201202028 六、發明說明： 【發明所屬之技術領域】 本發明是有關硬被覆膜’更詳細的說，本發明是有關 用以保護液晶顯示裝置(LCD)、電漿顯示面板(ΡΕ>Ρ)、有機 EL顯示裝置、場致發射（fieid emission)顯示褒置（Frj々、 陰極管顯示裝置（CRT)等之顯示裝置，觸控板等之表面而 使用的硬被覆膜。 【先前技術】 在液晶顯示裝置(LCD)、電漿顯示面板(PDP)等之影像 顯示裝置中，為了提高塑膠製的顯示裝置表面的物理強 度’盛行在該顯示裝置表面設置硬被覆層。然而，一直以 來的硬被覆層，表面很容易附著人之指紋（皮脂）、汗、化 妝品等污垢，導致損及製品的美觀，或是發生具有視辨性 或操作性之障礙等事實。又，一旦被指紋等污垢附著具 有以擦拭去除等之方法不容易去除之問題存在。 作為解決如此問題之手段者，已知有（1)塗布表面能量 低的具有全氟烷基之聚合物，而在表面賦予撥水/撥油性的 方法’（2)塗布同樣的表面能量低的具有聚二曱基石夕氧烧骨 幹之聚合物’而在表面賦予撥水/撥油性的方法，（3)藉由 在表面設置微細的凸凹，使撥水/撥油性更為提高，同時， 減少接觸面積使污垢不易附著的方法。然而，在此等方法 中，由於塗膜是撥油性，撥出已附著的皮脂、指紋等的油 分’而變成有污垢顯著的問題存在。 又’上述以外的方法則有：（4)藉由使表面超親水化， 4 323107 201202028 使污垢不易附著的方法，（5)塗布導入有前述之撥水或撥油 基，以及特定親水基的聚合物，改善污垢之去除性的方法。 然而，上述(4)的方法，雖然污垢不易附著，惟具有一旦附 著污垢反而不易除掉之缺點。又，（5)的方法，具有污垢引 人注目的缺點。 進一步，由與此等之方法不同的創意，也有提議（6) 使表面藉由撥水/親油化，則可以與皮脂成分相容，即使附 著也不會顯著的方法。例如，在專利文獻1是揭示，在基 材隔介矽氧烷鍵結而與硬脂酸酯基等結合的防止污垢顯著 之被膜。然而，此被膜並沒有充分的表面耐損傷性或耐久 性，又塗膜的形成必需進行煩雜的操作。在專利文獻2是 揭示，以含有：具有碳數12以上的烷基等作為撥水性基的 (甲基）丙烯酸酯當作共聚合成分之（曱基）丙烯酸系共聚合 物作為主成分之耐污染性賦予劑，及表面具有由此耐污染 性賦予劑所形成之塗膜的财污染性物品。然而，該财污染 性物品，污垢去除性的維持性差，同時，只具有前述耐污 染性賦予劑也只能得到硬度低的塗膜。在專利文獻3是揭 示，由碳數10以上的脂肪族或脂環式烷基的聚合物末端具 有自由基性雙鍵之單體，與具有硬化性官能基之單體，與 其他單體反應而得到的接枝聚合物當作主成分之塗料組成 物。然而，在此塗料組成物中，由於前述硬化性官能基基 本上是陽離子硬化性官能基，故反應速度緩慢，又，在UV 硬化終止時，尚具有經時持續反應的缺點。 [先前技術文獻] 5 323107 201202028 (專利文獻) 專利文獻1 專利文獻2 專利文獻3 【發明内容】 曰本特開2001-353808號公報 曰本特開2004-359834號公報 曰本特開2009-249584號公報 [發明欲解決之課題] 、本發月之目的是提供一種硬被覆膜，其表面硬度高， 並且可以容易地去除指紋等污垢。 本發月之其他目的是提供一種硬被覆膜，進一步，可 以長時間維持污垢去除性。 本發明之另外目的是提供一種硬被覆膜，進一步，即 使附著指紋等污垢也不易引人注目。 [解決課題之手段] 本發明人等為了達成上述目的經過精心檢討之結 果，發現，若硬被覆膜的硬被覆層係藉由將由丙烯酸系單 體或寡聚物、與特定量的具有自由基聚合性基的撥水/親油 性樹脂、以及自由基聚合起始劑所成的自由基硬化性組成 物加以硬化而形成時，可以得到表面硬度高，即使附著指 紋等污垢也不顯著，且能簡單地拭除該污垢之優良效果， 遂而完成本發明。 亦即，本發明係提供一種硬被覆膜，係在透明基材薄 膜之至少單面具有硬被覆層的硬被覆膜，其特徵為前述硬 被覆層係將含有丙烯酸系單體或寡聚物(A)、與相對於該丙 稀酸系單體或寡聚物(A)之總量100重量份為0.025至5重 323107 6 201202028 量份之具有自由基聚合性基的撥水/親油性樹脂(B)、以及 自由基聚合起始劑（c)之自由基硬化性組成物加以硬化而 得之層，該硬被覆層表面之鉛筆硬度為2H以上。 作為前述丙烯酸系單體或寡聚物(A)者’係以至少含有 多官能（甲基）丙稀酸酯為佳。 作為前述具有自由基聚合性基的撥水/親油性樹脂（B) 者，係以具有自由基聚合性基，且在側鏈具有碳數10以上 的非芳香族烴基之丙烯酸系聚合物為佳。 作為前述透明基材薄膜者，可以使用聚酯系、丙烯酸 系或聚烯烴系薄膜等。 硬被覆層表面之鉛筆硬度是以3H以上者為佳。 硬被覆膜的霧度(haze)值是以1.8 %以下者為佳。 硬被覆膜可作為保護顯示裝置或觸控板表面的硬被 覆膜使用。 [發明效果] 依據本發明之硬被覆膜，其硬被覆層由於是將含有丙 烯酸系單體或募聚物、與特定量之具有自由基聚合性基的 撥水/親油性樹脂之組成物經硬化而形成，故表面硬度高， 並且即使附著指紋等污垢也可以容易地去除。又，由於硬 被覆層呈現親油性，故有即使附著指紋等污垢也不顯著之 優點。進一步，由於具有自由基聚合性基的撥水/親油性樹 脂與丙烯酸系單體或募聚物反應並形成交聯結構，故可以 維持長期的污垢去除性。 【實施方式】 7 323107 201202028 [實施發明之最佳形態] 本發月的硬被覆獏係在透明基材薄膜之至少單面 有硬被覆層。 ' [透明基材薄臈] 作為透明基材薄膜者，只要具有透明性與適度的機械 強度的薄膜即可而無特別限定。作為構成該薄膜的樹脂 者’例如可以列舉：聚對苯二甲酸乙二s旨、聚萘二甲酸乙 二酯等之聚酯系樹脂；聚曱基丙烯酸甲酯等的丙烯酸系樹 脂；聚乙烯、聚丙歸等之聚稀煙系樹脂；環狀烯烴系樹脂； 聚碳酸s旨；纖維素三乙義、纖維素二乙㈣、纖維素乙 酸醋丙酸醋、纖維素乙酸醋丁酸醋等之纖維素系樹脂；聚 醯胺’丙烯腈'丁二烯-苯乙稀樹脂(ABS樹脂）、丙埽腈_笨 乙烯樹脂(AS樹脂)等之聚苯乙烯系樹脂;聚芳香酸酯⑽乂 arylate)、聚砜；聚醚砜；聚醚酮；聚醚酮醯亞胺；聚醯亞 胺；聚偏氯乙烯；聚乙烯醇；乙烯_乙烯醇共聚合樹脂等。 作為透明基材薄膜者，其中，從透明性高，可撓性優之觀 點而言’以聚酯系樹脂薄膜、丙烯酸系樹脂薄膜或聚烯烴 系樹脂薄膜為佳。 透明基材薄膜的可視光之透過率，例如是以60%以上 為佳，更佳是80%以上，特佳是90%以上。 透明基材薄膜的厚度是依用途不同而異，一般是2〇 至300 μιη，而以50至188 μηι為佳。 [硬被覆層] 本發明中硬被覆層係將含有丙烯酸系單體或寡聚物 8 323107 201202028 (A)、與相對於該丙婦酸系單體或寡聚物（a)之總量1 〇〇重 量份具有0.025至5重量份之具有自由基聚合性基的撥水/ 親油性樹脂（B)、以及自由基聚合起始劑（匸)之自由基硬化 性組成物加以硬化而得之層。 [丙烯酸系單體或寡聚物(A)] 作為丙烯酸系單體或寡聚物(A)者，可以是單官能的丙 烯酸系單體或寡聚物、多官能的丙烯酸系單體或寡聚物的 任何一者’可以使用各別之1種或組合2種以上。 作為卓官能的丙烯酸系單體者，例如可列舉：（曱基） 丙烯酸甲酯、（甲基）丙烯酸乙酯、（曱基）丙烯酸丙酯、（甲 基）丙烯酸異丙酯、（曱基）丙烯酸丁酯、（曱基）丙烯酸異丁 酯、（曱基）丙烯酸3級丁酯、（甲基）丙烯酸戊酯、（曱基）丙 烯酸3級戊酯、（甲基）丙烯酸己酯、（曱基）丙烯酸庚酯、（甲 基）丙烯酸辛酯、（曱基）丙烯酸異辛酯、（甲基）丙烯酸2_乙 基己酯、（甲基）丙烯酸壬酯、（甲基）丙烯酸異壬酯、（甲基） 丙烯酸癸酯、（甲基）丙烯酸異癸酯、（曱基）丙烯酸十二烷 酯、（甲基）丙烯酸十三烷酯、（罗基）丙烯酸十四烷酯、（甲 基）丙烯酸十六烷酯、（▼基）丙烯酸十八烷酯等（甲基）丙烯 酸烷酯；（甲基）丙烯酸2_甲氧基乙酯、（甲基）丙烯酸 2_乙氧基乙酯、（曱基）丙烯酸3·甲氧基丙酯、（甲基）丙烯酸 1·甲氧基丁醋等（甲基）丙烯酸炫氧基烧基酯；（甲基）丙烯酸 裱戊酯、（甲基）丙烯酸環己酯、三環[5.2.1.〇2,6]癸烷單甲醇， (甲基）丙稀曰、（f基）丙烯酸金剛燒酯、（甲基）丙烯酸異 冰片酯等具有脂環式烴基的（尹基）丙烯酸酯；（甲基）丙烯酸 323107 9 201202028 苯酯等（曱基）丙烯酸芳基酯；（曱基）丙烯酸苄酯、（曱基）丙 烯酸2-苯基乙酯等（甲基）丙烯酸芳烷基酯；（甲基）丙烯酸 2-羥基乙酯、（曱基）丙烯酸2-羥基丙酯、（甲基）丙烯酸2-羥基丁酯等含羥基的（甲基）丙烯酸酯；（甲基）丙烯酸等含有 叛基的單體；丙稀酸胺、曱基丙稀醢胺、Ν,Ν-二曱基（曱基) 丙烯醯胺、（曱基）丙烯醯基嗎啉等含醯胺基的單體；（曱基) 丙烯酸胺基乙酯、（曱基）丙烯酸二甲基胺基乙酯、（曱基) 丙烯酸三級丁基胺基乙酯等之含有胺基的單體；環氧丙基 (曱基）丙烯酸酯等含有環氧丙基的單體等。 作為多g能之丙稀酸系单體者，例如可列舉：乙二醇 一（曱基）丙烯1西曰、一乙一醇二（曱基）丙婦酸g旨、聚乙二醇 二（甲基）丙烯酸酯、丁二醇二（曱基）丙烯酸酯、新戊二醇二 (曱基）丙烯酸酯、己二醇二（甲基）丙烯酸酯、壬二醇二（甲 基）丙烯酸酯、三環[5.2.1.02,6]癸烷二甲醇二（甲基）丙烯酸 酯等2官能的（甲基）丙烯酸酯；三羥甲基乙烷三（甲基）丙烯 酸酯、三羥曱基丙烷三（甲基）丙烯酸酯、丙三醇三（甲基） 丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、二（三羥甲基）丙^ 三（甲基）丙烯酸酯、二季戊四醇三（甲基）丙烯酸酯等3官能 之（甲基）丙烯酸酯、季戊四醇四（甲基）丙烯酸酯、二（三羥 甲基）丙烧四（甲基）丙稀酸醋、二#戊四醇四（甲基）丙稀酸 醋、二季戊四醇五（甲基）丙稀酸醋、二(三㈣基）丙烧五（甲 基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸酯、二（三羥甲基） 丙燒六（甲基）丙婦酸酯等之4官能以上的^基）丙稀酸醋。 作為丙烯酸系寡聚物者，例如可列舉：環氧基（甲基） 323107 10 201202028 丙烯酸酯、聚酯（曱基）丙烯酸酯、胺基曱酸酯（曱基） 酯等。丙烯酸系寡聚物的分子量，通常是未達1〇〇〇。 丙烯酸系單體或寡聚物(A)，以不含有有機聚聚矽 單體及氟化烷基之單體為佳。 使 作為丙烯酸系單體或寡聚物(A)者，以至少含有多官心 (曱基）丙烯酸酯（多官能的丙烯酸系單體）為佳。多官萨 基）丙烯酸酯之中，也以3官能以上的（甲基）丙烯酸酯^較 佳，4官能以上的（甲基）丙烯酸酯為更佳，6官能以上的 基）丙烯酸酯為特佳。多官能（甲基）丙烯酸酯[例如，2官能 以上的（甲基）丙烯酸酯，較佳是4官能以上的（甲基）丙烯酸 酯，更佳是6官能以上的（甲基）丙烯酸酯]之使用量較佳^ ，烯酸系單體或寡聚物(A)全體的50重量％以上，以7〇重 里/〇以上為更佳，以85重量％以上為特佳。 [具有自由基聚合性基的撥水/親油性樹脂(B)] 在具有自由基聚合性基的撥水/親油性樹脂（B)中，作 為自由基聚合性基者，可列舉如：（甲基）丙烯醯基[包含（甲 基）丙埽醯氧基]、乙烯基等。其_，又以（甲基）丙烯醯氧基 為佳。 作為具有自由基聚合性基的撥水/親油性樹脂(B)者， 係在分子内，只要具有撥水/親油性部位及至少一個自由基 聚合性基即可。作為撥水/親油性部位者，例如可列舉：在 側鍵具有碳數10以上的#芳香族烴基之丙烯酸聚合物鏈 。此種在侧鏈具有碳數1〇以上的非芳香族烴基之丙烯酸 聚合物鏈部之樹脂亦包含在丙烯酸系聚合物中。又，在具 11 323107 201202028 有自由基聚合性基的撥水/親油性樹脂（B)中’自由基聚合 性基可以是位於主鏈（例如，丙烯酸聚合物鏈等）之側鏈部 位，也可以位在主鏈之末端部位。 作為前述碳數ίο以上的非芳香族烴基者，例如可列 舉：癸基、異癸基、十一烷基、十二烧基、十三烷基、十 四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十 九烧基、二十烧基、二十一烧基、一十一烧基等碳數10 以上的直鏈狀或分枝鏈狀烷基；環癸基、環十二烷基、金 剛烷基、異冰片烷基、三環[5·2.1.02,6]癸基、三環[6.2· 1.02,7] 十一烷基、四環[4.4.0.12’5.17，10]十二烷基等碳數10以上的 脂環式烴基；前述脂環式烴基與亞甲基、伸乙基等碳數1 至4左右的伸烷基1或2個以上結合之基等。非芳香族烴 基之碳數，例如是10至24，而以至20為佳，更佳是 10至18左右。 在側鏈具有碳數10以上的非芳香族烴基之丙烯酸聚 合物鏈（及具有該聚合物鏈之丙烯酸系聚合物），可將至少 含有：具有碳數1〇以上的非芳香族烴基之（曱基）丙烯酸酯 的單體成分加以聚合而得到。 作為具有碳數10以上的非芳香族烴基之（甲基）丙烯酸 酯的代表例者，例如可列舉··（甲基）丙烯酸癸酯、（甲基) 丙烯酸十二烷酯、（甲基）丙烯酸十三烷酯、（曱基）丙烯酸十 四烧酉曰、（甲基）丙稀酸十六烧醋、（甲基）丙稀酸十八烧醋等 烧基部分之碳數為10以上（例如10至24，以10至20為 佳’更佳是1〇至18)之（甲基）丙烯酸烷酯；（甲基）丙烯酸 12 323107 201202028 金剛烷酯、（甲基）丙烯酸異冰片烷酯、三環[5.2.1.02,6]癸烷 單甲醇（甲基）丙烯酸酯等具有碳數為1〇以上（例如1〇至 24,以1〇至20為佳，更佳是1〇至18)之脂環式烴基之（曱 基）丙烯酸酯等。此等可以單獨使用或組合2以上而使用。 在前述單體成分中，亦可以包含具有碳數1〇以上的 非芳香族烴基之（甲基）丙烯酸酯以外之單體。 作為具有碳數10以上的非芳香族烴基之（甲基）丙烯酸 酯以外之單體者，例如可以列舉：（甲基）丙烯酸甲酯、（甲 基）丙烯酸乙酯、（曱基）丙烯酸丙酯、（甲基）丙烯酸異丙酯、 (甲基）丙烯酸丁酯、（曱基）丙烯酸異丁酯、（甲基）丙烯酸三 級丁酉曰、（甲基）丙稀酸戊醋、（甲基）丙烯酸三級戊醋、（甲 基）丙烯酸己酯、（甲基）丙烯酸庚酯、（甲基）丙烯酸辛酯、（甲 基）丙烯酸異辛酯、（，基）丙烯酸2-乙基己酯、（曱基）丙烯 酸壬酯、（曱基）丙烯酸異壬酯等之（曱基）丙烯酸Ci 9烷酯； (甲基）丙烯酸2-曱氧基乙酯、（曱基）丙烯酸2_乙氧基乙酯、 (甲基）丙烯酸3-甲氧基丙醋、（甲基）丙烯酸3_曱氧基丁酯 4之（曱基）丙烯酸烧氧基院酉旨；（甲基）丙稀酸環戊醋、（甲 基）丙烯酸環己酯等具有碳數3至9的脂環式烴基的（甲基） 丙烯酸酯；（曱基）丙烯酸苯酯等之（曱基）丙烯酸芳基酯；（曱 基）丙烯酸苄酯、（曱基）丙烯酸2-苯基乙酯等（曱基）丙烯酸 方烧基醋，（甲基）丙稀酸2-經基乙醋、（曱基）丙浠酸2-經 基丙酯[=1，2-丙二醇-1_(曱基）丙烯酸酯]、（曱基）丙烯酸2_ 羥基丁酯等含有羥基的（甲基）丙烯酸酯；（曱基）丙嫦酸等含 有敌基的單體；丙浠醯胺、曱基丙稀趨胺、Ν,Ν-二曱基（曱 323107 13 201202028 基）丙晞醢胺、（甲基）丙稀醢基嗎琳等含有酿胺基的單體. (曱基）丙稀酸胺基乙醋、（甲基）丙稀酸二甲基胺基乙㊉、（甲 基）丙烯酸三級丁基胺基乙酯等含有胺基的單體；環氧丙美 (甲基）丙烯酸酯[=(甲基）丙烯酸2,3-環氧丙酯]等含有環氧 基(環氧丙基等）的單體等。 含有碳數10以上的非芳香族烴基之（曱基）丙烯酸酯以 外之單體者，可以使用多官能之丙烯酸系單體。作為多官 能之丙烯酸系單體者，可以列舉如：乙二醇二（甲基）丙烯 酸酯、二乙二醇二（甲基）丙烯酸酯、聚乙二醇二（甲基）丙烯 酸酯、丁二醇二（甲基）丙烯酸酯、新戊二醇二（甲基）丙烯酸 酯、己二醇二（甲基）丙烯酸醋、壬二醇二（甲基）丙稀酸醋、 二環[5.2.1.02’6]癸烷二甲醇二（曱基）丙烯酸酯等2宫能的 (曱基）丙烯酸醋；三經甲基乙烧三（甲基）丙稀酸醋、三經甲 基丙烷三（甲基）丙烯酸酯、丙三醇三（甲基）丙烯酸酯、季戊 7醇三（甲基）丙烯酸醋、二(三經甲基)丙燒三（甲基)丙稀酸 二季戊四醇三（甲基）丙稀酸醋I 3官能的（甲基）丙稀酸 酉曰，季戊四醇四（甲基）丙烯酸酯、二（三羥曱基）丙烷四（甲 基)丙婦酸醋、二季細醇四（甲基）丙烯酸醋、二季戊四醇 五（甲基）丙稀酸醋、二(三經甲基）丙燒五（甲基）丙稀酸醋、 二季戊四醇六（甲基)丙稀酸酯、二(三Μ甲基）丙烧六（甲基） 丙烯Ua等4 g此以上的（甲基）丙稀酸g旨；環氧基（甲基） 丙稀酸酯；聚酯（甲基)丙稀酸g旨；胺基甲酸自旨（甲基）丙稀酸 酉旨等。 在上述側鏈具有碳數10以上的非芳香族烴基之丙稀 323107 14 201202028 酸系聚合物中，於分子内導入自由基聚合性基的方法並無 特別限定。 例如，在丙烯酸系聚合物鏈之側鏈中導入自由基聚合 性基的方法，可例舉如⑴使具有碳數ίο以上的非芳香族 烴基之（甲基）丙烯酸酯與多官能的丙烯酸系單體共聚合， 而得在分子内具有未反應之（甲基）丙烯醯基的聚合物的方 法，（ii)使具有碳數10以上的非芳香族烴基之（曱基）丙烯 酸酯，與具有反應性官能基X的自由基聚合性單體共聚合 後，使所得聚合物側鏈之反應性官能基X，與具有可與前 述反應性官能基X反應之官能基y的自由基聚合性單體反 應的方法。也可以使用合併⑴與（ii)的方法。 上述⑴中，作為多官能的丙烯酸系單體者，可以使用 上述例示物質。上述(ii)中，作為具有反應性官能基X的自 由基聚合性單體者，例如可列舉：（甲基）丙烯酸等具有羧 基作為官能基X的自由基聚合性單體；（甲基）丙烯酸2-羥 基乙酯、（曱基）丙烯酸2-羥基丙酯等具有羥基作為官能基 X的自由基聚合性單體；3-(曱基）丙烯氧基丙基三甲氧基矽 烷等具有烷氧基矽烷基作為官能基X的自由基聚合性單體 等。又，上述(ii)中，具有可與反應性官能基X反應之官能 基y的自由基聚合性單體者，官能基X為叛基之情形，可 列舉（曱基）丙烯酸3,4-環氧基環己基甲酯、（曱基）丙烯酸環 氧丙酯[=(曱基）丙烯酸2,3-環氧基丙酯]等具有環氧基作為 官能基y的自由基聚合性單體；官能基X為經基之情形， 可列舉馬來酸酐、（曱基）丙烯醯基異氰酸酯等具有酸酐基 15 323107 201202028 或異氰酸酯基作為官能基y的自由基聚合性單體；官能基 X為烷氧基矽烷基之情形，可列舉（甲基）丙烯酸2-羥基乙 酯、（甲基）丙烯酸2-羥基丙酯、3-(曱基）丙烯氧基丙基三曱 氧基矽烷等具有羥基或烷氧基矽烷基作為官能基y的自由 基聚合性單體等。 前述共聚合可使用偶氮雙異丁腈等慣用的自由基聚 合起始劑，藉由常法進行。例如，可以在有機溶劑中，以 30至120°C左右的溫度進行聚合。作為有機溶劑者，例如 可以列舉：曱苯、二曱苯等之芳香族烴；己烷、辛烷等的 脂肪族烴；環己烷等脂環式烴；乙酸乙酯、乙酸丁酯、乙 酸異丁酯等酯；曱醇、乙醇、異丙醇、丁醇等醇；丙酮、 曱基乙基酮、曱基異丁基酮等酮等。此等之有機溶媒可以 單獨使用，亦可以組合2種以上而使用。上述(ii)中，藉 由共聚合而得之聚合物與具有可與官能基X反應之官能基 y的自由基聚合性單體的反應，係在溶媒中或溶媒之不存 在下，於例如60至140°C左右的溫度實施。作為溶媒者， 可以列舉前述之有機溶媒等。 所得聚合物的數平均分子量（換算苯乙烯），例如是500 至50000，而以800至25000左右為佳。聚合物的數平均 分子量太小時，作成塗膜時的撥水/親油性容易下降。又， 聚合物的數平均分子量過大時，對溶媒之溶解性容易降低。 如此所得之具有自由基聚合性基的撥水/親油性樹脂 (B)，係可以將反應後的反應液直接使用於配合丙烯酸系單 體或寡聚物(A)及自由基聚合起始劑（C)，因應需要，也可 16 323107 201202028 以藉由沉殺精製等經單離精製後而使用。 具有自由基聚合性基且在侧鏈具有碳數10以上的非 芳香族煙基之丙烯酸系聚合物中，構成該聚合物之單體成 分中’作為具有碳數10以上的非芳香族烴基之（曱基）丙烯 酸醋者’以燒基部分的碳數為1〇至16的烷基（曱基）丙婦 酸酯為佳，其中，又以十二烷基（甲基）丙烯酸酯為特佳。 