201041740 六、發明說明： 【發明所屬之技術領域】 , 本發明係關於光學用保護薄膜及其製造方法以及偏光 板及其製造方法，更詳細地，本發明係關於下述光學用保 護薄膜、更有效地製造其之方法，該光學用保護薄膜爲作 爲液晶顯示裝置中的偏光板和1/4波長片用、或者作爲觸 控面板用、光碟的覆蓋薄膜、各種顯示器的保護薄膜等而 適宜的具有硬塗層功能的光學用保護薄膜，還關於採用上 f) 述光學用保護薄膜的偏光板及其製造方法。 背景技術 【先前技術】 一直以來’具有硬塗層功能的光學用保護薄膜在各種 圖像顯示裝置’例如LCD(液晶顯示器）、觸控面板、CRT(陰 極射線管）、PDP(等離子顯示面板）、EL(場致發光元件）等 中，以表面保護開始，以防眩性、抗反射等目的而使用。 Q 而且’還在LCD中使用’以保護偏光片。該光學用保護薄 膜一般在基材薄膜上具有由熱硬化、活性能量線硬化等形 成的硬塗層。 另一方面，近年來’作爲資訊記錄介質的光碟的發展 異常顯著。在記錄容量增加的同時，也開發出了 CD、DVD、 ^ 甚至BD。至於BD，發展到了具有最大50GB左右的記錄 . 容量。在這些光碟中也經常使用作爲保護薄膜和覆蓋薄膜 的具有硬塗層功能的光學用保護薄膜。 可是’液晶顯示裝置爲以液晶層所具有的電光學特性 201041740 調製入射的直線偏光、以射出側的偏光板作爲透射率的強 弱和著色的信號而視覺化的裝置。即，將偏光用於其顯示 . 的原理，所以偏光板爲必需的構件。該偏光板爲將自然光 . 變爲直線偏光的元件。現在，特別是用於液晶顯示裝置量 產實用化的偏光板的多數爲在聚乙烯醇薄膜形成的基材薄 膜上，將碘、二色性的染料等的二色性的材料進行染色、 吸附，延伸取向而構成偏光膜，在該偏光膜的兩面或單面 貼合光學上透明而且具有機械強度的保護薄膜而使用。而 ❹ 且，作爲上述保護薄膜，要求雙折射小、光學上各向同性 程度高；光線透射率高；耐熱性優良；機械性能優良；平 面性良好；與偏光片的黏結性良好等。爲此，一直以來使 ^ 用纖維素系薄膜（參照專利文獻1)。 現在，作爲纖維素系薄膜，一般使用三乙酸酯（以下也 « 稱作TAC)。可是，TAC薄膜的耐濕熱性不充分，如果將 TAC薄膜作爲偏光片保護薄膜使用的偏光板在高濕度下使 〇 用，則具有偏光度、色調等的偏光板的性能低下的缺點。 又，TAC薄膜相對斜方向的入射光產生相位差。該相 位差近年來伴隨液晶顯示器的大型化的發展，顯著地影響 到了視角特性。 再者，在液晶顯示裝置中，來自於通常光源的射出光 Λ 根據圓偏光構件圓偏光化、將其通過1/4波長片進行直線 ' 偏光化，供給偏光板。而且，對於上述1/4波長片，也設 置具有硬塗層功能的光學用保護薄膜。 201041740 作爲耐濕性良好、耐久性優異的保護薄膜，揭示有將 丙烯酸系樹脂單體或丙烯酸系樹脂組成物成形而得到的薄 • 膜貼合到兩面的偏光板（參照專利文獻2)。可是，有在貼合 . 時使用黏結劑、在貼合前進行塗布的必要，在生產性上不 好’而且作爲將保護薄膜在兩面進行貼合時使用的黏結 劑’雖有在光學上各向同性優異所以較佳的記載，但也不 過僅例舉了一般的聚乙烯醇系黏結劑、胺基甲酸酯系黏結 _ 劑、環氧系黏結劑、丙烯酸系黏結劑。即，關於符合本發 〇 明的黏結劑層的黏結劑的種類、性狀如果沒有任何規定、 任何考慮的場合，擔心基於黏結劑和保護薄膜之間的折射 率不同而產生的視認性的惡化等情況。又，該保護薄膜中 , 沒有形成硬塗層。 < 再者，在專利文獻3中，揭示了光學薄膜以及將該光 學薄膜在偏光片的至少一個面上形成而得到的偏光板，該 光學薄膜將電離放射線硬化性樹脂組成物交聯硬化而得 〇 到，該電離放射線硬化性樹脂組成物含有（A)重量平均分子 量爲50000〜80000的單官能（甲基）丙烯酸聚合物70~95 質量％以及（B)具有多官能的自由基聚合性不飽和雙鍵的化 合物5~30質量％。該光學薄膜爲改良了可撓性以及薄膜運 送性的薄膜，作爲黏合於該光學薄膜時的黏結劑，只不過 " 例舉了 一般的PVA系黏結劑、環氧系黏結劑、丙烯酸系黏 ' 結劑、聚烯烴系黏結劑、聚乙烯醚系黏結劑、橡膠系黏結 劑’關於黏結劑的種類、性狀沒有任何規定。它們的問題 201041740 點與上述同樣。進而，通過向（A)成分裏添加（B)成分擔 心因相分離等而導致的光學特性的惡化。又，該光學薄膜 • 中沒有形成硬塗層。 - 作爲偏光板中使用的保護薄膜，即使不是現在使用的 TAC薄膜，只要透明性優異、具有光學上各向同性即可， 多數擠塑薄膜可以進行替代。但是，偏光膜（偏光片）現在 一般爲聚乙烯醇系薄膜，所以’與該薄膜的密接性存在困 0 難，又，爲了要求成本便宜的材料，沒有到達實用性的程 度也是現狀。 專利文獻 專利文獻1:日本特開平7-120617號公報 . 專利文獻2:日本特開2007-128025號公報 • 專利文獻3:日本特開2008-129212號公報 【發明內容】 本發明是在這樣的狀況下提出的，其目的在於提供光 〇 學用保護薄膜、更有效地製造其之方法、以及採用該光學 用保護薄膜的偏光板及其製造方法，該光學用保護薄膜特 別適用於偏光板，透明性優異、具有光學各向同性，同時， 耐濕性良好，耐久性優異，而且對偏光膜的密接性良好、 具有硬塗層功能。 本發明人爲了達到上述目的，進行了長期的深入的硏 . 究’結果發現可以得到下述光學用保護薄膜，由硬塗層/ 樹脂層/黏結劑層構成，而且無論哪層都含有（甲基）丙烯酸 201041740 酯系化合物80質量％以上而構成，由此可以將各層界面上 的反射抑制在極低的水準，同時，使各層間密接性飛越性 . 地提高，進而，作爲整體的薄膜強度也優異。 _ 進而，發現將該光學用保護薄膜貼合在偏光膜上，在 偏光膜的另一側也依序層疊含有（甲基）丙烯酸酯系化合物 80質量％以上的黏結劑層以及樹脂層，由此得到的偏光板 具有非常好的視認性等的光學特性，而且可高效地提高各 層的強度，因此，與以前相比，能夠得到薄的偏光板。又， 〇 發現可以得到下述偏光板，將耐濕性優異的（甲基）丙烯酸 酯系化合物作爲除本發明的偏光板的偏光膜外的所有層的 主成分，由此，所得到的偏光板與以前的TAC薄膜作爲基 材的情況相比，耐濕性以及耐漏光性均優異。本發明是基 b 於上述知識與見識而完成的。 即，本發明提供： (1) 一種光學用保護薄膜，其爲將硬塗層（A)、樹脂層（B) Q 以及黏著劑層（c)依序層積而形成的層積薄膜，其特徵在 於··各層均含有80質量％以上的（甲基）丙烯酸酯系化合物。 (2) 根據上述（1)項所記載的光學用保護薄膜，其特徵在 於：樹脂層（B)在溫度23°C的儲藏彈性模數E’爲0.5MPa 以上。 " (3)根據上述（1)或（2)項所記載的光學用保護薄膜，其 ' 特徵在於：黏著劑層（c)係含有多官能活性能量線硬化型化 合物，且在活性能量線照射後的溫度2 3。(：時的儲藏彈性模 201041740 數G’爲0.3MPa以上。 (4) 根據上述（1)~(3)項中任一項所記載的光學用保護 • 薄膜，其特徵在於：硬塗層（A)係對活性能量線感應型組成 . 物層照射活性能量線而形成的。 (5) —種上述（1)~(4)項中任—項所記載的光學用保護 薄膜的製造方法’其特徵在於：包括： (a) 在工程片的一面上’通過澆鑄法形成樹脂層的步 ^ 驟； 〇 (b) 在上述樹脂層（B)上形成硬塗層（A)的步驟；以及 (c) 將上述工程片剝離，在露出的樹脂層（B)面上接合設 置於剝離片上的黏著劑層（C)面以貼合的步驟。 . (6)根據上述（5)項所記載的光學用保護薄膜的製造方 ^ 法’其特徵在於：上述步驟（b)中的硬塗層係對活性能量線 感應型組成物層照射活性能量線而形成的。 (7) —種偏光板，其特徵在於：使偏光膜與上述（1)~ (4) 〇 項中任一項所記載的光學用保護薄膜的黏著劑層（C)面接 合而層積得到。 (8) —種偏光板，其特徵係由：使偏光膜與上述（1)~(4) 項中任一項所記載的光學用保護薄膜的黏著劑層（C)面接 合而層積，且進一步在該偏光膜的另一面側依序層積黏著 ' 劑層（D)以及樹脂層（E)，而且（D)及（E)的各層均爲含有80 • 質量％以上的（甲基）丙烯酸酯系化合物之層所構成的。 (9) 一種附黏著劑層之偏光板，其特徵在於：在上述（8) 201041740 項所述的偏光板的上述樹脂層（E)的露出面側進一步具有 黏著劑層（F)，該黏著劑層（F)含有80質量％以上的（甲基} • 丙烯酸酯系化合物。 . (1〇)—種如上述（8)項所記載之偏光板之製造方法，其 • 特徵在於包括： (a)在工程片的一面上，通過澆鑄法形成樹脂層（B)的步 驟； ^ (b)在上述樹脂層（B)上形成硬塗層（A)的步驟； (c) 將上述工程片剝離，在露出的樹脂層（B)面上接合設 置於剝離片上的黏著劑層（C)面以貼合的步驟；以及 (d) 將上述剝離片剝離，將露出的黏著劑層（C)面貼合 , 至偏光膜的一個面上的步驟； (e) 在另一個工程片的一面上，通過澆鑄法形成樹脂層 (E)的步驟；以及 (f) 在上述樹脂層（E)上，以剝離片上設有的黏著劑層（D) 〇 的露出側的面進行接合的方式進行貼合的步驟；再者， (g) 將上述黏著劑層（D)的上述剝離片剝離，貼合在上述 偏光膜的另一面上的步驟。 (11)根據上述（10)項所記載的偏光板之製造方法，其 特徵在於：上述步驟（b)中的硬塗層（A)係對活性能量線感應 ' 型組成物層照射活性能量線而形成的。 • (12)根據上述（1〇)或（11)項所記載的偏光板之製造方 法，其特徵在於··其中黏著劑層（C)及/或黏著劑層（D)含有 -10- 201041740 多官能活性能量線硬化型化合物，而且具有（h)在上述步驟 (g)之後照射活性能量線的步驟。 * (13) —種附黏著劑層之偏光板之製造方法，其特徵在 . 於：對上述（10)或（1 1)項所得到的偏光板進行（k)在上述樹 脂層（E)上的露出面上，以剝離片上設有的黏著劑層（F)面 進行接合的方式進行貼合的步驟。 (14)根據上述（13)項所記載的附黏著劑層之偏光板之 ^ 製造方法，其特徵在於：黏著劑層（C)、黏著劑層（D)和黏 〇 著劑層（F)中的至少一層含有多官能活性能量線硬化型化 合物，而且具有（1)在上述步驟（k)之後照射活性能量線的步 驟。 . 根據本發明，提供光學用保護薄膜、高效製造其的方 法、以及採用該光學用保護薄膜的偏光板及其製造方法， 該光學用保護薄膜特別適合作爲偏光板使用，透明性優 異、具有光學各向同性的同時，耐濕性良好，耐久性優異， 〇 而且對偏光膜的密接性良好、具有硬塗層功能。 【實施方式】 實施發明之最佳形態 首先，對本發明的光學用保護薄膜進行說明。 [光學用保護薄膜】 ' 本發明的光學用保護薄膜的特徵爲，將硬塗層（A)、樹 • 脂層（B)以及黏著劑層（C)依序層積而形成的層積薄膜，各 層均含有80質量％以上的（甲基）丙烯酸酯系化合物，而且 -11- 201041740 (A)層、（B)層以及（C)層的合計厚度爲15-130// m。又，所 謂的（甲基）丙烯酸酯系化合物是指丙烯酸酯系化合物及/ * 或甲基丙烯酸酯系化合物。同類詞語也表示相同的含義。 . 又，所謂含有表示作爲聚合物或硬化物的單體單元而含有。 [樹脂層（B)] 本發明的光學用保護薄膜中，作爲（B)層而形成的樹脂 層作爲（甲基）丙烯酸酯系化合物，爲含有80質量％以上的 (甲基）丙烯酸酯（共）聚合物的層。 〇 作爲該樹脂層，從機械特性以及成形性的觀點來看， 含有重量平均分子量（MW)爲5萬~50萬，分子量分佈處於 (重量平均分子量Mw/數量平均分子量Μη)爲1.5~3.0的 . 範圍的（甲基）丙烯酸酯（共）聚合物爲佳。如果重量平均分子 ^ 量Mw比5萬小，則所得到的樹脂層的薄膜強度有低下的 情況，重量平均分子量Mw如果大於50萬，則黏度變得過 高，有作業性低下的情況。又，分子量分佈如果比1.5窄， 則所得的樹脂層存在耐衝擊性差的情況，分子量分佈如果 超過3.0，則所得的樹脂層的物理強度低下，存在尺寸精 度惡化的情況。從這樣的觀點出發，重量平均分子量Mw 在10萬~30萬的範圍爲更佳，15萬~25萬的範圍爲尤佳。 又，所謂（共）聚合物指的是同元聚合物及/或共聚物。 ' 上述重量平均分子量（Mw)以及數量平均分子量（Μη) ' 爲以凝膠滲透色譜（GPC)法測量的換算爲標準聚苯乙烯的 値。 -12- 201041740 再者’作爲該樹脂層’從透明性、耐濕性、光學各向 同性、機械強度、吸水率、尺寸穩定性等的平衡的觀點考 • 慮’含有甲基丙烯酸甲酯同元聚合物、及/或甲基丙烯酸甲 - 酯單元在80質量％以上的（甲基）丙烯酸酯共聚物爲佳。 該樹脂層爲上述的（甲基）丙烯酸酯共聚物的場合，作 爲與甲基丙烯酸甲酯進行共聚的（甲基）丙烯酸酯，例如， 可以採用烷基的碳原子數爲2~20左右的單官能（甲基）丙 0 烯酸酯系單體。具體來說可以從（甲基）丙烯酸乙酯、（甲基） 丙烯酸丁酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸第三丁 酯、（甲基）丙烯酸己酯、（甲基）丙烯酸環己酯、（甲基）丙烯 酸2 -乙基己酯、（甲基）丙烯酸十二烷基酯、（甲基）丙烯酸 . 十八烷基酯、（甲基）丙烯酸異冰片基酯、丙烯酸2-羥基乙 酯等中適宜選擇至少一種而使用。 該共聚合用的（甲基）丙烯酸酯，相對於所有的單體， 較佳係採用20質量％以下的比例，適宜用於對樹脂層賦予 〇 可撓性等的目的。又，可以從（甲基）丙烯酸、巴豆酸、馬 來酸、衣康酸等的單體（含有羧基的單體）中至少選擇一種 來替換共聚用的（甲基）丙烯酸酯，或者與其組合使用。此 場合也如前述，共聚合用的單體的合計量，相對於所有單 體，較佳係採用20質量％以下的比例。 ' 聚合方法沒有特別的限制，可以採用已經公知的各種 方法例如本體聚合、溶液聚合、懸浮聚合、乳化聚合等方 法。 -13- 201041740 該樹脂層最好採用澆鑄法（溶液流延法）而形成的。具 體來說，首先將像上述那樣製造的（甲基）丙烯酸酯（共）聚合 . 物溶於適當的有機熔劑’例如乙酸乙酯、甲基乙基酮 '或 . 者甲苯等，進而，添加增塑劑等的添加劑，配置糖稀狀膠 漿。該膠漿在完全除去不純物、氣泡後，作爲支撐體，例 如採用工程片，在其單面上流動展開、形成該樹脂層。又， 作爲工程片，如果是一般使用的話，可以沒有限制而使用。 ^ 例如，較佳係例舉在與樹脂層接觸的面一側設有矽氧烷系 Ο 或氟系的剝離層的聚烯烴系薄膜、聚對苯二甲酸乙二醇酯 薄膜等。 含有如此形成的（甲基）丙烯酸酯（共）聚合物的樹脂 ， 層，其厚度在l〇~80//m左右、較佳爲20~50/zm，而且 • 較佳係在溫度2 3 °C的儲藏彈性模數E ’爲0.5 M Pa以上，爲 2 MPa以上爲更佳。關於其上限沒有特別限制，通常爲 70MPa左右。樹脂層的厚度如果在上述範圍，可以充分發 G 揮·作爲保護薄膜的性能。又，如果上述儲藏彈性模數E，不 足0.5 M Pa時，該樹脂層的機械強度低，作爲保護薄膜的 性能變得不充分。 又，溫度23°C時的儲藏彈性模數E，爲基於Jis K 7244-4而測定的値。 [硬塗層（A)] 本發明的光學用保護薄膜中，在如上形成的樹脂層 上作爲（A)層設置硬塗層。通過設置硬塗層，不僅可以防止 -14- 201041740 表面的劃傷，而且可以提高光學用保護薄膜的薄膜強度， 具有降低樹脂層的膜厚的效果。 - 在該硬塗層的形成中，可以採用活性能量線感應型組 . 成物。 〈活性能量線感應型組成物〉 作爲活性能量線感應型組成物較佳係含有⑴多官能性 (甲基）丙烯酸酯系單體及/或（甲基）丙烯酸酯系預聚物、（u) 二氧化矽系微粒及/或（iii)有機微粒。 〇 又，在本發明中，所謂活性能量線，指電磁波或帶電 粒子放射線中具有能量子的部分，即，紫外線、電子束等。 (l)(i)多官能性（甲基）丙烯酸酯系單體及/或（甲基）丙烯酸 - 酯系預聚物 _ 在本發明中，作爲活性能量線感應型組成物採用多官 能性（甲基）丙烯酸酯系單體及/或（甲基）丙烯酸酯系預聚 物。 〇 作爲上述多官能性（甲基）丙烯酸酯系單體，可以例舉 1,4-丁二醇二（甲基）丙烯酸酯、1,6-己二醇二（甲基）丙烯酸 酯、新戊二醇二（甲基）丙烯酸酯、聚乙二醇二（甲基）丙烯酸 酯、羥基新戊酸新戊二醇二（甲基）丙烯酸酯、二環戊基二（甲 基）丙烯酸酯、己內脂改性二環戊烯基二（甲基）丙烯酸酯、 環氧乙烷改性磷酸二（甲基）丙烯酸酯、烯丙基化環己基二 ' (甲基）丙烯酸酯、二（甲基）丙烯酸異三聚氰酸酯、三羥甲基 丙烷三（甲基）丙烯酸酯、二季戊四醇三（甲基）丙烯酸酯、丙 -15- 201041740 酸改性二季戊四醇三（甲基）丙烯酸酯、季戊四醇三（甲基） 丙烯酸酯、環氧丙烷改性三羥甲基丙烷三（甲基）丙烯酸 * 酯、三（丙氧基乙基）異三聚氰酸酯、丙酸改性二季戊四醇 五（甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸酯、己內酯 改性二季戊四醇六（甲基）丙烯酸酯等多官能（甲基）丙烯酸 酯。這些單體可以使用一種、也可以兩種以上組合使用。 另一方面，作爲上述（甲基）丙烯酸酯系預聚物，可以 0 例舉聚酯丙烯酸酯系、環氧丙烯酸酯系、胺基甲酸酯丙烯 酸酯系、多元醇丙烯酸酯系等。這裏，作爲聚酯丙烯酸酯 系預聚物，可以通過例如多元羧酸與多元醇縮合而得到的 在兩末端具有羥基的聚酯低聚物的羥基以（甲基）丙烯酸酯 ^ 化’或者在多元羧酸中加成環氧烷烴而得到的低聚物的末 . 端的羥基以（甲基）丙烯酸酯化而得到。 環氧丙烯酸酯系預聚物，可以通過例如，使比較低分 子量的雙酚型環氧樹脂、酚醛型環氧樹脂的環氧乙烷環與 〇 (甲基）丙烯酸進行反應、酯化而得到。胺基甲酸酯丙烯酸 酯系預聚物，可以通過例如，聚醚多元醇、聚酯多元醇與 聚異氰酸酯的反應得到的聚胺基甲酸酯低聚物以（甲基）丙 烯酸進行酯化而得到。再者，多元醇丙烯酸酯系預聚物可 以通過聚醚多元醇的羥基以（甲基）丙烯酸進行酯化而得 到。這些預聚物可以使用一種，也可以兩種以上組合使用。 又，上述多官能（甲基）丙烯酸酯系單體也可以倂用。 (2)(ii)二氧化矽系微粒 -16- 201041740 在本發明中，作爲（ii)二氧化矽系微粒可以採用膠體狀 二氧化矽微粒及/或具有表面官能基的二氧化矽微粒。 * 膠體狀二氧化矽微粒的平均粒徑爲l~400nm左右， - 或者作爲具有表面官能基的二氧化矽微粒，可以例舉例如 含有（甲基）丙烯醯基的基團作爲表面官能基的二氧化矽微 粒（以下，也稱爲反應性二氧化矽微粒）。 上述反應性二氧化矽微粒，例如可以通過使平均粒徑 0 爲〇.〇〇5~l/zm左右的二氧化矽微粒表面的矽烷醇基與具 有可以同該矽烷醇基進行反應的官能基的含有聚合性不飽 和基的有機化合物進行反應，由此獲得。作爲聚合性不飽 和基團，例如可以例舉自由基聚合性的（甲基）丙烯醯基。 - 作爲可與上述矽烷醇基反應的具有官能基的含有聚合 . 性不飽和基的有機化合物，例如較佳係下述通式（I )表示 的化合物等 R1201041740 VI. [Technical Field] The present invention relates to an optical protective film, a method for producing the same, a polarizing plate, and a method for producing the same, and more particularly, the present invention relates to the following optical protective film, The optical protective film is suitable for use as a polarizing plate and a quarter-wavelength film in a liquid crystal display device, or as a cover film for a touch panel, a cover film for an optical disk, a protective film for various displays, and the like. An optical protective film having a hard coat function, and a polarizing plate using the optical protective film described in the above f) and a method for producing the same. BACKGROUND ART [Prior Art] Optical protective films having a hard coat function have been conventionally used in various image display devices such as an LCD (Liquid Crystal Display), a touch panel, a CRT (Cathode Ray Tube), and a PDP (Plasma Display Panel). In EL (electroluminescence element), etc., surface protection is started, and it is used for the purpose of anti-glare and anti-reflection. Q and 'also used in LCD' to protect the polarizer. The optical protective film generally has a hard coat layer formed by heat hardening, active energy ray hardening or the like on the base film. On the other hand, in recent years, the development of optical discs as information recording media has been remarkable. At the same time as the recording capacity has increased, CDs, DVDs, ^ and even BDs have also been developed. As for BD, it has developed a record with a maximum of 50GB. Capacity. An optical protective film having a hard coat function as a protective film and a cover film is also often used in these optical disks. However, the liquid crystal display device is a device that modulates the incident linear polarized light with the electro-optical characteristic 201041740 of the liquid crystal layer, and visualizes the polarizing plate on the emitting side as the transmittance and the colored signal. That is, the polarized light is used for the principle of its display, so the polarizing plate is an essential member. The polarizing plate is an element that converts natural light into linear polarized light. In many cases, in particular, a polarizing plate used for mass production of a liquid crystal display device is dyed and adsorbed on a base film formed of a polyvinyl alcohol film by a dichroic material such as iodine or a dichroic dye. The polarizing film is formed by extending the orientation, and a protective film which is optically transparent and has mechanical strength is bonded to both surfaces or one surface of the polarizing film. Further, as the above protective film, it is required to have small birefringence, high optical isotropy, high light transmittance, excellent heat resistance, excellent mechanical properties, good flatness, and good adhesion to a polarizer. For this reason, a cellulose-based film has been conventionally used (see Patent Document 1). Now, as a cellulose-based film, triacetate (hereinafter also referred to as TAC) is generally used. However, the TAC film is insufficient in heat and humidity resistance. When a polarizing plate used as a polarizer protective film is used under high humidity, the performance of a polarizing plate having a degree of polarization, a color tone, or the like is lowered. Further, the TAC film has a phase difference with respect to the incident light in the oblique direction. This phase difference has recently accompanied the development of large-scale liquid crystal displays, which has significantly affected the viewing angle characteristics. Further, in the liquid crystal display device, the emission light from the normal light source is circularly polarized according to the circularly polarizing member, and is linearly polarized by the 1/4 wavelength plate to be supplied to the polarizing plate. Further, for the above-mentioned quarter-wavelength sheet, an optical protective film having a hard coat function is also provided. 