201035257 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種塑膝表面之耐彳寂復^ 裇場性、硬度、柔 性、耐指紋可見性及指紋拭除性 ， ^ , "了進行表面塗佈之 活性能量射線硬化型硬塗層用樹脂組合 。 。更詳細而言， 係關於一種適合塗佈於聚酯、丙烯酴、一 二乙醯纖維素、聚 碳酸酯等塑膠表面，透明且耐擦傷性 度優異之活性能 Ο201035257 VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a skin-resistant surface of a knee-shaped surface, hardness, flexibility, fingerprint visibility and fingerprint erasability, ^, " A surface energy-coated resin for an active energy ray-curable hard coat layer is applied. . More specifically, it relates to an active material which is suitable for coating on a plastic surface such as polyester, acryl, yttrium cellulose, polycarbonate, etc., and which is excellent in transparency and scratch resistance.
量射線硬化型硬塗層用樹脂組合物， 九再疋闕於一種耐指 紋可見性及指紋拭除性優異，因此適合 „ , 用於觸摸面板顯示 器中使用之膜或藉由模内成形而製造之開關面板之硬塗層 的活性能量射線硬化型樹脂組合物。所謂耐指紋可見性， 制指紋按壓痕跡之不明顯程度，所謂指紋栻除性，係指 附著之指紋按壓痕跡之拭除容易程度。 進而，本發明係提供一種硬塗膜，其可獲得於成形品表 面部分之曲面部不產生龜裂且具有上述特性之成形品。 又’本發明因成形性亦特別優異，故亦適合於模内成形時 所使用之膜之硬塗層。 【先前技術】 當剛’於以汽車行業、家電行業、電子行業為代表之各 種產業巾’塑膠得到Α量使用。如此Α4地使職膠係由 於其加JL性、透明性優異，以及輕量、價廉、光學特性優 異等理由n塑膠與玻璃等相比具有柔軟、表面容易 @下劃痕等缺點。^ 了改良該等缺點，通常之方法係於塑 膠表面塗佈硬塗齊,卜作為該硬塗劑，係使用聚_氧系、丙 146212.doc 201035257 烯酸系、三聚氰胺系等熱硬化型硬塗劑。其中，尤其是聚 石夕氧系硬塗劑之硬度較高品質優異，因此較多地使用，但 其硬化時間較長，價格昂貴，並不適合於對連續加工之膜 設置之硬塗層。 近年來，開發出感光性之丙烯酸系硬塗劑並逐漸加以利 用（專利文獻1)。此種感光性硬塗劑係藉由照射紫外線等活 性能量射線而立即硬化形成較硬之皮膜，因此加工處理速 度較快，並且具有硬度、耐擦傷性等優異之性能，總成本 較為低廉，因此成為目前硬塗劑之主流。尤其是使用於聚 酉旨等膜之連續加工。 作為使用感光性硬塗劑的塑膠膜，有聚酯膜、丙烯酸 膜、聚碳酸醋膜、氯乙烯膜、三乙醯纖維素膜、聚醚颯膜 等，聚酯膜由於具有各種優異之特性因而受到最廣泛之使 用。該聚酯膜例如可用作：玻璃之飛散防止膜、汽車之遮 光膜、白板用表面膜、整體廚房表面防污膜，或者電子材 料方面之CRT(Cathode-ray tube，陰極射線管）平板電視、 觸摸面板顯示器、液晶顯示器（LCD，Uquid巧灿！ ⑴叫ay)、電聚顯示器（PDP，plasma d_ay㈣叫、有機 EL⑷ectroluminescence，電致發光）顯示器等之功能性 膜，又’其廣泛地用於家電製品之機體或開關面板、行動 電話或個人電腦之殼體、汽車内部裝飾用零件。 進而’除了塑膠膜以外，聚碳酸醋或丙稀酸等之片材或 於基板上實&硬塗所得者亦用作光碟或背光裝置周邊之液 晶關聯構件。 146212.doc 201035257 近來，開始對塗佈有硬塗劑之基材要求所謂耐擦傷性之 作為硬塗層之性能，並且亦要求其以外之功能性。例如， 設置有膜之CRT、LCD、PDp、觸摸面板等顯示體中，會 • 產生由於反射而難以看到顯示體畫面導致眼睛容易疲勞之 Μ題’因此根據用途，有時需要具有防止表面反射功能之 硬塗層處理（專利文獻2)β 又，亦在開發使用界面活性劑或導電性金屬氧化物而賦 〇 予抗靜電功能之硬塗層（專利文獻3)。 進而，亦存在對硬塗層要求延伸性或柔軟性等與作為硬 塗層之耐擦傷性或硬度等特性相反之性能的情形。 如上所述，例如於行動電話或個人電腦等之殼體、儀錶 蓋等/飞車内部裝飾材料、AV(audi〇_visual，視聽）設備或家 電製品之顯示面板或開關按鈕等之成形加工等成形加工領 域中，膜之使用亦不斷增加。通常，塑膠製品之成形係使 用模具藉由射出成形而進行，但作為加工該製品表面之方 〇 法，提出有將膜安裝於模具内面，於成形之同時貼附於成 形品表面之方法，該方法係稱為模内成形或膜嵌入射出成 形等。即，可藉由將膜夾持於模具中，同時進行射出成 '形，而於成形之同時賦予膜之功能。進而，亦可藉由於該 女名之膜上印刷圖案或花紋，或者使用硬塗膜，而對成形 品賦予裝飾或硬度提昇等美觀性、功能性。 使用上述硬塗膜之成形有以下兩種：模内層壓（IML , mold lamination)，於基材膜上塗佈硬塗層，與硬塗膜—起 一體成形；以及模内裝飾（IMD，in m〇ld dec〇rati〇n)，於 146212.doc 201035257 具有脫模層之膜上塗佈硬塗層，成形加工後除去脫模膜 (專利文獻4)。 ' ' 又，用於射出成形之硬塗層由於係位於成形加工之塑膠 製品之最表面，因此表面硬度自不必說，亦需要光澤感等 美觀性及可經受成形加工之延伸性、柔軟性等性能;因 此」於基材膜上形成硬塗層之情形時，有—體成形出硬化 j父聯）之硬塗膜之方法，或首先僅形成硬塗膜之膜，成形 後進行硬化（交聯）之方法等。 上述各種顯示裝置、觸摸面板構件、成形品之開關㈣ 等亦要求賦予所謂耐指紋性，即指紋不附著、難以附著於 該等，表面之功能。然而，目前尚不知曉賦予不附著指紋 之功能之方法。因此改而要求附著指紋後可簡單地拭除之 性能。 ” 提高作為耐指紋性之指紋拭除性之方法例如有：將貌系 材料或聚石夕氧油等混合於塗佈組合物中使用’從而提高表 2之斥水·斥油性之方法。然而，敗及聚石夕氧為低折射率 '刀因此;6*將該等作為塗佈制於表面，則存在與指紋 =折射率差較大’即使少量附著指紋亦較為顯眼之缺點。 ^而亦存在下述缺點：若拭除不充分，則由於折射率差較 古’亚且具有斥水.斥油功能，而導致與指紋之接觸角變 :’更容易看到指紋。x，咖中，由於係於硬塗層上進 •八'亍P屌】目此若將氟系材料或聚矽氧油等混合於塗佈 2物中制’則具有因排斥印刷墨水故印刷無法進行之 1462l2.d, 201035257 又，目前為止尚不知曉耐指紋可見性優異之硬塗層。 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特開平9-48934號公報 [專利文獻2]曰本專利特開平9_丨459〇3號公報 [專利文獻3]日本專利特開平ι〇_231444號公報 [專利文獻4]曰本專利第3007326號公報 【發明内容】 〇 [發明所欲解決之問題] 本發明之目的在於提供一種改善上述缺點，硬度良好且 透明性較高，延伸性、柔軟性方面良好，耐指紋可見性、 指紋栻除性優異之活性能量射線硬化型硬塗層用樹脂組合 物。 [解決問題之技術手段] 本發明者等人為了解決上述課題而進行努力研究，結果 〇 發現含有特定化合物的特定物性範圍之樹脂組合物及其硬 化物可解決上述課題，從而完成本發明。 即’本發明係關於：The resin composition for the radiation hardening type hard coat layer is excellent in fingerprint visibility and fingerprint erasability, and is therefore suitable for use in a film used in a touch panel display or by in-mold forming. The active energy ray-curable resin composition of the hard coat layer of the switch panel. The so-called fingerprint-resistant visibility, the inconspicuous degree of fingerprint pressing marks, the so-called fingerprint eradication, refers to the ease of erasing the attached fingerprint pressing marks. Further, the present invention provides a hard coat film which can be obtained on a curved surface portion of a surface portion of a molded article without causing cracks and having the above-described characteristics. Further, the present invention is also excellent in formability, and is therefore also suitable for The hard coating of the film used in the in-mold forming. [Prior Art] When the plastics are used in the automotive industry, the home appliance industry, and the electronics industry, the plastics are used in large quantities. Because of its excellent JL property, excellent transparency, light weight, low cost, and excellent optical properties, n plastics are softer than glass, and the surface is easy. Such shortcomings. ^ The improvement of these shortcomings, the usual method is to apply hard coating on the surface of the plastic, as the hard coating agent, the use of poly-oxygen, C 146212.doc 201035257 olefinic acid, melamine and other heat Hardening type hard coating agent. Among them, especially the polysulfide hard coating agent has higher hardness and higher quality, so it is used more, but its hardening time is longer and expensive, and it is not suitable for the film of continuous processing. In recent years, a photosensitive acrylic hard coating agent has been developed and used gradually (Patent Document 1). Such a photosensitive hard coating agent is hardened immediately by irradiation with an active energy ray such as ultraviolet rays. Since the film is processed at a relatively high speed, and has excellent properties such as hardness and scratch resistance, and the total cost is relatively low, it is currently the mainstream of hard coating agents, especially for continuous processing of films such as polythene. The plastic film using the photosensitive hard coating agent includes a polyester film, an acrylic film, a polycarbonate film, a vinyl chloride film, a triethylene fluorene cellulose film, a polyether ruthenium film, etc., and the polyester film has each The excellent properties are thus the most widely used. The polyester film can be used, for example, as a scattering preventing film for glass, a light-shielding film for automobiles, a surface film for whiteboard, an antifouling film for a whole kitchen surface, or a CRT for electronic materials. -ray tube, cathode ray tube) flat panel TV, touch panel display, liquid crystal display (LCD, Uquid! (1) called ay), electro-poly display (PDP, plasma d_ay (four), organic EL (4) ectroluminescence, electroluminescence) display, etc. The film is also widely used in the body or switch panel of home appliances, the casing of a mobile phone or a personal computer, and the parts for automotive interior decoration. Further, in addition to the plastic film, a sheet of polycarbonate or acrylic The material or the hard coating on the substrate is also used as a liquid crystal associated member around the optical disc or backlight. 146212.doc 201035257 Recently, the performance of so-called scratch resistance as a hard coat layer has been demanded on a substrate coated with a hard coating agent, and functionalities other than those required are also required. For example, in a display body such as a CRT, LCD, PDp, or touch panel provided with a film, there is a problem that it is difficult to see the display screen due to reflection, which causes the eyes to be easily fatigued. Therefore, depending on the application, it is sometimes necessary to prevent surface reflection. Functional hard coat treatment (Patent Document 2) β In addition, a hard coat layer which imparts an antistatic function by using a surfactant or a conductive metal oxide has been developed (Patent Document 3). Further, there is a case where the hard coat layer is required to have properties such as elongation, flexibility, and the like which are opposite to those of the hard coat layer such as scratch resistance or hardness. As described above, for example, a casing such as a mobile phone or a personal computer, a meter cover or the like, a vehicle interior material, an AV (audio_visual) device, or a display panel or a switch button of a home appliance, etc. In the field of forming processing, the use of membranes is also increasing. Usually, the molding of a plastic product is carried out by injection molding using a mold. However, as a method of processing the surface of the product, a method of attaching the film to the inner surface of the mold and attaching it to the surface of the molded article at the same time is proposed. The method is called in-mold forming or film-embedding injection molding. That is, the film can be formed into a mold and simultaneously ejected into a shape to impart a function to the film while being formed. Further, the pattern or the pattern on the film of the girl's name or the hard coat film may be used to impart aesthetics and functionality such as decoration or hardness improvement to the molded article. There are two types of forming using the above hard coat film: in-mold lamination (IML, mold lamination), coating a hard coat layer on a base film, integrally forming with a hard coat film; and in-mold decoration (IMD, in M〇ld dec〇rati〇n), at 146212.doc 201035257 