由基氧，使影響硬被覆層表層 部硬化反應之氧化抑制減少，故能夠在表層部進行均匀之 硬化反應。依此，成型時施加於硬被覆層之應力被分散至 該層全體，故成型時發生裂紋亦被抑制。因此，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，因 具胺基之游離輻射線硬化樹脂之塗膜速硬性之效果，如i 不含胺基比較時，硬被覆層表面之硬化更加被促進而提升 表面硬度。 在上述塗布液中所含游離輻射線硬化型化合物中之具 胺基之游離輻射線硬化型化合物含量爲2.5質量％以上、95 φ 質量％以下較佳。在上述塗布液中所含游離輻射線硬化型化 合物中之具胺基之游離輻射線硬化型化合物含量下限以5 質量％以上較好、10質量％以上更好。又，上述含量之上限 以92.5質量％以下較好，90質量％以下更好，50質量％以 下最好。在上述塗布液中所含游離輻射線硬化型化合物中 之具胺基之游離輻射線硬化型化合物含量未達2.5質量％ 時，硬被覆層全體較難均匀硬化，故較難獲得成型時對紋 裂之耐性。又，具胺基之游離輻射線硬化型化合物如爲高 濃度時，因胺基引起之硬被覆層黃變較強，故上述含量如 -18- 201008991 超過95質量％，則有時損害高透明性。例如在硬 未積層面上實施印刷加工時，膜之顏色b値以2以 此時，上述具有胺基之游離輻射線硬化型化合物ί 量％以下較佳。 於本發明之上述塗布液中，含有1及/或2官 離輻射線硬化型化合物、及具3以上官能基之游 硬化型化合物，但於上述實施態樣中，其中一部 輻射線硬化型化合物具有胺基即可。又，1官能 射線硬化型化合物、或2官能基游離輻射線硬 物、或具3以上官能基之游離輻射線硬化型化合 一種爲具胺基之游離輻射線硬化型化合物亦爲較 施形式。 使用丙烯酸酯系游離輻射線硬化型化合物當 之游離輻射線硬化型化合物時，具胺基之丙烯酸 輻射線硬化型化合物如丙烯醯胺、7-胺基-3,7-(甲基）丙烯酸酯、異丁氧甲基（甲基）丙烯醯胺、三糸 基）丙烯醯胺、雙丙酮（甲基）丙烯醯胺、二甲胺乙 丙烯酸酯、二乙胺乙基（甲基）丙烯酸酯、Ν,Ν -二甲 丙烯醯胺四氯苯基（甲基）丙烯酸酯、Ν -乙烯甲醯 又，本發明者等除上述實施態樣外，再加上 覆層含有粒子，發現能夠更提升成型性，並使表 成型性更高度並存。關於硬被覆層含有粒子之結 更提升成型性之作用可做如下之思考。硬被覆層 升則成型時在硬度高之硬被覆層暫時發生強應力 被覆層之 .下較好， 善92.5質 能基之游 離輻射線 分之游離 基游離輻 化型化合 物中之任 適合之實 作具胺基 酯系游離 二甲辛基 反辛基（甲 基（甲基） 基（甲基） 胺等。 如在硬被 面硬度與 果，能夠 之硬度提 ，導致硬 -19- 201008991 被覆層一下子產生破裂（紋裂）。在此，硬被覆層含有粒子 之結果，成型時施加於硬被覆層之內部應力在游離輻射線 硬化型化合物與粒子之界面被緩和，除產生紋裂被抑制 外，在硬被覆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，延遲硬被覆層發生致命的破裂，結 果表現提升成型性之效果》 至於硬被覆層所含粒子，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、羥基磷灰石等無機粒子，交聯壓 克力粒子、交聯PMMA粒子、耐綸粒子、聚酯粒子、苯并 胍胺（benzoguanamin) /甲酵縮合物粒子、胍胺/三聚氰胺/甲醒 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，如矽石/壓克力複合化合物之有機/無機混種微粒等，但 ' 於本發明，粒子之種類並無特別限定。 粒子之形狀，如球狀、塊狀、板狀、纖維狀、薄片狀 Θ 等，但無特別限定，其中由分散性及與其他構件接觸時粒 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 00nm以下 爲宜，再者下限爲40nm以上、上限爲200nm以下較好，尤 其下限爲50nm以上、上限爲100nm以下更好。粒子之平均 粒徑小於10nm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。又，超過300nm時，硬被覆層可能變脆弱，成型 性減低。又，上述平均粒徑係使用庫爾特計數器（Coulter -20- 201008991 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，硬被覆層所含粒子含量以硬被覆層中之固 體成分計算爲5質量％以上、70質量％以下較好，尤其，前 述含量下限爲15質量％以上、上限爲50質量％以下特好。 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。另 —方面，粒子含量超過70質量％時，成型時發生多量前述 微小紋裂，使霧度上升（白化）損害成型體之透明性。 再者，本發明者等除上述實施態樣外，再加上在硬被 覆層含有游離輻射線硬化型有機矽樹脂時，發現能夠賦予 滑動性，提升表面之耐擦傷性，並使表面硬度與成型性高 度並存。又因此種形式，硬化反應使游離輻射線硬化型有 機矽樹脂本身交聯，同時有時亦與構成硬被覆層之游離輻 射線硬化型樹脂交聯，獲得模具成型時能夠防止有機矽樹 脂污染模具，及長期使用由本發明之成型用硬被覆膜成型 而成之成型體時，其表面之耐擦傷性功能不因時效受損等 新效果。 游離輻射線硬化型有機矽樹脂，如分子中具有烯基與 锍（或氫硫）基之自由基加成型、具有烯基與氫原子之氫甲 矽烷基化反應型、具有環氧基之陽離子聚合型、具有甲基 丙烯基之自由基聚合型等。其中以具有環氧基之陽離子聚 合型及具有甲基丙烯基之自由基聚合型較佳。 -21 - 201008991 分子中具有環氧基或（甲基）丙烯基之有機矽樹脂，如 環氧基丙氧丙基末端聚二甲基矽氧烷、（環氧基環己乙基） 甲基矽氧烷-二甲基矽氧烷共聚物、甲基丙烯醯氧丙基末 端聚二甲基矽氧烷、丙烯醯氧丙基末端聚二甲基矽氧烷 等。又，分子中具有乙烯基之有機矽樹脂，如末端乙烯基 聚二甲基矽氧烷、乙烯基甲基矽氧烷同聚物等。 於本發明，硬被覆層所含游離輻射線硬化型有機矽樹 脂添加量，相對於構成硬被覆層之上述游離輻射線硬化型 ❹ W 化合物100質量份，以配合0.15〜15質量份較好，0.3〜13 質量份更好，0.5〜5質量份最好。游離輻射線硬化型有機 矽樹脂配合量如未達下限，製成成型體時缺乏耐擦傷性提 升效果，又如超過上限，則形成硬被覆層時不能進行充分 之硬化。又，硬被覆層所含游離輻射線硬化型有機矽樹脂 使用1種或2種以上組合均可。 於本發明，因應成型用硬被覆膜用途，適當選擇或組 φ 合上述之游離輻射線硬化型化合物使用具胺基之化合物及 添加粒子於硬被覆層等較理想。特別適合之形式爲此等之 組合。依此，能夠使硬被覆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、更好表面硬度2H以上且伸長率30%以上之成型 用硬被覆膜，適合使用於汽車等之覆蓋構件或深底之箱 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 -22- 201008991 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* sketone)、爷基、苯偶姻、苯偶 姻甲醚、苯偶姻***、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、2,2-二甲氧基-2 -苯基苯乙酮、1-羥基環己基苯基酮等羰基 β 化合物，硫化四甲基胺硫甲醯基（tetramethylthiuram monosulfide)、二硫化四甲基胺硫甲醯基、硫卩山喔 (thioxanthene)、2 -氯硫Π山噃、2 -甲基硫卩山嗤等硫化物， 過氧化苯甲醯基、二（三級丁基）過氧化物等過氧化物等。 ' 此等光聚合引發可舉出三級丁基過氧化物等之過氧化物化 • 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100質 量份游離輻射線硬化型化合物之0.01質量份以上、15質量 ® 份以下較適當，使用量少時不僅反應慢、生產性不良，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，硬被覆層因聚合引發劑而有發生黃 變之問題。 於本發明，在上述塗布液中，爲防止製造時之熱聚合 或貯存時之暗反應，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質量份游離輻射線硬化型化合 物之0.005質量份以上、0.05質量份以下較佳。 -23- 201008991 於本發明，在上述塗布液中，以提升塗布時之作 控制塗布時之塗膜厚度爲目的，在不損害本發明之 圍內，可配合有機溶劑。 關於有機溶劑，由於使用低熔點基材膜時塗布 燥溫度或須調整爲150°C以下，故有機溶劑之沸點上 以上、150°C以下較佳。具體例如甲醇、乙醇、異丙 系溶劑，乙酸甲酯、乙酸乙酯、乙酸丁酯等乙酸酯系 丙酮、甲基乙基酮等酮系溶劑，甲苯等芳香族系溶 噚烷等環狀醚系溶劑等。此等溶劑可單獨或2種以 使用。 於本發明，在上述塗布液中，以減低塗布液之 力、改善硬被覆層之塗布外觀（尤其因微小泡沫引 失、異物附著引起之凹陷、乾燥製程時之撥拒）爲目 含有界面活性劑。 界面活性劑可適當使用習知陽離子系、陰離子 離子系，但由上述塗布液之變質或硬被覆層對基材 合性不良等問題，以不具極性之非離子系較好，而 活性能優異之有機矽系界面活性劑或氟系界面活 好。 至於有機矽系界面活性劑，可舉例如二甲基矽 矽烷、丙烯基矽烷、乙烯苯甲矽烷、乙烯苯甲胺基 縮水甘油基矽烷、锍基矽烷、二甲基矽烷、聚二甲 烷、聚烷氧基矽氧烷、氫化二烯改性矽氧烷、乙烯 矽氧烷、羥基改性矽氧烷、胺基改性矽氧烷、羧基 業性、 目的範 後之乾 V, 5 0°C 醇等醇 溶劑， 劑，二 上混合 表面張 起之缺 的，可 系、非 膜之黏 以界面 性劑更 、胺基 矽烷、 基砂氧 基改性 改性矽 -24- 201008991 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、巯基改性矽氧烷、氟改性矽氧烷、烷基 改性矽氧烷、苯基改性矽氧烷、烯基氧化物改性矽氧烷等。 至於氟系界面活性劑，可舉例如四氟化乙烯、全氟烷 基銨鹽、全氟烷基烷磺醯胺、全氟烷基烷磺酸鈉、全氟烷 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，對構成硬被覆層之 塗布液而言，界面活性劑含量爲0.01質量％以上較佳。另 一方面，由於界面活性劑滲出硬被覆層表面而污染接觸硬 被覆層者，故界面活性劑含量爲2.00質量％以下較佳。 ' 又，所使用界面活性劑以HLB爲2以上、12以下較佳。 使用HLB爲2以上之界面活性劑時，能夠以界面活性能提 _ 升塗平性。界面活性劑之HLB以3以上更好、4以上特好。 另一方面，使用HLB爲12以下之界面活性劑時，能夠抑 制滑動性之惡化。 又，所謂HLB係由美國Atlas Powder公司之W.C.Griffin 命名之HydrophilLyophil Balance之縮寫字，爲界面活性劑 分子中所含親水基與親油基之平衡當作特性値而指標化之 値。意指HLB値愈低則親油性愈高，反之HLB値愈高則親 水性愈高。 本發明之硬被覆層可因應須要配合各種添加劑。如爲 -25- .201008991 賦予拒水性之氟系或有機矽系化合物，爲提升塗布性或外 觀之消泡劑，以及防靜電劑或著色用染料及顔料等。 於本發明，硬被覆層以將有機溶劑中含有游離輕射線 硬化型化合物、粒子、光聚合引發劑、界面活性劑之塗布 液塗布在基材膜上乾燥後硬化而形成較佳。 積層硬被覆層之方法可舉習知方法，但以將上述塗布 液塗布在基材膜上乾燥後硬化之方法較適合。塗布法可舉 例如凹版塗布法、滾塗法（Kiss coating)、浸塗法、噴塗法、 W 簾幕塗布法、氣刀塗布法、刮刀塗布法、反向滾筒塗布法、 棒塗法、唇塗法（Lip coating)等習知塗布方法。其中，能夠 以卷對卷方式均匀塗布之凹版塗布法、尤其反向凹版塗布 法較佳。 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 φ 夠提升游離輻射線硬化型化合物、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、 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％ -26- 201008991 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生產性之減低。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 塗布液黏度上升引起塗平性之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，調整塗布液之固體成 分濃度、或有機溶劑種類、界面活性劑種類或配合量，使 塗布液黏度爲0.5cps以下、300cps以下較宜。 塗布並硬化後之硬被覆層厚度，依成型時之伸長程度 胃 而定，但使成型後之硬被覆層厚度爲0.5//m以上、50/zra 以下較佳。具體而言，成型前之硬被覆層厚度下限以0.6 /zm以上較好、以上更好。又，成型前之硬被覆層 厚度上限以100 μ m以下較好、80 // m以下更好、60私m以 下特好、20 以下最好。硬被覆層厚度如較0.6//m爲薄 時難以獲得硬化性，反之如超過100/zm時，表現硬被覆層 硬化不良或因硬化收縮引起卷邊不良之傾向》 $ 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40°C以上、120°C以下之溫度條件進行 較好，尤其以下限45°C以上、上限80°C以下更好。未達40 °C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、紋裂等塗膜小缺點，可能使外 觀不良。再者，膜因熱而強烈收縮，熱皺紋使膜之平面性 -27- 201008991 惡化，故成型時不能獲得均匀之伸長，或發生局部性伸長， 導致膜斷裂等成型性不良。 乾燥中施加於膜之張力以5 0N/m以上、300Ν/Π1以下較 好，尤其下限爲ΙΟΟΝ/m以上、上限爲250N/m以下較好。 膜張力未達50N/m時，膜在行進中會蛇行，無法塗布塗布 液。反之超過300N/m時，膜發生皺紋，使平面性惡化，或 使卷取膜之外觀不良。再者，基材膜之低溫成型性良好時， 乾燥中之膜向前進方向拉伸而寬方向則收縮，最壞情況下 引起斷裂等生產性問題發生。 於本發明，在不設置硬被覆層之一面，以不阻礙本發 明效果之範圍內可賦予硬被覆層、防靜電層、易黏著層、 黏合層、易滑動層、電磁波吸收層、含染料或顔料等色素 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被覆層。 照射之累計光量爲50ml/cm2以上、1000mJ/cm2以下，尤其 ❺ 下限爲300m〗/cm2以上、上限爲700mJ/cm2以下更好。又， 在氮氣環境下進行照射時，能夠減少氧化抑制，提升耐擦 傷性而較理想。累計光量未達50mJ/Cm2時，不能促進游離 輻射線硬化型化合物之聚合反應，使硬被覆層之表面硬度 顯著減低。累計光量超過1000mJ/cm2時，因受熱之影響或 使基材膜變形。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以下較好，尤其上限爲30 kGy以上、下限爲70kGy -28- 201008991 以下更好。未達5kGy時，不能促進游離輻射線硬化型化合 物之聚合反應，使硬被覆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膜。具體 而言雖因基材膜而異，如以含共聚合聚酯之雙軸定向聚酯 爲基材膜之成型用硬被覆膜而言，其鉛筆硬度測定値以Η 以上較好、2Η以上特好。在此，鉛筆硬度之評價以JIS _ K5600爲依據進行。 調整表面硬度之方法，可利用形成硬被覆層之塗布液 所含游離輻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胺基之游離輻射線硬化型化合物 含量，硬被覆層中之粒子存在量，硬被覆層之厚度等進行 改變。 本發明之成型用硬被覆膜爲耐擦傷性優異之膜。具體 而言雖因基材膜而異，如以含共聚合聚酯之雙軸定向聚酯 爲基材膜之成型用硬被覆膜而言，依據JIS-K5 600，用# 0 000之鋼絲棉以500 gf負載在表面來回20次，以目視觀察 有無發生擦傷及其程度，其結果以深度擦傷10條以下之少 量較好，完全無深度擦傷特好。 調整耐擦傷性之方法，可利用形成硬被覆層之塗布液 所含游離輻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胺基之游離輻射線硬化型化合物 -29- 201008991 含量，硬被覆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 言雖因基材膜而異，如以含共聚合聚酯之雙軸 膜之成型用硬被覆膜而言，在室溫及膜實際溫虔 長率均爲10%以上較好、20%以上更好、30%以 此所謂伸長率，係由成型用硬被覆膜切取長度 150mm之細長方形，於膜實際溫度160°C拉伸時 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 塗布液所含游離輻射線硬化型化合物中之1或 離輻射線硬化型化合物含量或具胺基之游離輻 化合物含量，硬被覆層中之粒子存在量等進行 本發明之成型用硬被覆膜，在不積層硬被 實施印刷加工時，以具有透明性較好。具體而 膜而異，如以含共聚合聚酯之雙軸定向聚酯爲 φ 型用硬被覆膜而言，其霧度爲5%以下較佳。調 法，可利用硬被覆層中之粒子存在量進行改變 本發明之成型用硬被覆膜，在不積層硬被 實施印刷加工時，以無著色爲宜。具體而言雖 異，如以含共聚合聚酯之雙軸定向聚酯爲基材 硬被覆膜而言，其色調b*之値爲2.0以下較佳 b*之方法，可利用形成硬被覆層之塗布液所含 硬化型化合物中之具胺基之游離輻射線硬化型 ' 或光聚合引發劑添加量進行改變。在此，色調 膜。具體而 聚酯爲基材 ί 1 6 0 °C時伸 上特好。在 1 0mm、寬度· 硬被覆層發 硬被覆層之 2官能基游 射線硬化型 改變。 覆層之一面 言雖因基材 基材膜之成 整霧度之方 〇 覆層之一面 因基材膜而 膜之成型用 i。調整色調 游離輻射線 化合物含量 b *係利用 -30- 201008991 色差計（日本電色工業公司製、ZE — 2000)，以C光源、視 角2度測定色調b *，以5次測定値之平均求得之値。 (成型用硬被覆膜輥） 本發明之成型用硬被覆膜輥，係將長條之成型用硬被 覆膜經連續卷取於圓柱形卷芯成輥狀之製程而製得。使用 成型用硬被覆膜輥時，能夠提升加工時之生產性，並對成 型體品質賦予安定性。長條之成型用硬被覆膜連續卷取於 圓柱形卷芯成輥狀之成型用硬被覆膜輥之長度依用途而無 特別限定，但以50m以上、5000m以下較好，100m以上、 3 000m以下更好。卷取長度短時，如在後製程實施印刷層 加工時成型用硬被覆膜輥之更換頻率高而使作業性惡化。 反之，卷取長度長時，成型用硬被覆膜因外部環境溫度而 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，並無特別限 定，但由加工性之觀點以100mm以上、2000mm以下較好， 500mm以上、1 500mm以下更好。 卷取成型用硬被覆膜之圓柱形卷芯以塑膠製卷芯較 好。如使用一般所使用紙製卷芯時，發生紙粉等附著於硬 被覆層而易成爲不良品。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英吋以上、6英吋以下較佳。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。 -31 - 201008991 將成型用硬被覆膜卷繞在圓柱形卷芯時，藉雙面膠帶 固定成型用硬被覆膜後開始卷取較佳。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5ym以上、50//m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，同時使硬被覆層與其反面之基材膜表面接觸部 _ 分，或與積層在基材膜上之如前述賦予機能性之層接觸部 分降低，使輥形態之保存安定性良好。凹凸高度之下限以 10#m較好、15#m更好。另一方面，凹凸高度之上限以 40ym較好、35/zm更好。凹凸高度過低時，因凹凸改善 φ 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，凹凸加工以在基材膜上形成硬被覆層前，預 先賦予在基材膜較佳。 (成型體） 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_m〇ld) 成型、壓伸成型、折彎成型、拉伸成型等成型方法成型之 -32- 201008991 成型用材料。使用本發明之成型用硬被覆膜成型時，硬被 覆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成型而成之成型體之硬被覆層 厚度’以0.5//m以上、50//m以下較好，0.5/im以上、1〇 /zm以下特好。成型體硬被覆層之厚度較0.5/zm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 基材膜之收縮而使硬被覆層表面引起波浪而損害外觀。反 之超過50/zm時，並不優於50/zm厚度硬被覆層之表面硬 度，品質上優點少。 如此成型之成型體，因具有硬被覆層以補強表面硬 度，可適合當作安裝於與外部接觸位置且要求耐擦傷性之 家電用銘板、汽車用銘板、空罐、建材、化粧板、化粧鋼 板、轉印片等成型構件。 [實施例] 玆以下述實施例詳細說明本發明。又，各實施例製得 之成型用硬被覆膜之特性，以下述方法測定、評價。 (1)伸長率 由製得之成型用硬被覆膜切取長度10mm、寬度150mm 之細長方形試驗片。在膜試驗片之實際溫度爲160°C之環境 下，一面以目視觀察外觀、一面固定膜兩端並以每分鐘 2 5 0mm之試驗速度拉伸，測定硬被覆層發生紋裂或泛白時 之膜長度。 設試驗前之膜試驗片長度爲a、試驗後之膜試驗片長 -33- 201008991 度爲b時，以下式計算伸長率。 伸長率（％) = (b - a)xl00 / a 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。 (2) 鉛筆硬度 依據JIS — K5 600，測定製得之成型用硬被覆膜之硬被 覆層之鉛筆硬度。壓痕以目視判定。 在此，鉛筆硬度爲Η以上判定爲具有優良表面硬度， ❹ ¥ 2Η以上判定爲具有特優表面硬度。 (3) 耐擦傷性 依據JIS— Κ5600，測定製得之成型用硬被覆膜硬被覆 層之耐擦傷性。使用#〇〇〇〇之鋼絲棉以500gf負載在硬被 覆層表面來回20次，以目視觀察有無發生擦傷及其程度。 根據觀察結果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B以上時判定耐擦傷性 φ 良好。 A:無擦傷發生，或觀察到少量程度之細傷。 B:觀察到細傷，但無深傷。 C:觀察到細傷，並觀察到少量程度之深傷。 D :觀察到多量深傷。 (4) 色調b * 製得之成型用硬被覆膜之色調b*，利用色差計（曰本 電色工業公司製、ZE — 2 00 0)，以C光源、視角2度測定色 調b*，並平均5次之測定値。 -34- 201008991 (5) 成型後之鉛筆硬度、硬被覆層厚度 於上述（1)之伸長率評價，在發生紋裂直前停止拉伸， 得拉伸成型後之成型體。將成型後之鉛筆硬度以上述（2)之 評價方法進行評價。又，成型後之硬被覆膜試驗片（成型體） 中央部之分光反射率以分光光度計（島津製作所製、UV-3150型）求得，並由波長400nm以上、600nm以下之波形以 峰谷（peak valley)法計算硬被覆層厚度。此時所須要之折射 率，由各實施例、比較例之硬被覆層塗布液製作硬被覆層 ® 之單層膜，利用阿貝（Abbe)折射計（ATAGO公司製、NAR — IT SOLID)求得。 (6) 有無發生皺紋 爲判定塗布塗布液後之乾燥溫度、膜張力是否適當， 而評價有無發生皺紋。在寬度1000mm、長度200m基材膜 上進行塗布硬化以設置硬被覆層時，如製得之成型用硬被 覆膜不發生皺紋則判定爲良好（〇），如發生則判定爲不良 Φ (X)。 (7) 塗布外觀 爲判定塗布塗布液後之乾燥溫度、膜張力是否適當， 而評價塗布外觀。在寬度1000 mm、長度200m基材膜上進 行塗布硬化以設置硬被覆層時，如硬被覆層完全無泛白、 塗布缺失、或撥拒則判定爲良好（〇）’如有缺陷則判定爲 不良（X)。 (8) 塗布前後之寬方向收縮率 爲判定塗布塗布液後之乾燥溫度、膜張力是否適當， -35- 201008991 而評價寬度方向收縮率。在寬度1000mm、長度200m基材 膜上進行塗布硬化以設置硬被覆層後測定膜寬度。設塗布 前之膜寬度爲a、塗布後之膜寬度爲b時，由下式求得塗布 前後之膜寬方向收縮率（寬方向收縮率）。寬方向收縮率爲 1.5 %以下時判定爲良好，超過1.5 %時判定爲不良。 寬方向收縮率（％)= (a— b)xl〇〇 / a (實施例1) 在兩面具易黏著層之含共聚合聚酯之雙軸定向聚酯膜 (東洋紡績公司製、SOFTSHINE : A1532、厚度125/zm)上， 使用線棒塗布下述之塗布液A，使塗布並硬化後形成之硬 被覆層厚度爲2ym，以溫度80°C熱風乾燥60秒，並在輸 出功率 120W/cm之高壓水銀燈下 20cm位置（累計光量 3 0〇111〗/(：1112)以8111/11^11速度通過，製得成型用硬被覆膜。 (塗布液A) 將下述材料以下述質量比混合，並攪拌30分鐘以上使 φ 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％ •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) -36- 201008991 •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％ (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 良好。所得結果示如表1。 (實施例2) 於實施例1，除將形成硬被覆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 64.4 8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 -37- •201008991 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： 3〇%、平均粒徑：50nm) •光聚合引發劑 1.14質量％ (Ciba Speciality Che mi cals 公司製、IRGACURE 184) ❹ •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。所得結果示如表1。 (實施例3) φ 於實施例1，除將形成硬被覆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) •甲基乙基酮 64.48質量％ •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) •三伸丙二醇二丙烯酸酯 7.44質量％ -38- 201008991 (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 7.44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) •光聚合引發劑 1.14質量％ ❹ (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。所得結果示如表1。 @ (實施例4) 於實施例1，除將形成硬被覆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％ •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) -39- 201008991 •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) •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) ❹ •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 φ 良好。所得結果示如表1。 (實施例5) 於實施例1，除將形成硬被覆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％ •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、 -40- 201008991 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) •矽石微粒 11.45質量％ (曰產化學工業公司製、ME K -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) . •有機砂系界面活性劑 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， φ 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。所得結果示如表1。 (實施例6) 於實施例1，除將形成硬被覆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) •甲基乙基酮 •新戊四醇三丙烯酸酯 6 4.4 8質量％ 2 1 . 7 5質量％ -41- 201008991 (新中村化學公司製、NK ESTER A - ΤΜΜ - 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％ (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 φ 良好。所得結果示如表1。 (實施例7) 於實施例1，除將形成硬被覆層之塗布液變更爲下述 之塗布液G以外，其他與實施例1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、 -42- 201008991 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 1.14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。所得結果示如表1。 φ (實施例8) 於實施例1，除將形成硬被覆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％ •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 ) -43- 201008991 •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 1 1.45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％ 參 (Dow Corning Toray 公司製、DC57) 製得之成型用硬被覆膜由於胺化合物的添加量多，著 色明顯稍微不佳，但，其成型性、表面硬度、耐擦傷性均 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。所得結果示如表1。 (實施例9) 於實施例1，除將形成硬被覆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。 (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 44 - 201008991 2) •二乙基胺乙基甲基丙烯酸酯 5.72質量％ (共榮社化學公司製、LIGHT ESTER DE、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) •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。所得結果示如表1。 (實施例10) ❷ 於實施例1，除將形成硬被覆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。 (塗布液J) 6 4.4 8質量％ 1 1.4 5質量％ •甲基乙基酮 •新戊四醇三丙烯酸酯 (新中村化學公司製、NK ESTER A - TMM - 3LM - N、 官能基數3 ) 7 3質量％ •三伸丙二醇二丙烯酸酯 -45- 201008991 (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) •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％[Technical Field] The present invention relates to a hard coating film for molding which is excellent in surface hardness and scratch resistance and which is excellent in moldability. [Prior Art] The film for molding has been represented by a polyvinyl chloride resin film. However, in recent years, it has been made of a polyester resin, a polycarbonate resin, and an acrylic resin which have a small environmental burden due to environmental resistance. The unstretched film and the biaxially oriented polyester resin film excellent in heat resistance and solvent resistance. (For example, refer to Patent Documents 1 to 1 0). For example, when the film for molding is attached to an external contact position in a nameplate for a home appliance or a car, or the like, the surface hardness of the film for reinforcing the film for reinforcement is prevented. For the purpose of improving the scratch resistance, a hard coating layer is provided on the surface. The method of providing a hard coating layer on a film for molding is generally carried out by a pneumatic molding method or a vacuum molding method, and then the hard coating layer is laminated by a post-processing method such as a dipping method or a spray method. However, in this method, the hard coating layer is laminated by a cluster type processing, so that the stability of the quality is also problematic in addition to the limited production speed. Therefore, there is a demand for a roll to roll type process in which a hard coating layer is placed on a film before molding and then molded to obtain a molded body. In the manner of laminating a hard coating layer before molding, the characteristics of the hard coating layer are required to have the same degree of surface hardness and scratch resistance as the method of providing a hard coating layer after the post-forming processing method, and also -4- 201008991 The moldability can be traced when deformation occurs. However, in general, a hard coating resin has a problem that the hard coating layer is too hard and has no moldability in order to satisfy the surface hardness, and the hard coating layer is cracked (the crack of the hard coating layer) due to deformation during molding. Therefore, there are many prior art proposals to harden a hard coating film which has a certain degree of surface hardness but has a softness of resin and which is laminated to enhance the formability, or a layer having a plurality of softness layers and a layer having a strong surface hardness. A hard coating W film having strong surface hardness and flexibility is obtained by laminating a substrate (see