TW201120156A

TW201120156A - Hard coat resin composition of ultra violet ray curable type, a hard coat film using such hard coat resin composition, and a formed article of hard coat

Info

Publication number: TW201120156A
Application number: TW099131939A
Authority: TW
Inventors: Yoshiyuki Yahagi; Toru Kurihashi; Yoshihiko Taira; Hirokazu Karino
Original assignee: Nippon Kayaku Kk
Priority date: 2009-10-20
Filing date: 2010-09-21
Publication date: 2011-06-16
Also published as: JP2011088962A; CN102040903A; KR20110043444A; TWI486408B; CN102040903B; JP5557274B2

Abstract

This invention provides a low cost, UV curable type hard coat resin composition which can be cured easily with ultra violet (UV) ray and exhibits a high hardness, a high adhesion, excellent transparency, resistance to dirt, and stretchability, and is suited for use as a material for insert-forming involving a bending process. This invention also provides a hard coat film having a hardened film coating as above, as well as a formed article having such a hardened film coating. The UV ray curable resin hard coat composition of this invention contains an epoxy (meth) acrylate (A), a photo-radical polymerizing initiator (B), and a dirt resisting agent (C), the epoxy (meth) acrylate (A) containing at least 3 or more than 3 of (meth) acryloyl group in the molecule and being obtained by reacting an epoxy resin (a) and a (meth) acrylic acid (b), the epoxy resin (a) being represented by the following formula (1) Wherein R may be the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group having a number of carbon atoms of 1 to 4, n represents an average of integers of 1 to 20.

Description

201120156 六、發明說明：【發明所屬之技術領域】- 本發明係關於一種紫外線硬化型硬塗層樹脂組成物，具有此種硬化層之硬塗層膜以及硬塗層成形物。詳細而言’係一種適合塗布於聚酯、丙烯酸、聚碳酸酯等塑膠薄膜表面上之备、外線硬化型硬塗層樹脂組成物。將本發明之树月曰組成物硬化所得之成形品，即使彎曲表面之曲面部分不會產生裂痕。此外，此硬化所得之成形物之紹筆硬度佳換s之’由於將本發明之樹脂組成物硬化所得成形品之彎曲性及成形性佳，因此，係-種適合在膜嵌入成形時使用之硬塗層膜。【先前技術】目則’塑膠是在以汽車業界、家電業界、電器電子業界為首之各種產業界中大量使用。如此大量使用塑膠之理由係因除了加工性、透明性以外，輕量、便宜、光學特性佳等理由使然。然而，由於塑膠比玻璃等更為柔軟，因此 1表面容易刮傷等之缺點。為了改良此等缺點，一般的手 ^係在塑膠表面進行塗覆硬塗層劑。此種硬塗層劑係使用聚石夕氧系塗料、丙烯酸系塗料、三聚氰胺系塗料等熱硬化二更塗層劑。此等當中，尤其聚矽氧系硬塗層劑，因硬度 η σ°質佳而大量使用。然而，聚矽氧系硬塗層劑硬化時 1長、價向’不適合連續加工之膜片上所設置之硬塗層。 “ 近年來’已開發並利用感光性之丙烯酸系硬塗層劑（感光f生硬塗層劑）（參照專利文獻1) α感光性硬塗層劑係藉由 4 322297 201120156 紫外線等放射線照射，立即硬化而形成硬皮膜。此種加工處理之速度越快，硬化物之硬度、耐擦傷性等也越佳。除此之外，由於感光性硬塗層劑總成本低，目前成為在硬塗層領域之主流。感光性硬塗層劑特別適合塑膠膜之連續加工。塑膠膜雖有聚酯膜、丙烯酸膜、聚碳酸酯膜、氯化乙烯膜、三醋酸纖維素膜、聚醚砜膜、聚環烯烴系膜等，但聚酯膜因各種優良特性而使用最廣泛。此種聚酯膜廣泛使用於防止玻璃飛散膜，或是汽車之遮光膜、白板用表面膜、系統廚具表面防污膜，在電子材料中，CRT平板電視、液晶顯示器（LCD)、電漿顯示器（PDP)、有機EL顯示器、觸控板等功能性膜。為使此等中任一者表面不會刮傷而塗布硬塗層。再者，於成形加工領域中使用膜片之場合亦正增加中。例如，行動電話及個人電腦等之筐架外殼體、儀表板蓋等汽車内裝材料、AV機器及家電製品之顯示面板及開關按鈕等之成形加工亦可使用膜片。塑膠製品之成形可使用模具進行射出成形。作為在此方式所得之塑膠製品表面加工之方法，將膜片裝附於模具之内面，與塑膠成形同時貼附於成形品表面之方法，稱為膜喪入喷射成形、模内（in-moId)成形等。再者，於裝附之膜片上印刷圖案或花樣，藉由硬塗層處理，而可提高成形品之裝飾及硬度等美觀性，或賦予功能性。射出成形所使用之硬塗層膜，有在基材膜上塗布硬塗層量與硬塗層膜一體成形之情況，和在具有離型層之膜上 5 322297 201120156 塗布硬塗層並在成形加工後剝除離型膜之情況（專利文獻 2)。由於射出成形所使用之硬塗層膜成為塑膠製品之表面，當然應具有表面硬度，光澤感、透明感等美觀性，及必要之承受成形加工之拉伸性、柔軟性等與表面硬度相反之性能。然而，以往之硬塗層劑，無法兼具硬化後之表面硬度（硬度）與延展性、柔軟性。換言之，硬度變高則拉伸性、柔軟性降低，相反地，拉伸性、柔軟性提高則硬度降低之情形，而不足以作為成形加工所使用之硬塗層劑。以往的硬塗層劑可列舉如上述文獻3至5所記載者。例如’前述文獻3以及前述文獻4所揭示之硬塗層劑，雖硬度足夠但拉伸性不足，再加上無法得到必要之透明性。由此可知，將柔軟性優先之組成，因無機物之影響使硬度及透明性不足。X，前述文獻5揭示之硬塗層劑，雖具有透明性，但硬度與拉伸性之關係亦與前述文獻3以及前述文獻4相同。此種硬塗層劑不適用於成形加工。此外，前述文獻6所揭示之硬塗層劑，雖然於膜嵌入成形中有用，但為了兼具硬度及拉伸性而含有多量之膠體氧化矽（colloidal Siuca)，有價格昂責之缺點。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開平9-48934號公報 [專利文獻2]日本特許第3007326號公報 [專利文獻3]日本特開2008-81696號公報 322297 6 201120156 [專利文獻4]日本特開2009-1598號公報 [專利文獻5]日本特開2008-94929號公報 [專利文獻6]日本特開2009-24168號公報【發明内容】 (發明欲解決之課題）本發明係提供一種便宜之紫外線硬化型硬塗層樹脂組成物，其可藉由以紫外線為首之放射線而容易地硬化，硬化物之硬度、密著性、透明性、防污性、以及拉伸性優，適合作為彎折步驟的膜嵌入成形時使用之硬塗層劑之材料，再者，亦提供具有此硬化層之硬塗層膜及硬塗層成形物。 (解決課題之手段）本發明人等為了解決上述課題，進行認真檢討之結果，發現含有特定化合物之紫外線硬化型硬塗層樹脂組成物可以解決前述課題，而完成本發明。換言之，本發明係關於以下者， (1) 一種成形膜用紫外線硬化型硬塗層樹脂組成物，係含有由通式（1)所示環氧樹脂（a)以及（曱基）丙烯酸（b)反應而得之分子中具有至少3個以上（曱基）丙烯醯基之環氧 (曱基）丙烯酸酯（A)、光自由基聚合起始劑（B)、以及防污劑（C)， 7 322297 201120156201120156 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to an ultraviolet curable hard coat resin composition, a hard coat film having such a hardened layer, and a hard coat formed article. More specifically, it is a composition for preparing an external hardening type hard coat resin which is suitable for application to a surface of a plastic film such as polyester, acrylic or polycarbonate. The molded article obtained by hardening the composition of the sapphire of the present invention does not cause cracks even in the curved portion of the curved surface. Further, since the molded article obtained by the hardening has a good hardness, the molded article obtained by curing the resin composition of the present invention has excellent flexibility and moldability, and therefore, it is suitable for use in film insert molding. Hard coating film. [Prior Art] The plastics are used in a wide variety of industries, including the automotive industry, the home appliance industry, and the electrical and electronics industry. Such a large amount of use of plastics is due to reasons such as light weight, low cost, and good optical properties in addition to workability and transparency. However, since the plastic is softer than glass, the surface is easily scratched. In order to improve these disadvantages, the general hand is to apply a hard coating agent on the surface of the plastic. As such a hard coat agent, a heat-curing two-coating agent such as a polychlorinated coating, an acrylic coating, or a melamine-based coating is used. Among these, in particular, a polyoxygen-based hard coat agent is used in a large amount because of the good hardness η σ°. However, when the polyoxygenated hard coat agent is hardened, the length of the hard coat layer is not suitable for the hard coat layer provided on the continuously processed film. "In recent years, the photosensitive acrylic hard coating agent (photosensitive hard coating agent) has been developed and utilized (see Patent Document 1). The α photosensitive hard coating agent is irradiated by ultraviolet rays such as 4 322297 201120156. Hardening to form a hard film. The faster the processing speed, the better the hardness, scratch resistance, etc. of the cured product. In addition, since the total cost of the photosensitive hard coating agent is low, it is currently in the hard coat layer. The mainstream of the field. The photosensitive hard coating agent is especially suitable for the continuous processing of plastic film. Although the plastic film has polyester film, acrylic film, polycarbonate film, vinyl chloride film, cellulose triacetate film, polyether sulfone film, A polycycloolefin film or the like, but the polyester film is most widely used because of various excellent properties. Such a polyester film is widely used for preventing a glass scattering film, or a light shielding film for a car, a surface film for a whiteboard, and an antifouling surface of a system kitchenware. A film, in an electronic material, a functional film such as a CRT flat panel television, a liquid crystal display (LCD), a plasma display (PDP), an organic EL display, a touch panel, etc., in order to prevent the surface from being scratched by any of these surfaces. In addition, the use of diaphragms in the field of forming and processing is increasing. For example, automotive interior materials such as mobile phone and personal computer such as rack outer casings and instrument panel covers, AV equipment and home appliances. A film can also be used for the forming process of the display panel and the switch button of the product. The molding of the plastic product can be carried out by using a mold. As a method for processing the surface of the plastic product obtained in this manner, the film is attached to the inner surface of the mold. The method of attaching to the surface of the molded article at the same time as the plastic molding is called film formation molding, in-mould molding, etc. Further, printing a pattern or a pattern on the attached film by hard The coating treatment can improve the aesthetics of the decoration and the hardness of the molded article, or impart functionality. The hard coat film used for injection molding has an amount of hard coating applied on the base film and is integrally formed with the hard coat film. In the case of coating a hard coat layer on a film having a release layer 5 322297 201120156 and peeling off the release film after the forming process (Patent Document 2). The hard coat layer used for injection molding The film becomes the surface of the plastic product, and of course, it should have the appearance of surface hardness, glossiness, transparency, and the like, and the tensile properties, flexibility, and the like which are necessary to withstand the surface hardness, etc. However, the conventional hard coat layer The surface hardness (hardness), the ductility, and the flexibility after hardening are not obtained. In other words, when the hardness is high, the stretchability and the flexibility are lowered. Conversely, when the stretchability and the flexibility are improved, the hardness is lowered. The hard coat agent used in the forming process is not sufficient. The conventional hard coat agent is as described in the above-mentioned documents 3 to 5. For example, the hard coat agent disclosed in the above-mentioned document 3 and the above-mentioned document 4, The hardness is sufficient, but the stretchability is insufficient, and the necessary transparency is not obtained. From this, it is understood that the composition which gives priority to flexibility is insufficient in hardness and transparency due to the influence of the inorganic substance. X, the hard coat agent disclosed in the above Document 5 has transparency, but the relationship between hardness and stretchability is also the same as that of the above-mentioned Document 3 and the aforementioned Document 4. Such a hard coat agent is not suitable for forming processing. Further, the hard coat agent disclosed in the above-mentioned Document 6 is useful for film insert molding, but contains a large amount of colloidal sulphide (colloidal Siuca) in order to have both hardness and stretchability, and has a disadvantage of being expensive. [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open No. Hei 9-48934 (Patent Document 2) Japanese Patent No. 3007326 [Patent Document 3] Japanese Patent Laid-Open No. 2008-81696 No. 322297 6 201120156 [ [Patent Document 5] Japanese Laid-Open Patent Publication No. 2008-94929 [Patent Document 6] JP-A-2009-24168 (Patent Document) (Problems to be Solved by the Invention) The invention provides an inexpensive ultraviolet curable hard coat resin composition which can be easily hardened by radiation including ultraviolet rays, hardness, adhesion, transparency, antifouling property, and stretchability of the cured product. Preferably, it is suitable as a material of a hard coat agent used for insert molding of a film as a bending step, and a hard coat film and a hard coat form having the hardened layer are also provided. (Means for Solving the Problems) The present inventors have found that the ultraviolet curable hard coat resin composition containing a specific compound can solve the above problems, and the present invention has been completed. In other words, the present invention relates to the following (1) an ultraviolet curable hard coat resin composition for a formed film comprising the epoxy resin (a) and (fluorenyl) acrylic acid represented by the general formula (1). An epoxy (fluorenyl) acrylate (A) having at least 3 (fluorenyl) acrylonitrile groups in the molecule obtained by the reaction, a photoradical polymerization initiator (B), and an antifouling agent (C) , 7 322297 201120156