A hard coat layer is coated on a film having a release layer, and a release film is removed after molding (Patent Document 4). ' 'In addition, since the hard coat layer for injection molding is located on the outermost surface of the formed plastic product, the surface hardness is self-evident, and the glossiness and the like are required, and the elongation, flexibility, etc. of the forming process can be withstood. Performance; therefore, when a hard coat layer is formed on a base film, a hard coat film of a hardened j parent is formed, or a film of a hard coat film is first formed, and hardening is formed after forming Method). The above various display devices, touch panel members, and switches (4) of molded articles are also required to impart so-called fingerprint resistance, that is, a function in which the fingerprint does not adhere to each other and is difficult to adhere to the surface. However, methods for imparting a function of not attaching a fingerprint are not known at present. Therefore, it is required to simply erase the performance after attaching the fingerprint. The method for improving the fingerprint erasability as the fingerprint resistance is, for example, a method of mixing a morphological material or a polysulfuric acid oil in a coating composition to improve the water repellency and oil repellency of Table 2. The failure and the polysulfide oxygen are low refractive index 'knife; therefore, 6* coating these on the surface, there is a disadvantage that the fingerprint = refractive index difference is larger, even if a small amount of fingerprint is attached. There are also the following disadvantages: if the erasing is insufficient, the refractive index difference is more ancient and has the function of water repellent and oil repellent, resulting in a contact angle with the fingerprint: 'It is easier to see the fingerprint. x, coffee Since it is attached to the hard coat layer, it is necessary to mix the fluorine-based material or the polyoxygenated oil in the coating 2 to make it impossible to print due to the exclusion of the printing ink. .d, 201035257 Further, a hard coat layer excellent in fingerprint visibility is not known. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 9-48934 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei 9-丨459〇3 [Patent Document 3] Japanese Patent [Patent Document 4] Japanese Patent No. 3007326 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] An object of the present invention is to provide an improvement in the above disadvantages, which is excellent in hardness and high in transparency. A resin composition for an active energy ray-curable hard coat layer which is excellent in stretchability and flexibility, and which is excellent in fingerprint visibility and fingerprint removal property. [Technical means for solving the problem] The inventors of the present invention have solved the above problems. As a result of intensive studies, it has been found that a resin composition containing a specific physical property range of a specific compound and a cured product thereof can solve the above problems, thereby completing the present invention. That is, the present invention relates to:
/ (1) 一種活性能量射線硬化型硬塗層用樹脂組合物，其 係3有·分子中具有3個以上（甲基）丙烯醯基之多官能（曱 /基)丙，酸酯A合物⑷、及聚丁二醇骨架部分之數量平均 2子量為600以上的具有聚丁二醇骨架之(曱基)丙烯酸酯化 °物⑻’並且該組合物之折射率為145〜155，該组合物 之硬化膜與油酸之接觸角為25度以下； D 1462l2.d, 201035257 (2) 如上述（丨）之活性能量射線硬化型硬塗層用樹脂組合 物’其含有光聚合起始劑（C); (3) 如上述〇)或（2)之活性能量射線硬化型硬塗層用樹 脂組合物’其含有一次粒徑為1 nm〜200 nm之膠體二氧化 矽（D); (4) 如上述（1)至（3)中任一項之活性能量射線硬化型硬 塗層用樹脂組合物，其含有稀釋劑（E); (5) 如上述（丨）至中任一項之活性能量射線硬化型硬 塗層用樹脂組合物，其含有分子中具有1〜2個（甲基）丙烯 醯基之（曱基）丙烯酸系化合物（F); (6) 如上述（丨）至中任一項之活性能量射線硬化型硬 塗層用樹脂組合物，其中分子中具有3個以上（曱基）丙烯醯 基之多官能（曱基）丙烯酸酯化合物（A)，係含有活性氫之多 S能（曱基）丙烯酸酯化合物與聚異氰酸酯進行反應而獲得 之化合物； (7) 如上述（丨）至中任一項之活性能量射線硬化型硬 塗層用樹脂組合物’其中聚丁二醇骨架部分之數量平均分 子量為600以上的具有聚丁二醇骨架之（甲基）丙烯酸酯化合 物（B)，係分子中具有2個以上（曱基）丙烯醯基之（甲基）丙 稀酸胺基甲酸自旨化合物； (8) 如上述（1)至中任一項之活性能量射線硬化型硬 塗層用樹脂組合物，其中聚丁二醇骨架部分之數量平均分 子量為600以上的具有聚丁二醇骨架之（曱基）丙烯酸酯化合 物（B)的添加量係相對於樹脂組合物之固形物成分ι〇〇重量 146212.doc 201035257 %為0.1〜10重量％ ; (9) 一種膜，其包含如上述（丨）至（8)中任一項之活性能 量射線硬化型硬塗層用樹脂組合物之硬化膜； . (1〇) 一種基材，其包含如上述（1)至（8)中任一項之活性 能量射線硬化型硬塗層用樹脂組合物之硬化膜； (11) 一種顯示用構件，其包含如上述（1)至（8)中任一項 之活性能量射線硬化型硬塗層用樹脂組合物之硬化膜； 〇 (12) 一種觸摸面板構件，其包含如上述（1)至（8)中任一 項之活性能量射線硬化型硬塗層用樹脂組合物之硬化膜； (13) —種觸摸面板用硬塗膜，其包含如上述至中 任一項之活性能量射線硬化型硬塗層用樹脂組合物之硬化 膜； (14) 一種顯示器用硬塗膜，其包含如上述（1)至（8)中任 一項之活性能量射線硬化型硬塗層用樹脂組合物之硬化 膜； 〇 (15) —種硬塗膜，其係包含如上述（1)至（8)中任一項之 活性能量射線硬化型硬塗層用樹脂組合物之硬化膜，且用 於模内成形者； (16) —種成形物，其包含如上述（1)至（8)中任一項之活 性能量射線硬化型硬塗層用樹脂組合物之硬化膜。 [發明之效果] 根據本發明’可提供一種硬度優異，透明性、耐擦傷 性 '柔軟性、耐指紋可見性、指紋拭除性等優異，亦可用 於模内成形之活性能量射線硬化型硬塗層用樹脂組合物及 1462l2.dc, 201035257 其硬化物。 【實施方式】 本發明係關於一種活性能量射線硬化型硬塗層用樹脂組 合物，其係含有··分子中具有3個以上（甲基）丙埽醯基之多 官能（曱基）丙烯酸醋化合物⑷、及聚丁二醇骨架部分之數 量平均分子量為600以上的具有聚丁二醇骨架之（曱基）丙稀 酸酯化合物（B)，並且該組合物之折射率為丨45〜丨55，該 組合物之硬化膜與油酸之接觸角為25度以下。以下，對本 發明進行詳細說明。 作為本發明之活性能量射線硬化型硬塗層用樹脂組合物 中所含的分子中具有3個以上、較好的是3〜12個（甲基）丙 烯醯基之多官能（曱基）丙烯酸酯化合物（A)，例如可列舉： 二羥曱基丙烷三（曱基）丙烯酸酯、三羥甲基丙烷聚乙氧基 三（曱基）丙烯酸酯、表氯醇（ECH，epichl〇r〇hyddn)改質丙 三醇三（甲基）丙烯酸酯、環氧乙烷（E〇，ethylene 〇xid勾改 質丙二醇三（甲基）丙烯酸酯、環氡丙烷（p〇， oxide)改質丙三醇三丙稀酸酯、季戊四醇三（甲基）丙烯酸 6曰、EO改質填酸三（甲基）丙稀酸酯、己内醋改質三經甲基 丙烧二（曱基）丙炼酸g旨、EO改質三經甲基丙烧三（甲基）丙 烯酸酯、PO改質三羥曱基丙烷三（曱基）丙烯酸酯、二（三 經曱基）丙烧四（甲基）丙烯酸酯、二季戊四醇六（甲基）丙稀 酸酯、二季戊四醇五（曱基）丙烯酸酯、三季戊四醇八（甲 基）丙烯酸酯、三（丙烯醯氧基乙基）異氰尿酸酯、己内g旨改 質二季戊四醇六（甲基）丙烯酸酯、季戊四醇乙氧基四 146212.doc 10 201035257 基）丙烯酸酯、聚矽氧六（甲基）丙烯酸酯、雙酚A環氧二（甲 基）丙烯酸酯等環氧（曱基）丙烯酸酯、含有活性氫之多官能 (曱基）丙烯酸酯與聚異氰酸酯進行反應而獲得之多官能（甲 . 基）丙烯酸胺基曱酸酯等聚酯（甲基）丙烯酸酯或其他（甲基） 丙烯酸胺基甲酸酯等。再者，該等可單獨使用亦可將2種 • 以上混合使用。 作為上述含有活性氫之多官能（曱基）丙烯酸酯，例如可 〇 列舉：季戊四醇三（曱基）丙烯酸酯、二季戊四醇六（甲基） 丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯、二季戊四醇四 (甲基）丙烯酸酯、二季戊四醇三（甲基）丙烯酸酯、二季戊 四醇二（甲基）丙烯酸酯等季戊四醇類；三羥甲基丙烷二（甲 基）丙烯酸酯等羥甲基類；雙酚A二環氧丙烯酸酯等環氧丙 烯酸酯類等。其中，較好的是季戊四醇三丙烯酸酯、二季 戊四醇五丙烯酸酯。該等含有活性氫之多官能（曱基）丙烯 酸酯可單獨使用亦可將2種以上混合使用。 〇 作為上述聚異氰酸酯，可使用包含鏈狀飽和烴、環狀飽 和烴（脂環式）、芳香族烴之聚異氰酸酯。作為此種聚異氰 酸酯，例如可列舉：四亞甲基二異氰酸酯、六亞甲基二異 氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯等鏈狀飽和烴 . 聚異氰酸酯；異佛爾酮二異氰酸酯、二環己基甲烷二異氰 酸酯、亞甲基雙（4-環己基異氰酸酯）、氫化二苯基曱烷二 異氰酸酿 '氫化二曱苯二異氰酸酯、氫化甲苯二異氰酸酯 等％狀飽和烴（脂環式）聚異氰酸酯；2,4_甲苯二異氰酸 S曰、1 ’3-苯二曱基二異氰酸酯、對伸苯基二異氰酸酯、 146212.doc -11- 201035257 =3 —甲基-4,4’_二異氰酸醋、&異丙基-1，3-苯基二異氰酸 西曰1，5-萘二異㈣醋冑芳香族聚異氰酸醋。其中，較好 的：異佛爾酮二異氰酸酯、六亞甲基二異氰酸酯。該等聚 異氰酸酯可單獨使用亦可將2種以上混合使用。 产上述夕g月b (甲基）丙烯酸胺基曱酸酯係使上述含有活性 :之多官能(甲基)丙烯酸酯與聚異氰酸酯進行反應而獲 付。對於聚異氰酸酿，相對於含有活性氯之多官能（甲基） 、烯酉文中之1虽里之活性氫基，以其異氰酸醋基當量計 通常為0.1〜50當量之範圍’較好的是。」，當量之範圍。 反應溫度通常為30〜15〇°C，較好的是50〜H)(rC之範圍。將 利用使殘餘之異氰酸酿與過剩之正丁胺反應，以i N鹽酸 v亍反滴定之方法所计异出的聚異氰酸醋為〇 $重量％以下 的時間點作為反應之終點。 為了縮短反應時間，可Λ ^ 了添加觸媒。作為該觸媒’可使用 驗性觸媒或酸性觸媒之任一者。 作為該驗性觸媒，例如可料：三乙胺、二乙胺、二丁 胺、乱寺胺類’三丁基膦、三苯基膦等膦類，吡啶、吡咯 作為該酸性觸媒，你丨‘ π χ，你 可列舉：環烷酸銅、環烷酸鈷、 %烷酸鋅、三丁氧基鋁、 四丁知二鈦、四丁醇锆等金屬鹽 類；虱化鋁等路易斯酸類 Ζ乙基己烷錫、三月桂酸辛基 錫、二月桂酸二丁基錫、_ 一乙酸辛基錫#錫化合物。 於使用S亥％觸媒之情形卩主 ^ s. Λ 時，其添加量通常可設為相對於 聚異氰酸酯100重量份蛊Λ 里伤為ο.1重量份〜1重量份左右。 146212.doc 201035257 進而’反應時為了防止反應過程中產生聚合，較好的是 使+用聚合抑制劑(例如’對甲氧基苯酚、對苯二酚、甲基 對苯—紛、㈣P井等），其使用量相對於反應混合物為0.01 重量％〜1重量％左右，較好的是0.05重量％〜0.5重量％左 右。反應溫度為60〜150。(：，較好的是8〇〜12〇。(3。 對於本發明之活性能量射線硬化型硬塗層用樹脂組合物 中的分子中具有3個以上（曱基）丙烯醯基之多官能（甲基）丙 烯酸酯化合物（A)的含量，於將該樹脂組合物之固形物成 为设為1〇〇重量％之情形時，其含量通常為2〇 〇重量9 重量°/。’較好的是45.0重量％〜90 · 〇重量％。 作為本發明之活性能量射線硬化型硬塗層用樹脂組合物 中所含的聚丁 一醇骨架部分之數量平均分子量為600以上 的具有聚丁二酵骨架之（曱基）丙稀酸酯化合物（B)，例如可 列舉.聚丁二醇之聚酯（曱基）丙浠酸醋、聚丁二醇之環氧 (甲基）丙烯酸酯、聚丁二醇之（甲基）丙烯酸胺基曱酸酯 等。其中’較好的是聚丁二醇之（曱基）丙烯酸胺基甲酸 酯。聚丁二醇骨架部分之數量平均分子量較好的是 600〜10000左右。 作為該聚丁二醇之聚酯（甲基）丙烯酸酯或該聚丁二醇之 環氧（甲基）丙烯酸酯’例如可列舉下述合成例中所示之化 合物。 作為該聚丁二酵之（甲基）丙烯酸胺基曱酸酯，例如可列 舉：聚丁二醇骨架部分之數量平均分子量為600以上之聚 丁二醇，與六亞曱基二異氰酸酯、脂環式聚異氰酸酯、甲 146212.doc -13- 201035257 笨一異氰酉文自曰、笨二甲基二異氰酸酯、4,4，_二苯基曱燒二 異氰酸醋等有機聚異氰酸醋類，以及（甲基）丙烯酸2-經基 乙S曰、（甲基）丙烯酸2-羥基丙酯、丨，4，丁二醇單（甲基）丙烯 酸醋、ε-己内醋改質（甲基）丙烯酸2_羥基乙醋、季戊四醇 三（甲基）丙烯酸酯等含羥基之乙烯性不飽和化合物類之反 應物。聚丁二醇、有機聚異氰酸酯類、含羥基之乙烯性不 飽和化合物類分別可單獨使用亦可將2種以上混合使用。 又，亦可與聚丁二醇一併使用其他多元醇類。作為其他 多元醇類，可列舉：聚丁二醇以外之聚醚多元醇、乙二 醇、1，4-丁二醇、新戊二醇、聚己内酯多元醇、聚酯多元 醇、聚碳酸醋二醇等。 作為聚丁二醇之（甲基）丙烯酸胺基曱酸酯，較佳之化合 物例如可列舉：分子量為1〇〇〇〜2〇〇〇之聚丁二醇與異佛爾 酮二異氰酸酯及丙烯酸2-羥基乙酯之反應物（丙烯醯基：2 個）等。 上述聚丁二醇之（甲基）丙烯酸胺基甲酸酯可藉由如下方 式而獲得：以相對於聚丁二醇之羥基1當量，有機聚異氛 酸酿類之異氰酸酯基較好的是Μ〜2 〇當量，而於較好的是 70〜90°C下進行反應’繼而，以相對於該反應物1當量含 經基之乙細性不飽和化合物類為1 0〜1 5當量而進行反廣。 該聚丁二醇之（甲基）丙烯酸胺基甲酸酯較好的是於分子的2 個以上之末端部鍵結有丙烯醯基之化合物。 對於本發明之活性能量射線硬化型硬塗層用樹脂組合物 中’聚丁二醇骨架部分之數量平均分子量為600以上的具 146212.doc 14 201035257 有聚丁二醇骨架之（甲基）丙烯酸酯化合物（B)之含量，於將 該樹脂組合物之固形物成分設為100重量％之情形時，其 含量通常為〇.丨重量❶〜10重量❶/。，較好的是1重量％〜5重量 %。若（甲基）丙烯酸酯化合物（B)較少，則有指紋拭除性變 差之傾向，若過多則有硬塗層性下降之傾向。 本發明之活性能量射線硬化型硬塗層用樹脂組合物中可 含有光聚合起始劑（C)。作為該光聚合起始劑（c)，例如可 〇 列舉：安息香、安息香曱醚、安息香乙醚、安息香丙醚、 安息香異丁醚等安息香類；苯乙酮、2,2_二乙氧基_2_苯美 苯乙酮、1，1-二氯苯乙酮、2_羥基_2_甲基_苯基丙烷-^ _、二乙氧基苯乙酮、1-羥基環己基苯基酮、2_曱基— (曱硫基）苯基]-2-咪啉基丙烷酮等苯乙酮類；2_乙基蒽 醌、2-第三丁基蒽醌、2_氣蒽醌、2_戊基蒽醌等蒽醌類； 2,4-二乙基_9-氧硫p山蠖、2_異丙基_9_氧硫咄。星、2_氣_9-氧 硫咄嗟等9-氧硫咄嗤類；苯乙酮二甲縮酮、苯偶醯二甲縮 〇 酮等縮酮類；二苯甲酮、4-苯甲醯基-4，-甲基二苯基硫 醚、4,4'-雙曱基胺基二苯曱酮等二苯甲酮類；2,4,6-三甲 基苯甲醯基二苯基氧化膦、雙（2,4,6_三甲基苯甲醯基）苯基 氧化膦等膦氧化物類等。又，可列舉容易自市場獲取之汽 巴精化（Ciba Specialty Chemicals)公司製造之 184(1-羥基環己基苯基酮）、9〇7(2_甲基_ι_[4_(甲 硫基）苯基]-2-咪琳基丙院·卜酮）、BASF公司製造之 TP〇(2,4,6-三曱基苯曱醯基二苯基氧化膦）等。又，該等可 單獨使用亦可將2種以上混合使用。 146212.doc 15 201035257 對於本發明之活性能量射線硬化型硬塗層用樹脂組合物 中之光聚合起始劑之含量，於將該樹脂組合物之固形 。物成分設為WO重量％之情形時，其含量為〇重量％〜1〇重量 /〇左右，較好的是1重量°/d〜7重量。/。左右。 又，上述光聚合起始劑（C)亦可與硬化促進劑併用。作 為該硬化促進劑’例如可列舉：三乙醇胺、二乙醇胺、N_ 甲基二乙醇胺、苯甲酸2_甲基胺基乙酿、二甲基胺基苯乙 Z對-甲基胺基苯甲酸異戊酿、EPA等之胺類或2_疏基 苯并塞唑等供氫體。對於本發明之活性能量射線硬化型硬❹ 塗層用樹脂組合物中之該硬化促進劑之含量，於將該樹脂 组合物之固形物成分設為1〇〇重量％之情形時，其含量為〇 重量％〜5重量％左右。 〇 人本發明之活性能量射線硬化型硬塗層用樹脂組合物中可 3有一次粒徑為1 nm〜2〇〇 nm之膠體二氧化矽⑴）。該膠體 —氧化矽（D)可以分散於溶劑中之膠體溶液之形式而使 用，亦可以不含分散溶劑的微粉末之二氧化石夕之形式而使 用。作為該分散溶劑，例如可使用：甲醇、乙醇、異丙 醇、正丁醇、二丙酮醇等醇類；乙二醇等多元醇類或其衍 生物；甲基乙基酮、曱基異丁基酮、€己酮、二甲基乙醯 胺等乙酸乙g旨、乙酸正丁酯等酯類；甲苯、二甲苯 等非極性溶劑；丙烯酸2•經基乙自旨等丙烯_旨類.:他: 通有機溶顏，水等。