TW201213864A

TW201213864A - Three-dimensional image display device

Info

Publication number: TW201213864A
Application number: TW100126187A
Authority: TW
Inventors: Shinji Inagaki; Katsumi Maejima
Original assignee: Konica Minolta Opto Inc
Priority date: 2010-07-29
Filing date: 2011-07-25
Publication date: 2012-04-01
Also published as: WO2012014595A1

Abstract

Provided is a three-dimensional (3D) image display device which achieves reductions in crosstalk and tone change when a display unit is viewed in an oblique direction when a three-dimensional image is viewed, and has excellent viewability. This three-dimensional image display device is a three-dimensional image display device comprising a display unit and liquid crystal shutter glasses, and characterized in that a ?/4 plate and a polarizer are provided in this order from the viewing side in the display unit, a polarizer, a liquid crystal cell, and a ?/4 plate are provided in this order from the viewing side in the liquid crystal shutter glasses, and the total SRt1-n (where n represents an integer) of phase differences (Rt) in the thickness direction of all optical compensation layers and a phase difference (Rtc); in the thickness direction when the shutter of a liquid crystal cell is in a closed state satisfy the following expression (1). (expression 1): -100nm 1-n+Rtc) < 150nm

Description

201213864 六、發明說明：【發明所屬之技術領域】本發明係關於顯示裝置與液晶快門型眼鏡（ Glasses)所構成之立體影像顯示裝置。【先前技術】近年來提倡可顯示立體圖像之電視等之立體圖 ^ 裝置。對於顯示該立體圖像之方式之一，有觀看者用之立體圖像辨識用眼鏡，由觀測者將二次元圖像立體圖像之方式。此方式現有最被看好的是觀看者圖1所示之立體圖像辨識用眼鏡（G )，顯示圖像之中以時序交替切換視差圖像的右眼用圖像及左眼用映射出，而觀看液晶顯示器之圖像的方式（參考例文獻1 )。立體圖像辨識用眼鏡（G )，如圖1所示，係於 Φ 具備液晶快門（S 1 )及（S2 )，並連接控制該等液 (S1)及（S2)之控制電路C。如圖2所示之立體圖像顯示裝置，作爲映射在示器（LCD )上之圖像，係於兩片場域（field )中分配爲左眼用圖像（L1 )及右眼用圖像（R1 )，依該等交互高速切換而顯示。自液晶顯示器（LCD ) 光爲直線偏光。再者’立體圖像辨識用眼鏡G之左快門（S 1 )及（S2 )之開閉切換係與左眼用圖像（右眼用圖像（R1)之切換同步進行。201213864 VI. Description of the Invention: [Technical Field] The present invention relates to a stereoscopic image display device comprising a display device and liquid crystal shutter glasses. [Prior Art] In recent years, a stereoscopic image device such as a television that can display a stereoscopic image has been proposed. One of the ways of displaying the stereoscopic image is a stereoscopic image recognition glasses for a viewer, and a stereoscopic image of the secondary image by the observer. In this method, the stereoscopic image recognition glasses (G) shown in FIG. 1 are most preferred, and the right-eye image and the left-eye image in which the parallax images are alternately switched in time series are displayed in the display image. The way to view the image of the liquid crystal display (refer to Example 1). The stereoscopic image-receiving glasses (G), as shown in Fig. 1, are provided with liquid crystal shutters (S1) and (S2), and are connected to a control circuit C for controlling the liquids (S1) and (S2). The stereoscopic image display device shown in FIG. 2 is an image mapped on a display (LCD) and is assigned as an image for the left eye (L1) and an image for the right eye in two fields. (R1), displayed in accordance with the interactive high-speed switching. The light from the liquid crystal display (LCD) is linearly polarized. Further, the opening and closing switching between the left shutters (S1) and (S2) of the stereoscopic image-receiving glasses G is performed in synchronization with the switching of the image for the left eye (the image for the right eye (R1)).

Shutter 像顯示配戴專辨識爲配戴如顯示器圖像而如專利左右眼晶快門液晶顯，各自時序將射出之右液晶 L1 )及 -5- 201213864 液晶快門（S 1 )及（S 2 )係如圖3所示，具有偏光板 (p 1 )及（P2 )及液晶層（LC )，入射至液晶快門（s 1 )及（S2)之直線偏光之光（L)之旋轉角，藉由使用液晶層（LC )加以控制，而控制自液晶快門（S 1 )及（S2 ) 所射出之光之透射率。如此藉由控制液晶顯示器（LCD ) 及立體圖像辨識用眼鏡（G )，如圖2所示，成爲於液晶顯示器（LCD )中，顯示左眼用圖像（L1 )時右眼用之液晶快門（S 1 )關閉而左眼用之液晶快門（S2 )開啓，相反地，顯示右眼用圖像（R 1 )時右眼用之液晶快門（S 1 )開啓而左眼用液晶快門（S 2 )關閉。又，除了可使用液晶顯示器（LCD)或如使用用以防止反射之圓偏光板之有機EL顯示器之所發出之光爲直線偏光之顯示器以外，亦可使用所發出之光不爲直線偏光之顯示器例如電漿顯示器或未使用用以防止反射之圓偏光板之有機EL顯示器等之自發光型顯示器。由上述液晶顯示器及立體圖像辨識用眼鏡所構成之立體圖像顯示裝置，於頭傾斜時，有亮度降低或色調產生變化之問題。爲了抑制頭傾斜時之亮度降低及抑制色調變化，於液晶顯示器之辨識側及立體圖像辨識用眼鏡之距離眼睛較遠側之表面上分別使用λ /4板係有效。又，於專利文獻2中，爲抑制外光之閃爍、提高眼鏡之亮度，揭示有使用僅使用一片偏光板之眼鏡之立體影像顯示裝置。該文獻中，使於顯示器之前面之圓偏光板、眼鏡之構成成爲λ /4板/液晶胞/直線偏光板，藉此可抑制於 201213864 頭傾斜時之串訊（看上去重影之現象）。如此，關於使用液晶快門之方式，有使用偏光板爲兩片之眼鏡之方式、使用偏光板爲一片之眼鏡之方式，無論任一種方式，爲改善頭傾斜時之顯示性能，λ /4板均有必要。尤其於使用偏光板係一片之眼鏡之方式更爲重要。且，由於立體影像顯示裝置越爲大型效果越大，故大型化之要求非常強烈。因此，要求可於大型顯示器中使用之大型λ /4板。 λ /4板有著與抗反射膜或液晶顯示裝置有關之多種用途，由先前之種種觀點已提案有經改良之λ /4板（例如參考專利文獻3〜6)。然而’有關於體（3D)影像觀賞時自斜向觀看顯示裝置時之串訊抑制以及色調變化之減低，以上述先前技術，尙不充分，而期望更改良技術之開發》 [先前技術文獻] [專利文獻] 專利文獻1 :特開平8-20 1 942號公報專利文獻2 :特開2002-82307號公報專利文獻3 :特開2 0 0 2 - 1 3 1 5 4 0號公報專利文獻4:特開2002-1 27244號公報專利文獻5 :特開2009-48204號公報專利文獻6:特開2006-89529號公報 201213864 【發明內容】 [發明欲解決之課題] 本發明係爲解決上述問題·狀況而發展者，其解決之課題係提供一種可減低在觀賞立體（3 D )影像時自斜面觀看顯示裝置時之串訊及色調變化，且具有優異之辨識性之立體影像顯示裝置。 [解決課題之手段] 本發明之上述課題藉由下列手段得以解決。 1. 一種立體影像顯示裝置，係由顯示裝置及液晶快門型眼鏡（Shutter Glasses)所構成之立體影像顯示裝置，其特徵爲於該顯示裝置，自視覺辨識側起依序設有λ/4 板及偏光子，於該液晶快門型眼鏡，自視覺辨識側起依序設有偏光子、液晶胞及λ/4板，全部之光學補償層之厚度方向相位差Rt之合計SRtu (其中η表示整數）以及液晶胞之快門關閉狀態時之厚度方向之相位差Rtc滿足下述式（1 )：式（1) : -l〇〇nm< (ZRti〜n+Rtc) <150nm。 2. 如前述第1項記載之立體影像顯示裝置，其中前述液晶快門型眼鏡之液晶胞驅動模式爲ECB模式。 3·如前述第1或2項記載之立體影像顯示裝置，其中前述λ/4板之至少一者之Νζ係數在1.1〜4.0之範圍內。 4.如前述第1至3項中任一項記載之立體影像顯示裝置’其中前述顯示裝置之λ/4板的Νζ係數大於前述液晶快 -8 - 201213864 門型眼鏡之λ/4板的Nz係數。 5·如前述第1至4項中任一項記載之立體影像顯示裝置’其中前述顯示裝置之λ/4板具有硬質塗層。 6 ·如前述第1至5項中任一項記載之立體影像顯示裝置’其中前述顯示裝置之λ/4板含有纖維素酯樹脂。 [發明效果] 藉由本發明之上述手段，可提供一種可減低觀看立體 (3D)影像裝置時自斜向觀看顯示裝置時之串訊及色調變化，且具有優異辨識性之立體影像顯示裝置。【實施方式】本發明之立體影像顯示裝置爲由顯示裝置與液晶快門型眼鏡所構成之立體影像顯示裝置，該顯示裝置自視覺辨識側起依序設有λ/4板及偏光子，於該液晶快門型眼鏡，自視覺辨識側起依序設有偏光子、液晶胞及λ / 4板，所有之光學補償層之厚度方向相位差Rt之合計ERt^n (其中η表示整數）與液晶胞之厚度方向之相位差Rtc滿足前述式（t )。該特徵爲申請專利範圍第1至第6項之請求項之發明之共通技術特徵。至於本發明之實施樣態，就展現本發明效果之觀點而言，前述液晶快門型眼鏡之液晶胞之驅動模式較好爲E C B 模式。又，前述λ/4板之至少一方之Nz係數較好爲ι.ι~4.0 之範圍內。而且，前述顯示裝置之λ/4板之Nz係數較好比 201213864 前述液晶快門型眼鏡之λ/4板之Nz係數大。本發明中，前述顯示裝置之λ/4板較好具有硬質塗層。又，該顯示裝置之λ/4板較好爲含有纖維素酯樹脂之樣態。以下針對本發明之構成要素、及實施本發明之形態· 樣態詳細加以說明。又，本說明書中，「~」係以包含其前後所記載之數値作爲下限値及上限値之意義使用。又，本申請案中使用之如下用語及符號之定義如下述。 (1) 「nXJ爲面內之折射率爲最大之方向（亦即，滯相軸方向）的折射率，「nyJ爲面內與滞相軸垂直之方向（亦即，進相軸方向）的折射率，「nz」爲厚度方向的折射率。另外，例如「nx = ny」並非僅指^與1^嚴格相等之情況，亦包含〜與ny實質上相等之情況。本說明書中所謂「實質上相等」亦包含在不對液晶面板整體之光學特性造成實用上影響之範圍內〜與心爲不同之情況的意思。 (2 ) 「面內相位差R〇」意指在23°C . 55%RH下以波長590nm之光測定之薄膜（層）面內之相位差値。R〇係於波長590 nm之薄膜（層）之滯相軸方向、進相軸方向之折射率分別設爲nx、ny，以d ( nm )設爲薄膜（層）之厚度時’以式：R〇= ( ηχ-riy) xd求 f守。 (3 ) 「厚度方向之相位差Rt」意指在23°C . 55%RH 下以波長590nm之光測定之厚度方向之相位差値。Rt爲於波長590 nm之薄膜（層）之滯相軸方向、進相軸方向、厚 201213864 度方向之折射率分別設爲nx、ny、nz，以d ( nm )設爲薄膜（層）之厚度時’以式：Rt={(nx+ ny)/2-nz)}xd求得。 (4 ) 「Nz係數」爲以式：Rt/Ro + 0.5計算出之値。 (立體影像顯示裝置之槪要）本發明之立體影像顯示裝置係由顯示裝置及液晶快門型眼鏡所構成之立體影像顯示裝置，其特徵爲於該顯示裝置，自視覺辨識側起依序設有λ/4板及偏光子，於該液晶快門型眼鏡，自視覺辨識側起依序設有偏光子、液晶胞及 λ/4板，所有之光學補償層之厚度方向相位差之合計SRtl~n (其中η表示整數）與液晶胞之厚度方向之相位差Rtc滿足下述式（1 ): 式（1) : -100nm< ( ZRt i ~n + Rtc ) < 1 5 Onm 此處，上述式（1 )中之表示自第一光學補償層至第η光學補償層之厚度方向之相位差之合計。Rhi及Rtc 之附加字「1」表示第一光學補償層，附加字「2」表示第二光學補償層，附加字「η」表示第η層之光學補償層，附加字「c」表示液晶胞。因此，本發明之立體影像顯示裝置具有第五層光學補償層時，上述式（1)中之SRtu，於第一至第五層之光學補償層之厚度方向之相位差分別設爲Rt丨〜Rt5時， ERti-n = Rti+Rt2 + Rt3 + Rt4 + Rt5 又’本申請案所謂「光學補償層」爲於顯示裝置之前側的偏光子與液晶快門型眼鏡之偏光子之間存在之λ/4板 -11 - 201213864 及TAC薄膜等之偏光板保護膜、其他相位差膜等。至於本發明之實施樣態，前述液晶快門型眼鏡之液晶胞之驅動模式就展現本發明效果之觀點而言，較好爲ECB 模式。關於該液晶胞之驅動模式之細節敘述於.後。另外’前述λ/4板之至少一方之Nz係數較好在1.1~4.0 之範圍內。而且，前述顯示裝置之λ/4板之Nz係數較好比前述液晶快門型眼鏡之λ/4板之Nz係數大。本發明中，前述顯示裝置之λ/4板較好具有硬質塗層 °又’該顯示裝置之λ/4板較好爲含有纖維素酯樹脂之樣態。以下針對本發明之立體影像顯示裝置之各構成要素加以詳細說明。以全部光學補償層之厚度方向相位差之合計SRtl~n ( 其中’ Π表示整數）與液晶胞之厚度方向之相位差Rtc之關係滿足下述式（1)爲其特徵，較好滿足下述式（2)，更好滿足下述式（3)。式（1) :-l〇〇nm< (ERt|〜n+Rtc) <150nm 式（2) : -50nm< ( ERti_n+ Rtc) < 8 0 n m 式（3) :-30nm< (ERt 卜 n+Rtc) <50nm 以下’針對本發明之立體影像顯示裝置之各構成要素加以詳細說明。 (λ/4板）本發明中使用之所謂「λ/4板」意指具有將某特定波 201213864 長之直線偏光轉換成圓偏光（或圓偏光轉換成直線偏光）之功能者。λ/4板相對於特定光之波長（通常爲可見光區域），層之面內相位差値R〇約爲1/4。本發明中，該λ/4板之至少一方之Nz係數較好在 1.1~4.0之範圍內。又，顯示裝置之λ/4板之Nz係數較好比液晶快門型眼鏡之λ/4板之Nz係數大。本發明中之前述顯示裝置之λ/4板較好具有硬質塗層。又，該顯示裝置之λ/4板較好爲含有纖維素酯樹脂之樣態。本發明之λ/4板以波長5 50nm測定之R〇 ( 550 )爲 110〜170nm之範圍內，R〇( 550)較好爲 120〜160nm，Ro( 550)更好爲 130 〜150nm。本發明之λ/4板由於在可見光之波長範圍內獲得幾乎完全的圓偏光，故較好爲在可見光波長之範圍內大致具有波長之1 /4之滯相之相位差板（薄膜）。所謂「在可見光之波長範圍內大槪1 /4之滞相」爲在波長400至700nm之越長波長時之滯相較大，於波長^5〇nm 測定之以下述式（i )表示之滯相値爲以R〇 ( 450 )與於波長5 50nm測定之滯相値Ro ( 5 50 )之差Ro ( 5 50 ) -R〇 ( 450 )較好爲2〜34nm，更好爲4〜32nm，最好爲8〜28nm。式（i ) : Ro= ( nx-ny ) xd .式（Π) ： Rt= { ( nx + ny) /2-nz } xd 式中，nx ' ny 爲於 23。。· 5 5%RH > 45 0nm、5 5 0nm 或 5 90nm下之折射率nx (薄膜之面內之最大折射率、亦指滯 -13- 201213864 相軸方向之折射率）、ny (薄膜面內與滯相軸垂直之方向之折射率），d爲薄膜之厚度（nm)。 R〇、Rt、Θ可使用自動雙折射率計測定。使用自動雙折射率計KOBRA-21ADH (王子計測設備（股）製造），在23 t、55%RH之環境下，藉由測定於各波長之複折射率計算出Ro。Θ係以薄膜長度方向作爲基準（（Γ )。 λ/4板之滯相軸與後述偏光子之透過軸之角度以實質上成爲45°之方式層合時獲得圓偏光板。所謂「實質上爲 45°」意指40〜5 0° » λ/4板之面內之滯相軸與偏光子之透過軸之角度較好爲41〜49°，更好爲42~48°，又更好爲43〜47。，最好爲44〜46°。該λ/4板之至少一方之Νζ係數較好在1.1〜4.0之範圍內，更好在1.3〜3.5之範圍內，最好爲1.5〜2.5之範圍內。〈纖維素酯樹脂〉本發明之λ/4板可使用各種樹脂基材製作，但較好爲含有纖維素酯樹脂之樣態。本發明中可使用之纖維素酯樹脂較好爲由纖維素（二 '三）乙酸酯、纖維素丙酸酯、纖維素丁酸酯、纖維素乙酸酯丙酸酯、纖維素乙酸酯丁酸酯、纖維素乙酸酯苯二甲酸酯、及纖維素苯二甲酸酯等選出之至少一種。該等中最佳之纖維素酯列舉爲纖維素三乙酸酯、纖維素丙酸酯、纖維素丁酸酯、纖維素乙酸酯丙酸酯或纖維素乙酸酯丁酸酯^ -14- 201213864 至於混合脂肪酸酯之取代度以具有碳原子數2〜4之醯基作爲取代基時，以乙醯基之取代度作爲X，丙醯基或丁醯基之取代度作爲Y時，以含有同時滿足下述式（I)及（ II )之纖維素酯之纖維素樹脂較佳。式（I ) 2.0S X+ Y 各 3.0 式（II ) OS XS 2.5 另外，本發明中使用之纖維素酯較好使用重量平均分子量Mw/數平均分子量Μη比爲1.5〜5.5者，最好使用 2.0~5.0，更好2.5〜5.0，又更好3.0〜5.0之纖維素酯。本發明中使用之纖維素酯之原料纖維素可爲木材紙漿甚至是棉籽絨亦可，木材紙漿爲可爲針葉樹亦可爲闊葉樹，但以針葉樹者較佳。就製膜時之剝離性之觀點而言較好使用棉籽絨。由該等製作之纖維素酯可經適當混合使用，或單獨使用。例如，源自棉籽絨之纖維素酯：源自木材紙漿（針葉樹）之纖維素酯：源自木材紙漿（闇葉樹）之纖維素酯之比率可以 100: 〇: 〇、 90: 10: 〇、 85: 15: 0、 50: 50: 0 、20: 80: 0、 10: 90: 0、〇: 100: 〇、〇: 〇: 100、 80: 10:10、85:0:15、40:30:30 使用。本發明中，將纖維素樹脂lg投入於20ml之純水（導電度0.1pS/cm以下，pH6.8)中，在25°C、lhr、氮氣氛圍下攪拌時之pH較好爲6〜7，導電度較好爲1〜i〇(^S/cm。又’本發明之λ/4板只要不損及本發明之效果，亦可倂用上述纖維素乙酸酯以外之熱可塑性樹脂。 -15- 201213864 此處’所謂「熱可塑性樹脂」亦指藉由加熱至坡璃轉移溫度或熔點可變得柔軟，可成形成目的形狀之樹脂^ 熱可塑性樹脂，作爲一般使用之樹脂，可使用聚乙烯 (PE)、高密度聚乙烯、中密度聚乙烯、低密度聚乙烯、聚丙烯（PP)、聚氯乙烯（PVC)、聚偏氯乙烯、聚苯乙烯（PS)、聚乙酸乙烯酯（pVAc )、鐵氟龍（註冊商標 )(聚四氟乙烯，PTFE) 、ABS樹脂（丙烯腈-丁二烯-苯乙烯樹脂）、AS樹脂、丙烯酸樹脂（PMMA )等。另外’特別要求強度或不易破壞之情況，可使用聚醯胺（PA )、尼龍、聚乙縮醛（POM )、聚碳酸酯（PC ) 、改質聚苯醚（m-PPE、改質PPE、PPO)、聚對苯二甲酸丁二酯（PBT)、聚對苯二甲酸乙二酯（PET)、玻璃纖維強化之聚對苯二甲酸乙二酯（GF-PET)、環狀聚烯烴（ COP )等。另外，要求高的熱變形溫度及可長期使用之特性時，可使用聚苯硫醚（PPS)、聚四氟乙烯（PTFE)、聚颯、聚醚颯、非晶聚丙烯酸酯、液晶聚合物、聚醚醚酮、熱可塑性聚醯亞胺（PI )、聚醯胺醯亞胺（PAI )等。又，依據本發明用途而定可進行樹脂種類、分子量之組合。另外’工業上係以硫酸作爲觸媒合成纖維素樹脂，但於該硫酸未完全被去除，殘留硫酸在熔融製膜時會引起各種分解反應，而對所得纖維素樹脂薄膜之品質造成影響，故本發明中使用之纖維素樹脂中殘留之硫酸含量以硫元素 -16- 201213864 換算較好在〇·卜40ppm之範圍。該等認爲係以鹽之形態含有。殘留硫酸含量超過4 0 p p m時由於熱熔融時模唇之附著物增加故較不佳。又，熱延伸時或熱延伸後之分條（ slitting)時容易斷裂故而不佳。雖較少較佳，但未達0.1 時不僅由於纖維素樹脂之洗淨步驟之負擔變得太大而不佳，且相反地有容易斷裂之情況而不佳。增加該洗淨次數或許會對該樹脂造成影響，但原因尙未不清楚。再者以 0.1~30ppm之範圍較佳。殘留硫酸含量同樣可藉由ASTM-D 8 1 7 - 9 6 '測定。又，含有其他（乙酸）等殘留酸之總殘留酸量較好爲 1000 ppm以下，更好爲500 ppm以下，又更好爲100 ppm以下。纖維素樹脂之洗淨除水外，亦可使用如甲醇、乙醇之弱溶劑，或者作爲結果若爲弱溶劑則可使用弱溶劑與良溶劑之混合溶劑，可去除殘硫酸以外之無機物、低分子之有機雜質。又，爲了提高纖維素樹脂之耐熱性、機械物性、光學物性等，可在溶解於纖維素樹脂之良溶劑中之後，於弱溶劑中再沉澱，去除纖維素樹脂之低分子量成分、其他雜質。進而，亦可於纖維素樹脂之再沉澱處理後，添加其他聚合物或低分子化合物。另外，本發明中使用之纖維素樹脂較好爲成爲薄膜時之亮點異物較少者。所謂亮點異物爲將兩片偏光板垂直配置（正交偏振（crossed nicols))，於其間配置纖維素樹 -17- 201213864 脂膜’對準自一面投射光源之光，自另一面觀察纖維素樹脂膜時，看見光源之光洩漏之點。此時評價所用之偏光板宜爲以無亮點異物之保護膜構成者，較好使用以玻璃板對偏光子予以保護者。亮點異物認爲其原因之一係纖維素樹脂中所含之未醋化或低醋化度之纖維素，使用亮點異物少之纖維素樹脂時，以過濾熔融之纖維素樹脂或纖維素樹脂溶液，或者於纖維素樹脂之合成後期之過程或獲得沉澱物之過程之至少任一者中，以一次溶液狀同樣經由過滅步驟亦可去除亮點異物。熔融樹脂由於黏度高，故以後者方法效率較高。雖有薄膜之膜厚愈薄則每單位面積之亮點異物數愈少 ’薄膜中所含纖維素樹脂之含量愈少亮點異物愈少之傾向 ’但較好亮點異物係亮點之直徑0.01 nm以上爲200個/cm2 以下，更好爲100個/cm2以下，又更好爲50個/cm2以下，再更好爲30個/cm2以下，又再更好爲10個/cm2以下，但最好爲全部沒有。另外，關於0.005〜0.01mm以下之亮點爲200 個/cm2以下較佳，更好爲1〇〇個/cm2以下，又更好爲50個 /cm2以下，再更好爲30個/cm2以下，又再更好爲1〇個/cm2 以下，最好爲全部沒有》藉由過濾去除亮點異物時，相較於單獨過濾纖維素樹脂，使添加混合有可塑劑、紫外線吸收劑、抗氧化劑、安定劑等而成之纖維素樹脂組成物（亦稱爲摻雜物）過濾，其提高亮點異物之去除效率較好。當然，亦可在纖維素樹脂合成時藉由溶解於溶劑中並經過濾而降低。過濾較好在 -18- 201213864 含有纖維素樹脂之溶融物之黏度爲1 000 OP以下過濾，更好爲5000P以下，又更好爲1 000P以下，再更好爲500P以下。至於濾材較好使用玻璃纖維、纖維素纖維、濾紙、四氟化乙烯樹脂等之氟樹脂等之過去習知者，但最好使用陶瓷、金屬等。至於絕對過濾精度較好使用50 μιη以下者，更好使用3 0μηι以下者，又更好使用1(^m以下者，再更好使用5μιη 以下者。該等可適宜組合使用。濾材可使用表面型亦可使 | 用浸漬型’但浸漬型者比較不易阻塞故較適用。本發明之λ/4板亦可爲適當混合纖維素樹脂以外之高分子成分者。混合之高分子成分較好爲與纖維素樹脂之相溶性優異者’作成薄膜時之透射率宜爲8 〇 %以上，更好爲 90%以上’又更好爲92%以上。 (有機溶劑）溶解纖維素酯形成纖維素酯溶液或摻雜物中有用之有 φ 機溶劑有氯系有機溶劑或非氯系有機溶劑。氯系有機溶劑可列舉爲二氯甲烷（methylene chloride)，適於對纖維素醋’尤其是纖維素三乙酸酯之溶解。基於目前之環境問題已探討非氯系有機溶劑之使用。非氯系有機溶劑可列舉爲例如乙酸甲酯、乙酸乙酯、乙酸戊酯、丙酮、四氫呋喃、 1，3-—氧雜環戊烷、丨，4_二噁烷 '環己酮、甲酸乙酯、 2,2,2-二氟乙醇、2,2,3,3_六氟_丨_丙醇、丨，3-二氟_2_丙醇、 1，1，1，3,3,3-六氟-2-甲基-2-丙醇、1，i，：i，3,3,3-六氟-2-丙醇、2,2,3’3,3 -五氟-1-丙醇、硝基乙烷等。對於纖維素三乙 -19- 201213864 酸酯使用該等有機溶劑時，亦可使用在常溫下溶解之方法，但藉由使用高溫溶解方法、冷卻溶解方法、高壓溶解方法等溶解方法可減少不溶物故較佳。相對於纖維素三乙酸酯之纖維素酯，可使用二氯甲烷，但較好使用乙酸甲酯、乙酸乙酯、丙酮。最好爲乙酸甲酯。本發明中，對於上述纖維素酯具有良好溶解性之有機溶劑稱爲良溶劑，又對於溶解顯示主要效果，其中大量使用之有機溶劑稱爲主（有機）溶劑或主要（有機）溶劑。本發明中使用之摻雜物除上述有機溶劑以外，較好含有1〜40質量％之碳原子數1~4之醇類。於將摻雜物澆鑄於金屬支撐體上後，使溶劑開始蒸發而醇之比率變多時，會使摻雜物膜（薄片（web ))凝膠化，該等溶劑可使用作爲使薄片強韌地自金屬支撐體輕易地剝離之凝膠化溶劑，其等之比例少時亦具有促進非氯系有機溶劑對纖維素酯溶解之角色。碳原子數1~4之醇類可列舉爲甲醇、乙醇、正丙醇、異丙醇、正丁醇、第二丁醇、第三丁醇。該等中就摻雜物之安定性優異、沸點亦較低、乾燥性優異等而言以乙醇較佳。該等有機溶劑單獨對於纖維素酯不具有溶解性故稱爲弱溶劑。就可提高良好薄膜面品質方面而言，較好調製成摻雜物中之纖維素酯之濃度爲15〜30質量％，摻雜物黏度爲100〜 500Pa . s之範圍。至於添加於摻雜物中之添加劑，有可塑劑、紫外線吸收劑、滞相調整劑、抗氧化劑、劣化防止劑、剝離助劑、 -20- 201213864 界面活性劑、染料、微粒子等。本發明中，關於微粒子以外之添加劑，可於纖維素酯溶液之調製過程中添加，亦可於微粒子分散液之調製過程中添加。液晶圖像顯示裝置中使用之偏光板中較好添加賦予耐熱耐濕性之可塑劑、抗氧化劑或紫外線吸收劑等。以下說明添加劑。 (以一般式A ( 1 )表示之化合物）以下敘述本發明之以下述一般式A (1)表示之化合物及參考化合物，但本發明並不限於該等。一般式A ( 1 )中，R!各獨立表示經取代或未經取代之烷基羰基，或者經取代或未經取代之芳基羰基， RrRs可相同亦可不同。又，下表中所述之R表示汉广^中之任一者。烷基羰基及芳基羰基之取代基較好爲下表中所示之烷基羰基及芳基羰基所具有之苯基、烷氧基等之取代基。The Shutter image shows that the wearer is specially designed to wear the image such as the display, such as the patented left and right eye shutter LCD display, the right timing will be emitted to the right liquid crystal L1) and -5 - 201213864 liquid crystal shutter (S 1 ) and (S 2) As shown in FIG. 3, the polarization angles of the linearly polarized light (L) incident on the liquid crystal shutters (s 1 ) and (S2) are provided by the polarizing plates (p 1 ) and (P2) and the liquid crystal layer (LC). The liquid crystal layer (LC) is used to control the transmittance of light emitted from the liquid crystal shutters (S1) and (S2). Thus, by controlling the liquid crystal display (LCD) and the stereoscopic image-receiving glasses (G), as shown in FIG. 2, the liquid crystal display (LCD) displays the liquid crystal for the right eye when the image for the left eye (L1) is displayed. The shutter (S 1 ) is closed and the liquid crystal shutter (S2) for the left eye is opened. Conversely, when the right eye image (R 1 ) is displayed, the liquid crystal shutter (S 1 ) for the right eye is opened and the liquid crystal shutter for the left eye is opened ( S 2 ) is off. Further, in addition to a display which can use a liquid crystal display (LCD) or an organic EL display using a circular polarizing plate for preventing reflection as a linearly polarized light, a display in which the emitted light is not linearly polarized can be used. For example, a self-luminous type display such as a plasma display or an organic EL display which does not use a circular polarizing plate for preventing reflection. The stereoscopic image display device comprising the liquid crystal display and the stereoscopic image-recognizing glasses has a problem that the brightness is lowered or the color tone is changed when the head is tilted. In order to suppress the decrease in brightness and suppress the change in color tone when the head is tilted, it is effective to use the λ /4 plate on the identification side of the liquid crystal display and the surface of the stereoscopic image recognition lens on the far side of the eye. Further, in Patent Document 2, in order to suppress the flicker of external light and increase the brightness of the glasses, a stereoscopic image display device using glasses using only one polarizing plate has been disclosed. In this document, the configuration of the circular polarizing plate and the glasses on the front side of the display is λ / 4 plate / liquid crystal cell / linear polarizing plate, thereby suppressing the crosstalk when the head tilts at 201213864 (the phenomenon of ghosting appears) . In this way, regarding the method of using the liquid crystal shutter, there is a method in which the polarizing plate is used as two pieces of glasses, and a method in which the polarizing plate is used as one piece of glasses, and in either case, in order to improve display performance when the head is tilted, the λ /4 board is Is necessary. It is especially important to use a piece of glasses with a polarizing plate. Moreover, since the larger the stereoscopic image display device is, the larger the effect is, the demand for the enlargement is very strong. Therefore, a large λ /4 board that can be used in a large display is required. The λ / 4 plate has various uses relating to an antireflection film or a liquid crystal display device, and a modified λ /4 plate has been proposed from various viewpoints (for example, refer to Patent Documents 3 to 6). However, there is a reduction in crosstalk suppression and a change in hue when viewing a display device from an oblique view in view of a body (3D) image. With the above prior art, it is not sufficient, and it is desired to change the development of good technology. [Prior Art Document] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A-2002-82307 (Patent Document No. JP-A-2002-82307) Patent Document 3: JP-A-2002-A. JP-A-2002-48204, JP-A-2009-48204, JP-A-2006-48204, JP-A-2006-64, 228 The development of the problem is to provide a stereoscopic image display device which can reduce crosstalk and color tone changes when viewing a display device from a beveled surface when viewing stereoscopic (3D) images, and has excellent visibility. [Means for Solving the Problems] The above problems of the present invention are solved by the following means. A stereoscopic image display device comprising a display device and a liquid crystal shutter type shutter (Shutter Glasses), wherein the display device is provided with a λ/4 plate from the visual recognition side. And the polarizer, in the liquid crystal shutter type glasses, the polarizer, the liquid crystal cell and the λ/4 plate are sequentially provided from the visual recognition side, and the total retardation phase difference Rt of all the optical compensation layers is SRtu (where η represents an integer And the phase difference Rtc in the thickness direction when the shutter of the liquid crystal cell is in the closed state satisfies the following formula (1): Formula (1): -l〇〇nm < (ZRti~n+Rtc) < 150 nm. 2. The stereoscopic image display device according to Item 1, wherein the liquid crystal cell driving mode of the liquid crystal shutter type glasses is an ECB mode. The stereoscopic image display device according to the first or second aspect, wherein the at least one of the λ/4 plates has a Νζ coefficient in a range of 1.1 to 4.0. 4. The stereoscopic image display device according to any one of the preceding items 1 to 3 wherein the Νζ/4 plate of the display device has a Νζ coefficient greater than that of the liquid crystal -8 - 201213864 λ/4 plate of the spectacles coefficient. The stereoscopic image display device of any one of the above-mentioned items 1 to 4 wherein the λ/4 plate of the display device has a hard coat layer. The stereoscopic image display device according to any one of the above items 1 to 5 wherein the λ/4 plate of the display device contains a cellulose ester resin. [Effect of the Invention] According to the above-described means of the present invention, it is possible to provide a stereoscopic image display device which is capable of reducing crosstalk and color change when viewing a display device from an oblique direction when viewing a stereoscopic (3D) video device, and having excellent visibility. [Embodiment] The stereoscopic image display device of the present invention is a stereoscopic image display device comprising a display device and liquid crystal shutter glasses, wherein the display device is provided with a λ/4 plate and a polarizer in this order from the visual recognition side. The liquid crystal shutter type glasses are provided with a polarizer, a liquid crystal cell, and a λ / 4 plate in order from the visual recognition side, and the total retardation phase difference Rt of all the optical compensation layers is ERt^n (where η represents an integer) and the liquid crystal cell The phase difference Rtc in the thickness direction satisfies the above formula (t). This feature is a common technical feature of the invention of the claims of claims 1 to 6. As for the embodiment of the present invention, in view of the effect of the present invention, the driving mode of the liquid crystal cell of the liquid crystal shutter type lens is preferably the E C B mode. Further, the Nz coefficient of at least one of the λ/4 plates is preferably in the range of ι.ι to 4.0. Further, the Nz coefficient of the λ/4 plate of the display device is preferably larger than the Nz coefficient of the λ/4 plate of the liquid crystal shutter type lens of 201213864. In the present invention, the λ/4 plate of the display device preferably has a hard coat layer. Further, the λ/4 plate of the display device is preferably in the form of a cellulose ester resin. Hereinafter, constituent elements of the present invention and aspects and aspects for carrying out the present invention will be described in detail. In the present specification, "~" is used in the sense that the number 値 described before and after is used as the lower limit 値 and the upper limit 値. Further, the following terms and symbols used in the present application are as follows. (1) "nXJ is the refractive index of the direction in which the refractive index in the plane is the largest (that is, the direction of the slow axis), "nyJ is the direction perpendicular to the slow axis in the plane (that is, the direction of the phase axis) The refractive index, "nz", is the refractive index in the thickness direction. In addition, for example, "nx = ny" does not mean that ^ is strictly equal to 1^, and includes a case where ~ is substantially equal to ny. In the present specification, "substantially equal" is also included in the range that does not affect the optical characteristics of the entire liquid crystal panel, and is different from the heart. (2) "In-plane phase difference R 〇" means a phase difference 値 in the plane of a film (layer) measured by light having a wavelength of 590 nm at 23 ° C. 55% RH. The refractive index of the R(R) system at a wavelength of 590 nm in the slow axis direction and the direction of the phase axis is set to nx and ny, respectively, and when d (nm) is the thickness of the film (layer), the formula is as follows: R〇= ( ηχ-riy) xd seeks f. (3) "Phase difference Rt in the thickness direction" means a phase difference 値 in the thickness direction measured by light having a wavelength of 590 nm at 23 ° C. 55% RH. Rt is the refractive index of the film (layer) at a wavelength of 590 nm in the slow axis direction, the phase in the axial direction, and the thickness in the 201213864 degree direction, and is set to nx, ny, and nz, respectively, and d (nm) is used as a film (layer). When the thickness is 'in the formula: Rt={(nx+ ny)/2-nz)}xd is obtained. (4) The "Nz coefficient" is calculated by the formula: Rt/Ro + 0.5. The stereoscopic image display device of the present invention is a stereoscopic image display device comprising a display device and liquid crystal shutter glasses, wherein the display device is sequentially provided from the visual recognition side. λ/4 plate and polarizer, in the liquid crystal shutter type glasses, the polarizer, the liquid crystal cell and the λ/4 plate are sequentially provided from the visual recognition side, and the total thickness difference of the optical compensation layers is SRtl~n (where η represents an integer) and the phase difference Rtc of the thickness direction of the liquid crystal cell satisfy the following formula (1): Formula (1): -100 nm < (ZRt i ~n + Rtc ) < 1 5 Onm Here, the above formula (1) represents the total of the phase differences in the thickness direction from the first optical compensation layer to the n-th optical compensation layer. The additional word "1" of Rhi and Rtc represents the first optical compensation layer, the additional word "2" represents the second optical compensation layer, the additional word "η" represents the optical compensation layer of the nth layer, and the additional word "c" represents the liquid crystal cell. . Therefore, when the stereoscopic image display device of the present invention has the fifth optical compensation layer, the phase difference in the thickness direction of the optical compensation layers of the first to fifth layers of SRtu in the above formula (1) is respectively set to Rt丨~ At Rt5, ERti-n = Rti+Rt2 + Rt3 + Rt4 + Rt5 Further, the "optical compensation layer" in the present application is λ/ between the polarizer on the front side of the display device and the polarizer of the liquid crystal shutter type glasses. 4 plate-11 - 201213864 and polarizing plate protective film such as TAC film, other retardation film, etc. As for the embodiment of the present invention, the driving mode of the liquid crystal cell of the liquid crystal shutter type lens is preferably an ECB mode from the viewpoint of exhibiting the effect of the present invention. The details of the driving mode of the liquid crystal cell are described later. Further, the Nz coefficient of at least one of the aforementioned λ/4 plates is preferably in the range of 1.1 to 4.0. Further, the Nz coefficient of the λ/4 plate of the display device is preferably larger than the Nz coefficient of the λ/4 plate of the liquid crystal shutter type lens. In the present invention, the λ/4 plate of the display device preferably has a hard coat layer, and the λ/4 plate of the display device preferably contains a cellulose ester resin. Hereinafter, each constituent element of the three-dimensional image display device of the present invention will be described in detail. The relationship between the phase difference of the thickness direction of all the optical compensation layers SRtl~n (wherein Π represents an integer) and the phase difference Rtc in the thickness direction of the liquid crystal cell satisfy the following formula (1), and preferably satisfies the following Formula (2) preferably satisfies the following formula (3). Formula (1): -l〇〇nm<(ERt|~n+Rtc) <150nm Formula (2): -50nm<( ERti_n+ Rtc) < 8 0 nm Formula (3) : -30 nm < (ERt n+Rtc) <50 nm or less' Each component of the stereoscopic image display device of the present invention will be described in detail. (λ/4 plate) The "λ/4 plate" used in the present invention means a function of converting linear polarization of a specific wave of 201213864 into circularly polarized light (or circularly polarized light into linearly polarized light). The in-plane phase difference 値R〇 of the λ/4 plate is about 1/4 with respect to the wavelength of the specific light (usually the visible region). In the present invention, the Nz coefficient of at least one of the λ/4 plates is preferably in the range of 1.1 to 4.0. Further, the Nz coefficient of the λ/4 plate of the display device is preferably larger than the Nz coefficient of the λ/4 plate of the liquid crystal shutter type glasses. The λ/4 plate of the aforementioned display device in the present invention preferably has a hard coat layer. Further, the λ/4 plate of the display device is preferably in the form of a cellulose ester resin. The λ/4 plate of the present invention has a R 〇 ( 550 ) of 110 to 170 nm measured at a wavelength of 5 50 nm, R 〇 550 is preferably 120 to 160 nm, and Ro (550) is more preferably 130 to 150 nm. Since the λ/4 plate of the present invention obtains almost complete circularly polarized light in the wavelength range of visible light, it is preferably a phase difference plate (film) having a phase of 1/4 of a wavelength in the range of visible light wavelength. The "stagnation phase which is greater than 1 / 4 in the wavelength range of visible light" is a large stagnation phase at a wavelength longer than the wavelength of 400 to 700 nm, and is determined by the following formula (i) at a wavelength of 5 〇 nm. The retardation 値 is the difference between the R 〇 ( 450 ) and the stagnation phase 値 Ro ( 5 50 ) measured at a wavelength of 50 50 nm. Ro ( 5 50 ) - R 〇 (450 ) is preferably 2 to 34 nm, more preferably 4 to 4 32 nm, preferably 8 to 28 nm. Equation (i): Ro= ( nx-ny ) xd . (式) : Rt= { ( nx + ny) /2-nz } xd where nx ' ny is 23. . · 5 5% RH > 45 0nm, 550 nm or 5 90nm refractive index nx (the maximum refractive index in the plane of the film, also refers to the refractive index of the lag-13-201213864 phase axis), ny (film surface) The refractive index in the direction perpendicular to the slow axis, and d is the thickness (nm) of the film. R〇, Rt, Θ can be measured using an automatic birefringence meter. Using an automatic birefringence meter KOBRA-21ADH (manufactured by Oji Scientific Instruments Co., Ltd.), Ro was calculated by measuring the complex refractive index at each wavelength in an environment of 23 t and 55% RH. The lanthanum is based on the longitudinal direction of the film ((Γ). When the stagnation axis of the λ/4 plate and the transmission axis of the polarizer described later are laminated at substantially 45°, a circular polarizing plate is obtained. 45° means 40~5 0° » The angle between the slow axis of the λ/4 plate and the transmission axis of the polarizer is preferably 41 to 49°, more preferably 42 to 48°, and better. 43~47., preferably 44~46°. The Νζ coefficient of at least one of the λ/4 plates is preferably in the range of 1.1 to 4.0, more preferably in the range of 1.3 to 3.5, and most preferably 1.5~ In the range of 2.5. <Cellulose Ester Resin> The λ/4 plate of the present invention can be produced using various resin substrates, but is preferably a cellulose ester resin. The cellulose ester resin which can be used in the present invention is more Good as cellulose (di-tris) acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate benzene At least one selected from the group consisting of dibasic acid esters and cellulose phthalates. The best cellulose esters are listed as cellulose triacetate and cellulose C. Acid ester, cellulose butyrate, cellulose acetate propionate or cellulose acetate butyrate ^ -14- 201213864 As for the degree of substitution of the mixed fatty acid ester to have a fluorenyl group having 2 to 4 carbon atoms In the case of a substituent, when the degree of substitution of the ethyl thiol group is taken as X, and the degree of substitution of the propyl fluorenyl group or the butyl fluorenyl group is taken as Y, the cellulose resin containing the cellulose ester satisfying the following formulas (I) and (II) is more preferable. Preferably, the formula (I) 2.0S X+ Y is 3.0 (II) OS XS 2.5 In addition, the cellulose ester used in the present invention preferably has a weight average molecular weight Mw/number average molecular weight Μn ratio of 1.5 to 5.5, preferably. The cellulose ester of 2.0~5.0, more preferably 2.5~5.0, and even more preferably 3.0~5.0. The cellulose of the cellulose ester used in the invention may be wood pulp or even cotton linters, and the wood pulp may be The coniferous tree may also be a broad-leaved tree, but it is preferably a coniferous tree. It is preferable to use cotton linter in terms of the releasability at the time of film formation, and the cellulose ester produced by the above may be suitably mixed or used alone. Cellulose ester derived from cottonseed: derived from wood pulp (needle Cellulose ester of leaf tree: The ratio of cellulose ester derived from wood pulp (dark tree) can be 100: 〇: 〇, 90: 10: 〇, 85: 15: 0, 50: 50: 0, 20: 80: 0, 10: 90: 0, 〇: 100: 〇, 〇: 〇: 100, 80: 10:10, 85:0:15, 40:30:30. In the present invention, the cellulose resin lg In 20 ml of pure water (conductivity 0.1 pS/cm or less, pH 6.8), the pH is preferably 6 to 7 when stirred at 25 ° C, 1 hr, and nitrogen atmosphere, and the conductivity is preferably 1 to i. 〇 (^S/cm. Further, the λ/4 plate of the present invention may be a thermoplastic resin other than the above cellulose acetate as long as the effects of the present invention are not impaired. -15- 201213864 Here, the term "thermoplastic resin" also refers to a resin which can be softened by heating to the transition temperature or melting point of the glass, and can be formed into a desired shape. Thermoplastic resin can be used as a resin for general use. Polyethylene (PE), high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (pVAc), Teflon (registered trademark) (polytetrafluoroethylene, PTFE), ABS resin (acrylonitrile-butadiene-styrene resin), AS resin, acrylic resin (PMMA), and the like. In addition, polyamine (PA), nylon, polyacetal (POM), polycarbonate (PC), modified polyphenylene ether (m-PPE, modified PPE) can be used in particular for strength or damage. , PPO), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), glass fiber reinforced polyethylene terephthalate (GF-PET), cyclic polyolefin (COP) and so on. In addition, when high heat distortion temperature and long-term use characteristics are required, polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), polyfluorene, polyether fluorene, amorphous polyacrylate, liquid crystal polymer can be used. , polyetheretherketone, thermoplastic polyimine (PI), polyamidimide (PAI), and the like. Further, a combination of a resin type and a molecular weight can be carried out depending on the use of the present invention. In addition, industrially, sulfuric acid is used as a catalyst to synthesize a cellulose resin. However, since the sulfuric acid is not completely removed, residual sulfuric acid causes various decomposition reactions during melt film formation, which affects the quality of the obtained cellulose resin film. The content of sulfuric acid remaining in the cellulose resin used in the present invention is preferably in the range of 40 ppm in terms of sulfur element-16-201213864. These are considered to be in the form of salt. When the residual sulfuric acid content exceeds 40 p p m, it is less preferable because the adhesion of the lip is increased during hot melting. Moreover, it is not preferable because it is easily broken at the time of heat stretching or slitting after heat stretching. Although less preferred, when it is less than 0.1, not only is the burden of the washing step of the cellulose resin too large, but it is not preferable because it is easily broken. Increasing the number of times of washing may affect the resin, but the reason is not clear. Further, it is preferably in the range of 0.1 to 30 ppm. The residual sulfuric acid content can likewise be determined by ASTM-D 8 1 7 - 9 6 '. Further, the total residual acid amount of the residual acid containing other (acetic acid) is preferably 1000 ppm or less, more preferably 500 ppm or less, still more preferably 100 ppm or less. In addition to water, the cellulose resin may be used as a weak solvent such as methanol or ethanol, or as a result, a weak solvent may be used as a mixed solvent of a weak solvent and a good solvent to remove inorganic substances and low molecules other than residual sulfuric acid. Organic impurities. Further, in order to improve the heat resistance, mechanical properties, optical properties, and the like of the cellulose resin, it may be reprecipitated in a weak solvent after being dissolved in a good solvent of the cellulose resin to remove low molecular weight components and other impurities of the cellulose resin. Further, other polymers or low molecular compounds may be added after the reprecipitation treatment of the cellulose resin. Further, it is preferred that the cellulose resin used in the present invention has a small amount of foreign matter when it is a film. The so-called bright spot foreign matter is to arrange two polarizing plates vertically (crossed nicols), and a cellulose tree-17-201213864 lipid film is disposed between them to align the light from one side of the light source, and the cellulose resin film is observed from the other side. When you see the point where the light from the light source leaks. The polarizing plate used for the evaluation at this time is preferably a protective film made of a foreign material having no bright spots, and it is preferable to use a glass plate to protect the polarizer. The bright spot foreign matter is considered to be one of the reasons for the cellulose which is not vinegar or low in vinegar contained in the cellulose resin, and to filter the molten cellulose resin or the cellulose resin solution when the cellulose resin having less foreign matter is used. In at least one of the process of synthesizing the cellulose resin or the process of obtaining a precipitate, the bright spot foreign matter can also be removed in the form of a single solution through the extinction step. Since the molten resin has a high viscosity, the latter method is highly efficient. Although the film thickness of the film is thinner, the number of bright spots per unit area is smaller. The less the content of the cellulose resin contained in the film is, the less the foreign matter is. The better the brightness of the bright spot is 0.01 nm or more. 200 pieces/cm2 or less, more preferably 100 pieces/cm2 or less, more preferably 50 pieces/cm2 or less, even more preferably 30 pieces/cm2 or less, and even more preferably 10 pieces/cm2 or less, but it is preferably None at all. Further, the bright spot of 0.005 to 0.01 mm or less is preferably 200 pieces/cm 2 or less, more preferably 1 inch/cm 2 or less, still more preferably 50 pieces/cm 2 or less, and even more preferably 30 pieces/cm 2 or less. Further, it is preferably 1 〇/cm 2 or less, preferably not all. By removing the bright foreign matter by filtration, the plasticizer, the ultraviolet absorber, the antioxidant, and the stabilizer are added in combination with the cellulose filter alone. The cellulose resin composition (also referred to as a dopant) formed by the agent is filtered, and the removal efficiency of the bright spot foreign matter is improved. Of course, it can also be reduced by dissolving in a solvent and filtering by cellulose resin synthesis. The filtration preferably is -18-201213864. The viscosity of the melt containing the cellulose resin is less than 1 000 OP, more preferably less than 5000 P, more preferably less than 1 000 P, and even more preferably less than 500 P. As the filter material, those conventionally used such as glass fiber, cellulose fiber, filter paper, fluororesin such as tetrafluoroethylene resin, etc., are preferably used, but ceramics, metals, and the like are preferably used. As for the absolute filtration accuracy, it is better to use 50 μιη or less, and it is better to use 3 0μηι or less, and it is better to use 1 (^m or less, and then 5μιη or less. These can be used in combination. The filter material can be used on the surface. The type may also be used as the impregnated type, but the impregnated type is relatively difficult to block. Therefore, the λ/4 plate of the present invention may be a polymer component other than the cellulose resin. The mixed polymer component is preferably When the compatibility with the cellulose resin is excellent, the transmittance when forming a film is preferably 8 〇% or more, more preferably 90% or more, and more preferably 92% or more. (Organic solvent) Dissolving cellulose ester to form cellulose ester The solvent or the dopant may be a chloro organic solvent or a non-chlorine organic solvent. The chlorine-based organic solvent may be exemplified by methylene chloride, which is suitable for cellulose vinegar, especially cellulose. Dissolution of triacetate. The use of non-chlorinated organic solvents has been investigated based on current environmental problems. Examples of non-chlorinated organic solvents are methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran. , 1,3- oxacyclohexane, hydrazine, 4 dioxin 'cyclohexanone, ethyl formate, 2,2,2-difluoroethanol, 2,2,3,3_hexafluoro_丨_propanol, hydrazine, 3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,i,:i,3 , 3,3-hexafluoro-2-propanol, 2,2,3'3,3-pentafluoro-1-propanol, nitroethane, etc. For cellulose triethyl-19-201213864 acid ester When an organic solvent is used, a method of dissolving at a normal temperature may be used, but it is preferable to use a dissolution method such as a high-temperature dissolution method, a cooling dissolution method, or a high-pressure dissolution method to reduce insoluble matter, which is preferable to the cellulose triacetate fiber. As the ester, methylene chloride can be used, but methyl acetate, ethyl acetate or acetone is preferably used, preferably methyl acetate. In the present invention, an organic solvent having good solubility for the above cellulose ester is called a good solvent. Further, the main effect of the dissolution is shown, and the organic solvent used in a large amount is referred to as a main (organic) solvent or a main (organic) solvent. The dopant used in the present invention preferably contains 1 to 40% by mass in addition to the above organic solvent. Carbon source An alcohol having a sub-number of 1 to 4. After the dopant is cast on the metal support, the solvent is started to evaporate and the ratio of the alcohol is increased, so that the dopant film (web) gels. These solvents can be used as a gelling solvent which allows the sheet to be easily peeled off from the metal support, and when it is small, the role of promoting the dissolution of the cellulose ester by the non-chlorinated organic solvent is also promoted. Examples of the alcohols of ~4 include methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, and third butanol. Among them, the dopant has excellent stability and a low boiling point. Ethanol is preferred in terms of excellent drying property, etc. These organic solvents are not referred to as a weak solvent because they do not have solubility in cellulose ester alone. In terms of improving the quality of the film surface, the concentration of the cellulose ester in the dopant is preferably 15 to 30% by mass, and the dopant viscosity is in the range of 100 to 500 Pa.s. As the additives to be added to the dopant, there are plasticizers, ultraviolet absorbers, retardation adjusters, antioxidants, deterioration inhibitors, release aids, -20-201213864 surfactants, dyes, fine particles, and the like. In the present invention, the additives other than the fine particles may be added during the preparation of the cellulose ester solution, or may be added during the preparation of the fine particle dispersion. A plasticizer, an antioxidant, an ultraviolet absorber or the like which imparts heat and moisture resistance is preferably added to the polarizing plate used in the liquid crystal image display device. The additives are explained below. (Compound represented by the general formula A (1)) Hereinafter, the compound represented by the following general formula A (1) and the reference compound of the present invention are described, but the present invention is not limited thereto. In the general formula A (1), R! each independently represents a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group, and the RrRs may be the same or different. Further, R described in the following table indicates any of Han Guang ^. The substituent of the alkylcarbonyl group and the arylcarbonyl group is preferably a substituent of a phenyl group, an alkoxy group or the like which the alkylcarbonyl group and the arylcarbonyl group shown in the following Table have.