(式中，R是相同或相異，表示氫原子、鹵原子或碳數1至 4之烴基，η表示平均值1至20之正數。）； (2) 如前述（1)所述之紫外線硬化型硬塗層樹脂組成物，其中，防污劑（C)為具有（曱基）丙烯醯基之聚矽氧烷； (3) 如前述（1)所述之紫外線硬化型硬塗層樹脂組成物，其中，防污劑（C)為具有（曱基）丙烯醯基之氟化合物； (4) 如前述（1)至（3)中任一項所述之紫外線硬化型硬塗層樹脂組成物，其中，通式（1)所示環氧樹脂（a)中R為曱基； (5) 如前述（1)至（4)中任一項所述之紫外線硬化型硬塗層樹脂組成物，復含有前述成分（A)以外之分子中具有至少3 個以上之（曱基）丙烯醯基之紫外線硬化型（曱基）丙烯酸酯 (D)； (6) 如前述（1)至（5)中任一項所述之紫外線硬化型硬塗層樹脂組成物，其復含有分子中具有2個（曱基）丙烯醯基之環氧（曱基）丙烯酸酯（E-1)及/或聚胺酯（曱基）丙烯酸酯 (E-2)； (7) 如前述（1)至（6)中任一項所述之紫外線硬化型硬塗層樹脂組成物，其復含有具有1至2個（曱基）丙烯醯基之反應性稀釋劑（F); (8) 如前述（1)至（7)中任一項所述之紫外線硬化型硬塗層 322297 201120156 樹脂組成物，其復含有稀釋劑（G); (9) 一種硬塗層膜，係具有如前述（1)至（8)中任一項所述之紫外線硬化型硬塗層樹脂組成物之硬化層； (10) —種碌塗層成形物，係具有如前述（〇至（8)中任一項所述之紫外線硬化型硬塗層樹腌組成物之硬化層。 (發明之效果）藉由本發明可提供一種紫外線硬化型硬塗層樹脂組成物，其具有良好硬度、透明性、防污性、拉伸性、以及柔軟性。再者亦提供具有此硬化層之硬塗層膜以及硬塗層成形物。本發明之紫外線硬化型硬塗層樹脂組成物是適合作為膜嵌入成形中之成形膜使用。【實施方式】以下，詳細說明本發明。本發明之紫外線硬化型硬塗層樹脂組成物（以下，稱為「樹脂組成物j )是使用通式（1)所示環氧樹脂（a)以及（甲基）丙烯酸（b)反應所得之分子中具有至少3個以上（甲基）丙烯醯基之環氧（曱基）丙烯酸酯（A)。(wherein R is the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and η represents a positive number of the average of 1 to 20). (2) Ultraviolet rays as described in the above (1) The hardening type hard coat resin composition, wherein the antifouling agent (C) is a polyfluorene oxide having a (fluorenyl) acrylonitrile group; (3) the ultraviolet curable hard coat resin as described in the above (1) The composition, wherein the antifouling agent (C) is a fluorochemical compound having a (fluorenyl) acrylonitrile group; (4) The ultraviolet curable hard coat resin according to any one of the above (1) to (3) In the epoxy resin (a) of the formula (1), R is a mercapto group; (5) The ultraviolet curable hard coat resin according to any one of the above (1) to (4) a composition comprising an ultraviolet curable (mercapto) acrylate (D) having at least three (fluorenyl) acrylonitrile groups in a molecule other than the component (A); (6) as described in (1) above (5) The ultraviolet curable hard coat resin composition according to any one of the invention, which further comprises an epoxy (fluorenyl) acrylate having two (fluorenyl) acrylonitrile groups in the molecule The ultraviolet curable hard coat resin composition according to any one of the above (1) to (6), which is characterized in that it is an E1) and/or a polyurethane (mercapto) acrylate (E). A reactive diluent (F) having 1 to 2 (fluorenyl) acrylonitrile groups; (8) The ultraviolet curable hard coat layer 322297 according to any one of the above (1) to (7), 201120156 And a resin composition comprising the ultraviolet curable hard coat resin composition according to any one of the above (1) to (8). (10) The hardened layer of the ultraviolet curable hard coat dendritic composition according to any one of the above (A). (Effect of the invention) According to the present invention, there is provided an ultraviolet curable hard coat resin composition which has good hardness, transparency, antifouling property, stretchability, and flexibility. Further, a hard coat film having the hardened layer is provided. Hard coat molded article. The ultraviolet curable hard coat resin composition of the present invention is suitable as a formed film in film insert molding. [Embodiment] The present invention will be described in detail below. The ultraviolet curable hard coat resin composition of the present invention (hereinafter referred to as "resin composition j") is an epoxy resin represented by the general formula (1). And an epoxy (fluorenyl) acrylate (A) having at least three (meth)acryl fluorenyl groups in the molecule obtained by the reaction of (meth)acrylic acid (b).

(式中，R是相同或相異，表示氫原子、鹵原子或碳數i至 4之烴基，η表示平均值1至20之正數。）通式（1)中碳數1至4之烴基，可為碳數1至4之飽和 322297 9 201120156 烴基或碳數2至4之錢和烴基，料直鏈、分支鍵或環狀皆可。具體上’可列舉如：曱基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、環丙基、環丁基、乙烯基、丙烯基、異丙烯基等。通式（1)所不環氧樹脂（a)中，R全部為氫原子者，或是甲基者為佳。-般而言，R全部為氫原子者可藉由曰本化藥EPPN-200系列，又，R全部為曱基者，同樣的玎藉由曰本化藥E0CN系列而獲得。、本發明中，通式（1)所示環氧樹脂（a)之R全部是甲基· 者為較佳。與R全部為氫原子者相比較，硬化物〆面保持良好之伸展度，同時可實現高硬度。通式（1)所示之環氧樹脂（&)之11平均值為丨至2〇。本發明中，n以1至15為佳，以5至12為更佳。本發明製造所使用之分子中具有至少3個以上（甲基）丙埽醯基之環氧（曱基）丙婦酸醋（A)時之化反應，相 2 1當量之環氧樹脂⑷之環氧基，（甲基）丙稀酸⑻之、、吻叶以90至12G當量％為佳。於此範圍内就可在比較安定 ^条件下製造。（甲基）丙稀酸（b)添加量過多時，過，（甲基）丙烯酸（b)會剩餘下來因而不佳。个後-日—…下反貞， _ ^釋而反應。本發财可使用之_，酿化，應不活性之溶劑即可並無特別料。較佳之^使用量得之樹脂之黏度及用途而適當，; (分子中具有至少3個以上（甲基）丙軸基之環氧（甲基） 10 322297 201120156 丙烯酸酯（A))為使用30至90質量％，較佳為50至80質量％之方式使用溶劑。作為前述溶劑使用者之具體例，可列舉如：甲苯、二曱苯、乙基苯及四甲基苯等芳香族系烴溶劑、己烷、辛烷、及癸烷等脂肪族系烴溶劑、以及該等之混合物之石油醚、無錯汽油（white gasoline)、及溶劑石油腦（solvent naphtha)等。此外，酯系溶劑可列舉如：醋酸乙酯、醋酸丙酯、及醋酸丁酯等烷基醋酸酯類、及r-丁内酯等環狀酯類、乙二醇單曱醚醋酸酯、二乙二醇單曱醚單醋酸酯、二乙二醇單 ***單醋酸酯、三乙二醇單***醋單酸酯、二乙二醇單丁醚單醋酸酯、丙二醇單曱醚單醋酸酯、及丁二醇單甲醚單醋酸酯等（單或多）伸烷基二醇單烷基醚單醋酸酯類、戊二酸二烷基、丁二酸二烷基、及己二酸二烷基等多羧酸烷酯類等。此外，醚系溶劑可列舉如：二***、及乙基丁.基醚等烷基醚類、乙二醇二甲醚、乙二醇二***、二丙二醇二曱醚、二丙二醇二***、三乙二醇二甲醚、及三乙二醇二乙醚等二醇醚類、四氫呋喃等環狀醚類等。此外，酮系溶劑可列舉如：丙酮、丁酮、環己酮、及異佛爾酮（isophorone)等。反應時，為了促進反應而以使用觸媒為佳，相對於反應物，即環氧樹脂（a)、（曱基）丙烯酸（b)及由情況之溶劑其他添加物之總量觸媒之使用量，為0. 1至10質量％。此 11 322297 201120156 時之反應溫度為60至15(TC，此外反應時間以5至60小時為佳。可使用之觸媒的具體例，可列舉如：三乙胺、苯曱基二甲基胺、三乙基氯化銨、苯甲基三甲基溴化銨、苯曱基二曱基磁化録、三苯膦（triphenylphosphine)、三苯銻（triphenylstibine) '曱基三苯銻、辛酸鉻，及辛酸鍅等已知一般之驗性觸媒等。此外’熱聚合抑制劑以使用對苯二酚單曱醚 (hydroquinone monomethyl ether)、2-甲基對苯二紛、對本一酚、一本基苦味醯耕（(11卩1161^1卩1(：^111丫(1『&2丨116)、二苯基胺及3, 5-二-第三丁基-4-曱酚為佳。本反應一邊適當取樣，一邊使樣品之酸價成為在5mg KOH/g以下，較佳是成為2mgK0H/g以下之時間點當作終點。由此所得之分子中具有至少3個以上（曱基）丙烯醯基之環氧（甲基）丙烯酸酯（A)之較佳分子量範圍，藉由GPC(凝膠滲透層析法）聚苯乙烯換算質量平均分子量為；[，〇〇〇至 30, 000之範圍，以5, 000至15, 000為較佳。此外，該等可單獨使用，亦可混合複數種後使用。本發明之紫外線硬化型硬塗層樹脂組成物中，於1〇〇質量％之（人）、（Β)、（C)、（D)、（Ε)及（F)成分之總量（以下簡稱「總量」）中’前述（Α)成分之含量通常為5至99. 9質量％，以10至99質量％為佳。不使用後述（D)成分、及/ 或（E)成分、及/或（F)成分、及/或（G)時，（A)成分之含量通常為80至99· 9質量％，以90至99質量％為佳。使用後述（D)成分、及/或（e)成分、及/或（F)成分、及/或（g) 12 322297 201120156 時’通常為5至95質量％，以l〇至90質量％為佳。本發明之紫外線硬化型硬塗層樹脂組成物是使用光自由基聚合起始劑（B)。光自由基聚合起始劑（B)可列舉如：安息香（benzoin)、安息香甲醚、安息香***、安息香丙醚、及安息香異丁醚等安息香類；笨乙酮、2, 2-二乙氧基一2-苯基苯乙酮、1，卜二氯苯乙酮、2_羥基_2_甲基_苯基丙―卜酉同、一乙氧基苯乙酮、1_經基環己基苯基酮、及曱基 -1-(4-(曱硫基）苯基）-2-(4-嗎啉基）—卜丙酮等苯乙酮類；2-乙基蒽醌、2-第三丁基蒽醌、2-氣蒽醌、及2_戊基蒽醌等蒽醌類；2, 4-二乙基噻吨酮、2-異丙基噻吨酮、及 2-氣嗜吨酮等β塞吨酮類；苯乙g同二曱基縮酮、及苯曱基二甲基縮酮等縮酮類；二苯曱酮、4_苯曱醯基_4，_甲基二苯硫醚、及4, 4’-雙甲基胺基苯曱醯苯等二苯甲酮類；氧化 2’ 4, 6-三甲基苯甲醯基二苯基膦、及氧化雙（2, 4, 6_三甲基苯甲醯基）-苯基膦等氧化膦類。此外，具體的，由市面上可容易獲得Ciba speciaity chemicals公司製 IRGACURE184(1-羥基環己基苯基酮）、IRGACURE9〇7(2_甲基 -1 -（4-(甲硫基）苯基）—2-(4-嗎啉基）一卜丙酮）及BASF公司製1^(^1^11丁？〇(氧化2,4,6-三曱基苯甲醯基二苯基膦）等。此外’該等可單獨使用，亦可混合2種以上後使用。本發明之紫外線硬化型硬塗層樹脂組成物中，於前述總量中，前述（B)成分之含量通常為〇.丨至2〇質量％，以 1至10質量％為佳。本發明之紫外線硬化型硬塗層樹脂組成物中，必要時 13 322297 201120156 可併用增感劑。可使用之增感劑，可列舉如：蒽 (anthracene)、9, 10-二曱氧基蒽、9, 10-二乙氧基蒽、9, 10-二丙氧基蒽、2-乙基-9, 10-二曱氧基蒽、2-乙基-9, 10-二乙氧基.葱、2 -乙基-9，10-二丙氧基,C、2_乙基_9，10-二（曱氧基乙氧基）蒽、荞、芘、二苯乙烯、4’ -硝基苯甲基-9, 10-二甲氧基蒽-2-磺酸酯、及4’-硝基苯甲基-9, 10-二乙氧基蒽-2-磺酸酯、及4’ -硝基苯甲基-9, 10-二丙氧基蒽-2-磺酸酯等，由溶解性及對紫外線硬化型硬塗層樹脂組成物之相溶性之觀點來看，以2-乙基-9, 10-二（曱氧基乙氧基）蒽為佳。使用增感劑時，相對於100質量％之光自由基聚合起始劑（B)，其使用量為1至200質量％，以5至150質量％為佳。本發明之紫外線硬化型硬塗層樹脂組成物包含有防污劑（C)。防污劑（C)可列舉如：聚石夕氧系化合物、氟系化合物、及丙烯酸系化合物等。藉由該防污劑之防污功能，可賦予撥水•撥油性等、提升痕跡擦拭性及指紋擦拭性等。此外，除了防污功能以外，提升加工性之塗平性、光滑性以及耐刮傷性，丙烯酸系化合物更可賦予再塗裝性等。前述防污劑（C)之聚矽氧系化合物，以具有（曱基）丙烯醯基之聚矽烷氧為佳。具有（曱基）丙烯醯基之聚矽烷氧也稱為聚矽氧丙烯酸酯、有機改質聚矽氧、有機改質聚矽烷氧，或是反應結合型有機改質聚矽氧丙烯酸酯等。具有（曱基）丙烯醯基之聚矽烷氧可列舉如：直鏈型二曱基聚矽烷氧 14 322297 201120156 之一部伤以烧基或聚鱗專有機改質，此改質末端上賦予丙 • 烯酸酯基者。藉由延長矽烷氧之長度，可提升表面光滑， •• 賦予離型性、耐結塊性等。其他，痕跡及指紋之擦拭也變得容易。此外，藉由提高有機改質率（（甲基）丙烯酸酯改質及聚趟改質之程度），可提升相溶性、再塗裝性（再塗布性）、印刷性。又，藉由導入丙烯醯基，變成可反應結合，可降低朝界面之移動性，藉由與基底樹脂反應可提升長期性能安定性。再者’可提升耐藥品性（鹼性溶液、有機溶劑等）。作為此等具有（甲基）丙烯醯基之聚矽烷氧者，例如：(wherein R is the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group having a carbon number of i to 4, and η represents a positive number of the average of 1 to 20.) A hydrocarbon group having 1 to 4 carbon atoms in the formula (1) It may be a saturated carbon number of 1 to 4, 322297 9 201120156 hydrocarbon group or carbon number 2 to 4 and a hydrocarbon group, which may be linear, branched or cyclic. Specifically, 'exemplified are: mercapto, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, cyclopropyl, cyclobutyl, vinyl, Propylene, isopropenyl and the like. In the epoxy resin (a) which is not in the formula (1), it is preferred that all of R is a hydrogen atom or a methyl group. In general, those in which R is a hydrogen atom can be obtained by the EPPN-200 series, and all of R are sulfhydryl groups, and the same oxime is obtained by the E0CN series. In the present invention, it is preferred that all of R of the epoxy resin (a) represented by the formula (1) is a methyl group. Compared with those in which R is all a hydrogen atom, the hardened surface maintains a good degree of elongation while achieving high hardness. The average value of 11 of the epoxy resin (&) represented by the formula (1) is 丨 to 2 〇. In the present invention, n is preferably from 1 to 15, more preferably from 5 to 12. The invention relates to a reaction of producing epoxy (indenyl) acetoacetic acid vinegar (A) having at least three (meth) propyl fluorenyl groups in a molecule used in the production, and a phase equivalent of epoxy resin (4) The epoxy group, (meth)acrylic acid (8), and the kiss leaves are preferably 90 to 12 G equivalent%. Within this range, it can be manufactured under relatively stable conditions. When the amount of (methyl)acrylic acid (b) added is too large, (meth)acrylic acid (b) may remain and is therefore unfavorable. After - the day - ... under the rumor, _ ^ release and reaction. The money that can be used for this is _, brewing, the solvent that should be inactive can be no special. Preferably, the viscosity and the use of the resin are appropriately selected; (Epoxy (methyl) having at least 3 (methyl) propyl groups in the molecule 10 322297 201120156 Acrylate (A)) is used 30 The solvent is used in a form of 90% by mass, preferably 50 to 80% by mass. Specific examples of the solvent user include aromatic hydrocarbon solvents such as toluene, diphenylbenzene, ethylbenzene, and tetramethylbenzene, and aliphatic hydrocarbon solvents such as hexane, octane, and decane. And petroleum ether, white gasoline, and solvent naphtha of such mixtures. Further, examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate; cyclic esters such as r-butyrolactone; and ethylene glycol monoterpene ether acetate; Ethylene glycol monoterpene ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoester, diethylene glycol monobutyl ether monoacetate, propylene glycol monoterpene ether monoacetate, And butanediol monomethyl ether monoacetate (single or multiple) alkyl glycol monoalkyl ether monoacetate, dialkyl glutarate, dialkyl succinate, and adipate dioxane A polycarboxylic acid alkyl ester or the like. Further, examples of the ether solvent include alkyl ethers such as diethyl ether and ethyl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dioxime ether, dipropylene glycol diethyl ether, and three. Glycol ethers such as ethylene glycol dimethyl ether and triethylene glycol diethyl ether; and cyclic ethers such as tetrahydrofuran. Further, examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone. In the reaction, it is preferred to use a catalyst for promoting the reaction, and the use of the total amount of the catalyst relative to the reactants, that is, the epoxy resin (a), (mercapto)acrylic acid (b), and other additives of the solvent.至质量质量。 The amount, from 0.1 to 10% by mass. The reaction temperature of this 11 322297 201120156 is 60 to 15 (TC, and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst which can be used include, for example, triethylamine and benzoguanamine. , triethylammonium chloride, benzyltrimethylammonium bromide, benzoyldifluorenyl magnetic record, triphenylphosphine, triphenylstibine 'mercaptotriphenyl sulfonium, chromium octoate, And known as general bismuth octanoate, etc. In addition, 'thermal polymerization inhibitors use hydroquinone monomethyl ether, 2-methyl-p-benzoic acid, p-phenol, one Bitter bitter cultivating (11卩1161^1卩1(:^111丫(1『&2丨116), diphenylamine and 3,5-di-t-butyl-4-nonanol is preferred The reaction is appropriately sampled, and the acid value of the sample is set to be 5 mg KOH/g or less, preferably 2 mg K0H/g or less, as the end point. The thus obtained molecule has at least 3 or more a preferred molecular weight range of the acryl(yl) acrylate (meth) acrylate (A) by GPC (gel permeation chromatography) polystyrene conversion The mass average molecular weight is [; 〇〇〇 to 30,000, preferably 5,000 to 15,000. Further, these may be used singly or in combination of plural kinds. The total amount of (human), (Β), (C), (D), (Ε) and (F) components in the type of hard-coating resin composition (hereinafter referred to as "total amount") The content of the above-mentioned (Α) component is usually from 5 to 99.9% by mass, preferably from 10 to 99% by mass. The component (D), and/or (E) component, and/or (F) described later are not used. In the case of the component and/or (G), the content of the component (A) is usually from 80 to 99.9% by mass, preferably from 90 to 99% by mass. The component (D) and/or the component (e) described later are used. And/or (F) component, and/or (g) 12 322297 201120156 'usually 5 to 95% by mass, preferably 10% to 90% by mass. The ultraviolet curable hard coat resin composition of the present invention The photoradical polymerization initiator (B) is used. The photoradical polymerization initiator (B) may, for example, be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and Benzoin such as isobutyl ether; acetophenone, 2, 2-diethoxy- 2-phenylacetophenone, 1, dichloroacetophenone, 2-hydroxy-2-methyl-phenyl Propionate, monoethoxyacetophenone, 1-cyclohexyl phenyl ketone, and mercapto-1-(4-(indolylthio)phenyl)-2-(4-morpholinyl) ) - acetophenones such as acetone; 2-ethyl hydrazine, 2-tert-butyl fluorene, 2-gas oxime, and 2 pentyl hydrazine; 2, 4- 2 β thioxanthone such as thioxanthone, 2-isopropyl thioxanthone, and 2-oxo-tonone; ketethylene ketone, dimethyl ketal, and benzoquinone dimethyl ketal Classes; benzophenones, 4-benzoinyl-4, _methyldiphenyl sulfide, and benzophenones such as 4,4'-bismethylaminophenyl benzene; oxidation 2' 4 , 6-trimethylbenzimidyl diphenylphosphine, and oxidized phosphines such as bis(2,4,6-trimethylbenzylidene)-phenylphosphine. Further, specifically, IRGACURE 184 (1-hydroxycyclohexyl phenyl ketone) and IRGACURE 9 〇 7 (2-methyl-1 -(4-(methylthio)phenyl), which are manufactured by Ciba Speciaity Chemical Co., Ltd., are commercially available. 2-(4-morpholinyl)-propanone) and 1^(^1^11??(oxidized 2,4,6-trimercaptobenzylidene diphenylphosphine) manufactured by BASF Corporation. In addition, these may be used alone or in combination of two or more. In the ultraviolet curable hard coat resin composition of the present invention, the content of the component (B) is usually 〇. 2% by mass, preferably 1 to 10% by mass. The ultraviolet curable hard coat resin composition of the present invention may be used in combination with a sensitizer if necessary. 13 322297 201120156 A sensitizer may be used, and examples thereof include: Anthracene, 9, 10-dimethoxy oxime, 9, 10-diethoxy fluorene, 9, 10-dipropoxy fluorene, 2-ethyl-9, 10-dimethoxy fluorene, 2-ethyl-9, 10-diethoxy. Onion, 2-ethyl-9,10-dipropoxy, C, 2-ethyl-9,10-di(decyloxyethoxy)蒽, 荞, 芘, stilbene, 4'-nitrobenzyl-9, 10-dimethyl Oxime-2-sulfonate, and 4'-nitrobenzyl-9, 10-diethoxyindole-2-sulfonate, and 4'-nitrobenzyl-9, 10- Dipropoxy fluorene-2-sulfonate, etc., from the viewpoint of solubility and compatibility with the ultraviolet curable hard coat resin composition, 2-ethyl-9, 10-di(decyloxy) When the sensitizer is used, it is used in an amount of from 1 to 200% by mass, preferably from 5 to 150% by mass, based on 100% by mass of the photoradical polymerization initiator (B). The ultraviolet curable hard coat resin composition of the present invention contains the antifouling agent (C). Examples of the antifouling agent (C) include a polyoxin compound, a fluorine compound, and an acrylic compound. The antifouling function of the antifouling agent can impart water repellency, oil repellency, etc., improved trace wiping and fingerprint wiping, etc. In addition to the antifouling function, it improves the smoothness, smoothness and scratch resistance of the processability. The acrylic compound may further impart recoatability, etc. The polyoxonium compound of the antifouling agent (C) is preferably a polydecaneoxy group having a (fluorenyl) acrylonitrile group. The polydecane oxygen having a (fluorenyl) acrylonitrile group is also called polyoxy oxyacrylate, organically modified polyfluorene oxide, organically modified polydecane oxygen, or a reaction-bound organically modified polyoxy acrylate. The polydecane oxygen having a (fluorenyl) acrylonitrile group can be exemplified by a linear dimercaptopolyoxyl group 14 322297 201120156 One part of the wound is made of a burnt-based or poly-scale organic-modified, and the modified end is given to C. • Ethyl ester base. By extending the length of the decane oxygen, it can improve the surface smoothness, • Provide release property, block resistance and the like. Others, wipes of fingerprints and fingerprints have also become easier. Further, by improving the organic reforming ratio (the degree of (meth) acrylate modification and polyfluorene modification), compatibility, recoatability (recoatability), and printability can be improved. Further, by introducing an acrylonitrile group, it becomes reactively bondable, and the mobility toward the interface can be lowered, and the long-term performance stability can be improved by reacting with the base resin. Furthermore, it can improve chemical resistance (alkaline solution, organic solvent, etc.). As such polyoxyalkylene having a (meth)acryl fluorenyl group, for example:

