TW201132722A - Adhesive optical film and image display device - Google Patents

Adhesive optical film and image display device Download PDF

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Publication number
TW201132722A
TW201132722A TW100102827A TW100102827A TW201132722A TW 201132722 A TW201132722 A TW 201132722A TW 100102827 A TW100102827 A TW 100102827A TW 100102827 A TW100102827 A TW 100102827A TW 201132722 A TW201132722 A TW 201132722A
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Taiwan
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adhesive
optical film
polymer
film
layer
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TW100102827A
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Chinese (zh)
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Masakuni Fujita
Akiko Sugino
Arata Fujihara
Masayuki Satake
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Nitto Denko Corp
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Publication of TW201132722A publication Critical patent/TW201132722A/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2451/00—Presence of graft polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2453/00—Presence of block copolymer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Laminated Bodies (AREA)

Abstract

Provided is an adhesive optical film in which an adhesive layer is disposed on an optical film with an undercoat layer interposed therebetween. The adhesive layer is formed from an adhesive containing, as the base polymer, a block copolymer or graft copolymer comprising (meth)acrylic polymer (A) segments having a glass transition temperature of 0 C or less and (meth)acrylic polymer (B) segments having a glass transition temperature of 40 C or more. The undercoat layer contains polymers. The adhesive optical film has initial and long-term reworkability and durability.

Description

201132722 六、發明說明： 【發明所屬技術領域】 發明領域 本發明係有關於一種黏著型光學薄膜。此外還有關於 使用該黏著型光學薄膜之液晶顯示裝置、有機el顯示裝 置、CRT、及PDP等影像顯示裝置。作為前述光學薄膜，例 如有偏光板、位相差板、光學補償薄膜、增亮膜(luminance improving film)、以及積層有該等之膜等。 尤其，當光學薄膜具有液晶光學補償層時，可有效地 作為用以改善顯示對比及顯示色之視角特性之光學補償薄 膜，此外，積層有偏光子者可有效地作為附光學補償功能 的橢圓偏光板。當中，又以液晶光學補償層可有效地利用 在配向有盤形液晶化合物之盤形波晶層。 C先前技術3 發明背景 液晶顯示器等必須從其影像形成方式在液晶格兩側配 置偏光元件，一般是黏貼有偏光板。又，液晶面板除偏光 板以外’為提升顯示器之顯示品質而逐漸開始使用各種光 學元件。例如’有使用作為著色防止的位相差板、用以改 善液晶顯示器視角之視角擴大薄膜、此外還有用以提高顯 示器對比之增亮膜等。該等薄膜總稱為光學薄膜。 將前述光學薄膜黏貼到液晶格時，通常是使用黏著 劑。又，光學薄膜與液晶格及光學薄膜間之接著，通常β 使用黏著劑來密封各個材料以減低光之損失。屆時，由於 201132722 黏者劑具有無料以乾燥步驟使光學薄mm定等優點，因 此’黏著劑-料㈣料衫㈣解面設 著劑層的黏著型光學薄膜。 卞為黏 作為月】述黏著劑所必須具備的必要特性，例如有 將光學薄膜貼合到液晶面板表面時，即使在貼錯貼合位 置]或在貼合面貼_異物諸況下，亦可未殘留糊膠將 光學薄膜魏晶面板表面_並再次貼合(㈣(feworl^ ; 及(2)在作為環蚊進試驗通f進行的加熱及加料耐久試 驗，不會有歸咎於點著劑之問題產生等。X，就再製性而 5，在結束作為影像顯示裝置之使用功用時，從環境對策 一例如再利用或廢棄等—觀點看來，以可輕易從液晶格等 剝離光學薄膜為佳。因此，有關於再製性，以經過長時間 後(例如製造1年後)再利用時，亦可毫無問題地加以再製者 為佳。 作為可滿足前述再製性與耐久性之黏著型光學薄膜， 有&出一種隔著藉由聚胺化合物所形成之定銷層（底塗 層）’在光學薄膜上積層有由具有基底聚合物(含有與胺基起 反應之官能基）之黏著劑所形成之黏著劑層者（專利文獻 1)。在專利文獻1中，前述黏著劑層中之黏著劑與定錨層中 之聚胺化合物係在定錨層中形成混合反應層，並將其混合 反應層厚度設計在定錨層全體層厚的5〇%以上，且定錯層 與黏著劑層之密封性相當良好。因此，在專利文獻丨之黏著 型光學薄膜中，剛製造出黏著型光學薄膜之後(初期）的再製 性可謂良好。但，即使在專利文獻丨之黏著型光學薄膜令， 201132722 經過長時間後的再製性（例如製造1年後之再製性）仍舊 不足。 又，作為形成黏著型光學薄膜之黏著劑層的黏著劑， 有提出使用一種含有由Al-B-A2(但，玻璃轉移溫度在100 °C以上之曱基丙烯酸烷基酯系聚合物（A)鏈段Al、A2、及 玻璃轉移溫度在-20°C以下之丙烯酸烷基酯系聚合物（B)鏈 段)形成之丙烯酸系三嵌段共聚物、且化學上不會交聯的黏 著劑（專利文獻2)。文獻中是有記載使用該黏著劑的黏著型 光學薄膜可耐前述再製性與耐久性。但，自前述黏著劑未 含有交聯劑一點看來，其乃以可省略交聯步驟且具優異生 產性為特徵，因此，黏著劑層與光學薄膜之密封性不夠充 分，且再製性從初期階段起便屬劣質品。 先前技術文獻 專利文獻 專利文獻1 :專利第4007920號說明書 專利文獻2:國際公開2008/065982號冊子 L發明内容3 發明揭示 發明欲解決之課題 本發明係一種在光學薄膜設置有黏著劑層的黏著型光 學薄膜，其目的在於提供一種在初期及經過長時間後之任 一階段中，皆可滿足再製性與耐久性的黏著型光學薄膜。 又，本發明之目的在於提供一種使用前述黏著型光學 薄膜之影像顯示裝置。 201132722 用以解決課題之手段 本韻·明人等在為解決前述課題而精闢研究之下發現， 可藉由卞述黏著梨光學薄膜來達成上述目的而完成本發明。 ，本發明有關於一種黏著型光學薄膜，其係黏著劑 層隔著底塗層設置在光學薄膜者’且其特徵在於：黏著劑 層係由含有嵌段共聚物或接枝共聚物作為基底聚合物之 黏著劑所形成，該等共聚物具有玻璃轉移溫度在o°c以下 之（甲基）雨烯酸系聚合物（A)鏈段及玻璃轉移溫度在4〇t：以 上之（甲基）丙烯酸系聚合物(B)鏈段’且底塗層含有聚合物 類。 在前述黏著型光學薄膜中，以（甲基）丙烯酸系聚合物 鏈段係總單體單元之50重量％以上為丙烯酸烷基酯且（甲基) 丙烯酸系聚合物(B)鏈段係總單體單元之15重量％以上為甲 基丙烯酸烷基酯為佳。 在前述黏著型光學薄膜中，黏著劑所含有之基底聚合 物為B-A-B之三嵌段共聚物(但’ A表示（曱基）丙烯酸系聚合 物（A)鏈段，且B表示（甲基）丙烯酸系聚合物（B)鏈段）為 佳。 在前述黏著型光學薄膜中，以底塗層之聚合物類為末 端具有1級胺基之聚合物為佳。又，以末端具有丨級胺基之 聚合物為於末端具有丨級胺基之聚（甲基）丙烯酸酯為佳。 又，末端具有1級胺基之聚合物中之1級胺基以來自於聚乙 烯亞胺系材料者為佳。 在别述黏著型光學薄膜中，底塗層相對於聚合物頬10〇 201132722 重量份以含有抗氧化劑〇·〇1〜5〇〇重量份為佳。 作為前述抗氧化劑，以選自苯酴系、構系、硫系及胺 系之抗氧化劑中之至少任丨種為佳。 i述黏著型光n膜宜為：前述光學薄膜於透明基材 薄膜之早面具有液晶光學補償層，且黏著劑層隔著底塗層 设置於遠液晶光學補償層者。該液晶光學補償層理想為盤 形液晶層。又，前述光學薄膜可適當地使用於在未形成液 晶光學補償層之側的透明基材薄膜之單面積層有偏光子 者。 又，本發明係有關於一種特徵在於使用前述黏著型光 學薄膜之影像顯示裝置。 發明效果 在本發明之黏著型光學薄膜中，係使用特定之嵌段共 聚物或接枝共聚物作為黏著劑層之黏著劑，該等共聚物具 有低玻璃轉移溫度之（甲基）丙稀酸系聚合物(A)鏈段及具有 高玻璃轉移溫度之（曱基）丙烯酸系聚合物(B)鏈段。該嵌段 共聚物或接枝共聚物係以其本身來展現作為黏著劑所要求 之黏著性與凝聚力。因此，雖然該嵌段共聚物或接枝共聚 物無需導入官能基或與交聯劑併用來作使用，但另一方 面’該嵌段共聚物或接枝共聚物對光學薄膜之密封性很差 且無法滿足再製性。 在本發明之黏著型光學薄膜中，藉由隔著底塗層設置 使用上述嵌段共聚物或接枝共聚物之黏著劑層，可在黏著 劑層之形成方面較使用一般具有官能基之交聯型之丙烯酸 201132722 系黏著劑的情況更加提升再製性。尤其，可使經過長時間 後之再製性⑽如製造丨年後之再製性)加以提升。 一通*，從再製性之觀點看來，雖然為了使黏著劑層與 光學4膜之密封性提升而設置有底塗層，但如專利文獻说 載’該底塗層與黏著劑層之密封性係藉由使底塗層與黏著 w日之又方g忐基起反應而進行。因此，在底塗層設置黏 著知丨層使密封性提升時，宜麵著劑層使用具有與底塗層 :之官能基具反應狀官能基的黏著劑。在本發曰月中，很 思外地’在將嵌段共聚物或接枝共聚物使用在黏著劑層 p便4嵌&共聚物或接枝共聚物未有化學性交聯、且 =具有與底塗層之官能基具反應性的官能基，藉由將該黏 =劑層與底塗層予以組合，亦有提⑩㈣丨層與底塗層之 社封f生尤其，在底塗層使用於末端具有以及胺基之聚合物 的it’兄下’光學賴與底塗層之密封性、及底塗層與黏著 劑層之密封性有所提升且再製性亦有提升。此推測是因為 $本發明之著型光學薄财，底塗層與黏著劑層形成混 。層在A合層中形成有底塗射之聚合物類與黏著劑層 黏著ϋ聚合物（嵌段共聚物或接枝共聚物）之物理性交 葬表見出密封性。尤其，在底塗層使用於末端具有1級胺 基之聚α %中於末端具有！級胺基之聚（甲基)丙稀酸醋的情 況下，該聚合物中作為構成單體含有甲基丙烯酸甲酯或甲 基丙烯酸等顯*高玻簡移溫度之成分，因此，與黏著劑 層中之基底聚合物(嵌段共聚物或接枝共聚物）中之玻璃轉 移⑽度在40 c以上的（甲基）丙烯酸系聚合物(β)鏈段（顯示 201132722 高玻璃轉移溫度之鏈段)之凝聚形成有物理性交聯。即， 使用具有習知官能基之丙烯酸系聚合物.之交聯物的黏著型 光學薄膜相較之下，本發明之黏著型光學薄膜作為黏著叫 層可更加大幅提升光學薄膜與黏著劑層之密封性，是因為 在本發明之黏著型光學薄膜中，黏著劑層與底塗層之密封 性並非如習知之黏著型光學薄膜藉由官能基含有成分之化 學交聯而形成者，而是因形成有較牢固的物理交聯所致。 圖式簡單說明 第1圖係本發明之黏著型光學薄膜之一例的剖面圖。 第2圖係本發明之黏著型光學薄膜之一例的剖面圖。 第3圖係本發明之黏著型光學薄膜之一例的剖面圖。 【實施方式3 用以實施發明之形態 以下，將參考圖式説明本發明。如第1圖顯示，例如 本發明之黏著型光學薄膜在光學薄膜A之單面隔著底塗層 B設置有黏著劑層C。第1圖中，雖在光學薄膜八之單面隔著 底塗層B設置有黏著劑層C，但亦可在另一單面隔有戋未隔 有與底塗層B相同或相異的底塗層，設置與黏著劑層c相同 或相異的黏著劑層。 第2圖中，本發明之黏著型光學薄膜係光學薄膜A在透 明基材薄膜Al 1之單面具有液晶光學補償層（例如，盤形液 晶層）A13之態樣，於該液晶光學補償層A13上隔著底塗層b 設置有黏著劑層C。在第2圖，雖例示出在透明基材薄膜A11 與液晶光學補償層A13之間設置配向膜a 12的態樣，但亦可 201132722 使用將透明基材薄膜All之單面作為摩擦處理者來替代配 向膜A12。 第3圖係在第2圖之黏著型光學薄膜中，使用於未形成 液晶光學補償層A13之側的透明基材薄膜Au之翠面積層 有偏光子A14、接著積層有透明保護薄膜Au者的態樣。第 3圖中，透明基材薄臈A11亦兼具偏光子AM之透明保護 薄膜。 以下將詳細説明本發明之黏著型光學薄膜之各構成。 在本發明之黏著劑層之形成係使用作為基底聚合物含 有具有玻璃轉移;盈度在(TCa下之（甲基)丙稀酸系&合物㈧ 鏈段、及玻璃轉移溫度在4(TC以上之（曱基）丙烯酸系聚合物 (B)鏈段的嵌段共聚物或接枝共聚物之黏著劑。 又’（甲基）丙稀酸系聚合物(A)鍵段之玻璃轉移溫度在〇 C以下，可在通常的使用溫度中，對被附體賦予可濕性與 作為黏著劑之柔軟性，以使在本發明之黏著劑層呈現接著 力。（曱基）丙烯酸系聚合物(Λ)鏈段之玻璃轉移溫度在_2(rc 以下為佳，較佳在_3〇。(：以下，通常，玻璃轉移溫度在_7〇 C以上要（曱基）丙烯酸系聚合物(A)鏈段之玻璃轉移溫 度在20 C以下，就低溫條件下之耐久性相當良好之觀點而 言相當適合。 刖述（甲基）丙烯酸系聚合物鏈段之玻璃轉移溫度在 40C以上，可在通常的使用溫度中賦予凝聚力，並可在本 發明之黏㈣1層表現良好的黏著特性與敵性。（f基）丙稀 酸系聚合物(B)鏈段之玻璃轉移溫度在8〇β(：以上為佳，較佳 10 ⑤ 201132722 在ioo°c以上，通常，玻璃轉移溫度在150°c以下。只要（曱 基）丙稀酸系聚合物(B)鏈段之玻璃轉移溫度在8〇。(^以上，就 咼溫條件下之耐久性相當良好之觀點而言相當適合。 前述嵌段共聚物或接枝共聚物可使用具有前述（曱基) 丙烯酸系聚合物(A)鏈段及（曱基）丙烯酸系聚合物⑻鏈段 者。例如，若將（甲基）丙烯酸系聚合物(A)鏈段設為A、且 將（曱基）丙烯酸系聚合物(B)鏈段設為B分別顯示，就嵌段共 聚物而言’例如有：以A-B表現之二嵌段共聚物、以A-B-A、 與B-A-B表現之三嵌段共聚物、此外還有四彼段共聚物、及 其以上將A、B予以組合者。又，就接枝共聚物而言，例如 有將A或B作為主鏈且將不同於主鏈之鏈段作為側鏈者。 而’ A、B有2個以上時，各A、B可相同亦可不同。 作為本發明之黏著劑之基底聚合物，雖然可使用前述 嵌段共聚物或接枝共聚物’但從易於控制玻璃轉移溫度與 分子量之觀點看來，以嵌段共聚物為佳◊嵌段共聚物之中， 從更易於控制黏著特性與主體性質（bulk properties)之觀點 看來，又以使用以B-A-B表現之三嵌段共聚物為佳。 前述嵌段共聚物或接枝共聚物之重量平均分子量為 50000〜3〇0000 ’從耐久性與再製性之兩者觀點看來，以 60000〜250000為佳、以70000〜230000較佳，且以 70000〜200000更佳。當分子量小於50000時’點著劑之凝聚 力會不夠充分，且在貼合光學薄膜使用時，耐久性會很差。 又，當分子量大於300000時，由於需要時間使黏著劑沾濕 被附體，因此在製造品之保管中會使可濕性進展而使接著 11 201132722 力上昇變得難以進行再製。 嵌段共聚物或接枝共聚物之分子量分布（Mw/Mn)為 1.0〜1.5，從在高溫之凝聚力很高且具優異耐久性之觀點看 來，以1.0-1.4為佳、且以1.0〜1.3較佳。 作為（曱基）丙烯酸系聚合物（A)鏈段之主單體單元之 (甲基）丙烯酸烷基酯，例如有烷基之碳數在1〜18之（曱基） 丙稀酸烧基S旨。而，（曱基）丙稀酸烧基S旨乃指丙稀酸烧基酉旨 及/或曱基丙烯酸烷基酯，本發明之（甲基）為同樣意思。具 體而言，例如有：（曱基）丙烯酸甲酯、（甲基）丙烯酸乙酯、 (曱基）丙烯酸丙酯、（甲基）丙烯酸η-丁酯、（甲基）丙烯酸t-丁酯、（曱基）丙烯酸η-己酯、（曱基）丙烯酸環己酯、（曱基) 丙烯酸2-乙基己酯、（甲基).丙烯酸η-辛酯、（甲基）丙烯酸十 二酯、（曱基）丙烯酸十三酯、（曱基）丙烯酸十八酯等（甲基) 丙烯酸烷基酯。該等可單獨使用、或組合2種類以上使用。 (曱基）丙烯酸系聚合物(Α)鏈段只要是以（曱基）丙烯酸 烷基酯為單體單元之主要成分且含有總單體單元之90重量 %以上（理想為95重量°/〇以上）、並滿足玻璃轉移溫度在0°C 以下者，在單體單元之種類或成分組成方面即未有特別限 制，但（曱基）丙烯酸系聚合物(A)鏈段以丙烯酸烷基酯為主 單體單元為佳。（甲基）丙烯酸系聚合物(A)鏈段在總單體單 元之50重量％以上、或是60重量％以上、還是70重量％以上 為丙烯酸烷基酯者，以有控制玻璃轉移溫度為佳。作為前 述（甲基）丙烯酸系聚合物(A)鏈段中之主單體單元之丙烯酸 烧基醋，在前述例示中亦以丙稀酸丙S旨、丙稀酸η- 丁醋、 12 ⑤ 201132722 丙稀酸2-乙基己酯、丙稀酸η-辛酯等院基碳數為1〜9之丙烯 酸烷基酯為佳。 從可獲得穩定的接著力與耐久性之觀點看來，前述嵌 段共聚物或接枝共聚物中之（甲基）丙烯酸系聚合物(Α)鏈段 之重量比以50%〜95%為佳，且以60〇/〇〜85〇/〇較佳。（甲基）丙 烯酸系聚合物(Α)鏈段之重量比低於50〇/〇時，接著力容易變 低。又，（甲基）丙稀酸系聚合物(Α)鏈段之重量比高於95% 時，由於（曱基）丙烯酸系聚合物(Β)鏈段之比例較少，因此 凝聚力會降低，且在耐久性之觀點上不宜作為光學薄膜用 黏著劑使用。 作為（甲基）丙烯酸系聚合物（Β)鏈段之主單體單元之 (曱基）丙烯酸烧基酯，例如有烧基碳數為1〜18之（甲基）丙烯 酸烷基酯。具體而言，舉如有：（甲基）丙烯酸甲酯、（甲基） 丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙烯酸η_丁酯、（甲 基）丙烯酸t-丁酯、（曱基）丙烯酸η_己酯、（甲基）丙烯酸環己 酯、（甲基）丙稀酸2-乙基己酯、（甲基）丙稀酸η_辛酯、（甲基） 丙烯酸十二酯、（甲基）丙烯酸十三酯、（曱基）丙烯酸十八 S曰、及（甲基）丙稀酸異灰醋等（甲基）丙稀酸院基醋。該等可 單獨使用、或組合2種類以上使用。 (甲基）丙烯酸系聚合物(Β)鏈段只要是以（甲基）丙烯酸 烷基酯為單體單元之主要成分且含有總單體單元之90重量 %以上（理想為95重量％以上）、並滿足玻璃轉移溫度在4〇〇c 以上者’在卓體單元之種類或成分組成方面即未有特別限 制’但總单體單元之15重量％以上、或是20重量％以上、還 13 201132722 是3〇重量％以上為曱基丙稀酸烧基§旨者，以有控制坡璃轉 移溫度為佳。作為前述（甲基）丙稀酸系聚合物⑼鍵段令之 主單體單元之曱基丙烯酸烷基酯，在前述例示中亦以曱基 丙彿酸曱s旨、曱基丙_乙自旨等院基碳數為卜2之曱基丙二 酸烷基酯為佳。 而，則述嵌4又共聚物或接枝共聚物中之（甲基）丙稀酸系 聚合物(B)鏈段之重量比，為上述（甲基）丙烯酸系聚合物(A) 鍵段以外之比例。 只要前述（曱基）丙烯酸系聚合物鏈段、（曱基）丙烯 酸系聚合物(B)鏈段在各鏈段之總單體單元之10重量％以下 範圍内，亦可含有前述（曱基）丙烯酸烷基酯以外之其他單體 單元。作為前述其他單體單元，例如有：甲基丙烯酸甲氧 乙酯、甲基丙烯酸乙氧乙酯、（甲基）丙烯酸二乙胺乙酯、（甲 基）丙烯酸2-羥乙酯、（甲基）丙烯酸2_胺乙酯、（甲基）丙烯酸 環氧丙酯、（甲基）丙烯酸四氫糠酯等具有官能基之（甲基）丙 浠酸酯；（甲基）丙烯酸、丁烯酸、丁稀二酸、順丁烯二酐、 反丁烯二酸等具有羧基之乙烯基系單體；（甲基）丙烯醯胺等 具有酿胺基之乙稀基系单體；苯乙稀、α -甲苯乙稀、P_甲 苯乙稀等芳香族乙烯基系單體；丁二烯、異戊二烯等共輛 二烯系單體；乙烯、丙烯等烯烴系單體；及，ε-己内酯、 戊内醋等内醋系早體專。該等例如可單獨、或可組合2種類 以上。 前述嵌段共聚物或接枝共聚物之製造方法在可獲得具 有前述（甲基）丙烯酸系聚合物(Α)鏈段、與（甲基）丙烯酸系 201132722 聚合物(B)鏈段之嵌段共聚物或接枝共聚物的情況下，並未 有特別限定，可採用依據公知手法之方法。一般在獲得分 子量分布狹窄的嵌段共聚物之方法係採用將構成單元之單 體予以活性聚合(living polymerize)之方法。作為此種活性 聚合之手法，例如有：將有機稀土金屬錯合體作為聚合反 應起始劑加以聚合之方法(特開平6-93060號公報）、將有機 鹼金屬化合物作為聚合反應起始劑，在鹼金屬或鹼土金屬 之鹽等礦酸鹽存在下加以陰離子聚合之方法（參考特公平 7-25859號公報）、將有機驗金屬化合物作為聚合反應起始 劑，在有機鋁化合物之存在下加以陰離子聚合之方法(特開 平11-335432號公報）、及原子轉移自由基聚合方法 (ATRP)(MaCrom〇i. Chem phys 2〇1 11〇8〜ιιΐ4頁(2咖年) 等。又’就獲得接枝共聚物之方法而言，舉如有專利第 4228026號說明書等中記載之方法。 上述製造方法之中，在將有機紹化合物作為除催化劑 之陰離子聚合方法的情況，由於在聚合期間之失活很少， 因此少有失活成分之均聚物的混入 劑之透明性很高。又，s 所獲 η X，由於早體之聚合轉化率很高因此 製造品中少有殘存單體，且可 用時，抑制貼合後之氣、、包生“：九千4膜用黏者劑使 段塊之分子結構會變成高=: rrm果Γ用於光學薄膜㈣著劑的情況下提高 而才久f生之政果。而且，妁 從了在較緩和的溫度 性聚合之觀點看來，於工業生產上具有少有環境負荷(主要 15 201132722 是消耗在用以控制聚合溫度之冷凍機的電力）之優點。 作為在上述有機鋁化合物之存在下之陰離子聚合方 法，例如可採用：在以有機鋰化合物、及以下述一般式G): air'r2r3---(i) (式中’ R1、R2及R3可為分別獨立且表示可具有取代基之烷 基、可具有取代基之環烷基、可具有取代基之芳香族基、 可具有取代基之芳烷基、可具有取代基之烷氧基、及可具 有取代基之芳氧基或N，N-二取代胺基，或是R1為表示前述 之任一基、且R2及R3 —起表示可具有取代基之亞芳二氧基 (arylenedioxy))所表現之有機紹化合物之存在下，視需求還 於反應系内使用二曱醚、二曱氧乙烷、二乙氧乙烷、12_冠 醚-4等乙醚；及三乙胺、N，N，N，，N，_四甲基乙二胺、 n，n，n’，N，，，n，，-五甲基二乙駐胺、u，4,7，1〇，i〇_六甲基三 乙烯四胺、吡啶、2,2，-聯吡啶等含氮化合物使（甲基）丙烯酸 酯聚合之方法等。 作為上述有機鋰化合物，例如有：甲基鋰、乙基鋰、 η-丙基链、異丙基鐘、n_ 丁基鐘、•丁基鐘、異丁基經、 tert-丁基鋰、n_戊基鋰、n_己基鋰、四亞甲基二鋰、五亞甲 基-鐘、六亞甲基二鍾等烧基鐘及炫二經；苯基鐘、…甲 苯基鐘、ρ·甲苯隸、二曱笨基鐘、料衫香基鐘及芳 香基二鋰；二苯基乙二酮鋰、二苯甲基鋰、三苯甲基鋰、 l’l-二苯基_3_甲基戊基經、甲基笨乙稀基鐘及由二異 丙烯苯與了基狀反應*生成之二料芳絲較芳烧基 二鋰；鋰二甲基乙酰胺、鋰二乙基乙酰胺、鋰二異丙基： ⑤ 16 201132722 跌胺等鐘胺；以及甲氧基链、乙氧基經、η-丙氧基鐘、異 丙氧基經、η_τ氧基鐘'丁氧基鐘、如_ 丁氧基鐘戊 氧基鋰G乳基鐘、庚氧基鐘、辛氧基經、苯氧基鐘、* 甲基錢基鐘、苯甲氧絲、4_甲基笨曱氧基鐘等醇鐘。 該等可單獨使用，亦可2種以上併用。 —又作為以上述—般式表示之有機紹化合物，例如有： 三甲基鋁、三乙基鋁、三n-丁基紹、三s·丁基鋁、三t•丁基 鋁、三異丁基链、三己基紹、三n_辛基紹、三2_乙基己二 鋁、及三苯基紹等三烧基紹；二甲基(2,6二抓丁基^ 基苯氧基)!呂、二甲基(2,6-二-齡丁苯氧基)銘二乙基Μ 一侧·丁基冰甲基苯氧基)紹、二乙基(2,6-二输丁苯氧 基)铭、二異丁基(2,6_二咖·丁基_4_子基苯氧基飧、二異 丁基(2,6-二她丁苯氧基)紹、二_η·辛基(2,6二侧·丁其 冰甲基苯氧卵呂、及二·η_辛基(2,6_二侧_丁苯氧難呂等 二烧基苯氧絲；甲基雙(2,6_二侧_ 丁基_4_甲基苯氧基） 鋁、甲基雙(2,6-二-tert_丁苯氧基)紹、乙基[2,2，_亞甲德(4 甲基如ert-丁苯氧基⑽呂、乙基雙(2,6_二佩丁基·4•甲苯 氧基)链、乙基雙(2,6_二侧·丁苯氧基)紹、乙基[2,2，_亞甲 雙⑷甲基冬祕丁笨氧基)]紹、異丁基雙似二姻·丁基 冰甲基苯氧基)紹、異丁基雙(2,6_二挪丁苯氧細 丁基[2,2，-亞甲雙(4_甲基_6姻丁苯氧基胁、n辛基雙 (2’f 丁基基苯氧基)紹、η辛基雙(2,6_二_祕 丁本乳基)紹、及η-辛基[2,2，_亞甲雙(4_，基_6侧·丁苯氧 基)]銘等炫基二苯氧基紹；甲氧雙(2,6_二姻丁基冰甲基 17 201132722 苯氧基)紹甲氧雙(2,6-二-tert.丁苯氧基)銘甲氧基[2,2，_ 亞f雙（4-甲基冬祕丁苯氧基)]紹、乙氧雙（2,6二侧丁 基-4-甲基苯氧轴、乙氧雙(2,6_:撼丁苯氧基)銘、乙 氧基[2,2，-亞甲雙(4_甲基·6侧_ 丁苯氧基胁、異丙氧雙 (2=二姻-丁基冰甲基苯氧基)紹、異丙氧雙〇二_祕 丁苯氧基）鋁、異丙氧基[2,2，_亞甲雙(4_甲基《eA 丁苯氧 基)]紹、祕丁氧雙(2,6_二彻_丁基冬甲基苯氧基)紹、加_ 丁氧雙(2,6-二抓丁苯氧基)紹、及_•丁氧基[2,2，_亞甲雙 (4-甲基-6-tert-丁苯氧基)]鋁等烷氧基二苯氧基鋁；以及三 (2,6-二-tert_丁基_4_甲基苯氧基)紹、三(2,6二苯基苯氧基） 鋁等三苯氧基鋁等。該等有機鋁化合物之中，又以異丁基 雙(2,6-二-tert-丁基-4-甲基苯氧基)鋁、異丁基雙(2 6二-如卜 丁苯氧基）鋁、及異丁基[2,2，-亞甲雙(4_曱基_6_tert_ 丁苯氧 基)]銘等較容易使用，又，在比較緩和的溫度條件下不會失 活且可進行丙烯酸酯之聚合之觀點上尤佳。該等可單獨使 用’亦可2種以上併用。 而，形成本發明之黏著劑層的黏著劑中，除前述嵌段 共聚物或接枝共聚物以外，可視需求使用異氰酸酯化合物 等交聯劑、增黏劑、塑化劑、玻璃纖維、玻璃珠、金屬粉、 以及從其他無機粉末等形成之填充劑、顏料、著色劑、填 充劑、抗氧化劑、紫外線吸收劑、矽烷耦合劑等又，在 未脫離本發明之目的範圍内，亦可適當使用各種添加劑。 又，亦可作為含有微粒子顯示光學擴散性之黏著劑層等。 底塗層係由含有聚合物類及抗氧化劑之底塗劑形成。 18 ⑤ 201132722 月’j述聚合物類之材料以對黏著劑層與光學薄膜(例如，液晶 光學補償層）任一者皆顯示良好的密封性、且形成具良好凝 聚力之皮膜者為佳。 作為前述聚合物類，可舉如聚胺酯系樹脂、聚酯系樹 脂、以及在分子中包含胺基之聚合物類。聚合物類之使用 形態可為溶劑可溶型、水分散型、或水溶解型其中一者。 例如有：水溶性聚胺酯、水溶性聚酯、水溶性聚醯胺等、 或水分散型樹脂（乙烯-酢酸乙烯基系乳化、（甲基）丙烯酸系 乳化等）。又，水分散型可使用以乳化劑將聚胺酯、聚酯、 聚醯胺等各種樹脂予以乳化者、或將水分散性親水基之陰 離子基、陽離子基或非離子基導入前述樹脂中而作為自乳 化（self-emulsification)物者等。又，可使用離子高分子錯 合體。 例如’該聚合物類在黏著劑層含有異氰酸酯系化合物 時’以具有與異氰酸酯系化合物具反應性之官能基者為 佳。作為前述聚合物類’以在分子中含有胺基之聚合物類 為佳。尤其，適合使用於末端具有1級胺基者，藉由與異氰 酸酯系化合物之反應可更牢固地密封並提升耐久性。於末 端具有1級胺基之聚合物，以於末端具有1級胺基之聚（曱基） 丙烯酸酯為佳。 作為在分子中含有胺基之聚合物類，例如有：聚乙烯 亞胺系、聚烯丙胺系、聚乙烯胺系、聚乙烯吡啶系、聚乙 烯吡咯啶系、二曱胺乙基丙烯酸酯等含胺基含有單體之聚 合物等。該等之中又以聚乙烯亞胺系為佳。作為聚乙烯亞 201132722 胺系材料只要為具有聚乙烯亞胺結構者即可，例如可為： 聚乙稀亞胺、加人聚丙烯酸g旨之伸乙亞胺加祕及/或聚乙 烯亞胺加成物。尤其，以於末端具^級胺基之聚（曱基）丙 烯酸醋之加人聚丙烯_之伸乙亞胺加成物及/或聚乙稀 亞胺加成物為宜。 聚乙稀亞胺並未有特別限制，可使用各種物。聚乙稀 亞胺之重量平均分子量縣树龍制，通妓在⑽〜1〇〇 萬左右。例如，就聚乙烯亞胺之市售品之例而言，可舉如 株式會社日本觸媒社製之Ep〇MlN sp系列（Sp_〇〇3、201132722 VI. Description of the Invention: Field of the Invention The present invention relates to an adhesive optical film. Further, there are also image display devices such as liquid crystal display devices, organic EL display devices, CRTs, and PDPs using the adhesive optical film. Examples of the optical film include a polarizing plate, a phase difference plate, an optical compensation film, a luminance improving film, and a film in which these layers are laminated. In particular, when the optical film has a liquid crystal optical compensation layer, it can be effectively used as an optical compensation film for improving the viewing contrast and viewing angle characteristics of the display color. In addition, a laminated photon can be effectively used as an elliptically polarized light with optical compensation function. board. Among them, the liquid crystal optical compensation layer can effectively utilize the disc-shaped crystal layer in the alignment with the discotic liquid crystal compound. C. Prior Art 3 Background of the Invention A liquid crystal display or the like must be provided with a polarizing element on both sides of a liquid crystal cell from its image forming mode, and a polarizing plate is generally adhered. Further, in addition to the polarizing plate, the liquid crystal panel has gradually begun to use various optical components in order to improve the display quality of the display. For example, there are a phase difference plate which is used as a coloring prevention, a viewing angle expansion film for improving the viewing angle of the liquid crystal display, and a brightness enhancement film for improving the contrast of the display. These films are collectively referred to as optical films. When the aforementioned optical film is adhered to the liquid crystal cell, an adhesive is usually used. Further, after the optical film and the liquid crystal cell and the optical film are followed, β is usually sealed with an adhesive to reduce the loss of light. At that time, since the 201132722 adhesive has the advantage of drying the optical thin mm by the drying step, the adhesive-material (4) shirt (4) is provided with an adhesive optical film of the agent layer.卞 is sticky. It is a necessary feature of the adhesive. For example, when the optical film is attached to the surface of the liquid crystal panel, even if it is attached to the wrong position, or when the adhesive surface is attached to the foreign matter, The surface of the optical film Weijing panel can be left unattached to the adhesive layer ((4) (feworl^; and (2) in the heating and feeding endurance test as a loop mosquito test, no blame on the point The problem of the agent is generated, etc. X is remanufacturable. 