201106004 六、發明說明： 【發明所屬之技術領域】 '本發明係關於防眩性硬被覆膜及使用它之偏光板，詳 細而言，本發明係關於一種設置有含有球狀有機微粒及球 狀矽系微粒之硬被覆層之具有耐擦傷性的防眩性硬被覆 膜，可在不使外部霧度値產生較大變化下使內部霧度値產 生變化，薄膜量產時容易進行外/內部霧度値的調整，且可 在不損及對比下獲得期望的60。鏡面光澤度及防眩性之防 眩性硬被覆膜，以及使用此防眩性硬被覆膜之偏光板。 【先前技術】 映像管（CRT)或液晶顯示器（LCD)、電漿顯示器（PDP) 等之顯示器中，光從外部入射至畫面，此光產生反射而難 以觀看顯示圖像，尤其近年來隨著顯示器的大型化，解決 上述課題者乃逐漸變成重要課題。作爲解決此問題的手段 之一 ’可列舉出使用具有防眩性硬被覆層之構件者。 近年來，防眩性膜中，除了以往以賦予防眩性爲目的 之表面凹凸所起因之外部霧度値之外，亦開始要求同時具 有用以降低閃斑而來自膜內部的光擴散性之內部霧度値。 此內部霧度値，可藉由在硬被覆層中含有與黏結劑樹 脂具有折射率差之微粒而發揮。然而，當僅使用1種與黏 結劑樹脂具有折射率差之微粒來製作防眩性膜時，該微粒 必須可同時有助於外/內部霧度値兩者。因此，因塡充材種 類及添加量之不同，使防眩性膜之外/內部霧度値兩者產生 變動，而有生產時難以調整外/內部霧度値之問題。 -4- 201106004 因此，爲了解決此問題，本發明者們係發現到一種添 加一定量的1種有機微粒（內部霧度値被固定），並藉由分 散劑（界面活性劑）的添加量來控制外部霧度之手法，而在 之前提出專利申請（日本特願2008-087295號說明書）》 另一方面’提出一種在透明基板上形成有由折射率 1.40〜1_60的樹脂顆粒與電解離輻射線硬化型組成物所構 成之防眩層的防眩膜。例如，專利文獻1中，係提出一種 爲了形成顯現出防眩性之凹凸而由塗膜膜厚以上的粒徑之 有機塡充材所構成之防眩膜，但當爲了提高防眩性而增大 凹凸時，會有霧度値上升，穿透鮮明度降低之問題。爲了 改善此情形，專利文獻2中，係提出一種藉由降低顯現出 防眩性之凹凸形成用之塗膜的膜厚以上的粒徑之有機塡充 材添加量，並添加塗膜的膜厚以下的粒徑之有機塡充材， 來製作出均衡的防眩膜者。 然而，實際上在上述方法中即使可取得光學物性的均 衡，亦因所用之微粒粒徑的變動度，會出現不存在凹凸之 場所’而無法全面獲得防眩性。此外，由於膜厚所導致之 外部霧度値的變動較大，而有安定生產性惡化之問題。此 外’此等系列，其膜厚是由微粒尺寸所決定，而存在有如 表面硬度般之難以藉由膜厚來調整該物性者。 先前技術文獻 專利文獻 專利文獻1日本特開平6-18706號公報 專利文獻2日本特許第3515401號公報 201106004 【發明内容】 發明所欲解決之課題 本發明係在上述狀況下所創作出之發明，該目的係提 供一種在透明塑膠膜的表面形成有具有耐擦傷性的硬被覆 層之防眩性硬被覆膜，可在不使外部霧度値產生較大變化 下使內部霧度値產生變化，薄膜量產時容易進行外/內部霧 度値的調整，且可在不損及對比下獲得期望的60°鏡面光澤 度及防眩性之防眩性硬被覆膜，以及使用此防眩性硬被覆 膜之偏光板。 用以解決課題之手段 本發明者們係爲了達成前述目的而進行精心硏究，結 果得知下列發現。 發現到使用含有活性能量線感應型組成物，以及平均 粒徑位於期望範圍之特定的球狀有機微粒、特定的球狀矽 系微粒、及界面活性劑之硬被覆層形成材料來形成硬被覆 層，並且將該硬被覆層的厚度構成爲分別較上述球狀有機 微粒及球狀矽系微粒的各平均粒徑更大，藉此可獲得適合 前述目的之防眩性硬被覆膜。 此外，發現到此防眩性硬被覆膜，可藉由將前述活性 能量線感應型組成物之硬化物的折射率與前述球狀有機微 粒的折射率及球狀矽系微粒的折射率之差，分別定在特 定範圍，並藉由在前述硬被覆層形成材料中含有界面活性 劑，而容易地獲得適合該目的者。 本發明係根據該發現而完成之發明。 201106004 亦即，本發明係提供： (1) 一種防眩性硬被覆膜，其特徵爲：於透明塑膠膜的表 面，具有：（A)含有（a)多官能性（甲基）丙烯酸酯系單體 及/或（甲基）丙烯酸酯系預聚物、與（b)二氧化矽系微粒 之活性能量線感應型組成物；（B)選自平均粒徑爲 1〜ΙΟμιη之丙烯酸系樹脂、丙烯酸-苯乙烯系樹脂、三聚 氰胺系樹脂、聚碳酸酯系樹脂、苯乙烯系樹脂及氯乙烯 系樹脂中之至少1種的球狀有機微粒；（C)選自平均粒 徑爲0.5〜ΙΟμιη之聚矽氧烷系樹脂、中空二氧化矽及多 孔質二氧化矽中之至少1種的球狀矽系微粒；以及（D) 使用含有界面活性劑之硬被覆層形成材料所形成之硬 被覆層；並且該硬被覆層的厚度係分別較上述（Β)成分 及（C)成分的各平均粒徑更大： (2) 如上述（1)項所述之防眩性硬被覆膜，其中（b)二氧化砂 系微粒爲具備含有（甲基）丙烯醯基之基作爲表面官能 基之二氧化矽微粒； (3) 如上述（1)或（2)項所述之防眩性硬被覆膜，其中（A)成分 的硬化物與（B)成分之折射率差係小於〇.02 ,且（A)成分 的硬化物與（C)成分之折射率差爲〇.02以上且小於 〇 . 2 ;以及 (4) —種偏光板，其係將如上述（1)至（3)項中任—項之防眩 性硬被覆膜的硬被覆層形成面之相反側的面貼合於偏 光件而構成。 201106004 發明之效果 根據本發明，可提供一種設置有含有球狀有機微粒及 球狀矽系微粒之硬被覆層之具有耐擦傷性的防眩性硬被覆 膜，可在不使外部霧度値產生較大變化下使內部霧度値產 生變化，薄膜量產時容易進行外/內部霧度値的調整，且可 在不損及對比下獲得期望的60°鏡面光澤度及防眩性之防 眩性硬被覆膜，以及使用此防眩性硬被覆膜之偏光板。 【實施方式】 本發明之防眩性膜的特徵爲：係於透明塑膠膜的表 面，具有：（A)含有（a)多官能性（甲基）丙烯酸酯系單體及/ 或（甲基）丙烯酸酯系預聚物、與（b)二氧化矽系微粒之活性 能量線感應型組成物；（B)顯示出平均粒徑爲1~1〇μιη以下 之特定的球狀有機微粒；（C)顯示出平均粒徑爲0.5〜ΙΟμιη 以下之特定的球狀矽系微粒；以及（D)使用含有界面活性劑 之硬被覆層形成材料所形成之硬被覆層；並且該硬被覆層 的厚度係分別較上述（Β)成分及（C)成分的各平均粒徑更 大。 [硬被覆層形成材料] 本發明之硬被覆層形成材料，係含有：（Α)活性能量線 感應型組成物，（Β)球狀有機微粒，（C)球狀矽系微粒，以 及（D)界面活性劑。 ((A)活性能量線感應型組成物） 前述硬被覆層形成材料中，用作爲（Α)成分之活性能量 線感應型組成物中’係含有（a)活性能量線硬化型化合物之 201106004 多官能性（甲基）丙烯酸酯系單體及/或（甲基）丙烯酸酯系預 聚物’以及（b)二氧化矽系微粒作爲必要成分。 又’本發明中’所謂活性能量線，是指電磁波或荷電 粒子束中具有能量量子者，亦即紫外線或電子束等❶ < (a)活性能量線硬化型化合物> 本發明中’（a)活性能量線硬化型化合物係使用多官能 性（甲基）丙烯酸酯系單體及/或（甲基）丙烯酸酯系預聚物。 前述多官能性（甲基）丙烯酸酯系單體，例如可列舉出 二（甲基）丙烯酸1，4-丁二醇酯、二（甲基）丙烯酸ι，6-己二醇 酯、二（甲基）丙烯酸新戊二醇酯 '二（甲基）丙烯酸聚乙二醇 酯、二（甲基）丙烯酸羥基三甲基乙酸新戊二醇酯、二（甲基） 丙烯酸二環戊酯、經己內酯改質之二（甲基）丙烯酸二環戊 酯、經環氧乙烷改質之二（甲基）丙烯酸磷酸酯、二（甲基） 丙烯酸烯丙基化環己酯、二（甲基）丙烯酸異氰酸酯、三（甲 基）丙烯酸三羥甲基丙烷酯、三（甲基）丙烯酸二新戊四醇 酯、經丙酸改質之三（甲基）丙烯酸二新戊四醇酯、三（甲基） 丙烯酸新戊四醇酯、經環氧丙烷改質之三（甲基）丙烯酸三 羥甲基丙烷酯、三（丙烯氧基乙基）異氰酸酯、經丙酸改質 之五（甲基）丙烯酸二新戊四醇酯、六（甲基）丙烯酸二新戊四 醇酯、經己內酯改質之六（甲基）丙烯酸二新戊四醇酯等之 多官能性（甲基）丙烯酸酯》此等單體可使用1種或組合2 種以上使用。 另一方面’前述（甲基）丙烯酸酯系預聚物，例如可列 舉出聚酯丙烯酸酯系、環氧丙烯酸酯系、胺基丙烯酸酯系、 201106004 多元醇丙烯酸酯系等。在此，聚酯丙烯酸酯系預聚物，例 如可藉由（甲基）丙烯酸，將藉由多價羧酸與多價醇的縮合 所得之兩末端具有羥基之聚酯低聚物的羥基進行酯化，或 是藉由（甲基）丙烯酸，將環氧烷加成於多價羧酸所得之低 聚物末端的羥基進行酯化而製得。 環氧丙烯酸酯系預聚物，例如可藉由將（甲基）丙烯酸 與分子量相對較低的雙酚型環氧樹脂或酚醛型環氧樹脂的 環氧乙烷環反應以進行酯化而製得。胺基丙烯酸酯系預聚 物，例如可藉由（甲基）丙烯酸，將藉由聚醚多元醇或聚酯 多元醇與聚異氰酸酯的反應所得之聚胺基甲酸酯低聚物進 行酯化而製得。再者，多元醇丙烯酸酯系預聚物，可藉由（甲 基）丙烯酸，將聚醚多元醇的羥基進行酯化而製得。此等預 聚物可使用1種或組合2種以上使用，此外，亦可與前述 多官能（甲基）丙烯酸酯系單體倂用。 < (b)二氧化矽系微粒> 本發明中，（b)二氧化矽系微粒可使用膠體狀二氧化矽 系微粒及/或具有表面官能基之二氧化矽系微粒。 膠體狀二氧化矽系微粒，其平均粒徑約爲1〜400nm左 右者，此外，具有表面官能基之二氧化矽系微粒，例如可 列舉出具有含（甲基）丙烯醯基作爲表面官能基之基的二氧 化矽系微粒（以下有稱爲反應性二氧化矽系微粒時）》 上述反應性二氧化矽系微粒，例如可藉由使具有可與 矽醇基反應之官能基之含聚合性不飽和基的有機化合物， 與平均粒徑〇·〇〇5~1μιη之二氧化矽系微粒表面的矽醇基進 -10- 201106004 行反應而製得。聚合性不飽和基，例如可列舉出自由基聚 合性的（甲基）丙烯醯基等。 前述具有可與矽醇基反應之官能基之含聚合性不飽和 基的有機化合物，例如可使用丙烯酸、氯化丙烯酸、丙烯 酸2-異氰酸基乙酯、丙烯酸縮水甘油酯、丙烯酸2,3_亞胺 基丙酯、丙烯酸2-羥乙酯、丙烯醯氧基丙基三甲氧矽烷等 以及對應於此等丙烯酸衍生物之甲基丙烯酸衍生物。此等 丙烯酸衍生物或甲基丙烯酸衍生物可單獨使用或組合2種 以上使用。 如此製得之含聚合性不飽和基的有機化合物所鍵結之 二氧化矽系微粒，係作爲活性能量線硬化成分，藉由活性 能量線的照射進行交聯而硬化》 此反應性二氧化矽系微粒，係具有可提升所得之硬被 覆膜的耐擦傷性之效果。 含有將具有聚合性不飽和基之有機化合物鍵結於此般 二氧化矽系微粒而成之化合物的活性能量線感應型組成物 (A)，市面上例如有JSR股份有限公司製，商品名稱「Opstar Z7 5 3 0」、「Opstar Z7524」、「0 p s t a r T U 4 0 8 6」等。 本發明中，此（b)成分之二氧化矽系微粒的含量，在（A) 成分之活性能量線感應型組成物的固形份中，一般爲5~90 質量％，較佳爲1 0〜70質量°/。。 又，此（b)成分的二氧化矽系微粒之二氧化矽粒子的平 均粒徑，可藉由雷射繞射· '散射法進行測定。此方法中， 係藉由將雷射光照射至分散有粒子之液體時之繞射·散射 -11- 201106004 光的強度變化，來測定平均粒徑。 ((B)球狀有機微粒） 本發明之硬被覆層形成材料中，用作爲（B)成分之球狀 有機微粒，可列舉出選自平均粒徑爲1〜10 μιη的範圍之丙 烯酸系樹脂、丙烯酸-苯乙烯系樹脂、三聚氰胺系樹脂、聚 碳酸酯系樹脂、苯乙烯系樹脂及氯乙烯系樹脂中之至少1 種的球狀有機微粒。當此球狀有機微粒的平均粒徑小於 Ιμιη時，防眩性的顯現可能不足，另一方面，當超過1〇 μπι 時，該球狀有機微粒的粒徑與所形成之硬被覆層的膜厚接 近，使該球狀有機微粒從透明塑膠膜表面之浮起量變小， 所以會強烈受到粒徑變動度的影響，或是於塗布時該球狀 有機微粒的分散性不足，可能使所形成之硬被覆層的凹凸 產生不均。較佳的平均粒徑爲2〜8 μιη。此平均粒徑爲根據 柯特粒子計數法所測定之測定値。粒徑分布，其以柯特粒 子計數法所測定之平均粒徑的±2 μιη以內的範圍之重量分 率，較佳爲70%以上。 本發明中，此（Β)成分之球狀有機微粒，可單獨使用1 種或組合2種以上使用，此外，該調配量，就防眩性能之 觀點來看，相對於前述（Α)成分之活性能量線感應型組成物 的固形份100質量份而言，較佳爲0.5 ~30質量份，尤佳爲 1〜2 0質量份，特佳爲3~15質量份。 本發明中，前述（Α)成分之活性能量線感應型組成物的 硬化物，與該（Β)成分之球狀有機微粒，就抑制內部霧度値 的上升之觀點來看，其折射率差較佳爲小於0.02，尤佳爲 -12- 201106004 0.01以下。此球狀有機微粒，主要是用於外部霧度値的調 整又，球狀有機微粒的折射率，爲根據ns K 7142的B 法所測定之測定値。此外，前述活性能量線感應型組成物 之硬化物的折射率，爲根據JIS K 7 1 42的A法所測定之測 定値。 ((C)球狀矽系微粒） 本發明之硬被覆層形成材料中，用作爲（C)成分之球狀 矽系微粒，可列舉出選自平均粒徑位於0.5〜10 μιη的範圍內 之聚矽氧烷系樹脂、中空二氧化矽及多孔質二氧化矽中之 至少1種的球狀矽系微粒。當此球狀矽系微粒的平均粒徑 小於0.5μιη時，作用於內部霧度値之效果不足，另一方面， 當超過1〇μιη時，與所形成之硬被覆層的膜厚差變小，會 因該球狀矽系微粒之粒徑的變動度而有對外部霧度値產生 影響之疑慮。較佳的平均粒徑爲1〜8 μπι，特佳的平均粒徑 爲2〜6μιη。又，此平均粒徑，此平均粒徑爲根據柯特粒子 計數法所測定之測定値。此外，粒徑分布，其以柯特粒子 計數法所測定之平均粒徑的±2μιη以內的範圍之重量分 率，較佳爲70%以上。 本發明中，此（C)成分之球狀矽系微粒，可單獨使用1 種或組合2種以上使用，此外，該調配量，就防眩性能之 觀點來看，相對於前述（Α)成分之活性能量線感應型組成物 的固形份100質量份而言，較佳爲0.5〜30質量份，尤佳爲 1~20質量份，特佳爲2〜15質量份。 本發明中，前述（Α)成分之活性能量線感應型組成物的 -13- 201106004 硬化物，與該（C)成分之球狀矽系微粒，就作用於內部霧度 値之觀點來看，其折射率差較佳爲0.02以上且小於0.2， 尤佳爲〇.〇4~0.1。當該折射率差小於0.02時，對內部霧度 値之作用可能不足，當超過〇.〇2時，有對穿透鮮明度產生 不良影響之疑慮。球狀矽系微粒的折射率，爲根據JIS K 7 1 42的B法所測定之測定値。 ((D)界面活性劑） 本發明之硬被覆層形成材料中，係使用界面活性劑作 爲（D)成分。此界面活性劑，只要是在膜厚較前述（C)球狀 矽系微粒的平均粒徑還大之硬被覆層中可抑制該球狀有機 微粒的沉降，於硬被覆層的表面附近存在多數個該微粒， 且具有提升防眩性能之作用者即可，該種類並無特別限定。 此界面活性劑，例如可列舉出在分子內具有來自烷基 的碳數爲1〜8之N，N-二烷基胺基的極性基者。就取得性之 觀點來看，特佳爲具有來自碳數爲2〜6之N，N-二烷基胺基 烷醇的極性基者。 前述N，N-二烷基胺基烷醇的具體例，可列舉出N，N-二甲基胺基乙醇、N，N-二乙基胺基乙醇、N，N-二丙基胺基 乙醇、N，N-二丁基胺基乙醇、N，N-二戊基胺基乙醇、Ν,Ν-二己基胺基乙醇等，以及以丙醇或丁醇取代此等化合物的 乙醇部分之化合物等。又，二烷基部分的2個烷基可爲相 同或不同。 具有來自 Ν，Ν-二烷基胺基烷醇的極性基之界面活性 劑，例如可列舉出經Ν,Ν-二烷基胺基烷醇改質之聚氧伸烷 -14- 201106004 二醇》 本發明中，（D)成分之界面活性劑，可單獨使用1種或 組合2種以上使用》此外，該調配量，就硬被覆層的防眩 性、耐擦傷性、其他物性、經濟性等的均衡之觀點來看， 相對於前述（A)成分之活性能量線感應型組成物的固形份 1〇〇質量份而言，較佳爲0.01〜10質量份，尤佳爲0.0 5〜5 質量份。 本發明中，藉由在硬被覆層形成材料中含有（D)界面活 性劑，使該界面活性劑的親油性部分吸附於（B)球狀有機微 粒的表面，並藉由所吸附之界面活性劑的親水性部分，使 (B)球狀有機微粒的表面予以親水化，在以親油性的（A)活 性能量線感應型組成物爲主成分之硬被覆層的形成過程 中，可視爲該（B)球狀有機微粒浮起至表面。因此，藉由使 (D)界面活性劑作用於（B)球狀有機微粒，主要可顯現外部 霧度値。另一方面，由於（C)球狀矽系微粒在表面具有矽醇 基等，所以被吸附在界面活性劑的親水性部分，並藉由不 對（D)界面活性劑的吸附產生作用之親油性部分，將（C)球 狀矽系微粒的表面予以親油化，並同樣在以親油性的（A) 活性能量線感應型組成物爲主成分之硬被覆層的形成過程 中，可視爲抑制往表面之浮起。因此，（C)球狀矽系微粒， 係藉由與（D)界面活性劑作用而主要僅顯現內部霧度値。 (光聚合起始劑） 本發明之硬被覆層形成材料中，可因應期望而含有光 聚合起始劑。此光聚合起始劑，例如可列舉出安息香、安 -15- 201106004 息香甲醚、安息香乙醚、安息香異丙醚、安息香正丁醚、 安息香異丁醚、苯乙酮、二甲基胺基苯乙酮、2,2-二甲氧 基-2-苯基苯乙酮、2，2 -二乙氧基-2-苯基苯乙酮、2_羥基- 2-甲基-1-苯基丙烷·1_酮、1-羥基環己基苯酮、2 -甲基 -1-[4-(甲基硫）苯基]-2-嗎啉基-丙烷-1-酮、4-(2_羥基乙氧 基）苯基-2(羥基-2-丙基）酮、二苯基酮、對苯基二苯基酮、 4,4'-二乙基胺基二苯基酮、二氯二苯基酮、2 -甲基蒽醌、 2-乙基蒽醌、2-三級丁基蒽醌、2-胺基蒽醌、2-甲基噻吨酮、 2-乙基噻吨酮、2-氯噻吨酮、2,4-二甲基噻吨酮、2,4-二乙 基噻吨酮、苯甲基二甲基縮酮、苯乙酮二甲基縮酮、對二 甲基胺基苯甲酸酯等。 此等可使用1種或組合2種以上使用，此外，該調配 量，相對於全活性能量線硬化型化合物1 〇〇質量份而言， 一般係在0.2〜10質量份的範圍內選擇。又，在此所謂全活 性能量線硬化型化合物，當使用反應性二氧化矽系微粒作 爲（b)二氧化矽系微粒時，係表示含有此者。 (硬被覆層形成材料的調製） 本發明中所用之硬被覆層形成材料，可因應必要，在 適當的溶劑中，分別以預定比率添加前述（A)成分之活性能 量線感應型組成物、（B)成分之球狀有機微粒、（C)成分之 球狀矽系微粒、（D)成分之界面活性劑以及因應期望所用之 光聚合起始劑，以及各種添加成分，例如抗氧化劑、紫外 線吸收劑、矽烷偶合劑、光安定劑、勻化劑、消泡劑等， 並藉由進行溶解或分散而調製出。 -16- 201106004 此時所用之溶劑’例如可列舉出己烷、庚烷等 族烴，甲苯、二甲苯等之芳香族烴，氯化甲烷、氯 等之鹵化烴，甲醇、乙醇、丙醇、丁醇等之醇類， 丁酮、2 -戊酮、異佛爾酮、環己酮等之酮類，乙酸 乙酸丁酯等之酯類，乙基賽路蘇等之賽路蘇系溶劑 如此調製出之硬被覆層形成材料的濃度、黏度 可進行被覆者即可，並無特別限制，可因應狀況適 定。 [透明塑膠膜] 本發明之防眩性硬被覆膜，係使用前述調製出 覆層形成材料，將硬被覆層形成於透明塑膠膜的至 上。 前述透明塑膠膜並無特別限制，可從作爲以往 硬被覆膜基材爲已知之塑膠膜中適當地選擇。此般 膠膜，例如可列舉出聚對苯二甲酸乙二酯（有稱爲 時）、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯等 膜、聚乙烯膜、聚丙烯膜、玻璃紙、二乙酸纖維素 乙酸纖維素膜（有稱爲「TAC膜」時）、乙酸纖維素] 聚氯乙烯膜、聚偏二氯乙烯膜、聚乙烯醇膜、乙烯 烯酯共聚物膜、聚苯乙烯膜、聚碳酸酯膜、聚甲基f 聚碾膜、聚醚醚酮膜、聚醚颯膜、聚醚醯亞胺膜、 胺膜、氟樹脂膜、聚醯胺膜、丙烯酸樹脂膜、降孩 脂膜、環烯烴樹脂膜等之塑膠膜。 又’當將本發明之防眩性硬被覆膜用作爲偏光 之脂肪 化乙烷 丙酮、 乙酯、 等。 ，只要 當地選 之硬被 少單面 光學用 透明塑 「PET」 之聚酯 膜、三 "酯膜、 -乙酸乙 乞烯膜、 聚醯亞 :烯矽樹 :板保護 -17- 201106004 膜用時，從光學等向性較佳等理由來看，透明塑膠膜尤佳 爲TAC膜。 此等塑膠膜可爲透明或半透明，此外，可經著色或無 著色，可因應用途來適當地選擇。例如當用作爲液晶顯示 體的保護用時，較佳爲無色的透明膜。 此等塑膠膜的厚度並無特別限制，可因應狀況適當地 選定，一般爲15〜300μιη，較佳爲30~2 00μιη之範圍。此外， 此塑膠膜，就提升與設置於該表面之層的密著性之目的 下，可因應期望，藉由氧化法或凹凸化法等對單面或雙面 施以表面處理。上述氧化法，例如可列舉出電暈放電法、 電漿處理、鉻酸處理（濕式）、火焰處理、熱風處理、臭氧· 紫外線照射處理等，此外，凹凸化法，例如可列舉出噴砂 法、溶劑處理法等。此等表面處理法，可因應塑膠膜的種 類來適當地選擇，一般就效果及操作性等之方面來看，較 佳爲使用電暈放電處理法。此外，亦可設置引體層。 [硬被覆層的形成] 可使用以往所知的方法，例如棒塗布法、刮刀塗布法、 輥塗布法、板片塗布法、壓模塗布法、凹版塗布法等，將 前述硬被覆層形成材料被覆於前述透明塑膠膜的至少單面 上以形成塗膜’乾燥後將活性能量線照射於此而使該塗膜 硬化，藉此形成硬被覆層。 活性能量線例如有紫外線及電子束等。上述紫外線， 可藉由高壓水銀燈、無電極燈、金屬鹵化物燈、氙氣燈等 取得’照射量一般爲100〜500mJ/cm2，另一方面，電子束 -18- 201106004 可藉由電子束加速器等取得，照射量一般爲15 0〜3 5 OkV。 此活性能量線中，特佳爲紫外線。當使用電子束時，可在 不需添加光聚合起始劑下製得硬化物。 如此形成之硬被覆層的厚度，本發明中係要求須較所 使用之（B)成分之球狀有機微粒（C)成分之球狀矽系微粒的 各平均粒徑更大，因此，其下限約爲3 μιη，至於上限，就 防止因硬被覆層的硬化收縮使硬被覆膜產生捲曲者之觀點 來看，約爲20μιη。較佳的厚度爲5〜15μιη之範圍。 [防眩性硬被覆膜] (光學特性） 如此形成之本發明之防眩性硬被覆膜的光學特性，係 有因形式的不同使較佳値有所差異之情況。 