201247408 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種作為轉移印刷用積層體之構成要素 之基膜、使用該基膜之轉移印刷用積層體、及該基膜之製 w方法，該轉移印刷用積層體可用以藉由轉印法而形成如 下褒飾成形品之表面之立體設計：汽車等車輛之内飾材料 或外飾材料，踢腳線（baseboard)、簷板（cornjce)等裝 修構件’窗框、門框等建具，牆壁、地板、頂棚等建築物 之内飾材料，電視接收器、行動電話零件、空調等家電製 品之框體、容器等。 【先前技術】 先前，於家電製品、化妝品容器、雜貨等成形品表面 印刷設計之方法，存在轉印法。所謂轉印法，係指如下方 法：使用於基體片材（基膜）上積層有由成為成形品表面 之保護層之層、設計印刷層、接著層等構成之轉印層的轉 移印刷用積層體，對該轉移印刷用積層體進行加熱加壓並 使其接著於作為被接著體之成形品表面後，將基體片材泰j 離’僅使轉印層轉移至成形品表面上。 作為該轉移印刷用積層體之基體片材（基膜），通常 使用聚對苯二曱酸乙二酯膜（例如，參照專利文獻1及2 )。 又，關於基體片材（基膜），作為由具有溶解溶出或 膨潤剝離之特性之樹脂構成的膜，有時亦使用聚乙稀醇 膜、聚乙烯丁醛膜、乙烯一乙烯醇共聚物膜等（例如，參 照專利文獻3 )。 201247408 近年來，對於藉由如上所述之轉印法對成形品進行之 設計之印刷，提高了下述要求：防止成形品表面之炫光， 或為謀求設計之高級化而將成形品表面之保護層設為消光 (消光風格）’或施加立體設計。 關於對該消光效果之要求，提出有：於基體片材上設 置有具有由分散有消光劑之水溶性樹脂構成之微細凹凸的 部分消光層之轉移印刷用積層體（例如，參照專利文獻 4) ;或使用如下轉移印刷用積層體之裝飾成形品，該轉移 印刷用積層體設置有含有平均粒徑〇卜2心之微粒子之 消光風格的硬塗層（成為保護層）（例如，參照專利文獻 5) 〇 [專利文獻1]曰本特開2005〜96156號公報 [專利文獻2]日本特開2〇〇2— 293〇94號公報 [專利文獻3]日本特開2〇〇1__ 27〇293號公報 [專利文獻4]日本特開2〇〇1 —26〇596號公報 [專利文獻5]日本特開2_— 1 73858號公 【發明内容】 關於裝飾成形品’欲施加竭 ripple )、髮線紋樣、麻紋、皮革風格之花紋等^紋〇Sand 要求較高’正在研究藉由轉印法’®性設計之 設計》 1便地賦予此種立體性 關於上述專利文獻 使用平滑之基體片材而未進行消刷用積層體’由於 成形品之表面賦予消光效果。 工，因此無法對裝飾 4 201247408 關於專利文獻4及5揭示之轉移印刷用積層體，由於 獲得’肖光效果前之操作步驟較多而難以進行製造管理，無 法滿足製造成本。&而，所獲得之轉移印刷用積層體係止 步於賦予消光之程度，無法於裝飾成形品之表面施加立體 性設計。 本發明係鑒於此種情況而成者，目的在於提供一種用 轉移印刷用積層體之基膜、及使用該基膜之轉移印刷用 積層體、進而该基膜之製造方法’該轉移印刷用積層體不 僅基膜與剝離層（成為成形品之保護層之層）之剝離性優 異，進而，可對裝飾成形品之表面賦予絹紋、縐紋、砂 紋、髮線紋樣、麻紋、皮革風格之花紋等立體設計。 即’本發明之主旨係關於一種用於轉移印刷用積層體 之基膜’其係用以轉印立體設計者，其特徵在於具有高低 差5〜200 /zm之凹凸形狀。 又’本發明亦提供一種基膜之製造方法，其係構成用 以、形成表面具有凹凸之裝飾成形品之表面層之轉移印刷用 積層體的基膜之製造方法’其包含藉由使膜通過表面溫度 100〜180C之壓纹輥（emb〇ss r〇u)與表面溫度5〇〇c以上 之支承輥（back up r〇u )之間而對該膜賦予凹凸形狀之步 驟。 再者’硬化性樹脂層係於將本發明之轉移印刷用積層 體轉印至被轉印體上並剝離基膜後，構成被轉印體之表面 之層。通常，使用熱硬化性樹脂、活性能量射線硬化性樹 脂等’藉由硬化而成為用以保護被轉印體表面之保護層 5 201247408 (硬塗層）。 上述本發明之轉移印刷用積層體藉由使用具有凹凸形 狀之膜作為基體片材（基膜），可對硬化性樹脂層之基膜 側之面賦予凹凸形狀。藉由於硬化性樹脂層之剝離側之面 形成有凹凸形狀，不僅使基膜與轉移印刷後之保護層（硬 化性樹脂層硬化而成之層）之剝離性提高，而且亦使凹凸 形狀轉印於經轉印之硬化性樹脂層之基膜的剝離側之面， 即裝飾成形品之最表面。結果可獲得形成有具有立體性設 計之保護層（硬塗層）之裝飾成形品。 就使用本發明之基膜之轉移印刷用積層體而言，不僅 基膜與保護層（硬化性樹脂層硬化而成之層）之剝離性優 異，進而可於裝飾成形品之表面簡便地轉印絹紋、縐紋、 砂紋、髮線紋樣、麻紋'皮革風格之花紋等立體性設計。 藉此’於製造汽車等車輛之内飾材料或外飾材料，踢腳 線、簷板等裝修構件，窗框、門框等建具，牆壁、地板、 頂棚等建築物之内飾材料，電視接收器、行動電話零件、 空調等家電製品之框體、容器等用途之裝飾成形品方面， 非常有用》 【實施方式】 以下詳細說明本發明。 本發明之基膜係用以藉由轉印法於成形品表面形成具 有立體设計之保護層的轉移印刷用積層體之基膜，其係作 為於基膜上依序積層有硬化性樹脂層及印刷層之轉移印刷 用積層體之構成要素。 6 201247408 本發明之基膜具有高低差5〜200//m之凹凸形狀，較 佳為高低差10〜170//m’進而較佳為高低差1〇〜15〇μ ηι。若該高低差過小’則難以轉印形成立體設計β另一方 面，高低差過大之基膜有難以製造之傾向，並且有即便基 膜之凹凸形狀之高低差增大至特定以上，亦難以獲得具有 與該尚低差對應之高低差的立體設計之傾向。 此處’所謂膜之高低差，係圖i中「Η」（或Hi、Η2、 Η3 )所表示者，具體而言’係藉由使用雷射顯微鏡（基恩 士公司製造之彩色3D雷射顯微鏡νκ_ 97〇〇)，並自形成 基膜之硬化性樹脂層之面的最大高度之值減去最低高度之 值而測得。 所謂凹凸形狀，係指基膜之形成硬化性樹脂層之面的 表面之高低差之形狀，為可繪製花紋、紋樣之高低差。凹 凸之形狀可沿著膜之寬度方向、長度方向之任一者形成， 較佳為使膜整體形成凹凸形狀。於此情形日夺，各個凹凸可 几圖1 ( a)所不般為刮面矩形型者，亦可如圖工（匕）所示 t為剖面波型者。進而，亦可如目“Ο所示般，為不同 攸：之凹凸之組合。圖1 ( C )之例係具有包含3階段之高 路（H丨、H2、H3)的凹凸形狀之膜。於此種情形時，本 :明之㈣「膜之高低差」，係指最大高低差（Η"。進 ，凹凸形狀之凹部長度i中，以〜2」 部長度（圖1中，以、或、」表示）可於 數之長if相專（例如，連續式樣之情形），亦可為複 之長度組合而成者（例如，隨機式樣之情形）。並且， 7 201247408 繪製之花紋、紋樣之種類並無特別限定，例如可列舉.e 紋、縐紋、砂紋、髮線紋樣、麻紋、皮革風格之花紋等^ 如上所述之凹凸形狀例如可藉由對膜實施壓紋加工等 而獲得。 本發明之基膜可列舉聚對苯二曱酸乙二s|系樹脂膜、 聚稀煙系樹脂膜、乙烯醇系樹脂膜（聚乙烯醇系樹脂膜、 乙烯一乙烯醇系樹脂膜等）等各種膜，其中就與保護硬 化性樹脂層硬化而成之層）之剝離性之觀點而言，較佳為 由乙烯醇系樹脂膜構成者’更佳為聚乙烯醇系：脂膜，最 佳為聚乙烯醇膜。 於本發明中，所謂「由乙烯醇系樹脂膜構成」，係扑 ，包含積層有除乙稀醇系樹脂膜以外之其他層（膜或塗^ 等）之情形，但通常由乙烯醇系樹脂膜單獨構成基膜。 ^乙烯醇系樹脂膜可藉由對乙烯醇系樹脂進行製膜而獲 付。所谓乙烯醇系樹脂，只要為具有使乙稀酿單元息化而 ==烯醇單元者即可。因i作為乙_系樹脂，例如 1]舉.包含作為聚乙酸乙烯酿之息化物 =醇之改…改質聚乙稀醇)的聚乙稀醇系 為20〜60莫耳%左右之乙缔一乙稀醇系樹脂等。 ，較佳為使用聚乙稀醇系樹脂（聚乙稀醇及改質 稀醇），最佳為使用聚乙烯醇。 75烯醇系樹脂所含有之乙酸乙稀醋單元之息化度通 75莫耳❶/。以上’就與硬化樹脂層之脫模 為80莫耳％以上 201247408 上述改質聚乙稀醇可藉由使乙酸乙稀醋與其他不飽和 單體之聚合物皂化來製造，亦可藉由對聚乙烯醇進行後續 改質而製造。改質量較佳為1G莫耳％以下，尤佳為7莫耳 %以下，進而較佳為5莫耳％以下。 作為上述其他不飽和單體，例如可列舉：乙烯、丙 稀、異丁 、〇!—辛、嫌、— -4- — ,ι»^. 卞琊CL十一烯、α_十八烯等烯烴 類；丙烯酸、甲基丙烯酸、丁烯酸、;噴丁烯二酸、順丁烯 二酸酐、衣康酸等不飽和酸類或其鹽或單烷基酯或二烷基 酯等；丙烯腈、甲基丙烯腈等腈類；丙烯醯胺、甲基丙烯 酿胺等醯胺類；乙料酸、芳基續酸、甲基稀丙基確酸等 烯烴磺酸或其鹽；烷基乙烯基醚類；聚氧乙烯（甲基）烯丙 基醚、聚氧丙烯（甲基）烯丙基醚等聚氧伸烷基（甲基）烯丙基 醚；聚氧乙烯（甲基）丙烯酸酯、聚氧丙烯（甲基）丙烯酸酯等 聚氧伸烷基（甲基）丙烯酸酯；聚氧乙烯（曱基）丙烯醯胺聚 氧丙烯（甲基）丙烯醯胺等聚氧伸烷基（甲基）丙烯醢胺；Ν — 丙烯醯胺曱基三甲基氣化胺、烯丙基三甲基氯化胺、二甲 基稀丙基乙烯基酮、Ν—乙烯基吡咯啶酮、氣乙烯、偏二 氯乙烯、聚氧乙烯（1一（甲基）丙烯醯胺一 1，1 一二曱基丙基） 醚、聚氧乙烯乙烯醚、聚氧丙烯乙烯醚、聚氧乙烯烯丙 胺、聚氧丙烯烯丙胺、聚氧乙烯乙烯胺、聚氧丙烯乙烯胺 等。 又’作為後續改質之方法，可列舉使聚乙烯醇進行乙 酿乙酸醋化、縮醛化、胺酯（urethane )化、醚化、接枝 化、磷酸酯化 '氧基伸烷化之方法等。 201247408 又’作為聚乙烯醇系樹脂，亦可使用支鏈上具有1，2 一 一醇鍵之聚乙稀醇系樹脂。支鏈上具有1,2 —二醇鍵之聚乙 烯醇系樹脂，例如可藉由如下方法獲得：（A )使乙酸乙烯 酯與3,4 —二乙醯氧基—〖_ 丁烯之共聚物皂化之方法， (B)使乙酸乙烯酯與碳酸乙烯基伸乙酯之共聚物皂化及脫 碳酸之方法，（c)使乙酸乙烯酯與2,2_二烷基_4_乙烯 基一1，3 —二氧戊環之共聚物皂化及脫縮酮化之方法，（d) 使乙酸乙烯酯與甘油單烯丙基醚之共聚物皂化之方法等。 作為聚乙烯醇系樹脂，較佳為皂化度為75莫耳％以上 者，進而較佳為皂化度為78〜99.7莫耳％者，尤佳為皂化 度為85〜95莫耳％者14化度過低，則有與硬化樹脂層 之脫模性降低之傾向。 又’作為聚乙稀醇系樹脂於2Gt 4 4重量％水溶液之 黏度，較佳為1〇〜7〇mPa.s(2(rc)，進而較佳為15〜 6〇^.以20。(：），尤佳為2〇〜5〇1^.以2〇〇。若該 黏度過低’則有膜強度等機械物性降低之傾向，若過高 則有製膜性降低之傾向》 同 再者，上述黏度係根據JIS K6726而測定者。 進而，關於該聚乙烯醇系樹脂，為了防止膜 防止膜之強度降低，較理想為將樹脂中所含有之乙酸納之 量㈣為〇.8重量%以下、較佳為。·5重量。以下。關於該 含量之調整’㉟常為利用曱醇等醇或水進行洗淨 於本發明中 乙稀醇系樹脂膜， 例如聚乙烯醇系樹脂 201247408 膜係以如下方式製造。 於製造聚乙烯醇系樹脂膜時，就抗結塊性、消光等設 計性、或減少指紋對裝飾成形品之附著之觀點而言，較佳 含有填料，進而亦可視需要適當摻合塑化劑、界面活性 劑。 作為上述填料’可列舉多糖類及/或無機類。於多糖 類中，較佳為澱粉，例如可使用：生澱粉（玉米澱粉、馬 鈴薯澱粉、蕃薯澱粉、小麥澱粉、木薯（cassava)澱粉、 西米殺粉、樹薯（tapi〇ca)澱粉、帚蜀黍（s〇rghum bic〇1〇r Moench)澱粉、米澱粉、豆澱粉、葛澱粉、蕨澱粉、蓮澱 粉、荸薺澱粉等）；物理改質澱粉（α —澱粉、分離直鏈 殿粉、濕熱處理澱粉等）；酵素改質澱粉（水解糊精、酵 素分解糊精、直鏈澱粉等）；化學分解改質澱粉（酸處理 澱粉、次氣酸氧化澱粉、二醛澱粉等）；化學改質澱粉衍 生物（酯化澱粉、醚化澱粉、陽離子化澱粉、交聯澱粉等） 等。再者，作為化學改質澱粉衍生物中之酯化澱粉，可列 舉乙酸醋化澱粉、琥轴酸酯化澱粉、硝酸酯化澱粉、磷酸 醋化殿粉、脲磷酸酯化澱粉、黃原酸酯化澱粉、乙醯乙酸 6旨化殿粉等；作為醚化殺粉’可列舉稀丙基醚化殿粉、曱 驗化殿粉、羧甲基醚化澱粉、羥乙基醚化澱粉、羥丙基醚 化澱粉等；作為陽離子化澱粉，可列舉澱粉與2 _二乙基 胺基乙基氣化物之反應物，澱粉與2,3 —環氧丙基三甲基氣 化胺之反應物等；作為交聯澱粉，可列舉甲醛交聯澱粉、 表氣醇父聯殿粉、攝酸交聯澱粉、丙稀酸交聯澱粉等。其 201247408 中就獲仔之容易度或經濟性之觀點而言，可較佳地使用 生澱粉。 矽 球 在弓 鉀 維 又’作為無機類，例如可列舉：滑石、黏丨、二氧化 夕滿土、尚嶺土、雲母、石棉、石膏、石墨、玻璃氣 玻璃珠、硫酸弼、硫酸鋇、硫酸敍、亞硫_、碳酸 鬚晶狀碳酸約、碳酸鎂 '碳納紹石' 白雲石、欽酸 碳黑、玻璃纖維、氧化銘纖維、棚纖維、加工礦物纖 碳纖維'碳空心球、膨土、蒙脫石、銅粉等。 該等填料可單獨使用，亦可組合使用2種以上。 上述填料之含量相對於聚乙烯醇系樹脂1〇〇質量份， =為3〜30質量份，更佳為4,量份尤佳為5〜2〇 伤。若填料之含量過少，則有於製造膜時容易產生結 ^向’若過多’則有基膜之強度降低’轉移印刷時對 破轉印體之追隨性降低之傾向。 上述填料之平均粒徑較佳為Q1〜心m，尤佳為 則右〜ΓΓ，進而較佳為0.5〜2〇^。若平均粒徑過小， 則有於製造膜時容易產生結塊之傾向，若過大 硬化性樹脂層f；將 、§ )塗敷於基膜上時容易混入氣泡等 而增加缺陷等之傾向。 孔/包專 作為上述塑化劑，例如可列舉：甘油、二甘油、 油4甘油類，三乙— 一甘 等燒二醇類或：經；Γ 醇、聚丙二醇、二丙二醇 用2種以上。 土丙统等。該等可單獨使用’亦可併 於上述聚乙稀醇系樹脂中摻合之塑化劑之含量相對於 12 201247408 -享系樹脂刚質量份，較佳為2〇質量份 果齡〜15質量份。若上述塑化劑之含量過少’則有塑化效 果較低，導致所獲得之基膜斷裂之^塑化效 置穩定性降低之傾向。 右過多’則有放 摻合上述界面活性劑係為了提高作 製膜裝置之轉筒或傳送帶等之金屬表面與製 性，具體而言，例如可列，之膜的剝離 烯辛基壬醚、聚氣乙嫌+ 烯壬基苯醚、聚氧乙 基峻㈣院基苯麵、聚氧乙稀院基稀丙 :肝單二山梨糖醇肝單月桂酸醋、聚氧乙稀山梨糖 醇：車棕櫚酸酿、聚氧乙烯山梨糖醇肝單硬脂酸酯、聚氧 二二梨糖醇酐單油酸醋、聚氧伸院基貌基 聚氧乙稀月桂基胺、聚氧乙稀硬脂基胺等聚氧乙 席几基胺等。該等可單獨使用，亦可併用2種以上。其 2就剥離性之觀點而言’較佳為使用聚氧伸院基烧基越 Μ酿早乙醇錢鹽、聚氧乙晞院基胺、聚氧乙稀山梨糖醇 酐單月桂酸酯。 關於上述界面活性劑之含量，相對於聚乙烯醇系樹脂 κο質量份，較佳為0.01〜2〇質量份，更佳為〇 〇3〜丨5 ^ 量份。若上述界面活性劑之含量過少，則有製膜裝置之轉 筒或傳送帶等之金屬表面與製造之膜的剝離性降低而難以 製造之傾向，反之，若過多，則有於膜表面滲出並於塗敷 硬化性樹脂層時容易產生厚度不均之傾向。 進而’亦可於不妨礙本發明之效果之範圍内，摻合交 聯劑、抗氧化劑（紛系、胺系等）、穩定劑（填酸酯類等）、 13 201247408 著色料、番％L υχ 料、增量劑、消泡劑、防銹劑、紫外線 劑、以及甘 a *1人 、水溶性高分子化合物（聚丙烯酸鈉、聚環氡 乙院•、聚7 Μ 埽基吡咯啶酮、糊精、聚葡萄胺糖、曱殼音、 甲基纖維素、經乙其 ' &己基纖維素等）等其他添加劑。 稀醇系樹脂構成之基膜例如可按照如下方 η 外Ί 首先以特定摻合量摻合上述聚乙烯醇系樹脂、塌 料：塑化劑、界面活性劑等而製備膜形成材料》其次，使 膜形成材料自了字模流延至製膜傳送帶上或製膜轉筒上， 藉由乾燥而使其膜狀化，並視需要進而進行熱處理，藉此 製造基膜。 此處，上述所謂製膜傳送帶，係指具有架設於一 間並移動之環形傳送帶，使自丁字模流出之膜形成材料流 延至環形傳送帶上並且使其乾燥者。上述環形傳送帶例如 係由不鏽鋼構成，較佳為對其外周表面實施鏡面抛光。 又，上述所謂製膜轉筒，係指旋轉之筒型輥，使自丁 字模流出之膜形成材料流延至！個以上之旋轉筒型輕 使其乾燥者。 關於乾燥溫度，於使用製膜傳送帶之情形時，通常較 佳為80〜160t ’尤佳為90〜15〇t。若乾燥溫度過低則 有J燥不足而降低製品外觀之傾向，若過高，則有熱處理 較向而使含水率過低之傾向。 又，於使用製膜轉筒之情形時’製膜第一轉筒通常較 佳為〜lom為82〜99t。若乾燥溫度過低則 14 201247408 有乾燥不足而降低製品外觀之傾向，若過离， 一 ⑴有熱處理 過南而使含水率過低之傾向。此處，上述所謂製骐第— 筒係指使自τ字模流出之膜形成材料流延之位於 的筒型輥。 、玻上游側 於上述乾燥後，可視需要進行熱處理，作為該執處理 之方法，例如可列舉：熱親（包含軋光報）、熱風、遠红 外線、介電加熱等方法。又，進行熱處理之面較佳為與接 觸製膜傳送帶或製膜轉筒之面相反側之面。又，實施 理之膜之水分含量通常較佳為4〜8重4%左右 處理後之膜之水分含量通常較佳為2〜6重量％。 利用上述熱處理機之熱處理較佳為於50〜i80〇c進 Γ更佳為6〇〜16〇〇C，尤佳為7〇〜㈣。即，若上述敎 地理之溫度過低，則有時接觸製膜傳送帶或製膜第一轉筒 之面會產生捲曲’有於形成硬化性樹脂層之步驟及轉 ==良之傾向，若熱處理之溫度過高，則有由於膜 變軟而谷易產生敵褶’使品質降低之傾向。進而，關於上 述熱處理所需要之時間， 、 於為熱處理輥之情形時，雖由其 2溫度決定，但通常較佳為設為i〜⑽秒鐘較佳㈣ 〇 &鐘。上述熱處理通常係繼用 處理後，利用另一個熱處理親進行。 焊輥 招m /本發明中’上述熱處理較佳為對基膜之硬化性 樹脂層側之表面進行。 藉由上述方法而獲得聚乙稀醇系樹脂之基膜 之聚乙_系樹脂膜之含水率，較佳為q5〜ig重量％之範 15 201247408 固 切割步驟或硬化性樹脂層之二：容變脆而於 *之，若含水率過高，則有膜容易伸長==降 二或於硬化性樹脂層之形成步驟中層容’: 生厚度不均之傾向。 衝細層谷易產 再者，聚乙烯醇系樹脂膜之含水率例如可 以作(:::子工業公司製造之Μ8— “Μ而測定： 如可列舉如=乙稀醇系樹脂膜之含水率之調整方法，例 女了歹J舉如下所不之方法。 ^ 根據如下所示之含水率 —法而將聚乙烯醇系膜之含水率設定於上述範圍内。 (1)使對溶解有聚乙稀醇系樹脂之塗佈料進行乾燥並 製膜時之乾燥機溫度上下變動而 U 入、 琨仃眾乙烯％系樹脂膜之 0濕、除濕，藉由此種方法進行 Μ ^ ^ &手之凋整。關於塗佈 ，皿，由於該溫度對乾燥效率造成影響 之範圍内。又，於乾燥時，較佳為於較佳= 之fBi t佳為145〜60t之間且具有溫度梯度之至 二以上熱風乾燥機中進行，進而就水分調整之觀點而 5 ’較佳為進行1〜15分鐘之乾燥，更佳為進行卜⑺八 鐘之乾燥》 77 若上述乾燥溫度之梯度範圍過大，或乾燥時間過長， 則有過度乾燥之傾向，反之’若乾燥溫度之梯度範圍過 小，或乾燥時間過短，則有乾燥不足之傾向。 上述溫度梯度係於150〜5(rc之間階段性地改變乾燥 溫度者’通常較為有效的是，自乾燥開始時起緩緩提高溫 16 201247408 度&使其達到直至成為特定含水率為止而 溫度範圍的最高乾燥溫度，繼而緩緩降低乾燥溫产，=燥 最終達到目標含水率。苴俜A ' ’、又藉此 手，、係為了控制結晶性、剝離性、在 產性等而進行者，例如可列舉12〇t叫抓―mi⑽ 二:13〇c_12〇t: — llot、115°mu(rc〜9(rc 寸μ度梯度设定，可適當選擇並實施。 ⑴藉由於聚乙稀醇系樹脂膜之捲 ::::聚―加濕、除濕，從而進::: (3)藉由於聚乙稀醇系樹脂膜之捲取前或捲取後進行 之調整而進仃聚乙烯醇系樹脂膜之除濕，從而進行含水率 可根據以上方式獲得聚乙烯醇系樹脂膜。 :本發明中，乙稀醇系樹脂膜之厚度（於圖丨所示基 "、’以「tj表示）較佳為5〜BO”，尤佳為10〜1〇〇 二尤佳為20〜70…若膜變得過厚，則難 行賦+ 之凹凸形狀’若變得過薄，則有膜於進 凹凸形狀之加工時膜斷裂之虞。 以上述方式獲得之乙烯醇系樹脂膜 =板狀…發明所使用之高低差5〜2〇。二： 當處理可藉由對由作為原料之樹脂組成物製成之膜實施適 並& 4*而賦予。賦予尚低差5〜2〇〇"m之凹凸形狀之方法 膜…、特別限定’可採用壓紋加工或摩擦處理等。又 膜之後加工m 匕種 並…、限定，亦可藉由對製膜時使用之製骐傳送 201247408 帶或製膜轉筒施加凹凸形狀而於膜形成時形成 之高低差之凹凸形狀。然而，就容易獲得具有所期望5 低差之凹凸形狀、所期望之圖案形狀之觀點，關於容易： 各種設計（花紋、紋樣）對應之生產設備之見解而言，可 較佳地採用利用壓紋加工賦予形狀之方法。 壓紋加工係使用壓紋梃及支承觀，並藉由使乙 樹脂膜通過壓紋輥與支承輥之間而進行，於壓紋輥表面來 成有欲賦予之設計形狀（凹凸式樣v 作為該壓紋輥，可使用藉由離刻或車床加工等而使其 表面形成為Λ狀之金屬輥或陶究輥等。該凸部之形狀取決 於欲賦予之設計式樣。根據絹紋、罐紋、砂紋、髮線:文 樣、麻紋、皮革風格之花紋等，除可列舉格子狀 狀、龜甲狀、菱形狀等定形之連續& · 〜逻％武樣以外，亦可列舉將 各種尺寸t凸部組合而成之不定形#凸部之不連續式樣 等。於為連續式樣之情形時，凸部通常為1〇〜2〇〇網目， 較佳為20〜100網目。若該凸部之網目過小，則有難以於 膜上形成凹凸形狀之傾向，冑而有難以獲得具備具有所期 望之立體形狀之設計的膜之傾向H面，若網目過 大，則有難以獲得設計性優異之式樣之傾向。 又，作為壓紋輥之凹凸部之高低差，較佳為30〜500 M m，尤佳為40〜400 /z m，進而較佳為5〇〜3〇〇^ m。若高 二差過小，則有實施壓紋加工之膜的凹凸部之高低差^ 了，進而設計之轉印性降低，難以獲得所期望之設計之傾 向另一方面，雖然有隨著壓紋輥之凹凸部之高低差增 18 201247408 大，所獲得之膜的凹凸形狀之高低差亦增大之傾向，但於 壓紋輥之凹凸部之高低差達到特定程度時，則難以反映到 膜之凹凸形狀之尚低差上。進而，若壓紋輥之凹凸部之高 低差過大，則有壓紋加工後之臈變得容易產生皺褶等而使 膜之品質降低之傾向。 另一方面’作為支承輥，可較佳地使用表面硬度以基 於 JIS K 6253 之 A 形硬度試驗計（A type hardness tester) 計為80以上，且以D形硬度試驗計（Dtype以“加“ tester)计為90以下者。此處，所謂基於Jis κ 測定之 表面硬度H乂禾】帛㊣簧試驗機所獲得之壓針的壓入硬 度為基準之硬度’數值越高硬度越硬，D形硬度試驗計係 用於較A形硬度試驗計更硬之情形。 若支承輥之表面硬度過低，則有即便壓紋輥形成有具 有特定高低差之設計，仍難以對膜實施具有特定高低差之 壓紋加工的傾向。另一方面，若支承輥之表面硬度過高， !有谷易於膜上產生針孔等而使膜之品質降低之傾向。 於本發明中，作為支承觀’只要是具有上述範圍之輥 =硬度者即T，例如較佳為被覆有胺g旨系、聚梦氧系、 一、烯烴系等之合成橡膠等之輥。 妒诵二：發月卜較佳為藉由使乙烯醇系樹脂膜如上所述 ==紋概與支承槪之間而進行壓紋加工，由該支承觀 支承輥之2系樹脂膜對壓紋輥的推壓力可根據所使用之 常較佳為。.5:=及壓紋輥之凹凸形狀而適當選擇，通 a，更佳為1〜8MPa，尤佳為i〜 19 201247408 5MPa » 若該推壓力過小，則有即便使用具有充分之深度之壓 紋報’亦難以對膜賦予所期望之高低差之傾向，若過大， 則有壓紋加工後之膜之厚度部分性地變薄而機械強度容易 降低’並且產生針孔之傾向。 又，於本發明中，較佳為壓紋加工時之壓紋輥之表面 溫度為100〜18〇t，且支承輥之表面溫度為5〇t以上。壓 紋輥之更佳之表面溫度為1〇5〜17〇<t，尤佳為ιι〇〜16〇 C，支承輥之更佳之表面溫度為6〇〜11(rc，尤佳為〜 100〇C。 右壓紋輥之表面溫度過低，則有無法獲得具有充分之 深度之壓紋加工之傾向，若過高，則有壓紋加工時膜容易 伸長而使壓紋加工後之設計變得不均勻之傾向。若支承輥 之表面溫度過低’則有無法獲得具有充分之深度之壓紋加 工之傾向。 ’ 進而，於進行壓紋加工時，壓紋輥之加卫速度較佳為 設為MOOm/min，尤佳為設為2〜9〇m/min，進而較佳 為設為3〜80m/min，特佳為設為5〜5〇m/min。若該加 工速度過慢’則有生產效率降低之傾向，若過快，則心 易產生皺褶等而使品質降低之傾向。 令 又，於本發明中’作為實施有壓紋加工之乙烯醇系 脂膜’含水率較佳為2〜10重量％，更佳為3〜8重量％ 尤佳為4〜7重量％。若該含水率為上述範圍以外，則有° 以實施具有充分之深度之壓紋加工之傾向。 20 201247408 作為將乙烯醇系肖脂膜之含水率調整 法，可列廒如T 固之方 膜繼續進行法等：對製膜後乾燥前之乙稀醇系樹脂 C燦而調整含水率，或將含水率未達2重量％ 率。’肖系樹脂犋浸潰於水中或實施調濕等而調整含水 士此’可獲得用作基膜之具有高低差為5 之 凹凸形狀的乙稀醇系樹脂膜。 … 作為用作基骐之乙稀醇系樹脂膜（基 率，於23t、神 心辦裂伸長 。H調濕條件下較佳為150%以上，進而 ㈣〇%以上。若斷裂伸長率過低，則有於切割步驟戈 連續地形成硬化性樹脂層之步驟中產生斷紙之傾向\步驟或 再者作為斷裂伸長率之上限，通常為3 臈之斷裂伸長率俜栩 此處’ 丰係根據^1^7^7 ( 1999年）而測定。 上述乙烯醇系樹脂膜構成之基膜於 (於圖1中，以「丁主 丨观上之厚度 .u入 」表不，相當於實質上之膜厚t盥高彻 之°計量）就凹凸形狀賦予之容易性、轉印時二 印體之追隨性之觀點而…、约Γ轉印時對破轉 。，較佳為1〇〜35〇"m，尤佳 〜3。。”’進而較佳為2〇〜27〇”。若該厚二為 表示凹凸形狀較小，有 較】’則 厚度τ較大，則表-體’計之轉印性變差之傾向。若 右"凸形狀之高低差相料膜厚較大， 有谷易因壓紋加工蓉而 大’ 使膜斷裂之傾向。進而有 印時產生皺褶等而使轉 有令易於轉 如…4 士 變得不均勻之傾向。 如此獲件之本發明之基膜較佳為 防濕包裝之處理，並於，λ 叮无引a知之 ;10〜25°C之環境下以懸空狀態保 21 201247408 存0 其=欠’對本發明之轉移印刷用積層體進行說明。 <發明之轉移印刷用積層體係於上述基膜上積層有硬 化性樹脂層及印刷層者，進而亦可於上述印刷層上積層接 著層。 上述硬化性樹脂層係於剝離基膜時成為被轉印體（裝 飾成形品）之最外面之層’於剝離基膜前或剝離基膜後， 該硬化樹脂層硬化並成為用以保護被轉印體表面之保護 層。作為材質’例如可使用聚丙烯樹脂、聚酯樹脂、聚氣 乙烯樹脂、纖維素樹脂、橡膠聚合物、聚胺基甲酸酯樹 脂、聚乙酸乙烯酯樹脂等，除此以外，亦可較佳地使用紫 外線硬化性樹脂組成物或電子束硬化性樹脂組成物等活性 能量射線硬化性樹脂組成物、或熱硬化性樹脂組成物。於 本發明中，就成形品之耐化學品性、耐磨耗性之觀點而 5 ’較佳為使用活性能量射線硬化性樹脂組成物。 又，該活性能量射線硬化性樹脂組成物較佳為亦具有 藉由熱而硬化之性質（熱硬化性）。 該活性能量射線硬化性樹脂組成物較佳為，例如為 有丙稀酸系樹脂及胺酯（甲基）丙稀酸 (Urethane(meth)aCrylate )系化合物而成者，較佳為進而 有光聚合性單體而成者。 作為該丙稀酸系樹脂，例 之均聚物或共聚物，或以其他 合成分之丙烯酸系共聚物等。 如可列舉··丙烯酸酯系單體 乙烯性不飽和單體作為共聚 22 201247408 作為丙烯酸酯系單體，例如可列舉，（甲基）丙稀酸甲 酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙稀酸 丁酯、（曱基）丙烯酸己酯、（曱基）丙烯酸2 —乙基己酯、（曱 基）丙烯酸異壬酯、（曱基）丙烯酸苄酯、（曱基）丙烯酸環己 酯、（甲基）丙烯酸二甲胺基乙酯、（甲基）丙烯酸異辛醋、 (甲基）丙烯酸正辛酯、（曱基）丙稀酸月桂酯、（甲基）丙烯酸 2—曱氧基乙酯、（曱基）丙烯酸丁氧基乙酯、甲氧基三乙二 醇（曱基）丙烯酸酯等，其中較佳為烷基之碳數為1〜12之 丙烯酸烷基酯’尤其可較佳地使用（甲基）丙烯酸曱酯、（曱 基）丙烯酸乙酯、（曱基）丙烯酸丁酯、（甲基）丙烯酸2_乙基 己酯等脂肪族丙烯酸烷基酯。 作為其他乙稀性不飽和單體，例如可列舉：（曱基）丙 烯酸2—羥基乙酯、（甲基）丙烯酸2_羥基丙酯、（曱基）丙 埒酸氣一2—羥基丙酯、（曱基）丙烯酸四氫糠酯、（曱基） 丙烯酸2 —羥基一3 —笨氧基丙酯、二乙二醇（甲基）丙烯酸 酯、聚乙二醇（甲基）丙烯酸酯、N_羥曱基（甲基）丙烯醯胺 等含有經基之不飽和單體；甲基丙烯酸環氧丙基酯、甲基 丙稀酸稀丙基環氧丙基酯等含有環氧丙基基之不飽和單 體；2 —丙烯醯氧基乙基異氰酸酯、2 —甲基丙烯醯氧基乙 基異氰酸醋等含有異氰酸酯基之不飽和單體；丙烯醯胺、 甲基丙烯醯胺、N—(正丁氧基烷基）丙烯醯胺、N—(正丁氧 基炫•基）曱基丙烯酿胺等含有醯胺基之不飽和單體；丙烯醢 胺一3 —曱基丁基曱胺、二曱胺基烷基丙烯醯胺、二曱胺 基炫•基曱基丙烯醯胺等含有胺基之不飽和單體；乙烯磺 23 201247408 酸、芳基續酸、甲基稀丙基績酸等稀煙績酸 胺-2-甲基丙磺酸、茉内琊醞 -^ ^ 埽醆或其鹽等含有續酸基之 不飽和單體；苯乙嫌、 S 文乙烯酯、丙烯腈、丙烯醯胺 等0 該丙稀酸醋系單體及其他乙稀性不飽和單體之含有比 例（共聚合比）並無# PP $ 0 将別限疋，例如較佳為將丙烯酸酯系 單體ax為2G 1 GG重f % ’將其他乙稀性不飽和單體設為〇 〜80重量％，尤佳為將丙烯酸酯系單體設為4〇〜_重量 %’將其他乙烯性不飽和單體設為〇〜6〇重量％，進而較佳 為將丙稀㈣系單體設$ 8G〜⑽重量％，將其他乙稀性 不飽和單體設A 〇〜20重量％:丙烯酸酯系單體之含有 比例過少，則有硬化膜之封水性、耐滿熱性等耐久性降低 之傾向。 