其制量係相對於#體二氧化^ 】〇〇重量％通常為100重量％〜9〇〇重量％。 上述膠體二氧化矽可利用文獻公知之方法而製造，又， 146212.doc -16 - 201035257 亦可使用市售者。作為該膠體二氧切，例如可列舉： 產化學卫m製造之有機二氧切溶膠mek-st/。’日 又’亦可使用利用石夕烧偶合劑等對1氧 理而具有反應性基者。 纟面進仃處 於本發明t ’所謂—次粒徑意指凝聚解散時其粒子所具 有之最小粒徑，可作為BET(Brunaue卜Emmett_Teller ,布 厄特）法之平均粒徑進行測定。(1) A resin composition for an active energy ray-curable hard coat layer, which is a polyfunctional (曱/yl) propyl group having three or more (meth) acryl fluorenyl groups in a molecule; The (4) and the polytetramethylene glycol skeleton portion have an average number of 2 sub-components of 600 or more and have a polytetramethylene glycol skeleton (fluorenyl) acrylated material (8)' and the composition has a refractive index of 145 to 155. The contact angle of the cured film of the composition with oleic acid is 25 degrees or less; D 1462l2.d, 201035257 (2) The resin composition for active energy ray-curable hard coat layer of the above (丨) contains photopolymerization (3) A resin composition for an active energy ray-curable hard coat layer according to the above 〇) or (2), which contains colloidal cerium oxide (D) having a primary particle diameter of 1 nm to 200 nm (4) The resin composition for an active energy ray-curable hard coat layer according to any one of the above (1) to (3), which contains a diluent (E); (5) as described above (丨) to A resin composition for an active energy ray-hardening type hard coat layer comprising 1 to 2 (meth) acrylonitrile groups in a molecule (6) The resin composition for an active energy ray-curable hard coat layer according to any one of the above (A), wherein the polymer has three or more (fluorenyl) acrylonitrile groups in the molecule. a functional (fluorenyl) acrylate compound (A), which is a compound obtained by reacting an active hydrogen-containing poly S-energy sulfonate compound with a polyisocyanate; (7) as described above (丨) to any one of A resin composition for an active energy ray-curable hard coat layer, wherein a polytetramethylene glycol skeleton (meth) acrylate compound (B) having a polytetramethylene glycol skeleton portion having a number average molecular weight of 600 or more is in a molecule (A) A resin for active energy ray hardening type hard coat layer according to any one of the above (1) to (1), which is a (meth) acrylic acid amide group having two or more (fluorenyl) acrylonitrile groups. The composition in which the (meth) acrylate compound (B) having a polytetramethylene glycol skeleton having a number average molecular weight of 600 or more in the polytetramethylene glycol skeleton portion is added in an amount relative to the solid content of the resin composition. 〇weight 146212.doc 201035257 % is 0.1 to 10% by weight; (9) A film comprising the cured film of the resin composition for an active energy ray-curable hard coat layer according to any one of the above (A) to (8); (1) A cured film comprising the resin composition for an active energy ray-curable hard coat layer according to any one of the above (1) to (8); (11) a member for display, A cured film of the resin composition for an active energy ray-curable hard coat layer according to any one of the above (1) to (8); (12) A touch panel member comprising the above (1) to (8) (13) A hard coat film for a touch panel, comprising the active energy ray hardening type hard according to any one of the above (1) A hard coat film for a display comprising a hardening film for a display of an active energy ray hardening type hard coat layer according to any one of the above (1) to (8) Membrane; 〇 (15) - a hard coat film comprising any one of the above (1) to (8) (1) A molded article comprising the active energy of any one of the above (1) to (8) A cured film of a resin composition for a radiation hardening type hard coat layer. [Effect of the Invention] According to the present invention, it is possible to provide an active energy ray hardening type which is excellent in hardness, transparency, scratch resistance, flexibility, fingerprint visibility, fingerprint erasability, and the like, and can also be used for in-mold forming. A resin composition for coating and a cured product of 1462l2.dc, 201035257. [Embodiment] The present invention relates to a resin composition for an active energy ray-curable hard coat layer, which comprises a polyfunctional (fluorenyl) acrylate vinegar having three or more (meth) fluorenyl groups in a molecule. The compound (4) and the polytetramethylene glycol skeleton portion have a (meth) acrylate compound (B) having a polytetramethylene glycol skeleton having a number average molecular weight of 600 or more, and the composition has a refractive index of 丨45 丨55. The contact angle of the cured film of the composition with oleic acid is 25 degrees or less. Hereinafter, the present invention will be described in detail. The polyfunctional (fluorenyl) acrylic acid having 3 or more, preferably 3 to 12 (meth) acrylonitrile groups in the molecule contained in the resin composition for an active energy ray-curable hard coat layer of the present invention. Examples of the ester compound (A) include dihydroxymercaptopropane tris(mercapto) acrylate, trimethylolpropane polyethoxy tris(decyl) acrylate, and epichlorohydrin (ECH, epichhl〇r〇). Hyddn) modified glycerol tri (meth) acrylate, ethylene oxide (E 〇, ethylene 〇xid modified propylene glycol tri (meth) acrylate, cyclopropane (p〇, oxide) modified C Triol triacrylate, pentaerythritol tris(meth)acrylic acid 6 oxime, EO modified acid tris(methyl) acrylate, caprolactone modified trimethyl ketone bis(indenyl) propyl Acidification, EO modification, trimethoprimic tri(meth)acrylate, PO modified trishydroxypropylpropane tris(decyl)acrylate, di(tris-decyl)propane burnt four (A) Acrylate, dipentaerythritol hexa(methyl) acrylate, dipentaerythritol penta(indenyl) acrylate, diquat Octa(meth)acrylate, tris(propyleneoxyethyl)isocyanurate, modified gigapentaerythritol hexa(meth)acrylate, pentaerythritol ethoxylate 146212.doc 10 201035257 Epoxy (mercapto) acrylate such as acrylate, polyoxyhexa(hexa) acrylate, bisphenol A epoxy di(meth) acrylate, polyfunctional (fluorenyl) acrylate containing active hydrogen A polyester (meth) acrylate such as a polyfunctional (meth)acrylic acid phthalic acid ester obtained by a reaction of a polyisocyanate or another (meth)acrylic acid urethane or the like. Furthermore, these may be used alone or in combination of two or more types. Examples of the polyfunctional (fluorenyl) acrylate containing active hydrogen include, for example, pentaerythritol tris(mercapto) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, and a pentaerythritol such as pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate or dipentaerythritol di(meth)acrylate; or a methylol group such as trimethylolpropane di(meth)acrylate; Epoxy acrylate such as bisphenol A diepoxy acrylate. Among them, pentaerythritol triacrylate and dipentaerythritol pentaacrylate are preferred. These polyfunctional (fluorenyl) acrylates containing active hydrogen may be used singly or in combination of two or more. 〇 As the polyisocyanate, a polyisocyanate containing a chain saturated hydrocarbon, a cyclic saturated hydrocarbon (alicyclic) or an aromatic hydrocarbon can be used. Examples of such a polyisocyanate include chain saturated hydrocarbons such as tetramethylene diisocyanate, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate. Polyisocyanate; Ketone diisocyanate, dicyclohexylmethane diisocyanate, methylene bis(4-cyclohexyl isocyanate), hydrogenated diphenyl decane diisocyanate, hydrogenated diphenylene diisocyanate, hydrogenated toluene diisocyanate, etc. Saturated hydrocarbon (alicyclic) polyisocyanate; 2,4-toluene diisocyanate S曰, 1 '3-benzodiazepine diisocyanate, p-phenylene diisocyanate, 146212.doc -11- 201035257 =3 — Methyl-4,4'-diisocyanuric acid, & isopropyl-1,3-phenyl diisocyanine, 1,5-naphthalene diiso(tetra)acetic acid, aromatic polyisocyanate. Among them, preferred are isophorone diisocyanate and hexamethylene diisocyanate. These polyisocyanates may be used singly or in combination of two or more. The above-mentioned g-b-b (meth)acrylic acid amide-based phthalate is obtained by reacting the above-mentioned polyfunctional (meth) acrylate having an activity with a polyisocyanate. For the polyisocyanate, the active hydrogen group in the polyfunctional (methyl) or olefinic group containing active chlorine is usually in the range of 0.1 to 50 equivalents based on the isocyanate equivalent. Better. ", the range of equivalents. The reaction temperature is usually 30 to 15 ° C, preferably 50 to H) (rC range. The residual isocyanate is reacted with excess n-butylamine to counter-titrate with i N hydrochloric acid v亍The time point at which the polyisocyanate vinegar of the method is 〇% by weight or less is used as the end point of the reaction. In order to shorten the reaction time, a catalyst may be added. As the catalyst, an organic catalyst may be used or Any one of the acidic catalysts. For example, a phosphine such as triethylamine, diethylamine, dibutylamine or amphoteric amine such as 'tributylphosphine or triphenylphosphine, pyridine can be used. , pyrrole as the acidic catalyst, you 丨 ' π χ, you can list: copper naphthenate, cobalt naphthenate, zinc alkanoate, tributoxy aluminum, tetrabutyl hydride, zirconium tetrabutoxide, etc. Metal salts; Lewis acid such as bismuth hexaethyl hydride, octyl tin trilaurate, dibutyltin dilaurate, octyl tin methoxide tin compound. In the case of using S-% catalyst When s. Λ, the amount thereof is usually set to be ο.1 parts by weight to 1 part by weight relative to 100 parts by weight of the polyisocyanate. 