TW200302923A - Antiglare optical film, polarizing plate and display unit using the same - Google Patents

Abstract

An antiglare optical film comprising: a transparent film substrate having a fine unevenness surface structure provided on at least one side of the transparent film substrate, wherein a proportion of an oblique angle of not smaller than 10 DEG is not greater than 2% and an average interval of peaks in the fine unevenness surface is from 1 μ m to 50 μ m.

Description

200302923 玫、發明說明 (發明說明應敘明：發明所屬之技術領域、先前技術、內容、實施方式及圖式簡單說明） (一） 發明所屬之技術領域 本發明關係一種具有防眩特性之光學薄膜’一種具有防‘ 眩性質之抗反射薄膜，一種具有防眩性質之偏光板和一種 含有此等薄膜之顯示單元。 (二） 先前技術 在諸如陰極射線管（CRT)、電漿顯示面板（PDP)、電發光 顯示器（ELD)和液晶顯示器（LCD)等之顯示單元中，曾經應 φ 用設置防眩（減眩）薄膜或防眩之抗反射薄膜，作爲顯示器 之最外層，因而防止因外在光線反射而造成對比或反射之 降低。 然而，在如此之顯示器上，對於爲黑色之圖像，在斜看 之時，有白化之黑色或灰色。此現象以「黑色之不良減退」 ‘ 、「黑色不良提升」、「喪失黑色」、「白化黑色」或「不良白 性」表示。如此在黑色所呈現之黑圖像之反面狀況，「黑色 之良好減退」、「黑色之提升良好」、「無淡褪的黑色」、「緊修 密的黑色」、「淸晰的黑色」或「良好的白化」予以表示。 以上各種現象是因爲由於用作促進防眩性質之薄膜表面不 均勻（峯突/凹谷）結構加強光散射，且散射之光進入原爲黑 色部份之事實而形成。此因降低對比，損及高級圖像與顯 示，使顯示品質劣化而爲非所適宜。對此問題之反制’已 有建議減少薄膜表面上之粗粒和粗化。以此方法雖然在黑 色圖像中看到黑色，卻引起防眩性質劣化之另一問題。亦 200302923 即，難以造成看到黑色而防眩性質不被劣化之黑色圖像。 於影像顯示單元內，另一方面，需要減小像素之大小以 改善顯示品質（高淸晰度）。然而，如果從防眩抗反射薄膜 觀看高淸晰度顯示器，由於嚴重的眩光性，顯示器品質深 被劣化。雖然已知此項問題可以藉由改變膠合劑與塡充劑 之折射率以產生內部朦霧性而有效解決，但是此項方法伴 生若干困難，其如劣化黑色的牢固性，降低前面之對比， 並降低前面之亮度。另一方面，在品質上已知防眩性可藉 提高防眩性質而減輕。然而，如果防眩性質過度加強，圖 像變成不淸楚並殃及整個顯示表面，因而當顯示表面曝於 光線時，可看性大爲劣化（此現象被稱爲「白迹（white blur)」 。此即被視爲既非防眩膜亦非防眩抗反射膜以致於防眩性 質可供強化高淸晰度之顯示，使在造成黑色圖像以觀看黑 色之時，不致造成白迹或降低前面對比或前面亮度。 另外，爲求設置防眩光學薄膜，已硏究一種方法，涉及 在具有不均勻表面之支持物上施加抗反射膜；或另一方法 ，涉及以供形成不均勻表面用之粗糙粒子加至用以形成抗 反射層塗覆溶液內等等。然而，前一方法之缺點是在抗反 射層塗覆溶液從尖峯流至凹谷時，發生平面內膜之厚度不 均性，造成抗反射性質明顯比在平滑表面上之塗層低劣， 後一方法之缺點是具有約1微米或較大粒徑而爲足具防眩 性質之粗糙粒子，必須被埋設於厚度自〇 . 1至〇 . 3微米之 薄膜內，造成粗糙粒子之剝落。作爲克復此等問題之一種 方法，JP-A- 1 2 - 3 2 9 9 0 5揭示一種方法，涉及抗反射膜形成 200302923 後防眩性質之條件。在若干細部內，其間提出一種方法， 包括在一刻花輥下施壓於一具有抗反射層之抗反射膜，使 在抗反射層上形成不均勻性而無損於其抗反射性質。然而 ，如此之抗反射膜有其缺點，在延長之使用期中逐漸出現 降低之防眩性質。因前述各項原因，未有同時滿足所期望 之抗反射性質和薄膜強度於延長期間之實用塗覆抗反射膜 曾經出現。 (三）發明內容 本發明之一項目的爲提供一種防眩光學薄膜，使所欲觀 看之黑色爲黑色而呈現高度之前面對比。本發明之另一目 的爲提供一種防眩光學薄膜，可以裝設於高淸晰度顯示器 上而維持此類性質。本發明之再一目的是提供一種防眩光 學薄膜，能夠稍減出現白迹。本發明之再另一目的爲提供 一種防眩光學薄膜，甚至在長期使用之後，防眩性質仍不 改變或少有改變，尤其在高之溫度和濕度之嚴酷環境，無 損於原始性質。本發明之再一目的是提供一種含有如此防 眩光學薄膜之偏光板和顯示單元。 本發明之各個目的完成如後： (1)在透明薄膜基板至少一面上設置含有微細不均表面結 構之防眩光學薄膜，其特徵在於傾斜角不小於1 0 °者之比 例不大於2 %，且在微細不均勻表面中各峯突之平均間距爲 自1微米至50微米。 (2 )如（1 )所述之防眩光學薄膜，其中各峯突間之平均間距 爲自1微米至20微米。 200302923 (3 )如（1 )和（2)所述之防眩光學薄膜，其中對於在自1至2 平方微米（μ ni 2)之薄膜表面上所量測之規則反射面內各傾 斜角之平均’爲自不小於1 °至小於5。。 (4)如（1)至（3)所述之防眩光學薄膜，含有在其最上方表面 之抗反射層。 (5 )如（1 )至（3 )所述之防眩光學薄膜，其中係接受壓花粗化 薄膜表面，使本身有防眩性。 (6) 如（5)所述之防眩光學薄膜，其中由式（I)所定義之粗糙 度算術平均値R百分比不小於3 0 % : (I) R = Ra/Rb 其中Ra代表貯存於65°C和95%RH(相對濕度）大氣中1，000 小時後，抗反射層表面之算術平均粗糙度；而Rb代表貯存 於6 5 °C和9 5 % RH (相對濕度）大氣前抗反射層表面之算術平 均粗糙度。 (7) 如（4)至（6)所述防眩光學薄膜，其中抗反射層製自具有 比支持基板折射率較低之低折射層，一高折射層設於該支 持基板與該抗反射層之間，該高折射層之折射率高於支持 基板，且高折射層之厚度實質上爲一致。 (8 )如（7 )所述之防眩光學薄膜，其中一中折射層***設於 支持基板與高折射層之間，中折射層之折射率高於支持基 板者，中折射層之折射率低於高折射層，且中折射層之厚 度實質上爲一致。 (9)如（4 )至（8 )之防眩光學薄膜’其中在5 °角入射而波長 自4 5 0至6 5 0奈米之光線之鏡面反射平均値不大於〇 . 5 %。 -9- 200302923 (10) 如（4)至（8)之防眩光學薄膜，其中在5°角入射而波長 自4 5 0至6 5 0奈米之光線之鏡面反射平均値不大於〇 · 3 % ° w (11) 如（4)至（10)所述防眩光學薄膜，其中各層是塗覆含有· 成膜溶質和至少一種溶劑而成之塗覆組成物’以乾燥除去 溶劑，然後以熱度及/或離子輻射固化塗覆組成物而形成。 (1 2 )如（8 )至（11 )所述防眩光學薄膜’其中之中折射層、高 折射層和低折射層分別依所設定波長λ( = 5 0 0奈米）滿足如 下（I)、（II)、和（III)等關係： λ/4χ0.80<η1ά1<λ/4χ1 .00 (I) λ/2χ0.75<η2ά2<λ/2χ0.95 (II) λ/4χ0.95<η3ά3<λ/4χ1.05 (HI) 其中η 1代表中折射層之折射率；d 1代表中折射層厚度（奈 米）；n2代表高折射層之折射率；d2代表高折射層之厚度 (奈米）；η 3代表低折射層之折射率；且d 3代表低折射層之 厚度（奈米）。 (I3)如（7)至（I2)所述之防眩光學薄膜，其中低折射層製自丨 以熱固化或離子輻輻射固化含氟樹脂。 (1 4)如（7)至（13)所述防眩光學薄te ’其中高折射層形成於 塗覆一種塗覆組成物，含有一種超微材料，包含至少一種 金屬氧化物’選自包括欽、錶、銦、鋅、錫和銻等之氧化 物；一種陰離子性分散劑；一種具有Ξ官能或更高可聚合 基之可固化樹脂與聚合起始劑。採乾燥除去溶劑，然後以 熱及/或以離子輻輻射固化塗覆組成物。 0 5)如（7)至（1 4)所述之防眩光學薄膜，其中低折射層對於 200302923 純水具有不小於1 0 0 °之接觸角。 (1 6 )如（1 )至（1 5 )所述之防眩光學薄膜’至少具有一 夾插於低折射層和透明薄膜基板之間。 (1 7 )如（1 )至（1 6 )所述之防眩光學薄膜’至少具有一 射層夾插於防眩層與透明支持物之間。 (1 8 ) —種製備含有設於透明薄膜基板至少一面之微 均勻表面結構之防眩光學薄膜之方法’其特徵在於j 受壓花，使不小於1 0 °之傾斜角之比例不大於2 % ’ 細不均之表面中各峯突之平均間距爲自1微米至5 0 (1 9 )如（1 8 )所述防眩光學薄膜之製備方法，其中各 平均間距爲自1微米至20微米。 (2 0)如（1 8)和（19)所述防眩光學薄膜製備方法，其1 1至2平方微米之薄膜表面中所量規律反射面之平P 角爲自不小於1 °至小於5 °。 (21)如（18)至（20)所述防眩光學薄膜製備方法，其 上方表面層上設一抗反射層，且抗反射層之表面接受 (2 2)如（2 1)所述防眩光學薄膜之製備方法，其中由 所定義之算術平均粗糙度百分比R不小於3 0 % : (I) R = Ra/Rb 其中Ra代表抗反射層表面貯於65°C和95%RH (相對 大氣中1，0 0 0小時後之算術平均粗糙度；而RB代表 層表面在貯於65 °C和9 5%RH (相對濕度）大氣前之算 粗糙度。 (23)如（22)所述防眩光學薄膜之製備方法，其中已 硬塗層 向前散 細不 摸面接 且在微 微米。 峯突之 中在自 反射 中於最 壓花。 式⑴ 濕度） 抗反射 術平均 經接受 200302923 壓花之抗反射層再接受在含水量少於丨〇質量（重量）％之溶 液中，或在該溶液之蒸汽中，於自6 0 °C至2 0 0 °C之溫度， 處理 10, 〇〇〇 至 100,000 秒。 (24) —種製備含有防眩層且在透明薄膜基板至少一面上 設置有微細不均之表面結構而成之防眩光學薄膜之方法， 其特徵在於防眩層接受壓花，使不小於1 〇 °之傾斜角之比 例不於2 %，且在微細不均表面中各峯突之平均間距爲自1 微米至50微米。 (2 5 ) —種含有兩片表面保護膜分別層積於偏光器兩面之 偏光板，其特徵在於各表面保護膜至少有一採用如（1 )至 (1 7 )所述之防眩光學薄膜。 (2 6 ) —種偏光板，含有作爲至少一片表面保護膜之防眩光 學薄膜，其係在形成如（1 )至（1 7 )所述之防眩光學薄膜之前 ，用鹼溶液塗覆透明之支持物，使設有防眩層之反面，接 受皂化；或在其形成之後，用鹼溶液塗覆該防眩光學薄膜。 (27)如（25)和（26)所述之.偏光板，其中在各該表面保護膜 之中，除防眩光學薄膜外之薄膜，是一種具有光學補償層 之光學補償膜，其在與偏光器相反之該表面保護膜之一面 上，含有一種光學非等方向層，該非等方向層是一種具有 負的雙折射之層。製自具有碟形（Discotic)結構單元之化合 物’具有碟形結構單元之碟形物之表面傾斜於該表面保護 膜之表面，且由具有碟形結構單元之碟狀物之表面與該表面保 護膜之表面所成之角度，隨著光學非等方向層之深度而改變。 (2 8 ) —種顯示單元，至少具有一片如（丨）至（丨7 )所述之防眩 200302923 光學薄膜；或如（2 5)至（27)所述之偏極板。 (29) 如（28)所述之顯示單元，其係一種TN、STN、VA、IPS 或O C B模式之透射型、反射型或半透射型液晶顯示單元。 (30) —種至少具有一片如（25)至（27)所述偏光板之透射型 或半透射型液晶顯示單元，其特徵在於有一具有偏光選擇 層之偏光分離膜，夾插設於在觀看側反面之偏光板與背光 板之間。 (3 1 ) —種表面保護板，用於有機電發光（E L )顯示器，其爲 具有一 λ/4板，設於透明之保護膜，其爲設於如（2 5)和（27) 所述偏光板之一面而與防眩光學薄膜相反。 本發明之防眩光學薄膜基本構造將參考附圖舉例說明。 第1圖所示模式是發明防眩光學薄膜之一實施例，由一透 明支持物1、一硬塗層2和一低折射層依次構成。4爲各顆 粒。硬塗層2可由二或多層組成。 發明之防眩光學薄膜，在透明薄膜基板至少一面上具有 不均之表面結構，由於光散射現象而散射一反射影像而展 現防眩性質。 在本發明中，是以如後之方法決定傾斜角度及其比率。 亦即，面積0.5至2 μ m 2 (微米平方）之三角形之三個頂點在 透明薄膜基板之面上被推測決定。然後從這些頂點向上延 伸之三垂直線，分別相交所測之薄膜表面。然後在具有作 爲頂點之三個點之三角形之法線，與向上垂直延伸自支持 物之垂直線，兩線所成之夾角被視爲傾斜角度。在基板上量 出0.25mm2(毫米平方）或較大之面積，分成各三角形而進 -13· 200302923 行量測。然後表示1 〇 °傾斜角之各點之比率，或對在所量 所有各點上面之比率予以決定。 4 現在，更爲詳細說明傾斜角之量側方法。如第2圖所示· ，各垂直線向上垂直延伸自支持物上之三點A、B、C。這 些垂直線與表面相交之各點分別視爲A，、B ’和C，。三角形 之法線Df與自支持物垂直向上延伸之垂直線0’之間 的夾角Θ被視爲傾斜角。在支持物上之量測面積較佳爲 0.2 5mm2或較大。在支持物上劃分此面積成各個三角形， 進行量測。計算如此所測得各傾斜角度之平均値而獲得表 I 面之平均傾斜角。雖然有若干系統可用於此項量測，其一 實例將予說明。在此情形中，使用Micromap(USA)所製之 型號SXM 5 2 0-AS 150。若所用物鏡放大率爲（χίο)，以之爲 例，傾斜角量測於0.85微米之單元而量測面積爲0.48mm 2 。若加大物鏡之放大率，則量測單元和量測面積被減小。 量測之數據可用如MAT-LAB之軟體分析，因而能夠計算傾 斜角之分佈。所以1 〇 °或以上之傾斜角之比率可易予決定。丨 在本發明中，10°或其以上之傾斜角之比率爲在2%或較 少，更佳者爲1 %或較少。所以，防眩性質和使黑色圖像看 出黑色之效果兩者能夠被顯現。 在發明之防眩光學薄膜中，較佳者之平均傾斜角爲丨。或 較大而小於5 °。傾斜角可有一種在某種角度之峯突，而且 可表示二或多種峯突。例如，傾斜角可能有丨。之峯.突，表示 於1 0 °或其以上之比率爲2 %或較少而且具有4。之平均傾斜 角。或改變之，可有1.5。和5。之峯突，表示1〇。或其上之 -14- 200302923 比率爲2 %或較少而具有6 °之平均傾斜角。 關於表面之峯突和凹谷，不均表面之範圍與高度可以使 用表面粗糙度計量測。從薄膜表面剖面曲線之平均線劃出 隔開0 . 〇 1 2 5微米之兩個平行峯突列計標高。當曲線相交 於較低之峯突到計標高一或多次時，定義出一峯突。然後 以峯突之計數除所測距離而算出各峯突間之平均間隔。在 本發明中，各峯突間之平均間隔（S m )之範圍爲自1微米至 50微米，更佳者自1微米至20微米而最佳自1微米至15 微米。更特別而言，可用SE-3C型之表面粗糙度計（Kosaka Kenkyusho 製造），在 20,000 或 10,000 垂直放大率，0.25 之截斷値，量測長度2 . 5而記錄計水平放大率爲5 0。S m 可以減小，例如以加上大量顆粒，具有如與膜厚級次相同 之平均粒徑。然而，此已知方法造成白度之劣化。 爲了在高淸晰度監視器中僅藉適當設計微細不均之表面 結構而提供不表現眩光之防眩薄膜，其爲無可避免而接受 喪失黑色。雖然防眩性質與牢固黑色兩者可以利用內部散 射或內部朦糊建立至某一程度如上述，在此情況中無可避 免將降低對比。在本發明中，已發現眩光可防止於高淸晰 度監視器，而使黑色圖像看出黑色之效果之惡化可被防止 而無損於對比，有賴於控制1 0 °或其以上之傾斜角之比率 爲2%或較少；並控制Sm自1微米至50微米，或自1微 米至2 0微米。 表面傾斜角分佈和S m可以隨意控制於藉由適當選擇在 防眩層內顆粒之直徑與數量，在防眩層內顆粒對膠合劑之 -15- 200302923 比率，和乾膜之厚度。表面形狀可以藉適當選擇塗覆溶液 之物理性質予以控制。爲求更精確設計表面，最合適者爲 利用上述之壓花方法，壓花方法詳見於JPA 2 0 0 0 - 3 2 9 9 0 5 。亦即，所需表面形狀可以獲自設定壓花輥於所求表面之 傾斜角分佈和S m。然而，本發明之表面形狀可以獲自不受 限制之任意方法。. 在本發明中，硬塗層之折射率非以單一數値提示。亦即 其較佳者爲，硬塗層是一種折射率並不一致之層，有粒子 分散於構成硬塗層之材料之中。較佳者，構成硬塗層材料 之折射率爲在自1.57至2.00範圍內。據JPA 8 - 1 1 0 4 0 1所 稱爲例，若具有高折射率之材料選自1 〇 〇奈米或較小粒徑 之顆粒，且選自具有乙烯不飽和基各單體之一者，和鈦、 鋁、銦、鋅、錫、銻和銷等之氧化物，顆粒之粒徑爲足以 小於光之波長，不發生散射。因此，如此之材料從光學觀 點恰如一種均勻物質。硬塗層也可用作防眩層。或予變更 ，防眩層可另形成於硬塗層上。 較佳者，在硬塗層內所用化合物爲有飽和烴或聚醚作爲 主鏈之聚合物，更佳者爲具有飽和烴作爲主鏈之聚合物。 較佳者之膠合劑聚合物是已經被交聯。較佳者，具有飽和 烴作爲主鏈之聚合物是獲自於乙烯不飽和基單體之聚合作 用，爲了獲得可交聯之膠合劑聚合物，最好使用二或多個 乙烯不飽和基之單體。爲達到高折射率，最好在單體結構 內至少含有選自芳香環、氟除外之鹵素原子、硫、磷和氮 等原子等之一種。 -16- 200302923 具有二或多個乙烯不飽和基之單體，包括例如多羥醇與 (甲基）丙烯酸之酯類（例如，丙烯酸乙二醇二（甲基）酯、二 丙烯酸1，4 -二環己烷酯、四（甲基）丙烯酸季戊四醇酯、三 (甲基）丙烯酸季戊四醇酯、三（甲基）丙烯酸三羥甲基丙烷 酯、三（甲基）丙烯酸三羥甲基乙烷酯、五（甲基）丙烯酸二 季戊四醇酯、六（甲基）丙烯酸季戊四醇酯、四甲基丙烯酸 1，2，3 -環己烷酯、聚胺基甲酸酯聚丙烯酸酯、聚酯聚丙烯 酸酯）；乙烯基苯及其衍生物（例如，1，4 -二乙烯基苯、2 -丙烯醯乙基-4-乙烯基苯甲酸酯、1，4-二乙烯基環己酮）；乙 烯基楓（例如，二乙烯基碉）；丙烯醯胺（例如，亞甲基雙丙 烯醯胺）和甲基丙烯醯胺。 高折射率單體之例包括雙（4-甲基丙烯醯基硫苯基）化硫 、乙烯基萘、乙烯基苯基化硫和4 -甲基丙烯氧苯基- 4’ -甲 氧苯基硫醚。 較佳者，具有聚醚作爲主鏈之聚合物是以多官能基環氧 化物作開環聚合作用而合成。 施用之後，必須利用離子化射線或加熱，聚合具有乙烯 不飽和基之單體而予固化。 如此具有乙烯不飽和基之單體可以在有光自由基起始劑 或熱自由基起始劑之中以離子化射線照射或加熱予以聚合。 因此，抗反射膜可以形成於製備含有具有乙烯不飽和基 之單體；和光自由基起始劑或熱自由基起始劑等之塗覆溶 液，最好倂同粗糙顆粒和無機塡料，施用塗覆溶液於透明 支持物上，然後以離子化射線或加熱予以聚合。 -17- 200302923 光自由基起始劑之例，包括乙醯苯、二苯甲酮、Michler 苯甲酸苯醯酯、偕胺肟酯、四甲基秋蘭姆單化硫和噻噸酮。· 使用光***型之光自由基起始劑爲特佳。光***型光自由· 基起始劑如於SaichinUVKokaGijutsu所述（第159頁’ Kazuhiro Kobo，Gijutsu Joho Kyokai Κ·Κ· 1991 出版）。 市售之光***型光自由基起始劑如由Ciba Geigy Japnn製 成之 Irgacures(651， 184， 907)〇 每100質量份之多官能基單體，最好使用自o.l至15質量0 份之光聚合起始劑，更佳自1至1 〇質~量份。 除了光聚合起始劑外，可用光敏感劑。光敏感劑之特例包 括N-丁胺、三乙基胺、三-正丁基膦、Michler酮和噻噸酮。 作爲具有二或多個乙烯不飽和基單體之一種代替物或其 另類者，交聯結構可以用可交聯之基引入至膠合劑聚合物。 -可交聯之基包括例如異氰酸基、環氧基、氮丙啶基、噁唑 烷基、醛基、羰基、聯氨基、羧基、羥甲基和活性亞甲基 。再者，可用作單體而引入交聯結構者，如乙烯基磺酸、春 各種酸酐、氰基丙烯酸酯衍生物、蜜胺、醚化羥甲基、酯 類和胺基甲酸酯和如四甲氧基矽烷之金屬醇鹽。其亦可以 使用在分解反應結果中表現可交聯性之官能基，例如阻斷 之異氰酸基。在本發明中，可交聯之基並不限於上述之化 合物’而是可以使用在官能基分解結果而呈現反應性之化 合物。 在施用之後，如此具有可交聯基之化合物須予以交聯’ 例如加熱。 -18- 200302923 爲了提高構成硬塗層之材料之折射率，最好在硬化層內 含有粒徑爲1 0 0奈米或較小之微細顆粒，較佳爲5 0奈米或 較小，製自至少一種選自包括鈦、鋁、銦、鋅、錫、銻和 鉻等之氧化物之微細顆粒包括例如Ti〇2、Al2〇3、In2〇3、 ZnO、Zn02、Sb203、ITO 和 Zr02〇 無機微細顆粒用量較佳爲1 〇至9 〇質量％，更佳爲2 〇至 8 0質量％而特佳爲3 0至6 0質量％，基於硬塗層之總質量。 爲了加強防眩性質，防止因硬塗層之干擾而致反射性質 減退’並防止不規則之顏色，在硬塗層內使用無機化合物 或有機聚合物之粗糙顆粒。例如，較好使用矽石顆粒、T i 〇 2 顆粒、A 12 〇3顆粒、可交聯之丙烯酸基顆粒、苯乙烯顆粒 、可交聯之苯乙烯顆粒、蜜胺樹脂顆粒、苯並胍胺樹脂頼 粒或可交聯之矽氧烷顆粒。考慮在防眩硬塗層塗覆溶液中 各顆粒在生產時之優良分散穩定性（與膠合劑有高親和力） 和優良之沉降穩定性（低比重），更好者是使用有機聚合物 之顆粒。在本發明中粗糙顆粒之平均粒徑爲自〇 · 3微米至 1〇.〇微米範圍內，更佳自〇·5微米至7.〇微米而再更佳爲 自1微米至6微米。關於粗糙顆粒之形狀，可用球形或不 規則者。爲g某有穩定之防眩性質，最好使用球形顆粒。其 亦可以使用二或多種型式而互不相同之顆粒。 較佳者使用具有超過硬塗層1 / 3膜厚之粒徑之粗糙顆粒 粒位分佈可用C 〇 u 11 e r計數器法或離法測定。分佈是依 顆粒數量分佈而測定。硬塗層之乾膜厚度較佳爲自2微米 至1〇微米，更佳自3至6微米之範圍內。 -19- 200302923 作爲達到防眩性質之方法，J P 2 0 0 0 - 3 2 9 9 0 5揭示一種方 法’其中形成抗反射層，然後加入防眩性質而成防眩抗反· 射膜。更特定言，施加抗反射層，然後在此方法中用壓花-輥加壓於抗反射膜。此方法也可應用於本發明之防眩光學 薄膜。在此步驟中，較佳爲施加自1公斤力/厘米至1 〇 〇 〇 公斤力/厘米之壓力，並控制溫度自25 °C至3 0 0 °C。輥輪可 製自各種材料，例如，如鐵和鋁等金屬，和塑膠。 爲了強化抗反射功能，可以使用低折射層於防眩層上以 產生防眩抗反射膜。低折射層之折射率爲自1 · 3 8至1 · 4 9 ^ ，較佳自1.38至1.44之範圍內。 在抗反射膜內，最好使低折射層滿足如下之關係（I)。 ιηλ/4χ〇.7<η1 ά1<ιηλ/4χ1 .3 ⑴ 在上式中，m爲正單數（通常爲1); nl爲低折射層之折 射率；而d 1爲低折射層之膜厚度（奈米）。 較佳者之低折射層含有可因離子化射線而交聯之含氟化 合物和無機微細塡料，使有自0.0 3至〇 · 1 5之動態磨擦係數 φ 和自9 0。至1 2 0。之對水接觸角。在低折射層中所用可交聯 之含氟聚合物包括含有全氟烷基之矽烷化合物（例如十七 氟-1，1，2,2 -四癸基）三乙氧基矽烷）和具有含氟單體與用於 給予可交聯基之另一種單體作爲建構單體而成之含氟共聚 物。 含氟單體之特例包括氟烯烴（例如氟乙烯、偏二氟乙烯、 四氟乙烯、六氟乙烯、六氟丙烯、全氟-2,2-二甲基-1，3-二 噁茂），局部或完全氟化之（甲基）丙烯酸酯衍生（例如0saka -20- 200302923 O r g . Chemical Industry 戶斤產之 Viscoat 6FM，Daikin Industries所產M-2020)和完全或局部氟化之乙烯基醚。 · 用於給予可交聯基之單體，包括例如（甲基）丙烯酸酯單 · 體之原本具有可交聯官能基於分子中者，其如甲基丙烯酸 縮水甘油基酯，和具有例如羧基、羥基、胺基或磺酸基之 (甲基）丙烯酸酯單體（例如，（甲基）丙烯酸、（甲基）丙烯酸 羥甲基酯、（甲基）丙烯酸羥烷基酯、丙烯酸烯丙基酯）。已 知後者之單體在完成共聚合之後可使引入交聯結構，如 JPA 10-25388 和 JPA 10-147739 所稱。 · 亦可以不僅使用上述具有氟單體作爲構建單元之聚合物 ;而且可與無氟單體形成共聚物。可合倂使用之單體無特 別限制。例如，可以用烯烴（例如，乙烯、丙烯、間戊二烯 ' 、氯化乙烯、偏二氯乙烯），丙烯酸酯（例如，丙烯酸甲酯 · 、丙烯酸乙酯、丙烯酸2 _乙基己基酯），甲基丙烯酸酯（例 如，甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯 、二甲基丙烯酸乙二醇酯），苯乙烯衍生物（例如，苯乙烯 φ 、二乙烯基苯、乙烯基甲苯、α -甲基苯乙烯），乙烯基醚 (例如，甲基乙烯基醚），乙烯基酯（例如，乙酸乙烯酯、丙 酸乙烯酯、肉桂酸乙烯酯），丙烯醯胺（例如，Ν -第三丁基 丙烯醯胺、Ν -環己基丙烯醯胺），甲基丙烯醯胺和丙烯腈衍 生物。 作爲用於低折射層之無機顆粒，較佳用非晶質者。其較 佳例包括製自金屬氧化物、氮化物、硫化物和鹵化物，而 金屬氧化物特別適合，金屬原子之例包括N a、Κ、M g、C a -2 1 - 200302923 、Ba、A1、Zn、Fe、Cu、Ti、Sn、I n、W、Y、Sb、Mn、200302923 Description of the invention (The description of the invention should state: the technical field to which the invention belongs, the prior art, the content, the embodiments and the drawings) (1) The technical field to which the invention belongs The present invention relates to an optical film with anti-glare properties An anti-reflective film with anti-glare properties, a polarizing plate with anti-glare properties, and a display unit containing such films. (2) Prior art In the display units such as cathode ray tubes (CRT), plasma display panels (PDP), electroluminescent displays (ELD), and liquid crystal displays (LCD), anti-dazzle (anti-dazzle) has been applied ) Film or anti-glare anti-reflection film, as the outermost layer of the display, thus preventing contrast or reflection from being reduced due to external light reflection. However, on such a display, for a black image, there is whitened black or gray when viewed obliquely. This phenomenon is indicated by "bad black fade", "black bad lift", "lost black", "whitened black" or "bad whiteness". So the reverse of the black image presented in black, "good black fades", "black improves well", "black without fading", "tightly black", "clear black" or "Good whitening" is indicated. The above phenomena are due to the fact that the uneven surface (peak / valley) structure of the film used to promote anti-glare properties enhances light scattering and the scattered light enters the original black part. This is undesirable because it reduces contrast, damages advanced images and displays, and degrades display quality. In response to this problem, it has been suggested to reduce coarse grains and roughening on the surface of the film. Although black is seen in a black image in this way, it causes another problem that the antiglare property is deteriorated. 200302923 That is, it is difficult to cause a black image in which black is seen and the antiglare property is not deteriorated. In the image display unit, on the other hand, it is necessary to reduce the size of the pixels to improve the display quality (high definition). However, if a high-definition display is viewed from an anti-glare anti-reflection film, the display quality is deeply deteriorated due to severe glare. Although it is known that this problem can be effectively solved by changing the refractive index of the adhesive and the filler to generate internal haze, this method is accompanied by several difficulties, such as the deterioration of the black's fastness, which reduces the previous contrast. And reduce the front brightness. On the other hand, it is known in quality that anti-glare properties can be reduced by improving anti-glare properties. However, if the anti-glare property is excessively strengthened, the image becomes unsightly and affects the entire display surface, so when the display surface is exposed to light, the visibility is greatly deteriorated (this phenomenon is called "white blur" ”. This is regarded as neither anti-glare film nor anti-glare anti-reflection film, so that the anti-glare property can enhance the high-definition display, so that when the black image is caused to view black, it will not cause white marks or decrease. Front contrast or front brightness. In addition, in order to provide an anti-glare optical film, one method has been studied, which involves applying an antireflection film on a support having an uneven surface, or another method, which is used for forming an uneven surface. Rough particles are added to the coating solution used to form the antireflection layer, etc. However, the disadvantage of the former method is that when the antireflection layer coating solution flows from the peak to the valley, uneven thickness of the in-plane film occurs. The anti-reflection property is obviously inferior to the coating on the smooth surface. The disadvantage of the latter method is that rough particles with anti-glare properties with a diameter of about 1 micron or larger must be buried in the thickness. In the thin film from 0.1 to 0.3 micrometers, peeling of coarse particles is caused. As a method to overcome these problems, JP-A- 1 2-3 2 9 9 0 5 discloses a method involving the formation of an anti-reflection film 200302923 Conditions for anti-glare properties. In several details, a method was proposed, including pressing an anti-reflection film with an anti-reflection layer under a engraved roller, so that unevenness was formed on the anti-reflection layer without damaging Its anti-reflection properties. However, such anti-reflection films have their shortcomings, and gradually reduce the anti-glare properties during prolonged use. Due to the foregoing reasons, the desired anti-reflection properties and film strength have not been simultaneously extended. The practical application of anti-reflection film during this period has appeared. (3) Summary of the Invention One of the items of the present invention is to provide an anti-glare optical film, so that the black to be viewed is black and presents a high degree of face-to-face ratio. Another aspect of the present invention One object is to provide an anti-glare optical film that can be installed on a high-definition display while maintaining such properties. Yet another object of the present invention is to provide an anti-glare optical film. It is enough to slightly reduce the appearance of white spots. Another object of the present invention is to provide an anti-glare optical film. Even after long-term use, the anti-glare properties remain unchanged or rarely changed, especially in the severe environment of high temperature and humidity. The original properties are not impaired. Another object of the present invention is to provide a polarizing plate and a display unit containing such an anti-glare optical film. Each of the objects of the present invention is completed as follows: (1) A thin film containing fine The anti-glare optical film with a uniform surface structure is characterized in that the proportion of those with an inclination angle of not less than 10 ° is not more than 2%, and the average pitch of each peak in a fine uneven surface is from 1 micrometer to 50 micrometers. (2 ) The anti-glare optical film according to (1), wherein the average distance between the peaks is from 1 micrometer to 20 micrometers. 200302923 (3) The anti-glare optical film according to (1) and (2), wherein The average value of the inclination angles in the regular reflection plane measured on the film surface from 1 to 2 square micrometers (μ ni 2) is from not less than 1 ° to less than 5. . (4) The anti-glare optical film according to (1) to (3), which contains an anti-reflection layer on the uppermost surface thereof. (5) The anti-glare optical film according to (1) to (3), wherein the surface of the film is subjected to embossing to roughen the film so as to have anti-glare properties. (6) The anti-glare optical film according to (5), wherein the roughness arithmetic mean 値 R percentage defined by formula (I) is not less than 30%: (I) R = Ra / Rb where Ra represents stored in After 1,000 hours in the atmosphere at 65 ° C and 95% RH (relative humidity), the arithmetic average roughness of the surface of the anti-reflection layer; and Rb represents the resistance before storage at 65 ° C and 95% RH (relative humidity). The arithmetic average roughness of the surface of the reflective layer. (7) The anti-glare optical film according to (4) to (6), wherein the anti-reflection layer is made of a low-refractive layer having a lower refractive index than the supporting substrate, and a high-refractive layer is provided on the supporting substrate and the anti-reflection Between layers, the refractive index of the high refractive layer is higher than that of the supporting substrate, and the thickness of the high refractive layer is substantially the same. (8) The anti-glare optical film according to (7), wherein a middle refractive layer is interposed between the supporting substrate and the high refractive layer, and the refractive index of the middle refractive layer is higher than that of the supporting substrate, and the refractive index of the middle refractive layer is The rate is lower than that of the high refractive layer, and the thickness of the middle refractive layer is substantially the same. (9) The anti-glare optical film according to (4) to (8), wherein the average specular reflection of the light incident at a 5 ° angle and a wavelength from 450 to 650 nm is not more than 0.5%. -9- 200302923 (10) The anti-glare optical film as described in (4) to (8), in which the average specular reflection of light incident at a 5 ° angle and a wavelength from 450 to 650 nm is not greater than 0 · 3% ° w (11) The anti-glare optical film according to (4) to (10), wherein each layer is coated with a coating composition containing a film-forming solute and at least one solvent to remove the solvent after drying, and then It is formed by curing the coating composition with heat and / or ion radiation. (1 2) The anti-glare optical film according to (8) to (11), wherein the middle refractive layer, the high refractive layer, and the low refractive layer are respectively set according to the set wavelength λ (= 500 nm) as follows (I ), (II), and (III): λ / 4χ0.80 < η1ά1 < λ / 4χ1 .00 (I) λ / 2χ0.75 < η2ά2 < λ / 2χ0.95 (II) λ / 4χ0.95 < η3ά3 < λ / 4χ1.05 (HI) where η 1 represents the refractive index of the intermediate refractive layer; d 1 represents the thickness of the intermediate refractive layer (nanometer); n2 represents the refractive index of the highly refractive layer; d2 represents the thickness of the highly refractive layer (Nano); η 3 represents the refractive index of the low refractive layer; and d 3 represents the thickness (nano) of the low refractive layer. (I3) The anti-glare optical film according to (7) to (I2), wherein the low-refractive layer is made of a fluororesin cured by heat curing or ionizing radiation. (1 4) The anti-glare optical thin film te 'according to (7) to (13), wherein the high-refractive layer is formed by coating a coating composition containing an ultrafine material containing at least one metal oxide' selected from the group consisting of The oxides of chitin, table, indium, zinc, tin and antimony; an anionic dispersant; a curable resin with a fluorene function or higher polymerizable group and a polymerization initiator. The solvent is removed by drying, and the coating composition is cured by heat and / or ionizing radiation. 