又’構成該聚合物之單體成分中作為具有碳數1〇以 上的非芳香族烴基之（甲基）丙烯酸酯以外的單體者，可以 列舉如：（a)(曱基）丙烯酸丁酯等的Cl_8烷基（曱基）丙烯酸 醋、（b)(甲基）丙烯酸環己酯等的c5 6(甲基）丙烯酸環烷酯、 (c)(甲基）丙烯酸苄酯、（d)(甲基）丙烯酸2_羥基丙酯等之含 羥基之（曱基）丙烯酸酯、（e)(曱基）丙烯酸等之含羧基之單 體、（f)乙二醇二（甲基）丙烯酸酯或丙三醇三（子基）丙烯酸酯 等多官能（曱基）丙烯酸酯、(曱基）丙烯酸環氧丙酯等含 有環氧基之（甲基）丙烯酸酯、（h)3_(曱基）丙烯醯氧基丙基三 曱氧基矽烷等含有烷氧基矽烷基之（曱基）丙烯酸酯、（i)(甲 基）丙烯醯基異氰酸酯等具有異氰酸酯基的（甲基）丙烯酸 酯等。此等可以使用組合2種以上者。使用2種以上之具 有碳數10以上的非芳香族烴基之（曱基）丙烯酸酯以外的單 體時，該等之較佳組合為··⑴⑷，與⑷及/或⑷，與選 自（f)、（g)、⑻及(i)中至少i種之組合，（2)(a)，與⑼及/ 或⑷，與⑷及/或⑷，與選自（f)、（g)、㈨及⑴中至少丄 種之組合。總之’以⑷與(b)與⑷與(d)與⑹與⑺躲)之組 合為合適。 323107 17 201202028 於具有自由基聚合性基且在侧鏈具有碳數1〇以上的 非芳香族經基之丙烯酸系聚合物中’相對於構成該聚合物 之全單體成分，具有碳數10以上的非芳香族烴基之（甲基） 丙烯酸酯的比率，例如是15重量。/。以上（例如15至95重 量〇/。），而以20重量％以上（例如20至9〇重量％)為佳，以 30重量％以上（例如30至80重量。/〇)為更佳。此比率太少 時，不易得到撥水/親/由性，且污染去除性、对指紋附著性 容易降低。又，此比率過多時’塗膜的硬度容易下降。 具有自由基^^合性基且在側鍵具有碳數1 〇以上的非 芳香族烴基之丙烯酸系聚合物的雙鍵當量，例如是100至 3000 g/eq ’ 而以 200 至 2000 g/eq 為佳，以 300 至 1〇〇〇 g/eq為更佳。 作為具有自由基聚合性基的撥水/親油性樹脂(B)者’ 除了上述之外’可列舉在側鏈具有碳數1〇以上的非芳香族 烴基之丙烯酸系聚合物鏈部作為撥水/親油性部位，且在前 述丙烯酸系聚合物鏈之末端部位具有自由基聚合性基的樹 脂。 如此之樹月曰，可以藉由，例如，在含有反應性官能基 X之鏈轉移劑的存在下，將至少含有具有碳數10以上的非 芳香族烴基之（甲基）丙烯酸酯的單體成分加以聚合後，將 丙烯酸系聚合物鏈末端之官能基X，以及，可與前述官能 基X反應之具有官能基y的自由基聚合性單體，反應而製 造。 作為含有S忐基X之鏈轉移劑者，只要具有作為鏈轉 18 323107 201202028 移部機能的氫硫基，與其他之官能基X即可，而無特別限 定，例如可列舉：氫硫基乙酸、氫硫基丙酸、氫硫基琥珀 酸、硫代蘋果酸、硫代水楊酸等具有羧基作為官能基X的 鏈轉移劑；2-氫硫基乙醇、1-氫硫基-1-丙醇、3-氳硫基-2-丁醇、1-硫代丙三醇、氫硫基酚等具有羥基作為官能基X 的鏈轉移劑；3-氫硫基丙基三甲氧基矽烷、3-氩硫基丙基 曱基二曱氧基矽烷等具有烷氧基矽烷基作為官能基X的鏈 轉移劑等。 聚合是可以與前述的共聚合同樣進行。所得聚合物的 數平均分子量（換算苯乙烯），例如是500至100000，而以 800至50000左右為佳。聚合物的數平均分子量太小時， 作成塗膜時的撥水/親油性容易降低，又，聚合物的數平均 分子量太大時，對於溶媒的溶解性容易降低。 具有可與前述官能基X反應之官能基y的自由基聚合 性單體者，可以列舉與前述相同者。其中，從反應性等之 觀點而言，以具有異氰酸酯基的自由基聚合性單體為佳。 前述聚合物，以及，具有可與官能基X反應之官能基 y的自由基聚合性單體之反應，係在溶媒中或溶媒不存在 下，例如是以60至140°C左右的溫度實施。作為溶媒者， 可以列舉前述之有機溶媒等。藉由該反應，可以得到具有 自由基聚合性基的撥水/親油性樹脂（B)[側鏈具有碳數10 以上的非芳香族烴基之丙烯酸聚合物鏈部作為撥水/親油 部位，並且在前述丙烯酸聚合物鏈的末端部位具有自由基 聚合性基的樹脂]。 19 323107 201202028 構成聚合物的單體成分之例子，及該單體成分的理想 組合是與前述相同。 如此所得的聚合物，也可以將反應後之反應液，直接 使用配合在丙烯酸系單體或寡聚物（A)及自由基聚合起始 劑（C)中，因應需要，也可以藉由沉澱精製等經單離精製後 而使用。 又，作為具有自由基聚合性基的撥水/親油性樹脂（B) 者，亦可使前述所得之丙烯酸聚合物鏈的末端部位（或側鏈) 具有自由基聚合性基的撥水/親油性樹脂之自由基聚合性 基進一步進行聚合，作成含有：在側鏈具有碳數10以上的 非芳香族烴基之丙烯基聚合物鏈，與在側鏈具有自由基聚 合性基的乙烯基聚合物鏈之接枝共聚合物，並以此作為具 有自由基聚合性基的撥水/親油性樹脂(B)使用。 該接枝共聚合物，係藉由下述反應而可得到，例如， 將上述所得之丙烯酸聚合物鏈的末端部位（或側鏈）具有自 由基聚合性基的撥水/親油性樹脂，與多官能的丙烯酸系單 體或具有反應性官能基X之自由基聚合性單體，因應需 要，與其他之自由基聚合性單體共聚合，使用具有反應性 官能基X之自由基聚合性單體作為單體(b2)時，將聚合後 之聚合物，以及，具有可與前述反應性官能基X反應之官 能基y之自由基聚合性單體反應而可以得到該接枝共聚合 物。 作為多官能之丙烯酸系單體、具有反應性官能基X之 自由基聚合性單體、具有可與反應性官能基X反應之官能 20 323107 201202028 基y之自由基聚合性單體者，可以使用前述例示者。 作為其他之自由基聚合性單體者，可以使用作為前述 具有碳數10以上的非芳香族烴基之（曱基）丙烯酸酯以外的 單體所例示者。 接枝共聚合物，可以藉由溶液自由基聚合等慣用的方 法來製造。在溶液聚合中使用的溶媒’可以使用前述的有 機溶媒。接枝共聚合物的重量平均分子量，例如是1〇〇〇 至200000，而以5000至100000左右為佳。 構成接枝共聚合物的早體成分之例’及該單體成分之 理想組合是與前述同樣。 [自由基聚合起始劑（C)] 自由基聚合起始劑（C)是為了促進丙烯酸系單體或寡 聚物(A)、具有自由基聚合性基的撥水/親油性樹脂（B)之硬 化而使用。自由基聚合起始劑（C)可以單獨使用，亦可以組 合2種以上而使用。 作為自由基聚合起始劑(c)者，可以使用一般在自由其 聚合中使用的公知之光自由基聚合起始劑、熱自由基聚ς 起始劑。作為光自由基聚合起始劑的代表例子，可以列舉 如：3,3’，4,4，-四（三級丁基過氧羰基）笨醯笨、3,3,_二（三級 I基過氧羰基)-4,4，-二（曱氧基羰基）苯醯苯、三級丁基 笨甲酸酯等過氧化酯類；三級丁基過氧化氫、二-三級丁其 過氧化物等過氧化物類；苯偶因、笨偶因甲基_、苯偶= 乙基醚等笨偶因/苯偶因烷基醚類；乙醯苯、2,2-二曱氧美 -2-苯基乙醯苯、2,2_二乙氧基_2_苯基乙醯笨、ι，“二氣2 323107 21 201202028 酿苯等乙醢勒；W基·環己基苯基·酮等環己基苯基酮 類，2-曱基蒽醌、2-乙基蒽醌等蒽醌類；2,4_二甲基噻噸酮、 2,4-二乙基噻噸酮等噻噸酮類；乙醯苯二甲基縮鲷、苄基 二曱基縮酮等縮_類；苯醯苯等苯醯苯類；咕噸酮 (Xanthone)類；〗，7_雙(9_吖啶基)庚烷；環戊二烯鈦化合物 (titanocene)]芳香族硬鏽鹽(Aryi i〇(j〇nium sait)、芳香族婆 I，#作為熱自由基聚合起始劑的代表例子，可以列舉 如：2,2’-偶氮雙異丁腈、2,2,_偶氮雙(2,4-二甲基戊腈）、2,2，_ 偶氮雙(4-曱氧基·2,4-二曱基戊腈）、2,2，_偶氮雙(2甲基丙 酸)二曱酯、2,2’-偶氮雙(2·甲基丙酸)二乙酯、2,2，_偶氮雙(2· 曱基丙酸)二丁 S旨等偶氮化合物，苯甲醯過氧化物、月桂酿 過氧化物、過氧三甲基乙酸三級丁酿㈣別pa pivalate)、1，1-雙（過氧化三級丁基）環己烷等有機過氧化 物、過氧化氫等。將過氧化物當作自由基聚妓始劑使用 時，也可以組合還原劑作為氧化還原型之起始劑。 [自由基硬化性組成物] 本發明中，自由基硬化性組成物是含有丙稀酸系單體 或寡聚物⑷、具有自由絲合性基的撥水/親油性樹脂 (B)、與自由基聚合起始劑(〇。 在自由基硬化性組成物中，具有自由基聚合性基的撥 水/親油性樹脂(B)之量，相對於丙烯酸系單體或寡聚物(A) 之總量100重量份’具有0.025至5重量份，理想是〇 〇3 至4.5重量份’而以〇.〇5至4重量份為更佳。具有自由基 聚合性基的撥水/親油性樹月曰（B)之量太少時，除了污毕物 323107 22 201202028 質的去除性降低之外，同時當指紋附著時’指紋容易變得 顯著。相反的，具有自由基聚合性基的撥水/親油性樹脂（B) 之量太多時’硬被覆詹的表面硬度容易變低。尤其是’不 使用丙烯酸系單體或寡聚物（A)，只以具有自由基聚合性基 的撥水/親油性樹脂（B)與自由基聚合起始劑（C)形成硬被 覆層時，表面硬度會顯著下降。 自由基聚合起始劑（C)之量，依其種類之不同而異，相 對於丙烯酸系單體或寡聚物（A)與具有自由基聚合性基的 撥水/親油性樹脂(B)之總量100重量份，例如是〇.1至μ 重量份，而以0.5至10重量份為佳，以1至6重量份左右 為更佳。自由基聚合起始劑（C)之量太少時，會具有不能充 分進行硬化之情形，相反的，太多時，塗膜具有變脆之情 形。 在自由基硬化性組成物中，於調整塗布性等之目的 下，以使用有機溶媒等溶劑為佳。作為上述溶劑者，雖依 丙烯酸系單體或寡聚物(A)或具有自由基聚合性基的撥水/ 親油性樹脂(B)之種類不同而異’但並無特別之限定，例如 可以列舉：曱基乙基酮、曱基異丁基_、環己酮等酮類； 甲笨、二曱苯等烴；乙酸乙酯、乙酸丁酯、乙酸3_甲氧基 丁酯、乙酸曱氧基丙酯、乙二醇單甲基醚乙酸酯等酯；甲 醇、乙醇、異丙醇、甲氧基丙醇、3_甲氣基丁醇、乙氧基 乙醇等醇；二異丙醚、乙二醇二甲基醚、四氫呋喃等醚等。 溶劑之量，相對於丙烯酸系單體或寡聚物(A)與具有自由基 聚合性基的撥水/親油性樹脂(B)的合計量（1〇〇重量份），係 23 323107 201202028 以5至500重量份為佳。 在上述自由基硬化性組成物中，除了上述之外，在不 阻害本發明效果之範圍内，也可以添加其他之樹脂、消泡 劑、光增感劑、紫外線吸收劑、抗氧化劑、光安定劑、結 塊防止劑、塗平劑、界面活性劑、增量劑、顏料、染料、 防錄劑、抗靜電劑、導電材、可塑劑、滑劑、樹脂微粒子、 無機微粒子等之各種添加劑。 相對於去除溶劑的全成分（全不揮發分），自由基硬化 性組成物中之丙烯酸系單體或寡聚物（A)及具有自由基聚 合性基的撥水/親油性樹脂（B)的佔有比率，其合計例如為 70重量％以上，而以在80重量％以上為佳，更佳是90重 量％以上，特佳是95重量％以上。 作為將自由基硬化性組成物塗布到透明基材薄膜上 之方法，例如可列舉：旋塗法、刷塗法、喷霧法（吹付法）、 浸潰法、刮刀塗布法、輥塗法、流塗法、棒塗法、凹版塗 布法、空氣刀塗布法等。塗布後，在使用溶劑之情形係將 溶劑加以乾燥，理想是藉由活性能量線照射使硬化，而在 透明基材薄膜表面形成硬被覆層。 作為照射之活性能量線者，可以使用紫外線、X光線、 電子線等。其中，從安全性、反應效率等工業性之觀點等 而言，以使用紫外線為最良好。所用紫外線的波長是以200 至400 nm為佳，良好的照射條件，例如是照度1至1000 mW/cm2，照射量是0.1至10000 mJ/cm2，作為活性能 量線的照射裝置者，例如可以使用：高壓水銀燈、低壓水 24 323107 201202028 銀燈、金屬鹵素燈、準分子（Excimer)燈等之燈光源、氬離 子雷射或氦離子雷射等之脈衝、連續之雷射光源等。 又，在上述硬化處理中進行加熱處理時，由於容易充 分進行硬化，故佳。熱處理是以硬化處理之後為佳，條件 是依自由基硬化性組合物所塗布之透明基材薄膜的種類不 同而異，例如，在室温至18〇。(：之溫度進行10分鐘至i週 左右為佳。 硬被覆層的厚度，例如是以2至1 〇〇um為佳，更佳是 3至50um。在硬被覆層較上述理想範圍薄的情形，耐擦傷 性具有下降之情形，較厚時成本方面變成不利，又創意性 會具有下降的情形，或硬被覆層本身有變得容易剝離之情 形〇 ，如此操作，可以得到具有表面硬度高之硬被覆層的硬 被覆膜。本發明的硬被覆膜的硬被覆層之錯筆硬度是在扭 以上’更佳是在3H以上。 又’本發明的硬被覆膜的硬被覆層在耐擦傷性方面優 異。例如，在鋼絲綿（Steelw〇〇1; #〇〇〇〇)負載ikgf的鐘， 進行20次往復賴硬被覆層表面之試驗時，並未擦傷。 又，本發_硬被_的硬被覆層在耐指_著性 物質去除性方面健在硬被覆層表面附著具有 ^矣’即使在黑底上附者，缺也不顯著。又，在硬被覆 t面附著具有指紋，以擦拭紙擦拭操作在5次以内 疋在3次以内）就可以去除指紋。 一 又，本發明的硬被覆膜的硬被覆層對水之接觸角為例 323107 25 201202028 如80度以上’而以85度以上為特佳。對k 8。度時’潑水性低’拭除指“皮二:觸角未達 發明的硬被覆膜之硬被覆層相餅於正==。又’本 角為例如10度以下，而以在δ户 二（H D)之接觸 六烧(―)之接觸角太大時，親：生低，當正十 著時，變得非常醒目，X，光澤度也會降低Γ皮月旨附 又，本發明的硬被覆膜之霧度值小，全光線 I硬被覆膜的霧度值為例如20%以下，而以在！ 下（尤其是1.5%以下）為佳。例如，在硬被覆層的厚度為^ ⑽’透明基材薄膜為聚對苯二甲酸乙二醋，其厚度為⑽ um時’霧度值疋2.0%以下，而以在丨8%以下（尤其是1 5% 以下）為特佳。全光線透過率為例如85%以上，而以在9〇% 以上為特佳。全光線透過率未達85%時，作為光學材料使 用有困難的情形，或創意性有下降之情形。 本發明的硬被覆膜，由於具有如上述之特性，例如， 用於作為保護液晶顯示裝置（LCD)、電漿顯示裝置面板 (PDP)、有機 EL顯示裝置、場致發射顯示裝置(FRD)、陰 極管顯示裝置（CRT)等之顯示裝置或觸控板，尤其是平板 顯不裝置之表面而使用的硬被覆膜。 實施例 以下，根據實施例詳細的說明本發明，但本發明並不 侷限於此等實施例。 實施例1 在作為丙烯酸系單體[多官能（甲基）丙烯酸酯]的二季 26 323107 201202028 戍四醇六丙埽酸醋（Daicel_CyteC公司製，商品名 「DPHA」）1〇〇重量份中，添加具有自由基聚合性基的撥 水/親油性樹脂[富士化成工業公司製，商品名 「ZX-214_A」；具有自由基聚合性基及撥水/親油性基之丙 烯酸系寡聚物的乙酸丁酯/異丙醇溶液；雙鍵當量560 g /叫(不择發分)]〇·〇6重量份(樹脂：0.03重量份），及自由 基聚合起始劑（汽巴特化公司製，商品名「IRGACURE 184」；自由基光聚合起始劑）3 〇〇重量份，並將所得之組成 物以甲基乙基酮稀釋，使不揮發分成為4〇重量％而得到塗 膜組成物。 接著’在膜厚188mn之聚對苯二曱酸乙二酯薄膜（三 菱樹脂（股）公司製’商品名「〇321E188W76A」、PET薄膜） 之單面，將上述之塗膜組成物使用棒塗機#12塗布後，藉 由乾燥機在1〇〇 C乾燥1分鐘，照射紫外線而硬化[光源： 高壓水銀燈、輸送速度：15 m /分鐘、照射次數：3次、 累積光量：lOOOmJ/cm2]，可以得到表面具有厚度約6um 之塗膜(硬被覆層）的PET薄膜。 將如此所得之表面具有塗膜(硬被覆層）之pET薄膜放 置在室溫中24小時後’對於表面之塗膜測定鉛筆硬度、财 鋼絲綿性、耐指紋附著性、污染物質去除性、對水/正十六 烷(nHD)之接觸角。又，對PET薄膜與塗膜全體測定霧度 值及全光線透過率’將測定結果在表1中表示。 實施例2至6、比較例1至4 除了將丙烯酸系單體[多官能（甲基）丙烯酸酯]、具有自 323107 27 201202028 由基聚合性基的撥水/親油性樹脂、及自由基聚合起始劑之 配合比率變更成如表1所示之外，其餘與實施例1同樣操 作，可以得到表面具有厚度約6um之塗膜（硬被覆層）的 PET薄膜。 將如此所得之表面具有塗膜（硬被覆層）之PET薄膜放 置在室溫中24小時後，對於表面之塗膜，測定鉛筆硬度、 耐鋼絲綿性、耐指紋附著性、污染物質去除性、對水/正十 六烷(nHD)之接觸角。又，對PET薄膜與塗膜全體測定霧 度值、全光線透過率。將測定結果在表1中表示。 評估方法 (1) 鉛筆硬度 根據JIS K 5600，使用拉伸硬度（鉛筆法）試驗裝置（新 東科學公司製，商品名「HE1DON-14D」），負重1 kg、45 度法，在測定距離30 mm評估鉛筆硬度。以3H及2H之 鉛筆，分別測定5次，分別以3次以上沒有擦傷之情形當 作「〇」，具有3次以上擦傷之情形當作「X」。 (2) 耐鋼絲綿性（耐擦傷性） 在#0000鋼絲綿負荷重量1 kg，往復20次擦拭時，以 沒有擦傷者當作「〇」，有擦傷者當作「X」。 (3) 耐指紋附著性 使指紋附著在塗膜上，放在黑底上以目視觀察指紋的 附著程度。指紋不顯著者當作「〇」，稍微顯著者當作「Λ」。 (4) 污染物質去除性 使指紋附著在塗膜上，以擦拭紙擦拭評估指紋去除 28 323107 201202028 性。以去除指紋為止的擦拭紙之擦拭次數表示。若為4次 則是可允許範圍，但以在3次以下者為佳。 (5) 對水/正十六烷(nHD)之接觸角 使用自動或動態接觸角計（協和界面科學公司製，型式 DCA-UZ)，對於塗膜，測定5點之約5uL的各液之接觸角 並加以平均。 (6) 霧度值或全光線透過率 霧度值或全光線透過率是使用霧度值計（Haze meter) (日本分光公司製，商品名「300A型」），測定5點以上， 並加以平均。霧度值是根據JIS K 7136之基準測定。 29 323107 201202028 I< 比較例 寸 〇 Ο »—Η | 3.00 1 X X X 〇 CO γΉ in ΙΛ rH 0.8 to f-H σί CO o i—1 Ο | 3.30 1 X X X 〇 CO 卜 § CO CD 〇 寸 r-H σ> (Μ o 1 ο.οι 1 | 3.00 | 〇 〇 〇 〇 (Λ 卜 cd in oi 00 o eg r-H σ> ιΗ 1 loo 1 Ο | 3.00 1 〇 〇 〇 〇 UO CO s csi csi 0.8 實施例 CD 1 loo 1 to LTD 1-H CO X 〇 X 〇 CO CM 00 00 5.9 00 寸 ι—l σί LQ I loo 00 1 3.09 1 〇 〇 〇 〇 CO 卜 :5.5 ca t-H 寸 τ—4 σ> 寸 O s CO 〇 〇 〇 〇 00 δ ! 4.8 00 o 寸 0¾ CO 1 loo LO Ο | 3.02 1 〇 〇 〇 〇 CO co 00 :4·5 00 d 91.4 CM 100 ι»Ι Ο | 3.00 1 〇 〇 〇 〇 CO 00 CO 00 o CD r*H σ> rH 1 loo s ο | 3.00 1 〇 〇 〇 〇 寸 CO 寸 CO 0.8 o r*H σ> |重量份| 1重量份1 |重量份| 硬化性組成物 i 丙烯酸系單體(A) 1 1 具有自由基聚合性基之撥水/親油性樹脂（Β) 自由基聚合起始劑（c) 鉛筆硬度 3 H 鉛筆硬度 2 Η 耐鋼絲絲性 耐指纹附著性 污染物質去除性 水接觸角 nHD接觸角 霧度值 全光線透過率 30 323107 201202028 如表1所示，實施例之硬被覆膜，其硬度、耐指紋附 著性、污染物質去除性及透明性方面皆優異。相對於此， 比較例3及4之硬被覆膜，硬度方面差，比較例1及2之 污染物質去除性方面差。 【圖式簡單說明】 無。 