BYK-UV3500、BYK-UV3570C 皆為 BYK-Chemie 公司製）、TEG〇 Rad 系列之 2100、2200N、2250、2500、2600、2700(皆為 Degussa 公司製）、X-22-2445、X-22-2455、X-22-2457、 [22-2458 、 X-22-2459 、 X-22-1602、X-22-1603、X-22-1615 、 X-22-1616 、 X-22-1618 、 X-22-1619 、 X-22-2404 、 X-22-2474、X-22-174DX、X-22-82(U、X-22-2426、X-22-164A 及X-22-164C(皆為信越化學工業（股份有限公司）製）等可由市面上獲得’但並非以該等為限。此外，該等可單獨使用，亦可混合2種以上後使用。此等具有（甲基）丙烯醯基之聚矽烷氧之分子量，以及 (曱基）丙烯醯基數並無特別規定，關於（曱基）丙烯醯基數以1分子中1至6個為佳，以1至3個為更佳。本發明中使用氟系化合物作為前述防污劑（C )時，以使用具有（曱基）丙烯醯基之氟化合物為佳。具有（曱基）丙烯酸基之氟化合物可列舉如：在改質全敦聚峻之末端上賦予 322297 15 201120156 (曱基）丙烯醯基者。藉由延長全氟碳之長度，以及增加氟含有量，可提升表面光滑性，可賦予離型性、耐結塊性等。此外，即使觸摸表面也不容易留下指紋，附著於表面上痕跡及指紋變得容易拭去。又，藉由提高有機改質率（（曱基）丙烯酸酯改質性及聚醚改質性之程度），可提升相溶性、再塗裝性（再塗布性）、印刷性。此外，藉由導入（曱基）丙烯酿基，變成可反應結合，可降低朝界面之移動性，藉由與基材樹脂反應也可提升長期性能安定性。再者，可提升耐藥品性（鹼性溶液、有機溶劑等）。此等作為具有（甲基）丙烯酿基之II化合物之商品者，可列舉如：Daikin工業（股份有限公司）製之 Optool DAC'Optool DAC~HP、R-lll〇、 R-1210、R-1420、R-1620、R-i82〇、r-2〇20、R-5210、R-5410、 R-5610、R-5810、R-7210 及 R_731〇等。此外，該等可單獨使用’亦可混合2種以上而使用。此等具有（曱基）丙烯醯基之氟化合物之分子量，以及 (曱基）丙烯醯基數並無特別規定，關於（曱基）丙烯醯基數以1分子中有1至2個為佳。本發明之樹脂組成物中使用具有（曱基）丙烯醯基之聚石夕烧氧時，與使用具有（甲基）丙烯醯基之氣化合物的情形相比較時，雖然硬化物表面之指紋擦拭容易度稍為差，但硬化物表面痕跡之擦拭容易度相當。再者，光滑性也較佳，硬化物表面也不容易到傷。本發明之樹脂組成物中使用具有（曱基）丙義基之氟化合物的情形，與具有（甲基）丙稀醯基之聚矽烷氧相比較時，撥油性（抵抗油質之性質）良好。 322297 16 201120156 本發明之紫外線硬化型硬塗層樹脂組成物中，於1〇〇質量％之前述總量中，前述（c)成分之含量通常為〇〇1至 10質量％，以0. 05至5質量％為佳，以至3質量％為更佳。本發明之紫外線硬化型硬塗層樹脂組成物，亦可使用前述（A)成分以外之分子中具有至少3個以上（甲基）丙烯醯基之紫外線硬化型（甲基）丙烯酸酯（D)。作為分子中具有至少3個以上（甲基）丙烯醯基之紫外線硬化型（甲基）丙烯酸酯（D)者，係以分子内具有3至個（甲基）丙烯醯基之多官能（甲基）丙烯酸酯為佳，例如，可使用具有經基之多官能（甲基）丙烯酸酯化合物與聚異氰酸醋化合物之反應物的多官能胺酯（甲基）丙烯酸酯類、三 (甲基）丙稀酸三經甲基丙烧酯、三（甲基）丙稀酸三經甲基丙院聚乙氧基酯、三（曱基）丙烯酸季戊四醇酯、四（曱基）丙烯酸季戊四醇酯、四（甲基）丙烯酸二三羥曱基丙烷酯、六（甲基）丙烯酸二新戊四醇酯、八（甲基）丙烯酸三新戊四醇醋等聚酯（甲基）丙烯酸酯類、及參（丙烯酸乙基）異氰酸酯等。作為該具有羥基之多官能（甲基）丙烯酸酯化合物者，可列舉如：三（曱基）丙烯酸新戊四醇酯、五（甲基）丙稀酸 —新戊四醇酯、四（曱基）丙烯酸二新戊四醇酯、三（曱基）丙烯酸二新戊四醇酯、二（甲基）丙烯酸二新戊四醇酯等新戊四醇酿類、三羥曱基丙烷二（甲基）丙烯酸酯等羥曱基酯類、雙酚A二環氧（曱基）丙烯酸酯等環氧（甲基）丙烯酸酯 17 322297 201120156 類等。作為較佳例子可列舉如：三（曱基）丙烯酸新戊四醇酯、五（曱基）丙烯酸二新戊四醇酯。此等多官能（曱基）丙烯酸S旨化合物可單獨使用，亦可混合2種以上而使用。該聚異氰酸酯可列舉如：以鏈狀飽和烴、環狀飽和烴、芳香族烴為基本構成之聚異氰酸酯。此種聚異氰酸酯可列舉如：四亞曱基二異氰酸酯、六亞甲基二異氰酸酯、2, 2, 4-三曱基六亞曱基二異氰酸酯等鏈狀飽和烴基異氰酸酯、異佛爾酮二異氰酸酯、二環己基曱基二異氰酸酯、亞曱基雙 (4-環己基異氰酸酯）、氫化二苯基曱基二異氰酸酯、氫化二曱苯二異氰酸酯、氫化曱苯二異氰酸酯等環狀飽和烴基異氰酸酯、2, 4-曱苯基二異氰酸酯、1，3-苯二曱基二異.氰酸酯、對伸苯基二異氰酸酯、3, 3’-二甲基-4, 4’-二伸苯基二異氰酸酯、6-異丙基-1,3-苯基二異氰酸酯、1，5-萘二異氰酸酯等芳香族多異氰酸酯。較佳之例子可列舉如：異佛爾酮二異氰酸酯、六亞甲基二異氰酸酯等。此等多異氰酸酯可單獨使用，亦可混合2種以上而使用。該多官能胺酯（曱基）丙烯酸酯可藉由將前述具有羥基之多官能（甲基）丙烯酸酯與前述多異氰酸醋反應而獲得。相對於具有羥基之紫外線硬化型多官能（曱基）丙烯酸酯中 1當量之羥基，多異氰酸酯中異氰酸酯基之當量，通常為 0. 1至50當量之範圍，以0. 1至10當量之範圍為佳。反應溫度通常為30至150°C，以50至100°C範圍為佳。反應終點為殘存之異氰酸酯與過量之正丁基胺反應，未反應之正丁基胺以1N鹽酸藉由逆滴定方法計算出殘存 18 322297 201120156 之異說酸鳝量，當多異氰酸酯化合物在0.5質量％以下時作為反應終了。為達到縮短該反應時間之目的也可添加觸媒。此觸媒可使用驗性觸媒或酸性觸媒中任一者。作為鹼性觸媒者可列舉如：°比啶、吡咯、三乙基胺、二乙基胺、二丁基胺等胺類、錢、三丁基膦及三苯基膦等膦類。此外，作為酸性觸媒者可列舉如：環烧酸銅（COpper naphthenate)、環烧酸始 '環燒酸鋅、三丁氧基鋁、四丁氧基三鈦、四丁氧基二錯等金屬烷氧化物類、氯化鋁等路易斯酸類、2-乙基己院錫、辛基錫三月桂酸酯、二丁基錫二月桂酸酯、辛基錫二醋酸酯等錫化合物。相對於1〇〇質量％之聚異氰酸酯，此等觸媒之添加量通常為〇· 1質量％以上，1質量％以下。再者’反應時以使用為了防止反應中聚合之聚合抑制劑（例如對-甲氧基苯酚（p-Methoxyphenol)、對苯二酚、甲基對苯二齡、硫代二苯胺（phenothiazine)等）為佳’相對於反應混合物，該聚合抑制劑之使用量為〇.〇1質量％以上，1質量％以下，以0. 05質量％以上，0. 5質量％以下為佳。本發明之紫外線硬化型硬塗層樹脂組成物中，使用前述（D)成分時，可單獨使用，亦可混合2種以上而使用。本發明之紫外線硬化型硬塗層樹脂組成物中，於1〇〇質量％之前述總量中，（D)成分之含量通常為0至別質量 %，使用時以10至60質量％為佳。本發明之紫外線硬化型硬塗層樹脂組成物，亦可使用 19 322297 201120156 分子中具有2個（f基）丙烯醯基之（甲基）丙烯酸酯（E)。其 _ ’以使用環氧（甲基）丙烯酸酯（E-1)及/或胺酯（甲基）丙烯酸酯（E-2)為佳。環氧（甲基）丙烯酸酯（E-1)之具體例，可列舉如：聚縮水甘油化合物（雙酚A型環氧樹脂、雙酚F型環氧樹脂、酚酚醛清漆（novolac)型環氧樹脂、參酚甲基型環氧樹脂、聚乙二醇二縮水甘油醚、甘油聚縮水醚、三羥甲基丙烷聚縮水甘油醚等）與（甲基）丙烯酸之反應物的環氧（甲基）丙烯酸類。特別是以雙酚A型環氧樹脂與丙烯酸之反應物的環氧（甲基）丙烯酸酯為佳。雙酚A之重複單元，以使用大於 1者之環氧（曱基）丙烯酸酯為較佳。此等聚縮水甘油化合物之重複單元相當多，由於有2 個（甲基）丙婦醯基，因此柔軟性佳。因此，使用環氧（甲基）丙烯酸酯（E-1)作為本發明之紫外線硬化型硬塗層樹脂組成物之（E)成分時，可賦予本發明之紫外線硬化型硬塗層樹脂組成物拉伸性、柔軟性。此種環氧樹脂與（甲基）丙烯酸反應之羧酸化反應，可與環氧（曱基）丙烯酸酯（A)之同樣製法而獲得。 fee酯（曱基）丙烯酸酯（E-2)之具體例，可列舉如乙二醇、1,4-丁二醇、聚四亞曱基二醇、新戊二醇、聚己内酯多元醇、聚酯多元醇、聚碳酸酯二醇等多元醇類，與六亞曱基二異氰酸1旨、脂環式聚異氰㈣、苯曱基二異氣酸醋、笨二曱基二異氰酸醋、4, 4，-二笨基曱基二異氰酸醋等有機聚異氰酸酯類，與2-羥乙基（曱基）丙烯酸酯、2_羥丙基（曱 322297 20 201120156 基）丙烯酸酯、1，4-丁二醇單（曱基）丙烯酸酯、2_羥乙基（甲基）丙烯酸酯之ε -己内酯加成物、新戊四醇三（甲基）丙烯酸δ旨等含有經基之乙烯性不飽和化合物類之反應物"。多元醇類、有機聚異氰酸酯類、含有羥基之乙烯性;^飽和二= 物類分別可單獨使用，亦可使用複數種。作為此種胺酯（曱基）丙烯酸酯（E-2)之較佳者，可列舉如：聚四亞甲基二醇、新戊二醇、異佛爾酮二異氮酸醋、 2-羥乙基丙烯酸酯之反應物等。此種胺酯鍵結多，由於具有2個（曱基）丙烯醯基，因此富有柔軟性。因此，使用胺酯（甲基）丙烯酸酯（Ε-2)作為本發明之紫外線硬化型硬塗層樹脂組成物之（Ε)成分使用時，可賦予本發明紫外線硬化型硬塗層樹脂組成物拉伸性、柔軟性。胺醋（甲基）丙烯酸酯（Ε-2)較佳每1當量多元醇類之羥基與1· 1至2.0當量之有機聚異氰酸酯類之異氰酸酯基反應，以在70至90t為佳，接著，每丨當量之多元醇^ 與有機聚異氰酸酯類之反應物，與1至當量含有羥美之乙烯性不飽和化合物類反應而獲得。本發明之紫外線硬化型硬塗層樹脂組成物中，使用前述（E)成分時，可單獨使用（Ε_υ成分及/或（E_2)成分，亦可2種以上混合後使用。本發明之紫外線硬化型硬塗層樹脂組成物中，於1〇〇質量％前述總量中，前述（E)成分之含量通常為〇至6〇質量％ ’使用時以5至40質量％為佳。本發明之紫外線硬化型硬塗層樹脂組成物亦可使用具 322297 21 201120156 有1至2個（甲基）丙烯醯基之反應性稀釋劑（F) β 該反應性稀釋劑可列舉如：二（甲基）丙烯酸聚乙二醇酯、二（f基）丙嫦酸三丙二醇酯、幾基三甲基乙酸新戊二醇之己内酯加成物之二（甲基）丙烯酸酯（例如：日本化藥（股份有限公司）製，KAYARAD ΗΧ-220、ΗΧ-620等）、雙酚Α之Ε0加成物之二（甲基）丙稀酸酯、二（甲基）丙烯酸 1，4一丁二醇酯、二（甲基）丙烯酸1，6-己二醇酯、二（甲基）丙烯酸1，9-壬二醇酯、（甲基）丙烯酸三環癸烷酯、（甲基）丙烯酸二環戊二烯氧基乙基酯、（甲基）丙烯酸二環戊基酯、（甲基）丙烯酸異茨基酯、（甲基）丙烯酸金剛烷酯等脂環式（甲基）丙烯酸酯類、苯基去水甘油（曱基）丙烯酸酯、 (甲基）丙烯酸苯甲基酯等具有芳香環之（甲基）丙烯酸酯類、（甲基）丙烯酸四氫呋喃酯 ' (甲基）丙烯酸嗎福啉酯等雜環（甲基）丙烯酸酯類、（〒基）丙烯酸2_羥乙基酯、（曱基）丙烯酸2-羥丙基酯、（甲基）丙烯酸4_羥丁基酯等具有羥基之（曱基）丙烯酸酯類、（曱基）丙烯酸乙基卡必醇酯等。該等可單獨使用，亦可混合2種以上而使用。本月之兔外線硬化型硬塗層樹脂組成物中，於1 〇〇質量％之前述總量中，前述（F)成分之含量通常為0至50 質量％，使用時以5至3〇質量％為佳。本發明之紫外線硬化型硬塗層樹脂組成物中亦可使用稀釋劑（G)。該稀釋劑可列舉如：τ_τ内醋、戊内醋、内曰Τ庚内醋、α -乙醢基_γ-丁内§旨、及£ -己内酯等内酯類；二卩等烷、1，2-甲氧基曱烷、二乙二醇二甲 22 322297 201120156 醚、二乙二醇二***、二乙二醇二丁醚、丙二醇單曱醚、丙二醇單***、三乙二醇二甲醚、三乙二醇二***、四乙二醇二曱醚、及四乙二醇二***等醚類；碳酸伸乙酯、及碳酸伸丙酯等碳酸酯類；丁酮、曱基異丁酮、環己酮、及苯乙酮等酮類；酚、曱酚、及二曱酚等酚類；醋酸乙酯、醋酸丁酯、乳酸乙酯、乙基纖維素醋酸酯、丁基纖維素醋酸酯、卡必醇醋酸酯、卡必醇醋酸丁酯、及丙二醇單曱基乙基醋酸酯等酯類；曱苯、二曱苯、二乙苯、及環己烷等烴類；三氯乙烧、四氯乙烧、及單氯苯（monochlorobenzene) 等鹵化煙類等、石油趟、及石油腦（petroleum naphtha) 等石油系溶劑等有機溶劑、2, 2, 3, 3-四氟丙醇等氟系醇類、全氟丁基曱基醚、及全氟丁基乙基醚等氫氟醚；曱醇、乙醇、異丙醇、及正丙醇等醇類；兼具酮和醇兩者性能之二丙酮醇（diacetone alcohol)等。該等可單獨使用，亦可混合2種以上而使用。本發明之紫外線硬化型硬塗層樹脂組成物中，相對於 100質量％之前述總量，前述（G)成分之含量通常為0至900 質量％，使用時以40至300質量％為佳。本發明之紫外線硬化型硬塗層樹脂組成物中，因應必要時在提升硬度之目的下可添加平均粒子徑為lnm以上， 200nm以下之膠體氧化矽（H)。該膠體氧化矽（H)，可作為分散膠體氧化矽於溶媒中之膠體溶液，或是未含有分散溶媒之微粉末氧化矽而使用。前述膠體氧化矽（H)之分散媒，可使用例如：曱醇、乙 23 322297 201120156 醇、異丙醇、正丁醇、二㈣醇等醇類、乙二醇等多類及其衍生物、丁酮、甲基異丁調、環己酮、二甲基乙酿胺等酮類 '㈣乙s旨、醋酸正Tg|等賴、甲苯、二甲笨等非極性溶媒、2_紅基丙烯酸§旨等丙賴自旨類及一般有機溶劑類。相對於_質量％之膠體氧㈣，分散媒之量通常為100至900質量％。此等膠體氧化石夕⑻可藉由習知方法製造或由市面上購得而使用。例如，日產化學工業股份有限公司製之·A NOSILICASOL: GMEK-ST等。平均粒徑必需要使用—以上 200mn以下者，以5nm以上1〇〇nm以下為佳以1〇咖以上 50nm以下為更佳。5nm以上lOOnm以下可確保透明性，1〇咖以上50nm以下透明性、尺寸皆可得到良好之結果。並且，平均粒徑係指凝集崩解時，可維持該粒子之最小粒徑之意思，可藉由BET法、動態光散射法、電子顯微鏡觀察等而測定膠體氧化矽（H)之平均粒徑。本發明之紫外線硬化型硬塗層樹脂組成物中，相對於 100質量％之前述總量’前述（H)成分之含量通常為〇至1〇〇質量％。再者，本發明之紫外線硬化型硬塗層樹脂組成物中，因應必要可於該紫外線硬化型硬塗層樹脂組成物中添加紫外線吸收劑、光安定劑、抗氧化劑、消泡劑、聚合抑制劑、交聯劑等’可賦予各別目的之功能性。紫外線吸收劑例如苯並三σ坐系化合物、二苯甲酮系化合物、三0井系化合物等，光安定劑例如受阻胺系化合物、苯甲酸酯系化合物等，抗 322297 24 201120156 氧化劑例如酚系化合物等，聚合抑制劑例如對-甲氧基苯酚、曱基對苯二酚、對苯二酚等，消泡劑例如聚矽氧系化合物等，交聯劑例如前述聚異氰酸酯類、三聚氰胺化合物等。再者，本發明之紫外線硬化型硬塗層樹脂組成物中，因應必要時可使染料或顏料分散，可能使著色。本發明之紫外線硬化型硬塗層樹脂組成物，可藉由將刖述（A)成分、（b)成分、（c)成分、因應必要時（D)成分、 (E)成分、（f)成分、（G)成分及復必要時（H)成分以及其他成分’以任意順序混合而獲得。藉此所得之本發明紫外線硬化型硬塗層樹脂組成物，有經時間之安定性。本發明之硬塗層膜係藉由於基材膜上設置本發明之紫外線硬化型硬塗層樹脂組成物之硬化層而獲得。具體上，本發明之硬塗層膜可藉由於基材膜上將本發明紫外線硬化型硬塗層樹脂組成物塗布成乾燥後之膜厚通常為〇.l#m 以上50 # m以下，以1 // οι以上20 // m以下為佳，以2 # m 以上以下為較佳’經乾燥後以紫外線或電子束照射形成硬化膜而獲得。本發明中可使用之基材膜，可列舉如：聚酯、聚丙烯、聚乙烯、聚丙烯酸酯、聚碳酸酯、三醋酸纖維素、聚醚颯、環烯烴系聚合物等。使用之膜也可為設置成易接著層者、軟塗層者、施以花紋印刷或著色者、賦予耐光性及抗靜電性者、經電暈處理等表面處理者、經離塑處理者。 322297 25 201120156 對未發明之紫外線上的塗布方法，可鄉硬化型硬塗層樹脂組成物之基材膜布、凹板塗布、反式凹2 :棒塗布、線棒塗布、空氣刀塗塗布、模具塗布、_^布、微凹板塗布、微反式凹板旋轉塗布及健塗布等布、真空模具塗布、浸潰塗布、本發明之紫外線硬使用紫外線或電子切型硬塗麟脂，域物之硬化’可脂組成物藉由紫外線^切狀紫祕硬化㈣塗層樹 x t ^ 化時，可使用氙氣燈、高壓水銀燈、金^素燈等具有紫外線照射裝置作為光源，必要時對應光量、光源配置等而調整。使用高壓水銀燈時，以相對於一盞具有80至240W/cm2能量之燈，以移動速度5至60m/ 分鐘而硬化者為佳。另一方面，本發明之紫外線硬化型硬塗層樹脂組成物藉由電子束硬化時，以使用具有1 〇〇至 500eV能量之電子束加速裝置為佳。此外，本發明之紫外線硬化型硬塗層樹脂組成物通常於大氣中硬化，其他於以惰性氣體置換之環境中經放射線照射而硬化為佳。惰性氣體置換時，硬化時氧氣濃度在1 體積％以下，以0. 5體積％以下為佳。惰性氣體只要是對本發明紫外線硬化型硬塗層樹脂組成物之硬化無影響者即可而無特別限定，其中，尤以使用氮氣為佳。再者，本發明之硬塗層膜包含於基材上塗布多層重疊之本發明紫外線硬化型硬塗層樹脂組成物者（多層塗布）。藉由多層塗布可得到較高硬度之本發明硬塗層膜。藉此所得之本發明硬塗層膜有經歷時間變動仍保持安 322297 26 201120156 定，密著性、透明性、防污性良好，特別是硬度及伸展度間之平衡良好。因此，適合作為於折彎步驟之膜嵌入成形時使用之硬塗層膜之材料，特別適合於硬塗層膜一體成形時。本發明硬塗層成形物中所使用之成形物可藉由習知方法製造。具體上，可列舉如模具射出成形等。使用材料之具體例，可列舉如：聚乙烯、聚丙烯、聚酯、聚碳酸酯、丙烯腈-丁二烯-苯乙烯共聚物（ABS)、及聚甲基丙烯酸酯 (P丽A)等塑膠材料。其他，金屬材料亦可使用於本發明硬塗層成形物中所使用之成形物。本發明硬塗層成形物可藉由本發明硬塗層膜連同基材膜與前述成形物一體成形之方式，或剝除該硬塗層膜之基材膜，將硬塗層轉印於前述成形物之方法而獲得。藉此所得之本發明硬塗層成形物，成形物之凹凸部份、曲面部分等硬塗層無裂痕而有光澤感、透明感。再加上表面即使有痕跡或指紋也容易擦拭，具有撥油性等防污性，再者具有表面高硬度。此外，本發明之硬塗層成形物可將本發明紫外線硬化型硬塗層樹脂組成物直接塗布於成形物上。此時塗布之方法，可列舉如浸潰塗布、旋轉塗布、喷霧塗布等。此時之硬化，可使用與前述本發明紫外線硬化型硬塗層樹脂組成物之硬化相同之方法。 [實施例] 以下，藉由實施例更詳細地說明本發明，但本發明並 27 322297 201120156 非限定於該些實施例者。此外，實施例中若無特別說明者，份表示質量％。軟化點、環氧當量在以下條件測定。 1) 環氧當量：根據JIS K 7236 : 2001之方法測定。 2) 軟化點：根據JIS K 7234 : 1986之方法測定。 3) 酸價：根據JIS K 0070 : 1992之方法測定。 4) GPC測定條件是如以下。BYK-UV3500 and BYK-UV3570C are all manufactured by BYK-Chemie Co., Ltd., TMG〇Rad series 2100, 2200N, 2250, 2500, 2600, 2700 (all manufactured by Degussa), X-22-2445, X-22- 2455, X-22-2457, [22-2458, X-22-2459, X-22-1602, X-22-1603, X-22-1615, X-22-1616, X-22-1618, X -22-1619, X-22-2404, X-22-2474, X-22-174DX, X-22-82 (U, X-22-2426, X-22-164A and X-22-164C (both It is available from Shin-Etsu Chemical Co., Ltd., etc., but it is not limited to these. It can be used alone or in combination of two or more. These have (meth) propylene. The molecular weight of the polydecane oxygen of the fluorenyl group and the number of the (fluorenyl) acrylonitrile group are not particularly limited, and the number of the (fluorenyl) acrylonitrile group is preferably from 1 to 6 in 1 molecule, more preferably from 1 to 3. In the case where a fluorine-based compound is used as the antifouling agent (C) in the present invention, a fluorine compound having a (fluorenyl) acryl group is preferably used. The fluorine compound having a (fluorenyl) acrylate group may be, for example, modified. 3222 on the end of Quandeng Jujun 97 15 201120156 (Alkyl) acrylonitrile base. By extending the length of perfluorocarbon and increasing the fluorine content, the surface smoothness can be improved, and the release property, blocking resistance, etc. can be imparted. It is not easy to leave fingerprints, and the traces and fingerprints attached to the surface become easy to wipe off. Moreover, by increasing the organic modification rate (the degree of (meth) acrylate modification and polyether modification), Improve compatibility, recoatability (recoatability), and printability. Further, by introducing a (mercapto) acryl-based base, it becomes reactively bondable, and the mobility toward the interface can be reduced, and reacted with the substrate resin. It is also possible to improve long-term performance stability. Further, it is possible to improve chemical resistance (alkaline solution, organic solvent, etc.). As a commodity of a compound having a (meth)acrylic base II, for example, Daikin Industries (Co., Ltd.) Optool DAC'Optool DAC~HP, R-lll〇, R-1210, R-1420, R-1620, R-i82〇, r-2〇20, R-5210, R-5410 , R-5610, R-5810, R-7210 and R_731〇, etc. In addition, these can be separate It can also be used in combination of two or more types. The molecular weight of the fluorine compound having a (fluorenyl) acrylonitrile group and the number of (fluorenyl) acrylonitrile groups are not particularly specified, and the number of (fluorenyl) acrylonitrile groups is 1 One or two of the molecules are preferred. When the polyphenol having a (fluorenyl) acrylonitrile group is used in the resin composition of the present invention, when compared with the case of using a gas compound having a (meth) acrylonitrile group, although the fingerprint of the surface of the cured product is wiped The ease of use is slightly poor, but the wiping surface marks are easily wiped. Furthermore, the smoothness is also good, and the surface of the cured product is not easily damaged. When a fluorine compound having a (fluorenyl)propenyl group is used in the resin composition of the present invention, the oil repellency (the property against oil quality) is good when compared with the polyalkylene oxide having a (meth) propyl fluorenyl group. 