0 5) The anti-glare optical film according to (7) to (1 4), wherein the low-refractive layer has a contact angle of not less than 100 ° with respect to 200302923 pure water. (1 6) The anti-glare optical film 'according to (1) to (1 5) has at least one interposed between the low-refractive layer and the transparent film substrate. (1 7) The anti-glare optical film 'according to (1) to (16) has at least one radiating layer interposed between the anti-glare layer and the transparent support. (18) A method of preparing an anti-glare optical film containing a micro-uniform surface structure provided on at least one side of a transparent film substrate, characterized in that j is embossed so that the ratio of the inclination angle of not less than 10 ° is not more than 2 % 'The average pitch of each peak in the uneven surface is from 1 micron to 50 (19) The method for preparing the anti-glare optical film as described in (1 8), wherein each average pitch is from 1 micron to 20 Microns. (2 0) The method for preparing the anti-glare optical film according to (1 8) and (19), wherein the flat P angle of the regular reflecting surface measured in the film surface of 1 to 2 square micrometers is from not less than 1 ° to less than 5 °. (21) The method for preparing an anti-glare optical film according to (18) to (20), wherein an anti-reflection layer is provided on the upper surface layer, and the surface of the anti-reflection layer receives the anti-reflection layer as described in (2 1) A method for preparing a glare optical film, wherein the defined arithmetic average roughness percentage R is not less than 30%: (I) R = Ra / Rb where Ra represents the surface of the antireflection layer stored at 65 ° C and 95% RH (relatively The arithmetic mean roughness in the atmosphere after 1,000 hours; and RB represents the calculated roughness of the layer surface before storage at 65 ° C and 9 5% RH (relative humidity). (23) As shown in (22) The preparation method of the anti-glare optical film is described, in which the hard coating layer is scattered forward without touching the surface and is in the micrometer. Among the peaks, the self-reflection is the most embossed. The embossed anti-reflection layer is then treated in a solution with a moisture content of less than 0 mass%, or in the steam of the solution, at a temperature from 60 ° C to 200 ° C. 00 to 100,000 seconds. (24) A method for preparing an anti-glare optical film containing an anti-glare layer and provided with a micro uneven surface structure on at least one side of a transparent film substrate, characterized in that the anti-glare layer receives embossing so that it is not less than 1 The ratio of the inclination angle of 0 ° is not less than 2%, and the average pitch of each peak in the fine uneven surface is from 1 micrometer to 50 micrometers. (2 5) A polarizing plate comprising two surface protection films laminated on both sides of a polarizer, characterized in that each surface protection film has at least one antiglare optical film as described in (1) to (17). (2 6) A polarizing plate containing an anti-glare optical film as at least one surface protective film, which is coated with an alkali solution and transparent before forming the anti-glare optical film as described in (1) to (17) The anti-dazzling layer is coated with an anti-dazzling optical film on the opposite side provided with the anti-dazzling layer; or after the formation, the anti-dazzling optical film is coated with an alkali solution. (27) The polarizing plate as described in (25) and (26), wherein the film other than the anti-glare optical film in each of the surface protective films is an optical compensation film having an optical compensation layer, which is Opposite to the polarizer, one surface of the surface protection film contains an optical anisotropic layer, which is a layer having negative birefringence. The surface of a dish with a discotic structural unit, the surface of the dish with a discotic structural unit is inclined to the surface of the surface protective film, and is protected by the surface of the dish with the discotic structural unit and the surface The angle formed by the surface of the film varies with the depth of the optical anisotropic layer. (2 8) A display unit having at least one antiglare 200302923 optical film as described in (丨) to (丨 7); or a polarizing plate as described in (2 5) to (27). (29) The display unit according to (28), which is a TN, STN, VA, IPS, or O C B mode transmissive, reflective, or transflective liquid crystal display unit. (30) A transmissive or semi-transmissive liquid crystal display unit having at least one polarizing plate as described in (25) to (27), characterized in that it has a polarizing separation film with a polarizing selection layer, and is inserted between the Between the polarizing plate on the side and the back surface and the backlight plate. (3 1) A surface protection plate for an organic electroluminescence (EL) display, which is provided with a λ / 4 plate and is provided in a transparent protective film, which is provided in places such as (2 5) and (27) One side of the polarizing plate is opposite to the anti-glare optical film. The basic structure of the anti-glare optical film of the present invention will be exemplified with reference to the drawings. The mode shown in Fig. 1 is an embodiment of the anti-glare optical film of the invention, which is composed of a transparent support 1, a hard coat layer 2 and a low refractive layer in this order. 4 is each particle. The hard coating layer 2 may be composed of two or more layers. The anti-glare optical film of the invention has an uneven surface structure on at least one side of the transparent film substrate, and scatters a reflected image due to a light scattering phenomenon to exhibit anti-glare properties. In the present invention, the inclination angle and its ratio are determined by the following method. That is, three vertices of a triangle having an area of 0.5 to 2 m 2 (micron square) are speculatively determined on the surface of the transparent thin film substrate. Three vertical lines extending from these vertices then intersect the measured film surface. Then, at the normal line of the triangle with three points as vertices, and the vertical line extending vertically upward from the support, the angle formed by the two lines is regarded as the angle of inclination. Measure 0.25mm2 (millimeter square) or a larger area on the substrate, divide it into triangles, and measure. Then, the ratio of the points at the inclination angle of 10 °, or the ratio above all the points measured, is determined. 4 Now, the measuring method of the tilt angle will be described in more detail. As shown in Figure 2, each vertical line extends vertically upward from three points A, B, and C on the support. The points where these vertical lines intersect the surface are regarded as A ,, B ', and C, respectively. The angle Θ between the normal Df of the triangle and the vertical line 0 'extending vertically upward from the support is regarded as the tilt angle. The measurement area on the support is preferably 0.2 5 mm2 or larger. Divide this area into triangles on the support and measure. Calculate the average 値 of each inclination angle thus measured to obtain the average inclination angle of the surface I. Although several systems are available for this measurement, an example will be described. In this case, the model SXM 5 2 0-AS 150 manufactured by Micromap (USA) was used. If the magnification of the objective lens used is (xίο), as an example, the tilt angle is measured in a unit of 0.85 micrometers and the measurement area is 0.48 mm 2. If the magnification of the objective lens is increased, the measurement unit and the measurement area are reduced. The measured data can be analyzed by software such as MAT-LAB, so the distribution of the tilt angle can be calculated. Therefore, the ratio of the inclination angle of 10 ° or more can be easily determined.丨 In the present invention, the ratio of the inclination angle of 10 ° or more is 2% or less, and more preferably 1% or less. Therefore, both the anti-glare property and the effect of making a black image look black can be exhibited. In the anti-glare optical film of the invention, the average tilt angle of the preferred one is 丨. Or Larger than 5 °. The inclination angle may have a peak at a certain angle, and may represent two or more peaks. For example, the tilt angle may be 丨. The peaks and peaks represent a ratio of 2% or less and a value of 4 at 10 ° or more. The average tilt angle. Or change it to 1.5. And 5. The peak of the peak is 10. -14-200302923 or above has a ratio of 2% or less with an average tilt angle of 6 °. Regarding the peaks and valleys of the surface, the range and height of the uneven surface can be measured by surface roughness measurement. From the average line of the film surface profile curve, draw two elevation peaks separated by 0,125 μm. A peak is defined when the curve intersects from a lower peak to one or more elevations. Then divide the measured distance by the peak count to calculate the average interval between each peak. In the present invention, the average interval (S m) between the peaks ranges from 1 micrometer to 50 micrometers, more preferably from 1 micrometer to 20 micrometers, and most preferably from 1 micrometer to 15 micrometers. More specifically, a surface roughness meter (manufactured by Kosaka Kenkyusho) of the SE-3C type can be used with a vertical magnification of 20,000 or 10,000, a truncation of 0.25, a measurement length of 2.5, and a horizontal magnification of 50 for the recorder. S m can be reduced, for example, by adding a large number of particles, having an average particle size as in the film thickness order. However, this known method causes deterioration in whiteness. In order to provide a glare-free anti-glare film in a high-definition monitor by appropriately designing only a fine uneven surface structure, it is unavoidable to lose the black color. Although both anti-glare properties and solid black can be established to some extent using internal diffusion or internal haze as described above, in this case it is inevitable that the contrast will be reduced. In the present invention, it has been found that glare can be prevented on a high-definition monitor, and the deterioration of the effect of black in seeing black images can be prevented without compromising contrast, which depends on controlling the ratio of the inclination angle of 10 ° or more 2% or less; and control Sm from 1 micrometer to 50 micrometers, or from 1 micrometer to 20 micrometers. The surface inclination angle distribution and S m can be arbitrarily controlled by appropriately selecting the diameter and number of particles in the anti-glare layer, the ratio of particles to the adhesive in the anti-glare layer, and the thickness of the dry film. The surface shape can be controlled by appropriately selecting the physical properties of the coating solution. In order to design the surface more accurately, the most suitable method is to use the embossing method mentioned above. The embossing method is detailed in JPA 2 0 0 0-3 2 9 9 0 5. That is, the desired surface shape can be obtained from setting the inclination angle distribution and S m of the embossing roller on the desired surface. However, the surface shape of the present invention can be obtained by any method without limitation. In the present invention, the refractive index of the hard coating layer is not indicated by a single number. That is, it is preferable that the hard coat layer is a layer having a non-uniform refractive index, and particles are dispersed in a material constituting the hard coat layer. Preferably, the refractive index of the material constituting the hard coat layer is in the range from 1.57 to 2.00. According to JPA 8-1 1 0 4 0 1 as an example, if a material with a high refractive index is selected from particles of 1000 nanometers or smaller, and is selected from one of the monomers having an ethylenically unsaturated group In the case of oxides of titanium, aluminum, indium, zinc, tin, antimony, and pins, the particle size is sufficiently smaller than the wavelength of light, and no scattering occurs. Therefore, such a material looks like an even substance from an optical point of view. Hard coatings can also be used as anti-glare layers. Alternatively, the anti-glare layer may be formed on the hard coating layer. Preferably, the compound used in the hard coat layer is a polymer having a saturated hydrocarbon or polyether as a main chain, and more preferably a polymer having a saturated hydrocarbon as a main chain. The preferred binder polymer is already crosslinked. Preferably, the polymer having a saturated hydrocarbon as a main chain is obtained from the polymerization of an ethylenically unsaturated monomer. In order to obtain a crosslinkable adhesive polymer, it is preferable to use two or more ethylenically unsaturated groups. monomer. In order to achieve a high refractive index, it is preferable that the monomer structure contains at least one selected from the group consisting of aromatic rings, halogen atoms other than fluorine, sulfur, phosphorus, nitrogen, and the like. -16- 200302923 monomers having two or more ethylenically unsaturated groups, including, for example, esters of polyhydric alcohols and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, diacrylate 1,4 -Dicyclohexane, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate Ester, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexane tetramethacrylate, polyurethane polyacrylate, polyester polyacrylic acid Esters); vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 2-propenylethyl-4-vinylbenzoate, 1,4-divinylcyclohexanone); Vinyl maple (eg, divinylfluorene); acrylamide (eg, methylenebisacrylamide) and methacrylamide. Examples of high refractive index monomers include bis (4-methacrylfluorenylthiophenyl) sulfide, vinylnaphthalene, vinylphenylsulfide, and 4-methacryloxyphenyl-4'-methoxybenzene Thioether. Preferably, the polymer having polyether as the main chain is synthesized by ring-opening polymerization of a polyfunctional epoxy compound. After application, it is necessary to polymerize the monomer having an ethylenically unsaturated group by ionizing radiation or heat to be cured. Such a monomer having an ethylenically unsaturated group can be polymerized by irradiation or heating with ionizing rays in a light radical initiator or a thermal radical initiator. Therefore, the anti-reflection film can be formed by preparing a coating solution containing a monomer having an ethylenically unsaturated group; and a photo radical initiator or a thermal radical initiator, etc., preferably with rough particles and inorganic materials. The coating solution is applied on a transparent support, and then polymerized by ionizing radiation or heating. -17- 200302923 Examples of photo-radical initiators include acetophenone, benzophenone, Michler benzoyl benzoate, amidoxime, tetramethylthiuram monosulfide and thioxanthone. · The use of photo-cleavable photo-radical initiators is particularly preferred. The photo-cleavable photo-free radical-based initiator is described in Saichin UVKoka Gijutsu (page 159 'Kazuhiro Kobo, published by Gijutsu Joho Kyokai KK · 1991). Commercially available photocleavable photoradical initiators, such as Irgacures (651, 184, 907) made by Ciba Geigy Japnn, are preferably used from ol to 15 parts by mass per 100 parts by mass of polyfunctional monomer. The photopolymerization initiator is more preferably from 1 to 10 parts by mass. In addition to the photopolymerization initiator, a photosensitizer can be used. Specific examples of photosensitizers include N-butylamine, triethylamine, tri-n-butylphosphine, Michler ketone and thioxanthone. As an alternative to the monomer having two or more ethylenically unsaturated groups or an alternative thereof, a crosslinked structure may be introduced into the binder polymer with a crosslinkable group. -Crosslinkable groups include, for example, isocyanato, epoxy, aziridinyl, oxazolyl, aldehyde, carbonyl, hydrazine, carboxyl, methylol and reactive methylene. Furthermore, those that can be used as monomers to introduce crosslinked structures, such as vinyl sulfonic acid, various anhydrides, cyanoacrylate derivatives, melamine, etherified methylol, esters and urethanes, and Such as metal alkoxides of tetramethoxysilane. It is also possible to use a functional group that exhibits crosslinkability in the results of the decomposition reaction, such as a blocked isocyanate group. In the present invention, the crosslinkable group is not limited to the aforementioned compound ', but a compound that exhibits reactivity as a result of the decomposition of the functional group can be used. After application, such a compound having a crosslinkable group must be crosslinked ', such as by heating. -18- 200302923 In order to increase the refractive index of the material constituting the hard coating layer, it is best to contain fine particles with a particle size of 100 nm or smaller in the hardened layer, preferably 50 nm or smaller. Fine particles selected from at least one oxide including titanium, aluminum, indium, zinc, tin, antimony, chromium, and the like include, for example, Ti02, Al203, In203, ZnO, Zn02, Sb203, ITO, and Zr02. The amount of the inorganic fine particles is preferably 10 to 90% by mass, more preferably 20 to 80% by mass and particularly preferably 30 to 60% by mass, based on the total mass of the hard coating layer. In order to enhance the anti-glare property, prevent the reflection property from deteriorating due to the interference of the hard coating layer, and prevent irregular colors, rough particles of inorganic compounds or organic polymers are used in the hard coating layer. For example, it is preferable to use silica particles, Tio2 particles, A1203 particles, crosslinkable acrylic-based particles, styrene particles, crosslinkable styrene particles, melamine resin particles, benzoguanamine Resin particles or crosslinkable silicone particles. Considering the excellent dispersion stability of the particles in the anti-glare hard coat coating solution during production (high affinity with the adhesive) and excellent sedimentation stability (low specific gravity), it is better to use particles of organic polymers . The average particle diameter of the rough particles in the present invention is in the range of from 0.3 m to 10.0 m, more preferably from 0.5 m to 7.0 m, and even more preferably from 1 m to 6 m. As for the shape of the coarse particles, spherical or irregular ones can be used. For g has stable anti-glare properties, it is best to use spherical particles. It is also possible to use two or more different types of particles. It is preferred to use rough particles having a particle diameter exceeding 1/3 of the thickness of the hard coating layer. The particle size distribution can be measured by a C o u 11 e r counter method or an ionization method. The distribution is determined by the number of particles. The dry film thickness of the hard coat layer is preferably in a range from 2 μm to 10 μm, and more preferably in a range from 3 to 6 μm. -19- 200302923 As a method for achieving anti-glare properties, J P 2 0 0 0-3 2 9 9 0 5 discloses a method ′ in which an anti-reflection layer is formed, and then anti-glare properties are added to form an anti-glare anti-reflection film. More specifically, an anti-reflection layer is applied, and then in this method, the anti-reflection film is pressed with an embossing-roller. This method can also be applied to the anti-glare optical film of the present invention. In this step, it is preferable to apply a pressure from 1 kgf / cm to 1000 kgf / cm and to control the temperature from 25 ° C to 300 ° C. Rollers can be made from a variety of materials, such as metals such as iron and aluminum, and plastic. In order to enhance the anti-reflection function, a low-refractive layer may be used on the anti-glare layer to generate an anti-glare anti-reflection film. The refractive index of the low-refractive layer is in the range from 1.38 to 1.449, preferably in the range from 1.38 to 1.44. In the antireflection film, the low-refractive layer preferably satisfies the following relationship (I). ιηλ / 4χ〇.7 < η1 ά1 < ιηλ / 4χ1 .3 ⑴ In the above formula, m is a positive singular (usually 1); nl is the refractive index of the low refractive layer; and d 1 is the film thickness of the low refractive layer (Nami). The preferred low-refractive layer contains a fluoride-containing compound and an inorganic fine aggregate that can be cross-linked by ionizing rays, so that it has a dynamic friction coefficient φ from 0.0 3 to 0.15 and from 90. To 1 2 0. Its contact angle to water. The crosslinkable fluoropolymer used in the low-refractive layer includes a silane compound containing a perfluoroalkyl group (for example, heptafluoro-1,1,2,2-tetradecyl) triethoxysilane and a A fluorinated copolymer composed of a fluoromonomer and another monomer for giving a crosslinkable group as a building monomer. Specific examples of fluorinated monomers include fluoroolefins (e.g. fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxane) , Partially or fully fluorinated (meth) acrylate derivatives (such as 0saka -20- 200302923 O rg. Chemical Industry Viscoat 6FM, Daikin Industries M-2020) and fully or partially fluorinated vinyl ether. · Monomers for imparting crosslinkable groups, including, for example, (meth) acrylate monomers · The bodies that originally had crosslinkable functionality are based on molecules such as glycidyl methacrylate, and have, for example, carboxyl groups, (Meth) acrylate monomers of hydroxyl, amine or sulfonic acid groups (eg, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate ester). It is known that the latter monomers can be introduced into a crosslinked structure after completion of copolymerization, such as JPA 10-25388 and JPA 10-147739. · It is also possible to use not only the above-mentioned polymer having a fluoromonomer as a building unit, but also to form a copolymer with a non-fluorine monomer. There are no particular restrictions on the monomers that can be used in combination. For example, olefins (eg, ethylene, propylene, piperylene ', vinyl chloride, vinylidene chloride), acrylates (eg, methyl acrylate ·, ethyl acrylate, 2-ethylhexyl acrylate) can be used , Methacrylates (for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate), styrene derivatives (for example, styrene φ, divinyl Benzene, vinyl toluene, α-methylstyrene), vinyl ethers (for example, methyl vinyl ether), vinyl esters (for example, vinyl acetate, vinyl propionate, vinyl cinnamate), acrylic acid Amines (eg, N-third butylacrylamide, N-cyclohexylacrylamide), methacrylamide, and acrylonitrile derivatives. As the inorganic particles used in the low-refractive layer, amorphous ones are preferably used. Preferred examples include metal oxides, nitrides, sulfides, and halides, and metal oxides are particularly suitable. Examples of metal atoms include Na, K, Mg, Ca-2 1-200302923, Ba, A1, Zn, Fe, Cu, Ti, Sn, I n, W, Y, Sb, Mn,