Patent Documents 11 to 14). (Patent Document 1) Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. JP-A No. 2002- 249652 (Patent Document 7) Japanese Laid-Open Patent Publication No. 2005-305354 (Patent Document 11). JP-A-2005-30553 (Patent Document 11) JP-A-2007-284626 (Patent Document 13) Japanese Laid-Open Patent Publication No. Hei. No. 2007- 3 No. 3728 (Patent Document 14) International Publication No. 2008/029666 A description of the booklet [Invention] 201008991 "The subject to be solved by the invention" The hard coating film disclosed in the documents 11 and 13 has a suitable surface hardness, and the moldability is limited only by the bending property and the punching process; and the hard coating film proposed in Patent Document 12 Although it has stretchability, the surface hardness cannot be satisfied. Further, although the hard coating film proposed in Patent Document 14 attempts to coexist with surface hardness and moldability, in the field where higher moldability or higher surface hardness is required, sufficient performance may not be exhibited. That is, the above patent document cannot provide a hard coating film for molding which satisfies both the characteristics of high surface hardness and high moldability. The object of the present invention is to solve the above problems, that is, to provide a hard coating layer to be processed and laminated on a film for molding before molding, which contributes to improvement in productivity and quality stability, and has both surface hardness and scratch resistance. And a hard-coated 'film for molding, which is characterized by both the properties of the mold and the moldability when the molding is deformed. "Means for Solving the Problem" φ The inventors of the present invention have finally paid attention to the above problems and finally completed the invention. That is, the present invention is as follows. The first invention is a hard coating film for molding having a hard coating layer which is applied to at least one surface of a base film and cured to form a hard coating layer. The coating liquid contains at least three or more functional groups of free radiation hardening. The compound of the type and the free radiation curing compound of the 1 and/or 2 functional group, wherein the content of the free radiation curing compound of the 1 and/or 2 functional groups in the free radiation curing compound contained in the coating liquid is 5 mass % or more and 95% by mass or less. 201008991 According to a second aspect of the invention, in the hard coating film for molding, the base film is a biaxially oriented polyester film containing a copolymerized polyester. According to a third aspect of the invention, in the hard coating film for molding, at least one of the radiation-hardening type compounds contained in the coating liquid is a free radiation curing type compound having an amine group. According to a fourth aspect of the invention, in the hard coating film for molding, the hard coating 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 hard coating layer is 5% by mass or more and 70 mass%. %the following. According to a fifth aspect of the invention, in the hard coating film for molding, the hard coating layer contains an exothere radiation-curable organic bismuth resin, and the content of the radical ray-curable organic bismuth resin in the hard coating layer is relative to the above-mentioned free radiation. 100 parts by mass of the linear hardening compound is 0. 15 parts by mass or more and 15 parts by mass or less. The sixth invention is a molded body formed by molding the above-mentioned hard coating film for molding. According to a seventh aspect of the invention, in the molded article, the thickness of the hard coating layer is 0. 5 or more, 50//m or less. According to a eighth aspect of the invention, there is provided a method for producing a hard coating film roll for molding, which is a roll for forming a hard coating film for forming a hard coating layer which is formed by applying a coating liquid to at least one surface of a base film. The method is characterized in that the coating liquid contains at least an organic solvent, an ionizing radiation-curable compound having a functional group of 3 or more, and an ionizing radiation-curable compound having 1 and/or 2 functional groups, and the coating liquid contains free radiation. The content of the ruthenium-based and/or bifunctional-based radiation-hardening type compound in the wire-curable compound is 5% by mass or more and 95% by mass or less, and after applying the coating liquid, the film tension is 201008991 50 N/m or more, 3 The hard coating layer is provided by drying and hardening under conditions of 00 N/m or less and a temperature of 40 ° C or more and 120 ° C or less. "Effect of the Invention" The hard coating film for molding of the present invention has both surface hardness, scratch resistance, and moldability capable of following deformation during molding. Since the present invention has a surface hardness and an excellent stretchability, it is suitable for use in the case of a member for a nameplate or a building material. Further, when an amine-based radical ray-curable resin and/or particles are used in accordance with a preferred embodiment of the present invention, both surface hardness and moldability can be more highly coherent, and are suitable for use in a box. The components of the body. Further, the present invention does not require the hard coating film processing after molding to contribute to productivity and quality stability in molding processing, and when it is used as a film roll for molding in a preferred embodiment of the present invention, The molded body is excellent in quality stability. [Embodiment] (Base film) φ In the present invention, the base film is not particularly limited, but is characterized by having moldability. Here, the moldability means that the molded body can be formed by a molding process such as mold molding, air pressure molding, or vacuum molding. Specifically, when a part of the high stress is generated in the partially stretched portion due to the molding, the base film has a film stress characteristic which can be formed without being broken. Such a base film is, for example, polyester, acrylic, cellulose, polyethylene, polypropylene, polyolefin, polyvinyl chloride, polycarbonate, phenol, or polyurethane. Plastic film or plastic sheet, etc., and any two or more of these. Among them, a polyester film having a good balance between heat resistance and flexibility is preferred. The base film is preferably a polyester film containing a copolymerized polyester excellent in moldability at the time of heat molding at a low temperature or a low pressure. The copolymerized polyester is (a) a copolymerized polyester composed of a glycol component containing an aromatic dicarboxylic acid component, ethylene glycol, a branched aliphatic diol or an alicyclic diol; or b) A copolymerized polyester composed of a terephthalic acid or isophthalic acid aromatic dicarboxylic acid component and a glycol containing glycol component is suitable. As the above copolymerized polyester, when a copolymerized polyester composed of a glycol component containing an aromatic dicarboxylic acid component, ethylene glycol, a branched aliphatic diol or an alicyclic diol is used, the aromatic The dicarboxylic acid component is preferably selected from terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid or such ester-forming derivatives as the total amount of terephthalic acid and/or naphthalene dicarboxylic acid relative to the dicarboxylic acid component. The amount of the component 'is preferably 70 mol% or more, more preferably 85 mol% or more, more preferably 95 mol% or more, and most preferably 1 mol%. In the polyester film containing a copolymerized polyester of the present invention, the film constituent component contains a copolymerized polyester component, and the specific aspect thereof is as follows: (1) the base film is composed entirely of copolymerized polyester; (2) contains a total of The polymerized polyester is used as a part of the constituent component of the substrate film (for example, a resin composition composed of a mixed copolymerized polyester and polyethylene terephthalate or polyethylene naphthalate or other homopolyester); (3) The base film is composed of a plurality of layers of a polyester layer containing a copolymerized polyester and a polyester layer containing no copolymerized polyester. The base film 'is particularly suitable as a biaxially stretched film from the viewpoint of heat resistance and solvent resistance. Examples of the stretching method include a tubular stretching method, a simultaneous biaxial stretching method, a sequential biaxial stretching method, and the like, but from the viewpoints of planarity, dimensional stability of 201008991, uneven thickness, and the like, It is preferred to use a sequential biaxial stretching method. For example, a sequential biaxial stretching method in which a polyester film is used as a substrate film is stretched by a roll in a longitudinal direction at 50 ° C or more and 110 ° C or less. 6 times or more, 4. 0 times, and then preheating with a tenter dryer, the brittle temperature of the polyester glass is 4 (more than TC, below +65 °C, it can be stretched in the width direction). 2 times or more and 5.0 times or less. Further, after biaxial stretching, heat setting treatment may be carried out at a temperature of 40 ° C or more and 10 ° C or less of the melting point of the polyester. In the base film used in the present invention, in order to impart workability (e.g., take-up property after lamination), it is preferred that the film contains particles to form protrusions on the surface of the film. Particles contained in the film, such as vermiculite, kaolinite, talc, calcium carbonate, zeolite, alumina and other inorganic particles, acrylic, PMMA, nylon, polystyrene, polyester, benzoguanamin A heat-resistant polymer particle such as a condensate. From the viewpoint of transparency, the content of the particles in the film is preferably a small amount, such as 1 ppm or more and 1000 ppm or less. From the viewpoint of transparency, it is preferred to select particles which are close to the refractive index of the resin. Further, since the film imparts various functions as needed, it may contain a light stabilizer (anti-UV agent), a coloring matter, an antistatic agent, and the like. When the hard coating film for molding is subjected to printing processing on one side of the hard coating layer which is not laminated, the total light transmittance of the base film is 80% or more, and the haze is preferably 5% or less. When the transparency of the base film is poor, the visibility is lowered when the printed layer is viewed from the hard coating layer. The base film used in the present invention may be a single layer film or a composite film of two or more layers of a layered surface layer and a center layer. Composite membranes have the advantage of individually designing the function of the surface layer and the center layer. For example, on the one hand only on the thinner surface of the table --10-201008991, the surface layer contains particles to form irregularities on the surface to maintain the operability. On the other hand, the central layer having a thick thickness is substantially free of particles, and the composite film can be further improved. Transparency. The method for producing the composite film is not particularly limited. However, in consideration of productivity, the raw materials of the surface layer and the center layer are extruded from respective extruders and introduced into the same die to obtain an unstretched sheet, to at least It is preferable to laminate the so-called co-extrusion method oriented in the uniaxial direction. The thickness of the base film used in the present invention varies depending on the raw material, and when the polyester film is used, the lower limit of the thickness is preferably 35/zm or more, more preferably 50/m or more. On the other hand, the upper limit of the thickness is preferably 260 v or less, more preferably 200 M or less. When the thickness is small, not only the workability is poor, but also when the hard coating layer is dried by heating to reduce the residual solvent, the film is likely to be thermally wrinkled and the planarity is deteriorated. On the other hand, when the thickness of the film is thick, not only is there a problem in cost, but when it is taken up in a roll shape, flatness is likely to occur due to winding property. (Intermediate layer) The hard coating film for molding of the present invention is formed by laminating a hard coating layer on one surface of a base film. However, it is preferable to provide an intermediate layer for the purpose of improving the adhesion between the base film and the hard coating layer. Further, in order to improve the transparency of the base film without containing particles therein, an intermediate layer containing particles is simultaneously provided in the production of the base film, and workability can be imparted to the base film. The constituent resin of the intermediate layer may, for example, be a polyester resin, a polyurethane resin, a polyester polyurethane resin, an acrylic resin, a melamine resin or the like, but a base resin thereof. It is important to select the adhesiveness of the material film and the hard coating layer. For example, when the resin constituting the base film and the hard coating layer is an acrylic resin, it is made of acrylic, copolymerized -11-201008991 polyester, polyester. It is preferred to select at least one of the type of polyurethanes and the like. For the purpose of improving the adhesion and water resistance, a crosslinking agent may be contained in the intermediate layer to form a crosslinked structure. The crosslinking agent is, for example, urea, epoxy, melamine or isocyanate. Further, a graft copolymer resin having self-crosslinking property may be used as a resin without using a crosslinking agent. The intermediate layer may contain various particles for the purpose of forming irregularities on the surface of the substrate film before forming the hard coating layer to improve slidability. The particles contained in the intermediate layer, such as vermiculite, kaolinite, talc, calcium carbonate, zeolite, alumina and other inorganic particles, 'acrylic, PMM A, nylon, polystyrene, polyester, benzoguanamine ( Organic particles such as benzoguanamin) / formaldehyde condensate. Further, from the viewpoint of transparency, it is preferred to select particles which are close to the refractive index of the resin to be used. The method of setting the intermediate layer is preferably a coating method. The coating method uses a conventional coating method such as a gravure coating method, a kiss coating method, a dip coating method, a spray coating method, a curtain coating method, an air knife coating method, a reverse roll coating method, and the like. In the case of a film, a coating method of a coating layer (or a Kin-line) is provided, or an intermediate layer is provided by an off-line coating method in which a coating film is formed after a substrate film is produced. Among these methods, the twist coating method is not only advantageous in terms of cost, but also contains particles in the intermediate layer, and it is not necessary to contain particles in the base film, and it is preferable to highly improve transparency. (Hard coating layer) The hard coating film for molding of the present invention has a hard coating layer laminated on at least one surface of the base film directly or through an intermediate layer. In the present invention, the hard coating layer is a film which reinforces the surface hardness of the base material composed of the base film and improves the scratch resistance, and has a higher hardness than the base material, and has a deformation during molding -12-201008991 A layer that can follow the excellent formability. More specifically, the hard coating film for molding of the present invention has a surface hardness of at least a pencil hardness of not more than Η, and has an elongation of at least 10% or more according to the evaluation method described later, and is therefore suitable for use as a nameplate for household appliances or the like. It is used for building materials. The hard coating layer used in the present invention must have an epitaxial radiation-curable resin as a main component. Thus, it is not necessary to heat-treat as the thermosetting resin hardens, and it is possible to reduce the heat shrinkage of the substrate film due to heat, which is suitable. In the present invention, the radiation-hardening type compound is a compound which causes polymerization and/or reaction as a result of irradiation with any one of electron beam, radiation, and ultraviolet rays. The compound which causes polymerization and/or reaction results in a hard coating