TW201221586A

TW201221586A - Ink composition and decorative sheet produced using same

Info

Publication number: TW201221586A
Application number: TW100129734A
Authority: TW
Inventors: Masahiro Yasuhara; Akihiko Katashima; Masakazu Kaneko; Hiroshi Kishida; Junichi Kuroki; Kazuyuki Takasawa; Hidehiko Masaki; Hiroshi Miyama
Original assignee: Dainippon Printing Co Ltd
Priority date: 2010-08-20
Filing date: 2011-08-19
Publication date: 2012-06-01
Also published as: JP2012041479A; JP5732778B2; CN103052693B; WO2012023543A1; TWI492993B; CN103052693A

Abstract

Provided is an ink composition for use in the formation of a decorative sheet, which can impart high hardness to a decorative molded article, can also impart moldability required for forming a molded article having a more complicated shape, and enables the formation of a tuck-free hardcoat-layer-forming layer merely by thermal drying if necessary. This ink composition comprises: a polyfunctional radical-polymerizable prepolymer having at least one ionizing-radiation-curable functional group (A) selected from the group consisting of a vinyl group, a (meth)acryloyl group and an allyl group and having a weight average molecular weight of 50000 or more; reactive inorganic particles each having an ionizing-radiation-curable functional group (B) on the surface thereof; and a polyfunctional isocyanate compound.

Description

201221586 六、發明說明：【發明所屬之技術領域】本發明係關於一種油墨組成物，更詳而言之，係關於一種形成加飾薄片用之油墨組成物，其可賦予加飾成形品優異之高硬度性、能賦予可製得複雜形狀之成形性、並且具有耐黏連性》【先前技術】以往’於具有三維曲面等複雜表面形狀之樹脂成形體之加飾’係使用射出成形同時加飾方法。所謂係使用射出成形同時加飾方法，係指於射出成形之際，使插入於模具內之加飾薄片、與射出注入於模穴內之熔融之射出樹脂一體化’而於樹脂成形體表面實施加飾之方法。於該方法，根據與樹脂成形體一體化之加飾薄片之構成的不同，—般而言’係大致分爲射出成形同時層合加飾法與射出成形同時轉印加飾法。於射出成形同時轉印加飾法中，使加飾薄片密合於模具內面而合模後，將熔融於模穴內之射出樹脂射出使該加飾薄片與射出樹脂一體化’接著，將加飾成形品冷卻由模具取出後，將基材薄膜剝離，藉此製得轉印有轉印層之加飾成形品。如此所得之加飾成形品，除以往所使用之家庭用電化製品、汽車內裝品等領域外，近年來，例如伴隨電腦市場的擴大’包含日常可攜帶之行動個人電腦之筆記型電腦之 -5- 201221586 領域的使用、或汽車外裝、行動電話領域之使用亦受到注目。於該等領域中，對於加飾薄片，要求可賦予加飾成型品優異之高硬度性等表面特性的同時、亦具有可得形狀更複雜之成形品之成形性。爲了滿足如此之要求，提出一種具有使用含有低分子量之聚合物與多官能異氰酸酯之活性能量線硬化性樹脂組成物之保護層的轉印材料（例如，專利文獻1 )。然而，使用有該樹脂組成物之保護層難以作成無黏性，爲了作成無黏性’需要以1 50 °c之高溫之烘烤或長時間之加熱處理。又’於上述之保護層，亦具有無法因應高硬度性等表面特性中之更嚴苛之要求的問題。於可得高硬度性等表面物性的目的下，提出一種具有含低分子量之聚合物、硬化劑與凝膠二氧化矽粒子之保護層的轉印材料（例如，專利文獻2 )。然而，該保護層，對於鉛筆硬度之Η以上之更嚴苛要求不足，且於將加飾薄片捲繞成滾筒狀時會有黏連（內移）的情形，再者，對於形狀更複雜之成形品，會有保護層白化而產生塗裝破裂的問題。高硬度性等表面特性與耐黏連及成形性爲相對的性能’能以高等級實現該等相對性能之加飾薄片目前並不存在。專利文獻1 :日本專利第3 2 3 3 5 9 5號公報專利文獻2:日本特開2009- 1 3 721 9號公報【發明內容】 -6 - 201221586 〔發明欲解決之課題〕因此，本發明之目的在於提供一種形成加飾薄片用之油墨組成物，其於賦予加飾成型品優異之高硬度性的同時，亦賦予可得形狀更複雜之成形品之成形性，且可視需要僅以熱乾燥將硬塗層形成層作成無黏性。又，本發明之另一目的在於，提供使用上述油墨組成物之加飾成形品之製造方法。再者，本發明之又一目的在於，提供以上述製造方法所製得之加飾成形品。〔解決課題之手段〕本發明之油墨組成物，係含有下列而成：具有選自乙烯基、（甲基）丙烯醯基及烯丙基所構成群中之至少一種之電離輻射線硬化性官能基A之重量平均分子量爲50000以上的多官能性自由基聚合性預聚物；於表面具有電離輻射線硬化性官能基B之反應性無機粒子；與多官能異氰酸酯化合物。又’本發明之另一樣態之加飾薄片，係於基材薄膜之單面’至少依序具備脫模層與硬塗層形成層之加飾薄片，其中’該硬塗層形成層係使用上述之油墨組成物所形成者再者，本發明之另一樣態之加飾成形品之製造方法，其係使用上述加飾薄片之加飾成形品之製造方法，其含有 201221586 於射出成形模具內配置該加飾薄片之步驟；將熔融樹脂射出至該射出成形模具之模穴內，進行冷卻、固化，而使樹脂成形體與加飾薄片層合一體化之射出步驟；將該樹脂成形體與該加飾薄片層合一體化後之成形體，由該射出成形模具取出之步驟；將加飾薄片之基材薄膜由該成形體剝離之步驟；及使用電離輻射線使設置於該成形體上之硬塗層形成層硬化之硬塗層形成步驟。 .本發明，係提供以上述之製造方法所製得之加飾成形品。〔發明的效果〕藉由本發明，可實現於賦予加飾成型品優異之高硬度性的同時，亦賦予可得形狀更複雜之成形品之成形性，且可視需要僅以熱乾燥將硬塗層形成層作成無黏性之可賦予加飾薄片優異之製造效率之油墨組成物。【實施方式】 <油墨組成物〉本發明之油墨組成物，作爲必須成分含有：具有選自乙烯基、（甲基）丙烯醯基及烯丙基所構成群中之至少一種之電離輻射線硬化性官能基A之重量平均分子量爲50000 以上的多官能性自由基聚合性預聚物；於表面具有電離輻 -8 - 201221586 射線硬化性官能基B之反應性無機粒子；與多官能異氰酸酯化合物。以下，說明構成本發明之油墨組成物之各成分 <具有電離輻射線硬化性官能基A之多官能性自由基聚合性預聚物> 本發明中，所謂「電離輻射線硬化性」，係指具有於電磁波或荷電粒子線之中可使分子交聯、聚合之能量量子者’亦即，藉由紫外線或電子線等之照射而激發、產生聚合反應，藉此交聯、硬化之性能。又，所謂「電離輻射線硬化性官能基」，係指可發揮電離輻射線硬化性之官能基之意’係指具有乙烯基（甲基）丙烯醯基及烯丙基之乙烯性不飽和鍵之官能基之意。多官能性自由基聚合性預聚物，只要具有電離輻射線硬化性官能基A之預聚物即可，並無特別限制，較佳可舉例如’（甲基）丙烯酸丙烯酸酯系預聚物、胺基甲酸酯（甲基）丙烯酸酯系預聚物、聚酯（甲基）丙烯酸酯系預聚物、環氧（甲基）丙烯酸酯系預聚物、及聚醚（甲基）丙烯酸酯系預聚物等預聚物，其中，較佳爲（甲基）丙烯酸丙烯酸酯系預聚物。本發明中，可將該等預聚物單獨或組合複數使用。201221586 VI. Description of the Invention: [Technical Field] The present invention relates to an ink composition, and more particularly to an ink composition for forming a decorative sheet, which can be excellent for decorative molded articles. High hardness, ability to impart formability in a complicated shape, and adhesion resistance. [Prior Art] In the past, the decoration of a resin molded body having a complicated surface shape such as a three-dimensional curved surface was performed by injection molding. Decoration method. In the case of injection molding, the decorative sheet inserted into the mold is integrated with the molten injection resin injected into the cavity, and is applied to the surface of the resin molded body. The method of decoration. In this method, depending on the configuration of the decorative sheet integrated with the resin molded body, it is generally classified into a simultaneous injection molding method and an injection molding simultaneous transfer and decoration method. In the simultaneous injection-molding method of injection molding, the decorative sheet is adhered to the inner surface of the mold to be closed, and then the injection resin melted in the cavity is injected to integrate the decorative sheet with the injection resin. After the molded article is cooled and taken out from the mold, the base film is peeled off, whereby a decorative molded article to which the transfer layer is transferred is obtained. In addition to the fields of household electric products and automobile interiors that have been used in the past, in recent years, for example, with the expansion of the computer market, the notebook computer including the daily portable mobile personal computer - 5- 201221586 The use of the field, or the use of automotive exteriors and mobile phones, has also attracted attention. In such a field, it is required to impart surface properties such as excellent high hardness to the decorative molded article, and also to form a molded article having a more complicated shape. In order to satisfy such a demand, a transfer material having a protective layer using an active energy ray-curable resin composition containing a low molecular weight polymer and a polyfunctional isocyanate has been proposed (for example, Patent Document 1). However, it is difficult to form a protective layer using the resin composition to make it non-tacky, and it is necessary to perform baking at a high temperature of 150 ° C or heat treatment for a long period of time in order to make it non-sticky. Further, in the above protective layer, there is a problem that it is not possible to cope with more stringent requirements such as high hardness. A transfer material having a protective layer containing a polymer having a low molecular weight, a hardener, and gel cerium oxide particles is proposed for the purpose of obtaining surface properties such as high hardness (for example, Patent Document 2). However, the protective layer is less stringent than the pencil hardness, and there is a problem of adhesion (internal movement) when the decorative sheet is wound into a roll shape, and further, the shape is more complicated. In the molded article, there is a problem that the protective layer is whitened and the coating is broken. Surface properties such as high hardness and resistance to adhesion and formability The decorative sheet which can achieve such relative performance at a high level does not currently exist. Patent Document 1: Japanese Patent No. 3 2 3 3 5 9 5 Patent Document 2: Japanese Laid-Open Patent Publication No. 2009- 1 3 721 No. 197-2012 SUMMARY OF INVENTION [Problems to be Solved by the Invention] Accordingly, the present invention It is an object of the invention to provide an ink composition for forming a decorative sheet which imparts excellent hardness to a decorative molded article, and also imparts formability to a molded article having a more complicated shape, and can be only heat as needed. Drying forms the hard coat layer to be non-tacky. Further, another object of the present invention is to provide a method for producing a decorative molded article using the above ink composition. Further, another object of the present invention is to provide a decorative molded article obtained by the above production method. [Means for Solving the Problem] The ink composition of the present invention comprises the following: an ionizing radiation curable function having at least one selected from the group consisting of a vinyl group, a (meth) acryl fluorenyl group, and an allyl group; A polyfunctional radically polymerizable prepolymer having a weight average molecular weight of 50,000 or more in the group A; a reactive inorganic particle having an ionizing radiation curable functional group B on the surface; and a polyfunctional isocyanate compound. Further, the decorative sheet of another aspect of the present invention is provided on at least one side of the base film, at least sequentially provided with a decorative sheet of a release layer and a hard coat layer, wherein 'the hard coat layer is used Further, the method for producing a decorative molded article according to another aspect of the present invention is the method for producing a decorative molded article using the decorative sheet, which comprises 201221586 in an injection molding die. a step of arranging the decorative sheet; a step of exposing the molten resin to the cavity of the injection molding die, cooling and solidifying, and laminating the resin molded body and the decorative sheet; and forming the resin molded body a step of laminating and integrating the formed sheet of the decorative sheet by the injection molding die; a step of peeling off the base film of the decorative sheet from the molded body; and disposing the molded body on the formed body using ionizing radiation The hard coat layer forms a hard-hardened hard coat layer forming step. The present invention provides a decorative molded article obtained by the above-described production method. [Effects of the Invention] According to the present invention, it is possible to impart excellent hardness to the decorative molded article, and to impart moldability to a molded article having a more complicated shape, and it is possible to thermally dry only the hard coat layer as needed. The formation layer is formed into an ink composition which is non-tacky and which imparts excellent manufacturing efficiency to the decorative sheet. [Embodiment] <Ink Composition> The ink composition of the present invention contains, as an essential component, an ionizing radiation having at least one selected from the group consisting of a vinyl group, a (meth)acryl fluorenyl group, and an allyl group. a polyfunctional radically polymerizable prepolymer having a weight average molecular weight of 50,000 or more; a reactive inorganic particle having an ionizing radiation -8 - 201221586 ray curable functional group B on the surface; and a polyfunctional isocyanate compound . Hereinafter, each component constituting the ink composition of the present invention <a polyfunctional radical polymerizable prepolymer having an ionizing radiation curable functional group A> will be described. In the present invention, "ionizing radiation curability", It refers to an energy quantum that can crosslink and polymerize molecules in an electromagnetic wave or a charged particle line, that is, a polymer that is excited by ultraviolet light or electron beam to generate a polymerization reaction, thereby crosslinking and hardening. . In addition, the term "ionizing radiation-curable functional group" means a functional group capable of exhibiting ionizing radiation curability, and means an ethylenically unsaturated bond having a vinyl (meth) acryloyl group and an allyl group. The meaning of the functional group. The polyfunctional radically polymerizable prepolymer is not particularly limited as long as it has a prepolymer of ionizing radiation curable functional group A, and is preferably, for example, a '(meth)acrylic acrylate-based prepolymer. , urethane (meth) acrylate prepolymer, polyester (meth) acrylate prepolymer, epoxy (meth) acrylate prepolymer, and polyether (methyl) A prepolymer such as an acrylate prepolymer is preferably a (meth)acrylic acrylate prepolymer. In the present invention, the prepolymers may be used singly or in combination.

