TW201028292A - Process for producing composite polarizing plate - Google Patents
Process for producing composite polarizing plate Download PDFInfo
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- TW201028292A TW201028292A TW98142236A TW98142236A TW201028292A TW 201028292 A TW201028292 A TW 201028292A TW 98142236 A TW98142236 A TW 98142236A TW 98142236 A TW98142236 A TW 98142236A TW 201028292 A TW201028292 A TW 201028292A
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- transparent protective
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
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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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polarising Elements (AREA)
Abstract
Description
201028292 , 六、發明說明: 、 【發明所屬之技術領域】 ·. 本發明係有關一種複合偏光板的製造方法。 : 【先前技術】 液晶顯示裝置係活用其消耗電力低且以低電力動 作、輕量且薄型等之特徵,而可使用於各種顯示用裝置。 此液晶顯示裝置係由液晶胞(liquid crystal cell)、偏光板、 相位差薄膜、聚光片、擴散膜、導光板、及光反射片等許 多光學構件所構成。因此,藉由構成此等光學構件之薄膜 ❿ 或薄片的片數删減或膜厚減少等改良,可謀求液晶顯示裝 置之生產效率或亮度的提昇及輕量、薄型化等,如此之研 究正在盛行中。 進一步,於液晶顯示裝置係被要求亦可承受嚴苛的耐 久條件。例如在汽車導航系統用之液晶顯示裝置中,有時 其被放置之車内的溫度或溼度會變成非常高,又,即使在 行動電話、攜帶型終端機器等之顯示器或電視、電腦用之 g 顯示器等中,依該等之使用環境或設置場所,有時會被曝 露於溫度及濕度的變化激烈的條件下,故尋求亦可承受如 此嚴苛條件的使用之製品性能。 液晶顯示裝置之零件的偏光板一般係成為在偏光膜 之雙面或單面層合有透明保護膜之構造。例如,偏光膜係 對聚乙烯醇系樹脂薄膜進行單軸延伸與二色性色素的染色 後,進行硼酸處理而引起交聯反應,然後,藉水洗、乾燥 來製造。二色性色素係使用蛾或二色性有機染料。於依如 4 321675 201028292 此做法所得到之偏光膜的雙面或單面層合保軸而 光板’並組入至液晶顯示裝置中而個。^呆護膜係常使 以二乙醯基纖維素(triacetyl ceuui〇se)為代表之纖維素用 酸酉旨系樹脂薄膜,其厚度通例為3〇至i2〇em左右。’、乙 保護膜之層合係常使用由聚乙烯醇系樹脂之水溶 =、’ 的接著劑。 冓成 於吸附配向有二色性色素之偏光膜的雙面或單面 〇 用由聚乙烯醇系樹脂之水溶液所構成的接著劑而層合由^ 乙酸基纖維素所構成之保護膜的偏光板,係在濕件; 長時間使用時,有偏光性能降低、或保護膜與偏 離之問題存在。 膘易剝 因此,使至少一者的保護膜嘗試以纖維素乙酸酯系以 外的樹脂構成。例如,於JPH08-43812-A中已記載在偏光 骐之雙面層合保護膜的偏光板中,使其保護膜之至少一 以具有相位差薄膜之功能的熱塑性降冰片埽系樹脂^成。 又,於^1109-325226^中已記载使偏光膜之保^層中^ 至少一者以雙折射性的薄膜構成。 θ 3-方面,苯乙烯系樹脂薄膜係因苯乙烯系樹脂 鏈的分極率大於主鏈的分極率(有時稱為分極成負),故 度方向之折射率大的負的相位差薄膜正被研究。此處 度方向之折射率大的負的相位差薄膜係#aa+ 厚 斛t 糸知虽面内之最大折 射率方向(慢軸方向)的折射率為nx,於面内與其正交之方 向(快軸方向)的折射率為ny,厚度方向之折射率為、時, 具有咕ηχ>%之關係,且以(㈣抑叫所定義之^係 321675 201028292 數大約為〇之薄膜。但苯乙烯系樹脂薄膜係於耐熱性、機 . 械強度及耐藥品性上有問題,未達實用化。 有關苯乙烯系樹脂之耐熱性,已知可藉由使形成玻璃 ' 轉移溫度(以下,有時簡稱為Tg)高的樹脂之單體、例如降 冰片烯或馬來酸酐進行共聚合而被改善,但即使藉由如此 之共聚合,亦無法充分改善機械強度或耐藥品性。 亦已提出許多使其他單體與苯乙烯共聚合,或使其他 樹脂層層合於苯乙稀系薄膜的技術。例如,於W0 99/64500 中已記載將以苯乙烯作為代表例之芳香族乙烯基單體與α Ο -烯烴的本質上無規共聚物製成薄膜,亦暗示形成該薄膜與 其他之聚合物層的多層構造。又,於US2002/0169267A1 或JP2003-207640-A中已記載使以苯乙烯作為代表例之芳 香族乙烯基單體與非環狀烯烴單體及環狀烯烴單體共聚合 之三元共聚物製成相位差薄膜。進一步,於JP2003-90912-A 中已記載使由降冰片烯系樹脂所構成之配向薄膜與由苯乙 烯-馬來酸酐共聚合樹脂所構成之配向薄膜,介由接著劑層 ^ 而層合並形成相位差薄膜,於JP2004-167823-A中已記載 於聚烯烴系之多層薄膜層合聚苯乙烯系薄片。進一步,於 JP2006-192637-A中已記載由苯乙烯系樹脂所構成的第1 層、與由已調配橡膠粒子之丙烯酸系樹脂組成物所構成的 第2層,不介由接著劑層而層合,以作為相位差薄膜。 但是,使用苯乙烯系樹脂薄膜作為相位差薄膜時,為 達成所希望之相位差特性及機械強度,無法擴展苯乙烯系 樹脂薄膜之寬度,因此,可製作之薄膜的寬度會小於偏光 6 321675 201028292 - 膜之見度,或在以往附相位差薄膜之偏光板的製造方法中 a有其生產性明顯降低之問題。亦即,此時,若使偏光板、 » 與寬小於偏光板之相位差薄膜進行貼合,則會產生未貼合 相位差薄膜之偏光板部分。另外,若欲將偏光板切成貼合 於液晶胞之預定形狀,一般係相對於長度方向而裁切成直 角或斜角·’再裁切成其預定形狀,但因受此裁切,而使未 貼5相位差薄膜之偏光板部分係被廢棄。進一步,因該未 貼合相位差薄膜之偏光板部分亦算在裁切長度中,故生產 ®性明顯地降低。 又,進一步,使用苯乙烯系樹脂薄臈之相位差薄膜係 在兼作為偏光膜之保護膜而使用時,有時與偏光膜之接著 性差。 【發明内容】 ,發月之目的係在於提供一種生產性優良地製造旅 合偏光板的方法,該複合偏光板係由偏光板與使用笨匕攝 ❹系樹脂薄膜且寬度小於偏光板之相位差薄膜所層合而成, 並且偏光膜與相位差薄膜之密著力優異者。 本發明係包含下述者。 心—種複合偏光板之製造方法,該複合偏光板係鼻 =差⑽’其係由具有3層構造之延伸薄膜所構) 者^们層構造為由苯乙料如旨所構成之核層、與層/ ::成:層之雙面且由含有橡膠粒子之(曱基)丙烯酸系4 月曰組成物所構成之皮層的3層構造;以及 201028292 附單面透明保護膜之偏光板,其係層合於前述相位差 薄膜上,且於偏光膜之單面具有透明保護膜者; 而該製造方法之特徵係包含下述步驟(A)、步驟(B)、 步驟(C)、步驟(D)及步驟(E),或是包含下述步驟(A)、步驟 (B)、步驟(C)、步驟(F)及步驟(G): (A) 於偏光膜之單面貼合透明保護膜,於相反側之面 貼合具有黏著性之剝離性薄膜,製作附單面透明保護膜之 偏光板的步驟; (B) 將附單面透明保護膜之偏光板配合相位差薄膜之 寬度而沿著長度方向進行裁切的步驟; (C) 從偏光膜面除去剝離性薄膜之步驟; (D) 於相位差薄膜之單面、以及已除去剝離性薄膜之 附單面透明保護膜之偏光板的偏光膜面之至少一者,形成 在80°C中顯示O.IMPa以上之貯存彈性模數(storage elastic modulus)的黏著劑層之步驟; (E) 於已除去剝離性薄膜之附單面透明保護膜之偏光 板的偏光膜面,介由前述黏著劑層而貼合相位差薄膜之步 驟; (F) 於相位差薄膜之單面、以及已除去剝離性薄膜之附 單面透明保護膜之偏光板的偏光膜面之至少一者,形成含 有藉活性能量線之照射或加熱而進行硬化之環氧化合物的 樹脂組成物層,於該樹脂組成物層上重疊另一偏光板的偏 光膜面或相位差薄膜之步驟; (G) 藉由使該樹脂組成物層硬化,以於附單面透明保 8 321675 201028292 - 護膜之偏光板的偏光膜面,介由該樹脂組成物之硬化層而 • 貼合相位差薄膜之步驟。 . <2>如<1>項之方法,其中,該方法係依序包含步驟 (A)、步驟(B)、步驟(C)、步驟(D)及步驟(E),在步驟(D) 中,前述黏著劑層係形成於已除去剝離性薄膜之附單面透 明保護膜之偏光板的偏光膜面。 <3>如<1>項之方法,其中,該方法係依序包含步驟 (A)、步驟(C)、步驟(D)、步驟(B)及步驟(E),在步驟(D) ® 中,前述黏著劑層係形成於已除去剝離性薄膜之附單面透 明保護膜之偏光板的偏光膜面。 <4>如<1>項之方法,其中,該方法係依序包含步驟 (A)、步驟(B)、步驟(C)及步驟(E),且包含步驟(D),在步 驟(D)中,前述黏著劑層係形成於相位差薄膜之單面。 <5>如<1>項之方法,其中,該方法係依序包含步驟 (A)、步驟(B)、步驟(C)、步驟(F)及步驟(G),在步驟(F)中, ❹該樹脂組成物層係形成於已除去剝離性薄膜之附單面透明 保護膜之偏光板的偏光膜面。 <6>如<1>項之方法,其中,該方法係依序包含步驟 (A)、步驟(B)、步驟(C)及步驟(G),且包含步驟(F),在步 驟(F)中,該樹脂組成物層係形成於相位差薄膜之單面。 <7>如<2>或<3>項之方法,其中,在步驟(卩)中,前述 環氧化合物係含有:於分子内具有1個以上結合於脂環式 環之環氧基的化合物。 <8>如<1>至<7>項中任一項之方法,其中,核層之膜 9 321675 201028292 厚為10至lOOym,皮層之膜厚為1〇至ι〇〇瓜。 <9〉如小至<8>項中任一項之方法其中核層之玻 璃轉移溫度為12(^以上,皮層之破_移溫度為12叱以 下。 ―::㈣〉至<9>項令任一項之方法,其中,相位差 f =度係比步驟㈧所製作之附單面透明保護膜之偏 光板的寬度小10%以上。 ⑷中〈^如^至鲁項中任—項之方法,其中,在步驟 =中^_與透明賴麟使用含㈣乙騎緒腊或 %<虱樹月曰之接著劑而貼合。 菩南丨之方法,其巾,在㈣(a)巾,前述接 為3有藉活性能量線之照射或加熱而進行硬化之環氧 化合物的樹脂組成物。 TB之㈣ #用人古^°<12>項之方法’其巾,偏光職透明保護膜之 3有則述環氧化合物的樹脂組成物之貼合,係包含下 述步驟: 0 r ηΓΓ,之單面、及透明保護膜之單面的至少一者, 二盡:t前述環氧化合物之樹脂組成物層,並於前述含有 :驟m的樹脂組成物層上重疊另—偏光板或透 之步驟;以及 叉眠 胺品,别述含有環氧化合物的樹脂組成物層硬化’於偏光 ==述含有環氧化合物的樹脂組成物之硬化層而貼 口达明保濩膜之步驟。 14>如<12>或<13>項之方法其中’在步驟(人)中之 321675 10 201028292 - 前述環氧化合物係含有:於分子内具有1個以上結合於脂 環式環之環氧基的化合物。 - <15>如<1>至<14>項中任一項之方法,其中,前述透 明保護膜之厚度為20至300/zm。 <16>如<1>至<15>項中任一項之方法,其中,前述黏 著劑層之厚度為1至40/i m。 若依本發明之複合偏光板的製造方法,則於與相位差 薄膜貼合前,將附單面透明保護膜之偏光板配合相位差薄 ® 膜的大小而沿著長度方向來裁切,分成與相位差薄膜貼合 之附單面透明保護膜之偏光板、與不與相位差薄膜貼合之 附單面透明保護膜之偏光板,俾不會招致生產性降低。 進一步,附單面透明保護膜之偏光板之不與相位差薄 膜貼合之部分係可使用於其他製品,故全體之生產性明顯 地提高。 又,依本發明所得到之複合偏光板係相位差薄膜與偏 Q 光膜之密著性亦優異,具有高的耐久性能。 進一步,於被裁切之附單面透明保護膜之偏光板的偏 光膜側,藉由先貼合具有黏著性之剝離性薄膜,俾可防止 透明保護膜與偏光膜之貼合、或在裁切時之偏光膜的損傷。 依本發明所得到之複合偏光板係可適宜使用於液晶 顯示裝置,尤其是具備橫電場模式之液晶胞,亦即具備 IPS (In-Plane-Switching)胞的液晶顯示裝置。 【實施方式】 <複合偏光板之製造方法> 11 321675 201028292 本發明之複合偏光板的製造方法中,該複合偏光板係 具備: 相位差薄膜,其係由具有3層構造(皮層/核層/皮層) 之延伸薄膜所構成者,該3層構造為由苯乙烯系樹脂所構 成之核層、與層合於前述核層之雙面且由含有橡膠粒子之 (甲基)丙烯酸系樹脂組成物所構成之皮層的3層構造;以 及 附單面透明保護膜之偏光板,其係層合於前述相位差 薄膜上,且於偏光膜之單面具有透明保護膜者; 而該製造方法之特徵係包含下述步驟(A)、步驟(B)、 步驟(C)、步驟(D)及步驟(E),或是包含下述步驟(A)、步驟 (B)、步驟(C)、步驟(F)及步驟(G) ·· (A) 於偏光膜之單面貼合透明保護膜,於相反側之面 貼合具有黏著性之剝離性薄膜,製作附單面透明保護膜之 偏光板的步驟; (B) 將附單面透明保護膜之偏光板配合相位差薄膜之 寬度而沿著長度方向進行裁切的步驟; (C) 從偏光膜面除去剝離性薄膜之步驟; (D) 於相位差薄膜之單面、及已除去剝離性薄膜之附 單面透明保護膜之偏光板的偏光膜面之至少一者,形成在 80°C中顯示O.IMPa以上之貯存彈性模數的黏著劑層之步 驟; (E) 於已除去剝離性薄膜之附單面透明保護膜之偏光 板的偏光膜面,介由前述黏著劑層而貼合相位差薄膜之步 12 321675 201028292 • (F)於相位差薄膜之單面、及已除去剝離性薄膜之附單 / 面透明保護膜之偏光板的偏光膜面之至少一者,形成含有 藉活性能量線之照射或加熱而硬化之環氧化合物的樹脂組 成物層,於該樹脂組成物層上重叠另一偏光板的偏光膜面 或相位差薄膜之步驟; (G)藉由使該樹脂組成物層硬化,俾於附單面透明保 護膜之偏光板的偏光膜面,介由該樹脂組成物之硬化層而 ® 貼合相位差薄膜之步驟。 於本發明之複合偏光板的製造方法中,使附單面透明 保護膜之偏光板的偏光膜與相位差薄膜之貼合介由在80 °C中顯示O.IMPa以上的貯存彈性模數之黏著劑層而進行 之方法(包含步驟(A)、步驟(B)、步驟(C)、步驟(D)及步驟 (E)之方法)的較佳態樣係可舉例如:依序包含步驟(A)、步 驟(B)、步驟(C)、步驟(D)及步驟(E),在步驟(D)中,前述 © 黏著劑層係形成於已除去剝離性薄膜之附單面透明保護膜 之偏光板的偏光膜面的態樣(以下有時記為第一態樣);依 序包含步驟(A)、步驟(C)、步驟(D)、步驟(B)及步驟(E), 在步驟(D)中,前述黏著劑層係形成於已除去剝離性薄膜之 附單面透明保護膜之偏光板的偏光膜面的態樣(以下有時 記為第二態樣);以及依序包含步驟(A)、步驟(B)、步驟(C) 及步驟(E),且復包含步驟(D),在步驟(D)中,前述黏著劑 層係形成於相位差薄膜之單面的態樣(以下有時記為第三 態樣)。 13 321675 201028292 使附單面透明保護膜之偏光板的偏光膜與相位差薄 、 膜之貼合介由含有藉活性能量線之照射或加熱進行硬化之 \ 環氧化合物的樹脂組成物層而進行之方法(包含步驟(A)、 — 步驟(B)、步驟(C)、步驟(F)及步驟(G)之方法)的較佳態樣 係可舉例如:依序包含步驟(A)、步驟(B)、步驟(C)、步驟 (F)及步驟(G),在步驟(F)中,該樹脂組成物層係形成於已 除去剝離性薄膜之附單面透明保護膜之偏光板的偏光膜面 的態樣(以下有時記為第四態樣);以及依序包含步驟(A)、 步驟(B)、步驟(C)及步驟(G),且復包含步驟(F),在步驟(F) © 中,該樹脂組成物層係形成於相位差薄膜之單面的態樣(以 下有時記為第五態樣)。 [1]步驟(A) 在本發明之複合偏光板的製造方法中,首先,於偏光 膜之單面貼合透明保護膜,於相反側之面貼合具有黏著性 之剝離性薄膜,製作附單面透明保護膜之偏光板。 (偏光膜) ^ 於本發明之複合偏光板的製造方法所使用之偏光膜 係具有從自然光使某一方向的直線偏光選擇性地透過之功 能者。可舉例如:於聚乙烯醇系薄膜吸附、配向有碘之碘 系偏光膜;於聚乙烯醇系薄膜吸附、配向有二色性染料的 染料系偏光膜;及經塗佈向液性(lyotropic)液晶狀態之二色 性染料,而已配向、固定之塗佈型偏光膜等。此等之碘系 偏光膜、染料系偏光膜、及塗佈型偏光膜係具有從自然光 使某一方向之直線偏光選擇性地透過且吸收另一方向之直 14 321675 201028292 · - 線偏光的功能者,故稱為吸收型 、 纟本發明m法所使用的偏㈣翁僅可為上 :述之吸收型偏光膜,亦可為被稱為反射型偏光膜或散射型 偏光膜者,其係具有從自然光使某一方向的直線偏光選擇 性地透過,且反射或散射另—方向之直線偏光的功能。又, ==並不限定於具體舉例之偏光膜,只要是具有從自然 光使某一方向的直線偏光選擇性地透過之功能者即可。在 ❹^之偏光财,宜使用辨視性優異之吸收型偏光膜,其 中,更宜為偏光度及透過率優異之硬系偏光膜。 上述聚乙烯醇系薄膜所使用之聚乙烯醇系樹脂係可 藉由使聚醋酸乙烯醋系樹脂進行專化而得到。就聚醋酸乙 稀酯系樹脂而言,除了醋酸乙烯酯之單獨聚合物之聚醋酸 乙烯醋外,可舉例如醋酸乙烯醋及可與醋酸乙稀酉旨共聚合 之其他單體之共聚物等。可與醋酸乙婦醋共聚合之其他單 體係可舉例如不飽和緩酸類、不飽和石黃酸類、稀烴類及乙 ❹烯基醚類。 聚乙烯醇系樹脂之皂化度一般為85至100mol%,更 宜為98至lOOmol%。聚乙烯醇系樹腾亦哥输斑性亦可 使用例如經藤類改性之聚乙烯基曱縮醛 (polyvinylformal)、聚乙烯基乙縮醛(polyvinylacetal)、及聚 乙烯基丁縮醛(polyvinylbutyral)。聚乙烯醇系樹脂之聚合 度一般為1000至10000左右,宜為15〇〇至loooo左右。 將如此之聚乙烯醇系樹脂製膜而成者係可使用於作 為偏光膜之原材薄膜。將聚乙烯醇系樹脂製膜之方法係無 321675 15 201028292 :別=、,可依公知之方法進行製膜。聚乙烯醇系原材薄-膜之厚度並無制限定,但例如為2至l5G# Μ右。' 偏光膜~般係經過如下之步驟來製造··調整由如上述 , 之聚乙烤醇系樹脂所構成的原材薄膜之水分的調濕步驟;· 使聚乙稀醇系樹脂薄膜進行單轴延伸之步驟;使聚乙稀醇 系樹脂薄膜以二色性色素進行染色而吸附該二色性色素之 步驟,使吸附配向有二色性色素之聚乙稀醇系樹腸薄膜以 硼馱水溶液進行處理之步驟;及在以硼酸水溶液進行處理 後進行水洗之步驟。 單軸延伸係可於以二色性色素進行染色之前進行,亦 可與染色同時進行,亦可於染色之後進行。當使 在以二色性色素染色之後進行時,此單軸延伸可於硼酸處 理之前進行,亦可於硼酸處理中進行。又,亦可於此等之 複數階段進行單軸延伸。單軸延伸時,可在周速相異之輥 輪間朝單軸延伸,亦可使用熱輥輪並朝單軸進行延伸。又, 可為在大氣中進行延伸等之乾式延伸,亦可為在以溶劑膨 潤之狀態下進行延伸之濕式延伸。延伸倍率一般為4至$ 〇 倍。水洗後,乾燥所得到之偏光膜的厚度例如可為i至% β m。 (透明保護膜) 本發明之製造方法所使用的透明保護膜係宜為由透 明性、機械強度、熱安定性、水分遮蔽性、及相位差值之 女疋性優異的材料所構成。如此之透明保護膜用材料係無 特別限定,但可舉例如曱基丙烯酸曱酯系樹脂等(甲基)丙 321675 16 201028292 • 烯酸系樹脂、聚丙烯系樹脂等鏈狀烯烴系樹脂、環狀稀煙 系樹脂、聚氯化乙烯系樹脂、纖維素系樹脂、苯乙稀系樹 • 脂、丙烯腈/ 丁二烯/苯乙婦系樹脂、丙埽腈/苯乙稀系樹月旨、 聚醋酸乙坏醋糸树脂、I偏一乳乙稀(polyvinylidene chloride)系樹脂、聚醯胺系樹脂、聚縮酸·系樹脂、聚碳酸 醋系樹脂、改性聚苯謎系樹脂、聚對敢酸丁二g旨系樹脂、 聚對駄酸乙二醋系樹脂、聚礙系樹脂、聚_颯系樹脂、聚 芳酸醋糸樹脂、聚酿胺酿亞胺糸樹脂及聚酿亞胺系樹脂。 〇 此等樹脂係可分別單獨或與其他之1種類以上組合而 使用。又,此等樹脂亦可在進行任意之適當的聚合物改性 後再使用,此聚合物改性係可舉例如共聚合、交聯、分子 末端、立體規則性控制、及包含侔醅& λ I ^ 3彳午隨異種聚合物間之反應 時的混合等改性。 此等之中,透明保護膜之材料宜使用甲基丙烯酸甲醋 系樹脂等(甲基)丙烯酸系樹脂、聚對駄酸乙二醋系樹脂、 聚丙烯系樹脂等鏈狀烯烴系樹脂、纖維素系樹脂。 J基丙烯酸甲醋系樹脂係含有5〇重量%二之甲基 •甲醋早元的聚合物。甲基丙烯酸甲醋單元之含量宜 為7〇重量%以上,亦可為1〇〇重早7°之才重且 元為i。。重量%之聚合物係使曱基里基,甲醋單 得到之曱基丙烯酸甲酯單獨聚合物。甲s曰早獨聚合所 主基:_ "旨系樹脂—般係可在以甲基丙稀酸 甲酉曰作為主成分之早官能單體、多官、 起始劑及鏈卿叙共存下崎聚合 自由基聚。 321675 17 201028292 可與曱基丙烯酸甲酯共聚合之單官能單體並無特別 、 限定,但可舉例如甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲 、 基丙烯酸環己酯'甲基丙烯酸苯酯、甲基丙烯酸苯甲酯、201028292, VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method of manufacturing a composite polarizing plate. [Prior Art] The liquid crystal display device can be used in various display devices by utilizing characteristics such as low power consumption, low power operation, light weight, and thinness. This liquid crystal display device is composed of a plurality of optical members such as a liquid crystal cell, a polarizing plate, a retardation film, a condensing sheet, a diffusion film, a light guide plate, and a light reflection sheet. Therefore, improvement in the production efficiency or brightness of the liquid crystal display device, light weight, and thinness can be achieved by improving the number of thin films or sheets of the optical members or the reduction in film thickness, etc. Prevailing. Further, liquid crystal display devices are required to withstand severe durability conditions. For example, in a liquid crystal display device for a car navigation system, the temperature or humidity in the car to be placed therein may become very high, and even in a display such as a mobile phone or a portable terminal device, or a display for a television or a computer. In the case of such use environments or installation locations, exposure to extreme changes in temperature and humidity may result in the performance of articles that can withstand such severe conditions. The polarizing plate of the parts of the liquid crystal display device generally has a structure in which a transparent protective film is laminated on both sides or one side of the polarizing film. For example, the polarizing film is obtained by subjecting a polyvinyl alcohol-based resin film to uniaxial stretching and dyeing of a dichroic dye, followed by boric acid treatment to cause a crosslinking reaction, and then washing with water and drying. The dichroic dye system uses a moth or a dichroic organic dye. Yu Yiru 4 321675 201028292 The double-sided or single-sided laminated polarizing film obtained by this method is laminated and incorporated into a liquid crystal display device. The film is a resin film for cellulose which is represented by triacetyl phthalocyanine (triacetyl ceuui〇se), and its thickness is generally from about 3 Å to about i 〇 。 em. For the laminate of the protective film of B, an adhesive of water-soluble =, ' is used for the polyvinyl alcohol-based resin. A double-sided or one-sided enamel which adsorbs a polarizing film having a dichroic dye, and a polarizing film composed of an aqueous solution of a polyvinyl alcohol-based resin is used to laminate a polarizing film of a protective film composed of cellulose acetate. The board is attached to a wet piece; when used for a long time, there is a problem that the polarizing performance is lowered, or the protective film and the deviation are present.膘 Easy peeling Therefore, at least one of the protective films is attempted to be composed of a resin other than cellulose acetate. For example, it is described in JPH08-43812-A that a polarizing plate of a double-sided laminated protective film of polarized light is used, and at least one of the protective films is formed of a thermoplastic norbornene resin having a function of a retardation film. Further, it is described in the above-mentioned Japanese Patent Publication No. 1109-325226, that at least one of the protective layers of the polarizing film is formed of a birefringent film. In the case of θ 3 , the styrene resin film has a polarization ratio of the styrene resin chain larger than that of the main chain (sometimes referred to as a polarization), and the negative retardation film having a large refractive index in the direction is positive. Studied. The negative retardation film having a large refractive index in the direction is #aa+ thick 斛t. Although the refractive index in the in-plane maximum refractive index direction (slow axis direction) is nx, it is orthogonal to the plane ( The refractive index in the fast axis direction is ny, and the refractive index in the thickness direction is 、ηχ>%, and the number of 321675 201028292 defined by (4) is about 〇. But styrene The resin film is problematic in heat resistance, mechanical strength, and chemical resistance, and has not been put into practical use. Regarding the heat resistance of the styrene resin, it is known that the glass transition temperature can be formed (hereinafter, sometimes A monomer of a resin having a high Tg), such as norbornene or maleic anhydride, is improved by copolymerization, but even by such copolymerization, mechanical strength or chemical resistance cannot be sufficiently improved. A technique of copolymerizing other monomers with styrene or laminating other resin layers to a styrene film. For example, an aromatic vinyl monomer having styrene as a representative example is described in WO 99/64500. Ben with alpha Ο-olefin The above-mentioned random copolymer is formed into a film, and it is also suggested to form a multilayer structure of the film and other polymer layers. Further, an aromatic vinyl having styrene as a representative example has been described in US2002/0169267A1 or JP2003-207640-A. A ternary copolymer in which a base monomer is copolymerized with a non-cyclic olefin monomer and a cyclic olefin monomer to form a retardation film. Further, it is described in JP 2003-90912-A that a norbornene-based resin is used. The alignment film and the alignment film composed of the styrene-maleic anhydride copolymerized resin are laminated to form a retardation film via the adhesive layer, and are described in the multilayer film layer of the polyolefin system in JP2004-167823-A. Further, a polystyrene-based sheet is described. Further, JP 2006-192637-A describes a first layer composed of a styrene resin and a second layer composed of an acrylic resin composition containing rubber particles. The laminate is laminated as a retardation film. However, when a styrene resin film is used as the retardation film, the styrene system cannot be expanded to achieve desired phase difference characteristics and mechanical strength. The width of the lipid film, therefore, the width of the film that can be produced is smaller than that of the polarized light 6 321675 201028292 - the visibility of the film, or in the manufacturing method of the polarizing plate with the phase difference film in the past, a has a problem of significantly reduced productivity. In other words, when the polarizing plate and the polarizing plate are bonded to the retardation film having a width smaller than that of the polarizing plate, a portion of the polarizing plate in which the retardation film is not bonded is formed, and if the polarizing plate is to be cut into a bonded film, The predetermined shape of the liquid crystal cell is generally cut at right angles or oblique angles with respect to the length direction. 'It is then cut into its predetermined shape. However, due to the cutting, the polarizing plate portion of the film having no 5 retardation film is attached. Was abandoned. Further, since the portion of the polarizing plate which is not attached to the retardation film is also counted in the cutting length, the production quality is remarkably lowered. Further, when the retardation film using a styrene resin thin film is used as a protective film for a polarizing film, the adhesion to the polarizing film may be inferior. SUMMARY OF THE INVENTION The purpose of the moon is to provide a method for producing a traveling polarizing plate which is excellent in productivity, and the composite polarizing plate is made of a polarizing plate and a film which is abruptly smaller than a polarizing plate. The film is laminated, and the adhesion between the polarizing film and the retardation film is excellent. The present invention encompasses the following. A method for producing a heart-type composite polarizing plate, wherein the composite polarizing plate is composed of a stretched film having a three-layer structure, and the layer is constructed as a core layer composed of a benzene-based material. a three-layer structure of a skin layer composed of a layer composed of a (ruthenium-based) acrylic-based April composition containing rubber particles on both sides of the layer/:::: and a polarizing plate with a single-sided transparent protective film of 201028292, The method is laminated on the retardation film and has a transparent protective film on one side of the polarizing film; and the manufacturing method has the following steps (A), (B), (C), and steps. (D) and step (E), or include the following steps (A), (B), (C), (F) and (G): (A) bonding on one side of the polarizing film a transparent protective film, a step of bonding a peeling film having adhesiveness on the opposite side, and a polarizing plate with a single-sided transparent protective film; (B) a polarizing plate with a single-sided transparent protective film is blended with a retardation film a step of cutting along the length in the width direction; (C) a step of removing the peeling film from the surface of the polarizing film; (D) a phase difference At least one of a single side of the film and a polarizing film surface of the polarizing plate with a single-sided transparent protective film from which the peeling film has been removed forms a storage elastic modulus exhibiting an O.IMPa or more at 80 ° C (storage elastic modulus) (E) a step of bonding the retardation film through the adhesive layer to the polarizing film surface of the polarizing plate with the one-side transparent protective film on which the peeling film has been removed; (F) Forming at least one of a single side of the retardation film and a polarizing film surface of the polarizing plate with the one-side transparent protective film from which the peeling film is removed, forming an epoxy compound containing hardening by irradiation or heating by active energy rays a resin composition layer, a step of superposing a polarizing film surface or a retardation film of another polarizing plate on the resin composition layer; (G) by hardening the resin composition layer to provide a single-sided transparent security 321675 201028292 - The polarizing film side of the polarizer of the film, the hardened layer of the resin composition, and the step of bonding the phase difference film. <2> The method of the item <1>, wherein the method comprises the step (A), the step (B), the step (C), the step (D) and the step (E), in the step ( In D), the adhesive layer is formed on a polarizing film surface of a polarizing plate with a single-sided transparent protective film on which a peelable film is removed. <3> The method of the item <1>, wherein the method comprises the step (A), the step (C), the step (D), the step (B) and the step (E) in the step (D). In the ® , the adhesive layer is formed on the polarizing film surface of the polarizing plate with the single-sided transparent protective film on which the peelable film is removed. <4> The method of <1>, wherein the method comprises the steps (A), (B), (C) and (E) in sequence, and the step (D), in the step In (D), the adhesive layer is formed on one side of the retardation film. <5> The method of item <1>, wherein the method comprises the step (A), the step (B), the step (C), the step (F) and the step (G), in the step (F). The resin composition layer is formed on the polarizing film surface of the polarizing plate with the single-sided transparent protective film on which the peelable film is removed. <6> The method of <1>, wherein the method comprises the step (A), the step (B), the step (C) and the step (G), and the step (F), in the step In (F), the resin composition layer is formed on one side of the retardation film. The method of the above item, wherein, in the step (卩), the epoxy compound contains one or more epoxy groups bonded to the alicyclic ring in the molecule. Base compound. The method of any one of <1> to <7>, wherein the core layer film 9 321675 201028292 has a thickness of 10 to 100 μm, and the skin layer has a film thickness of 1 〇 to ι 〇〇 melon. The method of any one of the items <8> wherein the glass transition temperature of the core layer is 12 (^ or more, and the breaking temperature of the skin layer is 12 Å or less. ―:: (4)> to < 9) The method of any one of the preceding claims, wherein the phase difference f = degree is less than 10% of the width of the polarizing plate of the single-sided transparent protective film produced in the step (8). (4) 中^^^^^^^^^ The method of any of the items, wherein, in the step = ^^_ and the transparent Lai Lin use the adhesive containing (4) B. 