layer. The radiation-hardening type compound used in the present invention, such as a melamine-based, acrylic-based, or organic lanthanide-based radiation-hardening type compound, wherein an acrylate-based free radiation-curable compound is obtained from the viewpoint of obtaining high surface hardness. Further, in the present invention, the radical radiation-curable compound is not limited to a single Φ body, a precursor, and of course, an isobaric hardening type resin which is polymerized and/or reacted. For example, the acrylate-based radiation-hardening type compound is exemplified by, but not limited to, polyurethane acrylate, polyester acrylate, epoxy acrylate, or polyol acrylate. The acrylate-based free radiation hardening type compound. The hard coating layer of the present invention is obtained by coating a coating liquid containing at least three or more functional groups of an epitaxial radiation-curable compound and a one-and/or two-functional radical radiation-curable compound on a substrate film. Any one of the line and the radiation 'ultraviolet light' is irradiated to cause polymerization and/or reaction to make it hard-13-201008991. When an acrylate-based radiation-hardening type compound is used as the radical radiation-curable compound, the monofunctional (monofunctional) acrylate-based radiation-hardening type compound of the present invention contains at least one molecule in the molecule ( The compound of the methyl) acrylonitrile group is not particularly limited. For example, acrylamide, (meth) propylene oxime morpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide , isodecyloxyethyl (meth) acrylate, isodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl diethylene glycol (meth) acrylate , third octyl (meth) acrylate, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, lauryl (Meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, hydrazine, hydrazine - dimethyl (meth) acrylamide tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromo _ Phenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (A) Acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, vinyl caprolactam, Ν-vinylpyrrolidone, fluorene-vinylformamide, phenoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromobenzene (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, mercapto (meth) acrylate, methyl triethylene glycol (meth) acrylate Ester, cyclohexyl (meth) acrylate, 壬-14- 201008991 phenyl (meth) acrylate, derivatives such as caprolactam conversion, acrylic acid, etc., and the like. When an acrylate-based radical ray-curable compound is used as the radical radiation-curable compound, the bifunctional acrylate-based free-radiation-curable compound of the present invention can have two or more alcoholic hydroxyl groups in one molecule. A compound in which a hydroxyl group forms two (meth) acrylate compounds in a polyvalent alcohol. Specifically, for example, (a) a (meth)acrylic acid diester of an alkyl diol having 2 to 12 carbon atoms: such as ethylene glycol di(meth)acrylate or propylene betadiol di(methyl) Acrylate, L4 - butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, etc.; (b) polyoxygen (meth)acrylic acid diesters of alkyl diols such as bis-ethylene glycol di(meth) acrylate, triethylene glycol di(meth) acrylate, tetraethylene glycol bis (A) Acrylate, dipropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc.; (c) polyol methacrylic acid II Ester: such as neopentyl alcohol di(methyl) $ acrylate, etc.; (d) bisphenol A or bisphenol A hydride of ethylene oxide and propylene oxide adduct (meth) acrylate diester Class: such as 2,2'-bis(4-propoxyethoxyphenyl)propane, 2,2'-bis(4-propoxyoxypropoxyphenyl)propane, etc.; (e) first multivalent Isocyanate The reaction is carried out with a compound containing two or more alcoholic hydroxyl groups to obtain an isocyanate group-containing compound, and then reacted with an alcoholic hydroxyl group-containing (meth) acrylate to obtain two (meth) acryloxy groups in the molecule. Ethyl urethane (meth) acrylate; (f) reacting acrylic acid or methacrylic acid with a compound having two or more epoxy groups in the molecule to have two (meth) acryloxy groups in the molecule Cyclooxy-15- 201008991 (meth) acrylates, etc. When an acrylate-based free radiation-curable compound is used as the free|g-ray hardening type compound, the acrylate-based free radiation-curable compound having a trifunctional or higher functional group of the present invention may specifically use U) pentaerythritol III. (Meth) acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol Penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc.; (b) firstly polyvalent isocyanate compound and two or more alcohols The hydroxyl group-containing compound is reacted to obtain an isocyanate group-containing compound, and then reacted with an alcoholic hydroxyl group-containing (meth) acrylate to obtain an amine urethane having three or more (meth) acryloxy groups in the molecule. (c) an epoxy group having three or more (meth)acryloxy groups in a molecule obtained by reacting acrylic acid or methacrylic acid with a compound having three or more epoxy groups in a molecule. base Acrylates. In the present invention, the free radiation curing type compound contained in the coating liquid contains one or more kinds of free radiation curing compounds having three or more functional groups in addition to the free radiation curing type compound having one or two functional groups. It is important. In this case, in the hard coating layer after hardening, the free radiation curing compound component having a higher crosslinking density and having a trifunctional or higher functional group is present as a hard segment, and the free radiation hardening compound having 1 and/or 2 functional groups is present. The reaction is carried out in such a manner that the free radiation curable compound component of the 1 and/or 2 functional groups is present as a soft segment. The result of adjusting the free radiation hardening type compound of two or more different functional groups in a specific concentration range, -16-201008991 and the phase of the line on the 2 95 degree of coverage can be used to control the I - less line The hetero-crosslinked structure is introduced into the hard coating layer to impart surface hardness and scratch resistance to the hard segment, and the moldability is imparted by the stretchability of the soft segment, thereby obtaining a remarkable effect of self-contradictory characteristics. In the present invention, in order to coexist with the surface hardness of the crucible and the excellent moldability, that is, the pencil hardness of the crucible or more and the elongation of 1% or more of the crucible are present, and one of the free radiation curable compounds contained in the coating liquid is contained. The content of the radical ray-curable compound of the functional group and/or the functional group is preferably 5% by mass or more and not more than 5% by mass. When the content is less than 5% by mass, the flexibility of the film is not reduced, and it is not preferable to cause cracking in the hard coating layer during molding. 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, 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 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 said that it is possible to coexist with a pencil hardness of 2 Η or more and an elongation of 20% or more, and is suitable for a casing such as a steam-plated nameplate or a carry-on machine, and a film for molding having high hardness and high workability. Further, in addition to the above-described embodiment, the present inventors have found that an epi-radiation-curing compound using an amine group can be used as an epitaxial radiation-curing compound, and it has been found that surface hardness and moldability can be made more high. Further, among the radical radiation-curable compounds contained in the above coating liquid, it is preferred that one of them has an amine group. The use of an amine-based compound as the free radiation -17- 201008991 The result of the above-mentioned effects caused by the hardening compound can be considered as follows. If the hardness distribution of the hard coating layer is locally different, local cracking (grain cracking) is likely to occur when the hard coating layer is stretched. The reason for this difference in local hardness distribution is the polymerization inhibition (oxidation inhibition) of the free radiation curing resin due to oxygen. Here, when an amine group-containing compound 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 hard coating layer is reduced, so that it can be uniformly formed in the surface layer portion. Hardening reaction. As a result, the stress applied to the hard coating layer during molding is dispersed throughout the entire layer, so that cracking during molding is also suppressed. Therefore, it is possible to coexist with higher surface hardness and moldability. Further, in addition to the above effects, the effect of the coating film of the amine-based free radiation curing resin is such that when the amine-free group is compared, the hardening of the surface of the hard coating layer is promoted to enhance the surface hardness. The content of the radical-hardening type compound having an amine group in the radical radiation-curable compound contained in the above coating liquid is 2. It is preferably 5 mass% or more and 95 mass% or less. The lower limit of the content of the radical-hardening type compound having an amine group in the radical radiation-curable compound contained in the coating liquid is preferably 5% by mass or more, more preferably 10% by mass or more. Moreover, 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 radical radiation-hardening compound having an amine group in the free radiation-curable 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 hard coating layer, so that it is difficult to obtain resistance to cracking during molding. Further, when the radical-hardening type compound having an amine group is at a high concentration, the hard coating layer due to the amine group is yellowish, so that the above content, if -18-201008991 exceeds 95% by mass, sometimes impairs high transparency. Sex. For example, when the printing process is carried out on the hard uncovered layer, the color b of the film is 2, and in this case, the above-mentioned radical-curable compound having an amine group is preferably at most 5% by weight. The coating liquid of the present invention contains 1 and/or 2 radiation-hardening type compound and a hardening type compound having 3 or more functional groups, but in the above embodiment, one of the radiation hardening type is used. The compound may have an amine group. Further, a monofunctional ray-curable compound, a bifunctional radical radiation hardener, or an epitaxial radiation-hardening type having three or more functional groups, which is an amine-based epitaxial radiation-curable compound, is also a preferred embodiment. An amine-based acrylic radiation-curable compound such as acrylamide, 7-amino-3,7-(meth)acrylate when an acrylate-based free radiation-curable compound is used as the radiation-hardening type compound. , isobutoxymethyl (meth) acrylamide, tridecyl) acrylamide, diacetone (meth) acrylamide, dimethylamine acrylate, diethylamine ethyl (meth) acrylate Ν Ν Ν 二甲 二甲 二甲 二甲 四 四 四 四 四 四 四 四 乙烯 乙烯 乙烯 乙烯 乙烯 乙烯 乙烯 乙烯 乙烯 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本Improves formability and makes the formability more coherent. As for the hard coating layer containing the knot of the particles, the effect of improving the moldability can be considered as follows. When the hard coating layer is lifted, a strong stress coating layer temporarily occurs in the hard coating layer having a high hardness. Better, good 92. Any of the radical free radicalized compounds of the free radicals of the mass base can be made with an aminoester free methyl octyl octyl p-octyl (methyl (meth) yl (methyl) amine Etc. If the hard surface hardness and fruit, the hardness can be raised, resulting in the hard -19-201008991 coating layer suddenly cracked (grain crack). Here, the hard coating layer contains particles as a result, applied to the hard coating during molding The internal stress of the layer is moderated at the interface between the radical radiation-curable compound and the particle, and the effect of the micro-cracking which is not visually confirmed and visually confirmed in the hard coating layer is suppressed, and the hardening is delayed. The coating layer is fatally cracked, and the effect is to improve the formability. As for the particles contained in the hard coating layer, such as amorphous vermiculite, crystalline vermiculite, vermiculite-alumina composite oxide, kaolinite, talc, calcium carbonate (calcite type, ® gangue type), inorganic particles such as zeolite, alumina, hydroxyapatite, crosslinked acrylic particles, crosslinked PMMA particles, nylon particles, polyester particles, benzopyrene (benzoguanamin) / formazan condensate particles, guanamine / melamine / awake condensate particles, melamine / formaldehyde condensate particles and other heat-resistant polymer particles, such as vermiculite / acrylic composite compound organic / inorganic mixed particles In the present invention, the type of the particles is not particularly limited. The shape of the particles, such as a spherical shape, a block shape, a plate shape, a fibrous shape, or a flaky shape, is not particularly limited, and among them, dispersibility and others In the present invention, the average particle diameter of the particles is preferably 10 nm or more and 300 nm or less, and the lower limit is 40 nm or more and the upper limit is 200 nm or less. The lower limit is 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 nm, the average particle diameter is too small, and the effect of improving the surface hardness, scratch resistance, and moldability of the added particles may be reduced. In addition, when the thickness exceeds 300 nm, the hard coating layer may become weak and the moldability is reduced. Further, the above average particle size uses a Coulter counter (Coulter -20-201008991 counter) (Bec The average particle diameter of the particles obtained by dispersing the particles in a solvent which does not swell the particles is obtained by the company Km. Coulter Co., Ltd., and the content of the particles contained in the hard coating layer is calculated as the solid content in the hard coating layer. It is preferable that the lower limit of the content is 15% by mass or more and the upper limit is 50% by mass or less. When the particle content is less than 5% by mass, the surface hardness of the above-mentioned added particles may be caused. The effect of improving the scratch resistance and formability is reduced by all or one part. On the other hand, when the particle content exceeds 70% by mass, a large amount of the aforementioned minute crack occurs during molding, and the haze is increased (whitening) to impair the transparency of the molded body. Sex. Further, the inventors of the present invention have found that it is possible to impart slidability, improve the scratch resistance of the surface, and improve the surface hardness and the addition of the radiation-curable organic bismuth resin in the hard coating layer in addition to the above embodiment. The formability is highly coexistent. In this form, the hardening reaction crosslinks the free radiation-curable organic bismuth resin itself, and sometimes cross-links with the free radiation-curable resin constituting the hard coating layer, thereby preventing the organic bismuth resin from contaminating the mold when the mold is molded. When the molded article formed by the hard coating film for molding of the present invention is used for a long period of time, the surface scratch resistance function is not affected by the aging effect. An ionizing radiation-hardening organic hydrazine resin, such as a radical addition molding having an alkenyl group and a hydrazine (or hydrogen sulfide) group in the molecule, a hydroformylation reaction type having an alkenyl group and a hydrogen atom, and a cation having an epoxy group A polymerization type, a radical polymerization type having a methacryl group, and the like. Among them, a cationic polymerization type having an epoxy group and a radical polymerization type having a methacryl group are preferred. -21 - 201008991 An organic oxime resin having an epoxy group or a (meth) propylene group in the molecule, such as epoxy propyloxypropyl terminal polydimethyl methoxy oxane, (epoxycyclohexylethyl) methyl group a decane-dimethyl methoxy alkane copolymer, a methacrylic oxiranyl-terminated polydimethyl siloxane, an acryloxypropyl-terminated polydimethyl siloxane or the like. Further, an organic oxime resin having a vinyl group in the molecule, such as a terminal vinyl polydimethyl siloxane, a vinyl methyl fluorene homopolymer or the like. In the present invention, the amount of the radical radiation-curable organic eucalyptus resin to be added to the hard coating layer is 100 parts by mass based on 100 parts by mass of the above-mentioned free radiation curing type ❹ W compound constituting the hard coating layer. 