爲高對比型式時，內部霧度値一般爲〇〜10%。即使內 部霧度値位於此範圍並產生閃斑時，亦可達成高對比，所 以可因應顯示器種類（設計槪念）的不同而充分地適用。當 內部霧度値超過10%時，無法獲得高對比（變成泛用型式）。 此外，爲泛用型式時，內部霧度値一般爲5〜40%。當內部 霧度値小於5%時，抑制閃斑之性能不足，超過40%時，觀 看性會降低。泛用型式的防眩性硬被覆膜之較佳的內部霧 度値，一般爲1〇~3 0%，較佳爲15〜25 %。 此外，外部霧度値，就觀看性之觀點來看，高對比型 式及泛用型式均較佳爲20%以下，就防眩性之觀點來看， 均較佳爲1 %以上。又，所謂內部霧度値，係表示僅起因於 內部的光散射之霧度値，所謂外部霧度値，係表示僅起因 -19- 201106004 於表面凹凸所造成的光散射之霧度値，所謂總霧度値，係 表示前述內部霧度値與前述外部霧度値之總和。此外，總 霧度値’係相當於從防眩性硬被覆膜之依據JIS K 7136所 得之霧度値中，減去防眩性硬被覆膜的構成構件之透明塑 膠膜單體之依據JIS K 7136所得之霧度値之値。 以下係記載內部霧度値，外部霧度値，及總霧度値的 計算方法。 <硬被覆層的內部霧度値，外部霧度値，及總霧度値> 首先依據〗IS K 7136，測定出本發明之防眩性硬被覆 膜的霧度値以及該透明塑膠膜單體的霧度値。 將從前述防眩性硬被覆膜的霧度値中減去前述透明塑 膠膜單體的霧度値所得之値，設爲總霧度値。 接著將厚度20μιη的透明黏著薄片，黏附於防眩性硬 被覆膜的硬被覆層側來構成內部霧度値計算用試樣。依據 JIS Κ 7136，測定出該透明黏著薄片的霧度値及內部霧度値 計算用說樣的霧度値。 將從內部霧度値計算用試樣的霧度値中減去前述透明 黏著薄片的霧度値及透明塑膠膜單體的霧度値所得之値， 設爲光學膜之硬被覆層的內部霧度値》 最後，將從前述總霧度値中減去前述內部霧度値所得 之値，設爲外部霧度値。 又，前述透明黏著薄片的霧度値，如前述般，由於在 計算過程中被減去而不會直接影響內部霧度値，外部霧度 値’及總霧度値，所以並無特別限制，但就提高測定精度 -20- 201106004 之觀點來看，較佳係使用小於5%的霧度値。 再者，60°鏡面光澤度，髙對比型式及泛用型式均較佳 爲20〜130。當60°鏡面光澤度超過130時，表面光澤度變 大（光的反射變大），而對防眩性產生不良影響。當60°光澤 小於20時，容易產生泛白。此外，防眩性硬被覆膜的總透 光率較佳爲88%以上，尤佳爲90%以上。當總透光率小於 88%時，有透明性不足之疑慮。 前述60°鏡面光澤度爲根據JIS K 7105所測定之測定 値，總透光率爲根據JIS K 7 1 36所測定之測定値。 (效果） 本發明之防眩性硬被覆膜，係設置有含有球狀有機微 粒及球狀矽系微粒之硬被覆層，具有耐擦傷性，可在不使 外部霧度値產生較大變化下使內部霧度値產生變化，薄膜 量產時容易進行外/內部霧度値的調整，且可在不損及對比 下獲得期望的60°鏡面光澤度及防眩性。 (其他功能層） 本發明之防眩性硬被覆膜中，可因應必要，在賦予抗 反射性等之目的下，於最上層設置抗反射層，例如矽氧烷 系覆膜、氟系覆膜等。此時，該抗反射層的厚度較適當爲 0.0 5~1μιη。藉由設置此抗反射層，可消除來自太陽、螢光 燈的反射所產生之畫面的映射，此外，藉由抑制表面的反 射率，使總透光率上升而提升透明性。此外，藉由抗反射 層種類的不同，可達到抗帶電性的提升。 . (黏著劑層） -21- 201106004 本發明之防眩性硬被覆膜中，在塑膠膜之與硬被覆層 爲相反側的面上，可形成用以貼著於液晶顯示體等之被黏 著體之黏著劑層。構成此黏著劑層之黏著劑，較佳爲使用 適合於光學用途之例如丙烯酸系黏著劑、胺基甲酸酯系黏 著劑、聚矽氧烷系黏著劑。此黏著劑層的厚度，一般爲 5〜ΙΟΟμιη，較佳爲10~60μιη之範圍。 再者，於此黏著劑層上，可因應必要設置剝離薄片。 此剝離薄片，例如可列舉出在聚對苯二甲酸乙二酯、聚丙 烯等之各種塑膠膜上塗附有聚矽氧烷樹脂等的剝離劑者 等。此剝離薄片的厚度並無特別限制，一般爲20〜1 50 μιη。 形成有此般黏著劑層之防眩性硬被覆膜，乃適合用作 爲將防眩性能及耐擦傷性能等賦予至CRT、LCD、PDP等 之顯示器，尤其適合於LCD等之偏光板黏附用。 [偏光板] 本發明亦提供將前述本發明之防眩性硬被覆膜貼合於 偏光件而成之偏光板。 LCD的液晶胞，一般係具有下列構造，亦即以該配向 層位於內側並藉由間隔材形成預定間隔之方式，配置形成 有配向層之2片透明電極基板，並將該周邊予以密封使液 晶材料夾持於該間隙，並且於上述2片透明電極基板的外 側表面上’分別介於黏著劑層配設有偏光板之構造。 第1圖係顯示上述偏光板之i例的構成之立體圖。如 此圖所示般，該偏光板10 —般係具有將三乙酸纖維素（TAC) 膜2及2’貼合於聚乙烯醇系偏光件1的雙面上之3層構造 -22- 201106004 的基材，於該單面形成有用以貼著於液晶胞等的光學零件 之黏著劑層3,然後於此黏著劑層3貼著有剝離薄片4。此 外，此偏光板之與該黏著劑層3爲相反側的面上，一般係 設置有表面保護膜5。 本發明之偏光板，係在設置於偏光件1的雙面之TAC 膜2及Y中之一方的TAC膜上設置有上述本發明之硬被覆 層。當於偏光板設置有黏著劑層3、剝離薄片4及表面保 護膜5時，尤在表面保護膜5側的TAC膜2(側設置有本發 明之硬被覆層。 製造本發明之偏光板的方法，例如可進行下列所示之 操作。 又，第2圖係顯示本發明之偏光板之1例的構成之剖 面模式圖。 首先，係使用TAC膜般之無光學異向性的膜12'作爲 基材的透明塑膠膜，於該一方的面上形成本發明之硬被覆 層' 1 3，而構成防眩性硬被覆膜14。接著使用接著劑層1 5、 15'，將未形成硬被覆層13之TAC膜12積層於偏光件11 的單面，將前述防眩性硬被覆膜14積層於相反面。當透明 塑膠膜使用TAC膜時，爲了藉由以接著劑所形成之積層來 提升密著性，除了前述表面處理之外，亦可進行鹼化處理 等。 藉此可製得防眩性能及耐擦傷性能佳之偏光板20。偏 光板20亦可因應必要，在設置有硬被覆層13之面上，設 置如前述第1圖所示之可剝離的表面保護膜5，或是於該 -23- 201106004 相反面上’設置用以貼附於液晶胞等的光學零件之黏著劑 層1 6或剝離薄片1 7。 本發明之偏光板，以LCD的液晶胞爲首，可用作爲光 量調整用、偏光干涉應用裝置用、光學缺陷偵測器用等。 實施例 接著藉由實施例來詳細說明本發明，但本發明並不限 定於此等例子。 有機微粒及矽系微粒的平均粒徑及折射率，活性能量 線感應型組成物之硬化物的折射率及硬被覆膜的性能，係 依循下列方法求取》 <球狀有機微粒及球狀矽系微粒> (1) 平均粒徑 使用柯特粒子計數器[Beckman Coulter股份有限公司 製，商品名稱「Multi sizer 3」]，採用0.5%的離子交換水 作爲分散液，在2 5 t下藉由柯特粒子計數法進行測定。 (2) 折射率 將被檢測微粒載置於載玻片上，將折射率標準液滴至 微粒上後，蓋上覆蓋玻璃來製作出試樣。根據]IS K 7142 的B法，以顯微鏡觀察該試樣，以最難觀看出微粒的輪廓 之折射率標準液的折射率，作爲該微粒的折射率。 <活性能量線感應型組成物> (3) 硬化物的折射率 各調製例中，係製作出由活性能量線感應型組成物 (A)，光聚合起始劑及稀釋溶劑所構成之被覆劑。與實施例 -24- 201106004 相同，將此塗布於TAC膜[富士軟片股份有限公司製，商 品名稱「TAC80TD80ULH」]，以構成硬化物的折射率測定 用的硬被覆膜。根據JISK7142的A法，使用Atago股份 有限公司製的阿貝折射率計，對此求取硬被覆層的折射 率，並以此作爲活性能量線感應型組成物之硬化物的折射 率。 <硬被覆膜> (4) 總透光率 使用日本電色工業股份有限公司製的霧度計 「NDH-2000」，依據JISK7136，對實施例及比較例所製 作之防眩性硬被覆膜測定其總透光率。 (5) 硬被覆層的內部霧度値，外部霧度値，及總霧度値 使用日本電色工業股份有限公司製的霧度計 「NDH-2000」，依據JISK7136，對實施例及比較例所製 作之防眩性硬被覆膜，以及該膜的構成構件之透明塑膠膜 單體的霧度値。 從藉由前述測定所得之防眩性硬被覆膜的霧度値中減 去透明塑膠膜的霧度値，可計算出防眩性硬被覆膜之硬被 覆層的總霧度値》 接著將異氰酸酯交聯劑[東洋油墨製造公司製，商品名 稱「BHS-8515」]2質量份及甲苯100質量份添加於丙烯酸 系黏著劑[日本Carbide公司製，商品名稱「PE-121」]100 質量份以製作出黏著劑溶液。以使乾燥後的厚度成爲20 μιη 之方式將黏著劑溶液塗布於厚度50 μπι的聚對苯二甲酸乙 -25- 201106004 二酯膜[東洋紡績股份有限公司製，商品名稱「A43 00」]， 在100°C下進行3分鐘的乾燥而製作出透明黏著薄片。 將所製作之透明黏著薄片黏附於防眩性硬被覆膜的硬 被覆層側來構成內部霧度値計算用試樣。與前述相同，依 據JIS K 7136測定出該透明黏著薄片及內部霧度値計算用 試樣的各霧度値。 從內部霧度値計算用試樣的霧度値中減去透明黏著薄 片的霧度値及透明塑膠膜的霧度値，可計算出防眩性硬被 覆膜之硬被覆層的內部霧度値。 最後，從前述總霧度値中減去內部霧度値，可計算出 防眩性硬被覆膜之硬被覆層的外部霧度値。 (6) 防眩性的評估 在螢光燈下，以目視來觀察介於丙烯酸系黏著劑將硬 被覆膜黏附於丙烯酸樹脂黑板[住友化學股份有限公司製] 之樣本，並以下列判定基準來評估防眩性》 〇：螢光燈的抗映射性充分，且無泛白 △:螢光燈的抗映射性稍差，且有些許泛白 X :螢光燈的抗映射性不足，或是螢光燈的抗映射性充 分，但泛白程度較大使觀看性惡化 (7) 60°鏡面光澤度 使用日本電色工業股份有限公司製的光澤計 「VG2000」，依據JISK7105進行測定。 (8) 硬被覆層的厚度 對實施例及比較例所製作之防眩性硬被覆膜，以及該 -26- 201106004 防眩性硬被覆膜的製作中所用之透明塑膠膜的TAC(三乙 酸纖維素）膜的各膜，使用定壓厚度計[Nik〇n公司製’商品 名稱「MH-15M」]來測定厚度，並藉由取該差値來計算出 硬被覆層的厚度。 調製例1硬被覆層用被覆劑1 將作爲（A)活性能量線感應型組成物之硬被覆劑[JSR 股份有限公司製’商品名稱「〇PstarZ7524」，固形份濃度 70質量％，含有反應性二氧化矽微粒與多官能丙烯酸酯之 全活性能量線硬化型化合物65質量％ ’光聚合起始劑5質 量％，丁酮30質量％，硬化物的折射率1.50]100質量份， 作爲（B)球狀有機微粒之由丙烯酸樹脂所構成之聚甲基丙 烯酸甲酯微粒（以下亦有稱爲「PMMA」時）[綜硏化學公司 製，商品名稱「MX5 00」平均粒徑5μηι，折射率1.49]7.5 質量份，作爲（C)球狀矽系微粒之聚矽氧烷樹脂微粒 [Momentive Performance Materials Japan 公司製，商品名 稱「Tospearll20」，平均粒徑2μιη，折射率1·43]2質量份， 作爲（D)界面活性劑之己內酯·聚乙二醇-二丁基胺乙醇共 聚物[BYKJapan公司製，商品名稱「disperbyk 103」，依 據甲氧基丙基乙酸酯之40質量％稀釋品]1質量份，以及作 爲稀釋溶劑之丙二醇單甲醚90質量份均一地混合，而調製 出固形份約40質量％之硬被覆層用被覆劑1。 調製例2硬被覆層用被覆劑2 除了使用「Tospearl 120」4質量份作爲（C)球狀矽系微 粒之外，其他進行與調製例1相同之操作，而調製出固形 -27- 201106004 份約40質量％之硬被覆層用被覆劑2。 調製例3硬被覆層用被覆劑3 除了使用聚砂氧院系微粒[Momentive Performance Materials Japan公司製，商品名稱「Tospearl 145」，平均 粒徑4.5μιη，折射率1.43]7·5質量份作爲（C)球狀矽系微粒 之外，其他進行與調製例1相同之操作，而調製出固形份 約40質量％之硬被覆層用被覆劑3。 調製例4硬被覆層用被覆劑4 除了使用中空二氧化矽微粒[ABC NANOTECH公司 製，商品名稱「SI-130j ，平均粒徑3μιη，折射率1.46]4 質量份作爲（C)球狀矽系微粒之外，其他進行與調製例1相 同之操作，而調製出固形份約40質量％之硬被覆層用被覆 劑4。， 調製例5硬被覆層用被覆劑5 除了使用多孔質二氧化矽微粒[ABC NANOTECH公司 製，商品名稱「SI-230」，平均粒徑3μπι ’折射率1 ·46]4 質量份作爲（C)球狀矽系微粒之外，其他進行與調製例1相 同之操作，而調製出固形份約40質量°/。之硬被覆層用被覆 劑5。 調製例6硬被覆層用被覆劑6 除了不使用（C)球狀矽系微粒之外’進行與調製例1相 同之操作，而調製出固形份約40質量％之硬被覆層用被覆 劑6 〇 調製例7硬被覆層用被覆劑7 -28- 201106004 除了不使用（C)球狀矽系微粒及（D)界面活性劑之外’ 進行與調製例1相同之操作，而調製出固形份約4 0質量％ 之硬被覆層用被覆劑7。 調製例8硬被覆層用被覆劑8 除了不使用（D)界面活性劑之外，進行與調製例2相同 之操作，而調製出固形份約40質量％之硬被覆層用被覆劑 8 » 調製例9硬被覆層用被覆劑9 除了不使用（D)界面活性劑之外，進行與調製例3相同 之操作，而調製出固形份約40質量％之硬被覆層用被覆劑 9 〇 調製例10硬被覆層用被覆劑10 除了不使用（B)球狀有機微粒之外，進行與調製例2相 同之操作，而調製出固形份約40質量％之硬被覆層用被覆 齊！I 1 0。 調製例11硬被覆層用被覆劑11 除了不使用（B)球狀有機微粒之外，進行與調製例3相 同之操作，而調製出固形份約40質量％之硬被覆層用被覆 劑1 1。 調製例12硬被覆層用被覆劑12 除了不使用（B)球狀有機微粒之外，進行與調製例4相 同之操作，而調製出固形份約40質量％之硬被覆層用被覆 劑12。 -29- 201106004 調製例1 3硬被覆層用被覆劑1 3 除了不使用（B)球狀有機微粒之外，進行與調製例5相 同之操作，而調製出固形份約40質量％之硬被覆層用被覆 劑1 3。 第1表係顯示前述調製例1~13所得之硬被覆層用被覆 劑1〜1 3的性狀。 -30- 201106004 (D)界面 活性劑 含量 (質量份） Ό Ο \〇 vq VO o Ο o vq vq (C)球狀矽系微粒 含量 (質量份） σ\ Η Γ- ο 1 1 卜 o Γ*- 〇 折射 率 )a 1 1 鞾__< t 1 i 切3 ㈣ <Ν νο m cn 1 1 <N CN UO CO CO m *1siS 腰1 聚矽氧烷 樹脂 祕鋰 祕 丨1訟 -B- 多孔質二 氧化矽 1 1 遯 m ss ^ m K 遯 祕sg 嵌 聚矽氧烷 樹脂 祕S5 ^ m m 祕 11訟 •B- 多孔質二 氧化砂 (B)球狀有機微粒 含量(質 量份） Γ-* Ο 卜· 1 1 1 1 折射率 σ\ 1 1 1 1 平均粒 徑(_) yn I 1 1 1 PMMA 1 ^1 PMMA 1 1 1 1 ㈧活性能量線感應 型組成物 折射率 固形份含 量(質量） 8 硬被覆層 用被覆劑 的· t—蟑 cs cn 寸 VO 卜 〇0 ON 〇 cs c^i 調製例1 調製例2 調製例3 調製例4 調製例5 調製例6 調製例7 調製例8 調製例9 調製例10 調製例11 調製例12 調製例13 201106004 實施例1 將調製例1所得之硬被覆層用被覆劑1，以使硬彳匕膜 厚成爲約10 μιη之方式，藉由繞線棒塗布機塗布於厚度 80μιη之TAC膜[富士軟片股份有限公司製，商品名稱 「TAC80TD80ULH」]的表面。在70°C的烤爐中進行1分鐘 的乾燥後，以高壓水銀燈照射光量3 00mj/cm2的紫外線， 形成硬被覆層而製作出防眩性硬被覆膜。 第2表係顯示此硬被覆膜的性能。 實施例2~5，比較例1~7及參考例1 實施例1中，除了使用第2表所示之種類的各硬被覆 層用被覆劑來取代硬被覆層用被覆劑1之外’其他進行與 實施例1相同之操作’而製作出各種防眩性硬被覆膜。 第2表係顯示各硬被覆膜的性能。 -32- 201106004[Technical Field] [Invention] The present invention relates to an anti-glare hard coating film and a polarizing plate using the same, and in particular, the present invention relates to a device comprising spherical organic particles and a ball The anti-glare hard coating film having scratch resistance of the hard coating layer of the ruthenium-based fine particles can change the internal haze 不 without causing a large change in the external haze ,, and the film can be easily produced during mass production. / Internal haze adjustment, and can obtain the desired 60 without compromising the contrast. An anti-glare hard coating film with specular gloss and anti-glare properties, and a polarizing plate using the anti-glare hard coating film. [Prior Art] In a display such as a video tube (CRT) or a liquid crystal display (LCD) or a plasma display (PDP), light is incident from the outside to the screen, and this light is reflected and it is difficult to view the display image, especially in recent years. The increase in the size of the display has gradually become an important issue for those who have solved the above problems. One of the means for solving this problem is exemplified by the use of a member having an anti-glare hard coating layer. In recent years, in addition to the external haze which is caused by the surface unevenness for the purpose of imparting anti-glare properties, the anti-glare film has been required to have a light diffusing property from the inside of the film to reduce the flare. The internal haze is 値. This internal haze can be exhibited by containing fine particles having a refractive index difference with the binder resin in the hard coating layer. However, when only one type of particles having a refractive index difference from the binder resin is used to form an anti-glare film, the particles must be able to contribute both to the outer/internal haze. Therefore, depending on the type of the filling material and the amount of the filling, the external/internal haze of the anti-glare film is changed, and it is difficult to adjust the external/internal haze. -4- 201106004 Therefore, in order to solve this problem, the inventors have found that a certain amount of one type of organic fine particles is added (the internal haze is fixed), and the amount of the dispersing agent (surfactant) is added. The method of controlling