S 此處，（甲基）丙烯酸丙烯酸酯系預聚物，係（甲基 )丙烯酸烷基酯、與可與其共聚合之（甲基）丙烯酸環氧丙酯、（甲基）丙烯醯胺、（甲基）丙烯酸羥基烷基酯等 -9- 201221586 含有官能基之（甲基）丙烯酸系化合物烯酸、馬來酸 '富馬酸' 衣康酸等羧酸物。胺基甲酸酯（甲基）丙烯酸酯系預由將聚醚聚醇或聚酯聚醇之反應所得之物，以（甲基）丙烯酸酯化而得。聚酯（甲基）丙烯酸酯系預聚物，元羧酸與多元醇之縮合所得之於兩末端物之羥基，以（甲基）丙烯酸酯化，或加成環氧烷所得之預聚物之末端之羥基酸酯化而得。環氧（甲基）丙烯酸酯系預聚物，子量較低之雙酚型環氧樹脂或酚醛清漆乙院環，以（甲基）丙稀酸酯化而得。環氧（甲基）丙烯酸酯系預聚物以二元之羧基變性型之環氧（甲基）丙烯酸酯聚醚（甲基）丙烯酸酯系預聚物，之羥基以（甲基）丙烯酸酯化而得。上述之多官能性自由基聚合型預聚量，需要50000以上、較佳爲5 0000 > 53000〜115000。重量平均分子量若爲. 得油墨組成物之觸變性故容易塗佈，且。又，重量平均分子量，係以凝膠滲透定之値，係以於標準樣品使用聚苯乙烯 '或與（甲基）丙共聚合而成之預聚聚物，例如，可藉聚胺基甲酸酯預聚例如，可藉由將多具有羥基聚酯預聚者，將於多元羧酸，以（甲基）丙烯例如，可藉由將分型環氧樹脂之環氧又，亦可使用將該性羧酸酐局部變性系預聚物。可藉由將聚醚聚醇物之重量平均分子 / 145000 、更佳爲上述範圍內，則可可得良好之成形性層析（GPC )所測之條件所測定之値 10- 201221586 又，由可得優異之表面特性的觀點考量，上述之預聚物之爲100〜800、較佳爲150〜500、更佳爲150〜300。又，雙鍵當量，係電離輻射線硬化性官能基每lmol之分子量之意。 <反應性無機粒子> 本發明之油墨組成物，含有於表面具有電離顧射線硬化性官能基B之反應性無機粒子。電離輻射線硬化性官能基B，較佳可舉例如乙烯基、（甲基）丙烯醯基、及烯丙基之乙烯性不飽和鍵、或環氧基、矽烷醇基等，由高硬度性及提升耐刮痕性的觀點考量，以乙烯基、（甲基）丙烯醯基、及烯丙基較佳。無機粒子，較佳可舉例如二氧化矽粒子（凝膠二氧化矽、煙燻二氧化矽、沉降性二氧化矽等）、氧化鋁粒子、氧化銷粒子、氧化鈦粒子、氧化鋅粒子等金屬氧化物粒子等。由高硬度性的觀點考量，較佳爲氧化矽粒子及氧化鋁粒子，特佳爲二氧化砂粒子。無機粒子之形狀，可舉例如球、橢圓體、多面體、鱗片形等，而該等形狀以均勻、整粒爲佳。又，無機粒子之平均粒徑，可視油墨組成物所形成之層之厚度來加以適當選擇，而通常爲0.005〜0.5μιη、較佳爲〇.〇1〜Ο.ίμηι。又 ’所謂平均粒徑，係以動態光散射法測定溶液中之粒子，以累積分布表示粒徑分布時之50%粒徑（d50 :中位直徑） -11 - 201221586 ，可使用Microtrac粒度分析計（曰機裝股份有限公司製）測定。上述之無機粒子之中，由高硬度性的觀點考量，以異形無機粒子較佳。異形無機粒子’係平均連結數2〜4〇個之無機粒子連結凝集之無機粒子群所構成者，於本發明包含於無機粒子中。連結凝集，可爲規則、亦可爲不規則。形成無機粒子群之無機粒子，較佳可舉例如由二氧化矽（凝膠二氧化矽、煙燻二氧化矽、沉降性二氧化矽等）、氧化鋁、氧化锆、氧化鈦、氧化鋅等金屬氧化物所構成之無機粒子，由高硬度性的觀點考量，較佳爲二氧化矽或氧化鋁所構成之異形無機粒子。亦即，異形無機粒子，較佳爲，平均連結數2〜40個之二氧化矽粒子或氧化鋁粒子連結凝集之二氧化矽粒子群或氧化鋁粒子群所構成者，特佳爲，平均連結數2〜40個之二氧化矽粒子連結凝集之二氧化矽粒子群所構成之異形二氧化矽粒子。 ' 形成無機粒子群之無機粒子之形狀，較佳可舉例如球、橢圓體' 多面體、鱗片形等，該等形狀以均勻、整粒爲佳。形成無機粒子群之無機粒子的平均粒徑，較佳爲 0.005〜0.5μηι、更佳爲〇.〇1〜Ο.ίμηι。又，異形無機粒子之平均粒徑，可視油墨組成物所形成之層之厚度來加以適當選擇，而通常以0.005〜0.5 μ_ιη爲佳、更佳爲0.01〜 Ο.ΐμτη。又，此處之平均粒徑，係與上述之無機粒子之平均粒徑以相同方法測定。反應性無機粒子，較佳爲，上述之於二氧化矽粒子或 -12- 201221586 異形二氧化矽粒子之表面具有電離輻射線硬化性官能基B 之反應性二氧化矽粒子或反應性異形二氧化矽粒子，而以經矽烷耦合劑表面裝飾者爲佳》矽烷耦合劑，較佳可舉例如具有乙烯基、環氧基、（甲基）丙烯醯基、烯丙基等之周知之矽烷耦合劑，更具體而言，可舉例如γ-甲基丙烯氧基丙基甲基二甲氧矽烷、γ-甲基丙烯氧基丙基二甲基甲氧矽烷、γ-甲基丙烯氧基丙基三乙氧矽烷、γ-甲基丙烯氧基丙基二甲基乙氧矽烷、γ-丙烯氧基丙基三甲氧矽烷、γ-丙烯氧基丙基甲基二甲氧矽烷、γ-丙烯氧基丙基二甲基甲氧矽烷、γ-丙烯氧基丙基三乙氧砂院、γ -丙稀氧基丙基甲基二乙氧砂院、γ -丙稀氧基丙基二甲基乙氧矽烷、乙烯基三乙氧矽烷、γ-環氧丙氧基丙基三甲氧矽烷等。該等之中，較佳爲，γ-甲基丙烯氧基丙基三甲氧矽烷、γ-甲基丙烯氧基丙基甲基二甲氧矽烷、γ_ 甲基丙烯氧基丙基二甲基甲氧矽烷。將無機粒子以矽烷耦合劑表面裝飾之方法，並無特別限制，可採用周知之方法。可舉例如，將砂院稱合劑噴霧之乾式之方法、或使無機粒子分散於溶劑後加入矽烷親合劑使其反應之濕式之方法等。 <多官能異氰酸酯化合物> 本發明之油墨組成物，含有具2個以上異氰酸酯基之多官能異氰酸酯化合物。多官能異氰酸酯，可舉例如， 2,4-甲苯二異氰酸酯（TDI)、二甲苯二異氰酸醋（XDI) -13- 201221586 、萘二異氰酸酯、4,4-二苯基甲烷二異氰酸酯’或者，1，6-六亞甲基二異氰酸g 酮二異氰酸酯（IPDI)、亞甲基二異氰氫二異氰酸酯、加氫二苯基甲烷二異氰脂環式）二異氰酸酯等聚異氰酸酯。又異氰酸酯之加成體或聚合物，例如，甲成體、甲苯二異氰酸酯之三聚物（trim 之異氰酸酯化合物等》又，本發明中，多官能異氰酸酯化度性的觀點考量，特佳爲，具有選自乙烯醯基、烯丙基及環氧基所構成群中之線硬化性官能基C者。具體而言，較包 LR9000C商品名）」（BASF製）之具1 飽和鍵之官能基、與2個以上之異氰酸酸酯化合物。 <溶劑> 本發明之油墨組成物，除上述成分的目的下，亦可含有溶劑。溶劑，較佳二甲苯等烴類：甲醇、乙醇、異丙醇、甘醇、甲甘醇乙酸酯、甲基賽路蘇、乙路蘇等醇類；丙酮、甲乙酮、甲基異丁丙酮醇等酮類；甲酸甲酯、乙酸甲酯、酯、乙酸丁酯等酯類；硝基甲烷、N-甲氰酸酯等芳香族異指（HMDI )、異佛酸酯（MDI )、加酸酯等脂肪族（至，亦可爲該等各種苯二異氰酸酯之加 er )等、或封端化合物之中，由高硬烯基、（甲基）丙至少一種電離輻射兰爲，如「Laromer ί至少1個乙烯性不酯基之多官能異氰以外，於調整黏度可舉例如，甲苯、丁醇、異丁醇、甲基賽路蘇、丁基賽基酮、環己酮、二乙酸乙酯、乳酸乙基吡咯烷酮、Ν，Ν- -14- 201221586 二甲基甲醯胺等含氮化合物；丙二醇單甲醚、四氫呋喃、二噁烷、二氧戊環等醚類；二氯甲三氯乙烷、四氯乙烷等鹵素化烴；二甲亞颯、其他者；或該等之混合物。更佳之溶劑，可舉、甲基異丁基酮等。油墨組成物之溶劑之量，可視組成物之黏選擇，而符合該預聚物之固體成分、反應性無他後述之光聚合起始劑等之固體成分之含量， 10〜70質量％左右、較佳爲20〜50質量％之量。 <光聚合起始劑> 本發明之油墨組成物，亦可含有光聚合起合起始劑，可舉例如苯乙酮系、酮系、二苯基香系、縮酮系、蒽醌系、二硫化物系、硫雜蔥碳醯胺（thiuram)系、鑛化胺（fluoro amine 聚合起始劑。其中，較佳可舉例如苯乙酮系、基酮系。該等之光聚合起始劑，可分別單獨、使用。光聚合起始劑之含量，相對於該預聚物； 100質量份，較佳爲0.5〜10質量份左右、更佳: 份、再更佳爲3〜8質量份。 <其他成分> 本發明之油墨組成物，視所得之所欲物性二異丙醚、院、氯仿、碳酸丙烯等例如甲乙酮度加以適當機粒子及其通常爲成爲始劑。光聚酮系、安息酮系、甲硫 )系等之光酮系、二苯或組合複數之固體成分爲1〜8質量，亦可含有 -15- 201221586 各種添加劑。添加劑，可舉例如，紫外線吸收劑、紅外線吸收劑、光安定劑、聚合禁止劑、交聯劑、抗靜電劑、抗氧化劑、整平劑、觸變性賦予劑、耦合劑、可塑劑、消泡劑、充塡劑、熱自由基產生劑、鋁螯合劑等。又，本發明之油墨組成物，於不阻害其效果的範圍內，亦可含有丙烯酸系樹脂、纖維素系樹脂、胺基甲酸酯系樹脂、聚酯樹脂、環氧系樹脂等聚合物、或具有選自乙烯基、（甲基）丙烯醯基、烯丙基及環氧基所構成群中之至少一種電離輻射線硬化性官能基之單體，例如胺基甲酸酯 (甲基）丙烯酸酯、聚酯（甲基）丙烯酸酯、環氧（甲基 )丙烯酸酯、及聚醚（甲基）丙烯酸酯等多官能（甲基）丙烯酸酯等反應性單體。油墨組成物中之預聚物之固體成分之含量，相對於預聚物之固形分與反應性無機粒子之合計，以95質量％以下爲佳、更佳爲8 5質量％以下、特佳爲7 0質量％以下。又，預聚物之固體成分之含量之下限的範圍，以30質量％以上爲佳、更佳爲4 0質量％以上、特佳爲5 0質量％以上。聚合物之含量若爲上述範圍內，則於使用油墨組成物形成硬塗層形成層之際，塗佈油墨組成物於脫模層上所形成之硬塗層形成層，視需要可僅以熱乾燥作成無黏性。其之結果，於不進行藉電離輻射線之照射或高溫之烘烤等之半硬化處理之下，即使將薄片捲繞成滾筒狀亦不會黏連（內移）。又，由於不需要上述之半硬化處理，故於成形之際，即使成形前後之加飾薄片之面積比爲130%以上之深拉（deep -16- 201221586 drawing )，於最大延伸部亦無產生塗膜破裂或白化，能形成可良好地追尋模具形狀之硬塗層形成層。再者，藉由於成型轉印後使用電離輻射線將硬塗層形成層硬化，可得優異之高硬度性。又，油墨組成物中之多官能異氰酸酯化合物之固體成分之含量，相對於預聚物之固體成分100質量份，以1〜30 質量份爲佳、更佳爲1〜20質量份、再更佳爲3〜15質量份。多官能異氰酸酯化合物之固體成分之含量若爲上述範圍內，則可於維持優異之高硬度性與成形性之下，得到成形時之耐熱性。 <加飾薄片> 本發明之加飾薄片，係於基材薄膜之單面至少依序具備脫模層與硬塗層形成層者，硬塗層形成層係使用上述之油墨組成物所形成者。以下，參照圖1及圖2說明本發明之加飾薄片。圖1，係本發明之加飾薄片之一較佳樣態之截面模式圖。圖2，係本發明之加飾成形品之一較佳樣態之截面模式圖。本發明之加飾薄片1 0，如圖1所示，係於聚酯薄膜所構成之基材薄膜11之一表面，依序層合脫模層12、硬塗層形成層13、固定層（anchor layer) 14、圖案層15及接著層16，而於基材薄膜11之另一面（設置脫模層12之相反側之面）層合有抗靜電層19者。又，本發明之加飾成形品20，如圖2所示，係於樹脂 -17- 201221586 成形體21之表面，依序層合有接著層16、圖案層層I4及硬塗層形成層13硬化所成之硬塗層22者。明構成加飾薄片及加飾成形品之各構件。 <基材薄膜> 基材薄膜，可利用聚乙烯、聚丙烯等聚嫌烴聚氯乙烯、聚偏二氯乙烯、聚乙烯醇、乙稀·乙共聚物、乙烯•乙烯醇共聚物等乙烯系樹脂；聚酸乙二酯、聚對苯二甲酸丁二酯等聚酯系樹脂： )丙烯酸甲酯、聚（甲基）丙烯酸乙酯等丙稀酸聚苯乙烯等苯乙烯系樹脂、丙烯腈•丁二烯·苯物、三乙酸纖維素、賽璐玢 '聚碳酸酯、聚胺基等彈性體系樹脂所得者。該等之中，由成形性及好的觀點考量，較佳爲聚酯樹脂、特佳爲聚對苯二酯（以下稱爲「PET」）。基材薄膜之厚度，由成形性及形狀追尋性、的觀點考量’以25〜150μιη之範圍爲佳、以25〜圍爲更佳。 <脫模層12> 脫模層12’係用以使依序層合硬塗層形成層層14、圖案層15及接著層16所成之轉印層17容易膜11剝離所設之層。藉由具備脫模層12，可將轉貫、且谷易地由本發明之加飾薄片轉印至被轉印 15 '固定以下，說系樹脂；酸乙烯酯對苯二甲聚（甲基系樹脂；乙烯共聚甲酸酯系剝離性良二甲酸乙操作容易 7 5 μηι之範 1 3、固定由基材薄印層1 7確體，並可 -18- 201221586 將基材薄膜11、脫模層12、及視需要所設置之抗靜電層19 所構成之剝離層1 8確實地剝離。脫模層1 2，較佳可使用三聚氰胺樹脂系脫模劑、聚矽氧樹脂系脫模劑、氟樹脂系脫模劑、纖維素樹脂系脫模劑、尿素樹脂系脫模劑、聚烯烴樹脂系脫模劑、石蠟系脫模劑、丙烯酸樹脂系脫模劑及該等之複合型脫模劑等脫模劑。該等之中，由可使脫模層與硬塗層形成層之剝離強度爲既定範圍內、而確實地剝離剝離層1 8的觀點，較佳爲，三聚氰胺樹脂系脫模劑及丙烯酸樹脂系脫模劑、或丙嫌酸-三聚氰胺系等之將該等複合者。當使用三聚氰胺樹脂系脫模劑時，爲了促進脫模劑之硬化，以使用酸觸媒爲佳。上述酸觸媒並無特別限定，較佳可舉例如對甲苯磺酸、十二苯磺酸、二壬基萘磺酸、二壬基萘二磺酸等。酸觸媒之使用量，相對於三聚氰胺樹脂系脫模劑所含之三聚氰胺樹脂之固體成分，以0.05〜3 %左右爲佳、更佳爲〇 · 〇 5〜1 %。又，爲了促進脫模劑之硬化，較佳爲，以130〜17 0°C進行加熱處理30秒〜2分鐘左右。脫模層1 2之形成，可將於上述脫模劑添加必須之添加劑所成者溶解或分散於適當之溶劑所調製成之油墨，於基材薄膜1 1以周知之手段進行塗佈、乾燥。脫模層1 2之厚度，以0.1〜5μιη左右爲佳。 <硬塗層形成層> 硬塗層形成層，係使用上述之油墨組成物所形成之層 -19- 201221586 ，藉由硬化而成爲加飾成形品20中之硬塗層22。硬塗層22 ，係加飾成形品之最外層，係用以由磨耗或藥品等保護成形品或圖案層之層。因此，硬塗層形成層13，必須爲藉由硬化而具有優異之高硬度性與耐刮痕性、且具有耐藥品性及耐污染性等表面物性優異之性能之層。硬塗層形成層’可藉由將上述之油墨組成物，以凹版塗佈法、輥塗法、刮刀式塗佈、模具塗佈法等塗佈法、凹版印刷法、網版印刷法等進行塗佈，來形成。硬塗層形成層之厚度，較佳爲0.5〜30μπι之範圍、更佳爲3〜15μιη之範圍。厚度若爲上述範圍，則當然優異之高硬度性與耐刮痕性’並可得耐藥品性及耐污染性等表面物性，同時可得優異之成形性及形狀追尋性。又，於材料費的觀點上亦有利。 <固定層> 固定層14’係用體提升硬塗層形成層與接著層16、或具圖案層15時之與圖案層15之密合性，視需要所設置之層°固定層14，可由2液性硬化胺基甲酸酯樹脂、熱硬化性胺基甲酸酯樹脂、三聚氰胺系樹脂、纖維素酯系樹脂、含氯之橡膠樹脂、含氯之乙烯系樹脂、丙烯酸系樹脂、環氧系樹脂、乙烯系共聚合樹脂等所形成。例如，可藉由將該等之樹脂，於上述之硬塗層形成層13之上，以凹版塗佈法、輕塗法、刮刀式塗佈等塗佈法、凹版印刷法、網版印刷法等塗佈來形成。固定層I4之厚度，通常爲〇1〜5μιη左 -20- 201221586 右、較佳爲1〜5μπι左右。 <圖案層> 圖案層1 5，係用以賦予加飾成形品所欲之設計性之層，視需要所設置之層。圖案層1 5之圖案爲任意，可舉例如木紋、石紋、大理石紋、灰紋、幾何學花紋、文字等所構成之圖案。又，圖案層15，可將表現上述圖案之圖案層及整面內層單獨或組合來設置，整面內層，通常係作爲掩蔽層、著色層、著色掩蔽層等使用。圖案層15，通常係於如上述所形成之硬塗層形成層13 上、或固定層14之上，將含有以聚乙烯系樹脂、聚酯系樹脂、丙烯酸系樹脂、聚乙烯縮醛系樹脂、纖維素系樹脂等樹脂作爲黏結劑、以適當顏色之顏料或染料作爲著色劑之印刷油墨，藉由印刷來形成。印刷方法，可舉例如凹版印刷、平版印刷、絲網印刷、來自轉印薄片之轉印印刷、昇華轉印印刷、噴墨印刷等周知之印刷法。圖案層1 5之厚度，由設計性之觀點考量以5〜4〇μπι爲佳、5〜30μπι爲更佳 <接著層> 接著層1 6，係用以將轉印層1 7接著性佳地轉印至樹脂成形體所形成之層》該接著層16’係適當使用適合樹脂成形體之原料之感熱性或感壓性的樹脂。例如，當樹脂成形體之材質爲丙烯酸系樹脂時，較佳爲使用丙烯酸系樹脂。 -21 - 201221586 又’當樹脂成形體之材質爲聚苯醚•聚苯乙燃系樹脂、聚碳酸酯系樹脂、苯乙烯系樹脂時，較佳爲使用與該等樹脂具親合性之丙燦酸系樹脂、聚苯乙稀系樹脂、聚醯胺系樹脂等。再者’當樹脂成形體之材質爲聚丙烯樹脂時，較佳爲使用氯化聚烯烴樹脂、氯化乙烯-乙酸乙烯酯共聚物樹脂、環化橡膠、苯並呋喃-茚樹脂。接著層16之形成方法，可舉例如凹版塗佈法、輥塗法等塗佈法、凹版印刷法、網版印刷法等印刷法。又，當圖案層I5對樹脂成形體具有充分之接著性時，亦可不設置接著層16。接著層16之厚度，通常以〇」〜5 μιη左右爲佳。 <抗靜電層> 本發明之加飾薄片，亦可具備抗靜電層。抗靜電層19 ’係用以防止異物附著於加飾薄片所設置者，係設置於基材薄膜11之設置脫模層之面的相反面。抗靜電層所使用之抗靜電劑，較佳可舉例如羧酸系、磺酸系、磷酸系等陰離子界面活性劑；四級銨系等陽離子界面活性劑；烷基甜菜鹼系、烷基咪唑啉系、烷基丙胺酸系等兩性界面活性劑；環氧烷聚合物、環氧烷共聚物、脂肪族醇-環氧烷加成物等非離子系界面活性劑；碳、或金、鈾、銀、銅、鋁、鎳、鈦、鉬等各種金屬粉末等無機導電性物質：聚乙炔、聚吡咯、聚對苯撐、聚苯胺、聚噻吩、聚對苯撐伸乙烯、聚乙烯咔唑、或胺基羧酸、二羧酸及聚乙二醇所構成之聚醚酯醯胺樹脂等導電性高分子等。 -22- 201221586 抗靜電層’係藉由將上述之抗靜電劑及有機溶劑等所構成之塗料’以凹版印塗佈法、輥塗法等塗佈法、或凹版印刷法、網版印刷法等印刷法塗佈來形成。如此所形成之抗靜電層之厚度，通常以0.1〜5μιη爲佳。抗靜電層之厚度若爲上述範圍內，可有效率地得到優異之抗靜電性能。本發明之加飾薄片，硬塗層形成層可視需要僅藉熱乾燥作成無黏性，故耐黏連性優異，同時亦可賦予耐熱性，故製造效率優異。又，由於不需要進行用以作成無黏性之電離輻射線之照射或高溫之烘烤等之半硬化處理，故成爲具有優異之成形性及形狀追尋性者。再者，藉由於成型轉印後使用電離輻射線使硬塗層形成層硬化，可得優異之高硬度性及耐刮痕性。因此，可使用於家庭用電化製品、汽車內裝品等領域、或個人電腦之領域、特別是個人電腦之框體等廣泛之領域中。 <加飾成形品之製造方法> 本發明之加飾成型品之製造方法，含有：於射出成形模具內配置該加飾薄片之步驟（第1步驟）：將熔融樹脂射出至該射出成形模具之模穴內，進行冷卻、固化，而使樹脂成形體與加飾薄片層合一體化之射出步驟（第2步驟 ):將該樹脂成形體與該加飾薄片層合一體化後之成形體，由該射出成形模具取出之步驟（第3步驟）：將加飾薄片之基材薄膜由該成形體剝離之步驟（第4步驟）：及使用電離輻射線使設置於該成形體上之硬塗層形成層硬化之 -23- 201221586 硬塗層形成步驟（第5步驟）。以下，說明各步驟。 <第1步驟> 第1步驟，係將上述加飾薄片配置於成形模具內夾持之步驟。具體而言，係將加飾薄片，於可動模具與固定模具所構成之成形用模具，以使內使轉印層1 7爲內側、亦即使基材薄膜11爲固定模具側的方式，送入加飾薄片。此時，可一片一片送入數片之加飾薄片，亦可間歇地送入長條之加飾薄片的必要部分。於將加飾薄片配置於成形模具內之際，可進行下述來配置：（i ) 僅加熱模具，以對該模具真空抽吸以使其密合的方式配置；或（ii) 使用熱盤由轉印層17側加熱使其軟化，使加飾薄片以沿著模具內之形狀的方式預備成型，使其密合於模具內面合模。（ii )時之加熱溫度，較佳爲，基材薄膜11之玻璃轉移溫度附近以上、且未滿熔融溫度（或熔點）之範圍，通常係以玻璃轉移溫度附近進行^ 又，上述所謂玻璃轉移溫度附近，係玻璃轉移溫度± 5。(：左右之範圍，一般係70〜13 0又，於（ii)的情況下，爲了使加飾薄片更密合於成形模具表面，於以熱盤加熱加飾薄片使其軟化時，亦可進行真空抽吸。 <第2步驟> 第2步驟，係將熔融樹脂射出至模穴內，進行冷卻、固化，而使樹脂成形體與加飾薄片層合一體化之射出步驟 24- 201221586 。當射出樹脂爲熱可塑性樹脂時，可藉加熱熔融作成流動狀態，而當射出樹脂爲熱硬化性樹脂時，可適當加熱未硬化之液狀組成物而以流動狀態射出，並進行冷卻使其固化。藉此，加飾薄片與樹脂成形體一體化而貼附，成爲加飾成形品。射出樹脂之加熱溫度，雖係視射出樹脂，而一般爲180〜280 °C左右。加飾成形品所使用之射出樹脂，只要爲能射出成形之熱可塑性樹脂、或熱硬化性樹脂（含2液熱硬化性樹脂）即可，可使用各種樹脂。如此之熱可塑性樹脂材料，可舉例如聚苯乙烯系樹脂、聚烯烴系樹脂、AB S樹脂（含耐熱 ABS樹脂）、AS樹脂、AN樹脂、聚苯醚系樹脂、聚碳酸酯系樹脂、聚縮醛系樹脂、丙烯酸系樹脂、聚對苯二甲酸乙二酯系樹脂、聚對苯二甲酸丁二酯系樹脂、聚颯系樹脂、聚苯硫系樹脂等。