骑 或 or % 虱 曰 曰 。 。 。 。 。 菩 菩 菩 菩 菩 菩 菩 菩 菩 菩 菩 菩 菩 菩 菩 菩 菩 菩(a) a towel, which is a resin composition of an epoxy compound which is cured by irradiation or heating by an active energy ray. TB (4) #用人古^°<12> The protective transparent film 3 has a resin composition of the epoxy compound, and comprises the following steps: 0 r ηΓΓ, one side, and at least one of the single sides of the transparent protective film, two: t a resin composition layer of the epoxy compound, and superposing another polarizing plate or a transparent step on the resin composition layer containing the step m; In the case of a chelating amine product, the resin composition layer containing an epoxy compound is hardened by a polarizing layer = a hardened layer of a resin composition containing an epoxy compound and attached to a ruthenium film. 14 > The method of the item of <13> wherein 321675 10 201028292 in the step (person) - the epoxy compound contains a compound having one or more epoxy groups bonded to the alicyclic ring in the molecule. The method of any one of <1> to <14>, wherein the transparent protective film has a thickness of 20 to 300/zm. <16> as <1> to < The method of any one of the above-mentioned item, wherein the thickness of the adhesive layer is from 1 to 40/im. If the method for producing a composite polarizing plate according to the present invention is to be attached to the retardation film, The polarizing plate of the transparent protective film is cut along the length direction in accordance with the size of the retardation film, and is divided into a polarizing plate with a single-sided transparent protective film bonded to the retardation film, and is not bonded to the retardation film. The polarizing plate with a single-sided transparent protective film will not cause a decrease in productivity. Further, the portion of the polarizing plate with the one-sided transparent protective film that is not bonded to the retardation film can be used for other products, so that the productivity of the whole is remarkably improved. Further, the phase of the composite polarizing plate obtained by the present invention is The poor film and the Q-light film are also excellent in adhesion and have high durability. Further, the polarizing film side of the polarizing plate with the single-sided transparent protective film is cut, and the adhesive layer is adhered first. The release film prevents the adhesion of the transparent protective film to the polarizing film or the damage of the polarizing film during cutting. The composite polarizing plate obtained according to the present invention can be suitably used for a liquid crystal display device, and particularly a liquid crystal cell having a transverse electric field mode, that is, a liquid crystal display device having an IPS (In-Plane-Switching) cell. [Embodiment] <Manufacturing method of composite polarizing plate> 11 321675 201028292 In the method for producing a composite polarizing plate of the present invention, the composite polarizing plate comprises: a retardation film having a three-layer structure (cortex/nucleus) The layered/sheath layer is composed of a stretched film composed of a styrene resin and a double layer laminated on the both sides of the core layer and composed of (meth)acrylic resin containing rubber particles. a three-layer structure of a skin layer composed of a composition; and a polarizing plate with a single-sided transparent protective film laminated on the retardation film and having a transparent protective film on one side of the polarizing film; and the manufacturing method The feature includes the following steps (A), (B), (C), (D) and (E), or includes the following steps (A), (B), and (C) Step (F) and Step (G) · (A) The transparent protective film is bonded to one side of the polarizing film, and the adhesive film is adhered to the opposite side to form a transparent protective film with a single side. Step of polarizing plate; (B) Matching polarizing plate with one-sided transparent protective film with phase difference a step of cutting the width of the film along the length direction; (C) a step of removing the release film from the surface of the polarizing film; (D) a single side of the phase difference film and a single side transparent film with the release film removed At least one of the polarizing film faces of the polarizing plate of the protective film, the step of forming an adhesive layer exhibiting a storage elastic modulus of O.IMPa or more at 80 ° C; (E) the one side of the peeling film removed The polarizing film surface of the polarizing plate of the transparent protective film is bonded to the retardation film via the adhesive layer. 12 321675 201028292 • (F) One side of the retardation film and the attached sheet with the peeling film removed/ At least one of the polarizing film surfaces of the polarizing plate of the transparent protective film forms a resin composition layer containing an epoxy compound hardened by irradiation of an active energy ray or heat, and another polarizing plate is superposed on the resin composition layer a step of polarizing a film surface or a retardation film; (G) by hardening the resin composition layer, licking the polarizing film surface of the polarizing plate with a single-sided transparent protective film, and passing through the hardened layer of the resin composition ® Fit Phase Difference The step. In the method for producing a composite polarizing plate of the present invention, the bonding of the polarizing film of the polarizing plate with a single-sided transparent protective film to the retardation film is shown by a storage elastic modulus of O.IMPa or more at 80 ° C. A preferred embodiment of the method for carrying out the adhesive layer (including the steps (A), (B), (C), (D) and (E)) may include, for example, sequential steps. (A), step (B), step (C), step (D), and step (E), in the step (D), the aforementioned adhesive layer is formed on the one-side transparent protection of the stripped film The aspect of the polarizing film surface of the polarizing plate of the film (hereinafter sometimes referred to as the first aspect); the step (A), the step (C), the step (D), the step (B), and the step (E) are sequentially included. In the step (D), the adhesive layer is formed on a polarizing film surface of a polarizing plate with a single-sided transparent protective film from which a peelable film is removed (hereinafter sometimes referred to as a second aspect); The step (A), the step (B), the step (C) and the step (E) are sequentially included, and the step (D) is further included. In the step (D), the adhesive layer is formed on the phase difference film. The aspect of the face (hereinafter sometimes referred to as the third aspect). 13 321675 201028292 The polarizing film of the polarizing plate with a single-sided transparent protective film is made to have a phase difference, and the film is bonded to the resin composition layer of the epoxy compound which is hardened by irradiation or heating by active energy rays. A preferred embodiment of the method (including the steps (A), - (B), (C), (F), and (G)) may include, for example, step (A), Step (B), step (C), step (F), and step (G), in the step (F), the resin composition layer is formed on a polarizing plate with a single-sided transparent protective film from which the peelable film has been removed The aspect of the polarizing film surface (hereinafter sometimes referred to as the fourth aspect); and the step (A), the step (B), the step (C), and the step (G) are sequentially included, and the step (F) is further included In the step (F) ©, the resin composition layer is formed on one side of the retardation film (hereinafter sometimes referred to as a fifth aspect). [1] Step (A) In the method for producing a composite polarizing plate of the present invention, first, a transparent protective film is bonded to one surface of a polarizing film, and a peeling film having adhesiveness is bonded to the surface on the opposite side to prepare a film. A polarizing plate with a single-sided transparent protective film. (Polarizing film) ^ The polarizing film used in the method for producing a composite polarizing plate of the present invention has a function of selectively transmitting linearly polarized light in a certain direction from natural light. For example, a polyvinyl alcohol-based film is adsorbed and an iodine-based polarizing film is provided with an iodine; a dye-based polarizing film which adsorbs and aligns a dichroic dye with a polyvinyl alcohol-based film; and a liquid-phase (lyotropic) a dichroic dye in a liquid crystal state, and a coated polarizing film which has been aligned and fixed. These iodine-based polarizing films, dye-based polarizing films, and coating-type polarizing films have a function of selectively transmitting linearly polarized light in one direction from natural light and absorbing the other direction. 321675 201028292 · - Linear polarizing function Therefore, it is called an absorption type, and the partial (four) used in the m method of the present invention may be only the above-mentioned absorption type polarizing film, or may be a reflection type polarizing film or a scattering type polarizing film. It has a function of selectively transmitting linearly polarized light in a certain direction from natural light, and reflecting or scattering linear light in another direction. Further, == is not limited to the specific example of the polarizing film, and may be any function as long as it has a function of selectively transmitting linearly polarized light in a certain direction from natural light. In the case of 偏^, it is preferable to use an absorbing polarizing film having excellent visibility, and it is more preferably a hard polarizing film having excellent polarization and transmittance. The polyvinyl alcohol-based resin used in the above polyvinyl alcohol-based film can be obtained by specializing a polyvinyl acetate-based resin. In the case of the polyvinyl acetate-based resin, in addition to the polyvinyl acetate vinegar of the individual polymer of vinyl acetate, for example, a copolymer of vinyl acetate vinegar and another monomer copolymerizable with ethylene acetate may be mentioned. . Other single systems which can be copolymerized with ethyl acetate are, for example, unsaturated acid retardants, unsaturated rhein acids, dilute hydrocarbons and ethylenyl ethers. The degree of saponification of the polyvinyl alcohol-based resin is usually from 85 to 100 mol%, more preferably from 98 to 100 mol%. The polyvinyl alcohol-based tree can also be used, for example, by polyvinylidene-modified polyvinylformal, polyvinylacetal, and polyvinylbutyral. ). The degree of polymerization of the polyvinyl alcohol-based resin is generally from about 1,000 to 10,000, preferably from about 15 Torr to about loooo. A film made of such a polyvinyl alcohol-based resin can be used as a raw material film as a polarizing film. The method of forming a film of a polyvinyl alcohol-based resin is 321675 15 201028292 : No, the film can be formed by a known method. The thickness of the polyvinyl alcohol-based raw material thin film is not limited, but is, for example, 2 to 15G# Μ right. The polarizing film is manufactured by the following steps: a humidity conditioning step of adjusting the moisture of the raw material film composed of the above-mentioned polyb-baked alcohol-based resin; · Making the polyethylene-based resin film single a step of stretching the polyacetal resin film by dyeing the dichroic dye to adsorb the dichroic dye, and adsorbing the polyethylene glycol-based intestinal film having the dichroic dye to the boron bismuth a step of treating the aqueous solution; and a step of washing with water after treatment with an aqueous solution of boric acid. The uniaxial stretching system can be carried out before dyeing with a dichroic dye, or simultaneously with dyeing, or after dyeing. When it is carried out after dyeing with a dichroic dye, the uniaxial stretching can be carried out before the boric acid treatment, or in the boric acid treatment. Further, uniaxial stretching can be performed in the plural stages of these. For single-axis extension, it can be extended to a single axis between rolls with different peripheral speeds, or it can be extended to a single axis using a hot roll. Further, it may be a dry stretching such as stretching in the atmosphere, or may be a wet stretching in which the stretching is carried out in a state of being swollen with a solvent. The stretching ratio is generally 4 to $ 倍 times. After washing with water, the thickness of the polarizing film obtained by drying may be, for example, i to % β m. (Transparent Protective Film) The transparent protective film used in the production method of the present invention is preferably made of a material excellent in transparency, mechanical strength, thermal stability, moisture shielding property, and phase difference. The material for the transparent protective film is not particularly limited, and examples thereof include (meth)acrylic acid oxime ester-based resin (methyl) propylene 321675 16 201028292 • a chain olefin resin such as an olefinic resin or a polypropylene resin, or a ring Type thin smoke resin, polychlorinated vinyl resin, cellulose resin, styrene tree fat, acrylonitrile/butadiene/phenethyl styrene resin, acrylonitrile/styrene tree , polyacetate acetonitrile resin, polyvinylidene chloride resin, polyamine resin, polycondensate resin, polycarbonate resin, modified poly phenyl resin, poly For the acid, the succinic acid, the polyethylene terephthalate resin, the poly-resin resin, the poly-anthraquinone resin, the polyaryl phthalate resin, the polyarene resin, and the poly Amine resin. 〇 These resins may be used singly or in combination with one or more other types. Further, these resins may be used after any suitable polymer modification, such as copolymerization, crosslinking, molecular end, stereoregularity control, and inclusion of ruthenium & The λ I ^ 3 彳 is modified by mixing or the like in the reaction between the heterogeneous polymers. Among these, the material of the transparent protective film is preferably a chain olefin resin such as a (meth)acrylic resin such as a methyl methacrylate resin, a polyethylene terephthalate resin or a polypropylene resin, or a fiber. Prime resin. The J-based acrylic vinegar-based resin is a polymer containing 5% by weight of di-methyl-methyl ketone. The content of the methyl methacrylate unit is preferably 7% by weight or more, and may be 1 〇〇 as heavy as 7° and the weight is i. . The weight percent of the polymer is a methyl methacrylate alone polymer obtained from thiol thiol and methyl acetonate. A s 曰 曰 独 独 曰 : : : : : _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Nisaki polymerizes free radicals. 321675 17 201028292 The monofunctional monomer copolymerizable with methyl methacrylate is not particularly limited, but may, for example, be ethyl methacrylate, butyl methacrylate or cyclohexyl methacrylate methacrylate. Phenyl ester, benzyl methacrylate,
甲基丙烯酸2-乙基己酯、曱基丙烯酸2·羥乙酯等甲基丙烯 I 酸甲酯以外的甲基丙烯酸酯類;丙烯酸甲酯、丙烯酸乙酯、 丙稀酸丁酯、丙烯酸酯環己酯、丙烯酸苯酯、丙稀酸笨甲 酯、丙烯酸2-乙基己酯、丙烯酸2_羥乙酯等丙烯酸酯類,· 2·(羥甲基)丙烯酸甲酯、3-(羥乙基)丙烯酸甲酯、2_(羥甲基) 丙烯酸乙酯、2-(羥甲基)丙烯酸丁酯等羥基丙烯酸酯類;❹ 甲基丙烯酸、丙烯酸等不飽和酸類;氣苯乙烯、溴苯乙烯 等鹵化苯乙烯類;乙烯基甲苯、以_甲基苯乙烯等取代苯乙 稀類;丙烯腈、甲基丙稀腈等不飽和腈類;馬來酸酐、檸 康酸酐(Citraconicanhydride)等不飽和酸酐類,·以及苯基 來醯亞胺及環己基馬來醯亞胺等不飽和醯亞胺類。如此之 單體係可分別單獨使用,亦可與其他之一種以上组合而使 用。 可與甲基丙烯酸甲g旨共聚合之多官能單體並無特別© 限定,可舉例如乙二醇二(?基)丙稀酸醋、二乙二醇二(〒 基)丙烯酉文|曰、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲 基)丙烯酸酯、九乙二醇二(甲基)丙烯酸酯、十四乙二醇(甲 基)丙烯酸酯等乙二醇或其寡聚物的兩末端經基經丙稀酸 或甲基丙婦酸進行酯化者;使丙二醇或其寡聚物的兩末端 祕經丙烯酸或甲基丙烯酸進行酯化者;新戊二醇二(甲基) 丙稀酸酯、己二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙稀 321675 18 201028292 * 酸酉旨等2元酿沾¥-甘 使雙粉A、雙紛2經_酸或甲基丙婦酸進行醋化者; ,此等之时取代體==tIeneGXlde)加成物、或 行酯化者;使三声甲Γ 祕經丙婦酸或甲基丙婦酸進 或甲基丙稀酸進^旨化=、、季戊四醇等多元醇經丙稀酸 烯酸縮水甘油酯或’以及對於此等末端經基,使丙 環加成者;對於丙稀酸縮水甘油醋之環氧基進行開 齒素取代體等二元酸及此5 一酉^舰酸、駄酸、此等之 ::,,(甲旬丙婦酸芳及二乙婦基苯等二芳基化合物。 /、 乂且使用乙二醇二甲基丙烯酸酯、四乙二醇二甲芙 丙烯酸醋、及新戊二醇二甲基丙稀酸醋。 " 甲基丙烯酸甲酯系樹脂係亦可為再進行已共聚合於 樹月旨中之官能基間的反應而改性者。其反應係可舉例如丙 烯酸甲醋之甲酯基與2_(經甲基)丙烯酸曱酯之經基的高分 ❹子鏈内脫甲醇縮合反應、丙烯酸之羧基與2_(羥甲基)丙烯 酸甲酯之羥基的高分子鏈内脫水縮合反應等。 甲基丙烯酸曱酯系樹脂係可容易地澳4^療4备品^,就各 種商品名而言可舉例如Sumipex(住友化學(股)製)、 Acrypet(三菱Rayon(股)製、Delpet(旭化成(股)製)、 Parapet((股)Kuraray 製)及 Acryviewa((股)曰本觸媒製)等。 聚對酞酸乙二酯系樹脂係意指重複單元的80mol%以 上為由對酞酸乙二酯所構成之樹脂-,;r可爹:^其淹土叛酸 - 成分與二醇成·分。其他之二羧酸成分並無特別限定,但可 19 321675 201028292 舉例如異酞酸、對-冷-氧基乙氧基安息香酸、4,4f-二羧基 二苯基、4,4’-二羧基二苯甲酮、雙(4-羧基苯基)乙烷、己二 酸、癸二酸及1,4-二羧基環己烷。 其他之二醇成分並無特別限定,但可舉例如丙二醇、 丁二醇、新戊二醇、二乙二醇、環己二醇、雙酚A之環氧 乙烷加成物、聚乙二醇、聚丙二醇及聚四亞甲基甘醇 (tetramethylene glycol)。 此等二羧酸成分或二醇成分係分別依需要而可與其 他之1種類以上組合而使用。又,亦可併用對氧基安息香 酸等氧基羧酸。又,就其他之共聚合成分而言,亦可使用 含有少量之醯胺鍵、胺基曱酸酯(urethane)鍵、醚鍵、及碳 酸酯鍵等之二羧酸成分或二醇成分。 聚對酞酸乙二酯系樹脂之製造方法係可採用如下之 方法··使對酞酸及乙二醇(以及依需要之其他二羧酸或其他 二醇)直接聚縮合之方法;使對酞酸之二烷基酯及乙二醇 (以及依需要之其他二羧酸的二烷基酯或其他二醇)進行酯 交換反應後再聚縮合之方法;及使對酞酸(以及依需要之其 他二羧酸)乙二醇酯(以及依需要之其他二醇酯)在觸媒的 存在下聚縮合之方法等。進一步,亦可依需要而進行固相 聚合以提昇分子量,或減少低分子量成分。 又,所謂聚丙烯系樹脂係指使用聚合用觸媒而使上述 鏈狀烯烴系樹脂中,重複單元的80重量%以上為丙烯單體 的鏈狀烯烴單體進行聚合者。其中,宜為丙烯均聚物。 又,亦宜為以丙烯作為主體,且可與其共聚合之共單 20 321675 201028292 -體以1至2〇重量%之肤洛 -共聚合的共聚物。 。(較佳係3至10重量%之比率) * 使用丙烯共聚物時, 乂a methacrylate other than methyl methacrylate, such as 2-ethylhexyl methacrylate or 2-hydroxyethyl methacrylate; methyl acrylate, ethyl acrylate, butyl acrylate, acrylate Cyclohexyl ester, phenyl acrylate, methyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, etc., · 2 (hydroxymethyl) acrylate, 3- (hydroxyl Hydroxy acrylates such as ethyl methacrylate, ethyl 2-(hydroxymethyl) acrylate, butyl 2-(hydroxymethyl) acrylate; 不 unsaturated acids such as methacrylic acid and acrylic acid; styrene and bromobenzene Halogenated styrenes such as ethylene; vinyl toluene, styrene substituted with styrene, etc.; unsaturated nitriles such as acrylonitrile and methyl acrylonitrile; maleic anhydride, Citracononic anhydride, etc. Saturated acid anhydrides, and unsaturated quinone imines such as phenyl quinone imine and cyclohexyl maleimide. Such a single system may be used alone or in combination of one or more other types. The polyfunctional monomer which can be copolymerized with methyl methacrylate is not particularly limited, and examples thereof include ethylene glycol di(?) acrylate vinegar and diethylene glycol bis(indenyl) propylene hydrazine| Bismuth, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, tetradecyl glycol (meth)acrylate, etc. Ethylene glycol or its oligomers are esterified at both ends via a base of acrylic acid or methyl acetoacetate; and the ends of propylene glycol or its oligomer are esterified with acrylic acid or methacrylic acid; Neopentyl glycol di(meth) acrylate, hexanediol di(meth) acrylate, butanediol di(meth) propylene 321675 18 201028292 * 酉 酉 等 2 2 2 2 2 2 2 To make the double powder A, the double powder 2 by _ acid or methyl propyl benzoic acid for vinegarization; , at this time, the substitution body == tIeneGXlde) the adduct, or the esterification; the three-tone hyperthyroidism B-glycolic acid or methyl acetoin or methyl methacrylate into the =, pentaerythritol and other polyols by glycidyl acrylate or 'and for these terminal groups, so A propylene ring addition; a dibasic acid such as a dentate substituent for the epoxy group of glycerol acetal acrylate; and the quinone acid, citric acid, and the like::,, Diaryl compounds such as guar aryl and diethyl benzene. /, 乙二醇 and use ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and neopentyl glycol dimethyl acrylate " The methacrylic acid-based resin may be modified by further reacting the functional groups which have been copolymerized in the tree. The reaction may be, for example, methyl ketone of methyl acetonate. 2_(Methyl) decyl methacrylate, a high-strength deuterium chain de-methanol condensation reaction, a carboxyl group of acrylic acid and a hydroxyl chain of 2 - (hydroxymethyl) acrylate, a polymer chain dehydration condensation reaction, etc. The acryl-based acrylate-based resin can be easily used as a product, and various product names include, for example, Sumipex (manufactured by Sumitomo Chemical Co., Ltd.), Acrypet (Mitsubishi Rayon), and Delpet (Asahi Kasei ( Stocks), Parapet (Kuraray) and Acryviewa (the company). Polypyridic acid The diester-based resin means that 80 mol% or more of the repeating unit is a resin composed of ethylene terephthalate, and r can be used to form a tick-removing component with a diol. The carboxylic acid component is not particularly limited, but may be exemplified by isophthalic acid, p-col-ethoxy ethoxybenzoic acid, 4,4f-dicarboxydiphenyl, 4,4'-dicarboxydiphenyl. Methyl ketone, bis(4-carboxyphenyl)ethane, adipic acid, sebacic acid, and 1,4-dicarboxycyclohexane. Other diol components are not particularly limited, but examples thereof include propylene glycol and dibutyl Alcohol, neopentyl glycol, diethylene glycol, cyclohexanediol, ethylene oxide adduct of bisphenol A, polyethylene glycol, polypropylene glycol, and tetramethylene glycol. These dicarboxylic acid components or diol components can be used in combination with one or more types as needed. Further, an oxycarboxylic acid such as p-oxybenzoic acid may also be used in combination. Further, as the other copolymerization component, a dicarboxylic acid component or a diol component containing a small amount of a guanamine bond, an amino urethane bond, an ether bond, and a carbonate bond may be used. The method for producing a polyethylene terephthalate resin can adopt the following method: a method for directly polycondensing citric acid and ethylene glycol (and other dicarboxylic acids or other diols as needed); a method of transcondensing a dialkyl decanoate with ethylene glycol (and optionally a dialkyl ester of a dicarboxylic acid or other diol as needed) and then condensing the phthalic acid (and on demand) The other dicarboxylic acid) ethylene glycol ester (and other glycol esters as needed) is a method of polycondensation in the presence of a catalyst. Further, solid phase polymerization may be carried out as needed to increase the molecular weight or to reduce the low molecular weight component. In the above-mentioned chain olefin-based resin, a polymerized chain-like olefin monomer in which 80% by weight or more of the repeating unit is a propylene monomer is polymerized by a polymerization catalyst. Among them, it is preferably a propylene homopolymer. Further, it is also suitable to use propylene as a main component and to be copolymerized therewith. 20 321675 201028292 - a body-to-copolymerized copolymer of 1 to 2% by weight. . (preferably in a ratio of 3 to 10% by weight) * When a propylene copolymer is used, 乂