the external haze, and previously filed a patent application (Japanese Patent Application No. 2008-087295). On the other hand, it is proposed to form a resin particle having a refractive index of 1.40 to 1_60 and an ionizing radiation line on a transparent substrate. An anti-glare film of an anti-glare layer composed of a hardening type composition. For example, Patent Document 1 proposes an anti-glare film comprising an organic ruthenium material having a particle diameter of a coating film or more in order to form unevenness of anti-glare property, but is increased in order to improve anti-glare property. When there is a large unevenness, there is a problem that the haze rises and the penetration sharpness decreases. In order to improve this, in Patent Document 2, the amount of the organic cerium filling material having a particle diameter equal to or greater than the film thickness of the coating film for forming an anti-glare property is reduced, and the film thickness of the coating film is added. The following organic fillers of the particle size are used to produce a balanced anti-glare film. However, in actuality, even in the above method, even if the balance of the optical properties is obtained, the degree of variation in the particle diameter of the particles used may cause a place where no irregularities exist, and the anti-glare property cannot be obtained comprehensively. Further, the external haze 变动 varies greatly due to the film thickness, and there is a problem that the stability of the production is deteriorated. In addition, in such series, the film thickness is determined by the particle size, and there is a case where it is difficult to adjust the physical property by the film thickness as the surface hardness. OBJECTS OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The present invention is an invention created under the above circumstances, and the present invention is directed to the invention. It is an object of the invention to provide an anti-glare hard coating film having a hard coating layer having scratch resistance formed on the surface of a transparent plastic film, which can change the internal haze 不 without causing a large change in the external haze. When the film is mass-produced, it is easy to adjust the outer/internal haze, and it can obtain the desired 60° specular gloss and anti-glare anti-glare hard coating without damaging the contrast, and use this anti-glare property. Hard coated polarizing plate. Means for Solving the Problems The present inventors conducted intensive studies in order to achieve the above object, and as a result, the following findings were obtained. It has been found that a hard coating layer is formed using a composition comprising an active energy ray-sensitive composition and a specific spherical organic fine particle having an average particle diameter in a desired range, a specific spherical lanthanide fine particle, and a surfactant. Further, the thickness of the hard coating layer is made larger than the respective average particle diameters of the spherical organic fine particles and the spherical cerium-based fine particles, whereby an anti-glare hard coating film suitable for the above purpose can be obtained. Further, it has been found that the antiglare hard coating film can have a refractive index of the cured product of the active energy ray-inductive composition and a refractive index of the spherical organic fine particles and a refractive index of the spherical lanthanum-based fine particles. The difference is set to a specific range, and it is easy to obtain a person suitable for the purpose by including a surfactant in the hard coating layer forming material. The present invention is an invention completed in accordance with this finding. That is, the present invention provides: (1) An anti-glare hard coating film characterized in that: (A) contains (a) a polyfunctional (meth) acrylate on the surface of a transparent plastic film. a monomer and/or a (meth)acrylate prepolymer, and (b) an active energy ray-sensitive composition of the cerium oxide-based fine particles; (B) an acrylic acid selected from the group consisting of an average particle diameter of 1 to ΙΟμηη At least one of spherical organic fine particles of a resin, an acrylic acid-styrene resin, a melamine resin, a polycarbonate resin, a styrene resin, and a vinyl chloride resin; (C) is selected from an average particle diameter of 0.5 to a spherical ruthenium-based fine particle of at least one of a polyoxyalkylene-based resin, a hollow cerium oxide, and a porous cerium oxide; and (D) a hard formed by using a hard coating layer-forming material containing a surfactant; The thickness of the hard coating layer is larger than the average particle diameter of each of the above (Β) component and (C) component: (2) The antiglare hard coating film as described in the above item (1) , wherein (b) the silica sand-based fine particles are provided with (meth) propyl (3) The anti-glare hard coating film according to the above (1) or (2), wherein the hardened material of the component (A) and (B) The refractive index difference of the component is less than 〇.02, and the refractive index difference between the cured product of the component (A) and the component (C) is 〇.02 or more and less than 〇. 2 ; and (4) a polarizing plate. The surface on the opposite side to the hard coating layer forming surface of the antiglare hard coating film according to any one of the above items (1) to (3) is bonded to a polarizer. According to the present invention, it is possible to provide an anti-glare hard coating film having scratch resistance provided with a hard coating layer containing spherical organic fine particles and spherical cerium-based fine particles, without causing external haze The internal haze is changed under a large change, and the outer/internal haze is easily adjusted during mass production, and the desired 60° specular gloss and anti-glare can be obtained without compromising the contrast. A glare hard coating film, and a polarizing plate using the antiglare hard coating film. [Embodiment] The antiglare film of the present invention is characterized in that it is attached to the surface of a transparent plastic film and has: (A) a (a) polyfunctional (meth) acrylate monomer and/or (methyl) An acrylate-based prepolymer and (b) an active energy ray-inductive composition of the cerium oxide-based fine particles; (B) a specific spherical organic fine particle having an average particle diameter of 1 to 1 〇 μηη or less; C) a specific spherical lanthanide-based fine particle having an average particle diameter of 0.5 to ΙΟμηη; and (D) a hard coating layer formed using a hard coating layer-forming material containing a surfactant; and the thickness of the hard coating layer It is larger than the average particle diameter of each of the above (Β) component and (C) component. [Hard coating layer forming material] The hard coating layer forming material of the present invention contains: (Α) an active energy ray-inductive composition, (Β) spherical organic fine particles, (C) spherical lanthanum-based fine particles, and (D) ) surfactant. (A) active energy ray-inductive composition) In the hard coating layer forming material, the active energy ray-sensitive composition used as the (Α) component contains more than 201,106,004 of (a) active energy ray-curable compound. A functional (meth) acrylate type monomer and/or a (meth) acrylate type prepolymer ' and (b) cerium oxide type fine particles are essential components. Further, the term "active energy ray" in the present invention means an energy quantum in an electromagnetic wave or a charged particle beam, that is, an ultraviolet ray or an electron beam. <(a) Active energy ray-curable compound> In the present invention, the (a) active energy ray-curable compound is a polyfunctional (meth) acrylate monomer and/or a (meth) acrylate system. Prepolymer. Examples of the polyfunctional (meth)acrylate monomer include 1,4-butylene glycol di(meth)acrylate, ι,6-hexanediol di(meth)acrylate, and Methyl) neopentyl glycol acrylate diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Dicyclopentyl (meth)acrylate modified by caprolactone, di(meth)acrylic acid phosphate modified by ethylene oxide, allylated cyclohexyl di(meth)acrylate, two (meth)acrylic acid isocyanate, trimethylolpropane tri(meth)acrylate, dineopentyl tris(meth)acrylate, and propionic acid modified trispentaerythritol (meth)acrylate Ester, neopentyl glycol tris(meth)acrylate, trimethylolpropane tris(meth)acrylate modified with propylene oxide, tris(propyleneoxyethyl)isocyanate, modified with propionic acid Dipentaerythritol penta(meth)acrylate, dineopentaerythritol hexa(meth)acrylate, caprolactone Six nature polyfunctional (meth) acrylic acid esters of pentaerythritol new (meth) acrylate "These monomers may be used alone or in combination of two or more kinds. On the other hand, the (meth) acrylate-based prepolymer may, for example, be a polyester acrylate type, an epoxy acrylate type, an amino acrylate type, or a 201106004 polyol acrylate type. Here, the polyester acrylate-based prepolymer can be, for example, a hydroxyl group of a polyester oligomer