又，熱硬化性樹脂，可舉例如2液反應硬化型之聚胺基甲酸酯系樹脂、環氧系樹脂等。該等樹脂可單獨使用、亦可混合二種以上使用。 <第3步驟及第4步驟> 第3步驟，係將加飾薄片與樹脂成形體一體化後之成形體由模具取出之步驟’第4步驟，係由成形體將加飾薄片之基材薄膜剝離之步驟。基材薄膜11，由於具有脫模層 12，故於該脫模層12與硬塗層形成層13之境界面，可容易地將含基材薄膜11與脫模層12、及視需要所設置之抗靜電層1 9之剝離層1 8由加飾成形品2 0剝離。如此’可得於樹脂 -25- 201221586 成形體21之表面依序層合有接著層16、圖案層15、固定層 14及硬塗層形成層13之成形品。 <第5步驟> 第5步驟，係使用電離輻射線使上述第4步驟所得之成形品中之硬塗層形成層1 3硬化，而形成硬塗層之步驟。第 5步驟之硬化，可於氧濃度2%以下之環境氣氛下照射電離輻射線來進行。如此藉由進行硬化，可得更優異之高硬度性及耐刮痕性。可於氧濃度2%以下之環境氣氛，例如，可藉由使用氮、氬、氫等、較佳爲使用氮，或進行真空抽吸使氧濃度爲 2 %以下左右等之方法來得到。硬塗層形成層13之硬化’可照射電子線及紫外線等電離輻射線來進行。當使用電子線作爲電離輻射線時，關於其之加速電壓，可視所使用之預聚物或單體的種類、或硬塗層形成層13之厚度來加以適當選定，而通常加速電壓以 70〜300kV左右爲佳。照射線量，通常係以5〜3〇〇kGy( 0_5〜30Mrad)、較佳爲10〜50kGy(l〜5Mrad)之範圍選疋。又’電子線源’並無特別限制，例如，可使用柯克勞夫·沃耳吞型、凡德格拉夫型、共振變壓器型、絕緣核變壓器型、或直線型、闻頻局壓型、高頻型等各種電子線加速器。當使用紫外線作爲電離輕射線時，係照射含波長19〇〜3 80nm之紫外線者，其之照射線量爲5〇〇〜i5〇〇mj左右 -26- 201221586 。紫外線源並無特別限制，例如可使用高壓水銀燈、低壓水銀燈、金屬鹵素燈、碳弧燈等。如此所得之本發明之加飾成形品，係具有優異之高硬度性、耐藥品性或耐污染性等表面物性亦優異者。又’藉由使用可得能因應形狀更複雜之成形品之成形性的本發明之加飾薄片，可得成品外觀更優異之加飾成形品。本發明之加飾成形品，活用該等優異之特性，可使用於家庭用電化製品、汽車內裝品等領域、或個人電腦之領域、特別是個人電腦之框體等廣泛之領域中。實施例接著，藉由實施例更詳細地說明本發明，但本發明並不因該等實施例而產生任何限定。又，實施例之評價方法，係如以下方式進行。 1.試樣樣品之製作於基材薄膜（「F99 (商品編號）」，厚度：50μπι，東雷股份有限公司製）上，以塗佈量2g/m2凹版印刷三聚氰胺樹脂系脫模劑（添加三聚氰胺樹脂之固體含量比0.5% 之酸觸媒（對甲苯磺酸）），於150 °C之烘箱內加熱處理 6 0秒鐘而形成脫模層之上，以棒塗器塗佈各實施例及比較例所使用之油墨組成物，以1 〇〇 °C之烘箱內乾燥6 0秒鐘，製得試驗樣品。此處，油墨組成物之塗佈量係使乾燥後之油墨塗佈層之厚度成爲6g/m2之量。 -27- 201221586 2.耐黏連性（薄片捲繞適性）之評價於試驗樣品之油墨塗佈層面，疊合試驗樣品之製作所使用之PET薄膜，使用油墨黏連試驗機（「DG-BT (型號 )」，大和印刷股份有限公司製），於施加lkg/cm2之荷重之下，放置於40 °C之烘箱內12小時。之後，取出試驗樣品’將疊合之PET薄膜剝離。以下述基準評價剝離之PET 薄膜之油墨塗佈層之沾附（內移）。 A :完全無內移 B:雖有些許之內移，但於實用上無問題 C :內移顯著 3 .高硬度性之評價將試驗樣品以各實施例及比較例中之硬化方法硬化後 ’根據JIS K5600-5-4，使用鉛筆刮搔塗膜硬度試驗機（r D-NP (型號）’東洋精機製作所股份公司製）、及鉛筆刮搔値試驗用鉛筆（三菱鉛筆股份有限公司製）測定鉛筆硬度。以各硬度之鉛筆對油墨塗佈層進行刮搔試驗5次，將未產生痕跡3次以上之鉛筆硬度，作爲試驗樣品之鉛筆硬度。合成例1 (預聚物1之合成）於附冷卻器、滴入漏斗及溫度計之2L四口燒瓶，裝墳甲基異丁基酮（MIBK) 120g、甲乙酮（MEK) 210g，於 -28- 201221586 Μ四口燒瓶，以2小時由滴入漏斗滴下甲基丙烯酸環氧丙醋（GMA) 80g、曱基丙烯酸甲酯（μμα) 2〇§及偶氮系之起始劑（偶氮雙異丁腈，AIBN_1} 〇_7以所構成之混合液，於100〜110°C之溫度下反應4小時後，再加入偶氮系之起始劑（偶氮雙異丁腈，AIBN_2 ) O jg，保溫3小時後，冷卻至室溫。於其加入丙烯酸（AA) 40.6g、三苯膦2g、及甲氧苯酚〇.5g所構成之混合液，進行加成反應。以氫氧化鉀溶液之中和滴定’確認反應性生物之酸價的消失，使反應結束》所得之反應生成物（預聚物1)之重量平均分子量爲 8 0000，雙鍵當量爲2 50g/mol (計算値），固體成分爲30% 。又，重量平均分子量，係以凝膠滲透層析（GPC )所測定之値，係於標準樣品使用聚苯乙烯之條件所測定之値。合成例2 (預聚物2之合成）於合成例1 (預聚物1之合成）中’除將所使用之劑量改成表1所示之量以外，於合成例1同樣地’合成預聚物2 。將所得之預聚物2之重量平均分子量、雙鍵當量及樹脂固體成分示於表1。又，表中之配合組成欄之數値’皆爲公克。 -29- 201221586 [表l] 預聚物1 預聚物2 _ 配昼成 MI BK 120 120 MEK 210 210 GMA 80 80 — MMA 20 20 A IBN-1 0.75 1 A IBN-2 0.6 1 AA 40.6 40.6 三苯膦 2 2 甲氣苯酚 0.5 0.5 重量平均分子量 80000 25000 雙鍵當量(g/mol) 250 250 固體成分（質量％) 30 30 實施例1 (1 )加飾薄片之製造於基材薄膜（「F99 (商品編號）」，厚度：50μπι ’ 東雷股份有限公司製）上，以塗佈量2 g/m2凹版印刷以三聚氰胺系樹脂爲主成分之塗佈液（「美蘭265」（商品編號），日立化成工業股份有限公司製，異丁醇變性三聚氰胺樹脂）以形成脫模層，以塗佈量6 g/m2凹版印刷下述所示組成之油墨組成物而形成硬塗層形成層。油墨組成物：預聚物1 : 20.0質量份（固體成分6質量份）、丙烯酸丙烯酸酯系預聚物（合成例1所合成之預聚物1、分子量： 80000、雙鍵當量：250g/mol) 反應性異型二氧化矽粒子：10質量份（固體成分4質量份）、（「ELCOMV- 8 8 03 (商品編號）」，日揮觸媒化 -30- 201221586 成股份有限公司製，反應性異型二氧化矽粒子，平均連結數：規則地2〜10個，異形無機粒子之平均粒徑·· 2 5nm) 反應性多官能異氰酸酯：1質量份（固體成分1質量份 )、（「Laromer LR9000 (商品編號）」，BASF製）光聚合起始劑：0.4質量份（「IRGACURE184(商品編號）」，汽巴•曰本股份有限公司製，1-羥基環己基苯酮）溶劑：6.7質量份，甲乙酮與甲基異丁基酮之混合溶劑（配合比7 0 : 3 0 ) 接著，以塗佈量4g/m2凹版印刷以丙烯酸系樹脂爲主成分之塗料形成固定層，接著，將丙烯酸系印刷油墨以塗佈量8g/m2，凹版印刷木紋模樣形成圖案層，以厚度4μπι塗佈丙烯酸系塗佈液形成接著層。再者，於基材薄膜之設置脫模層之面的相反面，以塗佈量1 g/m2凹版印刷以陽離子系界面活性劑爲主成分之塗佈液（陽離子系界面活性劑.：四級銨鹽），形成抗靜電層，製得實施例1之加飾薄片。又’使用實施例1所使用之油墨組成物’根據上述1 .試驗樣品之製作製作試驗樣品，進行耐黏連性（薄片捲繞適性 )之評價、高硬度性之評價。評價結果係如下述表2所示 (2 )加飾成形品之製造將上述所得之加飾薄片’抽吸至加熱爲70 °C之模具使其密合於模具內面。模具’係使用8 0mm邊長之大小 -31 - 201221586 高度1 0mm、角部爲3維盤狀之深拉度高的形狀。另一方面，使用ABS樹脂（「Clastic MTH-2 (商品編號）」’日本A&L股份有限公司製）作爲射出樹脂，將其以2 3 0 °C作成溶融狀態後，射出至模穴內。冷卻、從模具取出後’將基材薄膜剝離’製得於樹脂成形品之表面依序具有接著層、印刷層、固定層及硬塗層形成層的成形品。再者’於大氣環境氣氛下，使用可變輸出型UV燈系統（「DRS-10/12QN (商品編號）j ’Fusion UV系統·日本股份有限公司製），以照射線量：1 OOOmJ，對該成形品照射紫外線，使硬塗層形成層硬化，作成硬塗層形成層，製得實施例1之樹脂成形品。 4.外觀（成形性）之評價對所得之樹脂成形品，以下述之基準評價其之外觀（成形性）。 A:於硬塗層（及其之形成層）完全無確認到塗裝破裂或白化，可良好地追尋模具之形狀 B:於硬塗層（及其之形成層）確認到些微之塗裝破裂或輕微的白化 C:於硬塗層（及其之形成層）雖確認到部分之塗裝破裂或輕微的白化，但於實用上無問題 D:於硬塗層（及其之形成層）確認到顯著之塗裝破裂或白化評價結果係如下述表2所示。 -32- 201221586 5 ·外觀（耐熱性）之評價又，對所得之樹脂成形品，以卞述之基準評價澆口部 (樹脂射出部）周圍的外觀（耐熱性）。 A :於硬塗層（及其之形成層）·完全無確認到流動所至之變形或白化 B :於硬塗層（及其之形成層）確認到些微之流動所至之變形或輕微的白化 C :於硬塗層（及其之形成層）雖確認到部分之流動所至之變形或輕微的白化，但於實用上無問題 D :於硬塗層（及其之形成層）確認到顯著之流動所至之變形或白化評價結果係如下述表2所示。實施例2、3及比較例1〜7 實施例1中，除將油墨組成物作成表2所示以外，與實施例1同樣地，製得實施例2、3及比較例1〜7之加飾薄片及加飾成形品。對所使用油墨組成物，進行上述之耐黏連性（薄片捲繞適性）之評價、高硬度性之評價，對所得之加飾成形品，進行上述之外觀評價。評價結果係如下述表 2所示。 -33- 201221586 [表2] Ϊ3 o a ~W" S/0 0 OS 001 r.s 寸Ό o <〇 s ϋ ο inS Here, the (meth)acrylic acrylate-based prepolymer is an alkyl (meth)acrylate, a glycidyl (meth)acrylate copolymerizable therewith, (meth)acrylamide, Hydroxyalkyl (meth)acrylate, etc.-9- 201221586 A carboxylic acid such as a functional group-containing (meth)acrylic compound enoic acid or maleic acid 'fumaric acid' itaconic acid. The urethane (meth) acrylate is obtained by preliminarily reacting a polyether polyol or a polyester polyol with (meth) acrylate. a polyester (meth) acrylate prepolymer, a condensation of a carboxylic acid with a polyhydric alcohol, a hydroxyl group obtained at both ends, a (meth) acrylate, or a prepolymer obtained by adding an alkylene oxide The hydroxyl group at the end is esterified. An epoxy (meth) acrylate prepolymer, a bisphenol type epoxy resin or a novolac lacquer having a low amount, which is obtained by (meth) acrylate. The epoxy (meth) acrylate type prepolymer is a binary carboxyl group-denatured epoxy (meth) acrylate polyether (meth) acrylate type prepolymer, and the hydroxyl group is (meth) acrylate. Get it. The above-mentioned polyfunctional radical polymerization type prepolymerization amount is required to be 50,000 or more, preferably 5 0000 > 53000 to 115,000. If the weight average molecular weight is thixotropy of the ink composition, it is easy to apply, and. Further, the weight average molecular weight is determined by gel permeation, and is a prepolymer having a polystyrene' or a copolymerized with (meth)propene as a standard sample, for example, a polyaminocarboxylic acid. For example, the prepolymerization of the ester can be carried out by prepolymerizing a plurality of hydroxy polyesters, and the (meth) propylene can be used, for example, by epoxy bonding of the epoxy resin. The carboxylic anhydride is a localized denatured prepolymer. By measuring the weight average molecular weight of the polyether polyol / 145000, more preferably within the above range, it is possible to obtain a good condition determined by the formability chromatography (GPC). 10 - 201221586 From the viewpoint of obtaining excellent surface characteristics, the above prepolymer is 100 to 800, preferably 150 to 500, more preferably 150 to 300. Further, the double bond equivalent is a molecular weight per 1 mol of the ionizing radiation curable functional group. <Reactive inorganic particles> The ink composition of the present invention contains reactive inorganic particles having an ionizing radiation-hardening functional group B on the surface. The ionizing radiation curable functional group B is preferably, for example, a vinyl group, a (meth)acryl fluorenyl group, an allyl ethylenically unsaturated bond, or an epoxy group or a stanol group. From the viewpoint of improving the scratch resistance, a vinyl group, a (meth) acrylonitrile group, and an allyl group are preferable. The inorganic particles are preferably metals such as cerium oxide particles (gel cerium oxide, smoked cerium oxide, sedimentary cerium oxide, etc.), alumina particles, oxidized pin particles, titanium oxide particles, and zinc oxide particles. Oxide particles and the like. From the viewpoint of high hardness, cerium oxide particles and alumina particles are preferred, and sand dioxide particles are particularly preferred. The shape of the inorganic particles may, for example, be a sphere, an ellipsoid, a polyhedron or a scale, and the shape is preferably uniform or sized. Further, the average particle diameter of the inorganic particles can be appropriately selected depending on the thickness of the layer formed of the ink composition, and is usually 0.005 to 0.5 μm, preferably 〇.〇1 to Ο.