上述丙烯酸系樹脂可藉由業者周知之方法而容易地製 造，例如使上述聚合成分於有機溶劑中進行自由基共聚。 如此可獲得本發明所使用之丙烯酸系樹脂，該丙烯酸 系樹脂之玻璃轉移溫度（Tg)較佳為20〜13(rc，尤佳為 30〜120°C，進而較佳為40〜110。(：。若玻璃轉移點（Tg) 過低’則有活性能量射線硬化性樹脂組成物等之硬化性樹 脂層帶有黏者性而於實施後加工時成為產生不良（步驟中 之捲縮、印刷不良等）的原因之傾向，若過高，則有於使 活性能量射線硬化性樹脂組成物等之硬化性樹脂層硬化而 形成保護層時變脆之傾向。 又，丙烯酸系樹脂之重量平均分子量（Mw )較佳為 24 201247408[Technical Field] The present invention relates to a base film which is a constituent element of a laminate for transfer printing, a laminate for transfer printing using the base film, and a method for producing the base film The transfer printing laminate can be used to form a three-dimensional design of the surface of the enamel molding product by a transfer method: an interior material or an exterior material of a vehicle such as an automobile, a baseboard, a sill (cornjce) ) such as decoration frames, window frames, door frames, etc., interior materials for buildings such as walls, floors, and ceilings, frames, containers for home appliances such as TV receivers, mobile phone parts, and air conditioners. [Prior Art] Previously, there was a transfer method for the surface printing design of molded articles such as home electric appliances, cosmetic containers, and miscellaneous goods. The transfer method is a method for transfer printing on a base sheet (base film) in which a transfer layer composed of a protective layer on the surface of a molded article, a design printed layer, an adhesive layer, or the like is laminated. After the transfer printing laminate is heated and pressed to be attached to the surface of the molded article as the adherend, the base sheet is transferred from the transfer layer to the surface of the molded article. As the base sheet (base film) of the laminate for transfer printing, a polyethylene terephthalate film is usually used (for example, refer to Patent Documents 1 and 2). Further, the base sheet (base film) may be a film composed of a resin having characteristics of dissolved elution or swelling and peeling, and a polyethylene glycol film, a polyvinyl butyral film, or an ethylene-vinyl alcohol copolymer film may be used. Etc. (for example, refer to Patent Document 3). 201247408 In recent years, in the printing of the design of the molded article by the transfer method as described above, the following requirements have been raised: the glare on the surface of the molded article is prevented, or the surface of the molded article is advanced in order to advance the design. The protective layer is set to extinction (extinction style) or a three-dimensional design is applied. In the case of the matte effect, a layered transfer printing layer having a partial matte layer having fine irregularities made of a water-soluble resin in which a matting agent is dispersed is provided on the base sheet (for example, see Patent Document 4). Or a decorative molded article for transferring a laminated body for printing, which is provided with a hard coat layer (as a protective layer) having an extinction pattern of fine particles having an average particle diameter of 2 (for example, refer to the patent document) 5) 专利 专利 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利[Patent Document 4] Japanese Laid-Open Patent Publication No. Hei 2 No. Hei. No. Hei. Line pattern, hemp pattern, leather pattern, etc., etc., are required to be higher. 'The design of the design by the transfer method' is being studied. 1 This kind of stereoscopicity is given. The above patent documents use a smooth base sheet. Material does not enter The layered body for eliminating the brushing has a matting effect on the surface of the molded article. In the case of the transfer printing laminate disclosed in Patent Documents 4 and 5, it is difficult to perform manufacturing management because the number of operation steps before the "shadow effect" is large, and the manufacturing cost cannot be satisfied. & However, the obtained transfer printing laminate system is stopped to impart a matte degree, and it is impossible to apply a three-dimensional design to the surface of the decorative molded article. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a base film for a transfer printing laminate, a transfer printing laminate using the base film, and a method for producing the base film. The body is excellent not only in the peeling property of the base film and the peeling layer (the layer serving as the protective layer of the molded article), but also on the surface of the decorative molded article to impart crepe, crepe, sand, hairline, hemp, and leather. Three-dimensional design of the pattern. That is, the subject matter of the present invention relates to a base film for transferring a laminated body for printing, which is used for transferring a three-dimensional designer, and is characterized by having a concave-convex shape with a height difference of 5 to 200 /zm. Further, the present invention provides a method for producing a base film, which comprises a method for producing a base film for a transfer printing laminate having a surface layer having a decorative molded article having irregularities on the surface, which comprises passing the film through A step of imparting an uneven shape to the film between an embossing roll (emb〇ss r〇u) having a surface temperature of 100 to 180 C and a backup roll (back up r〇u) having a surface temperature of 5 〇〇 c or more. Further, the "curable resin layer" is a layer which constitutes the surface of the transfer target after the transfer printing laminate of the present invention is transferred onto the transfer target and the base film is peeled off. Usually, a thermosetting resin, an active energy ray curable resin or the like is used to form a protective layer 5 201247408 (hard coat layer) for protecting the surface of the transfer target by curing. In the laminate for transfer printing of the present invention, a film having a concavo-convex shape is used as the base sheet (base film), and the surface of the curable resin layer on the base film side can be provided with a concavo-convex shape. When the surface of the peeling side of the curable resin layer is formed with a concavo-convex shape, not only the peeling property of the base film and the protective layer after the transfer printing (the layer in which the curable resin layer is cured) is improved, but also the uneven shape is transferred. The surface on the peeling side of the base film of the transferred curable resin layer, that is, the outermost surface of the decorative molded article. As a result, a decorative molded article formed with a protective layer (hard coat layer) having a three-dimensional design can be obtained. In the laminate for transfer printing using the base film of the present invention, not only the base film and the protective layer (layer in which the curable resin layer is cured) are excellent in releasability, but also can be easily transferred onto the surface of the decorative molded article. Three-dimensional design such as crepe, crepe, sand, hairline, and linen. This is used to manufacture interior materials or exterior materials for vehicles such as automobiles, skirting boards, fascia boards and other decorative components, window frames, door frames, etc., interior materials for walls, floors, ceilings, etc., TV receivers. It is very useful for decorative molded articles such as mobile phone parts, air conditioners, and the like for housings and containers of home electric appliances. [Embodiment] Hereinafter, the present invention will be described in detail. The base film of the present invention is a base film for forming a laminated body for transfer printing having a three-dimensionally designed protective layer on the surface of a molded article by a transfer method, which is formed by sequentially laminating a hardening resin layer on the base film. And the constituent elements of the laminated body for transfer printing of the printed layer. 6 201247408 The base film of the present invention has a concavo-convex shape with a height difference of 5 to 200 / / m, preferably a height difference of 10 to 170 / / m' and further preferably a height difference of 1 〇 15 15 〇 μ η. If the height difference is too small, it is difficult to transfer to form a three-dimensional design. On the other hand, the base film having an excessively high or low difference tends to be difficult to manufacture, and it is difficult to obtain even if the height difference of the uneven shape of the base film is increased to a specific level or more. There is a tendency to have a three-dimensional design with a height difference corresponding to the low difference. Here, the so-called film height difference is represented by "Η" (or Hi, Η2, Η3) in Figure i, specifically by using a laser microscope (color 3D laser manufactured by Keyence) The microscope νκ_97〇〇) was measured from the value of the maximum height of the surface of the curable resin layer forming the base film minus the value of the lowest height. The uneven shape refers to the shape of the height difference of the surface of the base film on which the surface of the curable resin layer is formed, and is a height difference between the pattern and the pattern. The shape of the concave convex can be formed along any of the width direction and the longitudinal direction of the film, and it is preferable that the entire film is formed into a concave-convex shape. In this case, each of the irregularities may be a rectangular shape of a scraped surface as shown in Fig. 1 (a), and t may be a profile wave type as shown in Fig. Further, as shown in the figure, the combination of the irregularities may be different. The example of Fig. 1 (C) is a film having a concavo-convex shape including three stages of high paths (H丨, H2, H3). In this case, Ben: Ming (4) "The height difference of the film" refers to the maximum height difference (Η". In the concave length i of the concave-convex shape, the length is ~2" (in Figure 1, with, or "," can be expressed in the length of the number (for example, the case of a continuous pattern), or the combination of the lengths of the complex (for example, the case of a random pattern). Moreover, 7 201247408 drawn patterns, patterns The type is not particularly limited, and examples thereof include a .e pattern, a crepe pattern, a sand pattern, a hairline pattern, a hemp pattern, a leather pattern, and the like. The uneven shape as described above can be embossed by, for example, a film. The base film of the present invention includes a polyethylene terephthalate resin film, a poly-smoke resin film, and a vinyl alcohol resin film (polyvinyl alcohol resin film, ethylene vinyl alcohol resin film). a film such as a hardened resin layer The viewpoint of releasability, preferable are 'more preferably a vinyl alcohol-based resin is a polyvinyl alcohol-based film by: resin film, polyvinyl alcohol film is the best. In the present invention, the term "consisting of a vinyl alcohol resin film" includes a layer (film or coating) in which a vinyl ether resin film is laminated, but usually a vinyl alcohol resin. The film alone constitutes a base film. The vinyl alcohol resin film can be obtained by forming a film of a vinyl alcohol resin. The vinyl alcohol-based resin may be any one having an ethylenic acid unit and an == enol unit. Since i is a B-based resin, for example, 1], a polyvinyl alcohol containing, as a polyvinyl acetate-dyed compound = alcohol modified (modified glycol), is about 20 to 60 mol%. A glycol-based resin or the like is formed. Preferably, a polyvinyl alcohol-based resin (polyethylene glycol and a modified dilute alcohol) is used, and polyvinyl alcohol is preferably used. The degree of chemical conversion of the ethyl acetate vinegar unit contained in the 75-enol resin is 75 ❶. The above-mentioned mold release with the hardened resin layer is 80% by mole or more. 201247408 The above modified polyethylene glycol can be produced by saponifying the polymer of ethyl acetate and other unsaturated monomers, or by Polyvinyl alcohol is produced by subsequent modification. The mass is preferably 1 Gmol% or less, more preferably 7 mol% or less, still more preferably 5 mol% or less. Examples of the other unsaturated monomer include ethylene, propylene, isobutyl, oxime-xin, susceptibility, --4-yl, ι»^. 