146212.doc 201035257 Further, in order to prevent polymerization during the reaction, it is preferred to use a polymerization inhibitor for + (for example, 'p-methoxyphenol, hydroquinone, methyl-p-benzene-, and (iv) P wells. And the amount thereof is from 0.01% by weight to about 1% by weight, preferably from 0.05% by weight to about 0.5% by weight, based on the reaction mixture. The reaction temperature is from 60 to 150. (:, preferably 8 〇~ (3) The polyfunctional (meth) acrylate compound having three or more (fluorenyl) acrylonitrile groups in the molecule in the resin composition for active energy ray-curable hard coat layer of the present invention (A) When the content of the solid content of the resin composition is set to 1% by weight, the content is usually 2% by weight and 9% by weight. Preferably, it is 45.0% by weight to 90% by weight. The (meth)acrylic acid having a polybutylene fermentation skeleton having a number average molecular weight of 600 or more as a polybutanol skeleton portion contained in the resin composition for an active energy ray-curable hard coat layer of the present invention The ester compound (B) can be exemplified, for example Polybutylene glycol polyester (mercapto) propionate vinegar, polybutylene glycol epoxy (meth) acrylate, polybutylene glycol (meth) acrylate phthalate, etc. Preferably, the (mercapto) urethane urethane of polytetramethylene glycol has a number average molecular weight of about 600 to 10,000. The polyester as the polytetramethylene glycol (A) The acrylate or the epoxy (meth) acrylate of the polytetramethylene glycol can be exemplified by the compounds shown in the following synthesis examples. As the polybutylidene amide (meth)acrylic acid amide For example, polytetramethylene glycol having a number average molecular weight of 600 or more in the polytetramethylene glycol skeleton portion, and hexamethylene diisocyanate, alicyclic polyisocyanate, and 146212.doc -13 - 201035257 Organic polyisocyanuric acid such as 酉文自曰, stupid dimethyl diisocyanate, 4,4,_diphenyl sulfonium diisocyanate, and 2-(ethyl) acrylate 2-hydroxypropyl (meth)acrylate, hydrazine, 4, butanediol mono(meth)acrylic acid vinegar, ε-caprolactone Mass (meth) acrylate, hydroxy ethyl ester 2_, pentaerythritol tri (meth) acrylate of hydroxy-containing ethylenic unsaturated compounds such as the anti-reactants. The polytetramethylene glycol, the organic polyisocyanate, and the hydroxyl group-containing ethylenically unsaturated compound may be used alone or in combination of two or more. Further, other polyols may be used together with the polytetramethylene glycol. Examples of the other polyhydric alcohols include polyether polyols other than polytetramethylene glycol, ethylene glycol, 1,4-butanediol, neopentyl glycol, polycaprolactone polyols, polyester polyols, and poly Carbonic acid diol and the like. As the (meth)acrylic acid amino phthalate of polytetramethylene glycol, preferred examples of the compound include polytetramethylene glycol having a molecular weight of 1 〇〇〇 2 〇〇〇 and isophorone diisocyanate and acrylic acid 2 - a reaction product of hydroxyethyl ester (propylene thiol: 2) or the like. The above (meth)acrylic acid urethane of polytetramethylene glycol can be obtained by using an organic polyisocyanate-derived isocyanate group in an amount of 1 equivalent to the hydroxyl group of the polytetramethylene glycol. Μ~2 〇 equivalent, and preferably carried out at 70 to 90 ° C. Then, 1 equivalent of the ethylenically unsaturated compound having a trans group relative to the reactant is 10 to 15 equivalents. Conduct anti-wide. The (meth)acrylic acid urethane of the polytetramethylene glycol is preferably a compound in which an acrylonitrile group is bonded to two or more terminal portions of the molecule. In the resin composition for an active energy ray-curable hard coat layer of the present invention, the polytetramethylene glycol skeleton portion has a number average molecular weight of 600 or more and has a polytetramethylene glycol skeleton (meth)acrylic acid having 146,212.doc 14 201035257 When the content of the ester compound (B) is 100% by weight based on the solid content of the resin composition, the content is usually 〇.丨 weight ❶ 1010 ❶/. Preferably, it is 1% by weight to 5% by weight. When the (meth) acrylate compound (B) is small, the fingerprint wiping property tends to be deteriorated, and if it is too large, the hard coat property tends to decrease. The photopolymerization initiator (C) may be contained in the resin composition for an active energy ray-curable hard coat layer of the present invention. As the photopolymerization initiator (c), for example, benzoin, benzoin ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, etc.; acetophenone, 2,2-diethoxy group 2_Benzene acetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methylphenylpropane-^, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone , 2_mercapto-(oxathio)phenyl]-2- morpholinopropanone and the like acetophenone; 2_ethyl hydrazine, 2-tert-butyl fluorene, 2 蒽醌 gas, 2_pentyl hydrazine and the like; 2,4-diethyl_9-oxothiop, and 2_isopropyl_9-oxathiazide. 9-oxopurine such as star, 2_qi_9-oxopurine, ketal such as acetophenone dimethyl ketal and benzoin dimethyl ketal; benzophenone, 4-phenyl ketone Benzophenone-4,-methyldiphenyl sulfide, 4,4'-bis-decylaminodibenzophenone, etc.; 2,4,6-trimethylbenzhydryldiphenyl A phosphine oxide such as phosphine oxide or bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide. Further, 184 (1-hydroxycyclohexyl phenyl ketone) and 9 〇 7 (2_methyl_ι_[4_(methylthio)) manufactured by Ciba Specialty Chemicals Co., Ltd., which is easily available from the market, can be cited. Phenyl]-2-merinyl propyl ketone), TP 〇 (2,4,6-trimercaptophenyl phenyldiphenylphosphine oxide) manufactured by BASF Corporation. Further, these may be used alone or in combination of two or more. 146212.doc 15 201035257 The content of the photopolymerization initiator in the resin composition for active energy ray-curable hard coat layer of the present invention is solidified in the resin composition. When the content of the component is WO% by weight, the content is 〇% by weight to about 1% by weight/〇, preferably 1% by weight/d to 7 parts by weight. /. about. Further, the photopolymerization initiator (C) may be used in combination with a curing accelerator. Examples of the curing accelerator include, for example, triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethyl benzoate, and dimethylaminophenyl Z-p-methylaminobenzoic acid. An amine such as an emulsifier, an EPA or the like, or a hydrogen donor such as a 2-benzoyl benzoxazole. The content of the hardening accelerator in the resin composition for active energy ray-curable hard enamel coating of the present invention is such that when the solid content of the resin composition is 1% by weight, the content is 〇% by weight to about 5% by weight. In the resin composition for an active energy ray-curable hard coat layer of the present invention, there may be a colloidal cerium oxide (1) having a primary particle diameter of 1 nm to 2 〇〇 nm. The colloidal cerium oxide (D) may be used in the form of a colloidal solution dispersed in a solvent, or may be used in the form of a fine powder of a fine powder containing no dispersing solvent. As the dispersion solvent, for example, an alcohol such as methanol, ethanol, isopropanol, n-butanol or diacetone; a polyhydric alcohol such as ethylene glycol or a derivative thereof; methyl ethyl ketone or decyl isobutyl amide can be used. Ethyl acetate such as ketone, hexanone or dimethylacetamide, esters such as n-butyl acetate; non-polar solvents such as toluene and xylene; acrylic acid 2; : He: Organically dissolves the skin, water, etc. The amount of the product is usually from 100% by weight to 9% by weight based on % by weight of the body. The above colloidal cerium oxide can be produced by a method known in the literature, and 146212.doc -16 - 201035257 can also be used commercially. As the colloidal dioxotomy, for example, an organic dioxygen sol mek-st/ manufactured by Chemegom can be cited. In addition, it is also possible to use a reactive base such as a diarrhea coupling agent or the like for oxygen. In the present invention, the so-called sub-grain size means the minimum particle diameter of the particles when agglomerated and dissolved, and can be measured as the average particle diameter of the BET (Brunaue Emmett_Teller, Bourget) method.
