200835602 九、發明說明： 【發明所屬之技術領域】 本發明係有關一種主要使用於顯示裝置用構件之硬塗 布膜、及使用該薄膜之防止反射膜。更詳言之，係有關可 抑制外光進入、眩光、彩虹狀色彩等情形，且高折射率硬 塗布層與熱可塑性樹脂薄膜之密接性優異的硬塗布膜。 【先前技術】 一般而言，使用於液晶顯示裝置（LCD)、電漿顯示板 (PDP)等顯示裝置之構件的硬塗布膜，係使熱可塑性樹脂膜 與硬塗布（HC)層經由易黏合層予以積層。另外，一般而言 顯示裝置用光學機能性膜係將機能相異的膜經由黏合劑層 予以貼合使用。而且，近年來由於大型平板顯示裝置之低 價格化市場的需求大爲增加。因此，於顯示裝置用構件中， 進行開發於一張硬塗布膜上積層其他的光學機能性層之複 合膜。例如，液晶顯示裝置（LCD)如在硬塗布膜上積層防止 外光進入之防止反射層（AR層）、光之集光或擴散時所使用 的稜形狀透鏡層、提高亮度之光擴散層等光學機能性層的 複合膜。 由硬塗布膜之基材所成的熱可塑性樹脂膜，係使用聚 對酞酸乙二酯（PET)、聚醯胺、丙烯酸、聚碳酸酯（PC)、三 乙醯基纖維素（TAC)、環狀聚烯烴等所成的透明薄膜。於此 等之基材薄膜中，特別是二軸配向聚酯薄膜，就優異的透 明性、尺寸安定性、耐藥品性而言，可廣泛使用作爲各種 光學機能性薄膜之熱塑性樹脂薄膜。 200835602 一般而言，如二軸配向聚酯薄膜或二軸配向聚醯胺薄 膜之二軸配向熱塑性薄膜時，由於薄膜表面爲高度結晶配 向，會有缺乏與各種塗料、黏合劑、油墨等之密接性的缺 點。因此’自古以來提案在二軸配向熱塑性樹脂薄膜表面 上，以各種方法賦予易密接性之方法。 另外’提案如聚烯烴薄膜之不具極性基的薄膜，由於 非常缺乏與各種塗料、黏合劑、油墨等之密接性，於事前 進行電暈放電處理、火焰處理等之物理處理或化學處理 後，在薄膜表面上以各種方法賦予易密接性的方法。 例如，使含有聚酯、丙烯酸、聚胺基甲酸酯、丙烯酸 接枝聚醋寺樹s曰之易黏合層，藉由塗布法設置於熱塑性樹 脂薄膜表面上，使熱塑性樹脂薄膜具有易密接性的方法， 爲一般已知的方法。於該塗布法中，在結晶配向完成前之 熱塑性樹脂薄膜上，直接或視其所需實施電暈放電處理 後，使含有使上述樹脂之溶液或樹脂以分散媒予以分散的 分散體之水性塗布液塗布於基材薄膜上、且乾燥後，至少 朝一軸方向進行延伸，然後，實施熱處理，使熱塑性樹脂 薄膜之結晶配向完成的方法（即線上塗布法），或製造熱塑 性樹脂薄膜後，在該薄膜上塗布水系或溶劑系塗布液後， 予以乾燥的方法（即離線塗布法），在工業上廣爲被實施。 另外，近年來光學機能構件’爲防止與導光板之密接 情形、提高透過性、減低翹曲情形等爲目的時，大多在兩 面上設置硬塗布層，或在與透鏡層、光擴散層等之光學機 能層相反的面上積層硬塗布層。 200835602 使用此等之透明塑膠薄膜基材，形成光學機能性膜 時，大多在基材上經由薄膜之易黏合層等，形成數μπι〜約 5 Ομιη之光學機能性層、例如硬塗布層等之硬化層。另外， 使機能不同的光學機能性膜經由黏合劑層貼合，使用作爲 顯示裝置用光學機能性膜。 然而，熱塑性樹脂薄膜爲二軸配向聚酯薄膜時，對折 射率（面方向）爲1.62〜1.65而言，例如以丙烯酸樹脂等所 形成的硬塗布層之折射率，通常爲以1 . 5 3爲中心之1 . 5 0〜 1 · 5 6。此外，一般而言位於中間之易黏合層，係以聚胺基 甲酸酯樹脂、聚酯樹脂等、或組合此等所成的樹脂爲主成 分予以形成。而且，該樹脂組成物層之折射率，通常爲1 .49 〜1 · 5 4 〇 因此，藉由二軸配向聚酯薄膜與易黏合層之折射率 差，在該界面上引起光反射情形，以與硬塗布表面之反射 光的干涉情形產生干涉斑（彩虹狀色彩）。因此，在硬塗布 膜上形成防止反射層（AR層）或防污層後，會有經貼合的影 像顯示裝置等物品之視認性惡化情形或高級感受損的情 形。 特別是在3波長螢光燈下，由於亮線光譜成分之比例 高，干涉斑顯著。近年來，3波長螢光燈之普及在一般家 庭中急速進行，故該干涉斑問題變得極爲重要。因此，形 成干涉斑問題之用途，在使用二軸配向聚酯薄膜作爲基材 之機能性塑膠薄膜上受到顯著的限制。要不然的話，得使 用具有千涉斑問題之機能性膜。實際上，在使用二軸配向 200835602 聚酯薄膜作爲基材之大型平面電視的領域中，目前搭載的 防止反射膜幾乎皆有干涉斑產生。 此外，在硬塗布層表面上積層由高折射率層/低折射率 層、或高折射率層/中折射率層/低折射率層所構成的防止 反射層時，藉由使硬塗布層予以高折射率化，可自防止反 射層省略高折射率層。結果，於製造防止反射膜時，可大 幅地減低成本。該傾向係因近年來強烈要求低成本化時， 愈來愈被推廣。 本發明人於專利文獻1中揭示著重於薄膜局部厚度不 齊的情形，且於製造具有以共聚合聚酯與聚胺基甲酸酯爲 主成分之固成份的塗布厚度0.1 g/m2之易黏合層的薄膜 後，藉由在該薄膜上進行壓延處理，使薄膜之局部厚度不 齊情形變小’以減低因基材薄膜厚度之不齊情形所引起的 干涉斑之積層聚酯薄膜。然而，積層折射率爲1.58以上、 1 · 6 5以下之硬塗布層時，雖具有優異的密接性、，惟上述干 涉斑情形顯著。 本發明人於專利文獻2中提案在由二軸配向聚對酞酸 乙二酯所成的基材薄膜上，設置添加具有不同相分離構造 之共聚合聚酯與聚胺基甲酸酯、及適當粒徑之無機粒子的 樹脂組成物層，可維持作爲光學用基材薄膜極爲重要的特 性之透明性，且與光學機能層之密接性高度優異的積層聚 酯薄膜，且提案樹脂組成物層之厚度2 0〜1 2 0 n m之例。惟 積層折射率爲1.58以上、1.65以下之硬塗布層時，雖具有 優異的密接性’惟上述之干涉斑情形顯著。 200835602 此外，於專利文獻3中揭示在至少一面之至少朝一軸 方向延伸的聚酯薄膜上具有含2種以上具金屬元素之有機 化合物的塗布層之積層聚酯薄膜，例如三乙醇胺鈦絡合物 與乳酸鈦作爲具有2種金屬元素之有機化合物。 而且，本發明人於專利文獻4中揭示在至少二軸延伸 聚酯薄膜之一面上具有由水性聚酯樹脂、與水溶性鈦螯合 化合物、水溶性醯酸鈦化合物、水溶性銷螯合化合物、或 水溶性锆醯酸鹽化合物所成的塗布層之二軸延伸聚酯薄 • 膜。 使硬塗布層之折射率與二軸配向聚酯薄膜相等時，就 減低干涉斑而言，沒有在二軸配向聚酯薄膜與硬塗布層之 間設置樹脂組成物層下，使硬塗布層與二軸配向聚酯薄膜 進行光學一體化，實質上沒有該兩層間之反射光，極爲理 想。然而’如上所述在二軸配向聚酯薄膜上直接設置硬塗 布層時，無法得到實用的密接力。換言之，於積層有高折 I 射率型硬塗布膜之光學用基材薄膜中，不爲干涉斑不顯 者、且具有充分密接性者。此外，於積層有硬塗布層、在 反面上積層有黏合劑層的光學用基材薄膜中，同時在硬塗 布層側、黏合劑層側上之干涉斑不顯著，具有充分密接性 者，仍尙未存在。 【專利文獻1】日本特開2001-71439號公報 【專利文獻2】國際公開第2006/57382號手冊 【專利文獻3】日本特開2006-76292號公報 【專利文獻4】專利第3 6 3 2044號公報 200835602 【發明內容】 本發明之目的係 時，另在反面上積層 接性優異的硬塗布膜 上述之課題，可 換言之，本發明 塗布膜，其係於由熱 薄膜表面上直接積層 布層之境界範圍上分 徵爲有機-無機複合體 酸酯樹脂、丙烯酸樹 層之折射率爲1 . 5 8〜 第2發明係爲上 具有在含共聚合聚酯 無機粒子之構造。 第3發明係爲上 側之基材薄膜表面上 酸酯樹脂、丙烯酸樹 第4發明係爲上 反側之基材薄膜表面 性聚酯樹脂與乳酸鈦 塗布液進行塗布、乾 第5發明係爲上 提供一種積層高折射率之硬塗布層 黏合劑層時，形成千涉斑不顯著且密 〇 藉由下述解決方法予以達成。 之硬塗布膜的第1發明，係爲一種硬 塑性樹脂所成的基材薄膜，在該基材 的硬塗布層、以及在基材薄膜與硬塗 散有機-無機複合體的硬塗布膜，其特 丨具有至少一種選自聚酯樹脂、胺基甲 脂中包埋有無機粒子之構造，硬塗布 1.65。 述之硬塗布膜，其中有機-無機複合體 及聚胺基甲酸酯之混合樹脂中包埋有 述之硬塗布膜，其中硬塗布層在相反 另具有至少含一種聚酯樹脂、胺基甲 脂之塗布層。 述之硬塗布膜，其中在與硬塗布層相 上具有塗布層，該塗布層係使含有水 化合物與三乙醇胺鈦絡合物化合物之 燥所成。 .述之硬塗布膜，其中以塗布液中所含 -10- 200835602 的水性聚酯樹脂之質量爲（A)，以乳酸鈦化合物之質量爲 (B)，及以三乙醇胺鈦絡合物化合物之質量爲（C)時， (A)/[(B) + (C)]爲 5 0/5 0 〜80/20，且（B)/(C)爲 3 5 /6 5 〜6 5 / 3 5。 第6發明係爲上述之硬塗布膜，其中硬塗布層具有在 硬化型樹脂中分散有無機微粒子之構造，硬塗布層之無機 微粒子的含量爲2 0〜8 0質量％。 第7發明係爲上述之硬塗布膜，其中基材薄膜內沒有 存在粒子，且基材薄膜內之粒子含量爲50ppm以下。 ^ 第8發明係爲上述之硬塗布膜，其中有機-無機複合體 之無機粒子爲二氧化矽粒子。 第9發明係爲一種光學機能性薄膜，其特徵爲在上述 之硬塗布膜之硬塗布層上積層有防止反射層或防污層。 發明效果 本發明係藉由涵蓋在基材薄膜與硬塗布層之間設置中 間層的習知技術指針，且使基材薄膜與硬塗布層基本上直 接予以積層，在其境界領域中使所定構造之複合體分散， ^ 可使實用的密接性與減低干涉斑倂存。 【實施方式】 爲實施發明之最佳形態 於本發明中，首先說明有關課題中記載的密接性與干 涉斑之定義。 (密接性之評估） 硬塗布層與基材薄膜間之密接性，係藉由在硬塗布層 上貼附膠帶，使其剝離，藉由棋盤格子剝離試驗予以評估。 -11- 200835602 具體的評估順序，於實施例之段落中詳述。本發明於棋盤 格子剝離試驗中以下述式所示密接性之値，以8 0 %以上較 佳，以85%以上更佳，以90%以上最佳。 密接性（％) = (1-格子之剝離個數/100個）χ100 存在有黏合劑層時，該黏合劑層之密接性係藉由使用 SUS板之JIS-Z- 023 7所規定的剝離試驗予以評估。具體的 評估方法於實施例之段落中詳述。 (干涉斑之評估） ^ 本發明中硬塗布膜側之干涉斑，係指在積層薄膜之黏 合劑層面上貼合黑色光澤膠帶，使硬塗布膜面爲上面，以 二波長型白色螢光燈爲光源，自斜方上方以目視觀察反射 光時，可以目視觀察的干涉斑（彩色狀色彩），其具體的評 估方法於實施例之段落中詳述。 黏合劑層側之干涉斑，係指在積層薄膜之硬塗布膜面 上貼合黑色光澤膠帶，以黏合劑層面爲上面，以三波長型 白色螢光燈爲光源，自斜方上方以目視觀察反射光時，可 ^ 以目視觀察的干涉斑（彩虹狀色彩），其具體的評估方法於 實施例之段落中詳述。 本發明之硬塗布膜，其特徵爲在基材薄膜之表面上直 接形成硬塗布層。換言之，使用透過型電子顯微鏡（ΤΕΜ)， 以倍率5萬倍〜20萬倍攝影時，在基材薄膜與硬塗布層之 界面上沒有觀察到樹脂組成物層。然後，在基材薄膜與硬 塗布層之境界範圍可觀察到下述之有機-無機複合體分 散。上述境界範圍亦可指基材薄膜與硬塗布層之界面附 -12- 200835602 近。藉由該構成，可達成充分的密接性與減低干涉斑之效 果，係爲本發明之新見解。 (1)基材薄膜 首先，有關本發明之基材薄膜的製造方法，以聚對酞 酸乙二酯（以下簡稱爲PET)爲代表例予以簡要說明，當然 不受該代表例所限制。 使實質上不含以賦予易滑性爲目的之粒子的PET粒料 充分進行真空乾燥後，供應給押出機，在2 7 0〜2 9 5 °C下熔 融押出成片狀，且進行冷卻硬化，使未配向PET薄片製膜。 此時，使熔融樹脂保持於2 7 0〜2 9 5 °C下熔融押出，在製程 的任意時段，爲除去該熔融樹脂中所含的異物時進行高精 度過濾處理。使所得的未配向薄片以在80〜12(TC下加熱 的輥’朝長度方向進行延伸2.5〜5.0倍，製得一軸配向PET 薄膜。 然後，在一軸配向PET薄膜之一面、或兩面上，塗布 下述之塗布液。塗布塗布液時，例如有可逆輥•塗布法、 照相凹版·塗布法、接觸·塗布法、輥刷法、噴霧塗布法、 氣刀塗布法、線圈棒塗布法、管狀刮刀法、含浸•塗布法 及簾幕•塗布法等，此等方法可單獨或組合進行。 然後，使薄膜之兩端部以夾子固定，導入在8 0〜1 8 〇。(： 下加熱的熱風區，乾燥後朝寬度方向進行延伸2.5〜5 . 〇 倍。繼後，導入在2 2 0〜2 4 0 °C之熱處理區，進行熱處理1 〜2〇秒’完成結晶配向。在該熱處理製程中，視其所需亦 可朝寬度方向或長度方向進行1〜1 2 %之鬆弛處理。 200835602 本發明使用的基材薄膜，以使熱塑性樹脂 或使熔融押出的未配向薄片視其所需朝長度方 向之一軸方向進行延伸，或朝二軸方向逐次二 時二軸延伸，且實施熱固定處理之二軸配向熱 膜爲宜。 另外，基材薄膜在不會損害本發明目的之 在上述薄膜上實施電暈放電處理、輝光放電處 理、紫外線照射處理、電子線照射處理、臭氧 0 面活性化處理。 本發明使用的基材薄膜之厚度，可在3 0〜 內，視使用的用途規格而定任意予以決定。基 度上限値，以2 50 μιη較佳，以200μπι更佳。此 厚度下限値，以50μηι較佳，以75μιη更佳。薄 5 0 μιη時，剛性或機械強度容易變得不充分。另 度超過300 μιη時，由於薄膜中存在的異物之絕 故光學缺點之頻率增高。而且，使薄膜切斷成 之隙縫性亦會惡化，製造成本提高。此外，由於 容易使長尺狀薄膜變得不易捲取成輥狀。 熱塑性樹脂以聚對酞酸乙二酯、聚對酞酸 對酞酸丁二酯、聚乙烯-2,6-萘酸酯、間規聚苯 烯系聚合物、聚碳酸酯、聚丙烯酸酯等爲宜。 如聚酯或聚醯胺之極性官能基的樹脂，就與密 之密接性而言較佳。 其中，以聚對酞酸乙二酯、聚乙烯-2,6 ·蔡 熔融押出， 向或寬度方 軸延伸或同 塑性樹脂薄 範圍內，可 理、火焰處 處理等之表 3 0 0 μ m範圍 材薄膜之厚 外，薄膜之 膜厚度未達 外，薄膜厚 對量增加， 所定寬度時 卜剛性變強， 丙二酯、聚 乙烯、原菠 而且，具有 接性改質層 :酸酯、聚對 -14- 200835602 酞酸丁二酯、聚對酞酸丙二酯或以此等樹脂之構成成分爲 主成分之共聚物較佳，換言之，以由聚對酞酸乙二酯所形 成的二軸配向薄膜更佳。 例如，形成基材薄膜之樹脂，使用以聚對酞酸乙二酯 爲基本架構之聚目η共聚物時’共聚合成分之比例未達20莫 耳％較佳。爲2 0莫耳％以上時，薄膜強度、透明性、耐熱 性不佳。可作爲共聚合成分使用的二羧酸成分，例如己二 酸、癸二酸等之脂肪族二羧酸、異酞酸、酞酸、及2,6-萘 ^ 二羧酸等之芳香族二羧酸、偏苯三酸及均苯四甲酸等之多 官能羧酸等。而且，可作爲共聚合成分使用的乙二醇，例 如二乙二醇、1，4_丁二醇、丙二醇及新戊醇等之脂肪酸二 醇；ρ-二甲苯醇等之芳香族二醇；1，4-環己烷二甲醇等之脂 肪族二醇；平均分子量爲1 5 0〜2 0 〇 0 0之聚乙二醇等。 另外，於上述之熱塑性樹脂中，在不會妨礙本發明效 果之範圍內，除觸媒以外可含有各種添加劑。添加劑例如 無機粒子、耐熱性高分子粒子、鹼金屬化合物、鹼土類金 屬化合物、磷化合物、抗靜電劑、紫外線吸收劑、耐光劑、 難燃劑、熱安定劑、抗氧化劑、凝膠化防止劑、界面活性 劑等。 上述之粒子就製造基材薄膜時、捲取成輥狀時、或捲 出時之處理性（平滑性、行走性、黏連性、捲取時伴隨空氣 之空氣除去性等）而言，爲使薄膜表面具有適當的表面凹凸 時所使用。 無機粒子例如碳酸鈣、磷酸鈣、非晶性二氧化矽、結 -15- 200835602 晶性玻璃纖維、高嶺土、滑石、二氧化鈦、氧化鋁、二氧 化矽-氧化鋁複合氧化物粒子、硫酸鋇、氟化鈣、氟化鋰、 沸石、硫化鉬、雲母等。另外，耐熱性高分子粒子例如交 聯聚苯乙烯粒子、交聯丙烯酸系樹脂粒子、交聯甲基丙烯 酸甲酯系粒子、苯并鳥糞胺•甲醛縮合物粒子、蜜胺•甲 醛縮合物粒子、聚四氟乙烯粒子等。 使用聚酯薄膜作爲基材薄膜時，於上述粒子中由於二 氧化矽粒子與聚酯樹脂之折射率較爲接近，可容易得高到 高透明性’故最適合於要求強透明性之用途。另外，要求 隱蔽性之用途，以如氧化鈦之白色顏料爲宜。而且，基材 薄膜中所含的粒子可以爲1種或數種倂用。 上述粒子之種類、平均粒徑、添加量，就透明性與處 理性之平衡性而g ’平均粒徑在0 . 〇 1〜2 μ m、薄膜中之粒 子含量在0.01〜5.0質量％的範圍內，視薄膜之用途予以決 定。 而且，使本發明使用的密接性改質基材薄膜使用於要 求高度透明性之用途時，於基材薄膜中以實質上不含造成 透明性降低原因之粒子較佳。 上述之「貫質上不含的粒子」，係指例如爲無機粒子 時’以砂光X線分析定量無機元素時爲5 〇 p p m以下，較佳 者爲10PPm以下，更佳者爲檢測臨界値以下之含量。此係 即使沒有在基材薄膜中積極添加粒子時’由於來自外來異 物之污染成分、或原料樹脂或薄膜製造製程中附著於管線 或裝置之污垢剝離，混入薄膜中之故。 -16- 200835602 另外，本發明使用的基材薄膜之層構成可以爲單層、 亦可爲賦予單層無法得到的機能之積層構造。爲積層構造 時，以共押出法爲宜。 以使用聚酯作爲基材薄膜之原料爲代表例時，有關基 材薄膜之製法於下述中詳細說明。 作爲薄膜原料所使用的聚酯粒料之特性黏度，以0.45 〜0.70dl/g之範圍較佳。特性黏度未達0.45dl/g時，於製 造薄膜時大多容易產生斷裂情形。另外，特性黏度大於 ® 〇.70dl/g時，濾壓大爲上昇，不易進行高精度過濾處理， 容易產生生產性降低的情形。而且，聚酯之特性黏度係可 使聚酯溶解於苯酚（6質量份）、與1，1，2,2-四氯乙烷（4質量 份）之混合溶劑中溶解，在3 0 °C下進行測定。 另外，本發明之硬塗布膜、或使用該膜之光學機能性 膜中，以除去造成光學缺點原因之原料聚酯中所含的異物 較佳。爲除去聚酯中之異物時，在熔融押出時溶融樹脂保 持於27 0〜29 5 °C之任意時段進行高精度過濾處理。熔融樹 ^ 脂於高精度過濾處理時所使用的濾材，沒有特別的限制， 爲不銹鋼燒結體之濾材時，以Si、Ti、Sb、Ge、Cu爲主成 分之凝聚物及高熔點有機物之除去性能優異爲宜。 熔融樹脂於高精度過濾處理時所使用的濾材之過濾粒 子尺寸（初期過濾效率95%)，以15μπι以下較佳。濾材之過 濾粒子尺寸大於1 5 μ m時，導致2 0 μ m以上異物之除去效果 變得不充分。藉由使用過濾粒子尺寸（初期過濾效率95%) 爲1 5 μπι以下之濾材進行熔融樹脂之高精度過濾處理，雖 -17- 200835602 有降低生產性的情形，惟爲製得沒有光學缺點之薄膜時， 極爲重要。 熔融樹脂於押出製程中，即使爲通過濾材之微細異 物’在薄片狀熔融物之冷卻製程中在異物周圍進行結晶 化，於配向製程中引起配向不均勻性，且有產生微小厚度 差異之透鏡狀態處。此處，在具有透鏡下光有折射或散射 情形’以肉眼觀察時較實際異物更大。該微小厚度之差異， 可觀測作爲凸部高度與凹部深度之差異，凸部高度爲1 μιη ® 以上、鄰接凸部之凹部深度爲〇·5μιη以上時，藉由透鏡效 果，即使大小爲2 0 μιη之形狀物時可以肉眼辨識爲5 0 μιη以 上之大小，另外，亦可辨識100 μιη以上大小之光學缺點。 爲得筒透明之薄膜時，以基材薄膜中不含粒子較佳， 粒子含量愈少、透明性愈高，因微小凹凸之光學缺點會有 更鮮明的傾向。此外，由於較厚的薄膜表面比較薄的薄膜 不易急冷，會有進行結晶化的傾向，必須於製造未配向薄 片時使薄膜全體予以急冷。使未配向薄片予以冷卻的方 ^ 法，以使熔融樹脂在回轉冷卻桶上自塑模之縫隙部押出成 薄片狀，使薄片狀熔融物密接於回轉冷卻桶上，予以冷卻 形成薄片的方法爲宜。使該未配向薄片之空氣面（與冷卻桶 接觸面之相反面）冷卻的方法，以吹附高速氣流予以冷卻的 方法極爲有效。 (2)有機-無機複合體（以下簡稱爲「複合體」） 本發明使用的複合體，具有在至少含有一種選自聚酯 樹脂、胺基甲酸酯樹脂、丙烯酸樹脂之樹脂的樹脂組成物 -18- 200835602 中包埋有無機粒子之構造。 上述複合體例如作成本發明之硬塗布膜的超薄切片， 藉由使用透過型電子顯微鏡（TEM)，以倍率5萬倍〜20萬 倍進行觀察，可確認存在於基材薄膜與硬塗布層之境界範 圍。上述複合體具有使無機粒子包埋於至少一種選自聚酯 樹脂、胺基甲酸酯樹脂、丙烯酸樹脂之樹脂組成物中的構 造。TEM觀察影像，視電子密度而定可觀察對比之濃淡情 形。無機粒子係電子密度高、濃，而選自聚酯樹脂、胺基 ^ 甲酸酯樹脂、丙烯酸樹脂之樹脂組成物係電子密度低、淡。 因此，上述複合體係爲與基材薄膜同等、或較基材薄膜更 淡的樹脂組成物包圍於較濃的無機粒子周圍之構造。本發 明中一個獨立的複合體，以含有一個無機粒子、或一個無 機粒子凝聚物所成者爲較佳的形態。 使有機-無機複合體中所含的至少1種選自聚酯樹脂、 胺基甲酸酯樹脂、丙烯酸樹脂之樹脂組成物，藉由透過型 電子顯微鏡（TEM)觀察時，以進行釕染色、餓染色、磷鎢酸 ^ 染色等之染色處理較佳。特別是釕染色可以聚酯樹脂、胺 基甲酸酯樹脂適合地染色。有機-無機複合體之各構成，可 藉由上述染色之染色像予以判斷。另外，亦可藉由局部元 素分析（SEM/EDX等），判斷有機-無機複合體之各構成。 上述複合體存在於基材薄膜與硬塗布層之境界範圍。 境界範圍係指基材薄膜與硬塗布層之界面附近。使本發明 之硬塗布膜藉由TE Μ觀察時，在基材薄膜與硬塗布層相接 的境界上可觀察到上述複合體。上述各複合體以存在於基 -19- 200835602 材薄膜與硬塗布層之兩方較佳。 上述複合體分散於基材薄膜與硬塗布層之境界範圍。 複合體分散係指使本發明之硬塗布膜藉由TEM觀察時，數 個複合體沒有全部聯在一起，爲分散存在之意。換言之， 無機粒子包圍於樹脂組成物所成的複合體，係爲個別獨立 存在之意，在基材薄膜與硬塗布層之間數個無機粒子沒有 藉由樹脂組成物連續連接的構造。連續連接的構造係指基 材薄膜與硬塗布層之境界上有作爲樹脂組成物之有機物的 ^ 狀態。本發明使用倍率5萬倍〜2 0萬倍之透過型電子顯微 鏡（TEM)觀察時，在硬塗布膜之基材薄膜與硬塗布層之境界 上，沒有觀察到由至少一種選自有機-無機複合體之構成成 分的聚酯樹脂、胺基甲酸酯樹脂、丙烯酸樹脂之樹脂組成 物存在，係爲重要。此處，沒有觀察到樹脂組成物存在， 係指使用倍率5萬倍〜20萬倍之透過型電子顯微鏡（TEM) 觀察時，境界範圍之樹脂層的厚度爲觀察之臨界値以下， 與沒有設置樹脂組成物之基材薄膜同等的狀態。具體而 ^ 言，硬塗布層與基材層之境界爲l〇nm以下，較佳者爲5nm 以以下。此係因藉由染色時之運作等，在硬塗布層與基材 層之境界有染色劑沉澱之故。有關境界範圍內鄰接的2個 複合體間之距離，沒有特別的限制，以具有100〜1 000nm 之距離較佳。 該複合體之較佳製法，如下詳述，例如在含有構成複 合體之樹脂與無機粒子之塗布液，在基材薄膜上極薄地塗 布•乾燥，然後，使由形成硬塗布層時之硬化型樹脂所成 -20- 200835602 的硬塗布劑進行塗布•乾燥的方法。藉由該製法，構成複 合體之樹脂至少部分藉由爲形成硬塗布層時之硬塗布劑予 以膨脹，然後，與硬塗布層之樹脂予以一體化。結果’在 沒有上述無機粒子存在的範圍內，塗布層藉由τ Ε Μ觀察沒 有存在的程度下，與硬塗布層之樹脂予以一體化。換言之， 使用倍率5萬倍〜20萬倍之透過型電子顯微鏡（ΤΕΜ)觀察 時，境界範圍之樹脂組成物的厚度爲觀察臨界値以下。 而且，本說明書中，使爲製得有機-無機複合體時之塗 ® 布液定義爲「塗布液（1 )」。另外，爲在與硬塗布層相反側 之基材薄膜表面上形成塗布層時所塗布的塗布液定義爲 「塗布液（2)」，分爲兩塗布液。 此外，藉由在上述無機粒子之周圍殘存構成複合體之 樹脂，結果，形成在基材薄膜與硬塗布層之間包埋複合體 的構造。習知技術對爲使基材薄膜與硬塗布層黏合時所設 置的獨立「層」而言，本發明改變其全部的想法，藉由使 複合體分散而黏合基材薄膜與硬塗布層。藉此，可維持充 分的密接性，且可顯著減低干涉斑。 而且，於下述說明中，使含有在具硬塗布層前之基材 薄膜上存在的構成複合體之樹脂與無機粒子的塗布層以密 接性改質層表示，以及使在基材薄膜上設有密接性改質層 之薄膜以密接性改質基材薄膜表示。如此藉由設置硬塗布 層，密接性改質層無法確認所定倍數之密接性改質基材薄 膜亦包含於本發明中。構成密接性改質層之樹脂組成、即 構成有機-無機複合體之樹脂組成，例如可使密接性改質基 -21 - 200835602 材薄膜之塗布表面、或硬塗布層/基材薄膜界面藉由紅外線 分光等予以分析、特定。 對聚酯樹脂、丙烯酸樹脂、胺基甲酸酯樹脂，對基材 薄膜及硬塗布層兩方而言具有密接性，且在硬塗布劑中所 含的有機溶劑可適當膨脹。上述樹脂可單獨使用，亦可2 種不同的樹脂（例如聚酯樹脂與胺基甲酸酯樹脂、聚酯樹脂 與丙烯酸樹脂、或胺基甲酸酯樹脂與丙烯酸樹脂）組合使 用。 ® 其中，形成基材之基材薄膜爲聚酯系基材薄膜時，就 與硬塗布層之密接性而言、及就上述膨脹性而言，構成複 合體之主要樹脂成分以含有共聚合聚酯及聚胺基甲酸酯較 佳。共聚合聚酯單獨與聚酯系基材薄膜之密接性雖充分， 惟與含有無機微粒子所得的硬塗布層之密接性不佳。而 且，由於爲較脆弱的樹脂，對切斷時之衝擊而言容易產生 凝聚破壞情形。 另外，單獨的聚胺基甲酸酯與含有無機微粒子之硬塗 ® 布層的密接性較爲優異。而且，與聚酯系基材薄膜之密接 性不佳。此外，使密接性改質基材薄膜捲取成輥狀時之耐 黏連性不佳。因此，使用具有由單獨的聚胺基甲酸酯所成 的密接性改質層之密接性改質基材薄膜所製造的硬塗布薄 膜或光學機能性薄膜，品質顯著降低。 爲避免上述問題時，必須於基材薄膜中含有多量的粒 子之複合體中含有粒徑大的粒子，或增加構成複合體之粒 子含量等。結果，由於薄膜之霧度値上昇，特別是作爲要 -22- 200835602 求透明性強的硬塗布膜或光學機能性薄膜之基材薄膜時’ 不爲企求。 藉由含有適當粒徑之無機粒子的複合體存在’在基材 薄膜與硬塗布層之境界範圍形成適當的凹凸’結果’可賦 予平滑性、捲取性、耐破裂性。因此’在基材薄膜中不一 定必須含有微粒子，可保持高透明性。 而且，使用此等聚酯樹脂作爲水系塗液時’係使用水 溶性或水分散性聚酯樹脂’惟爲進行該水溶性或水分散化 ^ 時，以使含磺酸鹼之化合物、或含羧酸鹼之化合物進行共 聚合較佳。其次，詳細說明有關複合體含有共聚合聚酯及 聚胺基甲酸酯爲主成分。 經由使含有共聚合聚酯及聚胺基甲酸酯之樹脂、含水 及醇之分散媒、以界面活性劑爲主要構成成分之水性塗布 液（1 )，連續塗布於行走的熱塑性樹脂薄膜之一面或兩面的 製程；使塗布層乾燥的乾燥製程；然後，至少朝一軸方向 0 進行延伸的延伸製程：以及使經延伸的薄膜進行熱固定處 理的熱固定處理製程，予以連續形成，製造設有密接性改 質層之密接性改質基材薄膜。此外，藉由使至少一種選自 環氧系交聯劑、蜜胺系交聯劑、噚唑啉系交聯劑之交聯劑 混合於塗布液（1)中予以熱處理，亦可形成適當的交聯構 造。 (塗布液（1)之調製製程） 於本發明中，使用塗布法時，塗布液（1)中所使用的材 料，爲樹脂及分散媒或溶劑。於本發明中，塗布液（1)以水 -23- 200835602 性較佳。此外，本發明除樹脂成分外，以倂用粒子及界面 活性劑較佳。另外，視其所需可使用抗靜電劑、紫外線吸 收劑、有機潤滑劑、抗菌劑、光氧化觸媒等之添加劑。 而且，於塗布液（1)中，爲促進樹脂之熱交聯反應時， 亦可添加觸媒，例如可使用無機物質、鹽類、有機物質、 鹼性物質、酸性物質及含金屬有機化合物等之各種化學物 質。另外，爲調節水溶液pH値時，亦可添加鹼性物質或酸 性物質。塗布液（1)係在分散媒或溶劑中、攪拌下、使樹脂 ^ 進行分散化或溶解，然後，除粒子、界面活性劑外，視其 所需倂用各種添加劑，且稀釋至企求的固形成分濃度爲止 予以調整。 另外，爲使塗布液（1)之樹脂成分及粒子均勻分散時， 以及爲除去粗大的粒子凝聚物及製程內塵埃等之異物時， 以使塗布液（1)進行精密過濾較佳。 爲使塗布液（1)進行精密過濾時之濾材的型式，只要是 具有上述性能即可，沒有特別的限制，例如單紗型、毛毯 型、篩網型。爲使塗布液（1)進行精密過濾時之濾材材質， 只要是具有上述性能且對塗布液（1)沒有不良影響者即 可，沒有特別的限制，例如不銹鋼、聚乙烯、聚丙烯、耐 龍等。 爲使塗布液（1)進行精密過濾時之濾材、以過濾粒子大 小（初期過濾效率：95%)爲25 μιη以下之濾材較佳，更佳者 過濾性能1 〇 μιη以下之濾材。最佳者係組合過濾性能不同 的過濾器使用的方法。使用過濾粒子尺寸大於2 5 μιη之濾 -24- 200835602 材時，容易使粗大凝聚物之除去效果變得不充分。因此， 無法以過濾除去的粗大凝聚物，藉由進行塗布乾燥後之一 軸配向或二軸配向製程的配向應力擴大，被視認爲1 〇〇μχη 以上之凝聚物，容易變成光學缺點的原因。 (a)樹脂 於本發明中，使用共聚合聚酯（PEs)與聚胺基甲酸酯 (P U)作爲構成複合體之樹脂時，就密接性而言較佳。此時， 塗布液（1)中之共聚合聚酯（PEs)與聚胺基甲酸酯（PU)之固 ® 形成分基準的質量比，以（PEs)/(PU) = 70/30〜30/70較佳， 以6 0/4 0〜40/60更佳。而且，複合體之樹脂可倂用上述共 聚合聚酯與聚胺基甲酸酯外之第3樹脂。此外，亦可倂用 交聯劑。 (共聚合聚酯） 例如，在複合體中使用共聚合聚酯時，以芳香族二羧 酸成分、與作爲二醇成分之乙二醇與支鏈狀二醇爲構成成 分較佳。上述支鏈狀二醇例如2，2 -二甲基-1，3 -丙二醇、2 -^ 甲基-2-乙基-1,3-丙二醇、2·甲基-2-丁基-1，3-丙二醇、2_ 甲基-2-丙基-1，3·丙二醇、2-甲基-2-異丙基-1，3-丙二醇、2-甲基-2-正己基-1，3·丙二醇、2,2-二乙基-1，3 -丙二醇、2 -乙 基-2·正丁基-1，3-丙二醇、2-乙基-2-正己基-1，3-丙二醇、 2，2-二-正丁基-1，3·丙二醇、2-正丁基-2·丙基-1，3-丙二醇、 及2,2 -二正己基-1，3_丙二醇等。 支鏈狀二醇成分之莫耳比，對全部二醇成分而言下限 値爲1 〇莫耳％較佳、更佳者爲20莫耳％。另外，上限値爲 -25 - 200835602 8 0莫耳％、更佳者爲7 0莫耳％、最佳者爲6 0莫耳％。 視其所需亦可倂用二乙二醇、丙二醇、丁二醇、己 1，4·環己烷二甲醇等。 芳香族二羧酸成分以對酞酸或異酞酸最佳。對 羧酸成分而言，亦可加入1 0莫耳％以下之範圍的其 族二羧酸、特別是二苯基羧酸及2,6-萘二羧酸等之 二羧酸予以共聚合。 構成複合體之共聚合聚酯，以使用水溶性或可 ^ 的樹脂較佳。因此，除上述之二殘酸成分外，爲使 有水分散性時以使用1〜1 0莫耳％範圍之5 -磺基異 鹼金屬鹽較佳，例如磺基對酞酸、5 -磺基異酞酸、 萘異酞酸-2，7-二羧酸及5-(4-磺基苯氧基）異酞酸或 屬鹽。 (聚胺基甲酸酯） 含有複合體所得的聚胺基甲酸酯、以水溶性或 散的樹脂較佳。例如含有嵌段型異氰酸酯基之樹脂 ^ 端異氰酸酯基以親水性基封端（以下簡稱爲嵌段）之 型水溶性胺基甲酸酯等。 異氰酸酯基之嵌段化劑，例如重亞硫酸鹽類及 基之苯酚類、醇類、內醯胺類、肟類、或活性亞甲 物類等。經嵌段化異氰酸酯基，係使胺基甲酸酯預 以親水化或水溶化。藉由製造薄膜時之乾燥製程或 處理製程，使上述之樹脂具有熱能量時，爲使嵌段 異氰酸酯基脫離時，使上述樹脂混入自己交聯的架 另外， 二醇或 全部二 他芳香 芳香族 水分散 聚酯具 酞酸的 4_磺基 其驗金 可水分 、使末 熱反應 含磺酸 基化合 聚物予 熱固定 化劑自 構之水 -26- 200835602 分散性共聚合聚酯予以固定化，且同時與上述之樹脂末端 基等進行反應。塗布液（1)調整中之樹脂，由於爲親水性， 故耐水性不佳，惟進行塗布、乾燥、熱固定、完成熱反應 時，由於胺基甲酸酯樹脂之親水基、即嵌段化劑被脫離， 故可製得耐水性良好的塗膜。 於上述嵌段化劑中，就容易在薄膜製造製程之熱處理 溫度、熱處理時間內自異氰酸酯基脫離而言，及就工業上 容易取得而言，以重亞硫酸鹽類最佳。上述聚胺基甲酸酯 ® 系樹脂中所使用的胺基甲酸酯預聚物，例如使（1)在分子內 至少具有2個活性氫原子之分子量爲200〜20,000的化合 物，（2)在分子內具有2個以上異氰酸酯基之有機聚異氰酸 酯，及視其所需（3 )在分子內至少具有2個活性氫原子之鏈 伸長劑進行反應所得的具有末端異氰酸酯基之化合物。 上述（1)在分子內至少具有2個活性氫原子之分子量爲 200〜20,000的化合物，一般已知者爲含有在末端或分子中 具有2個以上羥基、羧基、胺基或毓基者，更佳的化合物 主要爲直鏈狀或支鏈狀聚醚多醇及聚酯多醇等。而且，聚 醚多醇例如使環氧乙烷、環氧丙烷等之環氧烷類進行聚合 所得的化合物、或使氧化苯乙烯、氯雜環丙烷等進行聚合 所得的化合物、或此等之無規聚合、嵌段聚合或對多元醇 之加成聚合所得的化合物。 聚酯多醇可藉由使琥珀酸、己二酸、酞酸及馬來酸酐 等之多價飽和或不飽和羧酸、或該羧酸酐等、與乙二醇、 二乙二醇、1，4-丁二醇、新戊醇、1，6-己二醇及三羥甲基丙 -27- 200835602 烷等之多價飽和及不飽和醇類、較低的分子量之聚乙二醇 及聚丙二醇等之聚伸烷基醚二醇類、或此等醇類之混合物 進行縮合、製得。 另外，聚酯多醇例如可使用由內酯及羥基酸所得的聚 酯類、或在預先製造的聚酯類中使環氧乙烷或環氧丙烷等 加成的聚醚酯多醇類。 上述（2)之有機聚異氰酸酯，例如甲次苯基二異氰酸酯 之異構物類、4,4 -二苯基甲烷二異氰酸酯等之芳香族二異 ^ 氰酸酯類、苯二甲基二異氰酸酯等之芳香族脂肪族二異氰 酸酯類、異佛爾酮二異氰酸酯及4,4-二環己基甲烷二異氰 酸酯等之脂環式二異氰酸酯類、六亞甲基二異氰酸酯及 2，2,4-三甲基六亞甲基二異氰酸酯等之脂肪族二異氰酸酯 類、或使1種以上此等之化合物加成於三羥甲基丙烷等所 得的聚異氰酸酯類。 上述（3)在分子內至少具有2個活性氫原子之鏈伸長 馨 劑，例如乙二醇、二乙二醇、1，4 - 丁二醇、及1，6 -己二醇等 之二醇類、丙三醇、三羥甲基丙烷、及季戊四醇等之多元 醇類、乙二胺、六甲二胺、及吡畊等之二胺類、單乙醇胺 及二乙醇胺等之胺醇類、硫代二乙二醇等之硫代二乙二醇 類、或水。 使胺基甲酸酯預聚物合成時，通常使用上述（1)與上述 (2)、及視其所需上述（3)，藉由一段式或多段式異氰酸酯聚 加成方法，在150°C以下、較佳者爲70〜12〇°C之溫度下進 行反應5分鐘〜數小時。對上述（丨）及上述（3 )之活性氫原子 -28- 200835602 而言，上述（2)之異氰酸酯基之比例只要爲i以上可自由選 擇，惟所得的胺基甲酸酯聚合物中必須殘存有游離的異氰 酸酯基。此外，游離的異氰酸酯基之含量，對所得的胺基 甲酸酯預聚物之全部質量而言，只要是10質量％以下即 可，就考慮經嵌段化後之胺基甲酸酯聚合物之水溶液的安 定性時，以7質量％以下較佳。 所得的上述胺基甲酸酯預聚物，較佳者係使用重亞硫 酸鹽進行嵌段化。與重亞硫酸鹽水溶液混合，在約5分鐘 ® 〜1小時中均勻攪拌且進行反應。反應溫度以6 0 °c以下較 佳。然後，以水稀釋成適當濃度，形成熱反應型水溶性胺 基甲酸酯組成物。使用該組成物時，調製成適當的濃度及 黏度，通常在約8 0〜1 2 0 °C下進行加熱時，爲使嵌段劑之 重亞硫酸鹽進行解離，爲使活性異氰酸酯基再生時，藉由 在預聚物之分子內或分子間引起聚加成反應，生成聚胺基 甲酸酯聚合物，或具有引起加成於其他的官能基之性質。 上述說明的含有嵌段型異氰酸酯基之樹脂（B)的一 例’以第一工業製藥（股）製之商品名Elastron爲典型例。 Elastron係爲藉由重亞硫酸鈉使異氰酸酯基嵌段者，由於 在分子末端具有強力的親水性之胺基甲醯基磺酸酯基存 在，故爲水溶性。 (丙烯酸樹脂） 在複合體中使用丙烯酸樹脂時之水分散性或水溶性丙 烯酸樹脂，例如具有丙烯酸酯及/或甲基丙烯酸酯、或此等 與苯乙烯等之不飽和雙鍵、可與丙烯酸樹脂共聚合的脂肪 -29- 200835602 族化合物或芳香族化合物之共聚物。以作爲對硬塗布層而 言密接性優異的密接性改質層作爲親水性優異的丙烯酸-本乙燒共聚合樹脂’以藉由乳化聚合之水分散性丙儲酸-苯 乙烯無規共聚合樹脂最佳。 另外，本發明由於藉由使水分散性丙烯酸-苯乙烯共聚 合樹脂更堅固地黏合於基材薄膜上，對該共聚合樹脂以外 而言，倂用1 〇〜90質量％共聚合聚酯系樹脂時極爲有效。 較佳者使水分散性含磺酸金屬鹼之聚酯共聚合樹脂混合於 ® 水分散性丙烯酸-苯乙烯共聚合樹脂塗布液（1 )中，適合塗布 於基材薄膜上。 構成含有水分散性磺酸金屬鹼之聚酯共聚合樹脂的聚 酯之較佳例，如聚對酞酸乙二酯、聚伸乙基-2,6-萘酸酯、 聚-1，4-環己烷二亞甲基對酞酸酯。該聚酯視其所須爲30 莫耳％以下、較佳者爲1 5莫耳。/〇以下之上述酸成分或二醇 成分進行共聚合者，或與以該莫耳比由上述酸成分及二醇 成分所得的聚酯混合者。 W 另外，藉由在水分散性丙烯酸·苯乙烯共聚合樹脂中混 合有含水分散性磺酸金屬鹼之聚酯共聚合樹脂的塗布液（1) 中，添加水分散性或水溶性胺基甲酸酯樹脂（較佳者爲水分 散性、具有3個以上官能基之嵌段異氰酸酯樹脂），藉由水 分散性丙烯酸-苯乙烯共聚合樹脂與含水分散性磺酸金屬 鹼之聚酯共聚合樹脂的交聯反應，不會使與硬塗層之密接 性降低，且可提高塗膜表面之耐黏連性。 使用上述各樹脂時，藉由使含有上述成分之塗布液（1) -3 0 - 200835602 塗布於至少一面基材薄膜上予以乾燥進行。例如水分散性 丙嫌酸-苯乙烯共聚合樹脂、較佳者丙嫌酸酯及/或甲基丙 烯酸酯樹脂與苯乙烯之無規共聚合樹脂，及作爲水分散性 聚酯共聚合樹脂之含水分散性磺酸金屬鹼的聚酯共聚合樹 脂，以固形成分換算3 :2〜1 : 1之質量比例所配合的含樹脂 之塗布液（1 )時，固形成分濃度爲4〜1 5質量％，黏度爲4 〜6 0cps (藉由B型黏度計、在25cps下測定）。 本發明視其所須爲使丙烯酸樹脂進行交聯時，可使用 ® 異氰酸酯、環氧樹脂、噚唑啉、蜜胺等之交聯劑。 (b)溶劑 於本發明中，溶劑係廣泛包含不僅是可使樹脂溶解 者，且可使樹脂分散成粒子狀時所使用的分散媒。爲實施 本發明時，可使用有機溶劑、水性溶劑等之各種溶劑。 塗布液（1)所使用的溶劑，以使水、與乙醇、異丙醇、 苯甲醇等之醇類以佔全部塗布液（1 )之比例爲3 0〜5 0質量 %之範圍混合的混合液較佳。另外，未達1 〇質量％時，亦 ^ 可在可使醇類外之有機溶劑溶解的範圍內進行混合。惟於 塗布液（1)中，醇類與其他有機溶劑之合計量以未達5 0質 量％較佳。 有機溶劑之添加量對全部溶劑而言未達5 0質量％時， 具有於塗布乾燥時可提高乾燥性，且與水單獨相比時可提 高塗布層之外觀的優點。有機溶劑之添加量’對全部溶劑 而言爲5 0質量％以上時，溶劑之蒸發速度變快’容易引起 塗布中塗布液（1 )之濃度變化。結果，由於塗布液（1 )之黏度 -31- 200835602 上昇，塗布性降低，引起塗布膜之外觀不佳情形。另外， 因有機溶劑揮發，亦使火災等之危險性增高。 (d) 界面活性劑之倂用 使上述之水性塗布液（1)塗布於熱塑性樹脂薄膜（基材 薄膜）表面時，爲提高對該薄膜之濕潤性，且使塗布液（1) 均勻地塗布時，一般而言係使用界面活性劑。 界面活性劑只要是可得良好的塗布性，且在密接性改 質層之表面或內部可得適當的相分離構造者即可，沒有特 ® 別限定種類。於界面活性劑中，爲以微量添加得到良好的 塗布性時，以氟系界面活性劑較佳。添加量對塗布液（1)而 言以配合0.01〜0.18質量％較佳。 爲氟系界面活性劑時，對純水而言臨界膠束濃度之3 0 倍以下較佳。爲臨界膠束濃度之3 0倍以上時，由於塗布液 (1)中所含的粒子變得容易凝聚，故所得的積層薄膜之霧度 上昇，特別是作爲光學機能性薄膜之基材薄膜時不爲企 求。另外，因界面活性劑成分在密接性改質層表面上偏析， 對密接性有不良影響。此外，爲臨界膠束濃度以下時，無 法得到良好的塗布性。 (e) 粒子 使用硬塗布膜或該薄膜作爲要求高度透明性之光學機 能性薄膜時，基材薄膜之霧度以1 . 5 %以下較佳。上述之霧 度以1.0%以下更佳。霧度大於1.5%時，使薄膜使用於LCD 用透鏡薄膜或背光用基材薄膜等時，由於影像之鮮明度降 低，故不爲企求。 -32- 200835602 爲使基材薄膜之霧度爲1 · 5 %以下時，以基材薄膜中不 含粒子較佳。基材薄膜中不含粒子時，爲改善耐擦傷性或 ’捲取成輥狀時或捲出時之處理性（平滑性、行走性、黏連 性、捲取時伴隨空氣之除去空氣性等）時，使複合體分散於 基材薄膜與硬塗布層之境界範圍。 複合體中所含的無機粒子例如碳酸鈣、磷酸鈣、非晶 性二氧化矽、結晶性玻璃纖維、高嶺土、滑石、二氧化鈦、 氧化鋁、二氧化矽-氧化鋁複合氧化物粒子、硫酸鋇、氟化 • 鈣、氟化鋰、沸石、硫化鉬、雲母等之無機粒子、交聯聚 苯乙烯粒子、交聯丙烯酸系樹脂粒子、交聯甲基丙烯酸甲 酯系粒子、苯并鳥糞胺•甲醛縮合物粒子、蜜胺•甲醛縮 合物粒子、聚四氟乙烯粒子等之耐熱性高分子粒子。 於此等之粒子中，由於與樹脂成分之折射率較近，就 容易製得高透明之薄膜而言以二氧化矽粒子爲宜。 而且，粒子之形狀沒有特別的限制，就賦予易滑性而 言，以接近球狀之粒子較佳。 ® 複合體全量中佔有的粒子之含量，以2 〇質量％以下較 佳，以1 5質量％以下更佳，以1 〇質量％以下最佳。複合體 中之粒子含量大於20質量％時，透明性容易變得惡化且薄 膜之密接性亦容易變得不充分。另外，粒子之含量的下限 値，對複合體層而言以0 · 1質量％較佳，以1質量％更佳’ 以3質量％更佳。 此外，複合體中亦可含有2種以上平均粒徑不同的粒 子。而且，亦可含有同種粒子、平均粒徑不同者。粒子之 -33- 200835602 平均粒徑、及總含量皆在上述範圍內。塗布上述之塗布液 (1)時，爲除去塗布液（1)中粒子之粗大凝聚物時，以配置塗 布前塗布液經精密過濾處理的濾材較佳。 另外，粒子之平均粒徑以 2 0〜1 5 0 nm較佳，以 4 0〜 6 Onm更佳。平均粒徑未達20nm時，$易得到充分的耐黏 連性外，會有耐擦傷性惡化的傾向。此外，粒子之平均粒 徑大於1 5 Onm時，霧度上昇、且粒子容易脫落，故不爲企 求。 H 本發明中僅爲平均粒徑爲20〜150nm之粒子A時，無 法得到充分的耐黏連性及耐擦傷性。因此，爲更爲提高耐 黏連性及耐擦傷性時，以另外倂用少量的平均粒徑大的粒 子B較佳。平均粒徑大的粒子b之平均粒徑，以1 6 〇〜 lOOOnm較佳，以200〜80 Onm更佳。粒子B之平均粒徑未 達1 6 0 nm時，會使耐擦傷性、平滑性、捲取性惡化。此外， 粒子B之平均粒徑大於1 〇 〇 〇 nm時，會有霧度變得增高的 傾向。而且，粒子B以一次粒子經凝聚的凝聚體粒子較佳， 使用凝聚狀態之平均粒徑與一次粒子之平均粒徑比爲4倍 以上之粒子，就耐擦傷性而言較佳。 使用2種粒子時 > 例如粒子A (平均粒徑：2 0〜1 5 0 n m) 與粒子B(平均粒徑：160〜lOOOnm)之含量比（Pi/p2)爲5〜 3 0,且粒子B之含量對密接性改質層的固形成分而言爲〇」 〜1質量％。使2種特定粒徑之粒子含量控制於上述範圍， 以使密接性改質層表面之三次元中心面平均表面粗度予以 適當化，且使透明性、與處理性或耐黏連性倂存而言爲宜。 -34- 200835602 對密接性改質層而言，粒子B之含量大於1質量％時，會 有霧度顯著提高的傾向。 上述粒子之平均一次粒徑及平均粒徑之測定，藉由下 述方法進行。 使粒子以電子顯微鏡攝影，以1個最小粒子之大小爲 2〜5 mm之倍率，測定3 0 0〜5 0 0個粒子之最大粒徑，且其 平均値作爲平均一次粒徑或平均粒徑。而且，求取積層薄 膜之密接性改質層中粒子之平均粒徑時，使用透過型電子 顯微鏡（TEM)，以倍率12萬倍攝影積層薄膜之截面，求取 複合體之粒子的最大粒徑。由凝聚物所成的粒子B之平均 粒徑係使積層薄膜之密接性改質層的截面，使用光學顯微 鏡、以倍率200倍攝影3 00〜5 00個，測定其最大粒徑。 (f)交聯劑 如手機、PDA、手提型電腦之資訊終端機，在屋外使 用的機會增加。另外，衛星導航系統等所使用的觸控板， 在夏天高溫之車內所使用的材料亦增加。而且，即使在該 ^ 高溫、高濕之嚴苛環境下品質變化少之硬塗布膜、即耐濕 熱密接性優異的薄膜，在該用途中極爲企求。 該用途中使用本發明之硬塗布膜時，爲提高複合體之 耐濕熱性時，藉由在塗布液（1)中添加交聯劑，再進行熱處 理，以在樹脂中具有交聯構造較佳。交聯劑至少使用一種 選自環氧系交聯劑、蜜胺系交聯劑、噚唑啉系交聯劑、異 氰酸酯系交聯劑。交聯劑可考慮與塗布液（1)中使用的共聚 合聚酯樹脂之親和性、及耐濕熱密接性予以選擇。而且， -35- 200835602 由於過度的交聯時會損害適當的膨潤性，故不爲企求。 上述交聯劑對複合體之共聚合聚酯樹脂與交聯劑之合 計量（1〇〇質量％)而言，較佳者爲5〜40質量％，更佳者爲 10〜30質量％。交聯劑之含量大於40質量％時，複合體變 脆，且於形成由丙烯酸酯系樹脂所成的硬塗布層或擴散層 等之機能層後的加工製程中，無法得到充分的可忍耐高速 切斷之密接性。另外，交聯劑之含量未達5質量％時，不 易得到近年來所要求的耐久性。而且，於塗布液（1)中，爲 • 促進交聯時，視其所需亦可添加觸媒。 (爲形成有機-無機複合體時之塗布製程） 塗布上述水性塗布液（1)之製程，以在該薄膜之製程中 進行塗布的線上塗布法較佳。更佳者爲塗布於結晶配向完 成前之基材薄膜上。水性塗布液（1 )中之固形成分濃度以3 0 質量％以下較佳，更佳者爲i 〇質量％以下。固形成分濃度 之下限値以1質量％較佳，更佳者爲3質量％，最佳者爲5 質量％ °塗布有該水性塗布液（1)之薄膜，爲進行配向及熱 ® 固定處理時導入拉幅器中，然後進行加熱，藉由熱交聯反 應形成安定的被膜，形成密接性改質基材薄膜。 (塗布量） 未乾燥時之塗布量（以下簡稱爲濕式塗布量），以2g/m2 以上、未達1 0 g/m2較佳。濕式塗布量未達2 g/m2時，得 到設計之乾式塗布量（最終密接性改質層之塗布量）時，必 須使塗布液（1)之固形成分濃度提高。塗布液（i)之固形成分 濃度提高時，由於塗布液（1)之黏度變高，容易產生條狀塗 -36 - 200835602 布斑。另外，濕式塗布量爲1 〇 g/m2以上時，容易受到乾 燥爐內乾燥風的影響’谷易產生塗布斑。而且，爲防止因 塵埃附著之缺點時，以在清潔度爲等級5 0 0 0以下之清潔環 境下進行塗布塗布液（1 )較佳。 塗布量過多時，干涉斑容易變得顯著。塗布量過少時， 無法得到實用的密接性 另外，在上述乾燥爐中，以溫度維持於1 2 0 °c以上、 未達1 5 0 °C，且進行乾燥〇 · 1〜5秒較佳。乾燥時間以〇 . 5 ® 〜3秒更佳。乾燥時間未達〇 · 1秒時，塗膜之乾燥變得不充 分’通過自乾燥製程至橫延伸製程之間所配置的輥時，該 輥在乾燥不充分的塗布面上容易受到污染。此外，乾燥時 間大於5秒時’谷易引起薄g吴之結晶化情形，於橫延伸時 產生斷裂的頻率增加。 於上述之乾燥爐中，在1 2 0 °C以上、未達1 5 0 °C之溫度 下使塗膜乾燥後，直接使密接性改質基材薄膜冷卻至室溫 附近較佳。基材薄膜之表面溫度爲100 °C以上之高溫下自 φ 乾燥爐取出，在室溫附近之輥上使基材薄膜接觸時，因薄 膜收縮容易產生傷痕情形。 而且，於乾燥爐中爲防止來自乾燥風之塵埃混入，以 使用經HEPA過濾器清淨化的空氣較佳。此時所使用的 HEPA過濾器以使用具有可切斷95%以上之公稱過濾精度 0.5 μιη以上塵埃的性能之過濾器較佳。 另外，就提高塗布裝置之塗料器輥的精度（圓度與圓筒 度），且減低朝薄膜輥之長度方向的塗布厚斑而言有效。上 -37- 200835602 述之塗料器輥圓度，係以JIS B 062 1表示，以藉由使用記 錄式圓度測定器予以決定的最小範圍法之二個同心圓的各 半徑差所表示的指標。而且，輥之圓度的單位爲mm。此外， 塗料器輥之圓筒度係使該輥放置在定盤上的附有測微器之 塗佈輥朝軸線方向移動，在圓筒上面放置測定子之狀態 下，經過全長在各測定平面中實施測定，以此時讀取的最 大差之1/2所表示的指標。而且，圓筒度之單位爲mm。 於本發明中，藉由提高輥精度（圓度與圓筒度），可減 # 低長度方向之塗布層厚度的變動情形。具體而言，輥精度 (圓度與圓筒度）以未達5/1000mm較佳。 而且，於塗布塗布液（1)時，藉由使可逆塗布器之各輥 的表面加工性爲0.3 S以下，且塗佈輥及計數輥之精度（圓 度與圓筒度）未達5/1000、2/1000mm以上，可壓抑濕式塗 布量之變動，且壓抑制塗膜厚度之變動。較佳者可使用具 有塗佈輕及計數輥之精度（圓度與圓筒度）爲3/1000mm之 塗布輥。 ^ 另外，藉由使薄膜之張力爲4000〜10000N /原材料寬 度（原材料寬度爲1〜2m)，可保持工業規模上薄膜之平面 性，使塗布液（1)之轉印量變得均勻。而且，薄膜之張力視 薄膜之厚度而不同，藉由使較薄的薄膜施加較低的張力， 保持平面性。 薄膜之張力大於1〇〇 00N/原材料寬度時，會有薄膜變 形、或斷裂情形。此外，薄膜之張力未達4000N/原材料寬 度時，塗布時薄膜之平面性變得不充分，或薄膜產生蛇行 •38- 200835602 現象。結果，塗布液（1 )之轉印量在薄膜之長度方向變得不 均勻，藉由薄膜之濕式塗布量大爲變動，塗布量之厚度變 動亦變得更大。塗布層（密接性改質層）之折射率可以橢圓 形測定器予以測定。 (3)塗布層 本發明之較佳形態，係在與塗布層相反側之基材薄膜 表面上形成塗布層’且另外設置黏合劑層。積層構造爲黏 合劑層/塗布層/基材薄膜/硬塗布層之順序。 ^ 塗布層藉由在基材薄膜上塗布塗布液，再予以乾燥製 得。如上所述，爲製得該塗布層時，以塗布的塗布液定義 爲「塗布液（2 )」。於本發明中，爲形成塗布層時使用的塗 布液（2)，主要由水性聚酯樹脂、與水溶性乳酸鈦化合物、 水溶性三乙醇胺鈦絡合物化合物、與水系溶劑所成的水系 塗布液（2)。塗布液（2)中所含的乳酸鈦化合物與三乙醇胺鈦 絡合物化合物，可與水性聚酯樹脂進行交聯反應。藉由該 交聯反應生成更均勻的膜較佳。該交聯反應於使基材薄膜 ® 延伸時，藉由熱予以促進，結果，會有上述鈦化合物藉由 熱進行分解情形，所得的塗布層中不限於僅包含乳酸鈦化 合物與三乙醇胺鈦絡合物化合物。