201200352 六、發明說明： 【發明所屬之技術領域] 本發明係有關一種轉印薄膜，其係在例如合成樹脂系 基材 '木質系基材 '無機質系基材、金屬系基材等之各種 被轉印基材之表面上，用來轉印形成至少含有保護層的轉 印層。 【先前技術】 先前’在物品的裝飾方法方面，係利用使用到轉印薄 膜的轉印法’該轉印薄膜係在合成樹脂系基材、木質系基 材、無機質系基材、金屬系基材等各種被轉印基材的表面 上’可簡便地形成保護層等。該轉印法，係在由紙、或熱 塑性樹脂薄膜等所組成的基材薄膜上，將由硬度或抗溶劑 性等之表面物性優異的樹脂組成物所成的保護層設置成可 剝離的狀態，進一步可依照需要設置圖案層、接著層等（ 以下，該等與前述保護層合稱爲轉印層），製作轉印薄膜 ’將該轉印薄膜之轉印層面按壓於基材（被轉印基材）之表 面’或者於射出成形模具內預先設置轉印薄膜，藉由塡充 射出樹脂’而將轉印薄膜之轉印層與被轉印基材或者射出 樹脂接著後，藉由在轉印層與基材薄膜之界面剝離，去除 基材薄膜，而製造以轉印形成轉印層於被轉印基材上爲目 的之加飾品等之方法。近年來，對汽車內裝構件、家電構 件、電子設備外殼等之加飾法有極盛行的硏究。 201200352 上述保護層方面，爲了在 如表面硬度、抗磨損性、抗擦 等優異的表面物性，一般使用 硬化型樹脂等之硬化型樹脂， 合物與異氰酸酯化合物之反應 酸酯系樹脂，或分子中具有自 線硬化型（ionizing radiation 已經有各種使用（參照例如專fl 又，在使用作爲對家電構 時，除了該表面硬度等之諸物 痕（finger marks)、皮脂等油污 在針對抗指紋性的塗膜領 如在硬塗覆劑中調配氟系界面 拒水化的技術（參照例如專利 基的聚合性單體與具有聚氟烷 技術（參照例如專利文獻3)等 供抗指紋污染性於硬塗覆劑中 術’均是利用塗膜後氟基偏在 在轉印薄膜中的保護層係如前 離的狀態，亦即因空氣界面不 轉印後成爲保護層表面的面， 問題。 轉印後製品之表面上提供例 傷性、抗溶劑性 '抗藥品性 熱硬化型樹脂或活性能量線 具體言之，使用了屬聚醇化 產物的二液硬化型聚胺基甲 由基聚合性雙鍵的電離放射 curing)丙烯酸酯系樹脂等係 J文獻1)。 件或電子設備外殼等之加飾 性以外’亦謀求保護免於指 的功能（稱爲抗指紋性）。 域中已知的技術方面，有例 活性劑，將所得硬化膜予以 文獻2)，或使用具有長鏈烷 基的聚合性單體之共聚物的 利用來自氟的高拒水性，提 的技術。該等使用到氟的技 於空氣界面的性質。但是， 述在基材薄膜上設置成可剝 存在’故氟基無法偏在於在 而有無法獲得抗指紋性等的 201200352 [先行技術文獻] [專利文獻] [專利文獻1]日本特開平7-314995號公報 [專利文獻2]日本特開平10-110118號公報 [專利文獻3]日本特開2010-24283號公報 【發明內容】 [發明欲解決之課題] 本發明欲解決課題，係提供一種熱轉印用薄膜，其係 使用硬化性樹脂作爲保護層的轉印薄膜，其中所得保護層 之表面物性，特別是抗指紋性優異。 [解決課題之手段] 本發明人等’藉由添加環氧化植物油（甲基）丙烯酸酯 作爲硬化性樹脂層’亦即作爲自由基聚合性樹脂組成物層 之成分，而解決了上述課題。 亦即本發明係提供一種熱轉印用薄膜，其係在基材薄 膜上’具有依照自由基聚合性樹脂組成物層與加飾層之順 序積層的轉印層’其中該自由基聚合性樹脂組成物層含有 含自由基聚合性不飽和基之（甲基）丙烯酸樹脂及環氧化植 物油（甲基）丙烯酸酯。 [發明效果] 藉由本發明可獲得表面物性特別是抗指紋.性優異的加 飾成形品。 201200352 【實施方式】 (基材薄膜） 本發明使用的基材薄膜並無特別限定，可使用周知之 熱轉印用基材薄膜。具體言之，較佳爲使用例如聚對酞酸 乙二酯（PET)、聚萘二甲酸乙二酯（PEN)、聚醯胺6、 66(PA6,PA66) >聚醯亞胺（P I)、聚乙烯醇（P V A )等之耐熱 樹脂製薄膜。其中以PET樹脂製薄膜，因成本、美麗性優 異故最佳。基質樹脂薄膜1之厚度較佳爲20至125 μπι，若 考慮到對立體形狀之追隨（t r a c k i n g)性，則以3 5至7 5 μ m較 佳。 在該基材薄膜與後述轉印層之間，亦可設置脫模層。 脫模層的功能係將轉印於射出成形體的轉印層及基材薄膜 予以脫模的層’其中該射出成形體係屬被轉印基材或者射 出樹脂之成型物。脫模層被要求有與轉印層之脫模性，但 在操作之際，亦被要求基材薄膜與轉印層不致脫模程度之 與轉印層的接著性。 脫模層方面，可爲通常所使用之物，可使用聚矽氧樹 脂系、氟樹脂系、纖維素衍生物樹脂系、脲樹脂系、聚烯 烴樹脂系、三聚氰胺樹脂系等之脫模劑。例如，在使用 PET樹脂製薄膜作爲基質樹脂薄膜i的情形，較佳爲使用具 適度脫模性的聚矽氧樹脂系脫模劑。脫模層2可使用輥塗 布機等進行塗布，其厚度較佳爲Ο.ΟΙμπι至5μιη。 201200352 (轉印層） 在本發明之熱轉印用薄膜中，轉印層係指至少具有下 述之層：自由基聚合性樹脂組成物層，其爲轉印於被轉印 基材上所得轉印體之成爲最表層之層；及加飾層，其係在 該自由基聚合性樹脂組成物層與被轉印基材之間。 在該基材薄膜上，依照自由基聚合性樹脂組成物層與 加飾層之順序進行積層設置，使得加飾層成爲在該自由基 聚合性樹脂組成物層與被轉印基材之間。又，除了自由基 聚合性樹脂組成物層與加飾層之外，亦可設置接著層或可 隱蔽被轉印基材表面之凹凸的中間層等層。 (轉印層 自由基聚合性樹脂組成物層） 本發明使用的自由基聚合性樹脂組成物層，含有含自 由基聚合性不飽和基的（甲基）丙烯酸樹脂與環氧化植物油（ 甲基）丙烯酸酯。 (環氧化植物油（甲基）丙烯酸酯） 環氧化植物油（甲基）丙烯酸酯係指在不飽和植物油之 雙鍵上，以過乙酸、過苯甲酸進行環氧化的環氧化植物油 環氧基上，使（甲基）丙烯酸開環加成聚合而成的化合物。 本發明中，植物油係指在甘油與脂肪酸之三酸甘油_ 中，至少一個脂肪酸爲具有至少一個碳-碳不飽和鍵的脂 肪酸之三酸甘油酯之物，作爲該等植物油的代表性化合物 可例舉大麻籽油（hempseed oil)、亞麻仁油、蘇子油 (perilla oil)、臭氣油（oiticica oil)、橄欖油、可可亞油 201200352 (cacao oil)、木棉子油（kapok oil)、榧子油（kaya oil)、芥 子油（mustard oil)、杏仁油（apric〇t kernel oil)、桐油 (tung oil)、石栗油（candlenut oil)' 核桃油（walnut oil)、 罌栗油（poppy oil)、芝麻油、紅花油、日本蘿蔔種籽油 (Japanese radish seed o.i 1)、大豆油、大風子油 (chaulmoogra oil)、椿油（camellia oil)、玉米油（maize 〇 i 1)、油菜籽油、皂腳油（n i g e r s e e d o i 1)、米糠油、棕櫚 油（palm oil)、蔑麻油、葵花油（sun flower oil)、葡萄子油 (grape seed oil)、巴旦可仁油（almond oil)、松子油、棉好 油、椰子油（coconut oil)、落花生油、脫水蓖麻油等。 環氧化植物油（甲基）丙烯酸酯方面，具體言之，可例 舉環氧化大豆油丙烯酸酯（Sartomer化藥公司製CN111、 UCB 公司製 EBECRYL8 6 0、Cognis 公司製 Photomer 3005F)、環氧化亞麻仁油丙稀酸醒（Cognis公司製Photomer 3 0 8 2)等。 相對於自由基聚合性樹脂組成物之總固體含量，該環 氧化植物油（甲基）丙烯酸酯較佳爲添加〇·1至20重量％，最 佳爲1至10重量％之範圍。雖依照自由基聚合性樹脂組成 物之組成而定，但不足〇. 1 %時’抗指紋性能力恐宥不足’ 在超過20%的量，自由基聚合性樹脂組成物被塑化，塗膜 硬度恐會降低。 (含自由基聚合性不飽和基的（甲基）丙烯酸樹脂） 本發明使用的含自由基聚合性不飽和基的（甲基）丙嫌 酸樹脂並無特別限定’可使用以周知方法獲得之（甲基）丙 201200352 稀酸樹脂。具體言之，可例舉將甲基丙烯酸甲酯、甲基丙 稀酸乙酯、甲基丙烯酸丁酯 '甲基丙烯酸羥乙酯、甲基丙 稀酸環己酯、甲基丙烯酸乙基己酯、丙烯酸甲酯、丙烯酸 乙酯、丙烯酸丁酯、丙烯酸羥基乙酯、丙烯酸環己酯、丙 嫌酸乙基己酯、甲基丙烯酸、丙烯酸、丙烯腈、甲基丙烯 酸腈等之（甲基）丙烯酸系單體予以單獨或者共聚所得的（ 甲基）丙烯酸樹脂’或者以該（甲基）丙烯酸酯類作爲主成分 ’依照需要添加與該等可共聚的具有聚合性雙鍵的單體， 可例舉例如添加乙烯、丁二烯、異戊二烯、乙酸乙烯酯、 丙酸乙稀酯、丁酸乙稀醋、苯乙嫌、α -甲基苯乙嫌、乙 嫌甲苯、二乙烯苯、Ν -環己基順丁烯二醯亞胺、Ν -乙 基順丁烯二醯亞胺、Ν -苯基順丁烯二醯亞胺等作爲共聚 合成分的（甲基）丙烯酸樹脂。 該（甲基）丙烯酸樹脂可藉由通常的方法，將該（甲基） 丙烯酸系單體或者具有可共聚的聚合性雙鍵的單體進行聚 合而獲得。 導入聚合性不飽和基於該（甲基）丙烯酸樹脂的方法， 可例舉例如： 預先調配作爲該共聚成分的丙烯酸或甲基丙烯酸等之 含羧基聚合性單體，或甲基丙烯酸二甲基胺基乙酯、或二 甲基胺基丙基丙烯醯胺等之含胺基聚合性單體，予以共聚 ’獲得具有羧基或胺基的該共聚物，接著，使該羧基或胺 基與甲基丙烯酸環氧丙酯等之具有環氧丙基及聚合性不飽 和基的單體反應的方法； 201200352 預先調配作爲共聚成分之甲基丙嫌酸2_經基乙酯、丙 嫌酸2 -羥基乙酯等之含羥基單體’使之共聚，獲得具有羥 基的該共聚物’接著使該羥基與異氰酸酯乙基甲基丙烯酸 醋等之具有異氰酸酯基及聚合性不飽和基的單體反應的方 法； . 預先調配作爲該共聚合成分之甲基丙烯酸環氧丙酯等 之含環氧丙基聚合性單體，予以共聚，獲得具有環氧丙基 的該共聚物，接著使環氧丙基與丙烯酸或甲基丙烯酸之含 竣基聚合性單體反應的方法； 在聚合時’將硫代羥乙酸作爲鏈轉移劑使用，於共聚 物末端導入羧基’於該羧基上將甲基丙烯酸環氧丙酯等之 具有環氧丙基與聚合性不飽和基的單體予以反應的方法； 聚合引發劑方面，係使用偶氮雙氰戊酸等之含羧基偶 氮引發劑，於共聚物中導入羧基，於該羧基上將甲基丙烯 酸環氧丙酯等之具有環氧丙基與聚合性不飽和基的單體反 應的方法等。 其中，最簡便且較佳的方法是：預先將丙烯酸或甲基 丙烯酸等之含羧基單體或者甲基丙烯酸二甲基胺基乙酯或 二甲基胺基丙基丙烯醯胺等之含胺基單體共聚，使其羧基 或者胺基與甲基丙烯酸環氧丙酯等之具有環氧丙基及聚合 性不飽和基的單體反應的方法； 或者預先調配作爲該共聚合成分之甲基丙烯酸環氧丙 酯等之含環氧丙基聚合性單體，予以共聚，獲得具有環氧 -10 - 201200352 丙基的該共聚物，接著使環氧丙基與丙烯酸或甲基丙烯酸 之含羧基聚合性單體反應的方法。 該含有自由基聚合性不飽和基的（甲基）丙烯酸樹脂， 較佳爲含有自由基聚合性樹脂組成物之總固體含量之1 0至 99.9重量％，最佳爲40至99.9重量％之範圍。不足10%時， 由於添加在常溫下爲液狀的環氧化植物油（甲基）丙烯酸酯 ，表面恐有黏性（t a c k)殘存。 (其他成分光聚合引發劑） 以活性能量線使本發明之熱轉印用薄膜硬化的情形， 較佳爲使用光聚合引發劑於該自由基聚合性樹脂組成物層 。光聚合引發劑之例方面，可例舉例如二乙氧基乙醯苯、 1-羥基環己基-苯酮等之乙醯苯系化合物；安息香、安息 香異丙醚等之安息香系化合物；2,4,6 -三甲基安息香二苯 膦氧化物等之醯基膦氧化物系化合物；二苯酮、鄰苯甲醯 基苯甲酸甲基-4-苯基二苯酮等之二苯酮系化合物；2,4_二 甲基9-氧硫卩ill嘎等之9-氧硫灿唱系化合物；4,4’-二乙基胺 基二苯酮等之胺基二苯酮系化合物；聚醚系順丁烯二醯亞 胺羧酸酯化合物等，該等可合倂使用。相對於自由基聚合 性樹脂組成物之總固體含量，光聚合引發劑之使用量爲 0.1至20質量％，較佳爲0.5至15質量％。在光增感劑方面， 可例舉例如三乙醇胺、4-二甲基胺基苯甲酸乙酯等之胺類 。再者，已知有將苄基毓鹽或苄基吡啶鑰鹽 (benzylpyridinium)鹽、芳基鏡鹽等之鑰鹽作爲光陽離子引 201200352 發劑，亦可使用該等之引發劑，亦可倂用上述光聚合引發 劑。 (熱聚合引發劑） 又，在將本發明之熱轉印用薄膜進行熱硬化的情形時 ，亦可使用熱聚合引發劑於該自由基聚合性樹脂組成物層 上。熱聚合引發劑之例，可例舉過氧化氫、三級丁基氫過 氧化物、二-三級丁基過氧化物、二異丙苯（cumyl)氫過氧 化物等各種過氧化物；過硫酸鉀、過硫酸鈉或過硫酸銨等 各種過硫酸鹽；偶氮雙異丁腈、卜[(1-氰基-1-甲基乙基） 偶氮]甲醯胺、2,2’-偶氮雙[2-(5 -甲基-2-咪唑啉-2-基）丙烷 ]之二鹽酸鹽、2,2’-偶氮雙[2-(2-咪唑啉-2-基）丙烷]或其二 鹽酸鹽、2,2’ -偶氮雙[2-(4,5,6,7-四氫-111-1,3-二氮呼 (azepine)-2-基）丙烷]之二鹽酸鹽、2,2’-偶氮雙[N-(4-胺基 苯基）-2-甲基丙酮脒]之二鹽酸鹽或2,2’-偶氮雙（2-甲基丙 醯胺）之二鹽酸鹽等之各種偶氮系引發劑。尤其是在真空 成形法之情形’因對薄膜供予充分的熱，並瞬間成形，故 可適當使用熱聚合引發劑。 (異氰酸酯化合物） 又’在使本發明之熱轉印用薄膜熱硬化時，較佳爲作 爲該含有自由基聚合性不飽和基的（甲基）丙烯酸樹脂，係 選擇具有羥基的樹脂，且藉由添加異氰酸酯化合物，可導 入與來自自由基聚合性不飽和'基之交聯構造相異的胺基甲 酸酯交聯構造。 -12 - 201200352 前述含有自由基聚合性不飽和基，且具有羥基的（甲 基）丙烯酸樹脂方面，可例舉例如藉由下述兩種方法所獲 得的（甲基）丙烯酸樹脂：預先將丙烯酸或甲基丙烯酸等含 羧基單體予以共聚，使其羧基與甲基丙烯酸環氧丙酯等具 有環氧丙基與聚合性不飽和基的單體反應的方法；或預先 調配作爲該共聚成分之甲基丙烯酸環氧丙酯等之含環氧丙 基聚合性單體’予以共聚，獲得具有環氧丙基的該共聚物 ’接著，藉由使環氧丙基與丙嫌酸或甲基丙嫌酸之含殘基 聚合性單體反應的方法’或者將丙烯酸羥基乙酯等之具有 羥基的（甲基）丙烯酸酯共聚的（甲基）丙烯酸樹脂等。 異氰酸醋化合物方面，可例舉例如以二異氰酸甲苯酯 、—苯基甲院_4,4’·一異氰酸醋等芳香族二異氰酸醋類； —異氰酸間-本一甲醋、一異氰酸α，α，α，，α，_四甲基_間-苯 一甲醋寺之一異氰酸方院醋類作爲主原料的聚異氰酸醋、 一異氰酸四亞甲醋、一異氰酸1，5 -五亞甲醋、二里氰酸 1，6-六亞甲酯、二異氰酸2,2,4·(或2,4,4_)三甲基_丨，6_六亞 甲醋、離fee酸異氰醋、~異氰酸異佛爾酮醋、氫化二甲 苯二異氰酸酯、氫化二苯基甲烷二異氰酸酯、ls4_二異氰 酸環己酯、1，3-雙（二異氰酸酯甲基）環己烷、4,4，_二環己 基甲院一異氰酸醋等之fl曰肪族一異氰酸酯；由脂肪族二異 氰酸酯所得的屬脂肪族聚異氰酸酯的脲甲酸酯 (allophanate)型聚異氰酸酯、雙脲型聚異氰酸酯、加合物 型聚異氰酸醋及異三聚氰酸醋型聚異氰酸醋，可.適當地使 用任一種。 -13 - 201200352 此外，該聚異氰酸酯方面，亦可使用以各種封鎖劑封 端化的所謂封端聚異氰酸酯化合物。封鎖劑方面，可使用 例如甲醇'乙醇、乳酸酯等之醇類；酚、水楊酸酯等之含 酚性羥基化合物類；ε -己內醯胺、2 -吡咯啶酮等之醯胺類 ;丙酮肟、甲乙酮肟等之肟類；乙醯乙酸甲酯、乙醯乙酸 乙酯、乙醯基丙酮等之活性亞甲基化合物類等。藉由使用 封端聚異氰酸酯化合物，對於形成後述自由基聚合性樹脂 組成物層時的塗料，亦可使用如醇之含羥基溶劑。 (其他成分） 又，自由基聚合性樹脂組成物層亦可添加無機或者金 屬化合物、有機微粒等。無機或者金屬化合物方面，可例 舉二氧化矽、二氧化矽凝膠、二氧化矽溶膠、聚矽氧、蒙 脫石、雲母、氧化鋁、氧化鈦、滑石、硫酸鋇、硬脂酸鋁 、碳酸鎂、玻璃珠等。又，亦可使用將該無機或者金屬化 合物經有機處理的有機二氧化矽溶膠、丙烯酸改性二氧化 矽、奈米黏土（cloisite)等。有機微粒方面，可例舉例如聚 乙烯樹脂、丙烯酸樹脂、苯乙烯樹脂、氟樹脂、三聚氰胺 樹脂、聚胺基甲酸酯樹脂、聚碳酸酯樹脂及酚樹脂等之微 粒。該等可單獨使用，亦可倂用複數種。其他在無損於本 發明之效果的範圍內，亦可添加廣泛使用之添加劑，例如 紫外線吸收劑、均平劑、抗結塊劑等。 本發明使用的自由基聚合性樹脂組成物層之厚度方面 ，就被轉印基材或者射出成形體之表面保護及塗膜性之觀 點觀之，較佳爲1至50μιη，更佳爲3至40μιη。 "14 - 201200352 (加飾層） 加飾層中可使用廣泛使用之印刷油墨或塗料，可使用 凹版印刷、套版印刷、網版印刷、噴墨印刷、熱轉印印刷 等而形成。加飾層之乾燥膜厚較佳爲0.5至15 μιη,更佳爲1 至7μπι。又，關於無圖案（pattern)的著色層、或無色的清 漆樹脂層’亦可以塗布形成。 又，在印刷時的印刷花紋，只要是可產生版或者可印 字的圖形或文字，則任何種類印刷花紋均可。又亦可爲實 體（solid)版。 使用於印刷油墨或塗料的著色材方面，較佳爲使用周 知的有機顔料或者無機顏料進行印刷。 該有機顏料方面，可例舉喹吖酮（quinacrUone)系顏 料、酞菁系顏料、陰丹士林（indanthrene)系顏料、菲系顔 料、酞酮（phthalon)系顏料、二噚阱系顏料、異吲哚啉酮系 顔料、次甲基.偶氮次甲基系顏料、二酮基吡略并吡咯系 顏料、偶氮色料（azolake)顏料系顏料 '不溶性偶氮系顏料 、縮合偶氮系顏料等。 又’無機顏料方面，可例舉碳黑、氧化鐵系、氧化欽 系等之無機顏料；鋁粉、青銅（bronze)粉等之金屬粉顔料 :氧化鈦被覆雲母等之真珠光澤顏料等。 該油墨所含有的清漆用樹脂並無特別限定，不過可使 用例如丙烯酸樹脂系、聚胺基甲酸酯樹脂系、聚酯樹脂系 、乙烯樹脂系（氯乙烯、乙酸乙烯酯 '氯乙烯-乙酸乙稀醋 -15 - 201200352 共聚樹脂）、氯化烯烴樹脂系、乙烯-丙烯酸樹脂系 '石油 系樹脂系、纖維素衍生物樹脂系等周知的油墨。 又’油墨中所含有的有機溶劑方面，只要不侵入自由 基聚合性樹脂組成物層或者後述剝離性薄膜，則可無特別 限制的使用，具體例方面，可例舉例如甲苯、二甲苯、環 己烷、正己烷或者礦油精（mineral spirit)等之烴系有機溶 劑；乙酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸異丁酯、乙 二醇單甲醚乙酸酯、丙二醇單甲醚乙酸酯、二乙二醇單丁 醚乙酸酯或者乙酸·戊酯等之酯系有機溶劑；正丁醚、二噚 烷圜（diox ane)、乙二醇單甲醚、乙二醇單丁醚或者二乙二 醇等之醚系有機溶劑；丙酮、甲乙酮、甲異丁酮、甲基胺 基酮、二異丁酮或者環己酮等之酮系有機溶劑；N -甲基吡 略 Π定嗣等之含氣系 * 「Swasolve 310、Swasolve 1000、 Sw as olve 1500」 〔Cosmo石油股份有限公司製〕等之芳香 族石油溶劑系。該等有機溶劑可單獨使用，亦可倂用二種 以上。 在印刷油墨或塗料中，除了基材樹脂與著色劑之外， 亦可依照需要含有塑化劑、界面活性劑、抗氧化劑、紫外 線吸收劑、消光劑、溶劑等。 (熱轉印用薄膜之製造方法） 本發明之熱轉印用薄膜，最佳是在設置有該自由基聚 合性樹脂組成物層的基材薄膜上直接印刷或塗膜加飾層的 方法。又’亦可設置中間（底塗）層以確保該自由基聚合成 樹脂層與加飾層的層間密接性。 -16 - 201200352 在該基材薄膜上設置該自由基聚合性樹脂組成物層的 方法或者設置該加飾層的方法方面並無特別限定，例如可 適虽使用凹版印刷法、冑版印刷法、凹版套版印刷法、膠 版印刷法、網版印刷法等各種印刷方法，或凹版塗布法、 微凹版塗布法、輥塗布法、桿塗布（rod coating)法、滾塗 法、刀塗布法、氣刀塗布法 '切角塗布法、模塗布法、唇 塗布法、流動塗布法、浸漬塗布法、噴灑塗布法等各種周 知的塗膜方法。特別是可藉由凹版印刷、套版印刷、網版 印刷、噴墨印刷等形成加飾層，而爲了獲得高畫質影像， 則較佳爲凹版印刷。