Ga、V、Nb、Ta、Ag、Si、B、Bi、Mo、Ce、Cd、Be、Pb - 和N i。所有之中以M g、C a、B和S i爲更佳。其亦可以使-用含有兩種金屬之無機化合物。特佳者爲使用二氧化矽， 亦即矽石，作爲無機化合物。 無機顆粒之平均粒徑較佳在自〇 · 〇 〇 1至〇 · 〇 2微米範圍內 ，更佳爲0 · 0 0 5至〇 · 〇 5微米。亦爲較佳者，微細顆粒之粒 徑儘可能一致（均勻分散）。 無機微細顆粒之含量，較佳自5質量％至9 0質量％，更 ® 佳自1 〇質量％至7 0質量。/〇，又更佳者自2 0質量％至5 0質 量％之範圍內，基於低折射層之全部質量。 亦爲較佳者，使用無機微小顆粒於表面處理之後。表面 ~ 處理之例包括物理表面處理，其如電漿放電和電暈放電； - 和使用耦合劑之化學表面處理。較佳者爲使用耦合劑。作 爲耦合劑者，較佳爲利用一種有機烷氧基金屬化合物（例如 鈦耦合劑、矽烷耦合劑）。如果無機微細顆粒爲矽石，則用 φ 矽烷耦合劑特別有效。 防眩薄膜、薄抗反射膜，亦即防眩光學薄膜等之各層可 以形成於諸如浸塗法、空氣刀塗法、幕塗法、輥輪塗法、 線棒塗法、印板塗法或擠押塗法（u S P 2，6 8 1，2 9 4 )等塗覆方 法。二或多層可以同時塗覆。用於同時塗覆之方法載於USP 2,761，791; 2,941，898、 3,508,947 和 3,526,528;和 Yuji Harasaki，Cotingu Kogaku，第 253 頁 ’ Asakura Shoten(1973)。 如若含有顆粒之層無任何內散射，則防眩膜與防眩抗反 -22- 200302923 射膜之朦濁度較佳在自〇 %至1 8 %，更佳自0 %至1 5 %範圍 內。 - 若在含顆粒之層中具有內散射，其較佳範圍自1 5 %至 * 8 0 %，更佳自 2 0 % 至 6 5 °/〇。 作爲透明薄膜基板者，其較佳者使用具有8 0 %或較高透 光度之塑膠膜。構成塑膠膜之聚合物，包括例如纖維素酯 (例如三乙醯基纖維素、二乙醯基纖維素、乙酸酯丁酸酯纖 維素、丙醯基纖維素、丁醯基纖維素、乙醯基丙醯基纖維 素、硝基纖維素）。聚醯胺、聚碳酸酯、聚酯（例如聚乙二 醇對酞酸酯、聚乙二醇萘二酸酯、聚· 1，4 -環己烷二亞甲基 對酞酸酯、聚乙烯-1，2 -二苯氧乙烷-4，4 二羧酸酯、聚丁二 醇對酞酸酯）、聚苯乙烯（例如間規聚苯乙烯），聚烯烴（例 ' 如聚丙烯、聚乙烯、聚甲基戊烯）和萡烯聚合物膜（例如J S R 戶斤製 Ar ton，Nippon Zen on 戶斤製 Zeonor, Zeonex) j 聚丙烯 酸樹脂膜如聚甲基丙烯酸甲酯、聚胺基甲酸酯樹脂膜、聚 醚颯薄膜、聚酯薄膜、聚碳酸酯薄膜、聚楓薄膜、聚醚薄 φ 膜、聚甲基戊烯薄膜和聚醚酮薄膜。在所有之中，纖維素 酯、聚乙二醇對酞酸酯和聚乙二醇萘二酸酯爲較佳，纖維 素酯爲更佳，而纖維素之低脂肪酸酯又更佳。「低脂肪酸」 一詞指具有6或較少碳原子之脂肪酸。較佳者之碳原子數 爲2(纖維素乙酸酯）、3-(纖維素丙酸酯）或4-(纖維素丁酸 酯）。作爲纖維素酯者，纖維素乙酸酯如二乙醯基纖維素和 三乙醯基纖維素爲較佳。也可以用混合的脂肪酸酯，其如 纖維素乙酸酯丙酸酯或纖維素乙酸酯丁酸酯。 -23- 200302923 尤其，如若本發明之抗反射膜被用於偏光板之表面保護 膜，而偏光板用於液晶顯示器單元、有機電發光顯示器單 &gt; 元等，則採用三乙醯基纖維素爲較佳。或改變之，若用本 # 發明之抗反射膜層積於玻璃基板或如平面陰極管（CRT)、電 漿顯示面板（P D P )等，則聚乙二醇對酞酸酯或聚乙二醇萘二 酸酯爲合宜。 透明支持物之透光度較佳爲不小於8 0 %，更佳者不小於 8 6 %。透明支持物之朦濁度較佳不大於2.0 %，更佳不大於 0 1 . 〇 %。透明支持物之折射率較佳自1 . 4至1 . 7。 一般而言，纖維素乙酸酯之取代程度，在1 / 3部位中之 2 -、3 -和6 -羥基並未均勻分佈，而經觀察有一傾向，在6 -位之羥基之取代程度變爲較低。在本發明中於6位之羥基 取代程度爲高於在2-和3-位羥基者。 ~ 較佳者，在6 -位之羥基有自3 0 °/。至4 0 %之比率被醯基所 取代，更佳者爲3 1 %或更多，而特佳者爲3 2 %或更多。亦 爲較佳者，在纖維素乙酸酯之6 -位，醯基取代程度在0 . 8 8 φ 或在其上。 作爲纖維素乙酸酯者，可以用獲自在J P A 1 1 - 5 8 5 1中合 成例1 ( 0 0 4 3段至0 0 4 4段），合成例2 ( 0 0 4 8至0 0 4 9段）和 合成例3 ( 0 0 5 1至0 0 5 2段）所得之纖維素乙酸酯。 其次，詳述使用纖維素乙酸酯之情形。 一般情形，纖維素乙酸酯膜是產自溶劑鑄造法。在溶劑 鑄造法中，薄膜產自於用纖維素乙酸酯在有機溶劑內之溶 液（稠狀物）。作爲有機溶劑者，一般使用鹵化烴如二氯甲 -24- 200302923 烷。可用之有機溶劑載於日本發明與創新硏究所印行之 Kokai Giho(技術公開集合）（Kogi no.2001-1745，2001 年 3 月1 5日出版，下文簡稱公開集合2 0 0 1 - 1 7 4 5 )。雖然鹵化烴 如二氯甲烷者可以使用而無任何技術問題，然而最好基於 全球環境和工作環境之觀點使用實質上無鹵化烴之有機溶 劑。「實質上無有」之表示是指含有少於5質量％ (較佳爲2 質量％)之鹵化烴於有機溶劑內。 本發明之纖維素乙酸酯薄膜可含有例如在公開集合 2 0 0 1 - 1 74 5中第15至22頁所述之各種添加劑（例如：助塑 劑、抗紫外光劑、抗氧化劑、微細顆粒、光學性質控制劑） 。作爲光學性質控制劑者，較佳使用至少有兩個芳香環之 芳香族化合物作爲阻滯作用升高劑，因而控制聚合物膜之 阻滯作用。阻滯作用升高劑之特定例子載於例如公開集合 2 0 0 1 - 1 74 5 中之 JPA 2 0 0 0 · 1 1 1 9 1 4，J P A 2 0 0 0 - 2 7 5 4 6 和 PCT/JP 00/02 6 1 9。 較佳者，在本發明中用作透明薄膜基板之纖維素乙酸酯 薄膜爲預先經表面處理。作爲表面處理者，可用電暈放電 、輝光放電、火焰處理、酸處理、鹼處理或紫外光照射。 爲提高與後述之配向膜之黏著性，特別適合用酸或鹼處理 ，亦即皂化透明支持物。如此之表面處理，可用公開集合 2001-1745，第29至30頁所述方法。其亦爲可在形成防眩 光學薄膜之後，以鹼性溶液施於光學薄膜。其亦適合使用 一種防眩光學薄膜作爲表面保護膜，在形成防眩層一面之 反面上爲已被皂化者。 -25- 200302923 纖維素乙酸酯薄膜可預作底塗。用於底塗者可爲「公開 集合2001-1745」第30至31頁所載之方法。 · 在本發明中，所求防眩性質可得自如前述在壓花輥上施 ， 壓以有效壓花。由壓花所發展之不均勻性易隨時間延長而 逐漸減小。經就此現象進一步硏究，所得結果，有如下之 發現。一種具有比較高的水吸收性之塑膠材料，其如纖維 素酯（例如，三乙醯基纖維素、二乙醯基纖維素、丙醯基纖 維素、丁醯基纖維素、乙醯基丙醯基纖維素、硝基纖維素） ，其爲可作本發明防眩光學薄膜用之透明塑膠支持物所需 ® 之材料，接受由於在大氣之中水含量和熱之相乘效應而使 不均性之減退明顯加快之作用。然而，在接受涉及抗反射 層粗化之壓花，繼以熱水或熱水蒸汽處理，抗反射膜表現 I 不均勻性表面之暫時性減小，但是在延長使用或在高溫度 · 和濕度之嚴酷環境中之後，表現不均勻性之改變有重大之 減輕。對於用於獲得具有所需不均勻表面之抗反射膜所合 適之方法，亦即以所求防眩性質爲最終產物者，此種方法 φ 是一種合適之方法，包括設計不均勻表面，在用熱水或水 蒸汽處理之前，稍大於預期由於處理而減小之不均勻性， 使在熱水或水蒸汽處理後之不均勻表面仍爲適宜。 本發明具有防眩性質之抗反射膜之基本構造將配合附圖 予以說明。 [防眩性質之具備] 第3圖舉例說明設置具有防眩性質之塗覆型抗反射薄膜 方法。第3圖內，抗反射膜（21)被壓合於抗反射層（23)上 -26- 200302923 ，其一面經過壓花輥（2 4 )和承接輥（2 5 )，使在其至少一面 備有不均勻表面而顯現防眩性質，無礙於其抗反射性質。 在薄膜厚度中之一致性爲維持抗反射性質所必需，隨光干胃 涉各層之數量和設計而定。例如，具有一低折射層、一高 折射層和一中折射層層積成λ/4η之厚度之三層設計，各層 依序起自空氣界面層，厚度中一致性之上限爲各層之± 3 % 。若厚度一致性之上限超過以上定義之範圍，則所成抗反 射膜明顯顯現劣化之抗反射性質。防眩性質之程度可由壓 φ 花步驟中之方法條件予以控制，其如薄膜表面溫度、壓力 和操作速率，與具有抗反射膜之透明支持物之動態物理性 質。然而，在較溫和條件下之壓花，在薄膜平坦性、方法 穩定性、成本等之觀點，應爲合宜。 [用熱水處理] &lt; 用熱水處理經如此壓花之防眩抗反射膜，目的在防止壓 花表面上之不均性因延長使用而減退，依壓花表面性質之 維持和經濟兩者之立場，最好在壓花後之連續程序發生效 · 力。用熱水處理可以最簡易而完成，並以使已壓花之抗反 射膜通過熱水浴而有效，其溫度保持於預定範圍之內。相 同之效果也可以藉使經壓花之抗反射膜通過含水或其蒸汽 之溶液而作用。含水溶液之例包括一種水和可與混合之溶 劑成任意比例之混合物，其如較低分子量之單價醇（甲醇、 乙醇等），較低分子量之二價醇（乙二醇等）和較低分子量之 三價醇（丙三醇）。溶液之水含量較佳不低於1 〇質量％，更 佳爲不低於2 0質量％，再更佳爲不低於5 0質量％。然而， -27- 200302923 考慮經濟、環境污染、毒性等，純水爲最合適。熱水處理 之溫度較佳自不低於6 0 °C至不高於2 0 0 °C，較佳自不低於， 7 0 C至不咼於1 9 0。(：，最佳自不低於8 0 °C至不高於1 8 0 °C - 。熱水處理之溫度較佳不高於壓花之溫度。若熱水處理之 溫度超過壓花之溫度，在已壓花之表面上之不均勻性可易 被減少，造成難以控制操作之時間。熱水處理之時間密切 關係熱水處理溫度而較佳自不小於1秒至不大於丨〇 〇，〇 〇 〇 秒。然而考量生產力等，更佳者爲自不小於2秒至不大於 1 0 0，0 0 0秒，最佳者自不小於4秒至不大於} , 〇 〇 〇秒。 &lt; 本發明之防眩抗反射膜最好展現一種如式（1)所界定不 小於3 0 %之算術平均粗糙度之持有百分比： R = R a/Rb 式⑴ 其中R A代表抗反射層表面在貯存於6 5 °c和9 5 % R Η (相對濕 度）之is境1，〇 〇 〇小時後之昇術平均粗糖度；而R Β代表ί/ι 反射層在65 °c和95 %RH(相對濕度）之環境貯存前之算術平 均粗糙度。 本發明防眩抗反射薄膜之保持百分比R較佳爲不小於 4 0 %，更佳不小於5 0 %，再更佳爲不小於8 0 %，尤其不小 於 9 0%。 [表面粗糙度] 防眩抗反射薄膜之表面粗糙度可藉分析在掃描顯微鏡下 觀察具有防眩性質之樣品之不均勻表面所得之數據予以評 估。算術平均粗糙度（Ra)是依JIS-B- 0 6 0 1評定。在本發明 中，抗反射薄膜表面之算術平均粗糙度（Ra)落在自0·05至 2微米之範圍內。Ra較佳爲自〇.〇7至丨·5微米’更佳自〇.〇9 -28- 200302923 至1.2微米，最佳自〇1至1微米。若Ra落在〇·〇5微米 以下’不能得到充份之防眩功效。若Ra超過2微米，所 成抗反射膜在外來光線照射下解析度遭受退減而且影像有 白色之閃爍。 另外’在本發明中，在整個不均表面之密集度中，具有 自1至1 0微米週期之不均勻密集度比例者，較佳不少於 1 5 % ’更佳不少於2 〇 %，再更佳不少於2 5 %，最佳不少於 3 〇 % °若此比例增加，則所成防眩性質產生更細且更高之 組織。具有自1至1 〇微米週期之不均密集度比例是用能譜 密度分析法測定。能譜密度（PSD)是以下式（2)定義。 PSP=l/A|7c/2idxJ*dy.exp{i(px + qy)}z(x，y)|2 式（2) 其中A代表掃描區域；p各q各代表水平方向內之頻率； 而z(x，y)代表影像數據。然後決定具有自1至1〇微米週期 之不均勻密集度和全部不均勻表面密集度之根方平均値 (RMS)。不均勻密集度之根方平均値（rmS)由下式（3)定義。 RMS= ^PSDdpdq 式（3) 具有自1至1 0微米週期之不均勻密集度之比例相當於由 具有自1至10微米週期之不均勻密集度之根方平均値 (RMSmo)對全部不勻勻表面密集度（RMS*部）之比率， (R M S ! _! 〇 / R M S 全部)〇 在抗反射膜表面上相鄰各峯突間之平均間距較佳自1 〇 至60微米，更佳自15至40微米，最佳自15至20微米。 由峯突之頂至凹谷之底之平均深度較佳自0.05至2微米， 更佳自0 · 1至1微米。整個防眩抗反射膜之朦濁度較佳不 大於1 5 %。整個防眩抗反射膜之反射率最好不大於2.5 %。 -29- 200302923 [抗反射膜之形成] 第4圖爲舉例說明待壓花之抗反射膜基本層結構之示意~ 剖面圖。抗反射膜包含透明支持物（211)、硬塗層（212)、中&amp; 折射層（2 1 3 )、高折射層（2 1 4 )和低折射層（2 1 5 )，依序層積 。如J P - A - 5 9 - 5 0 5 0 1所載，光學厚度，亦即在如此一種三 層抗反射膜中，中折射層、高折射層和低折射層之折射率 與厚度之乘積，較佳約爲全波長λ之四分之一，或其整數 倍。 籲 然而，爲求明瞭本發明涉及低折射率之反射率性質與反 射光色調降低，必須使中折射層、高折射層和低折射層分 別針對所設計波長λ( = 5 0 0奈米）滿足如下各關係（I)、（Π) 和（III): λ/4χ0.80&lt;η1ά1&lt;λ/4χ1 .00 (I) ' λ/2χ0.75&lt;η2ά2&lt;λ/2χ0.95 (II) λ/4χ0.95&lt;η3ά3&lt;λ/4χ1 .05 (III) 其中η 1代表中折射層之折射率；d 1代表中折射層之厚度 φ (奈米）；n2代表高折射層之折射率；d2代表高折射層之厚 度（奈米）；n3代表低折射層之折射率；且d3代表低折射層 之厚度（奈米）。另外，對於由三乙醯基纖維素（折射率：1 .49) 製成之透明支持物，必須使η 1爲自1 . 6 0至1 . 6 5，n2爲自 1.85至1.95而n3爲自1.45至1.45。其對由聚乙二醇對酞 酸酯（折射率：1 . 6 6 )製成之透明支持物，也須使η 1爲自1 . 6 5 至 1·75，η2 爲自 1.85 至 2.05，且 η3 爲自 1.35 至 1.45。 己知若上述中折射層或高折射層之材料未能選用如此之折 -30- 200302923 射率時，結合具有高於預定之折射率之層和具有低於預定 之折射率之層所成之相當薄膜，原則上可以用於形成在光 學上實質相當於具有預定折射率之中折射層或高折射層。 此原則可被用以明瞭本發明之反射率性質。「實質爲三層_ 一詞在此意指一種含有與此相當之薄膜而成之四或五層抗 反射層。 本發明之抗反射性質得自於使上述之層構造能夠滿足低 的反射率和反射光色調的減低兩者。因此’若應用於液晶 顯示單元之最上表面爲例，本發明之防眩光學薄膜能夠提 供一種具有空前髙可視性之顯示單元。因爲在5 °入射角和 _5 °之發射角，自450奈米至650奈米波長範圍取其平均 數’鏡面反射率不大於0 · 5 %，較佳不大於〇 · 3 %。外在光 線於顯示單元表面之反射所導致之可見度劣化，可以被防 止至令人滿意之水平。另外，若以本發明防眩光學薄膜應 用於液晶顯示單元，當具有高度發光之外光如室內螢光燈 者所展現之色調將略被反射於其上而爲中性和無礙。 中折射層和高折射層是塗上一種塗覆組成物而形成，包 含一種無機粒狀材料，具有高折射率；一種熱或離子化射 線固化之單體，一種起始劑和一種溶劑。以乾燥除去溶劑 ’然後以熱及/或離子化射線固化所塗材料。作爲無機粒狀材 料’最好使用一種至少含有一種金屬氧化物，選自包括Ti、 h、Zn、Sri和Sb等之氧化物之一組。如此所形成之 中折射層和高折射層展現優異之耐刮損性和黏著性，優於 以塗覆具有高折射率之聚合物溶液而乾燥所塗材料者。爲 -3 1 - 200302923 了得到分散檫令4、斗 m153;03固化後之薄膜強度等’最好如 之(甲崎酸：單：專利6,21°，8 5 8 B1所述’配用多官能 散劑，於涂嘴 土 △ 1千棊）丙烯酸酯分 目文^ k塗覆組成物內。 尤其’筒折射_與 射層取好以塗覆含有無機粒狀材 成物，粒狀材料$小A 枓之塗覆組 枓至少含有一種金屬氧化物，選自包括Ti、 ZD h、Zb U等之氧化物之一組；—種起始劑^ 一種溶劑。以齡悴胳+ L如Hj和 草乙k除去溶劑，然後用熱和/或 化所塗材料。. 丁化射線固 無機 好自1 奈米， 分散成 料之平 見光因 和中折 低折 射線以 0.03 至 度，更 高於〇 不利。 則所成 粒狀材料卞迅 一 之ΐ均粒徑以Coulter計數器法量測得最 〇 &amp;米。若無機粒狀材料之平均粒徑不大於i 所成無機粒狀材料具有太大的比表面積，且因而在 用中…、足夠之安定性而不利。反之，若無機粒狀材 均粒徑不/丨、纟八， &lt; 1 〇 0奈米，則所成無機粒狀材料使可 折射率與膠合劑不同而生散射致爲不利。高折射層 S t朦濁度最好不大於3 %，更佳不大於1 %。 射層較佳制 衣目一種含氟化合物，爲用熱或以離子化 〃、、射而固化。該可固化材料之動態磨擦係數較佳自 0 · 1 5可固化材料對於純水之接觸角較佳不小於1 〇 〇 佳自 100¾ $ 1 2 〇度。若可固化材料之動態磨擦係數 .1 5，則所此 〃既固化材料在其表面承受擦拭時被刮損而 若可固仆料 【材料對於純水之接觸角落在低於1 0 0度， 可固化材Μ @ = 一 Θ又手印、油污等黏附而對防污性立場有所 -32- 200302923 不利。 該可固化含氟聚合化合物包括含全氟烷基之矽烷化合物 (例如（十七氟- ι，ι，2,2 -四癸基）三乙氧基矽烷）。可固化含氟 聚合化合物之其他實例包括一種含氟共聚物，含有成爲結 構單元之含氟單體和提供可交聯基之單體。 含氟單體單元之特例包括氟烯烴（例如氟乙烯、偏二氟乙 烯、四氟乙烯、六氟乙烯、六氟丙烯、全氟·2,2 -二甲基-1，3_ 二噁唑），局部或全部氟化之（甲基）丙烯酸烷酯衍生物（例 如 Piscoat 6FM(OSAKA ORGANIC CHEMICAL INDUSTRY LTD.所產），M-2020(DAKIIN INDUSTRIES LTD.生產），完 全或局部氟化之乙烯基醚等。在此等含氟單體單元中，較 佳者爲六氟丙烯，因其具有低折射率且可被輕易處理。 用於提供可交聯基之單體，包括例如在分子內具有可交 聯官能基之（甲基）丙烯酸酯單體，如縮水甘油基甲基丙燒 酸酯。用於提供可交聯基之其他單體實例，包括具有殘基 、控基、胺基、礦酸基、等之（甲基）丙燃酸酯單體（例如 (甲基）丙烯酸、羥甲基（甲基）丙烯酸酯、羥烷基（甲基）丙烯 酸酯、嫌丙基丙燒酸酯）。在JP-A-10-25388和jp-A-10-147739 中所揭示，後者各單體能夠具有被交聯之結構而在共聚合 之後配置於其中。所以，後者各單體特別有用。 若以氟化合物配置於低折射層中，其更佳者爲使用一種 具有可交聯官能基之含氟聚合物，其在塗覆後進行交聯。 聚合物之父聯最好用熱或離子化射線。可熱交聯之含氟聚 合物實例包括Opstar JN7 2 2 8 (JSR公司所產熱可交聯之含 -33 - 200302923 氟聚合物之商名，具有1.42之折射率和36質量％之含氟量）。 作爲離子化射線可交聯之含氟聚合物，最好使用一種在 其側鏈中具有乙烯型不飽和基之聚合物。此種具有乙烯型 不飽和基之聚合物，其交聯作用可用離子化射線照射而完 成。更爲合適者爲在程序當中加入光自由基聚合起始劑。 光自由基聚合起始劑之實例包括乙醯苯、二苯甲酮、 M i c h 1 e r苯甲酸苯醯酯、戊肟酯、四甲基秋蘭姆化單硫、噻 噸酮等。 尤其，光可***之光自由基聚合起始劑爲較佳。關於光 可***之光自由基聚合起始劑之詳情，可參考Kazuhira Takabo 之 ’’Saishin UV Kouka Gijutsu(現代紫夕f 光固化技 術）’’，Gijutsu Joho Kyokai 5 第 159 頁，1991。 市售光可***之光自由基聚合起始劑包括例如 IRGACURE 651、184 和 907(Ciba Geigy Japan Ltd.所產）。 光聚合起始劑最好用量爲自0.1至15重量份，更佳自1 至10重量份，基於含氟聚合物100重量份。 除光聚合起始劑，可用光敏感劑，光敏感劑之特例包括 正丁胺、三乙基胺、三正丁基膦、和Michler酮和噻噸酮。 離子化射線可交聯之含氟聚合物之其他實例包括一種在 側鏈中具有酸觸媒可交聯之官能基之聚合物，和一種離子 化射線產酸劑的結合；和一種以具有鹼觸媒反應性官能基 於其側鏈中之聚合物，與一種離子化射線產鹼劑的結合。 前者較佳。作爲酸觸媒可交聯之官能基，最好用環氧基。 作爲離子化射線產酸劑者最好用一種光產酸劑。光產酸劑 -34- 200302923 之實例包括三芳基銃鹽、和二芳基碘鏺鹽。 光產酸劑之用量，基於1 〇 〇重量份之含氟聚合物，較佳 用自0.1至15重量份，更佳自1至10重量份。 作爲離子化射線者可用紫外光（UV)、光線、電子射線、 輻射等，較佳者爲光線。在光線中紫外光較佳。紫外光源 之較佳者包括金屬鹵化物燈。高電壓汞蒸汽燈等，較佳爲 金屬鹵化物燈。U V之發光和劑量較佳爲儘可能大，只要無 基本上之負面效果，且較佳分別爲自5 0至1，0 0 0毫瓦/厘 米2和自200至1000毫焦/厘米2，更佳自150至600毫焦 /厘米2和自250至900毫焦/厘米2。 更佳者，以無機粒狀化合物分散於含氟聚合物內以提高 膜之強度。 關於含氟聚合物之物理性質，含氟聚合物展現自〇 . 〇 3至 〇 . 1 5之動態磨擦係數，和對於水爲自9 0至1 2 0 °之接觸角。 此中可用者不僅上述具有含氟單體作爲結構單元之聚合 物，而且也包括無氟原子之單體所成之共聚物。可用於與 前述聚合物結合之單體單元無特別限制。在此可用單體單 元之實例包括烯烴（乙烯丙烯、間戊二烯、氯乙烯、偏二氯 乙烯等），丙烯酸酯（丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁 酯、丙烯酸2 -乙基己基酯等），甲基丙烯酸酯（甲基丙烯酸 甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、二甲基丙烯酸 乙烯甘油等），苯乙烯衍生物（苯乙烯、二乙烯基苯、乙烯 基甲苯、α -甲基苯乙烯等），乙烯基醚（甲基乙烯基醚等）， 乙烯基酯（例如乙酸乙烯酯、丙酸乙烯酯、肉桂酸乙烯酯等） -3 5- 200302923 ，丙_醯胺（N-第三丁基丙烯醯胺、N-環己基丙烯醯胺等） ，甲基丙烯酸胺和丙燒腈衍生物。此等單體單兀揭不於 JP-A-10-25388 和 JP-A-10-147739。 作爲一種降低動態磨擦係數以提供耐刮損性之手段’可 以引用一種用於改善滑溜性之共聚物單元。一種引入聚二 甲基矽氧烷節段進入支鏈之方法，揭示於JP-A- 1 1 - 2 2 8 6 3 1 。此方法爲特別適合° 含氟樹脂用於形成低折射層者最好含有一種粒狀之S i 氧化物，在用以賦與本身之耐刮損性之前，配入其中。從 抗反射性質之立場，含氟樹脂之折射率最好盡可能低。然 而，如果降低含氟樹脂之折射率，含氟樹脂之耐刮損性變 差。因此，使含氟樹脂之折射率和粒狀S i氧化物加入量最 適化，耐刮損性和低折射率最好達於平衡。 作爲粒狀S i氧化物者，以矽石溶膠分散於市售之有機溶 劑，可以配入於塗覆組成物。或钨 N古隹七r/7 _【 4爲，以巾售之矽石粉末分 散於有機溶劑內。 爲求降低防眩光學薄膜之折 射率充份降低。具有不小於1 包括諸如氟化鎂和氟化鈣等無 含量之含氟化合物之有機材料 在薄膜被置於顯示單元之最外 與基板間之黏合性不足而欠缺 損性立場，低折射層最好含有 於其中之耦合劑。 射率，必須使低折射層之折 之折射率之材料，其實例 機材料；和諸如具有大的氟 。然而，此等含氟化合物， 面時’由於其頑強性不足和 耐刮損性。因it卜，# U此，基於耐刮 〜種無機粒狀材料 u料和一種配 -36- 200302923 作爲被配入於低折射餍 之⑴、檢k狀材料，較佳使用具有 低折射率者。無機粒狀材料 4之折射午較佳爲自1 · 3 0至1 · 4 9 。無機粒狀材料之實例包 估妙石和氣化鎂，尤其爲矽石。 該無機粒狀材料之zp &amp; ^ ^ 二k傻$父佳爲自〇〇〇1至〇·2微米 ’更佳自0.001至〇 〇5微 认 Q米。k子之粒徑最好盡可能一致 (單分散性）。 S亥無機粒狀材料，加J Θ 口入裏較佳自5至90質量份，更佳自 10至70質量份，特住白 和彳土自1 0至5 〇質量份，基於低折射層 之總重量 在本發明中， 〃切* 1土者’該無機粒狀材料在使用前接受 姐里作爲表面處理之方法，可用物理表面處理法， ®水放電處理和電暈放電處理；或化學表面處理法， 其如用耦合劑處理女 ^ &amp;此等處理方法中，較好爲用耦合劑 之處理方法。作段鈕八 F局稱θ劑者，較佳用一種有機烷氧金屬化 合物（例如鈦耦合割 r, 1=1 ^、矽烷耦合劑），包括如通式（1 - 1 )之化 口物以此則该無機粒狀材料爲矽石、矽烷耦合劑處理爲 特別有效。由诵寸 式（1 -1)之化合物爲較佳。 (Rl)『Si(〇R2)n 式（1-1) 宜中 R 1代表_链〜 一 〜植經過取代或未經取代之烷基或芳香基；R2 代表經過取代或条 一未取代之烷基或醯基；m代表自〇至3之 整數；且 n什李 自1至4之整數，其條件是m與η之和爲 由式（1 - 1 )所件连1 代表化合物說明如後。 在通式（1 - π由 η ! ’ R代表已取代或未取代之烷基或芳香基 4 200302923 。烷基例如包括甲基、乙基、丙基、異丙基、丁基、三級· 丁基、二級丁基、己基、癸基、十六烷基等。烷基較佳爲 Ci-Cso，更佳爲Ci-CM，尤其烷基。芳香基包括苯 基、萘基等，尤以苯基爲此等芳香基中之較佳者。 取代基無特別限制。在此可用之取代基例如包含鹵素 (氟、氯、溴等），羥基、硫醇基、異丙基、丙基、三級丁 基等），芳香基（苯基、萘基等），芳香雜環基（呋喃基、吡 唑基、吡啶基等），烷氧基（甲氧基、乙氧基、異丙氧基、 己氧基寺）’方氧基（苯氧基％ )*院硫基（甲硫基、乙硫基 等），芳硫基（苯硫基等），烯基（乙烯基、1-丙烯基等），烷 氧甲矽烷基（三甲氧甲矽烷基、三乙氧甲矽烷基等），醯氧 基（乙醯氧基、丙醯氧基、甲基丙烯氧基等），烷氧羰基（甲 氧羰基、乙氧羰基等），芳氧羰基（苯氧羰基等），氨基甲醯 基（氨基甲醯基、N -甲基氨基甲醯基、N，N-二甲基氨基甲醯 基、N -甲基-N -辛基氨基甲醯基等），醯胺基（乙醯胺基、苯 醯胺基、丙醯胺基、甲基丙烯胺基等）等。 在此等取代基中較合適者爲羥基、硫醇基、羧基、環氧 基、烷基、烷氧甲矽烷基、醯氧基、和醯胺基。在此等取 代基中特別合適者爲環氧基，可聚合之醯氧基（丙烯醯氧基 、甲基丙烯醯氧基），和可聚合之醯胺基（丙烯胺基、甲基 丙烯胺基）。此等取代基可被進一步取代。 R2代表已取代或未取代之烷基或醯基。烷基、醯基和其 上各取代基之說明與R1者相同。R2較佳爲未取代之烷基 或未取代之醯基，尤其是未取代之烷基。 -38- 200302923 註腳m代表自0至3之整數。註腳η代表自1至4之整 數。m和η之和爲4。若有多個R1或R2，R1或R2之多個 可爲相同或不同。註腳m較佳爲0.1或2，尤其爲1。 式（1 - 1)所代表之化合物之特例列出如下，但本發明不受 其限制。Ga, V, Nb, Ta, Ag, Si, B, Bi, Mo, Ce, Cd, Be, Pb-and Ni. Among them, M g, Ca, B, and Si are more preferable. It is also possible to use inorganic compounds containing two metals. Particularly preferred is the use of silicon dioxide, also known as silica, as an inorganic compound. The average particle diameter of the inorganic particles is preferably in a range of from 0.001 to 2.0 μm, and more preferably from 0.05 to 0.05 μm. It is also preferable that the particle diameter of the fine particles is as uniform as possible (uniformly dispersed). The content of the inorganic fine particles is preferably from 5 mass% to 90 mass%, and more preferably from 10 mass% to 70 mass. / 〇, and more preferably from 20% by mass to 50% by mass, based on the total mass of the low refractive layer. It is also preferable to use inorganic fine particles after surface treatment. Examples of surface treatment include physical surface treatments such as plasma discharge and corona discharge;-and chemical surface treatment using a coupling agent. Preferably, a coupling agent is used. As the coupling agent, an organic alkoxy metal compound (for example, a titanium coupling agent, a silane coupling agent) is preferably used. If the inorganic fine particles are silica, a φ silane coupling agent is particularly effective. Various layers of anti-glare film, thin anti-reflection film, that is, anti-glare optical film, can be formed on, for example, dip coating method, air knife coating method, curtain coating method, roller coating method, wire rod coating method, printing plate coating method or Extrusion coating method (u SP 2, 6 8 1, 2 9 4) and other coating methods. Two or more layers can be applied simultaneously. Methods for simultaneous coating are described in USP 2,761,791; 2,941,898, 3,508,947 and 3,526,528; and Yuji Harasaki, Cotingu Kogaku, p. 253 'Asakura Shoten (1973). If the layer containing particles does not have any internal scattering, the haze of the anti-glare film and anti-glare anti--22-200302923 film is preferably from 0% to 18%, more preferably from 0% to 15%. Inside. -If there is internal scattering in the particle-containing layer, its preferred range is from 15% to * 80%, more preferably from 20% to 65 ° / 〇. As the transparent thin film substrate, it is preferable to use a plastic film having a light transmittance of 80% or higher. Polymers that make up plastic films include, for example, cellulose esters (e.g., triethyl cellulose, diethyl cellulose, acetate cellulose butyrate, propyl cellulose, butyl cellulose, acetyl cellulose Propionyl cellulose, nitrocellulose). Polyamide, polycarbonate, polyester (such as polyethylene glycol terephthalate, polyethylene glycol naphthalate, poly 1,4-cyclohexanedimethylene terephthalate, polyethylene 1,2-diphenoxyethane-4,4 dicarboxylate, polybutylene terephthalate), polystyrene (such as syndiotactic polystyrene), polyolefin (such as polypropylene, Polyethylene, polymethylpentene) and pinene polymer films (eg Ar ton by JSR, Zeonor, Zepion by Nippon Zen on) j Polyacrylic resin films such as polymethyl methacrylate, polyamine Formate resin film, polyether fluorene film, polyester film, polycarbonate film, polymaple film, polyether thin φ film, polymethylpentene film, and polyetherketone film. Among all, cellulose esters, polyethylene glycol terephthalate and polyethylene glycol naphthalate are preferred, cellulose esters are more preferred, and cellulose low fatty acid esters are more preferred. The term "low fatty acid" refers to fatty acids having 6 or fewer carbon atoms. The preferred carbon number is 2 (cellulose acetate), 3- (cellulose propionate) or 4- (cellulose butyrate). As the cellulose ester, cellulose acetates such as diethylfluorenyl cellulose and triethylfluorenyl cellulose are preferred. It is also possible to use mixed fatty acid esters, such as cellulose acetate propionate or cellulose acetate butyrate. -23- 200302923 In particular, if the antireflection film of the present invention is used as a surface protection film of a polarizing plate, and the polarizing plate is used for a liquid crystal display unit, an organic electroluminescent display unit, etc., triethyl cellulose is used. Is better. Or change it, if the anti-reflection film of this invention is laminated on a glass substrate or such as a flat cathode tube (CRT), a plasma display panel (PDP), etc., then polyethylene glycol terephthalate or polyethylene glycol Naphthalate is suitable. The transmittance of the transparent support is preferably not less than 80%, and more preferably not less than 86%. The haze of the transparent support is preferably not more than 2.0%, more preferably not more than 0.1%. The refractive index of the transparent support is preferably from 1.4 to 1.7. Generally speaking, the degree of substitution of cellulose acetate is not uniformly distributed in the 1/3 position of the 2-, 3-, and 6-hydroxyl groups, and it has been observed that the degree of substitution of the 6-hydroxyl group changes. Is lower. The degree of substitution of the hydroxyl group at the 6-position in the present invention is higher than those at the 2- and 3-position hydroxyl groups. ~ More preferably, the hydroxyl group at the 6-position is from 30 ° /. The ratio of 40% to 40% is replaced by fluorenyl, more preferably 31% or more, and more preferably 32% or more. Also preferred, at the 6-position of cellulose acetate, the degree of fluorenyl substitution is 0.88 φ or above. As the cellulose acetate, those obtained from Synthesis Example 1 (0 0 4 3 to 0 0 4 4) in JPA 1 1-5 8 5 1 and Synthesis Example 2 (0 0 4 8 to 0 0 4 Step 9) and cellulose acetate obtained in Synthesis Example 3 (Steps 0 05 1 to 0 2 05). Next, the case where cellulose acetate is used is described in detail. In general, cellulose acetate films are produced by solvent casting. In the solvent casting method, the film is produced from a solution (thick substance) of cellulose acetate in an organic solvent. As the organic solvent, a halogenated hydrocarbon such as dichloromethyl-24-200302923 is generally used. Available organic solvents are listed in Kokai Giho (Technical Publication Collection) (Kogi no. 2001-1745, published on March 15, 2001, published by the Japan Institute of Invention and Innovation, hereinafter referred to as Public Collection 2 0 0 1-1 7 4 5). Although halogenated hydrocarbons such as dichloromethane can be used without any technical problems, it is preferable to use organic solvents which are substantially free of halogenated hydrocarbons from the viewpoint of global environment and working environment. The expression "substantially absent" means that the halogenated hydrocarbon is contained in an organic solvent in an amount of less than 5% by mass (preferably 2% by mass). The cellulose acetate film of the present invention may contain various additives (for example, plasticizers, anti-ultraviolet light agents, antioxidants, fines, etc.) as described in pages 15 to 22 of the public collection 2000 1-1 74 5 Particle, optical property control agent). As the optical property control agent, it is preferable to use an aromatic compound having at least two aromatic rings as a blocking effect increasing agent, and thus control the blocking effect of the polymer film. Specific examples of blocking effect elevating agents are contained in, for example, JPA 2 0 0 1-1 74 5 in the public collection 2 0 0 0 · 1 1 9 1 4, JPA 2 0 0 0-2 7 5 4 6 and PCT / JP 00/02 6 1 9. Preferably, the cellulose acetate film used as the transparent film substrate in the present invention is surface-treated in advance. As a surface treatment, corona discharge, glow discharge, flame treatment, acid treatment, alkali treatment or ultraviolet light irradiation can be used. In order to improve the adhesion with the alignment film described later, it is particularly suitable for treatment with acid or alkali, that is, saponified transparent support. For such surface treatment, the method described in Public Collection 2001-1745, pages 29 to 30 can be used. It can also be applied to the optical film in an alkaline solution after the anti-glare optical film is formed. It is also suitable to use an anti-glare optical film as a surface protection film, which is saponified on the side opposite to the side where the anti-glare layer is formed. -25- 200302923 Cellulose acetate film can be pre-primed. For primers, the methods described on pages 30 to 31 of "Open Collection 2001-1745" may be used. In the present invention, the desired anti-glare properties can be obtained by applying on an embossing roller as described above, and pressing to effectively emboss. The unevenness developed by embossing tends to decrease gradually with time. After further investigation of this phenomenon, the results obtained are as follows. A plastic material with relatively high water absorption, such as cellulose esters (for example, triethyl cellulose, diethyl cellulose, propyl cellulose, butyl cellulose, ethoxypropyl cellulose Cellulose, nitrocellulose), which is the material required for the transparent plastic support of the anti-glare optical film of the present invention, accepts heterogeneity due to the multiplicative effect of water content and heat in the atmosphere The effect of the decrease is significantly accelerated. However, after receiving embossing involving roughening of the anti-reflection layer and subsequent treatment with hot water or hot water steam, the anti-reflection film exhibits a temporary decrease in the unevenness of the surface, but after extended use or at high temperatures and humidity After the harsh environment, the change in performance unevenness has been significantly reduced. A suitable method for obtaining an anti-reflection film having a desired uneven surface, that is, the desired anti-glare property is the final product. This method φ is a suitable method, including designing an uneven surface. Before the hot water or steam treatment, the unevenness that is expected to decrease due to the treatment is slightly larger, so that the uneven surface after the hot water or steam treatment is still suitable. The basic structure of the anti-reflection film with anti-glare properties of the present invention will be described with reference to the drawings. [Equipment of anti-glare properties] Fig. 3 illustrates an example of a method for providing a coating type anti-reflection film having anti-glare properties. In FIG. 3, the anti-reflection film (21) is laminated on the anti-reflection layer (23) -26- 200302923, and one side of the anti-reflection film (21) passes through the embossing roller (2 4) and the receiving roller (2 5) so as to be on at least one side thereof. It has an uneven surface to show anti-glare properties without affecting its anti-reflection properties. Consistency in film thickness is necessary to maintain anti-reflective properties, depending on the number and design of layers involved in photodrying. For example, a three-layer design with a low-refractive layer, a high-refractive layer, and a medium-refractive layer laminated to a thickness of λ / 4η, each layer starting from the air interface layer in sequence, and the upper limit of consistency in thickness is ± 3 of each layer %. If the upper limit of the thickness consistency exceeds the above-defined range, the resulting anti-reflection film obviously exhibits deteriorated anti-reflection properties. The degree of anti-glare properties can be controlled by the method conditions in the pressing step, such as the film surface temperature, pressure, and operating rate, and the dynamic physical properties of a transparent support with an anti-reflection film. However, embossing under milder conditions should be appropriate in terms of film flatness, method stability, and cost. [Treatment with hot water] &lt; Treatment of the anti-glare anti-reflection film with such embossing with hot water, the purpose is to prevent the unevenness on the embossed surface from diminishing due to prolonged use. It is best to take effect on the continuous process after embossing. Treatment with hot water can be done most easily and effectively by passing the embossed anti-reflection film through a hot water bath, keeping its temperature within a predetermined range. The same effect can also be achieved by embossing the antireflection film through a solution containing water or its vapor. Examples of aqueous solutions include a mixture of water and a solvent that can be mixed in any proportion, such as lower molecular