having a hydroxyl group at both terminals obtained by condensation of a polyvalent carboxylic acid and a polyvalent alcohol by (meth)acrylic acid. Esterification, or by esterification of a hydroxyl group at the end of the oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid by (meth)acrylic acid. The epoxy acrylate-based prepolymer can be produced, for example, by reacting (meth)acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or a novolac type epoxy resin for esterification. Got it. An amino acrylate prepolymer, for example, esterified by a polyether polyol or a polyurethane oligomer obtained by reacting a polyester polyol with a polyisocyanate by (meth)acrylic acid And made. Further, the polyol acrylate-based prepolymer can be obtained by esterifying a hydroxyl group of a polyether polyol with (meth)acrylic acid. These prepolymers may be used alone or in combination of two or more kinds, or may be used in combination with the above-mentioned polyfunctional (meth)acrylate monomer. < (b) cerium oxide-based fine particles> In the present invention, (b) cerium oxide-based fine particles may be colloidal cerium oxide-based fine particles and/or cerium oxide-based fine particles having surface functional groups. Colloidal cerium oxide-based fine particles having an average particle diameter of about 1 to 400 nm, and cerium oxide-based fine particles having a surface functional group, for example, having a (meth)acryl fluorenyl group as a surface functional group The cerium oxide-based fine particles (hereinafter referred to as reactive cerium oxide-based fine particles). The above-mentioned reactive cerium oxide-based fine particles can be polymerized, for example, by having a functional group capable of reacting with a sterol group. The organic compound of the unsaturated group is obtained by reacting a sterol group on the surface of the cerium oxide-based fine particles having an average particle diameter of ~·〇〇5 to 1 μm to -10-201106004. The polymerizable unsaturated group may, for example, be a (meth)acryl fluorenyl group having a radical polymerizable property. The above-mentioned organic compound having a polymerizable unsaturated group capable of reacting with a sterol group, for example, acrylic acid, chlorinated acrylic acid, 2-isocyanatoethyl acrylate, glycidyl acrylate, acrylic acid 2, 3 can be used. _Iminopropyl propyl ester, 2-hydroxyethyl acrylate, acryloxypropyltrimethoxy decane, and the like, and methacrylic acid derivatives corresponding to such acrylic acid derivatives. These acrylic acid derivatives or methacrylic acid derivatives may be used singly or in combination of two or more. The cerium oxide-based fine particles bonded with the polymerizable unsaturated group-containing organic compound thus obtained are used as an active energy ray hardening component and are crosslinked by irradiation with an active energy ray to harden the reactive cerium oxide. The fine particles have an effect of improving the scratch resistance of the obtained hard coating film. An active energy ray-sensitive composition (A) containing a compound in which an organic compound having a polymerizable unsaturated group is bonded to the above-described cerium oxide-based fine particles is commercially available, for example, as manufactured by JSR Co., Ltd. Opstar Z7 5 3 0", "Opstar Z7524", "0 pstar TU 4 0 8 6", etc. In the present invention, the content of the cerium oxide-based fine particles of the component (b) is usually 5 to 90% by mass, preferably 1 to 10%, based on the solid content of the active energy ray-sensitive composition of the component (A). 70 mass ° /. . Further, the average particle diameter of the cerium oxide particles of the cerium oxide-based fine particles of the component (b) can be measured by a laser diffraction & 'scattering method. In this method, the average particle diameter is measured by the intensity change of the diffraction/scattering -11-201106004 light when the laser light is irradiated onto the liquid in which the particles are dispersed. ((B) spherical organic fine particles) The spherical organic fine particles as the component (B) in the hard coating layer forming material of the present invention include acrylic resins selected from the range of an average particle diameter of 1 to 10 μηη. A spherical organic fine particle of at least one of an acrylic-styrene resin, a melamine resin, a polycarbonate resin, a styrene resin, and a vinyl chloride resin. When the average particle diameter of the spherical organic fine particles is less than Ιμιη, the appearance of the anti-glare property may be insufficient. On the other hand, when it exceeds 1 μm, the particle diameter of the spherical organic fine particles and the film of the hard coating layer formed are formed. When the thickness is close, the amount of floating of the spherical organic particles from the surface of the transparent plastic film is reduced, so that the particle size variation is strongly affected, or the dispersibility of the spherical organic particles is insufficient at the time of coating, which may result in formation. The unevenness of the hard coating layer is uneven. A preferred average particle size is 2 to 8 μm. The average particle diameter is measured according to the Cotter particle counting method. The particle size distribution is preferably 70% or more by weight in the range of ± 2 μηη of the average particle diameter measured by the Cot particle counting method. In the present invention, the spherical organic fine particles of the above-mentioned (Β) component may be used singly or in combination of two or more kinds, and the blending amount is relative to the above (Α) component from the viewpoint of antiglare performance. The amount of the solid content of the active energy ray-sensitive composition is preferably from 0.5 to 30 parts by mass, particularly preferably from 1 to 20 parts by mass, particularly preferably from 3 to 15 parts by mass, per 100 parts by mass of the solid content. In the present invention, the cured product of the active energy ray-sensitive composition of the (Α) component and the spherical organic fine particles of the (Β) component have a refractive index difference from the viewpoint of suppressing an increase in internal haze 値It is preferably less than 0.02, and particularly preferably -12-201106004 0.01 or less. The spherical organic fine particles are mainly used for the adjustment of the external haze, and the refractive index of the spherical organic fine particles is measured by the B method according to ns K 7142. Further, the refractive index of the cured product of the active energy ray-inductive composition is a measured enthalpy measured according to the method A of JIS K 7 1 42. ((C) spheroidal bismuth-based fine particles) The spherical ruthenium-based fine particles as the component (C) in the hard coating layer forming material of the present invention may be selected from those having an average particle diameter of 0.5 to 10 μm. At least one of spherical fluorene-based fine particles of a polyoxyalkylene-based resin, hollow cerium oxide, and porous cerium oxide. When the average particle diameter of the spherical lanthanide particles is less than 0.5 μm, the effect of the internal haze 不足 is insufficient, and on the other hand, when it exceeds 1 μm, the film thickness difference with the formed hard coating layer becomes small. There is a concern about the influence of the particle size of the spherical lanthanide particles on the external haze. A preferred average particle diameter is from 1 to 8 μm, and a particularly preferred average particle diameter is from 2 to 6 μm. Further, the average particle diameter is the measured enthalpy measured by the Cotter particle counting method. Further, the particle size distribution is preferably 70% or more by weight in the range of ± 2 μm of the average particle diameter measured by the Cot particle counting method. In the present invention, the spherical cerium-based fine particles of the component (C) may be used singly or in combination of two or more kinds, and the blending amount is relative to the above (Α) component from the viewpoint of antiglare performance. The amount of the solid content of the active energy ray-sensitive composition is preferably from 0.5 to 30 parts by mass, particularly preferably from 1 to 20 parts by mass, particularly preferably from 2 to 15 parts by mass, per 100 parts by mass of the solid content. In the present invention, the hardened material of the active energy ray-inductive composition of the above-mentioned (Α) component and the spherical lanthanum-based fine particles of the component (C) act on the internal haze. The difference in refractive index is preferably 0.02 or more and less than 0.2, and particularly preferably 〇.〇4 to 0.1. When the refractive index difference is less than 0.02, the effect on the internal haze may be insufficient, and when it exceeds 〇.