5. When the function of the image display device is completed, the optical film can be easily peeled off from the liquid crystal cell or the like from the viewpoint of environmental measures such as reuse or disposal. Therefore, it is preferable that the remanufacturing property is re-manufactured without any problem after a long period of time (for example, after one year of manufacture). It is an adhesive type that satisfies the aforementioned remanufacturability and durability. An optical film having <a kind of pinning layer (undercoat layer) formed by a polyamine compound is laminated on the optical film by having a base polymer (containing a functional group reactive with an amine group) Adhesive formation Adhesive layer (Patent Document 1). In Patent Document 1, the adhesive in the adhesive layer and the polyamine compound in the anchor layer form a mixed reaction layer in the anchor layer, and the reaction layer is mixed. The thickness is designed to be more than 5% by weight of the entire layer of the anchor layer, and the sealing property of the fixing layer and the adhesive layer is quite good. Therefore, in the adhesive optical film of the patent document, the adhesive optical film is just manufactured. (Reproduction) The remanufacturing property is good. However, even in the adhesive optical film of the patent document, the remanufacturing after a long period of time (for example, the remanufacturing after one year of manufacture) is still insufficient. For the adhesive of the adhesive layer of the optical film, it is proposed to use an alkyl group-containing polymer (A) having a chain of Al, A2, which is composed of Al-B-A2 (but, a glass transition temperature of 100 ° C or higher). And an acrylic triblock copolymer formed by an alkyl acrylate polymer (B) segment having a glass transition temperature of -20 ° C or less and an adhesive which is not chemically crosslinked (Patent Document 2) There is a record in the literature. The adhesive type optical film using the adhesive is resistant to the above-mentioned reworkability and durability. However, since the above-mentioned adhesive does not contain a crosslinking agent, it is characterized in that the crosslinking step can be omitted and excellent productivity is exhibited. The sealing property of the adhesive layer and the optical film is insufficient, and the remanufacturing property is inferior from the initial stage. PRIOR ART DOCUMENT Patent Document Patent Document 1: Patent No. 4079920 Patent Document 2: International Publication 2008/065982 SUMMARY OF THE INVENTION The present invention is an adhesive optical film in which an adhesive layer is provided on an optical film, and an object thereof is to provide an adhesive film which can be satisfied in any stage at an initial stage and after a long period of time. An adhesive optical film having reproducibility and durability. It is another object of the invention to provide an image display device using the above-mentioned adhesive optical film. 201132722 Means for Solving the Problem In order to solve the above problems, the present inventors have found that the present invention can be achieved by repeating the above-described object of the adhesive pear optical film. The present invention relates to an adhesive optical film in which an adhesive layer is disposed on an optical film via an undercoat layer and characterized in that the adhesive layer is polymerized by a block copolymer or a graft copolymer as a substrate. Formed by an adhesive having a glass transition temperature of less than 0 ° C (meth) uronic acid polymer (A) segment and a glass transition temperature of 4 〇 t: or more (methyl The acrylic polymer (B) segment 'and the undercoat layer contains a polymer. In the above-mentioned adhesive optical film, 50% by weight or more of the (meth)acrylic polymer segment-based total monomer unit is an alkyl acrylate and a (meth)acrylic polymer (B) segment is a total It is preferred that 15% by weight or more of the monomer unit is an alkyl methacrylate. In the above adhesive optical film, the base polymer contained in the adhesive is a triblock copolymer of BAB (but 'A represents a (fluorenyl) acrylic polymer (A) segment, and B represents (methyl) The acrylic polymer (B) segment is preferred. In the above-mentioned adhesive optical film, it is preferred that the polymer of the undercoat layer has a polymer having a primary amino group at the terminal end. Further, a polymer having a mercapto amine group at the terminal is preferably a poly(meth)acrylate having a mercapto amine group at the terminal. Further, the first-stage amine group in the polymer having a 1-stage amine group at the end is preferably a material derived from a polyethyleneimine-based material. In the adhesive optical film described above, the undercoat layer is preferably contained in an amount of 1 to 5 parts by weight based on the weight of the polymer 頬 10 〇 201132722 parts by weight. The antioxidant is preferably at least any one selected from the group consisting of benzoquinone, constitution, sulfur and amine antioxidants. Preferably, the optical film is an optical film having a liquid crystal optical compensation layer on the early surface of the transparent substrate film, and the adhesive layer is disposed on the far liquid crystal optical compensation layer via the undercoat layer. The liquid crystal optical compensation layer is desirably a disk-shaped liquid crystal layer. Further, the optical film can be suitably used for a polarizer having a single-layer layer of a transparent base film on the side where the liquid crystal optical compensation layer is not formed. Further, the present invention relates to an image display device characterized by using the above-mentioned adhesive optical film. Advantageous Effects of Invention In the adhesive optical film of the present invention, a specific block copolymer or a graft copolymer is used as an adhesive for an adhesive layer having a low glass transition temperature of (meth)acrylic acid. A polymer (A) segment and a (fluorenyl) acrylic polymer (B) segment having a high glass transition temperature. The block copolymer or graft copolymer exhibits the adhesion and cohesive force required as an adhesive by itself. Therefore, although the block copolymer or graft copolymer does not need to be introduced into a functional group or used with a crosslinking agent, on the other hand, the block copolymer or graft copolymer has poor sealing properties to an optical film. And can not meet the remanufacturability. In the adhesive optical film of the present invention, by using the adhesive layer of the above block copolymer or graft copolymer through the undercoat layer, it is possible to use a functional group in the formation of the adhesive layer. The case of the bonded acrylic 201132722 adhesive is more reproducible. In particular, it is possible to enhance the remanufacturing after a long period of time (10), such as the remanufacturing after the manufacturing year. One pass*, from the viewpoint of remanufacturing, although an undercoat layer is provided for improving the sealing property of the adhesive layer and the optical film 4, as described in the patent literature, the sealing property of the undercoat layer and the adhesive layer is described. This is carried out by reacting the undercoat layer with the other side of the adhesion. Therefore, when the undercoat layer is provided with an adhesive layer to improve the sealing property, it is preferable to use an adhesive having a reactive functional group with a functional group of the undercoat layer. In the first month of the month, it is very interesting to use the block copolymer or graft copolymer in the adhesive layer, and the copolymer or graft copolymer is not chemically crosslinked, and has The reactive functional group of the functional layer of the undercoat layer is combined with the undercoat layer by the adhesive layer and the undercoat layer, and the enamel layer and the undercoat layer are also provided, especially in the undercoat layer. The sealability of the optical layer and the undercoat layer at the end of the polymer having an amine group and the sealing property of the undercoat layer and the adhesive layer are improved and the remanufacturability is also improved. This presumption is due to the fact that the undercoat layer is mixed with the adhesive layer. The physical burial table in which the layer forms a primer-coated polymer and an adhesive layer adhered ruthenium polymer (block copolymer or graft copolymer) in the A-layer is seen as a seal. In particular, the undercoat layer is used at the end of the poly-α% having a terminal amine group at the end! In the case of a polyamine-based poly(methyl) acrylate vinegar, the polymer contains a component of a high glass transition temperature such as methyl methacrylate or methacrylic acid as a constituent monomer, and thus The glass in the base polymer (block copolymer or graft copolymer) in the agent layer transfers (10) (meth)acrylic polymer (β) segments with a degree of 40 c or more (showing 201132722 high glass transition temperature) The agglomeration of the segments forms physical crosslinks. That is, in the case of using an adhesive type optical film having a crosslinked substance of an acrylic polymer having a conventional functional group, the adhesive type optical film of the present invention can greatly enhance the optical film and the adhesive layer as an adhesive layer. The sealing property is because in the adhesive optical film of the present invention, the sealing property of the adhesive layer and the undercoat layer is not formed by chemical crosslinking of a conventional adhesive film according to a functional group-containing component, but Formed by a stronger physical cross-linking. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an example of an adhesive optical film of the present invention. Fig. 2 is a cross-sectional view showing an example of the adhesive optical film of the present invention. Fig. 3 is a cross-sectional view showing an example of the adhesive optical film of the present invention. [Embodiment 3] Mode for Carrying Out the Invention Hereinafter, the present invention will be described with reference to the drawings. As shown in Fig. 1, for example, the adhesive optical film of the present invention is provided with an adhesive layer C on the single side of the optical film A via the undercoat layer B. In Fig. 1, although the adhesive layer C is provided on the single side of the optical film 8 via the undercoat layer B, it may be the same or different from the undercoat layer B on the other side. The undercoat layer is provided with an adhesive layer which is the same as or different from the adhesive layer c. In the second embodiment, the adhesive optical film-based optical film A of the present invention has a liquid crystal optical compensation layer (for example, a disk-shaped liquid crystal layer) A13 on one side of the transparent base film A11, and the liquid crystal optical compensation layer is used. An adhesive layer C is provided on the A13 via the undercoat layer b. In the second embodiment, the alignment film a 12 is provided between the transparent base film A11 and the liquid crystal optical compensation layer A13. However, it is also possible to use the single surface of the transparent base film All as a friction processor in 201132722. Instead of the alignment film A12. Fig. 3 is a view showing an adhesive type optical film of Fig. 2, which is used for a transparent base film Au on the side where the liquid crystal optical compensation layer A13 is not formed, and has a polarizing layer A14, followed by a transparent protective film Au. Aspect. In Fig. 3, the transparent substrate sheet A11 also has a transparent protective film of polarizer AM. The respective constitutions of the adhesive optical film of the present invention will be described in detail below. The formation of the adhesive layer of the present invention is used as a base polymer containing glass transition; the (meta) (meth)acrylic acid & compound (eight) segment under the TCa, and the glass transition temperature at 4 ( An adhesive for a block copolymer or a graft copolymer of a (meth)acrylic polymer (B) segment above TC. Further a glass transition of a (meth)acrylic acid polymer (A) bond segment When the temperature is below 〇C, the wettability of the adherend and the flexibility as an adhesive can be imparted at a usual use temperature to impart an adhesive force to the adhesive layer of the present invention. (Mercapto) acrylic polymerization The glass transition temperature of the (Λ) segment is preferably _2 (src or less, preferably _3 〇. (: Hereinafter, the glass transition temperature is above _7 〇C or more) (A) The glass transition temperature of the segment is 20 C or less, which is quite suitable from the viewpoint of excellent durability under low temperature conditions. The glass transition temperature of the (meth)acrylic polymer segment is 40 C or more. Cohesive force can be imparted in the usual use temperature, and can be used in the present invention (4) 1 Good adhesion characteristics and hostility. (f-based) acrylic polymer (B) segment glass transition temperature is 8 〇 β (: above, preferably 10 5 201132722 above ioo °c, usually, The glass transition temperature is below 150 ° C. As long as the glass transition temperature of the (fluorenyl) acrylic acid-based polymer (B) segment is 8 〇 (^ above, the durability under the enthalpy temperature condition is quite good) It is quite suitable. The foregoing block copolymer or graft copolymer may be one having the aforementioned (mercapto) acrylic polymer (A) segment and (mercapto) acrylic polymer (8) segment. For example, if The methyl)acrylic polymer (A) segment is set to A, and the (fluorenyl)acrylic polymer (B) segment is shown as B, and in the case of the block copolymer, for example: a diblock copolymer, a triblock copolymer expressed as ABA, and BAB, and further a tetra-segment copolymer, and a combination thereof, A and B. Further, in terms of a graft copolymer For example, there is a chain with A or B as the main chain and a branch different from the main chain as the side chain. And 'A, B has 2 In the above, each of A and B may be the same or different. As the base polymer of the adhesive of the present invention, although the above-mentioned block copolymer or graft copolymer may be used, it is easy to control the glass transition temperature and molecular weight. Among them, block copolymers are preferred as block copolymers, and from the viewpoint of easier control of adhesive properties and bulk properties, it is preferred to use a triblock copolymer represented by BAB. The weight average molecular weight of the block copolymer or the graft copolymer is 50,000 to 3 0000 0000. From the viewpoints of durability and remanufacturability, it is preferably 60,000 to 250,000, preferably 70,000 to 230,000, and 70,000 to 200,000 is better. When the molecular weight is less than 50,000, the cohesive force of the dot developer may be insufficient, and the durability may be poor when used in the bonded optical film. Further, when the molecular weight is more than 300,000, it takes time for the adhesive to wet the adherend, so that the wettability progresses during the storage of the manufactured product, and the subsequent increase in the force of 11 201132722 becomes difficult to reproduce. The molecular weight distribution (Mw/Mn) of the block copolymer or the graft copolymer is 1.0 to 1.5, and it is preferably 1.0-1.4 and 1.0 to 1.0 from the viewpoint of high cohesion at high temperature and excellent durability. 