【主要元件符號說明】 無0 31 323107201202028 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a hard coating film. In more detail, the present invention relates to a liquid crystal display device (LCD) and a plasma display panel (ΡΕ>Ρ). , an organic EL display device, a field emission display, a display device such as a Frj々, a cathode tube display device (CRT), or a hard coating film used for the surface of a touch panel or the like. In an image display device such as a liquid crystal display (LCD) or a plasma display panel (PDP), in order to improve the physical strength of the surface of a display device made of plastic, a hard coating layer is provided on the surface of the display device. Hard coating, the surface is easy to adhere to human fingerprints (sebum), sweat, cosmetics and other dirt, resulting in damage to the appearance of the product, or the occurrence of visual or operational obstacles. In addition, once fingerprints and other dirt Adhesion has a problem that it is not easily removed by wiping off, etc. As a means for solving such a problem, it is known that (1) a coating having a low surface energy has perfluoro a polymer of an alkyl group, and a method of imparting water/oil repellency on the surface' (2) coating a polymer having a polydiamine-based oxynphthene backbone having a low surface energy and imparting water/oil repellency on the surface The method of (3) is to increase the water/oil repellency by providing fine convexities and concaves on the surface, and at the same time, reducing the contact area to make the dirt difficult to adhere. However, in these methods, since the coating film is dialed In the oily state, the oil component such as sebum and fingerprints are removed, and there is a problem that the soil is noticeable. Further, the methods other than the above include: (4) By making the surface superhydrophilic, 4 323107 201202028 makes the dirt difficult to adhere. (5) A method of coating a polymer having a water-repellent or oil-repellent group and a specific hydrophilic group as described above to improve the removal of dirt. However, the method of the above (4), although the dirt is not easily adhered, has Once the dirt is attached, it is not easy to remove. Moreover, the method of (5) has the disadvantage of attracting attention. Further, by the different ideas from these methods, there are also proposals (6) Water-repellent/lipophilic, it is compatible with the sebum component, and it does not become remarkable even if it adheres. For example, in Patent Document 1, it is disclosed that the base material is separated by a siloxane coupling and a stearate group. The membrane is not particularly resistant to fouling. However, the film does not have sufficient surface damage resistance or durability, and the formation of the coating film requires complicated operations. Patent Document 2 discloses that it contains: having a carbon number of 12 The above-mentioned alkyl group or the like (meth)acrylate having a water-soluble group (meth)acrylate as a copolymer component as a main component, a stain resistance imparting agent, and a surface having such a stain resistance The contaminant article of the coating film formed by the agent. However, the contaminant article has poor maintainability of soil removal property, and at the same time, only the coating film having low hardness can be obtained only by the above-mentioned antifouling agent. Patent Document 3 discloses that a monomer having a radical double bond at the polymer terminal of an aliphatic or alicyclic alkyl group having 10 or more carbon atoms reacts with a monomer having a hardenable functional group and reacts with other monomers. The obtained graft polymer was used as a main component coating composition. However, in the coating composition, since the curable functional group is basically a cationic hardening functional group, the reaction rate is slow, and when UV curing is terminated, there is a disadvantage that the reaction proceeds continuously with time. [Prior Art Document] 5 323107 201202028 (Patent Document) Patent Document 1 Patent Document 2 Patent Document 3 [Summary of the Invention] Japanese Patent Laid-Open Publication No. 2001-353808, JP-A-2004-359834, JP-A-2009-249584 [Bulletin of the Invention] The purpose of this month is to provide a hard coating film having a high surface hardness and easily removing dirt such as fingerprints. Other purposes of this month are to provide a hard coating which further maintains soil removal for a long period of time. Another object of the present invention is to provide a hard coating film, and further, even if dirt such as fingerprints are attached, it is not noticeable. [Means for Solving the Problems] As a result of careful examination of the above objects, the inventors of the present invention found that the hard coating layer of the hard coating film is freely composed of an acrylic monomer or oligomer and a specific amount. When the water-repellent/lipophilic resin of the radical polymerizable group and the radically curable composition formed by the radical polymerization initiator are cured, the surface hardness is high, and even if a fingerprint or the like is adhered, the stain is not remarkable. The present invention can be completed by simply removing the excellent effect of the soil. That is, the present invention provides a hard coating film which is a hard coating film having a hard coating layer on at least one side of a transparent base film, characterized in that the hard coating layer contains an acrylic monomer or oligomerization. The amount of the substance (A) and the total amount of the acrylic acid monomer or the oligomer (A) is 0. 025 to 5 weight 323107 6 201202028 The water-repellent/lipophilic resin (B) having a radical polymerizable group and the radical hardening composition of the radical polymerization initiator (c) are hardened to obtain a layer The pencil hardness of the surface of the hard coating layer is 2H or more. The acrylic monomer or oligomer (A) is preferably at least a polyfunctional (meth) acrylate. The water-repellent/lipophilic resin (B) having a radical polymerizable group is preferably an acrylic polymer having a radical polymerizable group and having a non-aromatic hydrocarbon group having a carbon number of 10 or more in a side chain. . As the transparent base film, a polyester-based, acrylic-based or polyolefin-based film can be used. The pencil hardness of the surface of the hard coating layer is preferably 3H or more. The haze value of the hard coating is 1. 8 % or less is preferred. The hard coating can be used as a hard coating for protecting the surface of the display device or the touch panel. [Effect of the Invention] According to the hard coating film of the present invention, the hard coating layer is a composition of a water-repellent/lipophilic resin containing an acrylic monomer or a polymerizable polymer and a specific amount of a radical polymerizable group. It is formed by hardening, so the surface hardness is high, and it can be easily removed even if a fingerprint or the like is attached. Further, since the hard coating layer exhibits lipophilicity, there is an advantage that even if a fingerprint or the like is adhered to the dirt. Further, since the water-repellent/lipophilic resin having a radical polymerizable group reacts with the acrylic monomer or the polymerized polymer to form a crosslinked structure, long-term soil removal property can be maintained. [Embodiment] 7 323107 201202028 [Best Mode for Carrying Out the Invention] The hard coating of the present month has a hard coating layer on at least one side of a transparent base film. '[Transparent Substrate Thin Film] The transparent substrate film is not particularly limited as long as it has transparency and moderate mechanical strength. Examples of the resin constituting the film include a polyester resin such as polyethylene terephthalate or polyethylene naphthalate; an acrylic resin such as polymethyl methacrylate; and polyethylene. Polyacrylic resin; polycyclic carbon resin; cyclic olefin resin; polycarbonate s; cellulose trimethyst, cellulose diethylene (tetra), cellulose acetate vinegar vinegar, cellulose acetate vinegar butyric acid vinegar, etc. Cellulose resin; polystyrene resin such as polyamine amine acrylonitrile 'butadiene-styrene resin (ABS resin), acrylonitrile-styrene resin (AS resin); polyarylate (10)乂arylate), polysulfone; polyether sulfone; polyether ketone; polyether ketoximine; polyimine; polyvinylidene chloride; polyvinyl alcohol; ethylene_vinyl alcohol copolymer resin. The transparent base film is preferably a polyester resin film, an acrylic resin film or a polyolefin resin film from the viewpoint of high transparency and excellent flexibility. The transmittance of visible light of the transparent base film is, for example, preferably 60% or more, more preferably 80% or more, and particularly preferably 90% or more. The thickness of the transparent substrate film varies depending on the use, and is generally 2 to 300 μm, and preferably 50 to 188 μm. [Hard coating layer] The hard coating layer in the present invention contains an acrylic monomer or oligomer 8 323107 201202028 (A), and a total amount of 1 or the same with respect to the bupropion acid monomer or oligomer (a). 