〇2, there is a concern that the penetration sharpness is adversely affected. The refractive index of the spherical lanthanoid microparticles is measured by the B method according to JIS K 7 1 42. ((D) Surfactant) In the hard coating layer forming material of the present invention, a surfactant is used as the component (D). The surfactant may suppress sedimentation of the spherical organic fine particles in a hard coating layer having a film thickness larger than that of the (C) spherical cerium-based fine particles, and a majority is present in the vicinity of the surface of the hard coating layer. The particles may have an effect of improving the anti-glare property, and the type is not particularly limited. The surfactant may, for example, be a polar group having an N,N-dialkylamino group having from 1 to 8 carbon atoms in the molecule. From the standpoint of availability, it is particularly preferred to have a polar group derived from an N,N-dialkylaminoalkanol having 2 to 6 carbon atoms. Specific examples of the N,N-dialkylaminoalkanol include N,N-dimethylaminoethanol, N,N-diethylaminoethanol, and N,N-dipropylamino group. Ethanol, N,N-dibutylaminoethanol, N,N-dipentylaminoethanol, hydrazine, hydrazine-dihexylaminoethanol, etc., and the substitution of the ethanol portion of these compounds with propanol or butanol Compounds, etc. Further, the two alkyl groups of the dialkyl moiety may be the same or different. A surfactant having a polar group derived from an anthracene, a fluorene-dialkylaminoalkanol, for example, a polyoxyalkylene-14-201106004 diol modified by a hydrazine, a fluorenyl-dialkylaminoalkanol In the present invention, the surfactant of the component (D) may be used singly or in combination of two or more kinds. In addition, the blending amount is antiglare, scratch resistance, other physical properties, and economy of the hard coating layer. From the viewpoint of the equilibrium of the above-mentioned (A) component, the solid content of the active energy ray-sensitive composition is preferably 0.01 to 10 parts by mass, particularly preferably 0.0 5 to 5 parts by mass. Parts by mass. In the present invention, by containing (D) a surfactant in the hard coating layer forming material, the lipophilic portion of the surfactant is adsorbed to the surface of the (B) spherical organic fine particles, and the interface activity by adsorption The hydrophilic portion of the agent hydrophilizes the surface of the (B) spherical organic fine particles, and is considered to be formed during the formation of the hard coating layer containing the lipophilic (A) active energy ray-inductive composition as a main component. (B) The spherical organic particles float to the surface. Therefore, the external haze 主要 can be mainly exhibited by causing the (D) surfactant to act on the (B) spherical organic fine particles. On the other hand, since (C) spheroidal lanthanide particles have a sterol group or the like on the surface, they are adsorbed on the hydrophilic portion of the surfactant, and have a lipophilic effect by not adsorbing the (D) surfactant. In part, the surface of the (C) spheroidal lanthanide particles is oleophilic, and is also considered to be suppressed during the formation of a hard coating layer containing a lipophilic (A) active energy ray-sensitive composition as a main component. Float to the surface. Therefore, (C) spherical lanthanum microparticles mainly exhibit internal haze 藉 by acting on (D) a surfactant. (Photopolymerization initiator) The hard coating layer forming material of the present invention may contain a photopolymerization initiator as desired. The photopolymerization initiator may, for example, be benzoin, An-15-201106004, benzoic acid ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylamino group. Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-benzene Propane·1-ketone, 1-hydroxycyclohexylbenzophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one, 4-(2 _Hydroxyethoxy)phenyl-2(hydroxy-2-propyl)one, diphenyl ketone, p-phenyldiphenyl ketone, 4,4'-diethylaminodiphenyl ketone, dichloro Diphenyl ketone, 2-methyl hydrazine, 2-ethyl hydrazine, 2-tributyl hydrazine, 2-amino hydrazine, 2-methyl thioxanthone, 2-ethyl thioxanthone , 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylketal, acetophenone dimethyl ketal, two Methylaminobenzoic acid ester and the like. These may be used singly or in combination of two or more kinds, and the amount of the compound is generally selected from the range of 0.2 to 10 parts by mass based on 1 part by mass of the total active energy ray-curable compound. In addition, when the reactive cerium oxide-based fine particles are used as the (b) cerium oxide-based fine particles, the full-activity amount-strand-curable compound is used. (Preparation of hard coating layer forming material) The hard coating layer forming material used in the present invention may be added to the active energy ray-inductive composition of the above component (A) in a predetermined ratio in a suitable solvent, if necessary. B) spherical organic fine particles of the component, spherical lanthanide fine particles of the component (C), a surfactant of the component (D), and a photopolymerization initiator which is used as desired, and various added components such as an antioxidant, ultraviolet absorption A solvent, a decane coupling agent, a photostabilizer, a leveling agent, an antifoaming agent, etc., are prepared by dissolving or dispersing. -16- 201106004 The solvent used at this time includes, for example, a hydrocarbon such as hexane or heptane, an aromatic hydrocarbon such as toluene or xylene, a halogenated hydrocarbon such as chlorinated methane or chlorine, methanol, ethanol or propanol. Alcohols such as butanol, ketones such as butanone, 2-pentanone, isophorone, cyclohexanone, esters such as butyl acetate, and celecoxib solvents such as ethyl sirolius The concentration and viscosity of the hard coating layer forming material to be prepared may be covered, and are not particularly limited, and may be appropriately determined depending on the situation. [Transparent plastic film] The antiglare hard coating film of the present invention is formed by using the above-mentioned prepared coating layer forming material to form a hard coating layer on the transparent plastic film. The transparent plastic film is not particularly limited, and can be appropriately selected from plastic films known as conventional hard coating substrates. Examples of the film include polyethylene terephthalate (also referred to as polyethylene terephthalate), polybutylene terephthalate, polyethylene naphthalate, polyethylene film, and polypropylene film. , cellophane, cellulose acetate cellulose acetate film (when called "TAC film"), cellulose acetate] polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, vinyl ester copolymer film, Polystyrene film, polycarbonate film, polymethyl f-poly film, polyether ether ketone film, polyether ruthenium film, polyether phthalimide film, amine film, fluororesin film, polyamide film, acrylic resin Plastic film such as film, lipid film, and cycloolefin resin film. Further, the antiglare hard coating film of the present invention is used as a polarized fatty ethane acetone, ethyl ester or the like. As long as the local selection is hard to be single-sided optical transparent plastic "PET" polyester film, three " ester film, - ethyl acetate film, polyphthalamide: enegrain: plate protection -17- 201106004 film When used, the transparent plastic film is preferably a TAC film from the viewpoints of better optical isotropic properties and the like. These plastic films may be transparent or translucent, and may or may not be colored, and may be appropriately selected depending on the application. For example, when used as a protective layer for a liquid crystal display, a colorless transparent film is preferred. The thickness of the plastic film is not particularly limited and may be appropriately selected depending on the conditions, and is generally in the range of 15 to 300 μm, preferably 30 to 200 μm. Further, the plastic film can be surface-treated on one side or both sides by an oxidation method, a embossing method, or the like, for the purpose of improving the adhesion to the layer provided on the surface. Examples of the oxidation method include a corona discharge method, a plasma treatment, a chromic acid treatment (wet type), a flame treatment, a hot air treatment, an ozone/ultraviolet irradiation treatment, and the like, and the embossing method includes, for example, a sand blast method. , solvent treatment, etc. These surface treatment methods can be appropriately selected depending on the type of the plastic film, and it is generally preferable to use the corona discharge treatment method in terms of effects and operability. In addition, a puller layer can also be provided. [Formation of Hard Coating Layer] The hard coating layer forming material can be formed by a conventionally known method such as a bar coating method, a knife coating method, a roll coating method, a sheet coating method, a die coating method, a gravure coating method, or the like. The hard coating layer is formed by coating the at least one surface of the transparent plastic film to form a coating film. After drying, the active energy ray is irradiated thereon to cure the coating film. The active energy rays are, for example, ultraviolet rays and electron beams. The ultraviolet rays can be obtained by a high-pressure