。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。 It is preferably 5 mass%, and even more preferably 3 mass%. The ultraviolet curable hard coat resin composition of the present invention may be an ultraviolet curable (meth) acrylate (D) having at least three (meth) acrylonitrile groups in a molecule other than the component (A). . As the ultraviolet curable (meth) acrylate (D) having at least three (meth) acryl fluorenyl groups in the molecule, it is a polyfunctional group having 3 to (meth) acryl fluorenyl groups in the molecule (A) Acrylate is preferred, for example, a polyfunctional amine ester (meth) acrylate having a reaction of a polyfunctional (meth) acrylate compound with a polyisocyanate compound, and a tris (A) can be used. Trimethoprimic acid propyl propyl acrylate, tris (methyl) acrylic acid trimethoate polyethoxylate, tris(decyl)acrylic acid pentaerythritol ester, tetrakis(decyl) pentylene glycol acrylate Poly (meth) acrylates such as ditrihydroxydecylpropanyl tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tricate And ginseng (ethyl acrylate) isocyanate. Examples of the polyfunctional (meth) acrylate compound having a hydroxyl group include, for example, neopentyl glycol tris(decyl)acrylate, penta(methyl)acrylic acid-nepentaerythritol ester, and tetrakis(曱). Neopentyl glycol acrylate, tris(decyl) dipentaerythritol acrylate, dipentaerythritol di(meth) acrylate, etc., pentaerythritol, tris(hydroxy) propane Epoxy (meth) acrylates such as hydroxy hydroxy esters such as methyl acrylate and bisphenol A bis (decyl) acrylate 17 322297 201120156 and the like. Preferred examples thereof include neopentyl glycol (tris(meth))acrylate and dineopentaerythritol pentoxide. These polyfunctional (fluorenyl) acrylate S compounds may be used singly or in combination of two or more. The polyisocyanate may, for example, be a polyisocyanate having a basic structure of a chain saturated hydrocarbon, a cyclic saturated hydrocarbon or an aromatic hydrocarbon. Examples of such a polyisocyanate include a chain saturated saturated isocyanate such as tetradecyl diisocyanate, hexamethylene diisocyanate, 2, 2, 4-trimethylhexaadecyl diisocyanate, and isophorone diisocyanate. a cyclic saturated hydrocarbyl isocyanate such as dicyclohexyldecyl diisocyanate, fluorenylene bis(4-cyclohexyl isocyanate), hydrogenated diphenyl decyl diisocyanate, hydrogenated diphenylene diisocyanate or hydrogenated phthalic acid diisocyanate, 2 , 4-nonylphenyl diisocyanate, 1,3-benzenedidecyl diiso. cyanate, p-phenylene diisocyanate, 3, 3'-dimethyl-4, 4'-diphenylene An aromatic polyisocyanate such as isocyanate, 6-isopropyl-1,3-phenyl diisocyanate or 1,5-naphthalene diisocyanate. Preferable examples thereof include isophorone diisocyanate and hexamethylene diisocyanate. These polyisocyanates may be used singly or in combination of two or more. The polyfunctional amine ester (mercapto) acrylate can be obtained by reacting the aforementioned polyfunctional (meth) acrylate having a hydroxyl group with the aforementioned polyisocyanate. The range of 0.1 to 10 equivalents, in the range of 0.1 to 50 equivalents, in the range of 0.1 to 50 equivalents, in the range of 0.1 to 50 equivalents, in the range of 0.1 to 50 equivalents, in an amount of from 0.1 to 50 equivalents per equivalent of the hydroxyl group of the ultraviolet-curable polyfunctional (fluorenyl) acrylate having a hydroxyl group. It is better. The reaction temperature is usually from 30 to 150 ° C, preferably from 50 to 100 ° C. The end point of the reaction is the reaction of the remaining isocyanate with an excess of n-butylamine, and the unreacted n-butylamine is calculated by reverse titration with 1N hydrochloric acid to calculate the amount of residual acid yttrium 18 322297 201120156 when the polyisocyanate compound is at 0.5 mass. When it is less than %, it is the end of the reaction. A catalyst may also be added for the purpose of shortening the reaction time. This catalyst can use either an organic catalyst or an acidic catalyst. The basic catalyst may, for example, be a phosphine such as an amine such as pyridine, pyrrole, triethylamine, diethylamine or dibutylamine, or a phosphine such as tributylphosphine or triphenylphosphine. Further, examples of the acidic catalyst include, for example, COpper naphthenate, sulphuric acid-starting zinc sulphonate, tributoxyaluminum, tetrabutoxytrititanium, tetrabutoxy pentoxide, and the like. A Lewis compound such as a metal alkoxide or a Lewis acid such as aluminum chloride; a tin compound such as 2-ethylhexyl tin, octyltin trilaurate, dibutyltin dilaurate or octyltin diacetate. The amount of these catalysts added is usually 〇·1 mass% or more and 1 mass% or less with respect to 1% by mass of the polyisocyanate. Further, 'in the reaction, a polymerization inhibitor for preventing polymerization in the reaction (for example, p-Methoxyphenol, hydroquinone, methyl p-benzoate, phenothiazine, etc.) is used. 5质量百分比以下。 Preferably, the amount of the polymerization inhibitor is preferably 5% by mass or more, and 1% by mass or less, preferably 0.05% by mass or more, 0.5% by mass or less. In the ultraviolet curable hard coat resin composition of the present invention, when the component (D) described above is used, it may be used singly or in combination of two or more. In the ultraviolet curable hard coat resin composition of the present invention, the content of the component (D) is usually from 0 to 9% by mass, and preferably from 10 to 60% by mass, based on 1% by mass of the total amount. . The ultraviolet curable hard coat resin composition of the present invention may also be a (meth) acrylate (E) having two (f-group) acrylonitrile groups in the molecule of 19 322 297 201120156. Preferably, _ ' is preferably epoxy (meth) acrylate (E-1) and/or urethane (meth) acrylate (E-2). Specific examples of the epoxy (meth) acrylate (E-1) include polyglycidyl compounds (bisphenol A type epoxy resin, bisphenol F type epoxy resin, and novolac novolac type ring). Epoxy resin (reactive resin, phenolic methyl epoxy resin, polyethylene glycol diglycidyl ether, glycerol polyether ether, trimethylolpropane polyglycidyl ether, etc.) and (meth)acrylic acid Methyl) acrylic. In particular, an epoxy (meth) acrylate which is a reactant of a bisphenol A type epoxy resin and acrylic acid is preferred. The repeating unit of bisphenol A is preferably an epoxy (fluorenyl) acrylate having more than one. These polyglycidyl compounds have a relatively large number of repeating units, and since they have two (meth) butyl sulfonyl groups, they are excellent in softness. Therefore, when the epoxy (meth) acrylate (E-1) is used as the component (E) of the ultraviolet curable hard coat resin composition of the present invention, the ultraviolet curable hard coat resin composition of the present invention can be imparted. Stretchability and softness. The carboxylation reaction of the epoxy resin with (meth)acrylic acid can be carried out in the same manner as in the epoxy (fluorenyl) acrylate (A). Specific examples of the ester (mercapto) acrylate (E-2) include, for example, ethylene glycol, 1,4-butanediol, polytetramethylene glycol, neopentyl glycol, and polycaprolactone. Polyols such as alcohols, polyester polyols, and polycarbonate diols, and hexamethylene diisocyanate, alicyclic polyisocyanate (tetra), benzoquinone diiso-sour acid vinegar, stupid base Organic polyisocyanates such as diisocyanate, 4, 4,-di-p-mentyl diisocyanate, and 2-hydroxyethyl (decyl) acrylate, 2-hydroxypropyl (曱322297 20 201120156 Acrylate, 1,4-butanediol mono(indenyl) acrylate, 2-hydroxyethyl (meth) acrylate ε-caprolactone adduct, neopentyl alcohol tris(methyl) Acrylic acid δ is intended to contain a reactant of a vinyl group-containing ethylenically unsaturated compound. Polyols, organic polyisocyanates, and hydroxyl groups containing hydroxyl groups; and saturated two = species may be used singly or in combination. Preferred examples of such an amine ester (mercapto) acrylate (E-2) include polytetramethylene glycol, neopentyl glycol, isophorone diisoxamate, and 2-. A reaction of hydroxyethyl acrylate or the like. Such an amine ester has a large number of bonds and is rich in flexibility because it has two (fluorenyl) acrylonitrile groups. Therefore, when the amine ester (meth) acrylate (Ε-2) is used as the (Ε) component of the ultraviolet curable hard coat resin composition of the present invention, the ultraviolet curable hard coat resin composition of the present invention can be imparted. Stretchability and softness. The amine vinegar (meth) acrylate (Ε-2) is preferably reacted with from 1 to 1 to 2.0 equivalents of an organic polyisocyanate isocyanate group per 1 equivalent of the hydroxyl group of the polyol, preferably from 70 to 90 t, and then, The reaction product of each equivalent of the polyol and the organic polyisocyanate is obtained by reacting 1 to equivalent of a hydroxy-containing ethylenically unsaturated compound. In the ultraviolet curable hard coat resin composition of the present invention, when the component (E) is used, the component (Ε_υ component and/or (E_2) component may be used alone or in combination of two or more. In the above-mentioned total amount of the above-mentioned (E) component, the content of the above-mentioned (E) component is usually from 〇 to 6〇% by mass in the type of the hard-coating resin composition, and it is preferably from 5 to 40% by mass in use. The ultraviolet curable hard coat resin composition may also be used as a reactive diluent (F) β having 1-2297 (meth) acryl fluorenyl group having 322297 21 201120156. The reactive diluent may be, for example, di(methyl) a poly(ethylene glycol) acrylate, a bis(f)propionate tripropylene glycol ester, a di(meth) acrylate of a caprolactone adduct of a trimethylglycolic acid neopentyl glycol (for example: Nipponization) Pharmaceutics Co., Ltd., KAYARAD ΗΧ-220, ΗΧ-620, etc.), bisphenol ruthenium oxime 0 bis(methyl) acrylate, di(meth) acrylate 1,4 butyl Alcohol ester, 1,6-hexanediol di(meth)acrylate, di(meth)acrylic acid 1 9-decanediol ester, tricyclodecyl (meth)acrylate, dicyclopentadienyloxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate, (meth)acrylic acid An aromatic ring such as an alicyclic (meth) acrylate such as an isotyl ester or an adamantyl (meth) acrylate, a phenyl dehydroglycerin (mercapto) acrylate or a benzyl (meth) acrylate Heterocyclic (meth) acrylates such as (meth) acrylates, tetrahydrofuran (meth) acrylates, and hydroxyethyl (meth) acrylates; a mercapto (mercapto) acrylate having a hydroxyl group such as 2-hydroxypropyl acrylate or 4-hydroxybutyl (meth) acrylate, etc., such as ethyl carbitol acrylate. In the above-mentioned rabbit outer-line hardening type hard-coating resin composition, the content of the above-mentioned (F) component is usually 0 to 1% by mass of the total amount of the above-mentioned (F) component. 