〇〇The weight has 0. The layer obtained by curing the 205 to 5 parts by weight of the water-repellent/lipophilic resin (B) having a radical polymerizable group and the radically curable composition of a radical polymerization initiator (匸). [Acrylic monomer or oligomer (A)] As the acrylic monomer or oligomer (A), it may be a monofunctional acrylic monomer or oligomer, a polyfunctional acrylic monomer or an oligomer. Either one of the polymers may be used alone or in combination of two or more. Examples of the acrylic-functional monomer include (meth) methacrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate. ) butyl acrylate, isobutyl (meth) acrylate, grade 3 butyl (meth) acrylate, amyl (meth) acrylate, grade 3 amyl (meth) acrylate, hexyl (meth) acrylate, (decyl)heptyl acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylate Isodecyl ester, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (mercapto) acrylate, tridecyl (meth) acrylate, tetradecyl (cyclyl) acrylate , (meth)acrylic acid alkyl (meth)acrylate, (▼-) octadecyl acrylate, etc.; (meth)acrylic acid 2-methoxyethyl ester, (meth)acrylic acid 2_B Oxyethyl ester, (meth)acrylic acid 3·methoxypropyl ester, (meth)acrylic acid 1 Vinegar methoxybutyl (meth) acrylate ester burning Hyun group; (meth) acrylate mounted amyl (meth) acrylate, tricyclo [5. 2. 1. 〇2,6] decane monomethanol, (meth) propyl hydrazine, (f-based) acetonide ester, (meth) acrylate (iso) acrylate having an alicyclic hydrocarbon group; Methyl)acrylic acid 323107 9 201202028 aryl ester (mercapto) aryl acrylate; benzyl (meth) acrylate, 2-phenylethyl (meth) acrylate, etc. (alkyl) methacrylate; Hydroxy-containing (meth) acrylate such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, etc.; a monomer having a mercaptoamine, a mercaptoamine, a mercaptoamine, an anthracene, a fluorenylamine, a mercaptoamine or a mercaptoamine-containing monomer; (mercapto) an amine group-containing monomer such as aminoethyl acrylate, dimethylaminoethyl (meth) acrylate, tributyl butyl methacrylate (mercapto) acrylate; epoxy propyl ( A propylene group-containing monomer such as acrylate or the like. Examples of the polyacrylic acid-based monomer include ethylene glycol mono(indenyl)propene 1 oxime, monoethyl diol di(indenyl) propyl gluconate, and polyethylene glycol bis ( Methyl) acrylate, butanediol bis(indenyl) acrylate, neopentyl glycol bis(indenyl) acrylate, hexanediol di(meth) acrylate, decanediol di(meth) acrylate , three rings [5. 2. 1. 02,6] 2-functional (meth) acrylate such as decane dimethanol di(meth) acrylate; trimethylolethane tri(meth) acrylate, trishydroxypropyl propane tri (methyl) Acrylate, glycerol tri(meth) acrylate, pentaerythritol tri(meth) acrylate, bis(trimethylol) propyl tri(meth) acrylate, dipentaerythritol tri(meth) acrylate, etc. Trifunctional (meth) acrylate, pentaerythritol tetra(meth) acrylate, bis(trimethylol)propane tetrakis(meth) acrylate vinegar, bis-pentaerythritol tetra(methyl) propylene Sour vinegar, dipentaerythritol penta (meth) acrylate vinegar, bis(tris(tetra)yl)propene pentoxide (meth) acrylate, dipentaerythritol hexa(meth) acrylate, bis(trimethylol) propyl ketone A tetrafunctional or higher acrylic acid vinegar such as hexa(methyl)propionate. Examples of the acrylic oligomer include epoxy group (methyl) 323107 10 201202028 acrylate, polyester (mercapto) acrylate, and amino decanoate (mercapto) ester. The molecular weight of the acrylic oligomer is usually less than 1 Torr. The acrylic monomer or oligomer (A) is preferably a monomer which does not contain an organic polyfluorene monomer or a fluorinated alkyl group. It is preferred that the acrylic monomer or oligomer (A) contains at least a polyfunctional thiol acrylate (polyfunctional acrylic monomer). Among the acrylates, it is preferably a trifunctional or higher (meth) acrylate, a tetrafunctional or higher (meth) acrylate, and a hexa acrylate or higher acrylate. good. A polyfunctional (meth) acrylate [for example, a bifunctional or higher (meth) acrylate, preferably a tetrafunctional or higher (meth) acrylate, more preferably a hexafunctional or higher (meth) acrylate] The amount of use is preferably 50% by weight or more based on the total amount of the olefinic acid monomer or the oligomer (A), more preferably 7 Torr/Torr, and particularly preferably 85% by weight or more. [Water-repellent/lipophilic resin (B) having a radical polymerizable group] In the water-repellent/lipophilic resin (B) having a radical polymerizable group, examples of the radical polymerizable group include: Methyl)acrylonitrile (including (meth)propoxyl), vinyl, and the like. Further, it is preferably a (meth) propylene fluorenyloxy group. The water-repellent/lipophilic resin (B) having a radical polymerizable group may be a molecule, and may have a water-repellent/lipophilic portion and at least one radical polymerizable group. The water-repellent/lipophilic portion may, for example, be an acrylic polymer chain having an alkyl group having 10 or more carbon atoms in the side bond. Such a resin having an acrylic polymer chain portion having a non-aromatic hydrocarbon group having 1 or more carbon atoms in the side chain is also contained in the acrylic polymer. Further, in the water-repellent/lipophilic resin (B) having a radical polymerizable group of 11 323 107 201202028, the radical polymerizable group may be located at a side chain portion of a main chain (for example, an acrylic polymer chain). Can be located at the end of the main chain. Examples of the non-aromatic hydrocarbon group having the above carbon number λ or more include, for example, an anthracenyl group, an isodecyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, and ten. a linear or branched chain alkane having a carbon number of 10 or more, such as a hexaalkyl group, a heptadecyl group, an octadecyl group, a decyl group, a decyl group, a decyl group or an eleven alkyl group. Base; cyclodecyl, cyclododecyl, adamantyl, isobornyl, tricyclic [5·2. 1. 02,6] 癸基,三环[6. twenty one. 02,7] undecyl, tetracyclic [4. 4. 0. 12’5. 17,10] an alicyclic hydrocarbon group having a carbon number of 10 or more, such as a dodecyl group; the alicyclic hydrocarbon group is bonded to one or more alkyl groups having a carbon number of from 1 to 4 such as a methylene group or an exoethyl group; Base. The carbon number of the non-aromatic hydrocarbon group is, for example, 10 to 24, and more preferably 20 or more, still more preferably 10 to 18. The acrylic polymer chain having a non-aromatic hydrocarbon group having 10 or more carbon atoms in the side chain (and the acrylic polymer having the polymer chain) may contain at least a non-aromatic hydrocarbon group having a carbon number of 1 Å or more ( The monomer component of the fluorenyl acrylate is obtained by polymerization. Representative examples of the (meth) acrylate having a non-aromatic hydrocarbon group having 10 or more carbon atoms include, for example, decyl (meth)acrylate, dodecyl (meth)acrylate, and (methyl). The number of carbon atoms in the alkyl group such as tridecyl acrylate, decyl sulfonate, (meth) propyl hexahydrate, and (methyl) acryl octahydrate is 10 or more. (e.g., 10 to 24, preferably 10 to 20, more preferably 1 to 18) alkyl (meth)acrylate; (meth)acrylic acid 12 323107 201202028 adamantyl ester, isobornyl (meth)acrylate Ester, tricyclic [5. 2. 1. 