weight monovalent alcohols (methanol, ethanol, etc.), lower molecular weight divalent alcohols (ethylene glycol, etc.), and lower Molecular weight trivalent alcohol (glycerol). The water content of the solution is preferably not less than 10% by mass, more preferably not less than 20% by mass, and even more preferably not less than 50% by mass. However, -27- 200302923 Considering economy, environmental pollution, toxicity, etc., pure water is the most suitable. The temperature of the hot water treatment is preferably from not lower than 60 ° C to not higher than 200 ° C, more preferably from not lower than 7 0 C to not lower than 19 0. (: The best temperature is not less than 80 ° C to not more than 180 ° C-. The temperature of hot water treatment is preferably not higher than the temperature of embossing. If the temperature of hot water treatment exceeds the temperature of embossing The unevenness on the embossed surface can be easily reduced, making it difficult to control the operation time. The time of hot water treatment is closely related to the temperature of the hot water treatment and preferably from not less than 1 second to not more than 〇〇〇, 〇〇〇 seconds. However, considering productivity and the like, the better is from no less than 2 seconds to no more than 10,000 seconds, and the best is from no less than 4 seconds to no more than}, 0.00 seconds. & Lt The anti-glare anti-reflection film of the present invention preferably exhibits a holding percentage of an arithmetic average roughness not less than 30% as defined by formula (1): R = R a / Rb Formula ⑴ where RA represents the surface of the anti-reflection layer The average crude sugar content after 1,000 hours of storage at 65 ° C and 95% R Η (relative humidity); and R Β stands for // ι reflective layer at 65 ° c and 95% RH (relative humidity) arithmetic average roughness before environmental storage. The retention percentage R of the anti-glare anti-reflection film of the present invention is preferably not less than 40% More preferably, it is not less than 50%, even more preferably is not less than 80%, especially not less than 90%. [Surface roughness] The surface roughness of anti-glare anti-reflection film can be analyzed by scanning microscope to have anti-glare. The data obtained from the uneven surface of the sample is evaluated. The arithmetic average roughness (Ra) is evaluated in accordance with JIS-B-0 601. In the present invention, the arithmetic average roughness (Ra) of the surface of the antireflection film falls. In the range from 0.05 to 2 micrometers. Ra is preferably from 0.07 to 5 micrometers, more preferably from 0.09 -28 to 200302923 to 1.2 micrometers, most preferably from 0.01 to 1 micrometer. If Ra falls below 0.05 micrometers, no sufficient anti-glare effect can be obtained. If Ra exceeds 2 micrometers, the resolution of the resulting antireflection film is reduced under external light and the image has white flicker. In addition 'In the present invention, in the density of the entire uneven surface, the ratio of the uneven density from 1 to 10 micron period is preferably not less than 15%', more preferably not less than 20%, It is more preferably not less than 25%, and the best is not less than 30%. If this ratio is increased, the anti-glare properties will be produced. Finer and taller tissues. The proportion of uneven density with a period from 1 to 10 microns is determined by spectral density analysis. The spectral density (PSD) is defined by the following formula (2). PSP = 1 / A | 7c / 2idxJ * dy.exp {i (px + qy)} z (x, y) | 2 Formula (2) where A represents the scanning area; each q of p represents the frequency in the horizontal direction; and z (x, y) represents the image data. Then the root mean square error (RMS) of the uneven density with a period from 1 to 10 microns and the overall uneven surface density is determined. The root mean 値 (rmS) of the uneven density is defined by the following formula (3). RMS = ^ PSDdpdq Eq. (3) The proportion of uneven density with a period from 1 to 10 microns is equivalent to the root mean square (RMSmo) of all unevenness with a uniform density from 1 to 10 microns. Ratio of uniform surface density (RMS *), (RMS! _! 〇 / RMS all) 〇 average distance between adjacent peaks on the surface of the antireflection film is preferably from 10 to 60 microns, more preferably 15 to 40 microns, preferably from 15 to 20 microns. The average depth from the top of the peak to the bottom of the valley is preferably from 0.05 to 2 micrometers, more preferably from 0.1 to 1 micrometer. The haze of the entire anti-glare anti-reflection film is preferably not more than 15%. The reflectivity of the entire anti-glare anti-reflection film is preferably not more than 2.5%. -29- 200302923 [Formation of anti-reflection film] Figure 4 is a schematic ~ cross-sectional view illustrating the basic layer structure of the anti-reflection film to be embossed. The anti-reflection film includes a transparent support (211), a hard coat layer (212), a medium & refractive layer (2 1 3), a high refractive layer (2 1 4), and a low refractive layer (2 1 5). product. As stated in JP-A-5 9-5 0 5 01, the optical thickness, that is, the product of the refractive index and thickness of the middle refractive layer, high refractive layer, and low refractive layer in such a three-layer antireflection film, It is preferably about a quarter of the full wavelength λ, or an integer multiple thereof. However, in order to understand the reflectivity properties of the present invention with respect to the low refractive index and the reduction of the reflected light tone, the middle refractive layer, the high refractive layer, and the low refractive layer must satisfy the designed wavelength λ (= 50 nm) respectively. The following relationships (I), (Π), and (III): λ / 4χ0.80 &lt; η1ά1 &lt; λ / 4χ1 .00 (I) 'λ / 2χ0.75 &lt; η2ά2 &lt; λ / 2χ0.95 (II) λ / 4χ0.95 &lt; η3ά3 &lt; λ / 4χ1 .05 (III) where η 1 represents the refractive index of the middle refractive layer; d 1 represents the thickness φ (nanometer) of the middle refractive layer; n2 represents the refractive index of the high refractive layer; d2 represents The thickness of the high refractive layer (nanometer); n3 represents the refractive index of the low refractive layer; and d3 represents the thickness (nanometer) of the low refractive layer. In addition, for a transparent support made of triethylfluorenyl cellulose (refractive index: 1.49), it is necessary to make η 1 from 1.60 to 1.65, n2 from 1.85 to 1.95 and n3 to From 1.45 to 1.45. For a transparent support made of polyethylene glycol terephthalate (refractive index: 1.6), it is also necessary to make η 1 from 1.65 to 1.75 and η2 from 1.85 to 2.05, And η3 is from 1.35 to 1.45. It is known that if the material of the above-mentioned medium-refractive layer or high-refractive layer fails to use such a discount, it is a combination of a layer having a higher refractive index and a layer having a lower refractive index when the emissivity is -30-200302923. Quite a thin film, in principle, can be used to form an optically equivalent to a middle refractive layer or a high refractive layer having a predetermined refractive index. This principle can be used to clarify the reflectivity properties of the present invention. "The term is essentially three layers_ means here an anti-reflective layer comprising four or five layers containing equivalent films. The anti-reflective properties of the present invention are derived from enabling the above-mentioned layer structure to meet low reflectance And the reduction of the color tone of the reflected light. Therefore, 'if applied to the uppermost surface of a liquid crystal display unit as an example, the anti-glare optical film of the present invention can provide a display unit with unprecedented visibility. Because at 5 ° incident angle and _ The emission angle is 5 °, and the average value is taken from the wavelength range of 450 nm to 650 nm. The specular reflectance is not more than 0.5%, preferably not more than 0.3%. The reflection of external light on the surface of the display unit The deterioration of visibility caused by this can be prevented to a satisfactory level. In addition, if the anti-glare optical film of the present invention is applied to a liquid crystal display unit, the hue exhibited by those who have a high degree of light emission such as indoor fluorescent lamps will be slightly It is reflected on it to be neutral and unobstructed. The medium refractive layer and the high refractive layer are formed by coating a coating composition, and include an inorganic granular material with a high refractive index; a heat or ion Radiation-curable monomer, an initiator and a solvent. The solvent is dried to remove the solvent, and then the coated material is cured with heat and / or ionizing radiation. As the inorganic particulate material, it is preferable to use a material containing at least one metal oxide, It is selected from the group consisting of oxides of Ti, h, Zn, Sri, Sb, etc. The middle refractive layer and the high refractive layer thus formed exhibit excellent scratch resistance and adhesion, which is superior to coating with high refractive index. The polymer solution is dried at the rate of the polymer solution. It is -3 1-200302923. It is best to get the dispersion film 4, m153; 03 film strength after curing, etc. (Mazaki acid: Mono: Patent 6,21 °, 8 5 8 B1 'with a multifunctional powder, in the coating mouth soil △ 1 thousand 棊) acrylic ester sub-item ^ k coating composition. In particular, the tube refraction_ and the coating is taken for coating Contains inorganic granular material, granular material $ 小 A 枓 Coating group 枓 contains at least one metal oxide selected from the group consisting of oxides of Ti, ZD h, Zb U, etc .; ^ A solvent. Remove the solvent by age + L such as Hj and Cao, then use heat and / Or chemically coated materials. Dinghua ray solid inorganic is good from 1 nanometer, and the flat material of the dispersed material has a low refractive index of 0.03 to degrees, higher than 0. It is not good. The granulated material is 卞The average particle size of Xunyizhi is measured by Coulter counter method. The maximum particle size is measured by the Coulter counter method. If the average particle size of the inorganic granular material is not greater than i, the inorganic granular material has a large specific surface area, and is therefore in use. …, Sufficient stability is not favorable. Conversely, if the average particle size of the inorganic granular material is not / 丨, 纟, and <100 nm, the resulting inorganic granular material makes the refractive index different from the adhesive. It is disadvantageous to generate scattering. The haze of the high refractive layer St is preferably not more than 3%, more preferably not more than 1%. The radiation layer is preferably a fluorine-containing compound for clothing. It is cured by heat or ionization. The dynamic friction coefficient of the curable material is preferably from 0 · 15 and the contact angle of the curable material to pure water is preferably not less than 100 °, and preferably from 100 ¾ $ 12 °. If the dynamic friction coefficient of the curable material is .15, then the cured material is scratched when the surface is subjected to wiping, and if the curable material [the contact angle of the material to pure water is below 100 degrees, Curable material M @ = Θ and fingerprints, oil stains, etc. are adhered, which is unfavorable to anti-fouling position. The curable fluorine-containing polymer compound includes a perfluoroalkyl group-containing silane compound (for example, (heptadecafluoro-ι, ι, 2,2-tetradecyl) triethoxysilane). Other examples of the curable fluorine-containing polymer compound include a fluorine-containing copolymer containing a fluorine-containing monomer that becomes a structural unit and a monomer that provides a crosslinkable group. Specific examples of fluorinated monomer units include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro · 2,2-dimethyl-1,3_dioxazole) , Partially or fully fluorinated alkyl (meth) acrylate derivatives (such as Piscoat 6FM (produced by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), M-2020 (produced by DAKIIN INDUSTRIES LTD.), Fully or partially fluorinated vinyl Ether, etc. Among these fluorine-containing monomer units, hexafluoropropylene is preferred because it has a low refractive index and can be easily processed. Monomers for providing a crosslinkable group include, for example, having Crosslinkable functional group (meth) acrylate monomers, such as glycidyl methyl propionate. Examples of other monomers used to provide crosslinkable groups include residues, control groups, amine groups, (Meth) propionate monomers such as (meth) acrylic acid, hydroxymethyl (meth) acrylate, hydroxyalkyl (meth) acrylate, methacrylic acid, etc. Ester). As disclosed in JP-A-10-25388 and jp-A-10-147739, each of the latter monomers can have The crosslinked structure is disposed in the copolymer after copolymerization. Therefore, the latter monomers are particularly useful. If a fluorine compound is disposed in the low refractive layer, it is more preferable to use a fluorine-containing compound having a crosslinkable functional group Polymer, which is crosslinked after coating. The parent of the polymer is preferably heat or ionized. Examples of fluoropolymers that can be thermally crosslinked include Opstar JN7 2 2 8 (The heat produced by JSR Corporation can be crosslinked. Lianzhi-33-200302923 Commercial name of fluoropolymer, which has a refractive index of 1.42 and a fluorine content of 36% by mass). As a fluoropolymer that can be crosslinked by ionizing rays, it is best to use one of its side chains. A polymer having an ethylenically unsaturated group. The cross-linking effect of this polymer with an ethylenically unsaturated group can be completed by irradiation with ionizing rays. It is more appropriate to add a photoradical polymerization initiation in the program. Examples of the photo-radical polymerization initiator include acetophenone, benzophenone, Mich 1 er benzoate, pentoxime, tetramethylthiuram monosulfide, thioxanthone, and the like. In particular, photo-cleavable light radical polymerization For the details of the photo-cleavable photo-radical polymerization initiator, please refer to "Saishin UV Kouka Gijutsu (Modern Purple Nightflight Curing Technology)" by Kazuhira Takabo, Gijutsu Joho Kyokai 5 p.159 1991. Commercially available photo-cleavable photo-radical polymerization initiators include, for example, IRGACURE 651, 184, and 907 (produced by Ciba Geigy Japan Ltd.). The photo-polymerization initiator is preferably used in an amount of from 0.1 to 15 parts by weight, More preferably from 1 to 10 parts by weight, based on 100 parts by weight of the fluoropolymer. In addition to the photopolymerization initiator, a photosensitizer can be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, and Michler ketone and thioxanthone. Other examples of ionizable radiation-crosslinkable fluoropolymers include a polymer having an acid catalyst crosslinkable functional group in a side chain, and a combination of an ionizing radiation acid generator; and a base having an alkali The catalyst-reactive function is based on a polymer in its side chain combined with an ionizing ray alkali generator. The former is better. As the crosslinkable functional group of the acid catalyst, an epoxy group is preferably used. As the ionizing ray acid generator, a photoacid generator is preferably used. Examples of the photoacid generator -34- 200302923 include a triarylsulfonium salt, and a diaryliodonium salt. The amount of the photoacid generator is preferably from 0.1 to 15 parts by weight, more preferably from 1 to 10 parts by weight based on 100 parts by weight of the fluoropolymer. As the ionizing ray, ultraviolet light (UV), light, electron rays, radiation, etc. can be used, and light is preferred. Ultraviolet light is preferred in the light. Preferred UV light sources include metal halide lamps. A high-voltage mercury vapor lamp or the like is preferably a metal halide lamp. The luminescence and dose of UV are preferably as large as possible, as long as there are no substantial negative effects, and preferably from 50 to 1,000 mW / cm2 and from 200 to 1000 mJ / cm2, respectively. More preferably from 150 to 600 mJ / cm2 and from 250 to 900 mJ / cm2. More preferably, an inorganic particulate compound is dispersed in the fluoropolymer to increase the strength of the film. Regarding the physical properties of the fluoropolymer, the fluoropolymer exhibits a dynamic friction coefficient from 0.03 to 0.15, and a contact angle from 90 to 120 ° for water. Usable among them are not only the above-mentioned polymer having a fluorine-containing monomer as a structural unit, but also a copolymer made of a monomer having no fluorine atom. The monomer unit that can be used in combination with the aforementioned polymer is not particularly limited. Examples of usable monomer units include olefins (ethylene propylene, piperylene, vinyl chloride, vinylidene chloride, etc.), acrylates (methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate Esters, etc.), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, vinyl glycerol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, ethylene Methyl toluene, α-methylstyrene, etc.), vinyl ether (methyl vinyl ether, etc.), vinyl esters (such as vinyl acetate, vinyl propionate, vinyl cinnamate, etc.) -3 5- 200302923, Propylamine (N-third butylpropenylamine, N-cyclohexylpropenylamine, etc.), methacrylic acid amine and propionitrile derivatives. These monomers are not disclosed in JP-A-10-25388 and JP-A-10-147739. As a means for reducing the coefficient of dynamic friction to provide scratch resistance ', a copolymer unit for improving slippage can be cited. A method for introducing a polydimethylsiloxane segment into a branch chain is disclosed in JP-A- 1 1-2 2 8 6 3 1. This method is particularly suitable for those who use a fluororesin to form a low-refractive layer. It preferably contains a granular Si oxide, which is blended into it before it is used to impart its own scratch resistance. From the standpoint of anti-reflection properties, the refractive index of the fluororesin is preferably as low as possible. However, if the refractive index of the fluororesin is lowered, the scratch resistance of the fluororesin becomes poor. Therefore, the refractive index of the fluororesin and the amount of particulate Si oxide are optimized, and the scratch resistance and low refractive index are preferably balanced. As the particulate Si oxide, a silica sol is dispersed in a commercially available organic solvent, and it can be formulated into a coating composition. Or Tungsten N Gully Qi r / 7 _ [4 is, the silica powder sold as a towel is dispersed in an organic solvent. In order to reduce the refractive index of the anti-glare optical film, it is sufficiently reduced. Organic materials with a content of not less than 1 including non-content fluorinated compounds such as magnesium fluoride and calcium fluoride when the thin film is placed on the outermost side of the display unit and the substrate are insufficient in adhesion and lack a defect position, the low refractive layer is the most Good coupling agent contained in it. The emissivity must be the refractive index of the low-refractive layer material, examples of which are organic materials; and such as those with large fluorine. However, these fluorine-containing compounds are not effective due to their insufficient tenacity and scratch resistance. Because it is ## this, based on scratch-resistant ~ a kind of inorganic granular material and a compound -36- 200302923 as a low-refractive index, k-shaped material, preferably with a low refractive index . The refractive index of the inorganic granular material 4 is preferably from 1.30 to 1.49. Examples of inorganic granular materials include Miaoshi and fumed magnesium, especially silica. The zp & ^ ^ of the inorganic granular material is preferably from 0.001 to 0.2 microns, and more preferably from 0.001 to 0.05 micrometers. The particle size of k is preferably as uniform as possible (monodispersity). In the case of inorganic granular materials, J Θ is more preferably from 5 to 90 parts by mass, more preferably from 10 to 70 parts by mass, and from 10 to 50 parts by mass based on the low refractive layer. Total weight In the present invention, 〃 切 * 1 soiler 'The inorganic granular material is treated as a surface treatment method before use. Physical surface treatment, water discharge treatment and corona discharge treatment can be used; or chemical A surface treatment method, such as a treatment method using a coupling agent, is preferably a treatment method using a coupling agent. For those who are called θ agent in Section F, it is better to use an organic alkoxy metal compound (such as titanium coupling r, 1 = 1 ^, silane coupling agent), including chemical compounds such as the general formula (1-1) In this way, the inorganic granular material is particularly effective when treated with silica and a silane coupling agent. Compounds of formula (1 -1) are preferred. (Rl) "Si (〇R2) n Formula (1-1) Preferably, R 1 represents a _ chain ~ 1 ~ a substituted or unsubstituted alkyl or aromatic group; R 2 represents a substituted or unsubstituted Alkyl or fluorenyl; m represents an integer from 0 to 3; and n is an integer from 1 to 4, provided that the sum of m and η is represented by the formula (1-1) where 1 represents the compound. Rear. In the general formula (1-π, η! 'R represents a substituted or unsubstituted alkyl or aromatic group 4 200302923. The alkyl group includes, for example, methyl, ethyl, propyl, isopropyl, butyl, tertiary · Butyl, secondary butyl, hexyl, decyl, cetyl, etc. The alkyl group is preferably Ci-Cso, more preferably Ci-CM, especially alkyl. The aromatic group includes phenyl, naphthyl, etc., especially Phenyl is preferred among these aromatic groups. Substituents are not particularly limited. Usable substituents include, for example, halogen (fluorine, chlorine, bromine, etc.), hydroxyl, thiol, isopropyl, and propyl. , Tertiary butyl, etc.), aromatic groups (phenyl, naphthyl, etc.), aromatic heterocyclic groups (furanyl, pyrazolyl, pyridyl, etc.), alkoxy (methoxy, ethoxy, isopropyl (Oxy, hexyloxy)) 'square oxy (phenoxy%) * thiol (methylthio, ethylthio, etc.), arylthio (phenylthio, etc.), alkenyl (vinyl, 1 -Propenyl, etc.), alkoxysilyl (trimethoxysilyl, triethoxysilyl, etc.), alkoxy (ethoxy, propionyl, methacryloxy, etc.), alkoxy Oxycarbonyl Methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl (phenoxycarbonyl, etc.), carbamate (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl) , N-methyl-N-octylcarbamidine, etc.), amido (acetamido, benzamido, propylamido, methacrylamido, etc.) and the like. Among these substituents, a hydroxyl group, a thiol group, a carboxyl group, an epoxy group, an alkyl group, an alkoxysilyl group, a fluorenyloxy group, and a fluorenylamino group are more suitable. Particularly suitable among these substituents are epoxy groups, polymerizable fluorenyl groups (propylene fluorenyloxy group, methacryl fluorenyl group), and polymerizable fluorenyl amino groups (acrylamino group, methacrylamine) base). These substituents may be further substituted. R2 represents a substituted or unsubstituted alkyl or fluorenyl group. The descriptions of the alkyl group, the fluorenyl group and the substituents thereon are the same as those of R1. R2 is preferably an unsubstituted alkyl group or an unsubstituted fluorenyl group, especially an unsubstituted alkyl group. -38- 200302923 Footnote m represents an integer from 0 to 3. The footnote η represents an integer from 1 to 4. The sum of m and η is 4. If there are multiple R1 or R2, multiple of R1 or R2 may be the same or different. The footnote m is preferably 0.1 or 2, especially 1. Specific examples of the compound represented by the formula (1-1) are listed below, but the present invention is not limited thereto.