而且，本發明中不一定 必須使基材薄膜進行延伸。 塗布層之折射率，藉由使鈦化合物之組成變大，可較 單獨水系聚酯樹脂更高。使塗布層之折射率提高時，可藉 由含有金屬微粒子予以達成，惟藉由金屬微粒子會降低塗 布層之延伸性及硬塗布層與基材薄膜間之密接性。 -3 9 - 200835602 本發明使用的水性聚酯樹脂’亦可在其分子鏈中導入 羥基或羧基等之活性部位’特別是即使沒有導入時’由於 在高溫下酯鍵結部位引起可逆反應’故在任意部位引起交 聯反應，結果，製得緻密的膜。 @塗布層之水性聚酯樹脂與基材薄膜之密接性有關。 因此，塗布層中所含的水性聚酯樹脂之質量爲（A)、乳酸鈦 化合物之質量爲（B)、以及三乙醇胺鈦絡合物化合物之質量 爲（C)時，（A)/[(B) + (C)]之値以5 0/ 5 0以上較佳。該値爲 ® 5 0/5 0以上時，可提高光學用之必要透明性，且與在塗布層 上所形成的黏合層之密接性良好。另外，（A)/[(B) + (c)]之 値以8 0/20以下較佳，此時，藉由上述鈦化合物更爲充分 地進行交聯，提高折射率，因此，可提高高溫高濕下之密 接性（耐濕熱性），且在螢光燈下之彩虹狀色彩之抑制效果 變得充分。 另外，有關上述（B)及（C)，（B)/(C)之値以35/65〜65/35 較佳。在上述範圍內時，塗布液（2)之pH値約爲中性（pH ® 値爲6〜8)。結果，在該塗布層上積層異氰酸酯硬化型丙烯 酸樹脂系黏合劑時，可提高塗布層與黏合劑層之間的密接 在塗布層中含有乳酸鈦化合物及三乙醇胺鈦絡合物化 合物兩方之技術的意義，如下所述。 僅有1種上述鈦化合物時，會有塗布液（2)之p Η値爲 酸性、或鹼性偏大的傾向。在由鹼性偏大的塗布液（2)所得 的塗布層上積層異氰酸酯硬化型丙烯酸樹脂系黏合劑時， -40- 200835602 黏合層厚度方向容易產生硬化斑，結果，貼附於顯示裝置 前面時，貼附不佳時之再作業性降低。再作業性（rework性） 降低，係爲產生自顯示裝置前面剝離時黏合劑層之殘留量 變多的問題。而且，由酸性偏大之塗布液（2 )所得的塗布層 上積層異氰酸酯硬化型丙烯酸樹脂系黏合劑時，容易引起 黏合劑之硬化阻害情形，同樣地會降低上述再作業性。僅 有1種上述鈦化合物時，塗布液（2)之pH値爲酸性、或鹼 性。爲調整液體之pH値時，於酸性時可藉由添加胺、銨、 氫氧化鈉等之鹼性化合物，於鹼性時可藉由添加羧酸、鹽 酸、磺酸等之酸性化合物以調整pH値，惟此時塗布層與鈦 化合物與水性聚酯樹脂之相溶性降低，結果，塗膜變得不 均勻，與黏合層之彩虹狀色彩的抑制效果降低，且密接性 降低，故不適於本件之用途。 本說明書中，在經加熱的丁基溶纖劑中使聚酯樹脂進 行可塑化後，再加入溫水時該聚酯樹脂達成分散狀態時， 該聚酯樹脂形成水性聚醋.樹脂。爲使聚酯樹脂具有水性 時，在聚酯樹脂之分子鏈中導入羥基、羧基、磺酸基、磷 酸基、醚基等之親水性基，係爲重要、於上述之親水性基 中，就塗膜物性及密接性而言，以磺酸基較佳。 在聚酯中導入磺酸基時，磺酸化合物在聚酯之全部酸 成分中以1〜10莫耳％更佳。磺酸基量未達1莫耳％時，由 於無法使聚酯樹脂具有水性，與水溶性之鈦化合物的相溶 .性亦會降低，故無法製得均勻且透明的塗布層。另外，磺 酸基量大於1 0莫耳％時，高溫高濕下之密接性（耐濕熱性） -41 - 200835602 容易變得不佳。 此外，水性聚酯樹脂以玻璃轉移溫度爲4 (TC以上較 佳。因此，水性聚酯樹脂之酸成分以對酞酸、異酞酸、萘 二羧酸等之芳香族系爲主成分較佳。而且，二醇成分以乙 二醇、丙二醇、1，4-丁二醇、新戊醇等碳數較少的二醇、 或雙酚A之環氧乙烷加成物等之芳香族系較佳。另外，聚 酯樹脂之原料在不會降低薄膜之物性範圍內，亦可使用聯 苯等之剛直成分、或具有如溴、硫等折射率高的原子之二 ® 羧酸成分或二醇成分。水性聚酯樹脂之玻璃轉移溫度爲 4(TC以上時，在高溫高濕下之密接性（耐濕熱性）充分。此 外，爲提高聚酯樹脂之折射率時，亦可提高塗布層之折射 率。結果，可容易充分地抑制螢光燈下之彩虹狀色彩。 塗布層中亦含有乳酸鈦化合物與三乙醇胺鈦絡合物化 合物。較佳者係乳酸鈦化合物與三乙醇胺鈦絡合物化合物 皆爲水溶性。 水溶性乳酸鈦化合物之典型例，如羥基雙（乳酸）鈦（松 ®本製藥工業（股）製、TC310)。 另外，水溶性三乙醇胺鈦絡合物化合物之典型例，如 羥基雙（乳酸）鈦（松本製藥工業（股）製、TC400)。 在不會影響本發明效果的範圍內，於塗布層中亦可倂 用除上述主成分外之樹脂（例如丙烯酸樹脂、聚胺基甲酸酯 樹脂、聚酯樹脂、醇酸樹脂、聚乙烯醇等之乙烯樹脂）。而 且，在不會影響本發明效果之範圍內亦可倂用交聯劑，沒 有特別的限制。可使用的交聯劑例如尿素、蜜胺、苯幷鳥 -42- 200835602 糞胺等與甲醛之加成物、此等加成物與碳數爲1〜6之醇所 成的烷醚化合物等之胺基樹脂、多官能性環氧化合物、多 官能性異氰酸酯化合物、嵌段異氰酸酯化合物、多官能性 氮雜環丙烷化合物、噚唑啉化合物等。 於塗布層中以含有二氧化矽粒子較佳。藉由二氧化矽 之存在，可提高耐嵌段性或處理性。二氧化矽粒子可適當 使用市售的膠體二氧化矽粒子等。塗布層中所佔的二氧化 矽粒子之含量，以0.1〜20重量％較佳。 ® 使上述水系塗布液（2)塗布於聚酯薄膜表面時，爲提高 對薄膜之濕潤性、均勻地塗布塗布液（2)時，以適量添加習 知的陰離子系界面活性劑或非離子系界面活性劑較佳。 此外，於水系塗布液（2)中，爲使薄膜具有處理性、抗 靜電性、抗菌性等其他機能性時，可含有無機及/或耐熱性 高分子粒子、抗靜電劑、紫外線吸收劑、有機潤滑劑、抗 菌劑、光氧化觸媒等之添加劑。 塗布液（2)中使用的溶劑，可在對全部塗布液（2)而言以 未達5 0質量％之範圍內混合水以外之乙醇、異丙醇、苯甲 醇等之醇類。另外，未達1 〇質量％時，亦可在可溶解醇類 以外之有機溶劑的範圍內混合。惟塗布液（2 )中之醇類與其 他有機溶劑之合計量，以未達5 0質量％較佳。 於本發明中’最終所得的塗布層之塗布量，以〇 . 〇 2〜 0.5g/m2較佳。塗布層之塗布量爲〇.〇2 g/m2以上時，對黏 合性而言效果顯著，容易使螢光燈下彩虹狀色彩之抑制效 果變得充分。另外，塗布量爲0.5 g/m2以下時，螢光燈下 -43- 200835602 之彩虹狀色彩的抑制效果容易變得充分。塗布方法與硬塗 布膜側之有機-無機複合體形成用塗布時相同。 (4)硬塗層 構成硬塗層之硬化型樹脂，以電離放射線硬化型樹脂 較佳。電離放射線硬化型樹脂例如下述樹脂。 於電離放射線硬化型樹脂中，以具有丙烯酸系官能基 之樹脂較佳，更佳者爲聚酯丙烯酸酯、或胺基甲酸酯丙烯 酸酯。聚酯丙烯酸酯係由聚酯系多醇之低聚物的丙烯酸醋 ® 或甲基丙烯酸酯（以下丙烯酸酯及/或甲基丙烯酸酯記載爲 (甲基）丙烯酸酯）、或其混合物所構成。另外，胺基甲酸酯（甲 基）丙烯酸酯係使由多醇化合物與二異氰酸酯化合物所成 的低聚物予以（甲基）丙烯酸酯化者所構成。 構成（甲基）丙嫌酸酯之單體，例如（甲基）丙燒酸甲酯、 (甲基）丙嫌酸乙酯、（甲基）丙稀酸丁酯、2 -乙基己基（甲基） 丙烯酸酯、甲氧基乙基（甲基）丙烯酸酯、丁氧基乙基（甲基） 丙烯酸酯、苯基（甲基）丙烯酸酯。 此外’必須提高硬塗布層之硬度時，以倂用多官能單 體較佳。例如多官能單體如三羥甲基丙烷三（甲基）丙烯酸 酯、己一醇（甲基）丙烯酸酯、三丙二醇二（甲基）丙烯酸酯、 二乙二醇二（甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、 一季戊四醇六（甲基）丙烯酸酯、己二醇二（甲基）丙烯酸 酯、新戊醇二（甲基）丙烯酸酯。 聚酯系多醇之低聚物例如己二酸與二醇（乙二醇、聚乙 一醇、丙一醇、聚丙二醇、丁二醇、聚丁二醇等）或三醇（丙 -44- 200835602 三醇、三羥甲基丙烷等）、癸酸與二醇或三醇之縮合生成物 的聚己二酸酯多醇、或聚癸二酸酯多醇。而且，部分或全 部上述脂肪族二羧酸可以其他有機酸取代。例如，異酿酸、 對酞酸、或酞酸酐可使用作爲提高硬塗布層之硬度的成分。 在基材薄膜上形成硬塗布層時，爲提高水平性時，視 其所需可使用稀釋劑予以稀釋。稀釋劑例如苯、甲苯、二 甲苯等之芳香族煙、己院、庚院、辛院、壬院、癸院等之 脂肪族烴、甲基乙酮、二乙酮、二異丙酮等之酮等。稀釋 ® 劑之配合量在適當的黏度下予以適當選擇。 硬塗布層中所含的無機微粒子，例如非晶性二氧化 矽、結晶性玻璃塡充劑、二氧化矽、氧化鉻、二氧化鈦、 執化銘、寺之無機氧化物、一氧化砂-氧化銘複合氧化物粒 子、碳酸鎂、氫氧化鋁、硫酸鋇、碳酸鈣、磷酸錦、高嶺 土、滑石、硫酸鋇、氟化鈣、氟化鋰、沸石、硫化鉬、雲 母。 在硬塗布層表面上積層高折射率層/低折射率層、或高 ® 折射率層/中折射率層/低折射率層所構成的防止反射層 時，藉由使硬塗布層予以高折射率化，可自防止反射層省 略高折射率層。結果，可減低成本。爲提高硬塗布層之折 射率時，在硬塗布層中含有折射率高的無機微粒子極爲有 效。折射率尚的無機微粒子，例如氧化銷、氧化鈦。 硬塗布層中之無機微粒子的含量，爲20重量％以上、 80重量％以下，係爲重要。無機微粒子之含量未達20質量 %時，耐擦傷性不充分。此外，無機微粒子之含量大於8 〇 -45- 200835602 質量％時，會有透明性降低的傾向。而且，無機微粒子之 平均粒徑，就透明性而言以5〜1 0 0 n m較佳。而且，該平均 粒徑小的無機微粒子，容易凝聚、變得不安定。因此，爲 提局無機微粒子之分散安定性時，在無機微粒子之表面上 賦予光感應性基，且提高與硬化型樹脂之親和性較佳。 該含有無機微粒子之高折射率硬塗布劑，可取自市售 品。例如JSR股份有限公司製之紫外線硬化型樹脂 (Desolite); Z7400B、Z7410B)。而且，在丙烯酸系樹脂中 響 適量添加折射率咼的無機微粒子，且使折射率調整爲1 . 5 5 〜1·70，較佳者爲1·58〜1.65，更佳者爲1·60〜1.65之範 電離放射線硬化型樹脂，可藉由紫外線或電子線照射 予以硬化。照射紫外線時，係使甩超高壓水銀燈、高壓水 銀燈、低壓水銀燈、碳弧、金屬鹵化物燈等，在1 〇 〇〜 400nm(較佳者爲 200〜400nm)之波長範圍、以 1〇〇〜 3 0 0 0 m J / m 2之能量照射紫外線。另外，照射電子線時，使 ^ 用掃描型或簾幕型電子線加速器，具有加速電壓lOOOkeV 以下（較佳者爲1〇〇〜3 00keV)之能量，且照射l〇〇nm以下 波長範圍之電子線。 硬塗布層之厚度，在0·1〜30 μιη之範圍，視其用途予 以決定。更佳者爲1〜15μηι。硬塗布層之厚度在上述範圍 內時，硬塗布層之表面硬度高，不易受到擦傷。另外，硬 塗布層不易變脆，使硬塗布膜彎曲時硬塗布層不易產生破 裂情形。 -46 - 200835602 其次，本發明之光學機能性薄膜，係在與本發明之硬 塗布膜之硬塗布層相反面或其上，積層光學機能層，有下 述2種實施形態。 (a) 在與硬塗布層相反面上至少積層一層選自硬塗布 層、光擴散層、菱形狀透鏡層、電磁波吸收層、近紅線遮 斷層’透明導電層之光學機能層的光學機能性薄膜。 (b) 在硬塗布層上積層防止反射層或防污層之光學機 能性薄膜。 β (5)黏合劑層 爲形成亦可具有本發明之硬塗布膜的黏合劑層時之黏 合劑’就透明性、凝聚性、剝離特性之平衡性而言，例如 含有含作爲官能基之酸的丙烯酸系聚合物以及異氰酸酯系 交聯劑之丙烯酸系黏合劑。 丙烯酸系聚合物含有（甲基）丙烯酸烷酯及含酸之單體 作爲單體單位。（甲基）丙烯酸烷酯例如（甲基）丙烯酸甲酯、 0 (甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙烯酸丁 酯、（甲基）丙烯酸2-乙基己酯等，此等可單獨或組合使用。 含酸之單體例如（甲基）丙烯酸、衣康酸、馬來酸等之 含羧基單體、或此等之酸酐。藉由含酸之單體進行交聯等 賦予反應點。含酸之單體的比例，對100重量份（甲基）丙 烯酸烷酯而言爲1〜10重量份左右，較佳者爲2〜6重量份。 爲另外使丙烯酸系聚合物具有極性時，可使用（甲基） 丙烯酸羥基乙酯、（甲基）丙烯酸羥基丙酯等含羥基之單 體；Ν-羥甲基丙烯酸醯胺等含醯胺基單體；（甲基）丙烯腈 -47 - 200835602 等之含氰基單體；（甲基）丙烯酸環氧丙酯等之含環氧基單 體；醋酸乙烯酯等之乙烯酯類；苯乙烯、α-甲基苯乙烯等 之苯乙烯系單體等作爲共聚合單體。 丙烯酸系聚合物之聚合法，沒有特別的限制，可採用 溶液聚合、乳化聚合、懸浮聚合、UV聚合等之習知聚合法。 丙烯酸系聚合物之重量平均分子量，以約30萬〜250萬較 佳。 使用密接性較爲優異的異氰酸酯系交聯劑作爲交聯劑 ^ 時，爲提高凝聚性時視其所需亦可倂用環氧系交聯劑。 異氰酸酯系交聯劑係使用多官能異氰酸酯化合物，包 含在分子中具有2個以上異氰酸酯基之各種化合物。其典 型例如二苯基甲烷二異氰酸酯、甲次苯基二異氰酸酯、六 亞甲基二異氰酸酯、及此等之縮二脲、脲基甲酸酯、三聚 物、加成物等。異氰酸酯系交聯劑之配合份數、在不會影 響黏合物性之範圍內予以配合，一般而言，對1 0 0重量份 丙烯酸系聚合物而言約爲〇 · 2〜3重量份，較佳者爲〇 . 5〜2 重量份。 另外，倂用環氧系交聯劑時之環氧系交聯劑，係使用 多官能性環氧化合物’包含在分子中具有2個以上環氧基 之各種化合物。典型例如山梨糖醇四環氧丙醚、三羥甲基 丙烷環氧丙醚、四環氧丙基-1，3-雙胺基甲基環己烷、四環 氧丙基-m-苯二甲胺、三環氧丙基-Ρ-胺基苯酚等。環氧系 交聯劑之配合份數，可藉由對丙烯酸系聚合物之酸導入量 或環氧系交聯劑之構造而定，一般而言，對1 0 0重量份丙 -48 - 200835602 燦酸系聚合物而言約爲1〜8重量份，較佳者爲1〜 份。 於丙烯酸系黏合劑中亦可適當使用上述例示外 劑（聚胺化合物、蜜胺樹脂、尿素樹脂）、黏合賦予 塑劑、塡充劑、抗氧化劑、紫外線吸收劑、矽烷偶合 黏合劑層之形成方法，係使用習知的方法。具體 例如輥塗布、照相凹版塗布、可逆塗布、輥刷、噴霧 氣刀塗布法等。 ® 黏合劑層之厚度（乾燥厚度），沒有特別的限制 約爲5〜60μπι，較佳者爲5〜40μιη。而且，本發明 用表面保護薄膜之黏合劑層3，視其所需在至實用 之間可使分離器進行假黏合予以保護。 實施例 於下述中，使用實施例與比較例說明有關本發 布膜及使用它之光學機能性膜。本發明當然不受此 例所限制。而且，實施例中記載的基材薄膜、硬塗 ^ 光學機能性膜之物性或特性，使用下述方法予以評 (1)與硬塗布層之密接性 在貼附有兩面膠帶之厚度5 mm玻璃板上，以實 比較例所得的硬塗布膜或光學機能性膜之硬塗布 側，貼附於相反面上。然後，貫通硬塗布層，到達 樹脂A之1 00個格子狀切傷係使用隙間間隔2mm之 束予以形成。然後，將膠帶（Nichiban公司製）、405 寬度）貼附於格子狀切傷面上。於貼附時以橡皮擦 6重量 之交聯 劑、可 劑等。 :而言， 塗布、 ，通常 之光學 上提供 明硬塗 等實施 布膜、 估。 施例及 層爲表 熱塑性 切斷導 i ； 2 4mm 住殘留 -49- 200835602 於界面的空氣，予以完全密接後，使膠帶垂直剝離，藉由 目視由下述式求取密接性。而且’在1格內部分被剝離者 亦包含於剝離的個數中。 密接性（°/〇) = (ι —格子之剝離個數/100個）χΐ00 (2)黏合劑層之剝離性 以JIS-Z-0237法爲基準，在SUS板上貼合薄片藉由手 動進行180°剝離試驗，目視觀察SUS板上之狀態，以下 述基準予以判斷。 • ◎ : SUS板上自各種角度觀察沒有附著物及痕跡。 〇：SUS板上沒有附著物，惟某角度下可觀察到痕跡。 △ : SUS板上某角度下可觀察到附著物。 X : SUS板上可觀察到附著物。 (3-1)硬塗布層側之千涉斑（彩虹狀色彩）的評估 使硬塗布膜或光學機能性膜切成面積10cmx50cm，作 成試料薄膜。以與所得試料薄膜之易黏合層面的相反面爲 上面，貼合黑色光澤膠帶。以該試料薄膜之硬塗布面爲上 ^ 面，以3波長白色螢光燈（國際牌燈泡、F.L 15EX-N 15W) 爲光源，自斜上方以目視觀察反射光。以目視觀察的結果， 以下述基準區分。而且，觀察係以精通該評估的5名人員 進行，以最多欄作爲評估欄。假設2欄爲相同數目時採用 分爲3欄之中心値。例如，各採用◎與〇各爲2名、△爲 1名時爲〇；◎爲1名、〇與△爲2名時爲〇；◎與△各 爲2名、〇爲1名時爲Q。 ◎:即使自各種角度觀察時，皆沒有彩虹狀色彩現象。 -50- 200835602 〇：視某角度而定稍微有彩虹狀色彩現象。 △:稍有彩虹狀色彩現象。 X :有明顯的彩虹狀色彩現象。 (3-2)黏合劑層側之干涉斑（彩虹狀色彩）的評估 自評估對象之積層薄膜剝離黏合劑層之前，與上述 (3 -1)相同地先自硬塗布面側觀察干涉斑。然後，除去黏合 劑層後再觀察干涉斑。有關是否伴隨黏合劑層所觀察到的 干涉斑之變化，如下述予以評估。 視有無黏合劑層而定， ◎:即使自各種角度觀察時，皆沒有彩虹狀色彩現象增加。 〇：視某角度而定稍微有彩虹狀色彩現象增加。 △:稍有彩虹狀色彩現象增加。 X :有明顯的彩虹狀色彩現象增加。 (4) 硬塗布層之折射率測定 以JIS K 7 142爲基準，使用阿貝折射率計進行測定。 (5) 硬塗布層/基材薄膜之界面評估 使硬塗布膜之試料包埋於可視光硬化型樹脂（日本電 子Datum公司製、D- 8 00)中，在室溫下照射可視光予以硬 化。自所得的包埋區段使用裝設有鑽石刀之超薄切片裝置 製作厚度約70〜100 nm之超薄切片，在四氧化釕蒸氣中進 行染色30分鐘。使該經染色的超薄切片使用透過型電子顯 微鏡（曰本電子股份有限公司製、TEM2010)，觀察硬塗布層 之截面，予以照相。而且，照片之放大倍率適當設定於 1〇, 000〜100, 〇〇〇倍之範圍。此外，本發明之實施例1中， 200835602 放大倍率爲8 0,000倍（加速電壓200kV)。 (6 ) 塗布液之p Η値 使用pH値測定器ΕΧ-20(堀場製作所股份有限公司製） 進行測定。 (實施例1) (1)複合體用塗布液（1)之調合 爲製得複合體時之塗布液（1 )，以下述方法予以調製。 使二甲基對酞酸酯（95質量份）、二甲基異酞酸酯（95 • 質量份）、乙二醇（35質量份）、新戊醇（145質量份）、醋酸 鋅（0.1質量份）及三氧化銻（0.1重量份）加入反應容器中， 在180 °c下進行酯交換反應3小時。然後，添加5-鈉磺基 異酞酸（6.0質量份），在240 °C下進行酯交換反應1小時後， 在25CTC、減壓下（10〜0.2 mm H g)進行聚縮合反應2小時， 製得數平均分子量爲19,500、軟化點爲60 °C之共聚合聚酯。 使1.1質量份所得的共聚合聚酯（A)之15質量％水分散 液、〇 . 8質量份含有以重亞硫酸鈉予以嵌段化的異氰酸酯基 ^ 之自己交聯型聚胺基甲酸酯（B)的20質量％水溶液（第一工 業製藥製、Elastron H-3)、0.02質量份Elastron用觸媒（第 一工業製藥製、Cat 64)、56.3質量份水及41.6質量份異丙 醇予以混合。另外，添加〇 · 〇2質量份氟系非離子型界面活 性劑（大日本油墨化學工業製、Megafac F444)之10質量％ 水溶液、0 . 1 6質量份作爲粒子A之膠體二氧化矽（日產化學 工業製、Snowtex OL ;平均粒徑40nm)之20質量％水分散 液、0.03 7質量份作爲粒子B之乾式法二氧化矽（日本 -52- 200835602[Technical Field] The present invention relates to a hard coating film mainly used for a member for a display device, and an antireflection film using the film. More specifically, the present invention relates to a hard coat film which is excellent in adhesion between a high refractive index hard coat layer and a thermoplastic resin film in the case of suppressing external light entering, glare, rainbow color, and the like. [Prior Art] Generally, a hard coating film used for a member of a display device such as a liquid crystal display device (LCD) or a plasma display panel (PDP) allows the thermoplastic resin film and the hard coat (HC) layer to be easily bonded. Layers are layered. Further, in general, a display device uses an optical functional film system to bond a functionally different film through an adhesive layer. Moreover, in recent years, the demand for a low-priced market for large-sized flat panel display devices has greatly increased. Therefore, in the member for a display device, a composite film developed by laminating another optical functional layer on one hard coating film is developed. For example, a liquid crystal display device (LCD) such as a prismatic lens layer for preventing an external light from entering an antireflection layer (AR layer), a light collecting or diffusing light, a light diffusion layer for improving brightness, and the like are laminated on a hard coating film. A composite film of an optical functional layer. The thermoplastic resin film formed from the substrate of the hard coating film is made of polyethylene terephthalate (PET), polyamide, acrylic acid, polycarbonate (PC), and triethylenesulfonyl cellulose (TAC). A transparent film made of a cyclic polyolefin or the like. In the base film of the above, in particular, the biaxially oriented polyester film is widely used as a thermoplastic resin film of various optical functional films in terms of excellent transparency, dimensional stability, and chemical resistance. 200835602 In general, when a biaxially oriented thermoplastic film is used as a biaxially oriented polyester film or a biaxially oriented polyimide film, there is a lack of adhesion to various coatings, adhesives, inks, etc. due to the highly crystalline alignment of the film surface. Sexual shortcomings. Therefore, it has been proposed since the ancient times that the surface of the biaxially oriented thermoplastic resin film is provided with various methods to provide easy adhesion. In addition, the proposal is that a film having a non-polar base such as a polyolefin film is very lacking in adhesion to various coatings, adhesives, inks, etc., and is subjected to physical treatment or chemical treatment such as corona discharge treatment or flame treatment beforehand. A method of imparting easy adhesion to the surface of the film by various methods. For example, an easy-adhesive layer containing polyester, acrylic acid, polyurethane, and acrylic acid-grafted polyglycoside is applied to the surface of the thermoplastic resin film by a coating method to make the thermoplastic resin film easy to adhere. The method is generally known. In the coating method, after the corona discharge treatment is performed directly or after the corona discharge treatment is required on the thermoplastic resin film before the completion of the crystal alignment, the aqueous solution containing the dispersion in which the resin solution or the resin is dispersed as a dispersion medium is applied. After the liquid is applied onto the base film and dried, at least in one axial direction, and then heat-treated to complete the crystal alignment of the thermoplastic resin film (ie, the on-line coating method) or after the thermoplastic resin film is produced, The method of applying a water-based or solvent-based coating liquid to a film and then drying it (that is, an off-line coating method) is widely carried out industrially. In addition, in recent years, in order to prevent the adhesion to the light guide plate, improve the permeability, and reduce the warpage, the optical functional member is often provided with a hard coat layer on both surfaces, or with a lens layer or a light diffusion layer. A hard coating layer is laminated on the opposite side of the optical functional layer. 200835602 When such an optical plastic film substrate is used to form an optical functional film, an optical functional layer of several μm to about 5 μm, such as a hard coat layer, is formed on the substrate via an easy-adhesion layer of the film or the like. Hardened layer. Further, an optical functional film having different functions is bonded via an adhesive layer, and an optical functional film for a display device is used. However, when the thermoplastic resin film is a biaxially oriented polyester film, the refractive index (face direction) is 1. 62~1. In the case of 65, for example, the refractive index of the hard coat layer formed of an acrylic resin or the like is usually 1 degree. 5 3 is the center of 1 . 5 0~ 1 · 5 6. Further, in general, the easy-adhesion layer located in the middle is formed by using a polyurethane resin, a polyester resin, or the like as a main component. Further, the refractive index of the resin composition layer is usually 1. 49 〜1 · 5 4 〇 Therefore, by the refractive index difference between the biaxially oriented polyester film and the easy-adhesion layer, light reflection is caused at the interface, and interference spots are generated by interference with the reflected light of the hard coated surface ( Rainbow color). Therefore, when the antireflection layer (AR layer) or the antifouling layer is formed on the hard coat film, the visibility of the article such as the attached image display device may be deteriorated or the feeling of high quality may be impaired. Especially under the 3-wavelength fluorescent lamp, the interference speckle is remarkable due to the high proportion of the spectral components of the bright line. In recent years, the popularity of 3-wavelength fluorescent lamps has rapidly progressed in general households, so the problem of interference spots has become extremely important. Therefore, the use of the interference plaque problem is severely limited in the use of a functional plastic film using a biaxially oriented polyester film as a substrate. Otherwise, it is necessary to use a functional film with thousands of problems. In fact, in the field of large flat-panel televisions using a two-axis alignment of 200835602 polyester film as a substrate, almost all of the anti-reflection films currently mounted have interference spots. Further, when an antireflection layer composed of a high refractive index layer/low refractive index layer or a high refractive index layer/medium refractive index layer/low refractive index layer is laminated on the surface of the hard coat layer, the hard coat layer is given The refractive index is increased, and the high refractive index layer can be omitted from the antireflection layer. As a result, when the antireflection film is manufactured, the cost can be greatly reduced. This tendency has been increasingly promoted due to the strong demand for cost reduction in recent years. The inventors of the present invention disclosed in Patent Document 1 that the thickness of the film is not uniform, and the thickness of the coating having a solid component mainly composed of a copolymerized polyester and a polyurethane is 0. After 1 g/m 2 of the film of the easy-adhesive layer, the partial thickness of the film is reduced by calendering on the film to reduce interference spots caused by the uneven thickness of the substrate film. Laminated polyester film. However, the laminated refractive index is 1. When the hard coat layer of 58 or more and 1 · 6 5 or less has excellent adhesion, the above-mentioned interference spot is remarkable. The present inventors propose in Patent Document 2 that a copolymerized polyester having a different phase separation structure and a polyurethane are provided on a base film formed by biaxially-oriented polyethylene terephthalate, and The resin composition layer of the inorganic particles having an appropriate particle diameter maintains the transparency of the property which is extremely important as the optical base film, and the laminated polyester film which is excellent in adhesion to the optical functional layer, and the resin composition layer is proposed. An example of a thickness of 2 0 to 1 2 0 nm. Only the refractive index of the laminate is 1. 58 or more, 1. When the hard coat layer of 65 or less has excellent adhesion, the above-mentioned interference spot is remarkable. In addition, Patent Document 3 discloses a laminated polyester film having a coating layer containing two or more organic compounds having a metal element on a polyester film extending at least in one axial direction, for example, a triethanolamine titanium complex. Titanium lactate is used as an organic compound having two metal elements. Further, the inventors disclosed in Patent Document 4 that an aqueous polyester resin, a water-soluble titanium chelating compound, a water-soluble titanium ruthenate compound, a water-soluble pin chelating compound are provided on one side of at least a biaxially stretched polyester film. Or a biaxially stretched polyester thin film of a coating layer formed of a water-soluble zirconium silicate compound. When the refractive index of the hard coat layer is made equal to that of the biaxially oriented polyester film, the interference layer is reduced, and the hard coat layer is not provided under the resin composition layer between the biaxially oriented polyester film and the hard coat layer. The two-axis alignment polyester film is optically integrated, and is substantially free of reflected light between the two layers, which is highly desirable. However, when the hard coating layer is directly provided on the biaxially oriented polyester film as described above, practical adhesiveness cannot be obtained. In other words, in the substrate film for optics having a high refractive index type hard coat film laminated, it is not inferior to the interference spots and has sufficient adhesion. In addition, in the optical base film in which the hard coat layer is laminated and the adhesive layer is laminated on the reverse side, the interference spots on the hard coat layer side and the adhesive layer side are not conspicuous, and the adhesiveness is sufficient.尙 does not exist. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2001-71439 [Patent Document 2] International Publication No. 2006/57382 [Patent Document 3] Japanese Laid-Open Patent Publication No. 2006-76292 [Patent Document 4] Patent No. 3 6 3 2044 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The object of the present invention is to provide a hard coating film having excellent interlayer properties on the reverse side, and in other words, the coating film of the present invention is formed by directly laminating a layer on the surface of a thermal film. The range of the boundary is classified as an organic-inorganic composite acid ester resin, and the refractive index of the acrylic layer is 1. 5 8~ The second invention is a structure having a copolymerized polyester-containing inorganic particle. According to a third aspect of the invention, the acid ester resin on the surface of the upper substrate film and the fourth invention of the acrylic tree are coated on the upper side and the base film surface polyester resin and the titanium lactate coating liquid, and the fifth invention is When a hard coating layer adhesive layer having a high refractive index is laminated, the formation of thousands of spots is not significant and the sealing is achieved by the following solution. The first invention of the hard coating film is a base film formed of a hard plastic resin, a hard coat layer on the base material, and a hard coat film on the base film and the hard-coated organic-inorganic composite. The invention has at least one structure selected from the group consisting of a polyester resin and an aminomethyl ester embedded with inorganic particles, and is hard coated. 