02,6] decane monomethanol (meth) acrylate or the like having an alicyclic hydrocarbon group having a carbon number of 1 Å or more (for example, 1 to 24, preferably 1 to 20, more preferably 1 to 18). (fluorenyl) acrylate and the like. These can be used alone or in combination of two or more. The monomer component may contain a monomer other than the (meth) acrylate having a non-aromatic hydrocarbon group having 1 or more carbon atoms. Examples of the monomer other than the (meth) acrylate having a non-aromatic hydrocarbon group having 10 or more carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid. Ester, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl methacrylate, (ethyl) acetoacetate, (A) Acrylic acid tertiary pentyl vinegar, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethyl (meth) acrylate (i-(meth)acrylic acid Ci 9 alkyl ester such as hexyl ester, (decyl) decyl acrylate, isodecyl (decyl) acrylate; 2-methoxyethyl (meth) acrylate, (mercapto) acrylic acid 2 _Ethoxyethyl ester, 3-methoxypropane vinegar (meth) acrylate, 3 methoxy butyl (meth) acrylate 4 (mercapto) acrylonitrile alkoxylate; (methyl) (meth) propyl having an alicyclic hydrocarbon group having 3 to 9 carbon atoms such as cyclopentyl acrylate or cyclohexyl (meth)acrylate (nonyl) aryl acrylate, (benzyl) acrylate, benzyl (meth) acrylate, 2-phenylethyl (meth) acrylate, etc. Vinegar, (meth)acrylic acid 2-ethylidene vinegar, 2-mercaptopropyl phthalate [=1,2-propanediol-1_(indenyl) acrylate], (fluorenyl) a hydroxyl group-containing (meth) acrylate such as 2-hydroxybutyl acrylate; an ester group-containing monomer such as (mercapto)propionate; acrylamide, mercapto amide, hydrazine, fluorenyl-difluorenyl (曱323107 13 201202028 base) acrylamide, (meth) propyl hydrazine carbaryl and other monomers containing olefinic groups. (mercapto) amino acid ethyl acetoacetate, (meth) acrylic acid dimethylaminoethyl decene, (meth) acrylate tributyl butyl ethyl acrylate and other amine group-containing monomers; epoxy A monomer containing an epoxy group (epoxypropyl group or the like) such as propyl (meth) acrylate [= 2,3-glycidyl methacrylate]. A polyfunctional acrylic monomer can be used as the monomer other than the (nonyl) acrylate having a carbon number of 10 or more. Examples of the polyfunctional acrylic monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and butyl. Diol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylic acid vinegar, decanediol di(meth)acrylic acid vinegar, bicyclo[5 . 2. 1. 02'6] decane dimethanol di(indenyl) acrylate and other divalent energy (mercapto) acryl vinegar; trimethyl ethene tris(methyl) acrylate vinegar, trimethyl methacrylate Methyl) acrylate, glycerol tri(meth) acrylate, pentaerythritol tris (meth) acrylate vine, di (trimethyl) propyl tris(methyl) acrylate dipentaerythritol III ( Methyl) acrylate vinegar I 3 -functional bismuth (meth) acrylate, pentaerythritol tetra (meth) acrylate, bis(trihydroxy decyl) propane tetra (methyl) propylene vinegar, two seasons Alcohol tetra(meth)acrylic acid vinegar, dipentaerythritol penta (methyl) acrylate vinegar, di(trimethyl)propyl pentane penta(methyl) acrylate vinegar, dipentaerythritol hexa(methyl) acrylate Ethyl ester, di(trimethylenemethyl)propene-fired hexa(methyl)propene Ua, etc. 4 g or more of (meth)acrylic acid g; epoxy (meth) acrylate; polyester (A) The acrylic acid is intended to be a succinic acid; the carbamic acid is intended to be a (meth) acrylate. In the propylene-based 323107 14 201202028 acid polymer having a carbon number of 10 or more in the side chain, the method of introducing a radical polymerizable group into the molecule is not particularly limited. For example, a method of introducing a radical polymerizable group into a side chain of an acrylic polymer chain may, for example, be (1) a (meth) acrylate having a non-aromatic hydrocarbon group having a carbon number of ε or more and a polyfunctional acrylic group. a method of copolymerizing a monomer to obtain a polymer having an unreacted (meth) acrylonitrile group in a molecule, (ii) a (fluorenyl) acrylate having a non-aromatic hydrocarbon group having 10 or more carbon atoms, and After copolymerization of the radical polymerizable monomer having a reactive functional group X, the reactive functional group X of the obtained polymer side chain and the radical polymerizable property of the functional group y capable of reacting with the reactive functional group X are obtained. The method of monomer reaction. The methods of combining (1) and (ii) can also be used. In the above (1), as the polyfunctional acrylic monomer, the above-exemplified materials can be used. In the above (ii), examples of the radical polymerizable monomer having a reactive functional group X include a radical polymerizable monomer having a carboxyl group as a functional group X such as (meth)acrylic acid; a radically polymerizable monomer having a hydroxyl group as a functional group X, such as 2-hydroxyethyl acrylate or 2-hydroxypropyl (meth) acrylate; and an alkane such as 3-(indenyl) propyleneoxypropyltrimethoxydecane The oxyalkylene group is a radical polymerizable monomer of the functional group X or the like. Further, in the above (ii), the radical polymerizable monomer having a functional group y which is reactive with the reactive functional group X, and the functional group X is a thiol group, and (meth)acrylic acid 3,4- a radically polymerizable monomer having an epoxy group as a functional group y, such as epoxycyclohexylmethyl ester, (meth)acrylic acid propyl acrylate [=(indenyl)acrylic acid 2,3-epoxypropyl ester] When the functional group X is a trans group, a radical polymerizable monomer having an acid anhydride group 15 323107 201202028 or an isocyanate group as a functional group y such as maleic anhydride or (fluorenyl) acrylonitrile isocyanate may be mentioned; the functional group X is Examples of the alkoxyalkyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-(fluorenyl) propyleneoxypropyltrimethoxy decane. A hydroxyl group or an alkoxyalkyl group is a radical polymerizable monomer of the functional group y or the like. The above copolymerization can be carried out by a usual method using a conventional radical polymerization initiator such as azobisisobutyronitrile. For example, the polymerization can be carried out at a temperature of about 30 to 120 ° C in an organic solvent. Examples of the organic solvent include aromatic hydrocarbons such as toluene and diphenylbenzene; aliphatic hydrocarbons such as hexane and octane; and alicyclic hydrocarbons such as cyclohexane; ethyl acetate, butyl acetate, and acetic acid. An ester such as isobutyl ester; an alcohol such as decyl alcohol, ethanol, isopropanol or butanol; a ketone such as acetone, mercaptoethyl ketone or decyl isobutyl ketone. These organic solvents may be used singly or in combination of two or more. In the above (ii), the reaction of the polymer obtained by the copolymerization with the radical polymerizable monomer having a functional group y reactive with the functional group X is in the absence of a solvent or a solvent, for example, It is carried out at a temperature of about 60 to 140 °C. As a solvent, the above-mentioned organic solvent etc. are mentioned. The number average molecular weight (in terms of styrene) of the obtained polymer is, for example, from 500 to 50,000, and preferably from about 800 to 25,000. When the number average molecular weight of the polymer is too small, the water repellency/lipophilic property at the time of forming a coating film is liable to lower. Further, when the number average molecular weight of the polymer is too large, the solubility to the solvent is liable to lower. The water-repellent/lipophilic resin (B) having a radical polymerizable group thus obtained can be directly used in the reaction liquid after the reaction with an acrylic monomer or oligomer (A) and a radical polymerization initiator. (C), if necessary, can also be used by immersing and refining, etc. by 16 293107 201202028. In the acrylic polymer having a radical polymerizable group and having a non-aromatic tobacco group having a carbon number of 10 or more in the side chain, the monomer component constituting the polymer is 'as a non-aromatic hydrocarbon group having 10 or more carbon atoms. (Mercapto-based) Acrylic vinegar is preferably an alkyl (indenyl) propionate having a carbon number of from 1 to 16 in the alkyl group, wherein the dodecyl (meth) acrylate is good. Further, in the monomer component constituting the polymer, a monomer other than the (meth) acrylate having a non-aromatic hydrocarbon group having 1 or more carbon atoms may be exemplified by (a) (mercapto) butyl acrylate. C5 6 (meth)acrylic acid cycloalkane such as Cl_8 alkyl (fluorenyl) acrylate, (b) cyclohexyl (meth) acrylate, (c) benzyl (meth) acrylate, (d) a hydroxyl group-containing (mercapto) acrylate such as 2-hydroxypropyl (meth)acrylate, a carboxyl group-containing monomer such as (e) (fluorenyl)acrylic acid, or (f) ethylene glycol di(meth)acrylic acid An epoxy group-containing (meth) acrylate such as a polyfunctional (fluorenyl) acrylate such as an ester or a glycerol tris(yl) acrylate or a (meth) acrylate (meth) acrylate, (h) 3 _ (曱) (meth) acrylate having an isocyanate group such as an alkoxyalkyl group-containing (fluorenyl) acrylate such as an acryloxypropyltrimethoxy decane or (i) (meth) acryl decyl isocyanate Wait. These can be used in combination of two or more types. When two or more monomers other than the (nonyl) acrylate having a carbon number of 10 or more are used, the preferred combinations are (1) (4), (4) and/or (4), and (selected from ( a combination of at least i of f), (g), (8) and (i), (2) (a), and (9) and / or (4), and (4) and / or (4), and selected from (f), (g) , (9) and (1) combinations of at least one species. In short, the combination of (4) and (b) and (4) and (d) with (6) and (7) hiding is appropriate. 