ίμηι. In addition, the so-called average particle size is measured by dynamic light scattering method, and the particle size distribution is 50% particle diameter (d50: median diameter) -11 - 201221586. Microtrac particle size analyzer can be used. (Made in Machine Tool Co., Ltd.) Measurement. Among the above inorganic particles, from the viewpoint of high hardness, it is preferred that the inorganic particles are irregular. The heterogeneous inorganic particles are composed of an inorganic particle group in which the number of the inorganic particles is 2 to 4, and the inorganic particles are aggregated and aggregated, and are contained in the inorganic particles in the present invention. Link agglutination, which can be a rule or an irregularity. The inorganic particles forming the inorganic particle group are preferably, for example, cerium oxide (gel cerium oxide, smoked cerium oxide, sedimentary cerium oxide, etc.), alumina, zirconia, titanium oxide, zinc oxide, or the like. The inorganic particles composed of a metal oxide are preferably a non-shaped inorganic particle composed of ceria or alumina, from the viewpoint of high hardness. In other words, the heterogeneous inorganic particles are preferably composed of cerium oxide particles having an average number of connected atoms of 2 to 40 or alumina particles in which agglomerated cerium oxide particles or a group of alumina particles are formed, particularly preferably, an average link. The number of 2 to 40 cerium oxide particles is connected to the shaped cerium oxide particles composed of the aggregated cerium oxide particles. The shape of the inorganic particles forming the inorganic particle group is preferably, for example, a sphere, an ellipsoidal polyhedron or a scaly shape, and the shape is preferably uniform or sized. The average particle diameter of the inorganic particles forming the inorganic particle group is preferably 0.005 to 0.5 μm, more preferably 〇.〇1 to Ο.ίμηι. Further, the average particle diameter of the shaped inorganic particles can be appropriately selected depending on the thickness of the layer formed of the ink composition, and is usually preferably 0.005 to 0.5 μm, more preferably 0.01 to Ο.ΐμτη. Further, the average particle diameter herein is measured in the same manner as the average particle diameter of the above inorganic particles. The reactive inorganic particles are preferably reactive cerium oxide particles or reactive hetero-shaped oxidized particles having ionizing radiation-curable functional groups B on the surface of the cerium oxide particles or the -12-201221586 shaped cerium oxide particles. The ruthenium particles are preferably a decane coupling agent, preferably a decane coupling agent having a vinyl group, an epoxy group, a (meth) acryl fluorenyl group, an allyl group or the like. More specifically, for example, γ-methacryloxypropylmethyldimethoxydecane, γ-methylpropoxypropyldimethylmethoxysilane, γ-methylpropoxypropyl group Triethoxy decane, γ-methyl propyloxypropyl dimethyl ethoxy decane, γ-acryloxypropyl trimethoxy decane, γ-acryloxypropyl methyl dimethoxy decane, γ-propylene oxygen Propyl dimethyl methoxy decane, γ-propylene oxypropyl triethoxy sand, γ-propyloxypropyl methyl diethoxylate, γ-propyloxypropyl dimethyl Ethoxy decane, vinyl triethoxy decane, γ-glycidoxypropyl trimethoxy decane, and the like. Among these, γ-methacryloxypropyltrimethoxydecane, γ-methacryloxypropylmethyldimethoxydecane, and γ-methylpropoxypropyldimethylmethyl are preferred. Oxane. The method of decorating the inorganic particles with the surface of the decane coupling agent is not particularly limited, and a known method can be employed. For example, a dry method of spraying a sand compound as a mixture or a wet method of dispersing inorganic particles in a solvent and then adding a decane affinity agent to cause a reaction may be mentioned. <Polyfunctional isocyanate compound> The ink composition of the present invention contains a polyfunctional isocyanate compound having two or more isocyanate groups. The polyfunctional isocyanate may, for example, be 2,4-toluene diisocyanate (TDI), xylene diisocyanate (XDI)-13-201221586, naphthalene diisocyanate, 4,4-diphenylmethane diisocyanate' or , polyisocyanate such as 1,6-hexamethylene diisocyanate g ketone diisocyanate (IPDI), methylene diisocyanate diisocyanate, hydrogenated diphenylmethane diisocyanate ring diisocyanate. Further, an adduct or a polymer of an isocyanate, for example, a trimer or a toluene diisocyanate trimer (trim isocyanate compound or the like). In the present invention, the viewpoint of polyfunctional isocyanate degree is particularly preferable. A functional group having a linearly-curable functional group C selected from the group consisting of an ethylene fluorenyl group, an allyl group, and an epoxy group. Specifically, it has a functional group having a saturated bond of LR9000C (product name: BASF). And two or more isocyanate compounds. <Solvent> The ink composition of the present invention may contain a solvent in addition to the above components. Solvents, preferably hydrocarbons such as xylene: methanol, ethanol, isopropanol, glycol, methyl glycol acetate, methyl racerus, et al. alcohol; acetone, methyl ethyl ketone, methyl isobutyl acetonate Ketones such as alcohol; esters such as methyl formate, methyl acetate, ester, butyl acetate; aromatic hetero fingers (HMDI) such as nitromethane and N-cyanate, and isophora (MDI), plus An aliphatic group such as an acid ester (which may be added to er of these various benzene diisocyanates) or the like, or a highly hard alkenyl group or a (meth) propyl group of at least one ionizing radiation blue, such as " Laromer ί, in addition to at least one ethylenic non-ester group polyfunctional isocyanide, for adjusting the viscosity, for example, toluene, butanol, isobutanol, methyl stilbene, butyl ketone, cyclohexanone, two Ethyl acetate, lactic acid ethyl pyrrolidone, hydrazine, hydrazine - -14-201221586 dimethylformamide and other nitrogen-containing compounds; propylene glycol monomethyl ether, tetrahydrofuran, dioxane, dioxolane and other ethers; a halogenated hydrocarbon such as trichloroethane or tetrachloroethane; dimethyl hydrazine, others; or a mixture thereof. A more preferable solvent, such as methyl isobutyl ketone, etc. The amount of the solvent of the ink composition can be selected according to the viscosity of the composition, and conforms to the solid content of the prepolymer, and the reactivity is not described later. The content of the solid component such as the agent is about 10 to 70% by mass, preferably 20 to 50% by mass. <Photopolymerization initiator> The ink composition of the present invention may further contain a photopolymerization initiator, and examples thereof include an acetophenone system, a ketone system, a diphenyl scent system, a ketal system, and a hydrazine. A disulfide-based system, a thiuram-based thiuram system, or a mineralized amine (fluoroamine polymerization initiator). Among them, preferred are acetophenone-based and ketone-based systems. The initiator may be used alone or separately. The content of the photopolymerization initiator is relative to the prepolymer; 100 parts by mass, preferably about 0.5 to 10 parts by mass, more preferably: more, more preferably 3~ 8 parts by mass. <Other components> The ink composition of the present invention is obtained from the desired organic diisopropyl ether, hospital, chloroform, propylene carbonate or the like, for example, methyl ethyl ketone, and is usually used as a starting agent. The ketone-based, diphenyl-based or diphenyl-based compound such as a photopolyketone, a ketone-based or a methylsulfonate may have a solid content of 1 to 8 by mass, and may also contain various additives of -15 to 201221586. The additive may, for example, be an ultraviolet absorber, an infrared absorber, a light stabilizer, a polymerization inhibitor, a crosslinking agent, an antistatic agent, an antioxidant, a leveling agent, a thixotropic imparting agent, a coupling agent, a plasticizer, or a defoaming agent. Agent, sputum agent, thermal radical generator, aluminum chelating agent, and the like. Moreover, the ink composition of the present invention may contain a polymer such as an acrylic resin, a cellulose resin, a urethane resin, a polyester resin or an epoxy resin, within a range that does not impair the effect thereof. Or a monomer having at least one ionizing radiation curable functional group selected from the group consisting of a vinyl group, a (meth) propylene group, an allyl group, and an epoxy group, such as a urethane (methyl) A reactive monomer such as a polyfunctional (meth) acrylate such as an acrylate, a polyester (meth) acrylate, an epoxy (meth) acrylate, or a polyether (meth) acrylate. The content of the solid content of the prepolymer in the ink composition is preferably 95% by mass or less, more preferably 85 % by mass or less, based on the total of the solid content of the prepolymer and the reactive inorganic particles. 