65. a hard coating film in which a hard coating film is embedded in a mixed resin of an organic-inorganic composite and a polyurethane, wherein the hard coating layer has at least one polyester resin and an amine group on the contrary A coating layer of grease. The hard coat film has a coating layer on the surface of the hard coat layer, which is formed by drying a compound containing a water compound and a triethanolamine titanium complex. . A hard coating film in which the mass of the aqueous polyester resin contained in the coating liquid of -10 200835602 is (A), the mass of the titanium lactate compound is (B), and the compound of the triethanolamine titanium complex When the mass is (C), (A)/[(B) + (C)] is 5 0/5 0 to 80/20, and (B)/(C) is 3 5 /6 5 to 6 5 / 3 5. According to a sixth aspect of the invention, in the hard coat layer, the hard coat layer has a structure in which inorganic fine particles are dispersed in the curable resin, and the content of the inorganic fine particles in the hard coat layer is from 20 to 80% by mass. According to a seventh aspect of the invention, in the hard coating film described above, the particles are not present in the base film, and the content of the particles in the base film is 50 ppm or less. The eighth invention is the hard coat film described above, wherein the inorganic particles of the organic-inorganic composite are cerium oxide particles. The ninth invention is an optical functional film characterized in that an antireflection layer or an antifouling layer is laminated on the hard coat layer of the hard coat film. Advantageous Effects of Invention The present invention is a conventional technique in which an intermediate layer is provided between a base film and a hard coat layer, and the base film and the hard coat layer are substantially directly laminated, and the predetermined structure is made in the field of the boundary. The composite is dispersed, ^ can make practical adhesion and reduce interference. [Embodiment] In order to carry out the best mode of the invention, in the present invention, the definition of the adhesion and the interference spot described in the subject matter will be first described. (Evaluation of Adhesiveness) The adhesion between the hard coat layer and the base film was evaluated by attaching a tape to the hard coat layer and peeling it off by a checkerboard peel test. -11- 200835602 The specific evaluation sequence is detailed in the paragraphs of the examples. In the checkerboard peeling test of the present invention, the adhesiveness shown by the following formula is preferably 80% or more, more preferably 85% or more, and most preferably 90% or more. Adhesiveness (%) = (1 - number of peeling of the lattice / 100) χ 100 When the adhesive layer is present, the adhesiveness of the adhesive layer is peeled off by JIS-Z-023 7 using a SUS plate. The test is evaluated. The specific evaluation method is detailed in the paragraphs of the examples. (Evaluation of interference spots) ^ The interference spot on the side of the hard coating film in the present invention means that a black glossy tape is attached to the adhesive layer of the laminated film to make the hard coating film surface upper, and the two-wavelength white fluorescent lamp For the light source, when the reflected light is visually observed from above the oblique side, the interference spot (colored color) can be visually observed, and the specific evaluation method is detailed in the paragraph of the embodiment. The interference spot on the side of the adhesive layer refers to a black glossy tape attached to the hard coated film surface of the laminated film, with the adhesive layer as the upper surface and a three-wavelength white fluorescent lamp as the light source, visually observed from above the oblique side. When the light is reflected, the interference spot (rainbow color) can be visually observed, and the specific evaluation method is detailed in the paragraph of the embodiment. The hard coat film of the present invention is characterized in that a hard coat layer is directly formed on the surface of the base film. In other words, when a photograph was taken at a magnification of 50,000 times to 200,000 times using a transmission electron microscope (ΤΕΜ), no resin composition layer was observed at the interface between the base film and the hard coat layer. Then, the following organic-inorganic composite dispersion was observed in the boundary between the substrate film and the hard coat layer. The above-mentioned boundary range may also refer to the interface between the substrate film and the hard coat layer -12-200835602. With this configuration, it is possible to achieve sufficient adhesion and reduce the effect of interference spots, which is a new insight of the present invention. (1) Substrate film First, the method for producing a base film of the present invention will be briefly described by taking polyethylene terephthalate (hereinafter abbreviated as PET) as a representative example, and of course, it is not limited by this representative example. The PET pellets which do not substantially contain the particles for the purpose of imparting the slipperiness are sufficiently vacuum-dried, and then supplied to an extruder, melted and extruded into a sheet shape at 270 to 29.5 ° C, and subjected to cooling hardening. The film is formed into an unaligned PET sheet. At this time, the molten resin is melted and held at 270 to 29.5 °C, and high-precision filtration treatment is performed for removing the foreign matter contained in the molten resin at any time during the process. The resulting unaligned sheet was stretched in the longitudinal direction at a roll of 80 to 12 (heated under TC). 5~5. 0 times, a one-axis alignment PET film was obtained. Then, the coating liquid described below was applied to one side or both sides of the one-axis alignment PET film. When the coating liquid is applied, for example, there are a reversible roll coating method, a gravure coating method, a contact coating method, a roll brush method, a spray coating method, an air knife coating method, a coil bar coating method, a tubular blade method, and an impregnation/coating method. And curtains, coating methods, etc., these methods can be carried out individually or in combination. Then, both ends of the film were fixed by clips and introduced at 80 to 18 Torr. (: The hot air zone under heating, extending to the width direction after drying. 5~5. 〇 times. Subsequently, the heat treatment zone was introduced at 2 2 0 to 2 0 ° C, and heat treatment was carried out for 1 to 2 sec seconds to complete the crystal alignment. In the heat treatment process, a relaxation treatment of 1 to 12% may be performed in the width direction or the length direction as needed. 200835602 The base film used in the present invention is such that the thermoplastic resin or the unaligned sheet which is melted and extruded is extended in one direction in the longitudinal direction as needed, or two times in two directions in the two-axis direction, and heat-fixing is carried out. It is preferred to treat the two-axis alignment hot film. Further, the base film is subjected to corona discharge treatment, glow discharge treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, and ozone activation treatment on the film without impairing the object of the present invention. The thickness of the base film used in the present invention can be determined within a range of from 30 to 10 depending on the intended use. The upper limit of the base is preferably 2 50 μmη, more preferably 200 μπι. The lower limit of the thickness is preferably 50 μm, more preferably 75 μm. When the thickness is 50 μm, the rigidity or mechanical strength tends to be insufficient. When the temperature exceeds 300 μm, the frequency of optical defects increases due to the foreign matter present in the film. Further, the slit property of cutting the film is also deteriorated, and the manufacturing cost is improved. Further, since the long-sized film is easily made to be wound into a roll shape. The thermoplastic resin is polyethylene terephthalate, polyparaphthalic acid, butylene phthalate, polyethylene-2,6-naphthoate, syndiotactic polyphenylene polymer, polycarbonate, polyacrylate, etc. It is appropriate. A resin such as a polyester or a polyfunctional amine having a polar functional group is preferred in terms of adhesion to a dense one. Among them, polyethylene terephthalate, polyethylene-2,6 · Cai melt extrusion, extending to the width of the square axis or within the thin range of the plastic resin, the treatment, the treatment of the flame, etc. 3 0 0 μ m In addition to the thickness of the film of the range material, the film thickness of the film is not up to the outside, the thickness of the film is increased, and the rigidity is increased at a predetermined width. The propylene glycol, the polyethylene, the raw spine, and the sizing layer: the acid ester, Poly-p--14- 200835602 Copolymer of butyl phthalate, propylene terephthalate or a component of such a resin as a main component, in other words, formed by polyethylene terephthalate A biaxial alignment film is preferred. For example, in the case of forming a resin for a base film, the ratio of the copolymerized component is preferably less than 20 mol% when a polymethylene n-based copolymer having polyethylene terephthalate as a basic structure is used. When it is 20% by mole or more, the film strength, transparency, and heat resistance are not good. a dicarboxylic acid component which can be used as a copolymerization component, for example, an aliphatic dicarboxylic acid such as adipic acid or sebacic acid, an isonic acid, a citric acid, and an aromatic two of 2,6-naphthalene dicarboxylic acid A polyfunctional carboxylic acid such as a carboxylic acid, trimellitic acid or pyromellitic acid. Further, ethylene glycol which can be used as a copolymerization component, for example, a fatty acid diol such as diethylene glycol, 1,4-butanediol, propylene glycol or neopentyl alcohol; or an aromatic diol such as ρ-xylitol; An aliphatic diol such as 1,4-cyclohexanedimethanol; or a polyethylene glycol having an average molecular weight of from 150 to 20,000. Further, in the above thermoplastic resin, various additives may be contained in addition to the catalyst insofar as the effects of the present invention are not impaired. Additives such as inorganic particles, heat resistant polymer particles, alkali metal compounds, alkaline earth metal compounds, phosphorus compounds, antistatic agents, ultraviolet absorbers, light stabilizers, flame retardants, heat stabilizers, antioxidants, gelation inhibitors , surfactants, etc. The above-mentioned particles are obtained when the base film is produced, when it is wound into a roll shape, or when it is rolled out (smoothness, running property, adhesiveness, air removal property accompanying air during winding, etc.) It is used when the surface of the film has appropriate surface irregularities. Inorganic particles such as calcium carbonate, calcium phosphate, amorphous cerium oxide, knot -15-200835602 crystalline glass fiber, kaolin, talc, titanium dioxide, aluminum oxide, cerium oxide-alumina composite oxide particles, barium sulfate, fluorine Calcium, lithium fluoride, zeolite, molybdenum sulfide, mica, and the like. Further, the heat resistant polymer particles are, for example, crosslinked polystyrene particles, crosslinked acrylic resin particles, crosslinked methyl methacrylate particles, benzoguanamine, formaldehyde condensate particles, melamine formaldehyde condensate particles , polytetrafluoroethylene particles, and the like. When a polyester film is used as the base film, the refractive index of the ruthenium dioxide particles and the polyester resin is relatively close to the above particles, and it is easy to obtain high transparency. Therefore, it is most suitable for applications requiring strong transparency. In addition, the use of concealability is required, and a white pigment such as titanium oxide is preferred. Further, the particles contained in the substrate film may be used in one or more kinds. The type, average particle diameter, and addition amount of the above particles are in balance with transparency and workability, and the g ' average particle diameter is 0. 〇 1~2 μ m, the particle content in the film is 0. 01~5. Within the range of 0% by mass, the use of the film is determined. Further, when the adhesion-modifying base film used in the present invention is used for applications requiring high transparency, it is preferred that the substrate film contains substantially no particles which cause a decrease in transparency. The above-mentioned "particles which are not contained in the permeation" are, for example, inorganic particles, when the amount of the inorganic element is determined by sand X-ray analysis, it is 5 〇 ppm or less, preferably 10 ppm or less, and more preferably the detection threshold 値The following content. In this case, even if the particles are not actively added to the base film, the contamination is caused by foreign matter, or the dirt adhering to the line or the device during the production process of the raw material resin or the film is peeled off and mixed into the film. Further, the layer structure of the base film used in the present invention may be a single layer or a laminated structure which imparts a function which cannot be obtained by a single layer. In the case of a laminated structure, the co-extension method is preferred. When a polyester is used as a raw material of a base film, a method for producing a base film is described in detail below. The characteristic viscosity of the polyester pellets used as the raw material of the film is 0. 45 ~ 0. A range of 70 dl/g is preferred. Intrinsic viscosity is less than 0. At 45 dl/g, cracking is likely to occur in the production of a film. In addition, the intrinsic viscosity is greater than ® 〇. At 70 dl/g, the filtration pressure is greatly increased, and it is difficult to perform high-precision filtration treatment, which tends to cause a decrease in productivity. Further, the intrinsic viscosity of the polyester is such that the polyester is dissolved in a mixed solvent of phenol (6 parts by mass) and 1,1,2,2-tetrachloroethane (4 parts by mass) at 30 ° C. The measurement was carried out. Further, in the hard coat film of the present invention or the optical functional film using the film, it is preferred to remove foreign matter contained in the raw material polyester which causes optical defects. In order to remove foreign matter in the polyester, the molten resin is kept at a temperature of 27 0 to 29 ° C for a high-precision filtration treatment at the time of melt extrusion. The filter material used in the high-precision filtration treatment of the molten resin is not particularly limited, and in the case of a filter material of a stainless steel sintered body, agglomerates containing Si, Ti, Sb, Ge, and Cu as a main component and removal of a high-melting organic substance are used. Excellent performance is preferred. The filter particle size (initial filtration efficiency: 95%) of the filter material used in the high-precision filtration treatment of the molten resin is preferably 15 μm or less. When the filter particle size of the filter material is larger than 15 μm, the removal effect of foreign matter of 20 μm or more is insufficient. By using a filter material having a filter particle size (initial filtration efficiency of 95%) of 15 μm or less to perform high-precision filtration treatment of the molten resin, although -17-200835602 has a reduced productivity, a film having no optical disadvantage is produced. When it is extremely important. In the extrusion process of the molten resin, even if the fine foreign matter passing through the filter material is crystallized around the foreign matter in the cooling process of the flaky melt, the alignment unevenness is caused in the alignment process, and the lens state which causes the minute thickness difference is generated. At the office. Here, the case where the light is refracted or scattered under the lens is larger than the actual foreign matter when viewed by the naked eye. The difference in the small thickness can be observed as the difference between the height of the convex portion and the depth of the concave portion. When the height of the convex portion is 1 μηη ® or more and the depth of the concave portion of the adjacent convex portion is 〇·5 μm or more, the lens effect is even if the size is 2 0 . The shape of the μιη can be visually recognized as a size of 50 μm or more, and an optical defect of a size of 100 μm or more can be recognized. In order to obtain a film which is transparent, it is preferable that the base film does not contain particles, the particle content is less, and the transparency is higher, and the optical defects of minute irregularities tend to be more distinct. Further, since a thin film having a relatively thin film surface is not easily quenched, there is a tendency to crystallize, and it is necessary to rapidly cool the entire film when the unaligned film is produced. The method of cooling the unaligned sheet is such that the molten resin is extruded into a sheet shape from the slit portion of the mold on the rotary cooling barrel, and the sheet-like melt is adhered to the rotary cooling barrel to be cooled to form a sheet. should. The method of cooling the air surface of the unaligned sheet (opposite to the contact surface of the cooling tub) is extremely effective in cooling by blowing a high-speed air stream. (2) Organic-inorganic composite (hereinafter simply referred to as "complex") The composite used in the present invention has a resin composition containing at least one resin selected from the group consisting of a polyester resin, a urethane resin, and an acrylic resin. -18- 200835602 The structure of inorganic particles is embedded in it. In the above-mentioned composite, for example, an ultrathin section of the hard coat film of the invention is observed by a transmission electron microscope (TEM) at a magnification of 50,000 to 200,000 times, and it is confirmed that it exists in the base film and the hard coat layer. The realm of the realm. The above composite has a structure in which inorganic particles are embedded in at least one resin composition selected from the group consisting of a polyester resin, a urethane resin, and an acrylic resin. TEM observation of the image, depending on the electron density can be observed contrast contrast. The inorganic particles have a high electron density and a high density, and the resin composition selected from the group consisting of a polyester resin, an amine resin, and an acrylic resin has a low electron density. Therefore, the above composite system is a structure in which a resin composition which is equivalent to the base film or is lighter than the base film is surrounded by the rich inorganic particles. In the present invention, a separate composite is preferably formed by containing one inorganic particle or one inorganic particle agglomerate. When at least one resin composition selected from the group consisting of a polyester resin, a urethane resin, and an acrylic resin contained in the organic-inorganic composite is observed by a transmission electron microscope (TEM), ruthenium dyeing is performed. Dyeing treatment such as hungry dyeing, phosphotungstic acid dyeing, etc. is preferred. In particular, the enamel dyeing can be suitably dyed with a polyester resin or a urethane resin. The respective constitutions of the organic-inorganic composite can be judged by the dyed image of the above dyeing. Further, each composition of the organic-inorganic composite can be judged by local elemental analysis (SEM/EDX or the like). The above composite exists in the boundary between the substrate film and the hard coat layer. The boundary range refers to the vicinity of the interface between the substrate film and the hard coat layer. When the hard coat film of the present invention is observed by TE Μ, the above composite can be observed at the boundary between the base film and the hard coat layer. Each of the above composites is preferably present on both the base film of the base -19-200835602 and the hard coat layer. The above composite is dispersed in the boundary between the base film and the hard coat layer. The complex dispersion means that when the hard coat film of the present invention is observed by TEM, a plurality of composites are not all joined together and are dispersed. In other words, the composite in which the inorganic particles are surrounded by the resin composition is independent of each other, and a plurality of inorganic particles are not continuously connected by the resin composition between the base film and the hard coat layer. The continuously connected structure means a state in which the substrate film and the hard coat layer have an organic substance as a resin composition at the boundary. When the present invention is observed by a transmission electron microscope (TEM) at a magnification of 50,000 to 20,000 times, at least one selected from the group consisting of organic-inorganic is not observed in the boundary between the base film and the hard coating layer of the hard coating film. It is important to have a resin composition of a polyester resin, a urethane resin, or an acrylic resin which is a constituent component of the composite. Here, the presence of the resin composition was not observed, and when the observation was carried out by a transmission electron microscope (TEM) at