加飾層之乾燥膜厚較佳爲〇 5至1 5 μπι ，更佳爲1至7μηι。 又’藉由乾式積層法’將設置有該自由基聚合性樹脂 組成物層的基材薄膜與設置有該加飾層的任意剝離性薄膜 予以重疊’以使該聚合性樹脂層與該裝飾層呈相對向，藉 由乾式積層法（dry lamination)貼合，並以轉印的方法製 造。 因乾燥、加熱加壓而貼合的溫度並無特別限定，較佳 爲一面調整使用之基材薄膜之耐熱溫度等，一面進行。 已製造的熱轉印用薄膜亦可依照需要進行老化（aging) ，以提高層間密接性等》 (熱轉印用薄膜 膜厚） 本申請案之熱轉印用薄膜全體膜厚，因根據熱轉印方 法，故無特別限定，但就對被轉印基材之形狀追隨性的觀 點觀之，較佳爲21·5至200μιη’更佳爲30至150μιη。 -17 - 201200352 (接著劑層） 其他’在無損於本發明效果之範圍內，亦可進一步積 層任意之層。例如將本發明之熱轉印用薄膜與被轉印基材 黏貼的情形’較佳爲在加飾層之與被轉印基材連接的面上 設置接著層或黏著層。接著層或黏著層係目的在提高與黏 附體之接著力而供予之層，爲接著劑或黏著劑皆無妨，可 適當選擇接著於樹脂薄膜與黏附體的材質之物。 例如接著劑方面，可例舉例如丙烯酸樹脂、胺基甲酸 酯樹脂、胺基甲酸酯改性聚酯樹脂、聚酯樹脂、環氧樹脂 、乙烯-乙酸乙烯酯共聚樹脂（EVA)、氯乙烯樹脂、氯乙 烯-乙酸乙烯酯共聚樹脂、天然橡膠、SBR、NBR '聚砂氧 橡膠等合成橡膠等’並可使用溶劑型或無溶劑型之物。 又’在黏著劑方面，只要是在熱成形的溫度下，具有 黏性之物即可，可例舉例如丙烯酸樹脂、異丁稀橡膠樹脂 、苯乙烯-丁二烯橡膠樹脂、異戊二烯橡膠樹脂、天然橡 膠樹脂、聚矽氧樹脂等溶劑型黏著劑；或丙烯酸乳液樹脂 、苯乙烯丁二烯乳膠樹脂、天然橡膠乳膠樹脂、苯乙烯_ 異戊二烯共聚物樹脂、苯乙烯-丁二烯共聚物樹脂、苯乙 烯-乙烯-伸丁基共聚物樹脂、乙烯-乙酸乙烯酯樹脂、聚乙 烯醇、聚丙烯醯胺、聚乙烯甲醚等無溶劑型黏著劑等。 在本發明之熱轉印用薄膜設置有該接著層或黏著層的 情形時’可在設置有該自由基聚合性樹脂組成物層與加飾 層的薄膜上直接印刷或者塗膜，或重疊該自由基聚合性樹 -18 - 201200352 脂組成物層與該加飾層，以使其相對向，並以乾燥積層予 以轉印的方法等而獲得。在後者之情形，較佳爲將具有接 著層的加飾層轉印’但亦可將加飾層轉印後設置接著層。 (熱轉印方法） 本發明之熱轉印用薄膜可使用於周知轉印方法。具體 言之’可特別適合使用本發明之熱轉印用薄膜於下列方法 :射出成形同時轉印法’該方法係因應需要，將經預備成 形之熱轉印用薄膜設置於凹鑄模的表面，關閉兩鑄模，自 射出孔射出熔融樹脂至兩鑄模間的模孔（成形窩洞）內，使 射出樹脂冷卻固化後，開啓兩鑄模，將成形品與密接於此 成形品的熱轉印用薄膜自鑄模取出，僅剝離基體薄膜，獲 得於被轉印基材上轉印形成有轉印層的加飾品之；或真空 成型同時黏貼法，該方法係在已成形之被轉印基材上方， 載置熱轉印用薄膜，以使轉印層面向被轉印基材側，並將 薄膜加熱至軟化溫度以上後，在真空下，不使用模具而使 用被轉印基材來成形’同時直接黏貼於被轉印基材上等； 或硏光（lapping)同時轉印法等之在熱轉印時，拉伸成熱 轉印用薄膜’對加諸變形的立體形狀之成形轉印方法。但 是’對熱打印（hot stamp)等，拉伸成熱轉印用薄膜，不增 加變形的轉印法’亦可使用本發明之熱轉印用薄膜。 (活性能量線照射） 以活性能量線等將已轉印本發明熱轉印用薄膜的加飾 品之自由基聚合性樹脂組成物層予以硬化。活性能量線通 -19 - 201200352 常較佳爲使用可視光或紫外線。特別以紫外線較佳。紫外 線源方面’可使用太陽光線、低壓汞燈'高壓汞燈、超高 壓汞燈、碳弧燈、金屬鹵素燈、氙燈等。又，倂用熱時的 加熱源方面’可使用熱風、近紅外線等周知之熱源。 此時的照射量方面，較佳爲可完全使硬化性樹脂層硬 化的照射量，具體言之’較佳爲250mJ/Cm2至3 000mJ/cm2 之範圍。尤其是爲了使移動至與加飾層之界面的自·由基反 應性稀釋劑或自由基聚合性寡聚物等充分硬化，使與被轉 印基材之密接性提高，則更佳爲l〇〇〇mj/cm2至3 0 00mJ/cm2 之範圍。 剝離該基材薄膜的時機，可在照射該活性能量線之前 或之後。 (被轉印基材） 可轉印本發明之熱轉印用薄膜的被轉印基材並無特別 限定’可使用樹脂、金屬、玻璃、木 '紙等之各種形狀物 ’該形狀物可藉由塗裝、鍍敷、刮痕（scratch)等之常用加 飾法進行加飾。 又，被轉印基材之黏附面的材質與使用於本發明之熱 轉印用薄膜的熱塑性樹脂或油墨黏合劑之材質，若爲可熱 接著或者熱熔融之材質彼此間，則密接性更優異較佳。例 如被轉印基材之黏附面之材質爲丙烯酸系樹脂或苯乙烯系 之樹脂時’使用於熱轉印用薄膜的熱塑性樹脂之材質較佳 爲丙烯酸系樹脂。 ' -20 - 201200352 [實施例] 茲藉由實施例說明本發明如下。只要沒有特別說明， 「份」、「％」爲重量基準。 (評價方法） <密接性> 藉由JIS K-5400之棋盤眼Cellotape(註冊商標）剝離試 驗，評價密接性。基質（matrix)因使用PC/ABS樹脂，故以 2mm見方' 1〇〇方塊（square)進行評價。殘存的方塊爲1〇〇 個之物判定爲〇、雖殘存有100個方塊而有缺損爲10個以下 之情形判定爲△、其他判定爲X。 <指紋目視確認性> 在鐵氟龍薄片（Teflon，註冊商標）上，滴下油酸1〇μί ，以切割成3cm見方的胺基甲酸酯海綿（3Μ公司製Scotch品 牌），一面塗抹、一面拭除後，將其海綿之附著有油酸的 面，按壓於被評價品表面1 〇秒鐘，使油酸附著。 藉由使用色差計，計算油酸附著前後之dL *，作爲指 紋附著時目視確認性之代用特性値，以dL * S 1 . 5爲〇、 1.5<dL氺$3爲八、dL*<3爲X，進行評價。 <指紋拭除性> 與指紋目視確認性之評價同樣地，使油酸附著後，以 脫脂綿2次來回（各自使用新的面）拭掉，對其使用色差計， 自油酸附著前後之dL*計算得回復因數（recovery factor)， 藉以作爲指紋拭除性之代用特性値。以d L * S 8 0 %爲ο、 50%$(11^*<80%爲八、（11^*<50%爲><，進行評價。 -21 - 201200352 (含有自由基聚合性不飽和基的（甲基）丙烯酸樹脂之製造方 法） <參考例1> 在具備溫度計、攪拌機、回流冷卻器及氮氣導入管的 四口燒瓶中’放入950份乙酸丁酯，升溫至8(TC，在達到 同溫度時，就以4小時的時間滴下由9 7 0份丙烯酸丁酯、3 0 份甲基丙烯酸、7份2,2’-偶氮雙（2-甲基丁腈）所成的混合物 ，滴下完成後升溫至9 0 °C，保持1 0小時，繼續進行反應。 將反應液之溫度降至50°C，添加將0.2份三級丁基焦 兒茶酚溶解於2〇份乙酸丁酯的溶液，進一步添加20份甲基 丙烯酸環氧丙酯、3份二甲基胺基乙醇後，升溫至80 °C止 ，於同溫度下進行1 〇小時反應，獲得含有自由基聚合性不 飽和基的（甲基）丙烯酸樹脂（A1)溶液。 (成形方法） <射出成形方法> 將以後述方法所得的熱轉印用薄膜設置於東芝機械公 司製射出成形機^ EC75N-1.5Y」後，關閉模具。模具係 使用射出成形.體之形狀爲l〇〇(L)xlOO(W)x9(H)mm '角部 R=10mm、立起部之 R = 5R、模斜度（draft angle)18.5。之拖 盤狀之物。 以加熱器將模具調溫至5〇°C，以射出樹脂溫度265 °c 將帝人化成公司製射出樹脂「Multilon TN-3715B」射出 。自模具內移除射出成形體，使剝離性薄膜剝離，獲得使 -22 - 201200352 熱轉印用薄膜之自由基聚合性樹脂組成物層及加飾層被轉 印的射出成形體。其後，藉由進行總照射量〗〇 0 0 m J / c m 2 ( 波峰強度1 80mW/cm2)之紫外線照射，獲得加飾成形品。 <真空成形同時黏貼方法> 使用布施真空公司製「NGF-〇7〇9成形機」進行熱成 形。 將以後述方法獲得的熱轉印用薄膜之周圍完全以鉗夾 (cl amp)固定後’關閉成形機之上下模箱（b〇x)，使模箱內 幾乎成了完全真空狀態後’加熱器係使用Helius公司製中 紅外線加熱器，將該熱轉印用薄膜自上面間接加熱後，使 載置黏附體的桌子上升’在上模箱中吹入〇.2MPa之壓縮空 氣，將該熱轉印用薄膜黏貼於黏附體上，使其一體成形。 此外’加熱器與樹脂薄片S之距離爲2 5 0mm左右，黏 附體係使用縱80mmx橫150mmx厚度2mm之平板。 將剝離性薄膜剝離，藉由進行總照射量1 〇 〇 〇 m J / c m2 ( 波峰強度1 8 0 m W / c m2)之紫外線照射，獲得加飾成形品❶ <實施例1熱轉印用薄膜（D1)之製造方法> 相對於以參考例1獲得之含有自由基聚合性不飽和基 的（甲基）丙烯酸樹脂（A1)溶液的不揮發成分，添加5重量％ 環氧化大豆油丙嫌酸醋（Cognis公司製 Photomer 3005F)及 1重量％光聚合引發劑Irgacure 184(千葉特用公司製），而 調製自由基聚合性樹脂組成物（B 1 )。 -23 - 201200352 藉由使用桿凹版塗布機，將自由基聚合性樹脂組成物 (B1)塗布於東麗薄膜加工公司製聚對酞酸乙二酯（PET)薄 片「Cerapeel HP2/TB(S)」（膜厚 50μπ\)上，以 i〇〇°c 乾燥 1 分鐘，獲得具有乾燥後膜厚5μπι之自由基聚合性樹脂組成 物（Β1)層的薄膜（C1)。 對薄膜（C1)，藉由使用DIC製XS- 7 5 6 IM系油墨，以凹 版印刷機，在自由基聚合性樹脂組成物（Β 1)層，直接供予 似鋁細線花紋，獲得熱轉印用薄膜（D 1 )。 <實施例2熱轉印用薄膜（D2)之製造方法> 將具有該自由基聚合性樹脂組成物層的薄膜（C1)、與 使用DIC製XS-756IM系油墨，將似鋁細線花紋經凹版印刷 的OPP薄膜（東洋紡製 Pylen P2002)，在60°C下進行乾燥 積層，以使自由基聚合性樹脂組成物層及凹版印刷層呈相 對向後，藉由剝離OPP薄膜，而獲得熱轉印用薄膜（D2)。 <實施例3熱轉印用薄膜（D3)之製造方法> 相對於以參考例1獲得之含有聚合性不飽和基的（甲基 )丙烯酸樹脂（A1)溶液的不揮發成分，添加5重量％環氧化 大豆油丙烯酸酯（Cognis公司製 Photomer 3 005F)及1 0重量 %光聚合引發劑 Irgacure 1 84(Ciba Specialty股份有限公 司製）後，添加聚異氰酸酯「Burnock DN-981」（DIC股份 有限公司製），使其相對於該（甲基）丙烯酸樹脂（A1)之羥基 當量比爲36%，以調製自由基聚合性樹脂組成物（B 2)。 -24 - 201200352 藉由使用桿凹版塗布'機，將該組成物（B2)塗布於東麗 薄膜加工公司製PET薄片「Cerapeel HP2/TB(S)」（膜厚 50μηι)上，以100°C乾燥1分鐘，而獲得具有乾燥後膜厚 5μηι之自由基聚合性樹脂組成物（B2)層的薄膜（C2)。 對薄膜（C2)，藉由使用DIC製XS-756IM系油墨，以凹 版印刷機，在自由基聚合性樹脂組成物（Β 2 )層提供似鋁細 線花紋，而獲得熱轉印用薄膜（D3) » <實施例4熱轉印用薄膜（D4)之製造方法> 相對以參考例1獲得之含有聚合性不飽和基的（甲基） 丙烯酸樹脂（Α1)溶液的不揮發成分，添加5重量％環氧化亞 麻仁油丙烯酸酯（Cognis公司製 Photomer 3082)及10重量 %光聚合引發劑 Irgacure 184(Ciba Specialty股份有限公 司製）後，添加聚異氰酸酯「Burnock DN-981」（DIC股份 有限公司製）’使其相對於該（甲基）丙烯酸樹脂（A1)之羥基 當量比成爲3 6 % ’來調製自由基聚合性樹脂組成物（β 3 )之 塗料。 藉由使用桿凹版塗布機，將該組成物（B3)塗布於東麗 薄膜加工公司製PET薄片「Cerapeel HP2/TB(S)」（膜厚 5〇μιη)上’以100°C乾燥1分鐘，而獲得具有乾燥後膜厚 5μπι之自由基聚合性樹脂組成物（B3)層的薄膜（C3p 對薄膜（C3)，藉由使用DIC製XS-756IM系油墨，以凹 版印刷機在自由基聚合性樹脂組成物（B 3 )層供予似鋁細線 花紋，而獲得熱轉印用薄膜（D4)。 -25 - 201200352 (實施例5至8射出成形體之製造方法） 將以實施例1至4所得之熱轉印用薄膜（D1)至（D4)，依 照該射出成形方法’獲得具有圖案的射出成形體。所得之 射出成形體難以看見指紋，顯示出容易抹除的性能。結果 如表1所示。 (實施例9真空成形體之製造方法） 將以實施例1所得熱轉印用薄膜（D i )，依照該真空成 形同時黏貼方法，獲得具有圖案的真空成形體。所得之真 空成形體難以看見指紋’顯現出容易抹除的性能。結果如 表1所示。 [表1] 實施例5 實施例6 實施例7 實施例8 實施例9 熱轉印用薄膜名 D1 D2 D3 D4 D1 紐薄膜 PET PET PET PET PET 自由基聚合性樹脂組成名 B1 B1 B2 B3 B 1 加飾層 似鋁細線 (直接印刷） 似銘細線 (轉印） 似鋁細線 (直接印刷） 似鋁細線 (直接印刷） 似鋁細線 (直接印刷） 成形方法 射出成形 射出成形 射出成形 射出成形 真空成形 密雛 〇 〇 〇 〇 〇 指紋目視確認性 〇 〇 〇 〇 〇 指紋拭除性 〇 〇 〇 〇 〇 <比較例1使用無添加環氧化植物油（甲基）丙烯酸酯的熱 轉印用薄膜的射出成形體之例> 相對於以參考例1獲得之含有聚合性不飽和基的（甲基 )丙烯酸樹脂（A1)溶液的不揮發成分’ _加1 〇重量％光聚合 引發劑Irgacure 184(Ciba Specialty股份有限公司製）’以 調製自由基聚合性樹脂組成物（Η 1 )。 -26 - 201200352 藉由使用桿凹版塗布機，將自由基聚合性樹脂組成物 (H1)塗布於東麗薄膜加工公司製聚對酞酸乙二酯（PET)薄 片「Cerapeel HP2/TB(S)」（膜厚 50μιη)上，並以 100°C 乾燥 1分鐘，而獲得具有乾燥後膜厚5μπα之自由基聚合性樹脂 組成物（Η1)層的薄膜（HC1)。 藉由對薄膜（HC1)，使用DIC製XS-756IM系油墨，以 凹版印刷機在自由基聚合性樹脂組成物（Η 1)層直接供予似 鋁細線花紋，獲得熱轉印用薄膜（HD1)。 使用所得之熱轉印用薄膜（HD 1 )，依照該射出成形方 法，獲得具有圖案的射出成形體。所得之射出成形體容易 看見指紋，難以抹除。結果如表2所示。 <比較例2 使用含有氟系添加劑的熱轉印用薄膜的射出成 形體之例> 相對於以參考例1獲得之含有聚合性不飽和基的（甲基 )丙烯酸樹脂（Α1)溶液的不揮發成分，添加2重量％ Megafac RS-75(DIC製含氟UV硬化性樹脂）及1〇重量％光聚 合引發劑 Irgacure 184(Ciba Specialty股份有限公司製）， 以調製自由基聚合性樹脂組成物（H2)。 藉由使用桿凹版塗布機，將自由基聚合性樹脂組成物 (H 2)塗布於東麗薄膜加工公司製聚對酞酸乙二酯（PET)薄 片「Cerapeel HP2/TB(S)」（膜厚 50μιη)上，以 loot 乾燥 1 分鐘，而獲得具有乾燥後膜厚5 μιη之自由基聚合性樹脂組 成物（Η2)層的薄膜（HC2)。 -27 - 201200352 藉由對薄膜（HC2)使用DIC製XS-756IM系油墨，以凹 版印刷機，在自由基聚合性樹脂組成物（Η 2 )層直接供予似 鋁細線花紋，獲得熱轉印用薄膜（HD2)。此時，細線花紋 之印刷性稍差，一部分花紋脫落。 使用所得之熱轉印用薄膜（HD2)，依照該射出成形方 法，獲得具有圖案的射出成形體。雖然所得射出成形體的 指紋抹除性稍稍提高，但就密接性之觀點觀之則不良。此 可推定含氟添加劑在塗料之塗膜時，造成在空氣界面偏析 (segregation)，而使密接性不良。結果如表2所示。 <比較例3使用含有鐵氟龍微粒的熱轉印用薄膜之射出成 形體之例> 相對於以參考例1獲得之含有聚合性不飽和基的（甲基 )丙烯酸樹脂（A 1 )溶液的不揮發成分，添加2重量％鐵氟龍 微粒（喜多村公司製KTL-4N)及10重量％光聚合引發劑 Irgacure 184(Ciba Specialty股份有限公司製），以調製自 由基聚合性樹脂組成物（H3)。 藉由使用桿凹版塗布機’將自由基聚合性樹脂組成物 (H3)塗布於東麗薄膜加工公司製聚對酞酸乙二酯（pet)薄 片「Cerapeel HP2/TB(S)」（膜厚 5〇μηι)上，以 l〇〇°C 乾燥 1 分鐘’而獲得具有乾燥後膜厚5 μ m之自由基聚合性樹脂組 成物（H3)層的薄膜（HC3)。 藉由對薄膜（HC3)，使用DIC製XS-756IM系油墨，以 凹版印刷機，在自由基聚合性樹脂組成物（H3 )層，直接供 -28 - 201200352 予似鋁細線花紋’獲得熱轉印用薄膜（H D 3 )。此時細線花 紋之印刷性稍差，一部分花紋脫落。 使用所得之熱轉印用薄膜（HD3 )，依照該射出成形方 法，獲得具有圖案的射出成形體。雖然所得射出成形體的 指紋抹除性稍稍提高，但指紋目視確認性差。結果如表2 所示。 <比較例4使用含有氟系添加劑的熱轉印用薄膜之射出成 形體之例> 相對於以參考例1獲得之含有聚合性不飽和基的（甲基 )丙烯酸樹脂（A1)溶液的不揮發成分，添加2重量。/。 Sundhoma 28-3F(DH材料公司製，矽改性胺基甲酸酯丙烯 醋）及10重里％光聚合引發劑 Irgacure 184(Ciba Specialty股份有限公司製），以調製自由基聚合性樹脂組 成物（H4)。 藉由使用桿凹版塗布機，將自由基聚合性樹脂組成物 (H4)塗布於東麗薄膜加工公司製聚對酞酸乙二酯（pET)薄 片「Cerapeel HP2/TB(S)」（膜厚 50μιη)上，於 1〇〇。(：乾燥 1 分鐘，而獲得具有乾燥後膜厚5 μιη之自由基聚合性樹脂組 成物（Η4)層的薄膜（HC4)。 藉由對薄膜（HC4)，使用DIC製XS-756IM系油墨，以 凹版印刷機’在自由基聚合性樹脂組成物（Η 4)層，直接供 予似鋁細線花紋’獲得熱轉印用薄膜（H D 4)。此時細線花 紋之印刷性稍差’一部分花紋脫落。 -29 - 201200352 使用所得之熱轉印用薄膜（H D4)，依照該射出成形方 法，獲得具有圖案的射出成形體。雖然所得之射出成形體 的指紋抹除性稍稍提高，但密接性不良。此可推定含矽添 加劑在塗料的塗膜時，在空氣界面造成偏析而變差。結果 如表2所示。 [表2] 比較例1 比較例2 比較例3 比較例4 熱轉印用薄膜名 H D 1 H D 2 H D 3 H D 4 基材薄膜 PET PET PET PET 自由基聚合性樹脂組成物名 HI Η 2 Η 3 Η 4 加飾層 似鋁細線 (直接印刷） 似鋁細線 (直接印刷） 似鋁細線 (直接印刷） 似鋁細線 (直接印刷） 成形方法 射出成形 射出成形 射出成形 射出成形 密接性 〇 X 〇 X 指紋目視確認性 X X X X 指紋拭除性 X Δ Δ Δ 【圖式簡單說明】 〇 y i \\ 【主要元件符號說明】 〇 J \ -30 -[Technical Field] The present invention relates to a transfer film which is, for example, a synthetic resin-based substrate, a wood-based substrate, an inorganic substrate, a metal substrate, or the like. On the surface of the transfer substrate, a transfer layer for forming at least a protective layer is transferred. [Prior Art] Conventionally, in the method of decorating an article, a transfer method using a transfer film is used. The transfer film is a synthetic resin substrate, a wood substrate, an inorganic substrate, or a metal base. A protective layer or the like can be easily formed on the surface of various substrates to be transferred, such as a material. In the transfer film method, a protective layer made of a resin composition excellent in surface physical properties such as hardness or solvent resistance is provided in a peelable state on a base film composed of paper or a thermoplastic resin film. Further, a pattern layer, an adhesive layer, or the like may be provided as needed (hereinafter, the protective layer is referred to as a transfer layer), and a transfer film is formed to press the transfer layer of the transfer film on the substrate (transferred) The surface of the substrate is either provided with a transfer film in the injection molding die, and the transfer layer of the transfer film is transferred to the substrate to be transferred or the resin is ejected by squeezing the resin. The interface between the printed layer and the base film is peeled off, and the base film is removed to produce a decorative article or the like for transferring the transfer layer onto the transferred substrate. In recent years, there has been a great deal of research on the decoration methods of automobile interior components, home appliance components, and electronic equipment casings. 201200352 In order to achieve excellent surface properties such as surface hardness, abrasion resistance, and rub resistance, a cured resin such as a curable resin, a reaction product of an isocyanate compound, an acid ester resin, or a molecule is generally used. It has been used for various types of ionizing radiation. (For example, when it is used as a home appliance, in addition to the surface hardness, such as finger marks, sebum and other oil stains, it is resistant to fingerprints. The coating film has a technique of hydrating the fluorine-based interface in a hard coating agent (see, for example, a patent-based polymerizable monomer and a polyfluoroalkane technology (see, for example, Patent Document 3) for anti-fingerprint contamination. In the coating agent, the problem is that the fluorine layer is biased in the transfer film in the transfer film, such as the front side, that is, the surface which becomes the surface of the protective layer after the air interface is not transferred. A scratch-resistant, solvent-resistant 'anti-drug thermosetting resin or active energy ray is provided on the surface of the post-product. Specifically, a two-component hard liquefied product is used. Ionizing radiation of a polyaminomethyl group-based polymerizable double bond. Acrylate-based resin, etc. J. Document 1) In addition to the decorative properties of parts such as electronic devices and the like, it also seeks to protect against the function of the finger. For the anti-fingerprinting), there are known technical aspects in the field, such as the active agent, the obtained cured film is given in the literature 2), or the use of a copolymer of a polymerizable monomer having a long-chain alkyl group is highly rejected from fluorine. Water-based, lifting technology. These properties of fluorine are used in the air interface. However, it is described that the base film is provided so as to be peelable. Therefore, the fluorine group cannot be biased, and the anti-fingerprint property and the like cannot be obtained. [0012] [Patent Literature] [Patent Document 1] Japanese Patent Laid-Open No. 7- [Patent Document 2] Japanese Laid-Open Patent Publication No. H10-110118 (Patent Document 3) Japanese Laid-Open Patent Publication No. 2010-24283 (Summary of the Invention) [Problems to be Solved by the Invention] The present invention is to solve the problem and provide a heat. The film for transfer is a transfer film using a curable resin as a protective layer, and the surface protective properties of the obtained protective layer are particularly excellent in fingerprint resistance. [Means for Solving the Problems] The present inventors have solved the above problems by adding an epoxidized vegetable oil (meth) acrylate as a curable resin layer ‘that is, a component of a radical polymerizable resin composition layer. In other words, the present invention provides a film for thermal transfer which has a transfer layer having a layer of a layer of a radically polymerizable resin composition and a decorative layer on a substrate film, wherein the radical polymerizable resin The composition layer contains a (meth)acrylic resin containing a radical polymerizable unsaturated group and an epoxidized vegetable oil (meth) acrylate. [Effect of the Invention] According to the present invention, a decorative article having excellent surface physical properties, particularly excellent in fingerprint resistance, can be obtained. [Embodiment] (Base film) The base film used in the present invention is not particularly limited, and a known base film for thermal transfer can be used. Specifically, it is preferred to use, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyamine 6, 66 (PA6, PA66) > polyimine (PI) A film made of a heat resistant resin such as polyvinyl alcohol (PVA). Among them, a film made of PET resin is preferred because of its superior cost and beauty. The thickness of the matrix resin film 1 is preferably from 20 to 125 μm, and it is preferably from 35 to 75 μm in consideration of the following three-dimensional shape (t r a c k i n g). A release layer may be provided between the base film and a transfer layer to be described later. The function of the release layer is to transfer the transfer layer of the injection molded body and the layer from which the base film is released. The injection molding system is a transfer substrate or a molded product of the resin. The release layer is required to have a release property from the transfer layer, but at the time of operation, the substrate film and the transfer layer are also required to have no release property from the transfer layer. The release layer may be a commonly used one, and a release agent such as a polyoxygen resin, a fluororesin, a cellulose derivative resin, a urea resin, a polyolefin resin or a melamine resin may be used. For example, in the case of using a film made of a PET resin as the matrix resin film i, it is preferred to use a polyoxymethylene resin-based release agent having a moderate mold release property. The release layer 2 can be applied by a roll coater or the like, and its thickness is preferably from Ο.μπι to 5 μιη. 201200352 (Transfer layer) In the film for thermal transfer of the present invention, the transfer layer means a layer having at least a layer of a radical polymerizable resin composition which is obtained by transfer onto a substrate to be transferred. The layer of the transfer body is the outermost layer; and the decorative layer is between the layer of the radical polymerizable resin composition and the substrate to be transferred. The base film is laminated in the order of the radical polymerizable resin composition layer and the decorative layer so that the decorative layer is between the radical polymerizable resin composition layer and the substrate to be transferred. Further, in addition to the radical polymerizable resin composition layer and the decorative layer, a layer such as an adhesive layer or an intermediate layer which can conceal the unevenness of the surface of the substrate to be transferred may be provided. (Transfer layer radically polymerizable resin composition layer) The radically polymerizable resin composition layer used in the present invention contains a (meth)acrylic resin containing a radical polymerizable unsaturated group and an epoxidized vegetable oil (methyl group). Acrylate. (epoxidized vegetable oil (meth) acrylate) epoxidized vegetable oil (meth) acrylate refers to an epoxidized vegetable oil epoxy group which is epoxidized with peracetic acid or perbenzoic acid on a double bond of an unsaturated vegetable oil. A compound obtained by subjecting (meth)acrylic acid to ring-opening addition polymerization. In the present invention, the vegetable oil refers to a triglyceride of a fatty acid having at least one carbon-carbon unsaturated bond in glycerol and a fatty acid triglyceride, as a representative compound of the vegetable oil. Examples of hempseed oil, linseed oil, perilla oil, oiticica oil, olive oil, cocoa oil 201200352 (cacao oil), kapok