323107 17 201202028 In an acrylic polymer having a radical polymerizable group and having a non-aromatic radical having a carbon number of 1 Å or more in a side chain, 'having a carbon number of 10 or more with respect to the all monomer component constituting the polymer. The ratio of the non-aromatic hydrocarbon group (meth) acrylate is, for example, 15% by weight. /. The above (e.g., 15 to 95 weight 〇/.) is preferably 20% by weight or more (e.g., 20 to 9% by weight), more preferably 30% by weight or more (e.g., 30 to 80% by weight). When the ratio is too small, it is difficult to obtain water/pro/relation, and the stain removal property and the fingerprint adhesion are liable to be lowered. Further, when the ratio is too large, the hardness of the coating film is liable to lower. A double bond equivalent of an acrylic polymer having a radical group having a non-aromatic hydrocarbon group having a carbon number of 1 Å or more in a side bond, for example, 100 to 3000 g/eq ' and 200 to 2000 g/eq Preferably, it is preferably from 300 to 1 〇〇〇g/eq. In addition to the above, the water-repellent/lipophilic resin (B) having a radical polymerizable group is exemplified by an acrylic polymer chain portion having a non-aromatic hydrocarbon group having a carbon number of 1 Å or more in the side chain. a lipophilic portion and a resin having a radical polymerizable group at a terminal portion of the acrylic polymer chain. In the case of such a tree, a monomer containing at least a (meth) acrylate having a non-aromatic hydrocarbon group having 10 or more carbon atoms can be contained, for example, in the presence of a chain transfer agent containing a reactive functional group X. After the component is polymerized, a functional group X at the end of the acrylic polymer chain and a radical polymerizable monomer having a functional group y reactive with the functional group X are reacted and produced. The chain transfer agent containing the S-mercapto group X may be a hydrogenthio group as a function of the chain transfer of 18 323107 201202028, and other functional groups X may be used without particular limitation. For example, thioacetic acid is exemplified. a chain transfer agent having a carboxyl group as a functional group X, such as thiopropyl propionic acid, thiosulfosuccinic acid, thiomalic acid or thiosalicylic acid; 2-hydrothioethanol, 1-hydrothiol-1- a chain transfer agent having a hydroxyl group as a functional group X such as propanol, 3-decylthio-2-butanol, 1-thiopropanetriol or thiophenol; 3-hydrothiopropyltrimethoxydecane, A chain transfer agent having an alkoxyalkylene group as a functional group X, such as 3-arylthiopropylmercaptodioxanane. The polymerization can be carried out in the same manner as the above-mentioned copolymerization. The number average molecular weight (in terms of styrene) of the obtained polymer is, for example, from 500 to 100,000, preferably from about 800 to 50,000. When the number average molecular weight of the polymer is too small, the water repellency/lipophilic property at the time of forming the coating film is liable to lower, and when the number average molecular weight of the polymer is too large, the solubility to the solvent is liable to lower. The radical polymerizable monomer having a functional group y reactive with the above-mentioned functional group X may be the same as the above. Among them, from the viewpoint of reactivity and the like, a radical polymerizable monomer having an isocyanate group is preferred. The reaction of the above polymer and the radical polymerizable monomer having a functional group y reactive with the functional group X is carried out in a solvent or in the absence of a solvent, for example, at a temperature of about 60 to 140 °C. As a solvent, the above-mentioned organic solvent etc. are mentioned. By this reaction, a water-repellent/lipophilic resin (B) having a radical polymerizable group can be obtained (the acrylic polymer chain portion having a non-aromatic hydrocarbon group having a carbon number of 10 or more in the side chain is used as a water-repellent/lipophilic portion, Further, a resin having a radical polymerizable group at the terminal portion of the acrylic polymer chain]. 19 323107 201202028 An example of a monomer component constituting a polymer, and an ideal combination of the monomer component are the same as described above. In the polymer thus obtained, the reaction liquid after the reaction may be directly used in the acrylic monomer or oligomer (A) and the radical polymerization initiator (C), and may be precipitated if necessary. It is used after purification and purification. In addition, as the water-repellent/lipophilic resin (B) having a radical polymerizable group, the terminal portion (or side chain) of the acrylic polymer chain obtained as described above may have a radical polymerizable group. Further, the radical polymerizable group of the oleaginous resin is further polymerized to form a propylene-based polymer chain having a non-aromatic hydrocarbon group having 10 or more carbon atoms in a side chain, and a vinyl polymer having a radical polymerizable group in a side chain. The graft copolymer of the chain is used as the water-repellent/lipophilic resin (B) having a radical polymerizable group. The graft copolymer is obtained by the following reaction, for example, a water-repellent/lipophilic resin having a radical polymerizable group at a terminal portion (or a side chain) of the acrylic polymer chain obtained above, and A polyfunctional acrylic monomer or a radical polymerizable monomer having a reactive functional group X, if necessary, copolymerized with another radical polymerizable monomer, and a radical polymerizable single having a reactive functional group X is used. When the monomer is the monomer (b2), the polymer after polymerization and the radical polymerizable monomer having a functional group y reactive with the reactive functional group X are reacted to obtain the graft copolymer. As a polyfunctional acrylic monomer, a radical polymerizable monomer having a reactive functional group X, and a radical polymerizable monomer having a function capable of reacting with a reactive functional group X 323107 201202028 y, it can be used. The aforementioned example. As the other radical polymerizable monomer, those other than the (fluorenyl) acrylate having a non-aromatic hydrocarbon group having 10 or more carbon atoms can be exemplified. The graft copolymer can be produced by a conventional method such as solution radical polymerization. The above-mentioned organic solvent can be used as the solvent used in the solution polymerization. The weight average molecular weight of the graft copolymer is, for example, from 1 Å to 200,000, and preferably from about 5,000 to 100,000. An example of the composition of the early component constituting the graft copolymer and an ideal combination of the monomer component are the same as described above. [Radical Polymerization Initiator (C)] The radical polymerization initiator (C) is a water-repellent/lipophilic resin (B) which promotes an acrylic monomer or oligomer (A) and has a radical polymerizable group. ) used for hardening. The radical polymerization initiator (C) may be used singly or in combination of two or more. As the radical polymerization initiator (c), a known photoradical polymerization initiator or a thermal radical polyfluorene initiator which is generally used in the polymerization