15 to 15 parts by mass is better, 0. 3 to 13 parts by mass, 0. 5 to 5 parts by mass is the best. If the amount of the radiation-hardening type organic ruthenium resin is less than the lower limit, the effect of improving the abrasion resistance is not obtained when the molded body is formed, and if it exceeds the upper limit, sufficient hardening cannot be performed when the hard coating layer is formed. Further, the radiation-hardening type organic cerium resin contained in the hard coating layer may be used alone or in combination of two or more kinds. In the present invention, it is preferred to use an amine group-containing compound and an additive particle in a hard coating layer in accordance with the use of the hard coating film for molding. A particularly suitable form is a combination of these. According to this, the surface hardness and the moldability of the hard coating layer can be extremely high, and specifically, it is possible to obtain a surface hardness of 2H or more, an elongation of 20% or more, a surface hardness of 2H or more, and an elongation of 30% or more. The hard coating film for molding is suitable for use in a covering 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-mentioned 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 -22 to 201008991. 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* sketone, geranyl, benzoin, benzophenone Margin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methyl benzoic acid methyl ester, p-isopropyl-α-hydroxyphenyl isobutyl ketone, α-hydroxyphenylisobutyl ketone, 2,2-dimethyl a carbonyl β compound such as oxy-2-phenylacetophenone or 1-hydroxycyclohexyl phenyl ketone, tetramethylthiuram monosulfide, tetramethylammonium sulfonyl disulfide, sulfur Sulfide such as thioxanthene, 2-chlorosulfonium sulphate, 2-methylsulfonium sulphate, peroxide such as benzammonium peroxide or bis(tributyl) peroxide. The photopolymerization initiation may be a peroxide compound such as a tertiary butyl peroxide. These photopolymerization initiators may be used singly or in combination of two or more kinds. The amount of the photopolymerization initiator added is 0.1% 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 slow reaction but also poor productivity are obtained, and sufficient surface hardness and scratch resistance cannot be obtained because the unreacted material remains. On the other hand, if the amount of addition is too large, the hard coating layer may be yellowed due to the polymerization initiator. In the present invention, in the above coating liquid, in order to prevent thermal reaction during production or dark reaction during storage, conventional thermal polymerization inhibition such as hydroquinone, hydroquinone monomethyl ether or 2,5-tributylhydroquinone is added. The agent is suitable. The amount of the thermal polymerization inhibitor added is 0. 00 parts by mass of the free radiation-curable 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, in order to improve the thickness of the coating film at the time of coating, it is possible to blend an organic solvent without impairing the invention. In the organic solvent, since the coating drying temperature is adjusted to 150 ° C or lower when the low melting point base film is used, the boiling point of the organic solvent is preferably at least 150 ° C. Specific examples include methanol, ethanol, and isopropyl solvents; acetates such as methyl acetate, ethyl acetate, and butyl acetate; ketone solvents such as acetone and methyl ethyl ketone; and aromatic decanes such as toluene. An ether solvent or the like. These solvents may be used singly or in combination of two or more. In the present invention, the coating liquid is used to reduce the force of the coating liquid and to improve the coating appearance of the hard coating layer (especially due to loss of fine foam, depression due to adhesion of foreign matter, and rejection during drying process). Agent. Although the conventional cationic or anionic ion system can be suitably used for the surfactant, the problem of the deterioration of the coating liquid or the poor adhesion of the hard coating layer to the substrate is preferable, and the non-polar nonionic system is preferable, and the active energy is excellent. The organic lanthanide surfactant or fluorine interface is alive. As the organic lanthanoid surfactant, for example, dimethyl decane, propenyl decane, ethylene benzyl decane, ethylene benzylamine glycidyl decane, decyl decane, dimethyl decane, polydimethylene, poly Alkoxy oxirane, hydrogenated diene modified siloxane, ethylene oxirane, hydroxy modified siloxane, amine modified siloxane, carboxylate, dry V, 50 ° Alcohol solvent such as alcohol, solvent, and the surface of the two mixed surfaces, the adhesion of the non-membrane, the interface agent, the amino decane, the base oxy group modified 矽-24- 201008991 oxane Halogenated modified alkane, epoxy modified alkane, methacryloxy modified alkane, mercapto modified alkane, fluorine modified alkane, alkyl modified alkane , phenyl modified siloxane, alkenyl oxide modified oxane, and the like. Examples of the fluorine-based surfactant include tetrafluoroethylene, perfluoroalkylammonium salt, perfluoroalkyl alkanesulfonamide, sodium perfluoroalkylsulfonate, perfluoroalkyl potassium salt, and perfluoroalkane. Base carbonate, perfluoroalkyl sulfonate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl trimethyl ammonium salt, perfluoroalkyl amine sulfonate, perfluoroalkyl phosphate, Perfluoroalkyl alkane compounds, perfluoroalkyl alkyl beet® bases, perfluoroalkyl halides, and the like. From the viewpoint of improving the coating appearance and slidability, the surfactant content of the coating liquid constituting the hard coating layer is 0. 01% by mass or more is preferred. On the other hand, since the surfactant bleeds out of the surface of the hard coating layer and contaminates the contact with the hard coating layer, the surfactant content is 2. 00% by mass or less is preferred. Further, it is preferable that the surfactant used has an HLB of 2 or more and 12 or less. When a surfactant having an HLB of 2 or more is used, the leveling property can be improved by the interfacial activity. The HLB of the surfactant is preferably 3 or more, and 4 or more. On the other hand, when a surfactant having an HLB of 12 or less is used, deterioration of slidability can be suppressed. Also, the so-called HLB is made by W. Atlas Powder of the United States. C. The abbreviation of Griffin's named HydrophilLyophil Balance is the index of the balance between the hydrophilic group and the lipophilic group contained in the surfactant molecule. It means that the lower the HLB, the higher the lipophilicity. On the contrary, the higher the HLB is, the higher the hydrophilicity. The hard coating of the present invention can be formulated to match various additives. If it is -25- . 201008991 A fluorine-based or organic lanthanide compound that imparts water repellency, an antifoaming agent for improving coating properties or appearance, and an antistatic agent or a dye or pigment for coloring. In the present invention, the hard coating layer is preferably formed by applying a coating liquid containing a free light ray-curable compound, particles, a photopolymerization initiator, and a surfactant in an organic solvent to a substrate film, followed by drying and curing. A method of laminating a hard coating layer may be a conventional method, but a method of applying the above coating liquid to a substrate film after drying and hardening is suitable. The coating method may, for example, be a gravure coating method, a kiss coating method, a dip coating method, a spray coating method, a W curtain coating method, an air knife coating method, a knife coating method, a reverse roll coating method, a bar coating method, or a lip method. A conventional coating method such as Lip coating. Among them, a gravure coating method, particularly a reverse gravure coating method, which can be uniformly applied in a roll-to-roll manner is preferable. The method of dissolving or dispersing an epitaxial radiation-curable compound, a particle, a photopolymerization initiator, or the like contained in the coating liquid 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 increased by φ. Therefore, deterioration of the coating appearance due to undissolved matter can be suppressed. A conventional machine can be used for the disperser. Specifically, for example, ball mill, sand mill, Attritor, roller mill, mixer, colloid mill, ultrasonic homogenizer, emulsifier, bead mill, wet jet honing machine, paint shaker, butterfly Mixers, planetary mixers, Hanschel mixers, 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 to -26 to 201008991. When the solid content concentration of the coating liquid is adjusted to 5% by mass or more, the drying time after coating can be suppressed from being elongated, resulting in a decrease in productivity. 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 an increase in the viscosity of the coating liquid and the deterioration of the coating appearance due to the mixing. Further, from the viewpoint of coating appearance, the solid component concentration of the coating liquid, or the type of the organic solvent, the type of the surfactant, or the blending amount is adjusted so that the viscosity of the coating liquid is 0. Below 5cps, below 300cps is more suitable. The thickness of the hard coating layer after application and hardening depends on the degree of elongation during molding, but the thickness of the hard coating layer after molding is 0. It is preferably 5//m or more and 50/zra or less. Specifically, the lower limit of the thickness of the hard coating layer before molding is 0. 6 / zm or more is better, and the above is better. Further, the upper limit of the thickness of the hard coating layer before molding is preferably 100 μm or less, more preferably 80 // m or less, more preferably 60 private m or less, and most preferably 20 or less. Hard coating thickness is more than 0. When 6//m is thin, it is difficult to obtain hardenability. On the other hand, if it exceeds 100/zm, it tends to cause hardening of the hard coating layer or poor curling due to hardening shrinkage. $ If the coating liquid is pre-dried with an organic solvent or the like The method of coating on a substrate film and drying it is as known as hot air drying, 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 from 40 ° C to 120 ° C, more preferably from 45 ° C to more than 80 ° C. When the temperature is less than 40 °C, the problem may be caused by whitening, etc., except that the organic solvent contained in the coating liquid is not sufficiently removed. On the contrary, when the temperature exceeds 120 °C, the micro coating loss from the foam is easy to occur. Small defects such as micro-rejection and cracking may cause poor appearance. Further, the film is strongly shrunk by heat, and the thermal wrinkles deteriorate the planarity of the film -27 - 201008991, so that uniform elongation cannot be obtained during molding, or local elongation occurs, resulting in poor moldability such as film breakage. The tension applied to the film during drying is preferably 50 N/m or more and 300 Å/Π1 or less, and particularly preferably the lower limit is ΙΟΟΝ/m or more and the upper limit is 250 N/m or less. When the film tension is less than 50 N/m, the film will snake during traveling and the coating liquid cannot be applied. On the other hand, when it exceeds 300 N/m, the film wrinkles, the planarity is deteriorated, or the appearance of the wound film is poor. Further, when the low-temperature moldability of the base film is good, the film during drying is stretched in the advancing direction and shrinks in the width direction, and in the worst case, productivity problems such as breakage occur. In the present invention, the hard coating layer, the antistatic layer, the easy adhesion layer, the adhesive layer, the easy-slip layer, the electromagnetic wave absorbing layer, the dye-containing layer or the like may be imparted to the surface of the hard coating layer without impairing the effects of the present invention. Other functions such as a resin layer such as a pigment. In the present invention, ultraviolet rays are irradiated onto the coating liquid to form a hard coating layer. The cumulative amount of light to be irradiated is 50 ml/cm2 or more and 1000 mJ/cm2 or less, and particularly, the lower limit of ❺ is 300 m/cm2 or more, and the upper limit is 700 mJ/cm2 or less. Further, when irradiated in a nitrogen atmosphere, it is preferable to reduce oxidation inhibition and improve scratch resistance. When the cumulative amount of light is less than 50 mJ/cm 2 , the polymerization of the radical radiation-curable compound cannot be promoted, and the surface hardness of the hard coating layer is remarkably reduced. When the cumulative amount of light exceeds 1000 mJ/cm2, the substrate film is deformed by the influence of heat. Further, the cumulative amount of light of the present invention can be measured by "TOPR" "UVR-T35". Further, when the coating liquid is hardened by electron beam, the irradiation amount is preferably 5 kGy or more and 100 kGy or less, and particularly preferably 30 kGy or more, and the lower limit is 70 kGy -28 to 201008991. When it is less than 5 kGy, the polymerization of the radiation-hardening type compound cannot be promoted, and the surface hardness of the hard coating layer is remarkably reduced. When it exceeds 100 kGy, the life of the electron beam irradiation tube is remarkably reduced, which is disadvantageous in terms of production cost. (Hard coating film for molding) The hard coating film for molding of the present invention is a film having excellent surface hardness. Specifically, although it is different depending on the base film, for example, a hard coating film for molding using a biaxially oriented polyester containing a copolymerized polyester as a base film, the pencil hardness is preferably Η or more, 2Η. The above is especially good. Here, the evaluation of the pencil hardness was performed based on JIS_K5600. The method of adjusting the surface hardness by using the content of the 1 or 2 functionalized radical radiation-hardening compound or the content of the radical radiation-hardening compound having an amine group in the free radiation curing compound contained in the coating liquid forming the hard coating layer, The amount of particles present in the hard coating layer, the thickness of the hard coating layer, and the like are changed. The hard coating film for molding of the present invention is a film excellent in scratch resistance. Specifically, although it is different depending on the base film, for example, a hard coating film for forming a biaxially oriented polyester containing a copolymerized polyester as a base film, a wire of # 0 000 is used in accordance with JIS-K5 600. The cotton was loaded back and forth 20 times on the surface with a load of 500 gf to visually observe the occurrence of scratches and the degree thereof. As a result, it was preferable to scratch a small amount of 10 or less in depth, and it was excellent in no deep scratch at all. The method of adjusting the scratch resistance by using the content of the 1 or 2 functionalized radiation-hardening type compound or the radical radiation-hardening type compound having an amine group in the free radiation curing compound contained in the coating liquid for forming the hard coating layer 29-201008991 The content, the amount of particles present in the hard coating layer, etc. are changed. The hard coating film for molding of the present invention is excellent in moldability, and is different depending on the base film. For example, a hard coating film for forming a biaxial film containing a copolymerized polyester is practical at room temperature and film. The temperature and length ratio are both 10% or more, more preferably 20% or more, and 30%. The so-called elongation is obtained by cutting a rectangular shape having a length of 150 mm from a hard coating film for forming, and stretching at a film actual temperature of 160 ° C. The elongation at the time of striate or whitening is taken as the elongation (%). ® The method of adjusting the moldability (elongation) can be carried out by forming the content of the radiation-hardening type compound contained in the coating liquid or the content of the radiation-hardening type compound or the content of the free radiation compound having an amine group in the hard coating layer. The hard coating film for molding of the present invention is used in the presence of particles, and the like, and it is preferable to have transparency when it is subjected to printing