oil, kapok oil, Kaya oil, mustard oil, apric〇t kernel oil, tung oil, candlenut oil, walnut oil, poppy oil ), sesame oil, safflower oil, Japanese radish seed oi 1 , soybean oil, chaulmoogra oil, camellia oil, maize oil mai 1 , rapeseed oil, Soap oil (nigerseedoi 1), rice bran oil, palm oil, castor oil, sun flower oil, grape seed oil, almond oil, pine nut oil , cotton oil, coconut oil coconut oil), peanut oil, dehydrated castor oil and the like. In particular, an epoxidized vegetable oil (meth) acrylate may, for example, be epoxidized soybean oil acrylate (CN111 manufactured by Sartomer Chemical Co., Ltd., EBECRYL8 60 manufactured by UCB Co., Ltd., Photomer 3005F manufactured by Cognis Co., Ltd.), epoxidized linseed. The oil is awakened by acid (Photomer 3 0 8 2 by Cognis) and the like. The epoxidized vegetable oil (meth) acrylate is preferably added in an amount of from 1 to 20% by weight, preferably from 1 to 10% by weight, based on the total solid content of the radically polymerizable resin composition. Depending on the composition of the radically polymerizable resin composition, it is less than 〇. 1% of the 'anti-fingerprint ability is insufficient.' In the amount of more than 20%, the radically polymerizable resin composition is plasticized, and the film is coated. Hardness may be reduced. ((meth)acrylic resin containing a radical polymerizable unsaturated group) The (meth)acrylic acid containing a radical polymerizable unsaturated group used in the invention is not particularly limited, and can be obtained by a known method. (Methyl) C. 201200352 Diluted acid resin. Specifically, methyl methacrylate, ethyl methacrylate, butyl methacrylate hydroxyethyl methacrylate, cyclohexyl methacrylate, ethyl methacrylate may be exemplified. Ester, methyl acrylate, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, cyclohexyl acrylate, ethyl hexyl hexanoate, methacrylic acid, acrylic acid, acrylonitrile, methacrylic acid nitrile, etc. a (meth)acrylic resin obtained by copolymerizing the acrylic monomer alone or in combination with the (meth) acrylate as a main component, and a monomer having a polymerizable double bond copolymerizable with the polymerizable double bond, if necessary, For example, ethylene, butadiene, isoprene, vinyl acetate, ethyl propionate, ethyl butyrate, benzene, azo, alpha-methylbenzene, ethylbenzene, and diethylene are added. A (meth)acrylic resin which is a copolymerization component such as benzene, fluorene-cyclohexylmethyleneimine, hydrazine-ethyl maleimide or fluorenyl-p-butyleneimine. The (meth)acrylic resin can be obtained by polymerizing the (meth)acrylic monomer or a monomer having a copolymerizable polymerizable double bond by a usual method. In the method of introducing a polymerizable unsaturated resin based on the (meth)acrylic resin, for example, a carboxyl group-containing polymerizable monomer such as acrylic acid or methacrylic acid as the copolymerization component or dimethylamine methacrylate may be added in advance. An amine group-containing polymerizable monomer such as a ethyl ester or dimethylaminopropyl acrylamide, which is copolymerized to obtain the copolymer having a carboxyl group or an amine group, and then the carboxyl group or the amine group and the methyl group Method for reacting a monomer having a glycidyl group and a polymerizable unsaturated group, such as glycidyl acrylate; 201200352 pre-dispensing a methyl propylene succinic acid as a copolymerization component 2 - thioethyl ester, propylene acid 2 - hydroxy group Method for copolymerizing a hydroxyl group-containing monomer such as ethyl ester to obtain a copolymer having a hydroxyl group, and then reacting the hydroxyl group with a monomer having an isocyanate group or a polymerizable unsaturated group such as isocyanate ethyl methacrylate The epoxy group-containing polymerizable monomer such as glycidyl methacrylate as the copolymerization component is copolymerized in advance to obtain a copolymer having a glycidyl group, followed by a propylene oxide a method of reacting with a fluorenyl-containing polymerizable monomer of acrylic acid or methacrylic acid; using thioglycolic acid as a chain transfer agent during polymerization, introducing a carboxyl group at the end of the copolymer to epoxy methacrylic acid on the carboxyl group a method of reacting a monomer having a glycidyl group and a polymerizable unsaturated group such as propyl ester; and a carboxyl group-containing azo initiator such as azobiscyanovaleric acid, which is introduced into the copolymer, in terms of a polymerization initiator A method of reacting a carboxyl group with a monomer having a glycidyl group and a polymerizable unsaturated group, such as glycidyl methacrylate, on the carboxyl group. Among them, the easiest and preferred method is to preliminarily contain an amine containing a carboxyl group-containing monomer such as acrylic acid or methacrylic acid or dimethylaminoethyl methacrylate or dimethylaminopropyl acrylamide. Copolymerization of a base monomer, a method of reacting a carboxyl group or an amine group with a monomer having a glycidyl group and a polymerizable unsaturated group such as glycidyl methacrylate; or pre-dispensing a methyl group as the copolymerization component A propylene-containing polymerizable monomer such as glycidyl acrylate is copolymerized to obtain a copolymer having an epoxy-10 - 201200352 propyl group, followed by a carboxyl group of a propylene group and an acrylic acid or methacrylic acid. A method of reacting a polymerizable monomer. The (meth)acrylic resin containing a radical polymerizable unsaturated group preferably has a total solid content of the radical polymerizable resin composition of from 10 to 99.9% by weight, preferably from 40 to 99.9% by weight. . When the amount is less than 10%, the surface of the epoxidized vegetable oil (meth) acrylate which is liquid at room temperature may have a viscosity (t a c k) remaining on the surface. (Other component photopolymerization initiator) When the film for thermal transfer of the present invention is cured by an active energy ray, it is preferred to use a photopolymerization initiator in the radically polymerizable resin composition layer. Examples of the photopolymerization initiator include an acetophenone-based compound such as diethoxyethyl benzene or 1-hydroxycyclohexyl-benzophenone; a benzoin compound such as benzoin or benzoin isopropyl ether; a fluorenyl phosphine oxide compound such as 4,6-trimethylbenzoin diphenylphosphine oxide; a benzophenone system such as benzophenone or benzylidenebenzoic acid methyl-4-phenylbenzophenone a compound; a 9-oxosulfanyl compound such as 2,4-dimethyl 9-oxosulfonium; and an aminobenzophenone-based compound such as 4,4'-diethylaminobenzophenone; A polyether-based maleimide carboxylate compound or the like can be used in combination. The photopolymerization initiator is used in an amount of from 0.1 to 20% by mass, preferably from 0.5 to 15% by mass, based on the total solid content of the radically polymerizable resin composition. The light sensitizer may, for example, be an amine such as triethanolamine or ethyl 4-dimethylaminobenzoate. Further, it is known that a key salt such as a benzyl sulfonium salt or a benzylpyridinium salt or an aryl mirror salt is used as a photocationic cation 201200352 hair agent, and these initiators may also be used. The above photopolymerization initiator is used. (Thermal polymerization initiator) When the film for thermal transfer of the present invention is thermally cured, a thermal polymerization initiator may be used on the radically polymerizable resin composition layer. Examples of the thermal polymerization initiator include various peroxides such as hydrogen peroxide, tertiary butyl hydroperoxide, di-tertiary butyl peroxide, and cumyl hydroperoxide; Various persulfates such as potassium persulfate, sodium persulfate or ammonium persulfate; azobisisobutyronitrile, b[(1-cyano-1-methylethyl)azo]carbamamine, 2,2' - azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl) ) propane] or its dihydrochloride, 2,2'-azobis[2-(4,5,6,7-tetrahydro-111-1,3-diazepine-2-yl) Dihydrochloride of propane], dihydrochloride of 2,2'-azobis[N-(4-aminophenyl)-2-methylacetone oxime] or 2,2'-azobis ( Various azo initiators such as 2-dimethyl hydrazide) dihydrochloride. In particular, in the case of the vacuum forming method, since the film is sufficiently heated and formed in an instant, a thermal