1.3 is preferred. The (meth)acrylic acid alkyl ester as the main monomer unit of the (fluorenyl) acrylic polymer (A) segment, for example, an alkyl group having a carbon number of 1 to 18 (mercapto) acrylonitrile S purpose. Further, the (mercapto)acrylic acid group S means an acrylic acid group and/or an alkyl methacrylate, and the (meth) group of the present invention has the same meaning. Specifically, for example, (mercapto) methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, η-butyl (meth) acrylate, t-butyl (meth) acrylate , (fluorenyl) η-hexyl acrylate, cyclohexyl (decyl) acrylate, 2-ethylhexyl (meth) acrylate, (methyl) η-octyl acrylate, (meth) acrylate A (meth)acrylic acid alkyl ester such as ester, tridecyl (decyl) acrylate, octadecyl (decyl) acrylate. These may be used alone or in combination of two or more types. The (fluorenyl) acrylic polymer (Α) segment is a main component of a (mercapto)alkyl acrylate as a monomer unit and contains 90% by weight or more of the total monomer unit (ideally 95% by weight/〇) The above) and satisfying the glass transition temperature of 0 ° C or less are not particularly limited in terms of the kind or composition of the monomer unit, but the (indenyl) acrylic polymer (A) segment is an alkyl acrylate. It is preferred as the main monomer unit. Whether the (meth)acrylic polymer (A) segment is 50% by weight or more, or 60% by weight or more, or 70% by weight or more of the total monomer unit is an alkyl acrylate, and the controlled glass transition temperature is good. The acrylic acid-based vinegar as the main monomer unit in the (meth)acrylic polymer (A) segment is also exemplified by propylene acrylate, acrylic acid η-butyl vinegar, and 12 5 in the above-mentioned examples. 201132722 2-ethylhexyl acrylate, η-octyl acrylate, etc., preferably having an alkyl group having 1 to 9 carbon atoms. The weight ratio of the (meth)acrylic polymer (Α) segment in the aforementioned block copolymer or graft copolymer is from 50% to 95% from the viewpoint of obtaining stable adhesion and durability. Preferably, it is preferably 60 〇 / 〇 ~ 85 〇 / 〇. When the weight ratio of the (meth)acrylic polymer (Α) segment is less than 50 Å/〇, the adhesion is likely to be low. Further, when the weight ratio of the (meth)acrylic acid-based polymer (Α) segment is more than 95%, since the proportion of the (fluorenyl)acrylic polymer (Β) segment is small, the cohesive force is lowered. Further, it is not suitable as an adhesive for optical films from the viewpoint of durability. The (mercapto)acrylic acid alkyl ester which is the main monomer unit of the (meth)acrylic polymer (Β) segment has, for example, an alkyl (meth) acrylate having a carbon number of 1 to 18. Specifically, there are, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, η-butyl (meth)acrylate, t-butyl (meth)acrylate Ester, η-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, η octyl (meth) acrylate, (methyl) A (meth)acrylic acid-based vinegar such as dodecyl acrylate, tridecyl (meth) acrylate, octadecyl acrylate (meth) acrylate, and (meth) acrylic acid ash vinegar. These may be used singly or in combination of two or more types. The (meth)acrylic polymer (Β) segment is a main component of the (meth)acrylic acid alkyl ester as a monomer unit and contains 90% by weight or more (preferably 95% by weight or more) of the total monomer unit. And the glass transition temperature of 4 〇〇c or more is not particularly limited in terms of the type or composition of the unit, but the total monomer unit is 15% by weight or more, or 20% by weight or more, and 13 201132722 is more than 3% by weight of the thiol-acrylic acid base. It is better to control the transition temperature of the glass. The alkyl methacrylate which is the main monomer unit of the (methyl) acrylic acid-based polymer (9) bond group is also exemplified by fluorenyl propyl sulphate in the above-mentioned examples. It is preferred that the base carbon number of the hospital is a mercaptoalkyl malonate. Further, the weight ratio of the (meth)acrylic polymer (B) segment in the copolymer or graft copolymer is the above (meth)acrylic polymer (A) bond segment. The ratio other than that. The above (indenyl) acrylic polymer segment and the (indenyl)acrylic polymer (B) segment may be contained in the range of 10% by weight or less based on the total monomer units of each segment. Other monomer units than alkyl acrylates. Examples of the other monomer unit include methoxyethyl methacrylate, ethoxyethyl methacrylate, diethylamine ethyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate. (meth)propionate having a functional group such as 2-aminoethyl acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate; (meth)acrylic acid, butene a vinyl monomer having a carboxyl group such as an acid, a butyric acid, a maleic anhydride or a fumaric acid; a vinyl monomer having a brewing amine group such as (meth)acrylamide; An aromatic vinyl monomer such as dilute, α-toluene or P-toluene; a diene monomer such as butadiene or isoprene; an olefin monomer such as ethylene or propylene; Internal vinegar such as ε-caprolactone and pentane vinegar is specialized in early vinegar. These may be, for example, alone or in combination of two or more. The method for producing the aforementioned block copolymer or graft copolymer can obtain a block having the aforementioned (meth)acrylic polymer (Α) segment and the (meth)acrylic 201132722 polymer (B) segment. In the case of a copolymer or a graft copolymer, it is not particularly limited, and a method according to a known method can be employed. Generally, a method of obtaining a block copolymer having a narrow molecular weight distribution is a method of living polymerizing a monomer constituting a unit. The method of the living polymerization is, for example, a method in which an organic rare earth metal complex is polymerized as a polymerization initiator (JP-A-6-93060), and an organic alkali metal compound is used as a polymerization initiator. An anion polymerization method in the presence of a mineral salt such as an alkali metal or an alkaline earth metal salt (refer to Japanese Patent Publication No. Hei 7-25859), an organic metal compound as a polymerization initiator, and an anion in the presence of an organoaluminum compound A method of polymerization (JP-A-11-335432) and an atom transfer radical polymerization method (ATRP) (MaCrom〇i. Chem phys 2〇1 11〇8~ιιΐ 4 pages (2 coffee years), etc. The method of grafting the copolymer is as described in the specification of Patent No. 4228820, etc. Among the above-mentioned production methods, in the case of using an organic compound as an anionic polymerization method for removing a catalyst, it is lost during the polymerization. There is little activity, so the admixture of the homopolymer with few inactive components is highly transparent. Moreover, the η X obtained by s is high due to the high polymerization conversion rate of the early body. There are few residual monomers in the product, and when available, the gas after the bonding is inhibited, and the encapsulation ": 9400 membrane adhesives make the molecular structure of the segment become high =: rrm can be used for optics The film (4) is improved in the case of the agent and only lasts for a long time. Moreover, from the point of view of the milder temperature polymerization, it has little environmental load in industrial production (mainly 15 201132722 is consumed in Advantages of the electric power of the refrigerator for controlling the polymerization temperature. As the anionic polymerization method in the presence of the above organoaluminum compound, for example, an organolithium compound can be used, and the following general formula G): air'r2r3- (i) (wherein R 1 , R 2 and R 3 may each independently represent an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aromatic group which may have a substituent, may have a substituent An aralkyl group, an alkoxy group which may have a substituent, and an aryloxy group or an N,N-disubstituted amine group which may have a substituent, or R1 represents any of the foregoing groups, and R2 and R3 together An organic compound represented by an araldioxy group which may have a substituent In the presence of a compound, diethyl ether, dioxyl oxide, diethoxyethane, 12-crown-4, etc.; and triethylamine, N, N, N, are also used in the reaction system. ,N,_tetramethylethylenediamine, n,n,n',N,,,n,,-pentamethyldiethylamine,u,4,7,1〇,i〇_hexamethyl three A method of polymerizing a (meth) acrylate such as a nitrogen-containing compound such as ethylene tetraamine, pyridine or 2,2,-bipyridine. Examples of the organolithium compound include methyllithium, ethyllithium, and η-propyl. Chain, isopropyl clock, n-butyl clock, • butyl group, isobutyl group, tert-butyl lithium, n-pentyl lithium, n-hexyl lithium, tetramethylene dilithium, pentamethylene - bell, hexamethylene two clocks and other burning base clocks and dazzling two; phenyl clock, ... toluene clock, ρ · toluene, two 曱 基 基 clock, lacquer base clock and aromatic dilithium; Lithium phenylglyoximeone, lithium diphenylmethyl, lithium trityl, l'l-diphenyl-3-methylpentyl, methyl stupidyl and diisopropene benzene The base reaction* produces two aromatic filaments than the aryl dilithium; lithium dimethylacetamide, lithium Ethyl acetamide, lithium diisopropyl: 5 16 201132722 Amine amine and other amines; and methoxy chain, ethoxy group, η-propoxy clock, isopropoxy group, η_τoxy group Oxygen clock, such as _butoxy pentyl pentoxide lithium lactate, heptyloxy, octyloxy, phenoxy, * methyl benzyl clock, benzyl methoxide, 4 - methyl Alcohol clocks such as clumsy oxy bells. These may be used alone or in combination of two or more. - as an organic compound represented by the above general formula, for example: trimethyl aluminum, triethyl aluminum, tri-n-butyl succinyl, tris butyl aluminum, tri-t-butyl aluminum, three different Butyl chain, trihexyl succinyl, tri-n-octyl sulphate, tris-2-ethylhexaluminum, and triphenyl sulphate; dimethyl (2,6 di-butyl butyl phenoxy) Lu, dimethyl (2,6-di-n-butylphenoxy)-diethyl hydrazine, one side, butyl ice methyl phenoxy), and diethyl (2,6-di-butylene benzene) Oxy), diisobutyl (2,6-dica butyl-4-ylphenoxy oxime, diisobutyl (2,6-di-butylbutoxyphenoxy), bis · octyl (2,6 two sides, Ding Qibing, methyl phenoxy oxo, and bis η octyl (2,6_two-side butyl phenoxy phenoxylate); methyl bis ( 2,6_two-side _butyl_4-methylphenoxy) aluminum, methylbis(2,6-di-tert-butoxyphenoxy), ethyl [2,2,_methylene (4 methyl such as ert-butylphenoxy (10) lynate, ethyl bis(2,6-dipebutyl-4-cyloxy) chain, ethyl bis (2,6-di-tert-butylphenoxy) ), ethyl [2, 2, _ methylene bis (4) methyl winter secret butyl oxy)] Shao, isobutyl double like divorced Base ice methylphenoxy) succinyl, isobutyl bis (2,6-di-n-butylphenoxybutyl butyl [2,2,-methylene bis (4-methyl -6 butyl phenoxy) N-octyl bis(2'f butyl phenoxy) sulphate, η octyl bis (2,6 _ _ _ _ _ _ _ _ _ _ _), and η-octyl [2, 2, _ methylene double (4_, _6 side · butyl phenoxy)] Ming et al. dioxobicin; methoxybis (2,6-di-butyl butyl methyl group 17 201132722 phenoxy) s-methoxy bis ( 2,6-di-tert.butoxyphenoxy)Methoxy[2,2,_ sub-f-bis(4-methyl succinylphenoxy)] s, ethoxy double (2,6 two sides Butyl-4-methylphenoxyline, ethoxybis(2,6-:azetidineoxy), ethoxy[2,2,-methylenebis(4_methyl·6 side-butylene) Oxygen oxime, isopropoxy bis (2=bis-butyl-butyl-methyl phenoxy), isopropoxy bis-bis-bis-phenoxy phenoxy) aluminum, isopropoxy [2, 2, _ Methylene bis(4_methyl "eA butylphenoxy)], thiobutane bis (2,6-di-tert-butylmethylphenoxy), plus _butoxy double (2,6 - acridine phenoxy), and _•butoxy [2,2,_methylenebis(4-methyl-6-tert-butylphenoxy)] aluminum and other alkoxydiphenoxy Aluminum; and three (2,6-di-tert_butyl_4_ Triphenyloxy aluminum such as methylphenoxy), tris(2,6-diphenylphenoxy)aluminum, etc. Among these organoaluminum compounds, isobutyl bis(2,6-di- Tert-butyl-4-methylphenoxy)aluminum, isobutylbis(2 6-di-bubuphenoxy)aluminum, and isobutyl [2,2,-methylenebis(4_曱) The base_6_tert_butylphenoxy)] is easier to use, and is particularly preferable from the viewpoint of not deactivating under relatively mild temperature conditions and allowing polymerization of an acrylate. These may be used singly or in combination of two or more. Further, in the adhesive forming the adhesive layer of the present invention, in addition to the above-mentioned block copolymer or graft copolymer, a crosslinking agent such as an isocyanate compound, a tackifier, a plasticizer, a glass fiber, or a glass bead may be used as needed. a metal powder, a filler formed from other inorganic powders, a pigment, a colorant, a filler, an antioxidant, an ultraviolet absorber, a decane coupling agent, etc., may be appropriately used without departing from the object of the present invention. Various additives. Further, it can also be used as an adhesive layer containing fine particles to exhibit optical diffusibility. The undercoat layer is formed of a primer containing a polymer and an antioxidant. 18 5 201132722 The material of the polymer is preferably one which exhibits good sealing properties to either the adhesive layer and the optical film (for example, a liquid crystal optical compensation layer), and forms a film having a good cohesive force. The polymer may, for example, be a polyurethane resin, a polyester resin or a polymer containing an amine group in a molecule. The form of use of the polymer may be one of a solvent-soluble type, a water-dispersible type, or a water-soluble type. For example, water-soluble polyurethane, water-soluble polyester, water-soluble polyamine, or water-dispersible resin (ethylene-vinyl emulsifier, (meth)acrylic emulsifier, etc.). Further, the water-dispersible type may be obtained by emulsifying various resins such as polyurethane, polyester, and polyamidamine with an emulsifier, or introducing an anionic group, a cationic group or a nonionic group of a water-dispersible hydrophilic group into the resin. Self-emulsification, etc. Further, an ionic polymer-conjugate can be used. For example, when the polymer contains an isocyanate compound in the adhesive layer, it is preferred to have a functional group reactive with an isocyanate compound. The polymer is preferably a polymer having an amine group in its molecule. In particular, it is suitably used for those having a primary amine group at the terminal, and can be more firmly sealed and improved in durability by reaction with an isocyanate-based compound. A polymer having a grade 1 amine group at the terminal end is preferably a poly(indenyl) acrylate having a grade 1 amine group at the terminal. Examples of the polymer containing an amine group in the molecule include a polyethyleneimine system, a polyallylamine system, a polyvinylamine system, a polyvinylpyridine system, a polyvinylpyrrolidine system, and a decylamine ethyl acrylate. A polymer containing an amine group and the like. Among these, polyethyleneimine is preferred. As the polyethylene sub-201132722, the amine-based material may be any one having a polyethyleneimine structure, and may be, for example, a polyethyleneimine, a polyacrylic acid, a methylimine, and/or a polyethyleneimine. Additives. In particular, it is preferred to use a poly(ethylene) acetamide adduct and/or a polyethyleneimine adduct which is a poly(fluorenyl) acrylate having a terminal amine group. The polyethyleneimine is not particularly limited, and various materials can be used. The weight average molecular weight of the polyethyleneimine is made by the county tree dragon, which is around (10)~1 million. For example, an example of a commercially available product of polyethyleneimine is Ep〇MlN sp series (Sp_〇〇3, manufactured by Nippon Shokubai Co., Ltd.).