50% by mass, preferably 5 to 3% by mass in use. The ultraviolet curing type hard coating of the present invention A diluent (G) may also be used in the resin composition, and examples of the diluent include: τ_τ internal vinegar, pentane vinegar, vinegar vinegar, α-ethinyl γ-butane §, and £ - lactones such as caprolactone; dioxane, 1,2-methoxydecane, diethylene glycol dimethyl 22 322297 201120156 ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, Ethylene glycol monoethyl ether, propylene glycol monoethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dioxime ether, and ethers such as tetraethylene glycol diethyl ether; ethyl carbonate, and carbonic acid Carbonic esters such as propyl ester; ketones such as methyl ethyl ketone, decyl isobutyl ketone, cyclohexanone, and acetophenone; phenols such as phenol, indophenol, and diterpene; ethyl acetate, butyl acetate, Ethyl lactate, ethyl cellulose acetate, butyl cellulose acetate, carbitol acetate, butyl ketone acetate, and propylene glycol monodecyl ethyl acetate; benzene, diphenyl Hydrocarbons such as diethylbenzene and cyclohexane; halogenated tobacco such as trichloroethane, tetrachloroethane, and monochlorobenzene, petroleum sputum, and petroleum brain (petrole) Um naphtha) such as an organic solvent such as a petroleum solvent, a fluorine-based alcohol such as 2, 2, 3, 3-tetrafluoropropanol, a perfluorobutyl decyl ether, or a hydrofluoroether such as perfluorobutyl ethyl ether; Alcohols such as decyl alcohol, ethanol, isopropanol, and n-propanol; diacetone alcohol having both ketone and alcohol properties. These may be used singly or in combination of two or more. In the ultraviolet curable hard coat resin composition of the present invention, the content of the component (G) is usually from 0 to 900% by mass, and preferably from 40 to 300% by mass, based on 100% by mass of the total amount. In the ultraviolet curable hard coat resin composition of the present invention, colloidal cerium oxide (H) having an average particle diameter of 1 nm or more and 200 nm or less can be added for the purpose of improving hardness as necessary. The colloidal cerium oxide (H) can be used as a colloidal solution of a dispersed colloidal cerium oxide in a solvent or a fine powder of cerium oxide which does not contain a dispersing solvent. As the dispersion medium of the colloidal cerium oxide (H), for example, an alcohol such as decyl alcohol, ethylene 23 322297 201120156 alcohol, isopropyl alcohol, n-butanol or di(tetra)ol, or a plurality of derivatives such as ethylene glycol, and derivatives thereof can be used. Ketones such as butanone, methyl isobutylate, cyclohexanone, and dimethyletheneamine (4) Ethyl acetate, Tg/acetic acid, etc., non-polar solvent such as toluene, dimethicone, and 2-erythritol § The purpose of the general purpose and general organic solvents. The amount of the dispersion medium is usually from 100 to 900% by mass based on _% by mass of the colloidal oxygen (iv). These colloidal oxidized oxides (8) can be produced by a conventional method or commercially available. For example, A NOSILICASOL manufactured by Nissan Chemical Industries Co., Ltd.: GMEK-ST. The average particle diameter must be used—up to 200 nm or less, preferably 5 nm or more and 1 〇〇 nm or less, preferably 1 〇 coffee or more and 50 nm or less. 5 nm or more and 100 nm or less can ensure transparency, and the transparency and size of 1 〇 or more and 50 nm or less can obtain good results. Further, the average particle diameter means that the minimum particle diameter of the particles can be maintained when the aggregate is disintegrated, and the average particle diameter of the colloidal cerium oxide (H) can be measured by a BET method, a dynamic light scattering method, an electron microscope observation or the like. . In the ultraviolet curable hard coat resin composition of the present invention, the content of the above (H) component is usually from 〇 to 1% by mass based on 100% by mass of the total amount. Further, in the ultraviolet curable hard coat resin composition of the present invention, an ultraviolet absorber, a light stabilizer, an antioxidant, an antifoaming agent, and a polymerization inhibitor may be added to the ultraviolet curable hard coat resin composition as necessary. Agents, cross-linking agents, etc. can impart functionality for each purpose. The ultraviolet absorber is, for example, a benzotriazine compound, a benzophenone compound, a ternary compound, or the like, a light stabilizer such as a hindered amine compound or a benzoate compound, and the like, 322297 24 201120156 oxidizing agent such as phenol a compound or the like, a polymerization inhibitor such as p-methoxyphenol, mercaptohydroquinone or hydroquinone, an antifoaming agent such as a polyoxo compound, and a crosslinking agent such as the above polyisocyanate or melamine compound. Wait. Further, in the ultraviolet curable hard coat resin composition of the present invention, the dye or the pigment may be dispersed as necessary, and coloring may occur. The ultraviolet curable hard coat resin composition of the present invention can be described by (A) component, (b) component, (c) component, and if necessary (D) component, (E) component, (f) The component, the component (G), and the component (H) and other components when necessary are mixed in an arbitrary order. The ultraviolet curable hard coat resin composition of the present invention thus obtained has a stability over time. The hard coat film of the present invention is obtained by providing a hardened layer of the ultraviolet curable hard coat resin composition of the present invention on a substrate film. Specifically, the hard coat film of the present invention can be obtained by applying the ultraviolet curable hard coat resin composition of the present invention to a film thickness after drying, and the film thickness is usually 〇.l#m or more and 50#m or less. 1 // οι is above 20 // m is preferred, and 2 # m or more is preferred. After drying, it is obtained by ultraviolet or electron beam irradiation to form a cured film. The base film which can be used in the present invention may, for example, be polyester, polypropylene, polyethylene, polyacrylate, polycarbonate, cellulose triacetate, polyether oxime or cycloolefin polymer. The film to be used may be a person who is provided as an easy-to-layer layer, a soft coater, a person who applies a pattern or a color, a person who imparts light resistance and antistatic property, a surface treatment such as a corona treatment, or a person who is subjected to a release treatment. 322297 25 201120156 For the coating method on the uninvented ultraviolet ray, the base film cloth, the concave plate coating, the reverse concave 2: bar coating, the wire bar coating, the air knife coating, and the like can be used for the hardening type hard coating resin composition. Mold coating, _^ cloth, micro-concave coating, micro-reverse gravure coating and hard coating, vacuum die coating, dip coating, ultraviolet light hardening or electron-cut hard coating of the present invention, domain The hardening of the material's fat composition can be used as a light source by using a UV irradiation device such as a xenon lamp, a high-pressure mercury lamp or a gold lamp by using ultraviolet light, a sharp-cut purple hardening (four) coated tree, and a corresponding amount of light. Adjust the light source configuration. When a high-pressure mercury lamp is used, it is preferable to harden at a moving speed of 5 to 60 m/min with respect to a lamp having an energy of 80 to 240 W/cm2. On the other hand, when the ultraviolet curable hard coat resin composition of the present invention is cured by electron beam, it is preferred to use an electron beam acceleration device having an energy of 1 Torr to 500 eV. Further, the ultraviolet curable hard coat resin composition of the present invention is usually hardened in the atmosphere, and is preferably hardened by irradiation with radiation in an environment substituted with an inert gas. 5体积百分比以下以下。 Preferably, when the inert gas is replaced, the oxygen concentration is less than 1% by volume, preferably 0.5% by volume or less. The inert gas is not particularly limited as long as it does not affect the hardening of the ultraviolet curable hard coat resin composition of the present invention, and among them, nitrogen is particularly preferred. Further, the hard coat film of the present invention comprises a multilayer coating of the ultraviolet curable hard coat resin composition of the present invention which is coated with a plurality of layers on a substrate. The hard coat film of the present invention having a higher hardness can be obtained by multilayer coating. The hard coat film of the present invention thus obtained has a time-dependent change and remains good in adhesion, transparency, and antifouling property, and particularly has a good balance between hardness and elongation. Therefore, it is suitable as a material of the hard coat film used for the film insertion molding in the bending step, and is particularly suitable for the integrally formed hard coat film. The molded article used in the hard coat molded article of the present invention can be produced by a conventional method. Specifically, for example, mold injection molding or the like can be mentioned. Specific examples of the material to be used include polyethylene, polypropylene, polyester, polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS), and polymethacrylate (P-A). Plastic material. Alternatively, a metal material may be used for the molded article used in the hard coat molded article of the present invention. The hard coat layer of the present invention can be obtained by integrally forming a hard coat film of the present invention together with a base film and the above-mentioned molded product, or by peeling off the base film of the hard coat film, and transferring the hard coat layer to the aforementioned forming. Obtained by the method of things. In the hard-coated product of the present invention, the hard coat layer such as the uneven portion or the curved portion of the molded article has no crack and has a glossy feeling and a transparent feeling. Further, even if there are traces or fingerprints on the surface, it is easy to wipe, and it has antifouling properties such as oil repellency, and has a high surface hardness. Further, the hard coat molded article of the present invention can directly apply the ultraviolet curable hard coat resin composition of the present invention to a molded article. The method of coating at this time may, for example, be immersion coating, spin coating, spray coating or the like. In the case of hardening at this time, the same method as the hardening of the ultraviolet curable hard coat resin composition of the present invention described above can be used. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples. Further, in the examples, unless otherwise stated, the parts represent the mass%. The softening point and the epoxy equivalent were measured under the following conditions. 1) Epoxy equivalent: Measured according to the method of JIS K 7236:2001. 2) Softening point: Measured according to the method of JIS K 7234: 1986. 3) Acid value: Measured according to the method of JIS K 0070: 1992. 4) The GPC measurement conditions are as follows.