mercury lamp, an electrodeless lamp, a metal halide lamp, a xenon lamp, etc., and the irradiation amount is generally 100 to 500 mJ/cm2. On the other hand, the electron beam-18-201106004 can be obtained by an electron beam accelerator or the like. Obtained, the irradiation amount is generally 15 0~3 5 OkV. Among the active energy rays, ultraviolet rays are particularly preferred. When an electron beam is used, a hardened material can be obtained without adding a photopolymerization initiator. In the present invention, the thickness of the hard coating layer thus formed is required to be larger than the average particle diameter of the spherical lanthanoid particles of the spherical organic fine particles (C) component of the component (B) to be used, and therefore, the lower limit thereof It is about 3 μm, and as for the upper limit, it is about 20 μm from the viewpoint of causing the hard coating film to be curled due to hardening and shrinkage of the hard coating layer. A preferred thickness is in the range of 5 to 15 μm. [Anti-glare hard coating film] (Optical characteristics) The optical characteristics of the anti-glare hard coating film of the present invention thus formed may be different depending on the form. For high contrast type, the internal haze is generally 〇~10%. Even if the internal haze is within this range and a flare is generated, a high contrast can be achieved, so that it can be sufficiently applied depending on the type of display (design commemoration). When the internal haze is more than 10%, high contrast cannot be obtained (becomes a general-purpose type). In addition, when it is a general-purpose type, the internal haze is generally 5 to 40%. When the internal haze is less than 5%, the performance of suppressing the flare is insufficient, and when it exceeds 40%, the visibility is lowered. The preferred internal haze of the general-purpose anti-glare hard coating is generally from 1 〇 to 30%, preferably from 15 to 25%. Further, the external haze is preferably 20% or less in terms of visibility and high-contrast type and general-purpose type, and is preferably 1% or more from the viewpoint of anti-glare property. In addition, the internal haze is a haze which is caused only by internal light scattering, and the external haze is a haze of light scattering caused by surface unevenness only from -19 to 201106004. The total haze 値 represents the sum of the aforementioned internal haze 値 and the aforementioned external haze 。. In addition, the total haze 値' is equivalent to the basis of the transparent plastic film unit of the constituent member of the anti-glare hard coating film, which is obtained from the haze J according to JIS K 7136 of the anti-glare hard coating film. The haze obtained by JIS K 7136 is the same. The following is a description of the calculation method of internal haze 外部, external haze 値, and total haze 値. <Internal haze 値, external haze 値, and total haze 硬 of the hard coating layer> First, the haze of the antiglare hard coating film of the present invention and the transparent plastic were measured in accordance with IS K 7136 The haze of the membrane monomer is 値. The haze obtained by subtracting the haze of the above-mentioned transparent plastic film monomer from the haze of the above-mentioned anti-glare hard coating film is taken as the total haze 値. Next, a transparent adhesive sheet having a thickness of 20 μm was adhered to the hard coating layer side of the antiglare hard coating film to form a sample for internal haze 値 calculation. According to JIS Κ 7136, the haze 内部 and the internal haze of the transparent adhesive sheet were measured, and the haze 说 was calculated. The internal haze of the hard coating layer of the optical film is obtained by subtracting the haze of the transparent adhesive sheet and the haze of the transparent plastic film from the haze of the internal haze 値 calculation sample. Finally, the enthalpy obtained by subtracting the internal haze from the total haze 値 is set as the external haze 値. Further, the haze of the transparent adhesive sheet is not particularly limited as long as it is subtracted from the calculation process and does not directly affect the internal haze, the external haze, and the total haze. However, from the viewpoint of improving the measurement accuracy -20-201106004, it is preferred to use a haze of less than 5%. Further, the 60° specular gloss, the 髙 contrast type and the general use type are preferably 20 to 130. When the 60° specular gloss exceeds 130, the surface gloss becomes large (reflection of light becomes large), and the anti-glare property is adversely affected. When the 60° gloss is less than 20, whitening is liable to occur. Further, the total light transmittance of the antiglare hard coating film is preferably 88% or more, and particularly preferably 90% or more. When the total light transmittance is less than 88%, there is a concern that the transparency is insufficient. The 60° specular gloss is measured according to JIS K 7105, and the total light transmittance is measured according to JIS K 7 1 36. (Effect) The anti-glare hard coating film of the present invention is provided with a hard coating layer containing spherical organic fine particles and spherical cerium-based fine particles, and has scratch resistance, and does not cause a large change in external haze. The internal haze is changed, and the outer/internal haze is easily adjusted during mass production, and the desired 60° specular gloss and anti-glare can be obtained without compromising the contrast. (Other functional layer) In the anti-glare hard coating film of the present invention, an anti-reflection layer such as a siloxane-based coating or a fluorine-based coating may be provided on the uppermost layer for the purpose of imparting antireflection properties and the like as necessary. Membrane and the like. At this time, the thickness of the antireflection layer is suitably 0.0 5 to 1 μm. By providing such an anti-reflection layer, it is possible to eliminate the mapping of the image generated by the reflection of the sun and the fluorescent lamp, and to increase the transparency by increasing the total transmittance of light by suppressing the reflectance of the surface. In addition, the improvement in anti-chargeability can be achieved by the type of anti-reflection layer. (Adhesive layer) -21-201106004 In the anti-glare hard coating film of the present invention, the surface of the plastic film opposite to the hard coating layer can be formed to be adhered to the liquid crystal display or the like. Adhesive layer of adhesive. As the adhesive constituting the adhesive layer, for example, an acrylic adhesive, an urethane-based adhesive, or a polyoxyalkylene-based adhesive suitable for optical use is preferably used. The thickness of the adhesive layer is generally 5 to ΙΟΟμηη, preferably 10 to 60 μm. Further, on the adhesive layer, a release sheet may be provided as necessary. For the release sheet, for example, a release agent such as a polyoxymethane resin coated on various plastic films such as polyethylene terephthalate or polypropylene may be mentioned. The thickness of the release sheet is not particularly limited and is generally 20 to 150 μm. An anti-glare hard coating film having such an adhesive layer is preferably used as a display for imparting anti-glare properties, scratch resistance, and the like to a CRT, an LCD, a PDP, etc., and is particularly suitable for adhesion of a polarizing plate such as an LCD. . [Polarizing Plate] The present invention also provides a polarizing plate in which the antiglare hard coating film of the present invention is bonded to a polarizing member. The liquid crystal cell of the LCD generally has the following structure, that is, two transparent electrode substrates on which the alignment layer is formed by arranging the alignment layer on the inner side and forming a predetermined interval by the spacer, and sealing the periphery to make the liquid crystal The material is sandwiched between the gaps, and a structure in which the polarizer is disposed on the adhesive layer on the outer surface of the two transparent electrode substrates. Fig. 1 is a perspective view showing a configuration of an example of the polarizing plate. As shown in the figure, the polarizing plate 10 generally has a three-layer structure of -22-201106004 in which the cellulose triacetate (TAC) films 2 and 2' are bonded to both sides of the polyvinyl alcohol-based polarizing member 1. On the substrate, an adhesive layer 3 for adhering to an optical component such as a liquid crystal cell is formed on the single surface, and then the release sheet 4 is adhered to the adhesive layer 3. Further, on the surface of the polarizing plate opposite to the adhesive layer 3, a surface protective film 5 is generally provided. In the polarizing plate of the present invention, the hard coating layer of the present invention described above is provided on one of the TAC films 2 and Y provided on both sides of the polarizing material 1. When the adhesive layer 3, the release sheet 4, and the surface protective film 5 are provided on the polarizing plate, the TAC film 2 on the side of the surface protective