SP006、SP012、SP018、SP103、SP110、SP200 等）、及EPOMIN p-iooo等。該等中，又以Ep〇MINp_1〇〇〇為宜。 對聚丙烯酸酯之伸乙亞胺加成物及/或聚乙烯亞胺加 成物之聚丙烯酸酯，係依照常法將構成後述丙烯酸系黏著 劑之基底聚合物（丙烯酸系聚合物）的烷基（曱基）丙烯酸酯 及其共聚單體加以乳化聚合而製得^作為共聚單體，為使 伸乙亞胺等起反應而使用具有羧基等官能基之單體。具有 幾·基專官能基之單體的使用比例可由反應之伸乙亞胺等比 例加以適當調整。又，作為共聚單體，以使用笨乙烯系單 體者為宜。又，亦可設為藉由使另外所合成之聚乙烯亞胺 在丙稀酸酯中之羧基等起反應而將聚乙烯亞胺予以接枝化 之加成物。例如，在市售品之例而言，例如有株式會社曰 本觸媒社製之POLYMENTNK-380。 又’可使用丙烯酸系聚合物乳化之伸乙亞胺加成物及/ 或聚乙歸亞胺加成物等。例如，就市售品之例而言，可舉 20 ⑤ 201132722 如株式會社日本觸媒社製之p〇LYMENT SK-1000。 上述以外’作為於末端具有1級胺基之聚合物，例如有 使聚丙稀酸酿中之羧基或羥基與過剩的二異氰酸酯起反 應’並且使與過剩的二胺起反應並將1級胺基導入末端者。 又’於末端具有1級胺基之聚（甲基）丙烯酸酯係藉由將前述 (甲基）丙烯酸酯與於末端具有i級胺基之單體加以共聚合而 製得。於末端具有1級胺基之單體，例如有：胺基乙基（曱 基）丙烯酸酯及胺基丙基（曱基）丙烯酸酯等。 又，在底塗層除上述聚合物類以外，亦可視需求且可 在未脫離本發明之目的範圍内，適當地使用抗氧化劑等各 種添加劑。 作為底塗層含有之抗氧化劑，例如有：苯酚系、磷系、 硫磺系及胺系之抗氧化劑，可使用從該等任擇之至少1種。 該等中，又以苯酚系抗氧化劑為佳。 就苯盼系抗氧化劑之具體例而言，單環紛化合物例如 有：2,6-二-t-丁基-P-甲酚、2,6-二-t-丁基-4-乙酚、2,6-二環 己-4-甲酴、2,6-二異丙-4-乙酴' 2,6-二-t-戊基-4-曱龄、2,6-二小辛基-4-n-丙苯紛、2,6-二環己-4-n-辛苯盼、2-異丙_4_ 甲基_6-t- 丁苯紛、2-t- 丁基-4-乙基-6-t-辛本盼、2-異丁 -4-乙基-6-t-己苯酚、2-環己-4-n-丁基-6-異丙苯酚、苯乙烯化 混合甲紛、DL-α-生育酴、及硬脂酷/5 -(3.5-二-t-丁基-4-經 苯）丙酸酯等；2環酚化合物例如有：2,2’_亞曱雙(4_甲基_6_t_ 丁苯酚）、4,4，-亞丁基雙(3-甲基_6_t_丁苯紛）、4,4’-硫代雙(3_ 甲基-6小丁苯酚）、2,2，-硫代雙(4-甲基-6-t·丁苯盼）、4,4’- 21 201132722 亞甲雙(2,6-二-t-丁苯酚）、2,2’-亞曱雙[6-(1-甲基環己）-p-甲 酚]、2,2’-亞乙基雙（4,6-二-t-丁苯酚）、2,2’-亞丁基雙（2-t-丁基-4-曱酚）、3，6-二氧雜八亞曱雙[3-(3-t-丁基-4-羥基-5-甲基苯基）丙酸酯]、三伸甘醇雙[3-(3-t-丁基-5-曱基-4-羥苯） 丙酸酯]、1,6-己二醇雙[3-(3,5-二-t-丁基-4-羥苯）丙酸酯]、 及2,2’-硫代二伸乙基雙[3-(3,5-二-t- 丁基-4-羥苯）丙酸酯] 等；3環酚化合物例如有：1,1，3-三(2-甲基-4-羥基-5 + 丁苯 基）丁烷、1，3,5-三(2,6-二曱基-3-羥基-4-t-丁基节基）異三聚 氰酸酯、1，3,5-參[(3,5-二-t-丁基-4-羥苯基）丙醯基環氧乙烷] 異三聚氰酸酯、三(4-t-丁基-2,6-二甲基-3-羥苄基）異三聚氰 酸酯、及1，3,5-三曱基-2,4,6-三(3,5-二小丁基-4-羥苄基）甲苯 等；4環酚化合物例如有：肆[曱烯-3-(3,5-二-t-丁基-4-羥苯） 丙酸酯]曱烷等；含磷酚化合物例如有：雙(3,5-二-t-丁基-4-羥苄基乙膦酸）鈣、及雙（3,5-二-t-丁基-4-羥苄基乙膦酸） 鎳等。 作為磷系抗氧化劑之具體例，例如有：亞磷酸三辛酯、 亞磷酸三月桂酯、亞磷酸三（十三基）酯、亞磷酸三異癸酯、 亞磷酸苯二異辛酯、亞磷酸苯二異癸二異癸酯、亞磷酸苯 二（十三基）S旨、二苯異辛基亞磷酸酯、二苯異癸基亞磷酸酯、 二苯十三基亞磷酸酯、三苯基亞磷酸酯、三（壬苯基）亞磷酸 酯、三（2,4-二-t-丁苯基）亞磷酸酯、三（丁氧乙基）亞磷酸酯、 四（十三基)-4,4’-亞丁基雙（3-甲基-6-t-丁苯酚)-二亞磷酸酯、 4,4’-亞異丙基-二酚烷基亞磷酸酯（但，烷基為碳數12〜15左 右）、4,4’-亞異丙基雙(2-t-丁苯酚）.二(壬苯基）亞磷酸酯、 22 ⑤ 201132722 三（聯苯）亞磷酸酯、四（十三基)-1,1,3-三(2-甲基-5-t-丁基-4-羥苯）丁烷二亞磷酸酯、三(3,5-二-t-丁基-4-羥苯）亞磷酸酯、 水素化-4,4’-亞異丙基二酚聚亞磷酸酯、雙（辛苯基）•雙 [4,4’-亞丁基雙(3-曱基-6-t-丁苯酚)]· 1，6-己二醇二亞磷酸酯、 六（十三基)-1,1，3-三（2-曱基-4-羥基-5-t-丁苯酚）二亞磷酸酯、 參[4,4’-亞異丙基雙（2-t-丁苯酚)]亞磷酸酯、三（1,3-二硬脂 醯氧基異丙基）亞磷酸酯、9，10-二氫-0-膦雜菲-10-氧化酯、 肆(2,4-二-t-丁苯基)-4,4’-亞聯苯基二膦酸酯、二（十八基）季 戊四醇二亞磷酸酯、二（壬苯基）季戊四醇二亞磷酸酯、苯 基.4,4’-亞異丙基二酚•季戊四醇二亞磷酸酯、雙(2,4-二 -t-丁苯基）季戊四醇二亞磷酸酯、雙(2,6-二-t-丁基-4-曱基苯 基）季戊四醇二亞磷酸酯及苯雙酚-A-季戊四醇二亞磷酸 酯等。 硫黃系抗氧化劑以使用硫二丙酸二烷基酯及烷硫基丙 酸之多元醇I旨為佳。在此使用之硫二丙酸二烧基醋以具有 碳數6〜20之烷基之硫二丙酸二烷基酯為佳，又，烷硫基丙 酸之多元醇酯以具有碳數4〜20之烷基之烷硫基丙酸之多元 醇酯為佳。屆時，就構成多元醇酯之多元醇之例而言，可 舉如：甘油、三羥曱乙烷、三羥甲丙烷、季戊四醇及三羥 基乙基異三聚氰酸酯等。此種硫二丙酸二烷基酯，例如有： 硫代二丙酸二月桂基酯、硫二丙酸肉豆蔻基酯、及硫二丙 酸二（十八基）自旨等。另一方面，烧硫基丙酸之多元醇S旨例如 有：甘油三丁基硫代丙酸酯、甘油三辛基硫代丙酸酯、甘 油三月桂基硫代丙酸酯、甘油三硬脂醯硫代丙酸酯、三羥 23 201132722 甲乙烷三丁基硫代丙酸酯、三羥甲乙烷三辛基硫代丙酸 酯、三羥甲乙烷三月桂基硫代丙酸酯、三羥甲乙烷三硬脂 醯硫代丙酸酯、季戊四醇四丁基硫代丙酸酯、季戊四醇四 辛基硫代丙酸酯、季戊四醇四月桂基硫代丙酸酯、及季戊 四醇四硬脂醯硫代丙酸酯等。 就胺系抗氧化劑之具體例而言，例如有：雙（2,2,66_ 四甲基-4-哌啶基）癸二酸酯、琥珀酸二甲酯與丨_(2_羥基乙 基）-4-羥基-2,2,6,6-四曱基哌啶乙醇之重凝聚物、 队>^’”-肆-(4,6-雙-(丁基-(>^甲基-2,2,6,6-四甲基哌啶 -4-一）胺基)-三氮（口 +井）-2-—）-4,7-二氮雜癸烷-^0-二胺、 二丁胺· 1，3,5-三氮（口 +井）.n，N，-雙(2,2,6,6-四甲基-4-哌啶 基-1,6-六亞曱二胺與沐(2,2,6,6-四甲基-4-哌啶基）丁胺之重 凝聚物、聚{[6-(1,1,3,3-四曱基丁基）胺基— υ，％三氮（口 + 井）-2,4-二基][(2,2,6,6-四甲基-4-哌啶基）亞胺基]環己院 [(2,2,6,6-四曱基-4-哌啶基）亞胺基]}、肆(2,2,6,6•四曱基·4· 0底咬基)-1，2,3,4-丁烧四緩酸酯、2,2,6,6-四甲基-4-旅咬基苯 曱酸酯、雙_(1，2,6,6-五曱基-4-哌啶基)-2-(3,5-二-t-丁基-4-羥苄基)-2-n-丁基丙二酸酯、雙吖N_甲基_22,6,6_四甲基_4_ 哌》定基)癸二酸酯、1，Γ-(1，2-乙炫二基）雙(3,3,5,5-四甲基派 (口 +井）綱）、（混合2,2,6,6-四曱基-4-口底咬基/十三基+ 丁烷四羧酸酯、（混合1，2,2,6,6-五曱基-4-哌啶基/十三 基)-1，2,3,4-丁院四羧酸酯、混合[2,2,6,6-四曱基_4_派咬基/ 谷，/3，沒’，沒四曱基-3,9-[2,4,8，10-四氧雜螺旋(5,5)十一烷] 二乙基]-1，2,3,4-丁烷四羧酸酯、混合[ι，2,2,6,6-五曱基-4-哌 24 ⑤ 201132722 咬脚四甲基分⑽鼻四氧雜 一烧]二乙基H，2,3,4-丁院四魏s|、_、雙& $ 乙二胺-2,4-雙[N-丁基-N-(l，2,2,6,6-五甲基 _4 〇疋 土 土 基]-6-氣基-1，3,5-三氮（口 +井)凝聚物、聚[6_N如二基）胺 -1，3,5-三氮（口 +井戶认：基爪2,2,6 6 末)啉基 丫丞-4-哌啶基）巧 四 胺基]環己烧[(2,2,6,6-四甲基_4,娘唆基)酿亞胺]、_,·雔 (2,2,6,6-四曱基-4-0底咬基）六亞曱二胺與^2·二臭乙尸 聚物、及[N-(2,2,6,6-四甲基-4-哌啶基)_2_甲基_2 (2 2 6 6 曱基·4-哌啶基）亞胺基]丙醯胺等。 ，， 底塗層含有聚合物類及抗氧化劑時，通常是相對於聚 合物類100重量份，含有抗氧化劑001^目.於聚 里置'。抗氧化 劑之使用比例在未滿㈣重量份的情況下，無法期待作為 抗氧化劑之效果。另-方面’超過重量份時在投錯性 或外觀之觀點上並非理想。在重視投錨性或外觀之況 下，抗氧化劑之使用比例理想為0.1〜300重量份、更理邦為 1〜100重量份。 〜 又，在底塗層之形成上，除前述聚合物類以外，還可 含有交聯劑。例如，可混合並交聯與含胺基之聚合物類起 反應之化合物，使底塗層之強度提升。與含胺基之聚合物 类員起反應之化合物例如有環氧化合物等。 本發明之黏著型光學薄膜之製造，例如可藉由在光學SP006, SP012, SP018, SP103, SP110, SP200, etc.), and EPOMIN p-iooo. Among them, Ep〇MINp_1〇〇〇 is appropriate. The polyacrylate of the polyethylenimine adduct and/or the polyethyleneimine adduct is an alkane which constitutes a base polymer (acrylic polymer) of an acrylic adhesive to be described later according to a usual method. The base (fluorenyl) acrylate and the comonomer are obtained by emulsion polymerization to obtain a comonomer, and a monomer having a functional group such as a carboxyl group is used to cause a reaction such as ethylene or the like. The proportion of the monomer having a polyfunctional group can be appropriately adjusted by the ratio of the reacted ethyleneimine or the like. Further, as the comonomer, those which use a stupid vinyl monomer are preferred. Further, it may be an addition product obtained by grafting polyethyleneimine by reacting a separately synthesized polyethyleneimine with a carboxyl group or the like in acrylic acid ester. For example, in the case of a commercially available product, for example, POLYMENTNK-380 manufactured by Nippon Seiki Co., Ltd. is available. Further, an acrylic polymer emulsified ethyleneimine adduct and/or a polyethylenimine adduct can be used. For example, in the case of a commercially available product, p 5 LYMENT SK-1000 manufactured by Nippon Shokubai Co., Ltd., Inc., may be mentioned. Other than the above, as a polymer having a primary amine group at the terminal, for example, reacting a carboxyl group or a hydroxyl group in the polymerization of polyacrylic acid with an excess of diisocyanate and reacting with an excess of the diamine and a primary amine group Import the end. Further, a poly(meth)acrylate having a first-order amine group at the terminal is obtained by copolymerizing the above (meth) acrylate with a monomer having an i-stage amine group at the terminal. The monomer having a primary amino group at the terminal may, for example, be an aminoethyl (meth) acrylate or an aminopropyl (decyl) acrylate. Further, in addition to the above-mentioned polymer, the undercoat layer may be appropriately used as needed, and various additives such as an antioxidant may be suitably used without departing from the object of the present invention. The antioxidant contained in the undercoat layer may, for example, be a phenol-based, phosphorus-based, sulfur-based or amine-based antioxidant, and at least one of these may be used. Among these, phenolic antioxidants are preferred. As a specific example of the benzoin antioxidant, for example, a monocyclic compound is: 2,6-di-t-butyl-P-cresol, 2,6-di-t-butyl-4-ethylphenol , 2,6-dicyclohexan-4-carboxamidine, 2,6-diisopropyl-4-ethylhydrazine' 2,6-di-t-pentyl-4-indole, 2,6-dioxixin 4--4--propylbenzene, 2,6-dicyclohexan-4-n-octylbenzene, 2-isopropyl-4-methyl-3-6-t-butylbenzene, 2-t-butyl- 4-ethyl-6-t-octane, 2-isobutyl-4-ethyl-6-t-hexol, 2-cyclohex-4-n-butyl-6-isopropylphenol, styrene Mixed with A, DL-α-tocopherol, and stearic acid -5-(3.5-di-t-butyl-4-benzene)propionate; and 2-cyclic phenolic compounds such as: 2, 2' _Aachen bis (4_methyl_6_t_butylphenol), 4,4,-butylene bis(3-methyl_6_t_butylene), 4,4'-thiobis(3_methyl-6 Small butyral phenol), 2,2,-thiobis(4-methyl-6-t·butylbenzene), 4,4'- 21 201132722 methylene bis(2,6-di-t-butanol) , 2,2'-Azain bis[6-(1-methylcyclohexyl)-p-cresol], 2,2'-ethylenebis(4,6-di-t-butanol), 2 , 2'-butylidene bis(2-t-butyl-4-indolyl), 3,6-dioxa yttrium bis[3-(3-t-butyl-4-hydroxy-5- base Propionate], tri-glycol bis[3-(3-t-butyl-5-mercapto-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-( 3,5-di-t-butyl-4-hydroxyphenyl)propionate], and 2,2'-thiodiethylidene [3-(3,5-di-t-butyl-4) -Hydroxybenzene)propionate], etc.; 3-cyclic phenolic compounds are, for example, 1,1,3-tris(2-methyl-4-hydroxy-5 +butylphenyl)butane, 1,3,5-three (2,6-diamidino-3-hydroxy-4-t-butyl) cis isocyanate, 1,3,5-gin[(3,5-di-t-butyl-4) -hydroxyphenyl)propenyl oxirane] iso-polycyanate, tris(4-t-butyl-2,6-dimethyl-3-hydroxybenzyl)isocyanate, And 1,3,5-trimethyl-2,4,6-tris(3,5-dibutylbutyl-4-hydroxybenzyl)toluene or the like; the 4-cyclic phenol compound is, for example, hydrazine [decene-3 -(3,5-di-t-butyl-4-hydroxybenzene)propionate]decane, etc.; the phosphorus-containing phenol compound is, for example, bis(3,5-di-t-butyl-4-hydroxybenzyl) Calcium phosphinate, calcium, and bis(3,5-di-t-butyl-4-hydroxybenzylethylphosphonic acid) nickel. Specific examples of the phosphorus-based antioxidant include trioctyl phosphite, trilauryl phosphite, tris(tridecyl)phosphite, triisodecyl phosphite, phenylisooctyl phosphite, and sub Benzylisoxyl diisodecyl phosphate, benzene di(tridecyl) phosphite, diphenylisooctyl phosphite, diphenylisodecyl phosphite, diphenyltridecyl phosphite, three Phenyl phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(butoxyethyl)phosphite, tetrakis )-4,4'-butylidene bis(3-methyl-6-t-butanol)-diphosphite, 4,4'-isopropylidene-diphenol alkyl phosphite (but, alkane) Base is carbon number 12~15), 4,4'-isopropylidene bis(2-t-butanol). bis(indolyl)phosphite, 22 5 201132722 tris(biphenyl) phosphite Tetrakis(tridecyl)-1,1,3-tris(2-methyl-5-t-butyl-4-hydroxyphenyl)butane diphosphite, tris(3,5-di-t- Butyl-4-hydroxyphenyl)phosphite, hydrousylated-4,4'-isopropylidenediphenol polyphosphite, bis(octylphenyl)•bis[4,4'-butylene (3-mercapto-6-t-butanol)]·1,6-hexanediol diphosphite, hexakis(tridecyl)-1,1,3-tris(2-indolyl-4-hydroxyl) -5-t-butylphenol) diphosphite, ginseng [4,4'-isopropylidene bis(2-t-butanol)] phosphite, tris(1,3-bisstearyloxy) Isopropyl)phosphite, 9,10-dihydro-0-phosphonium-10-oxide, bis(2,4-di-t-butylphenyl)-4,4'-biphenylene Bisphosphonate, di(octadecyl)pentaerythritol diphosphite, bis(indolyl)pentaerythritol diphosphite, phenyl.4,4'-isopropylidenediphenol, pentaerythritol diphosphite, Bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-mercaptophenyl)pentaerythritol diphosphite and benzene bisphenol- A-pentaerythritol diphosphite, and the like. The sulfur-based antioxidant is preferably a polyol I using a dialkyl thiodipropionate or an alkylthiopropionic acid. The thiodipropionate dialkyl vinegar used herein preferably contains a dialkyl thiodipropionate having an alkyl group having 6 to 20 carbon atoms, and a polyhydric alcohol ester of an alkylthiopropionic acid having a carbon number of 4 A polyol ester of an alkylthiopropionic acid of an alkyl group of -20 is preferred. In the case of the polyol constituting the polyol ester, glycerin, trioxane, trimethylolpropane, pentaerythritol, and trihydroxyethyl isocyanurate may, for example, be mentioned. Examples of such dialkyl thiodipropionate include dilauryl thiodipropionate, myristyl thiodipropionate, and bis(octadecyl) thiodipropionate. On the other hand, the polythiol S which burns thiopropionic acid is, for example, tributyl thiopropionate, trioctyl thiopropionate, trilauryl thiopropionate, glycerin tri Lipid thiopropionate, trihydroxy 23 201132722 methyl ethane tributyl thiopropionate, trimethyl ethane trioctyl thiopropionate, trimethyl ethane trilaurate thiopropionic acid Ester, trimethylolethane tristearate thiopropionate, pentaerythritol tetrabutyl thiopropionate, pentaerythritol tetraoctyl thiopropionate, pentaerythritol tetralauryl thiopropionate, and pentaerythritol IV Stearic acid thiopropionate and the like. Specific examples of the amine-based antioxidant include bis(2,2,66-tetramethyl-4-piperidyl)sebacate, dimethyl succinate and 丨_(2-hydroxyethyl) Heavy condensate of 4-hydroxy-2,2,6,6-tetradecylpiperidineethanol, team>^'"-肆-(4,6-bis-(butyl-(>^甲甲-2,2,6,6-tetramethylpiperidin-4-yl)amino)-trinitrogen (mouth + well)-2--)-4,7-diazadecane-^0- Diamine, dibutylamine·1,3,5-trinitrogen (mouth+well).n,N,-bis(2,2,6,6-tetramethyl-4-piperidinyl-1,6- Heavier coagulation of hexamethylenediamine and mu (2,2,6,6-tetramethyl-4-piperidyl)butylamine, poly{[6-(1,1,3,3-tetradecyl) Butyl)amine — hydrazine, % trinitrogen (mouth + well)-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imido]cyclohexane [[2,2,6,6-tetradecyl-4-piperidinyl)imido]], 肆(2,2,6,6•tetradecyl·4·0 bottom bite)-1 , 2,3,4-butane sulphate, 2,2,6,6-tetramethyl-4-branched benzoate, bis(1,2,6,6-pentamethyl 4-piperidinyl)-2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate, biguanide N_methyl_22,6 ,6_tetramethyl_4_piperidinyl) sebacate, 1, Γ- (1,2-Ethyl diyl) bis (3,3,5,5-tetramethyl (port + well)), (mixed 2, 2, 6, 6-tetradecyl 4-port Otto/trideca + butane tetracarboxylate, (mixed 1,2,2,6,6-pentamethyl-4-piperidinyl/tridecyl)-1,2,3,4-butyl Hospital tetracarboxylic acid ester, mixed [2,2,6,6-tetradecyl _4_ sentbital base / valley, /3, no', no tetradecyl-3,9-[2,4,8, 10-tetraoxaspiro(5,5)undecane]diethyl]-1,2,3,4-butane tetracarboxylate, mixed [ι,2,2,6,6-pentamethyl -4-pipeline 24 5 201132722 bite foot tetramethyl group (10) nasal tetraoxo-burning] diethyl H, 2, 3, 4-butyl compound four Wei s |, _, double & $ ethylenediamine-2 ,4-bis[N-butyl-N-(l,2,2,6,6-pentamethyl-4) bauxite-6-glycol-1,3,5-trinitrogen + well) condensate, poly[6_N, such as diyl)amine-1,3,5-trinitrogen (mouth + well household: base claw 2, 2, 6 6 end) phenyl hydrazino-4-piperidinyl巧四胺基]cyclohexene [(2,2,6,6-tetramethyl-4,nitrienyl)-imine], _,·雔(2,2,6,6-tetradecyl) -4-0 bottom bite) hexamethylenediamine and ^2·diodore urethane, and [N-(2,2,6,6-tetramethyl-4-piperidinyl)_2_A Base 2 (2 2 6 6 decyl 4-piperidinyl)imide Base] propionamide and the like. When the undercoat layer contains a polymer and an antioxidant, it is usually contained in an amount of 100 parts by weight relative to the polymer, and contains an antioxidant 001. When the ratio of use of the antioxidant is less than (four) parts by weight, the effect as an antioxidant cannot be expected. On the other hand, when it exceeds the weight, it is not preferable from the viewpoint of misplacement or appearance. The antioxidant is preferably used in an amount of from 0.1 to 300 parts by weight, more preferably from 1 to 100 parts by weight, in view of the anchoring property or appearance. Further, in the formation of the undercoat layer, a crosslinking agent may be contained in addition to the above polymer. For example, a compound which reacts with an amine group-containing polymer can be mixed and crosslinked to increase the strength of the undercoat layer. The compound which reacts with the amine group-containing polymer member is, for example, an epoxy compound or the like. The manufacture of the adhesive optical film of the present invention can be performed, for example, by optical