G 烯、丁缔及1-已婦。其上丙細共聚合之共單體宜為乙 使乙烯以3至10重量%< ’因透明性比較優良’故宜為 使乙烯的共聚合比率成7比率=聚合的丙烯共聚物。藉由 性之效果。另外,若其比重量%以上,而顯現提高透明 會降低,有時會相及保^過20重量%,則樹脂之融點 其中,較宜為可溶於2^之甲耐熱性。 分)為1重量。以下的丙本^成分(⑽成 重量%以下的丙烯均聚物。 且為CXS成分為0.5 *樹:所係指從棉花織或木材紙漿(闊 的經基中之衆)專之原料纖維素所得到之纖維素 或丁醯基取的一部分或全部以乙酿基、丙醯基及/ ❹ 可,由纖維素之 混合醋等所構成者。其中,宜為三乙酸基心素 乙醯基纖維素薄膜、纖維素乙 及输: 乙酸醋丁_薄膜。 仏4膜、及纖維素 樹脂將:二甲基丙烯酸曱醋系樹脂、聚對駄酸乙二醋系 之透明佯1膜糸樹脂及纖維素系樹脂等製成接著於偏光膜 可方法,只要適當選擇對應該樹脂之方法即 流於金屬例如:使溶解於溶_垂 一或鼓體’乾燥除去溶劑而得到薄膜之溶 321675 21G ene, dibutyl and 1--women. The co-monomer in which the acrylic copolymerization is carried out is preferably ethylene in an amount of from 3 to 10% by weight based on the fact that the copolymerization ratio of ethylene is 7 ratio = polymerized propylene copolymer. By the effect of sex. Further, when the specific gravity is at least the weight, the transparency is lowered, and if it is 20% by weight or more, the melting point of the resin is preferably a heat resistance which is soluble in 2%. The fraction is 1 weight. The following propylene components ((10) propylene homopolymer of less than or equal to 8% by weight. The CXS component is 0.5 * tree: refers to the raw material cellulose from cotton woven or wood pulp (the broad base) A part or all of the obtained cellulose or butyl sulfonate may be composed of an ethyl ketone group, a propyl ketone group and/or a ruthenium group, and a cellulose vinegar or the like. Film, cellulose B and transport: Acetate butyl _ film. 仏4 film, and cellulose resin will: dimethacrylate vinegar resin, polyphthalic acid ethane vinegar transparent 佯1 film enamel resin and fiber A method of forming a resin or the like followed by a polarizing film, if a method corresponding to the resin is appropriately selected, that is, flowing a metal, for example, dissolving in a solvent or drying the solvent to remove a solvent to obtain a film 321675 21
V 201028292 劑洗禱法,及使樹脂加熱至其熔融溫度以上並進行混練, 而從模頭(die)擠壓出’冷卻’俾得到薄膜之熔融擠壓法。- 於此溶融擠壓法中可為單層薄膜之擠壓,又亦可為多層薄: 膜之同時擠壓。 做為如此所得到之透明保護膜而使用的薄膜係可容 易取到市售品。就甲基丙烯酸甲酯系樹脂薄膜而言,可各 自以商品名舉例如Sumipex (住友化學(股)製)、Acrylite (二菱 Rayon (股)製)、Acryplen (三菱 Rayon (股)製)、 Delaglass (旭化成(股)製)、Paraglass ((股)Kuraray 製)、❹V 201028292 The method of washing and praying, and heating the resin to above its melting temperature and kneading, and extruding the 'cooling' from the die to obtain a film by melt extrusion. - In this melt extrusion method, it can be a single layer of film extrusion, or a multilayer thin film: the film is simultaneously extruded. The film used as the transparent protective film thus obtained can be easily taken into a commercial product. The methyl methacrylate-based resin film may be, for example, each available under the trade names of Sumipex (manufactured by Sumitomo Chemical Co., Ltd.), Acrylite (manufactured by Mitsubishi Rayon Co., Ltd.), Acryplen (manufactured by Mitsubishi Rayon Co., Ltd.), Delaglass (Asahi Kasei Co., Ltd.), Paraglass (made by Kuraray), ❹
Comoglass ((股)Kuraray 製)及 Acryviewa ((股)曰本 觸媒製)。Comoglass (made by Kuraray) and Acryviewa (produced by the catalyst).
又’就聚對酞酸乙二酯系樹脂薄膜而言,可各自以商 品名舉例如Novaclear (三菱化學(股)製)及帝人A-PET 片材(帝人化成(股)製)。 又’就聚丙烯系樹脂薄膜而言,可各自以商品名舉例 如 FILMAX CPP 薄膜(FILMAX 公司製)、Suntox ( Sun Tox ❹ (股)製)、Tohcello ( Tohcello (股)製)、東洋纺 Pyrene Film (東洋紡績(股)製)、Torayfan ( Tomy薄膜加工(股) 製)、Nippon Polyace (曰本 Polyace (股)製)及太閣 FC (Futamura 化學(股)製)。 進一步,就纖維素系樹脂薄膜而言,可各自以商品名 舉例如 Fujitac TD (富士 Film (股)製)及 Konica minolta TAC Film KC ( Konica Minolta opto (股)製)。 本發明所使用之透明保護膜,係可賦予抗眩性(亦即 22 321675 201028292 •霧度,Haze)。賦予抗眩性之方法並無特別限定,但可舉 -例如丄於上述原料樹脂中混合無機微粒子或有機微粒子而 .進行薄膜化之方法;使用上述多層擠壓,一方為混合微粒 子之樹脂,另一方為未混合微粒子之樹脂,由上述兩方樹 脂:進行二層薄膜化之方法;以前述混合微粒子之樹脂挟 住剛述未混合微粒子之樹脂的兩側以進行三層薄膜化之方 法;以及於薄膜單側,塗佈將無機微粒子或有機微粒子混 合於硬化性黏結劑(binder)樹脂而成之塗佈液,使黏結劑樹 脂硬化而設置抗眩層之方法。 用以賦予抗眩性之無機微粒子並無特別限定,但可舉 例如二氧化矽(silica)、膠體二氧化矽、氧化鋁、氧化鋁溶 膠、銘矽酸鹽(aluminosilicate)、氧化鋁-二氡化發複合氧化 物、尚嶺土、滑石、雲母、碳酸鈣及鱗酸轉。又,有機微 粒子並無特別限定,但可舉例如交聯聚丙烯酸粒子、曱基 丙烯酸甲酯/苯乙烯共聚物樹脂粒子、交聯聚苯乙烯粒子、 ❿交聯聚甲基丙烯酸甲酯粒子、聚矽氧(silic〇ne)樹脂粒子及 聚酿亞胺粒子。 經賦予如此所得到之抗眩性的透明保護膜之霧度值 宜為6至45%的範圍内。若透明保護膜之霧度值低於6%, 則有時無法顯現充分的抗眩效果。又,若透明保護膜之霧 度值超過45%,則使用此薄膜而成之液晶顯示裝置的晝面 會白化,有時招致晝質之降低。 又’此霧度值係依據JIS K 7136,可使用例如霧度/ 透過率計ΗΜ·150((股)村上色彩技術研究所製)而測定。 23 321675 201028292 在測定霧度值時,為了防止薄膜之翹曲,較佳係使用例如 . 下述之測定試樣:以使抗眩性賦予面成為表面之方式,使 用光學上為透明之黏著劑將薄膜面貼合至玻璃基板而成之 : 測定試樣。 ' 在透明保護膜上可進一步層合導電層、硬塗層及低反 射層等功能層。又,構成透明保護膜之黏結劑樹脂亦可選 擇具有如此功能之樹脂組成物。 又,透明保護膜係於與偏光膜貼合前,宜先實施皂化 處理、電暈處理、及電漿處理等。 ❹ 透明保護膜之厚度並無特別限制,但一般從強度或處 理性等之觀點,為1至500//m左右,宜為20至300//m, 更宜為20至100 μ m。若為此範圍内之厚度,即可機械性 地保護偏光膜,即使曝露於高溫高濕下偏光膜亦不收縮, 而可保持安定之光學特性。 (透明保護膜貼合用接著劑) 使用於將偏光膜與透明保護膜予以接著的接著劑並 ^ 〇 無特別限定,但可舉例如含有聚乙烯醇系樹脂、環氧系樹 脂、胺基甲酸酯系樹脂、氰基丙烯酸酯系樹脂、丙烯醯胺 系樹脂等成分(以下有時記為接著劑成分)之接著劑(以 下,亦有時記為接著劑組成物)。其中,以水系之接著劑, 亦即將接著劑成分溶解於水者或分散於水者,因可更降低 接著劑層之厚度,故較宜使用。又,另一較佳之接著劑係 可舉例如由藉加熱或活性能量線之照射而使單體或募聚物 進行反應硬化而形成接著劑層之無溶劑樹脂組成物所構成 24 321675 201028292 • 者。 Ο 首先,說明有關水系之接著劑。就水系之接著劑而 “可舉例如含有聚乙烯醇系樹脂、水溶性之交聯性 樹脂或絲Ψ_旨緒鱗作為接著劑成分者。聚 系樹月旨係可使用作為水系接著劑所使用之各種公知 脂二又,水溶性之交聯性環氧樹脂可舉例如對於由二伸乙 基三胺或三伸乙基四胺等聚伸院基聚胺與己二酸等二緩酸 的反應所得狀聚賴㈣,使錢醇騎反應所得到之 聚醯胺環氧樹脂。如此之聚醯胺環氧樹脂的市售品可舉例 如 Sumirez Resin 65〇(住化 Chemtex(股)製)、如迅二z 675 (住化Chemtex (股)製)等。 使用水溶性之交聯性環氧樹脂作為接著劑成分時,於 其接著劑組成物中為了提高塗佈性與接著性,宜進一步混 合聚乙烯醇系樹脂等其他的水溶性樹脂。聚乙烯醇系樹脂 可舉例如部分矣化聚乙烯醇及完全息化聚乙烯醇、或叛基 ❹改性t乙稀醇、乙醒乙酿基改性聚乙稀醇、經曱基改性聚 乙烯醇、胺基改性聚乙烯醇等經改性的聚乙烯醇系樹脂。 其中,較宜使用醋駿乙烯酯與不飽和羧酸或其鹽之共聚物 的皂化物’亦即羧基改性聚乙烯醇。又,此處所謂之「羧 基」係包含-COOH及其鹽的概念。 市售之較佳的羧基改性聚乙烯醇可舉例如Kuraray Poval KL-506 ((股)Kuraray 製)、Kuraray Poval KL-318 ((股)Kuraray 製)、Kuraray Poval KL-118 ((股)Kuraray 製)、GosenalT-330(曰本合成化學工業(股)製)、Gosenal 25 321675 201028292 /曰本合成化學工業(股)製)、DR-0415 (電氣化 、製)、AF-17 (日本 vAM p〇val (股)製)、. (日本 VAMPoval(股)製)、Αρ·17(日本 VAMP〇val (股)製)。 ; 成_ 3有水溶性之交聯性環氣樹脂的接著劑,係可藉由將 裒氧樹月曰及依需要而加入之聚乙缚醇系樹脂等其他之水溶 性樹脂溶解於水,而調製成接著劑溶液 。此時,水溶性之 交聯性環氧樹脂之含量係相對於水100重量份,宜為0.2 至2重量份左右。又,調配聚乙烯醇系樹脂時,其調配量 ❹ 係相對於水100重量份’宜為1至10重量份左右,更宜為 1至5重量份左右。 另外,可適宜使用於水系之接著劑的胺基甲酸酯系樹 脂,可舉例如離子聚合物(ionomer)型的胺基甲酸酯樹脂、 尤其是聚酯系離子聚合物型胺基甲酸酯樹脂。此處,離子 聚合物型係指於構成胺基曱酸酯樹脂之骨架内’導入少量 之離子性成分(親水成分)者。又,聚酯系離子聚合物型 ❹ 胺基甲酸酯樹脂係指具有聚酯骨架之胺基甲酸酯樹脂,且 於其骨架内導入少量之離子性成分(親水成分)者。如此 之離子聚合物蜜胺基甲酸酯樹脂係不使用乳化劑而直接於 水中進行乳化而成為乳液,故可適宜使用於水系之接著 劑。聚酯系離子聚合物型胺基甲酸酯樹脂之市售品係例如 有HydranAP-2〇(大曰本油墨化學工業(股)製)、Hydran APX-101H(大曰本油墨化學工業(股)製)等,任一者均 可以乳液的形式得到。 26 321675 201028292 • 以離子聚合物型之胺基甲酸酯樹脂作為接著劑成分 / 時,其接著劑組成物中係宜進一步調配異氰酸酯系交聯 - 劑。異氰酸酯系交聯劑係指於分子内至少具有2個異氰酸 基(-NCO)之化合物,可舉例如2,4-甲苯二異氰酸酯、伸 苯基二異氰酸酯、4,4'-二苯基曱烷二異氰酸酯、1,6-六亞曱 基二異氰酸酯及異佛爾酮二異氰酸酯等聚異氰酸酯單體, 除此之外,亦可列舉如該等之複數分子加成於三羥基丙烷 等多元醇之加成體、二異氰酸酯3分子分別以單末端異氰 ® 酸基之部分形成三聚異氰酸酯環之3官能的三聚異氰酸酯 體、二異氰酸酯3分子分別以單末端異氰酸基之部分進行 水和、脫碳酸而形成之縮二脲(biuret)體等聚異氰酸酯改性 體等。可適宜使用之市售的異氰酸酯系交聯劑可舉例如 Hydran AssistC-Ι (大曰本油墨化學工業(股)製)等。 在含有離子聚合物型的胺基甲酸醋樹脂之水系接著 劑中,從黏度與接著性之觀點來看,胺基甲酸酯樹脂係宜 ❹以其濃度成為10至70重量%左右之方式溶解或分散於水 中,更宜為20至50重量%以下。又,調配異氰酸酯系交 聯劑時,其調配量係相對於胺基甲酸酯樹脂1〇〇重量份, 而以異氰酸酯系交聯劑成為5至100重量份左右的方式適 當選擇。 使用如此而成之水系接著劑時,藉由將該接著劑塗佈 於透明保護膜、或偏光膜之接著面,貼合兩者並乾燥,俾 可得到偏光膜與透明保護膜之層合體。 其次,說明有關由含有藉活性能量線之照射或加熱而 27 321675 201028292 硬化==?軸組成物所構成的接著劑。 有藉由加熱或活性能量線之照射而含 合物與聚合起始劑,但不含 之硬化性的化 r ^ ^ , 3有具思義罝之溶劑的硬化性組 有時δ己為硬化性組成物)。從反應性之觀點來 看,此硬化性之化合物宜為以陽離子聚合進行硬 宜為含有環氧化合物(環氧樹脂)。 1 或折射料的觀點來看,此環氧化合物係適 Ο 且.内不含有芳香環者。使用於分子内不含有芳 香環之環氧化合物的接著劑,例如記載於曰本特開 ==^^純° ^之不含有芳㈣之環氧化合物 可舉例如方香族環氧化合物的氫化物、脂環式環氧化人 物、及脂肪族環氧化合物等。 口 化入氧化合物的氣化物係指藉由使芳香族環氧 ❹ 氫:反應而1的存在下、加壓下對於芳香環選擇性地進行 μ侍到者。芳香族環氧化合物可舉例如雙酚Α之 由基M、雙盼F之二縮水甘油基醚、雙紛S之二 縮料等雙盼型環氧化合物;紛祕清漆⑽_ 酚祕、主^樹脂、甲紛盼駿清漆環氧樹脂、經基苯曱齡 : = = =等㈣清漆型之環氧樹 基轉、環氣化聚四經基=苯曱_之縮水甘油 宜為被氫化之他 寺夕g能型的環氧化合物。其中, 又吩A之-始, 脂環式環氣 义一縮水甘油基醚。 '合物係指於分子内至少具有1個結合於 321675 28 201028292 如下式所示之脂環式環的環氧基之化合物。Further, in the case of the polyethylene terephthalate resin film, for example, Novaclear (manufactured by Mitsubishi Chemical Corporation) and Teijin A-PET sheet (manufactured by Teijin Chemicals Co., Ltd.) can be used. In the case of the polypropylene resin film, for example, FILMAX CPP film (manufactured by FILMAX Co., Ltd.), Suntox (manufactured by Sun Tox Co., Ltd.), Tohcello (manufactured by Tohcello Co., Ltd.), and Toyobo Pyrene can be used. Film (Toyobo Co., Ltd.), Torayfan (Tomy Film Processing Co., Ltd.), Nippon Polyace (Sakamoto Polyace), and Taige FC (Futamura Chemical Co., Ltd.). Further, each of the cellulose-based resin films may be, for example, Fujitac TD (manufactured by Fujifilm Co., Ltd.) and Konica Minolta TAC Film KC (manufactured by Konica Minolta Opto Co., Ltd.). The transparent protective film used in the present invention imparts anti-glare properties (i.e., 22 321675 201028292 • Haze, Haze). The method of imparting the anti-glare property is not particularly limited, and examples thereof include a method in which inorganic fine particles or organic fine particles are mixed with the raw material resin, and a method of thinning is used. One of the above-mentioned multilayer extrusions is a resin in which fine particles are mixed, and the other is One of the resins is a resin in which no fine particles are mixed, and the two-side resin is a method of performing two-layer thinning; and the method of mixing the fine-grained resin on both sides of the resin in which the microparticles are not mixed to perform three-layer thinning; On the one side of the film, a coating liquid obtained by mixing inorganic fine particles or organic fine particles in a binder resin is applied, and the binder resin is cured to provide an antiglare layer. The inorganic fine particles for imparting anti-glare properties are not particularly limited, and examples thereof include silica, colloidal ceria, alumina, alumina sol, aluminosilicate, and alumina-dioxide. Chemical composite oxide, Shangling soil, talc, mica, calcium carbonate and scallops. Further, the organic fine particles are not particularly limited, and examples thereof include crosslinked polyacrylic acid particles, methyl methacrylate/styrene copolymer resin particles, crosslinked polystyrene particles, and ruthenium crosslinked polymethyl methacrylate particles. Silicium resin particles and polyaminin particles. The haze value of the transparent protective film to which the anti-glare property thus obtained is imparted is preferably in the range of 6 to 45%. If the haze value of the transparent protective film is less than 6%, a sufficient anti-glare effect may not be exhibited. Further, when the haze value of the transparent protective film exceeds 45%, the surface of the liquid crystal display device using the film may be whitened, which may cause a decrease in enamel. Further, the haze value is measured in accordance with JIS K 7136, for example, by using a haze/transmittance meter 150 (manufactured by Murakami Color Research Laboratory Co., Ltd.). 23 321675 201028292 When measuring the haze value, in order to prevent the warpage of the film, it is preferable to use, for example, the following measurement sample: an optically transparent adhesive is used so that the anti-glare imparting surface becomes a surface. The film surface is bonded to a glass substrate: The sample is measured. ' Functional layers such as conductive layer, hard coat layer and low reflective layer can be further laminated on the transparent protective film. Further, the binder resin constituting the transparent protective film may also be a resin composition having such a function. Further, the transparent protective film is preferably subjected to a saponification treatment, a corona treatment, a plasma treatment or the like before being bonded to the polarizing film.厚度 The thickness of the transparent protective film is not particularly limited, but is generally from 1 to 500 / / m, preferably from 20 to 300 / / m, more preferably from 20 to 100 μ m from the viewpoint of strength or rationality. If the thickness is within this range, the polarizing film can be mechanically protected, and the polarizing film does not shrink even when exposed to high temperature and high humidity, and the optical characteristics of stability can be maintained. (Binder for bonding a transparent protective film) The adhesive used for the polarizing film and the transparent protective film is not particularly limited, and examples thereof include a polyvinyl alcohol resin, an epoxy resin, and an amine group. An adhesive (hereinafter, also referred to as an adhesive composition) of a component such as an acid ester resin, a cyanoacrylate resin, or an acrylamide resin (hereinafter referred to as an adhesive component). Among them, a water-based adhesive, that is, a component in which an adhesive component is dissolved in water or dispersed in water, is preferably used because the thickness of the subsequent agent layer can be further reduced. Further, another preferred adhesive agent is, for example, a solvent-free resin composition in which a monomer or a polymer is subjected to reaction hardening by heating or active energy rays to form an adhesive layer. 24 321675 201028292 • . Ο First, explain the adhesives for the water system. In the case of the water-based adhesive, for example, a polyvinyl alcohol-based resin, a water-soluble cross-linkable resin, or a silk Ψ 旨 scale is used as an adhesive component. The poly-tree can be used as a water-based adhesive. Various known lipids are used, and the water-soluble crosslinkable epoxy resin may, for example, be a poly-lowering acid such as a polyethylamine or a tetraethylethylenetetramine. The obtained reaction product is obtained by the reaction of poly(methane) epoxy resin obtained by the reaction of the alcohol alcohol. The commercial product of such a polyamide resin is, for example, Sumirez Resin 65® (manufactured by Susei Chemtex Co., Ltd.). In the case of using a water-soluble crosslinkable epoxy resin as an adhesive component, in order to improve coatability and adhesion, in the case of using a water-soluble crosslinkable epoxy resin as an adhesive component, Further, it is preferable to further mix other water-soluble resins such as polyvinyl alcohol-based resins. Examples of the polyvinyl alcohol-based resin include partially deuterated polyvinyl alcohol and fully-interested polyvinyl alcohol, or tetamine-modified t-diethyl alcohol, and W Ethylene-modified polyvinyl alcohol, thiol-modified polyvinyl alcohol, amine A modified polyvinyl alcohol-based resin such as a modified polyvinyl alcohol. Among them, a saponified product of a copolymer of acetophenone and an unsaturated carboxylic acid or a salt thereof, that is, a carboxyl group-modified polyvinyl alcohol is preferably used. Here, the "carboxy group" as used herein includes the concept of -COOH and a salt thereof. Preferred carboxy-modified polyvinyl alcohols which are commercially available are, for example, Kuraray Poval KL-506 (manufactured by Kuraray Co., Ltd.), Kuraray Poval KL-318 (manufactured by Kuraray Co., Ltd.), and Kuraray Poval KL-118 (shares). Kuraray system), Gosenal T-330 (manufactured by Sakamoto Synthetic Chemical Co., Ltd.), Gosenal 25 321675 201028292 / Sakamoto Synthetic Chemical Industry Co., Ltd., DR-0415 (Electrification, System), AF-17 (Japan vAM) P〇val (share) system, .. (Japan VAMPoval (share) system), Αρ·17 (Japan VAMP〇val (share) system). An adhesive for the water-soluble crosslinkable cycloolefin resin, which is prepared by dissolving other water-soluble resins such as a fluorinated resin and a polyhydric alcohol resin which are added as needed, in water. It is prepared into an adhesive solution. In this case, the content of the water-soluble crosslinkable epoxy resin is preferably from about 0.2 to 2 parts by weight based on 100 parts by weight of water. Further, when the polyvinyl alcohol-based resin is blended, the amount thereof is preferably from 1 to 10 parts by weight, more preferably from 1 to 5 parts by weight, per 100 parts by weight of water. Further, the urethane-based resin which can be suitably used as an aqueous binder is exemplified by an ionomer type urethane resin, particularly a polyester-based ionic polymer type urethane. Ester resin. Here, the ionic polymer type refers to a small amount of an ionic component (hydrophilic component) introduced into the skeleton of the amino phthalate resin. Further, the polyester-based ionic polymer type urethane resin refers to a urethane resin having a polyester skeleton, and a small amount of an ionic component (hydrophilic component) is introduced into the skeleton. Such an ionic polymer melamine resin is emulsified directly in water without using an emulsifier to form an emulsion, and thus can be suitably used as a water-based adhesive. A commercially available product of a polyester-based ionic polymer type urethane resin is Hydran AP-2 (manufactured by Otsuka Ink Chemical Industry Co., Ltd.), and Hydran APX-101H (Otsuka Ink Chemical Industry Co., Ltd.) Any of them can be obtained in the form of an emulsion. 26 321675 201028292 • When an ionic polymer type urethane resin is used as the adhesive component /, it is preferable to further adjust an isocyanate crosslinking agent in the adhesive composition. The isocyanate crosslinking agent means a compound having at least two isocyanato groups (-NCO) in the molecule, and examples thereof include 2,4-toluene diisocyanate, phenylphenyl diisocyanate, and 4,4'-diphenyl group. a polyisocyanate monomer such as decane diisocyanate, 1,6-hexamethylene diisocyanate or isophorone diisocyanate, and addition of plural molecules such as trihydroxypropane The alcohol addition product and the diisocyanate 3 molecules respectively form a trifunctional isocyanate ring of a trimeric isocyanate ring and a diisocyanate 3 molecule of a mono-terminal isocyanate group, respectively. A polyisocyanate modified body such as water and a biuret formed by decarbonation. A commercially available isocyanate-based crosslinking agent which can be suitably used is, for example, Hydran AssistC-Ι (manufactured by Otsuka Ink Chemical Industry Co., Ltd.). In the aqueous binder containing an ionic polymer type urethane carboxylic acid resin, the urethane resin is preferably dissolved in such a manner that its concentration is about 10 to 70% by weight from the viewpoint of viscosity and adhesion. Or dispersed in water, more preferably 20 to 50% by weight or less. In addition, when the isocyanate-based crosslinking agent is blended, the amount thereof is appropriately selected from the group consisting of 1 part by weight of the urethane resin and 5 to 100 parts by weight of the isocyanate-based crosslinking agent. When the water-based adhesive thus obtained is used, the adhesive is applied to the transparent protective film or the back surface of the polarizing film, and the two are bonded together and dried to obtain a laminate of the polarizing film and the transparent protective film. Next, an explanation will be given of an adhesive composed of a composition comprising a hardened energy line or an irradiation of 27 321675 201028292 hardened ==? There is a combination of a compound and a polymerization initiator which is irradiated by heating or active energy rays, but does not contain a hardening property, and a hardening group of a solvent having a meaning of 思 is sometimes hardened. Sexual composition). From the viewpoint of reactivity, the curable compound is preferably an epoxy compound (epoxy resin) which is hardly cationically polymerized. 1 From the viewpoint of the refracting material, the epoxy compound is suitable and does not contain an aromatic ring. An adhesive used for an epoxy compound which does not contain an aromatic ring in the molecule, for example, an epoxy compound which does not contain aryl (IV), which is described in 曰 特 = ==^^^^^^^^^^^^^^^^^^^^ Materials, alicyclic epoxidized characters, and aliphatic epoxides. The vaporization of the oxygenated oxygen-containing compound means that the aromatic ring is selectively subjected to a reaction under the action of 1 in the presence of an aromatic oxime hydrogen: Examples of the aromatic epoxy compound include a double-powder type epoxy compound such as a bisphenol hydrazine group M, a double hop bis glycidyl ether, and a double bis bis condensate; a secret varnish (10) _ phenolic secret, main ^ Resin, A, junqing lacquer epoxy resin, benzoquinone age: = = =, etc. (4) varnish type epoxy resin base, cyclized polytetramethylene = benzoquinone _ glycidol should be hydrogenated He Temple g-type epoxy compound. Among them, the A-start, alicyclic ring-glycidyl ether. The term "compound" means a compound having at least one epoxy group bonded to an alicyclic ring represented by the following formula in 321675 28 201028292.