film 5 (the side is provided with the hard coating layer of the present invention. The polarizing plate of the present invention is produced). In the second embodiment, a cross-sectional schematic view showing the configuration of one example of the polarizing plate of the present invention is shown in Fig. 2. First, a film 12' having no optical anisotropy like a TAC film is used. The transparent plastic film as the base material is formed on the one surface of the hard coating layer '1 3 of the present invention to form the anti-glare hard coating film 14. Next, the adhesive layer 15 and 15' are used, and the adhesive film 15 is not formed. The TAC film 12 of the hard coating layer 13 is laminated on one surface of the polarizer 11, and the anti-glare hard coating film 14 is laminated on the opposite side. When the transparent plastic film is used as a TAC film, it is formed by an adhesive. In order to improve the adhesion, in addition to the surface treatment described above, alkalization treatment or the like can be performed. Thereby, the polarizing plate 20 having excellent anti-glare property and scratch resistance can be obtained. The polarizing plate 20 can also be provided as necessary. The surface of the hard coating layer 13 is provided as shown in Fig. 1 above. The peeled surface protection film 5, or the adhesive layer 16 or the release sheet 17 for attaching to the optical component of the liquid crystal cell or the like on the opposite side of the -23-201106004. The polarizing plate of the present invention is The liquid crystal cell of the LCD is used as the first, and can be used for the light amount adjustment, the polarization interference application device, the optical defect detector, etc. The embodiment will be described in detail by way of examples, but the invention is not limited thereto. The average particle diameter and refractive index of the organic fine particles and the lanthanoid particles, the refractive index of the cured product of the active energy ray-inductive composition, and the properties of the hard coating film are determined by the following methods. <Spherical organic fine particles and spherical cerium-based fine particles> (1) A Kirten particle counter [manufactured by Beckman Coulter Co., Ltd., trade name "Multi sizer 3") was used, and 0.5% ion-exchanged water was used as the average particle diameter. The dispersion was measured by Curt particle counting at 25 t. (2) Refractive index The particles to be detected are placed on a glass slide, and the refractive index standard is dropped onto the particles, and then the cover glass is covered to prepare a sample. According to the B method of IS K 7142, the sample is observed under a microscope, and the refractive index of the refractive index standard liquid which is the most difficult to see the outline of the fine particles is used as the refractive index of the fine particles. <Active energy ray-inductive composition> (3) Refractive index of cured product Each of the preparation examples is composed of an active energy ray-inducing composition (A), a photopolymerization initiator, and a diluent solvent. Coating agent. This was applied to a TAC film [manufactured by Fujifilm Co., Ltd., trade name "TAC80TD80ULH") in the same manner as in Example-24-201106004 to form a hard coating film for measuring the refractive index of the cured product. According to the A method of JIS K7142, the Abbe refractometer manufactured by Atago Co., Ltd. was used, and the refractive index of the hard coating layer was determined as the refractive index of the cured product of the active energy ray-inductive composition. <Hard coating film> (4) The total light transmittance was determined by using a haze meter "NDH-2000" manufactured by Nippon Denshoku Industries Co., Ltd., and the anti-glare properties produced in the examples and comparative examples were based on JIS K7136. The coating film was measured for its total light transmittance. (5) Internal haze 値 of the hard coating layer, external haze 値, and total haze 値 using a haze meter "NDH-2000" manufactured by Nippon Denshoku Industries Co., Ltd., according to JIS K7136, examples and comparative examples The prepared antiglare hard coating film and the haze of the transparent plastic film monomer of the constituent members of the film. By subtracting the haze of the transparent plastic film from the haze of the anti-glare hard coating film obtained by the above measurement, the total haze of the hard coating layer of the anti-glare hard coating film can be calculated. 2 parts by mass of an isocyanate crosslinking agent (manufactured by Toyo Ink Co., Ltd., trade name "BHS-8515") and 100 parts by mass of toluene were added to an acrylic adhesive [product name "PE-121", manufactured by Japan Carbide Co., Ltd.] 100 To make an adhesive solution. The adhesive solution was applied to a polyethylene terephthalate-25-201106004 diester film (manufactured by Toyobo Co., Ltd., trade name "A43 00"] having a thickness of 50 μm so that the thickness after drying was 20 μm. Drying was carried out at 100 ° C for 3 minutes to prepare a transparent adhesive sheet. The prepared transparent adhesive sheet was adhered to the hard coating layer side of the antiglare hard coating film to form a sample for internal haze 値 calculation. Similarly to the above, each haze 値 of the transparent adhesive sheet and the sample for internal haze 値 calculation was measured in accordance with JIS K 7136. The internal haze of the hard coating layer of the anti-glare hard coating film can be calculated by subtracting the haze of the transparent adhesive sheet and the haze of the transparent plastic film from the haze of the internal haze calculation sample. value. Finally, by subtracting the internal haze from the total haze, the external haze of the hard coating of the anti-glare hard coating can be calculated. (6) Evaluation of anti-glare property Under the fluorescent lamp, visually observe a sample in which an acrylic adhesive adheres a hard coating film to an acrylic resin [manufactured by Sumitomo Chemical Co., Ltd.] and uses the following criteria. To evaluate anti-glare" 〇: Fluorescent lamp has sufficient anti-mapping performance and no whitening △: Fluorescent lamp has poor resistance to mapping, and some whitening X: fluorescent lamp has insufficient resistance to mapping, or In the fluorescent lamp, the mapping resistance is sufficient, but the degree of whitening is large, and the visibility is deteriorated. (7) The 60° specular gloss is measured by JIS K7105 using a gloss meter "VG2000" manufactured by Nippon Denshoku Industries Co., Ltd. (8) The thickness of the hard coating layer The anti-glare hard coating film produced in the examples and the comparative examples, and the TAC of the transparent plastic film used in the production of the -26-201106004 anti-glare hard coating film (three) Each film of the cellulose acetate film was measured for thickness using a constant pressure thickness meter [product name "MH-15M" manufactured by Nik〇n Co., Ltd.), and the thickness of the hard coating layer was calculated by taking the difference. Preparation Example 1 Hard coating agent for hard coating layer 1 A hard coating agent (manufactured by JSR Co., Ltd., product name "〇PstarZ7524", having a solid content of 70% by mass, containing reactivity 65% by mass of the total active energy ray-curable compound of the cerium oxide fine particles and the polyfunctional acrylate, '5% by mass of the photopolymerization initiator, 30% by mass of methyl ethyl ketone, and 1.50% of the refractive index of the cured product; 100 parts by mass, as (B) ) Polymethyl methacrylate microparticles composed of acrylic resin (hereinafter referred to as "PMMA") (manufactured by Kyoritsu Chemical Co., Ltd., product name "MX5 00", average particle size 5 μηι, refractive index 1.49] 7.5 parts by mass of polysiloxane oxide fine particles of (C) spherical lanthanum microparticles [product name "Tospearll20", manufactured by Momentive Performance Materials Japan Co., Ltd., average particle diameter 2 μιη, refractive index 1.43] 2 parts by mass , as a (D) surfactant, a caprolactone-polyethylene glycol-dibutylamine ethanol copolymer [manufactured by BYK Japan, trade name "disperbyk 103", based on 40 masses of methoxypropyl acetate Diluted product] 1 part by mass, as well as a dilution solvent of propylene glycol monomethyl ether 90 parts by mass uniformly mixed, to thereby prepare a solids content of about 40 mass% of the hard coating layer with a coating agent. Preparation Example 2 Hard coating layer coating agent 2 The same operation as in Preparation Example 1 was carried out except that 4 parts by mass of "Tospearl 120" was used as the (C) spherical cerium-based fine particles, and a solid form of -27 - 201106004 parts was prepared. About 40% by mass of the coating agent 2 for the hard coating layer. In the preparation example 3, the coating agent 3 for the hard coating layer is used as a coating material 3 (manufactured by Momentive Performance Materials Japan Co., Ltd., trade name "Tospearl 145", average particle diameter: 4.5 μm, refractive index: 1.43). C) The same procedure as in Preparation Example 1 was carried