機種：TOSOH HLC-8220GPCModel: TOSOH HLC-8220GPC

管柱：TSKGEL Super HZM-N 溶離液：THF(四氫吱喃）；0. 35ml 1分鐘、溫度4〇〇c 檢測器：差動式折射計（differential refractometer) 分子量標準：聚苯乙烯實施例1 :調製環氧（甲基）丙烯酸酯（A) 於作為環氧樹脂（a)之表1中所記載之環氧樹脂（任一者皆為日本化藥製，將環氧當量、及通式（1)所示R、及n 平均值記载於表1)中，加入作為（甲基）丙烯酸（b)之丙烤酸（簡稱 AA，％=72)72g。接著’加入作為觸媒之三苯膦3g、作為溶劑之單酷酸丙二醇單甲基乙基酯，使固體成分（所得之環氧丙烯酸酯（A) 之計鼻量）成為70質量％，於100°C中反應50小時，得到裱氧丙烯酸酯（A)溶液。反應終點是由固形分酸價（AV)來決定，確認變成3mg KOH/g以下時’終止反應。酸價測定是測定反應溶液，而 28 322297 201120156 換算成固形分之酸價。表1中記載之分子量是藉由GPC經聚苯乙烯換算質量平均分子量之值為基準。比較例1:調製雙酚型羧酸酯化合物於作為環氧樹脂（a)之表1中所記載之雙酚型環氧樹脂中（環氧當量是在表1記載），加入作為（曱基）丙烯酸（b) 之丙烯酸（簡稱AA，Mw=72)72g。接著，加入作為觸媒之三苯膦3g、作為溶劑之單醋酸丙二醇單甲基乙基酯，使固體成分（所得之雙酚型羧酸酯化合物之計算量）成為70質量％，於100°C反應50小時，得到環氧丙烯酸酯溶液。反應終點由固體成分酸價（AV)決定，確認到達2mgKOH /g以下時結束反應。酸價測定藉由反應溶液測定，換算成固體成分之酸價。表1記載之分子量是藉由GPC經聚苯乙烯換算質量平均分子量之值為基準。 [表1 ] 實施例 (a) R~ η WPE(g/eq.) wt(g) Mw 實施例1-1 EOCN-102S 甲基 4 210 210 3500 實施例1-2 EOCN-103S 甲基 6 215 215 6000 實施例卜3 EOCN-104S 甲基 8 220 220 9000 實施例1 - 4 EPPN-201 氫原子 5 190 190 6800 比較例1 -1 EPPN-502 — — 175 175 3500 比較例卜2 NER-1202 一一 280 280 6000 29 322297 201120156 表中簡稱 EOCN-102S:日本化藥製甲酚酚醛清漆型環氧樹脂 EOCN-103S :日本化藥製曱酚酚醛清漆型環氧樹脂 EOCN-104S:日本化藥製甲酚酚醛清漆型環氧樹脂 EPPN-201:日本化藥製酚酚醛清漆型環氧樹脂 EPPN-502 :日本化藥製參酚曱基（TPM)型環氧樹脂 NER-1202 .日本化藥製多官能雙酚A(Bis_A)型環氧樹脂實施例2至8以及比較例2至14Column: TSKGEL Super HZM-N Dissolution: THF (tetrahydrofuran); 0. 35ml 1 minute, temperature 4〇〇c Detector: differential refractometer Molecular weight standard: polystyrene example 1 : Preparation of epoxy (meth) acrylate (A) Epoxy resin described in Table 1 as epoxy resin (a) (all of which are made by Nippon Kayaku, epoxy equivalent, and pass The average values of R and n shown in the formula (1) are shown in Table 1), and 72 g of a propene acid (abbreviated as AA, % = 72) as (meth)acrylic acid (b) was added. Then, 3 g of triphenylphosphine as a catalyst and monocarboxylic acid propylene glycol monomethyl ethyl ester as a solvent were added, and the solid content (the amount of the epoxy acrylate (A) obtained) was 70% by mass. The reaction was carried out at 100 ° C for 50 hours to obtain a solution of the oxime acrylate (A). The end point of the reaction was determined by the solid acid value (AV), and when it was confirmed to be 3 mg KOH/g or less, the reaction was terminated. The acid value is determined by measuring the reaction solution, and 28 322297 201120156 is converted into the acid value of the solid fraction. The molecular weights shown in Table 1 are based on the value of the GPC polystyrene-converted mass average molecular weight. Comparative Example 1: Preparation of a bisphenol type carboxylate compound in a bisphenol type epoxy resin described in Table 1 as an epoxy resin (a) (epoxy equivalent is shown in Table 1), and Acrylic acid (b) Acridine (abbreviated as AA, Mw = 72) 72 g. Next, 3 g of triphenylphosphine as a catalyst and monoacetic acid propylene glycol monomethyl ethyl ester as a solvent were added, and the solid content (calculated amount of the obtained bisphenol type carboxylate compound) was 70% by mass in 100°. C was reacted for 50 hours to obtain an epoxy acrylate solution. The reaction end point was determined by the solid content acid value (AV), and it was confirmed that the reaction was completed when it reached 2 mgKOH /g or less. The acid value was measured by the reaction solution and converted into the acid value of the solid component. The molecular weights shown in Table 1 are based on the value of the GPC polystyrene-converted mass average molecular weight. [Table 1] Example (a) R~ η WPE (g/eq.) wt(g) Mw Example 1-1 EOCN-102S Methyl 4 210 210 3500 Example 1-2 EOCN-103S Methyl 6 215 215 6000 Example 3 EOCN-104S Methyl 8 220 220 9000 Example 1 - 4 EPPN-201 Hydrogen Atom 5 190 190 6800 Comparative Example 1 -1 EPPN-502 — — 175 175 3500 Comparative Example 2 NER-1202 1 280 280 6000 29 322297 201120156 Abbreviation EOCN-102S in the table: Japanese chemical cresol novolac type epoxy resin EOCN-103S: Nippon chemical phenolic phenolic varnish type epoxy resin EOCN-104S: Nippon Chemical Co., Ltd. Cresol novolak type epoxy resin EPPN-201: phenolic novolac type epoxy resin EPPN-502 made from Nippon Chemical Co., Ltd.: TP-1 epoxy resin NER-1202 manufactured by Nippon Kayaku Co., Ltd. Polyfunctional bisphenol A (Bis_A) type epoxy resin Examples 2 to 8 and Comparative Examples 2 to 14

混合表2、表3及表4所示材料，將實施例2至8及比較例2至14之樹脂組成物，於厚度1〇〇Mm之易接著處理後PET膜（Toray股份有限公司製，Lumirror U46)上以溶劑乾燥後之膜厚約3 μ m藉由棒塗布機塗布，約go至1〇〇 C乾燥後’藉由紫外線照射器（jApAN STORAGE BATTERY C0，LTD. :CS30L-卜 1)高壓水銀燈：l2〇W/cm，燈高度：10cm，相對速度：l〇m/分鐘（能量：約3〇〇mw/cm2、約200mJ/cm2) 之條件下硬化所得之硬塗層膜。並且，表2、表3及表4 中單位表示「質量份」。 30 322297 201120156 [表2] 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 (A)成分實施例1-1 54.00 實施例卜2 54.00 54.00 32.00 32.00 實施例1-3 54.00 實施例1-4 54. 00 (B)成分起始劑1嵌1 2.000 2.000 2. 000 2.000 2.000 2.000 2.000 (C)成分 TEG(^2 0.200 0. 200 0.200 0.200 0.200 0.200 DAB3 1.000 (D)成分多官能胺酯1泶4 5.000 5.000 (E-1)成分環氧基丙,醢酯※5 8.000 (E-2)成分胺酯丙烯酸酯※6 8. 000 (F)成分 P_7 2.400 2. 400 (G)成分 1^隱 43.80 43.80 43.80 43.80 43.80 50.40 50.40 合計 100.0 100.0 100.0 100,0 100.0 100.0 100.0 [表3] 比較例2 比較例3 比較例4 比較例5 比較例6 比較例7 比較例8 (A)成分實施例1-2 54.20 (A)成分比較比較例卜1 54. 00 比較例卜2 54.00 (B)成分起始劑丨※！ 2.000 2.000 2.000 2.000 2.000 2.000 2.000 (C)成分 TEGC^2 0. 200 0.200 0.200 0. 200 0.200 0.200 (D)成分多官能胺酯丨※4 13. 60 13.60 17.70 21.80 (E-1)成分環氧基丙烯醖酯※5 21.80 (E-2)成分胺酯丙烯酸酯※6 21.80 17. 70 13.60 (F)成分 P_7 2.400 2.400 2.400 2.400 (G)成分 ME_ 43. 80 43. 80 60.00 60.00 60.00 60.00 43.80 合計 100.0 100.0 100.0 100.0 100.0 100.0 100.0 31 322297 201120156 [表4] 比較例9 比較例10 比較例11 比較例12 比較例13 比較例14 (A)成分實施例1-2 7.12 24.00 (A)成分比較肿廳9 54.00 7.12 24. 00 多官能胺酯2奈10 54.00 (B)成分起始劑1欲1 2.000 2.000 0. 750 0.750 起始劑之※” 3.000 3.000 0.750 0.750 (C)成分丽嵌2 0. 200 0.200 (F)成分 0.880 0. 880 (G)成分 ΜΕ_ 43.80 43.80 52.00 52. 00 25.70 25.70 (其他）氧化鋅※14 63.30 63.30 氧化錫※15 22.50 22.50 合計 100.0 100.0 100.0 100.0 100.0 100.0 (注） ※l :卜羥基環己基苯基酮 ※之：Degussa公司製，TEGO Rad 2250(2官能聚矽氧丙烯酸酯） ※3 : Daikin工業（股份有限公司）製，Optool DAC(丙烯酸酯改質全氟聚醚、丙烯酸酯改質全氟聚醚：20質量％) .4 :三丙烯酸新戊四醇酯與異佛爾酮二異氰酸酯之反應物 (6官能胺酯丙烯酸酯） ※5 :雙酚A環氧丙烯酸酯（2官能，理論分子量約2, 100) ※6:聚丁二醇與乙二醇與異佛爾酮二異氰酸酯與羥乙基丙烯酸酯之反應物（2官能胺酯丙烯酸酯） 32 322297 201120156 ※了：丙稀酸苯氧基乙基酉旨 ※8 :丁酮 ※9:五丙烯酸二新戊四醇酯與六丙烯酸二新戊四醇酯之混合物 ※^:五丙烯酸二新戊四醇醋與二異氰酸六亞曱基酯之反應物 ※^ : 2_甲基_1_(4_(曱硫基）苯基）-2_(4_嗎琳基）-1_丙酉同 ※12 :丙稀酸四氫咬喃酯 ※“：丙二醇單甲醚 ※14 : Hakusui tec(股份有限公司）製鎵摻雜氧化鋅商品名；Pazet GK-40、鎵摻雜氧化鋅：30質量％、PGM(丙二醇單曱醚）分散液 ※^:日產化學工業（股份有限公司）製磷摻雜氧化錫商品名；CELNAXCX-S200IP、磷摻雜氧化錫：20質量％、IPA(異丙醇）溶膠實施例2至8及比較例2至14所得之硬塗層膜，以下述項目評價，其結果表示於表4。 (鉛筆硬度）依JIS K 5600，使用鉛筆劃試驗機，測定實施例2至 8及比較例2至14所得之硬塗層膜之鉛筆硬度。詳細而言，於測定之實施例2至8及比較例2至14所得之硬塗層膜上，船筆以45度之角度，其上負載75Og之重物劃出5mm 左右，5次中有4次以上沒有劃傷表示鉛筆之硬度。 (财擦傷性） 33 322297 201120156 於鋼絲綿（steel wood) # 0000上，實施例2至8及比較例2至14所得之硬塗層膜負載250g/cm2之重物來回1〇次’以目視判定刮傷之狀況。評價5級：無到傷 4級：產生1至10條刮傷 3級：產生10至30條刮傷 2級：產生30條以上刮傷 1級：全面刮傷或是發生剝落 (拉伸率）以拉伸試驗機（Orientec股份有限公司製RTM-250)，將寬lOmmx長50mm之實施例2至8及比較例2至14所得之硬塗層膜，於常溫以每分鐘l〇mm之速度拉伸，以目視有裂痕之點表示拉伸率。例如，由50mm至75mm者記錄為拉伸率50%。同時，本評估也作為表示成形性之指標使用。愈高拉伸率則成形性愈優。 (密著性）依JIS K5600，在實施例2至8及比較例2至14所得之硬塗層膜之表面以2mm間隔，切割縱、橫6刀製作25個棋盤格。表示在其表面黏貼透明膠帶後，一口氣剝除時沒有剝離而殘存下來之格子個數。 (痕跡栻去性）使用黑/紅之痕跡印墨，於實施例2至8、及比較例2 至14所得之硬塗層膜之塗布面上書寫文字，以擦手紙進行 322297 34 201120156 擦拭，拭去性以目視判斷。評估A :在相同場所，可以擦拭10次以上 B :在相同場所，可以擦拭5至10次 C:在相同場所，可以擦拭1至4次 (指紋拭去性）自動接觸角計使用協和界面科學（股份有限公司）製 CA-V型，測定十六烷（HD)之接觸角。利用HD作為指紋拭去性之指標，接觸角越高指紋拭去性越佳。以HD=50°以上之接觸角為佳。 (全光線穿透率）霧度計使用東京電色（股份有限公司）製，TC-H3DPK測定。 (霧度值）霧度計使用東京電色（股份有限公司）製，TC-H3DPK測定。 %u. 35 322297 201120156 [表5] 鉛筆硬度擦傷性拉伸率密著性痕跡接觸角穿透準霧度值實施例2 Η 4級 65% 25/25 A 35· 92% 0.5% 實施例3 2Η 4級 55% 25/25 A 35。 92% ' 0.5% 實施例4 2Η 4級 50¾ 25/25 A 34' 92% 0. 5%_ 實施例5 F 3級 75¾ 25/25 A 36e 92¾ 0. 6¾ 實施例6 2Η 3級 55% 25/25 A 52e 92% 0. 6% 實施例7 2Η 4級 60% 25/25 A 35。 92¾ 0. 5% 實施例8 2Η 4級 60% 25/25 A 36° 92% 0. 5% 比較例2 2Η. 3級 5¾ 25/25 A 36' 92¾ 0. 6% 比較例3 Β 2級 90¾ 25/25 A 35· 92¾ 0.5¾ 比較例4 ΗΒ 2級 50% 25/25 A 34e 92% 0. 5% 比較例5 ΗΒ 2級 50% 25/25 A 35· 92% 0.6¾ 比較例6 Η 4級 20% 25/25 A 35， 92¾ 0.5¾ 比較例7 Η 4級 10¾ 25/25 A 35。 92% 0. 6% 比較例8 2Η 2級 55¾ 25/25 C r 92¾ 0.5¾ 比較例9 3Η 5級 2% 25/25 A 35。 92% 0.5% 比較例10 3Η 5級 4% 25/25 A 35。 91% 0_5% 比較例11 2Η 3級 4% 25/25 C 4。 88% 0.8% 比較例12 ΗΒ 1級 45% 25/25 C 4° 88¾ 0.7% 比較例13 2Η 3級 3% 25/25 C 3° 91¾ 0.4¾ 比較例14 ΗΒ 1級 50% 25/25 c 3e 91% 0.6¾ 由表5之實施例2至8之結果可清楚瞭解，本發明硬塗層膜可得到硬度與拉伸率之平衡為非常良好之結果，防污性（痕跡拭去性以及指紋拭去性）亦良好。改變（A)成分之比較例2，雖然硬度良好，但幾乎沒有拉伸，比較例3則是拉伸率良好，但硬度大幅劣化。不使用（A)成分之比較例 4至5，拉伸率雖良好，但硬度大幅下降，比較例6至7雖然稍微有硬度與拉伸率之平衡，但與本發明硬塗層膜相比 36 322297 201120156 較，結果較差。此外，不使用（C)成分之比較例8則是防污性不佳。將專利文獻4以及專利文獻5之實施例作為比較例9 至14參考。將專利文獻4以及專利文獻5之實施例中記載之樹脂成分換成本發明（A)成分之比較例9及10，硬度與本發明比較，具有同等以上之結果，但幾乎沒有拉伸。進行專利文獻4及專利文獻5之實施例中所記載之調配之比較例11及13，則是幾乎沒有拉伸，防污性也不足。再者，專利文獻4以及專利文獻5之實施例中所記載之調配樹脂成分以本發明（A)成分替換之比較例12及14，則是硬度及防污性不足。 (產業上之可利用性）本發明之硬塗層膜價廉，且密著性、透明性、防污性良好，特別是硬度與拉伸性之平衡良好。因此本發明之紫外線硬化型硬塗層樹脂組成物適合作為於如折彎步驟之膜嵌入成形時使用之硬塗層膜之材料。【圖式簡單說明】無。【主要元件符號說明】無0The materials shown in Tables 2, 3, and 4 were mixed, and the resin compositions of Examples 2 to 8 and Comparative Examples 2 to 14 were easily treated with a thickness of 1 〇〇Mm, followed by a PET film (manufactured by Toray Co., Ltd.). Lumirror U46) is dried in a solvent and the film thickness is about 3 μm. It is coated by a bar coater and dried after about go to 1 〇〇C. 'With UV illuminator (jApAN STORAGE BATTERY C0, LTD.: CS30L-b 1 High-pressure mercury lamp: l2 〇 W / cm, lamp height: 10 cm, relative speed: l 〇 m / minute (energy: about 3 〇〇 mw / cm2, about 200 mJ / cm 2) hardened film obtained by hard coating film. Further, the units in Table 2, Table 3, and Table 4 indicate "mass parts". 30 322297 201120156 [Table 2] Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 (A) Ingredient Example 1-1 54.00 Example 2 2 54.00 54.00 32.00 32.00 Example 1 3 54.00 Example 1-4 54. 