(式中,m表示2至5之整數)。 使此式中之(CH2) m中的氫原子除去1個或複數個 之形式的基結合於其他之化學構造的化合物,即可成為脂 環式環氧化合物。又,形成脂環式環之氫可經甲基或乙基 ® 等直鏈狀烷基適當取代。其中,宜使用具有環氧基環戊烷 環(上式中m=3者)或環氧基環己烷環(上式中m=4者) 之化合物。脂環式環氧化合物之具體例可舉例如下述者: 3.4- 環氧基環己烷羧酸3,4-環氧基環己基曱酯、 3.4- 環氧基-6-曱基環己烷羧酸3,4-環氧基-6-曱基環己 基曱酉旨、 雙(3,4-環氧基環己烷羧酸)伸乙酯、 ❹ 己二酸雙(3,4-環氧基環己基甲基)酯、 己二酸雙(3,4-環氧基-6-曱基環己基甲基)酯、 二乙二醇雙(3,4-環氧基環己基曱基醚)、 乙二醇雙(3,4-環氧基環己基甲基醚)、 2,3,14,15-二環氧基-7,11,18,21-四氧三螺-[5.2.2.5.2.2] 二十一烷(又,亦可命名為3,4-環氧基環己烷螺-2^6’-二噚 烷螺-3’’,5Π-二噚烷螺-3m,4’"-環氧基環己烷之化合物)、 4-(3,4-環氧基環己基)-2,6-二氧雜-8$環氧:基螺[5.5] Η—烧' 29 321675 201028292 4-乙烯基環己烯二氧化物、 雙-2,3-環氧基環戊基醚、以及 二環戊二稀二氧化物。 又,脂肪族環氧化合物係脂肪族多元醇或其環氧烷加 成物之聚縮水甘油基醚。可舉例如1,4- 丁二醇之二縮水甘 油基醚、1,6-己二醇之二縮水甘油基醚、甘油之三縮水甘 油基醚、三羥曱基丙烷之三縮水甘油基醚、聚乙二醇之二 縮水甘油基醚、聚丙二醇之二縮水甘油基醚、藉由對乙二 醇或聚丙二醇、甘油等脂肪族多元醇加成1種或2種以上 之環氧烷(環氧乙烷或聚環氧丙烷)所得到之聚醚多元醇 的聚縮水甘油基醚等。 此處所例示之環氧化合物係可分別單獨使用,亦可與 其他之1種以上混合而使用。 如此之環氧化合物的環氧當量一般為30至3000 g/eq,宜為50至1500 g/eq。若環氧當量低於30 g/eq,則 硬化後之透明保護膜的可撓性降低,或接著強度降低。另 外,若超過3 000 g/eq,則有時與其他之成分的相溶性降低。 在硬化性組成物中,為了使環氧化合物以陽離子聚合 硬化,而調配陽離子聚合起始劑。陽離子聚合起始劑係藉 由可見光線、紫外線、X線、及電子束等活性能量線的照 射、或加熱,俾產生陽離子種或路易士酸,開始環氧基之 聚合反應。不論為任一型式的陽離子聚合起始劑,就作業 性之觀點來看,皆因賦予潛在性而為佳。 以下,說明有關藉活性能量線的照射以產生陽離子種 30 321675 201028292 •或路易士酸之光陽離子聚合起始劑。若使用光陽離子聚合 〈起始劑,即可在常溫下硬化,減少必須考量因偏光膜之耐 熱性或熱膨服所造成的内部應力的顧慮,可良好地將透明 保護膜與偏光膜予以接著。又’光陽離子聚合起始劑係以 光進行觸媒作用’故即使混合於環氧化合物中,保存安定 性或作業性亦優異。豬活性旎量線的照射以產生陽離子種 或路易士酸之化合物係可舉例如芳香族重氮鹽(diaz〇nium salt)、芳香族錤鹽及^•香族疏鹽等鏽鹽、以及鐵_丙二烯 ❹(allene)錯合物等。其中,尤其因芳香族銃鹽係即使在 300nm以上之波長區域亦具有紫外線吸收特性,而可賦予 硬化性優異且具有良好之機械強度或接著強度之硬化物, 故較宜使用。 如此之光陽離子聚合起始劑係就市售品而言可容易 取得’可分別以商品名舉例如Kayarad PCI-220 (曰本化藥 (股)製)、Kayarad PCI-620(日本化藥(股)製)、UVI-6990 ❿(Union Carbide 公司製)、Adeka Optomer SP-150 ((股) ADEKA 製)、Adeka Optomer SP-170 ((股)ADEKA 製)、 CI-5102 (曰本曹達(股)製)、(:汀-1370 (曰本曹達(股) 製)、CIT-1682 (日本曹達(股)製)、CIP-1866S (曰本曹 達(股)製)、CIP-2048S (曰本曹達(股)製)、CIP-2064S (曰本曹達(股)製)、DPI-101 (Midori化學(股)製)、 DPI-102 (Midori 化學(股)製)、DPI-103 (Midori 化學 (股)製)、DPI-105(Midori 化學(股)製)、MPI-l〇3(Midori 化學(股)製)、MPI-105(Midori 化學(股)製)、ΒΒΙ-1〇1 31 321675 201028292 (Midori 化學(股)製)、BBI-102(Midori 化學(股)製)、 BBI-103 (Midori 化學(股)製)、BBI-105 (Midori 化學 (股)製)、TPS-101(Midori 化學(股)製)、TPS-102(Midori 化學(股)製)、TPS-103(Midori 化學(股)製)、TPS-105 (Midori 化學(股)製)、MDS-103 ( Midori 化學(股) 製)、MDS-105 (Midori 化學(股)製)、DTS-102 (Midori 化學(股)製)、DTS-103 (Midori 化學(股)製)、PI-2074 (Rhodia公司製)等。 光陽離子聚合起始劑之調配量係相對於環氧化合物 100重量份’ 一般為〇·5至20重量份,宜為1重量份至15 重量份。 於硬化性組成物中,依需要而可併用光增感劑。藉由 使用光增感劑,可使反應性提高,並可提昇硬化物之機械 強度或接者強度。 光增感劑可舉例如羰基化合物、有機硫化合物、過硫 化物 '氧化還原系化合物、偶氮及重氮化合物、_素化合 物、以及光還原性色素。調配光增感劑時,其調配量係以 光陽離子聚合性環氧樹脂組成物作為1〇〇重量份時,一般 為0.1至20重量份左右。 其次,說明有關熱陽離子聚合起始劑。藉加熱產生陽 離子種或路易士酸之化合物,可舉例如苯曱基鎳鹽、噻吩 鑌(thiophenium)鹽、四氫噻吩鏽(thi〇lanium)鹽、苯曱基銨、 吡啶鏽鹽、肼鑌(hydrazinium)鹽、羧酸酯、磺酸酯、及胺 醯亞胺。此等之熱陽離子聚合起始劑亦可容易地取得市售 321675 32 201028292 品,例如任一者皆可依商品名舉例如Adeka opton CP77 ’ ((股)ADEKA 製)、Adeka opton CP66((股)ADEKA 製)、 / CI-2639 (曰本曹達(股)製)、CI-2624 (曰本曹達(股) 製)、Sun Aid SI-60L (三新化學工業(股)製)、Sun Aid SI-80L (三新化學工業(股)製)、SunAidSI-100L (三新 化學工業(股)製)等。 併用前述之光陽離子聚合與熱陽離子聚合亦為有用 的技術。 ® 硬化性組成物亦可復含有氧雜環丁烧(oxetane)類或 多元醇類等促進陽離子聚合的化合物。 將如此所得到之硬化性組成物塗佈於透明保護膜及 偏光膜之至少一者而形成硬化性組成物層,於硬化性組成 物層上重疊另一者之偏光膜或透明保護膜後,藉由活性能 量線的照射或加熱而使硬化性組成物層硬化,俾可介由硬 化層而進行偏光膜與透明保護膜之貼合。將硬化性組成物 Q 塗佈於透明保護膜或偏光膜之方法並無特別限定,可採用 例如刮刀(doctor blade)、線棒(wire bar)、模具塗佈機(die coater)、逗號式塗佈機(comma coater)、及凹版廣,俺機等各 種之塗佈方式。硬化性組成物層之厚度一般為1私m以上、 50#ιη以下,宜為20//m以下,更宜為1〇#πι以下。 藉活性能量線之照射俾進行硬化性組成物層之硬化 時,所使用之光源並無特別限定’但可舉例如於波長400nm 以下具有發光分布的例如低壓水銀燈々甲;T米讓1曼、高壓 水銀燈、超高壓水銀燈、化學燈、黑光燈(black light lamp)、 321675 33 201028292 微波激發水銀燈及金屬_素燈。對於麻 、无化性組成物層之光 照射強度係依其組成物之硬化性而決定者 I特別限 定,但對於光陽離子聚合起始劑的活化為有致之波 的照射強度宜為0.1至lOOmW/cm2。若對於石 層之光照射強度未達0· 1 mW/cm2,則及庙 ;硬化性組成物 〜久應時間太 過100 mW/cm2 ’則由於從燈所發射 長’若超 〜热及硬化+ 的聚合時之發熱’俾有時會發生硬化性 生纟且成物 &、,、且成物的普 光膜之劣化。同樣地,對於硬化性組成物層之、汽變或偏 係依其組成物之硬化性而決定者,並無特^ ,照射時間 宜設定成使照射強度與照射時間之積所示的’值例如 10至5000 mJ/cm2。對於硬化性組成物層之積:光蕙成為 達10 mJ/cm2,則源自光陽離子聚合起始劑之二=量若未 生會不充分,有時硬化性組成物層之硬化不充八種的產 積分光量超過5000 mJ/cm2,照射時間變成非常又’若 產性提高上成為不利者。 〜’於生 藉熱進行硬化性組成物層之硬化時,可依一 方法進行加熱,其條件等亦無特別限定,但通常^所知之 硬化性組成物之熱%離子聚合起始劑會產生陽離子=° —於 易士酸之溫度以上進行加熱,例如為5〇至2〇〇它左種或路 即使以活性能量線之照射或加熱的任一者之條° 化時,宜在附單面透明保護膜之偏光板的偏光度、透件硬 色相、透明保護膜之透明性等各功能不降低的範圍^率、 硬化。使硬化性組成物層硬化而成之硬化層的厚度〜=订 50/zm以下,宜為20/zm以下,更宜為1〇//m。又般為 321675 34 201028292 • (剝離性薄膜) - 本發明之製造方法所使用的具有黏著性之剝離性薄 ▼ - 膜,可使用容易剝離之經低分子量的黏著劑處理之薄膜, 例如可使用聚對酞酸乙二酯、聚萘二甲酸乙二酯等聚酯系 樹脂;環狀烯烴系樹脂;及聚乙烯、聚丙烯、丙烯/乙烯共 聚物等鏈狀烯烴系樹脂。其中,從可適當調節黏著性且容 易從市售品取得之觀點來看,宜使用聚對酞酸乙二酯薄 膜、聚丙烯薄膜、及聚乙烯薄膜。 ® 剝離性薄膜係具有自我黏著性,可直接貼合於偏光膜 之與貼合有透明保護膜的面相反侧之面。 如此,藉由接著劑而於偏光膜之單面貼合透明保護膜 且於相反側之面貼合具有黏著性之剝離性薄膜的附單面透 明保護膜之偏光板,係暫時藉捲取裝置而被氯化乙烯管等 核所捲取。又,於偏光膜贴合透明保護膜之步驟、與於偏 光膜貼合剝離性薄膜之步驟係亦可先實施任一者,亦可同 ❹時地實施。 [2]步驟(B) 於本發明之第一態樣、第三態樣、第四態樣及第五態 樣中係將依上述做法所製作之於單面貼合剝離性薄膜的附 單面透明保護膜之偏光板,在第二態樣中係將於單面形成 黏著劑層之附單面透明保護膜之偏光板,配合相位差薄膜 之大小而沿著長度方向進行裁切(切割(slit))。附單面透明 保護膜之偏光板之裁切後的寬度係依照後述之相位差薄膜 的寬度而適當設定,但例如裁切後之附單面透明保護膜之 35 321675 201028292 偏光板的至少一切片係宜與後述之相位差薄膜的寬度為相 . 同的寬度。 \ 又,在第二態樣中,附單面透明保護膜之偏光板之裁 : 切係亦對經層合之黏著劑層一起進行。 ' 將附單面透明保護膜之偏光板予以裁切之方法並無 特別限定,但一般可採用使所捲取之附單面透明保護膜之 偏光板朝切割機(長度方向之裁切機)拉出而同時地進行裁 切,然後再捲取所裁切之複數個切片的方法。又,亦可採 用不捲取經配合相位差薄膜之寬度所裁切之偏光板,而是 ❹ 從此朝下一個步驟依序送出之方法。 [3] 步驟(C) 於本發明之第一態樣、第三態樣、第四態樣及第五態 樣中係從上述步驟(B)所裁切之附單面透明保護膜之偏光 板除去剝離性薄膜,在第二態樣中係從未裁切之附單面透 明保護膜之偏光板除去剝離性薄膜。 [4] 步驟(D) 〇 在本發明之第一態樣中係在步驟(B)所裁切且在步驟 (C)已除去剝離性薄膜之附單面透明保護膜之偏舟板的偏 光膜面(曾貼合有剝離性薄膜之面)上,在第二態樣中係在 步驟(C)已除去剝離性薄膜之未裁切的附單面透明保護膜 之偏光板的偏光膜面(曾貼合有剝離性薄膜之面)上,在第 三態樣中係於相位差薄膜之單面上,形成在80°C中具有 O.IMPa以上之貯存彈性模數的黏著劑層。 (黏著劑) 36 321675 201028292 用於形成黏著劑層的黏著劑係在8(rc之貯存彈性模 數為O.IMPa以上,宜為0.15MPa至1〇MPa。在8〇c)c之貯 存彈性模數未達O.IMPa時,無法追隨反覆處於 與低溫環境時所產生之偏光膜的尺寸變化,故有^生氣 泡、剝離等之不佳情形。又,此黏著劑之在23它的溫度^ 之貯存彈性模數宜為O.IMPa以上,更宜為〇2至。 又,貯存彈性模數一般有在溫度愈高之條件下會變愈低之 傾向,故若在80〇C測定的材料之貯存彈性模數為〇1胁 以上,-般在23。(:所収之相同材料之貯存彈性模數係顯 示其以上之值。在本案說明書中’黏著劑係與感壓性接著 劑(pressure sensitive adhesive)同意義。 此處,所謂貯存彈性模數(動態彈性模數)係意指一般 所使用之黏彈性測定的用語,其係對於試料隨時間而賦予 變化(振動)之變形或應力,測定隨其所產生之應力或變 形’俾藉由測定試料之力學性質的方法(動態黏彈性測定) ❺所求取之值。具體上,係指將依施加於試料之正弦波形的 變形(應力)所產生的應力(變形),分開成與變形(應力)為同 相位之成分與偏移90度之相位之成分的波時,從與變形 (應力)為同相位之應力(變形)成分所算出之彈性模數。貯存 彈性模數係可使用市售之黏彈性測定裝置,例如如後述之 實施例所示的動癌黏彈性測定裝置(Dynamic Analyzer RDA II : REOMETRIC公司製)而測定。黏彈性測定裝置之 溫度控制係可使用循環恒溫槽、電加熱器、電子致冷元件 (Peltier device)等各種公知的溫度控制裝置,可藉此而設定 37 321675 201028292 測定時之溫度。 於一般之圖像顯示裝置或適用於其之光學薄膜所使 用之黏著劑係其貯存彈性模數至多為O.IMPa左右,但本 發明之製造方法所使用的黏著劑係如上述般為其貯存彈性 模數高者。藉由具有如此高的貯存彈性模數,亦即藉由使 用硬的黏著劑,俾可彌補當放置於高溫環境下時或反覆處 於高溫環境與低溫環境時之凝集力不足,可抑制此時產生 之偏光膜的收縮所伴隨之尺寸變化。藉由此作用,本發明 之複合偏光板具有良好的耐久性。 於本發明之製造方法所使用的具體的高彈性黏著 劑,係可由例如主要含有丙烯酸系聚合物、聚矽氧系聚合 物、聚酯、聚胺基甲酸酯、聚醚等成分的組成物所構成。 其中,宜選擇使用如丙烯酸系聚合物般光學透明性優異, 保持適度的潤濕性或凝集力,與基材之黏著性亦優異,且 具有耐候性或耐熱性等,在加熱或加濕之條件下不產生浮 起或剝離等剝離問題者。在丙烯酸系聚合物中,以將具有 曱基、乙基及丁基等碳數為20以下的烷基之丙烯酸的烷基 酯、與由(甲基)丙烯酸或(甲基)丙烯酸羥乙酯等所構成之含 官能基的丙烯酸系單體,調配成玻璃轉移溫度宜為25°C以 下,更宜為〇°C以下之重量平均分子量為1〇萬以上之丙烯 酸系共聚物為有用者。 丙烯酸系聚合物並無特別限定,但可適宜使用(甲基) 丙烯酸丁酯、(曱基)丙烯酸乙酯、(曱基)丙烯酸酯異辛酯、 (甲基)丙烯酸2-乙基己酯等(甲基)丙烯酸酯系聚合物,或 38 321675 201028292 * 使用此等(曱基)丙烯酸酯之2種類以上之共聚合系聚合 物。又,對於此等丙烯酸系聚合物亦可將極性單體予以共 . 聚合。極性單體可舉例如(曱基)丙烯酸、(曱基)丙烯酸2-羥丙酯、(甲基)丙烯酸2-羥乙酯、(甲基)丙烯醯胺、(曱基) 丙烯酸2-Ν,Ν-二甲基胺基乙酯、(曱基)丙烯酸縮水甘油酯 等具有羧基、羥基、醯胺基、胺基、環氧基等極性官能基 的單體。 此等丙烯酸系聚合物係可單獨使用來作為黏著劑,但 ® 一般係製成調配有交聯劑之黏著劑組成物。交聯劑係可例 示如:為2價或多價金屬離子而與羧基之間形成羧酸金屬 鹽者;為聚胺化合物而與羧基之間形成醯胺鍵者;為聚環 氧化合物或多元醇化合物而與羧基之間形成酯鍵者;以及 為聚異氰酸酯化合物而與羧基之間形成醯胺鍵者。其中較 宜使用聚異氰酸酯化合物。 用以使黏著劑之貯存彈性模數成為高值之手段,並無 ❿特別限定,宜採用例如於上述之黏著劑組成物中調配寡聚 物,具體上係調配胺基甲酸酯丙烯酸酯系之寡聚物的方 法。進一步,對已調配如此之胺基甲酸酯丙烯酸酯系寡聚 物之黏著劑組成物照射能量線而硬化之方法,係因會成為 具有更高之貯存彈性模數,故較宜採用。調配有胺基曱酸 酯丙烯酸酯系寡聚物之黏著劑、或將其塗佈於支撐薄膜(分 隔膜(separator))上而使其紫外線硬化的附分隔膜的黏著劑 已為公知,可從黏著劑製造商取得。 於黏著劑組成物中,除了上述聚合物、交聯劑及募聚 39 321675 201028292 物之外,依需要而為了調整黏著劑之黏著力、凝集力、黏 性、彈性模數及玻璃轉移溫度等,亦可調配例如天然物或 合成物之樹脂類、賦予黏著性之樹脂、抗氧化劑、紫外線 吸收劑、染料、顏料、消泡劑、抗腐姓劑、光聚合起始劑 等適當添加劑。紫外線吸收劑可舉例如水揚酸酯系化合 物、或二苯甲酮系化合物、苯并三唑系化合物、氰基丙烯 酸酯系化合物、及鎳錯鹽系化合物。 又於本發明之製造方法所使用的黏著劑係可調配光 ,散,而作為㈣散性黏著劑。此處所使用之光擴散劑係 二要是與構絲著劑層之聚合物為折射率相異的微粒子即 可可使用由無機化合物所構成之微粒子或由有機化合物 (k合物)所構成之微粒子。 田無機(wherein m represents an integer from 2 to 5). The group in which one or more of the hydrogen atoms in the (CH2) m in the formula is removed is bonded to another chemically-formed compound to form an alicyclic epoxy compound. Further, the hydrogen forming the alicyclic ring may be appropriately substituted with a linear alkyl group such as a methyl group or an ethyl group. Among them, a compound having an epoxycyclopentane ring (m=3 in the above formula) or an epoxycyclohexane ring (m=4 in the above formula) is preferably used. Specific examples of the alicyclic epoxy compound include, for example, 3.4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexyldecyl ester, 3.4-epoxy-6-fluorenylcyclohexane. Carboxylic acid 3,4-epoxy-6-fluorenylcyclohexyl oxime, bis(3,4-epoxycyclohexanecarboxylic acid) ethyl ester, bismuth adipic acid bis (3,4-ring Oxycyclohexylmethyl)ester, bis(3,4-epoxy-6-fluorenylcyclohexylmethyl) adipate, diethylene glycol bis(3,4-epoxycyclohexylfluorenyl) Ether), ethylene glycol bis(3,4-epoxycyclohexylmethyl ether), 2,3,14,15-diepoxy-7,11,18,21-tetraoxatriazole-[5.2 .2.5.2.2] Tetane (also known as 3,4-epoxycyclohexane spiro-2^6'-dioxane spiro-3'',5Π-dioxane spiro-3m , 4'"-epoxycyclohexane compound), 4-(3,4-epoxycyclohexyl)-2,6-dioxa-8-epoxy: snail [5.5] Η- Burning ' 29 321675 201028292 4-vinylcyclohexene dioxide, bis-2,3-epoxycyclopentyl ether, and dicyclopentadiene dioxide. Further, the aliphatic epoxy compound is a polyglycidyl ether of an aliphatic polyol or an alkylene oxide adduct thereof. For example, diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerol, triglycidyl ether of trishydroxypropylpropane And diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, and one or more alkylene oxides are added by adding an aliphatic polyol such as ethylene glycol, polypropylene glycol or glycerin ( Polyglycidyl ether of a polyether polyol obtained by ethylene oxide or polypropylene oxide. The epoxy compounds exemplified herein may be used singly or in combination of one or more kinds. The epoxy equivalent of such an epoxy compound is generally from 30 to 3000 g/eq, preferably from 50 to 1500 g/eq. When the epoxy equivalent is less than 30 g/eq, the flexibility of the cured transparent protective film is lowered, or the strength is lowered. On the other hand, when it exceeds 3 000 g/eq, the compatibility with other components may be lowered. In the curable composition, a cationic polymerization initiator is formulated in order to cure the epoxy compound by cationic polymerization. The cationic polymerization initiator is irradiated with an active energy ray such as visible light, ultraviolet rays, X-rays, and electron beams, or heated to generate a cationic species or a Lewis acid to initiate polymerization of an epoxy group. Regardless of the type of cationic polymerization initiator, it is preferred from the viewpoint of workability to impart potential. In the following, description will be made regarding the irradiation of the active energy ray to produce a cationic species 30 321675 201028292 • or a photocationic polymerization initiator of Lewis acid. If a photocationic polymerization initiator is used, it can be hardened at room temperature, and the concern that the internal stress caused by the heat resistance of the polarizing film or the thermal expansion is considered must be considered, and the transparent protective film and the polarizing film can be well adhered to . Further, the photocationic polymerization initiator is photocatalytic, so that it is excellent in storage stability and workability even when it is mixed with an epoxy compound. The compound which irradiates the porcine active enthalpy line to produce a cationic species or a Lewis acid may, for example, be a diaz〇nium salt, an aromatic sulfonium salt, a rust salt such as a salt and a salt, and iron. _ allene complex and the like. Among them, the aromatic sulfonium salt is preferably used because it has ultraviolet absorbing properties even in a wavelength region of 300 nm or more, and can provide a cured product having excellent curability and good mechanical strength or adhesion strength. Such a photocationic polymerization initiator can be easily obtained as a commercial product, and can be separately marketed, for example, Kayarad PCI-220 (manufactured by Sakamoto Chemical Co., Ltd.), Kayarad PCI-620 (Nippon Chemical Co., Ltd.) ()), UVI-6990 ❿ (Union Carbide), Adeka Optomer SP-150 (made by ADEKA), Adeka Optomer SP-170 (made by Adeka), CI-5102 (Sakamoto Soda ( ())), (: Ting-1370 (Sakamoto Soda (share) system), CIT-1682 (Japan Soda (share) system), CIP-1866S (Sakamoto Soda (share) system), CIP-2048S (曰Ben Caoda (share) system, CIP-2064S (Sakamoto Soda (share) system), DPI-101 (Midori chemical (share) system), DPI-102 (Midori chemical (share) system), DPI-103 (Midori) Chemical (stock) system, DPI-105 (Midori Chemical Co., Ltd.), MPI-l〇3 (Midori Chemical Co., Ltd.), MPI-105 (Midori Chemical Co., Ltd.), ΒΒΙ-1〇1 31 321675 201028292 (Midori Chemical Co., Ltd.), BBI-102 (Midori Chemical Co., Ltd.), BBI-103 (Midori Chemical Co., Ltd.), BBI-105 (Midori Chemical Co., Ltd.) , TPS-101 (Midori Chemical Co., Ltd.), TPS-102 (Midori Chemical Co., Ltd.), TPS-103 (Midori Chemical Co., Ltd.), TPS-105 (Midori Chemical Co., Ltd.), MDS -103 (Midori Chemical Co., Ltd.), MDS-105 (Midori Chemical Co., Ltd.), DTS-102 (Midori Chemical Co., Ltd.), DTS-103 (Midori Chemical Co., Ltd.), PI-2074 (manufactured by Rhodia Co., Ltd.), etc. The amount of the photocationic polymerization initiator is generally from 5 to 20 parts by weight, preferably from 1 part by weight to 15 parts by weight, based on 100 parts by weight of the epoxy compound. The photo sensitizer may be used in combination with the light sensitizer, and the reactivity may be improved, and the mechanical strength or the strength of the cured product may be improved. The photo sensitizer may, for example, be a carbonyl compound. An organic sulfur compound, a persulfide compound, a redox compound, an azo, a diazo compound, a compound, and a photoreductive dye. When a photo-sensitizer is formulated, the compounding amount is a photo-cationic polymerizable epoxy resin. When the amount is 1 part by weight, it is usually about 0.1 to 20 parts by weight. . Next, the thermal cationic polymerization initiator will be described. The compound which generates a cationic species or a Lewis acid by heating may, for example, be a phenyl fluorenyl nickel salt, a thiophenium salt, a thi〇lanium salt, a benzoguanidine ammonium, a pyridine rust salt, or a hydrazine salt. (Hydrazinium) salt, carboxylate, sulfonate, and amidoximine. Such thermal cationic polymerization initiators can also be readily obtained from commercially available products 321675 32 201028292, for example, either by Adeka opton CP77 '(A), Adeka opton CP66 (for stocks) ) ADEKA system), / CI-2639 (Sakamoto Soda (system)), CI-2624 (Sakamoto Soda (system)), Sun Aid SI-60L (Sanshin Chemical Industry Co., Ltd.), Sun Aid SI-80L (Sanshin Chemical Industry Co., Ltd.), SunAidSI-100L (Sanshin Chemical Industry Co., Ltd.), etc. It is also a useful technique to use the aforementioned photocationic polymerization and thermal cationic polymerization. The hardening composition may further contain a compound which promotes cationic polymerization such as oxetane or polyol. The curable composition obtained in this manner is applied to at least one of the transparent protective film and the polarizing film to form a curable composition layer, and the other polarizing film or transparent protective film is superposed on the curable composition layer. The curable composition layer is cured by irradiation or heating of the active energy ray, and the polarizing film and the transparent protective film are bonded to each other via the hardened layer. The method of applying the curable composition Q to the transparent protective film or the polarizing film is not particularly limited, and for example, a doctor blade, a wire bar, a die coater, a comma coating may be employed. Various coating methods such as comma coater, gravure, and machine. The thickness of the curable composition layer is generally 1 sec or more and 50 Å or less, preferably 20/m or less, more preferably 1 〇 #πι or less. When the curing of the curable composition layer is performed by the irradiation of the active energy ray, the light source to be used is not particularly limited, but may be, for example, a low-pressure mercury lamp armor having a light-emitting distribution at a wavelength of 400 nm or less; High-pressure mercury lamp, ultra-high pressure mercury lamp, chemical lamp, black light lamp, 321675 33 201028292 Microwave-excited mercury lamp and metal lamp. The light irradiation intensity of the hemp and the non-chemical composition layer is particularly limited depending on the hardenability of the composition, but the activation intensity of the photocationic polymerization initiator is preferably 0.1 to 100 mW. /cm2. If the intensity of the light on the stone layer is less than 0·1 mW/cm2, then the temple; the hardening composition~ the long-term response time is too much 100 mW/cm2' because of the long-fired heat from the lamp The heat of the polymerization during the polymerization of 俾 俾 俾 俾 俾 俾 俾 俾 俾 俾 俾 俾 俾 俾 俾 俾 俾 俾 俾 俾 俾 俾 俾 俾 俾 俾 俾 俾 俾Similarly, the vaporization or partiality of the curable composition layer is determined depending on the hardenability of the composition, and the irradiation time should be set to a value indicated by the product of the irradiation intensity and the irradiation time. For example, 10 to 5000 mJ/cm2. For the product of the curable composition layer: if the pupil becomes 10 mJ/cm2, the amount derived from the photocationic