polymerization initiator can be suitably used. (Isocyanate compound) When the film for thermal transfer of the present invention is thermally cured, it is preferred to use a resin having a hydroxyl group as the (meth)acrylic resin containing a radical polymerizable unsaturated group. From the addition of the isocyanate compound, a urethane crosslinked structure different from the crosslinked structure derived from the radical polymerizable unsaturated ' group can be introduced. -12 - 201200352 The (meth)acrylic resin containing a radically polymerizable unsaturated group and having a hydroxyl group may, for example, be a (meth)acrylic resin obtained by the following two methods: acrylic acid is previously used. Or a method of copolymerizing a carboxyl group-containing monomer such as methacrylic acid to react a carboxyl group with a monomer having a glycidyl group and a polymerizable unsaturated group such as glycidyl methacrylate; or pre-dispensing as a copolymerization component Copolymerization of a propylene-containing polymerizable monomer such as glycidyl methacrylate to obtain a copolymer having a propylene group. Next, by making a propylene group and a propylene citrate or methyl propyl group A method of reacting a residue-containing polymerizable monomer with an acid, or a (meth)acrylic resin obtained by copolymerizing a (meth)acrylate having a hydroxyl group such as hydroxyethyl acrylate. The isocyanate compound may, for example, be an aromatic diisocyanate such as toluene diisocyanate or phenyl group _4,4'·monoisocyanate; - Polyisocyanuric acid, which is one of the main raw materials, one of the ones of methyl vinegar, one isocyanate, α, α, α, α, _ tetramethyl _ m-benzene-methine vinegar Monomethylene isocyanate, 1,5-pentamethylene methacrylate, 1,6-hexamethylene diacetyl cyanide, 2,2,4 (or 2,4 diisocyanate) , 4_) trimethyl 丨, 6_ hexamethylene vinegar, isotonic acid isocyanoacetone, ~ isocyanate isophorone vinegar, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, ls4_ two Cyclohexyl isocyanate, 1,3-bis(diisocyanatemethyl)cyclohexane, 4,4,2-dicyclohexylmethyl-isocyanate, etc. The allophanate type polyisocyanate, the diurea type polyisocyanate, the adduct type polyisocyanate and the isocyanuric acid type polyisocyanate obtained by the isocyanate are aliphatic polyisocyanate. Use any one as appropriate. Further, as the polyisocyanate, a so-called blocked polyisocyanate compound which is blocked with various blocking agents can also be used. As the blocking agent, for example, alcohols such as methanol 'ethanol, lactate, etc.; phenolic hydroxy compounds such as phenol and salicylic acid ester; decylamine such as ε-caprolactam and 2-pyrrolidone can be used. Classes; anthraquinones such as acetone oxime, methyl ethyl ketone oxime, etc.; active methylene compounds such as methyl acetate methyl acetate, ethyl acetate ethyl acetate, etidyl acetone, and the like. By using a blocked polyisocyanate compound, a hydroxyl group-containing solvent such as an alcohol can be used as the coating material for forming the radical polymerizable resin composition layer described later. (Other components) Further, an inorganic or metal compound, organic fine particles or the like may be added to the radical polymerizable resin composition layer. Examples of the inorganic or metal compound include cerium oxide, cerium oxide gel, cerium oxide sol, polyfluorene oxide, montmorillonite, mica, alumina, titania, talc, barium sulfate, and aluminum stearate. Magnesium carbonate, glass beads, and the like. Further, an organic cerium oxide sol, an acrylic modified cerium oxide, a cleasite or the like which is organically treated with the inorganic or metal compound may also be used. The organic fine particles may, for example, be particles of a polyethylene resin, an acrylic resin, a styrene resin, a fluororesin, a melamine resin, a polyurethane resin, a polycarbonate resin or a phenol resin. These may be used alone or in combination. Other additives which are widely used, such as ultraviolet absorbers, leveling agents, anti-caking agents, and the like, may be added to the extent that the effects of the present invention are not impaired. The thickness of the radically polymerizable resin composition layer used in the present invention is preferably from 1 to 50 μm, more preferably from 3 to 3, from the viewpoint of surface protection and film coating properties of the transfer substrate or the injection molded article. 40μιη. "14 - 201200352 (Additional layer) The widely used printing ink or coating can be used in the decorative layer, which can be formed by gravure printing, pattern printing, screen printing, inkjet printing, thermal transfer printing, and the like. The dried film thickness of the decorative layer is preferably from 0.5 to 15 μm, more preferably from 1 to 7 μm. Further, the coloring layer having no pattern or the colorless varnish resin layer ' may be formed by coating. Further, the printed pattern at the time of printing may be any type of printed pattern as long as it is a pattern or a letter that can be printed or printed. It can also be a solid version. For the coloring material for printing inks or coatings, it is preferred to carry out printing using well-known organic pigments or inorganic pigments. The organic pigment may, for example, be a quinacrone pigment, a phthalocyanine pigment, an indanthrene pigment, a phenanthrene pigment, a phthalone pigment, or a diterpene pigment. Isoindolinone pigment, methine azomethine pigment, diketoppyrrolopyrrole pigment, azolake pigment pigment 'insoluble azo pigment, condensed azo It is a pigment or the like. Further, the inorganic pigment may, for example, be an inorganic pigment such as carbon black, iron oxide or oxidized, or a metal powder pigment such as aluminum powder or bronze powder: a true pearlescent pigment such as titanium oxide coated mica. The resin for the varnish contained in the ink is not particularly limited, and for example, an acrylic resin, a polyurethane resin, a polyester resin, or a vinyl resin (vinyl chloride, vinyl acetate 'vinyl chloride-acetic acid) can be used. A well-known ink such as a vinyl acetate -15 - 201200352 copolymer resin), a chlorinated olefin resin system, an ethylene-acrylic resin type, a petroleum resin system, or a cellulose derivative resin system. In addition, the organic solvent to be used in the ink is not particularly limited as long as it does not intrude into the radically polymerizable resin composition layer or the release film described later. Specific examples thereof include toluene, xylene, and a ring. Hydrocarbon-based organic solvent such as hexane, n-hexane or mineral spirit; methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol An ester-based organic solvent such as methyl ether acetate, diethylene glycol monobutyl ether acetate or amyl acetate; n-butyl ether, dioxane, ethylene glycol monomethyl ether, ethylene An ether-based organic solvent such as an alcohol monobutyl ether or diethylene glycol; a ketone organic solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amino ketone, diisobutyl ketone or cyclohexanone; N-methyl Aromatic petroleum solvent system such as "Swasolve 310, Swasolve 1000, Sw as olve 1500" (made by Cosmo Petroleum Co., Ltd.). These organic solvents may be used singly or in combination of two or more. In the printing ink or coating, in addition to the base resin and the coloring agent, a plasticizer, a surfactant, an antioxidant, an ultraviolet absorber, a matting agent, a solvent, or the like may be contained as needed. (Manufacturing method of film for thermal transfer) The film for thermal transfer of the present invention is preferably a method of directly printing or coating a decorative layer on a base film provided with the radical polymerizable resin composition layer. Further, an intermediate (primer) layer may be provided to ensure that the radical polymerizes into the interlayer adhesion between the resin layer and the decorative layer. -16 - 201200352 The method of providing the radical polymerizable resin composition layer on the base film or the method of providing the decorative layer is not particularly limited, and for example, a gravure printing method, a stencil printing method, or the like may be used. Various printing methods such as a gravure printing method, an offset printing method, a screen printing method, or a gravure coating method, a micro gravure coating method, a