-21 - 201213864 [化1] 一般式A⑴-21 - 201213864 [Chemical 1] General A(1)

化合物編號 R 平均取代度 1-1 —c-ch3 6.0 1-2 —c-ch3 6.1 1-3 ο ". —c-ch3 6.5 1 - 4 —c-ch3 6.9 1—5 9 —c-ch3 7.0 1—6 ? —c-ch3 8.0 1-7 ~^^C}~ch3 6.1 1-8 〇尸—\ V/ CHs 6.5 1-9 6.9 1 -10 J-o 6.1 1-11 』〇 6.5 1-12 6.9 -22- 201213864 [化2] 化合物編號 R 平均取代度 1—13 〇 —c-chch3 ch3 6.Ϊ 1—14 0 —c-chch3 ch3 6.5 1 -15 ο —c-chch3 ch3 6.9 1-16 -c-cH2~^y 6.1 1-17 6.5 1 -18 6.9 1 -19 OCHj -c~vV~OCH3 och3 6.1 1-20 〇ch3 η /=< —c~\_y~OCH3 och3 6.5 1 -21 och3 η /=( "~c~\ y~〇cn^ OCH, 6.9 1-22 5.5 1-23 7.2 (合成例：本發明化合物之合成） -23- 201213864 [化3] 01°¾ ch2ohCompound No. R Average degree of substitution 1-1 —c-ch3 6.0 1-2 —c-ch3 6.1 1-3 ο ". —c-ch3 6.5 1 - 4 —c-ch3 6.9 1—5 9 —c-ch3 7.0 1—6 ? —c-ch3 8.0 1-7 ~^^C}~ch3 6.1 1-8 〇 — —\ V/ CHs 6.5 1-9 6.9 1 -10 Jo 6.1 1-11 』〇6.5 1-12 6.9 -22- 201213864 [Chemical 2] Compound No. R Average degree of substitution 1-13 〇-c-chch3 ch3 6.Ϊ 1—14 0 —c-chch3 ch3 6.5 1 -15 ο —c-chch3 ch3 6.9 1-16 -c-cH2~^y 6.1 1-17 6.5 1 -18 6.9 1 -19 OCHj -c~vV~OCH3 och3 6.1 1-20 〇ch3 η /=< —c~\_y~OCH3 och3 6.5 1 -21 Och3 η /=( "~c~\ y~〇cn^ OCH, 6.9 1-22 5.5 1-23 7.2 (Synthesis Example: Synthesis of the Compound of the Invention) -23- 201213864 [Chemical 3] 01°3⁄4 ch2oh

CH2ORCH2OR

H OR OR HH OR OR H

R (取代數）例示化合物A—1 例示化合物A—2 (1) 例示化合物A—3 (2) 例示化合物A—4 (3) 例示化合物A—5 、〇 w (7)o Ϊ6) -o (5)oR (Substitution number) Exemplary compound A-1 exemplified compound A-2 (1) Exemplary compound A-3 (2) Exemplary compound A-4 (3) Exemplary compound A-5, 〇w (7)o Ϊ6) -o (5)o

於具備攪拌裝置、回流冷凝器、溫度計及氮氣導入管之四頸燒瓶（Kolben)中饋入蔗糖34.2g(0.1莫耳）、苯甲酸酐180.8g( 0.8莫耳）、吡啶379.7g(4.8莫耳），邊攪拌下自氮氣導入管通入氮氣氣泡邊升溫，在7(TC進行酯化反應5小時。接著，使燒瓶內部減壓至4x1 02P a以下，以 60°C餾除過量吡啶後，使燒瓶內部減壓至1.3 XI OPa以下，升溫至120t，餾除苯甲酸酐、生成之苯甲酸之大部分。 -24- 201213864 接著，再添加甲苯1L、0.5質量％之碳酸鈉水溶液30〇g’在 5(TC攪拌30分鐘後，靜置，收取甲苯層。最後’將水l〇〇g 添加於收收之甲苯層中，在常溫下水洗30分鐘後’收取甲苯層，在減壓下（4xl〇2Pa以下）、於60°C飽除甲苯，獲得化合物A-1、A-2、A-3、A-4及A-5之混合物。以HPLC及 LC-MASS解析所得混合物，A-1爲7質量％，A-2爲58質量％，八-3爲23質量％，八-4爲9質量％，八-5爲3質量％。又，藉由使用矽膠之管柱層析儀純化所得混合物之一部分，獲得純度均爲1〇〇%之八-1、人-2、人-3、入-4及八-5。本發明中添加於纖維素乙酸酯薄膜中之以一般式A ( 1 )表示之化合物之總平均取代度爲6.1〜6.9，該取代度之範圍較好爲4.0〜8.0，取代度分布可藉由調節酯化反應時間、或混合取代度不同之化合物而調整成目標之取代度。 (可塑劑）本發明之λ/4板，就提高機械性質、賦予柔軟性、賦予耐吸水性、降低水蒸氣透過濾、調整滯相等之目的，較好添加作爲所謂可塑劑而已知之化合物，例如較好使用磷酸酯或羧酸酯。 λ/4板中可塑劑較好含有1〜40質量％，最好1~30質量％〇磷酸酯可列舉爲例如磷酸三苯酯、磷酸三甲苯酯、磷酸苯酯二苯酯等。羧酸酯可列舉爲例如苯二甲酸酯及檸檬酸酯等，至於 -25- 201213864 苯二甲酸酯可列舉爲例如苯二甲酸二甲酯、磷酸二乙醋、苯二甲酸二辛酯及苯二甲酸二乙基己酯等，又檸檬酸酯可列舉爲檸檬酸乙醯基三乙酯及檸檬酸乙醯基三丁酯。又其他可列舉爲油酸丁酯、亞油酸甲基乙醯酯、癸二酸二丁酯、三乙酸甘油酯（triacetin )等。就該目的而言亦較好使用烷基苯二甲醯基烷基乙醇酸酯。烷基苯二甲醯基烷基乙醇酸酯之烷基爲碳原子數1~8之烷基。烷基苯二甲醯基烷基乙醇酸酯可列舉爲甲基苯二甲醯基甲基乙醇酸酯、乙基苯二甲醯基乙基乙醇酸酯、丙基苯二甲醯基丙基乙醇酸酯、丁基苯二甲醯基丁基乙醇酸酯、辛基苯二甲醯基辛基乙醇酸酯、甲基苯二甲醯基乙基乙醇酸酯、乙基苯二甲醯基甲基乙醇酸酯、乙基苯二甲醯基丙基乙醇酸酯、丙基苯二甲醯基乙基乙醇酸酯、甲基苯二甲醯基丙基乙醇酸酯、甲基苯二甲醯基丁基乙醇酸酯、乙基苯二甲醯基丁基乙醇酸酯、丁基苯二甲醯基甲基乙醇酸酯、丁基苯二甲醯基乙基乙醇酸酯、丙基苯二甲醯基丁基乙醇酸酯、丁基苯二甲醯基丙基乙醇酸酯、甲基苯二甲醯基辛基乙醇酸酯' 乙基苯二甲醯基辛基乙醇酸酯、辛基苯二甲醯基甲基乙醇酸酯、辛基苯二甲醯基乙基乙醇酸酯等，較好使用甲基苯二甲醯基甲基乙醇酸酯、乙基苯二甲醯基乙基乙醇酸酯、丙基苯二甲醯基丙基乙醇酸酯、丁基苯二甲醯基丁基乙醇酸醋、辛基苯二甲醯基辛基乙醇酸酯。且亦可混合兩種以上之該等烷基苯二甲醯基烷基乙醇酸酯。且，亦較好使用日本專利第3 793 1 8 4號公報記載之以 201213864 下述一般式（1)〜（3)表示之檸檬酸酯系可塑劑作爲可塑劑。 [化4] 一般式⑴ ch2—COOC2H5 h3c—coo—c—cooc2hs CH2—COOC^Hjs [化5] 一般式In a four-necked flask (Kolben) equipped with a stirring device, a reflux condenser, a thermometer and a nitrogen introduction tube, 34.2 g (0.1 mol) of sucrose, 180.8 g (0.8 mol) of benzoic anhydride, and 379.7 g of pyridine (4.8 mol) were fed. The ear was heated while passing through a nitrogen gas bubble while stirring, and the esterification reaction was carried out for 5 hours at 7 (TC). Then, the inside of the flask was depressurized to 4×1 02 Pa or less, and the excess pyridine was distilled off at 60 ° C. The inside of the flask was depressurized to 1.3 XI OPa or less, and the temperature was raised to 120 t to distill off most of the benzoic anhydride and the resulting benzoic acid. -24- 201213864 Next, 1 L of toluene and 0.5% by mass of a sodium carbonate aqueous solution of 30% were added. g' is stirred at 5 (TC for 30 minutes, and the toluene layer is collected. Finally, water l〇〇g is added to the collected toluene layer, and after washing at room temperature for 30 minutes, the toluene layer is collected, and the pressure is reduced. The mixture was dissolved under reduced pressure (4×1 〇 2 Pa) at 60 ° C to obtain a mixture of the compounds A-1, A-2, A-3, A-4 and A-5. The obtained mixture was analyzed by HPLC and LC-MASS. A-1 is 7 mass%, A-2 is 58 mass%, octa-3 is 23 mass%, octa-4 is 9% by mass, and octa-5 is 3% by mass. Further, one part of the obtained mixture is purified by using a column chromatography of tannin to obtain VIII-1, human-2, human-3, in-4 and VIII-5 having a purity of 1%. The total average degree of substitution of the compound represented by the general formula A (1) added to the cellulose acetate film is 6.1 to 6.9, and the degree of substitution is preferably in the range of 4.0 to 8.0, and the degree of substitution can be adjusted by The degree of substitution is adjusted to the target by the esterification reaction time or the compound having a different degree of substitution. (Plasticizer) The λ/4 plate of the present invention improves mechanical properties, imparts softness, imparts water absorption resistance, and reduces water vapor permeability. For the purpose of filtering and adjusting the lag, it is preferred to add a compound known as a so-called plasticizer, for example, a phosphate or a carboxylic acid ester is preferably used. The plasticizer in the λ/4 plate preferably contains 1 to 40% by mass, preferably 1~. The 30% by mass of the phosphonium phosphate may, for example, be triphenyl phosphate, tricresyl phosphate or diphenyl phosphate. The carboxylic acid ester may, for example, be a phthalic acid ester or a citric acid ester. 201213864 phthalate ester can be exemplified by, for example, phthalic acid Ester, diethyl sulphate, dioctyl phthalate and diethyl hexyl phthalate, and citrate can be exemplified by ethyl citrate triethyl citrate and butyl citrate tributyl acrylate. Other examples include butyl oleate, methyl acetyl linoleate, dibutyl sebacate, triacetin, etc. For this purpose, an alkyl phthalic acid group is also preferably used. Alkyl glycolate. The alkyl group of alkyl phthalic acid alkyl glycolate is an alkyl group having 1 to 8 carbon atoms. The alkyl phthalic acid alkyl glycolate can be exemplified as methyl benzene. Dimethylhydrazine methyl glycolate, ethyl phthalic acid ethyl glycolate, propyl phthalic acid propyl glycolate, butyl phthalic acid butyl glycolate, octyl Benzo dimethyl octyl glycolate, methyl phthalic acid ethyl glycolate, ethyl phthalic acid methyl glycolate, ethyl phthalic acid propyl glycolate , propyl phenyl dimethyl ethyl glycolate, methyl phthalic acid propyl glycolate, methyl phthalic acid butyl glycolate, ethyl phthalic acid butyl Alcohol ester, butyl phthalic acid methyl glycolate, butyl phthalic acid ethyl glycolate, propyl phthalic acid butyl glycolate, butyl phthalate Propyl glycolate, methyl phthalic acid octyl glycolate 'ethyl phthalic acid octyl glycolate, octyl phthalyl methyl glycolate, octyl phthalate For mercaptoethyl glycolate, etc., it is preferred to use methyl phthalic acid methyl glycolate, ethyl phthalic acid ethyl glycolate, propyl phthalic acid propyl glycolate. , butyl phthalic acid butyl glycol vinegar, octyl phthalyl octyl glycolate. Further, it is also possible to mix two or more of the alkyl phthalocyanyl alkyl glycolate. Further, a citrate-based plasticizer represented by the following general formulas (1) to (3) of 201213864 described in Japanese Patent No. 3 793 184 is preferably used as a plasticizer. General formula (1) ch2—COOC2H5 h3c—coo—c—cooc2hs CH2—COOC^Hjs [Chemical 5] General

CH2-COOC12H26 h3c—COO—C，C00C2He I CH^-COOC^H^s [化6] -般式⑶ CH2 —C00C2Hs HjC - COO - C—C00C,iH25 ch2—COOC12ri25 另外，亦較好使用多價醇酯。本發明之λ/4板所用之多價醇酯係以如下一般式（4) 表示。 —般式（4 ) : R,- ( OH ) η 但，1^爲11價有機基，η爲2以上之正整數，OH基爲醇性及/或酚性羥基（羥基）。多價醇酯系可塑劑爲由二價以上之脂肪族多價醇與單羧酸之酯所成之可塑劑，較好分子內具有芳香環或環烷基環。較好爲2〜20價之脂肪族多價醇酯。較佳之多價醇之例可列舉爲例如以下者，但本發明不限於該等者。可列舉爲福壽草醇（adonitol )、阿拉伯糖醇（arabitol )、乙二醇、二乙二醇、三乙二醇、四乙二 -27- 201213864 醇、1，2-丙二醇、1,3-丙二醇、二丙二醇、三丙二醇、1，2-丁二醇、1，3-丁二醇、1，4-丁二醇、二丁二醇、1，2,4-丁三醇、1,5 -戊二醇、1，6-己二醇、己三醇、半乳糖醇（ galactitol)、甘露糖醇、3-甲基戊烷-1，3,5-三醇、頻那醇、山梨糖醇、三羥甲基丙烷、三經甲基乙烷 '木糖醇等。尤其，以三乙二醇、四乙二醇、二丙二醇、三丙二醇、山梨糖醇、三羥甲基丙烷、木糖醇較佳° 多價醇酯中使用之單羧酸並無特別限制，可使用習知之脂肪族單羧酸、脂環族單羧酸、芳香族單羧酸等。使用脂環族單羧酸、芳香族單羧酸就提高透濕性、保留性之觀點而言較佳。較佳之單羧酸之例可列舉爲如如下者，但本發明並不限於該等。至於脂肪族單羧酸可適當使用碳數1~32之直鏈或具有側鏈之脂肪酸。更好爲碳數1〜20，最好爲碳數卜10。含有乙酸時由於提高與纖維素酯之相溶性故較佳，亦較好混合使用乙酸與其他單羧酸。至於較佳之脂肪族單羧酸可列舉爲乙酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、正壬酸（pelargonic acid) 、癸酸、2-乙基-己酸、十一烷酸、月桂酸、十三烷酸、肉豆蔻酸、十五烷酸、棕櫚酸、十七烷酸、硬脂酸、十九烷酸、花生酸、山箭酸（behenic acid)、木焦油酸（ lignoceric acid)、蠘酸（cerotic acid)、二十五院酸、褐媒酸、峰花酸（melissic acid )、三十二院酸（ -28- 201213864 lacceratic acid)等飽和脂肪酸，--碳稀酸、油豆酸、亞油酸、綿羊油酸、花生四烯酸等不飽和月旨〇較佳之脂肪族單羧酸之例可列舉爲環戊烷羧酸烷羧酸、環辛烷羧酸、或該等之衍生物。較佳之芳香族單羧酸之例可列舉爲苯甲酸、甲之於苯甲酸之苯環上導入烷基者，聯苯羧酸、萘羧氫萘羧酸等具有兩個以上苯環之芳香族單羧酸，或衍生物。最好爲苯甲酸。多價醇酯之分子量並無特別限制，較好爲3 00” 更好爲3 5 0〜750。分子量較大者難以揮發故不佳，性、與纖維素酯之相溶性方面而言以分子量較小者多價醇酯中使用之羧酸可爲一種，亦可以兩種合。且，多價醇中之OH基可經全部酯化，亦可一接以OH基殘留。以下顯示本發明中使用之多價醇酯系可塑劑之合物，但本發明並不限於該等。酸、大肪酸等、環己苯酸等酸、四該等之 - 1 5 00 » 就透濕較佳。以上混部分直具體化 -29 - 201213864 [化7] 1 C4H9 - C - Ο - (CH2)2 - O - {CH2)2 - 0 - (CH2)2 - O - C - c4h9 0 〇 2 °- (CHj),-O-(CH2)j-O-(CH2),-O-C-CH2-COOC12H26 h3c—COO—C, C00C2He I CH^-COOC^H^s [Chemical 6] - General formula (3) CH2 — C00C2Hs HjC - COO - C—C00C, iH25 ch2—COOC12ri25 In addition, it is also better to use multi-price Alcohol ester. The polyvalent alcohol ester used in the λ/4 plate of the present invention is represented by the following general formula (4). General formula (4): R, - (OH) η However, 1^ is an 11-valent organic group, η is a positive integer of 2 or more, and OH group is an alcoholic group and/or a phenolic hydroxyl group (hydroxyl group). The polyvalent alcohol ester-based plasticizer is a plasticizer composed of an ester of a divalent or higher aliphatic polyvalent alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule. It is preferably an aliphatic polyvalent alcohol ester having a valence of 2 to 20 carbons. Examples of preferred polyvalent alcohols include, for example, the following, but the present invention is not limited to these. Can be cited as adonitol, arabitol (arabitol), ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene di-27-201213864 alcohol, 1,2-propanediol, 1,3 -propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1, 5-pentanediol, 1,6-hexanediol, hexanetriol, galactitol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbus Sugar alcohol, trimethylolpropane, trimethylethane ethane xylitol, and the like. In particular, the monocarboxylic acid to be used in the polyvalent alcohol ester of triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane or xylitol is not particularly limited. A conventional aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid or the like can be used. The use of an alicyclic monocarboxylic acid or an aromatic monocarboxylic acid is preferred in terms of improving moisture permeability and retention. Preferred examples of the monocarboxylic acid are as follows, but the present invention is not limited thereto. As the aliphatic monocarboxylic acid, a straight chain having a carbon number of 1 to 32 or a fatty acid having a side chain can be suitably used. More preferably, the carbon number is 1 to 20, and preferably the carbon number is 10. In the case of containing acetic acid, it is preferred to improve the compatibility with the cellulose ester, and it is also preferred to use acetic acid together with other monocarboxylic acids. Preferred aliphatic monocarboxylic acids are exemplified by acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, citric acid, 2-ethyl-hexanoic acid, and ten. Alkanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanic acid, arachidic acid, behenic acid, wood Saturated fatty acids such as lignoceric acid, cerotic acid, twenty-five acid, brown acid, melissic acid, and ternary acid (-28-201213864 lacceratic acid), - Examples of aliphatic aliphatic monocarboxylic acids, such as carbonic acid, oleic acid, linoleic acid, lanolinic acid, and arachidonic acid, are exemplified by cyclopentanecarboxylic acid alkanecarboxylic acid and cyclooctane. An alkanecarboxylic acid, or a derivative thereof. Examples of the preferred aromatic monocarboxylic acid include benzoic acid, an alkyl group introduced into a benzene ring of benzoic acid, and an aromatic group having two or more benzene rings such as a biphenylcarboxylic acid or a naphthoquinonecarboxylic acid. a monocarboxylic acid, or a derivative. It is preferably benzoic acid. The molecular weight of the polyvalent alcohol ester is not particularly limited, and is preferably 300 Å or more preferably 305 to 750. The larger molecular weight is difficult to volatilize, which is not preferable, and the compatibility with the cellulose ester is molecular weight. The carboxylic acid used in the smaller polyvalent alcohol ester may be one type or two types, and the OH group in the polyvalent alcohol may be completely esterified or may be OH group remaining. The following shows the present invention. The polyvalent alcohol ester-based plasticizer compound used in the present invention, but the present invention is not limited to these. Acid, fatty acid, etc., acid such as cyclohexyl benzoic acid, etc. - 1 5 00 » on moisture permeability佳. The above mixed part is directly embodied -29 - 201213864 [Chemical 7] 1 C4H9 - C - Ο - (CH2)2 - O - {CH2)2 - 0 - (CH2)2 - O - C - c4h9 0 〇2 °- (CHj), -O-(CH2)jO-(CH2), -OC-

3 ΛΛ-〇-ο-{ςΗ2); '~/ Ό 4 ^^-c-o-(ch2· 5 C4H9-C-0-^CH2-CH2-0-Jj-C-C4H9 O 4 o 6 C8H17-C-〇-^CH2-CH2-〇-^-C-C8H17 _ 0 o3 ΛΛ-〇-ο-{ςΗ2); '~/ Ό 4 ^^-co-(ch2· 5 C4H9-C-0-^CH2-CH2-0-Jj-C-C4H9 O 4 o 6 C8H17-C -〇-^CH2-CH2-〇-^-C-C8H17 _ 0 o

7 〇1_〇七 8 \ V" i ' 0 "f CH2CH2CH2 - °7 〇1_〇七 8 \ V" i ' 0 "f CH2CH2CH2 - °

9 C4H9-C-〇-(-CH2CH2CH2-〇^-C-C4H9 o o 10 c8h17i-〇"{ch2ch2ch2-o~^-c8h17 o o 11 〇^-〇和邮料-知-〇9 C4H9-C-〇-(-CH2CH2CH2-〇^-C-C4H9 o o 10 c8h17i-〇"{ch2ch2ch2-o~^-c8h17 o o 11 〇^-〇 and postal materials-Knowledge-〇

1212

14 C8H,t-C-〇-^CH2CH-〇^—c-cbh17 〇 ch3 〇 15<^_?-0如％„_〇)^_^) -30- 201213864 [化8] 1614 C8H,t-C-〇-^CH2CH-〇^-c-cbh17 〇 ch3 〇 15<^_?-0 as %„_〇)^_^) -30- 201213864 [化8] 16

CH 〇„2.〇^^0 CHi.o.c-0 17 o u ch2-o-c-c4h9 CHsCH^-C-CHj-O-C-C^Hg I 〇 ch2-o-c-c4h9o 18 19CH 〇„2.〇^^0 CHi.o.c-0 17 o u ch2-o-c-c4h9 CHsCH^-C-CHj-O-C-C^Hg I 〇 ch2-o-c-c4h9o 18 19

o II ch2-o-c-cbh17o II ch2-o-c-cbh17

CH,-0-CCH,-0-C

21 o-Ht cl21 o-Ht cl

CH CH 23 n2cH1 c ,c_CH CH 23 n2cH1 c ,c_

H2 CHH2 CH

H2 -c H2 cl c - •clH2 -c H2 cl c - •cl

H 0 1 Hi_c 201213864 [化9] 24 9P 〇=? 〇=? 〇〇 ch2-ch-ch-ch-ch2 ο ό ο I I I c-o c=o c=o 25 99 〇=c o=c ά ά CH-iH-CH-iH-CH, 0 0 0 26 ό ό ό ό ό ό27ρ ρρ CH, CH, 〇=C 0=0 ι I Ο ο o=c I ο o=c o=c I ι 0 οH 0 1 Hi_c 201213864 [Chemical 9] 24 9P 〇=? 〇=? 〇〇ch2-ch-ch-ch-ch2 ο ό ο III co c=oc=o 25 99 〇=co=c ά ά CH-iH -CH-iH-CH, 0 0 0 26 ό ό ό ό ό ό27ρ ρρ CH, CH, 〇=C 0=0 ι I Ο ο o=c I ο o=co=c I ι 0 ο

29 ch2—ch-ch-ch-ch2 ο ο ο I I ι c=o c=o c=o 2829 ch2—ch-ch-ch-ch2 ο ο ο I I ι c=o c=o c=o 28

ch2-ch2-c-ch2-ch2 ch3 〇t+t… ο » c=o όCh2-ch2-c-ch2-ch2 ch3 〇t+t... ο » c=o ό

-32- 201213864 [化 10]-32- 201213864 [化10]

33 34 35 ch2-ch-ch. 〇-r°-(33 34 35 ch2-ch-ch. 〇-r°-(

^rO c=o ό^rO c=o ό

該等化合物相對於纖維素酯宜含有1〜3 0質量％，較好含有1〜20質量％。又，爲了抑制延伸及乾燥中之滲出等，故以在200°C之蒸氣壓爲1 400Pa以下之化合物較佳。該等化合物在調製纖維素酯溶液時，可一起添加纖維素酯及溶劑，亦可於溶液調製中或調製後添加。又本發明中較好使用以下述一般式（5)表示之芳香族末端酯系可塑劑。These compounds are preferably contained in an amount of 1 to 30% by mass, preferably 1 to 20% by mass based on the cellulose ester. Further, in order to suppress bleeding during stretching and drying, a compound having a vapor pressure of 200 ° C or less and 1 400 Pa or less is preferable. When the cellulose ester solution is prepared, these compounds may be added together with a cellulose ester and a solvent, or may be added during solution preparation or after preparation. Further, in the present invention, an aromatic terminal ester-based plasticizer represented by the following general formula (5) is preferably used.

—般式（5) : B- ( G_A ) n-G-B -33- 201213864 (式中’ B表示苯單羧酸殘基，G表示碳數2〜12之烷二醇殘基或碳數6〜12之芳二醇殘基或碳數4〜12之氧基烷二醇殘基’ A表示碳數4~12之烷二羧酸殘基或碳數6〜12之芳二羧酸殘基，且η表示1以上之整數）。一般式（5)中，爲由以Β表示之苯單羧酸殘基與以G 表示之烷二醇殘基或氧基烷二醇殘基或芳二醇殘基、以A 表示之烷二羧酸殘基或芳二羧酸殘基所構成者，係藉由與一般聚酯系可塑劑同樣之反應獲得。本發明中使用之芳香族末端酯系可塑劑之苯單羧酸成分有例如苯甲酸、對第三丁基苯甲酸、鄰甲苯酸、間甲苯酸、對甲苯酸、二甲基苯甲酸、乙基苯甲酸、正丙基苯甲酸、胺基苯甲酸、乙醯氧基苯甲酸等，該等可分別使用一種或以兩種以上之混合物使用。本發明中使用之芳香族末端酯系可塑劑之碳數2〜12之烷二醇成分有乙二醇、1,2-丙二醇、1，3-丙二醇、1，2-丁二醇、1，3-丁二醇、2-甲基-1，3-丙二醇、1，4-丁二醇、1，5-戊二醇、2，2-二甲基-1，3-丙二醇（新戊二醇）、2,2-二.乙基-l，3-丙二醇（3,3-二羥甲基丙烷）、2-正丁基-2-乙基-1,3-丙二醇（3,3-二羥甲基庚烷）、3-甲基-1,5-戊二醇、ΜΕ 二醇、 2,2,4-三甲基 -1,3-戊二醇、 2-乙基 -1，3-己二醇、 2-甲基-1，8-辛二醇、1，9-壬二醇、1,10-癸二醇、1,12-十八烷二醇等，該等二醇可使用一種或以兩種以上之混合物使用。又，芳香族末端酯之碳數4〜12之氧基烷二醇成分有例 201213864 如二乙二醇、三乙二醇、四乙二醇、二丙二醇、三丙二醇等，該等二醇可使用一種或以兩種以上之混合物使用。又，芳香族末端酯之碳數6~12之芳二醇成分有例如氫醌、間苯二甲酚、雙酚A、雙酧F、雙酚等，該等二醇可使用一種或以兩種以上之混合物使用。芳香族末端酯之碳數4〜12之烷二羧酸成分有例如琥珀酸、馬來酸、富馬酸 '戊二酸、己二酸、壬二酸、癸二酸、十二烷二酸等，該等分別使用一種或以兩種以上之混合物使用。碳數6〜12之芳二羧酸成分有苯二甲酸、對苯二甲酸、1，5-萘二羧酸、1，4-萘二羧酸等。芳香族末端酯系可塑劑之數平均分子量較好爲300〜 2 000，更好爲500〜1 5 00之範圍。又，其酸價較好爲0.5 mgKOH/g以下’羥（羥基）價較好爲25mgKOH/g以下，更好爲酸價爲〇.3mgKOH/g以下，羥（羥基）價爲丨5mgK〇H/g 以下者。〈芳香族末端酯之酸價、羥（羥基）價〉所謂酸價係中和試料lg中所含之酸（存在於分子末端之羧基）所需之氫氧化鉀之毫克數。酸價及經（經基）價爲以JIS K0070 ( 1992 )爲準測定者。以下列示本發明中使用之芳香族末端酯系可塑劑之合成例。〈樣品編號1 (芳香族末端酯樣品）〉 -35- 201213864 於反應容器中一次饋入苯二甲酸820份（5莫] 1，2-丙二醇608份（8莫耳）、苯甲酸610份（5莫耳、爲觸媒之鈦酸四異丙酯0.30份，且於氮氣回流中攪才邊以安裝回流凝縮器使過量之—價醇回流， 130〜250 °C下持續加熱連續的去除生成之水直至酸價以下。接著在200~230°C下在6.65><103?3至最終4><1( 下之減壓下’去除餾出份，隨後經過濾獲得具有以-之芳香族末端酯。黏度（25°C，mPa· S) : 19815 酸價：0.4 〈樣品編號2 (芳香族末端酯樣品）〉於反應容器中’除使用己二酸500份（3.5莫耳、甲酸305份（2.5莫耳）、二乙二醇583份（5.5莫耳〕爲觸媒之鈦酸四異丙酯0.45份以外’全部與樣品編樣’獲得具有以下性質之芳香族末端酯。黏度（25°C，mPa.S) ： 90 酸價：0.05 〈樣品編號3 (芳香族末端酯樣品）〉於反應容器中，除使用苯二甲酸410份（2.5莫] 苯甲酸610份（5莫耳）、二丙二醇737份（5·5莫耳、爲觸媒之鈦酸四異丙酯0.4〇份以外，全部與樣品，編樣，獲得具有以下性質之芳香族末端酯系可塑劑。及作 e下，邊在成爲2 2Pa以 :性質、苯及作號1同 f ) ' 及作號1同 201213864 黏度（25C，mPa.S) :43400酸價：0.2以下，列示本發明中使用之芳香族末端酯系可塑劑之具體化合物，但本發明並不限於該等。General formula (5): B-( G_A ) nGB -33- 201213864 (wherein B represents a benzene monocarboxylic acid residue, and G represents an alkylene glycol residue having a carbon number of 2 to 12 or a carbon number of 6 to 12 The aryl diol residue or the oxyalkylene glycol residue having a carbon number of 4 to 12' A represents an alkyl dicarboxylic acid residue having 4 to 12 carbon atoms or an aromatic dicarboxylic acid residue having 6 to 12 carbon atoms, and η Indicates an integer greater than 1). In the general formula (5), it is an alkanecarboxylic acid residue represented by fluorene and an alkanediol residue or an oxyalkylene glycol residue or an aromatic diol residue represented by G, and an alkane represented by A. The carboxylic acid residue or the aryl dicarboxylic acid residue is obtained by the same reaction as a general polyester plasticizer. The benzene monocarboxylic acid component of the aromatic terminal ester-based plasticizer used in the present invention is, for example, benzoic acid, p-tert-butylbenzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, dimethylbenzoic acid, and B. Benzoic acid, n-propyl benzoic acid, aminobenzoic acid, ethoxylated benzoic acid, and the like may be used singly or in combination of two or more. The alkanediol component having 2 to 12 carbon atoms of the aromatic terminal ester-based plasticizer used in the present invention is ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1, 3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentethylene) Alcohol), 2,2-di.ethyl-l,3-propanediol (3,3-dimethylolpropane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3- Dimethylol heptane), 3-methyl-1,5-pentanediol, decanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1, 3-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-nonanediol, 1,12-octadecanediol, etc., such diols One type or a mixture of two or more types may be used. Further, the aromatic terminal ester has an alkyl alkanediol component having 4 to 12 carbon atoms; for example, 201213864, such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, etc., such diols may be used. One type or a mixture of two or more types is used. Further, the aromatic terminal ester has an aromatic diol component having 6 to 12 carbon atoms, for example, hydroquinone, meta-xylylene glycol, bisphenol A, biguanide F, bisphenol, etc., and the diols may be used alone or in combination. A mixture of the above is used. The aromatic terminal ester has a carbon number of 4 to 12 alkyl dicarboxylic acid components such as succinic acid, maleic acid, fumaric acid 'glutaric acid, adipic acid, sebacic acid, sebacic acid, dodecanedioic acid. Etc., these are used singly or in combination of two or more. The aromatic dicarboxylic acid component having 6 to 12 carbon atoms is phthalic acid, terephthalic acid, 1,5-naphthalene dicarboxylic acid or 1,4-naphthalenedicarboxylic acid. The number average molecular weight of the aromatic terminal ester type plasticizer is preferably from 300 to 2 000, more preferably from 500 to 1 500. Further, the acid value thereof is preferably 0.5 mgKOH/g or less, and the 'hydroxyl (hydroxyl) value is preferably 25 mgKOH/g or less, more preferably the acid value is 〇3 mgKOH/g or less, and the hydroxyl group (hydroxyl) is 丨5 mgK〇H. /g The following. <Acid valence and hydroxy (hydroxy) valence of aromatic terminal ester The so-called acid valence is the number of milligrams of potassium hydroxide required for neutralizing the acid (the carboxyl group present at the end of the molecule) contained in the sample lg. The acid value and the warp price are based on JIS K0070 (1992). The synthesis examples of the aromatic terminal ester type plasticizer used in the present invention are shown below. <Sample No. 1 (aromatic terminal ester sample)> -35- 201213864 820 parts (5 moles) of 1,2-propanediol (8 moles) and 610 parts of benzoic acid were fed into the reaction vessel at a time. 5 moles, 0.30 parts of tetraisopropyl titanate as a catalyst, and stirred under nitrogen reflux to install a reflux condenser to reflux excess valence alcohol, continuous heating at 130~250 °C for continuous removal The water is below the acid value, and then the distillate is removed at 200 to 230 ° C under 6.65 < 103 ? 3 to the final 4 > 1 (under reduced pressure), followed by filtration to obtain - Aromatic terminal ester. Viscosity (25 ° C, mPa · S) : 19815 Acid value: 0.4 <Sample No. 2 (aromatic terminal ester sample) > In the reaction vessel 'except using 500 parts of adipic acid (3.5 m 305 parts (2.5 moles) of formic acid, 583 parts (5.5 moles) of diethylene glycol, 0.45 parts of tetraisopropyl titanate as catalyst, 'all sample preparation' to obtain aromatic terminal esters having the following properties Viscosity (25°C, mPa.S): 90 Acid value: 0.05 <Sample No. 3 (aromatic terminal ester sample)> In the reaction vessel Except for 410 parts of phthalic acid (2.5 moles) 610 parts (5 moles) of benzoic acid, 737 parts of dipropylene glycol (5. 5 moles, 0.4 parts of tetraisopropyl titanate as catalyst), all with Sample, sample, to obtain an aromatic terminal ester plasticizer with the following properties: and as e, the edge becomes 2 2Pa to: nature, benzene and number 1 with f) ' and the number 1 with 201213864 viscosity (25C , mPa.S): 43400 Acid value: 0.2 or less, the specific compound of the aromatic terminal ester type plasticizer used in the present invention is shown, but the present invention is not limited to these.

Or 9 〔u-一 ^~y-OOOIH3£oloou—"HaIOOOH-H00o°— Ε ^ί^ιοοοι£ο^χο£οο£ο^χο£οοοο—^ ^ S 000」5£00~Η3£0 丨 08 — 351 丨〇3〇丨三0£0〇代5£3〇〇3-s ”5 «χϋOr 9 〔u-一^~y-OOOIH3£oloou—"HaIOOOH-H00o°— Ε ^ί^ιοοοι£ο^χο£οο£ο^χο£οοοο—^ ^ S 000”5£00~Η3£ 0 丨08 — 351 丨〇3〇丨3 0£0〇代5£3〇〇3-s ”5 «χϋ

οϋο I £υΜχϋ«χοο£ϋ«χα£οοοο L ^ ^1 〇3〇£3~50~5£3〇039 f-°«χϋ Οϋοιχο£ϋοοο1^χϋτοοο»χ^£ϋοοϋ—^^ {- 80—~Ηυ£°0~Η0£00ου ροοοό ? ^~^"ooo-d—^~-0〇〇0|-5>—〇0-5—^""^"-3000—^~^ ^1^ιοοοι^χο£οο£ο£οοοοι^£οτοοο£αι^ι^ί£οοου όε £0 000丄 -ΗΟΙο-οοοι-εχ·ο}-οοο Γ {- -37- 201213864Οϋο I £υΜχϋ«χοο£ϋ«χα£οοοο L ^ ^1 〇3〇£3~50~5£3〇039 f-°«χϋ Οϋοιχο£ϋοοο1^χϋτοοο»χ^£ϋοοϋ—^^ {- 80 —~Ηυ£°0~Η0£00ου ροοοό ? ^~^"ooo-d—^~-0〇〇0|-5>—〇0-5—^""^"-3000—^ ~^ ^1^ιοοοι^χο£οο£ο£οοοο ι^£οτοοο £αι^ι^ί£οοου όε £0 000丄-ΗΟΙο-οοοι-εχ·ο}-οοο Γ {- -37- 201213864

I ^—^—0001ΧΟ^ΧΟΙΟΙΧΟ^ΧΟΙΟΟΟΙ^ΧΟΤΟΟΟΙΧΟ^ΧΟΙΟΙΧ^ΙΟΟΟΟΙα^—^ {- «χο «χο "5 «χο ^^τοοο£ο£οο£ο£οο^χα£^οοο—^—^ ^^ιοϋο£ο^χϋο£ο£οο£ο£οοοο } 本發明中使用之芳香族末端酯系可塑劑之含量較好於纖維素酯薄膜中含有1〜20質量％，最好含有3〜11質量％。 (聚酯多元醇）本發明中使用之聚酯多元醇爲可藉由二元酸或該等之醋形成性衍生物與二元醇之縮合反應獲得之末端成爲羥（涇基）之聚合物。此處所謂酯形成性衍生物爲二元酸之醋化合物、二元酸之氯化物、二元酸之酸酐。前述聚酯多元醇可藉由芳香族二元酸與二醇之脫水反 -38- 201213864 應、二醇對芳香族二元酸酐之加成及脫水縮合反應、或藉由芳香族二元酸之酯化物與二醇之脫醇之縮合反應獲得。前述芳香族二元酸或該等之酯形成性衍生物可單獨使用具有10〜16個碳原子之芳香族二羧酸或其酯形成性衍生物，但亦可使用例如苯環構造、萘環構造、蒽環構造等具有芳香族環式構造之二羧酸或其酯形成性衍生物，可列舉爲例如具有取代基之鄰苯二甲酸、具有取代基之間苯二甲酸、具有取代之對苯二甲酸、具有取代基之苯二甲酸酐、 1，4-萘二羧酸酐、2,3-萘二羧酸、2,6-萘二羧酸、2,7-萘二羧酸、1,8-萘二羧酸、2，6-蒽二羧酸等或該等之酯化物及醯氯，1,8-萘二羧酸之酸酐等，該等於芳香族環上亦可具有取代基，該等可單獨使用或倂用兩種以上。較好爲I，4-萘二羧酸、2,3-萘二羧酸、2,6-萘二羧酸、2,7-萘二羧酸、 1，8-萘二羧酸及其酯化物，更好爲2,3-萘二羧酸、2,6-萘二羧酸及其酯化物，最好爲2,6-萘二羧酸及其酯化物。前述聚酯多元醇之二元酸之碳數之平均意指使用單一二元酸聚合聚酯多元醇時該二元酸之碳數，但使用兩種以上之二元酸聚合聚酯多元醇時，意指各該二元酸之碳數與其二元酸之莫耳分率之乘積之合計。本發明中，重要的是作爲聚酯多元醇之原料使用之二元酸之碳數之平均在10~ 16之範圍內。若該二元酸之碳數之平均爲1 〇以上，則滯相之展現性優異，若碳數之平均爲 1 6以下，則與纖維素酯之相溶性顯著優異。至於二元酸，較好碳數之平均爲10〜14，更好碳數之平均爲10〜12。 -39 - 201213864 若前述碳數之平均爲10〜16，則可倂用前述具有10〜16 個碳原子之芳香族二元酸與除此之外之二元酸。可倂用之二元酸較好爲具有4〜9個碳原子之二羧酸或其酯形成性衍生物，可列舉爲例如琥珀酸、戊二酸、己二酸、馬來酸、琥珀酸酐、馬來酸酐、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、苯二甲酸酐等或該等之酯化物及醯氯〇前述二醇可單獨使用或倂用兩種以上之例如乙二醇、二乙二醇、三乙二醇、1,2-丙二醇、1，3-丙二醇、2-甲基-1，3-丙二醇、1，2-丁二醇、1，3-丁二醇、1，4-丁二醇、2,3-丁二醇、1,5-戊二醇、新戊二醇、1,2-環戊二醇、1，3-環戊二醇、1，4-環己二醇等，其中以乙二醇、二乙二醇、1，2-丙二醇、2-甲基-1，3-丙二醇較佳，更好爲乙二醇、二乙二醇、1,2-丙二醇。本發明之聚酯多元醇可視需要在酯化觸媒存在下，使前述二元酸或該等之酯形成性衍生物與二醇，在例如180〜 25〇°C之溫度範圍內，以習知慣用之方法進行酯化反應〜25小時而製造。進行酯化反應時，亦可使用甲苯、二甲苯等溶劑，但 ^好1爲無溶劑或使用作爲原料使用之二醇作爲溶劑之方法前述酯化觸媒可使用例如鈦酸四異丙酯、鈦酸四丁酯 '對甲苯磺酸、氧化二丁基錫等。前述酯化觸媒相對於二 %酸或該等之酯形成性衍生物之總量丨〇〇質量份，較好使 -40- 201213864 用0.01〜0.5質量份。二元酸或該等之酯形成性衍生物與二醇反應時之莫耳比必須爲聚酯之末端基成爲羥（羥基）之莫耳比，因此相對於二元酸或該等之酯形成性衍生物1莫耳二醇爲1.1〜1〇莫耳。較好，相對於二元酸或該等之酯形成性衍生物1莫耳，二醇爲1.5〜7莫耳，更好，相對於二元酸或該等之酯形成性衍生物1莫耳，二醇爲2~5莫耳。另一方面，於前述聚酯多元醇中之羧基末端由於會降低濕度安定性，故其含量越低越佳。具體而言，酸價較好爲5.0以下，更好爲1 .0以下，最好爲0.5以下。此處所謂酸價意指中和試料1 g中所含之酸（試料中存在之羧基）所需之氫氧化鉀之毫克數。酸價爲以JIS K0070爲基準測定者。前述聚酯多元醇之羥（羥基）價（OHV )較好爲 3$mg/g〜220mg/g之範圍。此處所謂羥（羥基）價意指使試料lg中所含之OH基乙醯基化時，中和用以與羥（羥基）鍵結之乙酸所需之氫氧化鉀之毫克數。使用酸酐使試料中之OH基乙醯基化，且以氫氧化鉀溶液滴定未被使用之乙酸’由與初期之乙酸酐之滴定値之差求得。前述聚酯多元醇之羥（羥基）含量較好爲7 0%以上。經（羥基）含量少時，聚酯多元醇與纖維素酯之相溶性下降。因此，羥（羥基）含量較好爲70%以上，更好爲90% 以上，最好爲99%以上。本發明中，羥（羥基）含量爲50%以下之化合物不包 • 41 - 201213864 含於末端基之一方以羥（羥基）以外之基取代之羥（羥基 )聚酯多元醇。前述羥（羥基）含量可由下述式（A)求得。式（A) :Υ/Χχ100 =羥（羥基）含量（％) X:前述聚酯多元醇之羥（羥基）價（OHV) Υ ： 1/(數平均分子量（Μη) ) χ56χ2χ1000 前述聚酯多元醇較好具有30 0〜3000範圍內之數平均分子量，更好具有3 5 0~2000之數平均分子量。且，本發明之聚酯多元醇之分子量之分散度較好爲 1.0〜3.0，更好爲1.〇〜2.0。若分散度在上述範圍內，則可獲得與纖維素酯之相溶性優異之聚酯多元醇。且，前述聚酯多元醇較好含有50 %以上之分子量爲300〜1800之成分。藉由使數'平均分子量在前述範圍內，可大幅提高相溶性。將數平均分子量、分散度及成分含有率控制在上述之較佳範圍內之方法，較好爲相對於二元酸或該等之酯形成性衍生物1莫耳，使用2~5莫耳之二醇，且減壓餾除未反應之二醇之方法。減壓餾除之溫度較好爲100〜20(TC，更好爲12 0〜180°C ’最好爲13 0〜170 °C。減壓餾除時之減壓度較好爲 0.01 〜67kPa ( 0.1 〜500Torr )，更好爲 0.06〜27kPa ( 0.5 〜200 Torr)，最好爲〇_13 〜13kPa ( 1〜lOOTorr)。聚酯多元醇數平均分子量（Μη)及分散度可使用凝膠滲透層析儀（G P C )測定。測定條件之一例如下，但並不限於該等，亦可使用同等之測定方法。 -42- 201213864 溶劑··四氫呋喃（T H F ) 管柱··連接使用兩根TSKgel G2000HXL ( TOSOH (股 )製造）管柱溫度：40°C 試料濃度：0.1質量％裝置：HLC-8220 ( TOSOH (股）製造）流量：l.Oml/min 校正曲線：使用利用PStQuick F ( TOSOH (股）製造 )獲得之校正曲線就獲得本發明效果方面而言，較好於薄膜中含有5〜3 0 質量％之聚酯多元醇。更好爲5〜20質量。/〇。以下列示碳數10〜16之二元酸之具體例，但本發明並不限於該等。 (1 ) 2,6-萘二羧酸 (2 ) 2,3-萘二羧酸 (3 ) 2,6-蒽二羧酸 (4) 2,6 -萘二羧酸：琥珀酸（75: 25〜99: 1莫耳比） (5) 2,6-萘二羧酸：對苯二甲酸（50:50~99:1莫耳比） (6) 2,3-萘二羧酸：琥珀酸（75: 25〜99: 1莫耳比） (7) 2,3-萘二羧酸：對苯二甲酸（50: 5 0〜99 : 1莫耳比） (8) 2,6-蒽二羧酸：琥珀酸（5 0:50〜99:1莫耳比） (9) 2,6-蒽二羧酸：對苯二甲酸（25: 75〜99: 1莫耳 -43- 201213864 比） (10) 2,6-萘二羧酸：己二酸（67: 33〜99: 1莫耳比 ) (11) 2,3-萘二羧酸：己二酸（67: 33〜99: 1莫耳比 ) (12) 2,6-蒽二羧酸：己二酸（40: 6 0〜99: 1莫耳比 (紫外線吸收劑）本發明之λ/4板及光學薄膜中可含有紫外線吸收劑。可使用之紫外線吸收劑可列舉爲例如氧基二苯甲酮系化合物、苯并三唑系化合物、水楊酸酯系化合物、二苯甲酮系化合物、氰基丙烯酸酯系化合物、鎳錯鹽系化合物、三嗪系化合物等，但較好爲著色少之苯并三唑系化合物。又，亦較好使用特開平1 0- 1 8262 1號、特開平8 -3 3 75 74號、特開 200 1 -72782號記載之紫外線吸收劑，特開平6- 1 4 843 0號、特開 2002-31715號、特開 2002-169020號、特開 2002-47357 號、特開2002-3 63 42 0號、特開2003 - 1 1 3 3 1 7號記載之高分子紫外線吸收劑。至於紫外線吸收劑就防止偏光子或液晶劣化之觀點而言，波長3 7 Onm以下之紫外線之吸收能優異者，且就液晶顯示性之觀點而言，較好爲波長400nm以上之可見光之吸收少者。本發明中有用之紫外線吸收劑之具體例可列舉爲2-( 2’-羥基- 5’-甲基苯基）苯并三唑、2- (2’-羥基-3’，5’-二第 -44- 201213864 三丁基苯基）苯并三唑、2- (2，-羥基-3’-第三丁基- 5’-甲基苯基）苯并二哩、2- ( 2’-經基-3’，5’- 一桌二丁基本基 )-5-氯苯并三唑、2- ( 2，-羥基-3，- ( 3”，4”，5”，6”-四氫苯二甲醯胺甲基）-5’-甲基苯基）苯并三唑、2,2-亞甲基雙 (4- ( 1，1,3,3-四甲基丁基）-6- ( 2H-苯并三唑-2-基）酚 )、2- ( 2’-羥基- 3，-第三丁基- 5’-甲基苯基）-5-氯苯并三唑、2- ( 2H-苯并三唑-2-基）-6-(直鏈及側鏈十二烷基 )-4 -甲基酚、辛基- 3- [3 -第三丁基-4-羥基-5-(氯- 2H -苯并三唑-2-基）苯基]丙酸酯與2 -乙基己基- 3-[3-第三丁基-4-羥基-5- ( 5_氯-2-苯并三唑-2-基）苯基]丙酸酯之混合物等，但並不限於該等。又，市售品可適當使用TINUVIN 109 ' TINUVIN 171、TINUVIN 326 (均爲日本 BASF 公司製造 )。至於高分子紫外線吸收劑可列舉大塚化學公司製造之反應型紫外線吸收劑RUVA-93爲例。二苯甲酮系化合物之具體例可列舉爲2,4-二羥基二苯甲酮、2，2’-二羥基-4-甲氧基二苯甲酮、2-羥基-4-甲氧基-5-磺基二苯甲酮、雙（2-甲氧基-4-羥基-5-苯甲醯基苯基甲烷）等，但並不限於該等。本發明較佳使用之上述記載之紫外線吸收劑較好爲透明性高、防止偏光板或液晶元件之劣化優異之苯并三唑系紫外線吸收劑或二苯甲酮系紫外線吸收劑，最好使用不期望之著色少之苯并三唑系紫外線吸收劑。紫外線吸收劑對摻雜物之添加方法，只要是可將紫外線吸收劑溶解於摻雜物中者即可無限制地使用，但本發明 etc -45- 201213864 中較好爲將紫外線吸收劑溶解於二氯甲烷、乙酸甲酯、二噁烷等對纖維素酯爲良溶劑、或良溶劑與如低級脂肪族醇 (甲醇、乙醇、丙醇、丁醇等）之弱溶劑之混合有機溶劑中作成紫外線吸收劑溶液添加於纖維素酯溶液中並摻雜之方法。該情況下儘可能使摻雜物溶劑組成與紫外線吸收劑溶液之溶劑組成相同或接近較佳。紫外線吸收劑之含量爲 0.0 1〜5質量％，最好爲0.5〜3質量％。 (抗氧化劑）抗氧化劑較好使用受阻酚系之化合物，列舉爲例如 2，6-二第三丁基-對·甲酚、季戊四醇·肆[3- (3,5-二-第三丁基-4-羥基苯基）丙酸酯]、三乙二醇-雙[3-(3-第三丁基-5-甲基-4-羥基苯基）丙酸酯]、1，6-己二醇-雙[3-(3,5-二第三丁基-4-羥基苯基）丙酸酯]、2,4-雙-(正辛硫基）-6-(4·羥基-3,5 -二-第三丁基苯胺基）-1,3 ,5-三嗪、2,2-硫基-二伸乙基雙[3- (3,5-二-第三丁基-4-羥基苯基）丙酸酯 ]、十八烷基-3-(3,5-二-第三丁基-4-羥基苯基）丙酸酯、 N，N’-六亞甲基雙（3,5-二-第三丁基-4-羥基-氫桂皮醯胺）、1，3,5-三甲基-2,4,6-參（3,5-二-第三丁基-4-羥基苄基）苯、參-(3,5-二-第三丁基-4-羥基苄基）_異氰尿酸酯等》最好爲2,6 -二-第三丁基-對-甲酚、季戊四醇-肆[3-(3,5-二-第三丁基-4-羥基苯基）丙酸酯]、三乙二醇-雙[3-(3-第三丁基-5-甲基·4-羥基苯基）丙酸酯]。又例如亦可倂用 N，N，-雙[3- (3,5-二-第三丁基-4-羥基苯基）丙醯基]聯胺 -46- 201213864 等之聯胺系之金屬惰性劑或參（2，4 -二-第三丁基苯基）磷酸酯等磷系加工安定劑。該等化合物之添加量相對於纖維素酯以質量比計較好爲 lppm~l.〇%，更好爲 1〇〜lOOOppm。又，亦較好使用以下述一般式（L)表示之化合物。 [化 13] 一般式(L}I ^—^—0001ΧΟ^ΧΟΙΟΙΧΟ^ΧΟΙΟΟΟΙ^ΧΟΤΟΟΟΙΧΟ^ΧΟΙΟΙΧ^ΙΟΟΟΟΙα^—^ {- «χο «χο "5 «χο ^^τοοο£ο£οο£ο£οο^£α£^οοο—^—^ The content of the aromatic terminal ester-based plasticizer used in the present invention is preferably from 1 to 20% by mass, preferably from 3 to 8% by weight in the cellulose ester film. 11% by mass. (Polyester Polyol) The polyester polyol used in the present invention is a polymer which can be obtained as a hydroxyl group by a condensation reaction of a dibasic acid or a vinegar-forming derivative with a glycol. . The ester-forming derivative herein is a vinegar compound of a dibasic acid, a chloride of a dibasic acid, or an acid anhydride of a dibasic acid. The polyester polyol may be obtained by dehydration of an aromatic dibasic acid and a diol, anti-38-201213864, addition or dehydration condensation of a diol to an aromatic dibasic acid anhydride, or by an aromatic dibasic acid. The condensation reaction of the ester compound with the dealcoholization of the diol is obtained. The aromatic dibasic acid or the ester-forming derivative may be an aromatic dicarboxylic acid having 10 to 16 carbon atoms or an ester-forming derivative thereof, but for example, a benzene ring structure or a naphthalene ring may be used. Examples of the dicarboxylic acid having an aromatic ring structure such as a structure or an anthracene ring structure or an ester-forming derivative thereof, and examples thereof include phthalic acid having a substituent, phthalic acid having a substituent, and a substituted group. Phthalic acid, phthalic anhydride having a substituent, 1,4-naphthalene dicarboxylic anhydride, 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1 , 8-naphthalenedicarboxylic acid, 2,6-nonanedicarboxylic acid, or the like, or an esterified product thereof, and an anion of 1,8-naphthalenedicarboxylic acid, etc., which may have a substituent on the aromatic ring. These may be used alone or in combination of two or more. Preferred are I,4-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid and esters thereof. The compound is more preferably 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid or an ester thereof, and is preferably 2,6-naphthalene dicarboxylic acid and an ester thereof. The average carbon number of the dibasic acid of the polyester polyol means the carbon number of the dibasic acid when a single dibasic acid polymerized polyester polyol is used, but two or more dibasic acid polymerized polyester polyols are used. In the meantime, it means the sum of the product of the carbon number of each of the dibasic acids and the molar fraction of the dibasic acid. In the present invention, it is important that the carbon number of the dibasic acid used as a raw material of the polyester polyol is in the range of 10 to 16. When the average number of carbon atoms of the dibasic acid is 1 Torr or more, the exhibitability of the stagnation phase is excellent, and when the average carbon number is 16 or less, the compatibility with the cellulose ester is remarkably excellent. As for the dibasic acid, the average carbon number is 10 to 14, and the average carbon number is 10 to 12. -39 - 201213864 If the average carbon number is 10 to 16, the above-mentioned aromatic dibasic acid having 10 to 16 carbon atoms and the other dibasic acid may be used. The dibasic acid which can be used is preferably a dicarboxylic acid having 4 to 9 carbon atoms or an ester-forming derivative thereof, and examples thereof include succinic acid, glutaric acid, adipic acid, maleic acid, and succinic anhydride. , maleic anhydride, phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, etc. or the like, and the above-mentioned diols may be used singly or in combination of two or more kinds, for example, Glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butane Alcohol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1 , 4-cyclohexanediol, etc., wherein ethylene glycol, diethylene glycol, 1,2-propanediol, 2-methyl-1,3-propanediol is preferred, more preferably ethylene glycol, diethylene glycol 1,2-propanediol. The polyester polyol of the present invention may be subjected to the above-mentioned dibasic acid or the ester-forming derivative and the diol in the presence of an esterification catalyst, for example, in the temperature range of 180 to 25 ° C. It is customary to carry out the esterification reaction for ~25 hours to manufacture. When the esterification reaction is carried out, a solvent such as toluene or xylene may be used, but a solvent is not used or a diol used as a raw material is used as a solvent. The esterification catalyst may be, for example, tetraisopropyl titanate. Tetrabutyl titanate 'p-toluenesulfonic acid, dibutyltin oxide, and the like. The total amount of the esterification catalyst relative to the di-acid or the ester-forming derivative is preferably from 0.01 to 0.5 part by mass based on -40 to 201213864. The molar ratio of the dibasic acid or the ester-forming derivative to the diol must be such that the terminal group of the polyester becomes a hydroxyl (hydroxyl) molar ratio and thus forms relative to the dibasic acid or the ester The derivative 1 molar alcohol is 1.1 to 1 mole. Preferably, the diol is 1.5 to 7 moles, more preferably, relative to the dibasic acid or the ester-forming derivative 1 mole, relative to the dibasic acid or the ester-forming derivative 1 mole. The diol is 2 to 5 moles. On the other hand, since the carboxyl terminal in the above polyester polyol lowers the humidity stability, the lower the content, the better. Specifically, the acid value is preferably 5.0 or less, more preferably 1.0 or less, and most preferably 0.5 or less. The acid value herein means the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of the sample (the carboxyl group present in the sample). The acid value is measured based on JIS K0070. The hydroxy (hydroxyl) valence (OHV) of the polyester polyol is preferably in the range of from 3 $ mg/g to 220 mg/g. The hydroxy (hydroxy) valence herein means the number of milligrams of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxy group (hydroxyl group) when the OH group contained in the sample lg is acetylated. The OH group was acetylated in the sample using an acid anhydride, and the unused acetic acid was titrated with a potassium hydroxide solution by the difference from the initial titration of acetic anhydride. The hydroxy (hydroxyl) content of the aforementioned polyester polyol is preferably 70% or more. When the (hydroxyl) content is small, the compatibility of the polyester polyol with the cellulose ester is lowered. Therefore, the hydroxy (hydroxyl) content is preferably 70% or more, more preferably 90% or more, and most preferably 99% or more. In the present invention, the compound having a hydroxy (hydroxyl) content of 50% or less does not include a hydroxy (hydroxy) polyester polyol which is substituted with a group other than a hydroxyl group (hydroxyl group) in one of the terminal groups. The aforementioned hydroxy (hydroxyl) content can be determined by the following formula (A). Formula (A): Υ/Χχ100 = hydroxy (hydroxyl) content (%) X: hydroxy (hydroxyl) valence (OHV) of the aforementioned polyester polyol Υ : 1 / (number average molecular weight (Μη)) χ56χ2χ1000 The aforementioned polyester plural The alcohol preferably has a number average molecular weight in the range of from 30 to 3,000, more preferably an average molecular weight of from 305 to 2,000. Further, the polyester polyol of the present invention preferably has a molecular weight of 1.0 to 3.0, more preferably 1. to 2.0. When the degree of dispersion is within the above range, a polyester polyol excellent in compatibility with a cellulose ester can be obtained. Further, the polyester polyol preferably contains 50% or more of a component having a molecular weight of 300 to 1800. By making the number 'average molecular weight within the above range, the compatibility can be greatly improved. The method of controlling the number average molecular weight, the dispersity, and the component content ratio within the above preferred range is preferably 2 to 5 m per 1 mol of the dibasic acid or the ester-forming derivative. A method of diol and distilling off unreacted diol under reduced pressure. The temperature for vacuum distillation is preferably from 100 to 20 (TC, more preferably from 120 to 180 ° C. Preferably, it is from 130 to 170 ° C. The pressure reduction during vacuum distillation is preferably from 0.01 to 67 kPa. (0.1 to 500 Torr), more preferably 0.06 to 27 kPa (0.5 to 200 Torr), preferably 〇_13 to 13 kPa (1 to 100 Torr). The number average molecular weight (Μη) and dispersion of the polyester polyol can be used as a gel. Measurement by a permeation chromatography (GPC). One of the measurement conditions is, for example, but not limited to, and the same measurement method can be used. -42- 201213864 Solvent··Tetrahydrofuran (THF) Columns··Connected with two TSKgels G2000HXL (manufactured by TOSOH) Column temperature: 40 °C Sample concentration: 0.1% by mass Device: HLC-8220 (manufactured by TOSOH) Flow: l.Oml/min Calibration curve: Use PStQuick F (TOSOH ( In order to obtain the effect of the present invention, it is preferred that the film contains 5 to 30% by mass of the polyester polyol, more preferably 5 to 20% by mass. Specific examples of the dibasic acid of 10 to 16 are used, but the present invention is not limited to the above. (1) 2,6-naphthalene Acid (2) 2,3-naphthalenedicarboxylic acid (3) 2,6-nonanedicarboxylic acid (4) 2,6-naphthalenedicarboxylic acid: succinic acid (75: 25 to 99: 1 molar ratio) ( 5) 2,6-naphthalene dicarboxylic acid: terephthalic acid (50:50~99:1 molar ratio) (6) 2,3-naphthalenedicarboxylic acid: succinic acid (75: 25~99: 1 Mo Ear ratio) (7) 2,3-naphthalene dicarboxylic acid: terephthalic acid (50: 5 0~99 : 1 molar ratio) (8) 2,6-nonanedicarboxylic acid: succinic acid (5 0: 50~99:1 molar ratio) (9) 2,6-anthracene dicarboxylic acid: terephthalic acid (25: 75~99: 1 molar -43-201213864 ratio) (10) 2,6-naphthalene Carboxylic acid: adipic acid (67: 33 to 99: 1 molar ratio) (11) 2,3-naphthalenedicarboxylic acid: adipic acid (67: 33 to 99: 1 molar ratio) (12) 2, 6-decanedicarboxylic acid: adipic acid (40: 6 0 to 99: 1 molar ratio (ultraviolet absorber) The λ/4 plate and optical film of the present invention may contain an ultraviolet absorber. For example, an oxybenzophenone type compound, a benzotriazole type compound, a salicylate type compound, a benzophenone type compound, a cyanoacrylate type compound, a nickel-salt-salt type compound, and a triazine type are mentioned. Compound, etc., but preferably less colored Benzotriazole-based compound. In addition, it is also preferable to use the ultraviolet absorber described in JP-A No. Hei 1 0- 1 8262 No. 1 and JP-A No. 8 -3 3 75 74 and JP-A No. 2001-72782. The polymer ultraviolet absorber described in JP-A-2002-31715, JP-A-2002-169020, JP-A-2002-47357, JP-A-2002-3 63 42 0, and JP-A-2003-119-317. The ultraviolet absorber has an excellent absorption energy of ultraviolet rays having a wavelength of 3 7 Onm or less, and preferably has a low absorption of visible light having a wavelength of 400 nm or more from the viewpoint of liquid crystal display properties, from the viewpoint of preventing deterioration of a polarizer or a liquid crystal. By. Specific examples of the ultraviolet absorber useful in the present invention are exemplified by 2-( 2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(2'-hydroxy-3',5'-di -44- 201213864 Tributylphenyl)benzotriazole, 2-(2,-hydroxy-3'-t-butyl-5'-methylphenyl)benzoindole, 2-(2' -transcarbyl-3',5'-a table of dibutylcarbyl)-5-chlorobenzotriazole, 2-(2,-hydroxy-3,-(3",4",5",6"- Tetrahydrobenzidine methyl)-5'-methylphenyl)benzotriazole, 2,2-methylenebis(4-(1,1,3,3-tetramethylbutyl) -6-( 2H-benzotriazol-2-yl)phenol), 2-( 2'-hydroxy-3,-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole , 2-( 2H-benzotriazol-2-yl)-6-(linear and side chain dodecyl)-4-methylphenol, octyl-3- [3-t-butyl-4 -hydroxy-5-(chloro-2H-benzotriazol-2-yl)phenyl]propionate with 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5- (5 a mixture of _chloro-2-benzotriazol-2-yl)phenyl]propionate, etc., but is not limited thereto. Further, commercially available products can be suitably used as TINUVIN 109 'TINUVIN 171, TINUVIN 326 (all manufactured by BASF Corporation of Japan). As the polymer ultraviolet absorber, a reactive ultraviolet absorber RUVA-93 manufactured by Otsuka Chemical Co., Ltd. can be exemplified. Specific examples of the benzophenone-based compound include 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, and 2-hydroxy-4-methoxy group. 5-5-sulfobenzophenone, bis(2-methoxy-4-hydroxy-5-benzimidylphenylmethane), and the like, but is not limited thereto. The ultraviolet absorber described above, which is preferably used in the present invention, is preferably a benzotriazole-based ultraviolet absorber or a benzophenone-based ultraviolet absorber having high transparency and excellent deterioration of a polarizing plate or a liquid crystal element. A benzotriazole-based ultraviolet absorber which is less desirable in coloring. The method of adding the ultraviolet absorber to the dopant can be used without limitation as long as it can dissolve the ultraviolet absorber in the dopant, but it is preferred to dissolve the ultraviolet absorber in the present invention -45-201213864. Methylene chloride, methyl acetate, dioxane, etc. are prepared as a good solvent for the cellulose ester, or a mixed solvent of a good solvent and a weak solvent such as a lower aliphatic alcohol (methanol, ethanol, propanol, butanol, etc.) A method in which a UV absorber solution is added to a cellulose ester solution and doped. In this case, the dopant solvent composition is as much as possible or nearly as good as the solvent composition of the ultraviolet absorber solution. The content of the ultraviolet absorber is 0.0 1 to 5 mass%, preferably 0.5 to 3 mass%. (Antioxidant) The antioxidant is preferably a hindered phenol-based compound, which is exemplified by, for example, 2,6-di-t-butyl-p-cresol, pentaerythritol·肆[3-(3,5-di-t-butyl) -4-hydroxyphenyl)propionate], triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexyl Glycol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4.hydroxy-3 ,5-di-t-butylanilino)-1,3,5-triazine, 2,2-thio-diethylidene bis[3-(3,5-di-t-butyl-4 -hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylene double ( 3,5-di-t-butyl-4-hydroxy-hydrocinnamate, 1,3,5-trimethyl-2,4,6-paran (3,5-di-t-butyl- 4-hydroxybenzyl)benzene, cis-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, etc., preferably 2,6-di-t-butyl- P-cresol, pentaerythritol-indole [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], triethylene glycol-bis[3-(3-t-butyl) -5-Methyl 4-hydroxyphenyl)propionate]. Further, for example, a metal of a bisamine such as N,N,-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanyl] hydrazine-46-201213864 may be used. A phosphorus-based processing stabilizer such as an inert agent or ginseng (2,4-di-tert-butylphenyl) phosphate. The amount of the compound to be added is preferably from 1 ppm to 1.0% by mass based on the mass ratio of the cellulose ester, more preferably from 1 to 10,000 ppm. Further, a compound represented by the following general formula (L) is also preferably used. General (L}