卞琊CL undecene, α-octadecene, and the like. Olefins; acrylic acid, methacrylic acid, crotonic acid, unsaturated acids such as maleic acid, maleic anhydride, itaconic acid or salts thereof or monoalkyl or dialkyl esters; And nitriles such as methacrylonitrile; decylamines such as acrylamide and methacrylamide; olefin sulfonic acids or their salts such as acetic acid, aryl acid, methyl propyl acid; Polyethers such as polyoxyethylene (meth) allyl ether, polyoxypropylene (meth) allyl ether, polyoxyalkylene (meth) allyl ether; polyoxyethylene (meth)acrylic acid a polyoxyalkylene (meth) acrylate such as an ester or a polyoxypropylene (meth) acrylate; a polyoxyalkylene group such as a polyoxyethylene (fluorenyl) acrylamide polyoxypropylene (meth) acrylamide (Meth) acrylamide; hydrazine - acrylamide hydrazinyl trimethylated amine, allyl trimethylamine chloride, dimethyl propyl vinyl ketone, oxime vinyl Pyrrolidone, ethylene ethylene, vinylidene chloride, polyoxyethylene (1-(methyl) acrylamide-1,1 -dihydroxypropyl) ether, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, Polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, polyoxypropylene vinylamine, and the like. Further, as a method for subsequent modification, a method of making acetic acid acetalization, acetalization, urethane, etherification, grafting, and phosphorylation of a polyvinyl alcohol can be mentioned. Wait. 201247408 Further, as the polyvinyl alcohol-based resin, a polyvinyl alcohol-based resin having a 1,2-one alcohol bond in a branched chain can also be used. A polyvinyl alcohol-based resin having a 1,2-diol bond on a branch can be obtained, for example, by the following method: (A) copolymerization of vinyl acetate with 3,4-diethyloxy-?-butene a method of saponification, (B) a method of saponifying and decarbonating a copolymer of vinyl acetate and vinyl carbonate, and (c) a vinyl acetate with 2,2-dialkyl-4_vinyl-1 A method of saponifying and deketalizing a copolymer of 3-dioxolane, (d) a method of saponifying a copolymer of vinyl acetate and glycerin monoallyl ether, and the like. The polyvinyl alcohol-based resin preferably has a degree of saponification of 75 mol% or more, more preferably a degree of saponification of 78 to 99.7 mol%, and particularly preferably a degree of saponification of 85 to 95 mol%. When the degree is too low, the mold release property with the cured resin layer tends to decrease. Further, as the viscosity of the polyethylene glycol-based resin in a 2 Gt 4 4% by weight aqueous solution, it is preferably 1 〇 7 7 mPa.s (2 (rc), and further preferably 15 to 6 〇 ^. :), especially good for 2〇~5〇1^. to 2〇〇. If the viscosity is too low, there is a tendency for mechanical properties such as film strength to decrease, and if it is too high, there is a tendency for film formability to decrease. The viscosity is measured in accordance with JIS K6726. Further, in order to prevent the strength of the film from being lowered, it is preferable that the amount of the acetic acid contained in the resin (four) is 〇.8 by weight. % or less, preferably 5% by weight. The adjustment of the content '35 is usually washed with an alcohol or water such as decyl alcohol in the present invention, for example, a polyvinyl alcohol-based resin film, for example, a polyvinyl alcohol-based resin 201247408 The film is produced in the following manner. When the polyvinyl alcohol-based resin film is produced, it is preferable to contain a filler in view of design resistance against blocking, matting, or the like, and to reduce the adhesion of the fingerprint to the decorative molded article. It is necessary to appropriately mix a plasticizer and a surfactant. Carbohydrates and/or inorganics. Among the polysaccharides, starch is preferred. For example, raw starch (corn starch, potato starch, sweet potato starch, wheat starch, cassava starch, sago powder, cassava) can be used. (tapi〇ca) starch, 帚蜀黍(s〇rghum bic〇1〇r Moench) starch, rice starch, bean starch, Ge starch, fern starch, lotus starch, alfalfa starch, etc.; physical modified starch (α-starch) , separation of linear palace powder, wet heat-treated starch, etc.; enzyme modified starch (hydrolyzed dextrin, enzyme decomposition dextrin, amylose, etc.); chemical decomposition of modified starch (acid-treated starch, hypo-acid oxidized starch, two Aldehyde starch, etc.; chemically modified starch derivatives (esterified starch, etherified starch, cationized starch, crosslinked starch, etc.), etc. Further, as the esterified starch in the chemically modified starch derivative, acetic acid may be mentioned. Acetylated starch, succinate starch, nitrated starch, phosphoric acid yoghurt powder, urea phosphate esterified starch, xanthate starch, acetamidine acetate 6 chemistry powder, etc.; 'Can be cited Etherified temple powder, 曱 化 殿 殿 、 powder, carboxymethyl etherified starch, hydroxyethyl etherified starch, hydroxypropyl etherified starch, etc.; as cationized starch, starch and 2 _ diethylamino group B a reactant of a base gasification, a reaction product of a starch and a 2,3-epoxypropyltrimethylamined amine; and, as a crosslinked starch, a formaldehyde crosslinked starch, an epigas alcohol parent powder, and an acid Cross-linked starch, acrylic cross-linked starch, etc. In its 201247408, it is preferable to use raw starch from the viewpoint of ease of use or economical efficiency. Ryukyu is in the form of potassium, and as an inorganic type, for example Can be exemplified by: talc, viscous, oxidized Ximanite, Shangling soil, mica, asbestos, gypsum, graphite, glass gas glass beads, barium sulfate, barium sulfate, sulfuric acid, sulfurous acid, carbonic acid carbonate , magnesium carbonate 'carbon nashao stone' dolomite, acid black, glass fiber, oxidized Ming fiber, shed fiber, processed mineral fiber carbon fiber 'carbon hollow ball, bentonite, montmorillonite, copper powder and so on. These fillers may be used singly or in combination of two or more. The content of the above filler is from 3 to 30 parts by mass, more preferably 4, and particularly preferably 5 to 2% by weight based on 1 part by mass of the polyvinyl alcohol-based resin. When the content of the filler is too small, the film tends to be formed when the film is formed. If the amount is too large, the strength of the base film is lowered. The followability to the transfer transfer body during transfer printing tends to be lowered. The average particle diameter of the above filler is preferably from Q1 to m, and particularly preferably from right to ΓΓ, and further preferably from 0.5 to 2 Å. When the average particle diameter is too small, the film tends to be agglomerated when the film is produced. When the curable resin layer f is excessively applied, when §) is applied to the base film, bubbles or the like tend to be mixed to increase the defects. The pores/packages are specifically used as the plasticizer, and examples thereof include glycerin, diglycerin, oil 4 glycerol, triethyl-glycol and the like, or a mixture of: diol, polypropylene glycol, and dipropylene glycol. . Earth and other systems. The content of the plasticizer which can be used alone or in combination with the above polyvinyl alcohol-based resin is relative to 12 201247408 - the weight of the resin, preferably 2 parts by mass to 15 mass Share. If the content of the above-mentioned plasticizer is too small, the plasticizing effect is low, and the stability of the plasticization effect of the obtained base film breakage tends to be lowered. Too much right 'there is a blending of the above surfactants in order to improve the metal surface and the properties of the drum or conveyor belt of the film forming apparatus, specifically, for example, the stripping of the olefinic oxime ether and the polyethylene Suspected + ene phenyl ether, polyoxyethyl squad (four) yard benzene surface, polyoxyethylene sulphate base: liver mono sorbitol liver lauric acid vinegar, polyoxyethylene sorbitol: car palm Sour, polyoxyethylene sorbitol liver monostearate, polyoxyethylene sorbitan monooleate, polyoxyl extension base polyoxyethylene laurylamine, polyoxyethylene hard fat A polyamine ethenylamine such as a amide. These may be used alone or in combination of two or more. From the viewpoint of the releasability, it is preferable to use the polyoxyl extension base to brew the early ethanol salt, the polyoxyethylene ketone amine, and the polyoxyethylene sorbitan monolaurate. The content of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 〇3 to 丨5 parts by mass, based on the parts by mass of the polyvinyl alcohol-based resin. When the content of the surfactant is too small, the peeling property of the metal surface of the drum or the belt of the film forming apparatus and the produced film tends to be lowered, which makes it difficult to manufacture. On the other hand, if it is too large, it may bleed out on the surface of the film. When the curable resin layer is applied, the thickness tends to be uneven. Further, it is also possible to blend a crosslinking agent, an antioxidant (such as an amine, etc.), a stabilizer (filling ester, etc.), 13 201247408 coloring material, and %L in a range that does not impair the effects of the present invention. Υχ materials, extenders, defoamers, rust inhibitors, UV agents, and sugar a *1 person, water-soluble polymer compounds (sodium polyacrylate, polycyclic oxime, poly 7 Μ 吡 pyrrolidone) , dextrin, polyglucamine, clam shell, methyl cellulose, other additives such as B' & hexyl cellulose. The base film made of a dilute-based resin can be prepared by, for example, first mixing a polyvinyl alcohol-based resin, a bulking agent: a plasticizer, a surfactant, or the like with a specific blending amount to prepare a film-forming material. The film forming material is cast from a pattern onto a film forming conveyor or a film forming drum, dried by filming, and further heat treated as necessary to produce a base film. Here, the above-mentioned "film-forming conveyor belt" refers to an endless belt which is stretched over and moved so that the film forming material flowing out from the T-die flows onto the endless belt and is dried. The endless belt is made of, for example, stainless steel, and it is preferable to perform mirror polishing on the outer peripheral surface thereof. Further, the above-mentioned so-called film forming drum refers to a rotating drum type roll, and the film forming material flowing out from the T-die is cast to! More than one rotating cylinder is light and dry. Regarding the drying temperature, in the case of using a film forming belt, it is usually preferably from 80 to 160 t', particularly preferably from 90 to 15 ft. If the drying temperature is too low, there is a tendency for J to be insufficient to reduce the appearance of the product. If the drying temperature is too high, the heat treatment tends to be too low. Further, in the case of using a film forming drum, the first film forming film is usually preferably lom. 82 to 99t. If the drying temperature is too low, 14 201247408 has a tendency to reduce the appearance of the product due to insufficient drying. If it is too far apart, one (1) tends to have a heat treatment rate that is too low. Here, the above-mentioned so-called "cylinder" means a cylindrical roll in which the film forming material flowing out from the τ-shaped mold is cast. The glass upstream side may be subjected to heat treatment as needed after the drying, and examples of the method of the treatment include a thermal affinity (including calendering), hot air, far infrared, and dielectric heating. Further, the surface to be heat-treated is preferably the surface opposite to the surface on which the film forming belt or the film forming drum is contacted. Further, the moisture content of the film to be treated is usually preferably from 4 to 8 by about 4%, and the moisture content of the film after the treatment is usually preferably from 2 to 6% by weight. The heat treatment by the above heat treatment machine is preferably carried out at 50 to i80 〇c, preferably 6 〇 to 16 〇〇C, and more preferably 7 〇 to (4). In other words, if the temperature of the crucible geography is too low, the surface of the film forming conveyor or the film forming the first rotating drum may be curled. The step of forming the curable resin layer and the tendency to rotate == good, if heat treatment When the temperature is too high, there is a tendency that the film is soft due to the fact that the film tends to be entrapped. Further, the time required for the heat treatment is determined by the temperature of the heat-treating roller, but it is usually preferably i (10) seconds (4) 〇 & The above heat treatment is usually carried out by another heat treatment after the subsequent treatment. In the present invention, the heat treatment is preferably performed on the surface of the base film on the side of the curable resin layer. The water content of the polyethylene-based resin film of the base film of the polyethylene glycol-based resin obtained by the above method is preferably in the range of q5 to ig% by weight. 