Ο 作為上述膠體二氧化矽（D)，可使用其一次粒徑為工 nm 200 nm者，較好的是i nm〜1〇〇 nm者更好的是1 5〇 11111者。尤其是於1 nm〜100 nm之情形時，可確保透 明性’於1 nm〜5G nm之情形時，透明性與濁度可獲得 好之結果。 虽本發明之活性能量射線硬化型硬塗層用樹脂組合物中 3有次粒徑為1 nm〜200 nm的膠體二氧化矽（D)時，於將 °亥祕脂組合物之固形物成分設為100重量％之情形時，盆 3夏以除去分散介質之固形物成分計為0重量％〜70重量 /〇較好的是5重量°/〇〜5 0重量°/〇。 本發明之活性能量射線硬化型硬塗層用樹脂組合物中可 S有稀釋劑（E) ’例如可列舉：γ-丁内酯、γ-戊内酯、γ_己 内酉曰、γ-庚内酯、α_乙醯基_γ_ 丁内酯、ε_己内酯等内酯 類’二ρ号燒、1，2-二甲氧基甲烷、二乙二醇二甲醚、二乙 醇〜乙謎、一乙二醇二丁醚、丙二醇單曱醚、丙二醇單 乙醚、Ο As the above-mentioned colloidal cerium oxide (D), those having a primary particle diameter of 200 nm, preferably i nm to 1 〇〇 nm, more preferably 1 5 〇 11111 can be used. Especially in the case of 1 nm to 100 nm, transparency and turbidity can be obtained with good transparency at 1 nm to 5 G nm. When the resin composition for an active energy ray-curable hard coat layer of the present invention has a colloidal cerium oxide (D) having a secondary particle diameter of from 1 nm to 200 nm, the solid content of the lyophilized composition is In the case of 100% by weight, the pot 3 is determined to have a solid content of the dispersion medium of from 0% by weight to 70% by weight, preferably from 5 parts by weight to 5% by weight to 5% by weight. The resin composition for active energy ray-curable hard coat layer of the present invention may have a diluent (E). For example, γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ- Lactamactone, α-ethionyl_γ_butyrolactone, ε_caprolactone and other lactones such as 'two p-fired, 1,2-dimethoxymethane, diethylene glycol dimethyl ether, diethanol ~B puzzle, monoethylene glycol dibutyl ether, propylene glycol monoterpene ether, propylene glycol monoethyl ether,
四 二乙一醇二甲醚、三乙二醇二乙醚、四乙二醇二 乙二醇二乙醚等醚類；碳酸乙烯酯、碳酸丙烯酯 甲 等 146212.doc 17 201035257 碳酸®旨類；甲基乙基嗣、甲基異丁基酮、環己酮、苯乙嗣 等酮類；I紛、曱紛、二曱苯酴等齡類；乙酸乙顆、乙酸 正丁 3曰、乳酸乙酯、乙基溶纖劑乙酸酯、丁基溶纖劑乙酸 酯、卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇單曱醚乙 酸醋等醋類；甲苯、二甲苯、二乙基苯、冑己烷等烴類； 三氯乙烷、四氯乙烷、單氯苯等函化烴類；石油醚、石油 腦等石油系溶劑等之有機溶劑類；2H，3H-四氟丙醇等氟系 醇類；全氟丁基曱醚、全氟丁基乙醚等氟醚類；甲醇、乙 醇、異丙醇、正丙醇等醇類；兼具酮與醇兩者之性能之二 丙酮醇等。該等可單獨使用亦可將2種以上混合使用。 本發明之活性能量射線硬化型硬塗層用樹脂組合物中可 含有分子中具有1〜2個（曱基）丙烯醯基之（甲基）丙烯酸系化 合物（F)，該（曱基）丙烯酸系化合物（F)為成分（B)以外之化 合物，例如可列舉：聚乙二醇二（甲基）丙烯酸酯、三丙二 醇一（甲基）丙烯酸酯、羥基新戊酸新戊二醇之£_己内酯加 成物之—（曱基）丙烯酸酯（例如，日本化藥（股）製造，Ethers such as tetraethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol diethylene glycol diethyl ether; ethylene carbonate, propylene carbonate, etc. 146212.doc 17 201035257 Carbonic acid®; methyl Ketones such as ethyl hydrazine, methyl isobutyl ketone, cyclohexanone, phenethyl hydrazine; I, deciduous, diterpene benzoquinone and other ages; ethyl acetate, n-butyl acetate, ethyl lactate, B Base cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monoterpene ether acetate vinegar, etc.; toluene, xylene, diethylbenzene Hydrocarbons such as hexane; organic hydrocarbons such as trichloroethane, tetrachloroethane, monochlorobenzene, etc.; petroleum solvents such as petroleum ether and petroleum brain; 2H, 3H-tetrafluoropropanol Fluorine-based alcohols; fluoroethers such as perfluorobutyl decyl ether and perfluorobutyl ether; alcohols such as methanol, ethanol, isopropanol, and n-propanol; diacetone having both ketone and alcohol properties Alcohol, etc. These may be used alone or in combination of two or more. The resin composition for an active energy ray-curable hard coat layer of the present invention may contain a (meth)acrylic compound (F) having 1 to 2 (fluorenyl) acrylonitrile groups in the molecule, which is a (mercapto) acrylic acid. The compound (F) is a compound other than the component (B), and examples thereof include polyethylene glycol di(meth)acrylate, tripropylene glycol mono(meth)acrylate, and hydroxypivalic acid neopentyl glycol. - (mercapto) acrylate of the caprolactone adduct (for example, manufactured by Nippon Kayaku Co., Ltd.)
KAYARAD HX-220、KAYARAD HX-620 等）、雙紛八之 EO 加成物之二（甲基）丙烯酸酯、^4—丁二醇二（甲基）丙烯酸 酉曰、1,6-己一醇二（甲基）丙稀酸醋、1，9_壬二醇二（甲基）丙 烯酸S旨、脂環式（f基）丙烯酸酯類（三環癸烧（甲基）丙烯酸 醋、（曱基）丙烯酸雙環戊二烯氧基乙酯、（甲基）丙烯酸雙 環戊烯酯、（曱基）丙烯酸異捐酯、（甲基）丙烯酸金剛烧酯 等）、（曱基）丙烯酸苯基縮水甘油酯 '(曱基）丙稀酸苄酯、 (甲基）丙烯酸四氫糠酯、（甲基）丙烯醯基咪啉、具有羥基 146212.doc -18- 201035257 之（甲基）丙烯酸酯類G甲基）丙烯酸2_羥基乙酯、（甲基）丙 烯酸2_羥基丙酯、（甲基）丙烯酸4-羥基丁酯等）、乙基卡必 醇（甲基）丙烯酸g旨等。該等可單獨使用亦可將2種以上混合 使用。 對於本發明之活性能量射線硬化型硬塗層用樹脂組合物 中刀子中具有1〜2個（甲基）丙烯醯基之（甲基）丙烯酸系化 p物（F)之含s，於將該樹脂組合物之固形物成分設為i 〇 重量％之情形時’其含量為0重量％〜20.〇重量％，較好的是 1.0重量％〜10.0重量％。 進而’本發明之活性能量射線硬化型硬塗層用樹脂組合 物中’亦可視需要添加調平劑、消泡劑、紫外線吸收劑、 、’穩疋W抗氧化劑、聚合抑制劑、交聯劑、夥體二氧化 伟）以外之無機微粒、填充料等，而分別賦？目標之功 作為調平劑，較好的是倍用尤处 Μ〜 不妨礙耐減可見性之丙烯 Q &系、尚沸點溶劑系。 作為紫外線吸收劑，可、， 田納/ 〗举.本开三唑系化合物、二笨 甲酮糸化合物、三畊系化合物 與· * 介马光穩定劑，可列 舉.党阻胺系化合物、苯甲酸 劑，可列舉紛系化合物等。系化合物等;作為抗氧化 作為聚合抑制劑，可列舉： 酚、對苯-酚算，祚^孔基苯酚、甲基對苯二 對本一酚專，作為交聯劑，可 類、三聚氰胺化合物等。 述♦異flS夂酯 作為無機微粒，可列舉：録酸鋅 t鎵氧化鋅、摻鋁氧 H6212.doc 19 201035257 化辞、氧化錫、摻銻氧化錫、摻磷氧化錫、摻銦氧化錫等 導電性金屬氧化物以及氧化鈦、氧化锆等用以調整折射率 之金屬氧化物。 作為填充料，可列舉平均粒徑為微米級之二氧化石夕或壓 克力珠（acrylic beads)、胺酯珠（urethane bead)等，可為了 對塗膜表面賦予凹凸之目的而使用。 本發明之活性能量射線硬化型硬塗層用樹脂組合物係按 照任思之順序，將上述成分、成分以及視需要之成 分（C)、成分（D)、成分（E)、成分（F)及其他成分加以混人 而獲得。 口 本發明之活性能量射線硬化型硬塗層用樹脂組合物係 使其固形物成分為1〇〇%之情形（稀釋劑之折射率除外時） 時’ 25。(：下之折射率為1454.55之範圍的樹月旨組合物。若 折射率為該範圍外，則存在與所附著之指紋按壓痕跡之折 射率的差過大，指紋按壓痕跡變得非常容易看到之傾向。 如此而獲得的本發明之活性能量射線硬化型硬塗層用樹 脂組合物經時穩定。 藉由下述方式而獲得之膜亦包含於本發明中，即，將本 發明之活性能量射線硬化型硬塗層用樹脂組合物，以該樹 脂組合物乾燥後之膜厚通常為〇.! μηι〜5〇 、較好的是\ μιη〜20 μΐη2方式塗佈於基材膜上，進行乾燥後，昭射ζ 性能量射線形成硬化膜而獲得之膜。亦可藉由將本發明之 活性能量射線硬化型硬塗層用樹脂組合物設置於最表層， 而製成多層塗佈之膜加以使用。 146212.doc -20· 201035257 作為該基材膜並無特別限定，例如可列舉：聚酯、聚丙 稀、聚乙烯、聚丙稀酸醋、聚碳酸醋、三乙醯纖維素、聚 鍵硬、環稀烴系聚合物等。作為所使用之膜，可為·設置 有花紋或易黏接層、基礎層I’經實施電暈處理等表面處 理者’經實施脫模處理者。 作為該活性能量射線硬化型硬塗層用樹脂組合物之塗佈 方法，例如可列舉：棒式塗佈機塗佈、絲棒（Meyer bar)塗 〇 佈1刀塗佈、凹版印刷塗佈、反向凹版印刷塗佈、微凹 版P刷塗佈、微反向凹版印刷塗佈機塗佈、狹縫擠壓式塗 佈機塗佈、浸潰塗佈、旋轉式塗佈、噴霧塗佈等。 作為使本發明之活性能量射線硬化型硬塗層用樹脂組合 物硬化之活性能量射線，可列舉：紫外線、電子束等。 一於藉由紫外線進行硬化之情形時，作為光源可使用包含 氣氣燈、高塵水銀燈、金屬鹵素燈等之紫外線照射裝置， 並視需要調整光量、光源之配置等。於使用高壓水銀燈之 〇 情形時，較好的是以相對於1盞具有80〜120 W/cm2之能量 之4 ’搬送速度為5〜60 m/min而進行硬化。 :藉由電子束進行硬化之情形時，較好的是使用具有 1〇〇〜500 eV之能量之電子束加速裝置，此時，可不使用光 聚合起始劑（D)。 將本發明之活性能量射線硬化型硬塗層用樹脂組合物硬 化而獲得之硬化膜與油酸的接觸角較好的是乃度以下，更 好的是23度以下。若為3〇度以上，則即使折射率在 5 1.55之範圍内’亦容易看到附著之指紋按壓痕跡。油 146232.doc 201035257 δλ係成分與指紋按壓痕跡接近之物質，因此預想若與油酸 之接觸角較低則難以看到指紋按麼痕跡。 包含本發明之活性能量射線硬化型硬塗層用樹脂組合物 之硬化膜的基材亦包含於本發明中。又，包含該硬化膜之 顯示用構件、觸摸面板構件亦包含於本發明中。 進而，包含該硬化膜之觸摸面板用硬塗膜、顯示器用硬 塗膜、用於模内成形之硬塗膜亦包含於本發明中，包含該 硬化膜之觸摸面板、顯示器等成形物亦包含於本發明中。 [實施例] 以下，利用實施例更詳細地說明本發明，但本發明並不 受該等實施例之限定。又，只要未加以特別說明，實施例 中之份係表示重量份。 合成例1 向乾燥容器中加入1395.1份聚丁二醇（保土谷化學工業製 造之PTG-2000SN ;分子量為1993)、311 2份異佛爾酮二異 氰酸酯，一面攪拌一面緩緩升溫至8(rc為止，於⑼它下進 行反應。當異氰酸酯之比例達到6 7〜7_2%之範圍時，添加 167.4份丙烯酸2-羥基乙酯，〇.5份對甲氧基苯酚，再次缓 緩升溫至8(TC為止，一面攪拌5小時一面進行反應，繼而 添加0.15份月桂酸二丁基錫，進一步進行反應直至異氰酸 酯之比例達到0.1%以下，反應大致定量地結束為止。所合 成之聚丁二醇之丙烯酸胺基甲酸酯具有2個丙烯醯基。 合成例2 向乾燥容器中加入595，0份聚丁二醇（保土谷化學工業製 146212.doc -22· 201035257 造之PTG-850SN;分子量為850)、3112份異佛爾酮二異氰 酸酯，一面攪拌一面缓缓升溫至8〇t為止，於8〇t下進行 反應。當異氰酸酯之比例達到6.7〜7.2%之範圍時，添加 167.4份丙烯酸2-羥基乙酯、〇·5份對甲氧基苯酚，再次緩 缓升溫至80°C為止，-面授拌5小時一面進行反應，繼而 添加0.15份月桂酸二丁基錫，進而進行反應直至異氰酸酯 之比例達到0.1%以下，反應大致定量地結束為止。所合成 之聚丁二醇之丙烯酸胺基甲酸酯具有2個丙稀醯基。 fl U 合成例3 向乾燥容器中加入2030.0份聚丁二醇（保土谷化學工業製 造之PTG-2900;分子量為2900)、3U.2份異佛爾酮二異氰 酸酯，一面攪拌一面緩緩升溫至80°c為止，於8〇〇c下進行 反應。當異氰酸酯之比例達到6.7〜7·2%之範圍時，添加 167.4份丙烯酸2-羥基乙酯、〇.5份對甲氧基苯酚，再次緩 缓升溫至80°C為止，一面攪拌5小時一面進行反應，繼而 q 添加〇.15份月桂酸二丁基錫，進而進行反應直至異氰酸酯 之比例達到0.1%以下，反應大致定量地結束為止。所合成 之聚丁二醇之丙烯酸胺基曱酸酯具有2個丙烯醯基。 •合成例4 向乾燥容器中加入1395.1份聚丁二醇（保土谷化學工業製 造之PTG-2000SN ;分子量為1993)、235_2份六亞甲基二異 氰酸醋，一面攪拌一面緩緩升溫至80°c為止，於8〇t>c下進 行反應。當異亂酸g旨之比例達到6.7〜7.2%之範圍時，添加 184.7份丙烯酸2-羥基丙酯、〇·5份對甲氧基苯酚，再次缓 146212.doc -23· 201035257 緩升溫至80°C為止，一面攪拌5小時一面進行反應，繼而 添加0· 15份月桂酸二丁基錫，進而進行反應直至異氰酸酯 之比例達到0.1 %以下，反應大致定量地結束為止。所合成 之聚丁二醇之丙浠酸胺基甲酸酯具有2個丙烯醯基。 合成例5 向乾燥容器中加入1300.0份聚丁二醇二縮水甘油醚（四曰 市合成公司製造之£口〇§〇36丫；分子量為650)、146.9份丙浠 酸、0.5 份 TMAC(tetramethylammonium chloride，四曱基 氯化銨）、〇·5 份 BHT(dibutylhydroxytoluene，二丁 基經基 曱苯），缓缓升溫至98°C為止，於98°C下進行反應。所合 成之聚丁二醇之環氧丙烯酸酯之環氧當量為15800，酸值 為0.73，且具有2個丙烯醯基。 合成例6 將1000.0份聚丁二醇（保土谷化學工業製造之PTG-2000SN ;分子量為1993)、86·4份丙烯酸、0·4份酚噻畊、 0.8份硫酸、1000 ml正庚烧投入至燒瓶中，一面吹入經氮 氣稀釋之空氣，一面將餾出液以靜置層而分離成水層與庚 炫層，繼而一面使庚烧層返回至燒瓶一面進行反應。於德 出水之量大致達到理論量之時間點中止反應，將反應液滴 加至水中而使生成物析出，進行過濾，獲得聚丁二醇之二 丙稀酸S旨。 合成例7 向乾燥容器中加入1395.1份聚丙二醇（保土谷化學工業製 造之？卩0-200081^;分子量為2000)、235.2份六亞曱基二異 146212.doc -24- 201035257 氛酸醋’一面攪拌一面緩緩升温至8〇〇c為止，於8〇c>c下進 行反應。當異氰酸酯之比例達到6.7〜7 2%之範圍時，添加 184.7份丙烯酸2-羥基丙酯、〇 5份對曱氧基苯酚，再次缓 緩升溫至801為止，一面攪拌5小時一面進行反應，繼而 添加0.15份月桂酸二丁基錫，進而進行反應直至異氰酸酯 之比例達到0.1%以下，反應大致定量地結束為止。所合成 之聚丁二醇之丙烯酸胺基甲酸酯具有2個丙烯醯基。 Ο 〇 合成例8 向乾燥容器中加入1395.1份聚丁二醇（保土谷化學工業製 造之PTG-2000SN ;分子量為1993)、235.2份六亞曱基二異 氰酸酯，一面攪拌一面緩緩升溫至8(rc為止，於8〇(>c下進 行反應富異氰酸酯之比例達到6.7〜7.2%之範圍時，添加 425.7份季戊四醇三丙烯酸酯、〇 5份對甲氧基苯酚，再次 缓緩升溫至8(TC為止，-面攪拌5小時一面進行反應，繼 而添加0.15份月桂酸二丁基錫，進而進行反應直至異氰酸 酯之比例達到〇.1%以下，反應大致定量地結束為止。所合 成之聚丁二醇之丙烯酸胺基甲酸酯具有6個丙烯醯基。 合成例9 向乾燥容器中加入2030.0份聚丁二醇（保土谷化學工業製 造之PTG-2900;分子量為2900)、235 2份六亞甲基二異氰 酸酯，一面攪拌一面緩缓升溫至80。〇：為止，於8〇t下進行 反應。當異氰酸醋之比例達到6.7〜7.2%之範圍時，添加 425.7份李戊四醇三丙烯酸酯、〇.5份對甲氧基笨酚，再次 缓緩升溫至80。(：為止’-面授拌5小時一面進行反應，繼 146212.doc •25· 201035257 而添加o.15份月桂酸二丁基錫，進而進行反應直至異氛酸 酯之比例達到o.i。