薄骐(如液晶光學補償層）形成底塗層後，再形成黏著劑層而 進行。 S 底塗層之形成例如可使用塗布法、浸潰法、及喷霧法 25 201132722 等塗工法’將含有前述聚合物類及抗氧化劑之底塗劑之溶 液予以塗布並乾燥來形成底塗層。底塗層之層厚在 H)〜麵nm左右，並且以在5〇_5_m之範圍為佳。一旦底 塗層之層厚變薄，即可能會有不具作為主體(bulk)之性質而 無法顯不充分強度且無法獲得充分密封性之情況。又，一 旦過厚，财可能招致光學特性降低之虞。而，底塗層之 塗布量（固體含量）以每1平方公尺0.1〜5立方公分為佳。此 外，以料(U〜1立方公分 '甚至G1〜G5立方公分者為佳。 黏著劑層之形成係藉由積層在前述底塗層上而進行。 形成t法並未⑽㈣制，可舉如：塗布«_液)並加 以乾燥之方法、及藉由設置有黏著騎之__移之方 法等。塗布法可採用反塗布(_rSe _ing)、凹板塗模等 輥塗布法旋轉塗布法、管面塗布法(％謂_111§)、喷水 塗布法、浸潰法、及噴霧法等。 作為離5L膜之構成材料，例如有：紙、聚乙稀、聚丙 稀、聚對苯二甲酸乙二醇®旨等合成樹脂薄膜、橡膠膜、紙、After the thin film (e.g., liquid crystal optical compensation layer) is formed into an undercoat layer, an adhesive layer is formed. The formation of the S undercoat layer can be carried out, for example, by applying a coating method, a dipping method, and a coating method such as a spray method 25 201132722 to apply a solution containing the above-mentioned polymer and an anti-oxidant primer to form a primer layer. . The layer thickness of the undercoat layer is about H) to about nm, and is preferably in the range of 5 Å to 5 mm. Once the layer thickness of the undercoat layer is thinned, there may be cases where it does not have a bulk property and cannot exhibit insufficient strength and sufficient sealing property cannot be obtained. Moreover, once it is too thick, the money may incur a decline in optical characteristics. Further, the coating amount (solid content) of the undercoat layer is preferably 0.1 to 5 cubic centimeters per square meter. In addition, it is preferred that the material (U~1 cubic centimeters' or even G1 to G5 cubic centimeters. The formation of the adhesive layer is carried out by laminating on the undercoat layer. The formation of the t method is not (10) (4), and may be mentioned. : a method of coating «_liquid" and drying it, and a method of setting a sticky riding method. The coating method may be a roll coating method such as reverse coating (_rSe ing), a gravure coating method, a tube coating method (% _111 §), a water spray coating method, a dipping method, or a spray method. As a constituent material of the 5L film, for example, a synthetic resin film such as paper, polyethylene, polypropylene, or polyethylene terephthalate, a rubber film, or paper,

布、不織布、網狀抽j、&amp; I 發泡膜或金屬箔、及該等疊層體等 之適當的料料。為提高從㈣制之_性，亦可視 需求f離㈣4 氧處理、長舰處理、及氣化 處理專剝離處理。 者型料相料抗靜，亦可使用抗靜 =各#層:有抗靜電劑，又，亦可另外形成抗_ 電劑例如有:離子性界面活嶋 塞吩、聚料、聚“鱗導電聚合物系；及氧化錫、 ⑤ 26 201132722 化録、氧仙等金屬氧化 抗靜電效果'及抗靜 i ’尤其從光學躲、外觀、 點看來，宜使料電性〜_與加糾之敎性之觀 胺、聚塞吩等水溶性導物其中’又尤宜使用聚苯 聚合物。此乃因為，當使 1物'或是水分散性導電性 性導電性聚合物作為:靜溶性導電性聚合物或水分散 步驟抑制有機溶劑之光風“之形成材料時’在可於塗布 理想。 之Μ之觀點而言是謂 前述光學薄膜可舉為 板、光學補償薄膜、增齐腹、物。例如有偏光板、位相差 可作為前述光學薄^ 、此外還有積層有該等者等， 如第2圖顯示，本發明 在透明基材薄膜A11之單面且有如光學薄膜A—係 晶層）A13者。 光學補償層（如盤形液 透明基材薄膜可使用各種透明材料。例如有：聚對苯 二甲酸乙m或聚萘H二㈣等㈣系聚合物、 二醋酸纖維素或三醋酸纖維素等纖維素系聚合物、聚曱基 丙烯酸曱醋等丙稀酸系聚合物、及聚笨乙烯或丙稀腈、笨 乙稀共聚物(AS樹脂）專本乙稀系聚合物、聚碳酸酿系聚合 物等。又，就形成前述透明基材薄膜之聚合物之例而言， 亦可如：聚乙烯、聚丙烯、環系及具有降莰烯結構之聚烯 烴、如乙烯丙烯共聚物之聚烯烴系聚合物、塩化乙烯基系 聚合物、耐綸或芳香族聚醯胺等醯胺系聚合物、醯亞胺系 聚合物、颯系聚合物、聚醚颯系聚合物、聚鍵喊酮系聚合 27 201132722 物、聚苯硫系聚合物、乙稀醇系聚合物、二氯亞乙稀系t 合物、乙烯縮丁醛系聚合物、聚芳基系聚合物、聚甲搭系 聚合物、環氧系聚合物、或前述聚合物之調合物等。 又，特開2001-343529號公報(W001/37007)中記載之聚 合物薄膜，可舉如：含有在(A)側鏈具有取代及/或非取代亞 醯胺基之熱可塑性樹脂、及在(B)側鏈具有取代及/或非取代 苯基以及腈基之熱可塑性樹脂的樹脂組成物。就具體例而 言，例如有：含有由異丁烯與N-甲基馬來醯亞胺形成之交 替共聚物及丙烯腈苯乙烯共聚物的樹脂組成物薄膜《薄膜 可使用由樹脂組成物之混合擠製品等形成之薄膜。 透明基材薄膜之厚度可適當決定，一般從強度或處理 性等作業性及薄膜性等觀點看來’在卜兄叫爪左右。尤以 5-200μηι為佳。 又’透明基材薄膜以盡量未有著色為佳。因此，宜使 用以Rth=(nx-nz) · d(但，似為薄膜平面内之慢軸方向的折 射率、nz為薄膜厚方向之折射率、且d為薄膜膜厚）表現且 溥膜膜厚方向之位相差在·9〇ηηι〜+75ηιη之保護薄膜。藉由 使用該膜厚方向之位相差(Rth)在·9〇ηπι〜+75ηιη者，可大致 消除因透明基材薄膜所造成之偏光板之著色（光學性著 色）。膜厚方向位相差（Rth)更理想為·8〇ηηι〜+6〇ηιη，尤以 -70nm〜+45nm為佳。 從偏光特性或耐久性等觀點看來，透明基材薄膜以三 醋酸纖維料纖維素系聚合物或降㈣线合物為佳。: 以三醋酸纖維素等纖維素系聚合物為佳。 ⑤ 28 201132722 液晶光學補償層之形成，例如可使用聚合性液晶單體 ^戈液晶聚合物。該等聚合性液晶單體及/或液晶聚合物在 塗布到透日_薄膜上之後，可藉由配向、硬化㈤化)來形 成液晶光學補償層。栋+ β 則迷聚合性液晶單體時，通常會 使用光聚合反應起始劑。可未有限制地使用各種光聚合反 應起始劑。 前述光學補償層可為盤形液晶層。盤形液晶層係藉由 具有聚合性不飽和基之編彡液晶化合物之配向、硬化所形 成者。盤雜晶層可妓地作為光學補制❹，且可提 升視角、對比、及亮度等。盤形液晶化合物具有聚合性不 飽和基，係藉由配向且硬化該化合物而形成有盤形液晶 層。盤形液晶層以盤形液晶化合物呈傾斜配向者為宜。盤 形液晶層之層厚通常在〇·5〜1〇μηι左右。 盤形液晶化合物係具有負之折射率異方性（一軸性） 者，例如有：C. Destrade等研究報告、Mol. Cryst 71卷、ηι 頁（1981年）中所記載之曱苯誘導體、B_ K〇hne等研究報告、 Angew. Chem. 96卷、70頁（1984年）中所記載之環己烯誘導 體、及J. M· Lehn等研究報告、J_ Chem. Commun.、1794頁 (1985年)與J. Zhang等研究報告、J. Am. Chem. Soc. 116卷、 2655頁（1994年）中所記載之氣雜冠系（azacrown)或苯基乙 炔系巨環物等，一般是將該等作為分子中心之母核並具有 將直鏈之烷基或烷氧基、取代苯甲醯氧基等，作為其直鏈 而取代呈放射狀之結構，成顯示液晶性、一般包含稱為盤 形液晶者。但，只要分子本身具有負之一軸性且可賦予一 29 201132722 定配向者’並非限定於上述記載者。又，在本發明，盤形 液晶化合物係具有以熱、光等進行硬化反應之聚合性不飽 和基(例如有：丙烯醯基、曱基丙烯醯基、乙烯基、與丙烯 基等）者。而，盤形液晶層中最終所形成者沒有必要為前述 化合物，亦包含藉由聚合性不飽和基之反應而聚合或交 聯、且經高分子量化而失去液晶性者。 又，盤形液晶化合物乃指如藉由與各種盤形液晶化合 物及其他低分子化合物或聚合物之反應而不再顯示液晶性 之盤形液晶的反應生成物等，分子本身在光學上具有負之 一軸性的化合物整體。 盤形液晶之配向處理係將透明基板薄膜表面予以摩擦 處理或使用配向膜。就配向膜而言，例如有：無機物斜向 蒸發膜、或將特定有機高分子膜加以摩擦之配向膜。亦有 如由偶氮苯誘導體形成之LB膜，藉由光而引起異性化使分 子持有方向性且呈均一配列之薄膜等。有機配向膜可如： 聚醯亞胺膜、或烷基鏈改質系聚乙烯醇、聚乙烯縮丁醛、 聚曱基丙烯酸曱酯等形成疏水性表面之有機高分子膜。此 外，無機物斜向蒸發膜可如Si〇斜向蒸發膜。 使盤形液晶化合物呈傾斜配向，其手段例如可使用在 透明基材薄膜形成S&amp;向膜，接著塗布盤形液晶化合物(聚合 性液晶化合物)並使其呈傾斜配向狀態，之後再藉由紫外光 等光照射或熱加以蚊化等之方法。X，亦可使盤形液晶 傾斜配向在其他配向歸上後，彻絲上透明的接著劑 或感壓黏著劑轉移到透明支撑體上加以形成。 30 201132722 δ亥盤形液晶層可適當使用特開平8-95032號公報與專 利第2767382¾¾說明書中記載者a此種盤形液晶之傾斜配 向層形成在纖維素系高分子㈣上者，例如有富士軟片社 製之廣視角膜。 上述以外之液晶光學補償層可藉由例如向列液晶性單 體及/或聚合物加以形成。 又’如第3圖顯示’本發明之光學薄膜可使用在未形成 液晶光學補償層Al3之側的透明基材薄膜Au之單面積層 有偏光子A14、且緊接著積層有透明保護薄膜A15者。 偏光子A14係使用接著劑而貼合在透明基材薄膜 A11。而’第3圖中’透明基材薄膜AU雖兼具偏光子A&quot; 之透明保護_’但亦可在透明基材薄膜All積層在偏光子 之單面或兩面具有透明保護薄膜之偏光板。 偏光子並未有特別限定，可使用各種物。作為偏光子， 2如有使碘或_色性染料之二色性物質吸附到聚乙烯醇 缚膜、部分縮甲酸化聚乙烯醇系薄膜、乙酸乙稀自旨 系部分4化薄膜等親纽高分子㈣而單_伸者，可兴 ::等=醇之脫水處理物、或聚氣乙烯之去 : :專:稀系配向薄膜等。該等中，又以由聚乙 ，、蛾等—色性物f形成之偏光子為宜。 ’、、 並未有特別限制，-般在5〜80μιη左右。U子之厚度 以峨將聚乙稀醇系_予以染色並經㈣ 子例如可藉由將聚乙烯醇浸潰到峨之水溶液烏光 色，並延伸成原長度之3〜7倍而製成。視需求，亦可 31 201132722 可包含植或硫_、氣化料之糾鉀等水溶液中。此 外，視需求，’村在染色前將聚㈣醇㈣膜浸潰到水中 加以水洗。藉由水洗聚乙烯醇㈣m，可洗淨聚乙稀醇系 薄膜表面之赌或抗結塊劑，此外，亦有使聚乙稀醇系薄 膜膨湖而防止染色之非-致性等不均勻之效果。延伸可在 峨染色後進行’亦可在染色時加叫伸，又可在延伸後以 蛾染色。亦可在线视_水溶液或水浴巾加以延伸。 形成没置在則述偏光子之單面或兩面的透明保護薄膜 之材料’以優於透明性、機械強度、熱穩定性、水分阻隔 性、及均向性等者為佳。透明保護薄膜可使用同於透明基 材薄膜之材料。又，膜厚亦可相同。 而，透明基材薄膜與透明保護薄膜可使用相同的聚合 物材料’亦可使用不同的聚合物材料等。 前述偏光子與透明基材薄膜及透明保護薄膜通常是透 過水系接著劑等加以密封。水系接著劑例如有：異氰酸酯 系接著劑、聚乙烯醇系接著劑、膠質系接著劑、乙烯基系 乳膠系、水系聚胺酯、與水系聚酯等。而，在使偏光子與 透明器材薄膜及透明保護薄膜貼合時，可在透明基材薄膜 及透明保護薄膜施加活性化處理。活性化處理可採用各種 方法，例如可採用皂化處理、電暈處理、低壓uv處理 '或 電漿處理等。活性化處理尤其在透明基材薄膜為三醋酸纖 維素、降莰烯系樹脂、聚碳酸酯、或聚烯烴系樹脂等情況 下特別有效。 亦可是在不使前述透明保護薄膜之偏光子接著之面施 32 ⑤ 201132722 加過硬塗覆層、抗反射處理、抗黏、或以擴散以及防光眩 為目的之處理者。 又’除積層有前述偏光板之光學薄膜以外，使用在本 發明之黏著型光學薄膜的光學薄膜，亦可使用在液晶顯示 裝置等影像顯示裝置之形成來積層光學層。例如有··反射 板或反穿透板、位相差板（包含丨^或丨以等波長板）、及增亮 膜等使用在液晶顯示裝置等形成之光學層者。該等除可單 獨作為光學薄膜使用以外，亦可在實用上積層在前述偏光 板並可使用1層或2層以上。 在偏光板積層有前述光學層之光學薄膜，可藉由在液 晶顯示裝置等製造過程中依序別個積層之方式加以形成， 而，預先積層作為光學薄膜者，具有優於品質之穩定性或 組成作業等可使液晶顯示裝置等製造步驟提升之優點。積 層時，可使用黏著層等適當的接著機構。在進行前述偏光 板與其他料狀歸時，料光學财舰目的之位相 差特性等來設定適當的配置角度。 本^明之黏著型光學薄膜可適當地使用在液晶顯示裝 置等各種影賴示裝置之形成f。液晶顯示裝置之形成可 依據驾知加以進仃。即’液晶顯示裝置—般是藉由適當組 裝液晶格與黏著型光學薄膜、及視需求之照明系統等構成 零件並安裝驅動電路等而形成。在本發日种，除使用本發 明之黏著型光學薄膜之點以外，並未有特別㈣，因而可 π 依據習知。有關液晶格亦可使用例如型、⑽型、或 型荨任意型種。 33 201132722 可形成於液晶格之單側或兩側配置有黏著型光學薄膜 之液晶顯示裝置、或在照明系統使用背光或反射板者等適 當的液晶顯示裝置。屆時，本發明之光學薄膜可設置在液 晶格之單側或兩側。將光學薄膜設置在兩側時，該等可為 相同者’亦可為不同者。此外，在液晶顯示裝置之形成時’ 例如可將擴散板、防光眩層、抗反射膜、保護板、稜鏡陣 列、透鏡陣列片、光學擴散板、及背光等適當的零件，以1 層或2層以上配置在適當的位置。 實施例 以下，將以實施例具體說明本發明，惟，本發明非限 於該等實施例者。而，各例中之部及。/〇皆為重量基準。 使用在實施例及比較例之嵌段共聚物或接枝共聚物係 使用以常法加以乾燥精製過的薬品藉由以下顯示之製造例 所製得。此時’所製得之嵌段共聚物及接枝共聚物之分子 量、分子量分布、組成、各嵌段之玻璃轉移溫度、及聚合 轉化率之分析係藉由以下方法所實施。 (1)透膠層析術(GPC)之數目平均分子量(Μη)、重量平 均分子量(Mw)、與分子量分布(Mw/Mn)之測定： 裝置：東曹社製凝膠透過層析儀(HLC-8020)、 管柱：將東曹社製TSKgsl GMHXL、G4000HXL及 G5000HXL予以直列連結、 溶析液：四氫》夫喃、 溶析液流量：l.〇ml/分、 管柱溫度：40。(：、 34 ⑤ 201132722 檢測方法：示差折射率（RI)、 檢量曲線：使用標準聚苯乙烯作成。 (2) 氫質子核磁共振（1H_nMR)分光法之共聚物中之各 共聚合成分之含量測定： 裳置；日本電子株式會社製核磁共振裝置 (JNM-LA400)、 &gt;谷媒.重氣仿。 1H-NMR光譜中，3.6ppm及4.0ppm附近的訊號分別歸 屬曱基丙烯酸曱酯單元之酯基(_〇_CH3)、及丙烯酸〜丁酯單 元之醋基（-0-CH2-CH2_CH2-CH3)，並藉由其積分值之比來 算出共聚合成分之含量。 (3) 玻璃轉移溫度(Tg)之算出： 玻璃轉移溫度係從使用在共聚物製造之單體與各單體 之比例，自FOX之式所算出之理論值。 製造例1 (嵌段共聚物1之合成） 將三向旋塞附加到2L之三頸燒瓶、並以氮氣取代内部 以後，在室溫下加入含有甲苯868g、^二甲氧乙烧43 4g、 及異丁基雙(2,6·二-t·丁基_4_曱基苯氧基）鋁4〇 2mm〇i之甲 苯溶液60.0g，此外，並加入含有sec-丁基鋰6.37mmol之環 己烯與η-己烷之混合溶液3.68g。接著，在此之中加入甲義 丙烯酸甲酯（以下略稱為MMA)51_5g，並在室溫下攪拌的分 釭。緊接著，將聚合液之内部溫度冷卻到_3〇。〇，並以2個 鐘頭滴下丙烯酸η-丁酯（以下簡略為nBA)24〇g。接下來，力 35 201132722 入MMA51.5g並在室溫下授拌一晚後，添加甲醇3.5〇g使聚 合反應停止。將所得之反應液注入曱醇中，藉由爐過回收 沈澱物並使其乾燥，藉以製得340g的三嵌段共聚物1。 W-NMR測定與GPC測定之結果，上述三嵌段共聚物1 為PMMA-PnBA-PMMA之三嵌段共聚物，重量平均分子量 (^^)為7.9&gt;&lt;104’且數目平均分子量(1\/[11)為6.2\104、分子量 分布(Mw/Mn)為1.27。而，PMMA-PnBA-PMMA表示聚曱基 丙烯酸甲酯-聚丙烯酸η-丁酯-聚曱基丙烯酸曱酯。三嵌段共 聚物1之單體單元之重量比為ηΒΑ/ΜΜΑ=70/30。 製造例2 (嵌段共聚物2之合成） 製造例1中，除使用丙烯酸2_乙基己酯（以下簡略為 2ΕΗΑ)替代ηΒΑ以外，以與製造例1同樣的方式製得三嵌段 共聚物2。 h-NMR測定與GPC之結果，上述三嵌段共聚物2為 PMMA-P2EHA-PMMA之三嵌段共聚物，且重量平均分子量 (Mw)為9.2X104、數目平均分子量(Μη)為7.3xl04、分子量分 布(Mw/Mn)為 1_26。而，ΡΜΜΑ-Ρ2ΕΗΑ-ΡΜΜΑ表示聚甲基 丙烯酸曱酯-聚丙烯酸2-乙基己酯-聚甲基丙烯酸甲酯。三嵌 段共聚物2之單體單元之重量比為2EH A/MMA=69/31。 製造例3 (嵌段共聚物3之合成） 氮氣取代之500L反應器中，調和nBA80.9kg及丙烯酸t-丁基（以下簡略為tBA)2.1kg作為構成丙烯酸系聚合物嵌段 36 201132722 之單體，接著調和臭化第一銅580g並開始攪拌。之後，調 和使2,5-二溴己二酸二乙酯583g溶解在乙腈7.3kg之溶液 内、並以75°C保持30分鐘後，加入PMDTA 70g。在隨時加 入PMDTA並經過3小時後，加入曱苯82.5kg、氣化亞銅 400g、PMDTA 70g、及MMA35.6kg。反應結束後，加入甲 苯120kg稀釋反應溶液，並冷卻反應器使聚合停止。再將甲 苯加入所製得之丙烯酸系嵌段共聚物溶液中，使聚合物濃 度為25重量％。在該溶液中加入p-甲苯磺酸-水合物1.6kg， 以氮氣取代反應器内在150°C攪拌4小時後，將tBA之t-丁基 轉換成羧基而製得三嵌段共聚物3。 W-NMR測定與GPC之結果，上述三嵌段共聚物3為 PMMA-P[nBA/AA]-PMMA之三嵌段共聚物，且重量平均分 子量(Mw)為1·8χ105、數目平均分子量(Μη)為1.3xl〇5、分子 量分布(Mw/Mn)為 1.38。而，ΡΜΜΑ-Ρ[ηΒΑ/ΑΑ]-ΡΜΜΑ表 示聚曱基丙烯酸甲酯-[丙烯酸η-丁酯與丙烯酸之共聚物]-聚 甲基丙烯酸甲酯。三嵌段共聚物3之單體單元之重量比為 ηΒΑ/ΑΑ/ΜΜΑ=69/2/29。 製造例4 (接枝共聚物4之合成） 在具備冷卻管、氮氣導入管、溫度計、與攪拌機之反 應容器中，在室溫下加入甲苯233g、nBAlOOg、2,2’-偶氮 雙異丁腈0.2g並進行氮氣取代後，升溫到55°C進行6小時的 聚合反應，以製得聚丙烯酸η-丁酯之溶液。相對於該聚丙 烯酸η-丁酯之固體含量100部，加入在末端基具有甲基丙烯 37 201132722 醯基之曱基丙烯酸甲酯巨單體（東亞合成化學工業（株） 製）5〇部’並將甲苯作為溶媒進行通常的溶液聚合而製得接 枝共聚物4。 A-NMR測定與GPC之結果，上述接枝共聚物4中，重 量平均分子量（Mw)為2.2χ1〇5，且數目平均分子量（Mn)為 1.7xl〇5、分子量分布(Mw/Mn)為1.29。而，單體單元之重 量比為nBA/MMA=67/33。 製造例5 (三嵌段共聚物5之合成） 將三向旋塞附加到2L①三頸燒瓶並以氮氣取代内部之 後，在室溫下加入含有曱苯868g、1，2-二甲氧乙燒43 4g、 及異丁基雙(2,6-二-t-丁基-4·曱基笨氧基）鋁4〇 2mm〇1之甲 苯溶液60_0g，並且加入含有sec-丁基鋰6.37mm〇l之環己稀 與η-己烷之混合溶液3_68g。接著，在此之中加aMMA46 &amp; 與丙烯酸曱酯（以下簡略為MA)5.1g後，在室溫下授掉6〇分 鐘。緊接著，將聚合液之内部溫度冷卻到_3(rc，並以2個 鐘頭滴下nBA192g與MA48g之混合液。再者加入 MMA46.4g與MA5.1g以室溫攪拌一晚後’添加曱醇3 5〇§使 聚合反應停止。將所製得之反應液注入甲醇中，並藉由濟 過回收沈殿物使其乾燥後，製得334g的三嵌段共聚物5。 h-NMR測定與GPC測定之結果，上述三嵌段共聚物5 為 P[MMA/MA]-P[nBA/MA]-P[MMA/MA]之三嵌段共聚 物，且重量平均分子量(Mw)為12·1χ104、數目平均分子量 (Μη)為9.3 X 104、分子量分布（Mw/Mn)為1 3〇。而， 38 ⑤ 201132722 P[MMA/MA]-P[nBA/MA]-P[MMA/MA]表示[甲基丙烯酸曱 酯與丙烯酸曱酯之共聚物]-[丙烯酸}丁酯與丙烯酸曱酯之 共聚物]-[甲基丙烯酸曱酯與丙烯酸甲酯之共聚物]。三嵌段 共聚物5之單體單元之重量比為nBA/MA/MMA=56/l7/27。 實施例1 &lt;黏著劑層之形成&gt; 將以製造例1所製得之三嵌段共聚物1溶解至甲苯中調 製出固體含量濃度30%的黏著劑溶液之後，使用反向輥塗 法將該黏著劑溶液塗布到由已施加離型處理之聚酯薄膜 (厚度38μηι)形成的間隔物上，以使乾燥後之黏著劑層厚度 成為2〇μηι，並以155°C進行3分鐘加熱處理使溶劑揮發而製 得黏著劑層。 &lt;光學薄膜&gt; 使用富士軟片社製之廣視角（WV)薄膜。WV薄膜具有 在透明基材薄膜之纖維素系高分子薄膜上傾斜配向有盤形 液晶分子的盤形液晶層。 而，使WV薄膜分離成盤形液晶分子之傾斜配向層，並 以王子計測機器社製之KOBRA-21ADH測定；I =590nm之特 性。將面内最大折射率設為nx、將與具有面内最大折射率 之方向呈正交的方向折射率設為ny、並將膜厚方向之折射 率設為nz。令膜厚為d。透明支撐體為△ nd=(nx-ny)X (1=1211111、且1^11=(1^-112)\(!=10〇11111。另一方面，傾斜配向層 在光軸呈傾斜之方向，以在-50。〜50。之範圍内改變入射角來 測定位相差之結果，△ nd=30nm、Rth=l50nm、且平均傾斜 39 201132722 角 0=17。。 將前述W V薄膜之透明基材薄膜側予以皂化處理後，藉 由聚乙稀醇系接著劑使其皂化處理面與厚度20# m之聚乙 烯醇系偏光子（日東電工(株）製、SEG 5424WL)貼合。另一 方面’藉由前述同樣的聚乙烯醇系接著劑，使透明保護薄 膜（二醋酸纖維素薄膜、厚度8〇μΐΏ)貼合至偏光子之另一面， 以製成具有偏光板之光學薄膜（附光學補償層之偏光板）。 &lt;底塗劑之調製&gt; 在以固體含量為2%的方式將甲苯稀釋到於末端具有1 級胺基之丙烯酸酯（(株）日本觸媒製、p〇LYMENT ΝΚ38〇) 之溶液中’調製相對於前述溶液之固體含量100部而添加有 1部的苯酚系抗氧化劑（Chiba Speciality chemicals社製、 IRGANOX1010)之底塗劑。 &lt;黏著型光學薄膜之製作&gt; 使用彳干塗布裝(bar coater)將上述底塗劑塗布到上述附 光學補償層之偏光板的盤形液晶層表面並加以乾燥，以形 成塗布量0.2立方公分的底塗層（厚度8〇nmp接著，將形成 有上述黏著劑層之離型膜貼合至底塗層’以製作出黏著型 光學薄膜。 實施例2 除使用以製造例2所製得之三嵌段共聚物2來替代實施 例1中在黏著劑層之形成時以製造例i所製得之三嵌段共聚 物1以外’以與實施例1同樣的方式製作出黏著型光學薄膜。 實施例3 ⑤ 40 201132722 除使用以製造例3所製得之三嵌段共聚物3來替代實施 例1中在黏著劑層之形成時以製造例1所製得之三嵌段共聚 物1以外，以與實施例1同樣的方式製作出黏著型光學薄膜。 實施例4 除使用以製造例4所製得之接枝共聚物4來替代實施例 1中在黏著劑層之形成時以製造例1所製得之三嵌段共聚物 1以外，以與實施例1同樣的方式製作出黏著型光學薄膜。 實施例5 除使用以製造例5所製得之三嵌段共聚物5來替代實施 例1中在黏著劑層之形成時以製造例1所製得之三嵌段共聚 物1以外，以與實施例1同樣的方式製作出黏著型光學薄膜。 比較例1 與實施例1中在黏著型光學薄膜之製作相較之下，除未 設置底塗層以外，以同於實施例1的方式製作出黏著型光學 薄膜。 比較例2 &lt;丙烯酸系黏著劑之調製&gt; 基底聚合物係使用含有由nBA: MMA=70 : 30(重量比） 之隨機共聚物6形成之重量平均分子量165萬之丙烯酸系聚 合物（聚合起始劑係使用2,2’-偶氮雙異丁腈0.3部對單體100 部加以合成）的酢酸乙酯溶液（固體含量155%)。 &lt;黏著型光學薄膜之製作&gt; 除使用上述所製得之隨機共聚物6之溶液來替代實施 例1中在黏著劑層之形成時以製造例1所製得之三嵌段共聚 41 201132722 物1之溶液以外，以與實施例1同樣的方式製作出黏著型光 學薄膜。 比較例3 (板段共聚物7之合成） 除使用甲基丙烯酸η-丁酯（以下簡略為nBMA)來替代製 造例1中之MMA以外，以與製造例1同樣的方式製得三嵌段 共聚物7。 h-NMR測定與GPC之結果，上述三嵌段共聚物7為 PnBMA-PnB A-PnBMA之三嵌段共聚物，且重量平均分子量 (Mw)為1.2xl〇5、數目平均分子量(Μη)為9.2X104、分子量分 布（Mw/Mn)為1.30。而 ’ ΡηΒΜΑ-ΡηΒΑ-ΡηΒΜΑ表示聚甲基 丙稀酸η-丁醋-聚丙烯酸η-丁 g旨-聚曱基丙稀酸η_丁醋。三嵌 段共聚物5之單體單元之重量比為ηΒΑ/ηΒΜΑ=7〇/3〇。 &lt;黏著型光學薄膜之製作&gt; 除使用上述所製得之三嵌段共聚物7來替代 實施例1中 在黏著綱之形成如製造例1所製狀三嵌段共聚物w 外’以與實施例1同樣的方式製作出黏著型光學薄膜。 參考例1 &lt;丙烯酸系黏著劑之調製&gt; 基底聚σ物係使用含有由ηΒΑ :丙稀酸4·經基丁基 :簡略為4ΗΒΑ)=99 :丨（重量比)之隨機共聚物8所形成之 里平均刀子量165萬之丙烯醆系聚合物(聚合起始劑係使 偶氮雙異Τ腈〇·3部對單_部加以合成)之醉酸乙 /分液（固體a里15.5/0)。且，相對於上述丙烯酸系聚合拍 ⑧ 42 201132722 液之固體含量100部，將過氧化二笨甲醯（日本油脂（株）製、 NYPER BMT傷v)0.3部、三經甲丙院二甲苯二異氣酸賴 (三井武田化學(株）製、TAKENATE Dll〇N)0.02部、及含乙 醯乙醯基之矽烷耦合劑（综研化學(株）製、A_1〇〇)〇 2部加以 调配作為交聯劑，並調製出黏著劑溶液（固體含量丨2%)。 &lt;黏著型光學薄膜之製作&gt; 除使用含有上述所製得之隨機共聚物8的黏著劑溶液 來替代實施例1中在黏著劑層之形成時以製造例丨所製得之 二嵌段共聚物1之溶液以外，以與實施例丨同樣的方式製作 出黏著型光學薄膜。 對上述所製得之黏著型光學薄膜進行以下評估。並將 結果顯示在表1。 (黏著劑層與光學薄膜基材之密封性） 將上述黏著型光學薄膜切成25mmxl50mm之大小’並 將該黏著劑層面、及使銦-氧化錫蒸發至5 〇 μ m厚之聚對笨二 曱酸乙二醇醋薄膜表面之蒸發薄膜之蒸發面予以相接貼合 後’在23°C/60%RH環境下放置2〇分鐘以上。