15 201247408 Solid cutting step or curable resin layer 2: If it is too brittle, if the water content is too high, there is a tendency that the film is easily elongated ==2 or in the step of forming the curable resin layer. The water content of the polyvinyl alcohol-based resin film can be, for example, (::: manufactured by Seiko Industrial Co., Ltd.) - "Measurement: For example, the water content of the resin film such as = ethyl alcohol The method of adjusting the rate is as follows: ^ The moisture content of the polyvinyl alcohol-based film is set to the above range according to the moisture content method as shown below. The coating material of the polyvinyl alcohol-based resin is dried and the temperature of the dryer is changed up and down while the film is formed, and the U-injection and the deuterated ethylene-based resin film are wet and dehumidified by the method of Μ ^ ^ & With regard to coating, the dish, because of the influence of the temperature on the drying efficiency, and, in the case of drying, preferably, the fBi t is preferably between 145 and 60 t and has a temperature gradient. It is carried out in two or more hot air dryers, and further, from the viewpoint of moisture adjustment, 5' is preferably dried for 1 to 15 minutes, and more preferably dried for (8) eight times. 77 If the gradient of the above drying temperature is too large Or if the drying time is too long, there is a tendency to over dry Conversely, 'If the gradient of the drying temperature is too small, or the drying time is too short, there is a tendency for insufficient drying. The above temperature gradient is between 150 and 5 (the phase change of the drying temperature between rc' is usually more effective, since Slowly increase the temperature from the beginning of the drying cycle to the maximum drying temperature of the temperature range until the specific moisture content is reached, and then slowly reduce the dry temperature production. = Drying finally reaches the target moisture content. 苴俜A ' ', and by hand, in order to control crystallinity, peelability, productivity, etc., for example, 12〇t called grab-mi(10) 2:13〇c_12〇t: — llot, 115°mu ( Rc~9 (rc inch gradient setting, can be selected and implemented as appropriate. (1) By the volume of polyethylene resin film:::: poly- humidification, dehumidification, and thus::: (3) The polyvinyl alcohol-based resin film can be obtained by the dehumidification of the polyvinyl alcohol-based resin film before or after the winding of the polyvinyl alcohol-based resin film, thereby obtaining a polyvinyl alcohol-based resin film according to the above aspect. Medium, the thickness of the ethylenic resin film (in Figure 丨The base ", 'represented by "tj" is preferably 5~BO", especially preferably 10~1〇〇2, especially preferably 20~70... If the film becomes too thick, it is difficult to assign the convex shape of the + When the film is too thin, the film breaks when the film is processed into the uneven shape. The vinyl alcohol resin film obtained in the above manner = plate shape... The height difference used in the invention is 5 to 2 Å. The treatment can be carried out by applying a film to a film made of a resin composition as a raw material, and imparting a film having a low unevenness of 5 to 2 Å. It is embossed, rubbed, etc., and after the film is processed, it can be formed, and it can be formed by applying a concave-convex shape to the 201247408 tape or film-making drum for the film used in film formation. The uneven shape of the height difference. However, it is easy to obtain the viewpoint of the desired uneven shape and the desired pattern shape, and it is easy to use: embossing is preferable in terms of the production equipment corresponding to various designs (patterns, patterns). A method of processing a shape. The embossing process uses an embossing ruthenium and a support view, and the B-resin film is passed between the embossing roll and the backup roll, and the design shape to be imparted is formed on the surface of the emboss roll (the concave-convex pattern v is used as the The embossing roll may be a metal roll or a ceramic roll whose surface is formed into a shape by engraving or lathe processing, etc. The shape of the convex part depends on the design pattern to be imparted. , sand, hairline: pattern, hemp, leather style, etc., in addition to the grid shape, tortoise shell shape, diamond shape, etc., the shape of the continuous & · ~ %% 武 sample, can also be listed The indefinite shape of the convex portion of the size t convex portion, the discontinuous pattern of the convex portion, etc. In the case of the continuous pattern, the convex portion is usually 1 〇 2 〇〇 2 mesh, preferably 20 〜 100 mesh. If the mesh of the part is too small, it tends to be difficult to form a concave-convex shape on the film, and it is difficult to obtain a film having a design having a desired three-dimensional shape. If the mesh is too large, it is difficult to obtain excellent design properties. Style tendency. Also, as an embossing roller The height difference of the concave and convex portions is preferably 30 to 500 M m, more preferably 40 to 400 / zm, and further preferably 5 to 3 〇〇 ^ m. If the height difference is too small, embossing is performed. The difference in height between the uneven portions of the film is reduced, and the transfer property of the design is lowered, and it is difficult to obtain a desired design. On the other hand, although the height difference between the concave and convex portions of the embossing roll is increased, 18 201247408 is obtained. The height difference of the uneven shape of the film tends to increase. However, when the height difference of the uneven portion of the embossing roll reaches a certain level, it is difficult to reflect the difference in the uneven shape of the film. Further, if the embossing roll When the height difference between the uneven portions is too large, the crepe after embossing tends to cause wrinkles and the like, and the quality of the film tends to be lowered. On the other hand, as the backup roll, surface hardness can be preferably used based on JIS. K 6253 A type hardness tester is 80 or more, and is D-shaped hardness tester (Dtype is "plus" tester), and it is 90 or less. Here, the surface based on Jis κ measurement Hardness H乂禾] obtained by the 帛zheng spring testing machine The hardness of the needle is the hardness of the reference. The higher the value, the harder the hardness is. The D-shaped hardness tester is used for the harder case than the A-shaped hardness tester. If the surface hardness of the backup roll is too low, there is even embossing. The roll is formed with a design having a specific height difference, and it is still difficult to apply a embossing process having a specific height difference to the film. On the other hand, if the surface hardness of the backup roll is too high, there is a tendency that a pinhole or the like is formed on the film. In the present invention, as the support view, as long as it is a roll having a hardness of the above range, T, for example, it is preferably coated with an amine g, a polyoxyl system, or an olefin system. A roll of a synthetic rubber or the like. 妒诵二: The hair is preferably embossed by causing the vinyl alcohol-based resin film to be between the support and the support as described above, and the support roll is supported by the support. The pressing force of the 2 type resin film to the embossing roll can be preferably used depending on the use. .5:= and the irregular shape of the embossing roller is appropriately selected, and a is preferably 1 to 8 MPa, and more preferably i to 19 201247408 5 MPa » If the pressing force is too small, there is even a pressure having a sufficient depth. It is also difficult to impart a desired height difference to the film, and if it is too large, the thickness of the film after embossing is partially thinned, and the mechanical strength is liable to decrease, and the pinhole tends to be generated. Further, in the present invention, it is preferred that the surface temperature of the embossing roll during embossing is 100 to 18 Torr, and the surface temperature of the backup roll is 5 Torr or more. The better surface temperature of the embossing roller is 1〇5~17〇 <t, especially ιι〇~16〇C, the preferred surface temperature of the backup roll is 6〇~11 (rc, especially preferably ~100〇C.) If the surface temperature of the right embossing roll is too low, there is no Obtaining a tendency to have a sufficient depth of embossing, if it is too high, the film tends to be elongated during embossing, and the design after embossing tends to be uneven. If the surface temperature of the backup roll is too low, then There is a tendency to obtain an embossing process having a sufficient depth. Further, in the embossing process, the urging speed of the embossing roll is preferably set to MOOm/min, and particularly preferably set to 2 to 9 〇m. /min, further preferably set to 3 to 80 m/min, particularly preferably 5 to 5 〇 m/min. If the processing speed is too slow, there is a tendency for production efficiency to decrease, and if it is too fast, it is easy In the present invention, the water content of the vinyl alcohol-based lipid film which is subjected to embossing is preferably 2 to 10% by weight, more preferably 3 to 8 parts by weight. % is particularly preferably 4 to 7% by weight. If the water content is outside the above range, there is ° to carry out embossing with sufficient depth. 20 201247408 As a method of adjusting the water content of a vinyl alcohol-based cholesteric film, it can be classified into a method such as T-solid film, and the like: adjusting the ethyl alcohol-based resin C before drying after film formation Moisture content, or the moisture content is less than 2% by weight. 'Shaw resin 犋 is immersed in water or subjected to humidity control, etc., and the water content can be adjusted to obtain a base film having a concave-convex shape with a height difference of 5. Ethyl alcohol-based resin film. As a vinyl acetate resin film used as a base material (base rate, at 23t, Shenxin crack elongation. Under H humidity control condition, it is preferably 150% or more, and further (4)% or more. If the elongation at break is too low, there is a tendency to produce a paper break in the step of continuously forming the curable resin layer in the cutting step, or an upper limit of the elongation at break, which is usually an elongation at break of 3 俜.栩 ' ' 丰 丰 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ The table is not equivalent to the thickness of the film, which is substantially equal to the thickness of the film. The easiness, the followability of the two-print body at the time of transfer, etc., about the transfer when the transfer is broken. It is preferably 1〇~35〇"m, especially good~3." Preferably, the thickness is 2 〇 to 27 〇". If the thickness is small, the uneven shape is small, and if the thickness τ is larger, the transferability of the surface-body is deteriorated. The shape of the film has a large film thickness, and there is a tendency for the grain to be broken by the embossing process, and the film tends to break. In addition, wrinkles are generated when printing, and the transfer is easy to turn... 4 The base film of the present invention is preferably treated with a moisture-proof package, and is not known to be λ ;; in the environment of 10 to 25 ° C, it is kept in a suspended state. 