polymerization initiator is insufficient, and the hardening composition layer may not be cured. The amount of integrated light produced exceeds 5000 mJ/cm2, and the irradiation time becomes very high. When the curing of the curable composition layer is carried out by heat, the temperature may be heated by a method, and the conditions thereof are not particularly limited, but the heat % ion polymerization initiator of the hardening composition is generally known. Produce cation = ° - heating above the temperature of the acid, for example, 5 〇 to 2 〇〇, the left species or the road, even if it is irradiated or heated by the active energy ray, it should be attached The degree of polarization of the polarizing plate of the single-sided transparent protective film, the hard color of the transparent member, and the transparency of the transparent protective film are not reduced, and the curing is performed. The thickness of the hardened layer obtained by hardening the curable composition layer is set to 50/zm or less, preferably 20/zm or less, more preferably 1 〇//m. Further, it is 321675 34 201028292 • (Releasable film) - Adhesive peeling thin film used in the production method of the present invention - film, which can be easily peeled off by a low molecular weight adhesive film, for example, can be used A polyester resin such as polyethylene terephthalate or polyethylene naphthalate; a cyclic olefin resin; and a chain olefin resin such as polyethylene, polypropylene or propylene/ethylene copolymer. Among them, a polyethylene terephthalate film, a polypropylene film, and a polyethylene film are preferably used from the viewpoint that the adhesion can be appropriately adjusted and it is easy to obtain from a commercially available product. ® The release film is self-adhesive and can be directly bonded to the side of the polarizing film opposite to the surface to which the transparent protective film is attached. In this manner, a polarizing plate with a single-sided transparent protective film in which a transparent protective film is bonded to one surface of a polarizing film and a peeling film having an adhesive property is bonded to the opposite side by an adhesive is temporarily borrowed and wound. It is taken up by a core such as a vinyl chloride tube. Further, the step of laminating the transparent protective film on the polarizing film and the step of bonding the release film to the polarizing film may be carried out first or the same. [2] Step (B) In the first aspect, the third aspect, the fourth aspect and the fifth aspect of the present invention, a single-sided adhesive release film prepared according to the above method is attached The polarizing plate of the transparent protective film is a polarizing plate with a single-sided transparent protective film which forms an adhesive layer on one side in the second aspect, and is cut along the length direction in accordance with the size of the retardation film (cutting (slit)). The width of the polarizing plate with a single-sided transparent protective film is appropriately set according to the width of the retardation film to be described later, but for example, a single-sided transparent protective film is attached. 35 321675 201028292 At least one slice of the polarizing plate It is preferable that the width of the retardation film to be described later is the same width. In addition, in the second aspect, the polarizing plate with a single-sided transparent protective film is cut: the cutting system is also performed on the laminated adhesive layer. The method of cutting the polarizing plate with a single-sided transparent protective film is not particularly limited, but generally, a polarizing plate with a single-sided transparent protective film taken up may be used as a cutting machine (longitudinal cutting machine) Pull out and cut at the same time, and then rewind the cut of the plurality of slices. Further, it is also possible to use a method in which the polarizing plate cut by the width of the phase difference film is not taken up, and the method is sequentially sent from the next step to the next step. [3] Step (C) In the first aspect, the third aspect, the fourth aspect and the fifth aspect of the present invention, the polarizing of the one-sided transparent protective film cut from the above step (B) The peeling film was removed from the sheet, and in the second aspect, the peeling film was removed from the polarizing plate with a single-sided transparent protective film which was not cut. [4] Step (D) 〇 In the first aspect of the present invention, the polarizing of the boat plate which is cut in the step (B) and which has been removed from the peeling film in the step (C) On the film surface (the surface on which the peelable film has been attached), in the second aspect, the polarizing film surface of the polarizing plate with the uncut single-sided transparent protective film from which the peeling film has been removed in the step (C) is removed. In the third aspect, on the one surface of the retardation film, an adhesive layer having a storage elastic modulus of O.IMPa or more at 80 ° C was formed on the surface of the phase difference film. (adhesive) 36 321675 201028292 The adhesive used to form the adhesive layer is at 8 (the storage elastic modulus of rc is above 0.1 MMPa, preferably from 0.15 MPa to 1 MPa. Storage elasticity at 8 〇 c)c When the modulus is less than 0.1 MPa, it is impossible to follow the dimensional change of the polarizing film which is generated when it is in a low temperature environment, so that there are cases where bubbles or peeling occur. Further, the storage modulus of the adhesive at 23 is preferably O.IMPa or more, more preferably 〇2 to. Further, the storage elastic modulus generally tends to be lower as the temperature is higher. Therefore, if the storage elastic modulus of the material measured at 80 °C is 〇1 or more, it is generally 23. (: The storage elastic modulus of the same material received shows the above values. In the present specification, 'adhesive is the same as pressure sensitive adhesive. Here, the storage elastic modulus (dynamic "Elastic modulus" means the term of the commonly used viscoelasticity measurement, which is to impart deformation (vibration) deformation or stress to the sample over time, and to measure the stress or deformation generated by the sample. The method of mechanical properties (dynamic viscoelasticity measurement) The value obtained by ❺. Specifically, it refers to the stress (deformation) generated by the deformation (stress) applied to the sinusoidal waveform of the sample, and is divided into deformation and stress (stress). When the wave of the component of the same phase and the component of the phase shifted by 90 degrees is the elastic modulus calculated from the stress (deformation) component in the same phase as the deformation (stress), the storage elastic modulus can be used commercially. The viscoelasticity measuring device is measured, for example, by a cancer cell viscoelasticity measuring device (Dynamic Analyzer RDA II: manufactured by REOMETRIC Co., Ltd.) as described in the examples below. The temperature control system can use various known temperature control devices such as a circulating thermostat, an electric heater, and an electronic cooling element (Peltier device), thereby setting the temperature at the time of measurement of 37 321 675 201028292. Or the adhesive used in the optical film for use thereof has a storage elastic modulus of at most about 0.1 MPa, but the adhesive used in the production method of the present invention has the highest storage modulus of elasticity as described above. By having such a high storage elastic modulus, that is, by using a hard adhesive, the crucible can make up for insufficient cohesive force when placed in a high temperature environment or when it is repeatedly in a high temperature environment and a low temperature environment, and can suppress the occurrence of the time. The dimensional change accompanying the shrinkage of the polarizing film. By this action, the composite polarizing plate of the present invention has good durability. The specific high elastic adhesive used in the manufacturing method of the present invention can be, for example, mainly composed of acrylic acid. A composition of a component such as a polymer, a polyoxymethylene polymer, a polyester, a polyurethane, or a polyether. It is excellent in optical transparency like an acrylic polymer, maintains moderate wettability or cohesive force, is excellent in adhesion to a substrate, and has weather resistance, heat resistance, etc., and does not float under heating or humidification conditions. In the acrylic polymer, an alkyl ester of acrylic acid having an alkyl group having a carbon number of 20 or less, such as a mercapto group, an ethyl group, and a butyl group, and (meth)acrylic acid or The functional group-containing acrylic monomer composed of hydroxyethyl (meth)acrylate or the like is formulated so that the glass transition temperature is preferably 25 ° C or lower, more preferably 〇 ° C or less, and the weight average molecular weight is 1,000,000 or more. The acrylic copolymer is useful. The acrylic polymer is not particularly limited, but (meth) butyl acrylate, ethyl (meth) acrylate, (meth) acrylate isooctyl ester, (methyl) can be suitably used. (Meth) acrylate polymer such as 2-ethylhexyl acrylate or 38 321675 201028292 * Two or more kinds of copolymerized polymers of these (mercapto) acrylates are used. Further, polar monomers may be co-polymerized for these acrylic polymers. The polar monomer may, for example, be (mercapto)acrylic acid, 2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylamide, 2-mercaptoacetic acid 2-oxime A monomer having a polar functional group such as a carboxyl group, a hydroxyl group, a decylamino group, an amine group or an epoxy group, such as fluorene-dimethylaminoethyl ester or glycidyl acrylate. These acrylic polymers can be used alone as an adhesive, but ® is generally formulated as an adhesive composition formulated with a crosslinking agent. The crosslinking agent may, for example, be a metal carboxylic acid salt formed between a carboxyl group and a divalent or polyvalent metal ion; a guanamine bond formed between the carboxyl group and the carboxyl group; or a polyepoxide or a poly An alcohol compound forms an ester bond with a carboxyl group; and a polyamine isocyanate compound forms a guanamine bond with a carboxyl group. Among them, a polyisocyanate compound is preferably used. The means for making the storage elastic modulus of the adhesive high is not particularly limited, and it is preferred to use, for example, an oligomer in the above-mentioned adhesive composition, specifically to formulate a urethane acrylate system. The method of oligomers. Further, the method of curing the adhesive composition of the urethane acrylate-based oligomer by irradiation with an energy ray is preferred because it has a higher storage modulus. An adhesive having an amine phthalate acrylate-based oligomer or a separator-attached adhesive which is applied to a support film (separator) to cure ultraviolet rays is known. Obtained from the adhesive manufacturer. In the adhesive composition, in addition to the above polymer, cross-linking agent and polycondensation 39 321675 201028292, in order to adjust the adhesive adhesion, cohesive force, viscosity, elastic modulus and glass transition temperature, etc. Suitable additives such as resins of natural or synthetic materials, resins for imparting adhesion, antioxidants, ultraviolet absorbers, dyes, pigments, antifoaming agents, anti-corrosion agents, photopolymerization initiators, and the like may also be formulated. The ultraviolet absorber may, for example, be a salicylate-based compound, a benzophenone-based compound, a benzotriazole-based compound, a cyanoacrylate-based compound, or a nickel-salted salt-based compound. Further, the adhesive used in the production method of the present invention can be light-dispersed and dispersed as a (four) bulk adhesive. The light diffusing agent used herein is a fine particle having a refractive index different from that of the polymer of the structuring layer, i.e., a fine particle composed of an inorganic compound or a fine particle composed of an organic compound (k compound). Tian inorganic
二5物所構成之微粒子可舉例如氧化鋁(办 二物)所t化石夕(折射率:哗等。又,由有機化合物 ^ . 157成之微粒子可舉例如三聚氰胺珠粒(bead)(制Examples of the fine particles composed of the second and fifth substances include, for example, alumina (manufactured by the second method). The refractive index: ruthenium or the like. Further, the fine particles of the organic compound are exemplified by, for example, melamine beads (bead).
丙烯酸甲甲基两埽酸甲醋珠粒(折射率].价甲 15:、二本乙缔共聚物樹脂珠粒(折射卜 1¾酸酯珠粒(折 1.53)、聚苯乙烯珠粒(折射率./ 、聚乙烯珠粒街射与 率:上及聚彻赌珠粒(拆射率聚氣二稀珠粒(折 要從其折射率為i至2 :=,故調配之光_係 差構= 321675 40 201028292 以上,又,從圖像顯示裝置之亮度與辨認性之觀點來看 宜為0.01至0.5。可使用來作為光擴散劑之微粒子宜為球 形者,且以接近單分散者為佳,例如可適宜使用平均粒^ 在2至6# m左右的範圍之微粒子。 1 光擴散劑之調配量係考量調配其之光擴散性點著南 層所需之霧度值、或適用其之圖像顯示裝置的古 上L 叩冗度等而適 ❹ 當決定’但相對於構成黏著劑層之基材聚合物化 polymer)100重量份,一般為3至30重量份左右。 ^ 又’光擴散性黏著劑層所需之霧度值,從確保使 所得到之複合偏光板適用的圖像顯示裝置的亮度且同時使 顯示圖像不易產生滲染或模糊之觀點來看,宜為2〇至 的範圍。霧度係規定於JISK7105’為以(擴散透過率/全光° 線透過率)Xl〇〇(%)所示之值。 黏著劑層之厚度及光擴散性黏著劑層之厚度係依其 接著力等而決定,一般為1至40 之範圍。進一步,從 ❿令使用其所製造之複合偏光板保持良好的加工性,顯示高 的耐久性,且令使用該複合偏光板之圖像顯示裝置保持從 正面看時或從斜面看時之亮度,減絲 生滲染或模糊之觀點來看,此厚度更宜為3至25#瓜。 在本發明之第-態樣中,係在被裁切且已除去制離性 薄膜之附單面透明保護膜之偏光板的偏光膜面(曾貼人有 剝離性薄膜之面)上,形成上述之黏著劑層。在本發明:第 二態樣中,係於已除去翁離性實膜之(釆裁切之)附:單面透 明保護膜之偏光板的偏光臈面(曾貼合有剝離性薄膜之面) 321675 41 201028292 上’形成上述之黏著劑層。 黏著劑層之形成係宜採用於附單面透明保護膜之偏 光板之偏光膜面塗佈黏著劑溶液並進行乾燥的方法。又, 亦宜採用準借在經實施離型處理之支樓薄膜(分隔膜)的離 型處理面形成黏著劑層者(附分隔膜之黏著劑),並使其貼 合於上述偏光膜面之方法。 就黏著劑溶液而言,係使用例如於曱苯或醋酸乙醋等 有機溶劑中溶解或分散構成上述黏著劑組成物之原料,例Methyl methacrylate ruthenium acetate beads (refractive index). Valence 15: Two bi-binder copolymer resin beads (refracted bismuth beads (1.53), polystyrene beads (refraction) Rate. /, polyethylene beads street shot and rate: on the gambling beads (removal rate of gas two dilute beads (reduced from its refractive index i to 2: =, so the distribution of light _ system Difference = 321675 40 201028292 Above, in addition, from the viewpoint of brightness and visibility of the image display device, it is preferably 0.01 to 0.5. The fine particles used as the light diffusing agent are preferably spherical, and are close to monodisperse. Preferably, for example, a fine particle having an average particle size of about 2 to 6 #m can be suitably used. 1 The amount of the light diffusing agent is determined by adjusting the haze value of the light diffusing property to the south layer, or The image display device has an appropriate L 叩 redundancy and the like. When it is determined to be 'but the polymerized polymer of the substrate constituting the adhesive layer, 100 parts by weight, generally about 3 to 30 parts by weight. ^ The haze value required for the light diffusing adhesive layer is from an image display device which ensures application of the obtained composite polarizing plate From the viewpoint of brightness and at the same time, it is not easy to cause bleeding or blurring of the displayed image, and it is preferably in the range of 2 Å to 5. The haze is specified in JIS K7105' (diffusion transmittance / full-light transmittance) Xl〇〇 (%) The thickness of the adhesive layer and the thickness of the light diffusing adhesive layer are determined by the adhesion force, etc., and generally range from 1 to 40. Further, the composite produced by the use of the adhesive is used. The polarizing plate maintains good workability, exhibits high durability, and allows the image display device using the composite polarizing plate to maintain the brightness when viewed from the front or when viewed from the inclined surface, and the viewpoint of the silk infiltrated or blurred The thickness is more preferably from 3 to 25 # melon. In the first aspect of the invention, the polarizing film surface of the polarizing plate with the single-sided transparent protective film which has been cut and has been removed from the release film is used. The adhesive layer is formed on the surface of the peeling film. In the second aspect of the present invention, it is removed from the detached solid film (with a cut): one-sided transparent protection The polarizing surface of the polarizing plate of the film (the surface of the peeling film has been attached) 321675 4 1 201028292 The above-mentioned adhesive layer is formed. The formation of the adhesive layer is preferably applied to the polarizing film surface of the polarizing plate with a single-sided transparent protective film and the method of drying the adhesive solution. A method of forming an adhesive layer (adhesive with a separator film) on a release-treated surface of a film (separator film) subjected to release treatment, and attaching it to the surface of the polarizing film. In the case of a solution, the raw material constituting the above-mentioned adhesive composition is dissolved or dispersed in an organic solvent such as toluene or ethyl acetate.