70% by mass or less. Further, the range of the lower limit of the content of the solid content of the prepolymer is preferably 30% by mass or more, more preferably 40% by mass or more, and particularly preferably 50% by mass or more. When the content of the polymer is within the above range, when the ink composition is used to form the hard coat layer, the hard coat layer formed on the release layer by the ink composition is applied, and only heat may be used as needed. Dry to make it non-sticky. As a result, under the semi-hardening treatment without irradiation with ionizing radiation or baking at a high temperature, even if the sheet is wound into a roll shape, it does not adhere (internal movement). Further, since the above-described semi-hardening treatment is not required, even in the case of forming, even if the area ratio of the decorative sheet before and after the forming is 130% or more deep-drawing (deep -16 - 201221586 drawing), there is no occurrence in the maximum extension portion. The coating film is cracked or whitened, and a hard coat layer which can well follow the shape of the mold can be formed. Further, since the hard coat layer is hardened by using ionizing radiation after the transfer and transfer, excellent hardness is obtained. Further, the content of the solid content of the polyfunctional isocyanate compound in the ink composition is preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, even more preferably 100 parts by mass of the solid content of the prepolymer. It is 3 to 15 parts by mass. When the content of the solid content of the polyfunctional isocyanate compound is within the above range, heat resistance at the time of molding can be obtained while maintaining excellent high hardness and moldability. <Striped Sheet> The decorative sheet of the present invention is provided with a release layer and a hard coat layer on at least one side of the base film, and the hard coat layer is formed using the above ink composition. Former. Hereinafter, the decorative sheet of the present invention will be described with reference to Figs. 1 and 2 . BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a preferred embodiment of a decorative sheet of the present invention. Fig. 2 is a schematic cross-sectional view showing a preferred embodiment of the decorative molded article of the present invention. The decorative sheet 10 of the present invention, as shown in FIG. 1, is attached to one surface of the base film 11 composed of a polyester film, and sequentially laminates the release layer 12, the hard coat layer 13, and the fixed layer ( The anchor layer 14 and the pattern layer 15 and the subsequent layer 16 are laminated with the antistatic layer 19 on the other surface of the base film 11 (the surface on the opposite side to which the mold release layer 12 is provided). Further, as shown in Fig. 2, the decorative molded article 20 of the present invention is laminated on the surface of the molded article 21 of the resin -17-201221586, and the subsequent layer 16, the pattern layer I4, and the hard coat layer 13 are laminated in this order. Hardened 22 hardened coatings. The components constituting the decorative sheet and the decorative molded article are clearly formed. <Substrate film> The base film can be made of polyacrylic acid such as polyethylene or polypropylene, polyvinylidene chloride, polyvinyl alcohol, ethylene/ethyl copolymer, ethylene vinyl alcohol copolymer, or the like. Vinyl resin; polyester resin such as poly (ethylene diester) or polybutylene terephthalate: styrene resin such as methyl acrylate or poly(methyl) acrylate such as acrylic acid polystyrene; Acrylic acid, butadiene, benzene, cellulose triacetate, celluloid polycarbonate, polyamine, and other elastomeric resin. Among these, from the viewpoint of moldability and goodness, a polyester resin and a polyphenylene terephthalate (hereinafter referred to as "PET") are preferable. The thickness of the base film is preferably in the range of 25 to 150 μm and more preferably 25 to 25 in terms of moldability and shape followability. <Mold release layer 12> The release layer 12' is a layer for sequentially laminating the hard coat layer forming layer 14, the pattern layer 15 and the transfer layer 17 formed by the subsequent layer 16 to facilitate the peeling of the film 11. . By providing the release layer 12, it is possible to transfer the decorative sheet of the present invention to the transfer 15 'fixed below, said resin; vinyl acetate para-phenylene poly(methyl) Resin; Ethylene copolyformate-based exfoliative dicarboxylic acid B. Easy to operate. 7 5 μηι的范1 3, fixed by substrate thin printing layer 1 7 body, and -18- 201221586 substrate film 11, release layer 12. The release layer 18 composed of the antistatic layer 19 provided as needed is surely peeled off. The release layer 12 is preferably a melamine resin release agent, a polyoxymethylene resin release agent, or a fluorine. Resin-based release agent, cellulose resin-based release agent, urea resin-based release agent, polyolefin resin-based release agent, paraffin-type release agent, acrylic resin release agent, and composite release agents thereof In the above, the release strength of the layer from which the release layer and the hard coat layer can be formed is within a predetermined range, and the release layer 18 is surely peeled off. Preferably, the melamine resin is released. Agent and acrylic resin release agent, or acrylic acid-melamine When a melamine resin-based release agent is used, it is preferred to use an acid catalyst in order to promote the hardening of the release agent. The acid catalyst is not particularly limited, and preferably, for example, p-toluenesulfonic acid, Dodecylsulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalene disulfonic acid, etc. The amount of the acid catalyst used is 0.05 to 3 relative to the solid content of the melamine resin contained in the melamine resin-based release agent. Preferably, the amount is preferably about 5% to about 1%. Further, in order to promote the hardening of the release agent, it is preferably heat-treated at 130 to 170 ° C for about 30 seconds to about 2 minutes. In the formation of 1 2, an ink prepared by dissolving or dispersing the necessary additives in the above-mentioned release agent may be applied to the base film 1 1 by a known means. The thickness of the layer 12 is preferably about 0.1 to 5 μm. <Hardcoat layer forming layer> The hard coat layer forming layer is a hard coat layer 22 in the decorative molded article 20 by curing by using the layer -19-201221586 formed of the above ink composition. The hard coat layer 22, which is the outermost layer of the molded article, is used to protect the layer of the formed product or the patterned layer by abrasion or medicine. Therefore, the hard coat layer forming layer 13 must be a layer having excellent properties such as high hardness and scratch resistance by hardening and excellent in surface physical properties such as chemical resistance and stain resistance. The hard coat layer forming layer can be carried out by a coating method such as a gravure coating method, a roll coating method, a knife coating method, a die coating method, a gravure printing method, a screen printing method, or the like. Coating to form. The thickness of the hard coat layer forming layer is preferably in the range of 0.5 to 30 μm, more preferably in the range of 3 to 15 μm. When the thickness is in the above range, it is excellent in high hardness and scratch resistance, and surface properties such as chemical resistance and stain resistance can be obtained, and excellent formability and shape followability can be obtained. Also, it is advantageous from the viewpoint of material costs. <Fixed layer> The fixing layer 14' is used to lift the hard coat layer and the back layer 16, or the pattern layer 15 with the pattern layer 15, and if necessary, the layer is fixed. It may be a two-liquid hardening urethane resin, a thermosetting urethane resin, a melamine resin, a cellulose ester resin, a chlorine-containing rubber resin, a chlorine-containing vinyl resin, an acrylic resin, or the like. An epoxy resin, a vinyl copolymer resin, or the like is formed. For example, the resin may be applied to the above-mentioned hard coat layer forming layer 13 by a gravure coating method, a light coating method, a doctor blade coating method, a gravure printing method, or a screen printing method. The coating is formed to form. The thickness of the fixed layer I4 is usually 〇1~5μιη left -20-201221586 right, preferably about 1~5μπι. <Pattern Layer> The pattern layer 15 is a layer for imparting a desired design to a decorative molded article, and a layer to be provided as needed. The pattern of the pattern layer 15 is arbitrary, and examples thereof include a pattern formed of wood grain, stone grain, marble grain, gray grain, geometric pattern, or character. Further, the pattern layer 15 may be provided separately or in combination with the pattern layer and the