之後，用手將 聚對苯二曱酸乙二醇酯薄膜之端部予以剝離，並確認黏著 劑有附者在聚對本一曱酸乙二醇|旨薄膜側之後，使用島津 製作所製之張力試驗機AG-1來測定（25°C )在180。方向以 300mm/分之速度進行剝離時之應力（N/25mm)。 (接著力與再製性） 將上述黏著型光學薄膜裁斷成25rnm寬，並以2kg滾輪 往返推壓1次後黏貼至厚度〇.7mm之無鹼玻璃（康寧社製' 43 201132722 1737)。使用張力試驗機分別對該樣本以23°C硬化1小時者 (初期）、及硬化1年份者（1年後）測定出以剝離角度180°且剝 離速度300mm/min加以剝離時之接著力（N/25mm)。又，以 下述基準目測並評估其剝離後之玻璃表面之狀態。而，接 著力係進行上述評估50次之其平均值。 ◎:可未殘留糊膠加以剝離(接著力未滿20N/25mm) 〇：雖可未殘留糊膠加以剝離但重剝離（接著力 20N/25mm以上） △:產生糊膠殘留（0〜5片/50片） X :產生糊膠殘留（6片以上/50片） 44 ⑧ 201132722 評估 再製性(黏膠殘留） 1 1年後1 ◎ ◎ 〇 ◎ ◎ X X X X 初期 ◎ ◎ ◎ ◎ ◎ X &lt;]命 (内会破 ◎ 接著力(n/25mm) 1年後 卜 oo VO m in m 卜 初期 to CN 00 卜 〇\ 〇\ 密閉性 (N/25mm) (N 底塗層 之有無 41 黏著劑 聚合形態 &lt; Su| CL, &lt; 5 (N ω味 |'Ί Oh PMMA/P[nBA/AA]/PMMA (三嵌段共聚物3) &lt; |I 12 5味 £球 [PMMA/M A]/P [nB A/MA]/P [MM A/M A] (三嵌段共聚物5) &lt; S味 £郐 S、丨1 隨機共聚物6 &lt; PQ ^ 左荽 $鉍 0Q ^ £趔 S u| CL, 隨機共聚物8 共聚物之組成 (重量比） nBA/MMA =70/30 1 2EHA/MMA=69/31 nBA/AA/MMA=69/2/29 nBA/MMA=67/33 nBA/MA/MMA=56/l 7/27 nBA/MMA=70/30 nBA/MMA=70/30 nBA/nBMA=70/30 nBA/4HBA=99/l 實施例1 1 實施例2 實施例3 實施例4 實施例5 比較例1 比較例1 比較例1 比較例1 45 201132722 三嵌段共聚物中之各（共）聚合物鏈段的玻璃轉移溫 度為： PMMA ： 105°C ' ΡηΒΑ ： -45〇C ' P2EHA ： -55〇C ' P[MMA/MA] ： 92〇C ' P[nBA/MA] ： -36〇C 'Cloth, non-woven fabric, mesh-like j, &amp; I foamed film or metal foil, and suitable materials such as these laminates. In order to improve the _ sex from the (four) system, it is also possible to distinguish the demand from the (four) 4 oxygen treatment, long ship treatment, and gasification treatment. The material type material is anti-static, and anti-static = each layer can be used: there is an antistatic agent, and an anti-electric agent can be additionally formed, for example, an ionic interface, a live cockroach, a polymer, and a "scale". Conductive polymer system; and tin oxide, 5 26 201132722 chemical record, oxygen oxide and other metal oxidation antistatic effect 'and anti-static i' especially from the optical hiding, appearance, point, it is appropriate to make the electrical properties ~ _ and plus correction A water-soluble conductor such as a guanamine or a polycetrope, in which a polyphenylene polymer is particularly preferably used. This is because when a substance or a water-dispersible conductive conductive polymer is used as: The soluble conductive polymer or the water-dispersing step suppresses the glaze of the organic solvent. From the viewpoint of the above, the optical film can be referred to as a plate, an optical compensation film, or an augmented belly. For example, there may be a polarizing plate, a phase difference may be used as the optical thin film, or a laminate may be used. As shown in FIG. 2, the present invention is on one side of the transparent substrate film A11 and has an optical film A-system layer. ) A13. The optical compensation layer (for example, the disc-shaped liquid transparent substrate film can use various transparent materials, for example, polyethylene terephthalate m or polynaphthalene H bis (tetra), etc. (tetra) polymer, cellulose diacetate or cellulose triacetate. Cellulose-based polymer, acrylic polymer such as polydecyl acrylate vinegar, and polystyrene or acrylonitrile, stupid ethylene copolymer (AS resin), ethylene-based polymer, polycarbonate Further, as an example of the polymer forming the transparent base film, a polyethylene, a polypropylene, a ring system, and a polyolefin having a norbornene structure, such as an ethylene propylene copolymer, may also be used. An olefin polymer, a vinyl halide polymer, a guanamine polymer such as nylon or an aromatic polyamide, a quinone polymer, a fluorene polymer, a polyether fluorene polymer, or a polyketone Polymerization 27 201132722, polyphenylene sulfide polymer, ethylene glycol polymer, ethylene dichloride t compound, ethylene butyral polymer, polyaryl polymer, polymethylation polymerization a substance, an epoxy polymer, or a blend of the above polymers, etc. The polymer film described in JP-A-2001-343529 (W001/37007) may include a thermoplastic resin having a substituted or/or unsubstituted amidino group in the (A) side chain, and (B) A resin composition having a thermoplastic resin having a substituted and/or unsubstituted phenyl group and a nitrile group in a side chain. Specific examples include, for example, an alternating copolymer formed of isobutylene and N-methylmaleimide. And a film of a resin composition of an acrylonitrile styrene copolymer. The film may be a film formed of a mixed extruded product of a resin composition, etc. The thickness of the transparent substrate film may be appropriately determined, and generally workability and film properties such as strength and handling properties are obtained. Sexuality and other viewpoints seem to be in the vicinity of the brothers, especially in the case of 5-200μηι. Also, the transparent substrate film is preferably not colored as much as possible. Therefore, it is preferable to use Rth=(nx-nz)·d( However, it seems that the refractive index in the slow axis direction in the plane of the film, nz is the refractive index in the thickness direction of the film, and d is the film thickness of the film, and the phase difference in the thickness direction of the ruthenium film is in the range of 9 〇ηηι to +75 ηηη. Protective film by using the phase of the film thickness direction (Rth) in the case of 9〇ηπι~+75ηιη, the coloring (optical coloring) of the polarizing plate due to the transparent base film can be substantially eliminated. The phase difference (Rth) in the film thickness direction is more preferably 8 〇ηηι~ +6〇ηιη, particularly preferably -70 nm to +45 nm. From the viewpoint of polarizing characteristics or durability, the transparent base film is preferably a triacetate cellulose-based polymer or a reduced (tetra) linear compound. A cellulose-based polymer such as cellulose triacetate is preferred. 5 28 201132722 For the formation of a liquid crystal optical compensation layer, for example, a polymerizable liquid crystal monomer can be used. The polymerizable liquid crystal monomer and/or liquid crystal polymerization can be used. After the coating is applied to the transparent film, the liquid crystal optical compensation layer can be formed by alignment and hardening. In the case of a polymerizable liquid crystal monomer, a photopolymerization initiator is usually used. Various photopolymerization reaction initiators can be used without limitation. The aforementioned optical compensation layer may be a disk-shaped liquid crystal layer. The discotic liquid crystal layer is formed by alignment and hardening of a conjugated liquid crystal compound having a polymerizable unsaturated group. The disc layer can be used as an optical complement, and can improve viewing angle, contrast, and brightness. The discotic liquid crystal compound has a polymerizable unsaturated group, and a discotic liquid crystal layer is formed by aligning and hardening the compound. The discotic liquid crystal layer is preferably a tilted alignment of the discotic liquid crystal compound. The layer thickness of the disk-shaped liquid crystal layer is usually about 〜5~1〇μηι. The discotic liquid crystal compound has a negative refractive index anisotropy (uniaxiality), and examples thereof include: C. Destrade et al., Mol. Cryst 71, ηι (1981), anthraquinone inducer, B_K〇hne et al., Angew. Chem., vol. 96, p. 70 (1984), cyclohexene inducer, and J. M. Lehn et al., J_Chem. Commun., 1794 ( 1985) and J. Zhang et al., J. Am. Chem. Soc. 116, pp. 2655 (1994), azacrown or phenylacetylene macrocycles, etc. These are the cores of the molecular center and have a linear alkyl group, an alkoxy group, a substituted benzamidineoxy group or the like as a linear structure instead of a linear one, and exhibit liquid crystallinity and generally contain It is called a disc-shaped liquid crystal. However, as long as the molecule itself has a negative one-axis property and can be assigned to a 29 201132722, it is not limited to the above description. Further, in the present invention, the discotic liquid crystal compound has a polymerizable unsaturated group (for example, an acrylonitrile group, a mercapto fluorenyl group, a vinyl group, a propylene group or the like) which is hardened by heat, light or the like. Further, it is not necessary for the final formation of the discotic liquid crystal layer to be the above-mentioned compound, and it also includes a polymerized or crosslinked by a reaction of a polymerizable unsaturated group, and which loses liquid crystallinity by high molecular weight. Further, the discotic liquid crystal compound refers to a reaction product of a discotic liquid crystal which does not exhibit liquid crystallinity by reaction with various discotic liquid crystal compounds and other low molecular compounds or polymers, and the molecule itself is optically negative. One of the axial compounds as a whole. The alignment treatment of the disc-shaped liquid crystal is to rub the surface of the transparent substrate film or to use an alignment film. The alignment film may, for example, be an inorganic oblique evaporation film or an alignment film which rubs a specific organic polymer film. There is also a film which is formed of an azobenzene-inducing body, a film which is heterogeneous by light, and which has a directionality and is uniformly arranged. The organic alignment film may be an organic polymer film forming a hydrophobic surface such as a polyimide film or an alkyl chain-modified polyvinyl alcohol, polyvinyl butyral or polydecyl acrylate. Further, the inorganic oblique evaporation film can evaporate the film obliquely like Si. The discotic liquid crystal compound is oriented obliquely, and the method can be used, for example, to form a S&amp film on a transparent substrate film, followed by coating a discotic liquid crystal compound (polymerizable liquid crystal compound) and tilting it, followed by ultraviolet light. A method such as light irradiation or heat to mosquito or the like. X, or the tilting alignment of the disc-shaped liquid crystal may be formed after the other alignment is applied, and the transparent adhesive or the pressure sensitive adhesive on the filament is transferred to the transparent support. 30 201132722 δ 亥 形 液晶 液晶 - - - - - - - - - - - - - - - - - - - - - - - a 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士 富士Wide viewing angle film made by Soft Film. The liquid crystal optical compensation layer other than the above may be formed by, for example, a nematic liquid crystal monomer and/or a polymer. Further, as shown in Fig. 3, the optical film of the present invention can be used in a single-layer layer of a transparent base film Au on the side where the liquid crystal optical compensation layer Al3 is not formed, and a polarizing protective film A15 is laminated. . The polarizer A14 was bonded to the transparent base film A11 using an adhesive. On the other hand, in the third embodiment, the transparent base film AU has a transparent protective film _', but a polarizing plate having a transparent protective film on one side or both sides of the polarizing film may be laminated on the transparent base film All. The polarizer is not particularly limited, and various materials can be used. As a polarizer, 2, if a dichroic substance which makes iodine or a chromophoric dye is adsorbed to a polyvinyl alcohol film, a partially condensed polyvinyl alcohol film, or a vinyl acetate Polymer (4) and single _ stretcher, can be:: etc. = alcohol dehydration treatment, or gas-gas removal: : special: rare alignment film. In these, it is preferable to use a polarizer formed of a coloring matter f such as polyethylene, moth or the like. ‘,, there are no special restrictions, generally around 5~80μιη. The thickness of the U sub-particles is dyed with 峨 并 and can be made, for example, by dipping the polyvinyl alcohol into the black color of the aqueous solution of hydrazine and extending it to 3 to 7 times the original length. . Depending on the demand, 31 201132722 may include an aqueous solution such as phytosanitary or sulfur-based gasification. In addition, depending on the demand, the village was immersed in water in a poly(tetra) alcohol (tetra) membrane before washing to be washed with water. By washing the polyvinyl alcohol (tetra) m with water, the gambling or anti-caking agent on the surface of the polyethylene-based film can be washed, and in addition, the polyethylene-based film can be swollen to prevent non-uniformity such as non-uniformity of dyeing. The effect. The extension can be carried out after the dyeing of the enamel, or it can be added during the dyeing, and it can be dyed with moth after the extension. It can also be extended on-line as an aqueous solution or a bath towel. It is preferable to form a material of the transparent protective film which is not disposed on one side or both sides of the polarizer, which is superior to transparency, mechanical strength, thermal stability, moisture barrier property, and uniformity. The transparent protective film can be made of the same material as the transparent substrate film. Further, the film thickness may be the same. Further, the transparent base film and the transparent protective film may be made of the same polymer material, or different polymer materials or the like may be used. The polarizer, the transparent base film, and the transparent protective film are usually sealed with a water-based adhesive or the like. Examples of the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gum-based adhesive, a vinyl-based latex, an aqueous polyurethane, and an aqueous polyester. Further, when the polarizer is bonded to the transparent device