21 201247408 The laminate for transfer printing of the present invention will be described. <In the laminated system for transfer printing of the invention, a hard resin layer and a printed layer are laminated on the base film, and a layer may be laminated on the printed layer. When the curable resin layer is used as the outermost layer of the transfer target (decorative molded article) when the base film is peeled off, the cured resin layer is hardened and used to protect the transferred layer before or after peeling off the base film. A protective layer on the surface of the print. As the material 'for example, a polypropylene resin, a polyester resin, a polystyrene resin, a cellulose resin, a rubber polymer, a polyurethane resin, a polyvinyl acetate resin, or the like can be used, and other things are preferable. An active energy ray-curable resin composition such as an ultraviolet curable resin composition or an electron beam curable resin composition or a thermosetting resin composition is used. In the present invention, it is preferable to use an active energy ray-curable resin composition from the viewpoint of chemical resistance and abrasion resistance of the molded article. Further, the active energy ray-curable resin composition preferably has a property of being hardened by heat (thermosetting property). The active energy ray-curable resin composition is preferably, for example, an acrylic resin or an amine (meth)acrylic acid (Urethane (meth) a Crylate) compound, and preferably has a light. A polymerizable monomer is formed. Examples of the acrylic acid resin include a homopolymer or a copolymer, or an acrylic copolymer having another composition. For example, an acrylate-based monomer ethylenically unsaturated monomer is used as the copolymerization 22 201247408. Examples of the acrylate-based monomer include methyl (meth) acrylate and ethyl (meth) acrylate. Methyl) propyl acrylate, (meth) butyl acrylate, (hexyl) hexyl acrylate, 2-ethylhexyl (decyl) acrylate, isodecyl (decyl) acrylate, (fluorenyl) Benzyl acrylate, cyclohexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isooctyl methacrylate, n-octyl (meth) acrylate, (mercapto) acrylic acid Lauroate, 2-methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, methoxytriethylene glycol (mercapto) acrylate, etc., among which carbon of alkyl group is preferred The alkyl acrylates having a number of from 1 to 12 are particularly preferably used as decyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethyl (meth) acrylate. An aliphatic alkyl acrylate such as hexyl ester. Examples of the other ethylenically unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxypropyl propyl phthalate. , (fluorenyl) tetrahydrofurfuryl acrylate, (mercapto) acrylic acid 2-hydroxy-3-pyenoxypropyl ester, diethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, N-hydroxydecyl (meth) acrylamide and the like contain a trans-unsaturated monomer; glycidyl methacrylate, propyl propyl propyl propyl acrylate, etc. Base unsaturated monomer; 2 - unsaturated monomer containing isocyanate groups such as acryloxyethyl isocyanate, 2-methyl propylene methoxyethyl isocyanate; acrylamide, methacrylamide , N-(n-butoxyalkyl) acrylamide, N-(n-butoxyxanyl) decyl acrylamide and other unsaturated monomers containing amidino group; acrylamide- 3 - fluorenyl An amine-containing unsaturated monomer such as butyl decylamine, diammonium amino acrylamide, dimethyl fluorenyl decyl acrylamide; Sulfon 23 201247408 acid, aryl acid, methyl propyl acid, etc., such as acid amine-2-methylpropane sulfonic acid, monetine-^^ 埽醆 or its salt, etc. Unsaturated monomer; styrene-ethyl, S-vinyl ester, acrylonitrile, acrylamide, etc. The content ratio of the acrylic acid vinegar monomer and other ethylenically unsaturated monomers (copolymerization ratio) is not # PP $ 0 will be limited to, for example, preferably the acrylate monomer ax is 2G 1 GG weight f % 'the other ethylenically unsaturated monomer is 〇 〜 80% by weight, particularly preferably acrylate The monomer is set to 4 〇 to _% by weight. The other ethylenically unsaturated monomer is 〇 〇 6 〇 重量%, and further preferably the propylene (4) monomer is set to be 8 -8 〜 10% by weight. When the content ratio of the acrylate monomer is too small, the durability of the sealing film of the cured film tends to be lowered, such as water sealing property and heat resistance. The acrylic resin can be easily produced by a method known to a person skilled in the art, for example, the above-mentioned polymerization component is subjected to radical copolymerization in an organic solvent. Thus, the acrylic resin used in the present invention can be obtained, and the glass transition temperature (Tg) of the acrylic resin is preferably 20 to 13 (rc, more preferably 30 to 120 ° C, still more preferably 40 to 110. When the glass transition point (Tg) is too low, the curable resin layer such as the active energy ray-curable resin composition is sticky, and it is defective during the post-processing (crimping and printing in the step) When the curable resin layer such as the active energy ray-curable resin composition is cured to form a protective layer, it tends to become brittle. The weight average molecular weight of the acrylic resin tends to be too high. (Mw) is preferably 24 201247408
30,0〇〇〜8〇,〇〇〇 ο 100,000，尤佳為 若該丙烯酸系樹脂之重量平均分子量30,0〇〇~8〇,〇〇〇 ο 100,000, especially if the weight average molecular weight of the acrylic resin
性樹脂層時之膜厚均勻性，且 (Mw)過小，則 層軟化並且帶有黏著性而於在 生不良（步驟中之捲縮、印刷 過大’則有難以獲得塗敷硬化 且乾燥後之硬化性樹脂層之硬 度變高而比所需要高’於實施後加工時成為產生不良（產 生硬化性樹脂層之龜裂、層間剝離等）的原因之傾向。 胺醋（曱基）丙烯酸酯系化合物係於分子内具有胺醋鍵 之（甲基）丙烯酸酯系化合物，可藉由使含有羥基之（曱基）丙 烯酸系化合物與多元異氰酸酯化合物、進而視需要與多元 醇進行反應而製造。 作為上述含有羥基之（曱基）丙烯酸系化合物，例如可 列舉，（曱基）丙烯酸2—羥基乙酯、（曱基）丙烯酸2_羥基 丙酯、（甲基）丙烯酸2 —羥基丁酯、（甲基）丙烯酸4一經基 丁酯、（甲基）丙烯酸6—羥基己酯、2—(甲基）丙烯醯氧基 乙基一 2 —羥丙基鄰苯二曱酸酯、2 —羥基一3—(甲基）丙烯 醯氧基丙基（甲基）丙烯酸酯、己内酯改質（甲基）丙稀酸2一 經基乙酯、新戍四醇三（曱基）丙稀酸酯、二新戊四醇五（甲 基）丙烯酸酯、己内酯改質二新戊四醇五（甲基）丙烯酸酯、 己内酯改質新戊四醇三（曱基）丙烯酸酯、環氧乙烷改質二 新戊四醇五（甲基）丙烯酸酯、環氧乙烷改質新戊四醇三（曱 基）丙烯酸酯等，其中可較佳地使用具有3個以上之丙烯醯 25 201247408 基的含有羥基之（甲基）丙烯酸系化合物。又，該等可使用i 種或組合2種以上使用。 作為上述多元異氮酸醋化合物，例如可列舉芳香族 系、脂肪族系、脂環式系等之聚異氰酸酯，尤其可列舉： 曱苯二異氟酸酯、二苯基甲烷二異氰酸酯、氫化二苯基甲 烷二異氰酸酯、聚苯基甲烷聚異氰酸酯、改質二苯基甲烷 二異氰酸酯、氫化笨二甲基二異氰酸酯、笨二甲基二異氰 酸酯、六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸 酯、四甲基苯二甲基二異氰酸酯、異佛酮二異氰酸酯、降 莰烯二異氰酸酯、雙(異氰酸酯基曱基)環己烷、伸苯 基二異氰酸酯、離胺酸二異氰酸酯、離胺酸三異氛酸酯、 萘二異氰酸酯等聚異氰酸酯或該等聚異氰酸酯之三聚物化 合物或多聚物化合物，縮二腺型聚異氛酸醋、水分㈣聚 異氣酸醋（例如’日本聚㈣工業股份有限公司製造之 「Aquanaten)〇」、「Aquanateu。」、「Aquanw·」、 「Aquanate 210」等），十分你 )成該等聚異氰酸酯與多元醇之反應 產物等。 作為該多元醇，例如可列舉 乙二醇、二乙二醇、三 乙二醇、四乙二醇 聚乙二醇、丙二醇、二丙二醇、聚丙 二醇、丁二醇、聚丁 烧二甲醇、氫化雙盼 二醇、1，6 -己二醇、新戊二醇、環己 A、聚己内酯、三羥甲基乙烷、三羥 曱基丙烷 新戊四酵、聚新戍四醇、山 梨糖醇、甘露醇、甘油、 有聚環氧乙烷、聚環氧丙 聚甘油、聚丁二醇等多元醇；具 院、環氧乙烷/環氧丙烷之嵌段 26 201247408 或無規共聚合之至少1種構造的聚醚多元醇；作為該多元 醇或聚醚多元醇與順丁烯二酸酐、順丁烯二酸、反丁埽二 酸、衣康酸酐、衣康酸、己二酸、間苯二曱酸等多元酸之 縮合物的聚酯多元醇；己内酯改質聚四亞甲基多元醇等己 内醋改質多元醇·，聚烯烴系多元醇；氫化聚丁二烯多元醇 等聚丁二烯系多元醇等。 進而，作為該多元醇，例如亦可列舉：2,2 —雙（羥曱 基）丁酸、酒石酸、2,4 —二羥基苯甲酸、3,5 —二羥基苯曱 酸、2,2—雙（羥曱基）丙酸、2,2 —雙（羥乙基）丙酸、2,2 —雙 (經丙基）丙酸、二羥甲基乙酸、雙（4一羥苯基）乙酸、4,4一 雙（4 ~羥苯基）戊酸、尿黑酸等含有羧基之多元醇，或i，4 —丁二醇項酸鈉等含有磺酸基或磺酸鹽之多元醇等。 於使用聚異氰酸酯與多元醇之反應產物之情形時，例 如可用作使上述多元醇與上述聚異氰酸酯反應而獲得之含 有末端異氰酸酿基之聚異氰酸酯。於該聚異氰酸酯與多元 醇之反應中’為了促進反應，較佳為使用二月桂酸二丁基 錫之類的金屬觸媒或1>8_二氮雙環[54〇]十一烯_7之類 的胺系觸媒等。 作為上述胺酯（甲基）丙烯酸酯系化合物之製造方法， 例如可列舉：使含有羥基之（甲基）丙烯酸系化合物與多元 異氛酸醋化合物於惰性氣體環境下混合，通常於3〇〜8〇<>c 下反應2〜10小時之方法。於該反應中，較佳為使用辛烯 酉文錫一月桂酸一正丁基錫、辛酸紹、辛酸舒、乙酸卸、 辛酸亞錫、二伸乙基二胺等胺酯化觸媒。 27 201247408 胺Μ曱基)丙烯醆酯系化合物之重量平均分子量較佳 為3〇〇二_，進而較佳為議〜35〇〇，尤佳為·〜 3000〇若該重量平於八 -刀子量過小，則有硬化性樹脂層硬化 後凝集力不足之傾向，^ , 右過大，則有黏度過高而製造困難 之傾向。 再者’上述所謂重量平均分子量係指藉由標準聚苯乙 稀分子量換算之重量平约公名县 ife -fcA. 里卞Q刀子量，藉由於尚效液相層析儀 (昭和電工公司製造之「Shodex GPC system — ! i型」）中， 使用3支串聯之Shodex Gpc KF_8〇6L管柱（排除極限分 子量：2M07’分離範目：1〇〇〜2χ1〇7，王里論段數：ι〇〇〇〇 段/支，填充劑材質：苯乙稀_二乙烯基笨共聚物，填充 劑粒徑：10以m )而進行測定。 又，作為光聚合性單體，係於照射紫外線等光線時， 其自身進行聚合而形成聚合物者，通常存在具有一個官能 基之單官能性單體、及具有兩個以上官能基之多官能性單 體。作為S亥光聚合性單體’例如可例示如下。 作為上述單官能單體，例如可列舉：苯乙烯、乙烯基 曱苯、氣苯乙烯、α —甲基苯乙烯、（甲基）丙烯酸甲酯、 (甲基）丙烯酸乙酯、丙烯腈、乙酸乙烯酯 '(曱基）丙烯酸2 一羥基乙酯、（曱基）丙烯酸2—羥基丙酯、（曱基）丙烯酸2 一羥基丁酯、（曱基）丙烯酸苯氧基乙酯、（甲基）丙烯酸2 — 笨氧基—經基丙酯、（曱基）丙稀酸2~經基一 3 —苯氧基 丙酯、（甲基）丙烯酸3—氯一2 —羥基丙酯、甘油單（曱基） 丙烯酸酯、（曱基）丙烯酸環氧丙基酯、（甲基）丙烯酸月桂 28 201247408 酉曰、（甲基）丙稀酸環己脂、（曱基）丙烯酸異_基醋、（甲基） 丙烯酸三環癸酯、（甲基）丙烯酸二環戊烯基酯、（甲基）兩烯 酸二環戊烯基氧基乙酯、（曱基）丙烯酸二環戊酯、（甲基）丙 烯酸正丁酯、（曱基）丙烯酸己酯、（甲基）丙烯酸庚酯、（曱 基）丙稀酸辛酯、（甲基）丙烯酸壬酯、（甲基）丙烯酸癸酯、 (曱基）丙烯酸異癸酯、基）丙烯酸十二烷基酯、（甲基）丙 烯酸正硬脂基酯、（甲基）丙烯酸苄酯、苯酚環氧乙烷改質 Cn=2)(曱基）丙烯酸酯、壬基苯酚環氧丙烷改質（11=2.5) (甲基）丙稀酸醋、2—（甲基）丙烯醯氧基乙基酸式磷酸酯、2 一（曱基）丙烯醯氧基—2 —羥丙基鄰苯二曱酸酯等鄰苯二曱 酸衍生物之半（曱基）丙烯酸酯，（甲基）丙烯酸糠酯、（甲基） 丙烯酸四氫糠酯、卡必醇（甲基）丙烯酸酯、（曱基）丙烯酸苄 醋、（曱基）丙烯酸丁氧基乙酯、（甲基）丙烯酸烯丙酯、丙烯 醯基〇末啉、2 —羥乙基丙烯醯胺、N —羥甲基（曱基）丙烯醯 胺、N —乙烯基吡咯啶酮、2 —乙烯基吡啶、聚氧乙烯二級 燒基醚丙烯酸酯等。 又，作為上述多官能單體中之2官能單體，例如可列 舉：乙二醇二（曱基）丙烯酸酯、二乙二醇二（曱基）丙烯酸 酯、四乙二醇二（甲基）丙烯酸酯、聚乙二醇二（甲基）丙烯酸 酯、丙二醇二（曱基）丙烯酸酯、二丙二醇二（甲基）丙烯酸 酯、聚丙二醇二（曱基）丙烯酸酯、丁二醇二（曱基）丙烯酸 酯、新戊二醇二（曱基）丙烯酸酯、環氧乙烷改質雙酚A型 二（甲基）丙烯酸酯、環氧丙烷改質雙酚A型二（曱基）丙烯酸 酯、環己烷二甲醇二（甲基）丙烯酸酯、乙氧化環己烷二甲 29 201247408 醇二（甲基）丙烯酸酯、二羥甲基二環戊烷二（甲基）丙烯酸 酯、三環癸烷二曱醇二（甲基）丙烯酸酯、1，6 —己二醇二（甲 基）丙稀酸S旨、甘油二（甲基）丙烯酸酯、新戊四醇二（甲基） 丙烯酸酯、乙二醇二環氧丙基醚二（甲基）丙烯酸酯、二乙 二醇二環氧丙基醚二（甲基）丙烯酸酯、鄰苯二曱酸二環氧 丙基酯二（甲基）丙烯酸酯、羥基特戊酸改質新戊二醇二（甲 基）丙烯酸酯、異三聚氰酸環氧乙烷改質二丙烯酸酯等。 並且，作為上述多官能單體申之3官能以上之單體， 例如可列舉：三羥甲基丙烷三（甲基）丙烯酸酯、新戊四醇 三（曱基）丙烯酸酯、新戊四醇四（曱基）丙烯酸酯、二新戊四 醇五（曱基）丙烯酸酯、二新戊四醇六（甲基）丙烯酸酯、三 (曱基）丙烯醯氧基乙氧基三羥甲基丙烷、甘油聚環氧丙基 轉聚（曱基）丙烯酸酯、異三聚氰酸環氧乙烷改質三丙烯酸 醋、己内酯改質二新戊四醇五（甲基）丙烯酸酯、己内酯改 質二新戊四醇六（曱基）丙炼酸酯、己内酯改質新戊四醇三 (甲基）丙烯酸酯、己内酯改質新戊四醇四（甲基）丙烯酸酯、 環氧乙烷改質二新戊四醇五（曱基）丙烯酸酯、環氧乙烷改 質二新戊四醇六（曱基）丙烯酸酯、環氧乙烷改質新戊四醇 二（曱基）丙締酸酯、環氧乙院改質新戊四醇四（曱基）丙稀酸 酯、乙氧化甘油三丙烯酸酯等。 進而’亦可列舉其他丙烯酸之麥可（Michael )加成物 戍2丙稀酿氧基乙基一叛酸單醋’作為丙稀酸之麥可加 成物’可列舉：丙烯酸二聚物、甲基丙烯酸二聚物、丙烤 酸二聚物、曱基丙烯酸三聚物、丙烯酸四聚物、曱基丙稀 201247408 酸四聚物等。又，作為2 —丙烯醯氧基乙基二羧酸單酯， 係具有特定取代基之羧酸，例如可列舉：2 —丙烯醯氧基 乙基琥珀酸單酯、2~曱基丙烯醯氧基乙基琥珀酸單酯、2 丙稀醯氧基乙基鄰苯二甲酸單酯、2_甲基丙稀醯氧基 乙基鄰本一甲酸單酯、2一丙稀醢氧基乙基六氫鄰苯二甲 酸單酯、2 —曱基丙烯醯氧基乙基六氫鄰苯二曱酸單酯 等。進而’亦可列舉其他寡酯丙烯酸酯。 於本發明中，作為上述丙烯酸系樹脂、胺酯（曱基）丙 烯酸酯系化合物、光聚合性單體之含有比例，相對於丙烯 酸系樹脂100質量份，胺酯（甲基）丙烯酸酯系化合物較佳 為20〜300質量份’尤佳為4〇〜25〇質量份，進而較佳為 60〜200質量份，光聚合性單體較佳為5〜8〇質量份’尤佳 為10〜60質量份’進而較佳為15〜50質量份。 如此，可獲得含有丙烯酸系樹脂及胺酯（甲基）丙烯酸 酯系化合物、較佳為進而含有光聚合性單體之活性能量射 線硬化性樹脂組成物，於活性能量射線硬化性樹脂組成物 為紫外線硬化性樹脂組成物之情形時，較佳為進而含有光 聚合起始劑。於為電子束硬化性樹脂組成物之情形時，不 需要光聚合起始劑。 作為該光聚合起始劑，例如可列舉：二乙氧美苯乙 酮、2 —羥基一2 —曱基一1 一苯基丙烷一丨—酿j、苄基二曱 基縮酮、4_ (2 —羥基乙氧基）苯基—（2—羥基—2 —丙基）曱 綱、1 一羥基環己基苯基酮、2—曱基_2—昧啉基（4_1 硫基 甲基苯基）丙院一 1— _、2—苄基一2 —二甲胺基_1 31 201247408 口末啉基苯基）丁酮、2 -羥基一2 —甲基一1- [4- (1-甲基 乙烯基）苯基]丙酮寡聚物等苯乙酮類；安息香、安息香甲 醚、安息香乙醚、安息香異丙醚、安息香異丁醚等安息香 類；二苯基酮、鄰苯曱醯基苯甲酸曱酯、4 —苯基二苯基 酮、4 —苯曱醯基一 4’一甲基一二苯硫醚、3,3、4,4，_四（第 三丁基過氧化羰基）二笨基酮、2,4,6 —三甲基二苯基酮、4 —苯甲酿基一N，N —二曱基_N— [2—（1 —側氧基一2 —丙 烯基氧基）乙基]苯甲溴化銨、氣化（4 一苯曱醯基苄基）三曱 基鐘等二苯基酮類；2 —異丙基硫雜蒽酮、4 —異丙基硫雜 蒽酮、2,4 —二乙基硫雜蒽酮、2,4 一二氣硫雜蒽酮、1 —氯 —4 —丙氧基硫雜蒽酮、2—（3—二曱胺基一2 —羥基）一3,4 —二甲基一9H —硫雜蒽酮一9 一酮内消旋氣化物等硫雜蒽 酿)類；2,4,6 —三曱基苯曱醯基一二苯基氧化膦、雙（2,6 一 二曱氧基苯甲醯基）一 2,4,4 —三甲基一戊基氧化膦、雙 (2,4,6 —三曱基苯甲醯基）_苯基氧化膦等醯基氧化膦類 等。再者’該等光聚合起始劑可單獨使用1種，亦可併用2 種以上。 上述光聚合起始劑之含量相對於所使用之胺酯（甲基） 丙烯酸酯系化合物（於摻合光聚合性單體之情形時，為其 〇 4量）100質量份，較佳為〇 5〜15質量份，尤佳為〇 5 〜10質量份’進而較佳為1〜8質量份。 又’作為該等之助劑，亦可併用三乙醇胺、三異丙醇 ’4 又（一曱胺基）二苯基酮（米其勒酮）、4,4'— 雙（二乙基胺基）二苯基酮、2 —二曱胺基乙基苯曱酸、4 32 201247408 酯、4一二甲胺基苯甲酸異戊烷、4 乙基己酯、2,4 —二 等。 二甲胺基苯甲酸乙醋、4一二甲胺基笨甲酸(正丁氧基)乙 甲胺基苯甲酸2 — -二異丙基嚷》頓酮 该寺之中，較佳為使用苄基 一，，丨，必一 τ签滩明、丨—羥暴環 。基本基鋼、苯甲酿基異丙喊、4_(2 —經基乙氧基卜苯 基（2-經基-2-丙基）甲㈣、2—經基—2—甲基—卜苯基 丙院一1 — _。 於本發明中，硬化性樹脂層之厚度就耐磨耗性、耐化 學品性之觀點而言，較佳為卜⑼心，尤佳為2〜120" 進而較佳為2〜lOOym^若該厚度過薄，則有耐磨耗 -或ί化學。σ性降低之傾向，若過厚，則有轉印後之膜的 切割變得不充分而導致毛邊等之傾向。 於形成硬化性樹脂層時，可藉由凹版印刷塗佈法、輥 塗法、棒塗法、刮刀式塗佈法、唇式塗佈法等塗佈法，凹 I7刷法絲網印刷法等印刷法而使上述原料樹脂或原料 樹脂組成物積層。 於使用上述活性能量射線硬化性樹脂組成物之情形 夺可自於基膜上積層由活性能量射線硬化性樹脂組成物 構成之層（硬化性樹脂層）後直至將印刷層轉印至被轉 Ρ體上並剝離基膜之任意階段、或剝離基膜後之任意階段 、、射'舌丨生犯量射線並使其硬化而形成保護層（硬塗層）， 或者亦可於剝離基膜後照射活性能量射線並使其硬化而 形成保護層（硬塗層）。 33 201247408 例如，可列舉：（丨）於基膜上積層活性能量射線硬化 性樹脂組成物層後，照射活性能量射線而使其硬化之方 法；（2 )於基膜上積層活性能量射線硬化性樹脂組成物層 後，形成下述印刷層，其後自基膜側照射活性能量射線而 使其硬化之方法；（3)於進而進行積層直至下述接著層 後，自基膜側照射活性能量射線而使其硬化之方法；（4 ) 於將本發明之轉移印刷用積層體接著於被轉印體後，自基 膜側照射活性能量射線而使其硬化之方法；或（5)於將本 發明之轉移印刷用積層體接著於被轉印體後，剝離基膜並 照射活性能量射線而使其硬化之方法等H就熱轉印 時之對被轉印體之追隨性之觀點而言，較佳為（4 之方法。 〜入…Tt衝脂層硬 時，作為活性能量射線，例如可利用遠紫外線、紫外線 近紫外線 '紅外線等光線，x射線、r射線等電磁波、-， 此以外亦可利用電子束、質子射線、中子射線等，就硬 速度、照射裝置之獲得容易度、價格等而言，藉由 照射之硬化較為有利。 、 作為藉由紫外線照射而硬化之方法，只要使用發 150〜㈣⑽波段之光的高壓水銀燈、超高壓水銀燈、碳 燈：金屬南化物燈、氣氣燈、化學燈等，進行0.01〜10J cni左右之照射即可。於紫外線照射後， 加熱而謀求完全硬化。 了視需要進 於本發明中，印刷層係成為形成設計之層者，作為 34 201247408 刷層之材質’可使用如下著色油墨：其含有聚乙稀系樹 脂、聚醯胺系樹脂、聚輯系樹脂、丙烯酸系樹脂、聚胺賴 系樹脂、$乙烯縮醛系樹脂、聚酯胺酯系樹脂、纖維素酯 系樹脂、酸醇樹脂等樹脂作為黏合劑’並含有適當顏色^ 顏料或染料作為著色劑。 作為印刷層之形成方法’可使用平版印刷&、凹版印 刷法、絲網印刷法等通常之印刷法等。尤其是為了進行 多色印刷或灰階顯*，較佳為平版印刷法或凹版印刷法。 又’亦τ使用域印刷法於具有脫模性之膜上設置印刷 層’以印刷面與基膜之由活性能量射線硬化性樹脂組成物 構成之層（硬化性樹脂層）相接觸之方式配置，並利用乾 式層疊法進行貼合。 本發明之轉移印刷用積層體係積層有上述基膜、硬化 性樹脂層、印刷層纟，較佳為於印刷層之上層積層有 層。 接著層係用以使上述積層體接著於被轉印體面者。可 ;p刷層與成形品之接著力較弱之情形時形成。作為接著 層之材質’只要適當使用適合於被轉印體之原材料的感熱 陡？感壓性樹脂即可，例如可列舉：《酯系樹脂、丙烯酸 :樹月日、I苯乙烯系樹脂、聚醯胺系樹脂、氣化聚烯烴樹 月曰、氣化乙烯一乙酸乙烯酯共聚物樹脂、環化橡膠、苯并 呋喃—茚樹脂等。 作為接著層之形成方法，可列舉：凹版印刷塗佈法、 輥塗法、棒塗法、刮刀式塗佈法等塗佈法，凹版印刷法、 35 201247408 絲網印刷法等印刷法β χ，亦可利用層叠法等將由上述材 質所構成之具有接著性之片材貼合而形成接著層。又接 著層亦可兼作印刷層。 接者層之厚度就對被轉印體之追隨性之觀點而言，較 佳為〇.5 50 M m ’尤佳為1〜40 μ m，進而較佳為2〜3〇 y m。