can be used. As representative examples of the photoradical polymerization initiator, there may be mentioned, for example, 3,3', 4,4,-tetrakis (tertiary butylperoxycarbonyl), agglomerate, 3,3, _2 (three-stage I) Peroxyesters such as oxycarbonyl)-4,4,-bis(decyloxycarbonyl)benzoquinone, tertiary butyl benzoate; tertiary butyl hydroperoxide, di- or tertiary butyl Peroxides such as peroxides; benzoin, stupid methyl _, styrene = ethyl ether, etc. / benzoin alkyl ethers; acetophenone, 2,2-dioxane US-2-phenylethyl benzene, 2,2-diethoxy 2 phenyl phenyl hydrazine, ι, "digas 2 323107 21 201202028 styrene and other acetamidine; W-based cyclohexyl phenyl · cyclohexyl phenyl ketones such as ketones, anthraquinones such as 2-mercaptopurine and 2-ethylhydrazine; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, etc. Thioxanthone; acetophenone acetal, benzyl didecyl ketal, etc.; benzoquinones such as benzoquinone; xanthone; 〖, 7_double (9 _Acridine-based heptane; titanium tetradecene compound (titanocene)] aromatic hard rust salt (Aryi i〇 (j〇nium sait), aromatic po I, # as thermal radical polymerization Representative examples of the initiator include, for example, 2,2'-azobisisobutyronitrile, 2,2,-azobis(2,4-dimethylvaleronitrile), 2,2,_azo Bis(4-decyloxy-2,4-dimercaptophthalonitrile), 2,2,-azobis(2-methylpropionic acid) dinonyl ester, 2,2'-azobis (2·A Alkyl propionate, 2,2,-azobis(2·mercaptopropionic acid) dibutyl S, etc., benzoyl peroxide, laurel peroxide, peroxy-trimethyl Organic acetic acid such as tertiary acetic acid (four), p, pivalate, 1,1-bis(tributylphosphonium peroxide), hydrogen peroxide, etc. When the agent is used, a reducing agent may be used as a redox-type initiator. [Free radical curable composition] In the present invention, the radical curable composition contains an acrylic monomer or oligomer (4), A water-repellent/lipophilic resin (B) having a free silky group and a radical polymerization initiator (〇. In a radically curable composition, a water-repellent/lipophilic resin having a radical polymerizable group ( The amount of B) relative to the total amount of the acrylic monomer or oligomer (A) 100 The amount of parts' having 0. 025 to 5 parts by weight, ideally 〇 〇 3 to 4. 5 parts by weight and by 〇. 〇 5 to 4 parts by weight is more preferable. When the amount of water-repellent/lipophilic tree sputum (B) having a radical polymerizable group is too small, in addition to the deterioration of the removal property of the 236107 22 201202028, the fingerprint is likely to become conspicuous when the fingerprint is attached. . On the other hand, when the amount of the water-repellent/lipophilic resin (B) having a radical polymerizable group is too large, the surface hardness of the hard coating is likely to be low. In particular, when the hard coating layer is formed by using the water-repellent/lipophilic resin (B) having a radical polymerizable group and the radical polymerization initiator (C) without using an acrylic monomer or oligomer (A) The surface hardness will decrease significantly. The amount of the radical polymerization initiator (C) varies depending on the type thereof, and the water-repellent/lipophilic resin (B) having a radical polymerizable group with respect to the acrylic monomer or oligomer (A) The total amount is 100 parts by weight, for example, 〇. 1 to μ parts by weight, and 0. It is preferably 5 to 10 parts by weight, more preferably about 1 to 6 parts by weight. When the amount of the radical polymerization initiator (C) is too small, there is a case where it is not sufficiently hardened. On the contrary, when it is too much, the coating film becomes brittle. In the radical curable composition, it is preferred to use a solvent such as an organic solvent for the purpose of adjusting coatability and the like. The solvent is not particularly limited as long as it differs depending on the type of the acrylic monomer or the oligomer (A) or the water-repellent/lipophilic resin (B) having a radical polymerizable group, and is not particularly limited, and for example, Listed: ketones such as mercaptoethyl ketone, mercaptoisobutyl ketone, cyclohexanone; hydrocarbons such as methyl bromide and diphenylbenzene; ethyl acetate, butyl acetate, 3-methoxybutyl acetate, cesium acetate An ester such as oxypropyl ester or ethylene glycol monomethyl ether acetate; an alcohol such as methanol, ethanol, isopropanol, methoxypropanol, 3-methylbutanol or ethoxyethanol; Ether, ethylene glycol dimethyl ether, ether such as tetrahydrofuran, and the like. The amount of the solvent, based on the total amount (1 〇〇 by weight) of the acrylic monomer or oligomer (A) and the water-repellent/lipophilic resin (B) having a radical polymerizable group, is 23 323107 201202028 It is preferably 5 to 500 parts by weight. In the above-mentioned radical curable composition, in addition to the above, other resins, antifoaming agents, photosensitizers, ultraviolet absorbers, antioxidants, and light stabilizers may be added to the extent that the effects of the present invention are not impaired. Various additives such as agents, agglomeration inhibitors, leveling agents, surfactants, extenders, pigments, dyes, anti-recording agents, antistatic agents, conductive materials, plasticizers, slip agents, resin microparticles, inorganic microparticles, and the like. Acrylic monomer or oligomer (A) in the radical curable composition and water-repellent/lipophilic resin having a radical polymerizable group (B) with respect to the entire component (all non-volatile matter) from which the solvent is removed The total ratio is, for example, 70% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, and particularly preferably 95% by weight or more. Examples of the method of applying the radical curable composition to the transparent base film include a spin coating method, a brush coating method, a spray method (blowing method), a dipping method, a knife coating method, and a roll coating method. Flow coating method, bar coating method, gravure coating method, air knife coating method, and the like. After the application, the solvent is dried in the case of using a solvent, and it is preferred to harden by irradiation with an active energy ray to form a hard coating layer on the surface of the transparent substrate film. As the active energy ray for irradiation, ultraviolet rays, X rays, electron lines, or the like can be used. Among them, from the viewpoint of industrial properties such as safety and reaction efficiency, ultraviolet rays are most preferably used. The wavelength of the ultraviolet light used is preferably from 200 to 400 nm, and good irradiation conditions, for example, an illumination of 1 to 1000 mW/cm2, and an irradiation amount of 0. 1 to 10000 mJ/cm2, as an irradiation device for the active energy ray, for example, a high-pressure mercury lamp, a low-pressure water 24 323107 201202028 silver lamp, a metal halide lamp, an excimer lamp, or the like, an argon ion laser can be used. Or a pulse of a helium ion laser, a continuous laser source, or the like. Further, when the heat treatment is carried out in the above-mentioned hardening treatment, it is preferable because it is easily hardened sufficiently. The heat treatment is preferably carried out after the hardening treatment, provided that the type of the transparent base film applied by the radical curable composition differs, for example, from room temperature to 18 Torr. (The temperature is preferably from 10 minutes to about i week. The thickness of the hard coating layer is, for example, 2 to 1 〇〇 um, more preferably 3 to 50 um. In the case where the hard coating layer is thinner than the above-mentioned ideal range The scratch resistance has a declining condition. When the thickness is thick, the cost becomes unfavorable, and the creativity may have a decrease, or the hard coating layer itself may become easily peeled off. Thus, the surface hardness is high. The hard coating film of the hard coating layer. The hard coating layer of the hard coating film of the present invention has a erroneous hardness of more than or equal to 3' or more. Further, the hard coating layer of the hard coating film of the present invention is It is excellent in scratch resistance. For example, when the steel wool (Steelw〇〇1; #〇〇〇〇) load IKgf clock is tested 20 times on the surface of the hard coating layer, it is not scratched. The hard-coated hard coating layer adheres to the surface of the hard coating layer in terms of resistance to the smear-removing substance, and has a defect even if it is attached to the black matrix. In addition, the hard-coated t-surface is attached with a fingerprint. , wipe the paper wipe operation within 5 times疋Less than 3 times) you can remove fingerprints. Further, the contact angle of the hard coating layer of the hard coating film of the present invention to water is, for example, 323107 25 201202028, such as 80 degrees or more, and particularly preferably 85 degrees or more. For k 8. When the degree of 'low water repellency' is wiped out, it means "skin 2: the hard coating layer of the hard coating film of the invention is not positive ==. And the angle is, for example, 10 degrees or less, and (HD) When the contact angle of the contact with the six burns (-) is too large, the pro: low birth, when it is ten, it becomes very conspicuous, X, the glossiness also lowers the suede month, and the present invention The haze value of the hard coating film is small, and the haze value of the hard ray I hard coating film is, for example, 20% or less, and is in the following (especially 1. 