如形成10至40重量%溶液者。對於如此所形成之黏著劑 層亦可層合由經聚石夕氧系等離型劑實施處理之樹脂薄膜 所構成之分隔膜。 進步,於附單面透明保護膜之偏光板之偏光膜面形 f黏著劑層時’亦可依需要而對偏光膜面實施用以提昇密 者性=處理,例如實施電暈處理,亦可對貼合於偏光膜面 之黏著劑層之表面實施同樣的處理。 在本發明之第三態樣中 成上述之黏者劑層。 係於相位差薄膜之單面上形 ❹ f第三態樣中實施步驟(D) =施後述之步糊之前實施即可。亦 於步驟(A)之前實施,亦可與步 ,驟(Α)、步驟(Β)及步驟 之任一者併仃,或亦可於該等任—者 要係在步驟(C)除去剝離性薄膜 貫匕 有黏著劑叙妹減斷可。’供給單面开 又 於相位差薄膜之點著劑層的形成方法係可採用 321675 42 201028292 * 在附單面透明保護膜之偏光板之偏光膜面的黏著劑層之形 成中所記載的方法同樣之方法。 - (相位差薄膜) 本發明之製造方法所使用的相位差薄膜,係其核層為 由苯乙烯系樹脂所構成,且於其兩面形成由含有橡膠粒子 之(甲基)丙嫦酸系樹脂組成物所構成的皮層者。 構成核層之苯乙烯系樹脂,除了可為苯乙烯或其衍生 物之單獨聚合物以外,亦可為苯乙烯或其衍生物與其他共 ® 聚合性單體之二元或其以上之共聚物。此處,所謂苯乙烯 衍生物係指於苯乙烯結合有其他基的化合物,可舉例如鄰 甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、2,4-二甲基 苯乙烯、鄰乙基苯乙烯、對乙基苯乙烯等烷基苯乙烯;及 羥基苯乙烯、第三丁氧基苯乙烯、乙烯基安息香酸、鄰氯 本乙炸、對氣本乙稀等在笨乙細的苯核導入經基、.院氧基、 羧基、鹵素等之取代苯乙烯等。亦可使用如揭示於上述 Q US2002/0169267A1 或 JP2003-207640-A 之三元共聚物。苯 乙烯系樹脂宜為苯乙烯或苯乙烯衍生物與至少一種選自丙 烯腈、馬來酸酐、甲基丙两烯聽,甲裔及了二爆為暴遞£的共聚 物。構成核層之苯乙烯系樹脂係為了提昇核層之耐熱性, 其玻璃轉移溫度Tg宜為100°c以上,更宜為120°c以上。 由苯乙稀糸樹脂所構成之核層係宜設定成其厚度(膜 厚)為10至ΙΟΟμπι。其厚度未達10/im時,有時會因延 伸而不易顯現充分的遲延值Cretar Jati0h)。另外,若其厚度 超過100//m,則薄膜之衝擊強度易變弱,同時外部應力所 43 321675 201028292 ο 產生之遲延變化有變大之傾向,適用於液晶顯示裝置時易 , 產生發白等’或顯示性能易降低。 , 於由别述之苯乙稀系樹脂所構成的核層之雙面所配 置之皮層,係由在(曱基)丙烯酸系樹脂中調配橡膠粒子之 - (甲基)丙烯酸系樹脂組成物所構成。藉由調配橡膠粒子, 耐衝擊性或操作性會提昇。(甲基)丙烯酸系樹脂係可舉例 如曱基丙烯酸烷酯或丙烯酸烷酯之單獨聚合物、或甲基丙 烯酸烷酯與丙烯酸烷酯之共聚物等。甲基丙烯酸烷酯具體 上可舉例如甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯 ❹ 酸丙醋等’又,丙烯酸烷酯具體上可舉例如丙烯酸甲酯、 丙烯酸乙酯、丙烯酸丙酯等。如此之(甲基)丙烯酸系樹脂 係可使用作為汎用之(甲基)丙烯酸系樹脂所市售者。又, (甲基)丙烯酸系樹脂之中亦包含被稱為耐衝擊(曱基)丙烯 酸系樹脂者,又,亦包含於主鏈中具有戊二酸酐構造或内 酯環構造之被稱為高耐熱(甲基)丙烯酸系樹脂者。 於(甲基)丙烯酸系樹脂所調配之橡膠粒子宜為丙烯酸 ❹ 系者。丙烯酸系橡膠粒子係指以丙烯酸丁酯及丙烯酸2_乙 基己酯等丙烯酸烷酯作為主要的單體成分,且具有於多官 能單體的存在下聚合所得到之橡膠彈性的粒子。橡膠粒子 係亦可為單層形成具有如此之橡膠彈性的粒子者,亦可為 至少具有一層橡膠彈性層之多層構造體。多層構造之丙烯 酸系橡膠粒子係可列舉如「以具有如上述之橡膠彈性的粒 子作為核,其周圍以硬質之甲基丙烯酸烷酯系聚合物被覆 者;以硬質之甲基丙烯酸烷酯系聚合物作為核,於其周圍 321675 44 201028292 - 以具有如上述之橡膠彈性的丙烯酸系聚合物被覆者;將硬 質之核的周圍以具有橡膠彈性的丙埽酸系聚合物被覆,進 一步,於其周圍以硬質之甲基丙烯酸烷酯系聚合物被覆者 等。此等橡膠粒子係於彈性層所形成之粒子的平均直徑一 般在於50至400nm左右的範圍。 構成皮層之(甲基)丙烯酸系樹脂組成物中的上述橡膠 粒子之含量係相對於(甲基)丙烯酸系樹脂每100重量份, 一般為5至50重量份左右。(甲基)丙烯酸系樹脂及丙烯酸 ® 系橡膠粒子係以混合該等之狀態市售,故可使用其市售 品。已調配丙烯酸系橡膠粒子之(甲基)丙烯酸系樹脂的市 售品之例,可舉例如HT55X(住友化學(股)製)及 Technoloy(註冊商標)S001(住友化學(股)製)。如此之含有丙 烯酸系橡膠粒子的(甲基)丙烯酸系樹脂組成物一般係具有 160°C以下之Tg,但其較佳之Tg為120〇C以下,更宜為11〇 °C以下。 ❹ 由已調配橡膠粒子(較佳係丙烯酸系橡膠粒子)之(曱 基)丙烯酸系樹脂組成物所構成的皮層,其厚度宜為10至 100 # m 〇 若其厚度未達l〇#m,有很難製膜之傾向。另外,若 厚度超過100 # m’有不能忽視此(甲基)丙稀酸系樹脂層(皮 層)的延遲性的傾向。 如上述般’在本發明使用之相位差薄膜中,由苯乙烯 系樹脂所構成之核層係以其Tg為120。(:以上為佳,另外, 由已調配橡膠粒子之(曱基)丙稀酸系樹脂組成物所構成之 45 321675 201028292 皮層係以其Tg為赋以下為佳, 伸時,由苯乙糊脂所構成之核層係積極地二二; 子主鏈,選擇性地顯現異方性,另外,皮層传從 力學性之觀點皆不極力地配向高分子鏈,而宜更^等^ :之構造’故兩者之Tg不重疊’而由苯乙埽系樹脂所構 f之核層宜具有較由⑽配橡膠粒子之(M)丙婦酸系樹 脂組成物所構成之皮層還高的Tg。Such as the formation of 10 to 40% by weight of the solution. The pressure-sensitive adhesive layer thus formed may also be laminated with a separator film composed of a resin film treated with a polyoxo-based release agent. Progressively, when the polarizing film surface of the polarizing plate with a single-sided transparent protective film is used as the adhesive layer, the polarizing film surface can be used to enhance the confidentiality as needed. For example, corona treatment can be performed. The same treatment was applied to the surface of the adhesive layer bonded to the surface of the polarizing film. In the third aspect of the invention, the above-mentioned adhesive layer is formed. The step (D) is carried out in the third aspect of the single-surface shape ❹f of the retardation film; it can be carried out before the step of the step described later. It is also carried out before step (A), or may be combined with any of steps, steps, steps and steps, or may be used in step (C) to remove the stripping. The adhesive film can be broken by the adhesive. 'The method of forming the dot layer of the one-side opening and the phase difference film can be 321675 42 201028292 * The method described in the formation of the adhesive layer on the polarizing film surface of the polarizing plate with a single-sided transparent protective film The same method. - (Retardation film) The retardation film used in the production method of the present invention has a core layer made of a styrene resin, and a (meth)propionic acid resin containing rubber particles is formed on both surfaces thereof. The cortex composed of the composition. The styrene-based resin constituting the core layer may be a copolymer of styrene or a derivative thereof and two or more of the other copolymerizable monomers, in addition to the individual polymer of styrene or a derivative thereof. . Here, the styrene derivative refers to a compound in which other groups are bonded to styrene, and examples thereof include o-methyl styrene, m-methyl styrene, p-methyl styrene, and 2,4-dimethyl styrene. , alkyl styrene such as o-ethyl styrene or p-ethyl styrene; and hydroxy styrene, tert-butoxy styrene, vinyl benzoic acid, o-chlorobenz, and ethylene The fine benzene nucleus is introduced into a substituted styrene such as a thiol group, a methoxy group, a carboxyl group or a halogen. A terpolymer as disclosed in the above-mentioned Q US 2002/0169267 A1 or JP 2003-207640-A can also be used. The styrene-based resin is preferably a styrene or styrene derivative and at least one copolymer selected from the group consisting of acrylonitrile, maleic anhydride, methyl propylene oxide, and the second-generation explosion. The styrene-based resin constituting the core layer preferably has a glass transition temperature Tg of 100 ° C or more, more preferably 120 ° C or more, in order to improve the heat resistance of the core layer. The core layer composed of styrene resin is preferably set to have a thickness (film thickness) of 10 to ΙΟΟμπι. When the thickness is less than 10/im, it is sometimes difficult to develop a sufficient retardation value (Cretar Jati0h) due to the elongation. In addition, if the thickness exceeds 100//m, the impact strength of the film tends to be weak, and the external stress 43 321675 201028292 ο has a tendency to become delayed, which is easy to apply to a liquid crystal display device, and causes blushing, etc. 'Or display performance is easy to reduce. The skin layer disposed on both sides of the core layer composed of a styrene-based resin, which is described above, is a (meth)acrylic resin composition in which rubber particles are blended in a (fluorenyl) acrylic resin. Composition. By blending rubber particles, impact resistance or workability is improved. The (meth)acrylic resin may, for example, be a single polymer of an alkyl methacrylate or an alkyl acrylate, a copolymer of an alkyl methacrylate and an alkyl acrylate, or the like. Specific examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, methacrylic acid propyl vinegar, etc. Further, the alkyl acrylate may specifically be, for example, methyl acrylate, ethyl acrylate or acrylic acid. Propyl ester and the like. Such a (meth)acrylic resin can be used as a general-purpose (meth)acrylic resin. Further, the (meth)acrylic resin also includes an impact-resistant (fluorenyl) acrylic resin, and also includes a glutaric anhydride structure or a lactone ring structure in the main chain. Heat resistant (meth)acrylic resin. The rubber particles to be blended with the (meth)acrylic resin are preferably those of acrylic acid. The acrylic rubber particles are rubber elastic particles obtained by polymerizing an alkyl acrylate such as butyl acrylate or 2-ethylhexyl acrylate as a main monomer component and polymerizing in the presence of a polyfunctional monomer. The rubber particles may be a single layer to form particles having such rubber elasticity, or may be a multilayer structure having at least one rubber elastic layer. The acrylic rubber particles of the multilayer structure include, for example, "a particle having rubber elasticity as described above as a core, and a hard methacrylate-based polymer coating around the periphery; and a hard alkyl methacrylate polymerization" As a core, it is surrounded by 321675 44 201028292 - coated with an acrylic polymer having rubber elasticity as described above; the periphery of the hard core is covered with a rubber-elastic acrylic polymer, and further around it It is coated with a hard alkyl methacrylate polymer, etc. The average diameter of the particles formed by the rubber particles in the elastic layer is generally in the range of about 50 to 400 nm. The composition of the (meth)acrylic resin constituting the skin layer The content of the rubber particles in the product is usually about 5 to 50 parts by weight per 100 parts by weight of the (meth)acrylic resin. The (meth)acrylic resin and the acrylic® rubber particles are mixed. Commercially available products are commercially available, and commercially available products of (meth)acrylic resin having acrylic rubber particles are blended. For example, HT55X (manufactured by Sumitomo Chemical Co., Ltd.) and Technoloy (registered trademark) S001 (manufactured by Sumitomo Chemical Co., Ltd.), such a (meth)acrylic resin composition containing acrylic rubber particles is generally used. It has a Tg of 160 ° C or less, but preferably has a Tg of 120 ° C or less, more preferably 11 ° C or less. ❹ (曱-based) acrylic resin which has been blended with rubber particles (preferably acrylic rubber particles) The skin layer composed of the resin composition preferably has a thickness of 10 to 100 #m. If the thickness thereof is less than 10 m, it has a tendency to form a film. In addition, if the thickness exceeds 100 #m', the thickness cannot be ignored ( In the retardation film used in the present invention, the core layer composed of the styrene resin has a Tg of 120. The above is preferable, and the 45 321 675 201028292 cortex layer composed of the (meth)acrylic resin composition having the rubber particles blended is preferably a Tg of the following, and when stretched, by the phenyl bromide The nuclear layer of the formation is actively two or two; the sub-chain Selectively exhibiting anisotropy, in addition, the cortical layer is not strongly aligned to the polymer chain from the viewpoint of mechanical properties, but should be more ^ ^ ^ ^ the structure 'so the Tg of the two does not overlap ' and the phenelzine The core layer of the f structure of the resin preferably has a higher Tg than the skin layer composed of (10) the (M) propylene glycol resin composition of the rubber particles.
若欲製造本發明所使用之相位差薄瞑,只要例如便策 乙烯樹脂與已調配橡膠粒子之(甲基)丙烯酸酯系樹脂組成 物進行共擠朦,然後進行延伸即可。除此之外,亦可為分 別製作單層之薄膜後’藉由熱積層而熱融接,再加以延伸 之方法。If the phase difference thin film used in the present invention is to be produced, for example, the vinyl resin and the (meth) acrylate resin composition of the rubber particles to be blended may be co-extruded and then extended. In addition to this, it is also possible to heat-melt and laminate the film by a single layer after the film is formed separately.
相位差薄膜係於由本乙烤糸樹脂所構成之核層的雙 面,形成由調配橡膠粒子之(甲基)丙烯酸系樹脂組成物所 構成的皮層之3層構造。在此3層構造中,配置於兩面之 皮層一般為約相同之厚度。藉由如此地形成3層構造,俾 使由調配橡膠粒子之(曱基)丙烯酸系樹脂組成物所構成的 皮層發揮作為保護層之功能,成為機械強度或耐藥品性優 異者。 如以上般所構成之相位差薄膜係藉延伸而賦予面内 延遲性。延伸係可依公知之縱單軸延伸、或拉幅器橫單軸 延伸、同時雙轴延伸、逐次雙軸延伸等而進行,只要以得 到所希望的延遲值之方式進行延伸即可。 又,相位差薄膜係在無損本發明之目的之範圍中,亦 321675 46 201028292 *.可依需要而含有殘存溶劑、安定劑、可塑劑、抗老化劑、 -.抗靜電劑、及紫外線吸收劑等其他的成分。又,為滅少表 面粗糙度,亦可含有流平劑(leveHng agent)。 相位差薄膜之寬度係較上述步驟(A)所製作之附單面 透明保5蒦膜之偏光板還小10%以上,因生產性提畀的妹果 明顯,故佳。進一步,若其寬度為前述偏光板之40裏5〇〇/〇 的範圍,則藉由將附單面透明保護膜之偏光板切成其〆半 的寬度,俾使其雙方均可使用於相位差薄膜之貼合,故更 ®佳。 [5]步驟(E) 在本發明之第一態樣及第二態樣中,係將被裁切真形 成有黏著劑層之附單面透明保護膜之偏光板的黏著劑廣與 相位差薄膜予以貼合。在第三態樣中,係將於單面形成有 黏著劑層之相位差薄膜的黏著劑層、與被裁切之附單面透 明保護膜之偏光板的偏光膜面予以貼合。 G 將被裁切且形成有黏著劑層之附單面透明保護模之 偏光板的黏著劑層與相位差薄膜予以貼合之方法、將於單 面形成有黏著劑層之相位差薄膜的黏著劑層與被裁切之附 單面透明保護膜之偏光板的偏光膜面予以貼合之方法係炎 無特別限定’但可採用例如:使用貼合輥輪等,相對於附 單面透明保護膜之偏光板之偏光透過轴,以相位差薄嫉之 慢軸成為正交或平行之方式而進行層合之方法;或是相對 於偏光膜之偏光透過軸,以使相位羞薄膜之慢軸成為特定 角度之方式而進行貼合的方法。尤其是以使附單面透明保 321675 47 201028292 護膜之偏光板與相位 配合長邊方向而連續地貼刀從各自之長度輥輪拉出並 - 造複合偏光板,故宜採用合之方法,係因可生產性佳地製 .The retardation film is formed on the both sides of the core layer composed of the present baked resin, and has a three-layer structure of a skin layer composed of a (meth)acrylic resin composition containing rubber particles. In this three-layer structure, the skin layers disposed on both sides are generally about the same thickness. By forming the three-layer structure in this manner, the skin layer composed of the (fluorenyl) acrylic resin composition containing the rubber particles functions as a protective layer, and is excellent in mechanical strength or chemical resistance. The retardation film formed as described above is extended to impart in-plane retardation. The extension system can be carried out in accordance with a known vertical uniaxial extension, or a lateral uniaxial extension of the tenter, simultaneous biaxial stretching, sequential biaxial stretching, etc., as long as the extension is obtained in such a manner as to obtain a desired retardation value. Further, the retardation film is in the range which does not impair the object of the present invention, and is also 321675 46 201028292 *. Residual solvent, stabilizer, plasticizer, anti-aging agent, antistatic agent, and ultraviolet absorber may be contained as needed. Other ingredients. Further, in order to eliminate surface roughness, a leveling agent (leveHng agent) may be contained. The width of the retardation film is 10% smaller than that of the polarizing plate with a single-sided transparent protective film made in the above step (A), and it is preferable because the productivity of the product is obvious. Further, if the width is in the range of 5 〇〇/〇 of 40 in the polarizing plate, the polarizing plate with the single-sided transparent protective film is cut into a width of half of the polarizing plate, so that both sides can be used for the phase. The poor film fits, so it is better. [5] Step (E) In the first aspect and the second aspect of the present invention, the adhesive of the polarizing plate with the one-side transparent protective film which is formed with the adhesive layer is wide and the phase difference is The film is applied. In the third aspect, the adhesive layer on which the retardation film of the adhesive layer is formed on one side and the polarizing film surface of the polarizing plate with the single-sided transparent protective film to be cut are bonded. G. A method in which an adhesive layer of a polarizing plate with a single-sided transparent protective mold having an adhesive layer formed thereon is bonded to a retardation film, and a phase difference film having an adhesive layer formed on one side is adhered The method of bonding the layer of the agent to the polarizing film surface of the polarizing plate with the one-side transparent protective film to be cut is not particularly limited, but may be, for example, using a bonding roller or the like, and is transparently protected with respect to the attached surface. The polarization of the polarizing plate of the film is transmitted through the axis, and the slow axis of the phase difference is orthogonal or parallel to form a method of lamination; or the polarization transmission axis of the polarizing film is used to make the slow axis of the phase shame film A method of bonding to a specific angle. In particular, the polarizing plate with the single-sided transparent 321675 47 201028292 protective film and the phase matching long-side direction are continuously affixed from the respective length rollers to form a composite polarizing plate, so it is preferable to adopt a combined method. It is based on the ability to produce good quality.
[6]步驟(F) ° 在本發明之第四綠y ' 及步驟(C)所得到之經^ ,係於經過步驟(A)、步驟(B) 膜之偏光板的偏光膜面于、,去剥、=性薄臈的附單面透明保護 加熱進行硬化之環氧L形成含有藉活性能量線的照射或 成物層上重疊相位差薄月9的樹月曰纪成物層,並於該樹脂組 膜之單面形成含有料^。在第五態樣中,係於相位㈣❹ 環氧樹月旨的樹脂組^❹能量線的照射或加熱進行硬化之 除去剝離性薄膜 /、並於該樹脂組成物層上重疊已 面。 、、早面透明保護膜之偏光板的偏光膜 (含有糟活性能I始Μ 樹脂組成物)、、、照射或加熱進行硬化之環氧樹脂的 〇 的面二之附單面透明保護膜之偏光板 射或加熱進行硬化之rr所使用的含有藉活性能量線的照 為接著組成物)_=脂的樹脂組成物(以下,有時記 步驟⑷成=而言’即使在本步驟中亦可同樣地使用 著之環& °载之3有可使用於偏光膜與透明保護膜之接 物。:|化合物(環氧樹脂)與聚合起始劑的硬化性組成 芳夫η驟(Α)所錢般,環氧化合物宜為於分子内不含有 方香%者,又,—人 且3有於分子内至少具有1個結合於脂環 321675 48 201028292 - 式環之環氧基的環氧化合物(脂環式環氧化合物)。使用接 / 著組成物之附單面透明保護膜之偏光板的偏光膜面與相位 / 差薄膜之貼合,係可與偏光膜與透明保護膜之貼合同樣地 進行。 於附單面透明保護膜之偏光板的偏光膜面或相位差 薄膜之單面形成接著組成物之方法並無特別限定,但可採 用例如刮刀、線捧、模具塗佈機、逗號式塗佈機及凹版塗 佈機等各種塗佈方式。又,亦可利用在偏光膜與相位差薄 ® 膜之間滴下接著組成物後,以輥輪等加壓偏光膜與相位差 薄膜而均一地押開的方法。此處,輥輪之材質可使用金屬 或橡膠等,此等輥輪可為相同之材質,亦可為相異之材質。 接著組成物層之厚度一般為50/zm以下,宜為20//m以 下,更宜為l〇//m以下。 使於偏光膜面形成接著組成物層之附單面透明保護 膜之偏光板的接著組成物層與相位差薄膜重疊的方法,或 Q 是使於單面形成接著組成物層之相位差薄膜的接著組成物 層與附單面透明保護膜之偏光板的偏光膜面重疊之方法, 可採用例如:使用貼合輥輪等,相對於附單面透明保護膜 之偏光板之偏光透過軸,以使相位差薄膜之慢軸成為正交 或平行之方式而進行重疊的方法;或是相對於偏光膜之偏 光透過軸,以使相位差薄膜之慢軸成為特定角度之方式而 進行重疊的方法。尤其是使附單面透明保護膜之偏光板與 相位差薄膜分別從各自之長度輕輪拉出並配合長邊方向而 連續地重疊之方法,係因可生產性佳地製造複合偏光板, 49 321675 201028292 故宜採用。 在第五態樣中實施步驟(F)之時機係無特別限定,只要 在實施後述之步驟(G)之前實施即可。亦即,步驟(巧可於 步驟(A)之前實施,亦可與步驟(A)、步驟(B)及步驟(c)之 任一者併行,或亦可於該等任一者之後實施。重點是只要 係於步驟(C)除去剝離性薄膜之偏光膜面,供給單面形成有 接著組成物層之相位差薄膜即可。 步驟(G) 組[6] Step (F) ° The fourth green y ' and the step (C) obtained in the present invention are applied to the polarizing film of the polarizing plate passing through the film of the step (A) and the step (B), , peeling, thinning, single-sided transparent protection, heating, hardening, epoxy L, forming a layer containing the active energy line or the overlapping phase difference of the layer 9 on the layer of the moon, and A material containing a material is formed on one side of the resin film. In the fifth aspect, the resin layer of the phase (four) 环氧 epoxy resin is irradiated or heated to be cured to remove the peelable film / and is superposed on the resin composition layer. , a polarizing film of a polarizing plate of an early transparent protective film (a composition containing a poorly active energy I), and a surface of the epoxy resin which is irradiated or heated to be cured. The resin composition containing the active energy ray used for the rr of the polarizing plate or heated and hardened is the resin composition of the subsequent composition _=lipid (hereinafter, it is noted that step (4) is == even in this step) The same can be used for the ring & ° load 3 can be used for the polarizing film and the transparent protective film of the joint.: | compound (epoxy resin) and the polymerization initiator of the hardening composition of the square η (Α) As the money, the epoxy compound is preferably not contained in the molecule, and - human and 3 have at least one epoxy bonded to the epoxy ring of the alicyclic ring 321675 48 201028292 - ring Compound (alicyclic epoxy compound). The polarizing film surface of the polarizing plate with a single-sided transparent protective film attached to the composition is bonded to the phase/difference film, and can be attached to the polarizing film and the transparent protective film. In the same way, it is attached to a single-sided transparent protective film. The method of forming the subsequent composition of the polarizing film surface or the retardation film of the sheet is not particularly limited, but various coatings such as a doctor blade, a wire holder, a die coater, a comma coater, and a gravure coater can be used. In addition, a method in which the subsequent composition is dropped between the polarizing film and the retardation film, and the polarizing film and the retardation film are uniformly pressed by a roller or the like can be used. The material can be made of metal or rubber, etc. These rollers can be of the same material or different materials. The thickness of the composition layer is generally 50/zm or less, preferably 20//m or less. It is a method in which the subsequent composition layer of the polarizing plate with the one-side transparent protective film attached to the surface of the polarizing film is overlapped with the retardation film, or Q is formed on one side. The method of superposing the composition layer of the retardation film of the composition layer and the polarizing film surface of the polarizing plate with the one-sided transparent protective film may be, for example, using a bonding roller or the like, with respect to the one-side transparent protective film. The polarizing plate is polarized through the axis, A method of overlapping the slow axis of the retardation film so as to be orthogonal or parallel, or a method of superimposing the slow axis of the retardation film at a specific angle with respect to the polarization transmission axis of the polarizing film. In particular, a method in which a polarizing plate and a retardation film with a single-sided transparent protective film are respectively pulled out from respective lengths of the light wheel and continuously overlapped with the longitudinal direction is used, and a composite polarizing plate is manufactured with good productivity. 321675 201028292 It is preferable to adopt. The timing of implementing step (F) in the fifth aspect is not particularly limited, and may be carried out before the implementation of step (G) described later. That is, the step (in step (A) The previous implementation may be performed in parallel with either step (A), step (B), and step (c), or may be performed after any of the steps. The focus is on the step of removing the polarizing film surface of the peelable film in the step (C), and supplying a retardation film having a composition layer on one side. Step (G) group