201041740 A polarizing plate in which a thin film obtained by molding an acrylic resin monomer or an acrylic resin composition is bonded to both surfaces is disclosed as a protective film having excellent moisture resistance and excellent durability (see Patent Document 2). However, there is a need to use a bonding agent in the bonding, and it is necessary to apply it before bonding, and it is not good in productivity, and the adhesive used as a protective film on both sides is optically Although it is excellent in the case of being excellent in the same property, the general polyvinyl alcohol-based adhesive, the urethane-based adhesive agent, the epoxy-based adhesive, and the acrylic-based adhesive are exemplified. In other words, if there is no regulation or any consideration regarding the type and properties of the binder in accordance with the adhesive layer of the present invention, there is a concern that deterioration of visibility due to a difference in refractive index between the binder and the protective film may occur. Happening. Further, in the protective film, no hard coat layer was formed. < Further, Patent Document 3 discloses an optical film and a polarizing plate obtained by forming the optical film on at least one surface of a polarizing plate, wherein the optical film crosslinks and hardens the ionizing radiation curable resin composition. It is preferable that the ionizing radiation curable resin composition contains (A) a monofunctional (meth)acrylic polymer having a weight average molecular weight of 50,000 to 80,000 to 70 to 95% by mass and (B) a polyfunctional radical polymerizable property. The compound having an unsaturated double bond is 5 to 30% by mass. The optical film is a film which is improved in flexibility and film transportability, and is used as a binder for bonding to the optical film, and is exemplified by a general PVA-based adhesive, an epoxy-based adhesive, and an acrylic adhesive. 'Conjunction, polyolefin-based binder, polyvinyl ether-based binder, rubber-based binder' There is no regulation on the type and properties of the binder. Their problems 201041740 points are the same as above. Further, the addition of the component (B) to the component (A) is concerned with deterioration of optical characteristics due to phase separation or the like. Also, no hard coat layer is formed in the optical film. - As a protective film used in a polarizing plate, even if it is not a TAC film currently used, as long as it is excellent in transparency and optically isotropic, most extruded films can be replaced. However, since the polarizing film (polarizing sheet) is generally a polyvinyl alcohol-based film, the adhesion to the film is difficult, and the degree of practicability is not attained in order to obtain a material which is inexpensive. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2007-128. The object of the present invention is to provide a protective film for a pupil, a method for producing the same, and a polarizing plate using the protective film for optical, and a method for producing the same, which is particularly suitable for a polarizing plate. It is excellent in transparency, optically isotropic, and has excellent moisture resistance, excellent durability, good adhesion to a polarizing film, and a hard coat function. In order to achieve the above object, the present inventors have conducted intensive investigations for a long period of time. As a result, it has been found that the following optical protective film can be obtained, which is composed of a hard coat layer/resin layer/adhesive layer, and which layer is contained (A) The acrylate 201041740 ester compound is composed of 80% by mass or more, whereby the reflection at the interface of each layer can be suppressed to an extremely low level, and the adhesion between the layers can be improved, and the film strength as a whole can be improved. Also excellent. Further, it has been found that the optical protective film is bonded to the polarizing film, and a binder layer and a resin layer containing 80% by mass or more of the (meth) acrylate-based compound are sequentially laminated on the other side of the polarizing film. The polarizing plate thus obtained has optical characteristics such as excellent visibility and can effectively increase the strength of each layer. Therefore, a thin polarizing plate can be obtained as compared with the prior art. In addition, it has been found that the following polarizing plate can be obtained, and the (meth)acrylate compound having excellent moisture resistance is used as the main component of all layers except the polarizing film of the polarizing plate of the present invention, whereby the obtained polarized light is obtained. The board is excellent in moisture resistance and light leakage resistance as compared with the case where the conventional TAC film is used as a substrate. The present invention has been accomplished based on the above knowledge and knowledge. That is, the present invention provides: (1) An optical protective film which is a laminated film formed by sequentially laminating a hard coat layer (A), a resin layer (B) Q, and an adhesive layer (c). The feature is that each layer contains 80% by mass or more of a (meth) acrylate-based compound. (2) The protective film for optics according to the above aspect (1), wherein the resin layer (B) has a storage elastic modulus E' at a temperature of 23 ° C of 0.5 MPa or more. (3) The optical protective film according to the above (1) or (2), wherein the adhesive layer (c) contains a polyfunctional active energy ray-curable compound and is active energy ray The temperature after irradiation was 2 3 . The optical protective film according to any one of the above-mentioned items (1) to (3), characterized in that the hard coat layer ( A) The active energy ray-inductive type composition is formed by irradiating the active energy ray to the object layer. (5) The method for producing an optical protective film according to any one of the above items (1) to (4) And characterized in that it comprises: (a) a step of forming a resin layer by casting on one side of the engineering sheet; and (b) a step of forming a hard coat layer (A) on the above resin layer (B); (c) The step of peeling off the above-mentioned work piece and bonding the surface of the adhesive layer (C) provided on the release sheet on the exposed resin layer (B) surface. (6) According to the above item (5) The method for producing an optical protective film is characterized in that the hard coat layer in the step (b) is formed by irradiating an active energy ray-sensitive composition layer with an active energy ray. (7) A polarizing plate The optical protective film according to any one of the above items (1) to (4) The coating layer (C) is bonded and laminated. (8) A polarizing film which is characterized in that the polarizing film and the optical protective film according to any one of the above items (1) to (4) The adhesive layer (C) is joined and laminated, and the 'agent layer (D) and the resin layer (E) are sequentially laminated on the other side of the polarizing film, and (D) and (E) Each layer is composed of a layer containing 80% by mass or more of a (meth) acrylate-based compound. (9) A polarizing plate with an adhesive layer characterized by the above (8) 201041740 The exposed surface side of the resin layer (E) of the polarizing plate further has an adhesive layer (F) containing 80% by mass or more of a (meth} acrylate compound. (1〇) A method for producing a polarizing plate according to the above item (8), characterized in that: (a) a step of forming a resin layer (B) by casting on one side of the engineering sheet; ^ (b) a step of forming a hard coat layer (A) on the resin layer (B); (c) peeling off the above-mentioned engineering sheet on the exposed resin layer (B) a step of bonding the adhesive layer (C) disposed on the release sheet; and (d) peeling the release sheet to adhere the exposed adhesive layer (C) to one side of the polarizing film (e) a step of forming a resin layer (E) by casting on one side of another engineering sheet; and (f) an adhesive layer provided on the release sheet on the resin layer (E) And (g) peeling the peeling sheet of the adhesive layer (D) and bonding it to the other surface of the polarizing film. (11) The method for producing a polarizing plate according to the above item (10), characterized in that the hard coat layer (A) in the step (b) is applied to the active energy ray-inducing 'type composition layer to illuminate the active energy ray. And formed. (12) The method for producing a polarizing plate according to the above (1) or (11), characterized in that the adhesive layer (C) and/or the adhesive layer (D) contain -10- 201041740 A polyfunctional active energy ray-curable compound having (h) a step of irradiating an active energy ray after the above step (g). (13) A method for producing a polarizing plate with an adhesive layer, characterized in that: (k) is applied to the polarizing plate obtained in the above item (10) or (1) in the resin layer (E) The exposed surface on the upper surface is bonded to each other so as to be bonded to the surface of the adhesive layer (F) provided on the release sheet. (14) A method of producing a polarizing plate with an adhesive layer according to the above (13), characterized in that the adhesive layer (C), the adhesive layer (D), and the adhesive layer (F) At least one of the layers contains a polyfunctional active energy ray-curable compound and has (1) a step of irradiating the active energy ray after the above step (k). According to the present invention, there is provided a protective film for optics, a method for efficiently producing the same, and a polarizing plate using the optical protective film, and a method for producing the same, which is particularly suitable for use as a polarizing plate, and has excellent transparency and optical properties. At the same time of isotropy, it has good moisture resistance, excellent durability, good adhesion to a polarizing film, and a hard coat function. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION First, the optical protective film of the present invention will be described. [Optical protective film] The optical protective film of the present invention is characterized by laminating a hard coat layer (A), a resin layer (B), and an adhesive layer (C) in this order. Each layer contains 80% by mass or more of a (meth) acrylate-based compound, and the total thickness of the -11-201041740 (A) layer, (B) layer, and (C) layer is 15-130 / / m. Further, the (meth) acrylate type compound means an acrylate type compound and / * or a methacrylate type compound. Similar words also mean the same meaning. Further, it is contained in a monomer unit which is a polymer or a cured product. [Resin layer (B)] The resin layer formed as the (B) layer in the protective film for optical use of the present invention is a (meth) acrylate-based compound and contains 80% by mass or more of (meth) acrylate ( Co-) a layer of a polymer. 〇 as the resin layer, the weight average molecular weight (MW) is 50,000 to 500,000, and the molecular weight distribution is (weight average molecular weight Mw / number average molecular weight Μη) of 1.5 to 3.0 from the viewpoint of mechanical properties and moldability. A range of (meth) acrylate (co)polymers is preferred. When the weight average molecular weight Mw is less than 50,000, the film strength of the obtained resin layer may be lowered, and if the weight average molecular weight Mw is more than 500,000, the viscosity may become too high and workability may be lowered. When the molecular weight distribution is narrower than 1.5, the obtained resin layer may have poor impact resistance. When the molecular weight distribution exceeds 3.0, the physical strength of the obtained resin layer may be lowered, and the dimensional accuracy may be deteriorated. From such a viewpoint, the weight average molecular weight Mw is preferably in the range of 100,000 to 300,000, and particularly preferably in the range of 150,000 to 250,000. Further, the (co)polymer refers to a homopolymer and/or a copolymer. The above weight average molecular weight (Mw) and number average molecular weight (?n) are 値 converted to standard polystyrene measured by a gel permeation chromatography (GPC) method. -12- 201041740 In addition, 'as the resin layer' is considered to contain the balance of transparency, moisture resistance, optical isotropy, mechanical strength, water absorption, dimensional stability, etc. The (meth) acrylate copolymer having a meta-polymer and/or a methyl methacrylate unit of 80% by mass or more is preferred. When the resin layer is the above-mentioned (meth) acrylate copolymer, as the (meth) acrylate copolymerized with methyl methacrylate, for example, an alkyl group having a carbon number of about 2 to 20 may be used. A monofunctional (meth)propionate monomer. Specifically, it can be derived from ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate, (A) Cyclohexyl acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, (meth)acrylic acid, octadecyl ester, isobornyl (meth)acrylate Either at least one of ester, acrylic acid 2-hydroxyethyl ester and the like is used. The (meth) acrylate for the copolymerization is preferably used in an amount of 20% by mass or less based on the total of the monomers, and is suitably used for imparting flexibility to the resin layer. Further, at least one of a monomer (carboxyl group-containing monomer) such as (meth)acrylic acid, crotonic acid, maleic acid or itaconic acid may be used in place of or in combination with the (meth) acrylate for copolymerization. use. In this case, as described above, the total amount of the monomers for copolymerization is preferably 20% by mass or less based on the total of all the monomers. The polymerization method is not particularly limited, and various methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and the like can be employed. -13- 201041740 The resin layer is preferably formed by a casting method (solution casting method). Specifically, first, the (meth) acrylate (co)polymer produced as described above is polymerized in a suitable organic solvent such as ethyl acetate, methyl ethyl ketone or toluene, etc., and further added. An additive such as a plasticizer is provided with a saccharide-like paste. After completely removing the impurities and bubbles, the dope is used as a support, for example, by using an engineering sheet, and flowing on one surface thereof to form the resin layer. Further, as an engineering piece, if it is generally used, it can be used without limitation. For example, a polyolefin-based film or a polyethylene terephthalate film having a fluorinated fluorene-based or fluorine-based release layer provided on the surface side in contact with the resin layer is preferably used. The resin containing the (meth) acrylate (co)polymer thus formed, the layer having a thickness of about 10 to 80 / / m, preferably 20 to 50 / zm, and more preferably at a temperature of 2 3 The storage elastic modulus E' of °C is 0.5 M Pa or more, and more preferably 2 MPa or more. The upper limit is not particularly limited and is usually about 70 MPa. When the thickness of the resin layer is in the above range, the performance of the protective film can be sufficiently enhanced. Further, when the storage elastic modulus E is less than 0.5 MPa, the mechanical strength of the resin layer is low, and the performance as a protective film is insufficient. Further, the storage elastic modulus E at a temperature of 23 ° C is enthalpy measured based on Jis K 7244-4. [Hard Coat Layer (A)] In the optical protective film of the present invention, a hard coat layer is provided as the (A) layer on the resin layer formed as described above. By providing the hard coat layer, not only scratching of the surface of -14-201041740 can be prevented, but also the film strength of the optical protective film can be improved, and the film thickness of the resin layer can be reduced. - In the formation of the hard coat layer, an active energy ray-sensing type group can be used. <Active energy ray-sensitive composition> The active energy ray-sensitive composition preferably contains (1) a polyfunctional (meth) acrylate monomer and/or a (meth) acrylate prepolymer, (u) ) cerium oxide-based particles and/or (iii) organic particles. Further, in the present invention, the active energy ray means a portion having an energy beam in the electromagnetic wave or the radiation of the charged particle, that is, an ultraviolet ray, an electron beam or the like. (1) (i) Polyfunctional (meth) acrylate monomer and/or (meth) acrylate-ester prepolymer _ In the present invention, polyfunctionality is employed as an active energy ray-sensitive composition A (meth) acrylate monomer and/or a (meth) acrylate prepolymer. 〇 As the above polyfunctional (meth) acrylate monomer, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, new Pentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, dicyclopentyl di(meth)acrylate , hexapto-modified dicyclopentenyl di(meth) acrylate, ethylene oxide modified di(meth) acrylate, allylated cyclohexyl bis (meth) acrylate, (meth)acrylic acid isocyanurate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, C-15-201041740 acid-modified dipentaerythritol tris(methyl) Acrylate, pentaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane tris(meth)acrylic acid* ester, tris(propoxyethyl)isocyanate, propionic acid modification Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone Of polyfunctional dipentaerythritol hexa (meth) acrylate, (meth) acrylates. These monomers may be used alone or in combination of two or more. On the other hand, the (meth)acrylate prepolymer may be exemplified by a polyester acrylate type, an epoxy acrylate type, an urethane acrylate type, a polyol acrylate type, or the like. Here, as the polyester acrylate-based prepolymer, the hydroxyl group of the polyester oligomer having a hydroxyl group at both terminals, which can be obtained by, for example, condensation of a polyvalent carboxylic acid and a polyhydric alcohol, can be (meth) acrylate- The hydroxyl group at the end of the oligomer obtained by adding an alkylene oxide to the polyvalent carboxylic acid is obtained by (meth)acrylation. The epoxy acrylate-based prepolymer can be obtained by, for example, reacting and esterifying a relatively low molecular weight bisphenol epoxy resin or an oxirane ring of a novolac epoxy resin with hydrazine (meth)acrylic acid. . A urethane acrylate-based prepolymer which can be esterified with (meth)acrylic acid by, for example, a polyurethane polyol, a polyester urethane oligomer obtained by reacting a polyester polyol with a polyisocyanate And get it. Further, the polyol acrylate-based prepolymer can be obtained by esterification of a hydroxyl group of a polyether polyol with (meth)acrylic acid. These prepolymers may be used alone or in combination of two or more. Further, the above polyfunctional (meth) acrylate monomer may be used in combination. (2) (ii) cerium oxide-based fine particles -16 - 201041740 In the present invention, as the (ii) cerium oxide-based fine particles, colloidal cerium oxide fine particles and/or cerium oxide fine particles having a surface functional group may be used. * The colloidal cerium oxide microparticles have an average particle diameter of about 1 to 400 nm, or - as the cerium oxide microparticle having a surface functional group, for example, a group containing a (meth) acryl fluorenyl group as a surface functional group As the cerium oxide microparticles (hereinafter also referred to as reactive cerium oxide microparticles). The above-mentioned reactive cerium oxide microparticles can be, for example, a stanol group having a surface area of cerium oxide fine particles having an average particle diameter of about ~5 to 1/zm and a functional group capable of reacting with the stanol group. The organic compound containing a polymerizable unsaturated group is reacted, and thus obtained. The polymerizable unsaturated group may, for example, be a radically polymerizable (meth) acrylonitrile group. - a polymerizable unsaturated group-containing organic compound having a functional group reactive with the above stanol group, for example, preferably a compound represented by the following formula (I);
I Q CH2 = C - COR2 · . · (I) (式中，R1爲氫原子或甲基，R2爲鹵素原子或 —OCHaCHaNCO、一 OCHaCH - CH2、一 OCHaCH — CHa、 V \/I Q CH2 = C - COR2 · (I) (wherein R1 is a hydrogen atom or a methyl group, R2 is a halogen atom or -OCHaCHaNCO, an OCHaCH-CH2, an OCHaCH-CHa, V\/
0 N Η -OCHaCHaOH, ~OH, ~0(CH2)3 - SI(OCH3)3 表示的基團。） 作爲如此的化合物’例如可以使用丙烯酸、丙烯醯氯、 丙烯酸2 -異氰基乙酯、丙烯酸縮水甘油酯、丙烯酸2,3- -17- 201041740 亞胺基丙酯、丙烯酸2-羥基乙酯、丙烯醯氧基丙基三甲氧 基矽烷等以及與這些丙烯酸衍生物對應的甲基丙烯酸衍生 • 物。這些丙烯酸衍生物、甲基丙烯酸衍生物可以單獨使用、 . 也可以兩種以上組合使用。 含有如此得到的聚合性不飽和基團的有機化合物結合 的二氧化矽微粒，作爲活性能量線硬化成分，通過活性能 量線的照射交聯、硬化。 ^ 該反應性二氧化矽微粒具有提高所得的硬塗層薄膜的 耐擦傷性的效果。 對如此的二氧化矽微粒結合具有聚合性不飽合基團的 有機化合物而得到的化合物，作爲含有該化合物的活性能 - 量線感應型組成物，上市有例如 JSR(股）生產的、商品名0 N Η -OCHaCHaOH, ~OH, ~0(CH2)3 - SI(OCH3)3 represents a group. As such a compound, for example, acrylic acid, acrylonitrile chloride, 2-isocyanoethyl acrylate, glycidyl acrylate, 2,3--17-201041740 iminopropyl acrylate, 2-hydroxyethyl acrylate can be used. And acryloxypropyltrimethoxydecane, and the like, and methacrylic acid derivatives corresponding to these acrylic acid derivatives. These acrylic acid derivatives and methacrylic acid derivatives may be used singly or in combination of two or more. The cerium oxide fine particles in which the organic compound having the polymerizable unsaturated group obtained as described above is bound as an active energy ray hardening component are crosslinked and hardened by irradiation with an active energy ray. ^ The reactive cerium oxide microparticles have an effect of improving the scratch resistance of the obtained hard coat film. A compound obtained by combining such an organic compound having a polymerizable unsaturated group with such a cerium oxide microparticle as a living energy-line-type composition containing the compound, and a product produced by, for example, JSR (stock) is commercially available. name
爲[OPSTAR Z7530] 、 [OPSTAR Z7524] 、 [OPSTAR TU4086]等。 在本發明中，該（ii)成分的二氧化矽系微粒的含量在活 〇 性能量線感應型組成物的固體成分中，通常爲5~90質量％ 左右，較佳爲1〇~70質量％。 又，該（Π)成分的二氧化矽系微粒中的二氧化矽微粒的 平均粒徑可以雷射繞射散射法進行測定。在該方法中，通 過對微粒分散的液體照射雷射時的繞射、散射的光的強度 ' 變化，測定平均粒徑。 ‘ （3)(iii)有機微粒 在本發明中，可以將（ii)二氧化矽系微粒變爲（或倂 -18- 201041740 用）（iii)有機微粒。 作爲該有機微粒，可以例舉矽氧烷系微粒、三聚氰胺 • 系樹脂微粒、丙烯酸系樹脂微粒、丙烯酸-苯乙烯類共聚物 • 微粒、聚碳酸酯系微粒、聚乙烯系微粒、聚苯乙烯系微粒、 苯并胍胺系樹脂微粒等。 在本發明中，將硬塗層（A)、樹脂層（B)以及黏著劑層（C) 的全部以（甲基）丙烯酸酯系化合物作爲主成分，由此，將 0 在界面上的反射、折射抑制在最低限的水準，可得到視認 性良好的光學用保護薄膜。從這一點上考慮，有機微粒也 使用丙烯酸系樹脂微粒爲特佳的。 又，有機微粒的形狀沒有特別的限制，但是從防眩性 - 能的均一化、提高再現性等的觀點出發，球狀的形狀爲佳。 . 進而，該平均粒徑從防眩性能的觀點出發較佳爲 6〜l〇em，粒度分佈爲在平均粒徑：t2；um的範圍以內的重 量比率在70%以上爲佳。又，有機微粒的平均粒徑以及粒 〇 度分佈指的是通過庫特氏計數法而測定的値。 在本發明中，該（iii)成分的有機微粒可以單獨使用一 種，也可以組合使用兩種以上。又，其添加量從防眩性能 的觀點來說，相對上述（i)成分的活性能量線感應型組成物 的固體成分100質量份，較佳爲〇.1~30質量份、更佳爲 1 ~ 2 0質量份。 ' (4)光聚合引發劑 本發明中的活性能量線感應型組成物，根據希望可以 -19- 201041740 含有光聚合引發劑。作爲該光聚合引發劑，可以列舉出例 如安息香、安息香甲基醚、安息香乙基醚、安息香異丙基 • 醚、安息香正丁基醚、安息香異丁基醚、苯乙酮、二甲基 . 胺基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基 -2-苯基苯乙酮、2-羥基-2-甲基-1-苯基丙-1-酮、1-羥基 環己基苯基酮、2-甲基-1-[4-(甲基硫代）苯基]-2-嗎啉基-丙-1-酮、4-(2-羥基乙氧基）苯基-2-(羥基-2-丙基）酮、二 苯甲酮、對苯基二苯甲酮、4,4’-二乙基胺基二苯甲酮、二 〇 氯代二苯甲酮、2 -甲基蒽醌、2 -乙基蒽醌、2 -第三丁基蒽 醌、2 -胺基蒽醌、2 -甲基噻噸酮、2 -乙基噻噸酮、2 -氯代 噻噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、苄基二 , 甲基縮酮、苯乙酮二甲基縮酮、對二甲基胺基苯甲酸酯等。 _ 這些可以使用1種’也可以組合2種以上使用，相對 於1 00質量份所有活性能量線感應型化合物，其添加量通 常在0.2-10質量份的範圍內選擇。又，在此，所謂的所 〇 有活性能量線感應型化合物係在使用反應性二氧化矽微粒 的場合，需要包括（ii)二氧化矽系微粒在內的含義。 (5)活性能量線感應型化組成物的調配 本發明使用的活性能量線感應型組成物通過在適當的 溶劑中將上述的⑴成分、（ii)及/或（iii)成分、以及根據希 ' 望被使用的光聚合引發劑、各種添加成分、比如抗氧化劑、 • 紫外線吸收劑、矽烷系偶合劑、光穩定劑、均化劑 '消泡 劑等分別按照規定的比例添加、溶解或分散，由此進行調 -20- .201041740 配。 作爲此時使用的溶劑，可以使用例如己烷、庚烷等脂 - 肪烴，甲苯、二甲苯等芳香族烴，二氯甲烷、氯乙烯等鹵 • 代烴，甲醇、乙醇、丙醇、丁醇、丙二醇單甲基醚等醇， 丙酮、甲乙酮、2·戊酮、異佛爾酮、環己酮等酮，乙酸乙 酯、乙酸丁酯等酯，乙基溶纖劑等溶纖劑類溶劑。 作爲如此調配的硬塗層形成材料的濃度、黏度，只要 0 是可以塗布的狀況即可，沒有特別的限制，根據狀況可以 適當選定。 〈硬塗層（A)的形成〉 在本發.明中，在如上所述形成的樹脂層（B )上將上述活 - 性能量線感應型組成物，使用現有公知的方法，例如棒塗 . 布法、刮板塗布法、輥塗法、刮刀塗布法、模縫塗布法、 照相凹版印刷法等，進行塗布形成塗膜，乾燥處理後，對 其照射活性能量線，通過將該塗膜硬化，形成硬塗層（A)。 〇 作爲活性能量線，可以列舉出例如紫外線、電子束等。 上述紫外線可以由高壓水銀燈、無電極燈、鹵素燈、氙燈 等得到，照射量通常爲lOO-SOOmJ/cm2，另外，電子束 由電子束加速器等得到’照射量通常爲150~350kV。該活 性能量線中’特別合適的是紫外線。另外，在使用電子束 時’不添加光聚合引發劑，也可以得到硬化膜。 這樣形成的硬塗層的厚度通常在2~20ym左右，較佳 係在4~l〇ym的範圍。 -21- 201041740 (黏著劑層（c)) 本發明的光學用保護薄膜中，在樹脂層（B)的硬塗層側 • 的相反面設置黏著劑層作爲（C)層。 . 該黏著劑層（C)的形成，較佳係使用含有多官能活性能 量線硬化型化合物的活性能量線硬化型黏著性材料。 〈活性能量線硬化型黏著性材料〉 作爲該活性能量線硬化型黏著性材料（以下簡稱爲黏 著性材料），較佳係含有（iv)(甲基）丙烯酸酯共聚物、（v)多 〇 官能活性能量線硬化型化合物、（Vi)交聯劑、以及根據需要 含有（Vii)光聚合引發劑。 (l)(iv)(甲基）丙烯酸酯共聚物For [OPSTAR Z7530], [OPSTAR Z7524], [OPSTAR TU4086], etc. In the present invention, the content of the cerium oxide-based fine particles of the component (ii) is usually from 5 to 90% by mass, preferably from 1 to 70% by mass in the solid content of the active energy ray-inductive composition. %. Further, the average particle diameter of the cerium oxide fine particles in the cerium oxide-based fine particles of the (cerium) component can be measured by a laser diffraction scattering method. In this method, the average particle diameter is measured by irradiating the liquid in which the fine particles are dispersed with the intensity of the diffracted and scattered light when the laser is changed. ‘(3)(iii) Organic fine particles In the present invention, (ii) cerium oxide-based fine particles can be changed to (or for 倂-18- 201041740) (iii) organic fine particles. Examples of the organic fine particles include siloxane oxide fine particles, melamine resin fine particles, acrylic resin fine particles, acrylic-styrene copolymers, fine particles, polycarbonate fine particles, polyethylene fine particles, and polystyrene. Fine particles, benzoguanamine resin fine particles, and the like. In the present invention, all of the hard coat layer (A), the resin layer (B), and the adhesive layer (C) are made of a (meth) acrylate-based compound as a main component, thereby reflecting 0 at the interface. The refractive index is suppressed to the lowest level, and an optical protective film having good visibility can be obtained. From this point of view, the organic fine particles are also particularly excellent in the use of acrylic resin fine particles. In addition, the shape of the organic fine particles is not particularly limited, but a spherical shape is preferable from the viewpoints of uniformity of anti-glare property, energy reproducibility, and the like. Further, the average particle diameter is preferably 6 to 100 μm from the viewpoint of antiglare performance, and the particle size distribution is preferably 70% or more by weight in the range of the average particle diameter: t2; um. Further, the average particle diameter and the particle size distribution of the organic fine particles refer to the enthalpy measured by the Coulter's counting method. In the present invention, the organic fine particles of the component (iii) may be used singly or in combination of two or more. In addition, the amount of the solid energy component of the active energy ray-sensitive composition of the component (i) is preferably from 1 to 30 parts by mass, more preferably from 1% to 1 part by mass, based on the anti-glare property. ~ 20 parts by mass. (4) Photopolymerization initiator The active energy ray-inductive composition of the present invention may contain a photopolymerization initiator as desired, -19-201041740. Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, and dimethyl group. Aminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1 -Phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)one, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminodiphenyl Methyl ketone, dichloro benzophenone, 2-methyl hydrazine, 2-ethyl hydrazine, 2-tributyl hydrazine, 2-amino hydrazine, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl di, methyl ketal, acetophenone Dimethyl ketal, p-dimethylamino benzoate, and the like. _ These may be used singly or in combination of two or more kinds, and the amount of addition of all active energy ray-sensitive compounds to 100 parts by mass is usually selected in the range of 0.2 to 10 parts by mass. Here, in the case where the active energy ray-sensitive compound is used, it is necessary to include (ii) cerium oxide-based fine particles when using reactive cerium oxide fine particles. (5) Preparation of active energy ray-inducing composition The active energy ray-sensitive composition used in the present invention comprises the above-mentioned (1) component, (ii) and/or (iii) component, and according to Greek in a suitable solvent. 'The photopolymerization initiator to be used, various additives, such as antioxidants, UV absorbers, decane couplers, light stabilizers, leveling agents, defoamers, etc. are added, dissolved or dispersed in a predetermined ratio. , thus the adjustment -20-.201041740 match. As the solvent to be used at this time, for example, an aliphatic hydrocarbon such as hexane or heptane, an aromatic hydrocarbon such as toluene or xylene, or a halogenated hydrocarbon such as dichloromethane or vinyl chloride, methanol, ethanol, propanol or butyl can be used. Alcohol, propylene glycol monomethyl ether and other alcohols, acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone and other ketones, ethyl acetate, butyl acetate and other esters, ethyl cellosolve and other cellosolve Solvent. The concentration and viscosity of the hard coat layer forming material to be blended as described above are not particularly limited as long as 0 is acceptable, and may be appropriately selected depending on the situation. <Formation of Hard Coating Layer (A)> In the present invention, the above-mentioned living-performance amount line-inductive composition is applied to the resin layer (B) formed as described above, using a conventionally known method such as bar coating. A cloth coating method, a blade coating method, a roll coating method, a knife coating method, a die coating method, a gravure printing method, etc., coating a coating film, and after drying, irradiating an active energy ray through the coating film Hardened to form a hard coat layer (A). 〇 Examples of the active energy ray include ultraviolet rays, electron beams, and the like. The ultraviolet rays may be obtained by a high pressure mercury lamp, an electrodeless lamp, a halogen lamp, a xenon lamp or the like, and the irradiation amount is usually 100-SOOmJ/cm2, and the electron beam is obtained by an electron beam accelerator or the like. The irradiation amount is usually 150 to 350 kV. Particularly suitable in the performance line is ultraviolet light. Further, when an electron beam is used, a cured film can be obtained without adding a photopolymerization initiator. The thickness of the hard coat layer thus formed is usually about 2 to 20 μm, preferably in the range of 4 to 10 μm. -21-201041740 (Adhesive layer (c)) In the protective film for optical use of the present invention, an adhesive layer is provided as the (C) layer on the opposite side of the hard coat layer side of the resin layer (B). The adhesive layer (C) is preferably formed by using an active energy ray-curable adhesive material containing a polyfunctional active energy ray-curable compound. <Active Energy Ray-Curable Adhesive Material> The active energy ray-curable adhesive material (hereinafter simply referred to as an adhesive material) preferably contains (iv) a (meth) acrylate copolymer and (v) a ruthenium. A functional active energy ray-curable compound, a (Vi) crosslinking agent, and, if necessary, a (Vii) photopolymerization initiator. (l) (iv) (meth) acrylate copolymer
. 本發明的黏著性材料中，作爲（iv)成分而含有的（甲基J 丙烯酸酯共聚物沒有特別的限制，可以從一直以來作爲黏 « 結劑的樹脂成分而慣用的（甲基）丙烯酸酯共聚物中適宜選 擇任意的成分。作爲如此的（甲基）丙烯酸酯共聚物，較佳 Q 係可例舉例如酯部分的烷基的碳原子數爲4~20的（甲基） 丙烯酸酯與具有活性氫的官能性的單體與根據希望而採用 的其他單體形成的共聚物。 在此，作爲酯部分的烷基的碳原子數爲4~20的（甲基） 丙烯酸酯的例子，例舉有（甲基）丙烯酸丁酯、（甲基）丙烯酸 • 戊酯、（甲基）丙烯酸己酯、（甲基）丙烯酸環己酯、（甲基）丙 - 烯酸2 -乙基己酯、（甲基）丙烯酸異辛酯、（甲基）丙烯酸癸 酯、（甲基）丙烯酸十二烷基酯、（甲基）丙烯酸十四烷基酯' -22· 201041740 (甲基）丙烯酸十六烷基酯、（甲基）丙烯酸十八烷基酯等。這 些可以單獨使用，也可以兩種以上組合使用。 • 另一方面，作爲具有活性氫的官能基的單體的例子， 例舉有（甲基）丙烯酸2-羥基乙酯、（甲基）丙烯酸2-羥基丙 酯、（甲基）丙烯酸3-羥基丙酯、（甲基）丙烯酸2-羥基丁酯、 ' (甲基）丙烯酸3-羥基丁酯、（甲基）丙烯酸4-羥基丁酯等（甲 基）丙烯酸羥基烷酯；（甲基）丙烯酸單甲基胺基乙酯、（甲基） 0 丙烯酸單乙基胺基乙酯、（甲基）丙烯酸單甲基胺基丙酯、（甲 基）丙烯酸單乙基胺基丙酯等的（甲基）丙烯酸單烷基胺基烷 酯；丙烯酸、甲基丙烯酸、巴豆酸、馬來酸、衣康酸、檸 檬酸等的乙烯性不飽和羧酸等。這些單體可以單獨使用， - 也可以兩種以上組合使用。 _ 又，作爲根據希望而採用的其他單體的例子，例舉（甲 基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯等 的酯部分的烷基的碳原子數爲1~3的（甲基）丙烯酸酯；乙 〇 酸乙烯酯、丙酸乙烯酯等的乙烯酯類；乙烯、丙烯、異丁 烯等的烯烴類；氯乙烯、偏二氯乙烯等鹵代烯烴類；苯乙 烯、甲基苯乙烯等的苯乙烯系單體；丁二烯、異戊二烯、 氯丁二烯等的二烯系單體；丙烯腈、甲基丙烯腈等的腈系 單體；丙烯醯胺、N -甲基丙烯醯胺、N，N -二甲基丙烯醯胺 ' 等丙烯醯胺類等。這些可以單獨使用，也可以兩種以上組 ' 合使用。從對所得到的黏結劑層賦予黏著力的觀點出發， 作爲（iv)(甲基）丙烯酸酯共聚物，較佳係那些構成該共聚物 -23- 201041740 的單體中的50質量％以上，更佳係60~99質量％以上由上 述酯部分的烷基的碳原子數爲4~20的（甲基）丙烯酸酯構 ' 成。 . 上述（甲基）丙烯酸酯共聚物的共聚形態沒有特別的限 制，無規共聚物、嵌段共聚物、接枝共聚物中的任何一種 均可。又，分子量爲重量平均分子量計在50萬以上爲佳， 50萬~250萬爲更佳。該重量平均分子量如果不足50萬， € 會出現與被附著體的黏結性和耐久黏結性不充分的危險。 如果考慮黏結性以及耐久黏結性等’該重量平均分子量較 佳爲70萬~200萬。 又，上述重量平均分子量爲根據凝膠滲透色譜（GPC) - 法測量的換算爲標準聚苯乙烯的値。 再者，該（甲基）丙烯酸酯共聚物中，具備具有活性氫 的官能基的單體單元的含量較佳在〇.〇ι~ι〇質量％的範 圍。該含量如果不足0.0 1質量％，則交聯點過少，交聯不 Ο 充分，有黏著劑層產生凝聚破壞的危險；如果超過ίο質量 %，則有向液晶胞等的黏著適應性低下的危險。具備具有 該活性氫的官能基的單體單元的更佳含量在0.05-6.0質 量％的範圍，特別較佳在0.2~5.0質量％的範圍。進而，爲 了達成本發明的目的，作爲具備具有最佳活性氫的官能基 的單體，例舉有（甲基）丙烯酸2 -羥基乙酯以及丙烯酸，較 ' 佳係在（甲基）丙烯酸酯共聚物中具有〇.3~1〇質量％，特佳 係〇.5~5.0質量％的單體單元。 -24- 201041740 在本發明中，作爲（iv)成分，該（甲基）丙烯酸酯共聚物 可以選擇一種，也可以兩種以上組合使用。 • (2)(V)’多官能活性能量線硬化型化合物 . 在本發明中的黏著性材料中，作爲（v)成分而使用的多 官能活性能量線硬化型化合物，其重量平均分子量通常在 10萬以下，較佳爲300~1萬的範圍。 作爲如此的活性能量線硬化型化合物，可以例舉例如 八 活性能量線硬化型多官能預聚物及/或活性能量線硬化型 〇 多官能單體。上述活性能量線硬化型多官能預聚物爲自由 基聚合型和陽離子聚合型，作爲自由基聚合型的活性能量 線硬化型多官能預聚物，例如可以例舉聚酯丙烯酸酯系、 . 環氧丙烯酸酯系、胺基甲酸酯丙烯酸酯系、多元醇丙烯酸 酯系等。 在這裏，作爲聚酯丙烯酸酯系預聚物，可以通過使用 (甲基）丙烯酸，對比如通過多元羧酸和多元醇的縮合而獲 〇 得的在兩末端具有羥基的聚酯低聚物的羥基進行酯化，或 者通過使用（甲基）丙烯酸，對在多元羧酸中添加氧化烯而 獲得的低聚物的末端的羥基進行酯化而獲得。環氧丙烯酸 酯系預聚物，比如可以通過在較低分子量的雙酚型環氧樹 脂或酚醛清漆型環氧樹脂的環氧乙烷環中，反應（甲基）丙 ' 烯酸，進行酯化而獲得。胺基甲酸酯丙烯酸酯系預聚物， ' 比如可以通過使用（甲基）丙烯酸，對通過聚醚多元醇、聚 酯多元醇和聚異氰酸酯的反應而獲得的聚胺基甲酸酯低聚 -25- 201041740 物進行酯化而獲得。進而，多元醇丙烯酸酯系預聚物，可 以通過使用（甲基）丙烯酸，對聚醚多元醇的羥基進行酯化 • 而獲得。這些活性能量線硬化型多官能預聚物可以使用1 . 種，或2種以上組合使用。 另一方面，作爲陽離子聚合型的活性能量線硬化型多 官能預聚物，通常使用環氧系樹脂。作爲該環氧系樹脂， 可以舉出如使用表氯醇等，對雙酚樹脂或酚醛樹脂等多元 八 酚類進行環氧化的化合物；使用過氧化物等，對直鏈狀烯 Ο 烴化合物或環狀烯烴化合物進行氧化而獲得的化合物等。 另外，作爲活性能量線硬化型多官能單體，可以舉出 如’ 1,4 -丁二醇二（甲基）丙烯酸酯、1,6 -己二醇二（甲基） . 丙烯酸酯、新戊二醇二（甲基）丙烯酸酯、聚乙二醇二（甲基） . 丙烯酸酯、新戊二醇己二酸二（甲基）丙烯酸酯、羥基新戊 酸新戊二醇二（甲基）丙烯酸酯、二環戊基二（甲基）丙烯酸 酯、己內酯改性二環戊烯基二（甲基）丙烯酸酯、環氧乙烷 〇 改性磷酸二（甲基）丙烯酸酯、烯丙基化環己基二（甲基）丙烯 酸酯、二（甲基）丙烯酸異三聚氰酸酯、三羥甲基丙烷三（甲 基）丙烯酸酯、二季戊四醇三（甲基）丙烯酸酯、丙酸改性二 季戊四醇三（甲基）丙烯酸酯 '季戊四醇三（甲基）丙烯酸酯、 環氧丙院改性二經甲基丙院三（甲基）丙嫌酸酯、三[(甲基） 丙嫌醯氧基院基】異二聚氰酸醋類、丙酸改性二季戊四醇五 • (甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸酯、己內酯改 性一季戊四醇（甲基）丙嫌酸醋等多官能丙嫌酸醋。這些 -26- 201041740 活性能量線硬化型多官能單體可以使用1種，也 以上組合使用，另外，也可以聯用上述活性能量 - 多官能預聚物。 本發明中，作爲該（V)成分的多官能活性能量 化合物，可以減小交聯點，從可增加交聯密度的顴 較佳係多官能單體，作爲合適的成分，可以舉出 甲基丙烷三丙烯酸酯、二季戊四醇六丙烯酸酯、 _ 丙烯醢氧基烷基]異三聚氰酸酯類等。 〇 它們之中，特別適合使用三[(甲基）丙烯醯讀 異三聚氰酸酯類。該三[(甲基）丙烯醯氧基烷基】異 酯類，較佳係舉出如，三（2-丙烯醯氧基乙基）異 . 酯、三（3-丙烯醯氧基丙基）異三聚氰酸酯、三（2- 醯氧基乙基）異三聚氰酸酯、三（3 -甲基丙烯醯氧j 三聚氰酸酯等。 本發明中，作爲該（v)成分的多官能活性能量 Q 化合物的含量’在本發明中使用的黏著性材料的 中，從與偏光膜的黏結性的觀點，較佳係按照5〜 的比例含有’更佳係按照1 〇 ~ 3 〇質量。/。的比例含 (3)(vi)交聯劑 本發明的黏著性材料中作爲（vi)成分而使 ' 劑，沒有特別的限制，可以從作爲現有丙烯酸系 • 爲交聯劑而慣用的物質中適當選擇任意的物質而 爲這樣的交聯劑，可以舉出如，聚異氰酸酯化合 可以2種 線硬化型 線硬化型 丨點出發， 如，三羥 三[(甲基） R基烷基1 三聚氰酸 三聚氰酸 甲基丙烯 塞丙基）異 線硬化型 固體成分 5 0質量％ 有。 用的交聯 樹脂中作 使用。作 物、環氧 -27- 201041740 樹脂、三聚氰胺樹脂、尿素樹脂、二醛類、羥甲基聚合物、 氮雜環丙烷類化合物、金屬螯合物、金屬醇鹽、金屬鹽等， • 較佳係使用聚異氰酸酯化合物。 . 這裏，作爲聚異氰酸酯化合物的例子，可以列舉，甲 苯二異氰酸酯、二苯甲烷二異氰酸酯、亞二甲苯二異氰酸 酯等芳香族聚異氰酸酯、六亞甲基二異氰酸酯等脂肪族聚 異氰酸酯、異佛爾酮二異氰酸酯、氫化二苯甲烷二異氰酸 酯等脂環式聚異氰酸酯等，以及它們的縮二脲體、異三聚 Ο 氰酸酯體，還有，作爲與乙二醇、丙二醇、新戊二醇、三 羥甲基丙烷、蓖麻油等低分子含活性氫化合物的反應物的 加合物（比如，三羥甲基丙烷改性苯亞甲基異氰酸酯）等。 - 本發明中，該交聯劑可以1種單獨使用，也可以2種 以上組合使用。另外，其使用量根據交聯劑的種類而不同， 相對於100質量份作爲上述（iv)成分的（甲基）丙烯酸酯共 聚物’通常爲0_01~20質量份，較佳係在〇.1~1〇質量份 〇 的範圍內選定。 (4)(vii)光聚合引發劑 該活性能量線硬化型黏結性材料中，可根據需要使宜 含有光聚合引發劑。作爲光聚合引發劑，可以使用與硬塗 層（A)中記載的物質相同的物質。 該黏結性材料中’上述根據需要使用的光聚合引發劑 • 的含量，相對於100質量份作爲上述（v)成分的多官能的預 聚物和/或單體，通常爲0_5~20質量份左右，較佳爲 -28- 201041740 質量份。另外，作爲活性能量線，在使用電子線時，不需 要含有上述光聚合引發劑。 ' <含有活性能量線硬化型黏結性材料的塗布液的調配> • 含有該活性能量線硬化型黏結性材料的塗布液的調配 方法沒有特別的限制，可以通過比如在溶劑中加入上述（iv) 成分的（甲基）丙烯酸酯共聚物、（V)成分的多官能活性能量 線硬化型化合物、（Vi)成分的交聯劑、以及根據需要而使用 0 的（Vii)成分的光聚合引發劑，另外還有各種添加劑，比如， 抗氧化劑、紫外線吸收劑、光穩定劑、矽烷偶合劑、防靜 電劑、均化劑、消泡劑等，並攪拌混合，來調配含有活性 能量線硬化型黏著性材料的塗布液。 • 作爲上述溶劑，可以列舉如：己烷、庚烷等脂肪族烴、 , 甲苯、二甲苯等芳香族烴，二氯甲烷、二氯乙烷等鹵代烴， 甲醇、乙醇、丙醇、丁醇等醇，丙酮、甲乙酮、2-戊酮、 異佛爾酮、環己酮等酮，乙酸乙酯、乙酸丁酯等酯，乙基 〇 溶纖劑等溶纖劑類溶劑、丙二醇單甲醚等醇醚類溶劑等。 這些溶劑可以1種單獨使用，也可以2種以上組合使用。 作爲該塗布液中的活性能量線硬化型黏結性材料的濃 度，只要是該塗布液適於塗布的黏度即可，沒有特別的限 制。 <黏著劑層（C)的形成> 本發明的光學用保護薄膜中，在與上述樹脂層（B)的硬 塗層側的相反.面，設置黏著劑層作爲（C)層。該黏著劑層的 -29- 201041740 形成可按照如下方式進行。 比如’在工程片上設有表面具有硬塗層（A)的樹脂層（B) ' 時’可以使用首先剝離該工程片，露出與樹脂層的硬塗層 側相反的面’在該露出面上直接塗布包含上述黏著性材料 的塗布液’加熱使其乾燥而形成黏著劑層的方法，或者使 用在剝離片的剝離處理面上塗布包含該黏著性材料的塗布 液’加熱使其乾燥而形成黏著劑層，並將其轉印到上述樹 0 脂層的露出面上的方法等。另外，在黏著劑層中，爲了對 其進行保護，較佳係事先黏貼剝離片。 本發明中’作爲塗布含有黏著性材料的塗布液的方 法，可以使用比如刮板塗布法、輥塗法、棒塗布法、刮刀 • 塗布法、模縫塗布法、照相凹版印刷法等。 . 再有’作爲上述剝離片，可以舉出如玻璃紙、銅版紙、 層壓紙等紙，以及在各種塑膠膜上塗布了矽氧烷樹脂等剝 離劑的材料。該剝離片的厚度沒有特別的限制，通常爲 〇 20~150/zm 左右。 這樣形成的黏著劑層的厚度通常爲3~30#m左右，較 佳係在5〜2 0 // m的範圍。另外，活性能量線照射後的溫度 23 °C時的儲藏彈性模數G’，從耐久密著性等觀點考慮，較 佳爲0.3 M Pa以上，更佳係0.5 Μ P a以上》其上限沒有特 別的限制，通常爲30MPa左右。 " 另外，上述儲藏彈性模數（G ’）爲根據J I S K 7 2 4 4 - 6測 定的値。 -30- 201041740 通過上述黏著劑層，將本發明的光學用保護薄膜貼合 在被貼著體上，並照射活性能量線，由此，該光學用保護 ' 薄膜密封性良好地貼著在被貼著體上。 • 該黏著劑層與偏光膜（特別是聚乙烯醇系偏光膜）的密 封性優異。 作爲上述活性能量線，可以舉出如紫外線或電子線 等。上述紫外線可使用高壓水銀燈、無電極燈、氣燈等獲 ^ 每’另一方面’電子線可通過電子線加速器等獲得。該活 性能量線中，特別適合使用紫外線。另外，在使用電子線 時’不需要添加光聚合引發劑。 作爲活性能量線對該黏著劑層的照射量，根據該黏著 • 劑層的厚度而不同，在紫外線的場合較佳爲 . 5 0 ~ 1 0 0 0 m W / c m2 > 光量 50~1000mJ/cm2，在電子線的 場合較佳在10~1000krad的範圍內。 接著，對本發明的光學用保護薄膜的製造方法進行說 〇 明。 [光學用保護薄膜的製造方法1 本發明的光學用保護薄膜的製造方法的特徵在於，具 有： (a)在工程片的一面上，通過澆鑄法形成樹脂層（B)的步 驟； ' (b)在上述樹脂層（B)上形成硬塗層（A)的步驟；以及 (c)將上述工程片剝離，在露出的樹脂層（B)面上接合設 -31 - 201041740 置於剝離片上的黏著劑層（C)面以貼合的步驟。 上述（a)步驟、（b)步驟和（C)步驟中的樹脂層（B)、硬塗 ' 層（A)和黏著劑層（C)如上述說明中所示。 • 作爲各種圖像顯示裝置的表面保護薄膜，使用本發明 的光學用保護薄膜時，可根據需要，在上述硬塗層的表面 上設置用於產生抗反射性的抗反射層，比如，矽氧烷系薄 膜、氟系薄膜等。在此情況下，該抗反射層的厚度適合爲 〇 0.〇5~0.2#m左右。另外，波長550nm的反射率較佳爲 3.5 %以下。通過設置該抗反射層，可消除因太陽光、螢光 燈等的反射而產生的畫面的映入，另外，通過抑制表面的 反射率，總光線穿透率提高，透明性提高。 • 再有，在上述硬塗層中，可根據需要設置表面保護薄 . 膜。 這樣得到的本發明的光學用保護薄膜，（A)層、（B)層、 (C)層的總厚度在 15~130；um的範圍，較佳係在 〇 29~8〇em的範圍。 本發明的光學用保護薄膜具有硬塗層功能，適合作爲 '液晶顯示裝置中的偏光板或1/4波長板用，或觸控面板 用、光碟的保護薄膜、各種磁片的保護薄膜等，特別適合 作爲偏光板用的保護薄膜。 本發明還提供一種偏光板。以下對本發明的偏光板進 ' 行說明。 [偏光板】 -32- 201041740 本發明的偏光板按照以下方式進行層積，使本發明的 上述光學用保護薄膜的黏著劑層（c)的露出面側與偏光膜 • 接合，進而在該偏光膜的另一面側依序層積黏著劑層（D)、 . 樹脂層（E)。 <偏光膜> 本發明中使用的偏光膜採用通常使用的即可，沒有特別 的限制。較佳的可以舉出如，使親水性高分子薄膜吸附碘或 0 二色性染料，使其延伸取向的薄膜。作爲具體的例子，可以 通過使聚乙烯醇系薄膜染色、吸附碘或二色性染料，在硼酸 水溶液中單軸延伸，保持延伸狀態進行清洗、乾燥，由此獲 得偏光膜。單軸延伸的倍率通常爲4 ~8倍左右。作爲聚乙烯 醇系薄膜，可以使用“ KURARAY VINYLON” （可樂麗（股} . 製造）、“ TOHCELLO VINYLON” （Τ Ο H C E L L Ο (股）製造}、 “NIHON VI NYLON”（日本合成化學（股）製造）等市售品。 <黏著劑層（D)> 〇 本發明中的黏著劑層（D)可通過與上述的黏著劑層（c) 相同的組成和方法形成。