entire inner layer of the pattern, and the entire inner layer may be used as a masking layer, a colored layer, a colored masking layer or the like. The pattern layer 15 is usually on the hard coat layer 13 formed as described above or on the fixed layer 14, and will contain a polyethylene resin, a polyester resin, an acrylic resin, a polyvinyl acetal resin. A resin such as a cellulose resin is used as a binder, and a printing ink having a color or a dye of a suitable color as a coloring agent is formed by printing. The printing method may, for example, be a known printing method such as gravure printing, lithography, screen printing, transfer printing from a transfer sheet, sublimation transfer printing, or ink jet printing. The thickness of the pattern layer 15 is preferably from 5 to 4 〇μπι, and from 5 to 30 μπι, from the viewpoint of design. <Bottom Layer> Next, the layer 16 is used to transfer the transfer layer 17 to the layer formed by the resin molded body. The back layer 16' is suitably made of a material suitable for the resin molded body. A heat sensitive or pressure sensitive resin. For example, when the material of the resin molded body is an acrylic resin, an acrylic resin is preferably used. -21 - 201221586 In addition, when the material of the resin molded body is polyphenylene ether, polystyrene oxide resin, polycarbonate resin or styrene resin, it is preferred to use a resin having affinity with the resin. A curable resin, a polystyrene resin, a polyamine resin, or the like. Further, when the material of the resin molded body is a polypropylene resin, a chlorinated polyolefin resin, a vinyl chloride-vinyl acetate copolymer resin, a cyclized rubber, or a benzofuran-indene resin is preferably used. Next, a method of forming the layer 16 may be, for example, a coating method such as a gravure coating method or a roll coating method, a gravure printing method, or a screen printing method. Further, when the pattern layer I5 has sufficient adhesion to the resin molded body, the adhesion layer 16 may not be provided. The thickness of layer 16 is preferably about 〇5 to 5 μηη. <Antistatic layer> The decorative sheet of the present invention may further comprise an antistatic layer. The antistatic layer 19' is for preventing foreign matter from adhering to the decorative sheet, and is provided on the opposite side of the surface of the base film 11 on which the release layer is provided. The antistatic agent used for the antistatic layer is preferably an anionic surfactant such as a carboxylic acid type, a sulfonic acid type or a phosphoric acid type; a cationic surfactant such as a quaternary ammonium type; an alkylbetaine system or an alkylimidazole An amphoteric surfactant such as a porphyrin or an alkyl alanine; a nonionic surfactant such as an alkylene oxide polymer, an alkylene oxide copolymer or an aliphatic alcohol-alkylene oxide adduct; carbon, or gold or uranium Inorganic conductive substances such as silver, copper, aluminum, nickel, titanium, molybdenum and other metal powders: polyacetylene, polypyrrole, polyparaphenylene, polyaniline, polythiophene, polyparaphenylene extended ethylene, polyvinyl carbazole Or a conductive polymer such as a polyether ester guanamine resin composed of an aminocarboxylic acid, a dicarboxylic acid or a polyethylene glycol. -22- 201221586 Antistatic layer' is a coating method by gravure printing or roll coating, or gravure printing or screen printing by coating the above-mentioned antistatic agent and organic solvent. It is formed by coating by a printing method. The thickness of the antistatic layer thus formed is usually 0.1 to 5 μm. When the thickness of the antistatic layer is within the above range, excellent antistatic properties can be obtained efficiently. In the decorative sheet of the present invention, the hard coat layer can be formed into a non-tacky property by heat drying as needed, so that it is excellent in blocking resistance and heat resistance, so that the production efficiency is excellent. Further, since it is not necessary to perform semi-hardening treatment such as irradiation of ionizing radiation which is non-adhesive or baking at a high temperature, it is excellent in formability and shape pursuit. Further, since the hard coat layer is hardened by the use of ionizing radiation after the transfer printing, excellent hardness and scratch resistance can be obtained. Therefore, it can be used in a wide range of fields such as household electric products, automobile interiors, and the like, or in the field of personal computers, particularly in the form of personal computers. <Manufacturing Method of Decorative Molded Article> The method for producing a decorative molded article of the present invention includes a step of disposing the decorative sheet in the injection molding die (first step): ejecting the molten resin to the injection molding An injection step of cooling and solidifying the resin molded body and the decorative sheet in a cavity of the mold (second step): forming and integrating the resin molded body and the decorative sheet a step of taking out the injection molding die (third step): a step of peeling off the base film of the decorative sheet from the molded body (fourth step): and using the ionizing radiation to be disposed on the molded body The hard coat layer is layer hardened -23-201221586 hard coat layer forming step (step 5). Hereinafter, each step will be described. <First Step> The first step is a step of arranging the decorative sheet in a molding die. Specifically, the decorative sheet is applied to the molding die formed by the movable mold and the fixed mold so that the transfer layer 17 is inside and the base film 11 is fixed to the mold side. Add a thin sheet. At this time, a plurality of decorative sheets can be fed one by one, and the necessary portions of the long decorative sheets can be intermittently fed. When the decorative sheet is placed in the molding die, it may be arranged as follows: (i) heating only the mold to vacuum suction the mold to be in close contact; or (ii) using a hot plate The transfer layer 17 is heated and softened, and the decorative sheet is preliminarily molded along the shape of the mold to be adhered to the inner surface of the mold. (ii) the heating temperature at the time, preferably in the vicinity of the glass transition temperature of the base film 11 and not in the range of the melting temperature (or melting point), usually in the vicinity of the glass transition temperature, the so-called glass transfer Near the temperature, the glass transition temperature is ± 5. (: the range from left to right is generally 70 to 13 0. In the case of (ii), in order to make the decorative sheet more closely adhere to the surface of the molding die, when the decorative sheet is heated by a hot plate to soften it, Vacuum suction is performed. <Second Step> The second step is an injection step of discharging the molten resin into the cavity, cooling and solidifying, and laminating and integrating the resin molded body and the decorative sheet 24-201221586. When the injection resin is a thermoplastic resin, it can be melted by heating to form a flow state, and when the injection resin is a thermosetting resin, the unhardened liquid composition can be appropriately heated and emitted in a flowing state, and cooled and solidified. . Thereby, the decorative sheet and the resin molded body are integrated and attached to each other to form a decorative molded article. The heating temperature at which the resin is ejected is generally about 180 to 280 °C, although it is emitted as a resin. The injection resin used for the decorative molded article may be any thermoplastic resin or a thermosetting resin (including two liquid thermosetting resins), and various resins may be used. Examples of such a thermoplastic resin material include a polystyrene resin, a polyolefin resin, an AB S resin (including a heat resistant ABS resin), an AS resin, an AN resin, a polyphenylene ether resin, a polycarbonate resin, and a poly An acetal resin, an acrylic resin, a polyethylene terephthalate resin, a polybutylene terephthalate resin, a polyfluorene resin, a polyphenylene sulfide resin, or the like. Further, the thermosetting resin may, for example, be a two-liquid reaction-hardening type polyurethane resin or an epoxy resin. These resins may be used singly or in combination of two or more. <Third Step and Fourth Step> The third step is a step of taking out the molded body in which the decorative sheet and the resin molded body are integrated by the mold, and the fourth step is to form the base of the decorative sheet