without being laminated. Specifically, if the biaxially oriented polyester containing the copolymerized polyester is a hard coating film of the φ type, the haze is preferably 5% or less. The modification can be carried out by using the amount of particles present in the hard coating layer. The hard coating film for molding of the present invention preferably has no coloring when it is subjected to printing without lamination. Specifically, if the biaxially oriented polyester containing a copolymerized polyester is used as a substrate hard coating film, the h* b* is 2. The method of 0 or less preferably b* can be changed by the amount of the radical ray-curable type of the amine group or the amount of the photopolymerization initiator added to the hardening type compound contained in the coating liquid for forming the hard coating layer. Here, the color film. Specifically, the polyester is a substrate ί 1 at 60 ° C. The 2-functional ray-hardening type of the hard coating layer of the 10 mm thick and hard coating layer was changed. One of the coatings is due to the uniformity of the base substrate film. One of the coatings is formed by the base film. Adjusting the content of the hue free radiation compound b* is determined by using a -30-201008991 color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., ZE-2000), and measuring the hue b* with a C light source and a viewing angle of 2 degrees. Get it right. (Forming Hard Coating Roller) The hard coating roll for molding of the present invention is obtained by continuously winding a long hard coating film for forming into a cylindrical core roll into a roll form. When the hard coating roll for molding is used, the productivity at the time of processing can be improved, and the stability of the molded body can be imparted. The length of the hard coating film for forming the hard coating film in which the hard coating film is continuously wound into a cylindrical core is not particularly limited depending on the application, but is preferably 50 m or more and 5000 m or less, and 100 m or more. 3 000 m or less is better. When the winding length is short, the replacement speed of the hard coating roller for molding is high when the printing layer is processed in the post-process, and the workability is deteriorated. On the other hand, when the winding length is long, the hard coating film for molding expands and contracts due to the external environmental temperature, and the winding is caused to cause a poor appearance of the core portion. The width of the hard coating roll for molding is not particularly limited depending on the application, but is preferably 100 mm or more and 2000 mm or less from the viewpoint of workability, and more preferably 500 mm or more and 1,500 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 coating 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, winding of the core portion is entangled, resulting in poor workability in the post-process. On the other hand, when the diameter is large, the diameter of the roller is also large, and the handleability is poor. -31 - 201008991 When the hard coating film for molding is wound around a cylindrical core, it is preferable to fix the hard coating film for forming by double-sided tape. When double-sided tape is not used, roll film deviation 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 μm or more and 50//m or less. When the thickness is thinner, the workability is poor, and the fixing force of the film is also reduced. On the other hand, when the thickness 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 hard coating layer is brought into contact with the surface of the base film on the opposite side, or the layer which is laminated on the base film as described above. The contact portion is lowered to ensure good storage stability of the roll form. The lower limit of the height of the concave and convex is preferably 10#m and more preferably 15#m. On the other hand, the upper limit of the height of the concavities and convexities is preferably 40 μm or more, and more preferably 35 / zm. When the height of the concavities and convexities is too low, the effect of improving the stability of the φ roll form is small due to the unevenness. 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 in which a metal roll having a protrusion on the surface is pressed to impart unevenness. Further, the uneven processing is preferably applied to the base film before the formation of the hard coating layer on the base film. (Molded body) The hard coating film for molding of the present invention is suitably used for vacuum molding, air pressure molding, mold molding, press molding, laminate molding, in-mold molding, extrusion molding, and bending molding. Forming method such as stretch forming -32- 201008991 Forming material. When the hard coating film for molding of the present invention is used for molding, the hard coating layer is not cracked by deformation at the time of molding, and surface hardness and scratch resistance can be maintained. The thickness of the hard coating layer of the molded body formed by the hard coating film for forming is 0. 5 / / m or more, 50 / / m or less is better, 0. 5/im or more, 1〇 /zm or less. The thickness of the hard coating of the molded body is greater than 0. When the thickness is 5/zm, the hardenability is not obtained, and from the viewpoint of heat resistance, when the molded article is heated, the shrinkage of the substrate film is not followed, and the surface of the hard coating layer is caused to cause waves to impair the appearance. On the contrary, when it exceeds 50/zm, it is not superior to the surface hardness of the 50/zm thick hard coating layer, and the quality is less advantageous. The molded body thus formed has a hard coating layer to reinforce the surface hardness, and can be suitably used as a nameplate for household appliances, an automobile nameplate, an empty can, a building material, a cosmetic board, and a cosmetic steel plate which are attached to an external contact position and required to have scratch resistance. And a molded member such as a transfer sheet. [Examples] The present invention will be described in detail by way of the following examples. Further, the properties of the hard coating film for molding obtained in each of the examples were measured and evaluated by the following methods. (1) Elongation A thin rectangular test piece having a length of 10 mm and a width of 150 mm was cut out from the obtained hard coating film for molding. When the actual temperature of the film test piece was 160 ° C, the appearance was visually observed, and both ends of the film were fixed and stretched at a test speed of 250 mm per minute to measure the occurrence of cracking or whitening of the hard coating layer. Film length. The length of the film test piece before the test was a, and the film test piece length after the test was -33-201008991 degrees, and the elongation was calculated by the following formula. Elongation (%) = (b - a) xl00 / a 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. (2) Pencil hardness The pencil hardness of the hard coating layer of the obtained hard coating film for molding was measured in accordance with JIS - K5 600. The indentation was judged visually. Here, it is judged that the pencil hardness is Η or more to have an excellent surface hardness, and ❹ 2Η or more is judged to have a superior surface hardness. (3) Scratch resistance The scratch resistance of the obtained hard coating hard coating for molding was measured in accordance with JIS - Κ 5600. The surface of the hard coating layer was rubbed back and forth 20 times with a steel wire of #g〇〇〇〇 to observe the presence or absence of scratches and the extent thereof. According to the observation result, the level is determined according to the following criteria. When the scratch resistance level is C or more, the scratch resistance is judged, and when the grade is B or more, the scratch resistance φ is judged to be good. A: No scratches occurred, or a small degree of fineness was observed. B: Fine injuries were observed, but no deep injuries. C: A fine injury was observed and a small degree of deep injury was observed. D: A lot of deep injuries were observed. (4) The color tone b* of the hard coating film for molding obtained by the color tone b*, using a color difference meter (ZE-200) manufactured by Sakamoto Denshoku Industries Co., Ltd. And an average of 5 measurements of 値. -34- 201008991 (5) Pencil hardness and hard coating layer thickness after molding The elongation of the above (1) was evaluated, and the stretching was stopped before the occurrence of cleavage, and the molded body after the stretching molding was obtained. The pencil hardness after molding was evaluated by the evaluation method of the above (2). In addition, the spectral reflectance at the center of the hard-coated test piece (molded body) after molding was determined by a spectrophotometer (UV-3150, manufactured by Shimadzu Corporation), and the peak was formed by a waveform having a wavelength of 400 nm or more and 600 nm or less. The peak valley method calculates the thickness of the hard coating layer. In this case, a single layer film of a hard coating layer was prepared from the hard coating layer coating liquid of each of the examples and the comparative examples, and an Abbe refractometer (NAR-IT SOLID, manufactured by ATAGO Co., Ltd.) was used. Got it. (6) Whether or not wrinkles occurred In order to determine whether or not the drying temperature and film tension after application of the coating liquid were appropriate, it was evaluated whether or not wrinkles occurred. When coating hardening is performed on a substrate film having a width of 1000 mm and a length of 200 m to form a hard coating layer, if the hard coating film for molding is not wrinkled, it is judged to be good (〇), and if it occurs, it is judged to be poor Φ (X) ). (7) Appearance Appearance The coating appearance was evaluated by determining whether the drying temperature and film tension after application of the coating liquid were appropriate. When coating hardening is performed on a base film having a width of 1000 mm and a length of 200 m to provide a hard coating layer, if the hard coating layer is completely free from whitening, coating is missing, or rejected, it is judged to be good (〇). Bad (X). (8) Wide-direction shrinkage ratio before and after coating The width direction shrinkage ratio was evaluated by determining whether the drying temperature and film tension after application of the coating liquid were appropriate, -35-201008991. The film thickness was measured by applying hardening on a base film having a width of 1000 mm and a length of 200 m to form a hard coating layer. When the film width before coating was a and the film width after coating was b, the film width shrinkage ratio (width shrinkage ratio) before and after coating was determined by the following formula. Wide direction shrinkage is 1. When it is less than 5%, it is judged to be good, and it is more than 1. It was judged to be bad at 5%. Shrinkage in the width direction (%) = (a - b) xl 〇〇 / a (Example 1) A biaxially oriented polyester film containing a copolymerized polyester in a two-mask easy-adhesion layer (manufactured by Toyobo Co., Ltd., SOFTSHINE: A1532, thickness 125/zm), the following coating liquid A was applied using a wire bar, and the hard coating layer formed by coating and hardening was 2 μm thick, dried by hot air at a temperature of 80 ° C for 60 seconds, and at an output of 120 W/ 20 cm under the high-pressure mercury lamp of cm (accumulated light amount 3 0〇111) / (: 1112) was passed at a speed of 8111/11^11 to obtain a hard coating film for molding. (Coating liquid A) The following materials were used in the following qualities. Mix and stir for more than 30 minutes to dissolve φ. Secondly, use the filter of nominal filtration precision l"m to filter out the undissolved material to prepare coating liquid A. • 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). Tri-propylene glycol diacrylate 5. 73% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group 2) -36- 201008991 • Dimethylamine ethyl methacrylate 5. 72% by mass (made 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 (made by Ciba Speciality Chemicals, IRGACURE 184) • Organic lanthanide surfactant 0. 03% by mass (manufactured by 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 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 hard coating layer was changed to the coating liquid B described below. (Coating solution B) • Methyl ethyl ketone 64. 4 8 mass% • pentaerythritol triacrylate 17. 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 -37- •201008991 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: 3〇%, average particle diameter: 50 nm) • Photopolymerization initiator 1. 14% by mass (Ciba Speciality Che mi cals, IRGACURE 184) ❹ • Organic lanthanide surfactants 0. 03% by mass (manufactured by 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 3) φ In the same manner as in Example 1, except that the coating liquid for forming the hard coating layer was changed to the coating liquid C described below, the hard coating film for molding was obtained. (Coating liquid C) • Methyl ethyl ketone 64. 48% by mass • Pentaerythritol triacrylate 8. 02% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, functional group number 3) • Tri-propylene glycol diacrylate 7. 44% by mass -38- 201008991 (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group 2) • Dimethylamine ethyl methacrylate 7. 44% by mass (made 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 ❹ (manufactured by Ciba Speciality Chemicals, IRGACURE 184) • Organic lanthanide surfactant 0. 03% by mass (manufactured by 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 article 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) The hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coating layer was changed to the coating liquid D described below. (Coating liquid D) • Methyl ethyl ketone 64. 48% by mass • Neopentyl alcohol triacrylate 21. 75 mass% (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, functional group number 3) -39- 201008991 • 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) • Vermiculite particles 11. 45% by mass (manufactured by Nissan Chemical Industries, Ltd., MEK-ST-L, solid content ratio: 30%, average particle diameter: 50 nm) ❹ • Photopolymerization initiator 1. 14% by mass (made by Ciba Speciality Chemicals, IRGACURE 184) • Organic lanthanide surfactant 0. 03% by mass (manufactured by 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 φ. 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 hard coating layer was changed to the coating liquid E described below. (Coating liquid E) • Methyl ethyl ketone 64. 48% by mass • Pentaerythritol triacrylate 1. 15% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, -40- 201008991, 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) • Vermiculite particles 11. 45% by mass (ME K-ST-L, solid content: 30%, average particle size: 50 nm) • Photopolymerization initiator 1. 14% by mass (made by Ciba Speciality Chemicals, IRGACURE 184).  • Organic sand surfactants 0. 03% by mass (manufactured by 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, φ was obtained by using the obtained molded body formed by the hard coating film for molding, and the surface hardness thereof was also good. 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 hard coating layer was changed to the coating liquid F described below. (Coating liquid F) • Methyl ethyl ketone • Neopentyl alcohol triacrylate 6 4. 4 8 mass% 2 1 .  7 5 mass% -41- 201008991 (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - ΤΜΜ - 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 (MEK-ST-L, solid content: 30%, average particle size: 50 nm) ® • Photopolymerization initiator 1. 14% by mass ("IRGACURE 184" manufactured by Ciba Speciality Chemicals) • Organic lanthanide surfactant 0. 03% by mass (manufactured by 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 φ. 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 1 except that the coating liquid for forming the hard coating layer was changed to the coating liquid G described below. (Coating liquid G) • Methyl ethyl ketone 64. 48% by mass • Pentaerythritol triacrylate 1. 15% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, -42- 201008991 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. 14% by mass (made by Ciba Speciality Chemicals, IRGACURE 184) • Organic lanthanide surfactant 0. 03% by mass (manufactured by 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. φ (Example 8) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coating layer was changed to the coating liquid layer described below. (coating liquid Η) • methyl ethyl ketone 64. 48% by mass • Pentaerythritol triacrylate 1. 15% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - ΤΜΜ - 3LM - Ν, functional group number 3) -43- 201008991 • Dimethylamine ethyl methacrylate 21. 