若該厚度過薄，則有轉印時對被轉印體之追隨性降低 之傾向若過厚，則有成本變高之傾向，因此不經濟。 對使用本發明之轉移印刷用積層體並利用轉印法對被 轉印體面進行裝飾之方法進行說明。 首先，使轉移印刷用積層體之具有接著層之情形時的 接著層側、或不具有接著層之情形時之印刷層側密接於被 轉印體面。其次’冑用具備聚妙氧橡膠等对熱橡膠狀彈性 體之輥轉印機、升降（Up __ dQwn )轉印機等轉印機，經由 〇又疋為溫度80〜270°C左右、壓力49〇〜196〇Pa左右之條件 之耐熱橡膠狀彈性體自轉移印刷用積層體之基膜側施加熱 及壓力。藉A，接著層或印刷層接著於被轉印體表面。 右於冷卻後，藉由照射活性能量射線等使硬化性樹脂 層硬化而形成保護層（硬塗層）後，最後剝離基膜，則於 基臈與保護層（硬化之硬化性樹脂層：硬塗層）之界面引 起剝離’轉印結束。 再者’於上述步驟中’亦存在該活性能量射線硬化性 樹脂組成物藉由熱而稍微硬化之情況。 其次，對於使用本發明之轉移印刷用積層體，利用藉 由射出成形之成形同時轉印法對作為被轉印體之樹脂成形 36 201247408 品的面進行裝飾之方法進行說明。 首先’將轉移印刷用積層體送入由可動模具與固定模 具構成之成形用模具内。此時，可將片狀轉移印刷用積層 體逐片送入’亦可將長條狀積層體之必要部分間歇性地送 入。於使用長條狀轉移印刷用積層體之情形時，可使用具 為定位機構之搬送裝置，使轉移印刷用積層體之印刷層與 成形用模具之方向一致。又，若於間歇性地送入轉移印刷 用積層體時，利用感測器檢測轉移印刷用積層體之位置 後，以可動模具及固定模具將轉移印刷用積層體固定，則 可一直將轉移印刷用積層體固定於相同位置而不產生印刷 層之位置偏移’故而較為便利。 於成形用模具閉合後，使熔融之成形樹脂自澆口射出 並充滿模具内，於形成被轉印體之同時使轉移印刷用積層 體接著於其面。作為成形樹脂，可列舉：聚苯乙烯系樹 脂 '聚稀烴系樹脂、ABS樹脂、AS樹脂、AN樹脂等通用 樹脂。又’亦可使用聚苯喊一聚苯乙稀系樹脂、聚碳酸脂 系樹脂、聚縮醛系樹脂、丙烯酸系樹脂、聚碳酸脂改質聚 本醚樹脂、聚對苯二曱酸丁二酯、超高分子量聚乙烯樹脂 等通用工程樹脂，《聚脂、聚苯硫_系樹脂、聚苯喊 系樹脂、聚芳酯樹脂、聚醚醯亞胺樹脂、聚醯亞胺樹脂、 液晶聚酯樹脂、聚芳系耐熱樹脂等超級工程樹脂。進而， 亦可使用添加有玻璃纖維或無機填料等補強材料之複合樹 脂。該等樹脂成形品可為透明、半透明、不透明之任一 種。又，成形品可著色，亦可不著色。 37 201247408 將作為被轉印體之樹脂成形品冷卻後，打開成形用模 具並取出樹脂成形品。並且，若藉由活性能量射線照射等 使硬化性樹脂層硬化而形成保護層（硬塗層）後，最後剝 離基膜’則於基膜與保護層（硬化之硬化性樹脂層：硬塗 層）之界面引起剝離，轉印結束。又，亦可於打開成形用 模具並取出樹脂成形品，剝離基膜後，藉由活性能量射線 照射等使硬化性樹脂層硬化而形成保護層，使轉印結束。 [實施例] 以下’列舉實施例更具體地說明本發明，但只要不脫 離本發明之主旨，本發明並不限定於以下實施例。 再者’例中之「部」、「％」係意指重量基準。 實施例1 [基膜之製造] 利用T字模將由皂化度為88莫耳％且於20。(：之4%水 溶液黏度為23mPa · s之聚乙烯醇樹脂100份、作為填料之 澱粉（平均粒徑1 5以m ) 5份、界面活性劑（聚氧乙烯山梨 糖醇酐單月桂酸酯）〇·5份、作為塑化劑之甘油5份所構成 之20°/。水溶液吐出至表面溫度調整為9〇〇c的旋轉之不鏽鋼 製循環傳送帶而進行流延製膜，繼而利用調整為9 5。〇之熱 親進行兼作抗捲曲處理之熱處理而獲得厚度4〇//m之聚乙 烯醇膜。 利用2MPa之推壓力並以5m /min之加工速度使所獲 得之聚乙烯醇膜通過加熱至120°C的壓紋輥（凹凸形狀：絹 紋，高低差：250 y m，80網目）與加熱至80。(：之支承輥（輥 38 201247408 之表面硬度：以基於JIS Κ 6253之A形硬度試驗計計為90 ) 之間而實施壓紋加工，藉此獲得具有凹凸形狀之聚乙烯醇 膜（基膜）。針對所獲得之聚乙烯醇膜之表面’利用基恩 士公司製造之雷射顯微鏡測量膜表面之凹凸之高低差’結 果為130 μ m。 使用實施有上述壓紋加工之聚乙烯醇膜作為轉移印刷 用積層體之基膜。 [硬化性樹脂之製造] 以下述方式製備活性能量射線硬化性樹脂組成物。 對於Kaneka股份有限公司製造之聚曱基丙烯酸曱酯 「MN」之固形物成分50份，以總固形物成分濃度成為50% 之方式藉由2 — 丁酮稀釋混合日本合成化學工業公司製造 之胺酯丙烯酸酯「UV— 3520」之固形物成分40份及大阪有 機化學工業公司製造之光聚合性單體「Viscoat# 300」10份 而獲得溶液’於該溶液中，以相對於固形物成分1 00份成 為3份之方式混合長瀨產業公司製造之「irgacure 8 19」作 為光聚合起始劑。 [設計印刷用油墨之製造] 製備由黑色顏料10份、硝化纖維素5份、醇酸樹脂15 份、甲苯30份、乙酸乙酯30份、異丙醇1 〇份構成之凹版 印刷用油墨。 [熱壓接接著層用塗佈液之製造] 以相對於甲苯與2 — 丁酮之4 : 1 (重量比）混合溶劑 成為20%之方式於加熱環流條件下攪拌溶解日本合成化學 39 201247408 工業公司製造之聚酯「SP ~ 1 85」（聚酯樹脂）。 <轉移印刷用積層體之製造> 於上述製造之基膜之熱處理面上，利用棒式塗佈機以 厚度成為1 60 // m之方式塗佈上述活性能量射線硬化性樹脂 組成物，於8(TC將其乾燥15分鐘，藉此製作於基膜上積層 有厚度為80 // m之硬化性樹脂層的積層體（以）。 於積層體（α )之硬化性樹脂層面上，使用上述印刷 用油墨並藉由凹版印刷法形成格子狀花紋，獲得由基膜/ 硬化性樹脂層/印刷層構成之積層體（々）。 進而，於積層體（冷）之印刷層面上，利用棒式塗佈 機以厚度成為lOOym之方式塗佈上述熱壓接接著層用塗佈 液，於80°C將其乾燥15分鐘，藉此形成厚度為2〇/zm之熱 壓接接著層，獲得由基膜/硬化性樹脂層/印刷層/接著 層構成之積層趙（γ)。 使用所獲得之積層體（Τ )’以如下所述之方式製作 評價用樣本，並進行以下評價。 [評價用樣本之製作] 將所獲得之積層體（7 )與青板玻璃基板（厚度2.8mm) 於加溫至130°C之乾燥機内預熱3分鐘，使積層體（r )之 熱壓接接著劑熔解，利用手壓輥將該接著層面壓附至青板 玻璃基板而製作貼合樣本。 隔著基膜對所獲得之貼合樣本照射丨000mJ紫外線，使 硬化性樹脂層硬化而形成保護層（硬化之硬化性樹脂層： 硬塗層），製成評價用樣本。 40 201247408 [評價用樣本之評價：立體設計性] …針對評價用樣本，冑用基恩士公司製造之雷射顯微鏡 測里剝離基臈後之保護層（硬化之硬化性樹脂層）表面的 高低差。 實施例2〜5、比較例1 除如表1所示般改變壓紋加工之條件以外，以與實施 例1同樣之方式獲得由聚乙烯醇構成之基膜。 使用所獲得之聚乙烯醇製基膜，以與實施例i同樣之 方式製造積層ϋ(7〇 ’並評價立體設計性。將實施例及 比較例之評價結果示於表i。再者，關於表t中之支承親之 表面硬度’將利用A㈣度試驗計測定之值記作「八〇 〇」，將利用D形硬度試驗計測定之值記作「d〇〇」（「〇 〇」表示硬度值）。 [表1]The film thickness uniformity in the case of the resin layer, and if the (Mw) is too small, the layer is softened and has adhesiveness, and in the case of dysfunction (contraction in the step, excessive printing), it is difficult to obtain coating hardening and drying. The hardness of the curable resin layer tends to be higher than that required, and it tends to cause defects (causation of cracking of the curable resin layer, interlayer peeling, etc.) during post-processing. Amine vinegar (mercapto) acrylate system The compound is a (meth) acrylate compound having an amine vinegar bond in the molecule, and can be produced by reacting a hydroxy group-containing (fluorenyl) acrylate compound with a polyvalent isocyanate compound and, if necessary, a polyol. Examples of the hydroxyl group-containing (fluorenyl) acrylic compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. Methyl)acrylic acid 4-butylidene ester, 6-hydroxyhexyl (meth)acrylate, 2-(meth)acryloxyethyl 2-hydroxypropyl phthalate, 2-hydroxyl 3-(Meth) propylene methoxy propyl (meth) acrylate, caprolactone modified (meth) acrylic acid 2 - ethyl methacrylate, neodecyl alcohol tris (mercapto) acrylate , dipentaerythritol penta (meth) acrylate, caprolactone modified dine pentaerythritol penta (meth) acrylate, caprolactone modified pentaerythritol tris(fluorenyl) acrylate, ring Oxygen ethane modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified pentaerythritol tris(fluorenyl) acrylate, etc., wherein three or more propylene oximes are preferably used. 25 201247408 A hydroxyl group-containing (meth)acrylic compound, and may be used in combination of two or more kinds. Examples of the polybasic isocyanate compound include aromatic and aliphatic compounds. Examples of the polyisocyanate such as an alicyclic system include: anthraquinone diisofluoride, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, and modified diphenylmethane II. Isocyanate, hydrogenated benzyl diisocyanate, stupid dimethyl diiso Acid ester, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, tetramethyl dimethyl diisocyanate, isophorone diisocyanate, decene diisocyanate, bis (isocyanate fluorenyl) ring a polyisocyanate such as hexane, phenyl diisocyanate, diazonic acid diisocyanate, triisomeric acid triisocyanate or naphthalene diisocyanate or a terpolymer compound or a polymer compound of the polyisocyanate, a dimeric type Polyisocyanic acid vinegar, water (4) poly-gas vinegar (such as 'Aquanaten 〇 制造 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 A A A A A A A A A A A A A A A A A A A A A A A And a reaction product of the polyisocyanate and a polyhydric alcohol. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butanediol, polybutylene dimethanol, and hydrogenation. Bi-glycol, 1,6-hexanediol, neopentyl glycol, cyclohexene A, polycaprolactone, trimethylolethane, trihydrocarbyl propane neopentyl fermentation, polytetradecyl alcohol, Sorbitol, mannitol, glycerin, polyols such as polyethylene oxide, polyglycidylglycerol, polybutylene glycol, etc.; block, ethylene oxide/propylene oxide block 26 201247408 or random a polyether polyol having at least one structure copolymerized; as the polyol or polyether polyol with maleic anhydride, maleic acid, butyl bromide, itaconic anhydride, itaconic acid, Polyester polyol of a condensate of a polybasic acid such as diacid or isophthalic acid; caprolactone modified polytetramethylene polyol or the like, a propylene modified polyol, a polyolefin polyol; hydrogenated poly A polybutadiene-based polyol such as a butadiene polyol. Further, examples of the polyhydric alcohol include 2,2-bis(hydroxyindenyl)butyric acid, tartaric acid, 2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,2- Bis(hydroxyindenyl)propionic acid, 2,2-bis(hydroxyethyl)propionic acid, 2,2-bis(propyl)propionic acid, dimethylolacetic acid, bis(4-hydroxyphenyl)acetic acid a polyol containing a carboxyl group such as 4,4-bis(4-hydroxyphenyl)pentanoic acid or uric acid, or a polyhydric alcohol containing a sulfonic acid group or a sulfonate such as sodium i,4-butanediol. . In the case of using a reaction product of a polyisocyanate and a polyhydric alcohol, for example, it can be used as a polyisocyanate containing a terminal isocyanate group obtained by reacting the above polyol with the above polyisocyanate. In the reaction of the polyisocyanate with the polyol, in order to promote the reaction, it is preferred to use a metal catalyst such as dibutyltin dilaurate or 1>8-diazabicyclo[54〇]undecene-7. Amine catalysts, etc. The method for producing the above-described amine ester (meth) acrylate-based compound may, for example, be a method in which a (meth)acrylic compound containing a hydroxyl group and a polybasic oleic acid compound are mixed in an inert gas atmosphere, usually at 3 〇. 8〇<>c The method of reacting for 2 to 10 hours. In the reaction, an amine esterification catalyst such as octene bismuth vinate monobutyltin, octanoic acid, octanoic acid, acetic acid bromine, stannous octoate or diethylenediamine is preferably used. 27 201247408 Amino fluorenyl) propylene oxime ester compound preferably has a weight average molecular weight of 3 〇〇 _, and further preferably ～ 35 〇〇, especially preferably ～ 3000 〇 if the weight is equal to eight knives When the amount is too small, the curable resin layer tends to have insufficient cohesive strength after curing, and if the right is too large, the viscosity tends to be too high and manufacturing tends to be difficult. In addition, the above-mentioned weight average molecular weight refers to the weight of the standard polystyrene molecular weight conversion, which is about the weight of the nominal ife-fcA. 卞 刀 Q knife, which is manufactured by Showa Denko. In the "Shodex GPC system — ! i type"), three series of Shodex Gpc KF_8〇6L columns are used (excluding the limit molecular weight: 2M07' separation model: 1〇〇~2χ1〇7, Wang Li on the number of segments: 〇〇〇〇 〇〇〇〇 section / branch, filler material: styrene _ divinyl stupid copolymer, filler particle size: 10 in m) and measured. In addition, when a light-polymerizable monomer is irradiated with light such as ultraviolet rays, it is polymerized by itself to form a polymer, and usually a monofunctional monomer having one functional group and a polyfunctional group having two or more functional groups are present. Sexual monomer. The S-light polymerizable monomer ' can be exemplified as follows. Examples of the monofunctional monomer include styrene, vinyl fluorene benzene, gas styrene, α-methyl styrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile, and acetic acid. Vinyl ester '(mercapto)acrylic acid 2 monohydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, phenoxyethyl (meth)acrylate, (methyl) Acrylic acid 2 - phenyloxy-p-propyl propyl ester, (mercapto) acrylic acid 2 - carboxylic acid 3- phenoxypropyl ester, (meth)acrylic acid 3-chloro-2-hydroxypropyl ester, glycerol (fluorenyl) acrylate, (meth)acrylic acid propyl propyl ester, (meth)acrylic acid Laurel 28 201247408 酉曰, (meth) acrylic acid cyclohexyl acrylate, (fluorenyl) acrylate isopropyl vinegar, (meth)tricyclodecyl acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth) enoate, dicyclopentanyl (decyl) acrylate, N-butyl acrylate, (hexyl) hexyl acrylate, heptyl (meth) acrylate, (mercapto) propylene Octyl methacrylate, decyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl acrylate, n-stearyl (meth) acrylate, (A) Benzyl acrylate, phenol oxirane modified Cn=2) (fluorenyl) acrylate, nonylphenol propylene oxide modified (11=2.5) (methyl) acrylate vinegar, 2- (A Semi-(indenyl)acrylic acid of phthalic acid derivatives such as acryloxyethyl acid phosphate and 2-(indenyl) propylene oxy-2-hydroxypropyl phthalate Ester, decyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, carbitol (meth) acrylate, benzyl acetonate, butoxyethyl (meth) acrylate, Allyl methacrylate, propylene decyl porphyrin, 2-hydroxyethyl acrylamide, N-hydroxymethyl (decyl) acrylamide, N-vinyl pyrrolidone, 2-vinyl pyridine , polyoxyethylene secondary alkyl ether acrylate and the like. Further, examples of the bifunctional monomer in the above polyfunctional monomer include ethylene glycol di(decyl)acrylate, diethylene glycol di(decyl)acrylate, and tetraethylene glycol di(methyl). Acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(decyl)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol bis(indenyl)acrylate, butanediol di Mercapto) acrylate, neopentyl glycol bis(indenyl) acrylate, ethylene oxide modified bisphenol A type di(meth) acrylate, propylene oxide modified bisphenol A type II (fluorenyl) Acrylate, cyclohexane dimethanol di(meth) acrylate, ethoxycyclohexane dimethyl 29 201247408 alcohol di(meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, Tricyclodecanedioxyl di(meth)acrylate, 1,6-hexanediol di(meth)acrylic acid, glycerol di(meth)acrylate, neopentyl alcohol di(methyl) Acrylate, ethylene glycol diepoxypropyl ether di(meth)acrylate, diethylene glycol diepoxy Ethyl ether di(meth) acrylate, diepoxypropyl phthalate di(meth) acrylate, hydroxypivalic acid modified neopentyl glycol di(meth) acrylate, heterotrimerization Cyanate oxirane modified diacrylate and the like. Further, examples of the monomer having a