-39- 200302923 (1) (C細)4 一 Si (2) (C3H7〇)4 - Si (3) (i-C3H7〇)4 - Si (4) (CH3C〇2&gt;4 - Si (5) (CH3C〇2)2 - Si - (OC2Hb)2 (6) CH3 - Si - (OC2H6)3 (7) C2H5 - Si - (0〇2Ηδ)3 (8) t-C4H9 - Si—(OCH3)3 (9)-39- 200302923 (1) (C fine) 4 -Si (2) (C3H7〇) 4-Si (3) (i-C3H7〇) 4-Si (4) (CH3C〇2 &gt; 4-Si (5) (CH3C〇2) 2-Si-(OC2Hb) 2 (6) CH3-Si-(OC2H6) 3 (7) C2H5-Si-(0〇2Ηδ) 3 (8) t-C4H9-Si-(OCH3) 3 (9)

(ίο) (11) (12)(ίο) (11) (12)

CHrSi -（OCH3)3 •CH 厂 Si-(0CH3)3 -CH2〇CH2CHrSi - (OCH3)3 -CH2CH2CHrSi-(OCH3)3 CH2CH2CH2-Si-(OC2H5)3CHrSi-(OCH3) 3 • CH Plant Si- (0CH3) 3 -CH2〇CH2CHrSi-(OCH3) 3 -CH2CH2CHrSi- (OCH3) 3 CH2CH2CH2-Si- (OC2H5) 3

-40- (13) 200302923 (14) CA-^/CH2(O2CHrSi-(0CH3)3 75 0 (15) CA-\^CH2OCH2CH2CIVSi-(OC2H5)3-40- (13) 200302923 (14) CA-^ / CH2 (O2CHrSi- (0CH3) 3 75 0 (15) CA-\ ^ CH2OCH2CH2CIVSi- (OC2H5) 3

(16) C3F7CH2CH2-Si-(OC2H5)3 (17) C6Fi3CH2CH2-Si-(OC2H5)3 (18) co2ch2ch2ch2-sh〇ch3)3 (19) _/CH3 C02CH2CH2CHrSi-(0CH3)3 (2 0)(16) C3F7CH2CH2-Si- (OC2H5) 3 (17) C6Fi3CH2CH2-Si- (OC2H5) 3 (18) co2ch2ch2ch2-sh〇ch3) 3 (19) _ / CH3 C02CH2CH2CHrSi- (0CH3) 3 (2 0)

=\ C02CH2CHrSi-(0CH3)3 (2 1) C02CH2CH2CH2CHrSi-(0C2H5)3 CH2CHrSi-(OCH3)3 -4 1- (22) 200302923 (2 3) f^Y-CHrSi-(OCH3)3= \ C02CH2CHrSi- (0CH3) 3 (2 1) C02CH2CH2CH2CHrSi- (0C2H5) 3 CH2CHrSi- (OCH3) 3 -4 1- (22) 200302923 (2 3) f ^ Y-CHrSi- (OCH3) 3

(24) (25) HO - C-CH2CHrSi-(0CH3)3 0 (26) NH2CH2CH2CH2 - Si - (0 CH3)3 (27) HS - CH2CH2CH2—Si - (OCH3)3 (28) ch2och2ch2-sh〇ch3)3 (29) 々~〇—CH2〇CH2CH「Si 一 (0CH3)3 (3 0) (CH3〇)3 ~ Si - CH2CH2CH2CH2 - Si - (OCH3)3 -42- 200302923 (3 1) (CH3〇)3 - Si - CH2 CH2CH2CH2CH2CH2-Si - (〇CH3)3 (32) (CH3〇)2 - Si - CH2CH2CH2CH2 - Si - (OCH3)3(24) (25) HO-C-CH2CHrSi- (0CH3) 3 0 (26) NH2CH2CH2CH2-Si-(0 CH3) 3 (27) HS-CH2CH2CH2—Si-(OCH3) 3 (28) ch2och2ch2-sh〇ch3 ) 3 (29) 々 ~ 〇-CH2〇CH2CH 「Si- (0CH3) 3 (3 0) (CH3〇) 3 ~ Si-CH2CH2CH2CH2-Si-(OCH3) 3 -42- 200302923 (3 1) (CH3〇 ) 3-Si-CH2 CH2CH2CH2CH2CH2-Si-(〇CH3) 3 (32) (CH3〇) 2-Si-CH2CH2CH2CH2-Si-(OCH3) 3

I I CHs CH3 (33) C0NHCH2CH2CHrSi-(0CH3)2 (34) /CH3 SC0NHCHXHXHrSi-(0CHJ, (3 5) CO-N—CH2CH2CHrSi-(0CH3)： CH, (3 6) C〇-NHCH2CH2CH2CH2-Si-(0CH3). (3 7) C〇-NHCH2CH2CHrSi-(0CH3), CH, CH20CH2CH2 )2—Si-(OCH3)2 -43- (38) (39)200302923 -CH2OCH2CH2-Si-(OCH3)2 CH, (40) HO-C-CH2CH2CH2-Si-(OCH3)5II I ( 0 CH, (41) CH20CH2CH2 )2—Si-(0CH3), (42) C〇2CH2CH2CH2 )2—Si-(OCH3)2 (43) CH2=CH - Si - (OCH3)3 (44) CH2=CH - Si—(OCH3)3 ch3 (45) C02CH2CH2CHrSi-(OCH,), CH, -44- 200302923 (46) &lt;^h&quot;SH〇CH3〉3 · * (47) C02CH2CH2CHrSi-(0CH3)2 ό (48) HS - CH2CH2CH2 - Si - (OCHs)2 I · CHs 在适些特例中之特別適合者爲化合物（1 )、（ 1 2 )、（ 1 8 )和 (19)〇 式；U -1)之彳匕合物可以用於待配入於低折射層內之無機 k爿犬材*料之表面處_，使在製備低折射層塗覆溶液之前， 預先有效作表面處_。然而，在本發明中，其係特別適合 在低折射層塗覆溶液之製備當中，將通式（1 - 1 )之化合物加 至塗覆浴液內。式（1-1)化合物之加入量爲自0.5至1，000 φ 貞里％ ’較佳自5荽900質量。/〇，更佳自50至700質量％: ’基於無機k狀材料。在此程序中，過量之矽烷耦合劑最 好在塗覆和乾燥步驟蒸發。 在含有如此之無機粒狀材料之低折射層內，無機粒狀材 料較佳具有一種二維之網狀結構。第5圖表示從層之上方 觀看之二維網狀結構。二維網狀結構指示一種具有孔洞7 之結構如第5圖所示，於無機材料之原始粒子8在使塗層 乾燥之程序中之分佈不均所發生。「空洞7」一詞在此所用 •45- 200302923 是指無機粒狀林&amp;、f 抖8存在於低折射層，即使有，無機粒狀 材料之密度比_ ^ , ^ r 板d k小5 0倍以上。在二維結構中之網絡· 可以是不連繪。+ 如此之網狀結構之實例見於第6圖。此結_ 構在光學顯微_、掃描電子顯微鏡（sem)等之下可被確認。 在一較佳具M例中’：維網狀結構具有自0.3至1，〇〇〇 微米2之平均 _ . t _ 二洞面積，更k自1至I 0 0微米2。二維網狀 結構之空洞面稽0/ ,女齡β 、 貝/〇(在整個面積內空洞之比例）爲自4〇至 9 0 %，更佳自 S ίΊ 目至80%。平均空洞面積和空洞面積％可用 分析光學顯微照片^議照片而決定。在此狀況中網狀結省 構爲不連續如第6圖所示’槪略之平均空洞面積可以在不 連續網絡之延伸上假設想像中之網絡而予決定。 所認知者爲所形成之無機粒狀材料之二維網狀結構成爲 微細粗糙劑之角色以提供耐刮損性之明顯改善。然而，其 機轉爲未知。另外，形成本發明無機粒狀材料之二維網狀 結構之機轉爲未知。其所需要者僅在於結果形成如此之一 種結構。 防眩光學薄膜可另含有一硬塗層、一向前散射層、一抗&lt; 靜電層、一底塗層和一保護層設置於其中。 硬塗層較佳爲設置以提供透明薄膜基板之耐刮損性。硬 塗層亦提高透明薄膜基板對上層之黏著性。硬塗層較佳形 成於以適當加入一種無機塡料，其如矽石和礬土至具有寡 聚物之組成中’寡聚物則如多官能基之丙烯基單體、胺基 甲酸酯丙烯酸酯和環氧丙烯酸酯以及各種溶於溶劑內之聚 合起始劑’將如此所得之塗覆組成物施加於透明薄膜基板， -46- 200302923 乾燥所塗材料以除去溶劑，然後以熱及/或離子化射線固化 所塗材料。 在本發明防眩光學薄膜內，向前散射層較佳爲設置而提 供改善視角效果於當垂直或水平傾斜被加於液晶顯示單元 上之防眩光學薄膜之情形。以分散具有不同折射率之各種 粒子於,上述硬塗層內，則硬塗層也被當作向前散射層。 在防眩光學薄膜內之各層可以形成於浸塗法、氣刀塗法 、幕塗法、輥輪塗法、線棒塗法、印塗法、微印塗法或擠 壓塗法（美國專利2，6 8 1，3 9 4 )。微印塗法和印塗法因能減低 濕塗量至最小而消除乾燥不均勻性而較合宜。印塗法在厚 度橫向一致性之立場而言爲特別合宜。二或多層可以同時 施加。對於同時塗覆之方法細節，可參考美國專利 2,761，791、2,941，898、3,508,947 和 3,526,528 等；和 Yuj i Harasaki 之 ’’Kotingu Kougaku(塗覆工程）’’，第 253 頁， Asakura Shoten， 1973 。 如果防眩光學薄膜被用作偏光板各表面保護膜之一，則 必須使透明薄膜基板接受用鹼皂化於其與抗反射層相反之 一面。用於鹼皂化之特別手法可選自於如下兩種方法。方 法（1 )因能夠在用於一般用途之三乙醯基纖維素膜之同一 步驟而生效而爲較佳。然而方法（1)可能不利於鹼皂化，延 伸至透明薄膜基板之抗反射膜一面，造成透明薄膜基板表 面之鹼水解，以致劣化並在於其表面被遺留之皂化溶液沾 污。因此，方法（2)雖涉及特定步驟而仍合宜。 方法（1):包括浸漬具有抗反射層形成於其上之透明薄膜基 -47- 200302923 板於鹼溶液內，至少一次，皂化其背後表面。 方法（2):包括在形成抗反射膜於透明薄膜基板上之前或之^ 後，施用鹼溶液至抗反射膜反面防眩光學薄膜之一面，然 · 後使所塗材料接受加熱，用水淸洗及/或使中和，僅膜之背 面被皂化。 若用於顯示單元，本發明防眩光學薄膜最好位於顯示器 之最外面，例如，設置一壓感黏著層。若三乙醯基纖維素 被用作透明薄膜基板，則用三乙醯基纖維素爲保護膜以保 護偏光板之偏光層。因此，最好依成本觀點使用本發明防 ® 眩光學薄膜作爲如此之保護膜。 較佳者，本發明之防眩光學薄膜被用於偏光板表面保護 膜之可見一面。除防眩光學薄膜以外之薄膜爲光學補償薄 膜，含有光學非等方向層於與偏光板相反之表面保護膜之 一面。此種光學非等方向層爲由具有碟形結構單元且有負 的雙拆射之化合物所製成之一層。其較佳者，在碟形結構 單元之碟面向表面保護膜之面傾斜，且在碟形結構單元之 φ 碟面與表面保護膜面之間的夾角隨光學非等方向層之深度 方向改變。 較佳者，光學非等方向層由碟形液晶化合物製成。碟形 液晶化合物之例包括由C· Destrade等人在Mol· Cryst.第 71卷，第111頁（198 1)所硏究報導之苯衍生物；C. Destr ad e 等人在Mol· Cryst·第122卷，第141頁（1985)，和在 Physics Letter，A.第78卷，第82頁（1990)所硏究報導之 三平基苯衍生物；B. Kohne等人在Angew. Chem·，第96 -48- 200302923 卷，第7 0頁（1 9 8 4 )所硏究報導之環己烷衍生物；和J · Μ · Lehn 等人在 J. Chem. Commun·，第 1974 頁（1985)所硏究 和 Zhang 等人在 J. Am. C hem. Soc.第 116 卷，第 2655 頁 ( 1 9 94 )所硏究而報導之Aza-cr own和苯乙炔巨環。 一般而言，碟形液晶化合物具有一種結構，在其中此化 合物於其分子中被當作母核，被線形取代基如線形烷基、 烷氧基或經取代之苯醯氧基等以徑向圍繞，因而表現液晶 性質。然而，本發明並不限於此例，只要分子本身具有單 軸性質而能給予限定之配向。 在本發明中，不必使由液晶化合物製成之光學非等方向 層中之「液晶化合物」，在構成本發明橢圓偏光板之光學非 等方向層內具有液晶性質。亦即，低分子量之碟形液晶化 合物可以具有例如一種因熱或光而反應之基，因熱或光而 行聚合或交聯作用，產生不具液晶性質之聚合物，因而形 成一種光學上的非等方向層。 碟形液晶化合物之較佳例載於JPA 8 - 5 02 0 6。 在構成本發明橢圓偏光板之光學非等方向層中，其較佳 者，碟形液晶化合物之碟面傾斜至透明支持物面，且在其 碟與透明支持物之面間之夾角隨光學非等方向層之深度方 向改變。 碟形液晶化合物之碟面角度（傾斜角）通常隨光學非等方 向層深度方向中之距離之增加，從光學非等方向之底部起 而增加或減少。較佳爲使傾斜角隨距離之增加而加大。傾 斜角改變之實例包括連續加大、連續減小、間歇加大、間 •49- 200302923 歇 減 小 渉 及 達 加 大 和 連 續 減 小 的 改 變 和 涉 及 減 小 與 加 大 的 間 歇 改 變 〇 間 歇 改 變 在 深 度 方 向 中 含 有傾斜角表現 /fnr Μ 改 變 之 區 域 〇 較 佳 者 ， 傾 斜 角 之 增 減 雖 然 包 含 不 變 區 域 y 但 係 — 個 整 體 〇 其 更 佳 者 5 傾 斜 角 以 整 體 而 連 續 改 變 者 爲 更 佳 〇 光 學 非 等 方 向 靥 般 可 以 獲 自 於 施 用 以 碟 形 液 晶 化 合 物 和 其 他 化 合 物 於 溶 劑 中 所 成 之 溶 液 至 配 向 膜 上 乾 燥 然 後 加 熱 至 形 成 碟 形 向 列 相 之 溫 度 &gt; 然 後 於 維 持 配 向 狀 態 (亦即碟形向列相）之中予以冷卻 〇 或 爲 J 防 眩 光 學 薄, 膜 可 以 獲 白 於 以 碟 形 液晶化合物與其他化合物（與其合倂， 例 如 ， 可 聚 合 之 單 體 \ 光聚合起始劑）於溶劑中所成之溶液， 施 加 於 配 向 膜 上 乾 燥 然 後 加 熱 至 形 成 碟 形 向 列 相 之 溫 度 然 後 使 聚 合 (例1如紫外光照象 &quot; 〇 用 於: 本 發 明 中 使 碟 形 液 晶 化 合 物 成 碟 形 向 列 相 之 轉 移 溫 度 較 佳 在 白 70 至 3 0 0 °C 範 圍 內 更 佳 7〇至 1 7 0°C 〇 在 透 明 支 持 物 側 之 光 學 非 等 方 向 層 之 傾 斜 角 __ 般 可 以 被 控 制 於 選 擇 適 當 碟 形 液 晶 化 合 物 或 配 向 膜 材 料 y 或 選 擇II CHs CH3 (33) C0NHCH2CH2CHrSi- (0CH3) 2 (34) / CH3 SC0NHCHXHXHrSi- (0CHJ, (3 5) CO-N-CH2CH2CHrSi- (0CH3): CH, (3 6) C〇-NHCH2CH2CH2CH2-Si- ( 0CH3). (3 7) Co-NHCH2CH2CHrSi- (0CH3), CH, CH20CH2CH2) 2-Si- (OCH3) 2 -43- (38) (39) 200302923 -CH2OCH2CH2-Si- (OCH3) 2 CH, ( 40) HO-C-CH2CH2CH2-Si- (OCH3) 5II I (0 CH, (41) CH20CH2CH2) 2-Si- (0CH3), (42) C〇2CH2CH2CH2) 2-Si- (OCH3) 2 (43) CH2 = CH-Si-(OCH3) 3 (44) CH2 = CH-Si— (OCH3) 3 ch3 (45) C02CH2CH2CHrSi- (OCH,), CH, -44- 200302923 (46) &lt; ^ h &quot; SH〇 CH3〉 3 · * (47) C02CH2CH2CHrSi- (0CH3) 2 ό (48) HS-CH2CH2CH2-Si-(OCHs) 2 I · CHs Particularly suitable in some special cases are compounds (1), (1 2) Formulas of (1), (18) and (19); U-1) can be used at the surface of inorganic materials to be formulated in the low-refractive layer, so that low-refraction can be prepared. Before the layer coating solution, the surface is effectively prepared in advance. However, in the present invention, it is particularly suitable for adding a compound of the general formula (1-1) to the coating bath during the preparation of the low-refractive layer coating solution. The amount of the compound of the formula (1-1) to be added is from 0.5 to 1,000? / 〇, more preferably from 50 to 700 mass%: 'Based on an inorganic k-like material. In this procedure, excess silane coupling agent is preferably evaporated during the coating and drying steps. In the low-refractive layer containing such an inorganic granular material, the inorganic granular material preferably has a two-dimensional network structure. Figure 5 shows the two-dimensional network structure viewed from above the layers. The two-dimensional network structure indicates that a structure having pores 7 as shown in Fig. 5 occurs in the uneven distribution of the primary particles 8 of the inorganic material in the process of drying the coating. The term "void 7" is used here. • 45-200302923 refers to the inorganic granular forest & f jitter 8 exists in the low refractive layer. Even if there is, the density of the inorganic granular material is smaller than _ ^, ^ r plate dk 5 0 times or more. Networks in a two-dimensional structure can be unconnected. + An example of such a mesh structure is shown in Figure 6. This structure can be confirmed under optical microscopy, scanning electron microscope (sem), etc. In a preferred example, the dimensional network structure has an average _. T _ 2 hole area from 0.3 to 1,000 μm 2, and more preferably from 1 to 100 μm 2. The cavity surface of the two-dimensional network structure is 0 /, female age β, bei / 0 (the proportion of voids in the entire area) is from 40 to 90%, and more preferably from 80% to 80%. The average void area and% void area can be determined by analyzing optical micrographs and photographs. In this case, the mesh structure is discontinuous. As shown in Fig. 6, the approximate average void area can be determined by assuming an imagined network on the extension of the discontinuous network. It is recognized that the two-dimensional network structure of the formed inorganic granular material acts as a fine roughening agent to provide a marked improvement in scratch resistance. However, the opportunity turned unknown. In addition, the mechanism for forming the two-dimensional network structure of the inorganic granular material of the present invention is unknown. What is needed is only the result of such a structure. The anti-glare optical film may further include a hard coating layer, a forward scattering layer, an anti-static layer, an undercoat layer, and a protective layer disposed therein. The hard coat layer is preferably provided to provide scratch resistance of the transparent film substrate. The hard coating also improves the adhesion of the transparent film substrate to the upper layer. The hard coat layer is preferably formed by appropriately adding an inorganic filler, such as silica and alumina to the composition having oligomers. The oligomers are, for example, polyfunctional propylene monomers, urethane acrylic acid. Esters and epoxy acrylates and various polymerization initiators dissolved in a solvent 'apply the coating composition thus obtained to a transparent film substrate, -46- 200302923 dry the applied material to remove the solvent, and then heat and / or Ionizing radiation cures the coated material. In the anti-glare optical film of the present invention, the forward scattering layer is preferably provided to provide an effect of improving viewing angle in the case of an anti-glare optical film which is added to the liquid crystal display unit when vertical or horizontal tilt is applied. To disperse various particles with different refractive indices in the hard coating layer, the hard coating layer is also used as a forward scattering layer. Each layer in the anti-glare optical film can be formed by a dip coating method, an air knife coating method, a curtain coating method, a roll coating method, a wire rod coating method, a printing coating method, a micro-printing coating method, or an extrusion coating method (US patent 2, 6 8 1, 3 9 4). The micro-printing method and the printing method are more suitable because they can reduce the amount of wet coating to a minimum and eliminate drying unevenness. The printing and coating method is particularly suitable from the standpoint of thickness uniformity. Two or more layers can be applied simultaneously. For details of the simultaneous coating method, please refer to U.S. Patent Nos. 2,761,791, 2,941,898, 3,508,947, and 3,526,528; and `` Kotingu Kougaku (Coating Engineering) '' by Yuj i Harasaki, p. 253, Asakura Shoten, 1973 . If an anti-glare optical film is used as one of the surface protective films of the polarizing plate, the transparent film substrate must be saponified with an alkali on the side opposite to the anti-reflection layer. A particular method for alkali saponification can be selected from the following two methods. The method (1) is preferable because it can be effected in the same step as a triethyl cellulose cellulose film for general use. However, method (1) may be detrimental to alkali saponification, extending to the side of the anti-reflection film of the transparent film substrate, causing alkali hydrolysis of the surface of the transparent film substrate, which deteriorates and contaminates the surface with the saponification solution left behind. Therefore, the method (2) is suitable although it involves specific steps. Method (1): includes impregnating a transparent film base having an anti-reflection layer formed thereon. The plate is immersed in an alkaline solution at least once to saponify the back surface. Method (2): Before or after forming the anti-reflection film on the transparent film substrate, apply an alkali solution to one side of the anti-glare optical film on the reverse side of the anti-reflection film, and then subject the coated material to heat and rinse with water And / or neutralize, only the back of the film is saponified. If used in a display unit, the anti-glare optical film of the present invention is preferably located on the outermost side of the display, for example, a pressure-sensitive adhesive layer is provided. If triethyl cellulose is used as a transparent film substrate, triethyl cellulose is used as a protective film to protect the polarizing layer of the polarizing plate. Therefore, it is preferable to use the anti-glare optical film of the present invention as such a protective film from the viewpoint of cost. Preferably, the anti-glare optical film of the present invention is used for the visible side of the surface protective film of a polarizing plate. The films other than the anti-glare optical film are optical compensation films, and contain an optically non-isotropic layer on the side of the surface protective film opposite to the polarizing plate. This optically anisotropic layer is a layer made of a compound having a dish-shaped structural unit and negative double refraction. Preferably, the surface of the dish-shaped structural unit facing the surface protective film is inclined, and the angle between the φ dish surface of the dish-shaped structural unit and the surface protective film surface changes with the depth direction of the optical anisotropic layer. Preferably, the optical anisotropic layer is made of a dish-shaped liquid crystal compound. Examples of dish-shaped liquid crystal compounds include benzene derivatives reported by C. Destrade et al. In Mol. Cryst. Vol. 71, p. 111 (198 1); C. Destr. Ad et al. In Mol. Cryst. Vol. 122, p. 141 (1985), and trispinylbenzene derivatives reported in Physics Letter, A. Vol. 78, p. 82 (1990); B. Kohne et al. In Angew. Chem., Volumes 96-48-200302923, page 70 (1 984) of cyclohexane derivatives; and J.M. Lehn et al. In J. Chem. Commun., P. 1974 (1985 ) And Aza-cr own and phenylacetylene macrocycles reported and investigated by Zhang et al. In J. Am. C hem. Soc. Vol. 116, p. 2655 (19 94). Generally speaking, a dish-shaped liquid crystal compound has a structure in which the compound is regarded as a mother core in its molecule, and is linearly substituted by a linear substituent such as a linear alkyl group, an alkoxy group or a substituted phenylfluorenyl group. Surrounded, thus exhibiting liquid crystal properties. However, the present invention is not limited to this example, as long as the molecule itself has uniaxial properties and can give a limited alignment. In the present invention, it is not necessary to make the "liquid crystal compound" in the optically anisotropic layer made of a liquid crystal compound have liquid crystal properties in the optically anisotropic layer constituting the elliptically polarizing plate of the present invention. That is, the low-molecular-weight dish-shaped liquid crystal compound may have, for example, a group that reacts due to heat or light, polymerizes or crosslinks due to heat or light, and produces a polymer having no liquid crystal properties, thereby forming an optically non-crystalline Isometric layer. Preferred examples of the dish-shaped liquid crystal compounds are given in JPA 8-5 02 0 6. Among the optical anisotropic layers constituting the elliptically polarizing plate of the present invention, it is preferable that the dish surface of the dish-shaped liquid crystal compound is inclined to the surface of the transparent support, and the angle between the dish and the surface of the transparent support varies with the optical anisotropy. The depth direction of the isotropic layer changes. The dish angle (tilt angle) of the dish-shaped liquid crystal compound usually increases or decreases with the distance in the depth direction of the optical anisotropic layer, starting from the bottom of the optical anisotropic layer. It is preferable to increase the inclination angle as the distance increases. Examples of changes in the tilt angle include continuous increase, continuous decrease, intermittent increase, intermittent 49-200302923, rest reduction, and changes that increase and decrease continuously and intermittent changes that involve reduction and increase. The depth direction contains the area where the inclination angle expression / fnr Μ changes. The better, the increase and decrease of the inclination angle, although it contains the constant area y, is a whole. The better is. 5 The inclination angle is continuously changed as a whole. The best optical anisotropy can be obtained by applying a solution of a dish-shaped liquid crystal compound and other compounds in a solvent to an alignment film, drying it, and then heating it to a temperature at which a dish-shaped nematic phase is formed. It can be cooled in the state (ie, disc-shaped nematic phase) or J is anti-glare optically thin, and the film can be obtained by combining a disc-shaped liquid crystal compound with other compounds (combined with it, for example, can be Combined monomer \ photopolymerization initiator) solution in a solvent, applied to the alignment film to dry and then heated to a temperature to form a dish-shaped nematic phase and then polymerized (example 1 such as ultraviolet light image &quot; 〇Use In: In the present invention, the transfer temperature of the dish-shaped liquid crystal compound into a dish-shaped nematic phase is preferably in the range of white 70 to 300 ° C, more preferably 70 to 170 ° C, and the optics on the side of the transparent support. The inclination angle of the non-isotropic layer can generally be controlled by selecting an appropriate dish-shaped liquid crystal compound or alignment film material or selecting