00 (B) Initiator 1 Inlay 1 2.000 2.000 2. 000 2.000 2.000 2.000 2.000 (C) Component TEG (^2 0.200 0. 200 0.200 0.200 0.200 0.200 DAB3 1.000 (D) Component polyfunctional amine ester 1泶4 5.000 5.000 (E-1) component Epoxy propyl, oxime ester ※5 8.000 (E-2) component amine ester acrylate ※6 8. 000 (F) component P_7 2.400 2. 400 (G) Ingredient 1^Hidden 43.80 43.80 43.80 43.80 43.80 50.40 50.40 Total 100.0 100.0 100.0 100,0 100.0 100.0 100.0 [Table 3] Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 ( A) Ingredient Example 1-2 54.20 (A) Ingredients Comparative Example 1 54. 00 Comparative Example 2 54.00 (B) Initiator 丨※! 2.000 2.000 2.000 2.000 2.000 2.000 2.000 (C) Component TEGC^2 0. 200 0.200 0.200 0. 200 0.200 0.200 (D) Amine ester 丨*4 13. 60 13.60 17.70 21.80 (E-1) component epoxy propylene oxime ester ※5 21.80 (E-2) component amine ester acrylate ※6 21.80 17. 70 13.60 (F) component P_7 2.400 2.400 2.400 2.400 (G) component ME_ 43. 80 43. 80 60.00 60.00 60.00 60.00 43.80 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 31 322297 201120156 [Table 4] Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparison Example 14 (A) Ingredient Example 1-2 7.12 24.00 (A) Ingredients Comparison Tumor Hall 9 54.00 7.12 24. 00 Polyfunctional Amine Ester 2 Nai 10 54.00 (B) Ingredient Starting Agent 1 Desire 1 2.000 2.000 0. 750 0.750 Starting agent ※” 3.000 3.000 0.750 0.750 (C) Ingredients 2 0. 200 0.200 (F) Composition 0.880 0. 880 (G) Composition ΜΕ _ 43.80 43.80 52.00 52. 00 25.70 25.70 (Others) Zinc oxide ※14 63.30 63.30 Tin Oxide*15 22.50 22.50 Total 100.0 100.0 100.0 100.0 100.0 100.0 (Note) *l: Hydroxycyclohexyl phenyl ketone ※: manufactured by Degussa, TEGO Rad 2250 (2-functional polyoxy acrylate) *3 : Dai Kin Industrial Co., Ltd., Optool DAC (acrylate modified perfluoropolyether, acrylate modified perfluoropolyether: 20% by mass) .4 : Neopentyl triacrylate and isophorone II Reaction of isocyanate (6-functional amine ester acrylate) *5 : Bisphenol A epoxy acrylate (2-functional, theoretical molecular weight about 2, 100) *6: Polytetramethylene glycol with ethylene glycol and isophorone II Reaction of isocyanate with hydroxyethyl acrylate (2-functional amine ester acrylate) 32 322297 201120156 ※: Acetylate phenoxyethyl hydrazine ※8: Butanone ※9: Pentaerythritol pentaacrylate a mixture with dipentaerythritol hexaacrylate ※^: a reaction of pentaerythritol pentaacrylate with hexamethylene diisocyanate ※^ : 2_methyl_1_(4_(曱thio group) )Phenyl)-2_(4_?琳基基)-1_酉酉同*12: tetrahydroanthracene acrylate ※": propylene glycol monomethyl ether ※14 : Hakusui tec (company) gallium doping Trade name of zinc oxide; Pazet GK-40, gallium-doped zinc oxide: 30% by mass, PGM (propylene glycol monoterpene ether) dispersion ※^: Nissan Chemical Industry Co., Ltd. Company name: phosphorus-doped tin oxide trade name; CELNAXCX-S200IP, phosphorus-doped tin oxide: 20% by mass, IPA (isopropyl alcohol) sol Examples 2 to 8 and Comparative Examples 2 to 14 obtained hard coat film, The results are shown in the following items, and the results are shown in Table 4. (Pencil Hardness) The pencil hardness of the hard coat film obtained in Examples 2 to 8 and Comparative Examples 2 to 14 was measured in accordance with JIS K 5600 using a pencil stroke tester. In detail, on the hard coat films obtained in Examples 2 to 8 and Comparative Examples 2 to 14, the pens were drawn at an angle of 45 degrees, and the weight of the load of 75 Og was drawn by about 5 mm, and 5 times were No scratches of more than 4 times indicates the hardness of the pencil. (Crossage) 33 322297 201120156 On the steel wood # 0000, the hard coat film obtained in Examples 2 to 8 and Comparative Examples 2 to 14 was loaded with a weight of 250 g/cm 2 back and forth 1 time by visual inspection. Determine the condition of the scratch. Evaluation Level 5: No damage to level 4: 1 to 10 scratches 3: 10 to 30 scratches 2: More than 30 scratches 1 level: full scratch or peeling (stretching rate) The hard coat film obtained in Examples 2 to 8 and Comparative Examples 2 to 14 having a width of 10 mm and a length of 50 mm was subjected to a tensile tester (RTM-250, manufactured by Orientec Co., Ltd.) at a normal temperature of 1 mm per minute. The speed is stretched, and the stretch rate is expressed by the point where the crack is visually observed. For example, a tensile rate of 50% is recorded from 50 mm to 75 mm. At the same time, this assessment is also used as an indicator of formability. The higher the elongation, the better the formability. (Adhesiveness) According to JIS K5600, the surface of the hard coat film obtained in Examples 2 to 8 and Comparative Examples 2 to 14 was cut at intervals of 2 mm, and 25 squares were cut in the vertical and horizontal directions to make 25 checkers. Indicates the number of grids that remain without peeling off after a strip of scotch tape is applied to the surface. (marking and smearing) Using the black/red trace ink, the characters were written on the coated surfaces of the hard coat films obtained in Examples 2 to 8 and Comparative Examples 2 to 14, and wiped with a paper towel 322297 34 201120156. Wipe off by visual judgment. Evaluation A: In the same place, you can wipe more than 10 times. B: In the same place, you can wipe 5 to 10 times C: In the same place, you can wipe 1 to 4 times (fingerprint wipe-off) Automatic contact angle meter using Concord Interface Science (Company Co., Ltd.) A CA-V type was used to measure the contact angle of hexadecane (HD). Using HD as an indicator of fingerprint erasability, the higher the contact angle, the better the fingerprint wipeability. The contact angle above HD = 50° is preferred. (Total Light Transmittance) The haze meter was measured using TC-H3DPK manufactured by Tokyo Denshoku Co., Ltd. (Haze value) The haze meter was measured using TC-H3DPK manufactured by Tokyo Denshoku Co., Ltd. %u. 35 322297 201120156 [Table 5] Pencil hardness scratch-off elongation adhesion mark contact angle penetration quasi-haze value Example 2 Η Level 4 65% 25/25 A 35· 92% 0.5% Example 3 2Η Level 4 55% 25/25 A 35. 92% ' 0.5% Example 4 2Η 4 503⁄4 25/25 A 34' 92% 0. 5%_ Example 5 F 3 753⁄4 25/25 A 36e 923⁄4 0. 63⁄4 Example 6 2Η 3 55% 25 /25 A 52e 92% 0. 6% Example 7 2Η 4 levels 60% 25/25 A 35. 923⁄4 0. 5% Example 8 2Η 4th grade 60% 25/25 A 36° 92% 0. 5% Comparative example 2 2Η. 3rd grade 53⁄4 25/25 A 36' 923⁄4 0. 6% Comparative example 3 Β Level 2 903⁄4 25/25 A 35· 923⁄4 0.53⁄4 Comparative Example 4 ΗΒ Level 2 50% 25/25 A 34e 92% 0. 5% Comparative Example 5 ΗΒ Level 2 50% 25/25 A 35· 92% 0.63⁄4 Comparative Example 6 Η Level 4 20% 25/25 A 35, 923⁄4 0.53⁄4 Comparative Example 7 Η Level 4 103⁄4 25/25 A 35. 92% 0. 6% Comparative Example 8 2Η 2nd level 553⁄4 25/25 C r 923⁄4 0.53⁄4 Comparative Example 9 3Η Level 5 2% 25/25 A 35. 92% 0.5% Comparative Example 10 3Η Level 5 4% 25/25 A 35. 91% 0_5% Comparative Example 11 2Η Level 3 4% 25/25 C 4. 88% 0.8% Comparative Example 12 ΗΒ Level 1 45% 25/25 C 4° 883⁄4 0.7% Comparative Example 13 2Η Level 3 3% 25/25 C 3° 913⁄4 0.43⁄4 Comparative Example 14 ΗΒ Level 1 50% 25/25 c 3e 91% 0.63⁄4 From the results of Examples 2 to 8 of Table 5, it is clear that the hard coat film of the present invention can obtain a very good balance between hardness and elongation, and antifouling property (mark wiping property and Fingerprint wipeability) is also good. Change of the component (A) In Comparative Example 2, although the hardness was good, there was almost no stretching, and in Comparative Example 3, the elongation was good, but the hardness was largely deteriorated. In Comparative Examples 4 to 5 in which the component (A) was not used, although the elongation was good, the hardness was largely lowered, and Comparative Examples 6 to 7 had a slight balance between hardness and elongation, but compared with the hard coat film of the present invention. 36 322297 201120156 The result is poor. Further, Comparative Example 8 in which the component (C) was not used was inferior in antifouling property. The examples of Patent Document 4 and Patent Document 5 were referred to as Comparative Examples 9 to 14. In Comparative Examples 9 and 10 in which the resin components described in the examples of Patent Document 4 and Patent Document 5 were replaced with the components (A) of the invention, the hardness was equal to or higher than that of the present invention, but there was almost no stretching. In Comparative Examples 11 and 13 in the formulation described in the examples of Patent Document 4 and Patent Document 5, there was almost no stretching and the antifouling property was insufficient. In addition, in Comparative Examples 12 and 14 in which the compounding resin component described in the examples of Patent Document 4 and Patent Document 5 was replaced with the component (A) of the present invention, the hardness and the antifouling property were insufficient. (Industrial Applicability) The hard coat film of the present invention is inexpensive, and has good adhesion, transparency, and antifouling properties, and particularly has a good balance between hardness and stretchability. Therefore, the ultraviolet curable hard coat resin composition of the present invention is suitable as a material for a hard coat film which is used for insert molding in a film such as a bending step. [Simple description of the diagram] None. [Main component symbol description] No 0