roll coating method, a rod coating method, a roll coating method, a knife coating method, and a gas coating method. Various known coating methods such as a knife coating method, a chamfer coating method, a die coating method, a lip coating method, a flow coating method, a dip coating method, and a spray coating method. In particular, the decorative layer can be formed by gravure printing, pattern printing, screen printing, ink jet printing, etc., and in order to obtain a high-quality image, gravure printing is preferred. The dried film thickness of the decorative layer is preferably 〇 5 to 15 μm, more preferably 1 to 7 μm. Further, 'the base film provided with the radical polymerizable resin composition layer is overlapped with any peelable film provided with the decorative layer by the dry build-up method' to make the polymerizable resin layer and the decorative layer In the opposite direction, they were bonded by dry lamination and produced by transfer. The temperature to be bonded by drying, heating and pressurization is not particularly limited, but it is preferably carried out while adjusting the heat-resistant temperature of the base film to be used. The film for thermal transfer which has been produced can also be aging as needed to improve interlayer adhesion, etc. (film thickness for thermal transfer) The film thickness of the thermal transfer film of the present application is based on heat The transfer method is not particularly limited, but from the viewpoint of the shape followability of the substrate to be transferred, it is preferably from 21.5 to 200 μm, more preferably from 30 to 150 μm. -17 - 201200352 (Adhesive layer) Others Any layer may be further laminated without departing from the effects of the present invention. For example, in the case where the film for thermal transfer of the present invention is adhered to a substrate to be transferred, it is preferable to provide an adhesive layer or an adhesive layer on the surface of the decorative layer which is connected to the substrate to be transferred. The layer or the adhesive layer is preferably a layer for imparting adhesion to the adhesive, and may be an adhesive or an adhesive. The material adhering to the resin film and the adherend may be appropriately selected. For example, an adhesive agent may, for example, be an acrylic resin, a urethane resin, a urethane-modified polyester resin, a polyester resin, an epoxy resin, an ethylene-vinyl acetate copolymer resin (EVA), or a chlorine. A vinyl resin, a vinyl chloride-vinyl acetate copolymer resin, a natural rubber, a synthetic rubber such as SBR or NBR 'polysilicon oxide rubber, etc.' may be used in a solvent type or a solventless type. Further, in terms of the adhesive, as long as it is at a temperature of thermoforming, it may be a viscous material, and examples thereof include an acrylic resin, an isobutyl rubber resin, a styrene-butadiene rubber resin, and isoprene. Solvent-based adhesives such as rubber resin, natural rubber resin, and polyoxyxylene resin; or acrylic emulsion resin, styrene butadiene latex resin, natural rubber latex resin, styrene-isoprene copolymer resin, styrene-butyl A solvent-free adhesive such as a diene copolymer resin, a styrene-ethylene-butylene copolymer resin, an ethylene-vinyl acetate resin, a polyvinyl alcohol, a polypropylene decylamine or a polyvinyl methyl ether. When the film for thermal transfer of the present invention is provided with the adhesive layer or the adhesive layer, 'the film may be directly printed or coated on the film provided with the radical polymerizable resin composition layer and the decorative layer, or may be overlapped. The radically polymerizable tree-18 - 201200352 is obtained by a method of transferring a fat composition layer and the decorative layer so as to face each other and to transfer it by dry deposition. In the latter case, it is preferred to transfer the decorative layer having the subsequent layers, but it is also possible to provide an adhesive layer after transfer of the decorative layer. (Thermal transfer method) The film for thermal transfer of the present invention can be used in a known transfer method. Specifically, the film for thermal transfer of the present invention can be particularly suitably used in the following method: injection molding and simultaneous transfer method. The method is provided on the surface of the concave mold by preparing a film for thermal transfer. The two molds are closed, and the molten resin is ejected from the injection hole into the die hole (forming cavity) between the two molds, and after the injection resin is cooled and solidified, the two molds are opened, and the molded product and the thermal transfer film adhered to the molded article are self-contained. The mold is taken out, only the base film is peeled off, and the decorative piece formed by transferring the transfer layer on the transferred substrate is obtained; or the vacuum forming and pasting method is performed on the formed transfer substrate, The film for thermal transfer is placed so that the transfer layer faces the substrate to be transferred, and the film is heated to a softening temperature or higher, and then the substrate is formed by using the transferred substrate without using a mold under vacuum. On the substrate to be transferred, etc.; or a lapping simultaneous transfer method or the like, at the time of thermal transfer, the film is stretched into a film for thermal transfer to form a three-dimensional shape. However, the film for thermal transfer of the present invention can also be used as a transfer film which is stretched into a film for thermal transfer and is not deformed by hot stamping. (Active Energy Ray Irradiation) The layer of the radical polymerizable resin composition to which the decorative film of the thermal transfer film of the present invention has been transferred is cured by an active energy ray or the like. Active Energy Line -19 - 201200352 It is often preferred to use visible light or UV light. Particularly preferred is ultraviolet light. In terms of ultraviolet light source, solar light, low-pressure mercury lamp, high-pressure mercury lamp, ultra-high pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, etc. can be used. Further, a known heat source such as hot air or near-infrared rays can be used as the heating source when the heat is used. In terms of the amount of irradiation at this time, the amount of irradiation which can completely harden the curable resin layer is preferable, and specifically, it is preferably in the range of 250 mJ/cm 2 to 3 000 mJ/cm 2 . In particular, in order to sufficiently harden the radical reactive diluent or the radically polymerizable oligomer which has moved to the interface with the decorative layer, and to improve the adhesion to the substrate to be transferred, it is more preferable 〇〇〇mj/cm2 to 3 0 00mJ/cm2. The timing of peeling off the substrate film may be before or after the irradiation of the active energy ray. (Transferred Substrate) The substrate to be transferred which can transfer the film for thermal transfer of the present invention is not particularly limited to 'a variety of shapes such as resin, metal, glass, wood', etc. can be used. It is decorated by a common decoration method such as painting, plating, scratch, and the like. Further, the material of the adhesion surface of the substrate to be transferred and the material of the thermoplastic resin or the ink binder used in the film for thermal transfer of the present invention are more closely bonded between the materials which can be thermally or thermally melted. Excellent and better. For example, when the material of the adhesive surface of the substrate to be transferred is an acrylic resin or a styrene resin, the material of the thermoplastic resin used for the film for thermal transfer is preferably an acrylic resin. '-20 - 201200352 [Examples] The present invention will now be described by way of examples. Unless otherwise specified, "parts" and "%" are weight basis. (evaluation method) <Adhesiveness> The adhesion was evaluated by the checkerboard test of the Cellotape (registered trademark) of JIS K-5400. Since the matrix was PC/ABS resin, it was evaluated by a square of 2 mm square. The remaining squares are judged to be 〇, and if there are 100 squares remaining and the defect is 10 or less, it is judged as Δ, and the other judgment is X. <Fingerprint Visual Confirmation> On