a magnification of 50,000 times to 200,000 times, the thickness of the resin layer in the boundary range was below the critical value of observation, and was not set. The base film of the resin composition is in the same state. Specifically, the boundary between the hard coat layer and the substrate layer is 10 nm or less, preferably 5 nm or less. This is due to the precipitation of the dye at the boundary between the hard coat layer and the substrate layer by the operation during dyeing or the like. The distance between the adjacent two adjacent bodies in the boundary is not particularly limited, and it is preferably a distance of 100 to 1 000 nm. A preferred method for producing the composite is as follows. For example, the coating liquid containing the resin and the inorganic particles constituting the composite is coated and dried on the base film, and then hardened by forming a hard coating layer. A method of coating and drying a hard coating agent of -20-200835602. According to this production method, the resin constituting the composite is at least partially expanded by a hard coating agent for forming a hard coat layer, and then integrated with the resin of the hard coat layer. As a result, in the range where the above inorganic particles were not present, the coating layer was integrated with the resin of the hard coat layer to the extent that the coating layer was not observed by τ Ε 。. In other words, when observed with a transmission electron microscope (ΤΕΜ) having a magnification of 50,000 to 200,000 times, the thickness of the resin composition in the boundary range is below the observation threshold. Further, in the present specification, the coating liquid for the preparation of the organic-inorganic composite is defined as "coating liquid (1)". Further, the coating liquid applied when the coating layer is formed on the surface of the base film opposite to the hard coating layer is defined as "coating liquid (2)", and is divided into two coating liquids. In addition, a resin constituting the composite remains around the inorganic particles, and as a result, a structure in which the composite is embedded between the base film and the hard coat layer is formed. The prior art changes the overall idea of the "layer" which is provided when the base film and the hard coat layer are bonded, and the base film and the hard coat layer are bonded by dispersing the composite. Thereby, sufficient adhesion can be maintained and the interference spots can be remarkably reduced. Further, in the following description, the coating layer containing the resin and the inorganic particles which are present on the base film before the hard coat layer is represented by an adhesion-modified layer, and is provided on the base film. The film having the adhesion modifying layer is represented by a film of the adhesion-modified substrate. As described above, by providing the hard coat layer, the adhesion-modifying layer cannot be confirmed to have a predetermined multiple of the adhesion-modified substrate film included in the present invention. The resin composition constituting the adhesion-modifying layer, that is, the resin composition constituting the organic-inorganic composite, for example, the coating surface of the adhesion-modified base-21-200835602 material film or the hard coating layer/substrate film interface can be used Infrared spectroscopic analysis, etc. are analyzed and specified. The polyester resin, the acrylic resin, and the urethane resin have adhesiveness to both the base film and the hard coat layer, and the organic solvent contained in the hard coater can be appropriately expanded. The above resins may be used singly or in combination of two different resins (e.g., a polyester resin and a urethane resin, a polyester resin and an acrylic resin, or a urethane resin and an acrylic resin). In the case where the base film forming the substrate is a polyester base film, the main resin component constituting the composite contains copolymerization in terms of adhesion to the hard coat layer and the above expandability. Esters and polyurethanes are preferred. The adhesiveness of the copolymerized polyester alone and the polyester base film is sufficient, but the adhesion to the hard coat layer obtained by containing the inorganic fine particles is not good. Further, since it is a relatively weak resin, it is easy to cause agglomeration damage to the impact at the time of cutting. Further, the adhesion between the individual polyurethane and the hard coat layer containing inorganic fine particles is excellent. Further, the adhesion to the polyester base film is not good. Further, when the adhesion-modified substrate film is wound into a roll shape, the blocking resistance is poor. Therefore, the quality of the hard coat film or the optical functional film produced by using the adhesion-modified substrate film having the adhesion-modifying layer formed of the individual polyurethane is remarkably lowered. In order to avoid the above problem, it is necessary to contain a particle having a large particle diameter in a composite containing a large amount of particles in the base film, or to increase the content of the particles constituting the composite. As a result, the haze of the film is increased, and it is not particularly desirable as a substrate film of a hard coating film or an optical functional film which is required to be transparent to -22-200835602. When a composite containing inorganic particles having an appropriate particle diameter is present, 'the result of forming appropriate irregularities in the boundary between the base film and the hard coat layer' results in smoothness, take-up property, and crack resistance. Therefore, it is not necessary to contain fine particles in the base film, and high transparency can be maintained. Further, when such a polyester resin is used as the aqueous coating liquid, the water-soluble or water-dispersible polyester resin is used only when the water-soluble or water-dispersible chemical is used to make the sulfonic acid-containing compound or It is preferred that the carboxylic acid base compound is copolymerized. Next, it is explained in detail that the composite contains a copolymerized polyester and a polyurethane as a main component. The aqueous coating liquid (1) containing a resin containing a copolymerized polyester and a polyurethane, a dispersion medium containing water and alcohol, and a surfactant as a main component is continuously applied to one side of a traveling thermoplastic resin film. Or a two-sided process; a drying process for drying the coating layer; then, an elongation process extending at least in an axial direction of 0: and a heat-fixing process for thermally fixing the stretched film, continuously formed, and provided with a close joint The adhesive layer of the modified layer is modified to improve the substrate film. Further, by heat-treating at least one crosslinking agent selected from the group consisting of an epoxy crosslinking agent, a melamine crosslinking agent, and an oxazoline crosslinking agent in the coating liquid (1), it is also possible to form an appropriate one. Crosslinked structure. (Preparation Process of Coating Liquid (1)) In the present invention, when the coating method is used, the material used in the coating liquid (1) is a resin, a dispersion medium or a solvent. In the present invention, the coating liquid (1) is preferably water--23-200835602. Further, in addition to the resin component, the present invention is preferably a ruthenium-based particle and an surfactant. Further, an antistatic agent, an ultraviolet absorber, an organic lubricant, an antibacterial agent, a photocatalytic catalyst or the like may be used as needed. Further, in the coating liquid (1), in order to promote the thermal crosslinking reaction of the resin, a catalyst may be added, and for example, an inorganic substance, a salt, an organic substance, a basic substance, an acidic substance, a metal-containing organic compound, or the like may be used. Various chemicals. Further, in order to adjust the pH of the aqueous solution, an alkaline substance or an acidic substance may be added. The coating liquid (1) is dispersed or dissolved in a dispersion medium or a solvent under stirring, and then, in addition to the particles and the surfactant, various additives are used as needed, and diluted to the desired solid form. Adjust the concentration of the ingredients. Further, in order to uniformly disperse the resin component and the particles of the coating liquid (1), and to remove foreign matter such as coarse particle agglomerates and dust in the process, it is preferred to perform fine filtration of the coating liquid (1). The type of the filter medium for precisely filtering the coating liquid (1) is not particularly limited as long as it has the above-described properties, and is, for example, a single yarn type, a felt type, or a screen type. The material of the filter material in order to precisely filter the coating liquid (1) is not particularly limited as long as it has the above properties and does not adversely affect the coating liquid (1), such as stainless steel, polyethylene, polypropylene, and nylon. Wait. The filter medium for fine filtration of the coating liquid (1) is preferably a filter material having a filter particle size (initial filtration efficiency: 95%) of 25 μm or less, and more preferably a filter medium having a filtration performance of 1 μm or less. The best method is to combine the filters used to filter different performance. When the filter material having a particle size larger than 2 5 μηη is used, it is easy to reduce the removal effect of the coarse aggregate. Therefore, the coarse aggregate which cannot be removed by filtration is enlarged by the alignment stress of one of the axial alignment or the two-axis alignment process after the coating and drying, and it is considered that the aggregate of 1 〇〇μχη or more is likely to cause optical defects. (a) Resin In the present invention, when a copolymerized polyester (PEs) and a polyurethane (P U) are used as the resin constituting the composite, the adhesion is preferred. At this time, the copolymerized polyester (PEs) in the coating liquid (1) forms a mass ratio based on the solids of the polyurethane (PU) to (PEs) / (PU) = 70 / 30 ~ 30/70 is better, preferably 6 0/4 0~40/60. Further, the resin of the composite may be a third resin other than the above-mentioned copolymerized polyester and polyurethane. In addition, a crosslinking agent can also be used. (Copolymerized Polyester) For example, when a copolymerized polyester is used in the composite, it is preferred to use an aromatic dicarboxylic acid component and ethylene glycol as a diol component and a branched diol as constituent components. The branched diol is, for example, 2,2-dimethyl-1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, and 2-methyl-2-butyl-1. 3-propanediol, 2-methyl-2-propyl-1,3·propanediol, 2-methyl-2-isopropyl-1,3-propanediol, 2-methyl-2-n-hexyl-1,3· Propylene glycol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-n-butyl-1,3-propanediol, 2-ethyl-2-n-hexyl-1,3-propanediol, 2 , 2-di-n-butyl-1,3·propylene glycol, 2-n-butyl-2-propyl-1,3-propanediol, and 2,2-di-n-hexyl-1,3-propanediol. The molar ratio of the branched diol component is preferably 1 mol%, more preferably 20 mol%, based on the total diol component. In addition, the upper limit is -25 - 200835602 8 0% by mole, the better is 70% by mole, and the best is 60% by mole. Diethylene glycol, propylene glycol, butylene glycol, hexa-1, cyclohexane dimethanol, etc. may be used depending on the requirements. The aromatic dicarboxylic acid component is most preferably p-citric acid or isophthalic acid. The carboxylic acid component may be copolymerized by adding a dicarboxylic acid such as a dicarboxylic acid, particularly a diphenylcarboxylic acid or a 2,6-naphthalenedicarboxylic acid, in a range of 10 mol% or less. It is preferred to use a copolymerized polyester constituting the composite to use a water-soluble or pharmaceutically acceptable resin. Therefore, in addition to the above-mentioned two residual acid components, in order to make water dispersibility, it is preferred to use a 5-sulfoisoalkali metal salt in the range of 1 to 10 mol%, for example, sulfo-p-citric acid, 5-sulfonate. Isodecanoic acid, naphthoisophthalic acid-2,7-dicarboxylic acid and 5-(4-sulfophenoxy)isodecanoic acid or a genus salt. (Polyurethane) The polyurethane obtained by containing the composite is preferably a water-soluble or dispersed resin. For example, a resin containing a blocked isocyanate group is a water-soluble urethane having a terminal isocyanate group blocked with a hydrophilic group (hereinafter abbreviated as a block). Blocking agents for isocyanate groups, such as bisulfites and phenols, alcohols, indoleamines, anthraquinones, or active methylenes. The blocked isocyanate group is such that the carbamate is pre-hydrophilized or water-soluble. When the above-mentioned resin has thermal energy by a drying process or a treatment process for producing a film, when the blocked isocyanate group is detached, the resin is mixed into a self-crosslinking frame, and the diol or all of the two aromatic aromatic groups are added. Water-dispersible polyester with 4_sulfonic acid of citric acid. Its gold-receiving water can be used to make the final thermal reaction sulfonate-containing polymer preheating agent self-constructed water-26- 200835602 Dispersion copolymerized polyester is immobilized And at the same time, it reacts with the above-mentioned resin terminal group or the like. The resin in the coating liquid (1) is hydrophilic, so the water resistance is not good. However, when coating, drying, heat setting, and thermal reaction are completed, the hydrophilic group of the urethane resin is blocked. Since the agent is detached, a coating film having good water resistance can be obtained. Among the above blocking agents, it is easy to obtain from the isocyanate group in the heat treatment temperature of the film manufacturing process, the detachment from the isocyanate group in the heat treatment time, and the bisulfite salt in the industrially easy to obtain. The urethane prepolymer used in the above polyurethane resin, for example, (1) a compound having a molecular weight of at least 2 active hydrogen atoms in the molecule of 200 to 20,000, (2) An organic polyisocyanate having two or more isocyanate groups in the molecule, and a compound having a terminal isocyanate group obtained by reacting a chain extender having at least two active hydrogen atoms in the molecule as required. The above (1) a compound having a molecular weight of at least two active hydrogen atoms in the molecule of 200 to 20,000 is generally known to contain two or more hydroxyl groups, carboxyl groups, amine groups or sulfhydryl groups at the terminal or molecule, and more preferably Preferred compounds are mainly linear or branched polyether polyols and polyester polyols. Further, the polyether polyol is, for example, a compound obtained by polymerizing an alkylene oxide such as ethylene oxide or propylene oxide, or a compound obtained by polymerizing styrene oxide or chlorocyclopropane, or the like. A compound obtained by polymerization, block polymerization or addition polymerization of a polyol. The polyester polyol may be a polyvalent saturated or unsaturated carboxylic acid such as succinic acid, adipic acid, citric acid or maleic anhydride, or the like, and the like, and ethylene glycol, diethylene glycol, 1, Multi-valent saturated and unsaturated alcohols such as 4-butanediol, neopentyl alcohol, 1,6-hexanediol and trimethylolpropane-27-200835602, lower molecular weight polyethylene glycol and poly A polyalkylene glycol such as propylene glycol or a mixture of such alcohols is condensed and obtained. Further, as the polyester polyol, for example, a polyester obtained from a lactone or a hydroxy acid or a polyether ester polyol obtained by adding ethylene oxide or propylene oxide to a polyester produced in advance can be used. The organic polyisocyanate of the above (2), for example, an isomer of methylphenyl diisocyanate, an aromatic diisocyanate such as 4,4-diphenylmethane diisocyanate, or benzodimethyl diisocyanate Alicyclic diisocyanates such as aromatic aliphatic diisocyanates, isophorone diisocyanate and 4,4-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and 2,2,4-tri An aliphatic diisocyanate such as methylhexamethylene diisocyanate or a polyisocyanate obtained by adding one or more of these compounds to trimethylolpropane or the like. The above (3) a chain elongation agent having at least two active hydrogen atoms in the molecule, such as glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol Polyols such as glycerol, trimethylolpropane, and pentaerythritol, diamines such as ethylenediamine, hexamethyldiamine, and pyridinium, amines such as monoethanolamine and diethanolamine, and thio A thiodiethylene glycol such as diethylene glycol or water. When the urethane prepolymer is synthesized, the above (1) and the above (2) are used, and the above (3) is required, and the one-stage or multi-stage isocyanate polyaddition method is used at 150°. The reaction is carried out at a temperature of 70 or less, preferably 70 to 12 ° C, for 5 minutes to several hours. For the above (丨) and the active hydrogen atom of the above (3), -28 to 200835602, the ratio of the isocyanate group of the above (2) may be freely selected as long as it is i or more, but it is necessary to obtain the urethane polymer. Residual isocyanate groups remain. Further, the content of the free isocyanate group is considered to be 10% by mass or less based on the total mass of the obtained urethane prepolymer, and the blocked urethane polymer is considered. In the case of the stability of the aqueous solution, it is preferably 7 mass% or less. The obtained urethane prepolymer obtained is preferably blocked by using a heavy sulfite. Mix with a bisulfite aqueous solution and stir evenly for about 5 minutes ® 1 hour. The reaction temperature is preferably 60 ° C or less. Then, it is diluted with water to an appropriate concentration to form a thermally reactive water-soluble urethane composition. When the composition is used, it is prepared to have an appropriate concentration and viscosity, and when heated at about 80 to 120 ° C, the bisulfite salt of the block agent is dissociated to regenerate the active isocyanate group. The polyurethane polymer is formed by causing a polyaddition reaction in or between molecules of the prepolymer, or has a property of causing addition to other functional groups. An example of the block type isocyanate group-containing resin (B) described above is exemplified by the trade name Elastron manufactured by Dai-ichi Kogyo Co., Ltd. Elastron is an isocyanate group block which is water-soluble by the presence of a strong hydrophilic aminomethyl sulfonate group at the molecular terminal by sodium bisulfite. (Acrylic Resin) A water-dispersible or water-soluble acrylic resin when an acrylic resin is used in a composite, for example, having an acrylate and/or a methacrylate, or an unsaturated double bond such as styrene, or the like Resin copolymerized fat -29- 200835602 Group compound or copolymer of aromatic compound. The water-dispersible acrylic acid-styrene random copolymerization by emulsion polymerization is used as an acrylic acid-benzopyring copolymer resin excellent in hydrophilicity as an adhesion-adhesive layer excellent in adhesion to a hard coating layer. The resin is the best. Further, in the present invention, since the water-dispersible acrylic-styrene copolymer resin is more strongly bonded to the base film, the copolymerized polyester is used in an amount of from 1 to 90% by mass based on the copolymerized resin. It is extremely effective when used in resins. Preferably, the water-dispersible sulfonic acid metal base-containing polyester copolymer resin is mixed in the water-dispersible acrylic-styrene copolymer resin coating liquid (1), and is suitably applied to a substrate film. Preferred examples of the polyester constituting the polyester copolymer resin containing a water-dispersible sulfonic acid metal base, such as polyethylene terephthalate, polyethylene-2,6-naphthalate, poly-1,4 - cyclohexane dimethylene terephthalate. The polyester should be 30 mol% or less, preferably 15 mol. / The above-mentioned acid component or diol component is copolymerized or mixed with the polyester obtained from the above-mentioned acid component and diol component in the molar ratio. Further, a water-dispersible or water-soluble amine group is added to a coating liquid (1) of a polyester copolymer resin in which a water-dispersible sulfonic acid metal base is mixed with a water-dispersible acrylic acid-styrene copolymer resin. An acid ester resin (preferably a water-dispersible, block isocyanate resin having three or more functional