S 37 322297S 37 322297

Claims

201120156 七、申請專利範圍：201120156 VII. Patent application scope:

型？層樹f組成物’係用於成形膜， ' 丁％氣樹脂（a)以及（甲基）丙烯酸（b) 反應而得之分子中具有至少3個以上（曱基）丙稀醯基之壞乳（曱基）丙烯酸酷⑷、光自由基聚合起始劑⑻、以及防污劑（C)， 2.type? The layered tree f composition 'is used for forming a film, and the D-% gas resin (a) and (meth)acrylic acid (b) have at least 3 or more (mercapto) acrylonitrile groups in the molecule. Milk (mercapto) acrylic acid (4), photoradical polymerization initiator (8), and antifouling agent (C), 2.

如申》月專利範圍第1項所述之紫外線硬化型硬塗層樹脂組成物’其中，防污劑⑹為具有（甲基)丙烯醯基之聚石夕氧燒。 •如申Μ專利範圍第1項所述之紫外線硬化型硬塗層樹脂組成物，其中，防污劑（C)為具有（甲基）丙烯醯基之鼠化合物。 .如申清專利範圍第1至第3項中任一項所述之紫外線硬化型硬塗層樹脂組成物，其中，通式⑴所示環氧樹脂 (a)中R為γ基。 5.如申請專利範圍第1至第4項中任一項所述之紫外線硬化型硬塗層樹脂組成物，其復含有前述成分以外之刀子申具有至少3個以上（甲基）丙稀酿基之紫外線硬 201120156 化型（甲基）丙烯酸酯 6. 如申請專利範圍第5項所述之紫外線硬化型硬塗層樹脂組成物’其復含有分子中具有2個（甲基）丙烯醯基之環氧（甲基）丙烯酸酯（E-1)及/或聚胺酯（曱基）丙烯酸酯（E-2)。 7. 如申請專利範圍第6項所述之紫外線硬化型硬塗層樹脂組成物’其復含有具有1至2個（甲基）丙烯醯基之反應性稀釋劑（F)。 8. 如申請專利範圍第7項所述之紫外線硬化型硬塗層樹脂組成物，其復含有稀釋劑（G)。 9. 一種硬塗層膜’係具有申請專利範圍第1至第4項或第 8項中任一項所述之紫外線硬化型硬塗層樹脂組成物之硬化層。 10. —種硬塗層成形物，係具有申請專利範圍第1至第4 項或第8項中任一項所述之紫外線硬化型硬塗層樹脂組成物之硬化層。 201120156 四、指定代表圖：本案無圖式。 (一)本案指定代表圖為：第（）圖。 ‘ （二)本代表圖之元件符號簡單說明：五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： <?<?<?The ultraviolet curable hard coat resin composition as described in the first paragraph of the patent application of the present invention, wherein the antifouling agent (6) is a polyoxazine having a (meth) acrylonitrile group. The ultraviolet curable hard coat resin composition according to claim 1, wherein the antifouling agent (C) is a rat compound having a (meth) acrylonitrile group. The ultraviolet curable hard coat resin composition according to any one of claims 1 to 3, wherein R in the epoxy resin (a) represented by the formula (1) is a γ group. 5. The ultraviolet curable hard coat resin composition according to any one of claims 1 to 4, wherein the knife other than the above-mentioned component has at least 3 or more (meth) propylene The ultraviolet-curable hard-coating resin composition as described in claim 5 of the invention has two (meth)acryl-based groups Epoxy (meth) acrylate (E-1) and / or polyurethane (mercapto) acrylate (E-2). 7. The ultraviolet curable hard coat resin composition as described in claim 6, which further comprises a reactive diluent (F) having 1 to 2 (meth) acrylonitrile groups. 8. The ultraviolet curable hard coat resin composition according to claim 7, which further comprises a diluent (G). A hard coat film is a hardened layer of the ultraviolet curable hard coat resin composition according to any one of claims 1 to 4 or 8. A hard-coated article, which is a hardened layer of the ultraviolet curable hard coat resin composition according to any one of claims 1 to 4 or 8. 201120156 IV. Designated representative map: There is no schema in this case. (1) The representative representative of the case is: ( ). ‘ (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: <?<?<?

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