the Teflon sheet (Teflon, registered trademark), oleic acid 1 μμί was dropped to cut into a 3 cm square urethane sponge (Scotch brand manufactured by 3 Co., Ltd.) and smeared on one side. After wiping off, the surface of the sponge to which the oleic acid adhered was pressed against the surface of the evaluated article for 1 , to adhere the oleic acid. By using a color difference meter, dL* before and after the adhesion of oleic acid is calculated as a substitute characteristic of visual confirmation when the fingerprint is attached, and dL*S1.5 is used as the 〇, 1.5. <dL氺$3 is eight, dL* <3 is X, and evaluation was performed. <Fingerprint erasability> In the same manner as the visual confirmation of the fingerprint, after the oleic acid was adhered, the absorbent cotton was wiped back and forth twice (using a new surface each), and a color difference meter was used to adhere the oleic acid. The dL* before and after is calculated as a recovery factor, which is used as a surrogate feature of fingerprint erasability. Let d L * S 8 0 % be ο, 50%$(11^* <80% is eight, (11^* <50% is ><, evaluation. -21 - 201200352 (Method for producing (meth)acrylic resin containing radical polymerizable unsaturated group) <Reference Example 1> In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen introduction tube, 950 parts of butyl acetate was placed, and the temperature was raised to 8 (TC, and when it reached the same temperature, it was 4 hours. A mixture of 770 parts of butyl acrylate, 30 parts of methacrylic acid, and 7 parts of 2,2'-azobis(2-methylbutyronitrile) was added dropwise at a time. After the completion of the dropwise addition, the temperature was raised to 90 °C. The reaction was continued for 10 hours. The temperature of the reaction solution was lowered to 50 ° C, and a solution of dissolving 0.2 part of butyl catechol in 2 parts of butyl acetate was added, and 20 parts of methyl group was further added. After the epoxy propyl acrylate and 3 parts of dimethylaminoethanol were heated to 80 ° C, the reaction was carried out at the same temperature for 1 〇 to obtain a (meth)acrylic resin containing a radical polymerizable unsaturated group ( A1) solution (forming method) <Injection molding method> The film for thermal transfer obtained by the method described later is placed in a Toshiba Machine Co., Ltd. injection molding machine (EC75N-1.5Y), and the mold is closed. The mold was formed by injection molding. The shape of the body was l〇〇(L)x100(W)x9(H)mm', the corner portion R=10 mm, the rising portion R=5R, and the draft angle 18.5. Drag the disc. The mold was tempered to 5 〇 ° C by a heater, and the resin "Multilon TN-3715B" was produced by Teijin Chemical Co., Ltd. at a temperature of 265 °c. The injection molded body was removed from the mold, and the release film was peeled off to obtain an injection molded body in which the radically polymerizable resin composition layer and the decorative layer of the film for thermal transfer of -22 - 201200352 were transferred. Thereafter, the decorative article was obtained by irradiating ultraviolet rays with a total irradiation amount of 〇 0 0 m J / c m 2 (peak intensity of 1 80 mW/cm 2 ). <Method for simultaneously forming a vacuum forming method> Thermoforming was carried out using an "NGF-〇7〇9 molding machine" manufactured by Bosch Vacuum Co., Ltd. The periphery of the film for thermal transfer obtained by the method described later is completely clamped (cl amp), and then the upper mold box (b〇x) of the molding machine is closed, so that the mold box is almost completely vacuumed and then heated. The system uses a medium-infrared heater manufactured by Helius Co., Ltd., and indirectly heats the film for thermal transfer from above, and raises the table on which the adherend is placed, and blows compressed air of MPa2 MPa into the upper mold box to heat the heat. The transfer film is adhered to the adhesive body to be integrally formed. Further, the distance between the heater and the resin sheet S is about 250 mm, and the adhesion system is a flat plate having a length of 80 mm x a width of 150 mm and a thickness of 2 mm. The peelable film is peeled off, and the decorative article is obtained by irradiating ultraviolet rays with a total irradiation amount of 1 〇 〇 〇 m J / c m2 (peak intensity of 1 800 m W / c m2). <Production Method of Film for Thermal Transfer (D1) of Example 1> With respect to the nonvolatile component of the (meth)acrylic resin (A1) solution containing the radical polymerizable unsaturated group obtained in Reference Example 1, 5% by weight of epoxidized soybean oil, vinegar, vinegar (Photomer 3005F, manufactured by Cognis Co., Ltd.), and 1% by weight of photopolymerization initiator Irgacure 184 (manufactured by Chiba Specialty Co., Ltd.) were added to prepare a radically polymerizable resin composition (B 1 ). . -23 - 201200352 The free-radical polymerizable resin composition (B1) was applied to a polyethylene terephthalate (PET) sheet manufactured by Toray Film Processing Co., Ltd. by a gravure coater. "Cerapeel HP2/TB(S) The film (C1) having a layer of a radically polymerizable resin composition (Β1) having a film thickness of 5 μm after drying was obtained by drying at i〇〇°c for 1 minute (film thickness: 50 μπ). In the film (C1), a hot-transfer-like resin composition (Β1) layer was directly applied to a layer of a radically polymerizable resin composition (Β1) by using an XS-75 5 IM-based ink made of DIC to obtain a heat transfer. Printing film (D 1 ). <Example 2 Method for Producing Film for Thermal Transfer (D2)> A film (C1) having the radical polymerizable resin composition layer and an XS-756IM ink using DIC are used to form an aluminum-like fine line pattern. The gravure-printed OPP film (Pylen P2002 manufactured by Toyobo Co., Ltd.) was dried and laminated at 60 ° C so that the radically polymerizable resin composition layer and the intaglio printing layer were relatively rearward, and the heat transfer was obtained by peeling off the OPP film. Printed film (D2). <Example 3: Method for Producing Film for Thermal Transfer (D3)> Addition 5 to the nonvolatile component of the (meth)acrylic resin (A1) solution containing the polymerizable unsaturated group obtained in Reference Example 1 Addition of polyisocyanate "Burnock DN-981" (DIC shares) after 5% by weight of epoxidized soybean oil acrylate (Photomer 3 005F, manufactured by Cognis Co., Ltd.) and 10% by weight of photopolymerization initiator Irgacure 1 84 (manufactured by Ciba Specialty Co., Ltd.) The hydroxyl equivalent ratio of the (meth)acrylic resin (A1) was 36% to prepare a radically polymerizable resin composition (B 2 ). -24 - 201200352 The composition (B2) was applied to a PET sheet "Cerapeel HP2/TB(S)" (film thickness 50 μηι) made by Toray Film Processing Co., Ltd. at 100 ° C by using a gravure coating machine. After drying for 1 minute, a film (C2) having a layer of a radical polymerizable resin composition (B2) having a film thickness of 5 μm after drying was obtained. In the film (C2), an aluminum-like fine pattern is provided on the layer of the radical polymerizable resin composition (Β 2 ) by using an XS-756IM ink made of DIC, and a film for thermal transfer (D3) is obtained by a gravure printing machine. ) » <Example 4: Method for Producing Film for Thermal Transfer (D4)> 5 parts by weight with respect to the nonvolatile content of the (meth)acrylic resin (Α1) solution containing the polymerizable unsaturated group obtained in Reference Example 1 % epoxidized linseed oil acrylate (Photomer 3082, manufactured by Cognis Co., Ltd.) and 10% by weight of photopolymerization initiator Irgacure 184 (manufactured by Ciba Specialty Co., Ltd.), and then added polyisocyanate "Burnock DN-981" (manufactured by DIC Corporation) The coating of the radically polymerizable resin composition (β 3 ) was prepared by making the ratio of the hydroxyl equivalent of the (meth)acrylic resin (A1) to 3 6 %. The composition (B3) was applied to a PET sheet "Cerapeel HP2/TB(S)" (film thickness: 5 〇μιη) manufactured by Toray Film Processing Co., Ltd. using a bar gravure coater to dry at 100 ° C for 1 minute. A film having a layer of a radically polymerizable resin composition (B3) having a film thickness of 5 μm after drying (C3p to film (C3), by radical polymerization using a DIC XS-756IM ink, using a gravure printing machine The resin composition (B 3 ) layer is supplied with an aluminum-like fine line pattern to