對於步驟(F)所得到之重疊物(piie(j pr〇(juct)之接著名 成物層,藉由照射活性能量線或加熱而硬化,俾使附單汲 透明保護膜之偏光板之偏光膜面與相位差薄膜介由接著面 成物層的硬化層而貼合。 藉此而得到作為目的之複合偏光板,其係具備. ❹ 相位差薄膜,係由具有3層構造之延伸薄膜所構成 者,該3層構造為由苯乙烯系樹脂所構成之核層、愈層人 於前述核層之雙面且由含有橡膠粒子之(甲基)丙稀酸二 脂組成物所構成之皮層的3層構造;以及 附單面透明保護膜之偏光板’係層合於前述相位差薄 膜上’且於偏光膜之單面具有透明保護棋者。 藉活性能量線之照射俾進行接著組成物層之硬化 時’所使用之光源並無特別限定,但可舉例如於波長4〇〇nm 以下具有發光分布的低壓水銀燈、中壓水銀燈、高壓水銀 燈、超高麗水銀燈、化學燈、黑光燈、微波激發水銀燈及 金屬鹵素燈。對於接著組成物層之光照射強度係依其組成 321675 50 201028292 - 物之硬化性而決定者,並無特別限定,但對於光陽離子聚 ,合起始劑的活化為有效之波長區域的照射強度宜為0」至 ‘ 100mW/cm2。若對於接著組成物層之光照射強度未達〇」 mW/cm2 ’反應時間太長,若超過1〇〇 mw/cm2,則由於從 燈所發射之熱及接著組成物的聚合時之發熱,俾有時會發 生接著組成物的黃變或偏光膜之劣化。同樣地,對於接著 組成物層之光照射時間係依其組成物之硬化性而決定者, 並無特別限定,但例如宜設定成使照射強度與照射時間之 ❹積所示的積分光量成為10至5000 mJ/cm2。對於接著組成 物層之積分光里未達10 mj/cm2時,源自光陽離子聚合起 始劑之活性種的產生為不充分,有時黏著組成物層之硬化 會不充分。又’若積分光量超過5000 mj/cm2,則照射時 間變成非常長,於生產性提高上成為不利者。 藉熱進行接著組成物層之硬化時,可依一般所知之方 法進行加熱,其條件等亦無特別限定,但係在調配於接著 ⑩組成物中之熱陽離子聚合起始劑會產生陽離子種或路易士 酸之溫度以上進行加熱,例如為5〇至200¾左右。 在以加熱及活性能量線之照射的任一者之條件硬化 時,宜在附單面透明保護膜之偏光板的偏光度、透過率、 色相、透明保護膜之透明性、及相位差薄膜之相位差特性 等所得到之複合偏光板的各功能不降低的範圍中硬化。使 接者組成物之硬化層的厚度一般為50//m以下,宜為2〇 //m以下’更宜為lOem以下。 在本發明之製造方法中,於複合偏光板中之相位差薄 321675 51 201028292 膜的外面,亦可設有黏著劑層。該黏著劑層係可適宜使用 於與液晶胞等其他構件的貼合。於相位差薄膜之外面設有 黏著劑層的複合偏光板,一般當貼合至液晶胞時係配置成 使其相位差薄膜側與液晶胞呈相對向。 <液晶顯示裝置> 藉由本發明之製造方法所製造的複合偏光板,係可使 其相位差薄膜側與液晶胞介由黏著層而貼合,而可形成液 晶顯示裝置。貼合此複合偏光板之液晶顯示裝置的背面側 係可貼合同種之偏光板、或公知之偏光板。又,所貼合之 液晶面板的動作模式,宜為藉由本發明之複合偏光板的折 射率特性而被良好地光學補償之IPS (In-Plane-Switching) 模式。 實施例 以下,舉出實施例而更具體地說明本發明,但本發明 係不限定於此等之例。例中,表示使用量或含量之「份」 及「%」只要無特別聲明,即為重量基準。又,在以下之 例中,貯存彈性模數係以如下方法進行測定。 [貯存彈性模數之測定方法] 黏著劑之貯存彈性模數(G’)係製作由測定對象之黏 著劑所構成的直徑8mmx厚度1 mm的圓盤狀之試驗片,使 用動態黏彈性測定裝置(Dynamic Analyzer RDA II : REOMETRIC公司製),依據頻率1Hz之扭剪法設為初期 變形1N,以23°C及80°C之條件進行測定。 又,在後述之實施例及比較例中係使用如下述者作為 52 321675 201028292 ^黏著劑、接著劑、偏光膜及相位差薄膜。 (黏著劑薄片A) \ 構成黏者劑薄片A之黏著劑A係於丙烯酸丁酯與丙 烯酸之共聚物中調配胺基曱酸酯丙烯酸酯寡聚物,並進一 步添加異氰酸酯系交聯劑而成者。以上述之方法測定此黏 著劑A的貯存彈性模數時,在23。〇中為〇 4 Μρ&,在8〇 。(:中為0.18 MPa。在以下之實施例中,黏著劑係將上述組 成之有機溶劑溶液塗佈於已實施離型處理之厚度38em的 聚對酞酸乙二酯薄膜(分隔膜)的離型處理面,進行乾燥, 俾於其分隔膜之表面形成厚度15#m之黏著劑A之層,而 以附分隔膜之片狀黏著劑(黏著劑薄片A)之形式來使用。 (黏著劑薄片B) 黏著劑薄片B係市售之片狀黏著劑,未調配胺基甲酸For the overlap obtained in the step (F) (piie (j pr〇 (juct) connected to the famous layer, hardened by irradiation of active energy rays or heating, and polarized light of the polarizing plate attached with the transparent protective film The film surface and the retardation film are bonded together via a hardened layer which is a surface layer of the object layer. Thereby, a composite polarizing plate having a purpose of providing a 相位 retardation film by an extended film having a three-layer structure is obtained. In the constitution, the three-layer structure is a core layer composed of a styrene resin, and a skin layer composed of a layered person on both sides of the core layer and composed of a (meth)acrylic acid diester composition containing rubber particles. a three-layer structure; and a polarizing plate with a single-sided transparent protective film is laminated on the retardation film and has a transparent protective chess on one side of the polarizing film. The composition is irradiated by the active energy ray. The light source used in the hardening of the layer is not particularly limited, and examples thereof include a low-pressure mercury lamp having a light-emitting distribution at a wavelength of 4 〇〇 nm or less, a medium-pressure mercury lamp, a high-pressure mercury lamp, a super-high mercury lamp, a chemical lamp, a black lamp, and a microwave. Exciting water The silver lamp and the metal halide lamp are not particularly limited as long as the light irradiation intensity of the composition layer is determined according to the composition of the 321675 50 201028292 - the photocuring property, and the activation of the initiator is The irradiation intensity in the effective wavelength region is preferably from 0" to '100 mW/cm2. If the intensity of light irradiation to the composition layer is less than 〇" mW/cm2', the reaction time is too long, if it exceeds 1 〇〇mw/cm2, Due to the heat emitted from the lamp and the heat generated during the polymerization of the composition, the yellowing of the composition or the deterioration of the polarizing film sometimes occurs. Similarly, the light irradiation time for the composition layer is based on its composition. The amount of the integrated light is not particularly limited, but it is preferably set so that the integrated light amount indicated by the accumulation of the irradiation intensity and the irradiation time is 10 to 5000 mJ/cm 2 . At 10 mj/cm2, the production of the active species derived from the photocationic polymerization initiator is insufficient, and sometimes the hardening of the adhesive composition layer may be insufficient. Further, if the integrated light amount exceeds 5000 mj/cm2, the irradiation time becomes It is very long and is disadvantageous in productivity improvement. When the composition layer is hardened by heat, it can be heated by a generally known method, and the conditions thereof are not particularly limited, but are formulated in the following composition. The thermal cationic polymerization initiator may be heated above a temperature of a cationic species or a Lewis acid, for example, from about 5 Å to about 2003 Å. When it is hardened by heating or active energy rays, it is preferred to The polarizing plate with a single-sided transparent protective film is cured in a range in which the functions of the composite polarizing plate obtained by the polarizing plate, the transmittance, the transparency of the transparent protective film, and the phase difference characteristics of the retardation film are not lowered. The thickness of the hardened layer of the contact composition is generally 50/m or less, preferably 2 〇//m or less, and more preferably 10 or less. In the manufacturing method of the present invention, the phase difference in the composite polarizing plate is 321675 51 201028292, and an adhesive layer may be provided on the outside of the film. The adhesive layer can be suitably used for bonding to other members such as liquid crystal cells. A composite polarizing plate having an adhesive layer on the outer surface of the retardation film is generally disposed such that the phase difference film side faces the liquid crystal cell when bonded to the liquid crystal cell. <Liquid Crystal Display Device> The composite polarizing plate manufactured by the production method of the present invention can form a liquid crystal display device by bonding the phase difference film side and the liquid crystal cell through an adhesive layer. The back side of the liquid crystal display device to which the composite polarizing plate is bonded is a polarizing plate which can be attached to a contract or a known polarizing plate. Further, the operation mode of the liquid crystal panel to be bonded is preferably an IPS (In-Plane-Switching) mode which is favorably optically compensated by the refractive index characteristics of the composite polarizing plate of the present invention. EXAMPLES Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited thereto. In the example, the "parts" and "%" indicating the amount or content of use are based on weight unless otherwise stated. Further, in the following examples, the storage elastic modulus was measured by the following method. [Method for Measuring Storage Elastic Modulus] The storage elastic modulus (G') of the adhesive is a disk-shaped test piece having a diameter of 8 mm x 1 mm and composed of an adhesive to be measured, and a dynamic viscoelasticity measuring device is used. (Dynamic Analyzer RDA II: manufactured by REOMETRIC Co., Ltd.), the initial deformation was 1 N according to the torsion shear method at a frequency of 1 Hz, and the measurement was carried out under the conditions of 23 ° C and 80 ° C. Further, in the examples and comparative examples described later, the following were used as the adhesive, the adhesive, the polarizing film, and the retardation film. (Adhesive sheet A) \ Adhesive agent A constituting the adhesive sheet A is formulated with an amino phthalate acrylate oligomer in a copolymer of butyl acrylate and acrylic acid, and further added with an isocyanate crosslinking agent. By. When the storage elastic modulus of the adhesive A was measured by the above method, it was 23. 〇中为〇 4 Μρ&, at 8〇. (In the following examples, 0.18 MPa. In the following examples, the adhesive is applied to the organic solvent solution of the above composition to the polyethylene terephthalate film (separation film) having a thickness of 38 cm which has been subjected to release treatment. The surface is treated, dried, and formed on the surface of the separator film to form a layer of adhesive A having a thickness of 15 #m, and is used in the form of a sheet-like adhesive (adhesive sheet A) with a separator film. Sheet B) Adhesive sheet B is a commercially available sheet-like adhesive with unadjusted urethane
酉旨丙稀酸酯募聚物。以上述之方法測定構成黏著劑薄片B 之黏著劑B時,在23。(:中為0.05 MPa,在8〇。〇中為〇 〇4 ❹ MPa。 在以下之實施例及比較例中,就黏著劑薄片B而言, 係使用於已實施離型處理之厚度38# m的聚對酞酸乙二酯 薄膜(分隔膜)的離型處理面,設有厚度15_的黏著劑 B之層的市售的附分隔膜之片狀黏著劑。 (接著劑A) 於水1〇〇份中添加羧基改性聚乙烯醇(Kurarayp〇vai KL318 ’(股)Ku順y製)3份與水溶性聚酿胺環氧樹脂 (Sumirez Resin 650,住化 Chemtex (股)製)(固形分濃 321675 53 201028292 度30%之水洛液)15份,溶解而調製接著劑a。 (接著劑B) 使己二酸雙(3,4_環氧基環己基曱基)酯100份、氩 化雙酚A的二縮水甘油基醚乃份、及作為光陽離子聚合 起始劑之4,4’-雙(二笨基銃基)二苯基硫醚雙(六氟磷 酸酯)(50%碳酸伸丙酯溶液)22份(有效成分量)混合 後,進行脫泡,調製由硬化性環氧樹脂組成物所構成之接 著劑B。 (偏光膜) 將由平均聚合度約為2400且皂化度為99.9莫耳%以 上之聚乙烯醇所構成的厚度75 之聚乙烯醇膜以乾式進 行單軸延伸至約5倍,進一步,保持在繃緊狀態下,浸潰 於60°C之純水1分鐘後’在28。(:下浸潰於碘/碘化鉀/水之 重量比為0.05/5/100的水溶液中60秒。其後,在72〇C下 浸潰於碘化鉀/硼酸/水之重量比為8.5/8.5/100的水溶液中 3〇〇秒。繼而,以26°C之純水洗淨20秒鐘後,以65。(:乾 燥’得到於聚乙烯醇吸附配向有碘之偏光膜。 (相位差薄膜) 以笨乙烯-馬來酸酐系共聚合樹脂[Nova Chemical公 司製之「Dylark (註冊商標)D332」(Tg=13rc )作為核 層’以調配有平均粒徑200nm之丙烯酸系橡膠粒子約20% 之甲基丙烯酸系樹脂(住友化學股份公司製之「Technoloy (註冊商標)S001」)所使用之樹脂(Tg=105t:)作為皮 層’進行3層共擠壓,得到核層之厚度為60以m且於其雙 54 321675 201028292 u 面分別形成有厚度72/zm之皮層的樹脂3層薄膜。將此樹 * 脂3層薄膜於142°C延伸成2倍,得到總厚度為104//m、 面内延遲為140nm、Nz係數為0.0之負的相位差薄膜。在 此相位差薄膜之各層的膜厚係核廣約30 // m,各皮層分別 約為37 # m。又,所得到之長向的相位差薄膜的寬度為 720mm ° 〈實施例1〉 [步驟(A)] ® 將對於表面已實施皂化處理之厚度40#m的三乙醯 基纖維素薄膜(透明保護薄膜)介由接著劑A而貼合於偏 光膜之單面,於其相反側之面則貼合表面(與偏光膜之接著 面)具有自我黏著性之聚乙烯薄膜以作為具有黏著性之剝 離性薄膜,於60°C乾燥其層合體,得到於單面貼合有透明 保護薄膜之偏光板。所得到之長向的附單面透明保護膜之 偏光板的寬度為1490mm。此附單面透明保護膜之偏光板 Q 的外觀係即使受到乾燥之熱或與搬運輥輪之摩擦亦無傷 痕、破裂等損傷,而為良好。 [步驟(B)] 然後,使用切割機(slitter) ( Model FN25,(股)西村 製作所製J,將此附單面透明保護薄膜之偏光板配合相位差 薄膜之寬度而沿著長度方向進行裁切(切割),得到寬度 720mm的附單面透明保護薄膜之偏光板。此經切割之偏光 板的外觀係即使受到切割時之剪斷或與搬運輥輪之摩擦亦 無傷痕、破裂等損傷,而為良好。 55 321675 201028292 [步驟(C)及(D)] 從上述步驟(B)所裁切之偏光板剝離除去聚乙烯薄 膜,並立即於其偏光膜面上貼合黏著劑薄片A。 [步驟(E)] 對相位差薄膜以照射量16.8 kJ/m2實施電暈處理之 後,使其電暈處理面與上述步騍(B)所切割之附單面透 明保護溥膜之偏光板,介由上述步驟(C)及(d)所設置 之黏著劑層而貼合’得到複合偏光板。 如此所得到之複合偏光㈣外觀係無薄膜之浮起、剝 離、及氣泡等’為良好者。又,從此複合偏光板藉由裁切 而得到液晶胞貼合用的薄片時,可使用複合偏光板之全面 積中之96.6%。 將所侍到之複合偏光板的 t之㈣中放置π分鐘,以此作=分fs,,其次移至4 1〇〇循環的熱衝擊試驗。實施 … 裱,進行反覆 後亦未觀察到缺陷,而維 坷1之複合偏光板徐於試 〈比較例1> 、良好的狀態。 除了不裁切附單面透 係與實施例1同樣做法而製、β潯膜之偏光板以外,其 複合偏光板的外觀係無薄作,合偏光板 。如此所得到-艮好者。但與實施例〗间獏之净起、剝離、及氣泡等,j 樣地侍到薄片時,僅可使用複4 321675 56 201028292 • 偏光板之全面積中之48.3%。 . 〈比較例2〉 製作附單面透明保護薄膜之偏光板時,除了不使用表 面(與偏光膜之接著面)具有自我黏著性之聚乙烯薄膜以 外,其餘係與實施例1同樣做法而製作複合偏光板。所製 作之複合偏光板的外觀係在製作附單面透明保護薄膜之偏 光板時及裁切附單面透明保護薄膜之偏光板時,偏光膜會 受到損傷,而非可供於實用者。 ®〈實施例2〉 [步驟(A)] 將對於表面已實施皂化處理之厚度40/im的三乙醯 基纖維素薄膜(透明保護薄膜)介由接著劑B而貼合於偏 光膜之單面,於其相反側之面則貼合表面(與偏光膜之接著 面)具有自我黏著性之聚乙烯薄膜以作為具有黏著性之剝 離性薄膜,並以紫外線照射裝置(燈:FusionD燈,積分光 ❹量·· 1000mJ/cm2)進行紫外線照射,於室溫下放置1小時, 得到於單面貼合有透明保護薄膜之偏光板。所得到之長向 的附單面透明保護膜之偏光板的寬度為1490mm。又,此/ 附單面透明保護膜之偏光板的外觀係即使受到與搬運輥輪 之摩擦亦無傷痕、破裂等損傷,為良好。 [步驟(B)] 然後,將此附單面透明保護薄膜之偏光板以與實施例 1同樣做法而進行裁切,得到寬度720mm的附單面透明保 護薄膜之偏光板。此裁切後之附單面透明保護薄膜之偏光 57 321675 201028292 板的外觀係即使受到切割時之剪斷或與搬運輥輪之摩擦亦 無傷痕、破裂等損傷,為良好。 [步驟(C)及(D)] 從前述步驟(B)所切割之偏光板剝離除去聚乙烯薄 膜,並立即於其偏光膜面上貼合黏著劑薄片A。 [步驟(E)] 對相位差薄膜以照射量16.8 kJ/m2實施電暈處理之 後,使其電暈處理面與上述步驟(B )所分割之附單面透 明保護薄膜之偏光板,介由上述步驟(C)及(D)所設置 之黏著劑層而貼合,得到複合偏光板。 如此所得到之複合偏光板的外觀係無薄膜之浮起、剝 離、及氣泡等,為良好者。又,從此複合偏光板藉由裁切 而得到液晶胞貼合用的薄片時,可使用附單面透明保護薄 膜之偏光板之全面積中之96.6%。 將所得到之複合偏光板的相位差薄膜面使用黏著劑 薄片B而固定於鈉玻璃(使用來取代液晶胞),於50°C實 施20分鐘的高壓鍋處理而使複合偏光板密著於玻璃板。於 此狀態―下,在-35°C之環境中放置30分鐘,然後移至+85 °C之環境中放置30分鐘,以此作為1循環,進行反覆此 100循環的熱衝擊試驗。實施例2之複合偏光板係於試驗 後亦未觀察到缺陷,而維持良好的狀態。 〈比較例3〉 在實施例1中,除了將步驟(D)使用之黏著劑薄片 A變更成黏著劑薄片B以外,同樣地製作複合偏光板。如 58 321675 201028292 - 此所得到之複合偏光板的外觀係無薄膜之浮起、剝離、及 _氣泡等,為良好者。又,從此複合偏光板藉由裁切而得到 液曰曰胞貼合用的薄片時,可使用複合偏光板之全面積中之 96.6% ° 將所得到之複合偏光板的相位差薄膜面以黏著劑薄 片B固定於鈉玻璃(使用來取代液晶胞),於5〇。〇實施2〇 刀鐘的而壓鍋處理而使複合偏光板密著於玻璃板 。於此狀 ❹態下,在~35C之環境中玫置3〇分鐘,然後移至+85°c之環 境中放置30分鐘,以此作為i循環,進行反覆此1〇〇循環 的熱衝擊試驗。比較例3之偏光板係於試驗後在相位差薄 膜與玻璃之間的黏著劑層產生氣泡,而非足以實用者。 〈比較例4〉 在實施例2中,除了將步驟使用之黏著劑薄片 A變更成黏著劑薄片B以外,同樣地製作複合偏光板。如 此所得到之複合偏光板的外觀係無薄膜之浮起、剝離、及 ❹氣泡等’為良好者。又’從此複合偏光板藉由裁切而得到 液晶胞貼合用的薄片時’可使用複合偏光板之全面積中之 96.6% ° ' 將所得到之複合偏光板的相位差薄膜面以黏著劑薄 片B固定於鈉玻璃(使用來取代液晶胞),於5〇。〇實施2〇 分鐘的高$鍋處理而使複合偏光板密著於玻璃板。於此狀 態下,在-35°C之環境中放置3〇分鐘,然後移至+机之壤 境中放置30刀鐘以此作舄1循環,進奸反嘗祀了〇〇揭枣 的熱衝擊試驗。崎例4之偏光板係於試驗後在相位差^ 321675 59 201028292 膜與玻璃之間的黏著劑層產生氣泡,而非足以實用者。 〜 〈實施例3〉 ' " [步驟(A)] ’ 將對於表面已實施息化處理之厚度卿m #三乙酿 基纖維素薄膜(透明保護薄膜)介由接著劑A而貼合於偏 光膜之單面’於其相反側之面則貼合表面(與偏光膜之接著 面)具有自我黏著性之聚乙烯薄膜以作為具有黏著性之剝 離性薄膜,於60°C乾燥其層合體,得到於單面貼合有透明 保護薄膜之偏光板。所得到之長向的附單面透明保護膜之❹ 偏光板的寬度為1490mm。又,此附單面透明保護膜之偏 光板的外觀係即使受到乾燥之熱或與搬運輥輪之摩擦亦無 傷痕、破裂等損傷,為良好。 T … [步驟(C)及(D)] 然後,從此附單面透明保護膜之偏光板剝離除去聚乙 婦薄膜’並立即於其偏光膜面上貼合黏著劑薄片Α。 [步驟(B)] 使用切割機(Model FN25,(股)西村製作所製),將 〇 此附單面透明保護薄膜之偏光板配合相位差薄膜之寬度而 沿著長度方向進行裁切(切割),得到寬度72〇mm的附單 面透明保護薄膜之偏光板。此經切割之偏光板的外觀係即 使受到切割時之剪斷或與搬運輥輪之摩擦亦無傷痕、破裂 等損傷,為良好。 < [步驟(E)] 對相位差薄膜以照射量16.8 kJ/m2實施電暈處理之 321675 60 201028292 * 後,使其電暈處理面與上述步驟(B)所切割之附單面透 ' 明保護薄膜之偏光板,介由上述步驟(C)及(D)所設置丙 acrylate acrylate polymer. When the adhesive B constituting the adhesive sheet B was measured by the above method, it was 23. (: 0.05 MPa in the middle, 8 〇 in the 〇. 〇 4 ❹ MPa. In the following examples and comparative examples, in the case of the adhesive sheet B, it is used for the thickness 38# which has been subjected to the release treatment. A release-treated surface of a polyethylene terephthalate film (separator film) of m, which is provided with a commercially available separator-like sheet-like adhesive having a thickness of 15 mm of adhesive B. (Adhesive A) 3 parts of water, carboxy-modified polyvinyl alcohol (Kurarayp〇vai KL318 '(K)), and water-soluble polyamine epoxy resin (Sumirez Resin 650, manufactured by Chem Chemex) (solid content 321675 53 201028292 degrees 30% water Loose solution) 15 parts, dissolved to prepare the adhesive a. (Binder B) Adipic acid bis(3,4-epoxycyclohexyldecyl) ester 100 parts, diglycidyl ether of argon bisphenol A, and 4,4'-bis(diphenylphosphino)diphenyl sulfide bis(hexafluorophosphate) as photocationic polymerization initiator (50% of propylene carbonate solution) 22 parts (the amount of active ingredient) are mixed, and then defoamed to prepare an adhesive B composed of a curable epoxy resin composition. Light film) A polyvinyl alcohol film having a thickness of 75, which is composed of a polyvinyl alcohol having an average degree of polymerization of about 2400 and a degree of saponification of 99.9 mol% or more, is uniaxially stretched to about 5 times in a dry manner, and further, kept tight. In the state, after immersing in pure water at 60 ° C for 1 minute, 'at 28° (:: immersed in an aqueous solution of iodine/potassium iodide/water in a weight ratio of 0.05/5/100 for 60 seconds. Thereafter, at 72 〇C was immersed in an aqueous solution of potassium iodide/boric acid/water in a weight ratio of 8.5/8.5/100 for 3 sec. Then, after washing with pure water at 26 ° C for 20 seconds, it was 65. (: Drying 'A polarizing film obtained by adsorbing and dispersing iodine in polyvinyl alcohol. (Retardation film) A stupid ethylene-maleic anhydride copolymer resin [Dylark (registered trademark) D332 (Tg=13rc) manufactured by Nova Chemical Co., Ltd.) was used. Resin (Tg=105t:) used for methacrylic resin ("Technoloy (registered trademark) S001" manufactured by Sumitomo Chemical Co., Ltd.) of approximately 20% of acrylic rubber particles having an average particle diameter of 200 nm. 3 layers of co-extrusion as a skin layer, the thickness of the core layer is 60 m and in its double 54 32167 5 201028292 u A three-layer film of resin with a skin layer of 72/zm thickness is formed on each side. This three-layer film of the resin is extended twice at 142 ° C to obtain a total thickness of 104 / / m and an in-plane retardation of 140 nm. A retardation film having a negative Nz coefficient of 0.0. The film thickness of each layer of the retardation film is about 30 // m, and each of the skin layers is about 37 # m. Further, the obtained retardation film of the long direction has a width of 720 mm ° <Example 1> [Step (A)] ® A triacetonitrile-based cellulose film having a thickness of 40 #m which has been subjected to saponification treatment on the surface (transparent The protective film is bonded to one side of the polarizing film via the adhesive A, and the self-adhesive polyethylene film is adhered to the surface (the adhesive surface of the polarizing film) on the opposite side to serve as an adhesive film. The peelable film was dried at 60 ° C to obtain a polarizing plate having a transparent protective film laminated on one side. The obtained polarizing plate with a single-sided transparent protective film of a long direction had a width of 1490 mm. The appearance of the polarizing plate Q with the one-sided transparent protective film is good even if it is subjected to drying heat or friction with the conveying roller without damage such as scratches or cracks. [Step (B)] Then, using a slitter (Model FN25, manufactured by Nishimura Co., Ltd.), the polarizing plate with a single-sided transparent protective film is fitted along the width of the retardation film to cut along the length direction. By cutting (cutting), a polarizing plate with a width of 720 mm and a single-sided transparent protective film is obtained. The appearance of the cut polarizing plate is not damaged by scratches or cracks even when it is cut by cutting or rubbed with the conveying roller. 55 321675 201028292 [Steps (C) and (D)] The polyethylene film was peeled off from the polarizing plate cut in the above step (B), and the adhesive sheet A was immediately bonded to the surface of the polarizing film. [Step (E)] After the corona treatment is performed on the retardation film at an irradiation amount of 16.8 kJ/m 2 , the corona-treated surface and the polarizing plate with the single-sided transparent protective ruthenium film cut by the above step (B) are The composite polarizing plate is bonded by the adhesive layer provided in the above steps (C) and (d). The composite polarizing film obtained in this manner has no appearance of floating, peeling, and bubbles, etc. Again, from this composite polarizer When the sheet for liquid crystal cell bonding is obtained by cutting, 96.6% of the total area of the composite polarizing plate can be used. The (4) of t of the composite polarizing plate to be served is placed for π minutes, thereby making = fs , and then moved to the thermal shock test of the 4 1 〇〇 cycle. Implementation... 裱, no defects were observed after the reversal, and the composite polarizing plate of 坷1 was tested <Comparative Example 1>, good state. The appearance of the composite polarizing plate is not thin, and the polarizing plate is not cut except for the polarizing plate of the β-film which is manufactured in the same manner as in the first embodiment, and the polarizing plate is obtained. EXAMPLES When lifting, peeling, and air bubbles, etc., only 4 321675 56 201028292 • 48.3% of the total area of the polarizing plate can be used. <Comparative Example 2> Preparation In the case of a polarizing plate having a single-sided transparent protective film, a composite polarizing plate was produced in the same manner as in Example 1 except that a polyethylene film having a self-adhesive property on the surface (the surface of the polarizing film was not used) was used. The appearance of the polarizing plate is attached When the polarizing plate of the single-sided transparent protective film is cut and the polarizing plate with the single-sided transparent protective film is cut, the polarizing film may be damaged, and it is not available to the user. <Example 2> [Step (A)] A triethylenesulfonated cellulose film (transparent protective film) having a thickness of 40/im which has been subjected to saponification treatment on the surface is bonded to one side of the polarizing film via the adhesive B, and the surface is bonded to the opposite side ( A self-adhesive polyethylene film is used as a peeling film having adhesiveness, and is irradiated with ultraviolet rays by an ultraviolet irradiation device (light: Fusion D lamp, integrated light amount·1000 mJ/cm 2 ). After leaving at room temperature for 1 hour, a polarizing plate having a transparent protective film attached to one side was obtained. The obtained polarizing plate with a single-sided transparent protective film of a long direction had a width of 1490 mm. Further, the appearance of the polarizing plate with the one-sided transparent protective film is good even if it is rubbed against the conveyance roller without damage such as scratches or cracks. [Step (B)] Then, this polarizing plate with a one-side transparent protective film was cut in the same manner as in Example 1 to obtain a polarizing plate with a single-sided transparent protective film having a width of 720 mm. Polarized light with a single-sided transparent protective film after cutting 57 321675 201028292 The appearance of the board is good even if it is cut by cutting or rubbed against the conveying roller without damage such as scratches or cracks. [Steps (C) and (D)] The polyethylene film was peeled off from the polarizing plate cut in the above step (B), and the adhesive sheet A was immediately bonded to the surface of the polarizing film. [Step (E)] After the corona treatment is performed on the retardation film at an irradiation amount of 16.8 kJ/m 2 , the corona-treated surface and the polarizing plate of the single-sided transparent protective film divided by the above step (B) are subjected to a polarizing plate. The adhesive layers provided in the above steps (C) and (D) are bonded together to obtain a composite polarizing plate. The appearance of the composite polarizing plate thus obtained is excellent in the absence of floating, peeling, and air bubbles of the film. Further, when the composite polarizing plate is obtained by cutting to obtain a sheet for liquid crystal cell bonding, 96.6% of the total area of the polarizing plate with a single-sided transparent protective film can be used. The phase difference film surface of the obtained composite polarizing plate was fixed to a soda glass (used to replace the liquid crystal cell) using the adhesive sheet B, and subjected to a pressure cooker treatment at 50 ° C for 20 minutes to adhere the composite polarizing plate to the glass plate. . In this state, under the environment of -35 ° C for 30 minutes, and then placed in an environment of +85 ° C for 30 minutes, as a 1 cycle, the thermal shock test was repeated for the 100 cycles. The composite polarizing plate of Example 2 was not observed to have defects after the test, and maintained in a good state. <Comparative Example 3> In the first embodiment, a composite polarizing plate was produced in the same manner except that the adhesive sheet A used in the step (D) was changed to the adhesive sheet B. For example, 58 321675 201028292 - The appearance of the composite polarizing plate obtained is such that there is no film floating, peeling, and _ bubbles, etc., which is good. Further, when the composite polarizing plate is obtained by cutting to obtain a sheet for liquid cell bonding, the phase difference film surface of the obtained composite polarizing plate can be adhered using 96.6% of the total area of the composite polarizing plate. The agent sheet B was fixed to soda glass (used to replace the liquid crystal cell) at 5 Å. 