[式中’ R2〜Rs各相互獨立表示氫原子或取代基，尺6表示氫原子或取代基，η表示1或2，n爲1時，Ri表示取代基，且η爲2時，R,表示二價連結基]。前述一般式（L )中’ R2〜R5相互獨立表示氫原子或取代基。以R2〜R s表示之取代基並無特別限制，列舉爲例如院基（例如，甲基、乙基、丙基、異丙基、第三丁基、戊基、己基、辛基、癸基、三氟甲基等）'環烷基（例如，環戊基、環己基等）、芳基（例如，苯基、萘基等）、酿基胺基（例如’乙醯基胺基、苯甲醯基胺基等）、院硫基 (例如，甲硫基、乙硫基等）、芳硫基（例如，苯硫基、萘硫基等）、烯基（例如’乙烯基、2-丙烯基、3_丁稀基、1-甲基-3-丙烯基、3-戊烯基、1-甲基-3_ 丁烯基、心己稀基、環己烯基等）、鹵素原子（例如，氟原子、氯原子、溴原子、碘原子等）、炔基（例如’丙块基等）、雜環基 -47- 201213864 (例如，吡啶基、噻唑基、噁唑基、咪唑基等）、烷基磺醯基（例如，甲基磺醯基、乙基磺醯基等）、芳基磺醯基 (例如，苯基磺醯基、萘基磺醯基等）、烷基亞磺醯基（例如，甲基亞磺醯基等）、芳基亞磺醯基（例如，苯基亞磺醯基等）、磺基、醯基（例如，乙醯基、丙醯基、苯甲醯基等）、胺甲醯基（例如，胺基羰基、甲胺基羰基、二甲胺基羰基、丁胺基羰基、環己胺基羰基、苯基胺基羰基、2-吡啶基胺基羰基等）、胺磺醯基（例如，胺基磺醯基、甲基胺基磺醯基、二甲基胺基磺醯基、丁基胺基磺醯基、己基胺基磺醯基、環己基胺基磺醯基、辛基胺基磺醯基、十二烷基胺基磺醯基、苯基胺基磺醯基、萘基胺基磺醯基、2 -吡啶基胺基磺醯基等）、磺醯胺基（例如，甲烷磺醯胺基、苯磺醯胺基等）、氰基、烷氧基（例如，甲氧基、乙氧基、丙氧基等）、芳氧基（例如，苯氧基、萘氧基等）、雜環氧基、矽氧烷基、醯氧基（例如，乙醯氧基、苯甲醯氧基等）、磺酸基、磺酸之鹽、胺基羰氧基、胺基 (例如，胺基、乙基胺基；二甲基胺基、丁基胺基、環戊基胺基、2-乙基己基胺基、十二烷基胺基等）、苯胺基（例如，苯基胺基、氯苯基胺基、甲苯胺基、甲氧苯胺基（ anisidino ) '萘基胺基、2-吡啶基胺基等）、醯亞胺基、脲基（例如，甲基脲基、乙基脲基、戊基脲基、環己基脲基、辛基脲基、十二烷基脲基、.苯基脲基、萘基脲基、2-吡啶基胺基脲基等）、烷氧基羰基胺基（例如，甲氧基羰基胺基、苯氧基羰基胺基等）、烷氧基羰基（例如，甲氧 -48- 201213864 基鑛基、乙氧基鑛基、苯氧基擬基等）、芳氧基羯基（例如’苯氧基羰基等）、雜環硫基、硫脲基、羧基、羧酸之鹽、羥基、巯基、硝基等之各種基。該等取代基亦可經同樣的取代基進一步取代。前述一般式（L)中，R2〜R5較好爲氫原子或烷基。前述一般式（L )中，R6表示氫原子或取代基，以R6 表示之取代基可列舉爲與R2〜Rs所表示之取代基相同之基〇前述一般式（L)中，116較好爲氫原子。前述一般式（L)中，η表示1或2。前述一般式（L)中，η爲1時，I表示取代基，η爲2 時’ R 1表示二價連結基。R,表示取代基時，取代基可列舉爲與R2〜R5表示之取代基相同之基。R,表示二價連結基時 ’二價連結基之例可列舉爲可具有取代基之伸烷基、可具有取代基之伸芳基、氧原子、氮原子、硫原子、或該等連 φ 結基之組合。前述一般式（L)中，η較好爲1，此時之1^較好爲經取代或未經取代之苯基，更好爲經烷基取代之苯基。以下，列示本發明中之以前述一般式（L )表示之化合物之具體例，但本發明並不受限於以下之具體例。 -49- 201213864 [化 14] 101[wherein R 2 to Rs each independently represent a hydrogen atom or a substituent, the ruthenium 6 represents a hydrogen atom or a substituent, η represents 1 or 2, when n is 1, Ri represents a substituent, and when η is 2, R, Indicates a divalent linking group]. In the above general formula (L), 'R2 to R5' independently represent a hydrogen atom or a substituent. The substituent represented by R2 to R s is not particularly limited and is exemplified by, for example, a hospital group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group). , trifluoromethyl, etc.) 'cycloalkyl (eg, cyclopentyl, cyclohexyl, etc.), aryl (eg, phenyl, naphthyl, etc.), arylamino (eg 'ethinylamino, benzene Mercaptoamine, etc.), thiol (eg, methylthio, ethylthio, etc.), arylthio (eg, phenylthio, naphthylthio, etc.), alkenyl (eg, 'vinyl, 2- Propylene group, 3-butylenyl group, 1-methyl-3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, hexyl group, cyclohexenyl group, etc.), halogen atom ( For example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, an alkynyl group (for example, a 'propyl group, etc.), a heterocyclic group - 47 to 201213864 (for example, a pyridyl group, a thiazolyl group, an oxazolyl group, an imidazolyl group, etc.) ), alkylsulfonyl (for example, methylsulfonyl, ethylsulfonyl, etc.), arylsulfonyl (for example, phenylsulfonyl, naphthylsulfonyl, etc.), alkylsulfin Mercapto (for example, methyl amide Anthracenyl, etc., an arylsulfinyl group (for example, a phenylsulfinyl group, etc.), a sulfo group, a fluorenyl group (for example, an ethyl sulfonyl group, a propyl fluorenyl group, a benzhydryl group, etc.), an amine mercapto group (e.g., aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, butylaminocarbonyl, cyclohexylaminocarbonyl, phenylaminocarbonyl, 2-pyridylaminocarbonyl, etc.), aminesulfonyl ( For example, aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, hexylaminosulfonyl, cyclohexylaminosulfonyl, octyl Aminosulfonyl, dodecylaminosulfonyl, phenylaminosulfonyl, naphthylaminosulfonyl, 2-pyridylaminosulfonyl, etc., sulfonylamino (eg , methanesulfonamide, benzenesulfonylamino, etc.), cyano, alkoxy (eg, methoxy, ethoxy, propoxy, etc.), aryloxy (eg, phenoxy, naphthyloxy) , etc.), a heterocyclic oxy group, a decyloxy group, a decyloxy group (for example, an ethoxylated group, a benzhydryloxy group, etc.), a sulfonic acid group, a salt of a sulfonic acid, an aminocarbonyloxy group, an amine group (eg, amine group, ethyl amine group a dimethylamino group, a butylamino group, a cyclopentylamino group, a 2-ethylhexylamino group, a dodecylamino group, etc.), an anilino group (for example, a phenylamino group, a chlorophenylamino group, Toluidine, anisidino 'naphthylamino, 2-pyridylamino, etc.), quinone imine, ureido (eg, methylureido, ethylureido, pentylureido) , cyclohexylureido, octylureido, dodecylureido, phenylureido, naphthylureido, 2-pyridylaminoureido, etc.), alkoxycarbonylamine (for example, A An oxycarbonylamino group, a phenoxycarbonylamino group, etc.), an alkoxycarbonyl group (for example, a methoxy-48-201213864-based ore group, an ethoxylate group, a phenoxy group, etc.), an aryloxy group Various groups such as a group (e.g., 'phenoxycarbonyl group, etc.), a heterocyclic thio group, a thiourea group, a carboxyl group, a salt of a carboxylic acid, a hydroxyl group, a thiol group, a nitro group, and the like. These substituents may also be further substituted with the same substituents. In the above general formula (L), R2 to R5 are preferably a hydrogen atom or an alkyl group. In the above general formula (L), R6 represents a hydrogen atom or a substituent, and the substituent represented by R6 may be exemplified by the same substituent as represented by R2 to Rs. In the above general formula (L), 116 is preferably A hydrogen atom. In the above general formula (L), η represents 1 or 2. In the above general formula (L), when η is 1, I represents a substituent, and when η is 2, R 1 represents a divalent linking group. When R represents a substituent, the substituent may be the same as the substituent represented by R2 to R5. R, which is an example of the divalent linking group in the case of a divalent linking group, may be exemplified by an alkyl group which may have a substituent, an extended aryl group which may have a substituent, an oxygen atom, a nitrogen atom, a sulfur atom, or the like A combination of knots. In the above general formula (L), η is preferably 1, and at this time, 1 is preferably a substituted or unsubstituted phenyl group, more preferably an alkyl group-substituted phenyl group. Specific examples of the compound represented by the above general formula (L) in the present invention are shown below, but the present invention is not limited to the following specific examples. -49- 201213864 [Chem. 14] 101

103103

CH3CH3

CHS 105 107CHS 105 107

109109

-50- 201213864 [化 15]-50- 201213864 [化15]

112 ο112 ο

115115

ΟΟ

CH,CH,

-51 - 201213864 [化 16]-51 - 201213864 [Chem. 16]

該等化合物可分別使用一種或組合兩種以上使用，其調配量可在不損及本發明目的之範圍內適當選擇，但相對於纖維素酯100質量份，通常爲0.001~10.0質量份，較好爲 0·01〜5.0質量份，更好爲0.1〜3.0質量份。 (滞相調整劑）添加用於調整滞相之化合物可如歐洲專利91 1，656Α2 號說明書中記載，使用具有兩個以上之芳香族環之芳香族化合物。又，亦可倂用二種類以上之芳香族化合物。該芳香族化合物之芳香族環除芳香族烴環以外，亦包含芳香族性雜環。最好爲芳香族性雜環，芳香族性雜環一般而言爲不飽和雜環。其中，最好爲三嗪環。芳香族化合物所具有之芳香族環之數較好爲2~20個’ 更好爲2〜12個，又更好爲2~8個，最好爲3〜6個。兩個芳香族環之鍵結關係可分類成（a )形成縮合環之情況’ （b ) -52- 201213864 以單鍵直接鍵結之情況，及（c)透過連結基鍵結之情況 (由於係芳香族環，無法形成螺鍵結）。鍵結關係可爲（ a)〜（c)之任一種。 (a)之縮合環（兩個以上之芳香族環之縮合環）之例包含茚環、萘環、莫環、弗環、菲環、蒽環、苊烯環、并四苯（naphthacene )環 '芘環、吲哚環、異吲哚環、苯并呋喃環 '苯并噻吩環、吲哚嗪（indolizine )環、苯并噁唑環、苯并噻唑環、苯并咪唑環、苯并三唑環、嘌呤環、吲唑環、色烯（chr omen e )環、喹啉環、異喹啉環、喹啉啶環、喹嗖咐環、噌啉環、喹喔啉環、酞嗪環、喋啶（ pteridin)環、昨哇環、ιΓ「ιι定環、菲陡（phenanthridine) 環、咕噸（xanthene)環、吩曝（phenazine)環' 吩噻曉 (phenothiazine)環、吩卩惡噻（phenoxathiin)環、吩嚼曝（phenoxazine)環及嚷惠（thianthrene)環。較好爲萘環、奧環、吲哚環、苯并噁唑環、苯并噻唑環、苯并咪唑These compounds may be used singly or in combination of two or more kinds, and the amount thereof may be appropriately selected within the range not detracting from the object of the present invention, but is usually 0.001 to 10.0 parts by mass relative to 100 parts by mass of the cellulose ester. It is preferably from 0. 01 to 5.0 parts by mass, more preferably from 0.1 to 3.0 parts by mass. (Stagnation of a phase retarder) A compound for adjusting a retardation phase is added as described in the specification of European Patent No. 91,656Α2, and an aromatic compound having two or more aromatic rings is used. Further, two or more types of aromatic compounds may be used. The aromatic ring of the aromatic compound contains an aromatic heterocyclic ring in addition to the aromatic hydrocarbon ring. It is preferably an aromatic heterocyclic ring, and the aromatic heterocyclic ring is generally an unsaturated heterocyclic ring. Among them, a triazine ring is preferred. The number of aromatic rings possessed by the aromatic compound is preferably from 2 to 20', more preferably from 2 to 12, still more preferably from 2 to 8, more preferably from 3 to 6. The bonding relationship between two aromatic rings can be classified into (a) the case of forming a condensed ring' (b) -52- 201213864 in the case of a single bond direct bond, and (c) the case of a bond through a linker (due to It is an aromatic ring and cannot form a screw bond). The bonding relationship may be any one of (a) to (c). Examples of the condensed ring (a condensed ring of two or more aromatic rings) of (a) include an anthracene ring, a naphthalene ring, a molybdenum ring, an anthracene ring, a phenanthrene ring, an anthracene ring, a terpene ring, and a naphthacene ring. 'Anthracycline, anthracene ring, isoindole ring, benzofuran ring' benzothiophene ring, indolizine ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriene Oxazole ring, anthracene ring, indazole ring, chromene (chr omen e) ring, quinoline ring, isoquinoline ring, quinoline ring, quinone ring, porphyrin ring, quinoxaline ring, pyridazine ring , pteridin ring, yesterday wow ring, ιΓ "ιι定环, phenanthridine ring, xanthene ring, phenazine ring 'phenothiazine ring, 卩卩a phenoxathiin ring, a phenoxazine ring, and a thianthrene ring, preferably a naphthalene ring, an anthracene ring, an anthracene ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring.

苯并三唑環及喹啉環。 (b)之單鍵較好爲兩個芳香族環之碳原子間之鍵結。亦可以兩個以上之單鍵鍵結兩個芳香族環，在兩個芳香族環之間形成脂肪族環或非芳香族性雜環。 (c)之連結基與兩個芳香族之碳原子鍵結亦較佳。連結基較好爲伸院基、伸稀基、伸炔基、-C Ο -、- 0 -、-NH-、-S-或該等之組合。由組合而成之連結基之例示於下。又，以下之連結基之例之左右關係亦可相反。 -CO-0-、-CO-NH-、-伸烷基- 〇-、-NH-CO-NH-、-NH- -53- 201213864 CO-O-、-o-co-o-、-Ο-伸烷基-0-、-CO-伸烯基-、-CO-伸烯基- NH-、-CO -伸烯基- Ο-、-伸烷基- CO-O-伸烷基-o-co-伸烷基、-Ο-伸烷基-CO-O-伸烷基-O-CO-伸烷基 CO -伸烷基- CO-O-、-NH-CO -伸烯基-、-O-CO -伸烯基-。芳香族環及連結基亦可具有取代基。取代基之例包含鹵素原子（F、Cl、Br、I)、羥基、羧基、氰基、胺基、硝基、磺基、胺甲醯基、胺磺醯基、脲基、烷基、烯基、炔基、脂肪族醯基、脂肪族醯氧基、烷氧基、烷氧基羰基、烷氧基羰基胺基、烷硫基、烷基磺醯基、脂肪族醯胺基、脂肪族磺醯胺基、脂肪族取代之胺基、脂肪族取代之胺甲醯基、脂肪族取代之胺磺醯基、脂肪族取代之脲基及非芳香族性雜環基。烷基之碳原子述較好爲1〜8。相較於環狀烷基，鏈狀烷基者較佳，最好爲直鏈狀烷基。烷基亦可另具有取代基 (例如，羥基、羧基、烷氧基、烷基取代之胺基）。烷基 (包含經取代之烷基）之例包含甲基、乙基、正丁基、正己基、2-羥基乙基、4-羧基丁基、2-甲氧基乙基及2-二乙胺基乙基。烯基之碳原子數較好爲2〜8。相較於環狀烯基亦爲鏈狀烯基者較佳，最好爲直鏈狀烯基。烯基亦可進而具有取代基。烯基之例包含乙烯基、烯丙基及1-己烯基。炔基之碳原子數較好爲2〜8。相較於環狀炔基，鏈狀炔基者較佳，最好爲直鏈狀炔基。炔基亦可另具有取代基，炔基之例包含乙炔基、1-丁炔基及1-己炔基。脂肪族醯基之碳原子數較好爲1~10。脂肪族醯基之例 -54- 201213864 包含乙醯基、丙醯基及丁醯基。脂肪族醯氧基之碳原子數較好爲1~10。脂肪族醯氧基之例包含乙醯氧基。烷氧基之碳原子數較好爲1〜8。烷氧基亦可另具有取代基（例如，烷氧基）。烷氧基（包含經取代之烷氧基）之例包含甲氧基、乙氧基、丁氧基及甲氧基乙氧基。烷氧基羰基之碳原子數較好爲2〜10。烷氧基羰基之例包含甲氧基羰基及乙氧基羰基。烷氧基羰基胺基之碳原子數較好爲2〜10。烷氧基羰基胺基之例包含甲氧基羰基胺基及乙氧基羰基胺基。烷硫基之碳原子數較好爲1〜12。烷硫基之例包含甲硫基、乙硫基及辛硫基。烷基磺醯基之碳原子數較好爲1〜8 。烷基磺醯基之例包含甲烷磺醯基及乙烷磺醯基。脂肪族醯胺基之碳原子數較好爲1〜10。脂肪族醯胺基之例包含乙醯胺。脂肪族磺醯胺基之碳原子數較好爲1〜8。脂肪族擴醯胺基之例包含甲烷磺醯胺、丁烷磺醯胺及正辛烷磺醯胺。脂肪族取代之胺基之碳原子數較好爲1〜1 〇。脂肪族取代之胺基之例包含二甲胺基、二乙胺基及2-羧基乙胺基。脂肪族取代之胺甲醯基之碳原子數較好爲2〜1 0。脂肪族取代之胺甲醯基之例包含甲基胺甲醯基及二乙基胺甲醯基。月旨肪族取代之胺磺醯基之碳原子數較好爲1~8。脂肪族取代之胺磺醯基之例包含甲基胺磺醯基及二乙基胺磺醯基。脂肪族取代之脲基之碳原子數較好爲2〜10。脂肪族取代之脲基之例包含甲基脲基。非芳香族性雜環基之例包含哌啶基及嗎啉基。滯相調整劑之分子量較好爲300以上800以下。該等就 -55- 201213864 使用時及偏光板加工時抑制流出之觀點而言，可任意選擇分子構造之極性。具有1，3,5-三嗪環之化合物中較好爲以下述一般式（R )表示之化合物。 [化 17] -般式(R> R* xVntXnri ΝγΝ χ2 —般式（R)中，X1爲單鍵、-nr4-、-ο-或-S-; X2爲單鍵、-NR5-、-0-或- S-; X3 爲單鍵、-NR6-、-0-或- S-; R1、R2及R3爲烷基、烯基、芳基或雜環基；而且，R4、R5 及R6爲氫原子、烷基、烯基、芳基或雜環基。以一般式（ R)表示之化合物最好爲三聚氰胺化合物。三聚氰胺化合物中，一般式（R)中，X1、X2及X3分別爲-NR4-、-NR”及-NR6-，或X1、X2及X3爲單鍵，且R1 、R2及R3爲氮原子上具有游離原子價之雜環基。-xLr1、-X2-R2及-X3-R3較好爲相同之取代基。R1、R2及R3最好爲芳基。R4、Rs及Κ·6最好爲氫原子。上述烷基，相較於環烷基，鏈狀烷基者較佳。相較於具有分支之鏈狀烷基，以直鏈狀烷基者較佳。烷基之碳原子數較好爲1〜30，更好爲1〜2 0，又更好爲 1〜10，再更好爲1〜8，最好爲1〜6。烷基亦可具有取代基。取代基之具體例列舉爲例如鹵素原子、烷氧基（例如 -56- 201213864 甲氧基、乙氧基、環氧乙基氧基等各基）及醯氧基（例如，丙烯醯氧基、甲基丙烯醯氧基）等。上述烯基，相較於環狀烯基，以鏈狀烯基者較佳。相較於具有分支之烯基，以直鏈狀烯基者較佳。烯基之碳原子數較好爲2〜30，更好爲2〜2 0，又更好爲2〜10，再更好爲2〜8，最好爲2〜6。烯基亦可具有取代基。取代基之具體例列舉爲例如鹵素原子、烷氧基（例如甲氧基、乙氧基、環氧乙基氧基等各基）或醯氧基（例如，丙烯醯氧基、甲基丙烯醯氧基等各基）等。上述芳基較好爲苯基或萘基，最好爲苯基。芳基亦可具有取代基。取代基之具體例包含例如鹵素原子、羥基、氰基、硝基、羧基、烷基、烯基、芳基、烷氧基、烯氧基、芳氧基、醯氧基、烷氧基羰基、烯氧基羰基、芳氧基羰基、胺磺醯基、烷基取代之胺磺醯基、烯基取代之胺磺醯基、芳基取代之胺磺醯基、磺醯胺基、胺甲醯基、烷基取代之胺甲醯基、烯基取代之胺甲醯基、芳基取代之胺甲醯基、醯胺基、烷硫基、烯基硫基、芳硫基及醯基。上述烷基與上述烷基同義。烷氧基、醯氧基、烷氧基羰基、烷基取代之胺磺醯基、磺醯胺基、烷基取代之胺甲醯基、醯胺基、烷硫基與醯基之烷基部分亦與前述烷基同義。上述烯基與前述烯基同義。烯氧基、醯氧基、烯氧基羰基、烯基取代之胺磺醯基 -57- 201213864 '磺醯胺基、烯基取代之胺甲醯基、醯胺基、烯基硫基及醯基之烯基部分亦與前述烯基同義。上述芳基之具體例列舉爲例如苯基、α-萘基、β-萘基、4_甲氧基苯基、3,4-二乙氧基苯基、4-辛氧基苯基或4-十二烷基氧基苯基等各基。芳氧基、醯氧基、芳氧基羰基、芳基取代之胺磺醯基、磺醯胺基、芳基取代之胺甲醯基、醯胺基、芳硫基及醯基之部分之例與上述芳基同義。 X1、X2或乂3爲_\11-、-0-或-S-時之雜環基較好具有芳香族性。具有芳香族性之雜環基中之雜環爲一般不飽和雜環，較好爲具有最多雙鍵之雜環。雜環較好爲5員環、6員環或 7員環，更好爲5員環或6員環，最好爲6員環。雜環中之雜原子較好爲N、S或Ο等各原子，最好爲Ν 原子。具有芳香族性之雜環最好爲吡啶環（作爲雜環基爲例如2-吡啶基或4-吡啶基等各基）。雜環基亦可具有取代基。雜環基之取代基之例係與上述芳基部分之取代基之例相同。 X1' X2或X3爲單鍵時之雜環基較好爲氮原子上具有游離原子價之雜環基。氮原子上具有游離原子價之雜環基較好爲5員環、6員環或7員環，更好爲5員環或6員環，最好爲5員環。雜環基亦可具有複數之氮原子。又，雜環基中之雜原子亦可具有氮原子以外之雜原子 -58- 201213864 (例如，〇原子、s原子）。雜環基亦可具有取代基。雜環基之取代基之具體例係與上述芳基部分之取代基之具體例同義。以下列示氮原子上具有游離原子價之雜環基之具體例 [化 18] (Hc-2)Benzotriazole ring and quinoline ring. The single bond of (b) is preferably a bond between carbon atoms of two aromatic rings. It is also possible to bond two aromatic rings with two or more single bonds to form an aliphatic ring or a non-aromatic heterocyclic ring between the two aromatic rings. It is also preferred that the linking group of (c) is bonded to two aromatic carbon atoms. The linking group is preferably a stretching base, a stretching base, an alkyne group, -C Ο -, - 0 -, -NH-, -S- or a combination thereof. Examples of the linked groups formed by the combination are shown below. Further, the left-right relationship of the following examples of the linking group may be reversed. -CO-0-, -CO-NH-, -alkylene - 〇-, -NH-CO-NH-, -NH- -53- 201213864 CO-O-, -o-co-o-, -Ο -alkyl-O-, -CO-alkenyl-, -CO-alkenyl-NH-, -CO-alkenyl-anthracene-, -alkylene-CO-O-alkylene-o -co-alkylene, hydrazine-alkylene-CO-O-alkylene-O-CO-alkylene CO-alkylene-CO-O-, -NH-CO-alkenyl-, -O-CO - an alkenyl group -. The aromatic ring and the linking group may have a substituent. Examples of the substituent include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, a cyano group, an amine group, a nitro group, a sulfo group, an amine carbaryl group, an amine sulfonyl group, a ureido group, an alkyl group, an alkene group. Alkyl, alkynyl, aliphatic fluorenyl, aliphatic methoxy, alkoxy, alkoxycarbonyl, alkoxycarbonylamino, alkylthio, alkylsulfonyl, aliphatic guanylamine, aliphatic A sulfonamide group, an aliphatic substituted amine group, an aliphatic substituted amine methyl sulfonyl group, an aliphatic substituted amine sulfonyl group, an aliphatic substituted ureido group, and a non-aromatic heterocyclic group. The carbon atom of the alkyl group is preferably from 1 to 8. The chain alkyl group is preferred to the linear alkyl group, and is preferably a linear alkyl group. The alkyl group may further have a substituent (e.g., a hydroxyl group, a carboxyl group, an alkoxy group, an alkyl group-substituted amine group). Examples of alkyl groups (including substituted alkyl groups) include methyl, ethyl, n-butyl, n-hexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl and 2-diethyl Aminoethyl. The number of carbon atoms of the alkenyl group is preferably from 2 to 8. It is preferably a chain alkenyl group rather than a cyclic alkenyl group, and is preferably a linear alkenyl group. The alkenyl group may further have a substituent. Examples of alkenyl groups include vinyl, allyl and 1-hexenyl. The alkynyl group preferably has 2 to 8 carbon atoms. The chain alkynyl group is preferred to the cyclic alkynyl group, and is preferably a linear alkynyl group. The alkynyl group may further have a substituent, and examples of the alkynyl group include an ethynyl group, a 1-butynyl group, and a 1-hexynyl group. The number of carbon atoms of the aliphatic sulfhydryl group is preferably from 1 to 10. Examples of aliphatic sulfhydryl groups -54- 201213864 Contains ethyl thiol, propyl sulfhydryl and butyl sulfhydryl groups. The aliphatic methoxy group preferably has 1 to 10 carbon atoms. An example of an aliphatic methoxy group includes an ethoxy group. The alkoxy group preferably has 1 to 8 carbon atoms. The alkoxy group may further have a substituent (for example, an alkoxy group). Examples of the alkoxy group (including the substituted alkoxy group) include a methoxy group, an ethoxy group, a butoxy group, and a methoxyethoxy group. The number of carbon atoms of the alkoxycarbonyl group is preferably from 2 to 10. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. The alkoxycarbonylamino group preferably has 2 to 10 carbon atoms. Examples of the alkoxycarbonylamino group include a methoxycarbonylamino group and an ethoxycarbonylamino group. The number of carbon atoms of the alkylthio group is preferably from 1 to 12. Examples of the alkylthio group include a methylthio group, an ethylthio group and an octylthio group. The alkylsulfonyl group preferably has 1 to 8 carbon atoms. Examples of the alkylsulfonyl group include a methanesulfonyl group and an ethanesulfonyl group. The aliphatic guanamine group preferably has 1 to 10 carbon atoms. An example of an aliphatic guanamine group includes acetamide. The aliphatic sulfonamide group preferably has 1 to 8 carbon atoms. Examples of the aliphatic extended amidino group include methanesulfonamide, butanesulfonamide and n-octanesulfonamide. The number of carbon atoms of the aliphatic substituted amino group is preferably from 1 to 1 Torr. Examples of the aliphatic substituted amine group include a dimethylamino group, a diethylamino group, and a 2-carboxyethylamino group. The number of carbon atoms of the aliphatic substituted aminomethane group is preferably from 2 to 10%. Examples of the aliphatic substituted amine mercapto group include a methylamine methyl sulfonyl group and a diethylamine methyl fluorenyl group. The carbon number of the amine group substituted by the aliphatic group is preferably from 1 to 8. Examples of the aliphatic substituted aminoxime group include a methylamine sulfonyl group and a diethylamine sulfonyl group. The number of carbon atoms of the aliphatic group-substituted ureido group is preferably from 2 to 10. Examples of the aliphatic substituted urea group include a methylureido group. Examples of the non-aromatic heterocyclic group include a piperidinyl group and a morpholinyl group. The molecular weight of the stagnation modifier is preferably from 300 to 800. In the case of -55-201213864, the polarity of the molecular structure can be arbitrarily selected from the viewpoint of suppressing the outflow during processing and the processing of the polarizing plate. Among the compounds having a 1,3,5-triazine ring, a compound represented by the following general formula (R) is preferred. - General formula (R > R* xVntXnri Ν γ Ν — 2 In the general formula (R), X1 is a single bond, -nr4-, -ο- or -S-; X2 is a single bond, -NR5-, - 0- or -S-; X3 is a single bond, -NR6-, -0- or -S-; R1, R2 and R3 are alkyl, alkenyl, aryl or heterocyclic groups; moreover, R4, R5 and R6 The compound represented by the general formula (R) is preferably a melamine compound. In the melamine compound, in the general formula (R), X1, X2 and X3 are respectively -NR4-, -NR" and -NR6-, or X1, X2 and X3 are single bonds, and R1, R2 and R3 are heterocyclic groups having a free valence on a nitrogen atom. -xLr1, -X2-R2 and - X3-R3 is preferably the same substituent. R1, R2 and R3 are preferably an aryl group. R4, Rs and Κ6 are preferably a hydrogen atom. The above alkyl group is a chain alkyl group compared to a cycloalkyl group. Preferably, it is preferably a linear alkyl group as compared with a branched alkyl group. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 2 0 carbon atoms, more preferably 1 to 10, more preferably 1 to 8, and most preferably 1 to 6. The alkyl group may have a substituent. Specific examples of the substituent are exemplified by halogen. An atom, an alkoxy group (for example, each of a group such as -56-201213864 methoxy, ethoxy, or epoxyethyloxy), and a decyloxy group (for example, an acryloxy group or a methacryloxy group). The alkenyl group is preferably a chain alkenyl group compared to a cyclic alkenyl group, and is preferably a linear alkenyl group as compared with a branched alkenyl group. The number of carbon atoms of the alkenyl group is preferably 2 〜30, more preferably 2 to 2 0, still more preferably 2 to 10, still more preferably 2 to 8, and most preferably 2 to 6. The alkenyl group may have a substituent. Specific examples of the substituent are exemplified as a halogen atom, an alkoxy group (for example, each group such as a methoxy group, an ethoxy group, or an epoxyethyloxy group) or a decyloxy group (for example, each group such as a propylene methoxy group or a methacryloxy group). The above aryl group is preferably a phenyl group or a naphthyl group, and is preferably a phenyl group. The aryl group may have a substituent. Specific examples of the substituent include, for example, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, an alkyl group, an alkene group. Alkyl, aryl, alkoxy, alkenyloxy, aryloxy, decyloxy, alkoxycarbonyl, oxycarbonyl, aryloxycarbonyl, sulfonyl, alkyl substituted amine Alkyl, alkenyl substituted amine sulfonyl, aryl substituted sulfonyl, sulfonylamino, amine carbaryl, alkyl substituted amine carbhydryl, alkenyl substituted amine methyl sulfonyl, aryl Substituted amine indenyl, amidino, alkylthio, alkenylthio, arylthio and anthracenyl. The above alkyl is synonymous with the above alkyl. Alkoxy, decyloxy, alkoxycarbonyl, alkane The alkyl moiety substituted with an amine sulfonyl group, a sulfonylamino group, an alkyl-substituted amine carbaryl group, a decylamino group, an alkylthio group and a fluorenyl group is also synonymous with the aforementioned alkyl group. Synonymous. Alkenyloxy, decyloxy, alkenyloxycarbonyl, alkenyl substituted aminoximeyl-57- 201213864 'sulfonylamino, alkenyl substituted amine indenyl, amidino, alkenylthio The alkenyl moiety of the fluorenyl group is also synonymous with the aforementioned alkenyl group. Specific examples of the above aryl group are exemplified by, for example, a phenyl group, an α-naphthyl group, a β-naphthyl group, a 4-methoxyphenyl group, a 3,4-diethoxyphenyl group, a 4-octyloxyphenyl group or 4 - each group such as dodecyloxyphenyl. Examples of an aryloxy group, a decyloxy group, an aryloxycarbonyl group, an aryl-substituted amine sulfonyl group, a sulfonylamino group, an aryl-substituted amine mercapto group, a decylamino group, an arylthio group, and a mercapto group. It is synonymous with the above aryl group. The heterocyclic group in which X1, X2 or 乂3 is _\11-, -0- or -S- preferably has an aromatic character. The heterocyclic ring in the aromatic heterocyclic group is a generally unsaturated heterocyclic ring, and is preferably a heterocyclic ring having the most double bond. The heterocyclic ring is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and most preferably a 6-membered ring. The hetero atom in the hetero ring is preferably an atom such as N, S or oxime, and is preferably a ruthenium atom. The aromatic heterocyclic ring is preferably a pyridine ring (for example, a heterocyclic group is a group such as a 2-pyridyl group or a 4-pyridyl group). The heterocyclic group may also have a substituent. Examples of the substituent of the heterocyclic group are the same as those of the substituent of the above aryl moiety. When the X1' X2 or X3 is a single bond, the heterocyclic group is preferably a heterocyclic group having a free valence on the nitrogen atom. The heterocyclic group having a free valence on the nitrogen atom is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and most preferably a 5-membered ring. The heterocyclic group may also have a plurality of nitrogen atoms. Further, the hetero atom in the heterocyclic group may have a hetero atom other than a nitrogen atom -58-201213864 (for example, a ruthenium atom or an s atom). The heterocyclic group may also have a substituent. Specific examples of the substituent of the heterocyclic group are synonymous with the specific examples of the substituent of the above aryl moiety. The following is a specific example of a heterocyclic group having a free valence on a nitrogen atom. (Hc-2)

h3c CH, (He-3)H3c CH, (He-3)

-nP-nP

H3C-0-CO (He-4) V，3H3C-0-CO (He-4) V, 3

•NyK•NyK

If 0—r -C4H9 (He—6} (He-5)If 0—r -C4H9 (He—6} (He-5)

59- 201213864 [化 19] (Hc-7) (Hc-8)59- 201213864 [Chem. 19] (Hc-7) (Hc-8)

(Hc-9) (Hc-10)(Hc-9) (Hc-10)

(Hc-11) {Hc-12j(Hc-11) {Hc-12j

n-C4H9-〇-CO 以下列示具有1，3,5-三嗪環之化合物之具體例。又，以下所示之複數個R表示相同之基。 [化 20] ⑴〜(12)n-C4H9-〇-CO The specific examples of the compound having a 1,3,5-triazine ring are shown below. Further, a plurality of Rs shown below represent the same base. [20] (1) ~ (12)

RYNyRRYNyR

N 丫NN 丫N

RR

(1 ) 丁基 (2 ) 2-甲氧基-2-乙氧基乙基 (3 ) 5-~\--碳稀基 (4)苯基 (5 ) 4_乙氧基羰基苯基 (6) 4-丁氧基苯基 (7) 對-聯苯基 (8 ) 4-吡啶基 -60- 201213864 (9 ) 2-萘基 (1 0 ) 2-甲基苯基 (1 1 ) 3,4-二甲氧基苯基 (12 ) 2-呋喃基 [化 21] (13)(1) Butyl (2) 2-methoxy-2-ethoxyethyl (3) 5-~\--carbon-based (4) phenyl (5) 4-ethoxycarbonylphenyl ( 6) 4-butoxyphenyl (7) p-biphenyl (8 ) 4-pyridyl-60- 201213864 (9 ) 2-naphthyl (1 0 ) 2-methylphenyl (1 1 ) 3 ,4-dimethoxyphenyl(12)2-furanyl[21] (13)

[化 22] (14)-(79)[化22] (14)-(79)

R IR I

(14 )苯基(14) phenyl

(15 ) 3-乙氧基羰基苯基 (16 ) 3-丁氧基苯基 (17)間-聯苯基 (1 8 ) 3 -苯基硫苯基 (19 ) 3-氯苯基 (20 ) 3-苯甲醯基苯基 (21) 3-乙醯氧基苯基 (22 ) 3-苯甲醯基氧基苯基 (23) 3 -苯氧基羰基苯基 (24) 3-甲氧基苯基 -61 201213864 (25 ) 3-苯胺基苯基 (26) 3 -異丁醯基胺基苯基 (27) 3-苯氧基羰基胺基苯基 (28) 3- (3-乙基脲基）苯基 (29) 3- (3,3-二乙基脲基）苯基 (30 ) 3-甲基苯基 (3 1 ) 3-苯氧基苯基 (32) 3-羥基苯基 (33) 4-乙氧基羰基苯基 (34 ) 4-丁氧基苯基 (35 )對-聯苯基 (3 6 ) 4 -苯基硫苯基 (37 ) 4-氯苯基 (38 ) 4-苯甲醯基苯基 (39) 4-乙醯氧基苯基 (40 ) 4-苯甲醯基氧基苯基 (41 ) 4_苯氧基羰基苯基 (42 ) 4-甲氧基苯基 (43 ) 4-苯胺基苯基 (44) 4-異丁醯基胺基苯基 (45 ) 4-苯氧基羰基胺基苯基 (46 ) 4- ( 3-乙基脲基）苯基 (47 ) 4- ( 3,3-二乙基脲基）苯基 (48 ) 4-甲基苯基 -62- 201213864(15) 3-Ethoxycarbonylphenyl(16) 3-butoxyphenyl(17)m-biphenyl(1 8 ) 3 -phenylthiophenyl(19 ) 3-chlorophenyl (20 3-benzylidenephenyl (21) 3-ethoxycarbonylphenyl (22) 3-benzylideneoxyphenyl (23) 3-phenoxycarbonylphenyl (24) 3-methyl Oxyphenyl-61 201213864 (25 ) 3-anilinophenyl(26) 3 -isobutylguanidinophenyl (27) 3-phenoxycarbonylaminophenyl (28) 3- (3-ethyl Ureido)phenyl(29) 3-(3,3-diethylureido)phenyl(30) 3-methylphenyl(3 1 ) 3-phenoxyphenyl(32) 3-hydroxybenzene (33) 4-ethoxycarbonylphenyl (34) 4-butoxyphenyl(35)-p-biphenyl(3 6 ) 4 -phenylthiophenyl(37 ) 4-chlorophenyl ( 38) 4-Benzylmercaptophenyl (39) 4-ethenyloxyphenyl (40) 4-benzylideneoxyphenyl (41) 4-phenoxycarbonylphenyl (42) 4- Methoxyphenyl(43) 4-anilinophenyl(44) 4-isobutyldecylaminophenyl(45) 4-phenoxycarbonylaminophenyl(46) 4-(3-ethylureido Phenyl(47) 4-(3,3-diethylureido)phenyl(48) 4-methylphenyl-62- 201213864

(49 ) 4-苯氧基苯基 (5 0 ) 4 -羥基苯基 (51 ) 3,4-二乙氧基羰基苯基 (52 ) 3,4-二丁氧基苯基 (53 ) 3,4-二苯基苯基 (54) 3,4 -二苯基硫苯基 (55 ) 3,4-二氯苯基 (56 ) 3,4-二苯甲醢基苯基 (57 ) 3,4-二乙醯氧基苯基 (58 ) 3,4-二苯甲醯基氧基苯基 (59 ) 3,4-二苯氧基羰基苯基 (60 ) 3,4-二甲氧基苯基 (61 ) 3,4-二苯胺基苯基 (62 ) 3,4-二甲基苯基 (63 ) 3,4-二苯氧基苯基 (64) 3,4-二羥基苯基 (65 ) 2-萘基 (66 ) 3,4,5-三乙氧基羰基苯基 (67 ) 3,4,5-三丁氧基苯基 (68 ) 3,4,5·三苯基苯基 (69 ) 3,4,5-三苯基硫苯基 (70 ) 3,4,5-三氯苯基 (71 ) 3,4,5-三苯甲醯基苯基 (72 ) 3,4,5-三乙醯氧基苯基 -63- 201213864 (73) 3,4,5-三苯甲醯基氧基苯基 (74) 3,4,5-三苯氧基羰基苯基 (75 ) 3,4,5-三甲氧基苯基 (76 ) 3,4,5-三苯胺基苯基 (77 ) 3,4,5-三甲基苯基 (78 ) 3,4,5-三苯氧基苯基 (79 ) 3,4,5-三羥基苯基 [化 23] (80)~(145)(49) 4-Phenoxyphenyl(5 0 ) 4 -hydroxyphenyl(51 ) 3,4-diethoxycarbonylphenyl(52 ) 3,4-dibutoxyphenyl(53 ) 3 ,4-diphenylphenyl(54) 3,4-diphenylthiophenyl(55) 3,4-dichlorophenyl(56) 3,4-diphenylmethylphenyl (57) 3 , 4-diethoxyoxyphenyl (58) 3,4-dibenzoyloxyphenyl (59) 3,4-diphenoxycarbonylphenyl (60) 3,4-dimethoxy Phenylphenyl (61) 3,4-diphenylaminophenyl(62) 3,4-dimethylphenyl(63) 3,4-diphenoxyphenyl (64) 3,4-dihydroxybenzene (65) 2-naphthyl(66) 3,4,5-triethoxycarbonylphenyl(67) 3,4,5-tributyloxyphenyl (68) 3,4,5·triphenyl Phenylphenyl (69) 3,4,5-triphenylthiophenyl(70) 3,4,5-trichlorophenyl(71) 3,4,5-triphenylmethylphenyl (72) 3,4,5-triethoxymethoxyphenyl-63- 201213864 (73) 3,4,5-tritylmethyloxyphenyl (74) 3,4,5-triphenyloxycarbonylbenzene (75) 3,4,5-trimethoxyphenyl(76) 3,4,5-triphenylaminophenyl(77) 3,4,5-trimethylphenyl(78) 3,4, 5-triphenyloxyphenyl (79) 3,4,5-trihydroxyphenyl [23] (80)~(145)

(80 )苯基 (81) 3-乙氧基羰基苯基 (82 ) 3-丁氧基苯基 (83 )間-聯苯基 (8 4 ) 3 -苯基硫苯基 (85 ) 3-氯苯基 (86 ) 3-苯甲醯基苯基 (87 ) 3-乙醯氧基苯基 (88 ) 3-苯甲醯基氧基苯基 (89 ) 3-苯氧基羰基苯基 (90 ) 3-甲氧基苯基 (9 1 ) 3 -苯胺基苯基 (92) 3 -異丁醯基胺基苯基 -64- 201213864 (93 ) 3-苯氧基羰基胺基苯基 (94) 3- ( 3-乙基脲基）苯基 (95 ) 3- ( 3,3-二乙基脲基）苯基 (96 ) 3-甲基苯基 (97 ) 3-苯氧基苯基 (98 ) 3-羥基苯基 (99 ) 4-乙氧基羰基苯基 (1 00 ) 4-丁氧基苯基 (101 )對-聯苯基 (1 〇2 ) 4-苯基硫苯基 (1 03 ) 4-氯苯基 (1 〇4 ) 4-苯甲醯基苯基 (1〇5 ) 4-乙醯氧基苯基 (106 ) 4-苯甲醯基氧基苯基 (107 ) 4-苯氧基羰基苯基 (1 08 ) 4-甲氧基苯基 (109 ) 4-苯胺基苯基 (1 10 ) 4-異丁烯基胺基苯基 (111) 4 -苯氧基裁基胺基苯基 (112) 4- (3-乙基脲基）苯基 (1 13 ) 4- ( 3,3-二乙基脲基）苯基 (1 14 ) 4-甲基苯基 (1 1 5 ) 4-苯氧基苯基 (1 16 ) 4-羥基苯基 65- 201213864 (117) 3,4-二乙氧基羰基苯基 (118) 3,4-二丁氧基苯基 (119) 3,4-二苯基苯基 (120 ) 3,4-二苯基硫苯基 (121 ) 3,4-二氯苯基 (1 22 ) 3,4-二苯甲醯基苯基 (1 23 ) 3,4-二乙醯氧基苯基 (124) 3,4-二苯甲醯基氧基苯基 (125 ) 3,4-二苯氧基羰基苯基 (126 ) 3,4-二甲氧基苯基 (127 ) 3,4-二苯胺基苯基 (1 28 ) 3,4-二甲基苯基 (1 29 ) 3,4-二苯氧基苯基 (130) 3,4 -二羥基苯基 (131 ) 2-萘基 (132) 3,4,5-三乙氧基羰基苯基 (133 ) 3,4,5-三丁氧基苯基 (1 34 ) 3,4,5-三苯基苯基 (135) 3，4,5-三苯基硫苯基 (136 ) 3,4,5-三氯苯基 (1 37 ) 3,4,5-三苯甲醯基苯基 (1 38 ) 3,4,5-三乙醯氧基苯基 (139) 3,4,5-三苯甲醯基氧基苯基 (140) 3,4,5-三苯氧基羰基苯基 -66- 201213864 (141 ) 3,4,5-三甲氧基苯基 (142 ) 3,4,5-三苯胺基苯基 (M3 ) 3,4,5-三甲基苯基 (144 ) 3,4,5-三苯氧基苯基 (145 ) 3,4,5-三羥基苯基 [化 24] (146)〜(164}(80) phenyl(81) 3-ethoxycarbonylphenyl(82) 3-butoxyphenyl(83)m-biphenyl(8 4 ) 3 -phenylthiophenyl(85 ) 3- Chlorophenyl (86) 3-benzylidenylphenyl (87) 3-ethenyloxyphenyl (88) 3-benzylideneoxyphenyl (89) 3-phenoxycarbonylphenyl ( 90) 3-methoxyphenyl(9 1 ) 3 -anilinylphenyl(92) 3 -isobutylguanidinoaminophenyl-64- 201213864 (93 ) 3-phenoxycarbonylaminophenyl (94) 3-(3-Ethylureido)phenyl(95) 3-(3,3-diethylureido)phenyl(96) 3-methylphenyl(97) 3-phenoxyphenyl ( 98) 3-hydroxyphenyl (99) 4-ethoxycarbonylphenyl (1 00 ) 4-butoxyphenyl (101) p-biphenyl (1 〇 2 ) 4-phenylthiophenyl ( 1 03 ) 4-Chlorophenyl(1 〇4) 4-Benzylmercaptophenyl (1〇5) 4-Ethyloxyphenyl (106) 4-Benzylmercaptooxyphenyl (107) 4-phenoxycarbonylphenyl (1 08 ) 4-methoxyphenyl (109 ) 4-anilinylphenyl (1 10 ) 4-isobutenylaminophenyl (111) 4 -phenoxy Aminophenyl (112) 4-(3-ethylureido)phenyl(1 13 ) 4-( 3,3-diethylureido)phenyl(1 14 ) 4-methylphenyl (1) 1 5 ) 4-phenoxyphenyl (1 16 ) 4-hydroxyphenyl 65- 201213864 (117) 3,4-diethoxycarbonylphenyl (118) 3,4-dibutoxyphenyl (119) 3 , 4-diphenylphenyl (120) 3,4-diphenylthiophenyl (121 ) 3,4-dichlorophenyl (1 22 ) 3,4-diphenylmethylphenyl (1 23 3,4-diethoxymethoxyphenyl (124) 3,4-dibenylhydrinylphenyl (125) 3,4-diphenoxycarbonylphenyl (126) 3,4-di Methoxyphenyl (127) 3,4-diphenylaminophenyl (1 28 ) 3,4-dimethylphenyl (1 29 ) 3,4-diphenoxyphenyl (130) 3,4 -Dihydroxyphenyl (131) 2-naphthyl (132) 3,4,5-triethoxycarbonylphenyl (133 ) 3,4,5-tributyloxyphenyl (1 34 ) 3,4 ,5-triphenylphenyl (135) 3,4,5-triphenylsulfanylphenyl (136) 3,4,5-trichlorophenyl (1 37 ) 3,4,5-tritylhydrazine Phenylphenyl (1 38 ) 3,4,5-triethoxymethoxyphenyl (139) 3,4,5-tritylbenzyloxyphenyl (140) 3,4,5-triphenyloxide Phenylcarbonylphenyl-66- 201213864 (141 ) 3,4,5-trimethoxyphenyl (142 ) 3,4,5-triphenylaminophenyl (M3 ) 3,4,5-trimethylphenyl (144) 3,4,5-triphenyloxyphenyl (145) 3,4,5-trihydroxyphenyl [24] (146)~(164}