75 mass% (made by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1) • Vermiculite particles 1 1. 45% by mass (MEK-ST-L, solid content rate: 30%, average particle diameter: 50 nm) • Photopolymerization initiator 1. 14% by mass (made by Ciba Speciality Chemicals, IRGACURE 184) • Organic lanthanide surfactant 0. 03% by mass of the hard coating film for molding obtained by Dow Corning Toray Co., Ltd., DC57), the amount of the amine compound added is large, and the coloring is remarkably slightly poor, but the moldability, surface hardness, and scratch resistance are 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 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 hard coating layer was changed to the coating liquid I of the following. (Coating liquid I) • 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 3) • Tri-propylene glycol diacrylate 5. 73% by mass (made by Shin-Nakamura Chemical Co., Ltd. 'NK ESTER APG - 200, functional group 44 - 201008991 2) • Diethylamine ethyl methacrylate 5. 72% by mass (made by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DE, 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 (made by Ciba Speciality Chemicals, IRGACURE 184) • Organic lanthanide surfactant 0. 03% by mass (manufactured by 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) In the same manner as in Example 1, except that the coating liquid for forming the hard coating layer was changed to the coating liquid J described below, a hard coating film for molding was obtained. (Coating liquid J) 6 4. 4 8 mass% 1 1. 4 5 mass% • methyl ethyl ketone • neopentyl alcohol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, functional group number 3) 7 3 mass% • tri-propylene glycol diacrylate -45- 201008991 (Manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional base 2) • N-vinylformamide 5. 72% by mass (made by Arakawa Chemical Industry Co., Ltd., BEAMSET 770, functional group number 1) • Vermiculite particles 11. 45% by mass (MEK-ST-L, solid content: 30%, average particle size: 50 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， 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。所得結果示如表1。 (實施例11) 於實施例1，除將形成硬被覆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。 (塗布液K) •甲基乙基酮 67.93質量％ •新戊四醇三丙烯酸酯 11.58質量％ (新中村化學公司製、NK ESTER A - TMM - 3LM - N、 官能基數3) -46- 201008991 •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％ (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) •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。所得結果示如表1。 (實施例12) 於實施例1，除將形成硬被覆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。 (塗布液L) •甲基乙基酮 4.24質量％ •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、 -47- 201008991 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％ (曰產化學工業公司製、MEK- ST - L、固體成分率： ▼ 3 0%、平均粒徑：50nm) •光聚合引發劑 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。所得結果示如表1。 (實施例13) 於實施例1，除將形成硬被覆層之塗布液變更爲 之塗布液Μ以外，其他與實施例1相同，得成型用硬被覆 膜。 (塗布液Μ) 71.46質量％ η·72質量％ •甲基乙基酮 •新戊四醇三丙烯酸酯 -48- 201008991 (新中村化學公司製、NK ESTER A - ΤΜΜ - 3LM - N、 官能基數3) •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) •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％ 參 (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 1.17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 Q 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。所得結果示如表1。 (實施例14) 於實施例1，除將形成硬被覆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) •新戊四醇三丙烯酸酯 5.28質量％ -49- 201008991 (新中村化學公司製' NK ESTER A - ΤΜΜ - 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 2) •二甲基胺乙基甲基丙烯酸酯 2.64質量％ (共榮社化學公司製、LIGHT ESTER DM、官能基數1) •矽石微粒 88.88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 φ 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。所得結果示如表1。 (實施例15) 於實施例1，除將形成硬被覆層之塗布液變更爲下述 之塗布液◦以外，其他與實施例1相同’得成型用硬被覆 膜。 (塗布液0) •甲基乙基酮 58.76質量％ -50- 201008991 •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) 0 •矽石微粒 17.17質量％ (扶桑化學工業公司製、PL2L - MEK、固體成分率： 20%、平均粒徑：20nm) . •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) φ 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。所得結果示如表1。 (實施例16) 於實施例1，除將形成硬被覆層之塗布液變更爲下述 之塗布液Ρ以外，其他與實施例1相同’得成型用硬被覆 膜。 (塗布液Ρ) -51- 201008991 •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 17.17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％ (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。所得結果示如表1。 (實施例17) 於實施例1’除將形成硬被覆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。 -52- 201008991 (塗布液Q) •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) 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) •矽石微粒 17.17質量％ . (日本觸媒公司製、SEAHOSTAR KE- E50、固體成分 率：20%、平均粒徑：51 lnm) •光聚合引發劑 1.14質量％ (Ciba Speciality Chemicals 公司製、IRGACURE 184) φ ·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。所得結果示如表1。 (實施例18) 於實施例1，除將形成硬被覆層之塗布液變更爲下述 之塗布液R以外，其他與實施例1相同，得成型用硬被^ -53- 201008991(manufactured by Ciba Speciality Chemicals, IRGACURE 184) • 0.03 mass% organic surfactant (Dow Corning Toray Co., Ltd., 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. (Example 11) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coating layer was changed to the coating liquid K described below. (coating liquid K) • methyl ethyl ketone 67.93 mass% • neopentyl alcohol triacrylate 11.58 mass% (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, functional group number 3) -46- 201008991 • 3.75% by mass of propylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group 2) • dimethylamine ethyl methacrylate 5.79% by mass (produced 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 mass% (Ciba) Speciality Chemicals, Inc., IRGACURE 184) • Organic lanthanide surfactant 0.03 mass% (Dow Corning Toray Co., Ltd., DC57) Hard coating for molding, moldability, surface hardness, scratch resistance, coloration Both are good and are 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 12) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coating layer was changed to the coating liquid L described below. (Coating liquid L) • Methyl ethyl ketone 4.24% by mass • Neopentyl alcohol triacrylate 6.22% by mass (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, -47- 201008991 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 (produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1) • Vermiculite particles 82.73 mass% (manufactured by Seiko Chemical Industry Co., Ltd., MEK-ST-L, solid content ratio: ▼ 30%, average particle diameter: 50 nm) • Photopolymerization initiator 0.55 mass % (manufactured by Ciba Speciality Chemicals, IRGACURE 184) • 0.02% by mass of an organic lanthanide surfactant (manufactured by Dow Corning Toray Co., Ltd., DC57), a hard coating film for molding, moldability, surface hardness, and 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. (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 hard coating layer was changed to the coating liquid. (coating liquid Μ) 71.46 mass% η·72 mass% • methyl ethyl ketone • neopentyl alcohol triacrylate-48- 201008991 (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - ΤΜΜ - 3LM - N, functional group number 3) • Tri-propylene glycol diacrylate 5.86 mass% (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group 2) • dimethylamine ethyl methacrylate 5.86 mass% (manufactured by Kyoeisha Chemical Co., Ltd.) LIGHT ESTER DM, functional group number 1) • Vermiculite particles 3.90% by mass References (MEK-ST-L, solid content: 30%, average particle size: 50 nm) • Photopolymerization initiator 1.17 % by mass _ (manufactured by Ciba Speciality Chemicals Co., Ltd., IRGACURE 184) • Organic lanthanide surfactant 0.03 mass% (manufactured by Dow Corning Toray Co., Ltd., DC57), a hard coating film for molding, moldability, surface hardness, and resistance The scratch Q and the degree of coloration are 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. (Example 14) The hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coating layer was changed to the coating liquid N described below. (Coating liquid N) • Neopentyl alcohol triacrylate 5.28% by mass -49- 201008991 (Manufactured by Shin-Nakamura Chemical Co., Ltd. 'NK ESTER A - ΤΜΜ - 3LM - N, functional group 3) • Tri-propylene glycol diacrylate 2.64 mass % (Nippon Nakamura Chemical Co., Ltd., NK ESTER APG - 200, functional group number 2) • dimethylamine ethyl methacrylate 2.64% by mass (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1) • 矽89.88% by mass of stone particles (MEK-ST-L, solid content ratio: 30%, average particle diameter: 50 nm). Photopolymerization initiator 0.55 mass% (manufactured by Ciba Speciality Chemicals, IRGACURE 184) • 0.02% by mass of the organic lanthanoid surfactant (Dow Corning Toray Co., Ltd., DC57) The hard coating film for molding has good moldability, surface hardness, scratch resistance, and coloration degree. The hard coating is good. Further, the molded body formed by using the obtained hard coating film for forming has a good surface hardness. The results obtained are shown in Table 1. (Example 15) The hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coating layer was changed to the coating liquid layer described below. (coating liquid 0) • methyl ethyl ketone 58.76 mass% -50- 201008991 • pentaerythritol triacrylate 11.45 mass% (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, functional group number 3) • 3.73% by mass of propylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group 2) • 5.7% by mass of dimethylamine ethyl methacrylate (produced by Kyoeisha Chemical Co., Ltd., LIGHT) ESTER DM, functional group number 1) 0 • Vermiculite particles 17.17% by mass (made by Fuso Chemical Industry Co., Ltd., PL2L-MEK, solid content ratio: 20%, average particle diameter: 20 nm) • Photopolymerization initiator 1.14% by mass (Ciba Speciality Chemicals, Inc., IRGACURE 184) • Organic lanthanide surfactant 0.03 mass% (Dow Corning Toray Co., Ltd., DC57) φ A hard coating for molding, which has moldability, surface hardness, scratch resistance, and coloration. The degree is good, and it is good as a hard coating for molding. Further, the molded article 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) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coating layer was changed to the coating liquid layer described below. (Coating liquid Ρ) -51- 201008991 • 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) • 3.73% by mass of propylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group 2) • 5.7% by mass of dimethylamine ethyl methacrylate (produced by Kyoeisha Chemical Co., Ltd., LIGHT) ESTER DM, functional group number 1) • Vermiculite particles 17.17% by 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 Company, IRGACURE 184) • Organic lanthanide surfactant 0.03 mass% (Dow Corning Toray's 'DC57) Hard coating for molding, good moldability, surface hardness, scratch resistance, and coloration 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. (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 hard coating layer was changed to the coating liquid Q described below. -52- 201008991 (coating liquid Q) • methyl ethyl ketone 58.76% 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) • 3.73 mass% of propylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group 2) 5.7% by mass of dimethylaminoethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) LIGHT ESTER DM, functional group number 1) • Vermiculite particles 17.17% by mass. (Manufactured by Nippon Shokubai Co., Ltd., SEAHOSTAR KE-E50, solid content ratio: 20%, average particle diameter: 51 lnm) • Photopolymerization initiator 1.14% by mass (manufactured by Ciba Speciality Chemicals Co., Ltd., IRGACURE 184) φ · Organic lanthanide surfactant 0.03 mass% (manufactured by Dow Corning Toray Co., Ltd., DC57), a hard coating film for molding, moldability, surface hardness, and 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. (Example 18) The same procedure as in Example 1 was carried out except that the coating liquid for forming the hard coating layer was changed to the coating liquid R described below, and the hard molding for molding was obtained - 53-201008991

(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 •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、EPOSTAR S、平均粒徑：196nm) •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。所得結果示如表1。 (實施例19) 於實施例1，除將形成硬被覆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 -54 - 201008991(Coating liquid R) • Methyl ethyl ketone 72.50% 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 • dimethylamine ethyl methacrylate 5.72% by mass (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1) • Melamine/formaldehyde condensate particles 3.43% by mass (produced by Nippon Shokubai Co., Ltd., EPOSTAR S, average particle size: 196 nm) • Photopolymerization initiator 1.14% by mass (manufactured by Ciba Speciality Chemicals, IRGACURE 184) • Organic lanthanide interface The hard coating film for molding obtained by 0.03 mass% of the active agent (manufactured by Dow Corning Toray Co., Ltd., DC57) 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 had a good surface hardness. The obtained results are shown in Table 1. (Example 19) In Example 1, except that the coating liquid for forming the hard coating layer was changed Other than below the coating liquid S, the same manner as in Example 1 to obtain molding with a hard coating -54--201008991

(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) •三伸丙二醇二丙烯酸酯 5.93質量％ Φ(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) • Tri-propylene glycol Diacrylate 5.93 mass% Φ

(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 1.19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。所得結果示如表1。 (實施例20) 於實施例1，除將基材膜變更爲雙面具有易黏著層之 雙軸拉伸聚酯膜（東洋紡績公司製、COSMOSHINE: A4300、 厚度125 # m)外，其他與實施例1相同，得成型用硬被覆(manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group number 2) • dimethylamine ethyl methacrylate 5.92% by mass (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1) • Photopolymerization Initiator 1.19 mass% (manufactured by Ciba Speciality Chemicals Co., Ltd., IRGACURE 184) • Organic lanthanide surfactant 0.03 mass% (manufactured by Dow Corning Toray Co., Ltd., DC57), a hard coating film for molding, moldability and surface hardness It is excellent in scratch resistance and coloration, and 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 20) In addition to the biaxially-stretched polyester film (COSM HINE: A4300, thickness 125 # The same as in the first embodiment, a hard coating for molding is obtained.

-55- 201008991 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。所得結果示如表1。 (實施例21) 於實施例1，除將基材膜變更爲未拉伸聚碳酸酯膜（帝 人化成公司製、PC— 2151、厚度250/zm)外，且將形成硬 被覆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。 (塗布液T) •甲基乙基酮 20.98質量％ •異丙醇 40.50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 )-55- 201008991 The hard coating film for molding has good moldability, surface hardness, scratch resistance, and coloration, and is excellent 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 21) In the first embodiment, except that the base film was changed to an unstretched polycarbonate film (PC-2151, thickness 250/zm, manufactured by Teijin Chemicals Co., Ltd.), a coating liquid for forming a hard coating layer was formed. The hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid T described below was changed. (Coating liquid T) • Methyl ethyl ketone 20.98% by mass • Isopropanol 40.50% by mass • Neopentyl alcohol triacrylate 11.45% by mass (Nippon Nakamura Chemical Co., Ltd., NK ESTER A - TMM - 3LM - N, functional Cardinality 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 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％ -56- 201008991 (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。所得結果示如表1。 (實施例22) m 於實施例1，除塗布使塗布硬化後形成之硬被覆層厚 度爲1.1/zm外，其他與實施例1相同，得到成型用硬被覆 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。所得結果示如表1。 φ (實施例23) 於實施例1，除塗布使塗布硬化後形成之硬被覆層厚 度爲50 外，其他與實施例1相同，得到成型用硬被覆 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。所得結果示如表1。 (實施例24) -57- 201008991 於實施例1，除塗布使塗布硬化後形成之硬被覆層厚度 爲0.5/zm外，其他與實施例1相同，得到成型用硬被覆膜。 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。但使 用製得之成型用硬被覆膜成型之成型體的表面硬度有若干 不良。此係因經由成型之硬被覆層的厚度可維持表面硬度 之範圍以外者變薄之故。所得結果示如表1。 (實施例25) 於實施例1，除塗布使塗布硬化後形成之硬被覆層厚 度爲60//m外，其他與實施例1相同，得到成型用硬被覆 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。所得結果示如表1。 φ (比較例1) 於實施例1，除將形成硬被覆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) •甲基乙基酮 64.48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) -58- 201008991 •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 1.1 4質量％ (Ciba Speciality Chemicals 公司製、IRGACURE 184) •有機矽系界面活性劑 0.03質量％ (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。所得結果示如表1。 (比較例2) 於實施例1，除將形成硬被覆層之塗布液變更爲下述 之塗布液V以外’其他與實施例1相同，得成型用硬被覆 膜。 (塗布液V)• 3.73% by mass of propylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group 2) • 5.7% by mass of dimethylamine ethyl methacrylate (produced by Kyoeisha Chemical Co., Ltd., LIGHT) ESTER DM, functional group number 1) • 11.45 mass% of vermiculite particles (manufactured by Nissan Chemical Industries, Ltd., MEK-ST-L, solid content ratio: 30%, average particle diameter: 50 nm) • Photopolymerization initiator 1.14% by mass -56 - 201008991 (manufactured by Ciba Speciality Chemicals, IRGACURE 184) • 0.03 mass% organic surfactant (Dow Corning Toray Co., Ltd., DC57), a hard coating film for molding, moldability, surface hardness, and scratch resistance. Both the properties and the degree of coloration are 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. (Example 22) m The hard coating film for molding was obtained in the same manner as in Example 1 except that the thickness of the hard coating layer formed by coating hardening was 1.1/zm. The hard coating film for molding obtained 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. φ (Example 23) A hard coating film for molding was obtained in the same manner as in Example 1 except that the thickness of the hard coating layer formed by coating hardening was 50. 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 24) -57-201008991 A hard coating film for molding was obtained in the same manner as in Example 1 except that the thickness of the hard coating layer formed by coating hardening was 0.5/zm. 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. However, the surface hardness of the molded body formed by using the obtained hard coating film for molding is somewhat defective. This is because the thickness of the hard coating layer that is formed can be thinned beyond the range of the surface hardness. The results obtained are shown in Table 1. (Example 25) A hard coating film for molding was obtained in the same manner as in Example 1 except that the thickness of the hard coating layer formed by coating hardening was 60/m. The hard coating film for molding obtained 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. φ (Comparative Example 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 hard coating layer was changed to the coating liquid U described below. (coating liquid U) • methyl ethyl ketone 64.48% 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) -58- 201008991 • 11.45% by mass of vermiculite particles (MEK-ST-L, solid content: 3〇%, average particle size: 50nm) • Photopolymerization initiator 1.1% by mass (manufactured by Ciba Speciality Chemicals, IRGACURE 184) • 0.03 mass% organic surfactant (Dow Corning Toray Co., Ltd., DC57), which is a hard coating film for molding, which has good surface hardness, scratch resistance, and coloration, but has poor moldability. The hard coating for molding is also defective. The results obtained are shown in Table 1. (Comparative Example 2) The hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coating layer was changed to the coating liquid V described below. (coating liquid V)