〇The crucible is treated with a 2 knives and the composite polarizer is adhered to the glass. In this state, it is placed in the environment of ~35C for 3 minutes, and then moved to the environment of +85 °c for 30 minutes, as the i cycle, the thermal shock test is repeated for this 1 cycle. . The polarizing plate of Comparative Example 3 was caused to generate bubbles in the adhesive layer between the retardation film and the glass after the test, and was not sufficient for practical use. <Comparative Example 4> In the second embodiment, a composite polarizing plate was produced in the same manner except that the adhesive sheet A used in the step was changed to the adhesive sheet B. The appearance of the composite polarizing plate thus obtained is such that no floating, peeling, or enthalpy of the film is good. Further, 'when the composite polarizing plate is obtained by cutting to obtain a sheet for liquid crystal cell bonding, '96.6% of the total area of the composite polarizing plate can be used'. The phase difference film surface of the obtained composite polarizing plate is an adhesive. Sheet B was fixed to soda glass (used to replace the liquid crystal cell) at 5 Torr. 〇 Apply a 2 minute high pot treatment to make the composite polarizer adhere to the glass. In this state, put it in the environment of -35 ° C for 3 minutes, then move it to the soil of the machine to place 30 knives for this cycle of 1 ,, and then smash the heat of the simmering date. Impact test. The polarizing plate of Kakizaki 4 is after the test in the phase difference ^ 321675 59 201028292 The adhesive layer between the film and the glass generates bubbles, which is not sufficient for practical use. ~ <Example 3> ' " [Step (A)] ' The thickness of the surface of the surface of the cellulose m film (transparent protective film) is adhered to the adhesive A On the opposite side of the polarizing film, the self-adhesive polyethylene film is adhered to the surface (the bonding surface with the polarizing film) as a peeling film having adhesiveness, and the laminate is dried at 60 ° C. A polarizing plate having a transparent protective film attached to one side is obtained. The obtained long-direction single-sided transparent protective film has a width of 1490 mm. Further, the appearance of the polarizing plate with the one-sided transparent protective film is good even if it is subjected to heat of drying or friction with the conveyance roller without damage such as scratches or cracks. T ... [Steps (C) and (D)] Then, the polysilicon film was peeled off from the polarizing plate with a one-sided transparent protective film and the adhesive sheet was bonded immediately to the surface of the polarizing film. [Step (B)] Using a cutter (Model FN25, manufactured by Nishimura Seisakusho Co., Ltd.), the polarizing plate with the one-sided transparent protective film is cut along the length direction by the width of the retardation film (cutting) A polarizing plate with a single-sided transparent protective film having a width of 72 mm was obtained. The appearance of the cut polarizing plate is good even if it is sheared at the time of cutting or rubbed against the conveying roller without damage or cracking. < [Step (E)] After the corona treatment was performed on the retardation film at an irradiation dose of 16.8 kJ/m 2 , the corona-treated surface was cut with the single-sided surface cut by the above step (B). a polarizing plate for a protective film, which is provided by the above steps (C) and (D)
-T 之黏著劑層而貼合,得到複合偏光板。 如此所得到之複合偏光板的外觀係無薄膜之浮起、剝 離、及氣泡等,為良好者。又,從此複合偏光板藉由裁切 而得到液晶胞貼合用的薄片時,可使用複合偏光板之全面 積中之96.6% 〇 〈實施例4〉 © [步驟(A)] 將對於表面已實施皂化處理之厚度40/zm的三乙醯 基纖維素薄膜(透明保護薄膜)介由接著劑A而貼合於偏 光膜之單面,於其相反侧之面則貼合表面(與偏光膜之接著 面)具有自我黏著性之聚乙烯薄膜以作為具有黏著性之剝 離性薄膜,於60°C乾燥其層合體,得到於單面貼合有透明 保護薄膜之偏光板。所得到之長向的附單面透明保護膜之 Q 偏光板的寬度為1490mm。此偏光板的外觀係即使受到乾 燥之熱或與搬運輥輪之摩擦亦無傷痕、破裂等損傷,為良 好。 [步驟(B)] 然後,使用切割機(Model FN25,(股)西村製作所 製)’將此附單面透明保護薄膜之偏光板配合相位差薄膜之 寬度而沿著長度方向進行裁切(切割),得到寬度720mm 的附單面透明保護薄膜之偏光板。此被切割之偏光板的外 觀係即使受到切割時之剪斷或與搬運輥輪之摩擦亦無傷 61 321675 201028292 痕、破裂等損傷,為良好。 [步驟(D)] 對相位差薄膜以照射量16.8 kJ/m2實施電暈處理之 後,於其電暈處理面上貼合黏著劑薄片A。 [步驟(C)及(E)] 對於相位差薄膜之黏著劑層側及從上述步驟(B)所切 割之附單面透明保護膜之偏光板剝離除去聚乙烯薄膜的偏 光板之偏光薄膜側,以照射量16.8 kJ/m2實施電暈處理之 後,使偏光板與相位差薄膜介由上述步驟(D)所設置之 黏著劑層而貼合,得到複合偏光板。 如此所得到之複合偏光板的外觀係無薄膜之浮起、剝 離、及氣泡等,為良好者。又,從此複合偏光板藉由裁切 而得到液晶胞貼合用的薄片時,可使用複合偏光板之全面 積中之96.6%。 〈實施例5> [步驟(A)] 將對於表面已實施皂化處理之厚度40#m的三乙醯 基纖維素薄膜(透明保護薄膜)使用製造例1所得到之接 著劑A而貼合於製造例3所得到之偏光膜的單面,於其另 一面則貼合表面(與偏光膜之接著面)具有自我黏著性之聚 乙烯薄膜,於6CTC乾燥其貼合體,得到於單面貼合有透明 保護薄膜之偏光板。所得到之長向的附單面保護膜之偏光 板的寬度為1490mm。此附單面保護膜之偏光板的外觀係 即使受到乾燥之熱或與搬運輥輪之摩擦亦無傷痕、破裂等 62 321675 201028292 • 損傷,為良好。 ’[步驟(B)] » 然後,使用切割機(Model FN25,(股)西村製作所 製),將此附單面透明保護薄膜之偏光板配合相位差薄膜之 大小而沿著長度方向進行裁切(切割),得到寬度720mm 的附單面保護薄膜之偏光板。此被切割之偏光板的外觀係 即使受到切割時之剪斷或與搬運輥輪之摩擦亦無傷痕、破 裂等損傷,為良好。 ® [步驟(C)、步驟(F)及步驟(G)] 對相位差薄膜之單面以照射量16.8 kJ/m2實施電暈處 理,於其處理面塗佈接著劑B。然後,從上述步驟(B)所切 割之附單面保護膜之偏光板剝離除去聚乙烯薄膜,並立即 將附單面保護膜之偏光板與相位差薄膜重疊而使偏光薄膜 面與相位差薄膜之接著劑塗佈面相接,對其重疊物(piled product)以紫外線照射裝置(燈:Fusion D燈,積分光量: 0 l〇〇〇mJ/cm2)進行紫外線照射,於室溫下放置!小時,得到 複合偏光板。如此所得到之複合偏光板的外觀係無薄膜之 浮起、剝離、及氣泡等’為灸麵者㈣叉變勸此複会編光板 藉由裁切而得到液晶胞貼合用的薄片時,可使用附單面保 護膜之偏光板之全面積中之966%。 將所得到之複合偏光板的相位差薄膜面使用黏著劑 薄片而固定於鈉玻璃(使用來取代液晶胞),於5(rc實施 20分鐘的高祕處理而使複普偏光板.密著於賴板。於此 狀態下’在-35°C之環境中放置3〇分鐘,然後移至+85^之 321675 63 201028292 環境中放置30分鐘,以此作為1循環,進行反覆此100 循環的熱衝擊試驗。實施例5之複合偏光板係於試驗後亦 未觀察到缺陷,而維持良好的狀態。 〈比·較例5〉 除了不切割附單面保護薄膜之偏光板以外,其餘係與 實施例5同樣做法而製作複合偏光板。如此所得到之複合 偏光板的外觀係無薄膜之浮起、剝離、及氣泡等,為良好 者。但與實施例5同樣地得到薄片時,僅可使用附單面保 護薄膜之偏光板的全面積中之48.3%。 〈比較例6〉 於製作附單面保護薄膜之偏光板時,除了不使用表面 (與偏光膜之接著面)具有自我黏著性之聚乙烯薄膜以 外,其餘係與實施例5同樣做法而製作複合偏光板。所製 作之複合偏光板的外觀係在製作附單面保護薄膜之偏光板 時及切割偏光板時,偏光膜受到損傷,而非可供於實用者。 〈實施例6〉 [步驟(A)] 將對於表面已實施皂化處理之厚度40//m的三乙醯 基纖維素薄膜(透明保護薄膜)介由接著劑B而重疊於偏 光膜之單面,於其相反侧之面則貼合表面(與偏光膜之接著 面)具有自我黏著性之聚乙烯薄膜(剝離性薄膜),以紫外 線照射裝置(燈:Fusion D燈,積分光量:1000mJ/cm2)進 行紫外線照射,於室溫下放置1小時,得到於單面貼合有 透明保護薄膜之偏光板。所得到之長向的附單面保護膜之 64 321675 201028292 • 偏光板的寬度為1490mm。此附單面保護膜之偏光板的外 * 觀係即使受到與搬運輥輪之摩擦亦無傷痕、破裂等損傷, 為良好。 [步驟(B)] 然後,使用切割機(Model FN25,(股)西村製作所 製),將此附單面透明保護薄膜之偏光板配合相位差薄膜之 大小而沿著長度方向進行裁切(切割),得到寬度720mm 的附單面保護薄膜之偏光板。此被切割之偏光板的外觀係 ® 即使受到切割時之剪斷或與搬運輥輪之摩擦亦無傷痕、破 裂等損傷,為良好。 [步驟(C)、步驟(F)及步驟(G)] 使用相位差薄膜,與實施例5之步驟(C)、步驟(F) 及步驟(G)同樣操作而得到複合偏光板。如此所得到之 複合偏光板的外觀係無薄膜之浮起、剝離、及氣泡等,為 良好者。又,從此複合偏光板藉由裁切而得到液晶胞貼合 ❿用的薄片時,可使用附單面保護薄膜之偏光板的全面積中 之 96.6%。 將所得到之複合偏态板,妹拇振差&条膜面傷用黏著劑 薄片而固定於鈉玻璃(使用來取代液晶胞),於50°C實施 20分鐘的高壓鍋處理而使複合偏光板密著於玻璃板。於此 狀態下,在-35°C之環境中放置30分鐘,然後移至+85°C之 環境中放置30分鐘,以此作為1循環,進行反覆此1〇〇 循環的熱衝擊試驗。實施例6之複合偏光板係於試··驗後亦 未觀察到缺陷,而維持良好的狀態。 65 321675 201028292 [產業上之可利用性] 依本發明所得到之複合偏光板係可廣泛地利用於作 為在各種之液晶顯示裝置中的光學構件者,例如可利用於 作為電視等大型液晶顯示裝置、或電腦用顯示器、汽車導 航器、行動電話、攜帶式終端機器等所使用之中小型液晶 顯示裝置中的光學構件者。 【圖式簡單說明】 無。 【主要元件符號說明】 無。 66 321675The adhesive layer of -T is bonded to obtain a composite polarizing plate. The appearance of the composite polarizing plate thus obtained is excellent in the absence of floating, peeling, and air bubbles of the film. Further, when the composite polarizing plate is obtained by cutting to obtain a sheet for liquid crystal cell bonding, 96.6% of the total area of the composite polarizing plate can be used. <Example 4> © [Step (A)] The triacetyl cellulose film (transparent protective film) having a thickness of 40/zm subjected to saponification treatment is bonded to one side of the polarizing film via the adhesive A, and the surface is bonded to the surface on the opposite side (with a polarizing film) The polyethylene film having self-adhesiveness was used as a peeling film having adhesiveness, and the laminate was dried at 60 ° C to obtain a polarizing plate in which a transparent protective film was bonded to one side. The obtained polarizing plate of the long-side single-sided transparent protective film had a width of 1490 mm. The appearance of the polarizing plate is good even if it is subjected to dry heat or friction with the conveying roller without damage such as scratches or cracks. [Step (B)] Then, using a cutter (Model FN25, manufactured by Nishimura Seisakusho Co., Ltd.), the polarizing plate with a single-sided transparent protective film is cut along the length direction by the width of the retardation film (cutting) ), a polarizing plate with a width of 720 mm and a single-sided transparent protective film was obtained. The appearance of the cut polarizing plate is not damaged even when it is cut by the cutting or rubbing against the conveying roller. 61 321675 201028292 Damage such as marks and cracks is good. [Step (D)] After the corona treatment was carried out on the retardation film at an irradiation amount of 16.8 kJ/m2, the adhesive sheet A was bonded to the corona-treated surface. [Steps (C) and (E)] The polarizing film side of the polarizing plate on which the polyethylene film is peeled off from the side of the adhesive layer of the retardation film and the polarizing plate with the one-sided transparent protective film cut from the above step (B) After the corona treatment was performed at an irradiation amount of 16.8 kJ/m 2 , the polarizing plate and the retardation film were bonded together via the adhesive layer provided in the above step (D) to obtain a composite polarizing plate. The appearance of the composite polarizing plate thus obtained is excellent in the absence of floating, peeling, and air bubbles of the film. Further, when the composite polarizing plate is obtained by cutting to obtain a sheet for liquid crystal cell bonding, 96.6% of the total volume of the composite polarizing plate can be used. <Example 5> [Step (A)] A triacetonitrile-based cellulose film (transparent protective film) having a thickness of 40 #m which had been subjected to saponification treatment on the surface was bonded to the adhesive A obtained in Production Example 1 On one side of the polarizing film obtained in Production Example 3, a polyethylene film having a self-adhesive property bonded to the surface (the surface of the polarizing film) was bonded to the other surface, and the bonded body was dried at 6 CTC to obtain a single-sided bonding. A polarizing plate with a transparent protective film. The polarizing plate of the long-facing single-sided protective film obtained had a width of 1490 mm. The appearance of the polarizing plate with the one-sided protective film is not damaged or broken even if it is subjected to heat of drying or friction with the conveying roller. 62 321675 201028292 • Damage is good. '[Step (B)] » Then, using a cutting machine (Model FN25, manufactured by Nishimura Seisakusho Co., Ltd.), the polarizing plate with a single-sided transparent protective film is cut along the length direction in accordance with the size of the retardation film. (Cutting), a polarizing plate with a single-sided protective film having a width of 720 mm was obtained. The appearance of the cut polarizing plate is good even if it is sheared at the time of cutting or rubbed against the conveying roller without damage such as scratches or breakage. ® [Step (C), Step (F), and Step (G)] Corona treatment was performed on one side of the retardation film at an irradiation amount of 16.8 kJ/m2, and the adhesive B was applied to the treated surface. Then, the polyethylene film is peeled off from the polarizing plate with the single-sided protective film cut in the above step (B), and the polarizing plate with the single-sided protective film is immediately overlapped with the retardation film to make the polarizing film surface and the retardation film. Then, the coated surface of the agent is brought into contact with each other, and the laminated product is irradiated with ultraviolet rays by an ultraviolet irradiation device (light: Fusion D lamp, integrated light amount: 0 l〇〇〇mJ/cm 2 ), and left at room temperature! In hours, a composite polarizer is obtained. The appearance of the composite polarizing plate thus obtained is such that no floating, peeling, and air bubbles of the film are used as a moxibustion. (4) When the grading plate is obtained by cutting, a sheet for liquid crystal cell bonding is obtained. It is possible to use 966% of the total area of the polarizing plate with a single-sided protective film. The phase difference film surface of the obtained composite polarizing plate was fixed to a soda glass (used to replace the liquid crystal cell) using an adhesive sheet, and the reticle was subjected to a high-definition treatment for 20 minutes to make the reticle polarizing plate. Lai board. In this state, place in the environment of -35 ° C for 3 minutes, then move to +85^ of 321675 63 201028292 for 30 minutes in the environment, as a 1 cycle, repeat the heat of this 100 cycles Impact test. The composite polarizing plate of Example 5 did not observe defects after the test, and maintained a good state. <Comparative Example 5> Except that the polarizing plate with the one-side protective film was not cut, the other system was implemented. In the same manner as in Example 5, a composite polarizing plate was produced in the same manner. The appearance of the composite polarizing plate thus obtained was excellent in the absence of floating, peeling, and bubbles of the film. However, when a sheet was obtained in the same manner as in Example 5, only the sheet was used. 48.3% of the total area of the polarizing plate with a single-sided protective film. <Comparative Example 6> When making a polarizing plate with a single-sided protective film, it is self-adhesive except that the surface (with the bonding surface of the polarizing film) is not used. Poly A composite polarizing plate was produced in the same manner as in Example 5 except for the film. The appearance of the composite polarizing plate produced was caused by damage to the polarizing film when the polarizing plate with the single-sided protective film was formed and when the polarizing plate was cut, instead of <Example 6> [Step (A)] A triethylenesulfonyl cellulose film (transparent protective film) having a thickness of 40/m which has been subjected to saponification treatment on the surface is overlapped by the adhesive B. On the opposite side of the polarizing film, on the opposite side, a self-adhesive polyethylene film (peelable film) is adhered to the surface (the adhesive surface of the polarizing film), and the device is irradiated with ultraviolet light (light: Fusion D lamp, The amount of integrated light: 1000 mJ/cm 2 ) was irradiated with ultraviolet rays, and left at room temperature for 1 hour to obtain a polarizing plate having a transparent protective film attached to one side. The obtained long-facing single-sided protective film was obtained. 64 321675 201028292 • Polarized light The width of the plate is 1490 mm. The outer viewing system of the polarizing plate with a single-sided protective film is not damaged by scratches or cracks even if it is rubbed against the carrying roller. [Step (B)] Then, use The cutting machine (Model FN25, manufactured by Nishimura Seisakusho Co., Ltd.) cuts (cuts) the polarizing plate with a single-sided transparent protective film in accordance with the length of the retardation film to obtain a single-sided surface having a width of 720 mm. The polarizing plate for the protective film. The appearance of the polarized plate to be cut is good even if it is cut by cutting or rubbed against the carrying roller without damage or cracking. [Step (C), step (F And step (G)] using a retardation film, a composite polarizing plate was obtained in the same manner as in the step (C), the step (F) and the step (G) of Example 5. The appearance of the composite polarizing plate thus obtained was The film is floated, peeled off, and bubbles are good. Further, when the composite polarizing plate is obtained by cutting to obtain a sheet for liquid crystal cell bonding, 96.6% of the total area of the polarizing plate with the one-side protective film can be used. The obtained composite skew plate, the thumb vibration difference and the strip film surface damage adhesive sheet were fixed to the soda glass (used to replace the liquid crystal cell), and subjected to a pressure cooker treatment at 50 ° C for 20 minutes to make the composite polarized light. The plate is densely attached to the glass plate. In this state, it was allowed to stand for 30 minutes in an environment of -35 ° C, and then placed in an environment of +85 ° C for 30 minutes, and as a one cycle, a thermal shock test was repeated which was repeated for this cycle. The composite polarizing plate of Example 6 was not observed to have defects after the test, and was maintained in a good state. 65 321 675 201028292 [Industrial Applicability] The composite polarizing plate obtained by the present invention can be widely used as an optical member in various liquid crystal display devices, and can be used, for example, as a large liquid crystal display device such as a television. Or optical components in small and medium-sized liquid crystal display devices used in computer monitors, car navigators, mobile phones, and portable terminal devices. [Simple description of the diagram] None. [Main component symbol description] None. 66 321675
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JP2008315497A JP2010139703A (en) | 2008-12-11 | 2008-12-11 | Method for manufacturing composite polarizing plate |
JP2008315684A JP2010139729A (en) | 2008-12-11 | 2008-12-11 | Method for manufacturing composite polarizing plate |
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TW201028292A true TW201028292A (en) | 2010-08-01 |
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Family Applications (1)
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TW98142236A TW201028292A (en) | 2008-12-11 | 2009-12-10 | Process for producing composite polarizing plate |
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TW (1) | TW201028292A (en) |
WO (1) | WO2010067896A1 (en) |
Cited By (6)
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TWI507500B (en) * | 2010-09-20 | 2015-11-11 | Lg Chemical Ltd | Adhesive for polarizing plate and polarizing plate including the same |
TWI669335B (en) * | 2017-09-04 | 2019-08-21 | 韓國商曉星化學股份有限公司 | Acryl film |
US10495799B2 (en) | 2014-06-25 | 2019-12-03 | Dongwoo Fine-Chem Co., Ltd. | Ultra-thin polarizing plate and liquid crystal display device having same |
TWI727299B (en) * | 2019-04-03 | 2021-05-11 | 奇美實業股份有限公司 | Plate unit, cutting device for cutting the same, and method for manufacturing and processing the same |
TWI764783B (en) * | 2021-07-08 | 2022-05-11 | 大陸商業成科技(成都)有限公司 | Laminating method of polarizer and display thereof |
TWI828799B (en) * | 2018-11-19 | 2024-01-11 | 日商藤森工業股份有限公司 | Surface-protective film and optical component attached with the same |
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JP2012229372A (en) * | 2011-04-27 | 2012-11-22 | Nitto Denko Corp | Tacky adhesive composition and tacky adhesive sheet |
CN110461972B (en) | 2017-03-23 | 2022-04-22 | 三菱化学株式会社 | Laminate, double-sided adhesive sheet, and use thereof |
JP6368410B2 (en) * | 2017-08-24 | 2018-08-01 | リンテック株式会社 | Touch panel |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
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JP4376558B2 (en) * | 2002-07-04 | 2009-12-02 | 富士フイルム株式会社 | Polarizing plate bonding method and apparatus |
JP2004199045A (en) * | 2002-12-04 | 2004-07-15 | Sharp Corp | Optical film and liquid crystal display using it |
JP4306270B2 (en) * | 2003-02-12 | 2009-07-29 | 住友化学株式会社 | Polarizing plate, manufacturing method thereof, optical member, and liquid crystal display device |
JP5016788B2 (en) * | 2004-06-09 | 2012-09-05 | 富士フイルム株式会社 | Cellulose acylate film, polarizing plate and liquid crystal display device |
JP4569396B2 (en) * | 2004-06-16 | 2010-10-27 | 住友化学株式会社 | Retardation film and liquid crystal display device including the same |
JP4770176B2 (en) * | 2005-01-12 | 2011-09-14 | 住友化学株式会社 | Retardation film made of resin multilayer film |
JP2006309114A (en) * | 2005-03-30 | 2006-11-09 | Lintec Corp | Pressure-sensitive adhesive for polarizing plates, polarizing plate having pressure-sensitive adhesive, and production process for polarizing plate |
JP2006018323A (en) * | 2005-09-01 | 2006-01-19 | Nitto Denko Corp | Compound double refraction member |
JP2008040275A (en) * | 2006-08-08 | 2008-02-21 | Nippon Zeon Co Ltd | Polarizing plate for liquid crystal display |
JP5091440B2 (en) * | 2006-08-17 | 2012-12-05 | 日本カーバイド工業株式会社 | Pressure-sensitive adhesive composition for optical member surface protective film and optical member surface protective film |
JP2009258589A (en) * | 2008-03-26 | 2009-11-05 | Sumitomo Chemical Co Ltd | Composite polarizing plate, method of manufacturing composite polarizing plate, and liquid crystal display using it |
JP2009294502A (en) * | 2008-06-06 | 2009-12-17 | Sumitomo Chemical Co Ltd | Composite polarizing plate and liquid crystal display device using the same |
-
2009
- 2009-12-10 WO PCT/JP2009/071013 patent/WO2010067896A1/en active Application Filing
- 2009-12-10 TW TW98142236A patent/TW201028292A/en unknown
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI507500B (en) * | 2010-09-20 | 2015-11-11 | Lg Chemical Ltd | Adhesive for polarizing plate and polarizing plate including the same |
US10495799B2 (en) | 2014-06-25 | 2019-12-03 | Dongwoo Fine-Chem Co., Ltd. | Ultra-thin polarizing plate and liquid crystal display device having same |
TWI669335B (en) * | 2017-09-04 | 2019-08-21 | 韓國商曉星化學股份有限公司 | Acryl film |
TWI828799B (en) * | 2018-11-19 | 2024-01-11 | 日商藤森工業股份有限公司 | Surface-protective film and optical component attached with the same |
TWI727299B (en) * | 2019-04-03 | 2021-05-11 | 奇美實業股份有限公司 | Plate unit, cutting device for cutting the same, and method for manufacturing and processing the same |
TWI764783B (en) * | 2021-07-08 | 2022-05-11 | 大陸商業成科技(成都)有限公司 | Laminating method of polarizer and display thereof |
Also Published As
Publication number | Publication date |
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WO2010067896A1 (en) | 2010-06-17 |
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