N丫 N (146 )苯基 (147) 4-乙氧基羰基苯基 (148 ) 4-丁氧基苯基 (149) 對-聯苯基 (150) 4 -苯基硫苯基 (151 ) 4-氯苯基N丫N (146)phenyl (147) 4-ethoxycarbonylphenyl (148) 4-butoxyphenyl (149) p-biphenyl (150) 4-phenylthiophenyl (151) 4-chlorophenyl

(152 ) 4-苯甲醯基苯基 (153 ) 4-乙醯氧基苯基 (1 54 ) 4-苯甲醯基氧基苯基 (155 ) 4-苯氧基羰基苯基 (156 ) 4-甲氧基苯基 (157 ) 4-苯胺基苯基 (158 ) 4-異丁醯基胺基苯基 (159) 4·-苯氧基鑛基胺基苯基 (160) 4- (3 -乙基脈基）苯基 -67- 201213864 (161) 4- (3,3-二乙基脲基）苯基 (1 62 ) 4-甲基苯基 (1 63 ) 4-苯氧基苯基 (1 6 4 ) 4 -羥基苯基 [化 25] (165)-(183)(152) 4-Benzyldecylphenyl (153) 4-ethenyloxyphenyl (1 54 ) 4-benzylidyloxyphenyl (155 ) 4-phenoxycarbonylphenyl (156 ) 4-methoxyphenyl(157) 4-anilinophenyl(158) 4-isobutyldecylaminophenyl (159) 4·-phenoxy- orylaminophenyl (160) 4- (3 - Ethyl phenyl)phenyl-67- 201213864 (161) 4-(3,3-diethylureido)phenyl(1 62 ) 4-methylphenyl(1 63 ) 4-phenoxyphenyl (1 6 4 ) 4 -hydroxyphenyl [25] (165)-(183)

(165 )苯基(165)phenyl

(166 ) 4-乙氧基羰基苯基 (167 ) 4-丁氧基苯基 (168 )對-聯苯基 (169) 4 -苯基硫苯基 (1 70 ) 4-氯苯基 (1 71 ) 4-苯甲醯基苯基 (1 72 ) 4-乙醯氧基苯基 (173 ) 4-苯甲醯基氧基苯基 (174) 4-苯氧基羰基苯基 (1 75 ) 4-甲氧基苯基 (176 ) 4-苯胺基苯基 (177) 4 -異丁醯基胺基苯基 (178) 4-苯氧基羰基胺基苯基 (179 ) 4- ( 3-乙基脲基）苯基 (180) 4-(3,3-二乙基脲基）苯基 -68- 201213864 (1 8 1 ) 4-甲基苯基 (1 82 ) 4-苯氧基苯基 (183 ) 4-羥基苯基 [化 26](166) 4-Ethoxycarbonylphenyl (167 ) 4-butoxyphenyl (168 ) p-biphenyl (169) 4-phenylthiophenyl (1 70 ) 4-chlorophenyl (1 71) 4-Benzyldecylphenyl (1 72 ) 4-ethoxycarbonylphenyl (173 ) 4-benzylideneoxyphenyl (174) 4-phenoxycarbonylphenyl (1 75 ) 4-methoxyphenyl(176) 4-anilinophenyl(177) 4-isobutyldecylaminophenyl (178) 4-phenoxycarbonylaminophenyl(179) 4-(3-ethyl Ureido)phenyl(180) 4-(3,3-diethylureido)phenyl-68- 201213864 (1 8 1 ) 4-methylphenyl(1 82 ) 4-phenoxyphenyl ( 183 ) 4-hydroxyphenyl group [Chemical 26]

(184)〜(202>(184)~(202>

(1 84 )苯基(1 84 ) phenyl

(185 ) 4-乙氧基羰基苯基 (186) 4-丁氧基苯基 (187 )對-聯苯基 (188) 4 -苯基硫苯基 (1 89 ) 4-氯苯基 (1 90 ) 4_苯甲醯基苯基 (191 ) 4-乙醯氧基苯基 (192 ) 4-苯甲醯基氧基苯基 (193 ) 4-苯氧基羰基苯基 (1 94 ) 4-甲氧基苯基 (195 ) 4-苯胺基苯基 (196 ) 4-異丁醯基胺基苯基 (197 ) 4-苯氧基羰基胺基苯基 (198 ) 4- ( 3-乙基脲基）苯基 (199 ) 4- ( 3,3-二乙基脲基） (200 ) 4-甲基苯基 -69- 201213864 (201 ) 4-苯氧基苯基 ( 202) 4 -羥基苯基 [化 27] (203)-(221) R μ ΝγΝ (203 )苯基 (2〇4 ) 4-乙氧基羰基苯基 (205 ) 4-丁氧基苯基 (206 )對-聯苯基 ( 207) 4_苯基硫苯基 (208 ) 4-氯苯基 (209 ) 4-苯甲醯基苯基 (210) 4-乙醯氧基苯基 (211) 4-苯甲醯基氧基苯基 (212) 4_苯氧基羰基苯基 (213 ) 4-甲氧基苯基 (214 ) 4-苯胺基苯基 (215 ) 4-異丁醯基胺基苯基 (216 ) 4-苯氧基羰基胺基苯基 (217 ) 4- ( 3-乙基脲基）苯基 (218 ) 4- ( 3,3-二乙基脲基）苯 (219 ) 4-甲基苯基 ( 220) 4-苯氧基苯基 -70- 201213864 (221 ) 4-羥基苯基 [化 28] (222)-(419) Η(185) 4-ethoxycarbonylphenyl (186) 4-butoxyphenyl (187) p-biphenyl (188) 4-phenylthiophenyl (1 89 ) 4-chlorophenyl (1 90) 4-Benzylmercaptophenyl (191) 4-Ethyloxyphenyl (192) 4-Benzylmethyloxyphenyl (193) 4-phenoxycarbonylphenyl (1 94 ) 4 -methoxyphenyl(195) 4-anilinophenyl(196) 4-isobutyldecylaminophenyl(197) 4-phenoxycarbonylaminophenyl(198) 4-(3-ethylurea Phenyl (199) 4-(3,3-diethylureido) (200) 4-methylphenyl-69- 201213864 (201) 4-phenoxyphenyl(202) 4-hydroxybenzene (27)-(221) R μ ΝγΝ (203)phenyl(2〇4) 4-ethoxycarbonylphenyl(205) 4-butoxyphenyl(206)-diphenyl (207) 4-Phenylthiophenyl(208) 4-chlorophenyl(209) 4-Benzylmercaptophenyl (210) 4-Ethyloxyphenyl (211) 4-Benzylmethyl Oxyphenyl (212) 4-phenoxycarbonylphenyl (213) 4-methoxyphenyl (214) 4-anilinophenyl (215) 4-isobutylguanidinophenyl (216) 4- Phenoxycarbonylaminophenyl(217 ) 4-(3-ethylureido)phenyl(218) 4-(3,3-diethylureido)benzene (219) 4-Methylphenyl (220) 4-phenoxyphenyl-70- 201213864 (221 ) 4-hydroxyphenyl [Chem. 28] (222)-(419) Η

N丫 N (222 )苯基 (223 ) 4-丁基苯基N丫 N (222 )phenyl (223 ) 4-butylphenyl

(224) 4- (2-甲氧基-2-乙氧基乙基）苯基 (225 ) 4- ( 5 -壬基）苯基 (226 )對-聯苯基 (227 ) 4-乙氧基羰基苯基 (22 8 ) 4-丁氧基苯基 (229 ) 4-甲基苯基 (230 ) 4-氯苯基 (231) 4 -苯基硫苯基 (232 ) 4-苯甲醯基苯基 (23 3 ) 4-乙醯氧基苯基 (234 ) 4-苯甲醯基氧基苯基 (23 5 ) 4-苯氧基羰基苯基 (23 6 ) 4-甲氧基苯基 (23 7 ) 4-苯胺基苯基 (23 8 ) 4_異丁醯基胺基苯基 (2 3 9 ) 4-苯氧基羰基胺基苯基 -71 - 201213864 (240 ) 4- ( 3-乙基脲基）苯基 (241) 4- (3,3-二乙基脲基）苯基 (242 ) 4-苯氧基苯基 (243 ) 4-羥基苯基 (244 ) 3 -丁基苯基 (245) 3- (2-甲氧基-2-乙氧基乙基）苯基 (246) 3- (5 -壬基）苯基 (247 )間-聯苯基 (248 ) 3 -乙氧基羰基苯基 (249 ) 3 -丁氧基苯基 (250 ) 3 -甲基苯基 (251 ) 3-氯苯基 (2 52 ) 3 -苯基硫苯基 (25 3 ) 3 -苯甲醯基苯基 ( 2 54 ) 3-乙醯氧基苯基 (25 5 ) 3 -苯甲醯基氧基苯基 (25 6 ) 3 -苯氧基羰基苯基 ' (25 7 ) 3 -甲氧基苯基 (2 5 8 ) 3 -苯胺基苯基 (2 5 9 ) 3 -異丁醯基胺基苯基 ( 260 ) 3 -苯氧基羰基胺基苯基 (261 ) 3- ( 3-乙基脲基）苯基 (262) 3- ( 3,3-二乙基脲基）苯基 (263 ) 3 -苯氧基苯基 -72- 201213864 (264 ) 3 -羥基苯基 (265 ) 2-丁基苯基 (266) 2-(2-甲氧基-2-乙氧基乙基）苯基 (267 ) 2- ( 5 -壬基）苯基 (26 8 )鄰-聯苯基 (269 ) 2-乙氧基羰基苯基 (270 ) 2-丁氧基苯基(224) 4-(2-Methoxy-2-ethoxyethyl)phenyl(225) 4-(5-fluorenyl)phenyl(226)-p-biphenyl(227) 4-ethoxy Phenylcarbonylphenyl (22 8 ) 4-butoxyphenyl (229 ) 4-methylphenyl (230 ) 4-chlorophenyl (231) 4-phenylthiophenyl (232 ) 4-benzhydrazide Phenylphenyl (23 3 ) 4-acetoxyphenyl (234 ) 4-benzylideneoxyphenyl (23 5 ) 4-phenoxycarbonylphenyl (23 6 ) 4-methoxybenzene (23 7 ) 4-anilinophenyl(23 8 ) 4-isobutylguanidinophenyl (2 3 9 ) 4-phenoxycarbonylaminophenyl-71 - 201213864 (240 ) 4- ( 3- Ethylureido)phenyl(241) 4-(3,3-diethylureido)phenyl(242) 4-phenoxyphenyl(243) 4-hydroxyphenyl(244)3-butyl Phenyl(245) 3-(2-methoxy-2-ethoxyethyl)phenyl(246) 3-(5-fluorenyl)phenyl(247)m-biphenyl(248) 3 - Ethoxycarbonylphenyl(249)3-butoxyphenyl(250)3-methylphenyl(251)3-chlorophenyl(252)3-phenylthiophenyl(25 3 ) 3 - Benzylmercaptophenyl ( 2 54 ) 3-ethoxymethoxyphenyl (25 5 ) 3 -benzimidyloxyphenyl (25 6 ) 3 -phenoxycarbonylphenyl ' (25 7 ) 3 - Methoxyphenyl(2 5 8 ) 3 -anilinylphenyl(2 5 9 ) 3 -isobutylguanidinophenyl ( 260 ) 3 -phenoxycarbonylaminophenyl (261 ) 3- ( 3- Ethylureido)phenyl(262) 3-(3,3-diethylureido)phenyl(263)3-phenoxyphenyl-72- 201213864 (264) 3-hydroxyphenyl (265) 2-butylphenyl (266) 2-(2-methoxy-2-ethoxyethyl)phenyl(267) 2-(5-fluorenyl)phenyl(26 8 )o-biphenyl (269) 2-Ethoxycarbonylphenyl (270) 2-butoxyphenyl

(271 ) 2-甲基苯基 (272 ) 2-氯苯基 ( 273) 2 -苯基硫苯基 (274 ) 2-苯甲醯基苯基 (275 ) 2-乙醯氧基苯基 (276 ) 2-苯甲醯基氧基苯基 (277 ) 2-苯氧基羰基苯基 (27 8 ) 2-甲氧基苯基 (279 ) 2-苯胺基苯基 (28 0 ) 2-異丁醯基胺基苯基 (281) 2-苯氧基羰基胺基苯基 (2 82 ) 2- ( 3 -乙基脲基）苯基 (283) 2- (3,3-二乙基脲基）苯基 ( 284) 2-苯氧基苯基 (2 8 5 ) 2-羥基苯基 (2 8 6 ) 3,4-二丁基苯基 ( 2 8 7 ) 3,4-二（2-甲氧基-2-乙氧基乙基）苯基 -73- 201213864 (2 8 8 ) 3,4-二苯基苯基 (2 8 9 ) 3,4-二乙氧基羰基苯基 ( 290 ) 3,4-二-十二烷基氧基苯基 (291 ) 3,4-二甲基苯基 (292 ) 3,4-二氯苯基 (293 ) 3,4-二苯甲醯基苯基 (294 ) 3,4-二乙醯氧基苯基 (295 ) 3,4-二甲氧基苯基 ( 296 ) 3,4-二-N-甲基胺基苯基 (297 ) 3,4-二異丁醯基胺基苯基 (298 ) 3,4-二苯氧基苯基 ( 299) 3,4 -二羥基苯基 (3 00 ) 3,5 -二丁基苯基 (301) 3,5-二（2-甲氧基-2-乙氧基乙基）苯基 ( 3 02 ) 3,5-二苯基苯基 (3 03 ) 3,5 -二乙氧基羰基苯基 ( 3 04 ) 3,5 -二-十二烷基氧基苯基 (3 05 ) 3,5 -二甲基苯基 (3 06 ) 3,5 -二氯苯基 (3 07 ) 3,5 -二苯甲醯基苯基 (3 08 ) 3,5 -二乙醢氧基苯基 ( 3 09 ) 3,5 -二甲氧基苯基 (3 10 ) 3,5-二-N-甲基胺基苯基 (31 1 ) 3,5-二異丁醯基胺基苯基 -74- 201213864 (3 12 ) 3,5-二苯氧基苯基 (3 13 ) 3,5-二羥基苯基 (3 14 ) 2,4-二丁基苯基 (315) 2,4-二（2-甲氧基-2-乙氧基乙基）苯基 (3 1 6 ) 2,4-二苯基苯基 (3 17 ) 2,4_二乙氧基羰基苯基 (318) 2,4 -二-十二烷基氧基苯基(271) 2-methylphenyl(272) 2-chlorophenyl(273)2-phenylthiophenyl(274) 2-benzylidenylphenyl (275) 2-ethenyloxyphenyl ( 276) 2-Benzyl decyloxyphenyl (277) 2-phenoxycarbonylphenyl (27 8 ) 2-methoxyphenyl (279 ) 2-anilinylphenyl (28 0 ) 2-iso Butylaminophenyl(281) 2-phenoxycarbonylaminophenyl(2 82 ) 2-(3-ethylureido)phenyl(283) 2-(3,3-diethylureido) Phenyl ( 284) 2-phenoxyphenyl (2 8 5 ) 2-hydroxyphenyl (2 8 6 ) 3,4-dibutylphenyl ( 2 8 7 ) 3,4-di (2-A) Oxy-2-ethoxyethyl)phenyl-73- 201213864 (2 8 8 ) 3,4-diphenylphenyl (2 8 9 ) 3,4-diethoxycarbonylphenyl ( 290 ) 3,4-di-dodecyloxyphenyl (291 ) 3,4-dimethylphenyl (292 ) 3,4-dichlorophenyl (293 ) 3,4-dibenzimidylbenzene (294) 3,4-diethoxycarbonylphenyl (295) 3,4-dimethoxyphenyl(296) 3,4-di-N-methylaminophenyl (297) 3, 4-Diisobutyl mercaptophenyl (298 ) 3,4-diphenoxyphenyl ( 299 ) 3,4-dihydroxyphenyl (3 00 ) 3,5 -dibutylphenyl (301) 3 ,5-bis(2-methoxy-2-ethoxyl) Phenyl ( 3 02 ) 3,5-diphenylphenyl (3 03 ) 3,5-diethoxycarbonylphenyl ( 3 04 ) 3,5-di-dodecyloxyphenyl (3 05 ) 3,5-Dimethylphenyl (3 06 ) 3,5-dichlorophenyl (3 07 ) 3,5-diphenylmethylphenyl (3 08 ) 3,5 - 2 Nonyloxyphenyl (3,09) 3,5-dimethoxyphenyl(3 10 ) 3,5-di-N-methylaminophenyl (31 1 ) 3,5-diisobutylguanidino Phenyl-74- 201213864 (3 12 ) 3,5-diphenoxyphenyl (3 13 ) 3,5-dihydroxyphenyl (3 14 ) 2,4-dibutylphenyl (315) 2, 4-bis(2-methoxy-2-ethoxyethyl)phenyl(3 1 6 ) 2,4-diphenylphenyl(3 17 ) 2,4-diethoxycarbonylphenyl ( 318) 2,4-di-dodecyloxyphenyl

(3 19 ) 2,4-二甲基苯基 (3 20 ) 2,4-二氯苯基 (321) 2,4-二苯甲醯基苯基 (3 22 ) 2,4-二乙醯氧基苯基 (3 23 ) 2,4-二甲氧基苯基 ( 3 24 ) 2,4-二-N-甲基胺基苯基 (3W) 2,4-二異丁醯基胺基苯基 (3 26 ) 2,4-二苯氧基苯基 ( 327) 2,4 -二羥基苯基 (3 28 ) 2,3 -二丁基苯基 ( 3 29 ) 2,3 -二（2-甲氧基-2-乙氧基乙基）苯基 (3 3 0 ) 2,3 -二苯基苯基 (331) 2,3-二乙氧基羰基苯基 (332) 2,3-二-十二烷基氧基苯基 (3 3 3 ) 2,3 -二甲基苯基 (3 3 4 ) 2,3 -二氯苯基 (3 3 5 ) 2,3 -二苯甲醯基苯基 -75- 201213864 (3 3 6 ) 2,3 -二乙醯氧基苯基 (3 3 7 ) 2,3 -二甲氧基苯基 (3 3 8 ) 2,3 -二-N-甲基胺基苯基 ( 3 3 9 ) 2,3 -二異丁醯基胺基苯基 (3 40 ) 2,3 -二苯氧基苯基 (341 ) 2,3-二羥基苯基 (342 ) 2,6-二丁基苯基 ( 3 43 ) 2,6 -二（2-甲氧基-2-乙氧基乙基）苯基(3 19 ) 2,4-Dimethylphenyl(3 20 ) 2,4-dichlorophenyl(321) 2,4-diphenylmethylphenyl (3 22 ) 2,4-diethylhydrazine Oxyphenyl (3 23 ) 2,4-dimethoxyphenyl ( 3 24 ) 2,4-di-N-methylaminophenyl (3W) 2,4-diisobutylaminophenyl (3 26 ) 2,4-Diphenoxyphenyl (327) 2,4-dihydroxyphenyl (3 28 ) 2,3-dibutylphenyl ( 3 29 ) 2,3 -di(2- Methoxy-2-ethoxyethyl)phenyl(3 3 0 ) 2,3 -diphenylphenyl(331) 2,3-diethoxycarbonylphenyl (332) 2,3-di -dodecyloxyphenyl(3 3 3 ) 2,3 -dimethylphenyl(3 3 4 ) 2,3 -dichlorophenyl(3 3 5 ) 2,3 -dibenzimidyl Phenyl-75- 201213864 (3 3 6 ) 2,3-diethoxymethoxyphenyl (3 3 7 ) 2,3-dimethoxyphenyl (3 3 8 ) 2,3 -di-N- Methylaminophenyl(3 3 9 ) 2,3 -diisobutylguanidinophenyl (3 40 ) 2,3-diphenoxyphenyl (341 ) 2,3-dihydroxyphenyl (342 ) 2,6-dibutylphenyl( 3 43 ) 2,6-bis(2-methoxy-2-ethoxyethyl)phenyl

(344 ) 2,6-二苯基苯基 ( 345 ) 2,6-二乙氧基羰基苯基 ( 346) 2,6 -二-十二烷基氧基苯基 (347 ) 2,6-二甲基苯基 (3 48 ) 2,6-二氯苯基 (349 ) 2,6-二苯甲醯基苯基 (3 50 ) 2,6-二乙醯氧基苯基(344) 2,6-Diphenylphenyl(345) 2,6-diethoxycarbonylphenyl(346) 2,6-di-dodecyloxyphenyl (347) 2,6- Dimethylphenyl (3 48 ) 2,6-dichlorophenyl (349 ) 2,6-diphenylmethylphenyl (3 50 ) 2,6-diethoxymethoxyphenyl

(351 ) 2,6-二甲氧基苯基 (3 52 ) 2,6-二-N-甲基胺基苯基 (3 53 ) 2,6-二異丁醯基胺基苯基 (3 54 ) 2,6-二苯氧基苯基 ( 355) 2,6 -二羥基苯基 (3 56 ) 3,4,5 -三丁基苯基 ( 3 5 7 ) 3,4,5-三（2_甲氧基-2-乙氧基乙基）苯基 (3 5 8 ) 3,4,5-三苯基苯基 ( 3 5 9 ) 3,4,5-三乙氧基羰基苯基 -76- 201213864(351) 2,6-Dimethoxyphenyl(3 52 ) 2,6-di-N-methylaminophenyl(3 53 ) 2,6-diisobutylaminophenyl (3 54 ) 2,6-diphenoxyphenyl (355) 2,6-dihydroxyphenyl (3 56 ) 3,4,5-tributylphenyl (3 5 7 ) 3,4,5-tri (2 _Methoxy-2-ethoxyethyl)phenyl (3 5 8 ) 3,4,5-triphenylphenyl ( 3 5 9 ) 3,4,5-triethoxycarbonylphenyl- 76- 201213864

(3 60 ) 3,4,5 -三 (361 ) 3,4,5-三 (3 62 ) 3,4,5 -三 (3 63 ) 3,4,5 -三 (3 64 ) 3,4,5 -三 (3 65 ) 3,4,5 -三 (3 66 ) 3,4,5 -三 (3 67 ) 3,4,5 -三 (3 68 ) 3,4,5 -三 (3 69 ) 3,4,5 -三 (3 70 ) 2,4,6-三 (371 ) 2,4,6-三 (3 72 ) 2,4,6-三 ( 3 73 ) 2,4,6-三 (3 74 ) 2,4,6-三 (3 75 ) 2,4,6-三 (3 76 ) 2,4,6-三 (3 77 ) 2,4,6-三 ( 3 78 ) 2,4,6-三 (3 79 ) 2,4,6-三 (3 8 0 ) 2,4,6-三 (381) 2,4,6-三 (3 8 2 ) 2,4,6-三 (3 8 3 ) 2,4,6-三 -i 異苯經 -二烷基氧基苯基基苯基苯基甲醯基苯基醯氧基苯基氧基苯基 -甲基胺基苯基丁醯基胺基苯基氧基苯基基苯基基苯基 2-甲氧基-2-乙氧基乙基）苯基基苯基氧基羰基苯基 -二烷基氧基苯基基苯基苯基甲醯基苯基醯氧基苯基氧基苯基 -甲基胺基苯基丁醯基胺基苯基氧基苯基基苯基 -77- 201213864 (3 84 )五氟苯基 (3 8 5 )五氯苯基 (3 86 )五甲氧基苯基(3 60 ) 3,4,5 -three (361 ) 3,4,5-three (3 62 ) 3,4,5 -three (3 63 ) 3,4,5 -three (3 64 ) 3,4 , 5 - 3 (3 65 ) 3, 4, 5 - 3 (3 66 ) 3, 4, 5 - 3 (3 67 ) 3, 4, 5 - 3 (3 68 ) 3, 4, 5 - 3 (3 69) 3,4,5 -three (3 70 ) 2,4,6-three (371 ) 2,4,6-three (3 72 ) 2,4,6-three ( 3 73 ) 2,4,6 - three (3 74 ) 2,4,6-three (3 75 ) 2,4,6-three (3 76 ) 2,4,6-three (3 77 ) 2,4,6-three ( 3 78 ) 2,4,6-three (3 79 ) 2,4,6-three (3 8 0 ) 2,4,6-three (381) 2,4,6-three (3 8 2 ) 2,4,6 -Tris(3 8 3 ) 2,4,6-tri-i isophenyl-dialkyloxyphenylphenylphenylformamidophenyloxyphenyloxyphenyl-methylamine Phenyl phenyl decyl phenyl phenyl phenyl phenyl phenyl 2-methoxy-2- ethoxyethyl) phenyl phenyl oxy phenyl phenyl - dialkyl oxy phenyl Phenylphenyl-mercaptophenyl methoxy phenyloxyphenyl-methylaminophenylbutyrylamidophenyloxyphenyl phenyl-77- 201213864 (3 84 ) pentafluorophenyl (3 8 5 ) pentachlorophenyl (3 86 ) pentamethoxyphenyl

( 3 8 7 ) 6-N-甲基胺磺醯基-8-甲氧基-2-萘基 ( 3 8 8 ) 5 -N-甲基胺磺醯基-2-萘基 ( 3 89 ) 6-N-苯基胺磺醯基-2-萘基 ( 3 90 ) 5-乙氧基-7-N-甲基胺磺醯基-2-萘基 (391 ) 3-甲氧基-2-萘基 (3 92 ) 1 -乙氧基-2-萘基 ( 3 93 ) 6-N-苯基胺磺醯基-8-甲氧基-2-萘基 ( 3 94 ) 5 -甲氧基-7-N-苯基胺磺醯基-2-萘基 (3 95 ) 1 - ( 4-甲基苯基）-2-萘基 ( 3 96 ) 6,8 -二-N-甲基胺磺醯基-2-萘基 ( 397) 6-N_2-乙醯氧基乙基胺磺醯基-8-甲氧基-2-萘 (3 98 ) 5 -乙醯氧基-7-N-苯基胺磺醯基-2-萘基 ( 3 99 ) 3 -苯甲醯基氧基-2-萘基 (400 ) 5-乙醯基胺基-1-萘基 (401 ) 2_甲氧基-1-萘基 (402 ) 4-苯氧基-1-萘基 (403 ) 5-N-甲基胺磺醯基-1-萘基 ( 404 ) 3 -N-甲基胺甲醯基-4-羥基-1-萘基 ( 405 ) 5-甲氧基-6-N-乙基胺磺醯基-1-萘基 ( 406 ) 7-十四烷基氧基-1-萘基 -78- 201213864 ( 407 ) 4- ( 4-甲基苯氧基）-1-萘基 ( 408 ) 6-N-甲基胺磺醯基-1-萘基 ( 409 ) 3 -N，N-二甲基胺甲醯基-4-甲氧基-卜萘基 (410) 5-甲氧基-6-N-苄基胺磺醯基-卜萘基 (411) 3,6-二-N-苯基胺磺醯基-1-萘基 (412 )甲基 (413 )乙基( 3 8 7 ) 6-N-Methylamine sulfonyl-8-methoxy-2-naphthyl (3 8 8 ) 5 -N-methylamine sulfonyl-2-naphthyl ( 3 89 ) 6-N-phenylamine sulfonyl-2-naphthyl ( 3 90 ) 5-ethoxy-7-N-methylamine sulfonyl-2-naphthyl (391 ) 3-methoxy-2 -naphthyl(3 92 ) 1-ethoxy-2-naphthyl ( 3 93 ) 6-N-phenylamine sulfonyl-8-methoxy-2-naphthyl ( 3 94 ) 5 -methoxy 7-N-phenylamine sulfonyl-2-naphthyl(3 95 ) 1 - ( 4-methylphenyl)-2-naphthyl ( 3 96 ) 6,8 -di-N-methyl Aminesulfonyl-2-naphthyl ( 397 ) 6-N 2 -acetoxyethylamine sulfonyl-8-methoxy-2-naphthalene (3 98 ) 5 -ethyl oxime-7-N -Phenylamine sulfonyl-2-naphthyl(399)3-benzylideneoxy-2-naphthyl(400) 5-ethenylamino-1-naphthyl (401) 2-A Oxy-1-naphthyl (402) 4-phenoxy-1-naphthyl (403) 5-N-methylamine sulfonyl-1-naphthyl ( 404 ) 3 -N-methylamine formazan 4-hydroxy-1-naphthyl(405) 5-methoxy-6-N-ethylaminesulfonyl-1-naphthyl(406) 7-tetradecyloxy-1-naphthyl -78- 201213864 ( 407 ) 4- ( 4-Methylphenoxy)-1-naphthyl ( 408 ) 6-N-methylamine sulfonyl-1-naphthyl ( 409 ) 3 -N,N- Dimethylamine Mercapto-4-methoxy-naphthyl (410) 5-methoxy-6-N-benzylaminesulfonyl-naphthyl (411) 3,6-di-N-phenylaminesulfonyl-1 -naphthyl (412)methyl (413) ethyl

(414 ) 丁基 (415 )辛基 (4 1 6 )十二烷基 (417) 2-丁氧基-2-乙氧基乙基 (418 )苄基 (419) 4-甲氧基苄基(414 ) butyl (415 ) octyl (4 1 6 ) dodecyl (417) 2-butoxy-2-ethoxyethyl (418 ) benzyl (419) 4-methoxybenzyl

-79 ~ (420' 201213864 [化 29] (420)-79 ~ (420' 201213864 [化 29] (420)

HU、/N Y rrixiHU, /N Y rrixi

P-HN 丫 Μ HjC σ )9 r Kl 丫 N NHό. (422) 9 HN丫N、，P-HN 丫 Μ HjC σ )9 r Kl 丫 N NHό. (422) 9 HN丫N,,

rYiXX och3 ςιχ：rYiXX och3 ςιχ:

σQσQ

Xr (424)〜(426} 9Xr (424) ~ (426} 9

RR

TJXXTJXX

RR

H3COH3CO

r XT 〇CHsr XT 〇CHs

•VO cr (424)甲基 (425 )苯基 (426 ) 丁基 -80- 201213864 [化 30]• VO cr (424) methyl (425) phenyl (426 ) butyl -80- 201213864 [Chem. 30]

(43 0 )甲基 (431)乙基 (43 2 ) 丁基 (43 3 )辛基 ( 43 4 )十二烷基 ( 43 5 ) 2-丁氧基-2-乙氧基乙基 (436)苄基 (43 7 ) 4-甲氧基苄基 -81 - (439} 201213864 [化 31] (438) 9(43 0 )methyl (431) ethyl (43 2 ) butyl (43 3 ) octyl ( 43 4 ) dodecyl ( 43 5 ) 2-butoxy-2-ethoxyethyl (436 Benzyl (43 7 ) 4-methoxybenzyl-81 - (439} 201213864 [化31] (438) 9

C4H9 ⑻ HN〜<^N、丫丫、C4Hs(n) N丫 N „NH σC4H9 (8) HN~<^N, 丫丫, C4Hs(n) N丫 N „NH σ

9 H HWN、_ N 丫N 0"H (440)9 H HWN, _ N 丫N 0"H (440)

66

(441) O1 丫、lO N丫N ύ(441) O1 丫, lO N丫N ύ

-82- 201213864 [化 32] (442) (443)-82- 201213864 [化32] (442) (443)

本發明中，亦可使用三聚氰胺化合物作爲具有1，3，5 -三嗪環之化合物。三聚氰胺化合物較好係藉由以下述一般式（M)表示之三聚氰胺化合物與羰基化合物之聚合反應而合成。 [化 33]In the present invention, a melamine compound can also be used as the compound having a 1,3,5-triazine ring. The melamine compound is preferably synthesized by a polymerization reaction of a melamine compound represented by the following general formula (M) with a carbonyl compound. [化33]

ΚΙ ΚΙ ΜΚΙ ΚΙ Μ

R,6 丫丫、R13 + ΝγΝ R«/N、R14 一般式(Μ} R12 R11 R12 PH i 1 R16 Y Y R N 丫N R1S R14 + nH20 n 上述合成反應流程圖中，R11、R12、R13、R14、R15及 R16爲氫原子、烷基、烯基、芳基或雜環基。 -83- 201213864 上述烷基、烯基、芳基及雜環基以及該等之取代基係與前述一般式（R)中說明之各基、該等取代基同義。三聚氰胺化合物與羰基化合物之聚合反應與一般之三聚氰胺樹脂（例如，三聚氰胺甲醛樹脂等）之合成方法相同。又，亦可使用市售之三聚氰胺聚合物（三聚氰胺樹脂 )° 三聚氰胺聚合物之分子量較好爲2千~40萬。三聚氰胺聚合物之重複單位之具體例示於下。 [化 34] (MP-1MMP-50) -O-CHj H2C- N 丫 ΚΙ R«-N、R1« MP-1 ： R13 R14、 R15 ' R16 '：CH 2〇H MP-2 ： R13 R14、 R15 、R“ 1 ： CH 2〇CH 3 MP-3 ： R13 、 R14、 R1 5 ' R16 1 : CH 20-1-C4H9 MP-4 ： R13 > R14 ' R1 5 、R16 :CH 2 〇 - Π - C4H9 MP-5 ： R13 R14、 R15 、R16 1 : CH 2nhcoch=ch2 MP-6 ： R13、 R 14 > R1： ! > R1 6 : CH2NHCO(CH2)7CH=CH(CH2)7CH3 MP-7 ： R13 R14、 R15 ：CH 2〇H ； R16 ： CH2OCH3 MP-8 ： R13 > R14、 r16 ：CH 2〇H ； R15 ： CH2OCH3 MP-9 ： R13 R14 ： ch2 OH ； R丨5、 R16 ： CH2OCH3 MP-1 0 ：R1 3 、R16 ：CH 2〇H ；R14 、R15 ：CH7OCH3 ΜΡ-11 ： R13 ： CH2〇H ； R14 ' R15 > R16 ： CH2OCH3 201213864R,6 丫丫, R13 + ΝγΝ R«/N, R14 General formula (Μ) R12 R11 R12 PH i 1 R16 YYRN 丫N R1S R14 + nH20 n In the above synthetic reaction scheme, R11, R12, R13, R14, R15 and R16 are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. -83- 201213864 The above alkyl group, alkenyl group, aryl group and heterocyclic group and the substituents thereof are the above general formula (R) Each of the groups described in the above is synonymous with the substituents. The polymerization reaction of the melamine compound with the carbonyl compound is the same as the synthesis of a general melamine resin (for example, a melamine formaldehyde resin, etc.), and a commercially available melamine polymer may also be used. (melamine resin) ° The molecular weight of the melamine polymer is preferably from 2,000 to 400,000. Specific examples of the repeating unit of the melamine polymer are shown below. [Chem. 34] (MP-1MMP-50) -O-CHj H2C- N 丫ΚΙ R«-N, R1« MP-1 : R13 R14, R15 ' R16 ': CH 2〇H MP-2 : R13 R14, R15, R" 1 : CH 2〇CH 3 MP-3 : R13, R14, R1 5 ' R16 1 : CH 20-1-C4H9 MP-4 : R13 > R14 ' R1 5 , R16 : CH 2 〇- Π - C4H9 MP-5 : R13 R14, R15, R16 1 : CH 2nhcoch=ch2 MP-6 : R13, R 14 > R1: ! > R1 6 : CH2NHCO(CH2)7CH=CH(CH2)7CH3 MP-7 : R13 R14, R15 :CH 2〇H ; R16 : CH2OCH3 MP-8 : R13 > R14, r16 :CH 2〇H ; R15 : CH2OCH3 MP-9 : R13 R14 : ch2 OH ; R丨5, R16 : CH2OCH3 MP-1 0 : R1 3 , R16 : CH 2〇H ; R14 , R15 : CH7OCH3 ΜΡ-11 : R13 : CH2〇H ; R14 ' R15 > R16 : CH2OCH3 201213864

MP-1 2 :R13、R14、 R16 ： CH 2OCH 3 ： R 15 ： CH2〇H MP- 1 3 :R13、R16 : CH2〇CH 3 ； R1 4、R 15 ： CH2〇H MP- 1 4 :R13、R14、 R15 : CH 2〇H ； R16 ：CH 20-i-C4H9 MP- 1 5 :R13、R14、 R16 ： CH 2〇H ； R15 ：CH 2〇*ΐ-〇4Η9 MP-1 6 :R13、R14 : CH2〇H； R15、 R16 ：CH 2O-I-C4H9 MP- 1 7 :R13、R16 : CH2〇H； R14、 R15 :CH 2O-I-C4H9 MP- 1 8 :R13 : CH2OH ; R14、 R15、 R16 ：CH 2O-I-C4H9 MP-1 9 :R13、R14、 R16 ： CH 2O-1-C4H9 ；R1: 5 ： ch2oh MP-20 :r13、r16: CH2O-1-C4H9 ； R14 、R1: 5 : CH2OH MP-2 1 :R1 3、R14、 R15 ： CH 2〇H ； R1 6 ：CH 2〇·Π-〇4Η9 MP-22 :R13、R14、 R】6 : CH 2〇H ； R15 ：CH 2〇-Π-〇4Η9 MP-23 :R13、R14 : CH2OH； R15、 R1 6 ：CH 2O-II-C4H9 MP-24 :R13、R16 : CH2〇H； R14、 R15 :CH 2O-II-C4H9 MP-25 :R13 : CH2OH ; R14、 R15、 R1 6 ：CH 2O-II-C4H9 MP-26 :R13、R14、 R16 ： CH 2 0 · Π - C4H9 ；R1 5 ： ch2oh MP-27 :R13 、 R16 : CH2〇-n- C4H9 ；R14 、R1 5 : ch2oh MP-28 ： R13、R14 : CH2OH ; R15 : CH2OCH3 ； R16 ： CH20-I1-C4H9 MP-29 ： R13、R14 : CH2OH ; R15 : CH2〇-n-C4H9 ； R 16 : CH20CH3 MP-30 ： R13、R16 : CH 2OH ； R14 ： CH2OCH3 ； R15 ： CH20-11-C4H9 MP-31 ： R13 ： CH2OH ； R14 ' R15 ： CH2OCH3 ； R16 : CH20-11-C4H9 MP-32 ： R13 ： CH2〇H ； R14、R16 : CH2OCH3 ； R15 ： CH20-n-C4H9 MP-33 ： R13 ： CH2OH ； R14 ： CH2OCH3 ； R15、 R16 : CH2O-11-C4H9 MP-34 ： R13 : CH2OH ; R14、R15 : CH2〇-n-C4H9 ； R16 : CH2OCH3 MP-35 ： R13 ' R14 ： CH2〇CH3 ； R15 ： CH2OH ； R16 : CH2O-11-C4H9 -85- 201213864 MP-36 ： R13 ' R16 ： CH2OCH3 ； R14 ： CH2〇H ； R15 ： CH2〇-n-C4H9 MP-37 ： R13 ： CH2OCH3 ； R14 ' R15 ： CH2OH ； R16 ： CH20-n-C4H9MP-1 2 : R13, R14, R16 : CH 2OCH 3 : R 15 : CH2〇H MP- 1 3 : R13, R16 : CH2〇CH 3 ; R1 4, R 15 : CH2〇H MP- 1 4 : R13 , R14, R15 : CH 2〇H ; R16 : CH 20-i-C4H9 MP-1 5 : R13, R14, R16 : CH 2〇H ; R15 : CH 2〇*ΐ-〇4Η9 MP-1 6 :R13 , R14: CH2〇H; R15, R16: CH 2O-I-C4H9 MP- 1 7 : R13, R16 : CH2〇H; R14, R15: CH 2O-I-C4H9 MP- 1 8 : R13 : CH2OH ; R14 , R15, R16 : CH 2O-I-C4H9 MP-1 9 : R13, R14, R16 : CH 2O-1-C4H9 ; R1: 5 : ch2oh MP-20 : r13, r16: CH2O-1-C4H9 ; R14 R1: 5 : CH2OH MP-2 1 : R1 3, R14, R15 : CH 2〇H ; R1 6 : CH 2〇·Π-〇4Η9 MP-22 : R13, R14, R]6 : CH 2〇H ; R15: CH 2〇-Π-〇4Η9 MP-23 : R13, R14 : CH2OH; R15, R1 6 : CH 2O-II-C4H9 MP-24 : R13, R16 : CH2〇H; R14, R15 : CH 2O- II-C4H9 MP-25 : R13 : CH2OH ; R14, R15, R1 6 : CH 2O-II-C4H9 MP-26 : R13, R14, R16 : CH 2 0 · Π - C4H9 ; R1 5 : ch2oh MP-27 : R13, R16 : CH2〇-n- C4H9 ; R14 , R1 5 : ch2oh MP-28 : R13 R14 : CH2OH ; R15 : CH2OCH3 ; R16 : CH20-I1-C4H9 MP-29 : R13, R14 : CH2OH ; R15 : CH2〇-n-C4H9 ; R 16 : CH20CH3 MP-30 : R13 , R16 : CH 2OH ; R14 : CH2OCH3 ; R15 : CH20-11-C4H9 MP-31 : R13 : CH2OH ; R14 ' R15 : CH2OCH3 ; R16 : CH20-11-C4H9 MP-32 : R13 : CH2〇H ; R14, R16 : CH2OCH3 ; CH20-n-C4H9 MP-33 : R13 : CH2OH ; R14 : CH2OCH3 ; R15, R16 : CH2O-11-C4H9 MP-34 : R13 : CH2OH ; R14, R15 : CH2〇-n-C4H9 ; R16 : CH2OCH3 MP- 35 : R13 ' R14 : CH2〇CH3 ; R15 : CH2OH ; R16 : CH2O-11-C4H9 -85- 201213864 MP-36 : R13 ' R16 : CH2OCH3 ; R14 : CH2〇H ; R15 : CH2〇-n-C4H9 MP -37 : R13 : CH2OCH3 ; R14 ' R15 : CH2OH ; R16 : CH20-n-C4H9

MP-38 ： R13 ' R16 ： CH2O-11-C4H9 ； R14 ： CH2OCH3 ； R15 ： CH2OH MP-39 ： R13 ： CH2OH ； R14 ： CH2OCH3 ； R15 · CH2O-11-C4H9 ； R16 ： CH2NHCOCH=CH2 MP-40 : R13 : CH2OH ; R14 : CH2OCH3 ; R15 : CH2NHCOCH=CH2 ；R16 ： CH20-n-C4H9 MP-41 : R13 : CH2OH ; R14 : CH20-n-C4H9 ; R15 : CH2NHCOCH= CH2 ； R16 ： CH2OCH3 MP-42 ： R13 ： CH2OCH3 ； R14 ： CH2OH ； R15 ： CH2O-11-C4H9 ； R16 ：CH2NHCOCH=CH2 MP-43 ： R13 ： CH2OCH3 ； R14 ： CH2OH ； R15 ： CH2NHCOCH= CH2 ; R16 : CH20-n-C4H9 MP-44 : R13 : CH20-n-C4H9 ; R14 : CH2OCH3 ; R15 : CH2OH ; R16 ：CH2NHCOCH=CH2 MP-45 : R13 : CH2OH ; R14 : CH2OCH3 ; R15 : CH2NHCO(CH2)7CH= CH(CH2)7CH3 ; R16 : CH2NHCOCH=CH2 MP-46 : R13 : CH2OH ; R14 : CH2OCH3 ; R15 : CH2NHCOCH=CH2 ; R16 : CH2NHCO(CH2)7CH=CH(CH2)7CH3 MP-47 : R13 : CH2OH ; R14 : CH2NHCO(CH2)7CH=CH(CH2)7CH3 ; R15 : CH2NHCOCH=CH2 ; R16 : CH2OCH3 MP-48 ： R13 ： CH2OCH3 ； R14 ： CH2〇H ； R15 ： CH2NHCO(CH2)7CH= CH(CH2)7CH3 ; R16 : CH2NHCOCH=CH2 MP-49 ： R13 ： CH2OCH3 ； R14 ： CH2OH ； R15 ： CH2NHCOCH=CH2 ； -86- 201213864 R16 : CH2NHCO(CH2)7CH=CH(CH2)7CH3 MP-50 : R13 : CH2NHCO(CH2)7CH=CH(CH2)7CH3 ; R14 : CH2OCH3 ；R15 ： CH2OH ； R16 ： CH2NHCOCH=CH2 [化 35] <MP—51}〜(MP—100)MP-38 : R13 ' R16 : CH2O-11-C4H9 ; R14 : CH2OCH3 ; R15 : CH2OH MP-39 : R13 : CH2OH ; R14 : CH2OCH3 ; R15 · CH2O-11-C4H9 ; R16 : CH2NHCOCH=CH2 MP-40 : R13 : CH2OH ; R14 : CH2OCH3 ; R15 : CH2NHCOCH=CH2 ; R16 : CH20-n-C4H9 MP-41 : R13 : CH2OH ; R14 : CH20-n-C4H9 ; R15 : CH2NHCOCH= CH2 ; R16 : CH2OCH3 MP-42 : R13: CH2OCH3; R14: CH2OH; R15: CH2O-11-C4H9; R16: CH2NHCOCH=CH2 MP-43: R13: CH2OCH3; R14: CH2OH; R15: CH2NHCOCH=CH2; R16: CH20-n-C4H9 MP-44: R13: CH20-n-C4H9; R14: CH2OCH3; R15: CH2OH; R16: CH2NHCOCH=CH2 MP-45: R13: CH2OH; R14: CH2OCH3; R15: CH2NHCO(CH2)7CH=CH(CH2)7CH3; R16: CH2NHCOCH =CH2 MP-46 : R13 : CH2OH ; R14 : CH2OCH3 ; R15 : CH2NHCOCH=CH2 ; R16 : CH2NHCO(CH2)7CH=CH(CH2)7CH3 MP-47 : R13 : CH2OH ; R14 : CH2NHCO(CH2)7CH=CH (CH2)7CH3; R15: CH2NHCOCH=CH2; R16: CH2OCH3 MP-48: R13: CH2OCH3; R14: CH2〇H; R15: CH2NHCO(CH2)7CH=CH(CH2)7CH3; R16: CH2NHCOCH=CH2 MP-49 : R 13: CH2OCH3; R14: CH2OH; R15: CH2NHCOCH=CH2; -86- 201213864 R16: CH2NHCO(CH2)7CH=CH(CH2)7CH3 MP-50: R13: CH2NHCO(CH2)7CH=CH(CH2)7CH3; R14 : CH2OCH3 ; R15 : CH2OH ; R16 : CH2NHCOCH=CH2 [Chemical 35] <MP—51}~(MP—100)

CH： -O-CH CH, 1 HC—CH: -O-CH CH, 1 HC—

I R16 丫丫 R1*I R16 丫丫 R1*

N 丫N ^N. R15 R14 MP-5 1 ： R13 、 R14、 R15 、R16 ：CH2OH MP-52 ： R13 、 R14、 R15 、R16 ：CH2OCH 3 MP-53 ： R13 、 R14、 R15 、R16 ：CH2O-1-C4H9 MP-54 ： R13 R14、 R15 、R16 ：CH2〇-n- C4H9 MP-55 ： R13 、 R14、 R15 ' R16 ：ch2nhcoch=ch2 MP-56 ：R1 3 、R14 、R 15、R 16 ： CH2NHCO(CH2)7CH :H2)7CH 3 MP-57 ： R13 、 R14、 R15 ：ch2 OH ; R16 : CH2OCH3 MP-5 8 ： R13 、 R14、 R16 :ch2 OH ； R15 ： CH2OCH3 MP-59 ： R13 \ R14 ·· ch2 OH ； R15、R16 : CH2OCH3 MP-60 ： R13 > R16 ： ch2 OH ； R14、R15 : CH2OCH3 MP-61 ： R13 : CH2〇H ； R14、 R15、R16 : CH2OCH3 MP-62 ： R13 、 R14、 R16 ：ch2 OCH3 ; R15 : CH2OH MP-63 ： R13 R16 ： ch2 OCH3 ;R14 、 R1 5 ： ch2〇h MP-64 ： R13 、 R14、 R15 ：ch2 OH ； R16 ： CH2O-1-C4H9 MP-65 ： R1 3 、 R14、 R16 ：ch2 OH ； R15 ： CH2O-1-C4H9 -87- 201213864 MP-66 : R13 、 R14 ：ch2 OH ； R15、 R16 : CH2O-1-C4H9 MP-67 ： R13 、 R16 :ch2 OH ； R14、 R15 : CH2〇-i-C4H9 MP-68 ： R13 ； ch2 OH ； R14、 R15、 R16 : CH2O-1-C4H9 MP-69 ： R13 R14 、R16 ：CH 2O-1-C :4H9 ; R15 ： CH2〇H MP-70 ： R13 R16 ：ch2 O-1-C4H9 ； R14、 R15 ： CH2OH MP-71 ： R13 、 R14 、R15 :CH 2〇H ； R16 ： CH2〇-n-C4H9 MP-72 ： R13 、 R14 ' R16 ：CH 2〇H ； R15 ： CH2O-11-C4H9 MP-73 ： R13 、 R14 :ch2 OH ； R15、 R16 ： CH2〇-n-C4H9 MP-74 ： R13 、 R16 :ch2 OH ； R14、 R15 ： CH2O-11-C4H9 MP-75 ： R13 ch2 OH ； R14、 R15、 R16 : CH2〇-n-C4H9 MP-76 ： R13 R14 、R16 ：CH 2〇·Π-〇4Η9 * R15 ： CH2〇H MP-77 ： R13 R1 6 :ch2 〇 - n - c4h9 ; R14、 R15 ： CH2〇H MP-78 ： R1: 、 Rm 丨：ch2oh ；R15 ：CH 2OCH3 ； R16 : ch2 0-n-C4H9 MP-79 ： R13 、 R14 ：CH 2〇H ；R15 ： ch2 0-11-C4H9 > Ri :CH20CH3 MP-80 ： R1： i 、 R16 丨：CH2〇H ；R14 ：CH 2OCH3 ； R": ch2 O-II-C4H9 MP-8 1 ： R1： i . CH 2〇H ； R14 、R15 ：CH 2OCH3 ； R16 ： ch2 O-11-C4H9 MP-82 ： R1: i . CH 2〇H ； R14 ' R16 ：CH 2OCH3 ； R15 ： ch2 O-11-C4H9 MP-83 ： R,; i . CH 2〇H ； R14 ：ch2 OCH2 ,；R15 > R16 ： CH2〇-n-C4H9 -88- 201213864 MP-84 : R13 : CH2OH ; R14、R15 : CH20-n-C4H9 ; R16 ：CH2OCH3 MP-85 ： R13 ' R14 ： CH2OCH3 ； R15 ： CH2〇H ； R16 ： CH2O-11-C4H9 MP-86 ： R13 ' R16 ： CH2OCH3 ； R14 ： CH2〇H ； R15 ： CH2〇-n-C4H9 MP-87 ： R13 ： CH2OCH3 ； R14 ' R15 ： CH2OH ； R16 ：N 丫N ^N. R15 R14 MP-5 1 : R13 , R14 , R15 , R16 :CH2OH MP-52 : R13 , R14 , R15 , R16 :CH2OCH 3 MP-53 : R13 , R14 , R15 , R16 :CH2O- 1-C4H9 MP-54 : R13 R14, R15, R16 :CH2〇-n- C4H9 MP-55 : R13 , R14 , R15 ' R16 :ch2nhcoch=ch2 MP-56 :R1 3 , R14 , R 15 , R 16 : CH2NHCO(CH2)7CH:H2)7CH3MP-57: R13, R14, R15: ch2 OH; R16: CH2OCH3 MP-5 8 : R13, R14, R16: ch2 OH ; R15 : CH2OCH3 MP-59 : R13 \ R14 ·· ch2 OH ; R15, R16 : CH2OCH3 MP-60 : R13 > R16 : ch2 OH ; R14, R15 : CH2OCH3 MP-61 : R13 : CH2〇H ; R14, R15, R16 : CH2OCH3 MP-62 : R13 R14, R16: ch2 OCH3; R15: CH2OH MP-63: R13 R16: ch2 OCH3; R14, R1 5 : ch2〇h MP-64 : R13, R14, R15 : ch2 OH ; R16 : CH2O-1-C4H9 MP- 65 : R1 3 , R14, R16 : ch2 OH ; R15 : CH2O-1-C4H9 -87- 201213864 MP-66 : R13 , R14 :ch2 OH ; R15, R16 : CH2O-1-C4H9 MP-67 : R13 , R16 :ch2 OH ; R14, R15 : CH2〇-i-C4H9 MP-68 : R13 ; ch2 OH ; R14, R15, R16 : CH2O-1-C4H9 MP-69 : R13 R14 , R16 :CH 2O-1-C :4H9 ; R15 : CH2〇H MP -70 : R13 R16 :ch2 O-1-C4H9 ; R14, R15 : CH2OH MP-71 : R13 , R14 , R15 :CH 2〇H ; R16 : CH2〇-n-C4H9 MP-72 : R13 , R14 ' R16 :CH 2〇H ; R15 : CH2O-11-C4H9 MP-73 : R13 , R14 :ch2 OH ; R15, R16 : CH2〇-n-C4H9 MP-74 : R13 , R16 :ch2 OH ; R14, R15 : CH2O -11-C4H9 MP-75 : R13 ch2 OH ; R14, R15, R16 : CH2〇-n-C4H9 MP-76 : R13 R14 , R16 :CH 2〇·Π-〇4Η9 * R15 : CH2〇H MP-77 : R13 R1 6 : ch2 〇- n - c4h9 ; R14, R15 : CH2〇H MP-78 : R1: , Rm 丨: ch2oh ; R15 : CH 2OCH3 ; R16 : ch2 0-n-C4H9 MP-79 : R13 R14:CH 2〇H ;R15 : ch2 0-11-C4H9 > Ri :CH20CH3 MP-80 : R1: i , R16 丨:CH2〇H ; R14 :CH 2OCH3 ; R": ch2 O-II-C4H9 MP -8 1 : R1: i . CH 2〇H ; R14 , R15 : CH 2OCH3 ; R16 : ch2 O-11-C4H9 MP-82 : R1: i . CH 2〇H ; R14 ' R16 :CH 2OCH3 ; R15 : ch2 O-11-C4H9 MP-83 : R,; i . CH 2〇H ; R14 :ch2 OCH2 ,;R15 > R16 : CH2〇-n-C4H9 -88- 201213864 MP-84 : R13 : CH2OH ; R14, R15 : CH20-n-C4H9 ; R16 :CH2OCH3 MP-85 : R13 ' R14 : CH2OCH3 R15 : CH2〇H ; R16 : CH2O-11-C4H9 MP-86 : R13 ' R16 : CH2OCH3 ; R14 : CH2〇H ; R15 : CH2〇-n-C4H9 MP-87 : R13 : CH2OCH3 ; R14 ' R15 : CH2OH ; R16 :