groups) copolymerized with a water-dispersible acrylic-styrene copolymerized resin and a polyester of a water-dispersible sulfonic acid metal base The crosslinking reaction of the resin does not lower the adhesion to the hard coat layer, and the adhesion resistance of the surface of the coating film can be improved. When each of the above resins is used, the coating liquid (1) -300 - 200835602 containing the above components is applied onto at least one of the base film and dried. For example, a water-dispersible acrylic acid-styrene copolymer resin, preferably a random copolymerized resin of a propylene acrylate and/or methacrylate resin and styrene, and a water-dispersible polyester copolymer resin. The polyester copolymer resin having a water-dispersible sulfonic acid metal base is a solid concentration of 4 to 15 by mass when the resin-containing coating liquid (1) is blended in a mass ratio of 3:2 to 1:1. %, viscosity 4 to 6 0 cps (measured by a B-type viscometer at 25 cps). In the present invention, when it is necessary to crosslink the acrylic resin, a crosslinking agent such as an isocyanate, an epoxy resin, an oxazoline or a melamine can be used. (b) Solvent In the present invention, the solvent generally includes a dispersion medium which is used not only for dissolving the resin but also for dispersing the resin into particles. In order to carry out the invention, various solvents such as an organic solvent and an aqueous solvent can be used. The solvent used in the coating liquid (1) is a mixture of water and an alcohol such as ethanol, isopropyl alcohol or benzyl alcohol in a ratio of from 30 to 50% by mass based on the total of the coating liquid (1). The liquid is preferred. Further, when it is less than 1% by mass, it can be mixed in a range in which an organic solvent other than the alcohol can be dissolved. In the coating liquid (1), the total amount of the alcohol and the other organic solvent is preferably less than 5% by mass. When the amount of the organic solvent added is less than 50% by mass based on the total amount of the solvent, the drying property can be improved when the coating is dried, and the appearance of the coating layer can be improved when compared with water alone. When the amount of the organic solvent added is 50% by mass or more for all the solvents, the evaporation rate of the solvent becomes fast, and the concentration of the coating liquid (1) during coating tends to change. As a result, the viscosity of the coating liquid (1) rises from -31 to 200835602, and the coatability is lowered, causing a poor appearance of the coating film. In addition, due to the volatilization of the organic solvent, the risk of fire and the like is also increased. (d) When the aqueous coating liquid (1) is applied to the surface of a thermoplastic resin film (base film), the wettability of the film is improved, and the coating liquid (1) is uniformly coated. In general, surfactants are used. The surfactant may be a suitable phase separation structure as long as it has good coatability and a suitable phase separation structure on the surface or inside of the adhesion-modifying layer, and there is no particular limitation. Among the surfactants, when a good coating property is obtained in a small amount, a fluorine-based surfactant is preferred. The amount of addition to the coating liquid (1) is matched with 0. 01~0. 18% by mass is preferred. In the case of a fluorine-based surfactant, it is preferably 30 or less times the critical micelle concentration of pure water. When the concentration of the critical micelle is 30 or more, the particles contained in the coating liquid (1) are easily aggregated, so that the haze of the obtained laminated film is increased, particularly when it is used as a base film of an optical functional film. Not for the sake of the enterprise. Further, since the surfactant component is segregated on the surface of the adhesion-modifying layer, it has an adverse effect on the adhesion. Further, when it is below the critical micelle concentration, good coatability cannot be obtained. (e) Particles When a hard coating film or the film is used as an optical functional film requiring high transparency, the haze of the substrate film is 1. 5 % or less is preferred. The above haze is 1. 0% or less is better. The haze is greater than 1. At 5%, when the film is used for a lens film for LCD or a substrate film for backlight, the sharpness of the image is lowered, so it is not desirable. -32- 200835602 When the haze of the base film is 1.25 % or less, it is preferred that no particles are contained in the base film. When the base film does not contain particles, it is improved in scratch resistance or when it is rolled into a roll shape or when it is rolled out (smoothness, running property, blocking property, air removal with air during winding, etc.) When the composite is dispersed in the boundary between the substrate film and the hard coat layer. The inorganic particles contained in the composite are, for example, calcium carbonate, calcium phosphate, amorphous cerium oxide, crystalline glass fiber, kaolin, talc, titanium oxide, aluminum oxide, cerium oxide-alumina composite oxide particles, barium sulfate, Fluoride • Inorganic particles such as calcium, lithium fluoride, zeolite, molybdenum sulfide, mica, crosslinked polystyrene particles, crosslinked acrylic resin particles, crosslinked methyl methacrylate particles, benzoguanamine • Heat-resistant polymer particles such as formaldehyde condensate particles, melamine-formaldehyde condensate particles, and polytetrafluoroethylene particles. Among these particles, since the refractive index of the resin component is relatively close, it is preferred to use a ruthenium dioxide particle in the case of a film which is highly transparent. Further, the shape of the particles is not particularly limited, and it is preferable to impart smoothness to particles having a spherical shape. The content of the particles in the total amount of the complex is preferably 2% by mass or less, more preferably 15% by mass or less, and most preferably 1% by mass or less. When the content of the particles in the composite is more than 20% by mass, the transparency tends to be deteriorated and the adhesion of the film is likely to be insufficient. Further, the lower limit 含量 of the content of the particles is preferably 0.1% by mass for the composite layer, more preferably 1% by mass, and more preferably 3% by mass. Further, the composite may contain two or more kinds of particles having different average particle diameters. Further, it may contain the same kind of particles and have different average particle diameters. Particles -33- 200835602 The average particle size and total content are within the above range. When the coating liquid (1) described above is applied, in order to remove coarse aggregates of particles in the coating liquid (1), it is preferred to arrange a filter material which is subjected to precision filtration treatment before coating. Further, the average particle diameter of the particles is preferably from 20 to 150 nm, more preferably from 4 0 to 6 Onm. When the average particle diameter is less than 20 nm, it is easy to obtain sufficient blocking resistance, and the scratch resistance tends to be deteriorated. Further, when the average particle diameter of the particles is more than 15 Onm, the haze increases and the particles are liable to fall off, so that it is not required. In the present invention, when only the particles A having an average particle diameter of 20 to 150 nm are obtained, sufficient blocking resistance and scratch resistance cannot be obtained. Therefore, in order to further improve the blocking resistance and the scratch resistance, it is preferred to use a small amount of the particles B having a large average particle diameter. The average particle diameter of the particles b having a large average particle diameter is preferably from 16 to 100 nm, more preferably from 200 to 80 Onm. When the average particle diameter of the particles B is less than 160 nm, the scratch resistance, smoothness, and windability are deteriorated. Further, when the average particle diameter of the particles B is larger than 1 〇 〇 〇 nm, the haze tends to increase. Further, the particles B are preferably aggregated particles in which primary particles are agglomerated, and particles having an average particle diameter in agglomerated state and an average particle diameter ratio of primary particles of four or more times are preferable in terms of scratch resistance. When two kinds of particles are used, for example, the content ratio of the particles A (average particle diameter: 20 to 150 nm) to the particle B (average particle diameter: 160 to 100 nm) (Pi/p2) is 5 to 30, and The content of the particles B is 〇" to 1% by mass in terms of the solid content of the adhesion-modifying layer. The content of the particles of the two specific particle diameters is controlled within the above range, so that the average surface roughness of the three-dimensional center plane of the surface of the adhesion-modifying layer is appropriately adjusted, and the transparency, handling property, or blocking resistance are saved. It is appropriate. -34- 200835602 When the content of the particles B is more than 1% by mass in the adhesion-modifying layer, the haze tends to be remarkably improved. The measurement of the average primary particle diameter and the average particle diameter of the above particles was carried out by the following method. The particles were photographed by an electron microscope, and the maximum particle size of 300 to 500 particles was measured with a minimum particle size of 2 to 5 mm, and the average enthalpy was taken as the average primary particle diameter or average particle diameter. . Further, when the average particle diameter of the particles in the adhesion-modifying layer of the laminated film is obtained, a cross section of the laminated film is photographed at a magnification of 120,000 times using a transmission electron microscope (TEM) to determine the maximum particle diameter of the composite particles. . The average particle diameter of the particles B formed of the agglomerates was measured by the optical microscopy of the laminated film, and the maximum particle diameter was measured by using an optical microscope at a magnification of 200 times 300 to 500. (f) Crosslinking agents Information terminals such as mobile phones, PDAs, and hand-held computers have increased opportunities for use outside the home. In addition, the touch panels used in satellite navigation systems and the like have increased the materials used in summer high-temperature vehicles. In addition, a hard coating film having a small change in quality under a severe environment of high temperature and high humidity, that is, a film excellent in moisture-heat-resistant adhesion is extremely desired for this application. When the hard coat film of the present invention is used for this application, in order to improve the moist heat resistance of the composite, it is preferred to add a crosslinking agent to the coating liquid (1) and then heat-treat to have a crosslinked structure in the resin. . The crosslinking agent is at least one selected from the group consisting of an epoxy crosslinking agent, a melamine crosslinking agent, an oxazoline crosslinking agent, and an isocyanate crosslinking agent. The crosslinking agent can be selected in consideration of the affinity with the copolymerized polyester resin used in the coating liquid (1) and the wet heat resistance. Moreover, -35- 200835602 is not desirable because it will damage the proper swelling property due to excessive crosslinking. The crosslinking agent is preferably from 5 to 40% by mass, more preferably from 10 to 30% by mass, based on the total amount (% by mass) of the copolymerized polyester resin and the crosslinking agent of the composite. When the content of the crosslinking agent is more than 40% by mass, the composite becomes brittle, and sufficient processing speed cannot be obtained in a processing process after forming a functional layer such as a hard coating layer or a diffusion layer made of an acrylate resin. The tightness of the cut. Further, when the content of the crosslinking agent is less than 5% by mass, the durability required in recent years is not easily obtained. Further, in the coating liquid (1), when the crosslinking is promoted, a catalyst may be added as needed. (Coating Process for Forming Organic-Inorganic Composite) The on-line coating method of applying the above aqueous coating liquid (1) to coat the film in the process of the film is preferred. More preferably, it is applied to the substrate film before the completion of the crystal alignment. The solid content concentration in the aqueous coating liquid (1) is preferably 30% by mass or less, more preferably i 〇% by mass or less. The lower limit of the solid content concentration is preferably 1% by mass, more preferably 3% by mass, and most preferably 5% by mass. The film coated with the aqueous coating liquid (1) is used for alignment and heat treatment. The film is introduced into a tenter and then heated to form a stable film by thermal crosslinking reaction to form a film of the adhesion-modified substrate. (Coating amount) The coating amount at the time of drying (hereinafter simply referred to as wet coating amount) is preferably 2 g/m 2 or more and less than 10 g/m 2 . When the wet coating amount is less than 2 g/m2, the dry coating amount (the coating amount of the final adhesion improving layer) of the design is obtained, and the solid content concentration of the coating liquid (1) must be increased. When the solid content of the coating liquid (i) is increased, the viscosity of the coating liquid (1) becomes high, and the strip coating is likely to occur. Further, when the wet coating amount is 1 〇 g/m2 or more, it is likely to be affected by the dry wind in the drying oven. Further, in order to prevent the disadvantage of adhesion due to dust, it is preferred to apply the coating liquid (1) in a clean environment having a cleanliness level of 5,000 or less. When the amount of coating is too large, the interference spots are likely to become conspicuous. When the amount of application is too small, practical adhesion cannot be obtained. Further, in the above-mentioned drying furnace, it is preferable to maintain the temperature at 120 ° C or higher and less than 150 ° C and to dry it for 1 to 5 seconds. Drying time to 〇. 5 ® ~ 3 seconds is better. When the drying time is less than 〇 at 1 second, the drying of the coating film becomes insufficient. When the roller is disposed between the drying process and the lateral stretching process, the roller is easily contaminated on the coated surface which is insufficiently dried. Further, when the drying time is longer than 5 seconds, the grain tends to cause crystallization of the thin g wu, and the frequency of occurrence of the rupture during the lateral stretching increases. In the above-mentioned drying furnace, after the coating film is dried at a temperature of not higher than 150 ° C and not higher than 150 ° C, it is preferred to directly cool the adhesion-modified substrate film to room temperature. When the surface temperature of the base film is 100 ° C or higher, it is taken out from the φ drying oven, and when the substrate film is brought into contact on a roll near the room temperature, the film shrinkage is likely to cause scratches. Further, in order to prevent the intrusion of dust from the dry air in the drying furnace, it is preferable to use the air purified by the HEPA filter. The HEPA filter used at this time has a nominal filtration accuracy of 95% or more. A filter having a performance of 5 μιη or more of dust is preferred. Further, it is effective to increase the accuracy (roundness and cylindricality) of the coater roll of the coating device and to reduce the thickness of the coating applied to the longitudinal direction of the film roll. The roundness of the coater roll described in -37-200835602 is expressed by JIS B 062 1 and is expressed by the difference of the radii of the two concentric circles of the minimum range method determined by the recording roundness measuring device. . Moreover, the unit of the roundness of the rolls is mm. In addition, the cylindricality of the applicator roller is such that the applicator roller with the micrometer placed on the plate moves in the axial direction, and the measuring instrument is placed on the cylinder, and the entire length is measured at each measuring plane. The measurement is performed in the measurement indicated by 1/2 of the maximum difference read at this time. Moreover, the unit of the cylinder is mm. In the present invention, by increasing the accuracy of the roll (roundness and cylindricality), it is possible to reduce the variation of the thickness of the coating layer in the direction of the low length. Specifically, the roller accuracy (roundness and cylindricality) is preferably less than 5/1000 mm. Further, when the coating liquid (1) is applied, the surface processability of each of the rolls of the reversible coater is 0. 3 S or less, and the accuracy (roundness and cylindricality) of the coating roller and the counter roller are less than 5/1000 and 2/1000 mm or more, and the fluctuation of the wet coating amount can be suppressed, and the pressure suppresses the variation of the coating film thickness. Preferably, it is possible to apply a coating roll having a precision of lightness and a count roll (roundness and cylindricality) of 3/1000 mm. Further, by making the tension of the film 4000 to 10000 N / the material width (the material width is 1 to 2 m), the planarity of the film on the industrial scale can be maintained, and the amount of the coating liquid (1) can be made uniform. Moreover, the tension of the film varies depending on the thickness of the film, and the flatness is maintained by applying a lower tension to the thin film. When the tension of the film is greater than 1 〇〇 00 N / the width of the raw material, the film may be deformed or broken. Further, when the tension of the film is less than 4000 N/the width of the raw material, the planarity of the film becomes insufficient at the time of coating, or the film causes a meandering phenomenon of 38-200835602. As a result, the amount of transfer of the coating liquid (1) becomes uneven in the longitudinal direction of the film, and the amount of wet coating of the film largely fluctuates, and the thickness of the coating amount also becomes larger. The refractive index of the coating layer (adhesive modifying layer) can be measured by an elliptical measuring device. (3) Coating layer In a preferred embodiment of the present invention, a coating layer is formed on the surface of the base film opposite to the coating layer, and an adhesive layer is additionally provided. The buildup is in the order of the adhesive layer/coating layer/substrate film/hard coat layer. ^ The coating layer is obtained by applying a coating liquid on a substrate film and drying it. As described above, in order to obtain the coating layer, the coating liquid to be applied is defined as "coating liquid (2)". In the present invention, the coating liquid (2) used for forming the coating layer is mainly coated with an aqueous polyester resin, a water-soluble lactate compound, a water-soluble triethanolamine titanium complex compound, and an aqueous solvent. Liquid (2). The titanium lactate compound and the triethanolamine titanium complex compound contained in the coating liquid (2) can be crosslinked with the aqueous polyester resin. It is preferred to form a more uniform film by the crosslinking reaction. The crosslinking reaction is promoted by heat when the base film is extended, and as a result, the titanium compound is decomposed by heat, and the obtained coating layer is not limited to containing only titanium lactate compound and triethanolamine titanium. Compound. Further, in the present invention, it is not always necessary to extend the substrate film. The refractive index of the coating layer can be made higher than that of the water-based polyester resin by making the composition of the titanium compound larger. When the refractive index of the coating layer is increased, it can be achieved by containing metal fine particles, but the metal microparticles can reduce the elongation of the coating layer and the adhesion between the hard coating layer and the base film. -3 9 - 200835602 The aqueous polyester resin used in the present invention can also introduce an active site such as a hydroxyl group or a carboxyl group into its molecular chain, particularly when it is not introduced, because it causes a reversible reaction at an ester bond site at a high temperature. A crosslinking reaction is caused at any portion, and as a result, a dense film is obtained. The aqueous polyester resin of the @coated layer is related to the adhesion of the substrate film. Therefore, when the mass of the aqueous polyester resin contained in the coating layer is (A), the mass of the titanium lactate compound is (B), and the mass of the triethanolamine titanium complex compound is (C), (A)/[ It is preferable that (B) + (C)] is more than 50/50. When the 値 is + 5 0/5 0 or more, the necessary transparency for optical use can be improved, and the adhesion to the adhesive layer formed on the coating layer is good. Further, (A)/[(B) + (c)] is preferably 80/20 or less. In this case, the titanium compound is more sufficiently crosslinked to increase the refractive index, thereby improving the refractive index. The adhesion under high temperature and high humidity (damp heat resistance), and the suppression effect of the rainbow color under the fluorescent lamp becomes sufficient. Further, the above (B) and (C), and (B)/(C) are preferably 35/65 to 65/35. When it is in the above range, the pH of the coating liquid (2) is about neutral (pH ® 6 is 6 to 8). As a result, when the isocyanate-curable acrylic resin-based adhesive is laminated on the coating layer, the technique of adhering the coating layer and the adhesive layer to the coating layer containing the titanium lactate compound and the triethanolamine titanium complex compound can be improved. The meaning is as follows. When there is only one type of the above titanium compound, p Η値 of the coating liquid (2) tends to be acidic or alkaline. When an isocyanate-curable acrylic resin-based adhesive is laminated on the coating layer obtained from the coating liquid (2) having a large basicity, -40-200835602 is likely to cause a hardened spot in the thickness direction of the adhesive layer, and as a result, it is attached to the front surface of the display device. When the attachment is not good, the workability is lowered. The decrease in reworkability is a problem in that the residual amount of the adhesive layer increases when the front side of the display device is peeled off. Further, when the isocyanate-curable acrylic resin-based pressure-sensitive adhesive is applied to the coating layer obtained from the coating liquid (2) having a large acidity, the adhesion of the pressure-sensitive adhesive is likely to be caused, and the above-mentioned reworkability is similarly lowered. When only one of the above titanium compounds is used, the pH of the coating liquid (2) is acidic or basic. In order to adjust the pH of the liquid, an acidic compound such as a carboxylic acid, a hydrochloric acid or a sulfonic acid may be added to adjust the pH by adding an alkaline compound such as an amine, ammonium or sodium hydroxide when it is acidic.