/❶以下，反應大致定量地結束為止。所合 成之聚丁二醇之丙烯酸胺基甲酸酯具有6個丙烯醯基。 合成例10 向乾燥容器中加入1395.1份聚丁二醇（保土谷化學工業製 造之PTG-2000SN;分子量為1993)、235 2份六亞甲基二異 氰酸酯，一面攪拌一面緩緩升溫至8〇〇c為止，於8〇<t下進 行反應。當異氰酸酯之比例達到6.7〜72%之範圍時，添加 744.1份一季戊四醇二丙婦酸酯、〇5份對甲氧基苯盼，再 次緩緩升溫至80°C為止，一面攪拌5小時一面進行反應， 繼而添加0.15份月桂酸二丁基锡，進而進行反鹿直至異氛 酸酯之比例達到0.1 %以下，反應大致定量地結束為止。所 合成之聚丁二醇之丙烯酸胺基甲酸酯具有1〇個丙稀醯基。 實施例1〜14及比較例1〜5 利用棒式塗佈機，將以表1所示之比例調配各構成成分 所得之樹脂組合物’塗佈於已實施易黏接處理之 PET(polyethylene terephthalate’ 聚對苯二曱酸乙二醋）膜 (100 μπι)上’於約80〜100°C下進行乾燥後，利用紫外線照 射器（哈利盛東之知、明（Harison Toshiba Lighting)股份有限 公司：KUV-40151-1XKA-DM)，以高壓水銀燈：8〇 W/cm，燈高度：l〇cm，輸送速度：5 m/minx3次（能量： 約200 mW/cm2、約360 mJ/cm2)之條件進行硬化，獲得膜 厚約為4 μιη之硬塗膜。再者’表1中單位表示「份」。 146212.doc • 26 - 201035257 [表i] 實施例1 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 DPIL^l PET-3(^2 45.0 45.0 45.0 45.0 45.0 45.0 47.0 25.0 多官能胺基曱酸酯※3 ¢)成分 合成例1之化合物 2.5 0.5 2.5 合成例2之化合物 2.5 合成例3之化合物 2.5 合成例4之化合物 2.5 合成例5之化合物 2.5 合成例6之化合物 2.5 合成例7之化合物 合成例8之化合物 合成例9之化合物 合成例10之化合物 PTG2000SN (C)成分 Irg. ”々※斗 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 (D)成分 MEX-SI^5 35.0 MffiK-ST^6 35.0 (E)成分 MEX 25.0 25.0 25.0 25.0 25.0 25.0 25.0 MIBK 25.0 25.0 25.0 25.0 25.0 25.0 25.0 (F)成分 ππ^7 其他成分 高折射率劑※8 調平劑※9 合計 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0KAYARAD HX-220, KAYARAD HX-620, etc.), bis(8) EO adducts of di(meth)acrylate, ^4-butanediol di(meth)acrylate, 1,6-hexa Alcohol di(meth)acrylic acid vinegar, 1,9-nonanediol di(meth)acrylic acid S, alicyclic (f-) acrylate (tricyclic tercene (meth) acrylate, ( Mercapto) dicyclopentadienyloxyethyl acrylate, dicyclopentenyl (meth) acrylate, isomeric ester of (mercapto) acrylate, acetonide (meth) acrylate, etc., phenyl (fluorenyl) acrylate Glycidyl ester '(mercapto) benzyl acrylate, (meth) methacrylate, (meth) acryl quinazoline, (meth) acrylate having hydroxy 146212.doc -18- 201035257 G-methyl)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxypropyl ester, (meth)acrylic acid 4-hydroxybutyl ester, etc., ethyl carbitol (meth)acrylic acid g, and the like. These may be used alone or in combination of two or more. In the resin composition for an active energy ray-curable hard coat layer of the present invention, the s-containing (meth)acrylic p-substrate (F) having 1 to 2 (meth)acrylonyl groups in the knives in the knives is When the solid content of the resin composition is i% by weight, the content is from 0% by weight to 20.% by weight, preferably from 1.0% by weight to 10.0% by weight. Further, in the resin composition for active energy ray-curable hard coat layer of the present invention, a leveling agent, an antifoaming agent, an ultraviolet absorber, a 'stabilized W antioxidant, a polymerization inhibitor, a crosslinking agent may be added as needed. In addition to the inorganic particles, fillers, etc., other than the body The work of the target As a leveling agent, it is better to use it more than Μ~ propylene which does not hinder the visibility reduction. Q & As a UV absorber, it can be used, and it can be mentioned as a compound of a triazole compound, a dimethylene ketone oxime compound, a tri-farming compound, and a dimethyl-stabilizer. Examples of the benzoic acid agent include various compounds. As a polymerization inhibitor, as a polymerization inhibitor, phenol, p-benzene-phenol, porphine-based phenol, methyl-p-phenylene-p-butyl phenol, as a crosslinking agent, a melamine compound, etc. . Said iso-flS oxime ester as inorganic particles, for example: zinc cadmium t-gallium oxide, aluminum oxide H6212.doc 19 201035257 chemical, tin oxide, antimony-doped tin oxide, phosphorus-doped tin oxide, indium-doped tin oxide, etc. A conductive metal oxide, a metal oxide such as titanium oxide or zirconium oxide for adjusting the refractive index. Examples of the filler include carbon dioxide having an average particle diameter of a micron order, acrylic beads, urethane bead, and the like, and can be used for the purpose of imparting irregularities to the surface of the coating film. The resin composition for active energy ray-curable hard coat layer of the present invention contains the above components, components, and optional components (C), components (D), components (E), and components (F) in the order of any consideration. And other ingredients are mixed and obtained. The resin composition for an active energy ray-curable hard coat layer of the present invention has a solid content of 1% by weight (when the refractive index of the diluent is excluded). (The following composition is in the range of the refractive index of 1455.55. If the refractive index is outside the range, the difference in refractive index from the attached fingerprint pressing trace is too large, and the fingerprint pressing trace becomes very easy to see. The resin composition for an active energy ray-curable hard coat layer of the present invention obtained in this manner is stabilized over time. A film obtained by the following method is also included in the present invention, that is, the active energy of the present invention The resin composition for a radiation-hardening type hard coat layer is applied to a base film by a method of drying the resin composition after drying, and the film thickness is usually 〇 ! η 〜 〇 较好 较好 较好 较好 较好 20 20 20 20 20 20 20 20 20 20 20 20 20 After drying, the film obtained by forming a cured film by the amount of the ray is formed. The resin composition for active energy ray-curable hard coat layer of the present invention can be formed on the outermost layer to form a multilayer coated film. 146212.doc -20· 201035257 The substrate film is not particularly limited, and examples thereof include polyester, polypropylene, polyethylene, polyacrylic acid vinegar, polycarbonate, triacetyl cellulose, and poly bond. hard, A cycloaliphatic polymer or the like. The film to be used may be a person who has a pattern or an easy-adhesion layer, and a surface layer I' is subjected to a surface treatment such as corona treatment. The coating method of the resin composition for an energy ray hardening type hard coat layer is, for example, a bar coater coating, a Meyer bar coating, a gravure coating, a reverse gravure. Printing coating, micro gravure P brush coating, micro reverse gravure coater coating, slit extrusion coater coating, dip coating, spin coating, spray coating, etc. The active energy ray which is cured by the resin composition for an active energy ray-curable hard coat layer of the present invention may, for example, be an ultraviolet ray or an electron beam. When the film is cured by ultraviolet rays, a gas lamp may be used as the light source. Ultraviolet irradiation devices such as high-dust mercury lamps and metal halide lamps, and adjusting the amount of light and the arrangement of light sources as needed. When using a high-pressure mercury lamp, it is preferable to have 80 to 120 W/cm 2 with respect to 1 盏. Energy 4 'moving The curing is performed at a speed of 5 to 60 m/min. When the electron beam is used for hardening, it is preferred to use an electron beam acceleration device having an energy of 1 to 500 eV. In this case, photopolymerization may not be used. The starting agent (D). The contact angle of the cured film obtained by curing the resin composition for active energy ray-curable hard coat layer of the present invention with oleic acid is preferably at most or less, more preferably at least 23 degrees. If it is more than 3 degrees, even if the refractive index is in the range of 5 1.55, it is easy to see the attached fingerprint pressing marks. Oil 146232.doc 201035257 δλ is a substance close to the fingerprint pressing trace, so it is expected to be with oil. When the contact angle of the acid is low, it is difficult to see the fingerprint. The substrate comprising the cured film of the resin composition for an active energy ray-curable hard coat layer of the present invention is also included in the present invention. Further, the display member and the touch panel member including the cured film are also included in the present invention. Further, a hard coat film for a touch panel including the cured film, a hard coat film for a display, and a hard coat film for in-mold molding are also included in the present invention, and a molded article such as a touch panel or a display including the cured film is also included. In the present invention. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited. Further, the parts in the examples represent parts by weight unless otherwise specified. Synthesis Example 1 To a drying container, 1395.1 parts of polytetramethylene glycol (PTG-2000SN manufactured by Hodogaya Chemical Industry Co., Ltd.; molecular weight: 1993) and 3112 parts of isophorone diisocyanate were added, and the temperature was gradually raised to 8 (rc) while stirring. The reaction was carried out under (9). When the ratio of isocyanate reached 6 7 to 7 - 2%, 167.4 parts of 2-hydroxyethyl acrylate was added, and 5 parts of p-methoxyphenol was gradually heated to 8 ( The reaction was carried out while stirring for 5 hours, and then 0.15 parts of dibutyltin laurate was added, and the reaction was further carried out until the ratio of the isocyanate reached 0.1% or less, and the reaction was quasi-quantitatively terminated. The formate has two propylene groups. Synthesis Example 2 To the drying vessel, 595, 0 parts of polybutylene glycol (PTG-850SN made by Guardian Valley Chemical Industry 146212.doc -22·201035257; molecular weight 850), 3112 parts of isophorone diisocyanate, the temperature was gradually raised to 8 〇t while stirring, and the reaction was carried out at 8 〇t. When the ratio of isocyanate reached 6.7 to 7.2%, 167.4 parts of acrylic acid 2 was added. -Hydroxyethyl ester, hydrazine · 5 parts of p-methoxy phenol, the temperature was gradually raised to 80 ° C, and the reaction was carried out for 5 hours, and then 0.15 parts of dibutyltin laurate was added, and the reaction was further carried out until the ratio of isocyanate When the reaction amount is 0.1% or less, the reaction is substantially quantitatively completed. The acrylamide urethane of the synthesized polytetramethylene glycol has two acrylonitrile groups. fl U Synthesis Example 3 2030.0 parts of polytetramethylene glycol is added to a drying vessel. (PTG-2900 manufactured by Hodogaya Chemical Industry; molecular weight 2900), 3U. 2 parts of isophorone diisocyanate, slowly heated to 80 ° C while stirring, and reacted at 8 ° C. When isocyanate When the ratio is in the range of 6.7 to 7.2%, 167.4 parts of 2-hydroxyethyl acrylate and 5 parts of p-methoxyphenol are added, and the temperature is gradually raised to 80 ° C, and the reaction is carried out while stirring for 5 hours. Then, q is added with 15 parts of dibutyltin laurate, and the reaction is further carried out until the ratio of the isocyanate reaches 0.1% or less, and the reaction is quasi-quantitatively terminated. The synthesized polybutylene glycol amide phthalate has 2 C.醯基。·Synthesis Example 4 1395.1 parts of polytetramethylene glycol (PTG-2000SN manufactured by Hodogaya Chemical Industry Co., Ltd.; molecular weight 1993) and 235_2 parts of hexamethylene diisocyanate were added to a drying vessel while stirring. The reaction was carried out at 8 〇t>c until the temperature was raised to 80 ° C. When the ratio of the dissociated acid g was in the range of 6.7 to 7.2%, 184.7 parts of 2-hydroxypropyl acrylate and 〇·5 parts were added. Methoxy phenol, again 146212.doc -23· 201035257 The temperature was raised to 80 ° C, and the reaction was carried out while stirring for 5 hours, followed by the addition of 0.15 parts of dibutyltin laurate, and the reaction was further carried out until the ratio of isocyanate reached 0.1. Below %, the reaction is roughly quantitatively completed. The propionate urethane of the synthesized polytetramethylene glycol has two acrylonitrile groups. Synthesis Example 5 To a dry container, 1300.0 parts of polytetramethylene glycol diglycidyl ether (manufactured by Siken Synthetic Co., Ltd.; molecular weight: 650), 146.9 parts of propionic acid, and 0.5 part of TMAC (tetramethylammonium) were added. Chloride, tetradecyl ammonium chloride), bismuth 5 parts of BHT (dibutylhydroxytoluene, dibutyl fluorenyl benzene), the temperature was gradually raised to 98 ° C, and the reaction was carried out at 98 ° C. The epoxy acrylate of the synthesized polytetramethylene glycol had an epoxy equivalent of 15,800, an acid value of 0.73, and had 2 acrylonitrile groups. Synthesis Example 6 1000.0 parts of polytetramethylene glycol (PTG-2000SN manufactured by Hodogaya Chemical Industry Co., Ltd.; molecular weight: 1993), 86. 4 parts of acrylic acid, 0.4 parts of phenolic sulphate, 0.8 parts of sulfuric acid, and 1000 ml of n-gumane were put into operation. Into the flask, while diluting the air diluted with nitrogen, the distillate was separated into a water layer and a helium layer by standing on a layer, and then the helium layer was returned to the flask while the reaction was carried out. The reaction was stopped at the time when the amount of water discharged from the Germans reached the theoretical amount, and the reaction liquid droplets were added to water to precipitate a product, which was filtered to obtain a dipropylene glycol of polytetramethylene glycol. Synthesis Example 7 1395.1 parts of polypropylene glycol (manufactured by Hodogaya Chemical Industry Co., Ltd.; 卩0-200081^; molecular weight: 2000), 235.2 parts of hexamethylenediamine 146212.doc -24-201035257 sucrose vinegar were added to a drying vessel. The mixture was gently heated to 8 ° C while stirring, and the reaction was carried out at 8 ° C > c. When the ratio of the isocyanate is in the range of 6.7 to 7.2%, 184.7 parts of 2-hydroxypropyl acrylate and 5 parts of p-methoxyphenol are added, and the temperature is gradually raised to 801, and the reaction is carried out while stirring for 5 hours, and then the reaction is carried out. 0.15 parts of dibutyltin laurate was added, and the reaction was further carried out until the ratio of the isocyanate reached 0.1% or less, and the reaction was almost quantitatively completed. The acrylic urethane of the synthesized polytetramethylene glycol has two acrylonitrile groups. Ο 〇 Synthesis Example 8 1395.1 parts of polytetramethylene glycol (PTG-2000SN manufactured by Hodogaya Chemical Industry Co., Ltd.; molecular weight: 1993) and 235.2 parts of hexamethylene diisocyanate were added to a drying vessel, and the temperature was gradually raised to 8 while stirring. For rc, when the ratio of the reaction-rich isocyanate reached 6.7 to 7.2% under 8 〇 (>c, 425.7 parts of pentaerythritol triacrylate and 〇5 parts of p-methoxyphenol were added, and the temperature was gradually raised again to 8 ( The reaction was carried out until TC was stirred for 5 hours, and then 0.15 parts of dibutyltin laurate was added, and the reaction was further carried out until the ratio of the isocyanate reached 0.1% or less, and the reaction was quasi-quantitatively completed. The urethane urethane has 6 propylene fluorenyl groups. Synthesis Example 9 2030.0 parts of polytetramethylene glycol (PTG-2900 manufactured by Hodogaya Chemical Industry Co., Ltd.; molecular weight 2900) and 2352 parts of hexamethylene group were added to a drying vessel. The diisocyanate was gradually heated to 80 while stirring. The reaction was carried out at 8 Torr. When the ratio of isocyanic acid vine reached 6.7 to 7.2%, 425.7 parts of pentaerythritol tripropylene was added. Ester, 〇. 5 parts of p-methoxy phenol, once again slowly warmed to 80. (: until the '- face-to-face mixing for 5 hours while the reaction, followed by 146212.doc •25· 201035257 and added o.15 parts of lauric acid II Butyltin is further reacted until the ratio of the isocyanate reaches oi./❶ or less, and the reaction is substantially quantitatively completed. The acrylamide urethane of the synthesized polytetramethylene glycol has 6 propylene groups. 1395.1 parts of polytetramethylene glycol (PTG-2000SN manufactured by Hodogaya Chemical Industry Co., Ltd.; molecular weight: 1993) and 2352 parts of hexamethylene diisocyanate were added to the drying vessel, and the temperature was gradually raised to 8 〇〇c while stirring. The reaction was carried out at 8 Torr < t. When the ratio of isocyanate reached 6.7 to 72%, 744.1 parts of pentaerythritol dipropionate and 〇 5 parts of p-methoxybenzene were added, and the temperature was again slowly raised to 80. The reaction was carried out while stirring for 5 hours at ° C, and then 0.15 parts of dibutyltin laurate was added, and the ratio of the anti-deer to the isocyanate was 0.1% or less, and the reaction was quasi-quantitatively finished. Alcohol The acid urethane has 1 acrylonitrile group. Examples 1 to 14 and Comparative Examples 1 to 5 Resin compositions obtained by blending the respective components in the proportions shown in Table 1 by a bar coater 'Using a PET (polyethylene terephthalate' polyethylene terephthalate) film (100 μπι) that has been subjected to an easy adhesion treatment to dry at about 80 to 100 ° C, using an ultraviolet ray irradiator ( Harison Toshiba Lighting Co., Ltd.: KUV-40151-1XKA-DM), high pressure mercury lamp: 8〇W/cm, lamp height: l〇cm, conveying speed: 5 m/minx3 Hardening was carried out under the conditions of (secondary energy: about 200 mW/cm2, about 360 mJ/cm2) to obtain a hard coat film having a film thickness of about 4 μm. Furthermore, the unit in Table 1 indicates "parts". 