從生產性的觀點和光學特性考 慮，黏著劑層（D)較佳係與黏著劑層（C)相同。 <樹脂層（E)> 本發明中的樹脂層（E)可通過與上述的樹脂層（B)相同 的組成和方法形成。從生產性的觀點和光學特性考慮，樹 ' 脂層（E)較佳係與樹脂層（B)相同。 <偏光板之製造方法> -33- 201041740 作爲偏光板之製造方法，（a)在工程片的—面上，通過 澆鏡法形成樹脂層（B) ’（b)在上述樹脂層（b)上形成硬塗層 - (A)’（c)將上述工程片剝離，在露出的樹脂層（b)面上接合 - 設置於剝離片上的黏著劑層（C)面以貼合，由此製作在黏著 劑層（C)上帶有剝離片的光學用保護薄膜。另外，上述（b) 中的硬塗層（A)的形成，較佳係通過在上述活性能量線感應 性組成物層上照射活性能量線而形成的。 q 接著，（d)剝離上述剝離片’將露出的黏著劑層（c)的 面與偏光膜的另一個面貼合。 另一方面，（e)在另一工程片的一個面上，通過澆鑄法 形成樹脂層（E) ’（f)按照在剝離片上設置的黏著劑層（D)的 - 面與上述樹脂層（E)相接的方式貼合，由此準備用於保護偏 光膜的另一面側的保護薄膜。 接著，（g)將上述黏著劑層（D)的上述剝離片剝離，將上 述偏光膜的另一面貼合，由此製作本發明的偏光板。 〇 這裏，黏著劑層（c)與偏光膜，和黏著劑層（D)與偏光 膜的密封性更好，爲了進一步提高偏光板的強度，最好黏 著劑層（C)和黏著劑層（D)的至少一者，較佳係兩者都含有 多官能活性能量線硬化型化合物。在此情況下，較佳係作 爲在與偏光膜貼合後照射活性能量線的偏光板。 ' 作爲活性能量線的照射時機，可以在將偏光膜與各黏 ' 著層貼合之後進行，從步驟簡化的觀點，較佳係（h)在製作 上述（g)的偏光板之後，一起照射活性能量線。另外，活性 -34- .201041740 能量線可以從硬塗層（A)上方’或者從樹脂層（E)上方，或 者從它們兩側的任一側進行照射。活性能量線的種類、照 - 射條件等如前所述。 . [帶有黏著劑層的偏光板] 本發明的偏光板，爲了與液晶胞或其他光學構件貼 合，最好是在上述樹脂層（E)的露出面側還具有黏著劑層（F) 的偏光板。 _ <黏著劑層（F)> 〇 本發明中的黏著劑層（F)可通過與上述的黏著劑層（C) 同樣的組成和方法形成。從生產性的觀點和光學特性考 慮，較佳係黏著劑層（F)與黏著劑層（C)和黏著劑層（D)相同。 . <帶有黏著劑層的偏光板之製造方法> 對於通過上述製造方法製造的偏光板，（k)按照在剝離 片上設置的黏著劑層（F)的面與上述樹脂層（E)上的露出的 面相接的方式貼合，由此可製作本發明的帶有黏著劑層的 G 偏光板。 這裏，最好是黏著劑層（c)、黏著劑層（D)、以及黏著 劑層（F)的至少一層、最好所有層都含有多官能活性能量線 硬化型化合物，並照射活性能量線，作爲帶有黏著劑層的 偏光板。 ' 作爲活性能量線的照射時機，可以在將各層貼合之後 ' 進行，從步驟簡化的觀點，較佳係⑴在上述步驟（k)之後照 射活性能量線。另外，活性能量線可以從硬塗層（A)上方’ -35- 201041740 或者從黏著劑層（F)上設置的剝離片的上方，或者從它們兩 側的任一側進行照射。活性能量線的種類、照射條件等如 前所述。 ' 本發明的偏光板以LCD中的液晶胞用爲開始，可作爲 光量調節用、偏光干擾應用裝置用、光學缺陷檢測器用等 而使用。 [實施例j 0 以下，根據實施例對本發明進行更詳細的說明，但本 發明並不因這些實例而受到任何限制。 另外，關於各例中得到的評價用樣品I，按照以下方 法，對光學特性和硬塗層的耐久密著性進行評價。 ' <光學特性> • ( 1)總光線穿透率和霧度 使用日本電色工業公司製造的霧度計 “ NDH 2 0 0 0” ，根據J I S K 6 7 1 4進行測定。 ^ ( 2 ) 6 0 °C 鏡面光澤度 使用日本電色工業公司製造的霧度計“VG 2000” ， 根據JIS K 7105進行測定。 <耐久密著性> 將評價用樣品I在（A)60°C、90%RH、（B)90°C、以及 (C)FOM(碳弧（面板溫度：6(TC ))的條件下放置500小時之 後，通過以下方法評價硬塗層的耐久密著性。 (3)硬塗層的耐久密著性 -36- 201041740 上述環境下放置後的評價用樣品丨，根據JISK 5600-5-6’使用在其中心部以imm的間隔具有6個刃的 ' 多刃切入工具’按照縱橫爲6個的方式形成縱橫imm見 . 方的基底網眼’通過貼合、剝離黏著力爲10N/25mm的黏 者片的方式進fT測疋。結果’根據JISK 5600-5-6，以如 下基準進行評價。 0:切割邊緣完全平滑’所有方格網眼都沒有剝離。 1 :切割交叉點的塗膜有小程度的剝離。在交叉切割部 Ο 分受到影響的明確不超過5 %。 2 :塗膜沿切割邊緣和/或在交叉點處剝離。在交叉切 割部分受到影響的明確超過5%，但不超過1 5%。 . 3:塗膜沿切割邊緣，出現局部或整面的大規模剝離， 和/或網眼的各個部分出現局部或整面的剝離。在交叉切割 部分受到影響的明確超過1 5 %，但不超過3 5 %。 4 :硬塗層沿切割邊緣，出現局部或整面的嚴重剝離， 〇 和/或多處的網眼局部或整面地剝離。在交叉切割部分受到 影響的明確不超過35%。 5:在分類4中也無法分類的剝離程度的任一種。 (4)偏光膜與黏著劑層（C)的表面黏著力的測定 將實施例2和比較例2中得到的各自的偏光板剪裁成 25mmX100mm的樣品，根據JIS Z 0237的黏著力測定 ' 方法，使用拉伸試驗機[ORIENTEC公司製造’ “TENSILON”】，在剝離速度300mm/min、剝離角度180 -37- 201041740 t的條件下測定表面黏著力。 (5) 樹脂層（B)的儲藏彈性模數E’ ' 將實施例的樹脂層（比較例1中爲三乙醯基纖維素薄 • 膜）分別切割成5mmX30mm的長方形各3份，作爲試料。 根據JIS K72 44-4，使用動態黏彈性測定裝置[TA儀器公 司製造，裝置名稱“Q800DMA” ]，在11Hz下測定該試 料2 3°C時的儲藏彈性模數E’（Pa)，將各自3點的平均値作 & 爲儲藏彈性模數E ’。 (6) 黏著劑層（C)的儲藏彈性模數G’ 在剝離片[琳得科（股）製造，商品名 “ SP-PET38103 1 ”】的剝離層上塗布與實施例同樣的黏 • 著性材料，使乾燥後的膜厚爲25;zm，將乾燥獲得的黏著 _ 劑層從該剝離片上剝離，層積爲厚度約3 m m。對層積的黏 著劑層照射紫外線（光量：250mJ/ cm2)，切割成直徑8mm 的圓形，作爲試料。根據JIS K7244-6，使用黏彈性測定 G 裝置[Rheometrics公司（現TA儀器公司）製造，裝置名稱 DYNAMIC ANALYZER RDAII” ]，在 1Hz 下測定該試料 2 3°C時的儲藏彈性模數G’（Pa)。 (7) 重量平均分子量Mw和分子量分佈Mw/Mn的測定 對於實施例的樹脂層和黏著劑層的（甲基）丙烯酸酯共 聚物，使用凝膠滲透色譜（GPC)，在以下條件下進行測定’ ' 通過聚苯乙烯換算，計算重量平均分子量Mw和分子量分 怖 M w / Μ η。 -38- 201041740 (測定條件） GPC測定裝置：TOSOH(股）公司製造’“ HLC-8020’’In the adhesive material of the present invention, the (meth) acrylate copolymer which is contained as the component (iv) is not particularly limited, and (meth)acrylic acid which is conventionally used as a resin component of a tackifier can be used. Any such component is suitably selected from the ester copolymer. As such a (meth) acrylate copolymer, preferably, the Q system may, for example, be an alkyl group having an alkyl group having 4 to 20 carbon atoms in the ester moiety. A copolymer formed with a functional monomer having an active hydrogen and another monomer which is used as desired. Here, as an example of the (meth) acrylate having an alkyl group having 4 to 20 carbon atoms as an ester moiety Examples are butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethyl (meth)propionate Hexyl ester, isooctyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, tetradecyl (meth)acrylate' -22· 201041740 (methyl) Cetyl acrylate, octadecyl (meth) acrylate These may be used singly or in combination of two or more. On the other hand, examples of the monomer having a functional group having active hydrogen include 2-hydroxyethyl (meth)acrylate, ( 2-hydroxypropyl methacrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, (meth) acrylate 4 -Hydroxyalkyl (meth)acrylate such as hydroxybutyl ester; monomethylaminoethyl (meth)acrylate, monoethylaminoethyl (meth)acrylate, monomethylamine (meth)acrylate Monoalkylaminoalkyl (meth)acrylate, such as propyl acrylate, monoethylaminopropyl (meth) acrylate; acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citric acid Ethylene unsaturated carboxylic acid, etc. These monomers may be used alone or in combination of two or more. Further, as an example of another monomer which is used as desired, methyl (meth)acrylate is exemplified. , ethyl (meth) acrylate, propyl (meth) acrylate a (meth) acrylate having an alkyl group having 1 to 3 carbon atoms in the ester moiety; a vinyl ester such as vinyl phthalate or vinyl propionate; an olefin such as ethylene, propylene or isobutylene; a halogenated olefin such as ethylene or vinylidene chloride; a styrene monomer such as styrene or methyl styrene; a diene monomer such as butadiene, isoprene or chloroprene; a nitrile monomer such as methacrylonitrile; an acrylamide such as acrylamide, N-methyl acrylamide or N,N-dimethyl decylamine; these may be used alone or in combination of two or more. The above group is used in combination. From the viewpoint of imparting adhesion to the obtained binder layer, as the (iv) (meth) acrylate copolymer, those constituting the copolymer -23- 201041740 are preferred. 50% by mass or more, more preferably 60 to 99% by mass or more of the (meth) acrylate structure of the alkyl group having 4 to 20 carbon atoms in the ester moiety. The copolymerization form of the above (meth) acrylate copolymer is not particularly limited, and any of a random copolymer, a block copolymer, and a graft copolymer may be used. Further, the molecular weight is preferably 500,000 or more, and more preferably 500,000 to 2,500,000. If the weight average molecular weight is less than 500,000, there is a risk that the adhesion to the adherend and the durability of the adhesive are insufficient. The weight average molecular weight is preferably from 700,000 to 2,000,000 if the bonding property and the durable bonding property are considered. Further, the above weight average molecular weight is oxime converted to standard polystyrene measured by a gel permeation chromatography (GPC)-method. Further, in the (meth) acrylate copolymer, the content of the monomer unit having a functional group having an active hydrogen is preferably in the range of 〇.〇ι~ι〇% by mass. When the content is less than 0.01% by mass, the crosslinking point is too small, the crosslinking is insufficient, and the adhesive layer is likely to cause aggregation failure. If it exceeds ί% by mass, there is a risk of poor adhesion to the liquid crystal cell or the like. . A more preferable content of the monomer unit having a functional group having the active hydrogen is in the range of 0.05 to 6.0% by mass, particularly preferably in the range of 0.2 to 5.0% by mass. Further, in order to achieve the object of the present invention, as a monomer having a functional group having an optimum active hydrogen, 2-hydroxyethyl (meth)acrylate and acrylic acid are exemplified, and a (meth) acrylate is preferred. The copolymer has a monomer unit of 33 to 1% by mass, particularly preferably 55 to 5.0% by mass. In the present invention, the (meth) acrylate copolymer may be used singly or in combination of two or more kinds as the component (iv). (2) (V) 'Poly-functional active energy ray-curable compound. In the adhesive material of the present invention, the polyfunctional active energy ray-curable compound used as the component (v) has a weight average molecular weight of usually Below 100,000, preferably in the range of 300 to 10,000. As such an active energy ray-curable compound, for example, an active energy ray-curable polyfunctional prepolymer and/or an active energy ray-curable 〇 polyfunctional monomer can be exemplified. The active energy ray-curable polyfunctional prepolymer is a radical polymerization type or a cationic polymerization type, and examples of the radical polymerization type active energy ray-curable polyfunctional prepolymer include a polyester acrylate system and a ring. An oxy acrylate type, a urethane acrylate type, a polyol acrylate type, etc. Here, as the polyester acrylate-based prepolymer, a polyester oligomer having a hydroxyl group at both terminals can be obtained by, for example, condensation of a polyvalent carboxylic acid and a polyhydric alcohol using (meth)acrylic acid. The hydroxyl group is esterified or obtained by esterifying a hydroxyl group at the terminal of the oligomer obtained by adding an alkylene oxide to the polyvalent carboxylic acid by using (meth)acrylic acid. An epoxy acrylate-based prepolymer, for example, by reacting a (meth)propionic acid in an oxirane ring of a lower molecular weight bisphenol type epoxy resin or a novolac type epoxy resin Obtained. A urethane acrylate-based prepolymer, 'for example, a polyurethane oligomer obtained by a reaction of a polyether polyol, a polyester polyol, and a polyisocyanate by using (meth)acrylic acid - 25- 201041740 Obtained by esterification. Further, the polyol acrylate prepolymer can be obtained by esterifying a hydroxyl group of a polyether polyol using (meth)acrylic acid. These active energy ray-curable polyfunctional prepolymers may be used alone or in combination of two or more. On the other hand, as the cationic polymerization type active energy ray-curable polyfunctional prepolymer, an epoxy resin is usually used. Examples of the epoxy resin include a compound which epoxidizes a polyhydric octaphenol such as a bisphenol resin or a phenol resin by using epichlorohydrin or the like, and a linear olefin hydrocarbon compound or the like using a peroxide or the like. A compound obtained by oxidizing a cyclic olefin compound or the like. Further, examples of the active energy ray-curable polyfunctional monomer include '1,4-butanediol di(meth)acrylate and 1,6-hexanediol di(methyl). Acrylate, new Pentyl glycol di(meth)acrylate, polyethylene glycol di(methyl). acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(a) Acrylate, dicyclopentyl di(meth)acrylate, caprolactone modified dicyclopentenyl di(meth)acrylate, ethylene oxide oxime modified di(meth)acrylate , allylated cyclohexyl di(meth)acrylate, di(meth)acrylic acid isocyanurate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate , propionic acid modified dipentaerythritol tris(meth)acrylate 'pentaerythritol tri(meth)acrylate, epoxy propylene compound modified dimethicone tris(methyl)propanoate, three [(A) Base) propylene 醯 醯 院 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 The ester, dipentaerythritol hexa(meth) acrylate, caprolactone modified monopentaerythritol (methyl) propylene vinegar and the like are polyfunctional acrylic vinegar. These -26-201041740 active energy ray-curable polyfunctional monomers may be used singly or in combination of two or more. Alternatively, the above-mentioned active energy-polyfunctional prepolymer may be used in combination. In the present invention, the polyfunctional active energy compound as the component (V) can be reduced in cross-linking point, and a polyfunctional monomer which is preferably a cross-linking density, and a suitable component is a methyl group. Propane triacrylate, dipentaerythritol hexaacrylate, _ propylene methoxyalkyl] isocyanurate, and the like. Among them, tris[(methyl) propylene oxime isocyanate is particularly suitable. The tris[(methyl)acryloxyalkylene group] is preferably exemplified by, for example, tris(2-propenyloxyethyl)isoester, tris(3-propenyloxypropyl). Isocyanuric acid ester, tris(2-decyloxyethyl)isocyanate, tris(3-methylpropenyloxyl j cyanurate, etc. In the present invention, as the (v) The content of the polyfunctional active energy Q compound of the component 'In the adhesive material used in the present invention, from the viewpoint of the adhesion to the polarizing film, it is preferable to contain 'better' according to the ratio of 5 to 1. (3) (vi) Crosslinking agent The (vi) component of the adhesive material of the present invention is not particularly limited, and can be used as an existing acrylic acid. Among the substances which are conventionally used for the crosslinking agent, an arbitrary substance is appropriately selected, and