CH2O-11-C4H9 MP-88 ： R13 ' R16 ： CH2O-11-C4H9 ； R14 · CH2OCH3 ；CH2O-11-C4H9 MP-88 : R13 ' R16 : CH2O-11-C4H9 ; R14 · CH2OCH3 ;

R15 ： CH2〇H MP-89 : R13 : CH2OH ; R14 : CH2〇CH3 ; R15 : CH20-n-C4H9 ； R16 ： CH2NHCOCH = CH2 MP-90 ： R13 ： CH2OH ； R14 ： CH2OCH3 ； R15 · CH2NHCOCH= CH2 ; R16 : CH20-n-C4H9 MP-91 : R13 : CH2OH ; R14 : CH20-n-C4H9 ; R15 : CH2NHCOCH=R15 : CH2〇H MP-89 : R13 : CH2OH ; R14 : CH2〇CH3 ; R15 : CH20-n-C4H9 ; R16 : CH2NHCOCH = CH2 MP-90 : R13 : CH2OH ; R14 : CH2OCH3 ; R15 · CH2NHCOCH = CH2 ; R16 : CH20-n-C4H9 MP-91 : R13 : CH2OH ; R14 : CH20-n-C4H9 ; R15 : CH2NHCOCH=

CH2 ； R16 ： CH2OCH3 MP-92 ： R13 ： CH2OCH3 R14 CH2〇H ； R1 CH2〇- 11-C4H9 ； R16 : CH2NHCOCH = CH2 MP-93 ： R13 ： CH2OCH3 ； R14 ： CH2〇H ； R15 ： CH2NHCOCH = CH2 ； R16 ： CH2〇-n-C4H9 MP-94 ： R13 ： CH2O-11-C4H9 ； R14 ： CH2OCH3 ； R1S ： CH2〇H ； R16 ： CH2NHCOCH = CH2 MP-95 ： R13 ： CH2〇H ； R14 ： CH2OCH3 ； R15 ： CH2NHCO(CH2)7CH= CH(CH2)7CH3 ; R16 : CH2NHCOCH=CH2 • 89 - 201213864 MP-96 : R13 : CH2OH ; R14 : CH2OCH3 ; R丨5 : CH2NHCOCH = CH2 ; R16 : CH2NHCO(CH2)7CH = CH(CH2)7CH3 MP-97 : R丨3 : CH2OH ; R14 : CH2NHCO(CH2)7CH=CH(CH2)7CH3 ;R15 : CH2NHCOCH=CH2 ; R16 : CH2OCH3 MP-98 ： R13 ： CH2OCH3 ； R14 ： CH2〇H ； R15 ： CH2NHCO(CH2)7CH= CH(CH2)7CH3 ; R16 : CH2NHCOCH = CH2 MP-99 ： R13 ： CH2OCH3 ； R14 ： CH2〇H ； R15 ： CH2NHCOCH = CH2 ; R16 : CH2NHCO(CH2)7CH = CH(CH2)7CH3R2 : CH2OCH3 MP-92 : R13 : CH2OCH3 R14 CH2〇H ; R1 CH2〇- 11-C4H9 ; R16 : CH2NHCOCH = CH2 MP-93 : R13 : CH2OCH3 ; R14 : CH2〇H ; R15 : CH2NHCOCH = CH2 ; R16 : CH2〇-n-C4H9 MP-94 : R13 : CH2O-11-C4H9 ; R14 : CH2OCH3 ; R1S : CH2〇H ; R16 : CH2NHCOCH = CH2 MP-95 : R13 : CH2〇H ; R14 : CH2OCH3 ; : CH2NHCO(CH2)7CH=CH(CH2)7CH3; R16: CH2NHCOCH=CH2 • 89 - 201213864 MP-96 : R13 : CH2OH ; R14 : CH2OCH3 ; R丨5 : CH2NHCOCH = CH2 ; R16 : CH2NHCO(CH2)7CH = CH(CH2)7CH3 MP-97 : R丨3 : CH2OH ; R14 : CH2NHCO(CH2)7CH=CH(CH2)7CH3 ; R15 : CH2NHCOCH=CH2 ; R16 : CH2OCH3 MP-98 : R13 : CH2OCH3 ; R14 : CH2〇 H; R15: CH2NHCO(CH2)7CH=CH(CH2)7CH3; R16: CH2NHCOCH=CH2 MP-99: R13: CH2OCH3; R14: CH2〇H; R15: CH2NHCOCH = CH2; R16: CH2NHCO(CH2)7CH = CH (CH2)7CH3

MP-100 : R13 : CH2NHCO(CH2)7CH = CH(CH2)7CH3 ; R14 ： CH2OCH3 ； R15 ： CH2〇H ； R16 ： CH2NHCOCH = CH2 [化 36] (MP-101}〜(MP -150} ρ 9 -O-CH HC- R1«州丫MP-100 : R13 : CH2NHCO(CH2)7CH = CH(CH2)7CH3 ; R14 : CH2OCH3 ; R15 : CH2〇H ; R16 : CH2NHCOCH = CH2 [Chemical 36] (MP-101}~(MP -150} ρ 9 -O-CH HC- R1«州丫

MP-101 ： R13 ' R14、 R15 ' R16 ：CH2〇H MP-102 ： R13 、R14、 R15 、R16 ：CH2OCH3 MP-103 ： R13 、R14、 R15 、R16 ：CH2O-1-C4H9 MP-104 ： R13 、R14、 R15 、R16 :CH2〇-n-C4H9 MP-105 ： R13 、R14、 R15 、R16 ：ch2nhcoch = ch2 MP-106 ： R1: 5、R14 、R1 5、R1 6 : ch2nhco(ch2)7ch CH(CH2)7CH3 MP-107 ： R13 、R14、 R15 ：ch2 OH ； R16 ： CH2OCH3 -90- 201213864MP-101 : R13 ' R14, R15 ' R16 :CH2〇H MP-102 : R13 , R14 , R15 , R16 :CH2OCH3 MP-103 : R13 , R14 , R15 , R16 :CH2O-1-C4H9 MP-104 : R13 , R14, R15, R16 : CH2〇-n-C4H9 MP-105 : R13 , R14 , R15 , R16 : ch2nhcoch = ch2 MP-106 : R1: 5, R14 , R1 5 , R1 6 : ch2nhco(ch2)7ch CH (CH2)7CH3 MP-107 : R13, R14, R15 :ch2 OH ; R16 : CH2OCH3 -90- 201213864

c4h9 MP-1 22 C4H9 MP-1 23 C4H9 R1 R13 MP-1 24 ： R1 R14 R14 R1 6 R16 ： CH2〇H ； R15 ： CH2O-11- CH2OH ； R15、R16 ： CH20-n- CH2〇H ； R14、R15 ： CH2O-11- MP-108 ： R13、 R14 、R16 ：CH 2〇H ；R1 5 ： CH2OCH3 MP-109 : R13、 R14 :ch2 OH ； R15 、R1 6 ： CH2OCH3 MP- 1 1 0 ： R13、 R丨6 ：ch2 OH ； R14 、R1 5 ： CH2OCH3 MP-1 1 1 ： R13 ： ch2 OH ； R14、 R15 、R1 6 ： CH2OCH3 MP- 1 1 2 ： R13、 R14 、R16 ：CH 2OCH3 ； R15 ： CH2〇H MP-1 1 3 ： R13、 R16 :ch2 OCH 3 ; R 14、 R15 ： CH2〇H MP- 1 1 4 ： R13、 R14 、R15 ：CH 2〇H ；R1 6 ： CH20-i-C 4H9 MP- 1 1 5 ： R13、 R14 、R16 :CH 2〇H ；R1 5 : CH20-i-C 4h9 MP-1 1 6 ： R13、 R14 :ch2 OH ； R15 、R1 6 ： CH2〇-i-C 4H9 MP-1 1 7 ： R13、 R16 ：ch2 OH ； R14 、R1 5 ： CH2〇-i-C 4H9 MP-1 1 8 ： R13 : ch2 OH ； R14、 R15 、R1 6 ： CH2〇-i-C 4H9 MP-1 1 9 ： R13、 R14 、R16 ：CH 20-i -c4h 9 ; R15 : CH2 OH MP-120 ： R13、 R16 :ch2 O-1-C4H9 ；R1 4、R15 : CH2 OH MP-1 2 1 ：R13 、R 14 ^ R 15 . ch2 OH ；：R16 ： CH20-n- C4H9 MP-125 ： R13 : CH2〇H ； R14、R15、R16 : CH2〇-n- C4H9 MP-126 ： R13、R14、R16 ： CH20-n-C4H9 ； R15 ： -91 - 201213864 ch2〇h MP-127 ： R13、R16 ： CH2O-11-C4H9 ； R14、R15 ：C4h9 MP-1 22 C4H9 MP-1 23 C4H9 R1 R13 MP-1 24 : R1 R14 R14 R1 6 R16 : CH2〇H ; R15 : CH2O-11- CH2OH ; R15, R16 : CH20-n- CH2〇H ; R14 , R15 : CH2O-11- MP-108 : R13, R14 , R16 : CH 2〇H ; R1 5 : CH2OCH3 MP-109 : R13, R14 : ch2 OH ; R15 , R1 6 : CH2OCH3 MP-1 1 0 : R13 , R丨6 : ch2 OH ; R14 , R1 5 : CH2OCH3 MP-1 1 1 : R13 : ch2 OH ; R14, R15 , R1 6 : CH2OCH3 MP-1 1 2 : R13, R14, R16 : CH 2OCH3 ; CH2〇H MP-1 1 3 : R13, R16 :ch2 OCH 3 ; R 14 , R15 : CH2〇H MP- 1 1 4 : R13, R14, R15 :CH 2〇H ; R1 6 : CH20-iC 4H9 MP - 1 1 5 : R13, R14, R16 : CH 2〇H ; R1 5 : CH20-iC 4h9 MP-1 1 6 : R13, R14 : ch2 OH ; R15 , R1 6 : CH2〇-iC 4H9 MP-1 1 7 : R13, R16 : ch2 OH ; R14 , R1 5 : CH2〇-iC 4H9 MP-1 1 8 : R13 : ch2 OH ; R14, R15 , R1 6 : CH2〇-iC 4H9 MP-1 1 9 : R13, R14, R16: CH 20-i - c4h 9 ; R15 : CH2 OH MP-120 : R13, R16 : ch2 O-1-C4H9 ; 1 4, R15: CH2 OH MP-1 2 1 : R13 , R 14 ^ R 15 . ch2 OH ; : R16 : CH20-n- C4H9 MP-125 : R13 : CH2〇H ; R14, R15, R16 : CH2〇 -n- C4H9 MP-126 : R13, R14, R16 : CH20-n-C4H9 ; R15 : -91 - 201213864 ch2〇h MP-127 : R13, R16 : CH2O-11-C4H9 ; R14, R15 :

CH2〇H MP-128 : R13、R14 : CH2〇H ; R15 : CH2OCH3 ; R16 : CH2O-11-C4H9 MP-129 ： R13、R14 : CH2〇H ； R15 ： CH20-n-C4H9 ; R16 ： CH2OCH3 MP-130 ： R13 ' R16 ： CH2〇H ； R14 ： CH2OCH3 ； R15 ： CH20-n-C4H9 MP-131 ： R13 ： CH2〇H ； R14 ' R15 ： CH2OCH3 ； R16 ： CH2〇-n-C4H9 MP-132 : R13 : CH2OH ; R14、R16 : CH2OCH3 ; R15 : CH2〇-n-C4H9 MP-133 ： R13 ： CH2〇H ； R14 ： CH2OCH3 ； R15 ' R16 ： CH2〇-n-C4H9 MP-1 34 ： R13 ： CH2〇H ； R14、R15 : CH20-n-C4H9 ; R16 ： CH2OCH3 MP-135 ： R13 ' R14 ： CH2OCH3 ； R15 ： CH2〇H ； R16 ： CH2O-11-C4H9 MP-136 : R13、R16 : CH2OCH3 ; R14 : CH2OH ; R15 : CH2O-11-C4H9 MP-137 : R13 : CH2OCH3 ; R14、R15 : CH2OH ; R16 : CH2〇-n-C4H9 MP-138 : R13、R16 : CH20-n-C4H9 ; R14 : CH2OCH3 ; -92- 201213864CH2〇H MP-128 : R13, R14 : CH2〇H ; R15 : CH2OCH3 ; R16 : CH2O-11-C4H9 MP-129 : R13, R14 : CH2〇H ; R15 : CH20-n-C4H9 ; R16 : CH2OCH3 MP -130 : R13 ' R16 : CH2〇H ; R14 : CH2OCH3 ; R15 : CH20-n-C4H9 MP-131 : R13 : CH2〇H ; R14 ' R15 : CH2OCH3 ; R16 : CH2〇-n-C4H9 MP-132 : R13: CH2OH; R14, R16: CH2OCH3; R15: CH2〇-n-C4H9 MP-133 : R13 : CH2〇H ; R14 : CH2OCH3 ; R15 ' R16 : CH2〇-n-C4H9 MP-1 34 : R13 : CH2 〇H ; R14, R15 : CH20-n-C4H9 ; R16 : CH2OCH3 MP-135 : R13 ' R14 : CH2OCH3 ; R15 : CH2〇H ; R16 : CH2O-11-C4H9 MP-136 : R13, R16 : CH2OCH3 ; R15 : CH2O-11-C4H9 MP-137 : R13 : CH2OCH3 ; R14, R15 : CH2OH ; R16 : CH2〇-n-C4H9 MP-138 : R13 , R16 : CH20-n-C4H9 ; R14 : CH2OCH3 ; -92- 201213864

R15 : CH2OH MP-139 ： R13 ： CH2OH ； R14 ： CH2OCH3 ； R15 ： CH20-11-C4H9 ； R16 ： CH2NHCOCH = CH2 MP-140 ： R13 ： CH2〇H ； R14 ： CH2OCH3 ； R15 ： CH2NHCOCH = CH2 ； R16 ： CH2O-11-C4H9 MP-141 ： R13 ： CH2OH ； R14 ： CH2〇-n-C4H9 ； R15 ： CH2NHCOCH = CH2 ； R16 ： CH2OCH3R15 : CH2OH MP-139 : R13 : CH2OH ; R14 : CH2OCH3 ; R15 : CH20-11-C4H9 ; R16 : CH2NHCOCH = CH2 MP-140 : R13 : CH2〇H ; R14 : CH2OCH3 ; R15 : CH2NHCOCH = CH2 ; CH2O-11-C4H9 MP-141 : R13 : CH2OH ; R14 : CH2〇-n-C4H9 ; R15 : CH2NHCOCH = CH2 ; R16 : CH2OCH3

MP-142 ： R13 ： CH2OCH3 ； R14 ： CH2〇H ； R15 ： CH2〇- n-C4H9 ; R16 : CH2NHCOCH = CH2 MP-143 ： R13 ： CH2OCH3 ； R14 ： CH2〇H ； R15 ： CH2NHCOCH = CH2 ; R16 ·· CH20-n-C4H9 MP-144 ： R13 ： CH2O-11-C4H9 ； R14 ： CH2OCH3 ； R15 ： CH2〇H ； R16 ： CH2NHCOCH = CH2 MP-1 45 ： R1 3 ： CH2〇H ； R14 ： CH2OCH3 ； R15 ： CH2NHCO(CH2)7 CH = ch(ch2)7ch3 ,；R16 ：CH2NHCOCH=CH2 MP-1 46 ： R1 3 : CH2OH ; R14 ： CH2OCH3 ； R15 : CH2NHCOCH = CH2 ; R16 : CH2NHCO(CH2)7CH = CH(CH2)7CH3 MP-147 ： R13 ： CH2〇H ； R14 ： CH2NHCO(CH2)7CH = CH(CH2)7CH3 ; R15 : CH2NHCOCH = CH2 ; R16 : CH2OCH3 MP-148 : R13 : CH2OCH3 ; R14 : CH2OH ; R15 : CH2NHCO(CH2)7CH= CH(CH2)7CH3 ; R16 : CH2NHCOCH = CH2 MP-149 ·· R13 ： CH2OCH3 ； R14 ： CH2OH ； R15 ： CH2NHCOCH=CH2 ;R16 : CH2NHCO(CH2)7CH = CH(CH2)7CH3 MP-150 : R13 : CH2NHCO(CH2)7CH = CH(CH2)7CH3 ; R14 : -93- 201213864 CH2OCH3 ; R15 : CH2OH ; R16 : CH2NHCOCH = CH2 [化 37] (MP-151)~(MP-200)MP-142 : R13 : CH2OCH3 ; R14 : CH2〇H ; R15 : CH2〇- n-C4H9 ; R16 : CH2NHCOCH = CH2 MP-143 : R13 : CH2OCH3 ; R14 : CH2〇H ; R15 : CH2NHCOCH = CH2 ; · CH20-n-C4H9 MP-144 : R13 : CH2O-11-C4H9 ; R14 : CH2OCH3 ; R15 : CH2〇H ; R16 : CH2NHCOCH = CH2 MP-1 45 : R1 3 : CH2〇H ; R14 : CH2OCH3 ; CH2NHCO(CH2)7 CH = ch(ch2)7ch3,;R16:CH2NHCOCH=CH2 MP-1 46 : R1 3 : CH2OH ; R14 : CH2OCH3 ; R15 : CH2NHCOCH = CH2 ; R16 : CH2NHCO(CH2)7CH = CH( CH2)7CH3 MP-147 : R13 : CH2〇H ; R14 : CH2NHCO(CH2)7CH = CH(CH2)7CH3 ; R15 : CH2NHCOCH = CH2 ; R16 : CH2OCH3 MP-148 : R13 : CH2OCH3 ; R14 : CH2OH ; CH2NHCO(CH2)7CH=CH(CH2)7CH3; R16: CH2NHCOCH=CH2 MP-149 ·· R13 : CH2OCH3 ; R14 : CH2OH ; R15 : CH2NHCOCH=CH2 ; R16 : CH2NHCO(CH2)7CH = CH(CH2)7CH3 MP -150 : R13 : CH2NHCO(CH2)7CH = CH(CH2)7CH3 ; R14 : -93- 201213864 CH2OCH3 ; R15 : CH2OH ; R16 : CH2NHCOCH = CH2 [化37] (MP-151)~(MP-200)

H,Cn ^CH, H,Cn CHj -o-c c- I IH,Cn ^CH, H,Cn CHj -o-c c- I I

MP- 1 5 1 : R1 3 ' R1 4、 R15 、R16 : ch2oh MP-1 52 ： R1 3、R1 4 、 R15 、R16 : CH2OCH3 MP-1 53 ： R1: 3、R1 4 R15 ' R16 : CH2〇-i-C4H9 MP-1 54 ： R1 3、R1 4 、 R15 、R16 : CH2O-11-C4H9 MP-1 55 : R1: 3、R1 4 、 R15 、R16 : CH2NHCOCH=CH2 MP-1 56 ： R13、R14、R15、R16 : CH2NHCO(CH2)7CH = ch(ch2)7ch3 MP- 1 57 :R丨3 、R14 、R15 ：CH 2〇H ； R丨 6 . CH2OCH3 MP-1 58 ：R13 、R14 、R16 ：CH 2〇H ； R1 5 . CH2OCH3 MP-1 59 ：R13 、R14 ：ch2 OH ； R15、 R1 6 . CH2OCH3 MP-1 60 :R13 、R16 ：ch2 OH ； R14、 R1 5 . CH2OCH3 MP-1 6 1 :R13 ：ch2 OH ； R14、 R15、 R1 6 . ch2och3 MP-1 62 ：R13 、R14 、R16 ：CH 2och： 5 ; RI: 5 : CH2OH MP-1 63 :R13 、R16 :ch2 OCH 3 ； R1, RI: 5 ： ch2oh MP-1 64 :R13 、R14 、R15 ：CH 2〇H ； R1 6 . CH20-i-C4 h9 MP-1 65 :R13 、R14 、R16 ：CH 2〇H ； R1 5 . CH2〇-i-C4 h9 MP-1 66 :R13 、R14 :ch2 OH ； R15、 R1 6 ; CH2O-1-C4 h9 MP-1 67 :R13 、R16 ：ch2 OH ； R14、 R1 5 . CH2O-1-C4 h9 -94 - 201213864 MP-168 ： R13 MP-169 ： R13 MP-170 : R13 MP-1 7 1 : R1 CH2OH ; R14、R15、R16 : CH20-i-C4H9 R14、R16 : CH2〇-i-C4H9 ; R15 : CH2OH R16 : CH20-i-C4H9 ; R14、R15 : CH2OH 、R14、R15 : CH2〇H ； R16 : CH2〇-n- C4H9 MP-172 : R13、R14、R16 : CH2OH ; R15 : CH20-n- C4H9 MP-173 : R13、R14 : CH2OH ; R15、R16 : CH20-n- C4H9 MP-174 ： R13、R16 : CH2〇H ； R14、R15 : CH20-n- C4H9 MP-175 : R13 : CH2OH ; R14、R】5、R16 : CH20-n- C4H9 MP-176 ： R13、R14、R16 ： CH20-n-C4H9 ； R1MP-1 5 1 : R1 3 ' R1 4, R15, R16 : ch2oh MP-1 52 : R1 3, R1 4 , R15 , R16 : CH2OCH3 MP-1 53 : R1: 3, R1 4 R15 ' R16 : CH2〇 -i-C4H9 MP-1 54 : R1 3, R1 4 , R15 , R16 : CH2O-11-C4H9 MP-1 55 : R1: 3, R1 4 , R15 , R16 : CH2NHCOCH=CH2 MP-1 56 : R13, R14, R15, R16: CH2NHCO(CH2)7CH = ch(ch2)7ch3 MP-1 57: R丨3, R14, R15: CH 2〇H ; R丨6 . CH2OCH3 MP-1 58 : R13 , R14 , R16 :CH 2〇H ; R1 5 . CH2OCH3 MP-1 59 :R13 , R14 :ch2 OH ; R15, R1 6 . CH2OCH3 MP-1 60 :R13 , R16 :ch2 OH ; R14, R1 5 . CH2OCH3 MP-1 6 1 : R13 : ch2 OH ; R14, R15, R1 6 . ch2och3 MP-1 62 : R13 , R14 , R16 : CH 2och : 5 ; RI: 5 : CH2OH MP-1 63 : R13 , R16 : ch2 OCH 3 ; , RI: 5 : ch2oh MP-1 64 : R13 , R14 , R15 : CH 2〇H ; R1 6 . CH20-i-C4 h9 MP-1 65 : R13 , R14 , R16 : CH 2〇H ; R1 5 . CH2〇-i-C4 h9 MP-1 66 : R13 , R14 : ch2 OH ; R15, R1 6 ; CH2O-1-C4 h9 MP-1 67 : R13 , R16 : ch2 OH ; R14, R1 5 . CH2O-1 -C4 h9 -94 - 201213864 MP-168 : R13 MP-169 : R13 MP-170 : R13 MP-1 7 1 : R1 CH2OH ; R14, R15, R16 : CH20-i-C4H9 R14, R16 : CH2〇-i-C4H9 ; R15 : CH2OH R16 : CH20-i-C4H9 ; R14, R15 : CH2OH , R14 , R15 : CH2〇H ; R16 : CH2〇-n- C4H9 MP-172 : R13, R14, R16 : CH2OH ; R15 : CH20-n - C4H9 MP-173 : R13, R14 : CH2OH ; R15, R16 : CH20-n- C4H9 MP-174 : R13, R16 : CH2〇H ; R14, R15 : CH20-n- C4H9 MP-175 : R13 : CH2OH ; R14, R]5, R16: CH20-n- C4H9 MP-176 : R13, R14, R16 : CH20-n-C4H9 ; R1

CH2〇H MP-1 77 ： R13、R16 ： CH2O-11-C4H9 ； R14、R1CH2〇H MP-1 77 : R13, R16 : CH2O-11-C4H9 ; R14, R1

CH2〇H 16CH2〇H 16

MP-178 : R13、R14 : CH2OH ; R15 : CH2OCH3 ; R CH2O-II-C4H9 MP-1 79 ： R13、R14 ： CH2〇H ； R15 ： CH20-n-C4H9 R16 ： CH2OCH3 MP-1 80 ： R13 ' R16 ： CH2〇H ； R14 ： CH2OCH3 ； R15 CH2O-11-C4H9 MP-181 ： R13 ： CH2〇H ； R14 ' R15 ： CH2OCH3 ； R16 95- 201213864 CH2〇-n-C4H9 MP-182 : R13 : CH2OH ; R14、R16 : CH2OCH3 ; R15 : CH20-n-C4H9 MP-183: R13: CH2OH; R14: CH2OCH3; R15、R16: CH2〇-n-C4H9 MP-184 : R13 ： CH2〇H ； R14、R15 ： CH2〇-n-C4H9 ； R16 ： CH2OCH3 MP-185: R13' R14： CH2OCH3； R15： CH2〇H ； R16： CH2O-11-C4H9 MP-186 ： R13 ' R16 ： CH2OCH3 ； R14 ： CH2〇H ； R15 ： CH2〇-n-C4H9 MP-187 ： R13 ： CH2OCH3 ； R14 ' R15 ： CH2〇H ； R16 ： CH2O-11-C4H9MP-178 : R13, R14 : CH2OH ; R15 : CH2OCH3 ; R CH2O-II-C4H9 MP-1 79 : R13, R14 : CH2〇H ; R15 : CH20-n-C4H9 R16 : CH2OCH3 MP-1 80 : R13 ' R16 : CH2〇H ; R14 : CH2OCH3 ; R15 CH2O-11-C4H9 MP-181 : R13 : CH2〇H ; R14 ' R15 : CH2OCH3 ; R16 95- 201213864 CH2〇-n-C4H9 MP-182 : R13 : CH2OH ; R14, R16: CH2OCH3; R15: CH20-n-C4H9 MP-183: R13: CH2OH; R14: CH2OCH3; R15, R16: CH2〇-n-C4H9 MP-184: R13: CH2〇H; R14, R15: CH2 〇-n-C4H9 ; R16 : CH2OCH3 MP-185: R13' R14: CH2OCH3; R15: CH2〇H ; R16: CH2O-11-C4H9 MP-186 : R13 ' R16 : CH2OCH3 ; R14 : CH2〇H ; R15 : CH2〇-n-C4H9 MP-187 : R13 : CH2OCH3 ; R14 ' R15 : CH2〇H ; R16 : CH2O-11-C4H9

MP-188 : R13、R16 : CH20-n-C4H9 ; R14 : CH2OCH3 ; R15 ： CH2〇H MP-189 ： R13 ： CH2OH ； R14 ： CH2〇CH3 ： R15 ： CH2〇-n-C4H9 ; R16 : CH2NHCOCH = CH2 MP-190 ： R13 : CH2〇H ； R14 ： CH2OCH3 ； R15 ： CH2NHCOCH = CH2 ; R16 : CH20-n-C4H9 MP-191 ： R13 ： CH2〇H ； R14 ： CH20-n-C4H9 ： R15 : CH2NHCOCH = CH2 ； R16 ： CH2OCH3 MP-192 : R13 : CH2OCH3 ; R14 : CH2OH ; R15 : CH20-11-C4H9 ； R16 ： CH2NHCOCH = CH2 MP-193 ： R13 ： CH2OCH3 ； R14 ： CH2〇H ； R15 ： -96- 201213864 CH2NHCOCH = CH2 ； R16 ： CH2O-11-C4H9 MP-194 ： R13 ： CH2O-11-C4H9 ； R14 ： CH2OCH3 ； R15 ： CH2OH ； R16 ： CH2NHCOCH = CH2MP-188 : R13, R16 : CH20-n-C4H9 ; R14 : CH2OCH3 ; R15 : CH2〇H MP-189 : R13 : CH2OH ; R14 : CH2〇CH3 : R15 : CH2〇-n-C4H9 ; R16 : CH2NHCOCH = CH2 MP-190 : R13 : CH2〇H ; R14 : CH2OCH3 ; R15 : CH2NHCOCH = CH2 ; R16 : CH20-n-C4H9 MP-191 : R13 : CH2〇H ; R14 : CH20-n-C4H9 : R15 : CH2NHCOCH = CH2; R16: CH2OCH3 MP-192: R13: CH2OCH3; R14: CH2OH; R15: CH20-11-C4H9; R16: CH2NHCOCH = CH2 MP-193: R13: CH2OCH3; R14: CH2〇H; R15: -96- 201213864 CH2NHCOCH = CH2 ; R16 : CH2O-11-C4H9 MP-194 : R13 : CH2O-11-C4H9 ; R14 : CH2OCH3 ; R15 : CH2OH ; R16 : CH2NHCOCH = CH2

MP-195 ： R13 ： CH2〇H ； R14 ： CH2OCH3 ； R15 ： CH2NHCO(CH2)7CH = CH(CH2)7CH3 ; R16 : CH2NHCOCH = CH2 MP-196 ： R13 ： CH2〇H ； R14 : CH2OCH3 ； R15 : CH2NHCOCH = CH2 ; R16 : CH2NHCO(CH2)7CH = CH(CH2)7CH3 MP-197 : R13 ： CH2〇H ； R14 ： CH2NHCO(CH2)7CH = CH(CH2)7CH3 ; R15 : CH2NHCOCH = CH2 ; R16 : CH2OCH3 MP-198 ： R13 ： CH2OCH3 ； R14 ： CH2OH ； R15 ： CH2NHCO(CH2)7CH = CH(CH2)7CH3 ; R16 : CH2NHCOCH = CH2 MP-199 ： R13 ： CH2OCH3 ； R14 ： CH2〇H ； R15 ： CH2NHCOCH = CH2 ; R16 : CH2NHCO(CH2)7CH = CH(CH2)7CH3 MP-200 : R13 : CH2NHCO(CH2)7CH = CH(CH2)7CH3 ; R14： CH2OCH3； R15： CH2〇H； R16： CH2NHCOCH = CH2 本發明中，亦可使用組合兩種以上之上述重複單位之共聚物。亦可倂用兩種以上之均聚物或寡聚物。又，亦可倂用兩種以上之具有1，3,5_三嗪環之化合物。亦可倂用兩種以上之圓盤狀化合物（例如，具有1 , 3，5 -三嗪環之化合物與具有卟啉（porphyrin )骨架之化合物）本發明中較好使用苯甲酸苯酯化合物之至少一種作爲滯相調整劑，其中較好於纖維素樹脂中添加以下述一般式 (6)表示之苯甲酸苯酯化合物。 -97 - 201213864 [化 38] 一般式(句MP-195 : R13 : CH2〇H ; R14 : CH2OCH3 ; R15 : CH2NHCO(CH2)7CH = CH(CH2)7CH3 ; R16 : CH2NHCOCH = CH2 MP-196 : R13 : CH2〇H ; R14 : CH2OCH3 ; R15 : CH2NHCOCH = CH2 ; R16 : CH2NHCO(CH2)7CH = CH(CH2)7CH3 MP-197 : R13 : CH2〇H ; R14 : CH2NHCO(CH2)7CH = CH(CH2)7CH3 ; R15 : CH2NHCOCH = CH2 ; R16 : CH2OCH3 MP - 198 : R13 : CH2OCH3 ; R14 : CH2OH ; R15 : CH2NHCO(CH2)7CH = CH(CH2)7CH3 ; R16 : CH2NHCOCH = CH2 MP-199 : R13 : CH2OCH3 ; R14 : CH2〇H ; R15 : CH2NHCOCH = CH2 ; R16: CH2NHCO(CH2)7CH=CH(CH2)7CH3 MP-200: R13: CH2NHCO(CH2)7CH=CH(CH2)7CH3; R14: CH2OCH3; R15: CH2〇H; R16: CH2NHCOCH = CH2 In the present invention, It is also possible to use a copolymer in which two or more of the above repeating units are combined. It is also possible to use two or more kinds of homopolymers or oligomers. Further, two or more compounds having a 1,3,5-triazine ring may be used. It is also possible to use two or more kinds of discotic compounds (for example, a compound having a 1,3,5-triazine ring and a compound having a porphyrin skeleton). In the present invention, a phenyl benzoate compound is preferably used. At least one is used as a retardation modifier, and among them, a phenyl benzoate compound represented by the following general formula (6) is preferably added to the cellulose resin. -97 - 201213864 [化38] General (sentence

獨立表示氫原子或取代基，且R1、R2、R3、R4及R5中之至少一個表示電子給予性基，R8表示氫原子、碳數1~4之烷基、碳數2〜6之烯基、碳數2~6之炔基、碳數6〜12之芳基、碳數1〜12之院氧基 '碳數6〜12之芳氧基、碳數2~12之院氧基羰基、碳數2〜12之醯基胺基、氰基或鹵素原子）。 —般式（6)之式中，R1、R2、R3、R4、R5、r6、r7 、R9及R1()各獨立表示氫原子或取代基，取代基可使用後述之取代基T。Independently represents a hydrogen atom or a substituent, and at least one of R1, R2, R3, R4 and R5 represents an electron donating group, and R8 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkenyl group having 2 to 6 carbon atoms. , an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an oxy group having a carbon number of 1 to 12, an aryloxy group having a carbon number of 6 to 12, an oxycarbonyl group having a carbon number of 2 to 12, a mercapto group having a carbon number of 2 to 12, a cyano group or a halogen atom). In the formula (6), R1, R2, R3, R4, R5, r6, r7, R9 and R1() each independently represent a hydrogen atom or a substituent, and the substituent T may be used as the substituent.

Rl、R2、R3、尺4及r5中之至少—個表示電子給予性基。較好R 1、R3或R5中之至少一個爲電子給予性基，更好R3 爲電子給予性基。所謂電子給予性基表示Hammet之σρ値爲0以下者，較好使用 Chem. Rev.，91，165 ( 1991)記載之 Hammet 之 σρ 値爲〇以下者，更好使用-0.85〜0者。列舉爲例如，烷基、烷氧基、胺基、羥（羥基）等。至於電子給予性基較佳者爲烷基、烷氧基，更好爲烷氧基（較好爲碳數1~12，更好爲碳數卜8，又更好爲碳數 1~6’最好爲碳數1~4)。作爲R1較好爲氫原子或電子給予性基，更好爲烷基、 -98 - 201213864 烷氧基、胺基、羥（羥基），更好爲碳數1〜4之烷基、碳數1〜12之烷氧基，最好爲烷氧基（較好爲碳數1〜12，更好爲碳數卜8，又更好爲碳數1〜6，最好爲碳數1〜4)，最好爲甲氧基。作爲R2較好爲氫原子、烷基 '烷氧基、胺基、羥（羥基），更好爲氫原子、院基 '院氧基，又更好爲氫原子、烷基（較好爲碳數1〜4，更好爲甲基）、烷氧基（較好爲碳數1〜12，更好爲碳數1〜8，又更好爲碳數1〜6，最好爲碳數1〜4)。最好爲氫原子、甲基、甲氧基。作爲R3較好爲氫原子或電子給予性基，更好爲氫原子、烷基、烷氧基、胺基、羥（羥基），更好爲烷基、烷氧基，最好爲烷氧基（較好爲碳數1〜12，更好爲碳數1~8, 又更好爲碳數1〜6，最好爲碳數1〜4)。最好爲正丙氧基、乙氧基、甲氧基。作爲R4較好爲氫原子或電子給予性基，更好爲氫原子、烷基、烷氧基、胺基、羥（羥基），更好爲氫原子、碳數1〜4之烷基、碳數1~12之烷氧基（較好爲碳數1〜12，更好爲碳數1~8，又更好爲碳數1〜6，最好爲碳數1〜4 )，又更好爲氫原子、碳數1~4之烷基、碳數1~4之烷氧基，最好爲氫原子、甲基、甲氧基。作爲R5較好爲氫原子、烷基、烷氧基、胺基、羥（羥基）’更好爲氫原子、烷基、烷氧基，又更好爲氫原子、烷基（較好爲碳數1〜4，更好爲甲基）、烷氧基（較好爲碳數1〜12’更好爲碳數1〜8，又更好爲碳數1〜6，最好爲碳 -99- 201213864 數1〜4)。最好爲氫原子、甲基、甲氧基。 R6、R7、R9及R1()較好爲氫原子、碳數1〜12之烷基、碳數1~12之院氧基、鹵素原子，更好爲氫原子、鹵素原子，又更好爲氫原子。 R8表示氫原子、碳數1〜4之烷基、碳數2〜6之炔基、碳數6〜12之芳基、碳數1〜12之烷氧基、碳數6〜12之芳氧基、碳數2〜12之烷氧基羰基、碳數2〜12之醯基胺基、氰基或鹵素原子，可能之情況下亦可具有取代基，至於取代基可使用後述之取代基T。又，取代基亦可進一步經取代。至於R8較好爲碳數1~4之烷基、碳數2〜6之炔基、碳數 6〜12之芳基、碳數1~12之烷氧基、碳數2〜12之烷氧基羰基、氰基，更好爲碳數6〜12之芳基、碳數1〜12之烷氧基、碳數2〜12之烷氧基羰基、氰基，又更好爲碳數1〜6之烷氧基、碳數6〜12之芳基、碳數2〜6之烷氧基羰基、氰基’最好爲碳數1〜4之烷氧基、苯基、對-氰基苯基、對-甲氧基苯基、碳數2~4之烷氧基羰基、氰基。以一般式（6)表示之化合物中，更好之化合物爲以下述一般式（6-A)表示之化合物。 [化 39] -般式At least one of R1, R2, R3, 尺4 and r5 represents an electron donating group. Preferably, at least one of R 1 , R 3 or R 5 is an electron donating group, and more preferably R 3 is an electron donating group. The electron-donating group indicates that Hammet's σρ値 is 0 or less, and it is preferable to use the Hammet σρ 値 described in Chem. Rev., 91, 165 (1991) as the following, and it is preferable to use -0.85 to 0. For example, an alkyl group, an alkoxy group, an amine group, a hydroxyl group (hydroxy group) and the like are exemplified. The electron donating group is preferably an alkyl group or an alkoxy group, more preferably an alkoxy group (preferably having a carbon number of 1 to 12, more preferably a carbon number of 8, and more preferably a carbon number of 1 to 6'). It is best to have a carbon number of 1 to 4). R1 is preferably a hydrogen atom or an electron donating group, more preferably an alkyl group, -98 - 201213864 alkoxy group, an amine group, a hydroxyl group (hydroxy group), more preferably an alkyl group having 1 to 4 carbon atoms, and a carbon number of 1. The alkoxy group of -12 is preferably an alkoxy group (preferably having a carbon number of 1 to 12, more preferably a carbon number of 8, and more preferably a carbon number of 1 to 6, preferably a carbon number of 1 to 4). Preferably, it is a methoxy group. R2 is preferably a hydrogen atom, an alkyl 'alkoxy group, an amine group, a hydroxyl group (hydroxyl group), more preferably a hydrogen atom, a hospital base, and more preferably a hydrogen atom or an alkyl group (preferably carbon). a number of 1 to 4, more preferably a methyl group, an alkoxy group (preferably a carbon number of 1 to 12, more preferably a carbon number of 1 to 8, more preferably a carbon number of 1 to 6, preferably a carbon number of 1) ~4). It is preferably a hydrogen atom, a methyl group or a methoxy group. R3 is preferably a hydrogen atom or an electron donating group, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an amine group or a hydroxyl group (hydroxyl group), more preferably an alkyl group or an alkoxy group, and most preferably an alkoxy group. (It is preferably a carbon number of 1 to 12, more preferably a carbon number of 1 to 8, more preferably a carbon number of 1 to 6, preferably a carbon number of 1 to 4). Most preferred are n-propoxy, ethoxy, methoxy. R4 is preferably a hydrogen atom or an electron donating group, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an amine group or a hydroxyl group (hydroxyl group), more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or carbon. Alkoxy groups of 1 to 12 (preferably having a carbon number of 1 to 12, more preferably a carbon number of 1 to 8, more preferably a carbon number of 1 to 6, preferably a carbon number of 1 to 4), and more preferably The hydrogen atom, the alkyl group having 1 to 4 carbon atoms, and the alkoxy group having 1 to 4 carbon atoms are preferably a hydrogen atom, a methyl group or a methoxy group. R5 is preferably a hydrogen atom, an alkyl group, an alkoxy group, an amine group or a hydroxyl group (hydroxyl group), more preferably a hydrogen atom, an alkyl group or an alkoxy group, more preferably a hydrogen atom or an alkyl group (preferably carbon). A number of 1 to 4, more preferably a methyl group, an alkoxy group (preferably a carbon number of 1 to 12' is more preferably a carbon number of 1 to 8, more preferably a carbon number of 1 to 6, preferably a carbon-99. - 201213864 number 1~4). It is preferably a hydrogen atom, a methyl group or a methoxy group. R6, R7, R9 and R1() are preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a oxy group having 1 to 12 carbon atoms, a halogen atom, more preferably a hydrogen atom or a halogen atom, and more preferably A hydrogen atom. R8 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aryloxy group having 6 to 12 carbon atoms. a group, an alkoxycarbonyl group having 2 to 12 carbon atoms, a mercaptoamine group having 2 to 12 carbon atoms, a cyano group or a halogen atom, and may have a substituent as the case may be, and a substituent T which will be described later may be used as the substituent. . Further, the substituent may be further substituted. R8 is preferably an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkoxy group having 2 to 12 carbon atoms. a carbonyl group, a cyano group, more preferably an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a cyano group, more preferably a carbon number of 1 to 12 6 alkoxy group, aryl group having 6 to 12 carbon atoms, alkoxycarbonyl group having 2 to 6 carbon atoms, cyano group, preferably alkoxy group having 1 to 4 carbon atoms, phenyl group, p-cyanobenzene A group, a p-methoxyphenyl group, an alkoxycarbonyl group having 2 to 4 carbon atoms, or a cyano group. Among the compounds represented by the general formula (6), a more preferred compound is a compound represented by the following general formula (6-A). [化39] - General

—般式（6-Λ )中，R1、R2、R4、R5、R6、R7、R8、 R9及R1<}分別與一般式（6)中之該等同義’且較佳之範圍 -100- 201213864 亦同。 R"表示碳數1〜12之烷基。以R11表示之烷基可爲直鏈亦可爲分支，又亦可進一步具有取代基，但較好表示碳數 1〜12之烷基、更好表示碳數1〜8之烷基，又更好表示碳數 1〜6之烷基，最好表示碳數1〜4之烷基（列舉爲例如，甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基等 )° 以一般式（6 )表示之化合物中，更好之化合物爲以下述一般式（6-B)表不之化合物。 [化 40]In the general formula (6-Λ), R1, R2, R4, R5, R6, R7, R8, R9, and R1<} are respectively equivalent to the general formula (6) and the preferred range is -100-201213864 The same. R" represents an alkyl group having 1 to 12 carbon atoms. The alkyl group represented by R11 may be a straight chain or a branched group, or may further have a substituent, but preferably represents an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and more preferably Preferably, it is an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or Tributyl, etc.) ° Among the compounds represented by the general formula (6), a more preferred compound is a compound represented by the following general formula (6-B). [40]

—般式（6-B )中，R1、R2、R· R 1(5係與一般式（6)中之該等同義，且較佳之範圍亦同。 R11係與一般式（6-A)中同義，又較佳之範圍亦同。 X表示碳數1~4之烷基、碳數2〜6之快基、碳數6〜12之芳基、碳數1〜12之烷氧基、碳數6〜12之芳氧基、碳數2~12 之烷氧基羰基、碳數2~ 12之醯基胺基、氰基或鹵素原子。 R1、R2、R4、R5均爲氫原子時’ X較好爲院基、炔基、芳基、烷氧基、芳氧基，更好爲芳基、烷氧基、芳氧基，又更好爲烷氧基.（較好爲碳數1〜12，更好爲碳數1〜8，又更好爲碳數1〜6，最好爲碳數1〜4)，最好爲甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基。 -101 - 201213864 R1、R2、R4、R5中之至少一個有取代基時，X較好爲院氧基 '芳基、院氧基羰基、氰基，更好爲芳基（較好爲碳數6〜12)、氰基、烷氧基羰基（較好爲碳數2~12)，更好爲芳基（較好爲碳數6~12之芳基，更好爲苯基、對-氰基苯基、對-甲氧基苯基）、烷氧基羰基（較好爲碳數 2〜12，更好爲碳數2〜6，又更好爲碳數2〜4，最好爲甲氧基羰基、乙氧基碳基、正丙氧基羰基）、氰基，最好爲苯基、甲氧基羰基、乙氧基羰基、正丙氧基羰基、氰基。以一般式（6)表示之化合物中，更好之化合物爲以下述一般式（6-C)表示之化合物。 [化 41] R”0In the general formula (6-B), R1, R2, R·R 1 (5 is equivalent to the general formula (6), and the preferred range is the same. R11 and general formula (6-A) Synonymously, the preferred range is also the same. X represents an alkyl group having 1 to 4 carbon atoms, a fast group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and carbon. An aryloxy group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, a mercaptoamine group having 2 to 12 carbon atoms, a cyano group or a halogen atom. When R1, R2, R4 and R5 are each a hydrogen atom' X is preferably a group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, more preferably an aryl group, an alkoxy group, an aryloxy group, more preferably an alkoxy group. (preferably a carbon number of 1) 〜12, more preferably a carbon number of 1 to 8, more preferably a carbon number of 1 to 6, preferably a carbon number of 1 to 4), preferably a methoxy group, an ethoxy group, a n-propoxy group or an isopropyl group. Oxyl, n-butoxy. -101 - 201213864 When at least one of R1, R2, R4 and R5 has a substituent, X is preferably an oxy group, an oxycarbonyl group or a cyano group, more preferably An aryl group (preferably having a carbon number of 6 to 12), a cyano group or an alkoxycarbonyl group (preferably having a carbon number of 2 to 12), more preferably an aryl group (preferably having a carbon number of 6 to 12) An aryl group, more preferably a phenyl group, a p-cyanophenyl group or a p-methoxyphenyl group, or an alkoxycarbonyl group (preferably having a carbon number of 2 to 12, more preferably a carbon number of 2 to 6, more preferably Preferably, the carbon number is 2 to 4, preferably methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl), cyano, preferably phenyl, methoxycarbonyl, ethoxycarbonyl, n-propyl. The oxycarbonyl group and the cyano group. Among the compounds represented by the general formula (6), a more preferred compound is a compound represented by the following general formula (6-C).