trifunctional or higher functional group as the polyfunctional monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol tris(decyl)acrylate, and pentaerythritol. Tetrakis(yl) acrylate, dipentaerythritol penta(indenyl) acrylate, dipentaerythritol hexa(meth) acrylate, tris(indenyl) propylene methoxy ethoxy trishydroxymethyl Propane, glycerol polyepoxypropyl transfer poly(indenyl) acrylate, iso-cyanuric acid ethylene oxide modified triacrylate vinegar, caprolactone modified dipentaerythritol penta (meth) acrylate, Caprolactone modified dipentaerythritol hexa(indenyl) acrylate, caprolactone modified pentaerythritol tri(meth) acrylate, caprolactone modified pentaerythritol tetra (methyl) Acrylate, ethylene oxide modified dipentaerythritol penta(indenyl) acrylate, ethylene oxide modified dipentaerythritol hexa(indenyl) acrylate, ethylene oxide modified pentylene Tetraol bis(indenyl)propionate, epoxide modified neopentyltetrakis(mercapto) acrylate, ethoxylated glycerin triacrylate, and the like. Further, it is also possible to exemplify other acrylic propylene (Michael) adducts 丙 2 propylene oxide oxyethyl- tacrole mono vinegar as the acrylic acid adducts of acrylic acid. A methacrylic acid dimer, a propionic acid dimer, a methacrylic acid terpolymer, an acrylic acid tetramer, a mercapto propylene 201247408 acid tetramer, and the like. Further, the 2-propenyloxyethyl dicarboxylic acid monoester is a carboxylic acid having a specific substituent, and examples thereof include a 2-propenyloxyethyl succinic acid monoester and a 2-nonyl propylene oxime oxygen. Monoethyl succinate monoester, 2 propylene oxiranyl ethyl phthalate monoester, 2-methyl propyl oxiranyl ethyl phthalate monoester, 2- propylene oxiranyl ethyl ester Hexahydrophthalic acid monoester, 2-mercaptopropenyloxyethylhexahydrophthalic acid monoester, and the like. Further, other oligoester acrylates may also be mentioned. In the present invention, as the content ratio of the acrylic resin, the amine ester (mercapto) acrylate compound, and the photopolymerizable monomer, the amine ester (meth) acrylate compound is 100 parts by mass based on the acrylic resin. It is preferably 20 to 300 parts by mass, more preferably 4 to 25 parts by mass, still more preferably 60 to 200 parts by mass, and the photopolymerizable monomer is preferably 5 to 8 parts by mass, particularly preferably 10 to 10 parts by mass. 60 parts by mass' is further preferably 15 to 50 parts by mass. In this manner, an active energy ray-curable resin composition containing an acrylic resin and an amine ester (meth)acrylate compound, preferably further containing a photopolymerizable monomer, can be obtained, and the active energy ray curable resin composition is In the case of the ultraviolet curable resin composition, it is preferred to further contain a photopolymerization initiator. In the case of an electron beam curable resin composition, a photopolymerization initiator is not required. Examples of the photopolymerization initiator include diethoxy acetophenone, 2-hydroxy -2- fluorenyl 1- phenylpropane hydrazine, benzyl benzyl dimercapto ketal, and 4 _ ( 2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)indole, 1-hydroxycyclohexyl phenyl ketone, 2-indenyl-2- porphyrinyl (4_1 thiomethylphenyl) ) 丙院一一— _, 2-benzyl-2-dimethylamino-1 31 201247408 Oral phenyl phenyl) butanone, 2-hydroxy-2-methyl-1-[4- (1- Acetophenones such as methyl vinyl) phenyl]acetone oligomers; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin; diphenyl ketone, o-benzoyl Ethyl benzoate, 4-phenyldiphenyl ketone, 4-phenylindole- 4'-mono-diphenyl sulfide, 3,3,4,4,-tetra(t-butylperoxycarbonyl) Diphenyl ketone, 2,4,6-trimethyldiphenyl ketone, 4-benzyl-based N,N-diindenyl-N-[2-(1 - oxo- 2-propene (oxy)ethyl]ammonium bromide, gasified (4-phenylphenylbenzyl) Diphenyl ketones such as base clock; 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4 dioxin Ketone, 1-chloro-4-propoxythioxanthone, 2-(3-diaminoamino-2-hydroxy)-3,4-dimethyl- 9H-thioxanthone-9-one Racemic compounds such as racemic vapors; 2,4,6-trimercaptophenylphosphonium diphenylphosphine oxide, bis(2,6-dioxalylbenzyl)- 2, 4,4-trimethylphosphinophosphine oxide, fluorenylphosphine oxide such as bis(2,4,6-trimethyl benzhydryl)-phenylphosphine oxide, and the like. Further, the photopolymerization initiators may be used singly or in combination of two or more. The content of the photopolymerization initiator is 100 parts by mass, preferably 〇, based on the amine ester (meth) acrylate compound (in the case of blending the photopolymerizable monomer). 5 to 15 parts by mass, particularly preferably 5 to 10 parts by mass, and further preferably 1 to 8 parts by mass. 'As a auxiliaries of these, it is also possible to use triethanolamine, triisopropanol '4 (monodecyl) diphenyl ketone (Mitch), 4,4'-bis(diethylamine) Diphenyl ketone, 2-diaminoaminoethyl benzoic acid, 4 32 201247408 ester, 4-dimethylaminobenzoic acid isopentane, 4 ethylhexyl ester, 2,4 - 2, etc. Ethyl dimethylaminobenzoate, 4-dimethylamino benzoic acid (n-butoxy) ethylaminobenzoic acid 2 - diisopropyl hydrazine, among the temples, preferably benzyl Base one, 丨, will be a τ sign Ming, 丨 - hydroxy storm ring. Basic base steel, benzoic acid, isopropyl, 4_(2 - ethoxylated phenyl (2-carbyl-2-propyl)methyl (tetra), 2-yl- 2-methyl-benzene In the present invention, the thickness of the curable resin layer is preferably a (9) heart, particularly preferably 2 to 120" from the viewpoint of abrasion resistance and chemical resistance. If the thickness is too thin, there is a wear resistance - or ί chemistry. The σ property tends to decrease. If the thickness is too thick, the film after transfer is insufficiently cut, resulting in burrs, etc. When forming a curable resin layer, it can be applied by a gravure coating method, a roll coating method, a bar coating method, a knife coating method, a lip coating method, or the like, and a concave I7 brush screen printing method. The raw material resin or the raw material resin composition is laminated by a printing method such as a method. When the active energy ray-curable resin composition is used, a layer composed of an active energy ray-curable resin composition can be laminated on the base film ( After the hardening resin layer), until the printing layer is transferred onto the transferred body and peeled off at any stage of the base film, or the base film is peeled off At any stage, the lens is rubbed and rubbed to form a protective layer (hard coat), or the active energy ray may be irradiated after the base film is peeled off and hardened to form a protective layer (hard coat). 33 201247408 For example, a method in which an active energy ray-curable resin composition layer is laminated on a base film and then irradiated with an active energy ray to cure it is exemplified; (2) an active energy is deposited on the base film. After the radiation curable resin composition layer is formed, the following printed layer is formed, and then the active energy ray is irradiated from the base film side to be cured; (3) further layering is performed until the following subsequent layer, from the base film side (4) a method of curing the active energy ray by the irradiation of the active energy ray; (4) a method of curing the layered body for transfer printing of the present invention after the transfer target is irradiated with active energy rays from the base film side; or (5) After the transfer printing laminate of the present invention is applied to the transfer target, the base film is peeled off and the active energy ray is irradiated and cured, and H is used for the followability of the transfer target during thermal transfer. View In the case of (4), when the Tt is a hard layer, as the active energy ray, for example, ultraviolet rays such as far ultraviolet rays, ultraviolet rays near ultraviolet rays, electromagnetic waves such as x-rays and r-rays, and the like can be used. In addition to electron beams, proton rays, neutron rays, etc., it is advantageous to harden by irradiation, such as hard speed, availability of an irradiation device, price, etc., as a method of hardening by ultraviolet irradiation. As long as the high-pressure mercury lamp, the ultra-high pressure mercury lamp, the carbon lamp, the metal hydride lamp, the gas lamp, the chemical lamp, etc., which emit light of 150 to (four) (10) band, are used, and irradiation of about 0.01 to 10 J cni may be performed. Heating is carried out to achieve complete hardening. In the present invention, the printed layer is formed into a layer of design as required, and as a material of the 34 201247408 brush layer, the following colored ink can be used: it contains a polyethylene resin, polyamine Resin, poly-based resin, acrylic resin, polyamine-based resin, ethylene acetal resin, polyesteramine resin, cellulose ester resin, A resin such as an acid alcohol resin is used as a binder and contains a suitable color pigment or dye as a colorant. As a method of forming the printing layer, a usual printing method such as lithography & gravure printing or screen printing can be used. In particular, in order to perform multicolor printing or gray scale display, a lithographic printing method or a gravure printing method is preferred. In addition, the "printing layer is provided on the film having the mold release property using the domain printing method", and the printed surface is placed in contact with the layer (curable resin layer) composed of the active energy ray-curable resin composition of the base film. And using a dry lamination method for lamination. In the laminated system for transfer printing of the present invention, the base film, the curable resin layer, and the printed layer are laminated, and it is preferable that a layer is laminated on the printed layer. The layer is then used to cause the layered body to follow the body to be transferred. It can be formed when the p-brush layer and the molded article have weak adhesion. As the material of the next layer, the heat sensitivity of the material suitable for the transfer target is appropriately used. The pressure-sensitive resin may be, for example, "ester resin, acrylic acid: Shuyueji, I styrene resin, polyamine resin, gasified polyolefin tree, and gasified ethylene-vinyl acetate copolymerization" Resin, cyclized rubber, benzofuran-indene resin, and the like. Examples of the method for forming the adhesive layer include a coating method such as a gravure coating method, a roll coating method, a bar coating method, and a doctor blade coating method, a gravure printing method, and a printing method such as 35 201247408 screen printing method. The adhesive sheet formed of the above materials may be bonded together by a lamination method or the like to form an adhesive layer. The next layer can also double as a printed layer. The thickness of the contact layer is preferably from 5% to 50 μm, more preferably from 2 to 3 μm, from the viewpoint of the followability of the transferred body. When the thickness is too small, the tendency to lower the followability to the transfer target at the time of transfer tends to be too large, and the cost tends to be high, which is uneconomical. A method of decorating the surface to be transferred by the transfer method using the laminate for transfer printing of the present invention will be described. First, the printed layer side in the case where the transfer printing laminate has the adhesive layer on the subsequent layer side or in the case where the adhesive layer is not provided is adhered to the transferred body surface. Next, the use of a transfer machine such as a roll transfer machine or a lift (Up __ dQwn) transfer machine with a thermal rubber-like elastomer such as a polystyrene rubber is used, and the temperature is about 80 to 270 ° C and pressure. The heat-resistant rubber-like elastomer having a condition of about 49 〇 to 196 〇Pa is applied with heat and pressure from the base film side of the laminate for transfer printing. By A, the layer or printed layer is then applied to the surface of the transferred body. After cooling, the curable resin layer is cured by irradiation with an active energy ray or the like to form a protective layer (hard coat layer), and finally the base film is peeled off from the base layer and the protective layer (hardened curable resin