from the formed body. The step of stripping the material film. Since the base film 11 has the release layer 12, the base film 11 and the release layer 12 can be easily disposed at the interface between the release layer 12 and the hard coat layer 13. The release layer 18 of the antistatic layer 19 is peeled off from the decorative molded article 20. Thus, a molded article of the adhesive layer 25, the pattern layer 15, the fixed layer 14, and the hard coat layer 13 can be laminated in this order on the surface of the molded article 21 of the resin-25-201221586. <Step 5> The fifth step is a step of hardening the hard coat layer 13 in the formed article obtained in the above step 4 by using ionizing radiation to form a hard coat layer. The hardening in the fifth step can be carried out by irradiating the ionizing radiation in an atmosphere having an oxygen concentration of 2% or less. Thus, by hardening, more excellent high hardness and scratch resistance can be obtained. The ambient atmosphere having an oxygen concentration of 2% or less can be obtained, for example, by using nitrogen, argon, hydrogen or the like, preferably using nitrogen, or vacuum suction to have an oxygen concentration of about 2% or less. The hardening of the hard coat layer 13 can be carried out by irradiating electron beams and ionizing radiation such as ultraviolet rays. When an electron beam is used as the ionizing radiation, the accelerating voltage thereof can be appropriately selected depending on the kind of the prepolymer or monomer used or the thickness of the hard coat layer 13 to be formed, and the acceleration voltage is usually 70~. About 300kV is better. The amount of irradiation line is usually selected in the range of 5 to 3 〇〇 kGy (0 to 5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad). The 'electronic line source' is not particularly limited. For example, it can be used with K. K. Wolfer, Van der Graff type, resonant transformer type, insulated nuclear transformer type, or linear type, frequency-frequency type, Various electronic line accelerators such as high frequency type. When ultraviolet rays are used as the ionizing light rays, ultraviolet rays having a wavelength of 19 〜 to 380 nm are irradiated, and the irradiation amount thereof is about 5 〇〇 to i5 〇〇 mj -26-201221586. The ultraviolet source is not particularly limited, and for example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, or the like can be used. The decorative molded article of the present invention thus obtained is excellent in surface physical properties such as excellent high hardness, chemical resistance, and stain resistance. Further, by using the decorative sheet of the present invention which can obtain the moldability of a molded article having a more complicated shape, a decorative molded article having a more excellent appearance of the finished product can be obtained. The decorative molded article of the present invention can be used in a wide range of fields such as household electric products, automobile interiors, and the like, or in the field of personal computers, particularly in the form of personal computers. EXAMPLES Next, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited. Further, the evaluation methods of the examples were carried out in the following manner. 1. Sample sample was prepared on a base film ("F99 (product number)", thickness: 50 μm, manufactured by Toray Co., Ltd.), gravure printing melamine resin release agent at a coating amount of 2 g/m2 (addition) The melamine resin has a solid content of 0.5% acid catalyst (p-toluenesulfonic acid), and is heat treated in an oven at 150 ° C for 60 seconds to form a release layer, and each of the examples is coated with a bar coater. The ink compositions used in the comparative examples were dried in an oven at 1 ° C for 60 seconds to prepare test samples. Here, the coating amount of the ink composition is such that the thickness of the ink coating layer after drying is 6 g/m2. -27- 201221586 2. Evaluation of adhesion resistance (sheet winding suitability) on the ink coating level of the test sample, the PET film used in the production of the laminated test sample, using the ink adhesion tester ("DG-BT ( Model)", manufactured by Daiwa Printing Co., Ltd.), placed under an load of lkg/cm2 and placed in an oven at 40 °C for 12 hours. Thereafter, the test sample was taken out to peel off the laminated PET film. The adhesion (internal shift) of the ink coating layer of the peeled PET film was evaluated on the basis of the following criteria. A: No internal shifting B: Although there is some internal shift, there is no problem in practical use. C: Internal shift is remarkable. 3. Evaluation of high hardness. Test samples are hardened by the hardening methods in the respective examples and comparative examples. According to JIS K5600-5-4, a pencil scraping film hardness tester (r D-NP (model) 'Toyo Seiki Seisakusho Co., Ltd.) and a pencil scraping test pencil (manufactured by Mitsubishi Pencil Co., Ltd.) were used. The pencil hardness was measured. The ink coating layer was subjected to a scratch test five times with a pencil of each hardness, and the pencil hardness of which no trace was generated three times or more was used as the pencil hardness of the test sample. Synthesis Example 1 (Synthesis of Prepolymer 1) A 2 L four-necked flask equipped with a cooler, a dropping funnel and a thermometer was charged with methyl isobutyl ketone (MIBK) 120 g and methyl ethyl ketone (MEK) 210 g at -28- 201221586 Μ four-necked flask, 80g of methacrylic acid propylene glycol (GMA), methyl methacrylate (μμα) 2〇§ and azo-based initiator (azo azide) were dropped from the funnel for 2 hours. Butyronitrile, AIBN_1} 〇_7 is reacted at a temperature of 100 to 110 ° C for 4 hours, and then an azo-based initiator (azobisisobutyronitrile, AIBN 2 ) O jg is added. After holding for 3 hours, it was cooled to room temperature, and a mixed liquid of 40.6 g of acrylic acid (AA), 2 g of triphenylphosphine, and 5 g of methoxyphenol was added thereto to carry out an addition reaction. Neutralization titration 'Confirming the disappearance of the acid value of the reactive organism, and ending the reaction" The reaction product (prepolymer 1) obtained has a weight average molecular weight of 80,000 and a double bond equivalent of 2 50 g/mol (calculated 値). The solid content is 30%. Moreover, the weight average molecular weight is determined by gel permeation chromatography (GPC). The quasi-sample was measured using the conditions of polystyrene. Synthesis Example 2 (Synthesis of Prepolymer 2) In Synthesis Example 1 (Synthesis of Prepolymer 1), except that the dose used was changed to Table 1. In the same manner as in Synthesis Example 1, the prepolymer 2 was synthesized in the same manner. The weight average molecular weight, double bond equivalent, and resin solid content of the obtained prepolymer 2 are shown in Table 1. Further, in the composition column of the table The number 値' is all grams. -29- 201221586 [Table l] Prepolymer 1 Prepolymer 2 _ Dispensing into MI BK 120 120 MEK 210 210 GMA 80 80 — MMA 20 20 A IBN-1 0.75 1 A IBN- 2 0.6 1 AA 40.6 40.6 Triphenylphosphine 2 2 Methophenol 0.5 0.5 Weight average molecular weight 80000 25000 Double bond equivalent (g/mol) 250 250 Solid content (% by mass) 30 30 Example 1 (1) Manufacture of decorative sheets On a base film ("F99 (product number)", thickness: 50μπι 'made by Toray Co., Ltd.), a coating liquid containing melamine resin as a main component was gravure-coated at a coating amount of 2 g/m2 ("Meilan" 265" (product number), manufactured by Hitachi Chemical Co., Ltd., isobutanol The melamine resin was formed into a release layer, and the ink composition of the composition shown below was gravure-printed at a coating amount of 6 g/m 2 to form a hard coat layer. Ink composition: Prepolymer 1: 20.0 parts by mass (solid 6 parts by mass of the component, acrylic acrylate-based prepolymer (prepolymer 1 synthesized in Synthesis Example 1, molecular weight: 80000, double bond equivalent: 250 g/mol) Reactive hetero type cerium oxide particles: 10 parts by mass (solid 4 parts by mass), ("ELCOMV- 8 8 03 (product number)", cyclization -30-201221586, manufactured by Co., Ltd., reactive hetero-type cerium oxide particles, average number of links: regular 2 to 10 The average particle diameter of the heterogeneous inorganic particles · · 2 5 nm) Reactive polyfunctional isocyanate: 1 part by mass (solid content: 1 part by mass), ("Laromer LR9000 (product number)", manufactured by BASF) Photopolymerization initiator: 0.4 parts by mass ("IRGACURE 184 (commodity