such a crosslinking agent may be, for example, a polyisocyanate compounding agent may be used for two types of wire-curing type linear curing type defects, for example, tris-tris[[methyl ) R-alkyl group 1 cyanuric acid cyanuric acid methyl propylene propyl group) isotropic hardening type solid content 50% by mass. Used in cross-linking resins. Crops, Epoxy-27- 201041740 Resins, melamine resins, urea resins, dialdehydes, methylol polymers, aziridines, metal chelates, metal alkoxides, metal salts, etc. A polyisocyanate compound is used. Here, examples of the polyisocyanate compound include aromatic polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, and xylene diisocyanate, and aliphatic polyisocyanates such as hexamethylene diisocyanate and isophorone. Alicyclic polyisocyanates such as diisocyanate and hydrogenated diphenylmethane diisocyanate, and their biuret and isomeric phthalocyanate, and also as ethylene glycol, propylene glycol, neopentyl glycol, An adduct of a reactant of a low molecular weight active hydrogen-containing compound such as trimethylolpropane or castor oil (for example, trimethylolpropane-modified benzylidene isocyanate) or the like. In the present invention, the crosslinking agent may be used singly or in combination of two or more kinds. In addition, the amount of use thereof varies depending on the type of the crosslinking agent, and is usually 0 to 01 to 20 parts by mass based on 100 parts by mass of the (meth) acrylate copolymer as the component (iv), and is preferably 〇.1. ~1〇 mass parts are selected within the range. (4) (vii) Photopolymerization initiator In the active energy ray-curable adhesive material, a photopolymerization initiator may be contained as needed. As the photopolymerization initiator, the same ones as those described in the hard coat layer (A) can be used. In the adhesive material, the content of the photopolymerization initiator used as described above is usually 0 to 5 parts by mass based on 100 parts by mass of the polyfunctional prepolymer and/or monomer as the component (v). Left and right, preferably -28-201041740 parts by mass. Further, as the active energy ray, when the electron beam is used, it is not necessary to contain the above photopolymerization initiator. <Preparation of a coating liquid containing an active energy ray-curable adhesive material> The preparation method of the coating liquid containing the active energy ray-curable adhesive material is not particularly limited, and the above may be added by, for example, a solvent ( Iv) a (meth) acrylate copolymer of a component, a polyfunctional active energy ray-curable compound of the (V) component, a crosslinking agent of the (Vi) component, and photopolymerization of a component (Vii) using 0 as needed Initiator, in addition to various additives, such as antioxidants, UV absorbers, light stabilizers, decane coupling agents, antistatic agents, leveling agents, defoamers, etc., and mixing and mixing to prepare active energy line hardening A coating solution for a type of adhesive material. • Examples of the solvent include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane and dichloroethane, and methanol, ethanol, propanol and butyl. Alcohols such as alcohol, acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone and other ketones, ethyl acetate, butyl acetate and other esters, ethyl solvate and other cellosolve solvents, propylene glycol monomethyl An alcohol ether solvent such as ether. These solvents may be used alone or in combination of two or more. The concentration of the active energy ray-curable adhesive material in the coating liquid is not particularly limited as long as the coating liquid is suitable for coating. <Formation of Adhesive Layer (C)> In the optical protective film of the present invention, an adhesive layer is provided as the (C) layer on the opposite side to the hard coat side of the resin layer (B). The formation of the adhesive layer -29-201041740 can be carried out as follows. For example, 'on the engineering sheet, a resin layer (B) having a hard coat layer (A) on its surface may be used, and the work piece may be first peeled off to expose a surface opposite to the hard coat side of the resin layer' on the exposed surface. Directly applying a coating liquid containing the above-mentioned adhesive material to a method of drying and drying to form an adhesive layer, or applying a coating liquid containing the adhesive material on a release-treated surface of a release sheet, heating and drying to form an adhesive The agent layer is transferred to the exposed surface of the above-mentioned tree grease layer, and the like. Further, in the adhesive layer, in order to protect it, it is preferred to adhere the release sheet in advance. In the present invention, as a method of applying a coating liquid containing an adhesive material, for example, a doctor blade coating method, a roll coating method, a bar coating method, a doctor blade coating method, a die coating method, a gravure printing method, or the like can be used. Further, the above-mentioned release sheet may, for example, be a paper such as cellophane, coated paper or laminated paper, or a material obtained by coating a peeling agent such as a decyl oxide resin on various plastic films. The thickness of the release sheet is not particularly limited and is usually about 20 to 150/zm. The thickness of the adhesive layer thus formed is usually about 3 to 30 #m, preferably in the range of 5 to 2 0 // m. In addition, the storage elastic modulus G' at a temperature of 23 ° C after the irradiation of the active energy ray is preferably 0.3 M Pa or more, more preferably 0.5 Μ P a or more from the viewpoint of durability and the like. A special limit is usually around 30 MPa. " In addition, the above storage elastic modulus (G ') is 値 measured according to J I S K 7 2 4 4 - 6. -30-201041740 The optical protective film of the present invention is bonded to the adherend by the above-mentioned adhesive layer, and the active energy ray is irradiated, whereby the optical protective film is adhered to the film with good sealing properties. Stick to the body. • The adhesive layer and the polarizing film (especially a polyvinyl alcohol-based polarizing film) are excellent in sealing property. Examples of the active energy ray include ultraviolet rays or electron beams. The above ultraviolet rays can be obtained by using a high-pressure mercury lamp, an electrodeless lamp, a gas lamp, etc., and the electron beam can be obtained by an electron beam accelerator or the like. Among the live performance lines, ultraviolet rays are particularly suitable. Further, when an electron beam is used, it is not necessary to add a photopolymerization initiator. The amount of irradiation of the adhesive layer as the active energy ray varies depending on the thickness of the adhesive layer, and is preferably 0.5 0 to 1 0 0 0 m W / c m2 > light amount 50 to 1000 mJ. /cm2 is preferably in the range of 10 to 1000 krad in the case of an electron beam. Next, a method of producing the optical protective film of the present invention will be described. [Manufacturing Method 1 for Optical Protective Film] The method for producing an optical protective film according to the present invention includes: (a) a step of forming a resin layer (B) by a casting method on one surface of an engineering sheet; a step of forming a hard coat layer (A) on the above resin layer (B); and (c) peeling off the above-mentioned engineering sheet, and bonding the surface of the exposed resin layer (B) to -31 - 201041740 on the release sheet Adhesive layer (C) surface to fit the step. The resin layer (B), the hard coat layer (A) and the adhesive layer (C) in the above steps (a), (b) and (C) are as shown in the above description. • When the optical protective film of the present invention is used as the surface protective film of various image display devices, an antireflection layer for generating antireflection, such as xenon, may be provided on the surface of the hard coat layer as needed. An alkane film, a fluorine film, or the like. In this case, the thickness of the anti-reflection layer is suitably about 〇0.〇5~0.2#m. Further, the reflectance at a wavelength of 550 nm is preferably 3.5% or less. By providing the antireflection layer, reflection of a screen due to reflection by sunlight, a fluorescent lamp or the like can be eliminated, and by suppressing the reflectance of the surface, the total light transmittance is improved, and the transparency is improved. • Further, in the above hard coat layer, a surface protection thin film can be provided as needed. The optical protective film of the present invention thus obtained has a total thickness of the layer (A), the layer (B) and the layer (C) in the range of 15 to 130 μm, preferably in the range of 29 to 8 〇em. The optical protective film of the present invention has a hard coat function and is suitable as a polarizing plate or a quarter-wave plate in a liquid crystal display device, or a protective film for a touch panel, a disc, and a protective film for various magnetic sheets. It is particularly suitable as a protective film for polarizing plates. The invention also provides a polarizing plate. Hereinafter, the polarizing plate of the present invention will be described. [Polarizing Plate] -32-201041740 The polarizing plate of the present invention is laminated in such a manner that the exposed surface side of the adhesive layer (c) of the optical protective film of the present invention is bonded to the polarizing film, and the polarizing film is further bonded thereto. The other side of the film is sequentially laminated with an adhesive layer (D) and a resin layer (E). <Transfractive film> The polarizing film used in the present invention is not particularly limited as long as it is generally used. Preferably, for example, a film in which a hydrophilic polymer film is adsorbed with iodine or a dichroic dye to extend orient it is mentioned. As a specific example, a polyvinyl alcohol-based film can be dyed, adsorbed with iodine or a dichroic dye, uniaxially stretched in an aqueous solution of boric acid, and kept in an extended state, washed and dried to obtain a polarizing film. The magnification of the uniaxial extension is usually about 4 to 8 times. As a polyvinyl alcohol-based film, "KURARAY VINYLON" (manufactured by Kuraray Co., Ltd.), "TOHCELLO VINYLON" (Manufactured by ELL Ο HCELL Ο), and "NIHON VI NYLON" (Japan Synthetic Chemicals Co., Ltd.) can be used. Commercial product such as "manufacturing". <Adhesive layer (D)> The adhesive layer (D) in the present invention can be formed by the same composition and method as the above-mentioned adhesive layer (c). The adhesive layer (D) is preferably the same as the adhesive layer (C) in consideration of viewpoints and optical characteristics. <Resin layer (E)> The resin layer (E) in the present invention can pass through the above resin layer ( B) The same composition and method are formed. From the viewpoint of productivity and optical characteristics, the tree 'lipid layer (E) is preferably the same as the resin layer (B). <Manufacturing method of polarizing plate> -33- 201041740 As a method of producing a polarizing plate, (a) a resin layer (B) is formed by a mirror casting method on the surface of the engineering sheet. (b) A hard coat layer (A)' is formed on the resin layer (b) ( c) peeling off the above-mentioned engineering piece, bonding on the exposed resin layer (b) surface - being provided on the release sheet The surface of the adhesive layer (C) is bonded to each other to prepare an optical protective film having a release sheet on the adhesive layer (C). Further, the formation of the hard coat layer (A) in the above (b) is comparatively Preferably, the active energy ray is irradiated onto the active energy ray-inductive composition layer. q Next, (d) peeling off the peeling sheet 'will expose the surface of the adhesive layer (c) and the other of the polarizing film On the other hand, (e) forming a resin layer (E) by casting on one surface of another engineering sheet '(f) according to the surface of the adhesive layer (D) provided on the release sheet The resin layer (E) is bonded to each other to prepare a protective film for protecting the other surface side of the polarizing film. Next, (g) peeling off the peeling sheet of the pressure-sensitive adhesive layer (D), The other side of the polarizing film is bonded to thereby produce the polarizing plate of the present invention. Here, the adhesive layer (c) and the polarizing film, and the adhesive layer (D) and the polarizing film are more sealed, in order to further improve the polarized light. The strength of the sheet, preferably at least one of the adhesive layer (C) and the adhesive layer (D), Both of them contain a polyfunctional active energy ray-curable compound. In this case, it is preferably used as a polarizing plate that illuminates the active energy ray after bonding with the polarizing film. 