obtain a film for thermal transfer (D4). -25 - 201200352 (Manufacturing method of the injection molded body of Examples 5 to 8) (4) The obtained thermal transfer film (D1) to (D4) obtained an injection molded body having a pattern according to the injection molding method. The obtained injection molded body was difficult to see a fingerprint, and exhibited an easily smeared performance. (Example 9) Method of Producing Vacuum Formed Body The vacuum-molded body having the pattern was obtained by the vacuum forming film (D i ) obtained in Example 1 in accordance with the vacuum forming and pasting method. The molded body is difficult to see the fingerprint 'appears The results are easy to erase. The results are shown in Table 1. [Table 1] Example 5 Example 6 Example 7 Example 8 Example 9 Film for thermal transfer D1 D2 D3 D4 D1 New film PET PET PET PET PET Free radical polymerizable resin composition name B1 B1 B2 B3 B 1 Decorative layer like aluminum thin wire (direct printing) Like fine wire (transfer) Like aluminum thin wire (direct printing) Like aluminum thin wire (direct printing) Like aluminum thin wire (direct printing Forming method Injection molding Injection molding Injection molding Injection molding Vacuum forming close-up 〇〇〇〇〇 Fingerprint Visual confirmation 〇〇〇〇〇 Fingerprint erasing 〇〇〇〇〇 <Comparative Example 1 Example of an injection-molded article using a film for thermal transfer without adding epoxidized vegetable oil (meth) acrylate> With respect to the (meth) group containing a polymerizable unsaturated group obtained in Reference Example 1 The non-volatile component of the acrylic resin (A1) solution was added to 11% by weight of a photopolymerization initiator Irgacure 184 (manufactured by Ciba Specialty Co., Ltd.) to prepare a radically polymerizable resin composition (Η 1 ). -26 - 201200352 The free-radically polymerizable resin composition (H1) was applied to a polyethylene terephthalate (PET) sheet manufactured by Toray Film Processing Co., Ltd. by a gravure coater. "Cerapeel HP2/TB(S) (film thickness: 50 μm) was dried at 100 ° C for 1 minute to obtain a film (HC1) having a layer of a radical polymerizable resin composition (Η1) having a film thickness of 5 μπα after drying. By using an XS-756IM ink made of DIC for a film (HC1), an aluminum-like fine pattern is directly applied to a layer of a radical polymerizable resin composition (Η1) by a gravure printing machine to obtain a film for thermal transfer (HD1). ). Using the obtained film for thermal transfer (HD 1 ), an injection molded body having a pattern was obtained in accordance with the injection molding method. The resulting injection molded body is easy to see the fingerprint and is difficult to erase. The results are shown in Table 2. <Comparative Example 2 Example of an injection-molded article using a film for thermal transfer containing a fluorine-based additive> With respect to the (meth)acrylic resin (Α1) solution containing a polymerizable unsaturated group obtained in Reference Example 1 2% by weight of Megafac RS-75 (fluorine-containing UV curable resin of DIC) and 1% by weight of photopolymerization initiator Irgacure 184 (manufactured by Ciba Specialty Co., Ltd.) were added to prepare a radically polymerizable resin. (H2). The radically polymerizable resin composition (H 2 ) was applied to a polyethylene terephthalate (PET) sheet "Cerapeel HP2/TB(S)" (film) manufactured by Toray Film Processing Co., Ltd. by using a bar gravure coater. On a 50 μm thick basis, it was dried by loot for 1 minute to obtain a film (HC2) having a layer of a radical polymerizable resin composition (Η2) having a film thickness of 5 μm after drying. -27 - 201200352 By using a DIC XS-756IM ink for a film (HC2), a transfer film is directly applied to a layer of a radical polymerizable resin composition (Η 2 ) in a gravure printing machine to obtain a thermal transfer. Use film (HD2). At this time, the printability of the fine line pattern is slightly inferior, and a part of the pattern is peeled off. Using the obtained film for thermal transfer (HD2), an injection molded body having a pattern was obtained in accordance with the injection molding method. Although the fingerprint erasability of the obtained injection molded article was slightly improved, the viewpoint of the adhesion was poor. It is presumed that the fluorine-containing additive causes segregation at the air interface when the coating film of the coating is applied, and the adhesion is poor. The results are shown in Table 2. <Comparative Example 3: Example of using an injection molded body of a film for thermal transfer containing Teflon fine particles> With respect to the (meth)acrylic resin (A 1 ) containing a polymerizable unsaturated group obtained in Reference Example 1 To the non-volatile component of the solution, 2% by weight of Teflon particles (KTL-4N manufactured by Kitamura Co., Ltd.) and 10% by weight of a photopolymerization initiator Irgacure 184 (manufactured by Ciba Specialty Co., Ltd.) were added to prepare a radically polymerizable resin composition. (H3). The free-radical polymerizable resin composition (H3) was applied to a polyethylene terephthalate (pet) sheet "Cerapeel HP2/TB(S)" (film thickness) by Toray Film Coating Machine. A film (HC3) having a layer of a radical polymerizable resin composition (H3) having a film thickness of 5 μm after drying was obtained by drying at 1 ° C for 1 minute. By using a DIC XS-756IM ink for a film (HC3), a heat transfer can be directly applied to a layer of a radical polymerizable resin composition (H3) in a free-radical polymerizable resin composition (H3) layer. Printed film (HD 3). At this time, the printability of the fine line pattern is slightly inferior, and a part of the pattern is peeled off. Using the obtained film for thermal transfer (HD3), an injection molded body having a pattern was obtained in accordance with the injection molding method. Although the fingerprint erasability of the obtained injection molded article was slightly improved, the fingerprint visibility was poor. The results are shown in Table 2. <Comparative Example 4: Example of using an injection molded body of a film for thermal transfer containing a fluorine-based additive> With respect to the (meth)acrylic resin (A1) solution containing the polymerizable unsaturated group obtained in Reference Example 1 For non-volatile ingredients, add 2 weights. /. Sundhoma 28-3F (manufactured by DH Materials Co., Ltd., 矽-modified urethane acrylate) and 10% by weight of photopolymerization initiator Irgacure 184 (manufactured by Ciba Specialty Co., Ltd.) to prepare a radically polymerizable resin composition ( H4). The radically polymerizable resin composition (H4) was applied to a polyethylene terephthalate (pET) sheet "Cerapeel HP2/TB(S)" (film thickness) by Toray Film Processing Co., Ltd. using a bar gravure coater. 50μιη), at 1〇〇. (: drying for 1 minute, and obtaining a film (HC4) having a layer of a radically polymerizable resin composition (Η4) having a film thickness of 5 μm after drying. By using a DIC XS-756IM ink for the film (HC4), A film for thermal transfer (HD 4) is obtained by directly applying an aluminum-like fine pattern to a layer of a radically polymerizable resin composition (Η 4) in a gravure printing machine. At this time, the printability of the fine line pattern is slightly poor. -29 - 201200352 Using the obtained film for thermal transfer (H D4), an injection molded body having a pattern is obtained according to the injection molding method. Although the obtained print molded body has a slight improvement in fingerprint erasability, the adhesion is improved. It is presumed that the antimony-containing additive causes segregation at the air interface to deteriorate when the coating film of the coating material is applied. The results are shown in Table 2. [Table 2] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Thermal transfer Film name HD 1 HD 2 HD 3 HD 4 Substrate film PET PET PET PET Radical polymerizable resin composition name HI Η 2 Η 3 Η 4 Adding layer like aluminum thin line (direct printing) Like aluminum thin line (direct printing) Aluminum-like thin line ) Aluminum-like fine line (direct printing) Forming method Injection molding Injection molding Injection molding molding adhesion 〇X 〇X Fingerprint visual confirmation XXXX Fingerprint erasability X Δ Δ Δ [Simple diagram description] 〇yi \\ [Main components Explanation of symbols] 〇J \ -30 -