146212.doc • 26 - 201035257 [Table i] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 (A) Component DPIL^l PET-3 (^2 45.0 45.0 45.0 45.0 45.0 45.0 47.0 25.0 Polyfunctional amino decanoate*3 ¢) Component Synthesis Example 1 Compound 2.5 0.5 2.5 Synthesis Example 2 Compound 2.5 Synthesis Example 3 Compound 2.5 Synthesis Example 4 Compound 2.5 Synthesis Example 5 Compound 2.5 Compound of Synthesis Example 6 Synthesis of Compound of Synthesis Example 7 Synthesis of Compound of Example 8 Synthesis of Compound of Example 9 Synthesis of Compound of Example 10 PTG2000SN (C) Component Irg. "々※斗2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 (D) Component MEX -SI^5 35.0 MffiK-ST^6 35.0 (E) Component MEX 25.0 25.0 25.0 25.0 25.0 25.0 25.0 MIBK 25.0 25.0 25.0 25.0 25.0 25.0 25.0 (F) Component ππ^7 Other components High refractive index agent ※8 Leveling agent ※ 9 total 100.0 100.0 100 .0 100.0 100.0 100.0 100.0 100.0
-27- 146212.doc 201035257 實施例 9 實施例 10 實施例 11 實施例 12 實施例 13 實施例 14 比較例 1 比較例 2 比較例 3 比較例 4 比較例 5 25.0 45.0 37.5 45.0 45.0 47.5 45.0 45.0 25.0 45.0 45.0 2.5 2.5 5.0 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 50.0 20.0 25.0 25.0 25.0 25.0 25.0 」 25.0 25.0 25.0 11.7 25.0 25.0 25.0 25.0 25.0 25.0 25 0 25 0 25.0 25.0 25.0 5.0 33.3 0.005 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 (言主） ※1 · 一季戊四醇五丙稀酸酯/六丙稀酸酯混合物 ※2 .季戊四醇二丙稀酸g旨/四丙烯酸自旨混合物 ※3:曰本化藥公司製造之KAYARAD DPHA-40H(10官能 丙稀酸胺基曱酸醋） ※4 :汽巴精化公司製造，丨_羥基環己基苯基酮 -28- 146212.doc 201035257 ※5:日產化學工業公司製造之有機二氧化矽溶膠，固形 物成分為30%，MEK(甲基乙基酮）分散液（平均粒徑：1 〇 nm~l5 nm) ※6:日產化學工業公司製造之有機二氧化矽溶膠，固妒 物成分為30%，MIBK(曱基異丁基酮）分散液（平均粒複： 10 nm〜15 nm) ※了：丙烯酸四氫糠酯 ※8 :録酸辞溶膠，固形物成分為60%，曱醇分散液 〇 ※9 : BYK-Chemie公司製造，BYK306(矽系） 關於實施例1〜14、比較例1〜5中獲得之硬塗膜，對下述 項目進行評價，其結果示於表2。 (鉛筆硬度） 依據JIS κ 5600，使用鉛筆劃痕試驗機，測定上述組成 之塗佈膜之鉛筆硬度。詳細而言，於包含要測定之硬化皮 膜之聚醋膜上，以45度之角度設置鉛筆’自上方施加75〇 〇 g之負載’劃出5 mm左右痕跡，以5次中4次以上未形成劃 痕之鉛筆硬度進行表示。 (耐指紋可見性_〇 以間距為50〜1〇〇 μιη之樹脂模將下述人工指紋液壓印於 上述組成之塗佈膜上，藉由濁度測定來確認其印痕。 (耐指紋可見性_2) 目視確認（耐指紋可見性-1)之印痕。 〇：幾乎看不到 △.稍微看到 1462l2.d〇c •29- 201035257 χ :清楚地看到 (指紋拭除性-1) 施加200 g/cm2之負載將（耐指紋可見性 ^〈印痕反覆拭 除1 〇次’藉由濁度測定確認痕跡之殘留狀況。 (指紋拭除性-2) 目視確認（指紋拭除性-1)之痕跡之殘留狀況 〇：無痕跡殘留 △:稍有殘留 X :殘留顯眼 <人工指紋液> 利用以下之組成比製備使用。 油酸：6.1 % 橄稅油：29.3% 荷荷芭油：47.5% 角鯊烯：17.1% (接觸角） 使用自動接觸角儀（協和界面科學股份有限公司製造之 DM500)，測定上述組成之塗佈膜之接觸角。詳細而言， 於包含要敎之硬化皮膜之聚賴上滴加油酸進行測定°。 (延伸率） 使用拉伸試驗機（〇rientec股份有限公司製造之Μ. 25〇)，將寬10 mmx長5〇 mm之膜於常溫下以每分鐘5〇 mm 的速度進行延伸，表示出目視觀察到龜裂時之延伸率。例 如於75 mm嬈察到龜裂之膜之延伸率為（75 一 5〇)/5〇 = 146212.doc •30- 201035257 50%。 [表2]-27-146212.doc 201035257 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 25.0 45.0 37.5 45.0 45.0 47.5 45.0 45.0 25.0 45.0 45.0 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 50.0 20.0 25.0 25.0 25.0 25.0 25.0 ” 25.0 25.0 25.0 11.7 25.0 25.0 25.0 25.0 25.0 25.0 25 0 25 0 25.0 25.0 25.0 5.0 33.3 0.005 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 (speech main) *1 · Pentaerythritol penta- acrylate/hexa- acrylate mixture ※2. Pentaerythritol diacrylic acid g/tetraacrylic acid self-contained mixture ※3 : KAYARAD DPHA-40H (10-functional acrylamide) manufactured by Sakamoto Chemical Co., Ltd.曱 vinegar) *4: 汽 羟基 hydroxycyclohexyl phenyl ketone -28- 146212.doc 201035257 *5: Organic cerium oxide sol manufactured by Nissan Chemical Industries Co., Ltd., solid content is 30% , MEK (methyl ethyl ketone) dispersion (average particle size: 1 〇 nm ~ l5 nm) *6: Organic cerium oxide sol manufactured by Nissan Chemical Industries Co., Ltd., solid content of 30%, MIBK Isobutyl ketone) dispersion (average particle weight: 10 nm to 15 nm) ※: tetrahydrofurfuryl acrylate ※8: acid recording sol, 60% solid content, sterol dispersion 〇*9 : BYK - The hard coat film obtained in Examples 1 to 14 and Comparative Examples 1 to 5, manufactured by Chemie Co., Ltd., and the following items were evaluated. The results are shown in Table 2. (Pencil Hardness) The pencil hardness of the coating film of the above composition was measured in accordance with JIS κ 5600 using a pencil scratch tester. Specifically, on the polyacetal film containing the hardened film to be measured, the pencil 'loading 75 〇〇g from the top is set at an angle of 45 degrees to draw a trace of about 5 mm, and four or more times in five times. The hardness of the pencil forming the scratch is expressed. (Resistance to Fingerprint Visibility _ 树脂 树脂 树脂 树脂 树脂 树脂 之 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂_2) Visually confirm (print resistance to fingerprint -1). 〇: Almost no △. Slightly see 1462l2.d〇c •29- 201035257 χ : Clearly see (fingerprint eraser-1) Applying a load of 200 g/cm2 (receiving the fingerprint visibility ^ <printing back by 1 〇 ' 藉 藉 ' ' ' ' ' ' ' 浊 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹 指纹1) Residual condition of traces 〇: no trace residue △: slight residue X: residual conspicuous <artificial fingerprint liquid> Preparation and use using the following composition ratios Oleic acid: 6.1 % Olive oil: 29.3% Jojoba Oil: 47.5% squalene: 17.1% (contact angle) The contact angle of the coating film of the above composition was measured using an automatic contact angle meter (DM500 manufactured by Kyowa Interface Science Co., Ltd.). The sclerosing film of the hardened film is dripped with oleic acid to determine ° (elongation) Tensile testing machine (Μ. 25〇 manufactured by 〇rientec Co., Ltd.), a film having a width of 10 mmx and a length of 5 mm was extended at a temperature of 5 〇mm per minute at normal temperature, indicating that the crack was visually observed. The elongation of the film, for example, at 75 mm, the elongation of the film is (75 to 5 〇) / 5 〇 = 146212.doc • 30 - 201035257 50%. [Table 2]
由表2之結果可明確’包含本發明之活性能量射線硬化 〇 〇 型硬塗層用樹脂組合物之硬化皮膜的膜，其硬度、耐指紋 可見性及指紋栻除性良好。不含成分(B)之比較例!中，硬 度良好，但耐指紋可見性及指紋拭除性不佳。又，成分 (B)之骨架部為聚丙二醇之比較例2中’耐指紋可見性及指 紋拭除性亦較差。 雖骨架部為聚丁二醇但未附有二(甲基)丙烯醯基之比較 例3中紋拭除性較差。進而，折射率超過[Μ之比較 ”中才才曰紋可見性_2(目視）不佳，油酸之接觸角超過30 度之比較例5中，耐指紋可見性及指紋拭除性顯著較差。 146212.doc -31 - 201035257 又’包含多官能之具有丙烯醯基之成分（B)的實施例 12〜14中，硬度更加良好。 [產業上之可利用性] 使用本發明之活性能量射線硬化型硬塗層用樹脂組合物 而獲得之硬塗膜的硬度較高且耐指紋可見性及指紋拭除性 良好。又’該樹脂組合物之延伸率亦良好。因此，本發明 之活性能量射線硬化型硬塗層用樹脂組合物適合於觸摸面 板顯示器所使用之膜之硬塗層’又’適宜作為如具有變折 步驟之類的成形時所使用的硬塗膜之材剩_。 146212.doc 32·As is clear from the results of Table 2, the film comprising the hardened film of the resin composition for active energy ray-hardening 硬 type hard coat layer of the present invention has good hardness, fingerprint visibility and fingerprint removal property. In the comparative example without the component (B), the hardness is good, but the fingerprint visibility and the fingerprint erasability are not good. Further, in Comparative Example 2 in which the skeleton portion of the component (B) was polypropylene glycol, the fingerprint-resistant visibility and the fingerprint wiping property were also inferior. In Comparative Example 3, in which the skeleton portion was polytetramethylene glycol but not attached with a di(meth)acrylonitrile group, the pattern was inferior in wiping property. Further, in the comparative example 5 in which the refractive index exceeds the comparison of [Μ", the visibility of the crepe is poor (visual), and the contact angle of oleic acid exceeds 30 degrees, the fingerprint visibility and the fingerprint erasability are significantly poor. 146212.doc -31 - 201035257 Further, in Examples 12 to 14 containing a polyfunctional propylene group-containing component (B), the hardness was further improved. [Industrial Applicability] The active energy ray of the present invention was used. The hard coat film obtained by using the resin composition for a hard coat layer has a high hardness and good fingerprint visibility and fingerprint erasability. Further, the elongation of the resin composition is also good. Therefore, the active energy of the present invention The resin composition for a radiation hardening type hard coat layer is suitable for a hard coat layer of a film used for a touch panel display, and is also suitable as a material for a hard coat film used for molding such as a folding step. 146212 .doc 32·