一般式（6-C )中General formula (6-C)

R R. R‘R R. R‘

R R11及X係與一般式（6-B)中之該等同義，且較佳之範圍亦同。以一般式（6 )表示之化合物中，最好之化合物爲以下述一般式（6-D)袠示之化合物。 [化 42]R R11 and X are equivalent to those in the general formula (6-B), and the preferred range is also the same. Among the compounds represented by the general formula (6), the most preferred compound is a compound represented by the following general formula (6-D). [化42]

—般式（6-D)中，R2、r^r5係與一般式（6_c)中 -102- 201213864 之該等同義，且較佳之範圍亦同。R21、R22各獨立表示碳數1〜4之烷基。X1表示碳數6〜12之芳基、碳數2〜12之烷氧基羰基、或氰基。 R21表示碳數之烷基，較好爲碳數1~3之烷基’更好爲乙基、甲基。 R22表示碳數1~4之烷基，較好爲碳數1~3之烷基’更好爲乙基、甲基，又更好爲甲基。 X1爲碳數6~12之芳基、碳數2〜12之烷氧基羰基、或氰基，較好爲碳數6~1〇之芳基、碳數2~6之烷氧基羰基、氰基，更好爲苯基、對-氰基苯基、對·甲氧基苯基 '甲氧基擬基、乙氧基幾基、正丙氧基鑛基、氛基’更好爲本基、甲氧基羰基、乙氧基羰基、正丙氧基羰基、氰基。以一般式（6)表示之化合物中，最佳之化合物爲以下述一般式（6-E)表示之化合物。 [化 43]In the general formula (6-D), R2 and r^r5 are equivalent to those of -102-201213864 in the general formula (6-c), and the preferred range is also the same. R21 and R22 each independently represent an alkyl group having 1 to 4 carbon atoms. X1 represents an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a cyano group. R21 represents an alkyl group having a carbon number, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an ethyl group or a methyl group. R22 represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an ethyl group or a methyl group, more preferably a methyl group. X1 is an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a cyano group, preferably an aryl group having 6 to 1 carbon atoms and an alkoxycarbonyl group having 2 to 6 carbon atoms. More preferably, the cyano group is preferably a phenyl group, a p-cyanophenyl group, a p-methoxyphenyl 'methoxy alkoxy group, an ethoxy group, a n-propoxy group or an aryl group. Base, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, cyano. Among the compounds represented by the general formula (6), the most preferred compound is a compound represented by the following general formula (6-E). [化43]

-般式(6-E}- General (6-E}

一般式（6-E)中’ R2、R4及R5係與一般式（6-D)中之該等同義，且較佳之範圍亦同。但’任一個爲以-OR13 表示之基。此處，R"爲碳數1〜4之烷基。R21、R22、X1係與一般式（6-D)中之該等同義’且較佳之範圍亦同。較好，R4及R5之至少任一個爲以-〇r13表示之基’更好R4爲以-OR13表示之基。 -103- 201213864 R13表示碳數1〜4之烷基，較好爲碳數1〜3之烷基，更好爲乙基、甲基，又更好爲甲基。以下中，針對前述之取代基T加以說明。取代基T列舉爲例如烷基（較好爲碳數，更好爲碳數1〜12，最好爲碳數1〜8，例舉爲例如甲基、乙基、異丙基、第三丁基、正辛基、正癸基、正十六烷基、環丙基、環戊基、環己基等）、稀基（較好爲碳數2〜20、更好爲碳數2〜12，最好爲碳數2〜8，列舉爲例如乙烯基、烯丙基、2-丁烯基、3-戊烯基等）、炔基（較好爲碳數2〜20，更好爲碳數2〜12，最好爲碳數2〜8，列舉爲例如丙炔基、3-戊炔基等）、芳基（較好爲碳數6〜30，更好爲碳數6〜20，最好爲碳數6〜12，列舉爲例如苯基、對-甲基苯基、萘基等）、經取代或未經取代之胺基（較好爲碳數0~20，更好爲碳數0〜1 0，最好爲碳數0〜6，列舉爲例如胺基、甲胺基、二甲胺基、二乙胺基、二苄胺基等）、烷氧基（較好爲碳數1〜20，更好爲碳數1〜12，最好爲碳數1~8，列舉爲例如甲氧基、乙氧基、丁氧基）、芳氧基（較好爲碳數6〜20 ，更好爲碳數6〜1 6，最好爲碳數6〜1 2，列舉爲例如苯氧基、2-萘氧基等）、醯基（較好爲碳數1~20，更好爲碳數 1〜1 6，最好爲碳數1 ~ 1 2，列舉爲例如乙醯基、苯甲醯基、甲醯基、特戊醯基等）、烷氧基羰基（較好爲碳數2〜20，更好爲碳數2〜1 6，最好爲碳數2〜1 2，列舉爲例如甲氧基羰基、乙氧基羰基等）、芳氧基羰基（較好爲碳數7〜20，更好爲碳數7~16，最好爲碳數7〜10，列舉爲例如苯氧基羰基 -104 - 201213864 等）、醯氧基（較好爲碳數2〜20，更好爲碳數2~16，最好爲碳數2~1〇，列舉爲例如乙醯氧基、苯甲醯基氧基等）、醯基胺基（較好爲碳數2〜20，更好爲碳數2~16，最好爲碳數2〜10，列舉爲例如乙醯基胺基、苯甲醯基胺基等）、烷氧基羰基胺基（較好爲碳數2〜20，更好爲碳數2~16，最好爲碳數2~12，列舉爲例如甲氧基羰基胺基等）、芳氧基羰基胺基（較好爲碳數7〜20，更好爲碳數7〜16，最好爲碳數 $ 7〜1 2，列舉爲例如苯氧基羰基胺基等）、磺醯基胺基（較好爲碳數1~20，更好爲碳數1〜16，最好爲碳數1~12，列舉爲例如甲烷磺醯基胺基、苯磺醯基胺基等）、胺磺醯基（較好爲碳數〇〜20，更好爲碳數〇〜16，最好爲碳數0~12，列舉爲例如胺磺醯基、甲基胺磺醯基、二甲基胺磺醯基 '苯基胺磺醯基等）、胺甲醯基（較好爲碳數1~20，更好爲碳數1〜1 6，最好爲碳數1〜1 2，列舉爲例如胺甲醯基、甲基胺磺醯基、二乙基胺甲醯基、苯基胺甲醯基等）、烷硫基（ φ 較好爲碳數1~2〇，更好爲碳數1〜16，最好爲碳數1〜12，列舉爲例如甲硫基、乙硫基等）、芳硫基（較好爲碳數6~20 ’更好爲碳數6〜1 6，最好爲碳數6〜i 2，列舉爲例如苯硫基等）、磺醯基（較好爲碳數1〜20，更好爲碳數1〜16，最好爲碳數1〜12，列舉爲例如甲烷磺醯基、甲苯磺醯基等）、亞磺醯基（較好爲碳數1〜20，更好爲碳數1~16，最好爲碳數1〜12’列舉爲例如甲烷亞磺醯基、苯亞磺醯基等）、脲基（較好爲碳數1〜20’更好爲碳數卜16，最好爲碳數卜12 ’列舉爲例如脲基、甲基脲基、苯基脲基等）、磷酸醯胺 -105- 201213864 基（較好爲碳數1~2〇’更好爲碳數1〜16，最好爲碳數丨〜12 ，列舉爲例如乙基磷酸醯胺、苯基磷酸醯胺等）、羥基、疏基、鹵素原子（例如氟原子、氯原子、溴原子、碘原子 )、氰基、磺基、羧基、硝基、氧肟酸（hydroxamic acid )基、亞磺基、聯胺基、亞胺基、雜環基（較好爲碳數 1〜30，更好爲1〜12，至於雜原子爲例如氮原子、氧原子、硫原子，具體而言列舉爲例如咪唑基、吡啶基、喹啉基、呋喃基、哌啶基、嗎啉基、苯并噁唑基、苯并咪唑基、苯并噻唑基等）、矽烷基（較好爲碳數3〜40，更好爲碳數 3〜30，最好爲碳數3~24，列舉爲例如三甲基矽烷基、三苯基矽烷基等）等。該等之取代基亦可進一步經取代。又，取代基爲兩個以上時，可相同亦可不同。且，可能之情況亦可相互鍵結形成環。以下詳細說明以下述一般式（6)表示之化合物之具體例，但本發明並不受以下具體例之任何限制。 -106- 201213864 [化 44]In the general formula (6-E), 'R2, R4 and R5 are equivalent to the general formula (6-D), and the preferred range is also the same. But any one is based on -OR13. Here, R" is an alkyl group having 1 to 4 carbon atoms. R21, R22, and X1 are the same as those in the general formula (6-D) and the preferred range is also the same. Preferably, at least one of R4 and R5 is a group represented by -?r13, and R4 is preferably a group represented by -OR13. -103- 201213864 R13 represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an ethyl group, a methyl group or more preferably a methyl group. Hereinafter, the substituent T described above will be described. The substituent T is exemplified by, for example, an alkyl group (preferably a carbon number, more preferably a carbon number of 1 to 12, more preferably a carbon number of 1 to 8, and examples thereof include a methyl group, an ethyl group, an isopropyl group, and a third group). Base, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), a dilute group (preferably having a carbon number of 2 to 20, more preferably a carbon number of 2 to 12) It is preferably a carbon number of 2 to 8, and is, for example, a vinyl group, an allyl group, a 2-butenyl group, a 3-pentenyl group or the like, an alkynyl group (preferably having a carbon number of 2 to 20, more preferably a carbon number). 2 to 12, preferably a carbon number of 2 to 8, which is, for example, a propynyl group or a 3-pentynyl group, or an aryl group (preferably having a carbon number of 6 to 30, more preferably a carbon number of 6 to 20, most preferably It is preferably a carbon number of 6 to 12, which is, for example, a phenyl group, a p-methylphenyl group, a naphthyl group or the like, a substituted or unsubstituted amine group (preferably having a carbon number of 0 to 20, more preferably a carbon number). 0 to 1 0, preferably a carbon number of 0 to 6, as an amine group, a methylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group, etc., an alkoxy group (preferably a carbon number) 1 to 20, more preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, for example, methoxy, ethoxy, butoxy groups) An aryloxy group (preferably having a carbon number of 6 to 20, more preferably a carbon number of 6 to 1, 6 or preferably a carbon number of 6 to 12, for example, a phenoxy group, a 2-naphthyloxy group or the like) or a mercapto group. (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 1, 6 and preferably a carbon number of 1 to 12, and is exemplified by, for example, an ethyl fluorenyl group, a benzamidine group, a decyl group, a pentylene group. And alkoxycarbonyl group (preferably having a carbon number of 2 to 20, more preferably 2 to 1, and preferably 2 to 1 2 carbon atoms), for example, a methoxycarbonyl group, an ethoxycarbonyl group or the like. , an aryloxycarbonyl group (preferably having a carbon number of 7 to 20, more preferably a carbon number of 7 to 16, preferably a carbon number of 7 to 10, as exemplified by, for example, phenoxycarbonyl-104 - 201213864, etc.) a base (preferably having a carbon number of 2 to 20, more preferably a carbon number of 2 to 16, preferably a carbon number of 2 to 1 Å, for example, an ethoxy group, a benzhydryloxy group, etc.), a mercaptoamine a base (preferably having a carbon number of 2 to 20, more preferably a carbon number of 2 to 16, preferably a carbon number of 2 to 10, for example, an ethoxymethylamino group, a benzhydrylamino group, etc.), an alkoxy group a carbonylamine group (preferably having a carbon number of 2 to 20, more preferably a carbon number of 2 to 16, preferably a carbon number of 2 to 12, and is exemplified by, for example, methoxycarbonyl Alkylamino or the like, an aryloxycarbonylamino group (preferably having a carbon number of 7 to 20, more preferably a carbon number of 7 to 16, preferably a carbon number of 7 to 1 2, as exemplified by, for example, phenoxycarbonylamine Base, etc., sulfonylamino group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 16, preferably a carbon number of 1 to 12, and is exemplified by, for example, methanesulfonylamino group, benzenesulfonate Aminosulfonyl group, etc., an amine sulfonyl group (preferably having a carbon number of 〇20, more preferably a carbon number of 1616, preferably a carbon number of 0-12), for example, an amine sulfonyl group, a methylamine sulfonate Anthracenyl, dimethylamine sulfonyl 'phenylamine sulfonyl, etc.), an amine formazan group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 1, preferably a carbon number of 1) ～1 2 is exemplified by, for example, an amine carbaryl group, a methylamine sulfonyl group, a diethylamine carbaryl group, a phenylamine carbhydryl group, or the like, and an alkylthio group (φ is preferably a carbon number of 1 to 2 Å). More preferably, the carbon number is 1 to 16, preferably the carbon number is 1 to 12, and is, for example, a methylthio group or an ethylthio group, and an arylthio group (preferably having a carbon number of 6 to 20' is more preferably a carbon number. 6 to 1, 6 is preferably a carbon number of 6 to i 2, for example, a phenylthio group or the like, and a sulfonyl group (preferably having a carbon number of 1 to 20, more preferably The carbon number is 1 to 16, preferably the carbon number is 1 to 12, and is, for example, a methanesulfonyl group or a toluenesulfonyl group, or a sulfinyl group (preferably, the carbon number is 1 to 20, more preferably the carbon number is 1). ~16, preferably a carbon number of 1 to 12' is exemplified by, for example, a methanesulfinyl group, a sulfinyl group, or a urea group (preferably a carbon number of 1 to 20' is more preferably a carbon number of 16, most preferably Preferably, the carbon number 12' is listed as, for example, a urea group, a methylurea group, a phenylureido group, etc., and a guanamine phosphate-105-201213864 group (preferably a carbon number of 1 to 2 〇' is more preferably a carbon number of 1) ～16, preferably a carbon number 丨~12, which is exemplified by, for example, ethyl phosphoniumamine, phenylphosphonium amide, etc.), a hydroxyl group, a sulfhydryl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom). , cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfinyl group, hydrazine group, imido group, heterocyclic group (preferably having a carbon number of 1 to 30, more preferably 1) ～12, the hetero atom is, for example, a nitrogen atom, an oxygen atom or a sulfur atom, and specifically, for example, an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a piperidinyl group, a morpholinyl group, a benzoxazolyl group, Benzomidazole a base, a benzothiazolyl group, or the like, a decyl group (preferably having a carbon number of from 3 to 40, more preferably a carbon number of from 3 to 30, most preferably a carbon number of from 3 to 24, as exemplified by, for example, trimethyldecylalkyl, triphenyl Based on alkyl groups, etc.). These substituents may also be further substituted. Further, when the number of the substituents is two or more, they may be the same or different. Moreover, it is also possible that the cases may be bonded to each other to form a loop. The specific examples of the compounds represented by the following general formula (6) are described in detail below, but the present invention is not limited by the following specific examples. -106- 201213864 [化44]

A"1 H3CO H3co HacoA"1 H3CO H3co Haco

A-2 PCH： h3co h3co CO OCH3 a—3 H3CQV OCH3 h3co Α-4 OCHj H3CO- 3—=-°-〇-cn och3 A 一6A-2 PCH: h3co h3co CO OCH3 a-3 H3CQV OCH3 h3co Α-4 OCHj H3CO- 3—=-°-〇-cn och3 A-6

ο Μ C —ο ~0~£ A 一7 OCH,ο Μ C —ο ~0~£ A-7 OCH,

ο II C—ο h3co Α-8 〇CH3ο II C—ο h3co Α-8 〇CH3

OCH, ο II c，o Α-9 H3CO H3C0OCH, ο II c,o Α-9 H3CO H3C0

ο ιι -C 一 Οο ιι -C 一Ο

OrΟ- 仆 -107- 201213864 [化 45] A-10 H3co o H c一o A 一 11 A-12 h3co h3co h3co h3co h3co 〇ch3OrΟ- 仆-107- 201213864 A-10 H3co o H c ao A a 11 A-12 h3co h3co h3co h3co h3co 〇ch3

OCH,OCH,

o IIc—o A-13o IIc—o A-13

h3co HaCO och3 o II•c· -〇~CN分· c—och3 A-14 h3co h3co OCH* A-15 A-16 OCH，H3co HaCO och3 o II•c· -〇~CN points · c-och3 A-14 h3co h3co OCH* A-15 A-16 OCH,

H3CO o II •C一0 O II C —0H3CO o II • C 0 O II C — 0

A-17 H^CO h3co och3 c-oA-17 H^CO h3co och3 c-o

-108 201213864 [化 46] A—18 PCH： h3co-108 201213864 [Chem. 46] A-18 PCH: h3co

HjCO A-19 ,v 0 ft\. h3co c一o- -CHa A-20 h3CO 乂 μ /=\_ —c—o—^ >-och3 A-21 _ 叫。-〇- c o-^^-qc2Hs A-22 ^ HjC〇hQ_ C 〇-^^-OCaH7 A-23 n CjHs〇^w^ —c—o—OCHs A_24 ^"Λ C 〇-^^-〇c2h5 A-25 —. c2HS〇-<^y- C 〇-^^-〇c,h7 A—26 y_^ c3h7o-^]>— ° /=\ —C —0--^ 0CH3 A-27 ^ c^°-〇- ~c~°~^~^~〇cA A"28 c3H7o-^>- C °"~^~^~QC3H7 -109 201213864 [化 47] A-29 A-30 A 一 31 H3CO—-C — O 〇CeHn 〇eH130 _c—o 〇*ocHs c3h7o -c—o <y oc4h9 A-32 c3h7o 兰一〇hG^〇—(HjCO A-19 , v 0 ft\. h3co c-o- -CHa A-20 h3CO 乂 μ /=\_ —c—o—^ >-och3 A-21 _ Call. -〇- c o-^^-qc2Hs A-22 ^ HjC〇hQ_ C 〇-^^-OCaH7 A-23 n CjHs〇^w^ —c—o—OCHs A_24 ^"Λ C 〇-^^- 〇c2h5 A-25 —. c2HS〇-<^y- C 〇-^^-〇c,h7 A—26 y_^ c3h7o-^]>— ° /=\ —C —0--^ 0CH3 A -27 ^ c^°-〇- ~c~°~^~^~〇cA A"28 c3H7o-^>- C °"~^~^~QC3H7 -109 201213864 [化47] A-29 A -30 A -31 H3CO--C - O 〇CeHn 〇eH130 _c-o 〇*ocHs c3h7o -c-o <y oc4h9 A-32 c3h7o 兰一〇hG^〇—(

A 一 33 A—34 OCH，A a 33 A-34 OCH,

oc—o-Oc-o-

-C=CH och3 cnco^0— h3co A-35-C=CH och3 cnco^0— h3co A-35

h3co A-36H3co A-36

h3coH3co

-110- 201213864 [化 48] A-37 A 一 38 och3 H3CO —C-〇hQkc h3c och3_J~L Η /=\_ ΠH3co-f y-c—^-o—c c—c2h5 A 一 39 OCH,-110- 201213864 A-37 A-38 och3 H3CO —C-〇hQkc h3c och3_J~L Η /=\_ ΠH3co-f y-c—^-o—c c—c2h5 A a 39 OCH,

oo

h3co: h3co mO—^ ^-~0~C一C2H5H3co: h3co mO—^ ^-~0~C-C2H5

A 一 41 A 一 42 A-43 h3c〇 H3c〇A - 41 A - 42 A-43 h3c〇 H3c〇

H3c〇 A一45H3c〇 A-45

-111 - 201213864 [化 49] A-46 h3chn — c—c—c2h6 A 一 48 ^ ^-C—c—C2Hs A-49 h3co- >_〇· c-0-\ /- OCH2CH2OCH2CH3 A-50 h3co-111 - 201213864 A-46 h3chn — c—c—c2h6 A —48 ^ ^-C—c—C2Hs A-49 h3co- >_〇· c-0-\ /- OCH2CH2OCH2CH3 A-50 H3co

^〇hOkc 本發明中使用之以一般式（6)表示之化合物可藉由經取代之苯甲酸與酚衍生物之一般酯化反應而合成，若爲形成酯鍵反應則亦可使用任何反應。列舉爲例如，將經取代之苯甲酸官能基轉換成醯鹵化物後，與酚縮合之方法，使用縮合劑或觸媒使經取代之苯甲酸與酚衍生物脫水縮合之方法等。考慮製造製程時，較好爲使經取代之苯甲酸官能基轉化成醯鹵化物後，與酚縮合之方法。至於反應溶劑可使用烴系溶劑（列舉較佳者爲甲苯、二甲苯）、醚系溶劑（列舉較佳者爲二甲基醚、四氫呋喃、二噁烷等）、酮系溶劑、酯系溶劑、乙腈、二甲基甲醯胺、二甲基乙醯胺等。該等溶劑可單獨使用亦可混合數種使用，至於反應溶劑較好爲甲苯、乙腈、二甲基甲醯胺、 -112- 201213864 二甲基乙醯胺。反應溫度較好爲〇~150°C ’更好爲〇~i〇〇°c ’又更好爲〇~90°C，最好爲 20~90°C。本反應中較好不使用鹼，使用鹼時可爲有機鹼、無機鹼之任一種，較好爲有機鹼，且爲吡啶、三級烷基胺（列舉較好爲三乙基胺、乙基二異丙基胺等）。另外，本發明之λΜ板較好含有溶液之紫外線吸收光譜之最大吸收波長（Xmax)比2 5 0nm短波長的棒狀化合物作爲滯相調整劑。就滞相調整劑之功能之觀點而言，棒狀化合物較好具有至少一個芳香族環，更好具有至少兩個芳香族環。棒狀化合物較好具有直線之分子構造。所謂直線分子構造意指熱力學上最安定之構造中棒狀化合物之分子構造爲直線之意。熱力學上最安定之構造可藉由結晶構造解析或分子軌道計算而求得。例如，利用分子軌道計算軟體（例如 WinM〇PAC2000，富士通（股）製造）進行分子軌道計算，可求得化合物之生成熱成爲最小之分子構造。所謂分子構造爲直線意指如上述計算求得之熱力學上最安定之構造中，分子構造之角度爲14〇度以上。棒狀化合物較好顯示液晶性。棒狀化合物更好爲藉由加熱顯示液晶性（具有熱致液晶（thermotropic liquid crystal)性）。液晶相較好爲向列型相或層列型相。至於棒狀化合物較好爲以下述一般式（7 )表示之反式-1，4-環己烷二羧酸酯化合物。 -113- 201213864 —般式（7 ) : Ar1 -I^-Ar2 式（7)中，Ar1及Ar2各獨立爲芳香族基。本說明書中，芳香族基包含芳基（芳香族烴基）、經取代之芳基、芳香族性雜環基及經取代之芳香族性雜環基。芳基及經取代之芳基比芳香族性雜環基及經取代之芳香族性雜環基更佳。芳香族性雜環基之雜環通常爲不飽和。芳香族性雜環較好爲5員環、6員環或7員環，更好爲5員環或6員環。芳香族性雜環一般具有最多雙鍵。至於雜原子較好爲氮原子、氧原子或硫原子，更好爲氮原子或硫原子。芳香族性雜環之例包含呋喃環、噻吩環、吡咯環、噁唑環、異噁唑環、噻唑環、異噻唑環、咪唑環、吡唑環、肤咱（furazan ) 環、三唑環、吡喃環、吡啶環、嗒嗪環、嘧啶環、吡嗪環、及1，3, 5 -三嗪環。芳香族基之芳香族環較好爲苯環、呋喃環、噻吩環、吡咯環、噁唑環、噻唑環、咪唑環、三唑環、毗啶環、嘧啶環及吡嗪環。最好爲苯環。經取代之芳基及經取代之芳香族性雜環基之取代基之例包含鹵素原子（F、Cl、Br、I)、羥基、羧基、氰基、胺基、烷基胺基（例如，甲胺基、乙胺基、丁胺基、二甲胺基）、硝基、磺基、胺甲醯基、烷基胺甲醯基（例如， N·甲基胺甲醯基、N-乙基胺甲醯基、N，N-二甲基胺甲醯基 )、胺磺醯基、烷基胺磺醯基（例如，N-甲基胺磺醯基、 N-乙基胺磺醯基、N，N-二甲基胺磺醯基）、脲基、烷基脲基（例如，N-甲基脲基、N，N-二甲基脲基、N，N，N’-三甲基脲基）、烷基（例如，甲基、乙基、丙基、丁基、戊基 -114- 201213864 、庚基、辛基、異丙基、第二丁基、第三戊基、環己基、環戊基）、烯基（例如，乙烯基、烯丙基、己烯基）、炔基（例如，乙炔基、丁炔基）'醯基（例如，甲醯基、乙醯基、丁醯基、己醯基、月桂醯基）、醯氧基（例如，乙醯氧基、丁醯氧基、己醯氧基、月桂醯氧基）、烷氧基（例如’甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、庚氧基'辛氧基）、芳氧基（例如，苯氧基）、烷氧基羰基（ $ 例如，甲氧基羰基、乙氧基羰基、丙氧基羰基、丁氧基羰基、戊氧基羰基、庚氧基羰基）、芳氧基羰基（例如，苯氧基羰基）、烷氧基羰基胺基（例如，丁氧基羰基胺基、己氧基羰基胺基）、烷硫基（例如，甲硫基、乙硫基、丙硫基、丁硫基、戊硫基、庚硫基、辛硫基）、芳硫基（例如’苯硫基）、烷基磺醯基（例如，甲基磺醯基、乙基磺醯基、丙基磺醯基、丁基磺醯基、戊基磺醯基、庚基磺醯基、辛基磺醯基）、醯胺基（例如，乙醯胺基、丁醯胺基 Φ '己醯胺基、月桂醯胺基）及非芳香族雜環基（例如，嗎琳基、卩比嗓基）。經取代之芳基及經取代之芳香族性雜環基之取代基較好爲鹵素原子、氰基、羧基、羥基、胺基、烷基取代之胺基、醯基、醯氧基、醯胺基、烷氧基羰基、烷氧基、烷硫基及烷基。烷基胺基、烷氧基羰基、烷氧基及烷硫基之烷基部分與烷基亦可進一步具有取代基。烷基部分及烷基之取代基之例包含鹵素原子、羥基、羧基、氰基、胺基、烷基胺基、硝基、磺基、胺甲醯基、烷基胺甲醯基、胺磺醯 -115- 201213864 基、烷基胺磺醯基、脲基、烷基脲基、烯基、炔基、醯基、醯氧基、烷氧基、芳氧基、烷氧基羰基、芳氧基羰基、烷氧基羰基胺基、烷硫基、芳硫基、烷基磺醯基、醯胺基及非芳香族雜環基。烷基部分及烷基之取代基較好爲鹵素原子、羥基、胺基、烷基胺基、醯基、醯氧基、醯基胺基、院氧基幾基及院氧基。式（7 )中，L1爲由伸烷基、伸烯基、伸炔基、二價飽和雜環基、-〇_、-CO-及該等之組合所組成群組選出之二價連結基。伸烷基亦可具有環狀構造。環狀伸烷基較好爲伸環己基，最好爲1，4-伸環己基。作爲鏈狀伸烷基，直鏈狀伸烷基比具有分支之伸烷基更好。烷基之碳原子數較好爲1〜20，更好爲卜15，又更好爲1〜10，再更好爲1〜8, 最好爲1〜6。伸烯基及伸炔基，具有鏈狀構造比環狀構造更佳，具有直鏈狀構造比具有分支之鏈狀構造更佳。伸烯基及伸炔基之碳原子數較好爲2~10，更好爲2〜8，又更好爲2〜6，再更好爲2~4，最好爲2-(伸乙烯基或伸乙炔基）。二價飽和雜環基較好爲具有3員〜9員之雜環。雜環之雜原子較好爲氧原子、氮原子、硼原子、硫原子、矽原子、磷原子或鍺原子。飽和雜環之例包含哌啶環、哌嗪環、嗎啉環、吡咯啶環、咪唑啶環、四氫呋喃環、四氫吡喃環、1，3-二噁烷環、1,4-二噁烷環、四氫噻吩環、1，3-噻唑啶環、1，3-噁唑啶環、1，3-二氧雜環戊烷環、1,3-二硫雜環戊烷環及 1，3,2 -二氧雜硼雜環戊烷。最佳之二價飽和雜環基爲哌嗪_ -116- 201213864 1，4 -二基、1，3-二噁烷-2,5 -二基及1，3,2 -二氧雜硼雜環戊烷-夂5-二基。組合而成之二價連結基之例示於下： L-l : -0-C0 -伸烷基- CO-0- L-2: -C0-0 -伸烷基- 0- C0- L-3 : -0-C0 -伸烯基- C0-0- L-4 ： -C0-0 -伸烯基- 0- C0- L-5 ： -0-C0-伸炔基- ΟΟ-Ο- ΐ^ - 6 : - C Ο - Ο - 伸炔基 - 0 - C Ο - L-7: -0-C0-二價飽和雜環基-CO-0- L-8 : -CO-O-二價飽和雜基-0-CO- 一般式（7)之分子構造中’挾著L1之Ar1及Ar2所形成之角度較好爲140度以上。棒狀化合物更好爲以下述一般式（8 )表示之化合物。 —fe 式（8) ： Ar'-L2-X-L3-Ar2 式（8)中，Ar1及Ar2各獨立爲芳香族基。芳香族基之定義及其例係與式（7)之Ar1及Ar2相同。式（8)中，L2及L3各獨立爲伸烷基、-〇-、-CO-及由該等之組合組成之群組選出之二價連結基。伸烷基具有鏈狀構造者比環狀構造更佳，具有直鏈狀構造比具有分支之鏈狀構造更佳。伸烷基之碳原子數較好爲1 ~ 1 〇，更好爲 1〜8，又更好爲1~6，最好爲1~4，最好爲1或2(亞甲基或伸乙基）。L2及L3最好爲-0-C0-或-C0-0-。式（8 )中，X爲I，4-伸環己基、伸乙烯基或伸乙炔基 -117- 201213864 。以下列示以式（7 )表示之化合物之具體例。 [化 50] (1) Ο^Άΐ-心 c3H7—^^o-c-^^c-o-^^-c7h« CeH13 C8H17 H3c—ο- c-o—^~^r-CH3 ci—o-c—^~^-c-o— Br—O-C—^ c-o—^~^Br H3c-S—o-c—^ ^-0-0— c2HB—<^^-o-c-(^-c-o-^^-c2hs (n)C4H9-^-〇-C-(^)-C-〇H^- ( C5H,,—^^-O-C-^^-C-O-K^^- C5H,i 《）h,c-ch—^~~y~〇-c—^ y~c-〇—^~y~CH-CH3 (2) (3)^〇hOkc The compound represented by the general formula (6) used in the present invention can be synthesized by a general esterification reaction of a substituted benzoic acid with a phenol derivative, and any reaction can be used for the formation of an ester bond reaction. For example, a method in which a substituted benzoic acid functional group is converted into a hydrazine halide and then condensed with a phenol is used, and a substituted benzoic acid and a phenol derivative are dehydrated and condensed using a condensing agent or a catalyst. When the manufacturing process is considered, it is preferred to condense the substituted benzoic acid functional group into a hydrazine halide and then condense with the phenol. As the reaction solvent, a hydrocarbon solvent (exemplified by toluene or xylene), an ether solvent (e.g., preferably dimethyl ether, tetrahydrofuran, dioxane, etc.), a ketone solvent, an ester solvent, or the like can be used. Acetonitrile, dimethylformamide, dimethylacetamide, and the like. These solvents may be used singly or in combination of several kinds, and the reaction solvent is preferably toluene, acetonitrile, dimethylformamide, -112-201213864 dimethylacetamide. The reaction temperature is preferably from 〇 to 150 ° C Å, more preferably 〇 to i 〇〇 ° c ′ and more preferably from 〇 to 90 ° C, preferably from 20 to 90 ° C. In the reaction, it is preferred not to use a base. When a base is used, it may be any of an organic base or an inorganic base, preferably an organic base, and is a pyridine or a tertiary alkylamine (it is preferably a triethylamine or an ethyl group). Isopropylamine, etc.). Further, the λ plate of the present invention preferably contains a rod-like compound having a maximum absorption wavelength (Xmax) of the ultraviolet absorption spectrum of the solution and a wavelength shorter than 250 nm as a retardation adjuster. The rod-like compound preferably has at least one aromatic ring, more preferably at least two aromatic rings, from the viewpoint of the function of the retardation modifier. The rod-like compound preferably has a linear molecular structure. The so-called linear molecular structure means that the molecular structure of the rod-like compound in the thermodynamically most stable structure is a straight line. The most thermodynamically stable structure can be obtained by crystal structure analysis or molecular orbital calculation. For example, a molecular orbital calculation software (for example, WinM〇PAC2000, manufactured by Fujitsu Co., Ltd.) is used for molecular orbital calculation, and a molecular structure in which the heat of formation of a compound is minimized can be obtained. The molecular structure is a straight line meaning that the thermodynamically most stable structure obtained by the above calculation has a molecular structure angle of 14 以上 or more. The rod-like compound preferably exhibits liquid crystallinity. The rod-like compound is more preferably exhibiting liquid crystallinity by heating (having thermotropic liquid crystal). The liquid crystal phase is preferably a nematic phase or a smectic phase. The rod-like compound is preferably a trans-1,4-cyclohexanedicarboxylate compound represented by the following general formula (7). -113-201213864 General formula (7): Ar1 - I^-Ar2 In the formula (7), each of Ar1 and Ar2 is independently an aromatic group. In the present specification, the aromatic group includes an aryl group (aromatic hydrocarbon group), a substituted aryl group, an aromatic heterocyclic group, and a substituted aromatic heterocyclic group. The aryl group and the substituted aryl group are more preferred than the aromatic heterocyclic group and the substituted aromatic heterocyclic group. The heterocyclic ring of the aromatic heterocyclic group is usually unsaturated. The aromatic heterocyclic ring is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring. Aromatic aromatic heterocycles generally have the most double bonds. The hetero atom is preferably a nitrogen atom, an oxygen atom or a sulfur atom, more preferably a nitrogen atom or a sulfur atom. Examples of the aromatic heterocyclic ring include a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furazan ring, and a triazole ring. a pyran ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a 1,3,5-triazine ring. The aromatic ring of the aromatic group is preferably a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, a thiazole ring, an imidazole ring, a triazole ring, a pyridine ring, a pyrimidine ring or a pyrazine ring. It is preferably a benzene ring. Examples of the substituent of the substituted aryl group and the substituted aromatic heterocyclic group include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, a cyano group, an amine group, an alkylamine group (for example, Methylamino, ethylamino, butylamino, dimethylamino), nitro, sulfo, amidomethyl, alkylamine-methyl (for example, N-methylamine-methyl, N-B Amidoxime, N,N-dimethylaminecarbamyl, sulfonyl, alkylamine sulfonyl (eg, N-methylamine sulfonyl, N-ethylamine sulfonyl) , N,N-dimethylaminesulfonyl), ureido, alkylureido (for example, N-methylureido, N,N-dimethylureido, N,N,N'-trimethyl Alkyl group, alkyl (for example, methyl, ethyl, propyl, butyl, pentyl-114-201213864, heptyl, octyl, isopropyl, t-butyl, third pentyl, ring Hexyl, cyclopentyl), alkenyl (eg, vinyl, allyl, hexenyl), alkynyl (eg, ethynyl, butynyl) 'fluorenyl (eg, formazan, ethyl fluorenyl, Butyl, hexyl, lauryl), decyloxy (eg, ethoxylated, Alkoxy, hexyloxy, lauryloxy), alkoxy (eg 'methoxy, ethoxy, propoxy, butoxy, pentyloxy, heptyloxy' octyloxy), An aryloxy group (e.g., phenoxy), an alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, heptoxycarbonyl), An aryloxycarbonyl group (for example, phenoxycarbonyl), an alkoxycarbonylamino group (for example, a butoxycarbonylamino group, a hexyloxycarbonylamino group), an alkylthio group (for example, a methylthio group, an ethylthio group) , propylthio, butylthio, pentylthio, heptylthio, octylthio), arylthio (eg 'phenylthio"), alkylsulfonyl (eg, methylsulfonyl, ethyl sulfonate) Sulfhydryl, propylsulfonyl, butylsulfonyl, pentylsulfonyl, heptylsulfonyl, octylsulfonyl), decylamine (eg, acetamido, butylamine) 'Hexylamino, laurylamine' and non-aromatic heterocyclic groups (eg, morphinyl, indolyl). The substituent of the substituted aryl group and the substituted aromatic heterocyclic group is preferably a halogen atom, a cyano group, a carboxyl group, a hydroxyl group, an amine group, an alkyl group-substituted amine group, an anthracenyl group, a decyloxy group or a decylamine. Alkyl, alkoxycarbonyl, alkoxy, alkylthio and alkyl. The alkyl moiety of the alkylamino group, the alkoxycarbonyl group, the alkoxy group and the alkylthio group and the alkyl group may further have a substituent. Examples of the substituent of the alkyl moiety and the alkyl group include a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, an amine group, an alkylamino group, a nitro group, a sulfo group, an amine mercapto group, an alkylamine methyl group, an amine sulfonate.醯-115- 201213864 base, alkylamine sulfonyl, ureido, alkylureido, alkenyl, alkynyl, decyl, decyloxy, alkoxy, aryloxy, alkoxycarbonyl, aryloxy A carbonyl group, an alkoxycarbonylamino group, an alkylthio group, an arylthio group, an alkylsulfonyl group, a decylamino group, and a non-aromatic heterocyclic group. The substituent of the alkyl moiety and the alkyl group is preferably a halogen atom, a hydroxyl group, an amine group, an alkylamino group, a decyl group, a decyloxy group, a decylamino group, an alkoxy group, and an alkoxy group. In the formula (7), L1 is a divalent linking group selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, a divalent saturated heterocyclic group, -〇_, -CO-, and a combination thereof. The alkylene group may also have a cyclic structure. The cyclic alkyl group is preferably a cyclohexylene group, preferably a 1,4-cyclohexylene group. As the chain alkyl group, a linear alkyl group is more preferable than a branched alkyl group. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 15 or more, more preferably 1 to 10, still more preferably 1 to 8, more preferably 1 to 6. The alkenyl group and the alkynylene group have a chain structure which is better than the ring structure, and a linear structure is preferable to a chain structure having a branch. The number of carbon atoms of the alkenyl group and the alkynylene group is preferably from 2 to 10, more preferably from 2 to 8, more preferably from 2 to 6, more preferably from 2 to 4, most preferably from 2 to 2 Or ethynyl). The divalent saturated heterocyclic group is preferably a heterocyclic ring having 3 to 9 members. The hetero atom of the hetero ring is preferably an oxygen atom, a nitrogen atom, a boron atom, a sulfur atom, a ruthenium atom, a phosphorus atom or a ruthenium atom. Examples of the saturated heterocyclic ring include a piperidine ring, a piperazine ring, a morpholine ring, a pyrrolidine ring, an imidazolidinium ring, a tetrahydrofuran ring, a tetrahydropyran ring, a 1,3-dioxane ring, and a 1,4-dioxin. Alkane ring, tetrahydrothiophene ring, 1,3-thiazolidinyl ring, 1,3-oxazolidine ring, 1,3-dioxolane ring, 1,3-dithiolane ring and 1 , 3,2-dioxaborolane. The most preferred divalent saturated heterocyclic group is piperazine _ -116- 201213864 1,4 -diyl, 1,3-dioxane-2,5-diyl and 1,3,2-dioxaboron Cyclopentane-夂5-diyl. Examples of the combined divalent linking group are shown below: Ll : -0-C0 -alkylene-CO-0- L-2: -C0-0 -alkylene- 0-C0-L-3: - 0-C0 -Epentenyl-C0-0- L-4 : -C0-0 -Extend alkenyl- 0-C0- L-5 : -0-C0-Extend alkynyl- ΟΟ-Ο- ΐ^ - 6 : - C Ο - Ο - alkynyl- 0 - C Ο - L-7: -0-C0-divalent saturated heterocyclic group -CO-0- L-8 : -CO-O-divalent saturated hetero group -0-CO- In the molecular structure of the general formula (7), the angle formed by the Ar1 and Ar2 which are adjacent to L1 is preferably 140 degrees or more. The rod-like compound is more preferably a compound represented by the following general formula (8). —fe Formula (8): Ar'-L2-X-L3-Ar2 In the formula (8), each of Ar1 and Ar2 is independently an aromatic group. The definition of the aromatic group and its examples are the same as those of Ar1 and Ar2 of the formula (7). In the formula (8), L2 and L3 are each independently an alkyl group, -〇-, -CO-, and a divalent linking group selected from the group consisting of the combinations. The alkylene group has a chain structure better than the ring structure, and has a linear structure rather than a branched chain structure. The number of carbon atoms of the alkyl group is preferably from 1 to 1 Torr, more preferably from 1 to 8, more preferably from 1 to 6, most preferably from 1 to 4, most preferably from 1 or 2 (methylene or phenylene) base). L2 and L3 are preferably -0-C0- or -C0-0-. In the formula (8), X is I,4-cyclohexylene, vinylene or ethynyl-117-201213864. Specific examples of the compound represented by the formula (7) are shown below. [1] 50(1) Ο^Άΐ-心c3H7—^^oc-^^co-^^-c7h« CeH13 C8H17 H3c-ο- co-^~^r-CH3 ci-oc-^~^-co — Br—OC—^ co—^~^Br H3c-S—oc—^ ^-0-0— c2HB—<^^-oc-(^-co-^^-c2hs (n)C4H9-^- 〇-C-(^)-C-〇H^- ( C5H,, —^^-OC-^^-COK^^- C5H,i ")h,c-ch-^~~y~〇-c —^ y~c-〇—^~y~CH-CH3 (2) (3)

W (5)W (5)

(6) ⑺ (8) (9) (10) (12) h3c 〇-c—^ y~c-〇— ch3 -S-CH, -C4H9⑻(6) (7) (8) (9) (10) (12) h3c 〇-c-^ y~c-〇—ch3 -S-CH, -C4H9(8)

-118- 201213864 {C-H·*0 —o^c^~?=o~d}~=?o-{3~? v°{c>(n)-118- 201213864 {C-H·*0 —o^c^~?=o~d}~=?o-{3~? v°{c>(n)

010 = o ΦΓ o '―， o b£ i〕010 = o ΦΓ o '―, o b£ i]

«T*) £«0|0|0|«10|£0|0|0|£0|£0—^ ^10101^ ^10101^^—XO-IO-O-OlX^U-X'O-U-OUHU o=o=JL1 ^ Jrs ^ Jclo=^ ιβΗο'-οϋ-οιχ^υ-Ι·:}—丫 0--ΟΛ丫=0-0—^ IoUHUi.· 0 0 \ o y—L· o V £?'ο-£3λ丫0-=u人丫'ολυ£?ο-34ηύτίοότο^όΎ^ΪΟΎΟέό iχοότο^λοΎ^οότοχ i H 01 -WH3—^ Q - 0 —^ ϋ—O —^ *^3 —£°—0 H Js ^ icl I χοιίοιο^ιοι^οιοτ£ο.οχ o o {sr. {0£· O 0 § υ-υ-0-£0 ΗΟ」5-Η-?χ·ο-οΛγ0-=0人丫^oAro-NS-HUUHU-OH S-\—/o=^—^o=^^ Ho- s -119- 201213864 [化 52] (23) (24) HO- (25) (26) (27} (28> (30) 卩1 > (32) c8h17 C8H17 οη2-οη2-ο-〇Κ〇-〇Η^)-〇-〇Η〇- o-ch2-ch2-oh CH3-0-C-^~~^-0-C-^ ^-C-〇-^~^-C-〇-CHj C2H5-Q-C-^~y-0-C-^ ^-C-〇-^~y-C-〇-C2Hs (n)C4H9-0-C-«T*) £«0|0|0|«10|£0|0|0|£0|£0—^ ^10101^ ^10101^^—XO-IO-O-OlX^U-X'OU -OUHU o=o=JL1 ^ Jrs ^ Jclo=^ ιβΗο'-οϋ-οιχ^υ-Ι·:}—丫0--ΟΛ丫=0-0—^ IoUHUi.· 0 0 \ oy—L· o V £?'ο-£3λ丫0-=u人丫'ολυ£?ο-34ηύτίοότο^όΎ^ΪΟΎΟέό iχοότο^λοΎ^οότοχ i H 01 -WH3—^ Q - 0 —^ ϋ—O —^ *^ 3 —£°—0 H Js ^ icl I χοιίοιο^ιοι^οιοτ£ο.οχ oo {sr. {0£· O 0 § υ-υ-0-£0 ΗΟ”5-Η-?χ·ο- ΛΛγ0-=0人丫^oAro-NS-HUUHU-OH S-\—/o=^—^o=^^ Ho- s -119- 201213864 [52] (23) (24) HO- (25) (26) (27) (28) (28> (30) 卩1 > (32) c8h17 C8H17 οη2-οη2-ο-〇Κ〇-〇Η^)-〇-〇Η〇- o-ch2-ch2-oh CH3 -0-C-^~~^-0-C-^ ^-C-〇-^~^-C-〇-CHj C2H5-QC-^~y-0-C-^ ^-C-〇-^ ~yC-〇-C2Hs (n)C4H9-0-C-

-^~y~〇-C^ ^-C-〇-^~~^-C-〇-C4Hs(n) c6h13-o- C—^ y-C-〇-^~~^-C-〇-C6H13 csHii_〇^s"〇h〇~°^'0~ C6Hh ch3—^~y~c·。一^~^-〇-c-^~y-cH3 C2H5--^^- C-0 y~ o-c c2h5 (n)C4H9 c4h9 ⑻-^~y~〇-C^ ^-C-〇-^~~^-C-〇-C4Hs(n) c6h13-o- C—^ yC-〇-^~~^-C-〇-C6H13 csHii _〇^s"〇h〇~°^'0~ C6Hh ch3—^~y~c·.一^~^-〇-c-^~y-cH3 C2H5--^^- C-0 y~ o-c c2h5 (n)C4H9 c4h9 (8)

-120- 201213864 [化 53] ()CH3-〇—^ ^-0-0-^~^-0-0Η3 ()(n)C4H9-Q—^~y-C-Q—y-O-C—^~y-〇 C4H9(n) (35> 0^〇H〇hQ (36) ,_Q_〇U_0^_ CHa CH,-120- 201213864 [化53] ()CH3-〇-^ ^-0-0-^~^-0-0Η3 ()(n)C4H9-Q—^~yCQ—yOC—^~y-〇C4H9( n) (35> 0^〇H〇hQ (36) , _Q_〇U_0^_ CHa CH,

(37> /Γ\ η » /Γ\ P2H5--f V〇-C-C^c-C-〇-f y--c-c=c- °-o-° -C-C^C-C-O (40) (38) ⑻ C4Hs (39) ch3 o c2h5 C4H9(n) ch3 C2H5-d-07-^~y-Q"C-C=C-C-0 ~Qr (41) c7h15^-o-!^>Ic-^c7h1s ϋ c-o-c2hs (42)(37> /Γ\ η » /Γ\ P2H5--f V〇-CC^cC-〇-f y--cc=c- °-o-° -CC^CCO (40) (38) (8) C4Hs ( 39) ch3 o c2h5 C4H9(n) ch3 C2H5-d-07-^~y-Q"CC=CC-0 ~Qr (41) c7h15^-o-!^>Ic-^c7h1s ϋ co-c2hs ( 42)

-121 - 201213864 [化 54] (43> Γ\ ° ° CeHis-〇-V V-O-C-CH-CH-C-O—f V (44) _/~V_ ° ? 5—>-〇-C-CH=CH-C-〇-^ V· -CeH13 c7h16- C7Hie (45) c7h1s-〇- \~Qr 0-C-CH=CH-C-0 c7h15 (46) 〇7„„-1〇_^1〇_〇_〇.〇°^〇_0.1〇7«15 (47) CsHJ.0^yl〇^ry0.l^c ? -CsH,,-121 - 201213864 [43] (43) Γ\ ° ° CeHis-〇-V VOC-CH-CH-CO-f V (44) _/~V_ ° ? 5—>-〇-C-CH= CH-C-〇-^ V· -CeH13 c7h16- C7Hie (45) c7h1s-〇- \~Qr 0-C-CH=CH-C-0 c7h15 (46) 〇7„„-1〇_^1〇 _〇_〇.〇°^〇_0.1〇7«15 (47) CsHJ.0^yl〇^ry0.l^c ? -CsH,,

(50) (丨(n)C4H8 C4H9(n) (n)C4H9(50) (丨(n)C4H8 C4H9(n) (n)C4H9

〇4Η,(η) (51) cbh-^〇-〇h〇-c*h« (S2) AH”- “-O-o^-CH-o-O-0 -C-O-CeH,, (53)〇4Η,(η) (51) cbh-^〇-〇h〇-c*h« (S2) AH"- "-O-o^-CH-o-O-0 -C-O-CeH,, (53)

CgH^-O-C-O—〇-C—^ y-C-O—Q-C-O-CtH,} 具體例（1)〜（34) 、（41) 、（42) 、（46)、（ 47) 、（52) 、（53)爲在環己烷環之1位與4位上具有兩個不對稱碳原子。但，具體例（.1) 、( 4 ) ~ ( 34 )、( 41) 、（42) 、（46) 、（47) 、（52) 、（53)由於具有對稱之中間（meso )型分子構造故非光學異構物（光學活性），僅存在幾何異構物（反式型及順式型）。具胃$ (1)之反式型（1-反式）與順式型（1-順式）示於下' ° -122- 201213864 [化 55]CgH^-OCO—〇-C—^ yCO—QCO-CtH,} Specific examples (1) to (34), (41), (42), (46), (47), (52), (53) It has two asymmetric carbon atoms at the 1-position and 4-position of the cyclohexane ring. However, specific examples (.1), (4) ~ (34), (41), (42), (46), (47), (52), (53) have symmetry intermediate (meso) molecules The structure is not an optical isomer (optically active), only geometric isomers (trans and cis) exist. Trans-type (1-trans) and cis-type (1-cis) with stomach $ (1) are shown below - ° -122- 201213864 [Chem. 55]

如前述’棒狀化合物較好具有直線之分子構造。據此，反式型優於順式型。具體例（2)及（3)除幾何異構物外亦具有光學異構物（合計四種異構物）。關於幾何異構物，同樣是反式型優於順式型。關於光學異構物，並無特別優劣，爲D、L或消旋體之任一者均可。具體例（43 )〜 (45)中’在中心之伸乙烯鍵上有反式型與順式型。基於與上述相同之理由，反式型優於順式型。亦可倂用兩種以上之溶液之紫外線吸收光譜中最大吸收波長（Xmax )比25〇nm短之波長之棒狀化合物。棒狀化合物可參照文獻記載之方法合成。至於文獻可列舉爲Mol. Cryst. Liq. C r y s t.，5 3 卷，2 2 9 頁（1 9 7 9 年）；Μ ο 1. C r y s t · Liq. Cryst·，89 卷，93 頁（1 982 年）；Mol. Cryst· Liq. Cryst.，145 卷，111 頁（1 98 7年）；Mol. Cryst. Liq. Cryst.， 170 卷，43 頁（1 9 8 9 年）；J. Am. Chem. Soc., 113 卷，1349 頁（1991 年）；J. Am. Chem. Soc·，1 18卷，5346頁（1996 年）；J. Am . Chem. Soc., 92 卷，1 5 8 2 頁（1 9 7 0 年）；J · -123- 201213864The rod compound as described above preferably has a linear molecular structure. Accordingly, the trans type is superior to the cis type. Specific examples (2) and (3) also have optical isomers (four isomers in total) in addition to geometric isomers. Regarding geometric isomers, the same trans form is preferred over the cis type. Regarding the optical isomers, there is no particular advantage, and any of D, L or racemates can be used. In the specific examples (43) to (45), there are a trans-type and a cis-type on the center-stretching ethylene bond. For the same reasons as above, the trans form is superior to the cis type. It is also possible to use a rod-like compound having a wavelength at which the maximum absorption wavelength (Xmax) is shorter than 25 Å in the ultraviolet absorption spectrum of two or more kinds of solutions. The rod-like compound can be synthesized by the method described in the literature. The literature can be cited as Mol. Cryst. Liq. C rys t., 5 3, 2 2 9 (1 9 7 9); Μ ο 1. C ryst · Liq. Cryst·, vol. 89, p. 93 ( 1 982); Mol. Cryst· Liq. Cryst., vol. 145, p. 111 (1 98 7); Mol. Cryst. Liq. Cryst., vol. 170, p. 43 (1 9 8 9); J. Am. Chem. Soc., Vol. 113, p. 1349 (1991); J. Am. Chem. Soc., Vol. 18, p. 5346 (1996); J. Am. Chem. Soc., 92, 1 5 8 2 pages (1,970); J · -123- 201213864