out except for the spherical ruthenium-based fine particles, and the coating material 3 for a hard coating layer having a solid content of about 40% by mass was prepared. Preparation Example 4 Hard coating layer coating agent 4 (C) spherical lanthanum is used as the (C) spheroidal lanthanum particle (manufactured by ABC NANOTECH Co., Ltd., trade name "SI-130j, average particle diameter 3 μιη, refractive index 1.46", 4 parts by mass. In the same manner as in Preparation Example 1, the hard coating layer coating agent 4 having a solid content of about 40% by mass was prepared in the same manner as in Preparation Example 1. The coating material 5 for the hard coating layer of Preparation Example 5 was used except for the porous cerium oxide. Fine particle [product name "SI-230", manufactured by ABC NANOTECH Co., Ltd., average particle diameter 3 μπι 'refractive index 1 · 46] 4 parts by mass, the same operation as in the preparation example 1 was carried out, except for (C) spherical cerium-based fine particles. And the solid content is prepared to be about 40% by mass. The coating 5 for the hard coating layer. Preparation Example 6 The coating agent for a hard coating layer 6 The same operation as in Preparation Example 1 was carried out except that (C) spherical cerium-based fine particles were not used, and a coating composition for a hard coating layer having a solid content of about 40% by mass was prepared. 〇 Preparation Example 7 Hard coating layer coating agent 7 -28- 201106004 The same operation as in Preparation Example 1 was carried out except that (C) spherical lanthanum-based fine particles and (D) surfactant were not used, and solid content was prepared. About 40% by mass of the coating agent 7 for a hard coating layer. Preparation Example 8 Hard coating layer coating agent 8 The same operation as in Preparation Example 2 was carried out except that the (D) surfactant was not used, and the hard coating layer coating agent 8 » prepared with a solid content of about 40% by mass was prepared. Example 9 Hard coating layer coating agent 9 The same procedure as in Preparation Example 3 was carried out except that the (D) surfactant was not used, and a coating composition for a hard coating layer of about 40% by mass was prepared. 10 Hard coating layer coating agent 10 The same operation as in Preparation Example 2 was carried out except that (B) spherical organic fine particles were not used, and a hard coating layer having a solid content of about 40% by mass was prepared to be covered. I 1 0. Preparation Example 11 Hard coating layer coating agent 11 The same procedure as in Preparation Example 3 was carried out except that the (B) spherical organic fine particles were not used, and the hard coating layer coating agent 1 1 having a solid content of about 40% by mass was prepared. . Preparation Example 12 Hard coating layer coating agent 12 The same procedure as in Preparation Example 4 was carried out except that the (B) spherical organic fine particles were not used, and the hard coating layer coating agent 12 having a solid content of about 40% by mass was prepared. -29-201106004 Preparation Example 1 3 Coating Agent for Hard Coating Layer 1 The same operation as in Preparation Example 5 was carried out except that the spherical organic fine particles (B) were not used, and a hard coating of about 40% by mass of the solid content was prepared. The layer coating agent 13 is used. The first table shows the properties of the coating layers 1 to 13 for the hard coating layer obtained in the above Preparation Examples 1 to 13. -30- 201106004 (D) Surfactant content (parts by mass) Ό Ο \〇vq VO o Ο o vq vq (C) Spherical lanthanide particle content (parts by mass) σ\ Η Γ- ο 1 1 卜 o Γ *- 〇 refractive index) a 1 1 鞾__ < t 1 i cut 3 (four) <Ν νο m cn 1 1 <N CN UO CO CO m *1siS Waist 1 Polyoxyalkylene Resin Secret Lithium Secret 1 litigation - B- Porous Ceria 1 1 遁m ss ^ m K 遁 sg Inlaid polyoxyalkylene resin secret S5 ^ mm Secret 11 Litigation • B- Porous Sand Dioxide (B) Content of spherical organic particles (parts by mass) Γ-* Ο Bu· 1 1 1 1 Refractive index σ\ 1 1 1 1 Average particle size (_) yn I 1 1 1 PMMA 1 ^1 PMMA 1 1 1 1 (8) Active energy ray-inductive composition Refractive index solid content (mass) 8 Hard coating layer coating agent · t—蟑cs cn 寸 VO 〇 0 ON 〇 Cs c^i modulation example 1 modulation example 2 modulation example 3 modulation example 4 modulation example 5 modulation example 6 modulation example 7 modulation example 8 modulation example 9 modulation example 10 modulation example 11 modulation example 12 modulation example 13 201106004 embodiment 1 modulation example 1) The coating agent 1 for a hard coating layer was applied to a TAC film having a thickness of 80 μm by a wire bar coater so that the thickness of the hard coating layer was about 10 μm [[Fuji Film Co., Ltd., product name" The surface of the TAC80TD80ULH"]. After drying in an oven at 70 ° C for 1 minute, ultraviolet rays having a light amount of 300 mJ/cm 2 were irradiated with a high-pressure mercury lamp to form a hard coating layer to prepare an antiglare hard coating film. The second watch shows the performance of this hard coating. Examples 2 to 5, Comparative Examples 1 to 7 and Reference Example 1 In the first embodiment, except for the hard coating layer coating agent 1 of the type shown in the second table, the coating material 1 for the hard coating layer was used. The same operation as in Example 1 was carried out to produce various antiglare hard coating films. The second watch shows the performance of each hard coating. -32- 201106004
201106004 從前述第1表及第2表中可得知下列內容。 實施例1 ~3所得之本發明之防眩性硬被覆膜，即使改 變不易受到（D)界面活性劑的影響之（C)成分的球狀矽系微 粒的含量，主要是內部霧度値產生變化，外部霧度値並未 產生太大變化。此外，實施例4、5中，即使使用多孔質二 氧化矽或中空二氧化矽作爲（C)成分的球狀矽系微粒，亦可 良好地發揮防眩性賦予效果。 參考例1中，由於（A)成分的硬化物與（B)成分的球狀 有機微粒之折射率差小，所以內部霧度値小。另一方面， 實施例1〜3中，由於含有與（A)成分硬化物具有折射率差之 (C)成分的球狀矽系微粒，所以係顯現出內部霧度値。比較 例1~3中，由於不含界面活性劑，所以在較平均粒徑更大 之硬被覆層的膜厚（1〇 μηι)中，其防眩性不足。 如比較例4~7所示般，僅在不受到界面活性劑的影響 之（C)成分的球狀矽系微粒中，在較該粒子的平均粒徑更大 之硬被覆層的膜厚中，其防眩性不足。 產業上之可利用性 本發明之防眩性硬被覆膜，係設置有含有球狀有機微 粒及球狀矽系微粒之硬被覆層，具有耐擦傷性，並且可在 不使外部霧度値產生較大變化下使內部霧度値產生變化， 薄膜量產時容易進行外/內部霧度値的調整，且可在不損及 對比下獲得期望的防眩性。本發明之防眩性硬被覆膜，尤 其適合於偏光板用。 -34- 201106004 【圖式簡單說明】 第1圖係顯示偏光板之1例的構成之立體圖。 第2圖係顯示本發明之偏光板之1例的構成之剖面槙 式圖。 【主要元件符號說明】 1 聚乙烯醇系偏光件 2 TAC膜 2' TAC膜 3 黏著劑層 4 剝離薄片 5 表面保護膜 10 偏光板 11 偏光件 12 TAC膜 12' TAC膜 1 3 硬被覆層 14 防眩性硬被覆膜 15 接著劑層 1 5 ( 接著劑層 16 黏著劑層 17 剝離薄片 20 偏光板 -35-201106004 The following contents can be found from the first table and the second table. In the anti-glare hard coating film of the present invention obtained in Examples 1 to 3, even if the content of the spherical lanthanum-based fine particles of the component (C) which is not easily affected by the (D) surfactant is changed, the internal haze is mainly 値. Changes occur and the external haze does not change much. In addition, in the examples 4 and 5, even if the porous cerium oxide or the hollow cerium oxide is used as the spherical cerium-based fine particles of the component (C), the anti-glare imparting effect can be favorably exhibited. In Reference Example 1, since the difference in refractive index between the cured product of the component (A) and the spherical organic fine particles of the component (B) is small, the internal haze is small. On the other hand, in the examples 1 to 3, since the spherical cerium-based fine particles having the refractive index difference (C) component of the cured product of the component (A) are contained, the internal haze 显现 is exhibited. In Comparative Examples 1 to 3, since the surfactant was not contained, the anti-glare property was insufficient in the film thickness (1 μ μm) of the hard coating layer having a larger average particle diameter. As shown in Comparative Examples 4 to 7, only the spherical cerium-based fine particles of the component (C) which are not affected by the surfactant are in the film thickness of the hard coating layer which is larger than the average particle diameter of the particles. , its anti-glare is insufficient. Industrial Applicability The anti-glare hard coating film of the present invention is provided with a hard coating layer containing spherical organic fine particles and spherical cerium-based fine particles, and has scratch resistance and can prevent external haze. The internal haze 値 is changed under a large change, and the outer/internal haze 容易 is easily adjusted when the film is mass-produced, and the desired anti-glare property can be obtained without damaging the contrast. The antiglare hard coating film of the present invention is particularly suitable for use in a polarizing plate. -34- 201106004 [Simplified description of the drawings] Fig. 1 is a perspective view showing a configuration of one example of a polarizing plate. Fig. 2 is a cross-sectional view showing the configuration of an example of a polarizing plate of the present invention. [Main component symbol description] 1 Polyvinyl alcohol-based polarizing member 2 TAC film 2' TAC film 3 Adhesive layer 4 Release sheet 5 Surface protective film 10 Polarizing plate 11 Polarizing member 12 TAC film 12' TAC film 1 3 Hard coating layer 14 Anti-glare hard coating 15 Next layer 15 (Next layer 16 Adhesive layer 17 Release sheet 20 Polarizer -35-