'As an irradiation timing of the active energy ray, it is possible to The polarizing film is bonded to each of the adhesive layers, and from the viewpoint of simplification of the step, it is preferred that (h) the active energy ray is irradiated together after the polarizing plate of the above (g) is produced. In addition, the active-34-.201041740 The energy rays may be irradiated from above the hard coat layer (A) or from above the resin layer (E), or from either side of them. The types of active energy rays, the irradiation conditions, and the like are as described above. [Polarizing Plate with Adhesive Layer] The polarizing plate of the present invention preferably has an adhesive layer (F) on the exposed side of the resin layer (E) for bonding to a liquid crystal cell or other optical member. Polarizer. _ <Adhesive layer (F)> The adhesive layer (F) in the present invention can be formed by the same composition and method as the above-mentioned adhesive layer (C). From the viewpoint of productivity and optical properties, it is preferred that the adhesive layer (F) is the same as the adhesive layer (C) and the adhesive layer (D). <Manufacturing Method of Polarizing Plate with Adhesive Layer> With respect to the polarizing plate manufactured by the above-described manufacturing method, (k) according to the surface of the adhesive layer (F) provided on the release sheet and the above resin layer (E) The exposed surface of the upper surface is bonded to each other, whereby the G polarizing plate with an adhesive layer of the present invention can be produced. Here, it is preferable that at least one layer, preferably all layers of the adhesive layer (c), the adhesive layer (D), and the adhesive layer (F) contain a polyfunctional active energy ray-curable compound and irradiate the active energy ray. As a polarizing plate with an adhesive layer. The irradiation timing of the active energy ray can be carried out after the layers are bonded. From the viewpoint of simplification of the steps, it is preferred that (1) the active energy ray is irradiated after the above step (k). Alternatively, the active energy ray may be irradiated from above the hard coat layer (A) at -35-201041740 or from the release sheet provided on the adhesive layer (F), or from either side of both sides. The type of active energy ray, the irradiation conditions, and the like are as described above. The polarizing plate of the present invention is used for liquid crystal cells in an LCD, and can be used as a light amount adjusting device, a polarizing interference application device, an optical defect detector, or the like. [Example j 0 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by these examples. Further, with respect to the sample I for evaluation obtained in each example, the optical properties and the durability of the hard coat layer were evaluated in the following manner. ' <Optical characteristics> • (1) Total light transmittance and haze The measurement was carried out in accordance with J I S K 6 7 1 4 using a haze meter "NDH 2 0 0 0" manufactured by Nippon Denshoku Industries Co., Ltd. ^ ( 2 ) 60 ° C Specular gloss The haze meter "VG 2000" manufactured by Nippon Denshoku Industries Co., Ltd. was used for measurement according to JIS K 7105. <Endurance Adhesion> Sample I for evaluation was at (A) 60 ° C, 90% RH, (B) 90 ° C, and (C) FOM (carbon arc (panel temperature: 6 (TC )) After standing for 500 hours under conditions, the durability of the hard coat layer was evaluated by the following method: (3) Durability of the hard coat layer - 36 - 201041740 Samples for evaluation after being placed in the above environment, according to JIS K 5600- 5-6' uses a 'multi-edge cutting tool' that has six blades at the center of the imm interval. The vertical and horizontal imm is formed in a manner of six vertical and horizontal directions. The base mesh of the square is bonded and peeled. The result of the 10N/25mm adhesive sheet was measured by fT. The result was evaluated according to JIS K 5600-5-6 on the following basis: 0: The cut edge was completely smooth. All the square meshes were not peeled off. The coating of the dots has a small degree of peeling. The influence of the enthalpy in the cross-cutting portion is not more than 5%. 2: The coating film is peeled off along the cutting edge and/or at the intersection. The cross-cutting portion is affected more clearly than 5%, but not more than 1 5%. 3: The coating film along the cutting edge, there is a large-scale peeling of the local or full surface, / / Partial or full-face peeling of the various parts of the mesh. The impact on the cross-cut part is clearly more than 15%, but not more than 35 %. 4: Hard coating along the cutting edge, appearing partial or full-face Severe peeling, sputum and/or multiple meshes are partially or completely peeled off. The amount of influence on the cross-cutting part is not more than 35%. 5: Any of the degree of peeling that cannot be classified in Category 4. (4) Measurement of Surface Adhesion of Polarizing Film and Adhesive Layer (C) The respective polarizing plates obtained in Example 2 and Comparative Example 2 were cut into samples of 25 mm×100 mm, and the method was determined according to the adhesion of JIS Z 0237. The tensile tester [manufactured by ORIENTEC Co., Ltd.] "TENSILON" was used to measure the surface adhesion at a peeling speed of 300 mm/min and a peeling angle of 180 - 37 to 201041740 t. (5) Storage elastic modulus of the resin layer (B) The resin layer of the Example (the triethylenesulfonated cellulose thin film in Comparative Example 1) was cut into 3 pieces each of a rectangular shape of 5 mm×30 mm to prepare a sample. According to JIS K72 44-4, a dynamic viscoelasticity measuring device was used. [Manufactured by TA Instruments, The device name "Q800DMA"] was used to measure the storage elastic modulus E' (Pa) at 23 ° C at 11 Hz, and the average of the three points was & the storage elastic modulus E '. (6) The storage elastic modulus G' of the adhesive layer (C) is applied to the release layer of the release sheet [manufactured by Linda Co., Ltd., trade name "SP-PET38103 1 "), and the same adhesive material as in the embodiment is applied. The film thickness after drying was 25; zm, and the adhesive layer obtained by drying was peeled off from the release sheet to a thickness of about 3 mm. The laminated adhesive layer was irradiated with ultraviolet rays (light amount: 250 mJ/cm2), and cut into a circular shape having a diameter of 8 mm to prepare a sample. According to JIS K7244-6, the viscoelasticity measurement G device [manufactured by Rheometrics (now TA Instruments), device name DYNAMIC ANALYZER RDAII"] was used, and the storage elastic modulus G' at 2 3 ° C of the sample was measured at 1 Hz ( Pa) (7) Measurement of weight average molecular weight Mw and molecular weight distribution Mw/Mn For the (meth) acrylate copolymer of the resin layer and the adhesive layer of the examples, gel permeation chromatography (GPC) was used under the following conditions The measurement was carried out '', and the weight average molecular weight Mw and the molecular weight fraction Mw / Μ η were calculated by polystyrene conversion. -38- 201041740 (measurement conditions) GPC measuring device: "HLC-8020" manufactured by TOSOH Co., Ltd. '
• GPC柱（以下的順序通過）：TOSOH (股）公司製造 TSK guard column HXL-H TSK gel GMHXL(X2)• GPC column (the following sequence is passed): manufactured by TOSOH Co., Ltd. TSK guard column HXL-H TSK gel GMHXL (X2)
TSK gel G2000HXL 測定溶劑：四氫呋喃 ^ 測定溫度：4 0 °C Ο (8)耐漏光性 通過剪裁裝置[荻野精機製作所公司製造’ Supercutter “ΡΝ1-600” ]，將實施例3和比較例3中獲 • 得的帶有黏著劑層的偏光板調整成233mmX309mm的尺 寸之後，貼合到無鹼玻璃[CORNING公司製造，“ 1737” ] 上，然後，使用栗原製作所公司製造的高壓釜，在〇.5Mpa、 5 0 °C、20分鐘的條件下加壓。另外，上述貼合，按照在無 〇 鹼玻璃的表裏，使帶有黏著劑的偏光板成爲偏光軸爲正交 偏光狀態的方式進行。在該狀態下，在80°c放置200小 時。然後，在23°C，相對濕度50%的環境下放置2小時， 在相同環境下，通過以下方法評價漏光性。 使用大塚電子公司製造的“ MCPD-2000” ，測定第1 圖所示的各區域的亮度，通過式 △ L* = [(b + c + d + e) / 4]-a (其中，&，13,(：，<1，6各自爲八區域、8區域、（：區域、 -39- 201041740 D區域、E區域的預定測定點（各區域的中央部1部位）的亮 度}， 求出亮度差作爲漏光性。AL*的値越小，表示漏光 • 越少。 實施例1 (1)樹脂層（Β)的形成 作爲工程片，在厚度50/zm的聚對苯二甲酸乙二醇酯 q (PET)薄膜[三菱樹脂（股）製造，註冊商標“ DIAFOIL T100 TYPE” ]上，塗布聚甲基丙烯酸甲酯（同元聚合物重量平均 分子量Mw=20萬，分子量分佈Mw/Mn =約2.3，23°C時 的乾燥塗膜的儲藏彈性模數E’ = 5MPa)的25質量％濃度的 • 乙酸乙酯溶液，使乾燥後的厚度爲30#m，在100°C下進 . 行1分鐘乾燥處理，形成聚甲基丙烯酸甲酯製成的樹脂層。 (2 )硬塗層的形成 在上述（1)中形成的樹脂層上，塗布硬塗劑[琳得科（股） 〇 製造，商品名稱“ AGT- 100” ，丙烯酸類化合物的濃度40 質量％的丙二醇單甲醚（PGM)溶液]，使乾燥後的厚度爲 7 y m，乾燥之後，以250mJ/cm2的光量照射紫外線，形 成硬塗層。在該硬塗層表面上黏貼厚度50/zm的保護薄膜 [琳得科（股）製造，商品名稱“SPF/A1A” ’ PET製造卜 (3)帶有剝離片的黏著劑層（C)的製作 ' 在厚度爲38 的PET制剝離片[琳得科（股）製造， 商品名稱“SP-PET381031 ”】的剝離層面上塗布具有下 -40- 201041740 述組成的黏著性材料，使乾燥後的厚度爲10//m，然後， 加熱乾燥，製作帶有剝離片的黏著劑層。再有，爲了製作 儲藏彈性模數測定用的樣品，與上述同樣地製作帶有剝離 • 片的黏著劑層，以250mJ/cm2的光量對其照射紫外線。 測定照射了紫外線的黏著劑層的2 3 °C時的儲藏彈性模數 G’，爲 0.6MPa。 <黏著性材料的組成> 0 丙烯酸丁酯/丙烯酸甲酯/丙烯酸的質量比爲 77/20/3的丙烯酸共聚物（重量平均分子量Mw:80萬）100 質量份 作爲紫外線硬化型多官能丙烯酸酯的三（丙烯醯氧基 • 乙基）異三聚氰酸酯[東亞合成（股）製造，商品名稱 • “ARONIX M-315 ‘‘，分子量578】25質量份 作爲光聚合引發劑的二苯甲酮與1-羥基環己基苯基酮 的質量比爲1:1的混合物[汽巴精化公司製造，商品名稱 O “IRGACURE 500” 】1 質量份 作爲異氰酸酯類交聯劑的三羥甲基丙烷改性苯亞甲基 二異氰酸酯[日本POLYURETHANE(股）製造，商品名稱 "CORONATE L" ]2 質量份 (4)光學用保護薄膜的製作 將在上述（2)中獲得的工程片上設置的表面具有硬塗 層的樹脂層（B)的該工程片剝離，使與樹脂層（B}的硬塗層 相反一側的面露出，按照黏著劑層面與該露出面相接的方 -41- # 201041740 式貼合在上述（3)中獲得的帶有剝離片的黏著劑層（C)，製 作光學用保護薄膜。 (5)評價用樣品I的製作和評價 從在上述（4)中獲得的層積薄膜的剝離片的面，按照 250mJ/cm2的光量照射紫外線，之後，剪裁成 150mmX100mm，將剝離片剝離，黏貼到玻璃板上，製作 評價用樣品I。 ^ 對於該評價用樣品I，評價其光學特性和硬塗層的耐久 密著性。 實施例2 (1) 偏光膜的製作 - 將聚乙烯醇系薄膜[日本合成化學（股）製造，商品名稱 . “NIHONVINYLON” ]置於由1000質量份水、10質量份 碘、100質量份碘化鉀製成的3(TC的水溶液中，浸漬3分 鐘，使碘染色、吸附。接著，將上述浸漬後的薄膜浸入50 〇 乞的5質量％的硼酸水溶液中，向該薄膜的長軸方向單軸 延伸爲6倍。此過程中在硼酸水溶液中的浸漬時間爲5分 鐘。從硼酸水溶液中取出的薄膜保持單軸延伸狀態，置於 2 0°C的水中，浸漬5分鐘進行清洗，然後乾燥，由此獲得 偏光膜。 (2) 偏光板的製作 ' 將在實施例1 (4)中獲得的光學用保護薄膜的剝離片剝 離，將露出的黏著劑層（C)面與上述偏光膜的一個面貼合。 -42- .201041740 另一方面，按照與在實施例1(3)中獲得的帶有剝離片 的黏著劑層（C)同樣獲得的黏著劑層（D)的沒有設置剝離片 的一側的面，與和在實施例1(1)中獲得的樹脂層（B)同樣獲 • 得的樹脂層（E)相接的方式貼合，由此製作層積薄膜。 接著，將該層積薄膜的黏著劑層（D)上的剝離片剝離， 按照該黏著劑層（D)與偏光膜的另一面相接的方式貼合，獲 得硬塗層（A)/樹脂層（B)/黏著劑層（C)/偏光膜/黏著劑層 0 (D)/樹脂層（E)/工程膜這樣的結構體。 使用栗原製作所製造的高壓釜，在0.5 MPa、5 CTC的條 件下對該結構體進行20分鐘加壓，使其密著，從該結構體 的兩面照射紫外線（光量250mJ/cm2)，由此製作偏光板。 - 實施例3 . (1)帶有黏著劑層的偏光板的製作 將在實施例2中獲得的偏光板的工程膜剝離’按照與 在實施例1(3)的帶有剝離片的黏著劑層（C)同樣地獲得的 〇 黏著劑層（F)的沒有設置剝離片的一側的黏著劑層面與露 出的面相接的方式貼合，獲得硬塗層（A)/樹脂層（B)/黏著 劑層（C)/偏光膜/黏著劑層（D)/樹脂層（E)/黏著劑層（F)/ 剝離片構成的結構體。從該結構體的剝離片側照射紫外線 (光量250mJ/cm2)，由此製作帶有黏著劑層的偏光板。 比較例1 ' 除了使用三乙醯基纖維素膜[富士軟片（股）製造’商品 名稱‘‘ TD80UL” ，按照在B(帶狀）面側塗布硬塗劑的方式 -43- .201041740 配置]代替實施例1的樹脂層（B)以外，與實施例1同樣地 操作，獲得光學用保護薄膜。 比較例2 - (1)偏光板的製作 將在比較例1中獲得的光學用保護薄膜的黏著劑層（C) 的剝離片剝離，將露出的黏著劑層面與在實施例2 ( 1)中製 作的偏光膜的一個面貼合。 0 另一方面，按照與在實施例1(3)中獲得的黏著劑層（C) 同樣獲得的黏著劑層（D)的沒有設置帶有剝離片的黏著劑層 的剝離片的一側的面，與和在比較例1中使用的三乙醯基纖 維素膜的B(帶狀）面相接的方式貼合，由此製作層積薄膜。 ' 接著，將該層積薄膜的黏著劑層（D)上的剝離片剝離， . 按照該黏著劑層（D)與偏光膜的另一面相接的方式貼合，獲 得硬塗層（A)/TAC薄膜/黏著劑層（C)/偏光膜/黏著劑層 (D) /TAC薄膜/工程膜這樣的結構體。 〇 使用栗原製作所製的高壓釜，在〇.5MPa、50°c的條 件下對該結構體進行20分鐘加壓，使其密著，從該結構體 的兩面照射紫外線（光量250m J/cm2)，由此製作偏光板。 比較例3 (1)帶有黏著劑層的偏光板的製作 將在比較例2中獲得的偏光板的工程膜剝離’按照與 ' 在實施例1(3)的黏著劑層（C)同樣地獲得的帶有剝離片的 黏著劑層（F)的沒有設置剝離片的一側的黏著劑層（F)面與 -44- 201041740 露出的面相接的方式貼合，獲得硬塗層（A)/TAC薄膜/黏著 劑層（C)/偏光膜/黏著劑層（D)/TAC薄膜/黏著劑層（F)/剝 離片構成的結構體。從該結構體的剝離片側照射紫外線（光 量2 50m J/cm2)，由此製作帶有黏著劑層的偏光板。 對獲得的實施例以及比較例的光學用保護薄膜、偏光 板、以及帶有黏著劑層的偏光板進行表1所示的各種評價。 實施例1 ~ 3和比較例1 ~ 3的評價結果示於表1。 〇 〇 表1 實施 例1 實施 例2 實施 例3 比較 例1 比較 例2 比較 例3 光學用保護 薄膜的光學 特性 霧度(％) 12.7 / / 12.5 / / 60°鏡面光 澤度 98.0 / / 102.6 / / 總光線穿透 率(％) 90.8 / 90.7 / / 硬塗層的耐 久密著性 (500小時） 60。。、 90%RH 0 / / 4 / / 90°C乾燥 0 / 0 / FOM 0 / / 4 / / 偏光板的偏光膜與黏著劑 層的表面黏著力(N/25mm) / 20以 上※ / / / 帶有黏著劑層的偏光板的 耐漏光性(ΔΙ^*) / / 0.5 / / 2.5 ※由於樹脂層破壞，實際無法測定。 通過表1可知，本發明實施例1的光學用保護薄膜具 有與比較例1的TAC膜的光學用保護薄膜相同程度的光學 特性’而且在硬塗層的耐久密著性方面，比TAC膜的光學 -45- 201041740 用保護薄膜更優秀。 另外’通過使用實施例1的光學用保護薄膜製作的實 ' 施例2的偏光板的表面黏著力的試驗可知，偏光膜與黏著 • 劑層具有足夠的密封性。還知道，使用實施例2的偏光板 製作的實施例3的帶有黏著劑層的偏光板與比較例3的帶 有黏著劑層的偏光板相比，具有優異的耐漏光性。 產業上的利用可能性 q 本發明的光學用保護薄膜具有硬塗層功能，並且透明 性優異’具有光學上各向同性，同時耐熱性和耐濕性良好， 耐久性優異，而且對聚乙烯醇系偏光膜的密封性良好，適 合作爲比如液晶顯示裝置中的偏光板或1/4波長板使用， - 或者觸控面板用、光碟的保護薄膜、各種顯示器的保護薄 . 膜等’特別適合作爲偏光板使用。 