Org. Chem.，40 卷，420 頁（1 975 年）；Tetrahedron，48 卷 16號，3437頁（1 992年）。 (消光劑）本發明可於λ/4板中含有微粒子作爲消光劑，據此， λ/4板爲長條狀薄膜時，可使輸送或捲取變得容易。消光劑之粒徑較好爲1 〜0· 1 μιη之一次粒子或二次粒子。較好使用一次粒子之針狀比爲1.1以下之略球狀之消光劑。至於微粒子較好爲含有矽者，最好爲二氧化矽。本發明中較佳之二氧化矽微粒子可列舉爲日本Aerosil (股）製造之以 Aerosil R972、R972V、R974、R812、200、200V、 3 00、R202、0X50、TT600 (以上爲日本 AEROSIL (股）製造）之商品名銷售者，較好使用Aerosil 200V、R972、 R972V、 R974、 R202、 R812。聚合物之微粒子之例可列舉爲聚矽氧樹脂、氟樹脂及丙烯酸樹脂。較好爲聚矽氧樹脂，最好爲具有三次元網狀構造者，可列舉爲例如 TOSREARL 103 、 TOSREARL 105 、 TOSREARL 108 、 TOSREARL 120 、 TOSREARL 145 、 TOSREARL 3120及 TOSREARL 240 (東芝 SILICONE (股）製造）。二氧化矽微粒子之一次平均粒徑較好爲20nm以下，且表觀比重爲7〇g/L以上者。一次粒子之平均粒徑更好爲 5〜16 nm，又更好爲5~12nm。一次粒子之平均粒徑小較者霧濁度較低而較佳。表觀比重較好爲90〜200g/L以上，更 201213864 好爲100~200g/L以上。表觀比重大，可製作高濃度之微粒子分散液，不會產生霧濁、凝聚物而較佳。本發明中之消光劑之添加量較好每lm2之λ/4板爲0.01 ~ i.Og，更好爲 0.03~0.3g，又更好爲 0.08〜0.l6g。 (其他添加劑）除此之外，亦可添加高嶺土、滑石、矽藻土、石英、 ^ 碳酸鈣、硫酸鋇、氧化鈦、氧化鋁等無機微粒子，鈣、鎂等驗土類金屬之鹽等之熱安定劑。另外亦可添加界面活性劑、剝離促進劑、抗靜電劑、難燃劑、潤滑劑、油劑等。 (λ/4板之製造）本發明之λ/4板可藉溶液澆鑄法、熔融澆鑄法之任一種方法製造，但較好以溶液澆鑄法製造。本發明之λ/4板之製造係藉由將纖維素乙酸酯及前述 φ 可塑劑等添加劑溶解於溶劑中調製摻雜物之步驟，將摻雜物澆鑄於帶狀或滾筒狀之之金屬支撐體上之步驟，使澆鑄之摻雜物乾燥成爲薄片之步驟’自金屬支撐體剝離之步驟，延伸步驟、進而乾燥步驟’若需要則使獲得之薄膜再經熱處理之步驟，冷卻後捲取之步驟而進行。本發明之λ/4 板爲固體成分中較好含有60〜95質量％之纖維素乙酸酯者。針對調製摻雜物之步驟加以描述。摻雜物中之纖維素乙酸酯之濃度，於濃度高者在澆鑄於金屬支撐體上後可減低乾燥負荷而較佳’但纖維素乙酸醋之濃度過商時過攄時 •125- 201213864 之負荷增加，使過濾精度變差。該等並存之濃度較好爲 1 〇〜3 5質量％，更好爲1 5〜2 5質量％。本發明之摻雜物中使用之溶劑可單獨使用亦可倂用兩種以上，但混合纖維素乙酸酯酯之良溶劑與弱溶劑使用，就生產效率之觀點而言較佳，良溶劑多者，就纖維素乙酸酯酯之溶解性方面而言較佳。良溶劑與弱溶劑織混合比率之較佳範圍爲良溶劑70〜98質量％，弱溶劑2〜30質量％。所謂良溶劑、弱溶劑定亦爲可單獨溶解所使用之纖維素乙酸酯者爲良溶劑，單獨無法膨潤或溶解者爲弱溶劑。因此，根據纖維素乙酸酯之乙醯基取代度而改變良溶劑、弱溶劑，例如，使用丙酮作爲溶劑時，對纖維素酯之乙酸酯（乙醯基取代度2.4)成爲良溶劑，對纖維素之乙酸酯（乙醯基取代度2.8 )則成爲弱溶劑。本發明中使用之良溶劑並無特別限制，列舉爲二氯甲烷等有機鹵化合物或二氧雜環戊烷類、丙酮、乙酸甲酯、乙醯基乙酸甲酯等。列舉最佳者爲二氯甲烷或乙酸甲酯。又，本發明中使用之弱溶劑並無特別限制，較好使用例如甲醇、乙醇、正丁醇、環己烷、環己酮等。又，摻雜物中較好含有0.01〜2質量％之水。調製上述之摻雜物時之纖維素乙酸酯之溶解方法可使用一般方法。組合加熱與加壓時可加熱至常壓下之沸點以上。在溶劑之常壓之沸點以上且在加壓下不使溶劑沸騰之範圍之溫度下邊加熱邊攪拌溶解時，由於可防止凝膠或稱爲麵疙瘩之塊狀未溶解物之產生故較佳。且，亦可適當使 -126- 201213864 用將纖維素乙酸酯與弱溶劑混合而潤濕或膨潤後，再添加良溶劑之方法。加壓可藉由將氮氣等惰性氣體壓入之方法，或藉由加熱使溶劑之蒸氣壓上升之方法而進行。加熱較好自外部進行，例如套筒型者由於溫度控制容易故較佳。添加溶劑之加熱溫度越高，就纖維素乙酸酯之溶解性之觀點而言較佳，但加熱溫度過高時需要加大壓力使生產性變差。較佳之加熱溫度爲4 5 ~ 1 2 0 °C，更好爲6 0〜1 1 0 °C，又更好爲70°C〜1 05 °C。另外，壓力係以在設定溫度溶劑不會沸騰之方式調整。或者亦可使用冷卻溶解法，藉此可使纖維素乙酸酯溶解於乙酸甲酯等溶劑中。接著’使用濾紙等適當過濾材過濾該纖維素乙酸酯溶液。過濾材較好爲用以除去不溶物等之絕對過濾精度小者，但絕對過濾精度太小時會有容易造成過濾材阻塞之問題。因此較好爲絕對過濾精度0 · 0 0 8 m m以下之濾材，更好爲 0.001〜0.008mm之濾材，又更好爲0.003〜0.006mm之濾材》濾材之材質並無特別限制，可使用一般濾材，但以聚丙烯、鐵氟龍（註冊商標）等塑膠製之濾材，或不銹鋼等金屬製之濾材無纖維脫落者較佳。較好藉由過濾，去除、減低原料之纖維素乙酸酯中所含之雜質，尤其是亮點異物〇所謂亮點異物係使兩片偏光板以正交偏振狀態之方式配置’於其間放置纖維素酯薄膜，自一方之偏光板側照光 -127- 201213864 ，自另一方之偏光板側觀察時看見自相反側之光洩漏之點 (異物）之謂，較好直徑〇.〇lmm以上之亮點數爲200個 /cm2以下。更好爲100個/cm2以下，又更好爲50個/cm2以下，再更好爲〇〜1〇個/cm2以下。且，以0.01mm以下之亮點數少者較佳。摻雜物之過濾可藉一般方法進行，但在溶劑之常壓下之沸點以上，且在加壓下溶劑不沸騰之範圍之溫度下邊加熱邊過濾之方法，於過濾前後之濾壓差異（稱爲壓差）之上升較小故較佳。較佳之溫度爲45〜120°C，更好爲45〜70°C ，又更好爲45〜55°C。濾壓較小者較佳。濾壓較好爲1.6MPa以下，更好爲 1.2MPa以下，又更好爲l.OMPa以下。此處，針對摻雜物之澆鑄加以說明。澆鑄（cast )步驟中之金屬支撐體較好爲表面經鏡面修飾者。至於金屬支撐體較好使用不銹鋼帶或鑄造物之表面經電鍍修飾之滾筒。澆鑄之寬度可爲1〜4m。澆鑄步驟之金屬支撐體之表面溫度設定爲-50 °C至溶劑不沸騰不發泡之溫度以下。溫度高者可加速薄片之乾燥速度故較佳，但太高時使薄片發泡，會有平面性變差之情況。較佳之支撐體溫度係在〇~l〇〇°C適當決定，更好爲5〜3(TC。或者，藉由冷卻使薄片凝膠化，在含多量殘留溶劑之狀態下自滾筒剝離亦爲較佳之方法。控制金屬支撐體溫度之方法並無特別限制，有吹拂溫風或冷風之方法，或以溫水接觸金屬支撐體之內側之方法。使用溫水者可有效進行熱之傳遞，故金屬 128- 201213864 支撐體之溫度到達一定之時間越短越好。使用溫風時係考慮藉由溶劑之蒸發潛熱使薄片之溫度下降，有時使用溶劑之沸點以上之溫風，同時使用高於避免發泡之目的溫度之溫度的風。尤其較好改變自澆鑄至剝離之間之支撐體溫度及乾燥風之溫度，而進行有效率地乾燥。爲了使纖維素酯薄膜展現良好之平面性，自金屬支撐體剝離薄片時之殘留溶劑量較好爲1 〇~ 1 5 0質量％，更好爲 20~40質量％或60〜130質量％，最好爲20~30質量％或 70〜120質量％。又，較好使該金屬支撐體上之剝離位置之溫度成爲-50〜40°C，更好爲10〜40°C，最好爲15〜30°C。本發明中之殘留溶劑量係以下式定義。殘留溶劑量（質量％ ) = { ( M -N ) /N } X 1 0 0 又，Μ爲製造薄片或薄膜中或之後之任意時點採取之試料質量，Ν爲Μ在1 1 5 °C下加熱1小時後之質量。又，纖維素乙酸酯薄膜之乾燥步驟中，係自金屬支撐體剝離薄片，再經乾燥，使殘留溶劑量乾燥至0.5質量％以下。薄膜乾燥步驟一般採用以滾筒乾燥方式（使薄片交互通過上下配置之多個滾筒進行乾燥之方式）或以拉幅機方式輸送薄片同時乾燥之方式。自前述金屬支撐體剝離時，爲了利用剝離張力及隨後之輸送張力使薄片於縱向延伸，本發明中較好在自繞鑄支撐體剝離薄片時之剝離及輸送張力儘可能低之狀態下進行。具體而言，例如在50〜170N/m以下爲有效。此時，較好 -129- 201213864 施加20°C以下之冷風，使薄片急速固定化。纖維素乙酸酯薄膜可進一步藉由延伸處理調整折射率 (面內之滯相軸方向之折射率nx，與面內之滯相軸垂直之方向的折射率ny及厚度方向之折射率nz)。本發明之λ/4板以波長550nm測定之R〇( 550)爲110~170nm之範圍內，R〇 ( 550)較好爲 120〜160nm，Ro( 550)更好爲 13 0〜150nm 〇 * 本發明之λ/4板爲了在可見光之波長範圍內獲得幾乎完全之圓偏光，較好爲在可見光波長之範圍內具有約爲波長之1/4之滯相之相位差板（薄膜）。所謂「在可見光之波長範圍內約1 / 4之滯相」爲在波長400至700nm中之長波長之滯相較大，在波長450nm測定之以下述式（i )表示之滯相値R〇 ( 450 )與在波長5 5 0nm 測定之滯相値R〇 ( 550 )之差Ro ( 5 5 0 ) -Ro ( 450 )較好爲 2~34nm，更好爲4~32 nm，最好爲8〜28 nm。本發明之λ/4 板爲達成上述Ro ( 55 0 )，則控制單軸延伸之延伸倍率，或者實施不對稱之二軸延伸而調整折射率即可。延伸倍率係以使上述滯相値成爲λ/4之方式調整。二軸延伸處理可二方向同時延伸，亦可逐次延伸。因此，本發明之λ/4板之以後述式（ii)表示之薄膜厚度方向之滯相値Rt雖受延伸倍率之影響，但較好爲〇一00 nm之範圍。延伸較好利用薄膜輸送滾筒之周速差於輸送方向進行，或者於與輸送方向垂直之方向（稱爲寬度方向或TD方向 -130- 201213864 )，以夾具等夾持薄片之兩端以拉幅機方式進行，進而亦較好利用左右夾持之手段，可於左右獨立控制薄片之夾持長度（自夾持開始至夾持結束之距離）之拉幅機。又，本發明中亦較好使λ/4板或偏光子之任一種以延伸步驟於對薄膜之輸送方向爲45°之方向延伸。因此，若在由輥狀之聚合物薄膜構成之λ/4板之長度方向與面內之滞相軸之角度實質上爲45°，則僅以輥對輥 .層合在長度方向與透射軸實質上平行之輥狀偏光子及λ/4 板，可製造輥狀圓偏光板。同樣地，若由輥狀聚合物薄膜所成之偏光子之長度方向與吸收軸之角度實質上爲45 °，則僅以輥對輥層合於長度方向與透射軸實質上平行的輥狀之λ/4板，可製造輥狀圓偏光板。例如，長度方向與面內之滯相軸之角度實質上爲45° 之λ/4板，可藉由相對於長度方向實質上成45°之方向延伸處理輥狀之纖維素酯薄膜而製造。以下說明45°方向之延伸方法。爲了相對於長度方向實質成45°之方向斜向延伸纖維素乙酸酯薄膜，較好使用圖4所示之拉幅機。圖4爲顯示利用拉幅機進行斜向延伸之模式圖。本發明之延伸薄膜之製造係使用拉幅機進行。該拉幅機係在由烘箱之加熱環境下，以相對於薄膜行進方向（薄膜寬度方向之中點之移動方向）爲斜向方向，使自薄膜輥 (捲出輥）捲出之薄膜擴寬之裝置。該拉幅機具備有烘箱、使用以輸送薄膜之夾具行進之左右一對軌道、及在該軌 -131 - 201213864 道上行進之多數個夾具。以夾具夾持自薄膜輕供給於拉幅機入口部之薄膜兩端，將薄膜引導在拉幅機之出口部自夾具放開薄膜。將自夾具捲繞在卷芯上。一對軌道分別具有環狀之連續拉幅機之出口部放開對薄膜之夾持的夾具在外序回到入口部。又，拉幅機之軌道形狀係依據對欲製造之予配向角、延伸倍率等，成爲左右不對稱之形手動或自動而微調整。本發明中，可在使長條樹脂薄膜延伸，使配向角θ相對於延伸後之捲: 〜8 0°之範圍內，設定成任意角度。本發明中，具係成爲使前後夾具保持一定間隔，以一定速圖4顯示本發明之製造方法中使用之拉幅道（軌道圖型）。熱可塑性樹脂薄膜之捲出方後之薄膜之捲取方向（MD方向）D2不同，據具有較大配向角之延伸薄膜進行擴寬仍可獲得性。捲出角度θί爲延伸前之薄膜捲出方向D1與之捲取方向D2所成之角度。本發明中，如上述有40°〜80°配向角之薄膜，捲出角度係設定f ，較好爲15°<θί<50° »藉由使捲出角度0i在前使所得薄膜之寬度方向之光學特性之偏差變得 )° 自薄膜輥（捲出輥）捲出之熱可塑性樹脂機入口（符號a之位置），以左右夾具依序夾捲出並依序至烘箱內，放開之薄膜軌道，且在側行走且依延伸薄膜賦狀，且可藉之熱可塑性取方向爲40 ° 拉幅機之夾度行走。機軌道之軌向D 1與延伸此，即使對均一光學特延伸後薄膜爲了製造具 |10°<θΐ<60° 述範圍內，良好（變小膜，在拉幅持其兩端（ -132- 201213864 兩側），且隨著夾具行進而行進。在拉幅機入口（符號a 之位置）處，於對薄膜行進方向（捲出方向D1)略垂直方向上相對向之左右夾具CL、CR係在左右不對稱之軌道上行走，通過具有預熱區、延伸區、熱固定區之烘箱。此處，所謂略垂直係表示使前述面對面之夾具CL、CR彼此連結之直線與薄膜捲出方向D1所成之角度在90±Γ以內。所謂預熱區係指在烘箱入口部中，使夾持兩端之夾具之間隔維持一定間隔而行進之區間。延伸區爲使夾持兩端之夾具間隔拉開，至再度成爲一定之區間。又，冷卻區爲自延伸區後之夾具之間隔再度成爲一定之期間內，將區內之溫度設定成構成薄膜之熱可塑性樹脂的玻璃轉移溫度 Tg°C以下之區間。各區之溫度，相對於熱可塑性樹脂之玻璃轉移溫度Tg ，較好預熱區之溫度設定爲Tg + 5~Tg + 20°C，延伸區之溫度設定爲Tg〜Tg + 20°C，冷卻區之溫度設定爲Tg-30〜Tg°C。本發明之延伸步驟中之延伸倍率R ( W/Wo )較好爲 1.3 ~3.0，更好爲1.5〜2.8。延伸倍率在該範圍內時寬度方向之不均較小故較佳。拉幅延伸機之延伸區中，若於寬度方向對延伸溫度賦予差異，則寬度方向厚度不均可成爲更良好之程度。又，Wo表示延伸前之薄膜寬度，W表示延伸後之薄膜寬度。使薄片乾燥之手段並無特別限制，一般可利用熱風、紅外線、加熱輥、微波等進行，但就簡便方面而言，較好以熱風進行。 -133- 201213864 薄片乾燥步驟中之乾燥溫度較好在薄膜之玻璃轉移點-5°c以下、loot以上進行熱處理10分鐘以上60分鐘以下爲有效。較好在乾燥溫度爲100〜200°c，更好1 10〜160°C進行乾燥。經特定之熱處理後，捲取前以安裝切刀切掉端部而可獲得良好之捲取狀態故較佳。進而，較好對寬度兩端部進行滾花（knurling)加工。滾花加工可藉由壓向加熱之壓花輥而形成。壓花輥上形成有細的凹凸，藉由壓向該等而於薄膜上形成凹凸，可使端部變膨鬆。本發明之λ/4板位之寬度兩端部之滾花高度較好爲 4〜20μιη，寬度較好爲5~20mm〇又，本發明中，上述滾花加工較好設置在薄膜之製膜步驟中於乾燥結束後、捲取前。又，亦可較好使用藉由共澆鑄法成爲多層構成之λ/4 板。即使λ/4板爲多層構成之情況，亦可具有含有可塑劑之層，其爲蕊層、皮層、或其二者均可。本發明之λ/4板之表面的中心線平均粗糙度（Ra )較好爲 0.001 〜Ιμιη。本發明之λ/4板，其膜厚較好爲20~200μιη之範圍，更好爲20~100μπι’最好爲30〜80μπι。一般λ/4板之膜厚較厚者相位差容易變大，但本發明中之λ/4板由於具有偏光板保護膜之功能，有減低偏光板整體之膜厚之意，故在上述範圍內亦較佳。 -134- 201213864 透濕性爲以JIS Z 0208 ( 25°C、90%RH )爲準側定之値，較好爲200g/m2 24小時以下，更好爲l〇〜180g/m2 . 24小時以下，最好爲I60g/m2 · 24小時以下。尤其，膜厚 30〜80μιη之透濕性較好在上述範圍內。本發明之長條狀λ/4板具體而言顯示1〇〇~ l〇〇〇〇m左右之長度者，通常爲以輥狀提供之形態者。且，本發明之 λ/4板之寬度較好爲lm以上，更好爲l.4m以上，最好爲 1.4〜4m 〇 (硬質塗層）本發明之λ/4板上可設置有硬質塗層，該硬質塗層較好爲透明硬質塗層或防眩性硬質塗層之任一種。本發明中使用之硬質塗層至少設置在λ/4板之一面上。本發明中較好於前述硬質塗層上設置至少含有低折射率層之抗反射層。尤其，在汽車車用導航系統用途之情況下，爲了更提高辨識性，較好於防眩性硬質塗層上設置抗反射層。本發明中使用之硬質塗層爲防眩性時，表面上具有微細凹凸形狀，但該凹凸形狀係藉由於硬質塗層上含有微粒. 子而形成，且可藉由於硬質塗層中含有如下述之平均粒徑 0.0 1 μ m〜4 μ m之微粒子而形成。且，如後述，設於該防眩性硬質塗層上之抗反射層之最表面粗糙度，較好調整在以 JIS B 0601規定之中心線平均粗糙度（Ra)爲0·0 8μιη〜0·5μιη 之範圍。 -135- 201213864 透明硬質塗層之情況，較好爲以JIS B 060 1規定之中心線平均粗縫度（Ra)爲0.001〜Ο.ίμηα之透明硬質塗層，Org. Chem., Vol. 40, 420 (1 975); Tetrahedron, Vol. 48, No. 16, p. 3437 (1992). (Matting Agent) The present invention can contain fine particles as a matting agent in the λ/4 plate, whereby when the λ/4 plate is a long film, transportation or winding can be facilitated. The particle size of the matting agent is preferably a primary particle or a secondary particle of 1 to 0·1 μηη. It is preferred to use a slightly spherical matting agent having a needle-to-particle ratio of 1.1 or less. As for the fine particles, it is preferably a cerium oxide, preferably cerium oxide. Preferred cerium oxide microparticles in the present invention can be manufactured by Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, 0X50, TT600 (above Japanese AEROSIL) manufactured by Japan Aerosil Co., Ltd. For the trade name seller, it is preferred to use Aerosil 200V, R972, R972V, R974, R202, R812. Examples of the fine particles of the polymer include polyoxyxylene resins, fluororesins, and acrylic resins. Preferably, it is a polyoxyxylene resin, preferably a three-dimensional network structure, and is exemplified by, for example, TOSREARL 103, TOSREARL 105, TOSREARL 108, TOSREARL 120, TOSREARL 145, TOSREARL 3120, and TOSREARL 240 (Toshiba SILICONE) ). The primary particle diameter of the cerium oxide microparticles is preferably 20 nm or less, and the apparent specific gravity is 7 〇g/L or more. The average particle diameter of the primary particles is more preferably 5 to 16 nm, more preferably 5 to 12 nm. The smaller average particle size of the primary particles is better than the lower haze. The apparent specific gravity is preferably 90 to 200 g/L or more, and more preferably 201213864 is 100 to 200 g/L or more. The apparent ratio is large, and a high concentration of the fine particle dispersion can be produced without turbidity or agglomerates. The addition amount of the matting agent in the present invention is preferably 0.01 to i.Og, more preferably 0.03 to 0.3 g, and even more preferably 0.08 to 0.16 g per lm/4 of the lm2. (Other additives) In addition, inorganic fine particles such as kaolin, talc, diatomaceous earth, quartz, ^ calcium carbonate, barium sulfate, titanium oxide, and aluminum oxide, and salts of soils such as calcium and magnesium may be added. Thermal stabilizer. Further, a surfactant, a peeling accelerator, an antistatic agent, a flame retardant, a lubricant, an oil agent, or the like may be added. (Manufacture of λ/4 plate) The λ/4 plate of the present invention can be produced by any of a solution casting method and a melt casting method, but is preferably produced by a solution casting method. The λ/4 plate of the present invention is produced by dissolving a dopant such as cellulose acetate and the aforementioned φ plasticizer in a solvent to prepare a dopant, and casting the dopant into a metal such as a strip or a roll. The step of supporting the body, the step of drying the cast dopant into a sheet, the step of peeling from the metal support, the step of stretching, and the step of drying, if necessary, the step of heat-treating the obtained film, and then winding after cooling The steps are carried out. The λ/4 plate of the present invention is preferably a cellulose acetate having a solid content of 60 to 95% by mass. The steps for modulating the dopant are described. The concentration of cellulose acetate in the dopant can be reduced when the concentration is high on the metal support, but it is better when the concentration of cellulose acetate is too high. 125- 201213864 The load is increased to deteriorate the filtration accuracy. The concentration of the coexistence is preferably from 1 3 to 35 % by mass, more preferably from 1 5 to 25% by mass. The solvent used in the dopant of the present invention may be used singly or in combination of two or more, but a good solvent for mixing cellulose acetate esters with a weak solvent is preferred from the viewpoint of production efficiency, and a good solvent is preferred. It is preferred in terms of solubility of the cellulose acetate ester. The preferred range of the mixing ratio of the good solvent to the weak solvent is 70 to 98% by mass of the good solvent and 2 to 30% by mass of the weak solvent. The good solvent and weak solvent are also good solvents which can be used to dissolve the cellulose acetate used alone. Those which cannot be swollen or dissolved alone are weak solvents. Therefore, the good solvent and the weak solvent are changed depending on the degree of substitution of the cellulose acetate, and for example, when acetone is used as the solvent, the cellulose ester of the cellulose ester (the degree of substitution of acetyl group 2.4) is a good solvent. The cellulose acetate (degree of substitution of ethoxylated 2.8) becomes a weak solvent. The good solvent to be used in the present invention is not particularly limited, and examples thereof include an organic halogen compound such as methylene chloride or a dioxolane, acetone, methyl acetate, methyl acetoxyacetate or the like. The best listed are dichloromethane or methyl acetate. Further, the weak solvent used in the present invention is not particularly limited, and for example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone or the like is preferably used. Further, the dopant preferably contains 0.01 to 2% by mass of water. The method of dissolving the cellulose acetate in the preparation of the above dopant can be carried out by a general method. When combined heating and pressurization, it can be heated to above the boiling point under normal pressure. When the solvent is stirred at a temperature higher than the boiling point of the normal pressure and at a temperature which does not boil the solvent under pressure, it is preferred to prevent the formation of a gel or a mass of undissolved matter called a dough. Further, -126-201213864 may be suitably added by mixing cellulose acetate with a weak solvent to wet or swell, and then adding a good solvent. The pressurization can be carried out by a method of injecting an inert gas such as nitrogen or by a method of increasing the vapor pressure of the solvent by heating. The heating is preferably carried out from the outside, and for example, a sleeve type is preferred because of temperature control. The higher the heating temperature of the solvent to be added, the better the solubility of the cellulose acetate, but when the heating temperature is too high, it is necessary to increase the pressure to deteriorate the productivity. The heating temperature is preferably 4 5 to 1 2 0 ° C, more preferably 6 0 to 1 10 ° C, still more preferably 70 ° C to 1 05 ° C. In addition, the pressure is adjusted so that the solvent does not boil at the set temperature. Alternatively, a cooling dissolution method may be used, whereby the cellulose acetate may be dissolved in a solvent such as methyl acetate. Next, the cellulose acetate solution is filtered using a suitable filter material such as filter paper. The filter material is preferably one in which the absolute filtration accuracy for removing insoluble matter or the like is small, but if the absolute filtration accuracy is too small, the filter material may be easily clogged. Therefore, it is preferably a filter material having an absolute filtration accuracy of 0·0 0 8 mm or less, more preferably a filter material of 0.001 to 0.008 mm, and more preferably a filter medium of 0.003 to 0.006 mm. The material of the filter material is not particularly limited, and a general filter medium can be used. However, it is preferable to use a filter material made of plastic such as polypropylene or Teflon (registered trademark) or a filter material made of metal such as stainless steel without fiber loss. Preferably, the impurities contained in the cellulose acetate of the raw material are removed and reduced by filtration, especially bright spots foreign matter, so that the two polarizing plates are arranged in an orthogonal polarization state to place cellulose therebetween. Ester film, from one side of the polarizing plate side illumination -127- 201213864, when viewed from the other side of the polarizing plate side, the point of light leakage from the opposite side (foreign matter) is seen, the number of bright spots of better diameter 〇.〇lmm or more It is 200 pieces/cm2 or less. More preferably, it is 100 pieces/cm2 or less, more preferably 50 pieces/cm2 or less, and even more preferably 〇~1〇/cm2 or less. Further, it is preferable that the number of bright spots of 0.01 mm or less is small. The filtration of the dopant can be carried out by a general method, but the method of filtering under heating at a temperature above the atmospheric pressure of the solvent and under the condition that the solvent does not boil under pressure, the difference in filtration pressure before and after the filtration (called It is preferable that the rise of the pressure difference is small. The temperature is preferably 45 to 120 ° C, more preferably 45 to 70 ° C, still more preferably 45 to 55 ° C. It is preferred that the filter pressure is smaller. The filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and still more preferably 1.0 MPa or less. Here, the casting of the dopant will be described. The metal support in the casting step is preferably a mirror-finished surface. As for the metal support, it is preferred to use a stainless steel belt or a drum whose surface is electroplated. The width of the casting can be 1 to 4 m. The surface temperature of the metal support in the casting step is set to -50 ° C to a temperature below which the solvent does not boil and does not foam. It is preferable that the temperature is high to accelerate the drying speed of the sheet, but when it is too high, the sheet is foamed, and the flatness may be deteriorated. The preferred support temperature is suitably determined at 〇~l〇〇°C, more preferably 5 to 3 (TC. Alternatively, the sheet is gelled by cooling, and peeling from the roll in a state containing a large amount of residual solvent is also The method for controlling the temperature of the metal support is not particularly limited, and there is a method of blowing warm air or cold air, or a method of contacting the inner side of the metal support with warm water. The use of warm water can effectively transfer heat. Metal 128- 201213864 The temperature of the support reaches a certain time as short as possible. When using warm air, the temperature of the sheet is lowered by the latent heat of evaporation of the solvent, and sometimes the temperature above the boiling point of the solvent is used, and the temperature is higher than A wind that avoids the temperature of the target temperature of foaming. It is particularly preferable to change the temperature of the support body between the casting and the peeling and the temperature of the dry wind to perform efficient drying. In order to make the cellulose ester film exhibit good flatness, The amount of residual solvent when the sheet is peeled off from the metal support is preferably from 1 1 to 150% by mass, more preferably from 20 to 40% by mass or from 60 to 130% by mass, most preferably from 20 to 30% by mass or from 70 to 120% by weight. Further, the temperature at the peeling position on the metal support is preferably from -50 to 40 ° C, more preferably from 10 to 40 ° C, most preferably from 15 to 30 ° C. Residual solvent in the present invention The amount is defined by the following formula: Residual solvent amount (% by mass) = { ( M -N ) /N } X 1 0 0 Further, Μ is the sample quality taken at any time in or after the manufacture of a sheet or film. In the drying step of the cellulose acetate film, the sheet is peeled from the metal support and dried to reduce the residual solvent amount to 0.5% by mass or less. The drying step is generally carried out by means of a drum drying method (the method of drying the sheets by means of a plurality of rollers arranged in the upper and lower sides) or by conveying the sheets by a tenter method while drying. In order to utilize the peeling tension and the peeling of the metal support body, Subsequently, the tension is applied to extend the sheet in the longitudinal direction. In the present invention, it is preferred to carry out the peeling and the transport tension when the sheet is peeled off from the casting support as low as possible. Specifically, for example, it is 50 to 170 N/m or less. Valid. This Preferably, -129-201213864 applies a cold air of 20 ° C or less to rapidly fix the sheet. The cellulose acetate film can be further adjusted by the elongation treatment (the in-plane retardation axis direction refractive index nx, and The refractive index ny in the direction perpendicular to the axis of the slow axis in the plane and the refractive index nz in the thickness direction. The λ/4 plate of the present invention has a R 〇 (550) measured at a wavelength of 550 nm in the range of 110 to 170 nm, R 〇 ( 550) is preferably 120 to 160 nm, and Ro (550) is more preferably 13 0 to 150 nm. 〇* The λ/4 plate of the present invention is preferably at a wavelength of visible light in order to obtain almost complete circularly polarized light in the wavelength range of visible light. A phase difference plate (film) having a phase retardation of about 1/4 of the wavelength within the range. The "stagnation phase of about 1/4 in the wavelength range of visible light" is a large stagnation phase of a long wavelength at a wavelength of 400 to 700 nm, and the stagnation phase 値R 表示 expressed by the following formula (i) is measured at a wavelength of 450 nm. The difference between (450) and the stagnation 値R〇(550) measured at a wavelength of 550 nm is preferably 5 to 34 nm, more preferably 4 to 32 nm, and most preferably 8~28 nm. In order to achieve the above Ro (550), the λ/4 plate of the present invention may control the stretching ratio of the uniaxial stretching or adjust the refractive index by performing the asymmetric two-axis stretching. The stretching ratio is adjusted such that the retardation 値 is λ/4. The two-axis extension process can be extended simultaneously in two directions or sequentially. Therefore, the retardation 値Rt of the film thickness direction expressed by the later formula (ii) of the λ/4 plate of the present invention is affected by the stretching ratio, but is preferably in the range of 〇100 nm. The extension is preferably performed by using the peripheral speed difference of the film conveying roller in the conveying direction, or in a direction perpendicular to the conveying direction (referred to as the width direction or the TD direction -130-201213864), and clamping the both ends of the sheet with a jig or the like to stretch the width In the machine mode, it is also preferable to use the left and right clamping means to independently control the tenter length of the sheet (the distance from the start of the clamping to the end of the clamping). Further, in the present invention, it is also preferred that either of the λ/4 plate or the polarizer is extended in the direction in which the film is conveyed by 45° in the extending step. Therefore, if the angle between the longitudinal direction of the λ/4 plate composed of the roll-shaped polymer film and the in-plane stagnation axis is substantially 45°, only the roll-to-roller is laminated in the longitudinal direction and the transmission axis. A roller-shaped circular polarizer can be manufactured by a substantially parallel roll-shaped polarizer and a λ/4 plate. Similarly, when the length direction of the polarizer formed by the roll-shaped polymer film and the angle of the absorption axis are substantially 45°, only the roll-to-roller is laminated in a roll shape in which the longitudinal direction is substantially parallel to the transmission axis. A λ/4 plate can be used to manufacture a roll-shaped circular polarizing plate. For example, a λ/4 plate having a longitudinal direction and an in-plane retardation axis of substantially 45° can be produced by extending a roll-shaped cellulose ester film in a direction substantially 45° with respect to the longitudinal direction. The method of extending in the 45° direction will be described below. The tenter shown in Fig. 4 is preferably used in order to obliquely extend the cellulose acetate film in a direction substantially 45° with respect to the longitudinal direction. Fig. 4 is a schematic view showing the oblique extension using a tenter. The production of the stretched film of the present invention is carried out using a tenter. The tenter is widened by a film in a heating environment of the oven in a diagonal direction with respect to the traveling direction of the film (the moving direction of the dot in the film width direction), and the film rolled out from the film roll (winding roll) Device. The tenter is provided with an oven, a pair of left and right rails that travel using a jig for transporting the film, and a plurality of jigs that travel on the rails -131 - 201213864. The film is lightly fed from the film to both ends of the film at the entrance of the tenter, and the film is guided at the exit portion of the tenter to release the film from the jig. The self-clamp is wound on the core. The pair of rails each having a ring-shaped continuous tenter exiting the gripper for releasing the gripping of the film is returned to the inlet portion. Further, the track shape of the tenter is manually or automatically adjusted slightly depending on the pre-alignment angle, the stretch ratio, and the like to be manufactured. In the present invention, the elongated resin film may be stretched so that the alignment angle θ is set to an arbitrary angle within a range of 〜80° after the extension. In the present invention, the tenter track (track pattern) used in the manufacturing method of the present invention is shown at a constant speed in a predetermined interval between the front and rear jigs. The winding direction (MD direction) D2 of the film after the roll of the thermoplastic resin film is different, and the stretchable film having a larger alignment angle is still available for widening. The unwinding angle θί is an angle formed by the film unwinding direction D1 before the stretching and the winding direction D2. In the present invention, as described above, the film having an alignment angle of 40° to 80°, the winding angle is set to f, preferably 15° < θί < 50° » by making the unwinding angle 0i before making the width of the obtained film The deviation of the optical characteristics of the direction becomes) ° The entrance of the thermoplastic resin machine (the position of the symbol a) which is taken out from the film roll (winding roll), and the left and right jigs are sequentially taken out and sequentially placed in the oven, and released. The film track runs on the side and is shaped according to the stretch film, and can be walked by the 40 ° tenter in the direction of thermal plasticity. The track of the machine track extends toward D 1 and extends even if the film is uniformly stretched for a uniform optical extension of the film to a range of |10 ° < θ ΐ < 60 °, which is good (small film, holding both ends of the tenter (- 132- 201213864 both sides), and travel with the jig. At the tenter entrance (the position of the symbol a), the left and right clamps CL are slightly opposite to the film traveling direction (the winding direction D1). The CR system travels on the left and right asymmetrical tracks, and passes through an oven having a preheating zone, an extension zone, and a heat fixing zone. Here, the slightly vertical system means that the straight line connecting the face-to-face jigs CL and CR and the film are unwound. The angle formed by the direction D1 is within 90 ± 。. The preheating zone refers to the section in which the interval between the clamps at both ends of the oven is maintained at a constant interval in the entrance portion of the oven. The jigs are spaced apart and become a certain interval again. Further, the cooling zone is a period in which the interval between the jigs after the self-extension zone is again constant, and the temperature in the zone is set to the glass transition temperature of the thermoplastic resin constituting the film. The interval below Tg ° C. The temperature of each zone, relative to the glass transition temperature Tg of the thermoplastic resin, the temperature of the preferred preheating zone is set to Tg + 5~Tg + 20 ° C, and the temperature of the extension zone is set to Tg~ Tg + 20 ° C, the temperature of the cooling zone is set to Tg-30 to Tg ° C. The stretching ratio R (W/Wo ) in the extending step of the present invention is preferably from 1.3 to 3.0, more preferably from 1.5 to 2.8. When the magnification is within this range, the unevenness in the width direction is small, which is preferable. In the extension region of the tenter stretching machine, if the difference in the extension temperature is given in the width direction, the thickness in the width direction may not be more favorable. Wo represents the width of the film before stretching, and W represents the width of the film after stretching. The means for drying the sheet is not particularly limited, and generally can be carried out by hot air, infrared rays, heating rolls, microwaves, etc., but in terms of simplicity, it is preferable. It is carried out by hot air. -133- 201213864 The drying temperature in the drying step of the sheet is preferably at least 5 ° C below the glass transition point of the film, and the heat treatment for 10 minutes or more and 60 minutes or less is effective. The drying temperature is preferably 100~ 200°c, better 1 Drying is carried out at 10 to 160 ° C. After a specific heat treatment, it is preferred to use a cutter to cut the end portion before winding to obtain a good winding state. Further, it is preferable to knurl at both ends of the width ( Knurling) The knurling process can be formed by pressing the heated embossing roll. The embossing roll is formed with fine irregularities, and by forming a concavity and convexity on the film by pressing it, the end portion can be made bulky. The knurl height at both ends of the width of the λ/4 plate position of the present invention is preferably 4 to 20 μm, and the width is preferably 5 to 20 mm. Further, in the present invention, the knurling process is preferably performed on a film. In the film step, after the end of drying, before the coiling. Further, it is also preferable to use a λ/4 plate which is formed into a multilayer by a co-casting method. Even in the case where the λ/4 plate is composed of a plurality of layers, it may have a layer containing a plasticizer, which may be a core layer, a skin layer, or both. The center line average roughness (Ra) of the surface of the λ/4 plate of the present invention is preferably 0.001 to Ιμιη. The λ/4 plate of the present invention preferably has a film thickness of from 20 to 200 μm, more preferably from 20 to 100 μm, preferably from 30 to 80 μm. Generally, the film thickness of the λ/4 plate is relatively large, and the phase difference is likely to be large. However, the λ/4 plate of the present invention has the function of a polarizing plate protective film, and has the effect of reducing the film thickness of the entire polarizing plate. It is also better inside. -134- 201213864 The moisture permeability is determined by JIS Z 0208 (25°C, 90% RH), preferably 200g/m2 for 24 hours or less, more preferably l〇~180g/m2. 24 hours or less. It is preferably I60g/m2 · 24 hours or less. In particular, the moisture permeability of the film thickness of 30 to 80 μm is preferably within the above range. The long λ/4 plate of the present invention specifically shows a length of about 1 〇〇 to 1 〇〇〇〇 m, and is usually provided in the form of a roll. Further, the width of the λ/4 plate of the present invention is preferably lm or more, more preferably 1.4 m or more, and most preferably 1.4 to 4 m 硬 (hard coating). The λ/4 plate of the present invention may be provided with a hard coat. In the layer, the hard coat layer is preferably any one of a transparent hard coat layer or an anti-glare hard coat layer. The hard coat layer used in the present invention is provided on at least one side of the λ/4 plate. In the present invention, it is preferred that an antireflection layer containing at least a low refractive index layer be provided on the hard coat layer. In particular, in the case of the use of an automobile vehicle navigation system, in order to further improve the visibility, it is preferable to provide an anti-reflection layer on the anti-glare hard coat layer. When the hard coat layer used in the present invention has anti-glare properties, the surface has a fine uneven shape, but the uneven shape is formed by containing fine particles on the hard coat layer, and may be formed by the hard coat layer as described below. It is formed by fine particles having an average particle diameter of 0.01 μm to 4 μm. Further, as will be described later, the outermost surface roughness of the antireflection layer provided on the antiglare hard coat layer is preferably adjusted to a center line average roughness (Ra) of JIS B 0601 of 0·0 8 μm to 0. · Range of 5μιη. -135- 201213864 In the case of a transparent hard coat, it is preferably a transparent hard coat having a mean center-to-line (Ra) of 0.001 to ί.ίμηα as defined in JIS B 060 1

Ra較好爲0.002〜0.05μιη。中心線平均粗糙度（Ra)較好以光干涉式表面粗糙度測定器測定，例如可使用WYKO公司製造之非接觸表面微細形狀計測裝置WYKO NT-2000測定〇本發明中使用之防眩性硬質塗層中含有之粒子係使用例如無機或有機微粒子。無機微粒子可列舉爲氧化矽、氧化鈦、氧化鋁、氧化錫、氧化鋅、氧化鈣、硫酸鋇、滑石、高嶺土、硫酸鈣等〇又，作爲有機微粒子可列舉爲聚甲基丙烯酸甲酯丙烯酸酯樹脂微粒子、丙烯酸苯乙烯系樹脂微粒子、聚甲基丙烯酸甲酯樹脂微粒子、聚矽氧系樹脂微粒子、聚苯乙烯系樹脂微粒子、聚碳酸酯樹脂微粒子、苯胍系樹脂微粒子、三聚氰胺系樹脂微粒子、聚烯烴系樹脂微粒子、聚酯系樹脂微粒子、聚醯胺系樹脂微粒子、聚醯亞胺系樹脂微粒子、或聚氟化乙烯系樹脂微粒子等。本發明中以氧化矽微粒子或聚苯乙烯系樹脂微粒子最好。上述記載之無機或有機微粒子較好添加於防眩性硬質塗層之製作中使用之含有樹脂等之塗布組成物中。本發明中爲了對使用之防眩性硬質塗層賦予防眩性，無機或有機微粒子之含量，相對於防眩性硬質塗層製作用 -136- 201213864 之樹脂100質量份’較好成爲0.1質量份〜30質量份，更好成爲0.1質量份~20質量份之方式調配。爲賦予更佳防眩效果’較好相對於防眩性硬質塗層製作用之樹脂1 00質量份 ’使用1質量份〜I5質量份之平均粒徑〇.1μηι~1μιη之微粒子。又，亦較好使用兩種以上之不同平均粒徑之微粒子。又，本發明中使用之防眩性硬質塗層中亦較好含有抗靜電劑，至於抗靜電劑較好含有由Sn、Ti、In、Al、Ζη、 g Si、Mg、Ba、Mo、W及V所組成群組選出之至少一種元素作爲主成分，且體積電阻率成爲1〇7Ω· cm以下之導電性材料。前述抗靜電劑列舉爲具有上述元素之金屬氧化物、複合氧化物等。金屬氧化物之例較好爲ZnO、Ti02、Sn02、A1203、 Ιη2〇3、Si02、MgO、BaO、Mo02、V205等，或該等之複合氧化物，最好爲ZnO' ln203、Ti02及Sn〇2。含有異種原子 φ 之例爲例如相對於ZnO添加Al、In等，相對於Ti〇2添加Nb 、Ta等，或相對於Sn〇2添加Sb、Nb、鹵素元素等爲有效。該等異種原子之添加量較好在0.01〜25m〇l %之範圍，但最好在0.1〜15 mol %之範圍。又’該等具有導電性之金屬氧化物粉體之體積電阻率爲107Ω. cm以下，最好爲105Ω. cm以下。就賦予足夠之耐久性、耐衝擊性之觀點而言，透明硬質塗層或防眩性硬質塗層之膜厚較好爲0.5μηι〜ι5μιη之範圍，更好爲 1.0μιη~7μιηβ -137- 201213864 (活性能量線硬化樹脂）本發明中使用之硬質塗層較好含有藉由紫量線照射而硬化之活性能量線硬化樹脂。所謂活性能量線硬化樹脂爲利用如紫外線活性能量線照射而經過交聯反應等使之硬化之能量線硬化樹脂列舉爲以紫外線硬化性樹脂或性樹脂等爲代表者，但亦可爲利用紫外線或電活性能量線照射而硬化之樹脂。作爲紫外線硬化性樹脂可列舉爲例如紫外烯酸胺基甲酸酯系樹脂、紫外線硬化型聚酯丙脂、紫外線硬化型環氧丙烯酸酯系樹脂、紫外元醇丙烯酸酯系樹脂、或紫外線硬化型環氧樹) 紫外線硬化型丙烯酸胺基甲酸酯系樹脂一聚酯多元醇上反應異氰酸酯單體、或預聚物而上’進一步與丙烯酸2-羥基乙酯、甲基丙烯酸 (以下丙烯酸酯僅以丙烯酸酯表示作爲包含甲者）、丙烯酸2-羥基丙酯等之具有羥（羥基）系單體反應而容易獲得。例如，較好使用 151110 號中記載之 UNIDIC 1 7-8 06 (DIC (股）份與 CORONATE L (日本 Polyurethane (股）墨混合物等。紫外線硬化型聚酯丙烯酸酯系樹脂一般可末端之羥（羥基）或羧基上反應如丙烯酸2-羥外線活性能或電子束之樹脂。活性電子束硬化子束以外之線硬化型丙烯酸酯系樹線硬化型多指等。般可藉由於獲得之產物 2-羥基乙酯基丙烯酸酯之丙烯酸酯特開昭59-製造）1〇〇廷造）1份之藉由於聚酯基乙酯、丙 -138- 201213864 烯酸縮水甘油酯、丙烯酸之單體而容易地獲得（例如，特開昭59- 151112號）。紫外線硬化型環氧丙烯酸酯系樹脂可於環氧樹脂末端之羥（羥基）上反應如丙烯酸、丙烯醯氯' 丙烯酸縮水甘油酯之單體而獲得。紫外線硬化型多元醇丙烯酸酯系樹脂可列舉爲乙二醇 (甲基）丙烯酸酯、聚乙二醇二（甲基）丙烯酸酯、丙三醇三（甲基）丙烯酸酯、三羥甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、烷基改質之二季戊四醇五丙烯酸酯等。至於紫外線硬化型環氧丙烯酸酯系樹脂、紫外線硬化型環氧樹脂之例’顯示可有用之所用環氧系活性能量線反應性化合物。 (a) 雙酚A之縮水甘油醚（該化合物係藉由表氯醇與雙酚A之反應，以聚合度不同之混合物而獲得） (b) 於雙酚A等之具有兩個酚性OH之化合物上使表氯醇、環氧乙烷及/或環氧丙烷反應而成之末端上具有縮水甘油醚基之化合物 (c) 4,4’-亞甲基雙酚之縮水甘油醚 (d) 酚醛清漆樹脂或甲酚樹脂之酚甲醛樹脂之環氧化合物 (e) 具有脂環式環氧化物之化合物，例如雙（3,4_環氧基環己基甲基）草酸酯、雙（3,4-環氧基環己基甲基） -139- 201213864 己二酸酯、雙（3,4-環氧基-6-環己基甲基）己二酸酯 '雙 (3，4-環氧基環己基甲基庚二酸酯）、3,4-環氧基環己基甲基-3,4-環氧基環己烷羧酸酯、3，4-環氧基-1-甲基環己基甲基·3’，4’-環氧基環己烷羧酸酯、3,4-環氧基-1-甲基-環己基甲基-3’，4’_環氧基甲基環己烷羧酸酯、3,4_環氧基-6-甲基-環己基甲基-3’，4’-環氧基-6’-甲基-1’-環己烷羧酸酯、2-(3,4-環氧基環己基-5’，5’-螺-3”，4”-環氧基）環己烷-間-二噁烷 (f) 二元酸之二縮水甘油醚，例如二縮水甘油基草酸酯、二縮水甘油基己二酸酯、二縮水甘油基四氫苯二甲酸酯、二縮水甘油基六氫苯二甲酸酯、二縮水甘油基苯二甲酸酯 (g) 二醇之二縮水甘油醚，例如乙二醇二縮水甘油醚、二乙二醇二縮水甘油醚' 丙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚 '共聚（乙二醇-丙二醇）二縮水甘油醚、1,4-丁二醇二縮水甘油醚、 L 6 -己二醇二縮水甘油醚 (h )聚合物酸之縮水甘油酯，例如聚丙烯酸聚縮水甘油酯、聚酯二縮水甘油酯 (i )多價醇之縮水甘油醚，例如丙三醇三縮水甘油醚、三羥甲基丙烷三縮水甘油醚、季戊四醇二縮水甘油醚、季戊四醇三縮水甘油醚、季戊四醇四縮水甘油醚、葡萄糖三縮水甘油醚 (j )至於2-氟烷基-1，2-二醇之二縮水甘油醚係與前 -140- 201213864 述低折射率物質列舉之含氟樹脂之含氟環氧化合物之化合物例相同者 (k)含氟烷末端二醇縮水甘油醚可列舉爲上述低折射率物質之含氟樹脂之含氟環氧化合物等。上述環氧化合物之分子量，以平均分子量計爲2000以下，較好爲1 000以下。利用活性能量線使上述環氧化合物硬化時’爲了更提 0 高硬度，混合（h)或（i)之具有多官能基環氧基之化合物使用時爲有效。使環氧系活性能量線反應性化合物經陽離子聚合之光聚合起始劑或光增感劑爲藉由活性能量線照射可釋出陽離子聚合起始劑物質之化合物，最好，爲藉由照射釋出陽離子聚合起始能之路易斯酸之鑰鹽之一群複鹽。活性能量線反應性化合物環氧樹脂並非藉由自由基聚合，而是藉由陽離子聚合而聚合，形成交聯構造或網眼構 Φ 造。由於與自由基聚合不同不受反應系統中之氧之影響，故爲較佳之活性能量線反應性樹脂。本發明中有用之活性能量線反應性環氧樹脂係利用藉由活性能量線照射而釋出使陽離子聚合起始之物質之光聚合起始劑或光增感劑而聚合。至於光聚合起始劑，最好爲藉由光照射而釋出使陽離子聚合起始之路易斯酸之鎰鹽之複鹽之一群。該代表者爲以下述一般式（a)表示之化合物。一般式（a) ： [(R1)a(R2)b(R3)c(R4)dZ]w + [MeXv]w- -141 - 201213864 式中，陽離子爲鑰陽離子，Z爲S、Se、Te、P、As、 Sb、Bi、O、鹵素（例如，I、Br、Cl )、或 N = N (重氮），R1、R2、R3、R4爲可相同亦可不同而爲有機基。a、b、 c、d各爲0〜3之整數，a + b + c + d等於Z之價數。Me爲鹵化物錯合物之中心原子的金屬或半金屬（metalloid)，爲B、P 、As 、 Sb 、 Fe 、 Sn 、 Bi 、 A1 、 Ca 、 In 、 Ti 、 Zn 、 Sc 、 V 、 Cr、Mn、Co等。X爲鹵素，w爲鹵化錯合物離子之淨電荷，v爲鹵化錯合物離子中之鹵素原子之數。上述一般式（a)之陰離子[MeXv]w·之具體例可列舉爲四氟硼酸根（BF4_)、四氟磷酸根（PF4·)、四氟銻酸根（SbF4·)、四氟砷酸根（AsF4·)、四氯銻酸根（SbCl4· )等。Ra is preferably from 0.002 to 0.05 μm. The center line average roughness (Ra) is preferably measured by an optical interference type surface roughness measuring device. For example, the non-contact surface micro-shape measuring device WYKO NT-2000 manufactured by WYKO Co., Ltd. can be used to measure the anti-glare hardness used in the present invention. The particles contained in the coating are, for example, inorganic or organic fine particles. Examples of the inorganic fine particles include cerium oxide, titanium oxide, aluminum oxide, tin oxide, zinc oxide, calcium oxide, barium sulfate, talc, kaolin, calcium sulfate, and the like. Examples of the organic fine particles include polymethyl methacrylate acrylate. Resin fine particles, acrylic styrene resin fine particles, polymethyl methacrylate resin fine particles, polyoxynoxy resin fine particles, polystyrene resin fine particles, polycarbonate resin fine particles, benzoquinone resin fine particles, melamine resin fine particles, Polyolefin-based resin fine particles, polyester-based resin fine particles, polyamide-based resin fine particles, polyamidene-based resin fine particles, or polyfluorinated vinyl-based fine particles. In the present invention, cerium oxide microparticles or polystyrene resin microparticles are preferred. The inorganic or organic fine particles described above are preferably added to a coating composition containing a resin or the like which is used in the production of an antiglare hard coat. In the present invention, in order to impart anti-glare property to the anti-glare hard coat layer to be used, the content of the inorganic or organic fine particles is preferably 0.1 mass per 100 parts by mass of the resin of -136 to 201213864 for the preparation of the anti-glare hard coat layer. The amount is preferably 30 parts by mass, more preferably 0.1 parts by mass to 20 parts by mass. In order to impart a better anti-glare effect, it is preferable to use 1 part by mass to 1 part by mass of the fine particles having an average particle diameter of 1.1 μηι to 1 μm with respect to 100 parts by mass of the resin for producing an anti-glare hard coat layer. Further, it is also preferred to use two or more kinds of fine particles having different average particle diameters. Further, the antiglare hard coat layer used in the present invention preferably contains an antistatic agent, and the antistatic agent preferably contains Sn, Ti, In, Al, Mn, g Si, Mg, Ba, Mo, W. And at least one element selected from the group consisting of V is a main component, and the volume resistivity is a conductive material of 1 〇 7 Ω·cm or less. The antistatic agent is exemplified by a metal oxide, a composite oxide or the like having the above elements. Examples of the metal oxide are preferably ZnO, TiO 2 , SnO 2 , A 120 3 , Ι 〇 2 〇 3 , SiO 2 , MgO, BaO, Mo 2 , V 205, etc., or the composite oxides thereof, preferably ZnO ' ln 203, TiO 2 and Sn 〇 2. Examples of the hetero atom φ are added, for example, by adding Al or In to ZnO, adding Nb or Ta to Ti〇2, or adding Sb, Nb, a halogen element or the like to Sn〇2. The amount of the hetero atoms to be added is preferably in the range of 0.01 to 25 m%, but preferably in the range of 0.1 to 15 mol%. Further, the volume resistivity of the conductive metal oxide powder is 107 Ω·cm or less, preferably 105 Ω·cm or less. The film thickness of the transparent hard coat layer or the anti-glare hard coat layer is preferably in the range of 0.5 μηι to 1 5 μιη, more preferably 1.0 μιη to 7 μιη β -137 - 201213864, from the viewpoint of imparting sufficient durability and impact resistance. (Active Energy Ray-Cream Resin) The hard coat layer used in the present invention preferably contains an active energy ray-curable resin which is hardened by irradiation with a violet amount. The active energy ray-curable resin is an energy ray-curable resin which is cured by a crosslinking reaction or the like by irradiation with an ultraviolet active energy ray, and is exemplified by an ultraviolet curable resin or a resin, but may be ultraviolet ray or A resin that is hardened by irradiation with an electroactive energy ray. Examples of the ultraviolet curable resin include a UV urethane resin, an ultraviolet curable polyester acrylate, an ultraviolet curable epoxy acrylate resin, a UV acrylate resin, or an ultraviolet curing type. Epoxy resin) UV-curable urethane urethane resin-polyester polyol on the reaction of isocyanate monomer, or prepolymer, and further with 2-hydroxyethyl acrylate, methacrylic acid (the following acrylate only It is easily obtained by reacting a hydroxy(hydroxy) monomer such as acrylate with 2-hydroxypropyl acrylate or the like as a acrylate. For example, it is preferable to use UNIDIC 1 7-8 06 (DIC) and CORONATE L (Japanese Polyurethane ink mixture, etc.) in the 151110. The ultraviolet curable polyester acrylate resin generally has terminal hydroxyl groups ( A resin which reacts with a hydroxyl group or a carboxyl group, such as a 2-hydroxyl external active energy or an electron beam of a acrylate. A linear hardening type acrylate-based tree-hardening type multi-finger other than the active electron beam hardening beam, etc. -Hydroxyethyl acrylate acrylate 特开昭 59-manufactured) 1 〇〇造 ) 1 1 由于由于由于由于由于由于由于由于由于由于由于 138 138 138 138 138 138 138 138 138 138 138 138 138 138 138 138 138 138 138 138 138 138 138 It is easily obtained (for example, JP-A-59-151112). The ultraviolet curable epoxy acrylate resin can be obtained by reacting a monomer such as acrylic acid or acrylonitrile chloride 'glycidyl acrylate in a hydroxyl group (hydroxy group) at the end of the epoxy resin. Examples of the ultraviolet curable polyol acrylate resin include ethylene glycol (meth) acrylate, polyethylene glycol di(meth) acrylate, glycerin tri(meth) acrylate, and trimethylolpropane. Triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, alkyl modified dipentaerythritol pentaacrylate, and the like. Examples of the ultraviolet curable epoxy acrylate resin and the ultraviolet curable epoxy resin show an epoxy-based active energy ray-reactive compound which can be used. (a) Glycidyl ether of bisphenol A (this compound is obtained by reacting epichlorohydrin with bisphenol A in a mixture of different degrees of polymerization) (b) having two phenolic OHs in bisphenol A or the like a compound having a glycidyl ether group at the end of the compound obtained by reacting epichlorohydrin, ethylene oxide and/or propylene oxide (c) glycidyl ether of 4,4'-methylene bisphenol (d) An epoxy compound of a phenolic resin or a phenolic resin of a cresol resin (e) a compound having an alicyclic epoxide such as bis(3,4-epoxycyclohexylmethyl) oxalate, bis ( 3,4-Epoxycyclohexylmethyl)-139- 201213864 Adipate, bis(3,4-epoxy-6-cyclohexylmethyl) adipate bis (3,4-ring Oxycyclohexylmethylpimelate), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methyl Cyclohexylmethyl·3',4'-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methyl-cyclohexylmethyl-3',4'-epoxymethyl Cyclohexane carboxylate, 3,4-epoxy-6-methyl-cyclohexylmethyl-3',4'-epoxy-6'-methyl-1 '-Cyclohexane carboxylate, 2-(3,4-epoxycyclohexyl-5',5'-spiro-3",4"-epoxy)cyclohexane-m-dioxane ( f) diglycidyl ether of dibasic acid, such as diglycidyl oxalate, diglycidyl adipate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate Acid ester, diglycidyl phthalate (g) diglycidyl ether of diol, such as ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether 'propylene glycol diglycidyl ether, polyethylene Alcohol diglycidyl ether, polypropylene glycol diglycidyl ether 'copolymer (ethylene glycol-propylene glycol) diglycidyl ether, 1,4-butanediol diglycidyl ether, L 6 -hexanediol diglycidyl ether (h a glycidyl ester of a polymer acid, such as polyacrylic acid polyglycidyl ester, polyester diglycidyl ester (i) a glycidyl ether of a polyvalent alcohol, such as glycerol triglycidyl ether, trimethylolpropane tricondensate Glycerol ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, glucose triglycidyl The diglycidyl ether of the ether (j) to the 2-fluoroalkyl-1,2-diol is the same as the compound of the fluorine-containing epoxy compound of the fluorine-containing resin as recited in the above-mentioned -140-201213864 low refractive index substance. (k) The fluorine-containing alkane terminal glycol glycidyl ether may, for example, be a fluorine-containing epoxy compound of a fluorine-containing resin of the above-mentioned low refractive index material. The molecular weight of the above epoxy compound is 2,000 or less, preferably 1,000 or less, based on the average molecular weight. When the above epoxy compound is cured by the active energy ray, it is effective to use a compound having a polyfunctional epoxy group (h) or (i) in order to increase the hardness. A photopolymerization initiator or a photosensitizer for cationically polymerizing an epoxy-based active energy ray-reactive compound is a compound capable of releasing a cationic polymerization initiator material by irradiation with an active energy ray, preferably by irradiation A group of double salts of a key salt of a Lewis acid which releases a cationic polymerization initiation energy. The active energy ray-reactive compound epoxy resin is not polymerized by radical polymerization but is polymerized by cationic polymerization to form a crosslinked structure or a mesh structure. It is a preferred active energy ray-reactive resin because it is not affected by oxygen in the reaction system unlike free radical polymerization. The active energy ray-reactive epoxy resin useful in the present invention is polymerized by a photopolymerization initiator or a photosensitizer which releases a substance which initiates cationic polymerization by irradiation with an active energy ray. As the photopolymerization initiator, a group of double salts of a phosphonium salt of a Lewis acid which initiates cationic polymerization is released by light irradiation. The representative is a compound represented by the following general formula (a). General formula (a): [(R1)a(R2)b(R3)c(R4)dZ]w + [MeXv]w- -141 - 201213864 wherein cation is a key cation and Z is S, Se, Te , P, As, Sb, Bi, O, halogen (for example, I, Br, Cl), or N = N (diazo), and R1, R2, R3, and R4 may be the same or different and may be an organic group. a, b, c, and d are each an integer of 0 to 3, and a + b + c + d is equal to the valence of Z. Me is a metal or semimetal of the central atom of the halide complex, and is B, P, As, Sb, Fe, Sn, Bi, A1, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, and the like. X is a halogen, w is the net charge of the halogenated complex ion, and v is the number of halogen atoms in the halogenated complex ion. Specific examples of the anion [MeXv]w· of the above general formula (a) include tetrafluoroborate (BF4_), tetrafluorophosphate (PF4·), tetrafluoroantimonate (SbF4·), and tetrafluoroarsenate ( AsF4·), tetrachlorophosphonate (SbCl4·), and the like.