適當抹拭方法。&amp; 在反側（大氣側）之傾斜角一般可受控制於 選擇適當之碟形 N /欠晶化合物或各種化合物（例如，助塑劑、 表面活化劑、可取八啦 水θ單體、聚合物），與碟形液晶合倂使用 。再者，在傾斜角中之變化程度可以選擇而控制。 作爲助塑劑、表面活化劑、可聚合單體者可用任意之化 合物，只要能與碟形液晶化合物相容而不抑制碟形液晶化 -50· 200302923 口物之配向。在全邰之中，較佳使用可聚合單體（例如，有 ； 烯氧基、丙燦醯基和甲基丙烯醯基之化合物） 於自1至5 〇質量％之用量，基於碟形液晶。 作爲與碟形液晶化合物合倂使用之聚合物，可用任意 之a 口物只要可與碟形液晶化合物相容而不抑制液晶化 η物之配向。聚合物之例包括纖維素酯。纖維素酯之較佳 例巳括纖維素乙酸酯、纖維素丙酸酯、羥丙基纖維素和纖 維素乙fee @曰丁酸酯。如此之聚合物通常用量自〇 · 1至$ 〇質 量％(較佳自0.1至8質量％，更佳自〇1至5質量。/〇，基 於碟形液晶。 用於本發明由液晶化合物製成之光學非等方向層，是設 置於位在作爲透明支持物用之纖維素乙酸酯膜上之配向膜 之上。配向膜是由可交聯聚合物製成經抹拭之薄膜。 用於本發明之配向膜，其較佳例包括j p A 9 - 1 9 2 5 0 9所，述… 之配向膜。 本發明之防眩光學薄膜是用於顯示單元，其如液晶顯示 器（LCD)、電漿顯示面板（PDP)、電發光顯示器（ELD)和陰 極管（CRT)。若抗反射膜具有透明支持物，其較佳者’在防 眩光學薄膜側之透明支持物黏著於顯示單元之影像顯示面。 在LCD中有多種液晶胞。在STN式（超扭轉向列）式之液 晶胞內，柱形液晶分子貫質上被水平配向’並在無電壓施 加時以180。至27〇。扭轉。在TN (超轉向列）式之液晶胞內’ 柱形液晶分子實質上被水平配向而在無電壓施加時扭轉 -5 1 - 200302923 60。至 1 20。。 此等S TN式和TN式液晶胞已常被廣用於單色和彩色之‘ 液晶顯示單元，並有大量文獻報告。 ' 在一種V A (垂直對準）式之液晶胞內，柱形液晶分子實質 上被垂直配向於未施加電壓時。V A式液晶胞包括：（1 )狹 義的VA式液晶胞，其中柱形液晶分子實質上被垂直配向 於未施加電壓時，而此等分子在加上電壓時實質上爲水平 配向（載於JPA- 2 - 1 7 6 6 2 5 );以及（2)多域垂直對準（MVA)式 · 之液晶胞，具有擴大之視界（載於S ID 97 ’技術報告彙編 (會誌）2 8 ( 1 9 9 7 ) 8 4 5: ( 3 )n軸對稱微胞（n-ASM)式液晶胞， 其中柱形液晶分子實質上被垂直配向於未施加電壓之時， 而在施加電壓時此等分子成爲扭轉之多域型配向（載於 Nihon Ekisho Toronkai 會誌，5 8 - 5 9( 1 9 9 8));和（4)SURVAIVAL 式液晶胞（LCD International 98 公佈）。 OCB(光學補償彎屈）式液晶胞，是在液晶顯示單元中所 用之液晶胞內，柱形液晶分子實質上在胞之上、下兩部份® 以相反方向（對稱）配向，由美國專利4，5 8 3，8 2 5和5，4 1 0，4 2 2 揭不°医1爲柱形液晶分子被對稱配向於胞之上、下部，此 © Ιδ向式之液晶胞具有光學自償之功能。因此，這種 '液曰曰^ 皮稱爲光學補償彎屈（Ο C Β )液晶模式。這種Ο C ΒProper swabbing method. &amp; The inclination angle on the opposite side (atmospheric side) can generally be controlled by selecting an appropriate dish-shaped N / undercrystalline compound or various compounds (eg, plasticizer, surfactant, desirable Balatheta monomer, polymerization Material), combined with the dish-shaped LCD. Moreover, the degree of change in the tilt angle can be selected and controlled. As a plasticizer, a surfactant, and a polymerizable monomer, any compound can be used as long as it is compatible with the dish-shaped liquid crystal compound without inhibiting the dish-shaped liquid crystal -50 · 200302923 Orientation of the mouthpiece. Among the whole compounds, it is preferred to use polymerizable monomers (for example, compounds of alkenyl, propenyl, and methacryl groups) in an amount of from 1 to 50% by mass based on dish-shaped liquid crystals. As the polymer used in combination with the dish-shaped liquid crystal compound, any a-portion can be used as long as it is compatible with the dish-shaped liquid crystal compound without inhibiting the alignment of the liquid crystal η-substance. Examples of polymers include cellulose esters. Preferable examples of the cellulose ester include cellulose acetate, cellulose propionate, hydroxypropyl cellulose, and cellulose ethyl fee @ aybutyrate. Such polymers are usually used in an amount of from 0.1 to $ 0% by mass (preferably from 0.1 to 8% by mass, more preferably from 0.1 to 5% by mass. / 0, based on dish-shaped liquid crystals. Used in the present invention is made of liquid crystal compounds The formed optical anisotropic layer is disposed on an alignment film on a cellulose acetate film used as a transparent support. The alignment film is a wiped film made of a cross-linkable polymer. Preferred examples of the alignment film in the present invention include the alignment films described in jp A 9-1 9 2 5 0 9. The anti-glare optical film of the present invention is used in a display unit, such as a liquid crystal display (LCD). , Plasma display panel (PDP), electroluminescence display (ELD), and cathode tube (CRT). If the anti-reflection film has a transparent support, it is better to have a transparent support on the side of the anti-glare optical film adhere to the display unit The image display surface. There are many kinds of liquid crystal cells in the LCD. In the STN type (super twisted nematic) type liquid crystal cell, the columnar liquid crystal molecules are aligned horizontally by mass and 180 to 27 when no voltage is applied 〇.Twist. In the TN (super steering column) type liquid crystal cell 'cylindrical liquid crystal Molecules are essentially aligned horizontally and twisted when no voltage is applied-5 1-200302923 60. to 1 20 ... These S TN and TN liquid crystal cells have been widely used in monochrome and color LCD cells. There are many literature reports. 'In a VA (vertical alignment) type liquid crystal cell, the columnar liquid crystal molecules are substantially vertically aligned when no voltage is applied. The VA type liquid crystal cell includes: (1) a narrow VA type Liquid crystal cells, where the columnar liquid crystal molecules are substantially vertically aligned when no voltage is applied, and these molecules are substantially horizontally aligned when a voltage is applied (contained in JPA-2-1 7 6 6 2 5); and ( 2) Multi-domain vertical alignment (MVA) type LCD cell with an expanded horizon (contained in S ID 97 'Technical Report Compilation (Meeting) 2 8 (1 9 9 7) 8 4 5: (3) n Axisymmetric cell (n-ASM) type liquid crystal cell, in which the columnar liquid crystal molecules are substantially vertically aligned when no voltage is applied, and when a voltage is applied, these molecules become a twisted multidomain alignment (contained in Nihon Ekisho Toronkai society, 5 8-5 9 (1 9 9 8)); and (4) SURVAIVAL LCD cell (LCD Internati Announced onal 98). OCB (Optically Compensated Bend) type liquid crystal cell is a liquid crystal cell used in a liquid crystal display unit. The columnar liquid crystal molecules are substantially above the cell and the lower two parts are in opposite directions (symmetric). Alignment is disclosed in U.S. patents 4,5 8 3, 8 2 5 and 5, 4 1 0, 4 2 2. Medical 1 is a columnar liquid crystal molecule that is symmetrically aligned above and below the cell. The liquid crystal cell has the function of optical self-compensation. Therefore, this type of liquid is called an optically-compensated flexural (OCB) liquid crystal mode. This 〇 C Β

電壓時實質上 有利於具有的回應速率。 1雙折射）或液晶胞內，柱形液晶分子在未加 爲水平配向。這些液晶胞最常被用於彩色 -52- 200302923 TFT(薄膜電晶體）液晶顯示單元並有大量文獻報導。例如， Tony Reseai:ch center 印行之 E L、P D P、L C D 顯示器（2 0 0 1 ) 文中所載之此等液晶胞。 (四）實施方式 ί見在’本發明將參考如下之實施例作更詳細說明。然而 ’本發明不受其限制。 ^ $發明之防眩光學薄膜被用於透射型或半透射型液晶 元’一種照度提昇膜（具有偏光選擇層之偏光分離膜 ’例如Sumitomo 3M Co·，Ltd·所產之D-BEF)可被夾於設 在與觀看側相反面之偏光板與背光之間，得到具有較高可 觀看性之顯示單元。另外，如若結合一 λ/4板，本發明之 防眩光學薄膜可被用作表面保護片，用於有機EL顯示器 以減少來自其表面和其內部之反射。 實施例 實施例1 (用於硬塗層之塗覆溶液之製備） 以250克五丙烯酸二季戊四醇酯與六丙烯酸二季戊四醇 醋（NipponKayaku所製DPHA⑯）之混合物溶於439克甲基 乙基酮與環己酮（5 〇 / 5 〇質量％)之溶劑混合物內。於所得溶 液中加入以7.5克光聚合起始劑（CibaGeigy製之Irgacure® 9〇7)和 5.0 克光敏感（Nipp〇;n Kayakii 製 Kayacure ⑯ DETX)在 4 9克甲基乙基酮中之溶液。所成溶液經聚丙烯濾片（3微米 孔度）過濾’然後以紫外光固化。如此所得塗膜具有1 . 5 3 之折射率和4微米之膜厚。 -53- 200302923 (用於防眩硬塗層之塗覆溶液A之製備） 以4 1 6 5質量份由五丙烯酸二季戊四醇酯與六丙烯酸二 &gt; 季戊四醇酯（Nippon Kayaku製之DPHA®)所成混合物，於 _ 9 94 1質量份含有氧化銷分散物（JSR製之Z- 74 0 1 ®)用於硬 塗之塗覆溶液，1029質量份甲基乙基酮，3099質量份環己 酮和452質量份光聚合起始劑（CibaGeigy製之Irgacure® 9 0 7 ) —倂混合。 於所成溶液中另加入1 3 1 4質量份可交聯之聚苯乙烯顆 | 粒分散液，顆粒平均粒徑爲2微米（顆粒爲Soke n Kagaku 製之SX- 2 0 0 H®;顆粒/甲基乙基酮/環己酮=2 0/4 0/4 0 (質量 % ))，澈底攪拌而混合於一空氣分散器內，經濾器過濾而得 用於防眩高折射層之塗覆溶液。施用此溶液並以紫外光固 化而得塗膜，折射率爲1 . 6 1，膜厚1 . 4微米。 對於傾斜角分佈和表面粗糙度之變化，可交聯之聚苯乙 烯顆粒之粒徑自2至5微米而改變。 (用於防眩硬塗層之塗覆溶液B之製備） 鲁 於1 0 0 0質量份用於硬塗層之塗覆溶液A (蒸除溶劑並甩 紫外光固化後，折射率爲1 . 5 1 )，加入1 5 0質量份顆粒使有 向前散射之性質_，顆粒於製自聚苯乙烯，平均粒徑爲1 . 3 微米（SX-130H，SokenKagaku 製，折射率：1.61)。在空 氣分散器內攪拌所成混合物1 〇分鐘，經孔徑3微米之聚丙 烯濾片（P P E - 0 3 )過濾而得塗覆溶液B，用於使具向前散射 性質之硬塗層。 (用於低折射層之塗覆溶液之製備） -5 4- 200302923 以2 0 0質量份可熱交聯之氟化聚合物，折射率1 .43( JN-7228®，JSR製，固含量：6質量。/〇，溶劑：甲基乙基酮），’ 17 質量份矽石溶膠（MEK-ST®，Nissan Che mial Industries ·The response time is essentially conducive to voltage. 1 birefringence) or liquid crystal cells, the columnar liquid crystal molecules are not aligned horizontally. These liquid crystal cells are most commonly used in color-52-200302923 TFT (thin film transistor) liquid crystal display cells and have been extensively reported in the literature. For example, these LCD cells printed in Tony Reseai: ch center's E L, P D P, L C D display (2 0 0 1). (IV) Embodiments The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited thereto. ^ The invention's anti-glare optical film is used in transmissive or semi-transmissive mesogens. 'An illumination enhancement film (a polarizing separation film with a polarizing selection layer', such as D-BEF by Sumitomo 3M Co., Ltd.) can It is sandwiched between a polarizing plate and a backlight provided on the opposite side from the viewing side to obtain a display unit with high visibility. In addition, if a λ / 4 plate is combined, the anti-glare optical film of the present invention can be used as a surface protection sheet for an organic EL display to reduce reflection from its surface and its interior. EXAMPLES Example 1 (Preparation of a coating solution for a hard coating layer) A mixture of 250 g of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA (R) manufactured by Nippon Kayaku) was dissolved in 439 g of methyl ethyl ketone and Cyclohexanone (50/50 mass%) in a solvent mixture. To the resulting solution were added 4.9 g of a photopolymerization initiator (Irgacure® 907 manufactured by Ciba Geigy) and 5.0 g of light sensitive (Nippo; Kayacure (R) DETX manufactured by Kayakii) in 49 g of methyl ethyl ketone. Solution. The resulting solution was filtered through a polypropylene filter (3 micron porosity) and then cured with UV light. The coating film thus obtained had a refractive index of 1.5 3 and a film thickness of 4 μm. -53- 200302923 (Preparation of coating solution A for anti-glare hard coating) 4 1 6 5 parts by mass of dipentaerythritol pentaacrylate and di &gt; pentaerythritol hexaacrylate (DPHA® manufactured by Nippon Kayaku) A mixture containing 9-9 parts by mass of an oxidation pin dispersion (Z-74 0 1 ® manufactured by JSR) for a hard coating coating solution, 1029 parts by mass of methyl ethyl ketone, and 3099 parts by mass of cyclohexanone It was mixed with 452 parts by mass of a photopolymerization initiator (Irgacure® 9 0 7) manufactured by Ciba Geigy. Add 1 3 1 4 parts by mass of crosslinkable polystyrene particles to the resulting solution | particle dispersion with an average particle size of 2 microns (particles are SX- 2 0 0 H® manufactured by Soke n Kagaku; particles / Methyl ethyl ketone / cyclohexanone = 2 0/4 0/4 0 (mass%)), mixed with an air disperser with a clear bottom, and filtered through a filter to obtain an anti-glare high refractive layer coating Covering solution. A coating film was obtained by applying this solution and curing with ultraviolet light, the refractive index was 1.6, and the film thickness was 1.4 microns. With respect to changes in the tilt angle distribution and surface roughness, the particle size of the crosslinkable polystyrene particles varies from 2 to 5 m. (Preparation of coating solution B for anti-glare hard coating) Lu Yu 100 parts by mass of coating solution A for hard coating (after distilling off the solvent and curing with ultraviolet light, the refractive index is 1. 5 1), adding 150 parts by mass of particles to have the property of forward scattering. The particles are made of polystyrene with an average particle size of 1.3 microns (SX-130H, manufactured by SokenKagaku, refractive index: 1.61). The resulting mixture was stirred in an air disperser for 10 minutes and filtered through a polypropylene filter (PPE-0) with a pore size of 3 micrometers to obtain a coating solution B, which was used to make a hard coat with forward scattering properties. (Preparation of coating solution for low-refractive layer) -5 4- 200302923 Thermally crosslinkable fluorinated polymer with a refractive index of 1.43 (JN-7228®, manufactured by JSR, solid content) : 6 mass./〇, solvent: methyl ethyl ketone), '17 parts by mass of silica sol (MEK-ST®, Nissan Che mial Industries ·