5% or less) is preferred. For example, in the case where the thickness of the hard coating layer is ^ (10)', the transparent substrate film is polyethylene terephthalate, and the thickness thereof is (10) um, and the haze value is 疋 2. 0% or less, and especially below 8% (especially below 15%). The total light transmittance is, for example, 85% or more, and particularly preferably 9% by mass or more. When the total light transmittance is less than 85%, it is difficult to use as an optical material, or the creativity may be degraded. The hard coating film of the present invention has characteristics as described above, for example, as a protective liquid crystal display device (LCD), a plasma display device panel (PDP), an organic EL display device, and a field emission display device (FRD). A hard coating film used for a display device such as a cathode tube display device (CRT) or a touch panel, particularly a surface of a flat panel display device. EXAMPLES Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to the examples. Example 1 In 1 part by weight of the second season of the acrylic monomer [polyfunctional (meth) acrylate] 26 323107 201202028 decyl alcohol hexaacetate (product name "DPHA" manufactured by Daicel_CyteC Co., Ltd.), A water-repellent/lipophilic resin having a radical polymerizable group (trade name "ZX-214_A", manufactured by Fuji Chemical Industry Co., Ltd.; and acetic acid oligomer having a radical polymerizable group and a water-repellent/lipophilic group) Butyl ester / isopropanol solution; double bond equivalent 560 g / called (no choice of points)] 〇 · 〇 6 parts by weight (resin: 0. 03 parts by weight), and a radical polymerization initiator (manufactured by Vapart Chemical Co., Ltd., trade name "IRGACURE 184"; radical photopolymerization initiator) 3 parts by weight, and the resulting composition is methyl The base ketone was diluted to give a non-volatile content of 4% by weight to obtain a coating film composition. Then, the coating film composition was coated on one side of a polyethylene terephthalate film (manufactured by Mitsubishi Plastics Co., Ltd., product name "〇321E188W76A", PET film) having a film thickness of 188 nm. After coating #12, it was dried by a dryer at 1 ° C for 1 minute, and irradiated with ultraviolet rays to be hardened [light source: high pressure mercury lamp, conveying speed: 15 m / min, number of irradiation: 3 times, cumulative amount of light: lOOOOm/cm 2 ] A PET film having a coating film (hard coating layer) having a thickness of about 6 μm on the surface can be obtained. After the thus obtained pET film having a coating film (hard coating layer) was left at room temperature for 24 hours, 'the pencil hardness, the profitability of the steel wire, the fingerprint adhesion resistance, the contaminant removal property, and the pair were measured for the coating film on the surface. Contact angle of water/n-hexadecane (nHD). Further, the haze value and the total light transmittance were measured for the entire PET film and the coating film. The measurement results are shown in Table 1. Examples 2 to 6 and Comparative Examples 1 to 4 except that an acrylic monomer [polyfunctional (meth) acrylate], a water-repellent/lipophilic resin having a radical polymerizable group from 323107 27 201202028, and radical polymerization were used. A PET film having a coating film (hard coating layer) having a thickness of about 6 μm on the surface was obtained in the same manner as in Example 1 except that the mixing ratio of the initiator was changed as shown in Table 1. After the thus obtained PET film having a coating film (hard coating layer) was allowed to stand at room temperature for 24 hours, pencil hardness, steel wool resistance, fingerprint adhesion resistance, and contaminant removal property were measured for the surface coating film. Contact angle to water/n-hexadecane (nHD). Further, the haze value and the total light transmittance were measured for the entire PET film and the coating film. The measurement results are shown in Table 1. Evaluation method (1) Pencil hardness is measured according to JIS K 5600 using a tensile hardness (pencil method) tester (manufactured by Shinto Scientific Co., Ltd., trade name "HE1DON-14D"), weight 1 kg, 45 degree method, and measuring distance 30 Mm evaluates pencil hardness. The pencils of 3H and 2H were measured five times, respectively, and three or more times without scratching were used as "〇", and those with three or more abrasions were regarded as "X". (2) Resistance to steel wire (scratch resistance) When the weight of the #0000 steel wire is 1 kg and the temperature is 20 times, the person who is not scratched is regarded as "〇", and the person who is scratched is regarded as "X". (3) Anti-fingerprint adhesion The fingerprint was attached to the coating film and placed on a black matrix to visually observe the degree of adhesion of the fingerprint. Those whose fingerprints are not significant are regarded as "〇", and those who are not significant are regarded as "Λ". (4) Contaminant removal The fingerprint is attached to the coating film, and the fingerprint is removed by wiping the paper to remove the fingerprint. 28 323107 201202028 Sex. It is expressed by the number of wiping times of the wiping paper until the fingerprint is removed. If it is 4 times, it is an allowable range, but it is preferably 3 or less. (5) For the contact angle of water/n-hexadecane (nHD), an automatic or dynamic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., type DCA-UZ) is used. For the coating film, about 5 uL of each liquid at 5 points is measured. Contact angles and averaged. (6) The haze value or the total light transmittance haze value or the total light transmittance is measured by a haze meter (manufactured by JASCO Corporation, trade name "300A type"), and is measured at 5 or more points. average. The haze value was measured in accordance with JIS K 7136. 29 323107 201202028 I <Comparative example 〇Ο»—Η | 3.00 1 XXX 〇CO γΉ in ΙΛ rH 0.8 to fH σί CO oi—1 Ο | 3.30 1 XXX 〇CO § CO CD 〇 r rH σ> (Μ o 1 ο. Οι 1 | 3.00 | 〇〇〇〇 (Λ cd in oi 00 o eg rH σ> ιΗ 1 loo 1 Ο | 3.00 1 〇〇〇〇UO CO s csi csi 0.8 Example CD 1 loo 1 to LTD 1-H CO X 〇X 〇CO CM 00 00 5.9 00 inch ι—l σί LQ I loo 00 1 3.09 1 〇〇〇〇CO Bu: 5.5 ca tH inch τ—4 σ> Inch O s CO 〇〇〇〇00 δ ! 4.8 00 o inch 03⁄4 CO 1 loo LO Ο | 3.02 1 〇〇〇〇CO co 00 :4·5 00 d 91.4 CM 100 ι»Ι Ο | 3.00 1 〇〇〇〇CO 00 CO 00 o CD r*H σ> rH 1 loo s ο | 3.00 1 inch CO inch CO 0.8 or*H σ> |parts by weight | 1 part by weight 1 |parts by weight | hardenable composition i acrylic monomer (A) 1 1 Free radical polymerizable water-repellent/lipophilic resin (Β) Free radical polymerization initiator (c) Pencil hardness 3 H Pencil hardness 2 耐 Steel wire resistant fingerprint-adhesive pollutants Detachable water contact angle nHD contact angle haze value Total light transmittance 30 323107 201202028 As shown in Table 1, the hard coating of the examples is excellent in hardness, fingerprint adhesion, contaminant removal and transparency. On the other hand, the hard coating films of Comparative Examples 3 and 4 were inferior in hardness, and the contaminant removal properties of Comparative Examples 1 and 2 were inferior. [Simplified description of the drawing] None [Explanation of main component symbols] None 0 31 323107