【圖式簡單說明】 第1圖係顯示評價實施例、比較例得到的附黏著劑層 〇 之偏光板的耐漏光性的方法的說明圖》 【主要元件符號說明】 to 〇 -46 -TSK gel G2000HXL Determination solvent: tetrahydrofuran ^ Measurement temperature: 40 °C Ο (8) Light leakage resistance was obtained by the cutting device [Supercutter "ΡΝ 1-600" manufactured by Takino Seiki Co., Ltd.], and obtained in Example 3 and Comparative Example 3. • The polarizer with the adhesive layer is adjusted to a size of 233 mm X 309 mm, and then bonded to an alkali-free glass [1737" manufactured by CORNING, and then used in an autoclave manufactured by Kurihara Seisakusho Co., Ltd. at M.5Mpa. Pressurize at 50 ° C for 20 minutes. Further, in the above-described bonding, the polarizing plate with an adhesive is placed in a state in which the polarizing axis is in an orthogonally polarized state in the surface of the alkali-free glass. In this state, it was allowed to stand at 80 ° C for 200 hours. Then, it was allowed to stand in an environment of 23 ° C and a relative humidity of 50% for 2 hours, and the light leakage property was evaluated by the following method under the same environment. Using the "MCPD-2000" manufactured by Otsuka Electronics Co., Ltd., the brightness of each area shown in Fig. 1 was measured by the formula Δ L* = [(b + c + d + e) / 4] - a (where & , 13, (:, <1,6 are each eight regions, eight regions, (: region, -39-201041740 D region, and the predetermined measurement point of the E region (the luminance of the central portion of each region)] The difference in brightness is the light leakage. The smaller the * of AL*, the less the light leakage is. Example 1 (1) Formation of resin layer (Β) as an engineering sheet, polyethylene terephthalate having a thickness of 50/zm Alcohol ester q (PET) film [manufactured by Mitsubishi Resin Co., Ltd., registered trademark "DIAFOIL T100 TYPE"], coated with polymethyl methacrylate (weight molecular weight molecular weight Mw = 200,000, molecular weight distribution Mw / Mn) = about 2.3%, the storage modulus of the dried coating film at 23 ° C, E' = 5 MPa), the concentration of 25% by mass of the ethyl acetate solution, so that the thickness after drying is 30 #m, at 100 ° C Drying is performed for 1 minute to form a resin layer made of polymethyl methacrylate. (2) Formation of a hard coat layer on the resin layer formed in the above (1) Coated hard coating agent [manufactured by Linde Co., Ltd., trade name "AGT-100", propylene glycol monomethyl ether (PGM) solution having a concentration of 40% by mass of acrylic compound], and the thickness after drying is 7 μm. After drying, ultraviolet rays were irradiated with a light amount of 250 mJ/cm 2 to form a hard coat layer. A protective film having a thickness of 50/zm was adhered to the surface of the hard coat layer [Manufactured by Linde Co., Ltd., trade name "SPF/A1A" 'PET Production of (3) Preparation of Adhesive Layer (C) with Release Sheet] Coating on a peeling layer of a PET release sheet having a thickness of 38 [manufactured by Linde Co., Ltd., trade name "SP-PET381031") An adhesive material having a composition of the following -40 to 201041740, which has a thickness of 10/m after drying, and then dried by heating to prepare an adhesive layer with a release sheet. Further, in order to prepare a storage elastic modulus In the same manner as described above, an adhesive layer having a peeling sheet was prepared and irradiated with ultraviolet light at a light amount of 250 mJ/cm 2 . The storage elastic modulus G' at 23 ° C of the adhesive layer irradiated with ultraviolet rays was measured. , is 0.6MPa. <Adhesive material Composition > 0 Acrylic Copolymer (weight average molecular weight Mw: 800,000) in a mass ratio of butyl acrylate/methyl acrylate/acrylic acid of 77/20/3 100 parts by mass of tris(propylene) as an ultraviolet curing type multifunctional acrylate醯oxy•ethyl)isocyanurate [manufactured by East Asia Synthetic Co., Ltd., trade name: “ARONIX M-315 '', molecular weight 578] 25 parts by mass of benzophenone as photoinitiator and 1 a mixture of -hydroxycyclohexyl phenyl ketone in a mass ratio of 1:1 [manufactured by Ciba Specialty Chemicals, trade name O "IRGACURE 500"] 1 part by mass of trimethylolpropane modified benzene as an isocyanate crosslinking agent Methylene diisocyanate [manufactured by Japan POLYURETHANE Co., Ltd., trade name "CORONATE L"] 2 parts by mass (4) Preparation of optical protective film The surface provided on the engineering sheet obtained in the above (2) is hard coated. The engineered sheet of the resin layer (B) of the layer is peeled off, and the surface opposite to the hard coat layer of the resin layer (B) is exposed, and the surface of the adhesive layer is in contact with the exposed surface - 41- # 201041740 Obtained in (3) above The adhesive layer (C) with a release sheet was used to form an optical protective film. (5) Preparation and Evaluation of Sample I for Evaluation The surface of the release sheet of the laminated film obtained in the above (4) was irradiated with ultraviolet light at a light amount of 250 mJ/cm 2 , and then cut into 150 mm×100 mm, and the release sheet was peeled off and pasted. On the glass plate, a sample I for evaluation was prepared. ^ For the sample I for evaluation, the optical properties and the durability of the hard coat layer were evaluated. Example 2 (1) Preparation of polarizing film - A polyvinyl alcohol-based film [manufactured by Nippon Synthetic Chemical Co., Ltd., trade name "NIHONVINYLON"] was placed in an amount of 1000 parts by mass of water, 10 parts by mass of iodine, and 100 parts by mass of potassium iodide. The prepared 3 (aqueous solution of TC was immersed for 3 minutes to dye and adsorb iodine. Then, the immersed film was immersed in a 50 〇乞 5 mass% boric acid aqueous solution, and uniaxially oriented in the long axis direction of the film. The stretching time is 6 times. The immersion time in the boric acid aqueous solution is 5 minutes in this process. The film taken out from the boric acid aqueous solution is kept in a uniaxially stretched state, placed in water at 20 ° C, immersed for 5 minutes for washing, and then dried. Thus, a polarizing film was obtained. (2) Production of Polarizing Plate The peeling sheet of the optical protective film obtained in Example 1 (4) was peeled off, and the exposed adhesive layer (C) surface and one of the above polarizing films were removed. -42- .201041740 On the other hand, the adhesive layer (D) obtained in the same manner as the adhesive layer (C) with a release sheet obtained in Example 1 (3) was not provided with a release sheet. The side of one side, with and in embodiment 1 ( The resin layer (B) obtained in 1) is bonded together by the resin layer (E) obtained in the same manner, thereby producing a laminated film. Next, on the adhesive layer (D) of the laminated film The release sheet is peeled off, and the adhesive layer (D) is bonded to the other surface of the polarizing film to obtain a hard coat layer (A)/resin layer (B)/adhesive layer (C)/polarizing film/adhesion. The structure of the agent layer 0 (D) / the resin layer (E) / the engineering film. The structure was pressurized for 20 minutes under the conditions of 0.5 MPa and 5 CTC using an autoclave manufactured by Kurihara Seisakusho Co., Ltd. The polarizing plate was produced by irradiating ultraviolet rays (light amount: 250 mJ/cm 2 ) from both surfaces of the structure. - Example 3 (1) Production of polarizing plate with an adhesive layer Polarization obtained in Example 2 The engineered film of the sheet was peeled off. The adhesive layer on the side where the release sheet was not provided, which was obtained in the same manner as the adhesive layer (C) having the release sheet of Example 1 (3). Bonding to the exposed surface to obtain a hard coat layer (A) / resin layer (B) / adhesive layer (C) / polarizing film / adhesive layer (D) / tree A structure composed of a lipid layer (E)/adhesive layer (F)/peeling sheet, and a polarizing plate with an adhesive layer was prepared by irradiating ultraviolet rays (light amount: 250 mJ/cm2) from the side of the release sheet of the structure. 1 'In addition to the use of triethylene fluorene-based cellulose film [Fuji film (manufactured by the company) 'product name' ' TD80UL", according to the B (belt) side coating hard coating agent -43-.201041740 configuration] instead of implementation An optical protective film was obtained in the same manner as in Example 1 except for the resin layer (B) of Example 1. Comparative Example 2 - (1) Preparation of Polarizing Plate Adhesive of Optical Protective Film Obtained in Comparative Example 1 The release sheet of the layer (C) was peeled off, and the exposed adhesive layer was bonded to one surface of the polarizing film produced in Example 2 (1). On the other hand, according to the adhesive layer (D) obtained in the same manner as the adhesive layer (C) obtained in the embodiment 1 (3), the side of the release sheet in which the adhesive layer with the release sheet is not provided is provided. The surface was bonded to the B (ribbon) surface of the triacetyl cellulose film used in Comparative Example 1, thereby producing a laminated film. Next, the release sheet on the adhesive layer (D) of the laminated film is peeled off, and the adhesive layer (D) is bonded to the other surface of the polarizing film to obtain a hard coat layer (A). /TAC film/adhesive layer (C) / polarizing film / adhesive layer (D) / TAC film / engineering film structure.高压In the autoclave manufactured by Kurihara Seisakusho Co., Ltd., the structure was pressed for 20 minutes under conditions of 5 MPa and 50 ° C to be adhered, and ultraviolet rays were irradiated from both surfaces of the structure (light amount: 250 m J/cm 2 ). Thereby, a polarizing plate is produced. Comparative Example 3 (1) Preparation of polarizing plate with an adhesive layer The engineering film of the polarizing plate obtained in Comparative Example 2 was peeled off in the same manner as in the adhesive layer (C) of Example 1 (3). The adhesive layer (F) on the side of the obtained adhesive sheet (F) having the release sheet without the release sheet was attached to the exposed surface of -44 to 201041740 to obtain a hard coat layer (A). ) / TAC film / adhesive layer (C) / polarizing film / adhesive layer (D) / TAC film / adhesive layer (F) / peeling sheet structure. Ultraviolet rays (light amount: 50 mJ/cm2) were irradiated from the side of the release sheet of the structure to prepare a polarizing plate with an adhesive layer. The optical protective film, the polarizing plate, and the polarizing plate with the adhesive layer of the obtained examples and the comparative examples were subjected to various evaluations shown in Table 1. The evaluation results of Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 1. 1 Table 1 Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Optical characteristic haze of optical protective film (%) 12.7 / / 12.5 / / 60° specular gloss 98.0 / / 102.6 / / Total light transmittance (%) 90.8 / 90.7 / / Durable adhesion of hard coating (500 hours) 60. . , 90% RH 0 / / 4 / / 90 °C Dry 0 / 0 / FOM 0 / / 4 / / Polarizing film and adhesive layer surface adhesion (N / 25mm) / 20 or more ※ / / / Light leakage resistance of polarizing plate with adhesive layer (ΔΙ^*) / / 0.5 / / 2.5 * Due to the destruction of the resin layer, it is practically impossible to measure. As can be seen from Table 1, the optical protective film of Example 1 of the present invention has the same optical characteristics as the optical protective film of the TAC film of Comparative Example 1 and is superior to the TAC film in terms of durability of the hard coat layer. Optical -45- 201041740 is better with a protective film. Further, by the test of the surface adhesion of the polarizing plate of Example 2 produced by using the optical protective film of Example 1, the polarizing film and the adhesive layer had sufficient sealing properties. It is also known that the polarizing plate with an adhesive layer of Example 3 produced using the polarizing plate of Example 2 has excellent light leakage resistance as compared with the polarizing plate with an adhesive layer of Comparative Example 3. INDUSTRIAL APPLICABILITY q The optical protective film of the present invention has a hard coat function and is excellent in transparency. It is optically isotropic, and has good heat resistance and moisture resistance, excellent durability, and polyvinyl alcohol. The polarizing film has good sealing properties and is suitable for use as, for example, a polarizing plate or a quarter-wave plate in a liquid crystal display device, or a protective film for a touch panel, a disc, or a protective film for various displays. Use with polarizing plates. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an explanatory view showing a method of evaluating light leakage resistance of a polarizing plate with an adhesive layer obtained in the examples and the comparative examples. [Explanation of main component symbols] to 〇 -46 -