値, at this time, the compatibility between the coating layer and the titanium compound and the aqueous polyester resin is lowered, and as a result, the coating film becomes uneven, the effect of suppressing the rainbow color of the adhesive layer is lowered, and the adhesion is lowered, so it is not suitable for the article. Use. In the present specification, when the polyester resin is plasticized in the heated butyl cellosolve, and the polyester resin reaches a dispersed state when warm water is added, the polyester resin forms an aqueous polyester. Resin. When the polyester resin has water, it is important to introduce a hydrophilic group such as a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group or an ether group into the molecular chain of the polyester resin, and it is important in the above hydrophilic group. The sulfonic acid group is preferred in terms of coating properties and adhesion. When a sulfonic acid group is introduced into the polyester, the sulfonic acid compound is more preferably 1 to 10 mol% based on the total acid component of the polyester. When the amount of the sulfonic acid group is less than 1 mol%, since the polyester resin is not water-soluble, it is compatible with the water-soluble titanium compound. The properties are also lowered, so that a uniform and transparent coating layer cannot be obtained. Further, when the amount of the sulfonic acid group is more than 10 mol%, the adhesion under high temperature and high humidity (heat and humidity resistance) -41 - 200835602 tends to be poor. Further, the aqueous polyester resin has a glass transition temperature of 4 (TC or more. Therefore, the acid component of the aqueous polyester resin is preferably an aromatic component such as citric acid, isophthalic acid or naphthalene dicarboxylic acid. Further, the diol component is an aromatic system such as a glycol having a small carbon number such as ethylene glycol, propylene glycol, 1,4-butanediol or neopentyl alcohol, or an ethylene oxide adduct of bisphenol A. Further, the raw material of the polyester resin may be a rigid component such as biphenyl or a dicarboxylic acid component having a high refractive index such as bromine or sulfur, or a second component in the range of not lowering the physical properties of the film. When the glass transition temperature of the aqueous polyester resin is 4 (TC or more, the adhesion (heat and humidity resistance) under high temperature and high humidity is sufficient. Further, in order to increase the refractive index of the polyester resin, the coating layer can be improved. As a result, the rainbow-like color under the fluorescent lamp can be easily and sufficiently suppressed. The coating layer also contains a titanium lactate compound and a triethanolamine titanium complex compound. Preferably, the titanium lactate compound is complexed with triethanolamine titanium. The compounds are all water soluble. Typical examples of the titanium compound are, for example, hydroxybis(lactic acid) titanium (manufactured by Matsumoto Pharmaceutical Co., Ltd., TC310). Further, a typical example of a water-soluble triethanolamine titanium complex compound such as hydroxybis(lactic acid) titanium ( Matsumoto Pharmaceutical Co., Ltd., TC400). In the range that does not affect the effects of the present invention, a resin other than the above main components (for example, an acrylic resin, a polyurethane resin, or the like) may be used in the coating layer. A vinyl resin such as a polyester resin, an alkyd resin or a polyvinyl alcohol. Further, a crosslinking agent may be used without departing from the scope of the present invention, and a crosslinking agent such as urea may be used. , melamine, benzoquinone-42- 200835602 an amine-based resin such as an adduct of feces and formaldehyde, an alkyl ether compound such as an adduct and an alcohol having 1 to 6 carbon atoms, and polyfunctionality An epoxy compound, a polyfunctional isocyanate compound, a blocked isocyanate compound, a polyfunctional aziridine compound, an oxazoline compound, etc. Preferably, the coating layer contains cerium oxide particles, and the presence of cerium oxide Or block resistance can be improved handleability. Silicon dioxide particles can be suitably used a commercially available colloidal silicon dioxide particles and the like. The content of the silicon oxide particle coating layer occupied to 0. 1 to 20% by weight is preferred. ® When the aqueous coating liquid (2) is applied to the surface of the polyester film, a known anionic surfactant or nonionic system is added in an appropriate amount in order to improve the wettability of the film and uniformly apply the coating liquid (2). A surfactant is preferred. Further, in the aqueous coating liquid (2), in order to impart other functions such as handleability, antistatic property, and antibacterial property to the film, inorganic or/or heat resistant polymer particles, an antistatic agent, and an ultraviolet absorber may be contained. Additives such as organic lubricants, antibacterial agents, photo-oxidation catalysts, and the like. The solvent to be used in the coating liquid (2) may be an alcohol such as ethanol, isopropyl alcohol or benzyl alcohol other than water in a range of not more than 50% by mass based on the entire coating liquid (2). Further, when it is less than 1% by mass, it may be mixed in an organic solvent other than the alcohol. The total amount of the alcohol in the coating liquid (2) and the other organic solvent is preferably less than 50% by mass. In the present invention, the coating amount of the finally obtained coating layer is 〇. 〇 2~ 0. 5 g/m 2 is preferred. The coating amount of the coating layer is 〇. When 〇 2 g/m2 or more, the effect is remarkable for the adhesion, and it is easy to make the suppression effect of the rainbow color under the fluorescent lamp sufficient. In addition, the coating amount is 0. When it is 5 g/m2 or less, the suppression effect of the rainbow-like color under the fluorescent light -43- 200835602 is easy to become sufficient. The coating method is the same as that in the case of coating the organic-inorganic composite on the hard coat film side. (4) Hard coat layer A hardening type resin constituting a hard coat layer is preferably an ionizing radiation curable resin. The ionizing radiation curable resin is, for example, the following resin. Among the ionizing radiation curable resins, a resin having an acrylic functional group is preferred, and a polyester acrylate or a urethane acrylate is more preferred. The polyester acrylate is composed of acryl vinegar® or methacrylate (hereinafter referred to as (meth) acrylate) or a mixture thereof of an oligomer of a polyester-based polyol (hereinafter referred to as acrylate and/or methacrylate) . Further, the urethane (meth) acrylate is composed of a (meth) acrylated oligomer composed of a polyol compound and a diisocyanate compound. a monomer constituting a (meth)propionic acid ester such as methyl (meth)propionate, ethyl (meth)propionate, butyl (meth)acrylate, 2-ethylhexyl ( Methyl) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, phenyl (meth) acrylate. Further, when it is necessary to increase the hardness of the hard coat layer, it is preferred to use a polyfunctional monomer. For example, polyfunctional monomers such as trimethylolpropane tri(meth)acrylate, hexanol (meth) acrylate, tripropylene glycol di(meth) acrylate, diethylene glycol di(meth) acrylate Pentaerythritol tri(meth)acrylate, pentaerythritol hexa(meth) acrylate, hexanediol di(meth) acrylate, neopentyl alcohol di(meth) acrylate. Polyester oligomers such as adipic acid and diol (ethylene glycol, polyethylene glycol, propanol, polypropylene glycol, butylene glycol, polybutylene glycol, etc.) or triol (C-44- 200835602 Triol, trimethylolpropane, etc.), a polyadipate polyol of a condensation product of citric acid with a diol or a triol, or a polysebacate polyol. Further, some or all of the above aliphatic dicarboxylic acids may be substituted with other organic acids. For example, isotypic acid, p-citric acid, or phthalic anhydride can be used as a component for increasing the hardness of the hard coat layer. When the hard coat layer is formed on the base film, in order to improve the level, it may be diluted with a diluent as needed. Diluents such as benzene, toluene, xylene, etc., aromatic alcohols, hexyl, Gengyuan, Xinyuan, brothel, brothel, etc., aliphatic hydrocarbons, methyl ethyl ketone, diethyl ketone, diisopropanone, etc. Wait. The amount of the Dilution ® agent is appropriately selected at an appropriate viscosity. Inorganic fine particles contained in the hard coating layer, such as amorphous cerium oxide, crystalline glass cerium, cerium oxide, chromium oxide, titanium dioxide, sulphate, temple inorganic oxide, sulphur oxide-oxidation Composite oxide particles, magnesium carbonate, aluminum hydroxide, barium sulfate, calcium carbonate, gold phosphate, kaolin, talc, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, mica. When the antireflection layer composed of the high refractive index layer/low refractive index layer or the high + refractive index layer/medium refractive index layer/low refractive index layer is laminated on the surface of the hard coating layer, the hard coating layer is highly refracted The rate is high, and the high refractive index layer can be omitted from the antireflection layer. As a result, the cost can be reduced. In order to increase the refractive index of the hard coat layer, it is extremely effective to contain inorganic fine particles having a high refractive index in the hard coat layer. Inorganic fine particles having a refractive index such as an oxidation pin or titanium oxide. It is important that the content of the inorganic fine particles in the hard coat layer is 20% by weight or more and 80% by weight or less. When the content of the inorganic fine particles is less than 20% by mass, the scratch resistance is insufficient. Further, when the content of the inorganic fine particles is more than 8 〇 -45 to 200835602% by mass, the transparency tends to be lowered. Further, the average particle diameter of the inorganic fine particles is preferably from 5 to 100 nm in terms of transparency. Further, the inorganic fine particles having a small average particle diameter tend to aggregate and become unstable. Therefore, in order to improve the dispersion stability of the inorganic fine particles, a photo-sensitive group is imparted to the surface of the inorganic fine particles, and the affinity with the curable resin is improved. The high refractive index hard coating agent containing inorganic fine particles can be obtained from a commercially available product. For example, UV-curable resin (Desolite) manufactured by JSR Co., Ltd.; Z7400B, Z7410B). Further, an appropriate amount of inorganic fine particles having a refractive index 咼 is added to the acrylic resin, and the refractive index is adjusted to 1. 5 5 〜1·70, preferably 1.58~1. 65, the better is 1.60~1. 65 The ionizing radiation hardening resin can be hardened by ultraviolet light or electron beam irradiation. When irradiating ultraviolet rays, the ultra-high pressure mercury lamp, high-pressure mercury lamp, low-pressure mercury lamp, carbon arc, metal halide lamp, etc. are in the wavelength range of 1 〇〇 to 400 nm (preferably 200 to 400 nm), and 1 〇〇 The energy of 3 0 0 0 m J / m 2 is irradiated with ultraviolet light. Further, when the electron beam is irradiated, a scanning type or a curtain type electron beam accelerator is used, and an energy having an acceleration voltage of 1000 volts or less (preferably 1 〇〇 to 300 keV) is applied, and the wavelength range of 10 〇〇 nm or less is irradiated. Electronic line. The thickness of the hard coat layer is in the range of from 0.1 to 30 μm, depending on the use thereof. More preferably, it is 1 to 15 μm. When the thickness of the hard coat layer is within the above range, the surface of the hard coat layer is high in hardness and is not easily scratched. Further, the hard coat layer is less likely to become brittle, and the hard coat layer is less likely to be broken when the hard coat film is bent. -46 - 200835602 Next, the optical functional film of the present invention has an optical functional layer laminated on or opposite to the hard coat layer of the hard coat film of the present invention, and has the following two embodiments. (a) an optical functional film comprising at least one optical functional layer selected from the group consisting of a hard coat layer, a light diffusion layer, a rhombohedral lens layer, an electromagnetic wave absorbing layer, and a near red line cut-off layer transparent conductive layer on the opposite side of the hard coat layer . (b) An optical functional film in which an antireflection layer or an antifouling layer is laminated on the hard coat layer. When the β (5) binder layer is formed into a binder layer which may have the hard coat film of the present invention, the binder may contain, for example, an acid having a functional group in terms of balance of transparency, cohesiveness, and peeling property. Acrylic polymer and an acrylic adhesive of an isocyanate crosslinking agent. The acrylic polymer contains an alkyl (meth)acrylate and an acid-containing monomer as a monomer unit. Alkyl (meth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl ester, etc., these may be used singly or in combination. The acid-containing monomer is a carboxyl group-containing monomer such as (meth)acrylic acid, itaconic acid or maleic acid, or an acid anhydride thereof. The reaction point is imparted by crosslinking or the like with an acid-containing monomer. The proportion of the acid-containing monomer is from about 1 to 10 parts by weight, preferably from 2 to 6 parts by weight, per 100 parts by weight of the alkyl (meth) acrylate. When the acrylic polymer has a polarity, a hydroxyl group-containing monomer such as hydroxyethyl (meth)acrylate or hydroxypropyl (meth)acrylate may be used; and an anthranamine group such as hydrazine-hydroxymethyl methacrylate. Monomers; cyano group-containing monomers such as (meth)acrylonitrile-47 - 200835602; epoxy group-containing monomers such as glycidyl (meth)acrylate; vinyl esters such as vinyl acetate; styrene A styrene monomer such as α-methylstyrene or the like is used as a copolymerization monomer. The polymerization method of the acrylic polymer is not particularly limited, and a conventional polymerization method such as solution polymerization, emulsion polymerization, suspension polymerization, or UV polymerization can be employed. The weight average molecular weight of the acrylic polymer is preferably from about 300,000 to 2,500,000. When an isocyanate-based crosslinking agent having excellent adhesion is used as the crosslinking agent ^, an epoxy-based crosslinking agent may be used as needed to improve the cohesiveness. The isocyanate crosslinking agent is a polyfunctional isocyanate compound and contains various compounds having two or more isocyanate groups in the molecule. Typical examples thereof are diphenylmethane diisocyanate, methylphenyl diisocyanate, hexamethylene diisocyanate, and the like, such as biuret, allophanate, trimer, adduct and the like. The blending ratio of the isocyanate-based crosslinking agent is blended within a range that does not affect the adhesiveness. Generally, it is preferably about 2 to 3 parts by weight per 100 parts by weight of the acrylic polymer. Who is it? 5 to 2 parts by weight. Further, the epoxy-based crosslinking agent in the case of using an epoxy-based crosslinking agent is a compound containing two or more epoxy groups in a molecule, using a polyfunctional epoxy compound. Typical examples are, for example, sorbitol tetraglycidyl ether, trimethylolpropane epoxidized propyl ether, tetraethoxypropyl-1,3-diaminomethylcyclohexane, tetraepoxypropyl-m-benzene Methylamine, triepoxypropyl-guanidine-aminophenol, and the like. The compounding ratio of the epoxy-based crosslinking agent can be determined by the acid introduction amount of the acrylic polymer or the structure of the epoxy-based crosslinking agent, and generally, 100 parts by weight of C-48 - 200835602 The acid-based polymer is about 1 to 8 parts by weight, preferably 1 part by weight. The above-mentioned exemplary external agent (polyamine compound, melamine resin, urea resin), adhesion imparting plasticizer, chelating agent, antioxidant, ultraviolet absorbing agent, and decane coupling adhesive layer can also be suitably used for the acrylic adhesive. The method uses a conventional method. Specifically, for example, roll coating, gravure coating, reversible coating, roll brushing, spray air knife coating, and the like. The thickness (dry thickness) of the adhesive layer is not particularly limited to about 5 to 60 μm, preferably 5 to 40 μm. Further, the adhesive layer 3 of the surface protective film of the present invention can be protected by pseudo-bonding between the separators as needed and practically desired. EXAMPLES In the following, the present film and the optical functional film using the same are described using examples and comparative examples. The invention is of course not limited by this example. Further, the physical properties and characteristics of the base film and the hard coat optical functional film described in the examples were evaluated by the following method (1) The adhesion to the hard coat layer was 5 mm thick to the thickness of the double-sided tape. On the plate, the hard coat film obtained by the actual comparative example or the hard coat side of the optical functional film was attached to the opposite surface. Then, the hard coat layer was passed through, and 100 lattice-shaped cuts reaching the resin A were formed using a bundle having a gap of 2 mm. Then, tape (made by Nichiban Co., Ltd., 405 width) was attached to the lattice-shaped cut surface. 