film and the transparent protective film, the activation treatment can be applied to the transparent substrate film and the transparent protective film. The activation treatment may be carried out by various methods such as saponification treatment, corona treatment, low pressure uv treatment, or plasma treatment. The activation treatment is particularly effective in the case where the transparent base film is a cellulose triacetate, a norbornene resin, a polycarbonate, or a polyolefin resin. It is also possible to apply a treatment to the surface of the transparent protective film without applying a hard coating layer, anti-reflection treatment, anti-adhesion, or diffusion and anti-glare. Further, in addition to the optical film in which the polarizing plate is laminated, the optical film of the adhesive optical film of the present invention can be used to form an optical layer by forming an image display device such as a liquid crystal display device. For example, there is a reflection plate or a counter-transmission plate, a phase difference plate (including a 波长 or 丨 with a wave plate), and a brightness enhancement film or the like which is used in an optical layer formed by a liquid crystal display device or the like. These may be used alone as an optical film, or may be practically laminated on the polarizing plate and may be used in one layer or two or more layers. The optical film in which the optical layer is laminated on the polarizing plate can be formed by laminating in a manufacturing process such as a liquid crystal display device, and the layer is preliminarily laminated as an optical film, and has stability or composition superior to quality. The work or the like can improve the manufacturing steps such as the liquid crystal display device. When laminating, an appropriate bonding mechanism such as an adhesive layer can be used. In the case of performing the aforementioned polarizing plate and other material returns, the phase difference characteristics of the objective of the optical ship are set to set an appropriate arrangement angle. The adhesive optical film of the present invention can be suitably used in the formation of various kinds of viewing devices such as liquid crystal display devices. The formation of the liquid crystal display device can be carried out according to the driving knowledge. In other words, the liquid crystal display device is generally formed by appropriately assembling a liquid crystal cell, an adhesive optical film, and a lighting system as needed, and mounting a driving circuit or the like. In the present invention, there is no special (four) other than the point of using the adhesive optical film of the present invention, and thus it is possible to use π. For the liquid crystal cell, for example, the type, the (10) type, or the type 荨 can be used. 33 201132722 A liquid crystal display device in which an adhesive optical film is disposed on one side or both sides of a liquid crystal cell, or a suitable liquid crystal display device such as a backlight or a reflector in an illumination system can be formed. At this time, the optical film of the present invention can be disposed on one side or both sides of the liquid crystal lattice. When the optical film is placed on both sides, the same may be the same or different. Further, when the liquid crystal display device is formed, for example, a suitable layer such as a diffusion plate, an anti-glare layer, an anti-reflection film, a protective plate, a ruthenium array, a lens array sheet, an optical diffusion plate, and a backlight may be one layer. Or more than 2 layers are placed in the appropriate location. EXAMPLES Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to the examples. And, in each case, and. /〇 is the weight basis. The block copolymer or the graft copolymer used in the examples and the comparative examples was obtained by the following production examples using the products which were dried and purified by a usual method. The molecular weight, molecular weight distribution, composition, glass transition temperature of each block, and polymerization conversion ratio of the obtained block copolymer and graft copolymer at this time were carried out by the following methods. (1) Determination of the number average molecular weight (Μη), weight average molecular weight (Mw), and molecular weight distribution (Mw/Mn) of a gel permeation chromatography (GPC): Apparatus: a gel permeation chromatograph manufactured by Tosoh Corporation HLC-8020), pipe column: TSKgsl GMHXL, G4000HXL and G5000HXL manufactured by Dongcao Co., Ltd. are connected in series, and the solution is: tetrahydrogen, the flow rate of the solution: l.ml/min, column temperature: 40 . (:, 34 5 201132722 Test method: differential refractive index (RI), calibration curve: using standard polystyrene. (2) Content of each copolymerized component in the copolymer of hydrogen proton nuclear magnetic resonance (1H_nMR) spectrometry Measurement: Shou set; NMR apparatus (JNM-LA400) manufactured by JEOL Ltd., &gt; Valley medium. Heavy gas simulation. In the 1H-NMR spectrum, signals near 3.6 ppm and 4.0 ppm are respectively assigned to decyl methacrylate units. The ester group (_〇_CH3) and the butyl group of the butyl acrylate unit (-0-CH2-CH2_CH2-CH3), and the content of the copolymerized component is calculated by the ratio of the integral values thereof. (3) Glass Calculation of Transfer Temperature (Tg): The glass transition temperature is a theoretical value calculated from the formula of FOX from the ratio of the monomer to the monomer produced in the copolymer. Production Example 1 (Synthesis of Block Copolymer 1) After adding a three-way cock to a 2 L three-necked flask and replacing the inside with nitrogen, 868 g of toluene, 43 4 g of dimethoxyethane, and isobutyl bis (2,6·di-t) were added at room temperature. · butyl _4_mercaptophenoxy) aluminum 4 〇 2 mm 〇 i of toluene solution 60.0g, in addition, and including 3.78 g of a mixed solution of 6.37 mmol of cyclohexene and η-hexane of sec-butyllithium. Then, methyl methacrylate (hereinafter abbreviated as MMA) 51_5 g was added thereto, and stirred at room temperature. Then, the internal temperature of the polymerization liquid was cooled to _3 〇. 〇, and η-butyl acrylate (hereinafter abbreviated as nBA) 24 〇g was dropped in 2 hours. Next, force 35 201132722 into MMA51. After 5 g of the mixture was stirred at room temperature for one night, 3.5 〇g of methanol was added to stop the polymerization reaction. The obtained reaction liquid was poured into decyl alcohol, and the precipitate was recovered by a furnace and dried to obtain 340 g of three. Block copolymer 1. As a result of W-NMR measurement and GPC measurement, the above triblock copolymer 1 was a triblock copolymer of PMMA-PnBA-PMMA, and the weight average molecular weight (^^) was 7.9&gt; 'And the number average molecular weight (1\/[11) is 6.2\104, and the molecular weight distribution (Mw/Mn) is 1.27.), PMMA-PnBA-PMMA means polymethyl methacrylate-polyacrylic acid η-butyl ester-poly The oxime methacrylate. The weight ratio of the monomer units of the triblock copolymer 1 is ηΒΑ / ΜΜΑ = 70 / 30. Production Example 2 (Synthesis of Block Copolymer 2 In Production Example 1, a triblock copolymer 2 was obtained in the same manner as in Production Example 1 except that 2-ethylhexyl acrylate (hereinafter abbreviated as 2 Å) was used instead of η 。. The results of h-NMR measurement and GPC, The above triblock copolymer 2 is a triblock copolymer of PMMA-P2EHA-PMMA, and has a weight average molecular weight (Mw) of 9.2×10 4 , a number average molecular weight (Μη) of 7.3×10 4 , and a molecular weight distribution (Mw/Mn) of 1-26. . Further, ΡΜΜΑ-Ρ2ΕΗΑ-ΡΜΜΑ means polymethyl methacrylate-polyethyl 2-ethylhexyl acrylate-polymethyl methacrylate. The weight ratio of the monomer units of the three-block copolymer 2 was 2EH A / MMA = 69 / 31. Production Example 3 (Synthesis of Block Copolymer 3) In a 500 L reactor in which nitrogen was substituted, 80.9 kg of nBA and 2.1 kg of t-butyl acrylate (hereinafter abbreviated as tBA) were blended as a single constituting acrylic polymer block 36 201132722 After the body, the first copper 580g was tempered and stirred. Thereafter, 583 g of diethyl 2,5-dibromoadipate was dissolved in a solution of 7.3 kg of acetonitrile, and held at 75 ° C for 30 minutes, and then 70 g of PMDTA was added. After adding PMDTA at any time and after 3 hours, 82.5 kg of toluene, 400 g of cuprous vapor, 70 g of PMDTA, and 35.6 kg of MMA were added. After the completion of the reaction, 120 kg of toluene was added to dilute the reaction solution, and the reactor was cooled to stop the polymerization. Further, toluene was added to the obtained acrylic block copolymer solution to have a polymer concentration of 25% by weight. 1.6 kg of p-toluenesulfonic acid-hydrate was added to the solution, and the mixture was stirred at 150 ° C for 4 hours in a nitrogen-substituted reactor, and then t-butyl tBA was converted into a carboxyl group to obtain a triblock copolymer 3. As a result of W-NMR measurement and GPC, the above triblock copolymer 3 was a triblock copolymer of PMMA-P[nBA/AA]-PMMA, and the weight average molecular weight (Mw) was 1.8 χ105, and the number average molecular weight ( Μη) was 1.3×l〇5, and the molecular weight distribution (Mw/Mn) was 1.38. Further, ΡΜΜΑ-Ρ[ηΒΑ/ΑΑ]-ΡΜΜΑ indicates polymethyl methacrylate-[copolymer of η-butyl acrylate and acrylic acid]-polymethyl methacrylate. The weight ratio of the monomer units of the triblock copolymer 3 is ηΒΑ/ΑΑ/ΜΜΑ = 69/2/29. Production Example 4 (Synthesis of Graft Copolymer 4) To a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, and a stirrer, 233 g of toluene, nBAlOOg, and 2,2'-azobisisobutylate were added at room temperature. After 0.2 g of nitrile was substituted with nitrogen, the mixture was heated to 55 ° C for 6 hours to obtain a solution of poly(n-butyl acrylate).曱 曱 曱 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' The graft copolymer 4 was obtained by carrying out usual solution polymerization of toluene as a solvent. As a result of A-NMR measurement and GPC, the weight average molecular weight (Mw) of the above graft copolymer 4 was 2.2 χ1 〇 5, and the number average molecular weight (Mn) was 1.7 x 1 〇 5, and the molecular weight distribution (Mw/Mn) was 1.29. However, the weight ratio of the monomer units was nBA/MMA = 67/33. Production Example 5 (Synthesis of Triblock Copolymer 5) After attaching a three-way cock to a 2 L1 three-necked flask and replacing the inside with nitrogen, 868 g of toluene and 1,2-dimethoxyethane 43 were added at room temperature. 4g, and isobutyl bis(2,6-di-t-butyl-4.nonyloxy)aluminum 4〇2mm〇1 in toluene solution 60_0g, and added with sec-butyl lithium 6.37mm〇l A mixed solution of cyclohexane and η-hexane was 3_68 g. Next, 5.1 g of aMMA46 &amp; and decyl acrylate (hereinafter abbreviated as MA) was added thereto, and then allowed to stand at room temperature for 6 minutes. Then, the internal temperature of the polymerization liquid was cooled to _3 (rc, and a mixture of nBA 192 g and MA 48 g was dropped in 2 hours. Further, MMA 46.4 g and MA 5.1 g were added and stirred at room temperature for one night, and then sterol was added. 3 5 〇 § The polymerization reaction was stopped. The prepared reaction liquid was poured into methanol, and after drying the precipitate, the 334 g of the triblock copolymer 5 was obtained. h-NMR measurement and GPC As a result of the measurement, the above triblock copolymer 5 is a triblock copolymer of P[MMA/MA]-P[nBA/MA]-P[MMA/MA], and the weight average molecular weight (Mw) is 12.1χ104. The number average molecular weight (?η) is 9.3 X 104, and the molecular weight distribution (Mw/Mn) is 13 〇. And, 38 5 201132722 P[MMA/MA]-P[nBA/MA]-P[MMA/MA] [Copolymer of decyl methacrylate and decyl acrylate]-[Copolymer of butyl acrylate and decyl acrylate]-[Copolymer of decyl methacrylate and methyl acrylate] Triblock copolymer 5 The weight ratio of the monomer unit was nBA/MA/MMA=56/l7/27. Example 1 &lt;Formation of Adhesive Layer&gt; The triblock copolymer 1 obtained in Production Example 1 was dissolved in toluene Medium solids After the adhesive solution having a concentration of 30%, the adhesive solution was applied to the spacer formed of the release-treated polyester film (thickness 38 μm) by reverse roll coating to make the adhesive layer after drying. The thickness was 2 〇μηι, and heat treatment was performed at 155 ° C for 3 minutes to volatilize the solvent to obtain an adhesive layer. <Optical Film> A wide viewing angle (WV) film manufactured by Fujifilm Co., Ltd. was used. The WV film was transparent. The cellulose-based polymer film of the base film is obliquely aligned with a disc-shaped liquid crystal layer having disc-shaped liquid crystal molecules. The WV film is separated into an inclined alignment layer of disc-shaped liquid crystal molecules, and KOBRA-made by Oji Scientific Instruments Co., Ltd. 21ADH measurement; I = 590 nm characteristic. The maximum in-plane refractive index is nx, the refractive index in the direction orthogonal to the direction of the in-plane maximum refractive index is set to ny, and the refractive index in the film thickness direction is set to Nz. Let the film thickness be d. The transparent support is Δ nd=(nx-ny)X (1=1211111, and 1^11=(1^-112)\(!