製，平均粒徑：1 〇至2 0奈米，固含量：3 0質量％，溶劑 :甲基乙基酮），其餘爲135質量份之甲基乙基酮/環己酮 (在塗覆溶液中全部溶劑之甲基乙基酮/環己酮之質量組成 比=9 0 / 1 0 )，一倂混合攪拌，然後經孔徑爲1微米之聚丙烯 濾片過濾，得用於低折射層之塗覆溶液。 I (樣品1之製備） 以上述用於硬塗層之塗覆溶液用棒塗器施於三乙醯基纖 維素支持物（Fuji Photofilm製之TD-80UF)，於120°C乾燥 。然後將塗覆層固化，用紫外光照射（發光強度：4 0 0毫瓦 /厘米2，照射劑量：3 0 0毫焦/厘米2 )，使用氣冷金屬鹵化 物燈（Eye Graphics製），160瓦/厘米，形成厚度4微米之 硬塗層。 隨後，用棒塗器施用上述用於防眩硬塗層之塗覆溶液， φ 乾燥，以如上述硬塗層相同條件之紫外光固化，形成防眩. 硬塗層。改變施用劑量，製成防眩硬塗層厚度自〇 . 5微米 至7微米之樣品。如表1所列，以適當結合於防眩硬塗層 中可交聯之聚苯乙烯顆粒和薄膜厚度，製成表面傾斜角分 佈和表面粗糙度互不相同之所需樣品。 然後進一步以上述用於低折射層之塗覆溶液A用棒塗器 加於其上，乾燥於8 0 °C，加熱至1 2 0 °C經1 0分鐘而交聯， 產生厚度〇 . 〇 9 6微米之低折射層。 -55- 200302923 此樣品相當於第1圖所示狀況，在支持物1和防眩高折 射層2之間，用上述硬塗層用之塗覆溶液形成另一硬塗層。 [製備樣品2之方法] 一種在防眩硬塗層內不具可交聯之聚苯乙烯顆粒之樣品 ，以如樣品1之製法製成。一在表面上不具不均勻性之低 折射層形成於使用製備樣品1之方法。使用一面壓花之砑 光機（Yuri Roll製），並裝有鋼製壓花輥和表面覆有聚醯胺 材料之支承輥。壓花進行於具有所需表面形狀之壓花輥， 加壓壓力6 0 0公斤/厘米，預熱輥溫度1 2 (TC，壓花輥溫度 1 20 °C ，處理速度爲2米/分。於是獲得如表2所列具有各 種細度之防眩抗反射膜樣品。 由各實施例所產之防眩抗反射膜，各被浸入2.0N之 N a Ο Η水溶液於5 5 °C經2分鐘，因而皂化在膜背上之三乙 醯基纖維素表面。利用如此已處理之膜，倂同厚度8 0微米 已於相同條件皂化之三乙醯基纖維素膜（TAC-TD80U，Fuji Photofilm製），由聚苯乙烯醇吸收碘並拉伸而製片之偏光 片之兩面予以貼合保護而成偏光板。然後將一裝有透射TN. 液晶顯示單元之筆記型個人電腦之液晶顯示單元可觀看側 之偏光板（在背光與液晶胞之間設有具有Sumitomo 3M已 驗證之偏光選擇層D - B E F之偏光分離膜），用以上製成之 偏光板替換，使防眩抗反射膜作爲最外之面，繼予評估。 (防眩抗反射膜之評估） 如此所產生之防眩抗反射膜依下列項目評估。 因爲是一種防眩抗反射膜，理想者所產生光學薄膜具有 -56- 200302923 低反射性，充份的防眩性質，無閃耀而少白色斑迹，使黑 色圖像看來即爲黑色。 (1)防眩性質之評定 如是所製防眩抗反射膜結合於如上所述之顯示器上，一 無蓋無罩之螢光燈（ 8 0 00燃光/厘米2)被反射。然後依如下 標準評定所反射影像中之朦糊程度。 ” X ”指N G (不通過）之水平 燈 之 外 廓 不 能 或 稍 能 分 辨 燈 之 外 廓 有 ft, 模 糊 但 可 分 辨 ，，△ 燈 有 itb 朦 糊 丨’ X ’’ (2) 筒 淸 晰 度 監 視 器 之 可 用 性 評 估（眩光性） 爲 了 評 估 防 眩 抗 反 射 膜 於 局 淸 晰度監視器之可用 ί性， 以 上 所 產 製 之 防 眩 抗 反 射 膜 結 合 於 U X G A 1 5 吋 TFT- ΤΝ液晶 顯 示 單 元 (所設備光分離膜具有s umitomo 3 Μ 所製 備偏 光 擇 層 D -B ET 於 ‘背 1光 ；和 1液 :晶 胞 之 間），如上所 述， 然後 依 如 下 標 準 以 裸 眼 之 感 覺 評 定 〇 Mx π指NG (不 :通 [過 !)水平 y\\\ 眩 光 性 Μ ◎，， 稍 許 但 Μ 干 擾 之 眩 光 有 干 擾 之 眩 光 丨丨X &quot; (3 ) 5 °鏡面平均反射性 使 用 以 上 產 製 之 防 眩 抗 反 射 膜 ，用光譜儀（N i ρ ρ 〇 η B u n k 〇 製造）於4 5 0至6 5 0奈米波長範圍內量測5 °入射角之光譜反 射比。結果以4 5 0至6 5 0奈米之平均反射比表示。 -57- 200302923 (4) 使黑色圖像看如黑色之程度 使黑色圖像看來如同黑色之程度，在所得薄膜上之效果 ，用 Murakami Color Research Laboratory 所製變角光度計 量測。樣品被5 °方向之光照射，散射光從正規反射5 °偏離 4 〇 °方向（亦即4 5 °)。結果以對數表示。降低1或2之數値 分別指出散射光之侵越爲1 〇倍或1 〇 〇倍，因此使黑色圖像 看來稍非黑色。絕對値不具意義。亦即，某些經測定之樣 品之數値及差異之形成於散射光者，以對數計算。以與感 覺評定之數據比較之結果，發現各樣品表現之數値爲6.0 或較高者具有使黑色圖像看來一如黑色之效果優異。5.3 或較低之樣品因爲產生白化影像而不可用。自5 . 3至6.0 之樣品表現略有白化之影像。相差〇 . 2或較大之樣品可以 互相分辨。 (5) 白迹 在如（4 )之標準量測條件下呈現一黑色圖像。然後以一 2 米距離之白熾燈（5 0 0瓦）反射於顯示器之上方1 / 3，並評估 在整個顯示器中之白迹。 若白迹擴及顯示器之1 /2或更大，則明視度嚴重劣化。 &quot;X ’’表示N G (不通過）之水準。 白迹所擴及少於1/2 : ” 白迹所擴及超過1/2或更大&quot;X” (6 )平均傾斜角和1 0 °或以上之傾斜角之比率 使用 Model SXM520-AS150 之儀器（mama Microchip， USA)，用（xlO)倍數2放大鏡量測傾斜角於0.85微米之單 200302923 位，且量測面積爲〇 . 4 8毫米2。 量測之數據用軟體MAT-LAB分析，計算傾斜角之分佈， 從而產生所求數據。 表1表示在製備例1所產生各樣品在各實施例中之結果。 [表1] 樣品 編號 傾斜角 ^10。者 之比率 平均 傾斜角 (°) 各峯突中之 平均間距 (微米） 5°鏡面 平均 反射比 白迹 使黑色圖像 看來如同 黑色之程度 防眩性質 眩光性 附記 1 20% 7 60 0.8% X 4.9 〇 X 比較 2 10% 5 60 0.9% X 5.1 〇 X 比較 3 3% 4 45 1.1% 〇 5.4 Δ X 比較 4 3% 3 45 1.1% 〇 5.5 Δ X 比較 5 2% 1 90 1.2% 〇 6.3 X X 比較 6 2% 4.5 40 1.0% 〇 6.2 〇 〇 發明 7 2% 4.5 20 1.0% 〇 6.2 〇 ◎ 發明 8 2% 4.5 10 1.0% 〇 6.2 〇 ◎ 發明 根據本發明之樣品6、7和8能夠使黑色之顯示效果之黑 · 色圖像看到黑色如6 · 0或以上，而維持優良（〇）之防眩性 質。反之，既在之方法之比較樣品（第1、2、3、4和5)卻 不能達到6.0或以上而維持優良之防眩性質。 再者，可以瞭解根據本發明之樣品7和8，能夠改善眩 光性，爲可用於高淸晰度監視器而爲防眩抗反射膜。 實施例2 表2在製備例2所產生之各樣品之結果。本發明各個樣 品能夠達到使黑色顯示無任何白性而在防眩性質中不致有 -59- 200302923 任何麻煩。而且防眩性亦能改善。所以，已發現此等樣品 爲防眩抗反射膜而可用於高淸晰度監視器。其亦可被瞭解 此等樣品能夠維持屬於有利之白迹效果。 [表2] 樣品 編號 傾斜角 -10。者 之比率 平均 傾斜角 (°) 各峯突中之 平均間距 (微米） 5°鏡面 平均 反射比 白迹 使黑色圖像 看來如同 黑色之程度 防眩性質 眩光性 附記 1 2% 3 25 1.1% 〇 6.2 Δ 〇 發明 2 1% 3 15 1.0% 〇 6.4 Δ ◎ 發明 3 0.5% 3 10 1.0% 〇 6.7 Δ ◎ 發明· 4 0.5% 3 5 1.1% 〇 6.7 Δ ◎ 發明 5 2% 6 10 1.0% 〇 6.1 〇 ◎ 發明 6 1% 4.5 10 1.1% 〇 6.4 〇 ◎ 發明 實施例3 作爲具有以實施例1和2之防眩光學薄膜結合於其上之 透射TN液晶胞之液晶可見側中偏極板液晶胞側之保護膜 ;和在背光板側之偏光板在液晶胞側之保護膜，是使用廣 φ 視界薄膜（Fuji Photo film製之廣視界薄膜SA-12B)，具有. 光學補償層，其中碟形結構單元之碟面向表面保護膜面傾 斜，且碟形結構單元之碟面與表面保護膜面之間的夾角是 隨著光學非等方向層之深度方面改變。因此液晶顯示單元在 光室內表現優異之對比，在水平和垂直方向兩者之中具有極 爲寬廣之視角，具有極高之明視性，並能獲得優異之顯示品 質。 -60- 200302923 實施例4 作爲取代用於實施例1和2防眩硬塗層之塗覆溶液A，使 ’ 用一種用於防眩硬塗之塗覆溶液，設置一具有向前散射功能 · 之層。然後用具有此向前散射之防眩光學薄膜作爲最外面之 偏光板，且在液晶胞側構設寬視界薄膜（Fuji Photo film製之 寬視界膜SA-12B)而提供透射TN液晶顯示單元。 在實施例4比較，由於視角向下移而反轉分級，在其中；^ 限定角度有自4 0 °至6 0 °之改善。所以，明視性和顯示品質 極爲優異。 · 實施例5 若以產自實施例1和2之防眩光學薄膜，用壓感黏著劑 結合至有機電發光（E L)顯示單元表面之玻璃板，在玻璃袠 面之反射和反射比可以被規律化，因而可得到高明視性；^ 顯示單元。 實施例6 一 λ/4片被結合至設有產自實施例1和2之防眩光學薄 膜於一面之偏光板，在其具有防眩層側之反面。然後將偏 ^ 光板結合至有機EL顯示單元表面上之玻璃板。所以，袠 面反射和從表面玻璃內中之反射可被切除而獲得高度明@ 之圖像。System, average particle size: 10-20 nanometers, solid content: 30% by mass, solvent: methyl ethyl ketone), and the rest is 135 parts by mass of methyl ethyl ketone / cyclohexanone (in coating The mass composition ratio of methyl ethyl ketone / cyclohexanone of all solvents in the solution = 9 0/1 0), mixed and stirred once, and then filtered through a polypropylene filter with a pore size of 1 micron to obtain a low refractive layer. Of coating solution. I (Preparation of Sample 1) The above-mentioned coating solution for a hard coat layer was applied to a triethylfluorene-based cellulose support (TD-80UF manufactured by Fuji Photofilm) with a bar coater, and dried at 120 ° C. Then, the coating layer was cured and irradiated with ultraviolet light (luminous intensity: 400 mW / cm2, irradiation dose: 300 mJ / cm2), using an air-cooled metal halide lamp (manufactured by Eye Graphics), 160 W / cm to form a 4 micron hard coat. Subsequently, the above-mentioned coating solution for the anti-glare hard coating layer was applied with a bar coater, φ dried, and cured with ultraviolet light under the same conditions as the above-mentioned hard coating layer to form an anti-glare hard coating layer. The application dose was changed to make a sample with an anti-glare hard coating thickness of 0.5 to 7 microns. As shown in Table 1, required samples with different surface inclination angle distributions and surface roughnesses were made with the crosslinkable polystyrene particles and film thickness appropriately combined in the anti-glare hard coat layer. Then, the above-mentioned coating solution A for the low refractive layer was further added thereto with a bar coater, dried at 80 ° C, heated to 120 ° C and crosslinked for 10 minutes, resulting in a thickness of 〇. 〇 9 6 micron low refractive layer. -55- 200302923 This sample corresponds to the condition shown in Fig. 1. Between the support 1 and the anti-glare high-refractive layer 2, another hard coating layer is formed by using the coating solution for the hard coating layer described above. [Method for preparing sample 2] A sample having no crosslinkable polystyrene particles in the anti-glare hard coat layer is prepared by the method as in sample 1. A low-refractive layer having no unevenness on the surface was formed by using the method for preparing sample 1. An embossing calender (made by Yuri Roll) was used, and a steel embossing roll and a support roll covered with a polyamide material were installed. The embossing was performed on an embossing roller having a desired surface shape, a pressing pressure of 600 kg / cm, a preheating roller temperature of 12 (TC, an embossing roller temperature of 120 ° C, and a processing speed of 2 m / min. Thus, anti-glare anti-reflection film samples with various finenesses as listed in Table 2. The anti-glare anti-reflection films produced in the examples were each immersed in a 2.0 N N a 0 aqueous solution at 5 5 ° C for 2 hours. Minutes, thus saponifying the triethyl cellulose surface on the back of the film. Using the thus treated film, a triethyl cellulose film (TAC-TD80U, Fuji Photofilm) having a thickness of 80 micrometers and saponified under the same conditions was used. (Manufactured), a polarizing plate is formed by attaching and protecting both sides of a polarizer made of polystyrene alcohol by iodine absorption and stretching. Then a liquid crystal display unit of a notebook personal computer equipped with a transmissive TN. Viewing side polarizer (a polarizing separation film with Sumitomo 3M's verified polarizing selection layer D-BEF is provided between the backlight and the liquid crystal cell). Replace the polarizer made above to make the anti-glare anti-reflection film as The outermost surface will be evaluated. (Estimation) The anti-glare anti-reflection film produced in this way is evaluated according to the following items. Because it is an anti-glare anti-reflection film, the ideal optical film produced has -56- 200302923 low reflectivity, sufficient anti-glare properties, no glare Less white spots, so that the black image appears to be black. (1) Evaluation of anti-glare properties If the anti-glare anti-reflection film produced is combined with the above-mentioned display, an uncovered fluorescent lamp (8 0 00 light / cm2) is reflected. Then evaluate the degree of haze in the reflected image according to the following criteria. "X" means that the outer contour of the horizontal lamp of NG (not passing) cannot or can slightly distinguish the outer contour of the lamp. ft, fuzzy but recognizable, △ lamp has itb 丨 'X' '(2) Usability evaluation of tube sharpness monitor (glare) In order to evaluate anti-glare anti-reflection film in local clearness monitor Usability. The anti-glare anti-reflection film produced above is combined with UXGA 15-inch TFT-TN liquid crystal display unit (the equipment light separation film has sumitomo The 3 M polarizing selective layer D -B ET is prepared on the back of 1 light; and 1 liquid: between the unit cell), as described above, and then evaluated with naked eye feeling according to the following criteria: 0Mx π refers to NG (not: [ Pass!) Level y \\\ Glare M ◎, Slightly, but glare from M interference has glare from interference 丨 X &quot; (3) 5 ° mirror average reflectance Use the anti-glare anti-reflection film produced above, use A spectrometer (manufactured by Ni ρ ρ η η unk 〇) measures the spectral reflectance at an angle of incidence of 5 ° in the wavelength range of 450 to 650 nm. Results are expressed as an average reflectance from 450 to 650 nanometers. -57- 200302923 (4) The degree to which a black image looks like black The degree to which a black image appears to be black. The effect on the obtained film is measured with a variable angle photometer made by Murakami Color Research Laboratory. The sample is illuminated by light in a 5 ° direction, and the scattered light deviates from the normal reflection by 5 ° in a direction of 40 ° (that is, 45 °). Results are expressed in logarithm. Decreasing the number by 1 or 2 indicates that the aggression of the scattered light is 10 times or 100 times, respectively, thus making the black image appear slightly non-black. Definitely meaningless. That is, the number and the difference of some measured samples are formed on the scattered light and calculated on a logarithmic scale. As a result of comparison with the data of the sensory evaluation, it was found that a value of 6.0 or higher exhibited by each sample has an excellent effect of making a black image look like black. Samples of 5.3 or lower are not available because they produce whitened images. The samples from 5.3 to 6.0 showed slightly whitened images. Samples with a difference of 0.2 or larger can be distinguished from each other. (5) White trace A black image appears under standard measurement conditions such as (4). An incandescent lamp (500 watts) at a distance of 2 meters was then reflected 1/3 above the display, and the white mark across the display was evaluated. If the white mark extends to 1/2 or more of the display, the brightness is severely deteriorated. &quot; X ’’ stands for N G (Fail). White mark spread less than 1/2: ”White mark spread more than 1/2 or more &quot; X" (6) The ratio of the average tilt angle and the tilt angle of 10 ° or more Use Model SXM520-AS150 The instrument (mama Microchip, USA) uses a (xlO) multiple 2 magnifier to measure a single 200302923 bit with an inclination angle of 0.85 microns, and the measurement area is 0.48 mm2. The measured data is analyzed by software MAT-LAB, and the distribution of the inclination angle is calculated to generate the required data. Table 1 shows the results of the samples produced in Preparation Example 1 in the Examples. [Table 1] Sample No. Tilt angle ^ 10. Average ratio of inclination angle (°) Average distance between peaks (micron) 5 ° Specular average reflectance white traces make black images appear as black Antiglare properties Glare Note 1 20% 7 60 0.8% X 4.9 〇X comparison 2 10% 5 60 0.9% X 5.1 〇X comparison 3 3% 4 45 1.1% 〇5.4 Δ X comparison 4 3% 3 45 1.1% 〇5.5 Δ X comparison 5 2% 1 90 1.2% 〇6.3 XX Comparison 6 2% 4.5 40 1.0% 〇6.2 〇〇 Invention 7 2% 4.5 20 1.0% 〇6.2 〇 ◎ Invention 8 2% 4.5 10 1.0% 〇6.2 〇 ◎ Invention samples 6, 7, and 8 according to the present invention can make The black and color images of black display effect see black such as 6.0 or more, while maintaining excellent (〇) anti-glare properties. On the contrary, the comparative samples (Nos. 1, 2, 3, 4 and 5) of the above methods failed to achieve 6.0 or more while maintaining excellent anti-glare properties. Furthermore, it can be understood that samples 7 and 8 according to the present invention can improve glare, and are anti-glare anti-reflection films for use in high-definition monitors. Example 2 Table 2 shows the results of each sample produced in Preparation Example 2. Each sample of the present invention can achieve black display without any whiteness without any trouble in anti-glare properties. And anti-glare properties can be improved. Therefore, these samples have been found to be anti-glare anti-reflection films and can be used in high definition monitors. It is also understood that these samples are able to maintain a favorable white mark effect. [Table 2] Sample No. Tilt angle -10. Average ratio of inclination angle (°) Average distance between each peak (micron) 5 ° Specular average reflection ratio White trace makes black image look like black Anti-glare property Note 1 2% 3 25 1.1% 〇6.2 Δ 〇 Invention 2 1% 3 15 1.0% 〇6.4 Δ ◎ Invention 3 0.5% 3 10 1.0% 〇6.7 Δ ◎ Invention · 4 0.5% 3 5 1.1% 〇6.7 Δ ◎ Invention 5 2% 6 10 1.0% 〇 6.1 〇 ◎ Invention 6 1% 4.5 10 1.1% 〇6.4 〇 ◎ Invention Example 3 As the polarizing plate liquid crystal on the visible side of the liquid crystal having the transmissive TN liquid crystal cell bonded thereto with the anti-glare optical film of Examples 1 and 2 The protective film on the cell side; and the protective film on the liquid crystal cell side of the polarizer on the backlight plate side, using a wide φ field film (wide field film SA-12B made by Fuji Photo Film), with an optical compensation layer, where The disk of the structural unit is inclined toward the surface protective film surface, and the angle between the disk surface of the disk-shaped structural unit and the surface protective film surface changes with the depth of the optical non-isotropic layer. Therefore, the liquid crystal display unit has an excellent contrast in the light room, has extremely wide viewing angles in both horizontal and vertical directions, has extremely high visibility, and can obtain excellent display quality. -60- 200302923 Example 4 In place of the coating solution A for the anti-glare hard coating of Examples 1 and 2, a coating solution for the anti-glare hard coating was used, and a forward scattering function was provided. Of layers. Then, an anti-glare optical film having this forward scattering is used as the outermost polarizing plate, and a wide-view film (wide-view film SA-12B made by Fuji Photo Film) is provided on the liquid crystal cell side to provide a transmissive TN liquid crystal display unit. In the comparison of Example 4, the grading is reversed due to the downward movement of the viewing angle, and the ^ defined angle has an improvement from 40 ° to 60 °. Therefore, the visibility and display quality are extremely excellent. · Example 5 If the anti-glare optical films from Examples 1 and 2 are used, and the glass plate bonded to the surface of the organic electroluminescence (EL) display unit with a pressure-sensitive adhesive, the reflection and reflectance on the glass surface can be Regularization, so high visibility can be obtained; ^ display unit. Example 6 A λ / 4 sheet was bonded to a polarizing plate provided with an anti-glare optical film from Examples 1 and 2 on one side, on the opposite side of the side having the anti-glare layer. The polarizing plate is then bonded to a glass plate on the surface of the organic EL display unit. Therefore, the surface reflection and the reflection from the surface glass can be cut away to obtain a highly bright image.

實施例1 A - 1 0 A (硬塗層塗覆溶液A之製備） 以306質量份由五丙烯酸二季戊四醇酯和六丙烯酸二季 戊四醇酯（NIPPON KAYAKU CO.，LTD·所產DPHA)所成混 -61- 200302923 合物，溶於由1 6質量份甲基乙基酮和2 2 0質量份環己酮所 成之混合物內。然後於如此所得溶液加入7 . 5質量份之光 * 聚合起始劑（IRGACURE 9 0 7，產自 Ciba-Geigy Japan ^Example 1 A-10 A (Preparation of Hard Coating Solution A) 306 parts by mass of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA produced by NIPPON KAYAKU CO., LTD.) -61- 200302923 compound, dissolved in a mixture of 16 parts by mass of methyl ethyl ketone and 220 parts by mass of cyclohexanone. Then, 7.5 parts by mass of light * polymerization initiator (IRGACURE 9 07, produced by Ciba-Geigy Japan) was added to the solution thus obtained.

Limited)。然後攪拌混合物至溶解。再於混合物中加入450 質量份MEK-ST(平均粒徑自10至20奈米之Si02溶膠之甲 基乙基酮分散液，固含量濃度爲30質量份，產自NISSAN CHEMICAL INDUSTRIES，LTD·)。攪拌混合物，然後經孔 徑爲3微米之聚丙烯據片（PPE-03)過濾，製成硬塗層塗覆 溶液A。 · (二氧化鈦分散液之製備） 以30質量份之二氧化鈦超細粉末（TTO-55B, ISHIHARA TECHNO CORP·產），1質量份丙烯酸二甲基胺基乙基酯 (DMAEA，KOHJIN Co·，Ltd.產），6質量份含磷酸基陰離子 型分散齊!J(KAYARAD PM-21，NIPPON KAYAKU CO·，LTD. 產）和6 3質量份環己酮，在砂磨內分散至混合物平均粒徑 達到以C 〇 u 11 e r計數法所量測爲4 2奈米，製成二氧化鈦分 鲁 散液。 (中折射層塗覆溶液A之製備） 以〇· 1 1質量份光聚合起始劑（11^八〇111^ 9 0 7，（：“&amp;-Geigy Japan Ltd·產）和 0.04 質量份光敏感劑（KAYACURE DETX，NIPPON KAYAKU CO.，LTD.製），溶於由 75 質量份環Limited). The mixture was then stirred until dissolved. 450 parts by mass of MEK-ST (methyl ethyl ketone dispersion of SiO 2 sol with an average particle size of 10 to 20 nm, with a solid content concentration of 30 parts by mass, produced by NISSAN CHEMICAL INDUSTRIES, LTD.) . The mixture was stirred and then filtered through a polypropylene sheet (PPE-03) having a pore size of 3 m to prepare a hard coat coating solution A. · (Preparation of Titanium Dioxide Dispersion Liquid) 30 parts by mass of titanium dioxide ultrafine powder (TTO-55B, manufactured by ISHIHARA TECHNO CORP.), And 1 part by mass of dimethylaminoethyl acrylate (DMAEA, KOHJIN Co., Ltd. Production), 6 parts by mass of phosphate group-containing anionic dispersion! J (KAYARAD PM-21, manufactured by NIPPON KAYAKU CO., LTD.) And 63 parts by mass of cyclohexanone, dispersed in a sand mill until the average particle size of the mixture reaches Measured by Co ou 11 er counting method to 42 nanometers to prepare titanium dioxide dispersion powder. (Preparation of intermediate refractive layer coating solution A) 0.11 parts by mass of a photopolymerization initiator (11 ^ 80111111 907, (: "&amp; -Geigy Japan Ltd.") and 0.04 parts by mass Photosensitizer (KAYACURE DETX, manufactured by NIPPON KAYAKU CO., LTD.), Soluble in 75 parts by mass of ring

己酮與1 9質量份甲基乙基酮之混合物內。於如此所得溶液 中加入3 . 1質量份二氧化鈦分散物和2 · 1質量份由五丙烯 酸二季戊四醇酯和六丙烯酸二季戊四醇酯（DPH A，NIPPON -62- 200302923 KAYAKU CO.，LTD.產）所成混合物。攪拌此混合物於室溫 3 〇分鐘，然後用孔徑爲3微米之聚丙烯濾片（P P E - 0 3 )過濾 製成中折射層塗覆溶液。 (中折射層塗覆溶液B之製備） 以1.2質量份之光聚合起始劑（IRGACURE 907，Ciba-GeigyJapanLtd.產）和〇·4質量份光敏感劑（KAYACURE DETX，NIPPON KAYAKU CO·，LTD.產）溶入由 7 5 0 質量份環 己酮與1 9 0質量份甲基乙基酮所成之混合物內。於如是所 得之溶液中加入1 〇 5質量份之二氧化鈦分散物和2 1質量份 由五丙烯酸二季戊四醇酯和六丙烯酸二季戊四醇酯（DPHA， NIPPON KAYAKU CO.，LTD·產）之混合物。攪拌此混合物於 室溫30分鐘，然後用孔徑爲3微米之聚丙烯濾片（PPE-03) 過濾製成中折射層塗覆溶液B。 (高折射層塗覆溶液之製備） 以0.13質量份光聚合起始劑（IRGACURE 907，Ciba-Geigy Japan Limited產）和0.04質量份光敏感劑 (KAYACURE DETX，NIPPON KAYAKU CO·，LTD.產）溶於由 5 4質量份環己酮和1 8質量份甲基乙基酮所成之混合物內 。然後於如是所得溶液內加入2 6.4質量份二氧化鈦分散物 和1.6質量份由五丙烯酸二季戊四醇酯和六丙烯酸二季戊 四醇酯（DPH A，NIPPON KAYAKU CO·，LTD·產）之混合物內 。攪拌此混合物於室溫3 0分鐘’然後並用孔徑爲3微米之 聚丙烯濾片（P P E - 0 3 )過濾製成高折射層塗覆溶液。 (低折射層塗覆溶液之製備） -63- 200302923 以一種具有1·42折射率之熱可交聯含氟聚合物（jn-7228, J S R公司產）之6質量％甲基乙基酮溶液接受溶劑取代而得 具有1 〇質量％固含量之聚合物溶液，其係以含8 5質量％之 甲基異丁基酮和1 5質量。A 2 - 丁醇之混合溶劑配入。於7 0 質量％如此所得之聚合物溶液加入1 〇質量％之Μ E X - S T (S i Ο 2溶膠之甲基乙基酮分散液，溶膠平均粒徑爲自1 〇至 20奈米，固含量濃度爲30質量％，產自NISSAN CHEMICAL INDUSTRIES, LTD.)’ 42質量份甲基乙基酮和28質量份環 己酮。攪拌此混合物，經孔徑爲3微米之聚丙烯濾片 (P P E - 0 3 )過濾製成低折射層塗覆溶液。 (抗反射膜之製備） 以前述硬塗層塗覆溶液A用印塗器施於厚度80微米之 三乙醯基纖維素膜（TAC-TD80U，Fjui Photo Film Co.，Ltd. 產）上，然後乾燥於1 〇 (TC之溫度2分鐘。隨後，用紫外光 照射所塗材料’使塗層固化形成硬塗層（折射率：1 . 5 1 ;厚 度：6微米）。 隨後’以印塗器將前述中折射層塗覆溶液A施於硬塗層 上’乾燥於1 0 0 °C之溫度，然後用紫外光照射使塗層固化 形成中折射層（折射率：1 · 6 3，厚度：6 7奈米）。 用印塗器將前述高折射層塗覆溶液施於中折射層上，乾 燥於1 0 0 °C之溫度’然後用紫外光照射，使塗層固化形成 高折射層（折射率：1 · 9 〇 ;厚度：丨〇 7奈米）。 另外’用印塗器將前述低折射率塗覆溶液施於高折射層 上。然後於1 2 0 °C之溫度固化塗層，形成低折射層（折射率： 200302923 1 · 4 3 ;厚度：8 6奈米）。於是，製成抗反射膜。 (防眩性質之設置） 如是所得抗反射膜接受用單面壓花之砑光機（YURI ROLL CO.，LTD.產製）之壓花，機上具有鋼質壓化輥，有所 需之表面形狀；和一塗有聚醯胺材料於其表面而裝於其上 之支承輥。施用於1 ,〇〇〇公斤/厘米之壓力，預熱輥溫度爲 l〇〇°C ，壓花輥溫度16(TC ，操作速率2米/分，使傾斜角 不小於1 〇 °之比例者爲1 %，平均傾斜角爲4.5 °而各峯突間 之平均間距爲1 〇微米 (抗反射膜之評估） 然後評定所得薄膜如下之性質。 (1 )鏡面反射比 用一 V- 5 5 6型之光譜儀（JASCO公司製），具有ARV-474 型連接器於其上，在5°入射角和-5°出射角於自380至780 奈米波長內量測薄膜之鏡面反射比。然後於自4 5 0至6 5 0 奈米之波長範圍內平均各次之量測而得平均反應比，藉以 評定薄膜之抗反射性質。 (2)鉛筆硬度之評估 爲求得到耐刮性指數，依Π S K 5 4 0 0評定薄膜之鉛筆硬 度。抗反射膜被調節於25 (TC之溫度和60% RH濕度2小時 ，然後用2 Η至5 Η試驗鉛筆評定硬度。鉛筆以J I S S 6 0 0 6 界定，荷重500克，並依如下之標準。用最高允許硬度。 若樣品（η = 5)所發現刮損數量被評定爲自 〇至2者：通過（ΟΚ) 200302923 若樣品（n = 5)所發現刮損數量被評定爲3 或更多者：不通過（NG) ^ (3 )接觸角之量測 · 爲求得到表面耐污指數，光學材料被調節於2 5 t之溫度 和60°/〇RH之濕度2小時，然後量測對於純水之接觸角。於 是得到指印黏著性指數。 結果如下· 鏡面反射比：〇 . 2 7 % 鉛筆硬度評定：3 Η 量得接觸角：1 〇 3 ° (熱水處理） 將所得薄膜依表3所示條件浸入熱水進行熱水處理。然 後將接受如此熱水處理之薄膜曝於6 5 °C和9 5 %RH之高溫 度與濕度環境，使接受加速試驗，求取在延長使用期中壓 花表面上不均勻性之均勻化。然後在不同條件中和與未經 處理之產品比較。結果見於表3。 -66- 200302923 表3 熱水處理條件 粗糙度算術平均之維持百分比R 實施例 溫度（t ) 時間（秒） 100小時後 5 00小時後 1000小時後 1 A 60 60 5 5 5 1 5 0 2 A 60 1000 66 5 8 5 3 3 A 70 60 65 54 5 1 4 A 70 1000 75 64 5 7 5 A 8 0 6 0 92 9 0 8 5 6 A 80 1 20 94 9 1 89 7 A 90 6 0 96 9 5 92 8 A 90 1 20 98 97 96 9 A 1 00 1 90 82 73 1 0 A 1 00 6 0 98 97 95In a mixture of hexanone and 19 parts by mass of methyl ethyl ketone. To the solution thus obtained, 3.1 parts by mass of titanium dioxide dispersion and 2.1 parts by mass of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPH A, NIPPON -62- 200302923 KAYAKU CO., LTD.) Were added. Into a mixture. The mixture was stirred at room temperature for 30 minutes, and then filtered through a polypropylene filter (PPE-0) with a pore size of 3 microns to prepare a coating solution for a middle refractive layer. (Preparation of middle refractive layer coating solution B) 1.2 parts by mass of a photopolymerization initiator (IRGACURE 907, manufactured by Ciba-Geigy Japan Ltd.) and 0.4 parts by mass of a photosensitizer (KAYACURE DETX, NIPPON KAYAKU CO., LTD.) Production) is dissolved in a mixture of 750 parts by mass of cyclohexanone and 190 parts by mass of methyl ethyl ketone. To the solution thus obtained, 105 parts by mass of a titanium dioxide dispersion and 21 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, NIPPON KAYAKU CO., LTD.) Were added. The mixture was stirred at room temperature for 30 minutes, and then filtered through a polypropylene filter (PPE-03) having a pore size of 3 microns to prepare a middle refractive layer coating solution B. (Preparation of coating solution for high refractive layer) 0.13 parts by mass of a photopolymerization initiator (IRGACURE 907, manufactured by Ciba-Geigy Japan Limited) and 0.04 parts by mass of a photosensitizer (made by KAYACURE DETX, NIPPON KAYAKU CO., LTD.) Soluble in a mixture of 54 parts by mass of cyclohexanone and 18 parts by mass of methyl ethyl ketone. Then, 26.4 parts by mass of a titanium dioxide dispersion and 1.6 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPH A, NIPPON KAYAKU CO., LTD.) Were added to the resulting solution. The mixture was stirred at room temperature for 30 minutes' and then filtered through a polypropylene filter (PPE-0-3) having a pore size of 3 m to prepare a high refractive layer coating solution. (Preparation of coating solution for low refractive layer) -63- 200302923 A 6 mass% methyl ethyl ketone solution with a thermally crosslinkable fluoropolymer (jn-7228, manufactured by JSR) with a refractive index of 1.42 The solvent substitution is accepted to obtain a polymer solution having a solid content of 10% by mass, which is based on methyl isobutyl ketone containing 85% by mass and 15% by mass. A 2-Butanol mixed solvent. To 70% by mass of the polymer solution thus obtained was added 10% by mass of a methyl ethyl ketone dispersion of M EX-ST (S i 0 2 sol. The average particle diameter of the sol was from 10 to 20 nm. The content concentration was 30% by mass, and was produced from NISSAN CHEMICAL INDUSTRIES, LTD.) '42 parts by mass of methyl ethyl ketone and 28 parts by mass of cyclohexanone. The mixture was stirred and filtered through a polypropylene filter (PPE-0-3) having a pore size of 3 microns to prepare a low-refractive-layer coating solution. (Preparation of anti-reflection film) The aforementioned hard coat coating solution A was applied on a triethyl cellulose film (TAC-TD80U, manufactured by Fjui Photo Film Co., Ltd.) with a thickness of 80 micrometers using a print coater, and then Drying at 10 ° C for 2 minutes. Subsequently, the applied material was irradiated with ultraviolet light to cure the coating to form a hard coating layer (refractive index: 1.5 1; thickness: 6 microns). Subsequently, it was printed with an applicator. The aforementioned intermediate refractive layer coating solution A was applied on the hard coat layer and dried at a temperature of 100 ° C, and then the coating was cured by irradiation with ultraviolet light to form a intermediate refractive layer (refractive index: 1 · 63, thickness: 6 7nm). Apply the aforementioned high-refractive layer coating solution to the middle-refractive layer with a print coater, dry it at a temperature of 100 ° C, and then irradiate with ultraviolet light to cure the coating to form a high-refractive layer (refraction). Ratio: 1. 9 〇; thickness: 〇 07 nm). In addition, the aforementioned low refractive index coating solution was applied to the high refractive layer using a print coater. Then, the coating was cured at 120 ° C to form Low-refractive layer (refractive index: 200302923 1 · 4 3; thickness: 86 nm). Thus, an anti-reflection film was made. ( Setting of anti-glare properties) If the obtained anti-reflection film is embossed by a single-sided embossing calender (made by YURI ROLL CO., LTD.), The machine has a steel pressing roller and has the required surface Shape; and a support roller coated with polyamide material on its surface. A pressure of 1,000 kg / cm is applied, the temperature of the preheating roller is 100 ° C, and the temperature of the embossing roller 16 (TC, operating rate 2 m / min, the ratio of the inclination angle not less than 10 ° is 1%, the average inclination angle is 4.5 °, and the average distance between each peak is 10 microns (evaluation of anti-reflection film ) Then, the obtained film was evaluated for the following properties. (1) The specular reflectance was measured with a V-5 56 type spectrometer (manufactured by JASCO) with an ARV-474 type connector thereon at an incidence angle of 5 ° and -5. ° The exit angle is measured at the specular reflectance of the film in the wavelength range from 380 to 780 nm. Then the average response ratio is obtained by averaging the measurements in the wavelength range from 450 to 650 nm to evaluate Anti-reflective properties of the film. (2) Evaluation of pencil hardness In order to obtain the scratch resistance index, the film was evaluated according to SK 5 4 0 0 Pen hardness. The anti-reflection film is adjusted at 25 ° C and 60% RH for 2 hours, and then the hardness is evaluated with a 2Η to 55 test pencil. The pencil is defined by JISS 6 0 6 and the load is 500 grams, as follows The standard is to use the highest allowable hardness. If the number of scratches found in the sample (η = 5) is evaluated from 0 to 2: Pass (ΟΚ) 200302923 If the number of scratches found in the sample (n = 5) is evaluated as 3 Or more: failed to pass (NG) ^ (3) contact angle measurement · In order to obtain the surface stain resistance index, the optical material was adjusted to a temperature of 2 5 t and a humidity of 60 ° / 〇RH for 2 hours, and then Measure the contact angle for pure water. The fingerprint adhesion index is then obtained. The results are as follows: Specular reflection ratio: 0.27% Pencil hardness evaluation: 3 接触 Measured contact angle: 103 ° (hot water treatment) The obtained film was immersed in hot water under the conditions shown in Table 3 for hot water treatment. Then, the film subjected to such hot water treatment was exposed to a high temperature and humidity environment of 65 ° C and 95% RH, so that the accelerated test was performed to obtain the uniformity of the unevenness on the embossed surface during the extended service life. Then compare under different conditions and with untreated products. The results are shown in Table 3. -66- 200302923 Table 3 Percentage of Roughness Arithmetic Mean of Hot Water Treatment Conditions R Example Temperature (t) Time (seconds) 100 hours after 5 00 hours after 1000 hours 1 A 60 60 5 5 5 1 5 0 2 A 60 1000 66 5 8 5 3 3 A 70 60 65 54 5 1 4 A 70 1000 75 64 5 7 5 A 8 0 6 0 92 9 0 8 5 6 A 80 1 20 94 9 1 89 7 A 90 6 0 96 9 5 92 8 A 90 1 20 98 97 96 9 A 1 00 1 90 82 73 1 0 A 1 00 6 0 98 97 95