6 parts of a cross-linking agent, an agent, etc. are used as an eraser at the time of attachment. : In terms of coating, it is usually optically provided with a hard coating, etc. The examples and layers are thermoplastic cut-off guides; 2 4mm residual residue -49- 200835602 After the air at the interface is completely adhered, the tape is peeled off vertically, and the adhesion is obtained by visual observation from the following formula. Moreover, the part that was peeled off within 1 square is also included in the number of peeling. Adhesiveness (°/〇) = (ι—number of strips of the grid/100 pieces) χΐ00 (2) Peelability of the adhesive layer Based on the JIS-Z-0237 method, the sheet is bonded to the SUS plate by hand. The 180° peeling test was performed, and the state of the SUS plate was visually observed and judged based on the following criteria. • ◎ : There are no deposits or marks on the SUS board from various angles. 〇: There is no attachment on the SUS board, but traces can be observed at a certain angle. △ : Attachments can be observed at a certain angle on the SUS plate. X: Attachments were observed on the SUS plate. (3-1) Evaluation of Thousand Spots (Rainbow Color) on the Hard Coating Layer Side The hard coating film or the optical functional film was cut into an area of 10 cm x 50 cm to prepare a sample film. The black glossy tape was attached to the upper surface opposite to the easy-adhesive layer of the obtained sample film. The hard coated surface of the sample film is the upper surface, and the 3 wavelength white fluorescent lamp (International brand bulb, F. L 15EX-N 15W) is the light source, and the reflected light is visually observed from obliquely above. The results of the visual observation were distinguished by the following criteria. Moreover, the observations were conducted with 5 people who were proficient in the evaluation, with the most columns as the evaluation column. Assuming that the two columns are the same number, the center is divided into three columns. For example, when ◎ and 〇 are each 2, △ is 1 〇; ◎ is 1 〇, 〇 and △ are 2 〇; ◎ and △ are 2, and 〇 is 1 when Q . ◎: Even when viewed from various angles, there is no rainbow-like color phenomenon. -50- 200835602 〇: There is a slight rainbow color depending on a certain angle. △: A slight rainbow color phenomenon. X: There is a distinct rainbow-like color phenomenon. (3-2) Evaluation of interference fringes (rainbow color) on the adhesive layer side Before the laminated film peeling adhesive layer to be evaluated, the interference spots were observed from the hard coated surface side in the same manner as in the above (3 - 1). Then, the interference layer was observed after removing the adhesive layer. The change in interference spots observed with the adhesive layer is evaluated as follows. Depending on the presence or absence of the adhesive layer, ◎: There is no increase in rainbow color phenomenon even when observed from various angles. 〇: A little rainbow-like color increases depending on a certain angle. △: A slight rainbow color phenomenon increases. X: There is an obvious rainbow-like color phenomenon. (4) Measurement of refractive index of hard coat layer The measurement was carried out using an Abbe refractometer based on JIS K 7 142. (5) Interface evaluation of the hard coat layer/base film The sample of the hard coat film was embedded in a visible light-curable resin (D-800, manufactured by Datum Corporation, Japan), and hardened by irradiation with visible light at room temperature. . From the obtained embedding section, an ultrathin section having a thickness of about 70 to 100 nm was produced using an ultrathin sectioning device equipped with a diamond knife, and dyeing was carried out in osmium tetroxide vapor for 30 minutes. The dyed ultrathin section was observed using a transmission electron microscope (manufactured by Sakamoto Electronics Co., Ltd., TEM2010), and the cross section of the hard coating layer was observed and photographed. Moreover, the magnification of the photograph is appropriately set in the range of 1 〇, 000 〜 100, 〇〇〇. Further, in the first embodiment of the present invention, the 200835602 magnification is 80,000 times (acceleration voltage 200 kV). (6) The p Η値 of the coating liquid was measured using a pH 値 measuring instrument ΕΧ-20 (manufactured by Horiba, Ltd.). (Example 1) (1) Preparation of composite coating liquid (1) The coating liquid (1) in the case of producing a composite was prepared in the following manner. Dimethyl phthalate (95 parts by mass), dimethyl isodecanoate (95 • parts by mass), ethylene glycol (35 parts by mass), neopentyl alcohol (145 parts by mass), zinc acetate (0) . 1 part by mass) and antimony trioxide (0. 1 part by weight) was added to the reaction vessel, and transesterification was carried out at 180 ° C for 3 hours. Then, add 5-sodium sulfoisophthalic acid (6. 0 parts by mass), after transesterification at 240 ° C for 1 hour, at 25 CTC, under reduced pressure (10~0. 2 mm H g) A polycondensation reaction was carried out for 2 hours to obtain a copolymerized polyester having a number average molecular weight of 19,500 and a softening point of 60 °C. Make 1 part by mass of the obtained 15% by mass aqueous dispersion of the copolymerized polyester (A), hydrazine. 8 parts by mass of a 20% by mass aqueous solution (manufactured by Daiichi Pharmaceutical Co., Ltd., Elastron H-3) having a self-crosslinking type polyurethane (B) of an isocyanate group which is blocked with sodium bisulfite. 02 parts by mass of Elastron catalyst (first industrial pharmaceutical system, Cat 64), 56. 3 parts by mass of water and 41. 6 parts by mass of isopropyl alcohol were mixed. Further, a 10% by mass aqueous solution of 0% by mass of a fluorine-based nonionic surfactant (manufactured by Dainippon Ink and Chemicals, Megafac F444), and 0 was added. 16 parts by mass of a 20% by mass aqueous dispersion of colloidal cerium oxide (manufactured by Nissan Chemical Industry Co., Ltd., Snowtex OL; average particle diameter: 40 nm) as a particle A, 0. 03 7 parts by mass of dry method cerium oxide as particle B (Japan -52- 200835602
Aerosil 0X50 ;平均粒徑 200nm、平均一次粒徑 40nm)之 3 · 5質量％水分散液。然後，以5質量％碳酸氫鈉水溶液使 塗布液（1)之pH値調整爲6.2，且以過瀘粒子大小（初期過 濾效率：95%)爲10μιη之毛毯型聚丙烯製過濾器進行精密 過濾。以該所得的塗布液（1)作爲塗布液a。 (2)密接性改質基材薄膜之製造 使作爲原料聚合物之不含粒子、特性黏度爲0.62 dl/g (以苯酚：1，1，2,2-四氯乙烷=6:4之混合溶劑溶解且在30°C ® 下進行測定）之聚對酞酸乙二酯（PET)樹脂粒料，在135°C下 進行減壓乾燥6小時（ITorr)。然後，使乾燥後之PET樹脂 粒料供應給押出機，在約2 8 5 °C下熔融押出成薄片狀，且 在表面溫度保持於2 0 °C之金屬輥上進行急冷硬化，製得鑄 造薄膜。此時，除去熔融樹脂中之異物的濾材，係使用過 濾粒子尺寸（初期過濾效率：9 5 %)爲1 5 μιη之不銹鋼燒結濾 材。 使所得的鑄造薄膜以經加熱的輥群及紅外線加熱器、 ^ 在95°C下加熱，再以具有周速差之輥群、朝長度方向延伸 3.5倍，製得一軸配向PET薄膜。然後，使上述塗布液a 以過濾粒子尺寸（初期過濾效率：95%)爲10 μιη之毛毯型聚 丙烯製過濾器進行精密過濾，且以可逆輥法塗布於一軸配 向PET薄膜之一面上。而且，濕式塗布量爲5 g/m2。此外， 此時塗布器之塗佈輥及計數輥係使用藉由超硬鍍鉻加工處 理製作表面爲0.2S以下、且圓度與圓筒度爲3/1000 mm之 輥0 -53- 200835602 然後，在塗布器上方配置的分爲4區之乾燥爐中，以 第 1 區（13 5°C、1·〇 秒）、第 2 區（65。(：、2.2 秒）、第 3 區（40°C、 1.8秒）、第4區（30°C、1·8秒）使塗布面進行乾燥。使薄膜 自塗布至乾燥爐入口爲止之薄膜通過時間爲0.8秒。而且， 此時設定第1區之乾燥風的風速爲30m/秒，乾燥風之供氣 風量爲130m3/秒，排氣風量爲170m3/秒，自第2區至第4 區之供氣風量爲100 m3/秒、排氣風量爲150 m3/秒，在塗 布器側沒有乾燥風流通。而且，薄膜之張力爲7000N/原材 • 料，自塗布至乾燥爐入口之間以針輥固定薄膜兩端。 然後，使薄膜之端部以夾子夾住，導入溫度1 2 0 °C、 風速15m/秒之熱風區，朝寬度方向延伸4.3倍。其次，保 持朝寬度方向延伸的寬度下，順序連續通過第1熱固定區 (溫度：200°C )、第2熱固定區（溫度：225°C )、第3熱固定 區（溫度：23 0 °C )、第4熱固定區（溫度：23 0°C )、第5熱固 定區（溫度：210°C )、第6熱固定區（溫度：170°C )、第7熱 固定區（溫度：120 °C)。而且，在第6熱固定區中朝寬度方 ^ 向進行3 %緩和處理。然後，使薄膜兩端部沒有塗布的部分 進行修邊處理，以捲取裝置進行捲取，再於其寬度方向切 成4等份，製得寬度1000mm、薄膜長度ΙΟΟΟπι、薄膜厚度 1 2 5 μηι之密接性改質聚酯薄膜之卷物。而且，熱固定區之 熱風風速全部爲1 5m/秒、通過時間各區爲4.5秒、吹附熱 風之噴嘴間隔爲350mm、每1區之噴嘴數爲8個。 (3)硬塗布膜之製造 然後，以下述方法製得硬塗布膜。 -54- 200835602 爲形成硬塗布層時之塗布液，準備紫外線硬化型丙烯 酸酯單體、氧化锆超微粒子、甲基乙酮爲主成分之有機/無 機混合系硬塗布劑（JSR股份有限公司製、Desolite Z74 10B ;固形成分濃度：50質量％)。使該硬塗布劑在乾燥 厚度爲3 μπι下塗布於前期製造所得的密接性改質聚酯薄膜 之塗布液Α之塗布面上，在8 0 °C下乾燥3分鐘。然後，以 高壓水銀燈、在1 〇〇〇mJ/cm2之條件下照射紫外線，且使樹 脂硬化，形成硬塗布層。所得的硬塗布層之折射率爲1 . 6 5。 (實施例2) 於實施例1中，除使塗布液&之濕式塗布量改爲9§/1112 外，與實施例1相同地製得硬塗布膜。 (實施例3 ) 於實施例1中，除使硬塗布劑改爲下述所示之硬塗布 劑外，與實施例1相同地製得硬塗布膜。 (硬塗布劑之調整） 使3 2 · 0質量份二氧化鈦微粒子（石原產業（股）製、 TTO-55B)、4.5質量份含羧酸基之單體（東亞合成（股）製、 Aronix M-5 3 00)及6 5.5質量份環己酮，藉由砂等級化磨予 以分散，調製重量平均粒徑爲5 5 nm之二氧化鈦微粒子的分 散液。 於上述二氧化鈦微粒子之分散液中’混合二季戊四醇 六丙烯酸酯（日本化藥（股）製、DPHA)、與光游離聚合起始 劑（Ciba-geigy公司製、Irgacure 184;單體之合計量（二季 戊四醇六丙烯酸酯與陰離子性單體之合計量）而言爲5質量 -55- 200835602 %)，硬塗布層之折射率調整爲1.6〇。 (比較例1) 於實施例1中’除沒有塗布塗布液a、即沒有形成複 合體外’與實施例1相同地製得硬塗布膜。 (比較例2 ) 除爲製得複合體時之塗布液爲下述所示之塗布液b， 且濕式塗布量改爲8 g/m2外，與實施例1相同地製得硬塗 布膜。然而’該比較例中在基材薄膜與硬塗布膜之境界範 ® 圍內複合體沒有分散，在基材薄膜與硬塗布層之間達成形 成來自塗布液b之獨立層。 (密接性改質塗布液b之調合） 使7.5質量份實施例1所得的共聚合聚酯（A)之30質 量％水分散液、11 .3質量份含有以重亞硫酸鈉予以嵌段化 的異氰酸酯基之自己交聯型聚胺基甲酸酯（B)的20質量％ 水溶液（第一工業製藥製、Elastron H-3)、0.3質量份 Elastron用觸媒（第一工業製藥製、Cat64)、37.9質量份水 ^ 及39.6質量份異丙醇混合。另外，添加0.3質量份氟系非 離子型界面活性劑（大日本油墨化學工業製、Megafac F444) 之1 0質量％水溶液、2.3質量份作爲粒子A之膠體二氧化 石夕（日產化學工業製、Snowtex 0L;平均粒徑 40nm)之 20 質量％水分散液、〇 · 5質量份作爲粒子B之乾式法二氧化矽 (日本Aerosil 0X50;平均粒徑200nm、平均一次粒徑40nm) 之3 . 5質量％水分散液。然後，以5質量％碳酸氫鈉水溶液 使塗布液之pH値調整爲6 · 2，且以過濾粒子尺寸（初期過濾 -56- 200835602 效率：95%)爲1 0 μ m之毛毯型聚丙烯製過濾器進行精密過 濾，調整塗布液b。 (比較例3 ) 除硬塗布劑爲下述所示材料外，與實施例1相同地製 得硬塗布膜。 (硬塗布劑之調合） 使 67質量份硬塗布劑（大日精化製、Seika-Beam EXF01)、13質量份甲苯、及20質量份甲基乙酮予以混合。 • 所得的硬塗布層之折射率爲1 . 5 3。 有關各實施例、比較例所得的硬塗布膜，評估硬塗布 層/基材薄膜界面時，實施例1〜3可確認在含有共聚合聚 酯與聚胺基甲酸酯之樹脂上所包圍的二氧化矽粒子，存在 於硬塗布層/基材薄膜之境界。相鄰的2個該複合體間之距 離爲500〜1000 nm，有關複合體之範圍以外，在硬塗布層/ 基材薄膜之境界沒有觀察到含有共聚合聚酯/聚胺基甲酸 酯之樹脂層（觀察臨界値：5 nm以下）。而且，比較例1中， ^ 在硬塗布層/基材薄膜之境界沒有觀察到複合體、及含有共 聚合聚酯與聚胺基甲酸酯之樹脂層。另外，比較例2中在 硬塗布層/基材薄膜之間含有多數二氧化砂粒子，觀察到含 有厚度150nm之共聚合聚酯/聚胺基甲酸酯的獨立樹脂 層，沒有觀察到複合體。比較例3中，觀察到有機-無機複 合體，惟硬塗布層之折射率低，確認有干涉斑。 -57- 200835602 【表1】 濕式塗布量 (g/m2) 塗布液之固 形成分濃度 (質量％) 硬塗布層 之折射率 複合體 干涉斑 與硬塗布 層之密接 性(％) 實施例1 5 0.38 1.65 有 ◎ 98 實施例2 9 0.38 1.65 有 〇 100 實施例3 5 0.38 1.60 有 〇 100 比較例1 - - 1.65 - ◎ 3 比較例2 8 5.30 1.65 Μ j\\\ X 100 比較例3 5 0.38 1.53 有 X 100 (實施例4) (1) 黏合劑層側之塗布液（2)的調合 使13.74質量份共聚合聚酯水分散液（A)、2.51質量份 羥基雙（乳酸）鈦之44質量％溶液（松本製藥工業（股）、 TC 3 10)、1.38質量份異丙氧基雙（三乙醇胺化）鈦之80質量 °/。溶液（松本製藥工業（股）製、TC400)、41.37質量份水及 40.0 0質量份異丙醇混合，再添加0.50質量份作爲氟系非 ® 離子型界面活性劑之全氟烷基聚氧乙烯乙醇（住友3 Μ製、 FUorad FC-17 0C)之10質量％水溶液、0.50質量份膠體二 氧化砂微粒子（觸媒化成工業製、C a t a b i d S 1 8 0 P ;平均粒徑 80nm)水分散，調製塗布液（1)。以該塗布液（2)作爲塗布液 A。該塗布液A之pH値爲6 · 4。此等之組成如表丨所示。 (2) 黏合性改質基材薄膜之製造 與實施例1相同地製得的鑄造薄膜，以經加熱的輥群 -5 8 - 200835602 及紅外線加熱器、在9 5 °C下加熱，再以具有周速差之輥群、 朝長度方向延伸3.5倍，製得一軸配向PET薄膜。然後， 使上述塗布液a以可逆輥法塗布於一軸配向PET薄膜之一 面上。而且，濕式塗布量爲5g/m2。 在反面上使該塗布液A以過濾粒子尺寸（初期過濾效 率：95%)爲ΙΟμιη之毛毯型聚丙烯製過濾器進行精密過濾， 乾燥後之塗布量爲0.11 g/m2下予以塗布。 然後，與實施例1相同地，製得寬度1 000mm、薄膜長 ^ 度1 000m、薄膜厚度125 μιη之黏合性改質聚酯薄膜之輥。 (3)黏合劑層之形成 在上述製造所得的黏合性改質聚酯薄膜上以實施例1 爲基準製得硬塗布層。另外，在醋酸乙酯中以單體基體爲 3 5 %的方式，使1〇0份2-乙基己基丙烯酸酯及3份丙烯酸 進行共聚合，製得含有重量平均分子量50萬（聚苯乙烯換 算）之丙烯酸系聚合物的溶液。對1 〇〇份丙烯酸系聚合物（乾 燥重量）而言在該溶液中配合4份環氧系交聯劑（三菱瓦斯 ® 化學（股）製、Tetolight C)及1份異氰酸酯系交聯劑（日本聚 胺基甲酸酯工業（股）製、Coronate L)，然後加入醋酸乙酯， 調製濃度調整爲2 0 %之黏合劑溶液。使該黏合劑溶液以乾 燥膜厚爲25μπι下塗布於與硬塗層相反面之塗布面上，在 1 4〇 t下乾燥2分鐘，形成黏合劑層，製得硬塗布膜。 (實施例5) 除塗布液A之濕式塗布量改爲9 g/m2外，以與實施例 4相同的方法製得積層薄膜。 -59- 200835602 (實施例6) 使硬塗布劑改爲下述所示之硬塗布劑外’與實施例4 相同的方法製得積層薄膜。 使3 2.0質量份二氧化鈦微粒子（TTO-55 B、石原產業（股） 製）、4.5質量份含羧酸基之單體（Aronix M-5300、東亞合 成（股）製）及6 5 · 5質量份環己酮，藉由砂等級化磨予以分 散，調製質量平均粒徑爲5 5 nm之二氧化鈦微粒子的分散 液。於上述二氧化鈦微粒子之分散液中，混合二季戊四醇 W 六丙烯酸酯（DPHA、日本化藥（股）製）、與光游離聚合起始 劑（Ciba-geigy公司製、Irgacure 184 ;單體之合計量（二季 戊四醇六丙烯酸酯與陰離子性單體之合計量）而言爲5質量 %)，硬塗布層之折射率調整爲1.60。 (實施例7) 除使用紫外線硬化型丙烯酸酯單體、氧化锆超微粒 子、甲基乙酮爲主成分之有機/無機混合系硬塗布劑（JSR股 ^ 份有限公司製、Desolite Z7410A;固形成分濃度：50質量 %)作爲形成硬塗布層時之塗布液外，以與實施例4相同的 方法製得積層薄膜。所得的硬塗布層之折射率爲1 · 5 8。 (實施例8) 以表2爲基準，作成塗布液B。 除使用該塗布液B取代塗布液A外，以與實施例4相 同的方法製得硬塗布膜。 (實施例9) 以表2爲基準，作成塗布液C。 -60- 200835602 除使用該塗布液c取代塗布液A外，以與實施例1相 同的方法製得硬塗布膜。 (實施例10) (共聚合聚酯水分散液（B)之作成） 在反應容器中加入二甲基對酞酸酯（95質量份）、二甲 基異酞酸酯（95質量份）、乙二醇（105質量份）、二乙二醇（5() .質量份）、醋酸鋅（0.1質量份）及三氧化銻（〇·1質量份）’在 1 8 0°C下進行酯交換反應3小時。其次，添加5-鈉磺基異駄 ® 酸（6.0質量份），在240。(：下進行酯化反應1小時後’在 25 0°C、減壓下（10〜〇.2mmHg)進行聚縮合反應2小時，製 得數平均分子量爲2 5，000、玻璃轉移點爲40 °C之共聚合聚 酯。使該聚酯分散於水中，製得3 0質量％之共聚合聚酯水 分散液（B)。使用該共聚合聚酯水分散液（B)，以表2爲基 準作成塗布液D。 除使用塗布液D取代塗布液A外，以與實施例4相同 的方法製得硬塗布膜。 ❿ (實施例Π ) (共聚合聚酯水分散液（C)之作成） 在反應容器中加入 2,6-萘二羧酸二甲酯（109質量 份）、二甲基異酞酸酯（102質量份）、乙二醇（98質量份）、 二乙二醇（50質量份）、雙酚A之環氧乙烷加成物（3〇質量 份）、醋酸鋅（〇·1質量份）及三氧化銻（0.1質量份），在 下進行酯交換反應3小時。其次，添加5-鈉磺基異酞酸（6 〇 質量份），在240°C下進行酯化反應2小時後，在2 5 5 t：、 200835602 減壓下（1 0〜0 · 2 m m H g)進行聚縮合反應3小時，製得數平均 分子量爲15,000、玻璃轉移點爲88〇c之共聚合聚酯。使該 聚酯分散於水中，製得3 0質量％之共聚合聚酯水分散液 (C)。使用該共聚合聚酯水分散液（c)，以表2爲基準作成 塗布液E。 除使用塗布液E取代塗布液a外，以與實施例4相同 的方法製得硬塗布膜。 (實施例12) 钃P 以表2爲基準’作成塗布液F。 除使用該塗布液F取代塗布液a外，以與實施例4相 同的方法製得硬塗布膜。 (實施例13) 以表2爲基準，作成塗布液〇。 除使用該塗布液G取代塗布液a外，以與實施例4相 同的方法製得硬塗布膜。 (實施例1 4) • 以表2爲基準，作成塗布液H。 除使用該塗布液Η取代塗布液a外，以與實施例4相 同的方法製得硬塗布膜。 (實施例15) 以表2爲基準，作成塗布液I。 除使用該塗布液I取代塗布液A外，以與實施例4相 同的方法製得硬塗布膜。 -62- 200835602 (比較例4 ) 除沒有使用塗布液a塗布，即沒有形成複合體外，以 與實施例4相同的方法製得硬塗布膜。 (比較例5 ) 使7.5質量份實施例1所得的共聚合聚酯（A)之30質 量％水分散液、1 1 · 3質量份含有以重亞硫酸鈉予以嵌段化 的異氰酸酯基之自己交聯型聚胺基甲酸酯（B)的20質量％ 水溶液（第一工業製藥製、Elastron H-3)、0.3質量份 Elastron用觸媒（第一工業製藥製、Cat6 4)、37.9質量份水 及3 9.6質量份異丙醇予以混合。另外，添加0.3質量份氟 系非離子型界面活性劑（大日本油墨化學工業製、Megafac F44 4)之1 0質量％水溶液、2.3質量份作爲粒子A之膠體二 氧化砂（日產化學工業製、Snowtex 0L;平均粒徑40nm)之 20質量％水分散液、0.5質量份作爲粒子B之乾式法二氧化 矽（日本 Aerosil 0X50;平均粒徑 200nm、平均一次粒徑 4 0nm)之3.5質量％水分散液。然後，以5質量％碳酸氫鈉 水溶液使塗布液之pH値調整爲6 · 2，且以過濾粒子尺寸（初 期過濾效率：95%)爲1〇 μιη之毛毯型聚丙烯製過濾器進行 精密過濾，調整塗布液Κ。 在沒有塗布塗布液a下，除使用塗布液Κ取代塗布液 A，乾燥後塗布量〇.05 g/m2下進行塗布外，與實施例1相 同地製得黏合性改質聚酯薄膜。另外，在沒有積層塗布層 之面上藉由減壓氧電漿放電處理實施改質處理。而且，減 壓氧電漿放電處理之條件爲50W、2分鐘、1 3 .3Pa(l 00 -63- 200835602 mTorr)。然後，在減壓氧電漿放電處理面上以與實施例ι 相同的方法積層硬塗布層，在黏合性改質層面上以與實方拒 例1相同的方法積層黏合層，製得積層薄膜。 (比較例6 ) 除使爲製得複合體時之塗布液作爲下述所示之塗布、液 (Ο，使濕式塗布量爲8 g/m2外，以與實施例4相同的方法 製得積層薄膜。然而，該比較例在基材薄膜與硬塗布層之 境界範圍內沒有複合體分散情形，在基材與硬塗布層之間 ® 形成來自塗布液（c)之獨立層。 使複合體形成用塗布液（C)如下述予以調合。 使7 · 5質量份實施例1所得的共聚合聚酯（A)之3 0質 量％水分散液、1 1 · 3質量份含有以重亞硫酸鈉予以嵌段化 的異氰酸酯基之自己交聯型聚胺基甲酸酯（B )的2 0質量。/。 水溶液（第一工業製藥製、Elastron H-3)、0.3 質量份 Elastron用觸媒（第一工業製藥製、Cat64)、3 7·9質量份水 ^ 及3 9.6質量份異丙醇予以混合。另外，添加〇 . 3質量份氟 系井離子型界面活性劑（大日本油墨化學工業製、M e g a f a c F 4 4 4 )之1 〇質量％水溶液、2.3質量份作爲粒子A之膠體二 氧化矽（日產化學工業製、SnowtexOL;平均粒徑40nm)之 2 〇質量％水分散液、〇 . 5質量份作爲粒子B之乾式法二氧化 矽（日本 Aerosil 0X50 ;平均粒徑 200nm、平均一次粒徑 4 0nm)之3.5質量％水分散液。然後，以5質量％碳酸氫鈉 水溶液使塗布液之pH値調整爲6.2,且以過濾粒子尺寸（初 期過濾效率：9 5 % )爲1 0 μ m之毛毯型聚丙烯製過濾器進行 -64 - 200835602 精密過濾，調整塗布液（C)。 (比較例7) 在黏合劑層側上沒有設置塗布層，直接在熱塑性樹脂 薄膜積層黏合層外’以與實施例4相同的方法製得積層薄 膜。 (比較例8) 以表2爲基準調合塗布液J後’使用1 %氨水以使液 體之p Η値調整爲6.8。除使用上述P Η値經調整的塗布液J • 取代塗布液Α外’與實施例4相同的方法製得積層薄膜。 有關各實施例、比較例所得的積層薄膜’評估硬塗布 層/基材薄膜界面時，實施例4〜1 5可確認於含有共聚合聚 酯與聚胺基甲酸酯之樹脂上所包圍的二氧化矽粒子（相當 於本發明之有機-無機複合體），存在於硬塗布層/基材薄膜 之境界。相鄰的2個該複合體間之距離爲500〜1000 nm， 有關具有複合體之範圍，在硬塗布層/基材薄膜之境界沒有 觀察到含有共聚合聚酯與聚胺基甲酸酯之樹脂層（觀察臨 界値：5 nm以下）。而且，比較例4及比較例5中在硬塗布 層/基材薄膜之境界上沒有觀察到含有複合體、及共聚合聚 酯與聚胺基甲酸酯之樹脂層。另外，比較例6中有觀察到 在硬塗布層/基材薄膜之間含有多數二氧化矽粒子、含有厚 度150nm之共聚合聚酯與聚胺基甲酸酯之獨立樹脂層，沒 有觀察到複合體。比較例7及比較例8中有觀察到有機-無 機複合體’黏合層側皆有干涉斑。 -65- 200835602 【表2】Aerosil 0X50; an average particle diameter of 200 nm and an average primary particle diameter of 40 nm) of a 5% by mass aqueous dispersion. Then, the pH of the coating liquid (1) was adjusted to 6.2 with a 5 mass% sodium hydrogencarbonate aqueous solution, and the filter was made by a blanket type polypropylene filter having a size of perylene particles (initial filtration efficiency: 95%) of 10 μm. . The obtained coating liquid (1) was used as the coating liquid a. (2) The adhesion-modified substrate film is produced so as to have no particles as a raw material polymer and has an intrinsic viscosity of 0.62 dl/g (phen: 1,1,2,2-tetrachloroethane = 6:4) Polyethylene terephthalate (PET) resin pellets which were dissolved in a mixed solvent and measured at 30 ° C ® were dried under reduced pressure at 135 ° C for 6 hours (ITorr). Then, the dried PET resin pellets are supplied to an extruder, melted and extruded into a sheet at about 285 ° C, and quenched and hardened on a metal roll having a surface temperature maintained at 20 ° C to obtain a casting. film. At this time, the filter medium from which the foreign matter in the molten resin was removed was a stainless steel sintered filter having a filter particle size (initial filtration efficiency: 95%) of 15 μm. The obtained cast film was heated at 95 ° C by a heated roll group and an infrared heater, and further stretched 3.5 times in the longitudinal direction by a roll group having a peripheral speed difference to obtain a one-axis aligned PET film. Then, the coating liquid a was finely filtered by a blanket type polypropylene filter having a filtration particle size (initial filtration efficiency: 95%) of 10 μm, and applied to one surface of the one-axis alignment PET film by a reversible roll method. Moreover, the wet coating amount was 5 g/m2. Further, at this time, the application roller and the counter roller of the applicator are used to produce a roll having a surface of 0.2 S or less and a circularity and a cylindricalness of 3/1000 mm by super-hard chrome processing, and then, 0-53-200835602, In the drying furnace divided into 4 zones arranged above the applicator, the first zone (13 5 ° C, 1 · leap seconds), the second zone (65 (:, 2.2 seconds), the third zone (40 °) C, 1.8 sec), the fourth zone (30 ° C, 1.8 sec) was used to dry the coated surface, and the film passage time from the application of the film to the inlet of the drying furnace was 0.8 seconds. The dry wind has a wind speed of 30 m/sec, the dry air supply air volume is 130 m3/sec, the exhaust air volume is 170 m3/sec, and the supply air volume from the second zone to the fourth zone is 100 m3/sec. At 150 m3/sec, there is no dry air circulation on the applicator side. Moreover, the tension of the film is 7000 N/stock material, and the ends of the film are fixed by a pin roller from the coating to the inlet of the drying oven. The part is clamped and introduced into the hot air zone at a temperature of 1 2 ° ° C and a wind speed of 15 m / sec, extending 4.3 times in the width direction. Secondly, it is kept toward the width. The first heat-fixing zone (temperature: 200 ° C), the second heat-fixing zone (temperature: 225 ° C), and the third heat-fixing zone (temperature: 23 0 ° C), 4 hot fixed area (temperature: 23 0 ° C), 5th hot fixed area (temperature: 210 ° C), 6th hot fixed area (temperature: 170 ° C), 7th hot fixed area (temperature: 120 ° C And, in the sixth heat-fixing zone, the 3% relaxation treatment is performed toward the width direction. Then, the uncoated portions at both ends of the film are subjected to trimming treatment, and the winding device is used for winding, and then the width thereof. The direction was cut into 4 equal portions to obtain a roll of the adhesive modified polyester film having a width of 1000 mm, a film length of ΙΟΟΟπι, and a film thickness of 1 2 5 μηι. Moreover, the hot air velocity of the heat-fixing zone was all 15 m/sec, passed. The time zone was 4.5 seconds, the nozzle interval for blowing hot air was 350 mm, and the number of nozzles per zone was 8. (3) Fabrication of hard coating film Then, a hard coating film was obtained by the following method. -54- 200835602 a coating liquid when a hard coating layer is formed, and an ultraviolet curable acrylate monomer, zirconia ultrafine particles, An organic/inorganic hybrid hard coating agent containing a base ethyl ketone as a main component (manufactured by JSR Co., Ltd., Desolite Z74 10B; solid content concentration: 50% by mass). The hard coating agent was applied to a preliminary stage at a dry thickness of 3 μm. The coated surface of the coating liquid of the obtained adhesion-modified polyester film was dried at 80 ° C for 3 minutes, and then irradiated with ultraviolet rays under a condition of 1 〇〇〇mJ/cm 2 with a high-pressure mercury lamp. The resin is cured to form a hard coat layer. The resulting hard coating layer has a refractive index of 1.65. (Example 2) A hard coat film was obtained in the same manner as in Example 1 except that the wet coating amount of the coating liquid &amp was changed to 9§/1112. (Example 3) A hard coat film was obtained in the same manner as in Example 1 except that the hard coat agent was changed to the hard coat agent shown below. (Adjustment of hard coating agent) 3 2 · 0 parts by mass of titanium dioxide fine particles (manufactured by Ishihara Sangyo Co., Ltd., TTO-55B), 4.5 parts by mass of a monomer containing a carboxylic acid group (manufactured by Toagos Corporation, Aronix M-) 5 3 00) and 6 5.5 parts by mass of cyclohexanone were dispersed by a sand grading mill to prepare a dispersion of titania fine particles having a weight average particle diameter of 55 nm. In the dispersion of the above titanium dioxide fine particles, 'mixed dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., DPHA), and a photo-free polymerization initiator (manufactured by Ciba-geigy Co., Ltd., Irgacure 184; total amount of monomers ( The total amount of dipentaerythritol hexaacrylate and anionic monomer is 5 mass - 55 - 200835602%), and the refractive index of the hard coat layer is adjusted to 1.6 〇. (Comparative Example 1) A hard coat film was produced in the same manner as in Example 1 except that the coating liquid a was not applied, i.e., the composite body was not formed, in Example 1. (Comparative Example 2) A hard coat film was obtained in the same manner as in Example 1 except that the coating liquid obtained in the case of the composite was a coating liquid b shown below, and the wet coating amount was changed to 8 g/m2. However, in this comparative example, the boundary between the base film and the hard coat film was not dispersed, and a separate layer from the coating liquid b was formed between the base film and the hard coat layer. (Combination of the adhesion-adjusting coating liquid b) 7.5 parts by mass of a 30% by mass aqueous dispersion of the copolymerized polyester (A) obtained in Example 1, and 11.3 parts by mass of an isocyanate containing a block of sodium bisulfite a 20% by mass aqueous solution of the self-crosslinking type polyurethane (B) (manufactured by Daiichi Industrial Co., Ltd., Elastron H-3), 0.3 parts by mass of a catalyst for Elastron (manufactured by Daiichi Kogyo Co., Ltd., Cat64), 