=10〇11111. On the other hand, tilt The alignment layer is inclined in the direction of the optical axis to change the incident in the range of -50 to 50. To determine the phase difference, Δ nd = 30 nm, Rth = l50 nm, and the average tilt 39 201132722 angle 0 = 17. The saponification treatment of the transparent substrate side of the WV film is followed by a polyethylene glycol system. The saponified surface was bonded to a polyvinyl alcohol-based polarizer (manufactured by Nitto Denko Corporation, SEG 5424WL) having a thickness of 20 #m. On the other hand, a transparent protective film (diacetate film, thickness: 8 μM) was attached to the other side of the polarizer by the same polyvinyl alcohol-based adhesive as described above to prepare an optical film having a polarizing plate. (Polarizer with optical compensation layer). &lt;Preparation of primers&gt; The toluene was diluted to a solution having an amine group having a first-order amine group (manufactured by Nippon Shokubai Co., Ltd., p〇LYMENT ΝΚ38〇) at a solid content of 2%. A primer for a phenol-based antioxidant (manufactured by Chiba Speciality Chemical Co., Ltd., IRGANOX 1010) was added to 100 parts of the solid content of the solution. &lt;Production of Adhesive Optical Film&gt; The primer was applied to the surface of the disk-shaped liquid crystal layer of the polarizing plate with the optical compensation layer and dried by using a bar coater to form a coating amount of 0.2 cubic A sub-primary coating (having a thickness of 8 〇 nmp, followed by bonding a release film having the above-described adhesive layer to the undercoat layer) to produce an adhesive optical film. Example 2 was prepared by using Production Example 2. Adhesive optical film was produced in the same manner as in Example 1 except that the triblock copolymer 1 was produced in the same manner as in Example 1 except that the triblock copolymer 1 obtained in the production example i was used in the formation of the adhesive layer in Example 1. Example 3 5 40 201132722 In place of the triblock copolymer 3 obtained in Production Example 3, the triblock copolymer 1 obtained in Production Example 1 in the formation of the adhesive layer in Example 1 was used instead. An adhesive optical film was produced in the same manner as in Example 1. Example 4 Instead of using the graft copolymer 4 obtained in Production Example 4, instead of the formation of the adhesive layer in Example 1, it was produced. In addition to the triblock copolymer 1 obtained in Example 1, An adhesive optical film was produced in the same manner as in Example 1. Example 5 In place of the formation of the adhesive layer in Example 1, except that the triblock copolymer 5 obtained in Production Example 5 was used, the production example 1 was used. An adhesive optical film was produced in the same manner as in Example 1 except for the obtained triblock copolymer 1. Comparative Example 1 In contrast to the production of the adhesive optical film in Example 1, except that it was not provided An adhesive optical film was produced in the same manner as in Example 1 except for the undercoat layer. Comparative Example 2 &lt;Preparation of Acrylic Adhesive&gt; Base Polymer was used to contain nBA: MMA = 70: 30 (weight ratio) An acrylic polymer having a weight average molecular weight of 1.65 million formed by the random copolymer 6 (the polymerization initiator is a mixture of 0.3 parts of 2,2'-azobisisobutyronitrile and 100 parts of the monomer) Solution (solid content: 155%). &lt;Production of Adhesive Optical Film&gt; In addition to the use of the solution of the random copolymer 6 obtained above, in place of the formation of the adhesive layer in Example 1, it was produced in Production Example 1. Triblock copolymer 41 201132722 An adhesive optical film was produced in the same manner as in Example 1. Comparative Example 3 (Synthesis of plate segment copolymer 7) In place of Production Example 1, except that η-butyl methacrylate (hereinafter abbreviated as nBMA) was used. Triblock copolymer 7 was obtained in the same manner as in Production Example 1 except for MMA. As a result of measurement by H-NMR and GPC, the above triblock copolymer 7 was a triblock copolymer of PnBMA-PnB A-PnBMA. And the weight average molecular weight (Mw) was 1.2x1〇5, the number average molecular weight (Μη) was 9.2X104, and the molecular weight distribution (Mw/Mn) was 1.30. And Ρ ΒΜΑ ΒΜΑ Ρ Ρ ΒΑ ΒΑ Ρ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ ΒΜΑ The weight ratio of the monomer units of the three-block copolymer 5 is η ΒΑ / η ΒΜΑ = 7 〇 / 3 〇. &lt;Production of Adhesive Optical Film&gt; In addition to the use of the above-obtained triblock copolymer 7 in place of the formation of the adhesive in Example 1 as in the case of the triblock copolymer w prepared in Production Example 1 An adhesive optical film was produced in the same manner as in Example 1. Reference Example 1 &lt;Preparation of Acrylic Adhesive&gt; The base poly-sigma system used a random copolymer containing ηΒΑ: acrylic acid 4 · benzylidene: abbreviated as 4 ΗΒΑ) = 99 : 丨 (weight ratio) A propylene-based polymer having an average knife amount of 1.65 million in the formation (polymerization initiator is an azobisisomeric nitrile 〇·3 part to a single _ part). 15.5/0). Further, with respect to 100 parts of the solid content of the above-mentioned acrylic polymer ray 8 42 201132722 liquid, 0.3 parts of peroxidized dimercaptomethyl hydrazine (manufactured by Nippon Oil & Fat Co., Ltd., NYPER BMT injury v), and triacetin xylene 0.02 parts of sulphuric acid lysate (TAKENATE Dll〇N, manufactured by Mitsui Takeda Chemical Co., Ltd.), and yttrium coupling agent (made by Amika Chemical Co., Ltd., A_1〇〇) containing acetamidine As a crosslinking agent, an adhesive solution (solid content 丨 2%) was prepared. &lt;Production of Adhesive Optical Film&gt; In addition to the use of the adhesive solution containing the random copolymer 8 obtained above, instead of the diblock obtained by the production example in the formation of the adhesive layer in Example 1 An adhesive optical film was produced in the same manner as in Example 以外 except for the solution of the copolymer 1. The following evaluation was carried out on the above-mentioned adhesive optical film. The results are shown in Table 1. (Sealing property of the adhesive layer and the optical film substrate) The above-mentioned adhesive optical film is cut into a size of 25 mm x 150 mm and the layer of the adhesive and the indium-tin oxide are evaporated to a thickness of 5 〇 μm. After the evaporation surface of the evaporation film on the surface of the phthalic acid glycol vinegar film is attached, it is placed in a 23 ° C / 60% RH environment for 2 〇 minutes or more. Then, the end portion of the polyethylene terephthalate film was peeled off by hand, and it was confirmed that the adhesive was attached to the side of the film, and the tension of Shimadzu Corporation was used. The test machine AG-1 was used to measure (25 ° C) at 180. The stress at the time of peeling at a speed of 300 mm/min (N/25 mm). (Continuous force and remanufacturability) The above-mentioned adhesive optical film was cut into a width of 25 nm, and was pressed back and forth by a 2 kg roller, and then adhered to an alkali-free glass having a thickness of 〇7 mm ('2011-2011's '430 201132722 1737). When the sample was hardened at 23 ° C for 1 hour (initial) and 1 year after curing (1 year later), the adhesion force at the peeling angle of 180° and the peeling speed of 300 mm/min was measured by using a tensile tester ( N/25mm). Further, the state of the glass surface after peeling was visually observed and evaluated on the basis of the following criteria. However, the average value of the above evaluations was 50 times. ◎: The paste can be peeled off without leaving the adhesive (the force is less than 20N/25mm). 〇: Although the paste can be peeled off without peeling off, it is peeled off (the force is 20N/25mm or more). △: Residue of the paste is generated (0 to 5 pieces) /50 pieces) X : Produced paste residue (6 pieces or more / 50 pieces) 44 8 201132722 Evaluation of remanufacturing (viscose residue) 1 1 year later 1 ◎ ◎ 〇 ◎ ◎ XXXX Initial ◎ ◎ ◎ ◎ ◎ X &lt;] Life (internal break ◎ then force (n/25mm) 1 year later oo VO m in m initial to CN 00 〇 〇 \ 〇 \ airtight (N / 25mm) (N undercoat with or without 41 adhesive polymerization Form &lt; Su| CL, &lt; 5 (N ω味|'Ί Oh PMMA/P[nBA/AA]/PMMA (triblock copolymer 3) &lt; |I 12 5味£球 [PMMA/MA] /P [nB A/MA]/P [MM A/MA] (triblock copolymer 5) &lt;S-flavor S郐, 丨1 random copolymer 6 &lt; PQ ^ 荽$荽0Q ^ £趔S u| CL, composition of random copolymer 8 copolymer (weight ratio) nBA/MMA =70/30 1 2EHA/MMA=69/31 nBA/AA/MMA=69/2/29 nBA/MMA=67/33 nBA/MA/MMA=56/l 7/27 nBA/MMA=70/30 nBA/MMA=70/30 nBA/nBMA=70/30 nBA/4HBA=99/l Example 1 1 Real Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 1 Comparative Example 1 Comparative Example 1 45 201132722 The glass transition temperature of each (co)polymer segment in the triblock copolymer was: PMMA: 105° C ' ΡηΒΑ : -45〇C ' P2EHA : -55〇C ' P[MMA/MA] : 92〇C ' P[nBA/MA] : -36〇C '

PnBMA : 20〇C。 I：圖式簡單說明3 第1圖係本發明之黏著型光學薄膜之一例的剖面圖。 第2圖係本發明之黏著型光學薄膜之一例的剖面圖。 第3圖係本發明之黏著型光學薄膜之一例的剖面圖。 【主要元件符號說明】 A…光學薄膜 B…底塗層 C…黏著劑層 All…透明基材薄膜 A12…配向膜 A13…液晶光學補償層(盤形液晶層） A14…偏光子 A15…透明保護薄膜 ⑤ 46PnBMA: 20〇C. I: BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing an example of an adhesive optical film of the present invention. Fig. 2 is a cross-sectional view showing an example of the adhesive optical film of the present invention. Fig. 3 is a cross-sectional view showing an example of the adhesive optical film of the present invention. [Main component symbol description] A... Optical film B... Undercoat layer C... Adhesive layer All... Transparent substrate film A12... Alignment film A13... Liquid crystal optical compensation layer (disc liquid crystal layer) A14... Polarizer A15... Transparent protection Film 5 46

Claims (1)

201132722 七、申請專利範圍： 1. 一種黏著型光學薄膜，係黏著劑層隔著底塗層設在光學 薄膜上者，其特徵在於： 黏著劑層係由含有嵌段共聚物或接枝共聚物作為 基底聚合物之黏著劑所形成，該等共聚物具有：玻璃轉 移溫度在0°C以下之（曱基）丙烯酸系聚合物（A)鏈段； 及，玻璃轉移溫度在40°C以上之（曱基）丙烯酸系聚合物 (B)鏈段；且 底塗層含有聚合物類。 2. 如申請專利範圍第1項之黏著型光學薄膜，其中（甲基) 丙烯酸系聚合物（A)鏈段係總單體單元之5 0重量％以上 為丙烯酸烷基酯，且（曱基）丙烯酸系聚合物(B)鏈段係總 單體單元之15重量％以上為曱基丙烯酸烷基酯。 3. 如申請專利範圍第1項之黏著型光學薄膜，其中黏著劑 所含有之基底聚合物為B-A-B之三嵌段共聚物（但A表示 (曱基）丙烯酸系聚合物(A)鏈段，且B表示（曱基）丙烯酸 系聚合物(B)鏈段）。 4. 如申請專利範圍第1項之黏著型光學薄膜，其中底塗層 之聚合物類為末端具有1級胺基之聚合物。 5. 如申請專利範圍第4項之黏著型光學薄膜，其中於末端 具有1級胺基之聚合物為末端具有1級胺基之聚（曱基）丙 稀酸醋。 6. 如申請專利範圍第4項之黏著型光學薄膜，其中末端具 有1級胺基之聚合物中之1級胺基係來自聚乙烯亞胺系 47 201132722 材料者。 7·如申請專利顧第丨項之黏著型光學薄膜，其中底塗層 相對於聚合物類⑽重量份含有抗氧化劑〇〇1〜5〇〇重量 份。 8.如申請專利範㈣7項之黏著型光學賴，其中抗氧化 W係選自笨酚系、鱗系硫系及胺系之抗氧化劑中之至少 任1種氧化劑。 9·如申請專利範圍第1項之黏著型光學薄膜，其中光學薄 骐於透明基材薄膜之單面具有液晶光學補償層，且黏著 劑層係隔著底塗層設置於該液晶光學補償層上。 10. 如申請專利範圍第9項之黏著型光學薄膜，其中液晶光 千補i員層為盤形液晶（discotic liquid crystal)層。 11. 如申請專利範圍第9項之黏著型光學薄膜，其中光學薄 膜於未形成液晶光學補償層之側的透明基材薄膜之單 面上積層有偏光子。 12. —種影像顯示裝置’係至少使用有1片如申請專利範圍 第1〜11項中任一項之黏著型光學薄膜。 ⑧ 48201132722 VII. Patent application scope: 1. An adhesive optical film, which is provided on the optical film through an undercoat layer, is characterized in that: the adhesive layer is composed of a block copolymer or a graft copolymer. Formed as an adhesive for a base polymer having: a (mercapto)acrylic polymer (A) segment having a glass transition temperature of 0 ° C or less; and a glass transition temperature of 40 ° C or higher (Mercapto) acrylic polymer (B) segment; and the undercoat layer contains a polymer. 2. The adhesive optical film of claim 1, wherein the (meth)acrylic polymer (A) segment is more than 50% by weight of the total monomer unit of the alkyl acrylate, and The acrylic polymer (B) segment is 15% by weight or more of the total monomer unit, which is an alkyl methacrylate. 3. The adhesive optical film of claim 1, wherein the base polymer contained in the adhesive is a triblock copolymer of BAB (but A represents a (mercapto) acrylic polymer (A) segment, And B represents a (mercapto)acrylic polymer (B) segment). 4. The adhesive optical film of claim 1, wherein the polymer of the undercoat layer is a polymer having a terminal amine group at the end. 5. The adhesive optical film according to item 4 of the patent application, wherein the polymer having a primary amino group at the terminal is a poly(indenyl) acrylate having a terminal amine group at the terminal. 6. The adhesive optical film according to item 4 of the patent application, wherein the first-stage amine group of the polymer having a grade 1 amine group at the end is derived from the polyethyleneimine system 47 201132722 material. 7. The adhesive optical film according to the patent application, wherein the undercoat layer contains an antioxidant 〇〇1 to 5 parts by weight relative to the polymer (10) parts by weight. 8. The adhesive type optical ray according to claim 7 (4), wherein the antioxidant W is selected from at least one of an oxidizing agent selected from the group consisting of a phenol, a sulphur, and an amine. 9. The adhesive optical film of claim 1, wherein the optical thin film has a liquid crystal optical compensation layer on one side of the transparent substrate film, and the adhesive layer is disposed on the liquid crystal optical compensation layer via the undercoat layer. on. 10. The adhesive optical film of claim 9, wherein the liquid crystal light is a discotic liquid crystal layer. 11. The adhesive optical film of claim 9, wherein the optical film is laminated with a polarizer on a single side of the transparent substrate film on the side where the liquid crystal optical compensation layer is not formed. 12. An image-displaying apparatus is used in which at least one of the adhesive optical films of any one of claims 1 to 11 is used. 8 48
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