*甲基乙基酮 64.48質量％ •三伸丙二醇二丙烯酸酯 1 1.45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 11.45質量％ (共榮社化學公司製、LIGHT ESTER DM、官能基數1) •矽石微粒 1 1.45質量％ (曰產化學工業公司製、MEK - ST - L、固體成分率： 30%、平均粒徑：5〇nm) -59- 201008991 •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、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。 所得結果示如表1。 (實施例26) 將寬度1000mm、長度200m、兩面具易黏著層之含共 聚合聚酯之雙軸聚酯膜（東洋紡績公司製、SOFTSHINE : A1532、厚度125/zm)輥，以卷對卷方式使用微凹版方法及 . 下述塗布液W進行塗布，使塗布並硬化後之硬被覆層厚度 爲2/zm後’在膜張力i8〇N/m條件下以溫度80°C熱風乾燥 60秒’並在輸出功率i6〇W/cm之高壓水銀燈下20cm位置（累 計光量300nU/cm2)以lOm/min速度通過使之硬化，再將成 φ 型用硬被覆膜卷繞在直徑6英吋之聚丙烯製圓柱形卷芯， 製成寬度1 000mm、長度200m之成型用硬被覆膜輥。 (塗布液W) 將下述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ΐμιη之過濾器濾除未 溶解物，製成塗布液W。 •甲基乙基酮 28.24質量％ •甲苯 36.24質量％ •新戊四醇三丙烯酸酯 11.45質量％ -60- 201008991 (新中村化學公司製、NK ESTER A - ΤΜΜ - 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麁 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％ (日產化學工業公司製、ΜΕΚ - 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) 在基材膜上塗布硬化硬被覆層時，行進之膜未發生蛇 φ 行或皺紋，故生產性無問題而能夠製成。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 果示如表2。 (實施例27) 於實施例26，除將乾燥溫度變更爲40°C外，其他與實 施例26相同，製得成型用硬被覆膜輥。 在基材膜上塗布硬化硬被覆層時，行進之膜未發生蛇 -61- 201008991 行或皺紋，故生產性無問題而能夠製成。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 果示如表2。 (實施例28) 於實施例26，除將乾燥溫度變更爲120°C外’其他與 實施例26相同，製得成型用硬被覆膜輥。 在基材膜上塗布硬化硬被覆層時，行進之膜未發生蛇 行或皴紋，故生產性無問題而能夠製成。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 果示如表2。 (實施例29) 於實施例26，除將膜張力變更爲5 ON/m外，其他與實 施例26相同，製得成型用硬被覆膜輥。 在基材膜上塗布硬化硬被覆層時，行進之膜未發生蛇 行或皺紋，故生產性無問題而能夠製成。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 果示如表2。 (實施例30) -62- 201008991 於實施例26，除將膜張力變更爲30 0N/m外，其他與 實施例26相同，製得成型用硬被覆膜輥。 在基材膜上塗布硬化硬被覆層時，行進之膜未發生蛇 行或皺紋，故生產性無問題而能夠製成。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 果示如表2。 e (比較例3) 於實施例26,除將乾燥溫度變更爲3 0 °C外，其他與實 施例26相同，製得成型用硬被覆膜輥。 . 在基材膜上塗布硬化硬被覆層時，行進之膜未發生蛇 行或皺紋，故生產性無問題而能夠製成。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。所得結果示如表2。 H (比較例4) 於實施例26，除將乾燥溫度變更爲140°C外，其他與 實施例26相同，製得成型用硬被覆膜輥。 在基材膜上塗布硬化硬被覆層時，行進之膜未發生蛇 行但發生皺紋，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。所得結果示如表2。 (比較例5) 於實施例26，除將膜張力變更爲40N/m外，其他與實 -63- 201008991 施例26相同，製得成型用硬被覆膜輥。 在基材膜上塗布硬化硬被覆層時，雖無發生皺紋，但 行進之膜發生蛇行，故生產性不適合。由於行進之膜發生 蛇行，故不能製成成型用硬被覆膜》 (比較例6) 於實施例26，除將膜張力變更爲320N/m外，其他與 實施例26相同，製得成型用硬被覆膜輥。 在基材膜上塗布硬化硬被覆層時，行進之膜雖無發生 ❿ 蛇行，但發生皺紋，故生產性不適合。製得之成型用硬被 覆膜，其塗布外觀良好，但寬方向收縮率不良。所得結果 示如表2。 . (實施例31) 於實施例1，除將形成硬被覆層之塗布液變更爲下述 之塗布液R以外，其他與實施例1相同，得成型用硬被覆 膜。 鲁 （塗布液X) •甲基乙基酮 63.62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％ -64- 201008991 (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) •游離輻射線硬化型有機矽化合物 0.86質量％ 聚醚丙烯酸酯 (Tego Chemie Service GmbH 製、TEGO Rad2200N) •光聚合引發劑 1.14質量％ ❹ (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。所得結果示如表1。 ¢(實施例31) 於實施例1，除將形成硬被覆層之塗布液變更爲下述 之塗布液R以外，其他與實施例1相同，得成型用硬被覆 膜。 (塗布液Y) •甲基乙基酮 64.42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) -65- 201008991 •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 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)*Methyl ethyl ketone 64.48% by mass • Tri-propylene glycol diacrylate 1 1.45 mass% (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group 2) • Dimethylamine ethyl methacrylate 11.45 mass % (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1) • Vermiculite particles 1 1.45 mass% (manufactured by Seiko Chemical Industry Co., Ltd., MEK-ST-L, solid content ratio: 30%, average particle diameter: 5〇nm) -59- 201008991 • Photopolymerization initiator 1.14% by mass (manufactured by Ciba Speciality Chemicals, IRGACURE 184) • Organic lanthanide surfactant 0.03 mass% (manufactured by Dow Corning Toray Co., Ltd., DC57) The hard coating film is excellent in moldability and coloration, but has poor surface hardness and scratch resistance, and is also poor as a hard coating film for molding. The results obtained are shown in Table 1. (Example 26) A roll of a copolymerized polyester-containing biaxial polyester film (manufactured by Toyobo Co., Ltd., SOFTSHINE: A1532, thickness 125/zm) having a width of 1000 mm and a length of 200 m, and a roll-to-roll In the method, the micro-gravure method and the coating liquid W described below were applied so that the thickness of the hard coating layer after coating and hardening was 2/zm, and then dried at a temperature of 80 ° C for 60 seconds under the film tension i8 〇 N/m. 'And in the 20cm position (accumulated light quantity 300nU/cm2) under the high-pressure mercury lamp with output power i6〇W/cm, it is hardened by lOm/min, and then the φ type is wrapped with a hard coating film at a diameter of 6 inches. A cylindrical core made of polypropylene is formed into a hard coated roll for molding having a width of 1 000 mm and a length of 200 m. (Coating liquid W) The following materials were mixed in the following mass ratio, and stirred for 30 minutes or more to be dissolved. Next, the undissolved matter was filtered off using a filter of a nominal filtration precision ΐμιη to prepare a coating liquid W. • methyl ethyl ketone 28.24% by mass • toluene 36.24% by mass • pentaerythritol triacrylate 11.45% by mass -60- 201008991 (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A - ΤΜΜ - 3LM - N, functional group number 3) • 3.73% by mass of propylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group 2) • 5.7% by mass of dimethylamine ethyl methacrylate (made by Kyoeisha Chemical Co., Ltd., LIGHT) ESTER DM, functional group number 1) • 11.45 mass% of vermiculite particles (manufactured by Nissan Chemical Industries, Ltd., ΜΕΚ-ST-L, solid content ratio: 30%, average particle diameter: 50 nm) • Photopolymerization initiator 1.14% by mass. Ciba Speciality Chemicals, Inc., IRGACURE 184) • Organic lanthanide surfactant 0.03 mass% (manufactured by Dow Corning Toray Co., Ltd., DC57) When a hardened hard coating layer is applied to a substrate film, the film that has traveled does not have snake lines or wrinkles. Therefore, productivity can be produced without problems. The hard coating film for molding obtained was excellent in coating appearance and good in shrinkage in the width direction. Further, the hard coating film for molding obtained 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 26 except that the drying temperature was changed to 40 °C. When the hardened hard coating layer is applied onto the base film, the film that has traveled does not have a snake-61-201008991 line or wrinkles, so that productivity can be produced without any problem. The hard coating film for molding obtained was excellent in coating appearance and good in shrinkage in the width direction. Further, the hard coating film for molding obtained has the same moldability, surface hardness, and scratch resistance as in Example 1. 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 26 except that the drying temperature was changed to 120 °C. When the hardened hard coating layer is applied onto the base film, the film that travels does not cause serpentine or crepe, and thus productivity can be produced without any problem. The hard coating film for molding obtained was excellent in coating appearance and good in shrinkage in the width direction. Further, the hard coating film for molding obtained 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 29) A hard coating roll for molding was obtained in the same manner as in Example 26 except that the film tension was changed to 5 ON/m. When the hardened hard coating layer is applied onto the base film, the film that has traveled does not cause serpentine or wrinkles, so that productivity can be produced without any problem. The hard coating film for molding obtained was excellent in coating appearance and good in shrinkage in the width direction. Further, the hard coating film for molding obtained 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 30) -62-201008991 A hard coating roll for molding was obtained in the same manner as in Example 26 except that the film tension was changed to 30 N/m. When the hardened hard coating layer is applied onto the base film, the film that has traveled does not cause serpentine or wrinkles, so that productivity can be produced without any problem. The hard coating film for molding obtained was excellent in coating appearance and good in shrinkage in the width direction. Further, the hard coating film for molding obtained 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. e (Comparative Example 3) A hard coating roll for molding was obtained in the same manner as in Example 26 except that the drying temperature was changed to 30 °C. When the hardened hard coating layer is applied onto the base film, the traveling film does not wrap or wrinkle, so that productivity can be produced without any problem. The hard coating film for molding obtained has a good shrinkage ratio in the width direction, but the coating appearance is poorly whitened. The results obtained are shown in Table 2. H (Comparative Example 4) A hard coating roll for molding was obtained in the same manner as in Example 26 except that the drying temperature was changed to 140 °C. When the hardened hard coating layer is applied onto the base film, the film that travels does not wrap and wrinkles occur, 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 repulsion, and has a poor shrinkage in the width direction. The results obtained are shown in Table 2. (Comparative Example 5) In the same manner as in Example 26 of Example 26 except that the film tension was changed to 40 N/m, a hard coating roll for molding was obtained. When the hardened hard coating layer is applied onto the base film, wrinkles do not occur, but the film that travels is meandering, so that productivity is not suitable. Since the film that traveled was serpentine, it was not possible to form a hard coating film for molding. (Comparative Example 6) In the same manner as in Example 26 except that the film tension was changed to 320 N/m, the molding was carried out. Hard coated roller. When the hardened hard coating layer is applied onto the base film, the film that travels does not cause snagging, but wrinkles occur, so that productivity is not suitable. The hard coating film for molding obtained was excellent in coating appearance, but was inferior in shrinkage in the width direction. The results obtained are shown in Table 2. (Example 31) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coating layer was changed to the coating liquid R described below. Lu (coating liquid X) • methyl ethyl ketone 63.62% 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) • Three-stretch Propylene glycol diacrylate 5.73 mass% (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group number 2) • dimethylamine ethyl methacrylate 5.72% by mass -64- 201008991 (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1) • 11.45 mass% of vermiculite particles (manufactured by Nissan Chemical Industries, Ltd., MEK-ST-L, solid content ratio: 30%, average particle size··50 nm) • Free radiation hardening organic矽 compound 0.86 mass% polyether acrylate (manufactured by Tego Chemie Service GmbH, TEGO Rad 2200N) • Photopolymerization initiator 1.14% by mass ❹ (manufactured by Ciba Speciality Chemicals, IRGACURE 184) • Organic lanthanide surfactant 0.03 mass% (Dow) The hard coating film for molding prepared by Corning Toray Co., Ltd., which is obtained by the method of forming a hard coating film, is excellent in moldability, surface hardness, scratch resistance, and coloring 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 31) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coating layer was changed to the coating liquid R described below. (Coating liquid Y) • Methyl ethyl ketone 64.42% 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) -65- 201008991 • 3.73% by mass of propylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group 2) • 5.7% by mass of dimethylamine ethyl methacrylate (produced by Kyoeisha Chemical Co., Ltd., LIGHT) ESTER DM, functional group number 1) • Vermiculite particles 11,45 mass% (manufactured by Nissan Chemical Industries, Ltd., MEK-ST-L, solid content ratio: 30%, average particle diameter: 50 nm)

•游離輻射線硬化型有機矽化合物 0.06質量％ 聚醚丙烯酸酯 (Tego Chemie Service GmbH U、TEGO Rad2200N) •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。所得結果示如表1。 (實施例32) 於實施例1，除將形成硬被覆層之塗布液變更爲下述 之塗布液R以外，其他與實施例1相同，得成型用硬被覆 膜。 (塗布液Z) -66- 201008991 •甲基乙基酮 61.62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 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) •游離輻射線硬化型有機矽化合物 2.86質量％ 聚醚丙烯酸酯 (Tego Chemie Service GmbH 製、TEGO Rad2200N) •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。所得結果示如表1。 -67- 201008991 ο• Free radiation hardening type organic cerium compound 0.06 mass% Polyether acrylate (Tego Chemie Service GmbH U, TEGO Rad 2200N) • Photopolymerization initiator 1.14% by mass (manufactured by Ciba Speciality Chemicals, IRGACURE 184) • Organic lanthanide interface activity The hard coating film for molding obtained by 0.03 mass% (manufactured by Dow Corning Toray Co., Ltd., DC57) 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 32) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coating layer was changed to the coating liquid R described below. (Coating liquid Z) -66- 201008991 • Methyl ethyl ketone 61.62% 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) • 3.73% by mass of propylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group 2) • 5.7% by mass of dimethylamine ethyl methacrylate (produced by Kyoeisha Chemical Co., Ltd., LIGHT) ESTER DM, functional group number 1) • 11.45 mass% of vermiculite particles (manufactured by Seiko Chemical Industry Co., Ltd., MEK-ST-L, solid content ratio: 30%, average particle diameter: 50 nm) • Free radiation hardening type organic ruthenium compound 2.86% by mass of polyether acrylate (manufactured by Tego Chemie Service GmbH, TEGO Rad 2200N) • Photopolymerization initiator 1.14% by mass (manufactured by Ciba Speciality Chemicals, IRGACURE 184) • Organic lanthanide surfactant 0.03 mass% (Dow Corning Toray Co., Ltd.) The hard coating film for molding obtained by the method of DC57) 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. -67- 201008991 ο

-009 201008991 表2 有無發生皺紋 塗佈外觀 寬方向收縮率(％) 實施例26 〇 〇 0.0 實施例27 〇 〇 0.1 實施例28 〇 〇 1.3 實施例29 〇 〇 0.1 實施例30 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 1.6-009 201008991 Table 2 Appearance of wrinkle coating appearance Wide direction shrinkage ratio (%) Example 26 〇〇0.0 Example 27 〇〇0.1 Example 28 〇〇1.3 Example 29 〇〇0.1 Example 30 〇〇0.3 Comparative Example 3 〇X 0.0 Comparative Example 4 XX 2.4 Comparative Example 5 Cannot make Comparative Example 6 X 〇1.6

-69- 201008991 0 、.參-69- 201008991 0 ,.