37.9 parts by mass of water ^ and 39.6 parts by mass of isopropyl alcohol were mixed. In addition, 0.3% by mass of a fluorine-based nonionic surfactant (manufactured by Dainippon Ink and Chemicals, Megafac F444) and 2.3 parts by mass of colloidal silica dioxide as particles A were added (Nissan Chemical Industry Co., Ltd., Snowtex 0L; average particle diameter: 40 nm) 20% by mass aqueous dispersion, 〇·5 parts by mass of dry-process cerium oxide as particles B (Japan Aerosil 0X50; average particle diameter: 200 nm, average primary particle diameter: 40 nm) 3.5 Mass % aqueous dispersion. Then, the pH of the coating liquid was adjusted to 6.2 with a 5% by mass aqueous solution of sodium hydrogencarbonate, and a blanket type polypropylene made of 10 μm in a filtered particle size (initial filtration - 56 - 200835602 efficiency: 95%) was used. The filter is precisely filtered to adjust the coating liquid b. (Comparative Example 3) A hard coat film was produced in the same manner as in Example 1 except that the hard coater was the material shown below. (Combination of Hard Coating Agent) 67 parts by mass of a hard coating agent (manufactured by Daisei Seiki Co., Ltd., Seika-Beam EXF01), 13 parts by mass of toluene, and 20 parts by mass of methyl ethyl ketone were mixed. • The resulting hard coat layer has a refractive index of 1.53. With respect to the hard coat film obtained in each of the examples and the comparative examples, when the hard coat layer/base film interface was evaluated, Examples 1 to 3 were confirmed to be surrounded by the resin containing the copolymerized polyester and the polyurethane. The cerium oxide particles are present in the boundary of the hard coating layer/substrate film. The distance between two adjacent composites is 500~1000 nm. Except for the range of the composite, no copolymerized polyester/polyurethane is observed in the boundary of the hard coating layer/substrate film. Resin layer (observation critical enthalpy: 5 nm or less). Further, in Comparative Example 1, no composite or a resin layer containing a copolymerized polyester and a polyurethane was observed in the boundary between the hard coat layer and the base film. Further, in Comparative Example 2, a large amount of silica sand particles were contained between the hard coat layer/base film, and a separate resin layer containing a copolymerized polyester/polyurethane having a thickness of 150 nm was observed, and no composite was observed. body. In Comparative Example 3, an organic-inorganic composite was observed, but the refractive index of the hard coat layer was low, and interference spots were confirmed. -57-200835602 [Table 1] Wet coating amount (g/m2) Solid content concentration of coating liquid (% by mass) Adhesion between refractive index composite interference spots of hard coating layer and hard coating layer (%) Example 1 5 0.38 1.65 Yes ◎ 98 Example 2 9 0.38 1.65 〇 100 Example 3 5 0.38 1.60 〇 100 Comparative Example 1 - - 1.65 - ◎ 3 Comparative Example 2 8 5.30 1.65 Μ j\\\ X 100 Comparative Example 3 5 0.38 1.53 has X 100 (Example 4) (1) The coating liquid (2) on the side of the adhesive layer is blended so that 13.74 parts by mass of the copolymerized polyester aqueous dispersion (A) and 2.51 parts by mass of hydroxybis(lactic acid) titanium 44% by mass of solution (Satsumoto Pharmaceutical Co., Ltd., TC 3 10), 1.38 parts by mass of isopropoxy bis(triethanol aminated) titanium of 80% by mass. A solution (made by Matsumoto Pharmaceutical Co., Ltd., TC400), 41.37 parts by mass of water, and 40.0 parts by mass of isopropyl alcohol, and 0.50 parts by mass of perfluoroalkyl polyoxyethylene as a fluorine-based non-ionic surfactant. 10% by mass aqueous solution of ethanol (Sumitomo 3 、, FUorad FC-17 0C), 0.50 parts by mass of colloidal silica sand granules (catalyzed into a chemical system, Catabid S 1 8 0 P; average particle diameter 80 nm), water dispersion, The coating liquid (1) was prepared. This coating liquid (2) was used as the coating liquid A. The coating liquid A had a pH of 6.4. The composition of these is shown in the table. (2) Production of Adhesive Modified Substrate Film The cast film obtained in the same manner as in Example 1 was heated at a temperature of 95 ° C by a heated roll group - 5 8 - 200835602 and an infrared heater. A roller group having a peripheral speed difference was extended 3.5 times in the longitudinal direction to obtain a one-axis alignment PET film. Then, the coating liquid a was applied to one side of the one-axis alignment PET film by a reversible roll method. Further, the wet coating amount was 5 g/m2. On the reverse side, the coating liquid A was finely filtered with a filter type polypropylene filter having a filter particle size (initial filtration efficiency: 95%) as a ΙΟμηη, and coated at a coating amount of 0.11 g/m 2 after drying. Then, in the same manner as in Example 1, a roll of an adhesive modified polyester film having a width of 1 000 mm, a film length of 1 000 m, and a film thickness of 125 μm was obtained. (3) Formation of adhesive layer A hard coat layer was obtained on the basis of Example 1 on the adhesive modified polyester film obtained as described above. Further, copolymerization of 1 part by weight of 2-ethylhexyl acrylate and 3 parts of acrylic acid in a manner of a monomer base of 35 % in ethyl acetate was carried out to obtain a weight average molecular weight of 500,000 (polystyrene). A solution of the acrylic polymer converted). For the 1 part acrylic polymer (dry weight), 4 parts of an epoxy-based crosslinking agent (Mitsubishi Gas Chemical Co., Ltd., Tetolight C) and 1 part of an isocyanate crosslinking agent are blended in the solution. Japan Polyurethane Industrial Co., Ltd., Coronate L), and then ethyl acetate was added to prepare a binder solution having a concentration adjusted to 20%. The adhesive solution was applied onto the coated surface opposite to the hard coat layer at a dry film thickness of 25 μm, and dried at 14 ° t for 2 minutes to form a binder layer, thereby obtaining a hard coat film. (Example 5) A laminated film was obtained in the same manner as in Example 4 except that the wet coating amount of the coating liquid A was changed to 9 g/m2. -59-200835602 (Example 6) A laminate film was produced in the same manner as in Example 4 except that the hard coating agent was changed to the hard coating agent shown below. 3 2.0 parts by mass of titanium dioxide fine particles (TTO-55 B, manufactured by Ishihara Sangyo Co., Ltd.), 4.5 parts by mass of a carboxylic acid group-containing monomer (Aronix M-5300, manufactured by Toagos Corporation), and 6.5 mass The cyclohexanone was dispersed by a sand graded mill to prepare a dispersion of titanium dioxide fine particles having a mass average particle diameter of 55 nm. In the dispersion of the titanium dioxide fine particles, dipentaerythritol W hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) and a photo-free polymerization initiator (manufactured by Ciba-geigy Co., Ltd., Irgacure 184; (the total amount of dipentaerythritol hexaacrylate and an anionic monomer is 5% by mass), and the refractive index of the hard coat layer is adjusted to 1.60. (Example 7) An organic/inorganic hybrid hard coating agent containing a UV curable acrylate monomer, zirconia ultrafine particles, and methyl ethyl ketone as a main component (Desolite Z7410A, manufactured by JSR Corporation); Concentration: 50% by mass) A laminate film was obtained in the same manner as in Example 4 except that the coating liquid was formed as a hard coat layer. The resulting hard coat layer had a refractive index of 1 · 5 8 . (Example 8) A coating liquid B was prepared based on Table 2. A hard coat film was obtained in the same manner as in Example 4 except that the coating liquid B was used instead of the coating liquid A. (Example 9) A coating liquid C was prepared based on Table 2. -60-200835602 A hard coat film was obtained in the same manner as in Example 1 except that the coating liquid c was used instead of the coating liquid A. (Example 10) (Preparation of copolymerized polyester aqueous dispersion (B)) dimethyl phthalate (95 parts by mass) and dimethyl isononate (95 parts by mass) were added to a reaction container. Ethylene glycol (105 parts by mass), diethylene glycol (5 (part. mass parts), zinc acetate (0.1 parts by mass), and antimony trioxide (〇·1 part by mass) were esterified at 180 ° C The reaction was exchanged for 3 hours. Next, 5-sodium sulfosaisoindole acid (6.0 parts by mass) was added at 240. (1: After the esterification reaction was carried out for 1 hour, the polycondensation reaction was carried out at 25 ° C under reduced pressure (10 〇. 2 mmHg) for 2 hours to obtain a number average molecular weight of 2 5,000 and a glass transition point of 40. Copolymerized polyester of ° C. The polyester was dispersed in water to obtain 30% by mass of a copolymerized polyester aqueous dispersion (B). The copolymerized polyester aqueous dispersion (B) was used, as shown in Table 2 A coating liquid D was prepared as a standard. A hard coating film was obtained in the same manner as in Example 4 except that the coating liquid D was used instead of the coating liquid A. (Example Π) (Copolymerized polyester aqueous dispersion (C) Preparation) Dimethyl 2,6-naphthalenedicarboxylate (109 parts by mass), dimethylisodecanoate (102 parts by mass), ethylene glycol (98 parts by mass), diethylene glycol were added to the reaction vessel. (50 parts by mass), an ethylene oxide adduct of bisphenol A (3 parts by mass), zinc acetate (1 part by mass), and antimony trioxide (0.1 part by mass), followed by transesterification for 3 hours. Next, 5-sodium sulfisoisodecanoic acid (6 〇 parts by mass) was added, and after esterification at 240 ° C for 2 hours, under reduced pressure of 2 5 5 t:, 200835602 (1 0~0 · 2 mm H g) A polycondensation reaction was carried out for 3 hours to obtain a copolymerized polyester having a number average molecular weight of 15,000 and a glass transition point of 88 〇c. The polyester was dispersed in water to obtain a mass of 30%. % of the copolymerized polyester aqueous dispersion (C). Using the copolymerized polyester aqueous dispersion (c), the coating liquid E was prepared on the basis of Table 2. Except that the coating liquid E was used instead of the coating liquid a, A hard coat film was obtained in the same manner as in Example 4. (Example 12) 钃P The coating liquid F was prepared on the basis of Table 2. The same procedure as in Example 4 was carried out except that the coating liquid F was used instead of the coating liquid a. A hard coating film was obtained. (Example 13) A coating liquid was prepared on the basis of Table 2. A hard coating film was obtained in the same manner as in Example 4 except that the coating liquid G was used instead of the coating liquid a. 1 4) • A coating liquid H was prepared on the basis of Table 2. A hard coating film was obtained in the same manner as in Example 4 except that the coating liquid was used instead of the coating liquid a. (Example 15) Table 2 The coating liquid I was prepared in the same manner as in Example 4 except that the coating liquid I was used instead of the coating liquid A. -62-200835602 (Comparative Example 4) A hard coating film was obtained in the same manner as in Example 4 except that the coating liquid a was not applied, that is, the composite body was not formed. (Comparative Example 5) 7.5 parts by mass was carried out. 30% by mass aqueous dispersion of the copolymerized polyester (A) obtained in Example 1, and 11.3 parts by mass of self-crosslinking type polyurethane having an isocyanate group blocked with sodium bisulfite (B) 20% by mass aqueous solution (manufactured by Daiichi Industrial Co., Ltd., Elastron H-3), 0.3 parts by mass of Elastron catalyst (manufactured by Daiichi Kogyo Co., Ltd., Cat6 4), 37.9 parts by mass of water, and 39.6 parts by mass of isopropanol . In addition, 0.3% by mass of a fluorine-based nonionic surfactant (manufactured by Dainippon Ink and Chemicals Co., Ltd., Megafac F44 4), and a mass of 0.3% by mass of colloidal silica sand as particles A (manufactured by Nissan Chemical Industries, Ltd., 20% by mass aqueous dispersion of Snowtex 0L; average particle diameter 40 nm), 0.5 parts by mass of dry-process cerium oxide as particles B (Japan Aerosil 0X50; average particle diameter: 200 nm, average primary particle diameter: 40 nm), 3.5% by mass of water Dispersions. Then, the pH of the coating liquid was adjusted to 6.2 with a 5 mass% sodium hydrogencarbonate aqueous solution, and the filter was prepared by a blanket type polypropylene filter having a filter particle size (initial filtration efficiency: 95%) of 1 μm. , adjust the coating liquid Κ. The adhesive modified polyester film was obtained in the same manner as in Example 1 except that the coating liquid A was used instead of the coating liquid A, and the coating amount was 〇.05 g/m 2 after drying. Further, the reforming treatment was carried out by a reduced pressure oxygen plasma discharge treatment on the surface without the buildup coating layer. Further, the conditions for the discharge treatment of the reduced-pressure oxygen plasma were 50 W, 2 minutes, and 13.3 Pa (100 - 63 - 2008 35602 mTorr). Then, a hard coat layer was laminated on the reduced pressure oxygen plasma discharge treated surface in the same manner as in Example ι, and an adhesive layer was laminated on the adhesive modification layer in the same manner as in the actual rejection example to obtain a laminated film. . (Comparative Example 6) The coating liquid obtained in the case of obtaining a composite was obtained in the same manner as in Example 4 except that the coating liquid and the liquid shown below were applied at a wet coating amount of 8 g/m 2 . A laminated film. However, in the comparative example, there is no composite dispersion in the boundary between the substrate film and the hard coating layer, and a separate layer from the coating liquid (c) is formed between the substrate and the hard coating layer. The coating liquid for forming (C) was blended as follows. 7.5 parts by mass of the 30% by mass aqueous dispersion of the copolymerized polyester (A) obtained in Example 1, and 11.3 parts by mass of sodium sulfite were used. 20% by mass of the self-crosslinking type polyurethane (B) of the blocked isocyanate group, aqueous solution (manufactured by Daiichi Kogyo Co., Ltd., Elastron H-3), 0.3 parts by mass of catalyst for Elastron (p. An industrial pharmaceutical system, Cat64), 37.9 parts by mass of water^, and 39.6 parts by mass of isopropyl alcohol are mixed. In addition, 3 parts by mass of a fluorine-based well ion-type surfactant (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) , 1 eg 〇 mass % aqueous solution of M egafac F 4 4 4 ), 2.3 parts by mass as particle A 2 〇 mass % aqueous dispersion, 质量. 5 parts by mass of dry process cerium oxide as particle B (Japan Aerosil 0X50; average particle diameter: 200 nm, colloidal cerium oxide (manufactured by Nissan Chemical Industry, Snowtex OL; average particle diameter: 40 nm) An aqueous dispersion of 3.5% by mass of an average primary particle diameter of 40 nm). Then, the pH of the coating liquid was adjusted to 6.2 with a 5 mass% aqueous sodium hydrogencarbonate solution, and the filtered particle size (initial filtration efficiency: 95%) was 10 0 μm blanket type polypropylene filter was carried out -64 - 200835602 Precision filtration, and the coating liquid (C) was adjusted. (Comparative Example 7) No coating layer was provided on the side of the adhesive layer, and it was directly bonded to the thermoplastic resin film. A laminate film was produced in the same manner as in Example 4. (Comparative Example 8) After the coating liquid J was blended on the basis of Table 2, '1% ammonia water was used to adjust the liquid p Η値 to 6.8. P Η値Adjusted coating liquid J • A laminate film was produced in the same manner as in Example 4 except for the coating liquid. The laminate film obtained in each of the examples and the comparative examples was evaluated for the hard coat layer/base film interface. , Example 4 1 5 can be confirmed that the cerium oxide particles (corresponding to the organic-inorganic composite of the present invention) surrounded by the resin containing the copolymerized polyester and the polyurethane are present in the hard coating layer/substrate film The boundary between the two adjacent composites is 500~1000 nm. Regarding the range of the composite, no copolymerized polyester and polyaminocarboxylic acid are observed in the boundary of the hard coating layer/substrate film. Ester resin layer (observation critical enthalpy: 5 nm or less). Further, in Comparative Example 4 and Comparative Example 5, a resin layer containing a composite and a copolymerized polyester and a polyurethane was not observed in the boundary between the hard coat layer/base film. Further, in Comparative Example 6, a separate resin layer containing a plurality of cerium oxide particles and a copolymerized polyester having a thickness of 150 nm and a polyurethane was observed between the hard coat layer/base film, and no observation was observed. Complex. In Comparative Example 7 and Comparative Example 8, it was observed that the organic-inorganic composite body had interference spots on the adhesive layer side. -65- 200835602 [Table 2]
塗 布 液 共聚合聚酯水分散液 鈦化合物 界面 活性 劑 F444 平滑 材 SI80P 液 體 PH 値 聚酯纖 合物 乳酸鈦/三 乙醇胺鈦 絡合物 (A) (B) (C) TC310 TC400 A 13.74 2.51 1.38 0.5 0.5 6.4 65.1/34.9 50.0/50.0 B 13.74 3.02 1.10 0.5 0.5 6.3 65.1/34.9 60.2/39.8 C 13.74 2.00 1.66 0.5 0.5 6.9 65.1/34.9 39.9/60.1 D 10.55 3.60 1.97 0.5 0.5 6.7 50.0/50.0 50.1/49.9 E 16.88 1.44 0.79 0.5 0.5 6.6 80.0/20.0 50.1/49.9 F 11.31 2.22 2.45 0.5 0.5 8.2 53.6/46.4 33.3/66.7 G 18.99 0.73 0.39 0.5 0.5 7.5 90.0/10.0 50.7/49.3 Η 8.44 4.32 2.37 0.5 0.5 6.8 40.0/60.0 50.1/49.9 I 11.31 4.45 1.22 0.5 0.5 4.2 53.6/46.4 66.7/33.3 J 13.74 5.02 0.5 0.5 6.8 65.1/34.9 100.0/0.0Coating Liquid Copolymerization Polyester Aqueous Dispersion Titanium Compound Surfactant F444 Smoothing Material SI80P Liquid PH 値 Polyester Resin Titanium Lactate/Triethanolamine Titanium Complex (A) (B) (C) TC310 TC400 A 13.74 2.51 1.38 0.5 0.5 6.4 65.1/34.9 50.0/50.0 B 13.74 3.02 1.10 0.5 0.5 6.3 65.1/34.9 60.2/39.8 C 13.74 2.00 1.66 0.5 0.5 6.9 65.1/34.9 39.9/60.1 D 10.55 3.60 1.97 0.5 0.5 6.7 50.0/50.0 50.1/49.9 E 16.88 1.44 0.79 0.5 0.5 6.6 80.0/20.0 50.1/49.9 F 11.31 2.22 2.45 0.5 0.5 8.2 53.6/46.4 33.3/66.7 G 18.99 0.73 0.39 0.5 0.5 7.5 90.0/10.0 50.7/49.3 Η 8.44 4.32 2.37 0.5 0.5 6.8 40.0/60.0 50.1/49.9 I 11.31 4.45 1.22 0.5 0.5 4.2 53.6/46.4 66.7/33.3 J 13.74 5.02 0.5 0.5 6.8 65.1/34.9 100.0/0.0
-66 - 200835602 【表3】-66 - 200835602 [Table 3]
硬塗側 黏合劑層側 硬塗 複 硬塗 與硬塗 黏合 黏合 塗 濕式塗 塗 乾燥塗 層之 合 側干 層之密 劑層 劑層 布 布量 布 布量 折射 Μ 涉斑 接性 側干 之剝 液 (g/m2) 液 (g/m2) 率 (%) 涉斑 離性 實施例4 a 5 A 0.11 1.65 有 ◎ 98 ◎ ◎ 實施例5 a 9 A 0.11 1.65 有 ◎ 100 ◎ ◎ 實施例6 a 5 A 0.11 1.60 有 ◎ 100 ◎ ◎ 實施例7 a 5 A 0.11 1.58 有 〇 100 ◎ ◎ 實施例8 a 5 B 0.11 1.65 有 ◎ 100 ◎ ◎ 實施例9 a 5 C 0.11 1.65 有 ◎ 100 〇 ◎ 實施例10 a 5 D 0.11 1.65 有 ◎ 100 〇 ◎ 實施例12 a 5 E 0.11 1.65 有 ◎ 100 〇 ◎ 實施例13 a 5 F 0.11 1.65 有 ◎ 100 〇 Δ 實施例14 a 5 G 0.11 1.65 有 ◎ 100 Δ Δ 實施例15 a 5 H 0.11 1.65 有 ◎ 100 〇 Δ 實施例16 a 5 I 0.11 1.65 有 ◎ 100 〇 Δ 比較例4 - - A 0.11 1.65 - ◎ 3 ◎ ◎ 比較例5 - - K 0.05 1.65 - ◎ 65 X 〇 比較例6 c 8 A 0.11 1.65 &E /\\\ X 100 ◎ ◎ 比較例7 a 5 - 1.65 有 ◎ 100 X X 比較例8 a 5 J 0.11 1.65 有 ◎ 100 X Δ [產業上之利用價値] 本發明之硬塗布膜，由於可一邊維持實用的密接性， 且同時特別是即使於三波長螢光燈下干涉斑少，就作爲、液 晶顯示裝置或電漿顯示裝置等顯示裝置用途之構件，例如 積層防止反射層或防污層所成的光學機能性膜之基材，就 提高視認性而言極爲有用。 -67 -Hard coating side adhesive layer side hard coating hard coating and hard coating adhesion bonding wet coating dry coating layer side layer of dense layer layer layer cloth cloth cloth amount refraction 涉 斑 接 侧 侧 侧Stripping liquid (g/m2) liquid (g/m2) rate (%) plaque-off example 4 a 5 A 0.11 1.65 ◎ 98 ◎ ◎ Example 5 a 9 A 0.11 1.65 ◎ 100 ◎ ◎ Example 6 a 5 A 0.11 1.60 ◎ 100 ◎ ◎ Example 7 a 5 A 0.11 1.58 〇 100 ◎ ◎ Example 8 a 5 B 0.11 1.65 ◎ 100 ◎ ◎ Example 9 a 5 C 0.11 1.65 ◎ 100 〇 ◎ Example 10 a 5 D 0.11 1.65 ◎ 100 〇 ◎ Example 12 a 5 E 0.11 1.65 ◎ 100 〇 ◎ Example 13 a 5 F 0.11 1.65 ◎ 100 〇 Δ Example 14 a 5 G 0.11 1.65 ◎ 100 Δ Δ Example 15 a 5 H 0.11 1.65 ◎ 100 〇 Δ Example 16 a 5 I 0.11 1.65 ◎ 100 〇 Δ Comparative Example 4 - - A 0.11 1.65 - ◎ 3 ◎ ◎ Comparative Example 5 - - K 0.05 1.65 - ◎ 65 X 〇 Comparative Example 6 c 8 A 0.11 1.65 & E /\\\ X 100 ◎ ◎ Comparative Example 7 a 5 - 1.65 ◎ 1 00 XX Comparative Example 8 a 5 J 0.11 1.65 ◎ 100 X Δ [Industrial use price 値] The hard coating film of the present invention maintains practical adhesion while at the same time, especially even under a three-wavelength fluorescent lamp When the number of interference spots is small, it is useful as a member for a display device such as a liquid crystal display device or a plasma display device, for example, a substrate for an optical functional film formed by laminating an antireflection layer or an antifouling layer, and is extremely useful for improving visibility. . -67 -