實施例1 A至1 0 A之抗反射膜初始不但展現十分合宜之 反射性質，而且耐刮損性優異，純水有高接觸角，因而斥 水性或斥油性優異，使有優良耐污性，而高的鉛筆硬度使 · 其難被刮損。根據本發明而已接受熱水處理之實施例1 A 至10A之抗反射膜，甚至曝於65t和95%RH之高溫度和 濕度環境下1 〇 〇 〇小時後，其表面算術平均粗糙度之保持百 分比展現不小於3 0 %，因此有優異耐用性。The anti-reflection films of Examples 1 to 10 A not only exhibited very suitable reflective properties at the beginning, but also had excellent scratch resistance. Pure water had a high contact angle, so it had excellent water repellency or oil repellency, resulting in excellent stain resistance. And high pencil hardness makes it difficult to scratch. The anti-reflection films of Examples 1 A to 10A that have been subjected to hot water treatment according to the present invention, even after being exposed to high temperature and humidity environments of 65t and 95% RH for 1,000 hours, the surface arithmetic average roughness is maintained The percentage display is not less than 30%, so it has excellent durability.

實施例1 1 A 曾經熱水處理之實施例7 A抗反射膜被浸入於有5 5 t溫 度之2.0 N N a Ο Η水溶液2分鐘使在其背側之三乙醯基纖維 素皂化。一厚度80微米之三乙醯基纖維素膜在與上述相同 -67- 200302923 情形中接受皂化。一偏光片製自於使聚乙烯醇吸收碘，然 後將薄膜拉伸並與兩薄膜層積於其各側而予保護，製成偏 - 光板。然後如此所製之偏光板被用於以其抗反射膜置於最 s 外表面，取代在含有透射型TN液晶顯示單元（具有d-BEF ’爲具有產自Sumitomo 3M Co. Ltd·之偏光選擇層之偏光 分離膜，夾插於背光板和液晶胞之間）之筆記型個人電腦內 之觀看側偏光板。結果，獲得背量反射極小之顯示單元而 有非常高的顯示品質。 實施例1 2 Α Φ 依隨實施例1 1 A之皂化程序’但抗反射膜被用# 3棒塗以 一種1 . 0 N之Κ Ο Η水溶液於其有側，處理於6 〇它溫度經1 〇 秒鐘’用水洗’然後乾燥。然後將如此製成之偏光板裝於 液晶顯示單元上。結果’獲得具有如實施例〗丨Α高顯示品 質的顯示單元。Example 1 1 A Example 7 A, which had been subjected to hot water treatment, was immersed in a 2.0 N N a 0 Η aqueous solution having a temperature of 55 t for 2 minutes to saponify triethylfluorene-based cellulose on its back side. A triethylammonium cellulose film with a thickness of 80 microns was subjected to saponification in the same situation as above. A polarizer is made by allowing polyvinyl alcohol to absorb iodine, and then stretching the film and laminating it with two films on each side to protect it to make a polarizing plate. Then the polarizing plate made in this way is used to place the anti-reflection film on the outermost surface, instead of containing a transmissive TN liquid crystal display unit (with d-BEF 'is a polarizing choice made by Sumitomo 3M Co. Ltd. Layer of polarizing separation film, sandwiched between the backlight panel and the LCD cell) viewing side polarizer in a notebook personal computer. As a result, a display unit with extremely little back reflection is obtained with very high display quality. Example 1 2 Α Φ According to the saponification procedure of Example 1 1 A, but the antireflection film was coated with a # 3 rod with a 1.0 N aqueous solution of KO on its side, and treated at 60 ° C. 'Wash with water' for 10 seconds and then dry. The polarizing plate thus produced was then mounted on a liquid crystal display unit. As a result, a display unit having a high display quality as in the embodiment is obtained.

實施例1 3 A 在具有實施例1 2 A之抗反射膜裝設於其上透射型τ N液 馨 晶胞中’若在液晶胞側上之保護膜，和在觀看側上偏光板 側背光上的保護膜，各用一視角擴張膜（s A _丨2 B型廣視膜 ’ Fuji Photo Film Co· Ltd.)，含有一光學補償層，經安排 使碟形結構單元以其碟面傾斜於透明支持物表面，且由碟 形結構單元之碟形表面與透明支持物表面所形成之夾角隨 光學非等方向層之深度方向改變。結果，獲得在白光下有優 異對比之顯示單元，有極寬的水平和垂直視角，極爲優異之 明視性和高顯示品質。 -68- 200302923Example 1 3 A In a transmissive τ N liquid crystal cell having the anti-reflection film of Example 1 2 A mounted thereon, if the protective film is on the liquid crystal cell side, and the polarizer side backlight is on the viewing side Protective film on the surface, each with a viewing angle expansion film (s A _ 丨 2 B wide-view film 'Fuji Photo Film Co. Ltd.), containing an optical compensation layer, arranged to tilt the disc-shaped structural unit with its disc surface On the surface of the transparent support, and the angle formed by the dish-shaped surface of the dish-shaped structural unit and the surface of the transparent support changes with the depth direction of the optical anisotropic layer. As a result, a display unit having excellent contrast under white light is obtained, with extremely wide horizontal and vertical viewing angles, extremely excellent clearness and high display quality. -68- 200302923

實施例1 4 A 在某一側設有抗反射膜而製於實施例1 2 A之偏光板被層 積一 λ/4板至其在與抗反射膜相反之一面，然後將所得層 積物至在有機E L顯示單元中之表面玻璃板上。結果’獲 得具有極佳明視度，在其表面和表面玻璃之內部均無反射 之顯示單元。Example 1 4 A The anti-reflection film was provided on one side and the polarizing plate prepared in Example 1 2 A was laminated with a λ / 4 plate to the side opposite to the anti-reflection film, and then the obtained laminate was laminated. To a surface glass plate in an organic EL display unit. As a result, a display unit having excellent brightness and no reflection on the surface and the inside of the surface glass was obtained.

實施例1 5 A (防眩硬塗層塗覆溶液A之製備） 對2 4 5克市售之含矽石UV (紫外光）固化之硬塗溶液（獲 自修改J S R公司所產D e s 〇 Π t e Z 7 5 2 6之溶劑組成；溶劑組 成爲：57/43之甲基異丁基酮與甲基乙基酮之混合物；固 含量濃度：大約7 2 % ;固含量內之s 1 0 2含量大約3 8 % ;含 有可聚合單體和聚合起始劑）’加入19.6克Y-丙烯氧丙基 三甲氧基矽烷（KBM-5103，Shin-Etsu Chemical Co.，Ltd. 產）。然後用3 3 . 6克甲基異丁基酮稀釋此混合物。施用此 溶液並用紫外光固化塗物而得塗層，展現1 . 5 1之折射率。 然後加入44克由分散具有平均粒徑爲3 . 5微米之粒狀可 交聯聚苯乙嫌之25%甲基異丁基酮分散液（商名：8乂-3501! ’產自 Soken Chemical &amp; Engineering Co·, Ltd.)而得之分 散液於10,000rpm(每分轉數）於Polytron分散器中30分鐘 。隨後，於此混合物中加入5 7 · 8克之分散液，獲自分散一 種具有5微米平均粒徑之粒狀可交聯聚苯乙烯之2 5 %甲基 異丁基酮分散液（商名：SX-500H，產自Soken Chemical &amp; Engineering Co.，Ltd.)於 1 0,000rpm 於 polytr〇n 分散液器 200302923 內3 0分鐘。 經過孔徑爲3 0微米之聚丙烯濾片過濾前述混合物而製 成防眩硬塗層塗覆溶液Α。 (低折射層塗覆溶液A之製備） 於1 77克具有1 .42之折射率之可熱交聯之含氟聚合物 (JN_7228，JSR公司所產，固含量濃度：6%)中加入15.2 克矽石溶膠（MEK-ST;平均粒徑：10至20奈米，固含量 濃度·· 30%，NISSAN CHEMICAL INDUSTRIES，LTD.所產） ，9 5克甲基乙基酮和9 · 0克環己酮。攪拌此混合物，然後 用孔徑1微米之聚丙烯濾片過濾製成低折射層塗覆溶液A。 (樣品1 5 A ) (1 )防眩硬塗層之塗覆 施加上述防眩硬塗層塗覆溶液A至一卷厚度80微米之 三乙醯基纖維素（TAC-TD80U，產自 FujiPhotoFilmCo.， Ltd·)上，於其被展開之時，使用微印輥，直徑50毫米而 有每吋1 8 0線之印紋，深度4 0微米，在轉速爲3 0 r p m之 印輥上醫生刮刀之輸送速率爲5米/秒；然後在1 2 (TC溫度 乾燥4分鐘。再用輸出爲160瓦/厘米之氣冷金屬鹵化燈 (EYE-GRAPHICS Co. Ltd.生產）之紫外光照射塗層於400 毫瓦/厘米2之照度和3 0 0毫焦耳/厘米2之劑量於氮氣氛中 。使固化至在傾斜角不小於1 0 °之比例爲2 %之厚度，而平 均傾斜角爲4 · 5 °，且各峯突間之平均間距爲1 〇微米，因此 形成防眩硬塗層。然後收捲薄膜。 (2)低折射層之塗覆 200302923 以上述之低折射層塗覆溶液施加於一卷防眩硬塗層於其 上之三乙醯基纖維素膜於其被展開之時，用直徑5 0毫米而 有每吋1 8 0線且深度爲4 0微米之微印輥，在轉速爲3 0 r p m 之印輥上醫生刮刀之輸送速率爲1 〇米/秒，然後在8 0 °C溫 度乾燥2分鐘。塗層再用具有240瓦/厘米輸出之氣冷金屬 鹵素物燈（產自EYEGRAPHICS Co· Ltd·)之紫外光照射於 400毫瓦/厘米2之照度、3 0 0毫焦耳/厘米2之劑量和140 °C 溫度於氮氣氛中1 〇分鐘，使其因熱交聯而形成厚度達 0.0 9 6微米之低折射層。收捲薄膜。 樣品表面用金作真空金屬化，然後在S EM下照像。二維 網絡結構之呈現被確認於照片上。 樣品1 5 A在白迹、黑而爲黑之明視程度、防眩性質與閃 爍方面與樣品8相似而耐刮損性優異，其如鋼絨之耐擦拭 性和用濕棉花棒之耐擦拭性。 本申請案是基於日本專利申請案J P 2 0 0 2 - 2 3 8 7 0，申請於 2002年元月31日；和日本專利申請案JP 2002-4566，申 請於2 0 0 2年元月1 1日，其全部內容在此納爲參考，一如 其詳細之所表示。 (五）圖式簡單說明 第1圖是一剖面模型圖，表示根據本發明防眩光學薄膜 各層之構造。 第2圖是一模型圖，表示在本發明中傾斜角之量測。 第3圖舉例表示設置具有防眩性質之塗覆型抗反射膜之 方法實施例。 -7 1- 200302923 第4圖是一示意剖面圖，舉例表示待壓花之抗反射膜之 基本層結構。 第5圖舉例說明從層上觀看之二維網狀結構。 第6圖舉例說明從層上觀看之二維網狀結構。 主要部分之代表符號說明 1 透 明 支 持 物 2 硬 塗 層 3 低 折 射 層 4 顆 粒 7 空 孔 8 Μ j\ \\ 機 材 料 2 1 抗 反 射 膜 22 透 明 支 持 物 2 3 抗 反 射 層 24 壓 花 輥 2 5 支 承 輥 2 11 透 明 支 持 物 2 12 硬 塗 層 2 13 中 折 射 層 2 14 局 折 射 層 2 15 低 折 射 層Example 1 5 A (Preparation of anti-glare hard coat coating solution A) To 2 4 5 g of a commercially available silica-containing UV (ultraviolet) -cured hard coat solution (obtained from modified Des produced by JSR Corporation). The solvent composition of Π te Z 7 5 2 6; the solvent composition is: a mixture of methyl isobutyl ketone and methyl ethyl ketone of 57/43; solid content concentration: about 72%; s 1 0 within the solid content 2 content of about 38%; containing polymerizable monomers and polymerization initiator) '19 .6 g of Y-propoxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) was added. This mixture was then diluted with 33.6 grams of methyl isobutyl ketone. A coating was obtained by applying this solution and curing the coating with ultraviolet light, exhibiting a refractive index of 1.51. Then, 44 grams of a 25% methyl isobutyl ketone dispersion (trade name: 8 乂 -3501!) Produced by dispersing a particulate crosslinkable polystyrene having an average particle diameter of 3.5 microns was added. &amp; Engineering Co., Ltd.) in a Polytron disperser at 10,000 rpm (revolutions per minute) for 30 minutes. Subsequently, 57.8 g of a dispersion liquid was added to this mixture, and was obtained from a 25% methyl isobutyl ketone dispersion (a trade name: SX-500H, manufactured by Soken Chemical &amp; Engineering Co., Ltd.) at 10,000 rpm for 30 minutes in a polytrön disperser 200302923. The foregoing mixture was filtered through a polypropylene filter having a pore size of 30 m to prepare an anti-glare hard coat coating solution A. (Preparation of coating solution A for low-refractive layer) To 17.77 g of a heat-crosslinkable fluoropolymer having a refractive index of 1.42 (JN_7228, produced by JSR Corporation, solid content concentration: 6%) was added 15.2 Grams of silica sol (MEK-ST; average particle size: 10 to 20 nm, solid content concentration · 30%, manufactured by NISSAN CHEMICAL INDUSTRIES, LTD.), 95 grams of methyl ethyl ketone and 9.0 grams Cyclohexanone. This mixture was stirred, and then filtered through a polypropylene filter having a pore size of 1 m to prepare a low refractive layer coating solution A. (Sample 1 5 A) (1) Application of anti-glare hard coat coating The above-mentioned anti-glare hard coat coating solution A was applied to a roll of 80 micron-thick triacetyl cellulose (TAC-TD80U, produced by FujiPhotoFilmCo. , Ltd.), when it was unrolled, a microprinting roller was used, with a diameter of 50 mm and a pattern of 180 lines per inch, a depth of 40 microns, and a doctor blade on a printing roller at a speed of 30 rpm. The conveying rate is 5 m / s; then it is dried at 12 (TC temperature for 4 minutes. The coating is irradiated with ultraviolet light of an air-cooled metal halide lamp (produced by EYE-GRAPHICS Co. Ltd.) with an output of 160 W / cm.) Illumination at 400 mW / cm2 and a dose of 300 mJ / cm2 in a nitrogen atmosphere. Cured to a thickness of 2% at a tilt angle of not less than 10 °, and an average tilt angle of 4 · 5 °, and the average distance between the peaks is 10 microns, so an anti-glare hard coating is formed. Then the film is rolled up. (2) Coating of the low refractive layer 200302923 Apply the coating solution of the low refractive layer described above When a roll of triethyl cellulose film with an anti-glare hard coating layer on it was unrolled, a diameter of 50 mm was used with 180 threads per inch. A microprinting roller with a depth of 40 microns, a doctor blade conveying speed of 10 m / s on a printing roller with a rotation speed of 30 rpm, and then drying at 80 ° C for 2 minutes. The coating is reused with 240 watts / Cm output of air-cooled metal halide lamps (produced by EYEGRAPHICS Co. Ltd.) with ultraviolet light irradiated at 400 mW / cm2, a dose of 300 mJ / cm2, and a temperature of 140 ° C under nitrogen In the atmosphere for 10 minutes, it formed a low-refractive layer with a thickness of 0.096 micrometers due to thermal crosslinking. The film was rolled up. The surface of the sample was vacuum metallized with gold and then photographed under S EM. Two-dimensional network structure The appearance is confirmed on the photograph. Sample 1 5 A is similar to sample 8 in terms of whiteness, black and blackness of the visual acuity, anti-glare properties and flickering, and has excellent scratch resistance, such as steel wool scratch resistance And the wipe resistance of wet cotton swabs. This application is based on Japanese patent applications JP 2 0 2-2 3 8 70, filed on January 31, 2002; and Japanese patent application JP 2002-4566, The application is on January 11, 2002, the entire contents of which are hereby incorporated by reference, as shown in its detailed table (V) Brief Description of Drawings Figure 1 is a sectional model diagram showing the structure of each layer of the anti-glare optical film according to the present invention. Figure 2 is a model diagram showing the measurement of the tilt angle in the present invention. The figure shows an example of a method for setting a coating type anti-reflection film with anti-glare properties. -7 1- 200302923 Figure 4 is a schematic cross-sectional view illustrating the basic layer structure of the anti-reflection film to be embossed. Figure 5 illustrates the two-dimensional network structure viewed from the layer. Figure 6 illustrates the two-dimensional network structure viewed from the layer. Description of the representative symbols of the main parts 1 transparent support 2 hard coating 3 low refractive layer 4 particles 7 voids 8 μ j \ \\ machine material 2 1 antireflection film 22 transparent support 2 3 antireflection layer 24 embossing roller 2 5 Support roll 2 11 Transparent support 2 12 Hard coat layer 2 13 Middle refractive layer 2 14 Local refractive layer 2 15 Low refractive layer

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Claims (1)

200302923 拾、申請專利範圍 1 . 一種防眩光學薄膜，包含：一透明薄膜基板，具有微細 不均勻表面結構設於透明薄膜基板至少一側上，其中不 小於1 〇 °之傾斜角之比例不大於2 %，且在不均勻表面中 之各峯突之平均間距爲自1微米至50微米。 2 .如申請專利範圍第1項之防眩光學薄膜，其中各峯突之 平均間距爲自1微米至2 0微米。 3 .如申請專利範圍第1或2項之防眩光學薄膜，其中在自 1至2微米2薄膜表面所量測對於規律反射面之平均傾斜 角爲不小於1 °至小於5 °。 4 .如申請專利範圍第1至3項中任一項之防眩光學薄膜， 在其最上方表面上含有一抗反射層。 5 .如申請專利範圍第1至3項中任一項之防眩光學薄膜， 其中微細不均勻表面結構是以壓花粗化薄膜表面而形成 ，使防眩光學薄膜防眩。 6 .如申請專利範圍第5項之防眩光學薄膜，另含一抗反射 層，其中由如下式（I)所定義之算術平均粗糙度之保持百 分比R不小於3 0 % : R = Ra/Rb 式⑴ 其中RA代表防眩光學薄膜在65°c和95%RH(相對濕度） 之環境中貯存1，〇 〇 〇小時後之表面算術平均粗糙度；而 Rb代表防眩光學薄膜貯存於65 °C和95 %RH(相對濕度） 環境前之表面算術平均粗糙度。 7 .如申請專利範圍第1至4項中任一項之防眩光學薄膜， -73- 200302923 至少含有一向前散射層，夾插於防眩層與基板之間。 8 . —種製備防眩光學薄膜之方法，包含在透明薄膜基板之 至少一面上設置一微細不均勻表面結構，方法中包括： 薄膜表面之壓花，使不均勻表面中不小於1 〇 °之傾斜角 之比例不大於2 %，且各峯突之平均間距爲自1微米至 50微米。 9 .如申請專利範圍第8項之方法，其中各峯突之平均間距 爲自1微米至20微米。 1 〇 .如申請專利範圍第8或9項之方法，其中在自1至2微 米2之薄膜表面上所量得對於規律反射面之傾斜角爲自 不小於1 °至小於5 °。 1 1 .如申請專利範圍第8至1 0項中任一項之方法，其中防 眩光學薄膜包含一抗反射層於最上方之表面層上，且抗 反射層之表面接受壓花。 1 2 .如申請專利範圍第1 1項之方法，其中由如下式（I)所定 義之算術平均粗糙度之保持百分比R不小於3 0 % : R = Ra/Rb 式（I) 其中Ra代表抗反射層表面在65 °c和95 % RH (相對濕度） 之環境內貯存1，〇〇〇小時後之算術平均粗糙度；而Rb 代表抗反射層表面在貯存於6 5 °C和9 5 % RH (相對濕度） 前之算術平均粗糙度。 1 3 .如申請專利範圍第1 2項之方法，另含：使防眩光學薄 膜壓花後在含水量不小於1 〇重量％之溶液中或在溶液之 蒸汽中接受60°C至200°C之溫度1〇,〇〇〇至1〇〇,〇〇〇秒。 200302923 1 4 . 一種製備含有透明薄膜基板和被設置於基板至少一面 上之防眩層之防眩光學薄膜之方法，防眩層具有微細不 1 均勻之表面結構，方法包括：調整防眩層使不小於1 〇 ° · 之傾斜角之比例不大於2%，且在微細不均勻表面中各峯 突之平均間距爲自1微米至5 0微米。 1 5 . —種偏光板，包含一偏光片和分別層積於偏光片兩表面 上之兩表面保護膜，其中各表面保護膜至少有一爲根據 申請專利範圍第1至7項中任一項之防眩光學薄膜。 1 6 . —種顯示單元，含有如申請專利範圍第1至7項中任一 € 項之防眩光學薄膜，或如申請專利範圍第1 5項之偏光板。200302923 Patent application scope 1. An anti-glare optical film comprising: a transparent film substrate having a fine uneven surface structure provided on at least one side of the transparent film substrate, wherein the proportion of the inclination angle of not less than 10 ° is not greater than 2%, and the average pitch of each peak in the uneven surface is from 1 micrometer to 50 micrometers. 2. The anti-glare optical film according to item 1 of the patent application, wherein the average pitch of each peak is from 1 micrometer to 20 micrometers. 3. The anti-glare optical film according to item 1 or 2 of the patent application scope, wherein the average inclination angle of the regular reflective surface measured on the surface of the film from 1 to 2 microns 2 is not less than 1 ° to less than 5 °. 4. The anti-glare optical film according to any one of claims 1 to 3, comprising an anti-reflection layer on the uppermost surface. 5. The anti-glare optical film according to any one of claims 1 to 3, wherein the fine uneven surface structure is formed by embossing and roughening the surface of the film to make the anti-glare optical film anti-glare. 6. The anti-glare optical film according to item 5 of the scope of patent application, further comprising an anti-reflection layer, wherein the retention percentage R of the arithmetic average roughness defined by the following formula (I) is not less than 30%: R = Ra / Formula Rb: where RA stands for the arithmetic average roughness of the anti-glare optical film stored at 65 ° C and 95% RH (relative humidity) for 1,000 hours; and Rb stands for the anti-glare optical film stored at 65 ° C and 95% RH (relative humidity) Surface arithmetic average roughness before environment. 7. The anti-glare optical film according to any one of items 1 to 4 of the scope of application for patents, -73- 200302923 at least contains a forward scattering layer interposed between the anti-glare layer and the substrate. 8. A method for preparing an anti-glare optical film, comprising setting a fine uneven surface structure on at least one side of a transparent film substrate, the method includes: embossing the surface of the film so that the uneven surface is not less than 10 ° The ratio of the inclination angle is not more than 2%, and the average pitch of each peak is from 1 micrometer to 50 micrometers. 9. The method according to item 8 of the patent application, wherein the average pitch of each peak is from 1 micrometer to 20 micrometers. 10. The method according to item 8 or 9 of the scope of patent application, wherein the inclination angle of the regular reflecting surface measured on the film surface from 1 to 2 m 2 is not less than 1 ° to less than 5 °. 11. The method according to any one of claims 8 to 10 in the scope of patent application, wherein the anti-glare optical film comprises an anti-reflection layer on the uppermost surface layer, and the surface of the anti-reflection layer receives embossing. 1 2. The method according to item 11 of the scope of patent application, wherein the retention percentage R of the arithmetic average roughness defined by the following formula (I) is not less than 30%: R = Ra / Rb Formula (I) where Ra represents The surface roughness of the anti-reflection layer at 65 ° C and 95% RH (relative humidity) after 1 000 hours of arithmetic mean roughness; and Rb represents the surface of the anti-reflection layer at 6 5 ° C and 9 5 Arithmetic average roughness before% RH (relative humidity). 13. The method according to item 12 of the scope of patent application, further comprising: after embossing the anti-glare optical film, accepting 60 ° C to 200 ° in a solution having a water content of not less than 10% by weight or in the steam of the solution The temperature of C is 10,000 to 100,000 seconds. 200302923 1 4. A method for preparing an anti-glare optical film containing a transparent film substrate and an anti-glare layer provided on at least one side of the substrate. The anti-glare layer has a fine and uneven surface structure, and the method includes: adjusting the anti-glare layer so that The ratio of the inclination angle of not less than 10 ° is not more than 2%, and the average pitch of each peak in a fine uneven surface is from 1 micrometer to 50 micrometers. 15. A polarizing plate comprising a polarizer and two surface protective films laminated on both surfaces of the polarizer, wherein at least one of the surface protective films is one of any one of items 1 to 7 according to the scope of patent application. Anti-glare optical film. 16. A display unit containing an anti-glare optical film as in any one of the items 1 to 7 of the scope of patent application, or a polarizing plate as in the 15th scope of patent application. -75--75-