layer: hard) The interface of the coating) causes peeling to end the transfer. Further, in the above step, the active energy ray-curable resin composition is slightly hardened by heat. Next, a method of decorating the surface of the resin molded article 36 201247408 as a transfer target by the simultaneous transfer method by injection molding using the transfer laminated body of the present invention will be described. First, the transfer printing laminate is fed into a molding die composed of a movable mold and a fixed mold. In this case, the sheet-like transfer printing laminate can be fed one by one. The necessary portions of the long laminate can also be intermittently fed. In the case of using a laminate transfer printing laminate, the transfer device for the positioning mechanism can be made such that the printing layer of the transfer printing laminate conforms to the direction of the molding die. In addition, when the transfer printing laminate is intermittently fed, the position of the transfer printing laminate is detected by the sensor, and the transfer printing laminate is fixed by the movable mold and the fixed mold, so that the transfer printing can be performed all the time. It is convenient to use the laminate to be fixed at the same position without causing the positional shift of the printed layer. After the molding die is closed, the molten molding resin is ejected from the gate and filled in the mold, and the transfer printing body is formed on the surface while the transfer target is formed. The molding resin may, for example, be a general-purpose resin such as a polystyrene resin, a polyolefin resin, an ABS resin, an AS resin or an AN resin. Also, 'Polybenzene can be used as a polystyrene resin, a polycarbonate resin, a polyacetal resin, an acrylic resin, a polycarbonate modified polyether resin, and a polybutylene terephthalate. General engineering resins such as esters and ultrahigh molecular weight polyethylene resins, "Polyester, polyphenylene sulfide resin, polyphenylene resin, polyarylate resin, polyether sulfimide resin, polyimine resin, liquid crystal polymerization Super engineering resin such as ester resin or polyaryl heat resistant resin. Further, a composite resin to which a reinforcing material such as glass fiber or inorganic filler is added may be used. These resin molded articles may be either transparent, translucent or opaque. Further, the molded article may or may not be colored. 37 201247408 After cooling the resin molded article as the transfer target, the molding die is opened and the resin molded article is taken out. When the protective layer (hard coat layer) is formed by curing the curable resin layer by active energy ray irradiation or the like, the base film is finally peeled off from the base film and the protective layer (hardened curable resin layer: hard coat layer) The interface causes peeling and the transfer ends. Further, the mold for molding can be opened, and the resin molded article can be taken out, and after the base film is peeled off, the curable resin layer is cured by active energy ray irradiation or the like to form a protective layer, and the transfer is completed. [Examples] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples without departing from the spirit of the invention. In addition, the terms "part" and "%" in the 'examples' mean the weight basis. Example 1 [Production of base film] The degree of saponification was determined to be 88 mol% and 20 by using a T-die. (: 4% aqueous solution viscosity of 23 mPa · s of polyvinyl alcohol resin 100 parts, starch as a filler (average particle size of 15 to m) 5 parts, surfactant (polyoxyethylene sorbitan monolaurate) 〇·5 parts, 20 parts of glycerin as a plasticizer, 20°/. The aqueous solution is discharged to a rotating stainless steel endless belt whose surface temperature is adjusted to 9〇〇c, and is cast and formed, and then adjusted to 9 5. The heat of the crucible is also subjected to heat treatment for anti-crimping treatment to obtain a polyvinyl alcohol film having a thickness of 4 Å/m. The obtained polyvinyl alcohol film is passed through a pressing force of 2 MPa and at a processing speed of 5 m / min. An embossing roll heated to 120 ° C (concave shape: crepe, height difference: 250 ym, 80 mesh) and heated to 80. (: support roll (roller 38 201247408 surface hardness: based on JIS Κ 6253 A An embossing process was performed between 90% of the hardness tester, thereby obtaining a polyvinyl alcohol film (base film) having a concavo-convex shape. The surface of the obtained polyvinyl alcohol film was manufactured by Keyence Corporation. Laser microscope measures the unevenness of the surface of the film The result is 130 μm. The polyvinyl alcohol film subjected to the embossing described above is used as a base film for a laminate for transfer printing. [Production of Curable Resin] An active energy ray-curable resin composition is prepared in the following manner. 50 parts of the solid content of the polyalkyl methacrylate "MN" manufactured by Kaneka Co., Ltd., and the amine ester manufactured by Nippon Synthetic Chemical Industry Co., Ltd. was diluted by 2-butanone in such a manner that the total solid content concentration was 50%. 40 parts of the solid content of the acrylate "UV-3520" and 10 parts of the photopolymerizable monomer "Viscoat #300" manufactured by Osaka Organic Chemical Industry Co., Ltd. to obtain a solution in the solution to be compared with the solid content of 100 In the form of a three-part method, "irgacure 8 19" manufactured by Nagase Industries Co., Ltd. is used as a photopolymerization initiator. [Production of Ink for Design Printing] Preparation of 10 parts of black pigment, 5 parts of nitrocellulose, and alkyd resin 15 An ink for gravure printing comprising 30 parts of toluene, 30 parts of ethyl acetate, and 1 part by weight of isopropyl alcohol. [Manufacture of coating liquid for thermocompression bonding layer] with respect to toluene and 2 The butanone 4:1 (weight ratio) mixed solvent is 20% in a manner of stirring and dissolving the polyester "SP ~ 1 85" (polyester resin) manufactured by Nippon Synthetic Chemical Co., Ltd. under the heating circulation. (Production of the laminated body for printing) The active energy ray-curable resin composition is applied to the heat-treated surface of the base film produced as described above by a bar coater at a thickness of 1 60 // m. The TC was dried for 15 minutes to prepare a laminate in which a curable resin layer having a thickness of 80 // m was laminated on the base film. On the layer of the curable resin of the laminate (α), a grid pattern is formed by the gravure printing method using the printing ink, and a laminate comprising a base film/curable resin layer/print layer is obtained. Further, the coating liquid for a thermocompression bonding layer was applied to a printing layer of a laminate (cold) at a thickness of 100 μm by a bar coater, and dried at 80 ° C for 15 minutes. A thermocompression bonding layer having a thickness of 2 Å/zm was formed to obtain a laminated layer (γ) composed of a base film/curable resin layer/printing layer/adhesion layer. Using the obtained laminate (Τ)', samples for evaluation were prepared in the following manner, and the following evaluations were carried out. [Preparation of sample for evaluation] The obtained laminate (7) and a green glass substrate (thickness: 2.8 mm) were preheated in a dryer heated to 130 ° C for 3 minutes to heat the laminate (r). The adhesive was melted, and the bonding layer was pressed to the green glass substrate by a hand roller to prepare a bonded sample. The obtained bonded sample was irradiated with 丨000 mJ of ultraviolet light through a base film, and the curable resin layer was cured to form a protective layer (cured resin layer: hard coat layer), and a sample for evaluation was prepared. 40 201247408 [Evaluation of sample for evaluation: three-dimensional design] ... For the sample for evaluation, the surface of the protective layer (hardened curable resin layer) after peeling the base is measured by a laser microscope manufactured by Keyence difference. Examples 2 to 5 and Comparative Example 1 A base film made of polyvinyl alcohol was obtained in the same manner as in Example 1 except that the conditions of the embossing were changed as shown in Table 1. Using the obtained polyvinyl alcohol base film, laminated ruthenium (7 〇 ' was produced in the same manner as in Example i, and the three-dimensional design property was evaluated. The evaluation results of the examples and the comparative examples are shown in Table i. The surface hardness of the support member in Table t is described as "eight gossip" using the value measured by the A (four) degree tester, and the value measured by the D-shaped hardness tester is referred to as "d〇〇" ("〇〇" indicates the hardness value. ). [Table 1]
根據上述實施例及比較例之結果， J知.關於實施 例，由於使用具有所期望之高低差之凹凸形狀的基膜，故 201247408 而基膜與保護層（硬化性樹脂層硬化而成之層）之剝離性 優異，並且形成可識別出立體設計之保護層；相對於此， 於比較例1中，由於基膜之高低差過小’故而於所獲得之 保護層中，未形成可識別之立體設計（花紋）。 又，根據實施例2與比較例1之比較可知：若用於壓 紋加工之支承輥之表面硬度過小，則即便使用相同之壓紋 輥，且壓紋輥及支承輥之表面溫度相等，可賦予基膜之凹 凸形狀之高低差亦變小，進而無法獲得可有效地轉印立體 設計之轉移印刷用積層體。另一方面，根據實施例1與實 施例4之比較可知：雖然可與使用凸部之高低差大之壓紋 輥情況相對應而增大基膜之凹凸形狀之高低差（實施例 Ο ，但若基膜之凹凸形狀之高低差變大至特定以上，則有 難以反映到所獲得之保護層之立體設計的高低差之傾向。 因此’為了高效地轉印立體設計，較有效的是將基膜之高 低差設為5〜20〇em。 [產業上之可利用性] 使用本發明之基膜之轉移印刷用積層體不僅基膜與保 護層（硬化性樹脂層硬化而成之層）之剝離性優異，而且 可簡便地轉印絹紋、縐紋、砂紋、髮線紋樣、麻紋、皮革 風格之花紋等立體性設計。因此，於製造汽車等車輛之内 飾材料或外飾材料’踢腳線、簷板等裝修構件，窗框、門 框等建具，牆壁、地板、頂棚等建築物之内部材料，電視 接收器、行動電話零件、空調等家電製品之框體、容器等 用途之裝飾成形品時非常有用。 42 201247408 【圖式簡單說明】 圖1係用於說明本發明之基膜之凹凸形狀的模式圖。 【主要元件符號說明】 1基膜 43According to the results of the above-described examples and comparative examples, it is known that, in the examples, since the base film having the desired unevenness of the height difference is used, the base film and the protective layer (the layer formed by the hardening resin layer) The peeling property is excellent, and a protective layer capable of recognizing the three-dimensional design is formed; whereas in Comparative Example 1, since the height difference of the base film is too small, an identifiable solid is not formed in the obtained protective layer. Design (pattern). Further, according to the comparison between Example 2 and Comparative Example 1, it is understood that if the surface hardness of the backup roll for embossing is too small, even if the same embossing roll is used and the surface temperatures of the embossing roll and the backup roll are equal, The height difference of the uneven shape imparted to the base film is also small, and further, it is not possible to obtain a laminate for transfer printing which can be efficiently transferred to a three-dimensional design. On the other hand, according to the comparison between Example 1 and Example 4, it can be seen that the height difference of the uneven shape of the base film can be increased in accordance with the case of using the embossing roll having a large difference in height of the convex portion (Example Ο , When the height difference of the uneven shape of the base film is increased to a specific level or more, it tends to be difficult to reflect the level difference of the three-dimensional design of the obtained protective layer. Therefore, in order to efficiently transfer the three-dimensional design, it is effective to base the substrate. The height difference of the film is set to 5 to 20 〇em. [Industrial Applicability] The laminate for transfer printing using the base film of the present invention is not only the base film and the protective layer (the layer obtained by curing the curable resin layer) It has excellent peelability and can easily transfer three-dimensional designs such as crepe, crepe, sand, hairline, hemp, and leather-style patterns. Therefore, it is used to manufacture interior materials or exterior materials for vehicles such as automobiles. 'Chairboards, fascias and other decoration components, window frames, door frames, etc., interior materials for walls, floors, ceilings, etc., housings for TV receivers, mobile phone parts, air conditioners, etc. Decorated molding is very useful. 42201247408] [Brief Description of the drawings Figure 1 is a schematic diagram of the irregularities of the base film of the present invention for explaining a shape. The main element of the base film 1 REFERENCE NUMERALS 43