number)", manufactured by Ciba Barbine Co., Ltd., 1-hydroxycyclohexyl benzophenone) Solvent: 6.7 parts by mass, a mixed solvent of methyl ethyl ketone and methyl isobutyl ketone (mixing ratio 7 0 : 3 0 ) The coating layer was formed by coating a coating material having an acrylic resin as a main component at a coating amount of 4 g/m 2 , and then the acrylic printing ink was formed into a pattern layer by a gravure printing wood grain pattern at a coating amount of 8 g/m 2 . The acrylic coating liquid was applied at 4 μm to form an adhesive layer. Further, on the opposite side of the surface of the base film on which the release layer is provided, a coating liquid containing a cationic surfactant as a main component is applied by gravure printing at a coating amount of 1 g/m 2 (cationic surfactant): four A graded ammonium salt) was formed to form an antistatic layer, and the decorative sheet of Example 1 was obtained. Further, using the ink composition used in Example 1, a test sample was prepared in accordance with the above-mentioned test sample, and evaluation of blocking resistance (sheet winding suitability) and evaluation of high hardness were performed. The evaluation results are shown in the following Table 2. (2) Production of decorative molded article The decorative sheet obtained as described above was sucked into a mold heated at 70 ° C to be adhered to the inner surface of the mold. The mold 'uses a size of 80 mm side length -31 - 201221586 The height is 10 mm, and the corner is a three-dimensional disc-shaped deep-draw shape. On the other hand, ABS resin ("Clastic MTH-2 (product number)" - manufactured by Nippon A & L Co., Ltd.) was used as an injection resin, and it was melted at 2300 ° C, and then it was injected into a cavity. . After cooling and taking out from the mold, the substrate film is peeled off to obtain a molded article having an adhesive layer, a printing layer, a fixing layer and a hard coat layer. In addition, in the atmosphere of the atmosphere, a variable output type UV lamp system ("DRS-10/12QN (product number) j 'Fusion UV system, manufactured by Nippon Co., Ltd.) is used to illuminate the line amount: 1 OOOmJ. The molded article was irradiated with ultraviolet rays to harden the hard coat layer to form a hard coat layer, and the resin molded article of Example 1 was obtained. 4. Evaluation of Appearance (Formability) The obtained resin molded article was based on the following criteria. Evaluation of the appearance (formability) A: The hard coat layer (and its formation layer) was completely unidentified until the coating was broken or whitened, and the shape of the mold B was well pursued: in the hard coat layer (and its formation) Layer) confirmed slight cracking or slight whitening C: Although the hard coat layer (and its formation layer) confirmed part of the coating cracking or slight whitening, but practically no problem D: in hard coating The layer (and its formation layer) was confirmed to have a significant coating rupture or whitening evaluation result as shown in the following Table 2. -32 - 201221586 5 - Appearance (heat resistance) evaluation Further, for the obtained resin molded article, The basis of the evaluation of the gate part (tree Appearance (heat resistance) around the injection part A: In the hard coat layer (and its formation layer) · Deformation or whitening at the end of the flow without confirmation B: Confirmation of the hard coat layer (and its formation layer) Deformation or slight whitening to a slight flow C: Although the hard coating (and its formation layer) confirms the deformation or slight whitening of the partial flow, there is no problem in practical D: The coating (and its formation layer) confirmed that the deformation or whitening evaluation result to the significant flow was as shown in the following Table 2. Examples 2, 3 and Comparative Examples 1 to 7 In Example 1, except that the ink was composed The decorative sheets and the decorative molded articles of Examples 2 and 3 and Comparative Examples 1 to 7 were obtained in the same manner as in Example 1 except that the contents were the same as in Example 1. The above-mentioned ink composition was subjected to the above-mentioned adhesive resistance. The evaluation of the connectivity (sheet winding suitability) and the evaluation of the high hardness were performed on the obtained decorative molded article. The evaluation results are shown in the following Table 2. -33 - 201221586 [Table 2] Ϊ3 Oa ~W" S/0 0 OS 001 rs inch Ό o <〇 s ϋ ο in

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i- S ,屮起筚璀'汆堪|9画<1^1^4|如忉^趣赵「歡«超<0嵌朱，媼趙减«^砷飨(¥摧3)，|^起蹈_钽鹳赵，晷嵌®^^® • (％__)_ΦΙδφ® 豳晅e®l^K^ite<ni\)lfm趙摧契盤吆敏汆堪豳画瘁嵌ιβ^ίι® 。制4|啪^『«0:^忉-^「(||!1喏經>3§§->2031«」^阳^佐^鉬|§摧曲凿赵腚迁球鬆嵌網截，_?:©链忉呂隖矻'#-_^®^ Ik^s^^sfliH避趙»-«$8联长0 -「(黯躍ng粗)—3」：避趙槭酿靼脚私 (—0 寸：051¾¾¾昏-豬陌<-11|棒傘燊瓶 Hffl-车糊 B *「i!lngKJ-ls-:H3s」)H-^4W>W酸駿扫輯1«¥ ° is^ss^m 【圖式簡單說明】圖1，本發明之加飾薄片之一實施型態之截面模式圖 -34- 201221586 圖2，本發明之加飾成形品之一實施型態之截面模式圖。【主要元件符號說明】 I 〇 :加飾薄片 II :基材薄膜 1 2 :脫模層 1 3 :硬塗層形成層 14 :固定層 15 :圖案層 1 6 :接著層 1 7 :轉印層 1 8 :剝離層 1 9 :抗靜電層 20 :加飾成形體 21 :樹脂成形體 22 :硬塗層 -35-I- S, 屮筚璀 '汆 | 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 趣趣趣趣趣趣趣趣趣趣趣趣趣趣|^开始_钽鹳赵,晷嵌®^^® • (%__)_ΦΙδφ® 豳晅e®l^K^ite<ni\)lfm Zhao 契吆吆吆汆汆汆 ι ι ι ι ι Ίι® .制4|啪^『«:^忉-^"(||!1喏经>3§§->2031«"^阳^佐^Mo*|§摧曲凿赵腚迁球松?网截,_?:©链忉吕隖矻'#-_^®^ Ik^s^^sfliH Avoid Zhao»-«$8Coordinated 0 - "(黯跃ng粗)-3": Avoid Zhaohuang靼 foot private (—0 inch: 0513⁄43⁄43⁄4 faint - pig strange <-11| rod umbrella bottle Hffl-car paste B * "i!lngKJ-ls-:H3s") H-^4W>W acid Chun sweep 1 «¥° is^ss^m [Simple description of the drawings] Fig. 1, a cross-sectional view of one embodiment of the decorative sheet of the present invention - 34 - 201221586 Fig. 2, an embodiment of the decorative molded article of the present invention Cross-sectional mode diagram of the state. [Description of main component symbols] I 〇: decorative sheet II: base film 1 2 : release layer 1 3 : hard coat layer 14 : fixed layer 15 : pattern layer 1 6 : adhesive layer 1 7 : transfer layer 18 : peeling layer 1 9 : antistatic layer 20 : decorative molded body 21 : tree Molded body 22: hard coat layer -35-

Claims

201221586 VII. Patent application scope: ι_ An ink composition characterized by having the following: Having at least one selected from the group consisting of ethylene, (meth) acryl fluorenyl and allyl groups; The polyfunctional radically polymerizable prepolymer having a weight average molecular weight of the ionizing radiation curable functional group A of 50,000 or more; a reactive inorganic particle having an ionizing radiation curable functional group B on the surface; and a polyfunctional isocyanate compound. 2. The ink composition of claim 1, wherein the reactive inorganic particles are reactive cerium oxide particles and/or reactive shaped cerium oxide particles. 3. Ink according to claim 1 or 2. In the composition, the polyfunctional radically polymerizable prepolymer is a (meth)acrylic acrylate-based prepolymer. 4. The ink composition according to any one of claims 1 to 3, wherein the polyfunctional isocyanate compound has a selected from the group consisting of a vinyl group, a (meth) propylene group, an allyl group, and an epoxy group. At least one of the constituent groups is an ionizing radiation curable functional group C. 5. A decorative sheet attached to a single side of a substrate film, at least sequentially provided with a decorative sheet of a release layer and a hard coating layer, characterized in that the hard coating layer is used as an application The ink composition of any one of the first to fourth aspects of the invention is formed. 6. The decorative sheet of claim 5, wherein the substrate film is provided with an antistatic layer on the opposite side of the surface of the substrate film on which the release layer is provided. A method for producing a decorative molded article of a decorative sheet according to the invention of claim 5 or 6, wherein the decorative sheet is disposed in the injection molding die. a step of ejecting molten resin into a cavity of the injection molding die, cooling and solidifying, and laminating and integrating the resin molded body and the decorative sheet; laminating the resin molded body and the decorative sheet a step of removing the integrally formed molded body from the injection molding die; a step of peeling off the base film of the decorative sheet from the molded body; and forming a hard coat layer formed on the molded body using ionizing radiation Hardened hard coat forming step. 8 - A decorative molded article obtained by the manufacturing method of claim 7 of the patent application. S -37-