Co谳 成型後 硬被蘭 Um) VO in v〇 1 縫硬度 ffi <N ffi (N X <N 成型用硬被覆膜 1 ! 色調b* CN CN (N 1 1 耐擦傷性 < < < 1 ! 鱗硬度 ffi CN P： K Oi 伸長率 (%) OJ cn A 被覆層 8 翠 i ^ § 盈 _ § ® » 鋰龌 β 憝鹅蓉 Φ <π m m ^ 挪：挪 到 oo cn cn *〇 cs f1 i 粒子 (質量％) \o cs 衊 OJ vn cj 塗佈液中之游離輻射線硬化型化合物 Μ g ί s 1 g 簾 Ψ N f | si 喊 25.0 25.0 25.0 m g 裝 麫 S| 雜 4π 卹 翠 S | 运 m O 50.0 o 實施例31 實施例32 實施例33 — 0L_ 201008991 [產業上之利用可能性] 本發明之成型用硬被覆膜由於具有硬被覆層而補強基 材膜之表面硬度，故使用本發明之成型用硬被覆膜成型之 成型體，適合於要求耐擦傷性之家電、汽車銘板用或建材 用構件’行動電話手機、音響、手提錄放音機、ic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。又’在成型加工製造上，成型前將硬被覆層加 工、積層於基材膜之結果，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。 【圖式簡單說明】 無。 【主要元件符號說明】 無。 -71 -Co谳 after hard molding Um) VO in v〇1 seam hardness ffi <N ffi (NX <N hard coating for molding 1 ! hue b* CN CN (N 1 1 scratch resistance <<< 1 ! Scale hardness ffi CN P: K Oi Elongation (%) OJ cn A Coating 8 Cui i ^ § Ying _ § ® » Lithium 龌β 憝Goose Φ <π mm ^ Move: Move to oo cn Cn *〇cs f1 i Particles (% by mass) \o cs 蔑OJ vn cj Free radiation hardening compound in coating solution Μ g ί 1 m Curtain Ψ N f | si Shout 25.0 25.0 25.0 mg 麫S| Example 4 Example 32 Example 03 - 0L_ 201008991 [Industrial Applicability] The hard coating film for molding of the present invention reinforces the base film by having a hard coating layer Since the surface hardness is used, the molded body formed by using the hard coating film for molding of the present invention is suitable for household appliances, automobile nameplates, or building materials for abrasion resistance, mobile phone, audio, portable recorder, and ic recording. Portable devices such as car navigation devices, car satellite navigators, PDA phones, etc., or notebooks, etc. In the manufacturing process, the hard coating layer is processed and laminated on the base film before molding, which contributes to the improvement of productivity and quality stability, and contributes greatly to the industry. [Simplified illustration] None. Description of component symbols] None. -71 -

Claims (1)

201008991 七、申請專利範圍·· 1. 一種成型用硬被覆膜，係具有在基材膜之至少一面上塗 布塗布液使其硬化而成之硬被覆層之成型用硬被覆膜， 上述塗布液至少含有具3以上之官能基之游離輻射線 硬化型化合物、及1及/或2官能基之游離輻射線硬化型 化合物， 上述塗布液所含游離輻射線硬化型化合物中之1及/或 2官能基之游離輻射線硬化型化合物含量爲5質量％以 •上、95質量％以下。 2. 如申請專利範圍第1項之成型用硬被覆膜，其中該基材 膜爲含有共聚合聚酯之雙軸定向聚酯膜》 3. 如申請專利範圍第1或2項之成型用硬被覆膜，其中該 I 塗布液所含游離輻射線硬化型化合物中之至少1種爲胃 胺基之游離輻射線硬化型化合物。 4. 如申請專利範圍第1至3項中任一項之成型用硬被胃 _ 膜，其中該硬被覆層中含有平均粒徑l〇nm以上、3〇Qnm 以下之粒子’且硬被覆層中之該粒子含量爲5質量％ & 上、70質量％以下。 5. 如申請專利範圍第1至4項中任一項之成型用硬被胃 膜，其中該硬被覆層中含有游離輻射線硬化型有機 脂，硬被覆層中之該游離輻射線硬化型有機矽樹 量，相對於該游離輻射線硬化性化合物100質量份爲〇15 質量份以上、1 5質量份以下。 6. —種成型體，係由如申請專利範圍第1至5項中任_ $ -72- 201008991 之成型用硬被覆膜進行成型而形成。 7. 如申請專利範圍第6項之成型體，其中硬被覆層之厚度 爲0.5vm以上、50/zm以下。 8. —種成型用硬被覆膜輥之製造方法，其係具有在基材膜 之至少一面上塗布塗布液使其硬化而成之硬被覆層之成 型用硬被覆膜之輥之製造方法， 其特徵爲上述塗布液至少含有有機溶劑、具3以上之 官能基之游離輻射線硬化型化合物、及1及/或2官能基 〇 之游離輻射線硬化型化合物， 上述塗布液所含游離輻射線硬化型化合物中之1及/或 2官能基之游離輻射線硬化型化合物含量爲5質量％以 k 上、95質量％以下， A 在塗布上述塗布液後’以膜張力50N/m以上、300N/m 以下及溫度40°C以上、120°C以下之條件進行乾燥並硬化 而設置硬被覆層。 ❹ -73- 201008991 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： ίΚ 〇 J\\\201008991 VII. Patent application range 1. A hard coating film for molding, which is a hard coating film for forming a hard coating layer obtained by applying a coating liquid to at least one surface of a base film, and the coating is applied. The liquid contains at least an ionizing radiation-curable compound having a functional group of 3 or more, and an ionizing radiation-hardening compound having 1 and/or 2 functional groups, wherein the coating liquid contains 1 and/or of an ionizing radiation-curable compound; The content of the 2-radical radiation-hardening type compound is 5% by mass or more and 95% by mass or less. 2. The hard coating film for forming according to claim 1, wherein the base film is a biaxially oriented polyester film containing a copolymerized polyester. 3. For molding according to claim 1 or 2 The hard coating film, wherein at least one of the free radiation curing compounds contained in the I coating liquid is a gastric radiation-based free radiation curing compound. 4. The hard-coated stomach film according to any one of claims 1 to 3, wherein the hard coating layer contains particles having an average particle diameter of 10 nm or more and 3 〇 Q nm or less and a hard coating layer The content of the particles in the middle is 5% by mass & upper and 70% by mass or less. 5. The hard coat film for molding according to any one of claims 1 to 4, wherein the hard coating layer contains free radiation hardening type organic fat, and the free radiation line hardening type organic in the hard coating layer The amount of eucalyptus is 15 parts by mass or more and 15 parts by mass or less based on 100 parts by mass of the radical radiation curable compound. 6. A molded body formed by molding a hard coating film for molding according to any of claims 1 to 5 of _ $-72-201008991. 7. The molded article of claim 6, wherein the hard coating layer has a thickness of 0.5 vm or more and 50/zm or less. 8. A method for producing a hard coating film roll for molding, which is a method for producing a hard coating film for forming a hard coating layer obtained by applying a coating liquid to at least one surface of a base film to be cured The coating liquid is characterized in that the coating liquid contains at least an organic solvent, an ionizing radiation-curable compound having a functional group of 3 or more, and an ionizing radiation-curable compound having 1 and/or 2 functional groups, and the coating liquid contains free radiation. The content of the free radiation curing type compound of the 1 and/or 2 functional groups in the linear curing type compound is 5% by mass or more and 95% by mass or less, and A is applied at a film tension of 50 N/m or more after applying the coating liquid. The hard coating layer is provided by drying and hardening under conditions of 300 N/m or less and a temperature of 40 ° C or more and 120 ° C or less. ❹ -73- 201008991 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: ίΚ 〇 J\\\ 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： 201008991 98.10. 1 55. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 201008991 98.10. 1 5 尺寸安定性、厚度不均匀等之觀點，以逐次雙軸拉伸法較 佳。例如使用聚酯膜當作基材膜時之逐次雙軸拉伸法，於 50°C以上、110°C以下向長度方向以滾筒拉伸1.6倍以上、 4.0倍以下’接著使用拉幅烘乾機（tenter)預熱後，在聚酯 之玻璃轉脆溫度一40 °c以上、+ 65 °C以下可向寬度方向拉 伸1.2倍以上、5.0倍以下。再者，於雙軸拉伸後，可在聚 酯熔點之-40°C以上、-l〇°C以下之溫度進行熱固定處理。From the viewpoints of dimensional stability, uneven thickness, etc., the sequential biaxial stretching method is preferred. For example, a sequential biaxial stretching method in which a polyester film is used as a base film is stretched by 1.6 times or more in a longitudinal direction at 50° C. or more and 110° C. or less, and then stretched by 1.6 times or less. After the preheating of the tenter, the glass may be stretched by 1.2 times or more and 5.0 times or less in the width direction at a temperature of 40 ° C or more and + 65 ° C or less. Further, after biaxial stretching, heat setting treatment can be carried out at a temperature of -40 ° C or more and -10 ° C or less of the melting point of the polyester. 本發明所使用之基材膜，爲賦予操作性（如積層後之卷 取性），以膜中含有粒子而使膜表面形成突起較好。膜中所 含有的粒子’如矽石、高嶺石、滑石、碳酸鈣、沸石、礬 土等無機粒子，壓克力、PMMA、耐綸、聚苯乙烯、聚酯、 苯并胍胺（benzoguanamin)甲醛縮合物等耐熱性高分子粒 子。由透明性之觀點，膜中粒子之含量以少量爲宜，如lppm 以上、lOOOppm以下。再由透明性之觀點，以選擇與使用 樹脂之折射率相近之粒子爲宜。又，由於膜因應需要而賦 予各種功能’故可含有耐光劑（防紫外線劑）、色素、防靜 電劑等。 成型用硬被覆膜’如在其不積層硬被覆層之一面實施 印刷加工時’基材膜之總光線穿透率以80%以上，且霧度 以5 %以下爲宜。基材膜之透明性差，則由硬被覆層方看印 刷層時視認性減低。 本發明所使用之基材膜，以單層膜或以積層表面層與 中心層之2層以上之複合膜均可。複合膜有各別設計表面 層與中心層之功能之優點。例如一方面只在厚度較薄之表 -10- 201008991 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，sketone)、苄基、苯偶姻、苯偶 姻甲醚、苯偶姻***、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、2,2-二甲氧基-2 -苯基苯乙酮、1-羥基環己基苯基酮等羰基 ❿ 化合物，硫化四甲基胺硫甲醯基（tetramethylthiuram monosulfide)、二硫化四甲基胺硫甲醯基、硫卩山卩星 (thioxanthene)、2 -氯硫[J山嘎、2 -甲基硫[1山嘎等硫化物， 過氧化苯甲醯基、二（三級丁基）過氧化物等過氧化物等。 ' 此等光聚合引發劑中較佳之例可舉出二（三級丁基）過氧化 • 物等之過氧化物化合物。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100質量份游離輻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，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，硬被覆層因聚合引 發劑而有發生黃變之問題。 於本發明，在上述塗布液中，爲防止製造時之熱聚合 或貯存時之暗反應，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質量份游離輻射線硬化型化合 物之0.005質量份以上、0.05質量份以下較佳。 -23- .201008991 以下較佳。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生產性之減低。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 防止塗布液黏度上升引起塗平性之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，調整塗布液之固 體成分濃度、或有機溶劑種類、界面活性劑種類或配合量， 使塗布液黏度爲〇.5cps以下、300cps以下較宜。 塗布並硬化後之硬被覆層厚度，依成型時之伸長程度 而定，但使成型後之硬被覆層厚度爲0.5jC/m以上、5〇vm 以下較佳。具體而言，成型前之硬被覆層厚度下限以0.6 以上較好、1.0/zm以上更好。又，成型前之硬被覆層 厚度上限以100 # m以下較好、80从m以下更好、60 μ m以 下特好、20//m以下最好。硬被覆層厚度如較〇.6/zm爲薄 時難以獲得硬化性，反之如超過100#m時，表現硬被覆層 硬化不良或因硬化收縮引起卷邊不良之傾向》 Q 如塗布液配合有機溶劑等而須要預乾燥時，塗布在基 材膜上並乾燥之方法，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40°C以上' 120°C以下之溫度條件進行 較好，尤其以下限45°C以上、上限80°C以下更好。未達40 °〇時，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、紋裂等塗膜小缺點，可能使外 觀不良。再者’膜因熱而強烈收縮，熱皺紋使膜之平面性 -27- .201008991 施例26相同，製得成型用硬被覆膜輥。 在基材膜上塗布硬化硬被覆層時，雖無發生皴紋，但 行進之膜發生蛇行，故生產性不適合。由於行進之膜發生 蛇行，故不能製成成型用硬被覆膜。 (比較例6) 於實施例26，除將膜張力變更爲320N/m外，其他與 實施例26相同，製得成型用硬被覆膜輥。 在基材膜上塗布硬化硬被覆層時，行進之膜雖無發生 蛇行，但發生皺紋，故生產性不適合。製得之成型用硬被 覆膜，其塗布外觀良好，但寬方向收縮率不良。所得結果 示如表2。 (實施例31) 於實施例 1，除將形成硬被覆層之塗布液變更爲下述 ' 之塗布液X以外，其他與實施例1相同，得成型用硬被覆 膜。 Φ (塗布液X) •甲基乙基酮 63.62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％ -64- .201008991 (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) •游離輻射線硬化型有機矽化合物 0.86質量％ 聚醚丙烯酸酯 (Tego Chemie Service GmbH 製、TEGO Rad2200N) •光聚合引發劑 1.14質量％ ^ (Ciba Speciality Chemicals 公司製、IRGACURE 1 84) •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。所得結果示如表1。 @ (實施例3 2) 於實施例1，除將形成硬被覆層之塗布液變更爲下述 之塗布液Y以外，其他與實施例1相同，得成型用硬被覆 膜。 (塗布液Y) •甲基乙基酮 64.42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) -65- ,201008991 •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 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) ❹ •游離輻射線硬化型有機矽化合物 0.06質量％ 聚醚丙烯酸酯 (Tego Chemie Service GmbH 製、TEGO Rad2200N) •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。所得結果示如表1。 (實施例33) 於實施例1，除將形成硬被覆層之塗布液變更爲下述 之塗布液Z以外，其他與實施例1相同，得成型用硬被覆 膜。 (塗布液Z) -66-In the base film used in the present invention, in order to impart workability (e.g., take-up property after lamination), it is preferred that the film contains particles to form protrusions on the surface of the film. Particles contained in the film such as vermiculite, kaolinite, talc, calcium carbonate, zeolite, alumina and other inorganic particles, acrylic, PMMA, nylon, polystyrene, polyester, benzoguanamin Heat resistant polymer particles such as formaldehyde condensate. From the viewpoint of transparency, the content of the particles in the film is preferably a small amount, such as 1 ppm or more and 1000 ppm or less. From the viewpoint of transparency, it is preferred to select particles which are close to the refractive index of the resin. Further, since the film imparts various functions as needed, it may contain a light stabilizer (anti-UV agent), a coloring matter, an antistatic agent, and the like. When the hard coating film for molding is subjected to printing processing on one side of the hard coating layer, the total light transmittance of the substrate film is 80% or more, and the haze is preferably 5% or less. When the transparency of the base film is poor, the visibility is lowered when the printed layer is viewed from the hard coating layer. The base film used in the present invention may be a single layer film or a composite film of two or more layers of a layered surface layer and a center layer. Composite membranes have the advantage of individually designing the function of the surface layer and the center layer. For example, it is preferable to add a photopolymerization initiator to the above coating liquid on the one hand only on a thin gauge sheet -10-201008991. 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 (sketone), benzyl, benzoin, benzophenone Margin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methyl benzoic acid methyl ester, p-isopropyl-α-hydroxyphenyl isobutyl ketone, α-hydroxyphenylisobutyl ketone, 2,2-dimethyl a carbonyl ruthenium compound such as oxy-2-phenylacetophenone or 1-hydroxycyclohexyl phenyl ketone, tetramethylthiuram monosulfide, tetramethylammonium sulfonyl disulfide, sulfur Peroxidation of thioxanthene, 2-chlorosulfur [J Hawthorn, 2-methylsulfuric acid [1 sulphate, benzoyl peroxide, bis(tributyl) peroxide] Things and so on. A preferred example of such a photopolymerization initiator is a peroxide compound such as a di(tertiary butyl) peroxide. These photopolymerization initiators may be used singly or in combination of two or more kinds. The amount of the photopolymerization initiator to be added is preferably 0.01 parts by mass or more and 15 parts by mass or less per 100 parts by mass of the radical radiation-curable compound contained in the coating liquid, and is not only slow in reaction but also in productivity when used in a small amount. Poor, because the unreacted material remains, sufficient surface hardness and scratch resistance cannot be obtained. On the other hand, if the amount of addition is too large, the hard coating layer may cause yellowing due to polymerization initiator. In the present invention, in the above coating liquid, in order to prevent thermal reaction during production or dark reaction during storage, conventional thermal polymerization inhibition such as hydroquinone, hydroquinone monomethyl ether or 2,5-tributylhydroquinone is added. The agent is suitable. The amount of the thermal polymerization inhibitor to be added is preferably 0.005 parts by mass or more and 0.05 parts by mass or less per 100 parts by mass of the radical radiation-curable compound contained in the coating liquid. -23- .201008991 The following is preferred. When the solid content concentration of the coating liquid is adjusted to 5% by mass or more, it is possible to suppress the drying time after application from being elongated and the productivity is lowered. 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 an increase in the viscosity of the coating liquid and the deterioration of the coating appearance due to the coating. Further, from the viewpoint of the appearance of the coating, the solid content concentration of the coating liquid, the type of the organic solvent, the type of the surfactant, or the blending amount are adjusted so that the viscosity of the coating liquid is preferably 0.5 cps or less and 300 cps or less. The thickness of the hard coating layer after application and hardening depends on the degree of elongation at the time of molding, but the thickness of the hard coating layer after molding is preferably 0.5 jC/m or more and 5 〇 vm or less. Specifically, the lower limit of the thickness of the hard coating layer before molding is preferably 0.6 or more, more preferably 1.0/zm or more. Further, the upper limit of the thickness of the hard coating layer before molding is preferably 100 #m or less, more preferably 80 or less, more preferably 60 μm or less, and most preferably 20/m or less. When the thickness of the hard coating layer is thinner than .6/zm, it is difficult to obtain hardenability. On the other hand, if it exceeds 100#m, it tends to cause hardening of the hard coating layer or the tendency of curling due to hardening shrinkage. Q If the coating liquid is organic When a solvent or the like is required to be pre-dried, 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 ° C or more and 120 ° C or less, and particularly preferably 45 ° C or higher and 80 ° C or lower. When the temperature is less than 40 °C, the problem of whitening may occur in addition to the fact that the organic solvent contained in the coating liquid cannot be sufficiently removed. On the other hand, when the temperature exceeds 120 °C, small coating defects such as minute coating loss, minute repulsion, and cracking are likely to occur, which may cause poor appearance. Further, the film was strongly shrunk by heat, and the heat wrinkles made the film flatness -27-201008991 Example 26, and a hard coating roll for molding was obtained. When the hardened hard coating layer is applied onto the base film, the crepe does not occur, but the film that travels is meandering, so that productivity is not suitable. Since the film that travels is meandering, it is impossible to form a hard coating film for molding. (Comparative Example 6) A hard coating roll for molding was obtained in the same manner as in Example 26 except that the film tension was changed to 320 N/m. When the hardened hard coating layer is applied onto the base film, the film that travels does not wander, but wrinkles occur, so that productivity is not suitable. The hard coating film for molding obtained was excellent in coating appearance, but was inferior in shrinkage in the width direction. The results obtained are shown in Table 2. (Example 31) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coating layer was changed to the coating liquid X of the following. Φ (coating liquid X) • methyl ethyl ketone 63.62% 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) • Three-stretch Propylene glycol diacrylate 5.73 mass% (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group number 2) • dimethylamine ethyl methacrylate 5.72% by mass -64-.201008991 (manufactured by Kyoeisha Chemical Co., Ltd.) LIGHT ESTER DM, functional group number 1) • 11.45 mass% of vermiculite particles (manufactured by Nissan Chemical Industries, Ltd., MEK-ST-L, solid content ratio: 30%, average particle diameter: 50 nm) • Free radiation hardening type organic germanium Compound 0.86 mass% Polyether acrylate (manufactured by Tego Chemie Service GmbH, TEGO Rad 2200N) • Photopolymerization initiator 1.14% by mass ^ (manufactured by Ciba Speciality Chemicals, IRGACURE 1 84) • Organic lanthanide surfactant 0.03 mass% (Dow The hard coating film for molding obtained by Corning Toray Co., Ltd., DC57) 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 3 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 hard coating layer was changed to the coating liquid Y described below. (Coating liquid Y) • Methyl ethyl ketone 64.42% 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) -65- , 201008991 • 3.73 mass% of propylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional group 2) • 5.7% by mass of dimethylamine ethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) LIGHT ESTER DM, functional group number 1) • 11.45 mass% of vermiculite particles (manufactured by Seiko Chemical Industry Co., Ltd., MEK-ST-L, solid content ratio: 30%, average particle diameter: 50 nm) 游离 • Free radiation hardening organic矽 compound 0.06 mass% polyether acrylate (manufactured by Tego Chemie Service GmbH, TEGO Rad 2200N) • Photopolymerization initiator 1.14% by mass (manufactured by Ciba Speciality Chemicals, IRGACURE 184) • Organic lanthanide surfactant 0.03 mass% (Dow Corning) The hard coating film for molding obtained by Toray Co., Ltd., DC57) 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 33) A hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coating layer was changed to the coating liquid Z described below. (coating solution Z) -66-
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