I 且，其他陰離子可列舉爲過氯酸離子（Cior)、三氟甲烷亞硫酸離子（CF3S〇r)、氟磺酸離子（FS〇3_)、甲苯磺酸離子、三硝基苯酸陰離子等。該等陰離子鹽中以使用芳香族鐵鹽作爲陽離子聚合起始劑最有效，其中較好爲特開昭50- 1 5 1 996號、特開昭50· 158680號等中所述之芳香族鹵鑰鹽，特開昭50-151997號、特開昭52-30899號、特開昭59-55420號、特開昭55-1 2 5 1 05號等中記載之VIA族芳香族鑰鹽，特開昭56-8428號、特開昭5 6- 1 49402號、特開昭57- 1 9242 9號等中記載之氧代鏑鹽，特公昭49- 1 7040號等中記載之芳香族重氮鑰鹽，美國專利第4，1 3 9,65 5號等中記載之噻喃鑰鹽（ thiopyrylium)等。又’可舉例爲鋁錯合物或光分解性矽 -142- 201213864 化合物系聚合起始劑等。上述陽離子聚合起始劑可倂用二苯甲酮、苯偶因異丙基醚、噻噸酮等光增感劑。又’具有環氧丙烯酸酯基之活性能量線反應性化合物時’可使用正丁基胺、三乙胺、三正丁基膦等光增感劑。該活性能量線反應性化合物中使用之光增感劑或光起始劑，相對於紫外線反應性化合物1 0 0質量份，以〇 · 1質量份〜15質量份於使光反應即以足夠，較好爲1質量份〜10質量 Φ 份。該增感劑較好爲在近紫外線區域至可見光區域中具有吸收極大者。本發明中有用之活性能量線硬化樹脂組成物中，聚合起始劑一般相對於活性能量線硬化性環氧樹脂（預聚物） 100質量份，較好使用0.1質量份〜15質量份，更好添加1質量份〜10質量份之範圍。且’亦可將環氧樹脂與上述胺基甲酸酯丙烯酸酯型樹脂、聚醚丙烯酸酯型樹脂等倂用，該情況下，較好併用活 Φ 性能量線自由基聚合起始劑與活性能量線陽離子聚合起始劑。又，本發明中使用之硬質塗層可使用氧雜環丁烷（ oxetane)化合物。使用之氧雜環丁環化合物爲含有氧或硫之具有三員環之氧雜環丁烷環之化合物。其中以具有含有氧之氧雜環丁烷環之化合物較佳。氧雜環丁烷環亦可經鹵素原子、鹵烷基、芳基烷基、烷氧基、烯丙基氧基、乙醯氧基取代。具體而言，列舉爲3,3-雙（氯甲基）氧雜環丁烷、3,3-雙（碘甲基）氧雜環丁烷、3，3-雙（甲氧基甲基 -143- 201213864 )氧雜環丁烷、3，3-雙（苯氧基甲基）氧雜環丁烷、基-3-氯甲基氧雜環丁烷、3，3-雙（乙醯氧基甲基）氧丁烷、3,3-雙（氟甲基）氧雜環丁烷、3,3-雙（溴甲氧雜環丁烷、3，3-二甲基氧雜環丁烷等。又，在本發可爲單體、寡聚物、聚合物之任一種。本發明中使用之硬質塗層可於上述記載之活性能硬化樹脂中混合習知之熱可塑性樹脂、熱硬化性樹脂膠等親水性化合物等之黏結劑而使用。該等樹脂較好分子中具有極性基。至於極性基列可列舉爲-COOM、、-NR2、-NR3X、-S03M ' -OSO3M ' -PO3M2 ' -ΟΡΟ 其中，Μ代表氫原子、鹼金屬或銨基，χ代表形成胺酸，R代表氫原子、烷基）等。本發明中使用之硬質塗層含有活性能量線硬化型時’活性能量線之照射方法可於支撐體上塗設防眩性塗層、抗反射層（中至高折射率層及低折射率層）等照射活性能量’但較好於塗設硬質塗層時照射活性能〇本發明中使用之活性能量線只要是以紫外線、電、γ射線等使化合物活性化之能量源則可無限制地使但較好爲紫外線、電子束’尤其就操作簡易可容易獲能量之觀點而言，以紫外線較佳。使紫外線反應性化光聚合之紫外線之光源，只要是產生紫外線之光源即可使用任何者。例如’可使用低壓水銀燈 '中壓水銀高壓水銀燈' 超高壓水銀燈、碳弧燈、金屬鹵素燈、 3-甲雜環基）明中量線或明於其 -ΟΗ iM ( 鹽之樹脂硬質之後量線子束用，得高合物可而燈、氣氣 -144- 201213864 燈等。又，亦可使用ArF準分子雷射、KrF準分子雷射、準分子燈或同步輻射光等。照射條件隨著各種燈而不同，但照射光量較好爲20mJ/cm2以上，更好爲50mJ/cm2〜10000 mJ/cm2 ’ 最好爲 5〇mJ/cm2〜2000mJ/cm2。紫外線照射可對構成硬質塗層與後述之抗反射層之複數層（中折射率層、高折射率層、低折射率層）之各層，於每設置一層即照射，亦可層合後照射。或者亦可組合該 0 等而照射。就生產性之觀點而言，以層合多層後照射紫外線較佳。又，同樣亦可使用電子束。電子束可列舉爲Cockcroft-Walton型、Van de Graaff型、共振變壓型、絕緣蕊變壓器型、直線型、Dynamitron型、高頻型等各種電子束加速器釋出之具有50〜lOOOkeV，較好100~300keV能量之電子束。本發明中使用之上述活性能量線反應性化合物經起始光聚合或光交聯反應，可僅以上述活性能量線反應性化合 φ 物起始，但由於聚合之衍生期長，聚合起始緩慢，故較好使用光增感劑或光起始劑，藉由該等可提前聚合。本發明中使用之硬質塗層含有活性能量線硬化樹脂時，於活性能量線照射中，可使用光反應性起始劑、光增感劑。具體而言，可列舉爲苯乙酮、二苯甲酮、羥基二苯甲酮、米氏（Michael )酮、α-戊基肟酯、噻噸酮等及該等之衍生物。又，在環氧丙烯酸酯系樹脂之合成中使用光反應劑時，可使用正丁基胺、三乙胺、三正丁基膦等增感劑。 -145- 201213864 塗佈乾燥後揮發去除溶劑成分之紫外線硬化性樹脂組成物中所含光反應起始劑及/或光增感劑之使用量，較好爲組成物之1質量％~1〇質量％，最好爲2.5質量％〜6質量％。又，使用紫外線硬化性樹脂作爲活性能量線硬化樹脂時，在不妨礙前述紫外線硬化性樹脂之光硬化之程度下，亦可於紫外線硬化性樹脂組成物中含有後述之紫外線吸收劑。爲提高硬質塗層之耐熱性，可以不抑制光硬化反應之方式選擇使用抗氧化劑。可列舉爲例如，受阻酚衍生物、硫代丙酸衍生物、亞磷酸衍生物等。具體而言，可列舉爲 4,4’-硫基雙（6-第三丁基-3-甲基酚）、4,4’-亞丁基雙（6-第三丁基-3-甲基酚）、1，3,5-參（3,5-二-第三丁基羥基苄基）異氰尿酸酯、2,4,6-參（3,5-二-第三丁基-4-羥基苄基）均三甲基苯、二-十八烷基-4-羥基-3,5-二第三丁基苄基磷酸酯等。紫外線硬化性樹脂可由例如ADEKA Optomer KR、BY 系列之 KR-400 ' KR-410 ' KR-5 5 0、KR-5 66、KR-567、 BY-3 20B (以上爲 ADEKA (股）製）、KOEI Hard 之八-101-KK、A-101-WS、C-3 02、C-401-N、C-501、M-101、 M-102、T-102、D-102 ' NS-1 01、FT-102Q8、MAG-1-P20 、AG-106、M-101-C(以上爲廣榮化學工業（股）製）、 SEIKA BEAM 之 PHC2210 ( S ) 、PHCX-9 ( K-3 )、 PHC2213、DP-10、DP-20、DP-30、P 1 000 ' P1100、P1200 、P1300、P1400、P1500、P 1 600 > SCR900 (以上爲大日 -146- 201213864 精化工業（股）製）、KRM 703 3、KRM703 9、KRM71 30 、KRM 7131、UVECRYL 2920 1、U V E C R Y L 2 9 2 0 2 (以上爲 DAICEL UCB (股）製）、R C - 5 0 1 5、R C - 5 0 1 6、R C-5020、RC-5 03 1、RC-5100、RC-5102、RC-5120、RC-5122 、RC-5152、RC-5171、RC-5180、RC-5181 (以上爲 DIC ( 股）製）、AUREX No. 3 40透明漆（中國塗料（股）製）、SUN LAID H-601 (三洋化成工業（股）製）、SP-1509 、SP- 1 507 (以上爲昭和高分子（股）製）、RCC-15C ( 日本 GRACE (股）製）、ARONIX M-6100 ' M-8030 ' M-8060 (以上、東亞合成（股）製），或其他市售者中適當選擇使用。含有活性能量線硬化樹脂之塗佈組成物之固體成分濃度較好爲10質量％〜95質量％，係依據塗佈方法選擇適當濃度。本發明所使用之硬質塗層及抗反射層亦較好含有界面活性劑，界面活性劑較好爲矽氧系或氟系界面活性劑。矽氧系界面活性劑較好爲由疏水基係二甲基聚矽氧烷，親水基係聚氧伸烷基構成之非離子界面活性劑。非離子界面活性劑係在水溶液中不具有解離成離子之基之界面活性劑之總稱，但爲除疏水基以外具有多價醇類之羥（羥基）作爲親水性基，或具有聚氧伸烷基鏈（聚氧伸乙基）等作爲親水基者。親水性隨著醇性羥（羥基）之數量變多，或聚氧伸烷基鏈（聚氧伸乙基鏈）變長度而變強。本發明之非離子界面活性劑之特徵爲具有二甲基聚矽 -147- 201213864 氧烷作爲疏水性基。使用由疏水性基爲二甲基聚矽氧烷，親水性基爲聚氧伸烷基構成之非離子界面活性劑時，可提高防眩性硬質塗層或低折射率層之不均或膜表面之防污性。由聚甲基矽氧烷構成之疏水基認爲係於表面配向而形成不易污染之膜表面者。係使用其他界面活性劑無法獲得之效果β 該等非離子活性劑之具體例列舉爲例如日本UN IC A ( 股）製造之矽氧界面活性劑SILWET L-77、L-720、L-7001 、L-7002、L-7064、Y-7006、FZ-2101、FZ-2104、FZ-2105 、 FZ-2110 、 FZ-2118 、 FZ-2120 、 FZ-2122 、 FZ-2123 、FZ-2130 、 FZ-2154 、 FZ-2161 、 FZ-2162 、 FZ-2163 、 FZ-2164 、 FZ-2166 、 FZ-2191等》又，歹IJ 舉爲 SUPERSILWET SS-280 1、SS-2802、SS-2803 、 SS-2804 、 SS-2805等〇另外，該等由疏水基爲二甲基聚矽氧烷，親水基爲聚氧伸烷基構成之非離子系之界面活性劑之較佳構造，較好爲二甲基聚矽氧烷構造部分與聚氧伸烷基鏈交互重複鍵結而成之直鏈狀嵌段共聚物。由於主鏈骨架之鏈長較長，且爲直鏈狀構造，故較優異。認爲其理由係藉由成爲親水基與疏水基交互重複而成之嵌段共聚物，可使一個活性劑分子於複數處以被覆其之方式吸附於二氧化矽微粒子表面之故。該等之具體例列舉爲例如日本UNICA (股）製造之矽氧界面活性劑 ABN SILWET FZ-2203、FZ-2207、FZ-2208 -148- 201213864 等。氟系界面活性劑可使用疏水基係具有全氟碳鏈之界面性劑。至於種類列舉爲氟烷基羧酸、N-全氟辛烷磺基戊二酸二鈉、3-(氟烷氧基）-1-烷基磺酸鈉、3-(ω-氟烷醯基乙胺基）-1-丙烷磺酸鈉、Ν-(3-全氟辛烷磺醯胺）丙基-Ν，Ν-二甲基-Ν_羧基亞甲基銨甜菜鹼、全氟烷基羧酸、全氟辛烷磺酸二乙醇醯胺、全氟烷基磺酸鹽、N-丙基-Ν- ( 2-羥基乙基）全氟辛烷磺醯胺、全氟烷基磺醯胺丙基三甲基銨鹽、全氟烷基-Ν-乙基磺醯基甘胺酸鹽、磷酸雙 (Ν-全氟辛基磺醯基-Ν-乙胺基乙基）等。本發明中非離子界面活性劑係較佳。I, other anions may be exemplified by perchloric acid ions (Cior), trifluoromethane sulfite ions (CF3S〇r), fluorosulfonic acid ions (FS〇3_), toluenesulfonic acid ions, trinitrobenzoic acid anions, and the like. . Among the anionic salts, the use of an aromatic iron salt as a cationic polymerization initiator is most effective, and among them, the aromatic halide described in JP-A-50-151 996, JP-A-50-158680, etc. is preferred. Key salt, VIA group aromatic key salt described in JP-A-50-151997, JP-A-52-30899, JP-A-59-55420, JP-A-55-1 2 5 1 05, etc. An oxo sulfonium salt described in JP-A-56-148, No. 5-6-49402, JP-A-57-119242, and the aromatic diazonium described in JP-A-49-17040 Key salt, thiopyrylium or the like described in U.S. Patent No. 4,1,3,65,5, et al. Further, it may be exemplified by an aluminum complex or a photodecomposable 矽-142-201213864 compound as a polymerization initiator. The above cationic polymerization initiator may be a photo sensitizer such as benzophenone, benzoin isopropyl ether or thioxanthone. Further, when an active energy ray-reactive compound having an epoxy acrylate group is used, a photo sensitizer such as n-butylamine, triethylamine or tri-n-butylphosphine can be used. The photo sensitizer or photoinitiator used in the active energy ray-reactive compound is sufficient to react light with 1 part by mass to 15 parts by mass based on 100 parts by mass of the ultraviolet ray reactive compound. It is preferably 1 part by mass to 10 parts by mass. The sensitizer preferably has a large absorption in the near ultraviolet region to the visible region. In the active energy ray-curable resin composition useful in the present invention, the polymerization initiator is generally used in an amount of from 0.1 part by mass to 15 parts by mass, more preferably from 0.1 part by mass to 15 parts by mass, based on the active energy ray-curable epoxy resin (prepolymer). It is preferable to add a range of 1 part by mass to 10 parts by mass. Moreover, the epoxy resin may be used in combination with the above urethane acrylate type resin or polyether acrylate type resin. In this case, it is preferred to use a living Φ performance amount linear radical polymerization initiator and activity. Energy line cationic polymerization initiator. Further, as the hard coat layer used in the present invention, an oxetane compound can be used. The oxetane compound used is a compound having a three-membered ring oxetane ring containing oxygen or sulfur. Among them, a compound having an oxetane ring containing oxygen is preferred. The oxetane ring may also be substituted by a halogen atom, a haloalkyl group, an arylalkyl group, an alkoxy group, an allyloxy group or an ethoxy group. Specifically, it is exemplified by 3,3-bis(chloromethyl)oxetane, 3,3-bis(iodomethyl)oxetane, 3,3-bis(methoxymethyl- 143- 201213864) oxetane, 3,3-bis(phenoxymethyl)oxetane, -3-chloromethyloxetane, 3,3-bis(ethoxime) Methyl)oxybutane, 3,3-bis(fluoromethyl)oxetane, 3,3-bis(bromomethoxane, 3,3-dimethyloxetane Further, the present invention may be any one of a monomer, an oligomer, and a polymer. The hard coat layer used in the present invention may be a conventional thermoplastic resin which is mixed with the above-exemplified active energy hardenable resin and thermosetting. It is used as a binder such as a hydrophilic compound such as a resin glue. These resins preferably have a polar group in the molecule. The polar group can be exemplified by -COOM, -NR2, -NR3X, -S03M ' -OSO3M ' -PO3M2 ' - ΟΡΟ wherein Μ represents a hydrogen atom, an alkali metal or an ammonium group, χ represents an amine acid, R represents a hydrogen atom, an alkyl group, and the like. When the hard coat layer used in the present invention contains an active energy ray-curable type, the active energy ray irradiation method can apply an anti-glare coating layer, an anti-reflection layer (medium to high refractive index layer, and a low refractive index layer) to the support. The active energy 'but preferably the irradiation active energy when the hard coating is applied. The active energy ray used in the present invention can be made without limitation by an energy source that activates the compound by ultraviolet rays, electricity, gamma rays or the like. It is preferable that the ultraviolet rays and the electron beams are preferably ultraviolet rays from the viewpoint of easy operation and easy energy acquisition. The ultraviolet light source which is reactive with ultraviolet light can be used as long as it is a light source that generates ultraviolet light. For example, 'Low-pressure mercury lamp' medium-pressure mercury high-pressure mercury lamp 'Ultra high pressure mercury lamp, carbon arc lamp, metal halide lamp, 3-methylheterocyclic group') medium-quantity line or clear- ΟΗ iM (salt of salt resin) For the beam beam, the high-light compound can be used for lamps, gas-144-201213864 lamps, etc. Also, ArF excimer laser, KrF excimer laser, excimer lamp or synchrotron radiation can be used. The amount of the irradiation light is preferably 20 mJ/cm 2 or more, more preferably 50 mJ/cm 2 to 10000 mJ/cm 2 ', preferably 5 〇 mJ/cm 2 to 2000 mJ/cm 2 . UV irradiation can constitute a hard coating. The layers of the plurality of layers (the medium refractive index layer, the high refractive index layer, and the low refractive index layer) of the antireflection layer described later may be irradiated for each layer, or may be laminated and then irradiated. Alternatively, the layer may be combined. In terms of productivity, it is preferable to irradiate ultraviolet rays by laminating a plurality of layers. Also, an electron beam can be used. The electron beam can be exemplified by Cockcroft-Walton type, Van de Graaff type, resonance transformation type, Insulation core transformer type, straight type An electron beam having an energy of 50 to 1000 volts, preferably 100 to 300 keV, which is released by various electron beam accelerators such as Dynamitron type and high frequency type. The above active energy ray-reactive compound used in the present invention is subjected to initial photopolymerization or photocrossing. The coupling reaction may start only with the above active energy ray reactive compound φ, but since the polymerization is long and the polymerization starts slowly, it is preferred to use a light sensitizer or a photoinitiator. When the hard coat layer used in the present invention contains an active energy ray-curable resin, a photoreactive starter or a photosensitizer can be used for the active energy ray irradiation. Specifically, it can be exemplified by acetophenone. , benzophenone, hydroxybenzophenone, Michael ketone, α-amyl oxime ester, thioxanthone, etc. and derivatives thereof. Further, used in the synthesis of epoxy acrylate resin In the case of a photoreactive agent, a sensitizer such as n-butylamine, triethylamine or tri-n-butylphosphine may be used. -145- 201213864 The photoreaction contained in the ultraviolet curable resin composition which volatilizes and removes the solvent component after coating and drying Starter and/or photosensitivity The amount of use is preferably from 1% by mass to 1% by mass of the composition, preferably from 2.5% by mass to 6% by mass. Further, when an ultraviolet curable resin is used as the active energy ray-curable resin, the ultraviolet ray is not hindered In the ultraviolet curable resin composition, the ultraviolet absorber may be contained in the ultraviolet curable resin composition. To improve the heat resistance of the hard coat layer, the antioxidant may be selected so as not to inhibit the photocuring reaction. For example, a hindered phenol derivative, a thiopropionic acid derivative, a phosphorous acid derivative, etc., specifically, 4,4'-thiobis(6-t-butyl-3-methylphenol) ), 4,4'-butylidene bis(6-tert-butyl-3-methylphenol), 1,3,5-gin (3,5-di-t-butylhydroxybenzyl) isocyanuric acid Acid ester, 2,4,6-paraxyl (3,5-di-t-butyl-4-hydroxybenzyl)-trimethylbenzene, di-octadecyl-4-hydroxy-3,5-di Third butyl benzyl phosphate and the like. The ultraviolet curable resin can be, for example, ADEKA Optomer KR, BY series KR-400 'KR-410 ' KR-5 50, KR-5 66, KR-567, BY-3 20B (above, ADEKA) KOEI Hard VIII-101-KK, A-101-WS, C-3 02, C-401-N, C-501, M-101, M-102, T-102, D-102 ' NS-1 01 , FT-102Q8, MAG-1-P20, AG-106, M-101-C (above is Guangrong Chemical Industry Co., Ltd.), SEIKA BEAM PHC2210 (S), PHCX-9 (K-3), PHC2213, DP-10, DP-20, DP-30, P 1 000 'P1100, P1200, P1300, P1400, P1500, P 1 600 > SCR900 (above is Dayi-146- 201213864 Refined Industry Co., Ltd.) ), KRM 703 3, KRM703 9, KRM71 30, KRM 7131, UVECRYL 2920 1, UVECRYL 2 9 2 0 2 (above is DAICEL UCB (share) system), RC - 5 0 1 5, RC - 5 0 1 6 R C-5020, RC-5 03 1, RC-5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (The above is DIC (share) system ), AUREX No. 3 40 Clear Paint (China Coatings Co., Ltd.), SUN LAID H-601 (Sanyo Chemical Industry Co., Ltd.), SP-1509, SP-1 507 (above) It is manufactured by Showa Polymer Co., Ltd., RCC-15C (made by Japan GRACE Co., Ltd.), ARONIX M-6100 ' M-8030 ' M-8060 (above, East Asia Synthetic Co., Ltd.), or other marketers. Use it appropriately. The solid content of the coating composition containing the active energy ray-curable resin is preferably from 10% by mass to 95% by mass, and an appropriate concentration is selected depending on the coating method. The hard coat layer and the antireflection layer used in the present invention preferably contain an interfacial agent, and the surfactant is preferably a ruthenium oxide type or a fluorine type surfactant. The rhodium-based surfactant is preferably a nonionic surfactant composed of a hydrophobic group dimethyl polyoxyalkylene and a hydrophilic group polyoxyalkylene group. A nonionic surfactant is a general term for a surfactant which does not have a group which dissociates into an ion in an aqueous solution, but has a hydroxyl group (hydroxyl group) having a polyvalent alcohol as a hydrophilic group other than a hydrophobic group, or has a polyoxyalkylene oxide. A base chain (polyoxyethylene) or the like is used as a hydrophilic group. The hydrophilicity becomes larger as the amount of the alcoholic hydroxyl group (hydroxyl group) increases, or the polyoxyalkylene chain (polyoxyalkylene chain) becomes longer. The nonionic surfactant of the present invention is characterized by having dimethyl polyfluorene-147-201213864 oxyalkylene as a hydrophobic group. When a nonionic surfactant composed of a hydrophobic group of dimethylpolysiloxane and a hydrophilic group of a polyoxyalkylene group is used, unevenness or film of the antiglare hard coat layer or the low refractive index layer can be improved. The antifouling properties of the surface. The hydrophobic group composed of polymethyloxane is considered to be attached to the surface to form a film surface which is less likely to be contaminated. The effect is not obtained by using other surfactants. Specific examples of the nonionic surfactants are, for example, the oxime surfactants SILWET L-77, L-720, L-7001 manufactured by UN IC A (shares), Japan. L-7002, L-7064, Y-7006, FZ-2101, FZ-2104, FZ-2105, FZ-2110, FZ-2118, FZ-2120, FZ-2122, FZ-2123, FZ-2130, FZ- 2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164, FZ-2166, FZ-2191, etc. Also, 歹IJ is SUPERSILWET SS-280 1, SS-2802, SS-2803, SS-2804 Further, SS-2805 is a preferred structure of the nonionic surfactant which is composed of a hydrophobic group of dimethyl polyoxyalkylene and a hydrophilic group of a polyoxyalkylene group, preferably a dimethyl group. A linear block copolymer in which a polyoxyalkylene moiety is repeatedly bonded to a polyoxyalkylene chain. Since the main chain skeleton has a long chain length and a linear structure, it is excellent. The reason for this is considered to be that the block copolymer which is formed by repeating the interaction between the hydrophilic group and the hydrophobic group allows one active agent to be adsorbed on the surface of the cerium oxide fine particles in a plurality of places. Specific examples of such are listed as 矽oxygen surfactants ABN SILWET FZ-2203, FZ-2207, FZ-2208-148-201213864, etc., manufactured by UNICA, Japan. As the fluorine-based surfactant, an interface agent having a perfluorocarbon chain in a hydrophobic group can be used. The types are exemplified by fluoroalkylcarboxylic acid, disodium N-perfluorooctanesulfosyl glutarate, sodium 3-(fluoroalkoxy)-1-alkylsulfonate, and 3-(ω-fluoroalkanethiol. Sodium ethylamino)-1-propane sulfonate, Ν-(3-perfluorooctane sulfonamide) propyl-hydrazine, hydrazine-dimethyl-hydrazine-carboxymethylene ammonium betaine, perfluoroalkyl Carboxylic acid, perfluorooctane sulfonate diethanolamine, perfluoroalkyl sulfonate, N-propyl-indole-(2-hydroxyethyl)perfluorooctanesulfonamide, perfluoroalkylsulfonamide Aminopropyltrimethylammonium salt, perfluoroalkyl-indole-ethylsulfonylglycine, bis(indenyl-perfluorooctylsulfonyl-fluorene-ethylaminoethyl) phosphate, and the like. The nonionic surfactant in the present invention is preferred.

該等氟系界面活性劑係以MEGAFAC、EF TOP、 SURFLON、FTERGENT、UNIDYNE、FLORIDE、ZONYL 等之商品名銷售。較佳之添加量以硬質塗層及抗反射層之塗佈液中所含固體成分爲準爲0.01〜3.0%，更好爲0.02〜1.0%。亦可倂用其他界面活性劑而使用，亦較好適宜倂用例如磺酸鹽系、硫酸酯系、磷酸酯鹽系等陰離子界面活性劑，或倂用具有聚氧乙烯鏈作爲親水基之醚型、醚酯型等非離子界面活性劑等。塗設本發明之硬質塗層時之溶劑可由例如烴類、醇類、酮類、酯類、二醇醚類、其他溶劑中適當選擇使用，或混合使用。較好使用含有5質量％以上，更好含有5質量 %〜80質量％以上之丙二醇單（C1〜C4)烷基醚或丙二醇單 -149- 201213864 (C1-C4)烷基醚酯之溶劑。硬質塗層組成物塗佈液之塗佈方法可使用凹版塗佈器、旋轉塗佈器、線塗佈器、輥塗佈器、逆轉輥塗佈器、擠出塗佈器 '空氣刮板塗佈器、噴霧塗佈器、噴墨法等習知之方法。塗佈量以濕膜厚計5μηι~30μπι爲適當，更好爲 10μιη~20μηι。塗佈速度較好爲l〇m/分鐘〜200m/分鐘》塗佈防眩性硬質塗層組成物並乾燥後，較好照射紫外線或電子束等活性能量線進行硬化處理，但前述活性能量線之照射時間較好爲0.5秒~5分鐘，就紫外線硬化性樹脂之硬化效率、作業效率等而言更好爲3秒~2分鐘。 [抗反射層] 本發明中使用之抗反射層亦可僅爲低折射率層之單層構成，但設置多層之折射率層亦較佳。於λ/4板上具有硬質塗層，且可考慮折射率、膜厚、層數、層順序等以於其表面上利用光學千涉減低反射率之方式予以層合。抗反射層係藉由組合比支撐體之折射率高之高折射率層及比支撐體之折射率低之低折射率層而構成，最好爲由三層以上之折射率層構成之抗反射層，且較好爲自支撐體側起以中折射率層（比支撐體或防眩性硬質塗層之折射率高，比高折射率層之折射率低之層）/高折射率層/低折射率層之順序層合折射率不同之三層而成者。或，亦較好使用交互層合兩層以上之高折射率層與兩層以上之低折射率層而成之四層以上之層構成之抗反射層 -150- 201213864 本發明之抗反射層之較佳層構成之例表示如下。此處之/係表示層合配置。 (λ/4板）/透明硬質塗層/低折射率層 (λ/4板）/透明硬質塗層/高折射率層/低折射率層 (λ/4板）/透明硬質塗層/中折射率層/高折射率層/低折射率層 (λ/4板）/防眩性硬質塗層/低折射率層 (λ/4板）/防眩性硬質塗層/高折射率層/低折射率層 (λ/4板）/防眩性硬質塗層/中折射率層/高折射率層/ 低折射率層爲使污損或指紋之擦拭變得容易，可在最表面之低折射率層上進一步設置防污層。防污層較好使用含氟有機化合物。只要是可利用光學干涉減低反射率者，則對於該等之層構成即無特別限制。且，上述層構成亦可適當設置中間層’較好爲例如含有導電性聚合物微粒子（例如交聯陽離子性微粒子）或金屬氧化物微粒子（例如，S η Ο 2、IΤ Ο等 )之抗靜電層等。〈低折射率層〉本發明中使用之低折射率層較好使用以下之中空球狀二氧化矽系微粒子。 -151 - 201213864 (中空球狀二氧化矽系微粒子）中空球狀微粒子爲（I)由多孔質粒子與設置於該多孔質粒子上之被覆層構成之複合粒子，或（Π)內部具有孔洞’且內容物以溶劑、氣體或多孔質物質塡充而成之孔洞粒子。又’低折射率層若含有（Ϊ)複合粒子或（Π)孔洞粒子之任一種即可，或者亦可含有二者。又’孔洞粒子爲內部具有孔洞之粒子，孔洞係由粒子壁圍繞。孔洞內係以調製時使用之溶劑、氣體或多孔質物質等之內容物予以塡充。該等中空球狀微粒子之平均粒徑宜爲5〜3 00nm，較好爲10〜200nm之範圍。使用之中空球狀微粒子係依據形成之透明被膜之厚度適當選擇，且較好成爲所形成之低折射率層等之透明被膜之膜厚之2/3〜1/10之範圍。該等中空球狀微粒子爲了形成低折射率層，較好以分散於適當介質中之狀態使用。分散介質較好爲水、醇（例如，甲醇、乙醇、異丙醇）及酮（例如，甲基乙基酮、甲基異丁基酮）、酮醇（例如二丙酮醇）。複合粒子之被覆層之厚度或孔洞粒子之粒子壁之厚度宜在1〜2 Onm，較好爲2〜15 nm之範圍。複合粒子之情況，被覆層之厚度未達lnm時，會有無法完全被覆粒子之情況，會有後述之塗佈液成分的聚合度低之矽酸單體、寡聚物等容易進入到複合粒子之內部而減少內部之多孔性，而無法充分獲得低折射率效果之情況。又，被覆層之厚度超過 2 Onm時，前述矽酸單體、寡聚物無法進入到內部，而有複合粒子之多孔性（細孔容積）降低無法充分獲得低折射率 -152- 201213864 效果之情況。又於孔洞粒子之情況，粒子壁之厚度未達 1 nm時，會有無法維持粒子形狀之情況，又厚度超過20nm 時，會有無法充分展現低折射率效果之情況。複合粒子之被覆層或孔洞粒子之粒子壁較好以二氧化矽作爲主成分。又，亦可含有二氧化矽以外之成分’具體而言，列舉爲 Al2〇3 、 B2〇3 、 Ti02 、 Zr02 、 Sn02 、 Ce02 、 P203、Sb203、M〇03、Zn02、W03等。構成複合粒子之多 I 孔質粒子列舉爲由二氧化矽組成者，由二氧化矽與二氧化矽以外之無機化合物所組成者、由CaF2、NaF、NaAlF6、 MgF等所組成者。其中最適用者爲由二氧化矽與二氧化矽以外之無機化合物之複合氧化物所組成之多孔質粒子。二氧化矽以外之無機化合物可列舉爲ai2o3、b2o3、Ti02、 Zr02、Sn02 ' Ce02、P2〇3 ' Sb203、Mo03、Zn02、W03 等之一種或兩種以上。該種多孔質粒子，於以Si〇2表示二氧化矽、以氧化物換算（MOx )表示二氧化矽以外之無機化 φ 合物時之莫耳比MOx/Si02宜爲0.000 1 ~1.0，較好爲 0.001〜0.3之範圍。多孔質粒子之莫耳比M0x/Si02未達 0.000 1者難以獲得，即使獲得細孔容積亦小，無法獲得折射率低之粒子。又，多孔質粒子之莫耳比MOx/Si〇2超過 1.0時，由於二氧化矽之比率變少，故細孔容積變大，進而有難以獲得折射率低者之情況。該種多孔質粒子之細孔容積宜爲0.1〜1.5ml/g，較好爲〇·2〜l.5ml/g之範圍。細孔容積未達〇.imi/g時，無法獲得折射率充分低之粒子，超過1 . 5ml/g時會有微粒子強度降低 -153- 201213864 ，所得被膜之強度降低之情況。又，該種多孔質粒子之細孔容積可藉水銀壓入。又，作爲孔洞粒子之內容物，列舉有粒子調製時溶劑、氣體、多孔質物質等。溶劑中亦包含調製孔時使用之粒子前驅物之未反應物、使用之觸媒等。多孔質物質，列舉爲於前述多孔質粒子中例舉表示物所構成者。該等內容物可爲由單一成分所組成者爲複數種成分之混合物。該種中空球狀微粒子之製造方法較好採用例如 7-133105號公報之段落編號[〇〇10]~[[0033]揭示之化物膠體粒子之調製方法。具體而言，複合粒子由矽、二氧化矽以外之無機化合物構成時，係由以下第3步驟製造中空球狀微粒子。第1步驟：多孔質粒子前驅物之調製於第1步驟，預先分別調製二氧化矽原料與二以外之無機化合物原料之鹼性水溶液，或調製二氧料與二氧化矽以外之無機化合物原料之混合水溶液據成爲目的之複合氧化物之複合比例，將該水溶液下緩慢添加於pH 1 0以上之鹼性水溶液中而調製多孔前驅物。至於二氧化矽原料係使用鹼金屬、銨或有機鹼鹽。鹼金屬之矽酸鹽係使用矽酸鈉（水玻璃）或砂有機鹼可列舉爲四乙基銨鹽等四級銨鹽、單乙醇月安醇胺、三乙醇胺等胺類。又，銨之矽酸鹽或有機驗法求得使用之洞粒子又作爲之化合，亦可特開平複合氧二氧化之第1〜氧化矽化矽原，且依於攪拌質粒子之矽酸酸鉀。、二乙之矽酸 -154- 201213864 鹽亦包含將氨、四級銨氫氧化物'胺化合物等添加於矽酸液中而成之鹼性溶液。另外，二氧化矽以外之無機化合物之原料係使用鹼可溶之無機化合物。具體而言可列舉爲由A1、B、Ti、Zr、 Sn、Ce、P、Sb、Mo、Zn、W等選出之元素之含氧酸（ oxoacid)、該含氧酸之鹼金屬鹽或鹼土類金屬鹽、銨鹽、四級銨鹽。更具體而言，以鋁酸鈉 '四硼酸鈉、碳酸錆銨、銻酸鉀、錫酸鉀、鋁矽酸鈉、鉬酸鈉、硝酸鉋銨、磷酸鈉爲適宜。添加該等水溶液之同時混合水溶液之pH値產生變化，但並不特別需要將該pH値控制在特定範圍內之操作。水溶液最後成爲依據無機氧化物之種類及其混合比例決定之pH 値。此時水溶液之添加速度並無特別限制。又，製造複合氧化物粒子時，亦可使用晶種粒子之分散液作爲起始原料。該晶種粒子並無特別限制，可使用si〇2、ai2o3、Ti02 或Zr02等之無機氧化物或該等之複合氧化物之微粒子，通常使用該等之溶膠。另亦可以由前述製造方法獲得之多孔質粒子前驅物分散液作爲晶種粒子分散液。使用晶種粒子分散液時，將晶種粒子分散液之pH調整至1 0以上之後，攪拌下將該晶種粒子分散液中之前述化合物之水溶液添加於上述鹼性水溶液中。該情況下，亦不需進行必要之分散液之pH控制。如此使用晶種粒子時，調製之多孔質粒子之粒徑控制容易，可獲得粒度整齊者❶ 上述H氧化;砂原料及無機化合物原料在鹼性側具有高 -155- 201213864 的溶解度。然而，在該溶解度大之pH區域中混合二者時，矽酸離子及鋁酸離子等之含氧酸之離子之溶解度下降，該等複合物析出而成長爲微粒子，或，於晶種粒子上析出而引起粒子成長。從此，微粒子之析出、成長時，並不一定需要如過去方法般進行pH之控制。第1步驟中之二氧化矽與二氧化矽以外之無機化合物之複合比例，相對於二氧化矽之無機化合物換算成氧化物 (MOx ) ，MOx/Si02之莫耳比宜爲0.05~2.0，較好爲 0.2〜2.0之範圍。在該範圍內，二氧化矽之比例變少，則多孔質粒子之細孔容積增大》然而，即使莫耳比超過2.0，多孔質粒子之細孔容積亦幾乎不增加。另一方面，莫耳比未達0.05時，細孔容積變小。調製孔洞粒子時，MOx/Si02 之莫耳比宜在〇.25~2.0之範圍內。第2步驟：自多孔質粒子去除二氧化矽以外之無機化合物第2步驟係自前述第1步驟中獲得之多孔質粒子前驅物選擇性地去除二氧化矽以外之無機化合物（矽與氧以外之元素）之至少一部份》具體的去除方法有使用無機酸或有機酸溶解去除多孔質粒子前驅物中之無機化合物，或與陽離子交換樹脂接觸進行離子交換去除。又，第1步驟中獲得之多孔質粒子前驅物爲矽與無機化合物構成元素透過氧鍵結而成之網眼構造之粒子。如此藉由自多孔質粒子前驅物去除無機化合物（矽與氧以外之元素），更以多孔質獲得細孔容積大之多孔質粒子。且’ -156- 201213864 若自多孔質粒子前驅物去除無機氧化物（素）之量增多，則可調製孔洞粒子。又，在自多孔質粒子前驅物去除二氧化合物之前，較好於第1步驟中獲得之多分散液中，添加使二氧化矽之鹼金屬鹽脫有氟取代之烷基之矽烷化合物之矽酸液或合物，而形成二氧化矽保護膜。二氧化矽爲0.5〜15nm之厚度即可。又即使形成二氧於該步驟中之保護膜爲多孔質膜且厚度較孔質粒子前驅物去除前述二氧化矽以外之藉由形成該二氧化矽保護膜，可保持自多孔質粒子前驅物去除前述二氧化矽以。又，形成後述之二氧化矽被覆層時，多不會因被覆層而阻塞，因此不會使細孔容述之二氧化矽被覆層。又，去除之無機化由於粒子未被破壞，故不一定需要形成保另外，調製孔洞粒子時，宜事先形成膜。調製孔洞粒子之際，若去除無機化合氧化矽保護膜、該二氧化矽保護膜內之溶孔質固體成分所組成之孔洞粒子之前驅物之前驅物上形成後述之被覆層時，形成之壁而形成孔洞粒子。添加用於形成上述二氧化矽保護膜之在可保持粒子形狀之範圍下較少較好。二矽與氧以外之元化矽以外之無機孔質粒子前驅物鹼而得之包含含水解性有機矽化保護膜之厚度若化矽保護膜，由薄，故仍可自多無機化合物。粒子形狀，且可外之無機化合物孔質粒子之細孔積降低地形成後合物之量少時，濩膜。該二氧化矽保護物，則獲得由二劑、未溶解之多，於該孔洞粒子被覆層成爲粒子二氧化矽源之量氧化矽源之量過 -157- 201213864 多時，二氧化矽保護膜之厚度變得太厚，故會有難以自多孔質粒子前驅物去除二氧化矽以外之無機化合物之情況。至於二氧化矽保護膜形成用中所使用之水解性有機矽化合物，可使用以一般式RnSi(OR’）4-n [R、R’ ：烷基、芳基、乙烯基、丙烯酸基等烴基，n = 0、1、2或3]表示之烷氧基矽烷。尤其，較好使用氟取代之四甲氧基矽烷、四乙氧基矽烷、四異丙氧基矽烷等四烷氧基矽烷。至於添加方法爲將作爲觸媒之少量鹼或酸添加於該等烷氧基矽烷、純水及醇之混合溶液中而成之溶液添加於前述多孔質粒子之分散液中，使烷氧基矽烷水解並使生成之矽酸聚合物沉著於無機氧化物粒子之表面上。此時，亦可將烷氧基矽烷、醇、觸媒同時添加於分散液中。至於鹼觸媒可使用氨、鹼金屬之氫氧化物、胺類。且，作爲酸觸媒可使用各種無機酸與有機酸。多孔質粒子前驅物之分散介質爲水單獨、或水對於有機溶劑之比例較高時，亦可使用矽酸液形成二氧化矽保護膜》使用矽酸液時，可於分散液中添加特定量之矽酸液，同時添加鹼使矽酸液沉著於多孔質粒子之表面上。又，亦可倂用矽酸液與上述烷氧基矽烷而製作二氧化矽保護膜。第3步驟：二氧化矽被覆層之形成第3步驟中’係藉由將含有含氟取代之烷基之矽烷化合物之水解性有機矽化合物或矽酸液等添加於第2步驟中調製之多孔質粒子分散液（孔洞粒子之情況爲孔洞粒子前驅物分散液）中’以水解性有機矽化合物或矽酸液等聚合 -158- 201213864 物被覆粒子之表面而形成二氧化矽被覆層。用於二氧化矽被覆層形成中使用之水解性有機矽化合物可使用以一般式RnSi(OR’）4-n [R、R’ ··烷基、芳基、乙烯基、丙烯酸基等烴基，n = 0、1、2或3]表示之烷氧基矽烷。尤其，較好使用四甲氧基矽烷、四乙氧基矽烷、四異丙氧基矽烷等四烷氧基矽烷。至於添加方法爲將作爲觸媒之少量鹼或酸添加於該等烷氧基矽烷、純水及醇之混合溶液中而成之溶液，添加於前述多孔質粒子（孔洞粒子之情況爲孔洞粒子前驅物）之分散液中，使烷氧基矽烷水解並使生成之矽酸聚合物沉著於多孔質粒子（孔洞粒子之情況爲孔洞粒子前驅物）之表面上。此時，亦可將烷氧基矽烷、醇、觸媒同時添加於分散液中。至於鹼觸媒可使用氨、鹼金屬之氫氧化物、胺類。另外，酸觸媒可使用各種無機酸與有機酸。多孔質粒子（孔洞粒子之情況爲孔洞粒子前驅物）之分散介質爲水單獨、或與有機溶劑之混合溶劑，於水對有機溶劑之比率較高之混合溶劑之情況，亦可使用矽酸液形成被覆層。所謂矽酸液爲使水玻璃等鹼金屬矽酸鹽之水溶液經離子交換處理而脫鹼之矽酸之低聚合物之水溶液。矽酸液係添加於多孔質粒子（孔洞粒子之情況爲孔洞粒子之前驅物）分散液中，同時添加鹼使矽酸低聚合物沉著於多孔質粒子（孔洞粒子之情況爲孔洞粒子前驅物）之表面上。又，矽酸液亦可與上述烷氧基矽烷倂用而使用於被覆層形成用。用於形成被覆層中使用之有機矽化合物或 -159- 201213864 矽酸液之添加量，只要爲可充分被覆膠體粒子表面之程度即可，以使最終獲得之二氧化矽被覆層之厚度成爲l~20nm 之量，添加於多孔質粒子（孔洞粒子之情況爲孔洞粒子前驅物）分散液中。又形成前述二氧化矽保護膜時係以使二氧化砂保護膜與二氧化砂被覆層之合計厚度成爲l~20nm之範圍之量，添加有機矽化合物或矽酸液。接著，加熱處理形成有被覆層之粒子之分散液。藉由加熱處理，於多孔質粒子之情況，可使被覆多孔質粒子之二氧化矽被覆層緻密化，獲得以二氧化矽被覆層被覆多孔質粒子而成之複合粒子之分散液。且於孔洞粒子前驅物之情況，使形成之被覆層緻密化成爲孔洞粒子壁，獲得內部經溶劑、氣體或多孔質固體成分塡充之具有孔洞之孔洞粒子之分散液。此時之加熱處理溫度，只要是可阻塞二氧化矽被覆層之微細孔之程度則無特別限制，較好爲80~300°C之範圍。加熱處理溫度未達80°C則會有無法使二氧化矽被覆層之微細孔完全阻塞而無法緻密化之情況，且會有處理時間需要長時間之情況。另外加熱處理溫度超過3 00°C而長時間處理時有成爲緻密粒子之情況，而有無法獲得低折射率效果之情況。如此獲得之無機微粒子之折射率低至未達1.42。該種無機微粒子據推測，由於保持多孔質粒子內部之多孔性，或內部具有孔洞，故爲折射率低者。本發明中使用之低折射率層之折射率較好爲1.30〜1.50，更好爲1.35〜1.44。 -160- 201213864 本發明中可使用市售之上述Si〇2微粒子。市售粒子之具體例列舉爲觸媒化成工業公司製造之P-4等。具有外殼層、內部爲多孔質或孔洞之中空球狀二氧化矽微粒子A在低折射率層塗佈液中之含量（質量）較好爲 10〜80質量％，更好爲20〜60質量％。 (四烷氧基矽烷化合物或其水解物）本發明中使用之低折射率層較好含有四烷氧基矽烷化合物或其水解物作爲其溶凝膠材料。本發明中使用之低折射率層用材料亦較好使用前述無機矽氧化物以外之具有有機基之矽氧化物。該等通常稱爲溶凝膠材料，但可使用金屬醇酸鹽、有機烷氧基金屬化合物及其水解物。尤其，以烷氧基矽烷、有機烷氧基矽烷及其水解物較佳。至於該等例，列舉爲四烷氧基矽烷（四甲氧基矽烷、四乙氧基矽烷等）、烷基三烷氧基矽烷（甲基三甲氧基矽烷、乙基三甲氧基矽烷等）、芳基三烷氧基矽烷（苯基三甲氧基矽烷等）、二烷基二烷氧基矽烷、二芳基二烷氧基矽烷等。最好爲四烷氧基矽烷及其水解物。且’亦較好使用具有各種官能基之有機烷氧基矽烷（乙烯基三烷氧基矽烷、甲基乙烯基二烷氧基矽烷、γ_縮水甘油氧基丙基三烷氧基矽烷、γ-縮水甘油氧基丙基甲基二烷氧基矽烷、β-( 3,4-環氧基二環己基）乙基三烷氧基矽烷' γ-甲基丙烯醯氧基丙基三烷氧基矽烷、γ-胺基丙基三烷氧基矽烷、γ-毓基丙基三烷氧基矽烷、γ-氯丙基三烷氧 -161 - 201213864 基矽烷等）、含有全氟烷基之矽烷化合物（例如，（十五氟-1，1，2,2-十四烷基）三乙氧基矽烷、3,3,3-三氟丙基三甲氧基矽烷等）。尤其使用含氟之矽烷化合物，就層之低折射率化及賦予撥水·撥油性方面而言係較佳。使上述四烷氧基矽烷水解時，混合前述無機微粒子就提高膜強度而言係較佳。本發明中使用之低折射率層較好含有前述矽氧化物與下述之矽烷偶合劑。具體之矽烷偶合劑之例，列舉爲甲基三甲氧基矽烷、甲基三乙氧基矽烷、甲基三甲氧基乙氧基矽烷、甲基三乙醯氧基矽烷、甲基三丁氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三乙醯氧基矽烷、乙烯基三甲氧基乙氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、苯基三乙醯氧基矽烷、γ-氯丙基三甲氧基矽烷、γ-氯丙基三乙氧基矽烷、γ-氯丙基三乙醯氧基矽烷、3，3,3-三氟丙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基三乙氧基矽烷、γ-(β -縮水甘油氧基乙氧基）丙基三甲氧基砂院、β-( 3,4-環氧基環己基）乙基三甲氧基砂院、β-(3,4_環氧基環己基）乙基三乙氧基砂院、γ_丙條醯氧基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基砂院、γ -胺基丙基三甲氧基砂院、γ -胺基丙基三乙氧基矽院、γ -巯基丙基三甲氧基矽烷、γ -锍基丙基三乙氧基矽烷、Ν-β-(胺基乙基）-γ-胺基丙基三甲氧基矽烷及β·氰基 -162- 201213864 乙基三乙氧基矽烷。又，對於矽具有2取代之烷基之矽烷偶合劑之例，列舉爲二甲基二甲氧基矽烷、苯基甲基二甲氧基矽烷、二甲基二乙氧基矽烷、苯基甲基二乙氧基矽烷、γ-縮水甘油氧基丙基甲基二乙氧基矽烷、γ-縮水甘油氧基丙基甲基二甲氧基矽烷、γ-縮水甘油氧基丙基苯基二乙氧基矽烷、γ-氯丙基甲基二乙氧基矽烷、二甲基二乙醯氧基矽烷、γ-丙烯醯氧基丙基甲基二甲氧基矽烷、γ-丙烯醯氧基丙基甲基二乙氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、 γ-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、γ-锍基丙基甲基二甲氧基矽烷、γ-毓基丙基甲基二乙氧基矽烷、γ-胺基丙基甲基二甲氧基矽烷、γ·胺基丙基甲基二乙氧基矽烷、甲基乙烯基二甲氧基矽烷及甲基乙烯基二乙氧基矽烷。該等中，較好爲分子內具有雙鍵之乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三乙醯氧基矽烷、乙烯基三甲氧基乙氧基矽烷、γ-丙烯醯氧基丙基三甲氧基矽烷及γ-甲基丙烯醯氧基丙基三甲氧基矽烷、對於矽具有2取代之烷基者之γ-丙烯醯氧基丙基甲基二甲氧基矽烷、γ-丙烯醯氧基丙基甲基二乙氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、甲基乙烯基二甲氧基矽烷及甲基乙烯基二乙氧基矽烷，最好爲γ-丙烯醯氧基丙基三甲氧基矽烷及γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ-丙烯醯氧基丙基甲基二甲氧基矽烷、γ-丙烯醯氧基丙基甲基二乙氧基矽烷、γ-甲基丙 -163- 201213864 烯醯氧基丙基甲基二甲氧基矽烷及γ-甲基丙烯醯氧基丙基甲基二乙氧基矽烷。矽烷偶合劑之具體例列舉爲信越化學工業股份有限公司製造之 ΚΒΜ-3 03、ΚΒΜ-403、ΚΒΜ-402、ΚΒΜ-403、 ΚΒΜ- 1 403、ΚΒΜ-502、ΚΒΜ- 503、ΚΒΕ-5 02 ' ΚΒΕ-503、 ΚΒΜ-603 ' ΚΒΕ-603、ΚΒΜ-903 ' ΚΒΕ-903、ΚΒΕ-9103、 ΚΒΜ-802、ΚΒΜ-803 等。亦可倂用兩種以上之偶合劑。除上述列示之矽烷偶合劑以外，亦可使用其他的矽烷偶合劑。其他矽烷偶合劑列舉爲原矽酸之烷酯（例如，原矽酸甲酯、原矽酸乙酯、原矽酸正丙酯、原矽酸異丙酯、原矽酸正丁酯、原矽酸第二丁酯、原矽酸第三丁酯）及其水解物》利用偶合劑進行表面處理之具體方法如下述。該等矽烷偶合劑較好預先以必要量之水進行水解。矽烷偶合劑經水解時，前述之矽氧化物粒子及具有有機基之矽氧化物之表面容易反應，而形成更強固之膜。又，亦可預先於塗佈液中添加經水解之矽烷偶合劑。又，低折射率層亦可含有5〜5 0質量％之量的聚合物。聚合物具有使微粒子接著，維持含有孔隙之低折射率層之構造的功能。聚合物之使用量係調整爲不充塡孔隙而可維持低折射率層之強度。聚合物之量較好爲低折射率層之總量之10~3 0質量％。爲了以聚合物接著微粒子，較好（1 ) 使聚合物結合於微粒子之表面處理劑上，或（2 )以微粒子爲蕊，於其周圍形成聚合物殼，或（3 )使用聚合物作 -164- 201213864 爲微粒子間之黏合劑。（1 )之結合於表面處理劑之聚合物較好爲（2)之殼聚合物或（3)之黏合劑聚合物。（2 )之聚合物較好爲在調製低折射率層之塗佈液之前，藉由在微粒子周圍之聚合反應而形成。（3)之聚合物較好爲於低折射率層之塗佈液中添加單體，在塗佈低折射率層之同時或塗佈之後，藉由聚合反應而形成。較好組合上述（ 1)〜（3)中之兩者或全部而進行，最好爲以（1)與（3 )之組合，或（1 )〜（3 )全部之組合進行。針對（1 )之表面處理、（2 )殼及（3 )黏合劑依序加以說明。 (1 )表面處理微粒子（尤其是無機微粒子）較好實施表面處理，以改善與聚合物之親合性。表面處理可分類成如電漿放電處理或電暈放電處理之物理表面處理，及使用偶合劑之化學表面處理。較好僅實施化學表面處理，或組合實施物理表面處理與化學表面處理。至於偶合劑較好使用有機烷氧基矽烷化合物（例如，鈦偶合劑、矽烷偶合劑）。微粒子係由Si02組成時，以前述矽烷偶合劑實施表面處理特別有效〇利用偶合劑之表面處理，係藉由將偶合劑添加於微粒子之分散物中，將分散物在室溫至60°C之溫度下，放置數小時至1 0天而實施。爲了促進表面處理反應，亦可於分散物中添加無機酸（例如，硫酸、鹽酸、硝酸、鉻酸、次亞氯酸、硼酸、原矽酸、磷酸、碳酸）、有機酸（例如，乙酸、聚丙烯酸、苯磺酸、酚、聚穀胺酸）、或該等之鹽（ -165- 201213864 例如，金屬鹽、銨鹽）。 (2 )殼形成殼之聚合物較好爲具有飽和烴作爲主。較好於主鏈或側鏈中含有氟原子之聚合物，鏈中含有氟原子之聚合物。較好爲聚丙烯酸酯烯酸酯，最好爲氟取代之醇與聚丙烯酸或聚甲酯。殻聚合物之折射率隨著聚合物中之氟原子而下降。爲了降低低折射率層之折射率，殼聚有35~80質量％之氟原子，更好含有45〜75質量。含有氟原子之聚合物較好藉由含有氟原子之和單體之聚合反應而合成。含有氟原子之乙烯體之例，列舉爲氟烯烴（例如，氟乙烯、偏氟氟乙烯、六氟丙烯、全氟-2,2-二甲基-1，3-二氧、氟化乙烯基醚及·氟取代之醇與丙烯酸或甲基形成殼之聚合物亦可爲由含有氟原子之重含氟原子之重複單位所組成之聚合物。不含氟單位較好藉由不含氟原子之乙烯性不飽和單體而獲得。不含氟原子之乙烯性不飽和單體之例烴（例如，乙烯、丙烯、異戊間二烯、氯化乙乙烯）、丙烯酸酯（例如，丙烯酸甲酯、丙烯烯酸2-乙基己酯）' 甲基丙烯酸酯（例如，甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、乙二烯酸酯）、苯乙烯及其衍生物（例如，苯乙烯鏈之聚合物更好爲於側或聚甲基丙基丙烯酸之之含量增加合物較好含 %之氟原子乙烯性不飽性不飽和單化乙烯、四雜環戊烯）丙烯酸之酯複單位與不原子之重複之聚合反應，列舉爲烯烯、偏氯化酸乙酯、丙基丙烯酸甲醇二甲基丙、二乙烯基 -166- 201213864 苯、乙烯基甲苯、α-甲基苯乙烯）、乙烯基醚（例如，甲基乙烯基醚）、乙烯基酯（例如，乙酸乙烯酯、丙酸乙嫌酯、桂皮酸乙烯酯）、丙烯醯胺（例如，N-第三丁基丙烯醯胺、N-環己基丙烯醯胺）、甲基丙烯醯胺及丙烯腈。倂用後述之（3)之黏合劑聚合物時，亦可於殼聚合物中導入交聯性官能基，藉由使殼聚合物與黏合劑聚合物交聯而化學性鍵結。殼聚合物亦可具有結晶性。殼聚合物之玻璃轉移溫度（Tg )比形成低折射率層時之溫度高時，容易維持低折射率層內之微孔隙。但，Tg比形成低折射率層時之溫度高時，會有微粒子不熔著，無法使低折射率層形成爲連續層（結果使強度降低）之情況。該情況下，較好倂用後述之（3)之黏合劑聚合物，宜藉由黏合劑聚合物使低折射率層形成爲連續層。在微粒子周圍形成聚合物殼，獲得蕊殼微粒子。蕊殼微粒子中由無機微粒子所成之蕊較好含有5〜90體積％，更好含有15~80體積％。亦可倂用兩種以上之蕊殼微粒子。且，亦可倂用沒有殼之無機微粒子與蕊殼粒子。 (3 )黏合劑黏合劑聚合物較好爲具有飽和烴或聚醚作爲主鏈之聚合物，更好爲具有飽和烴作爲主鏈之聚合物。黏合劑聚合物較好經交聯。具有飽和烴作爲主鏈之聚合物較好利用乙烯性不飽和單體之聚合反應而獲得。爲獲得經交聯之黏合劑聚合物，較好使用具有兩個以上之乙烯性不飽和基之單體。具有兩個以上之乙烯性不飽和基之單體之例，列舉爲 -167- 201213864 多價醇與（甲基）丙烯酸之酯（例如，乙二醇丙烯酸酯、1,4-環己烷二丙烯酸酯、季戊四醇丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、三三（甲基）丙烯酸酯、三羥甲基乙烷三（甲基、二季戊四醇四（甲基）丙烯酸酯、二季戊四 )丙烯酸酯、季戊四醇六（甲基）丙烯酸酯、烷四甲基丙烯酸酯、聚胺基甲酸酯聚丙烯酸酯烯酸酯）、乙烯基苯及其衍生物（例如，1，4-' 4-乙烯基苯甲酸-2-丙烯醯基乙基酯、i，4-二酮）、乙烯基颯（例如，二乙烯基颯）、丙烯，亞甲基雙丙烯醯胺）及甲基丙烯醯胺。具有鏈之聚合物較好利用多官能基環氧化合物之開而合成。替代具有兩個以上之乙烯性不飽和基此之外，亦可藉由交聯性基之反應，將交聯構合劑聚合物中。交聯性官能基之例，列舉爲異環氧基、吖啶基、噁唑啉基、醛基、羰基、聯、羥甲基及活性亞甲基。乙烯基磺酸、酸酐、酯衍生物、三聚氰胺、醚化羥甲基、酯及胺基利用作爲導入交聯構造之單體。亦可使用如嵌基之於分解反應結果顯示交聯性之官能基。另並不限於上述化合物，亦可爲顯示使上述官能之反應性者。黏合劑聚合物之聚合反應及交聯之聚合起始劑係使用熱聚合起始劑或光聚合起好爲光聚合起始劑。光聚合起始劑之例爲苯乙二（甲基）四（甲基）羥甲基丙烷 )丙烯酸酯醇五（甲基 1,2,3 -環己、聚酯聚丙二乙烯基苯乙烯基環己醯胺（例如聚醚作爲主環聚合反應之單體或除造導入於黏氰酸酯基、胺基、羧基氰基丙嫌酸甲酸酯亦可段異氰酸酯外，交聯基基分解結果反應中使用始劑，但更酮類、苯偶 -168- 201213864 因類、二苯甲酮類、氧化膦類、縮酮類、蒽醌類、偶氮化合物、過氧化物類、2,3-二烷基二、二硫醚化合物類、氟胺化合物類或芳香族锍類之例列舉爲2,2-二乙氧基苯乙酮、對-二甲基羥基二甲基苯基酮、1_羥基環己基苯基酮、2- 基-2-嗎啉基苯丙酮及2 -苄基-2-二甲胺基-1-( 基）-丁酮。苯偶因類之例列舉爲苯偶因甲基 ^ 乙基醚及苯偶因丙基醚。二苯甲酮類之例列舉、2，4-二氯二苯甲酮、4,4-二氯二苯甲酮及對- 。氧化膦類之例列舉爲2,4,6-三甲基苯甲醯基〇黏合劑聚合物較好將單體添加於低折射率中，在塗佈低折射率層之同時或塗佈之後藉由視需要進一步交聯反應）而形成。低折射率層亦可添加少量之聚合物（例如，聚乙烯醇、聚 φ 甲基丙烯酸甲酯、聚丙烯酸甲酯、二乙醯纖維纖維素、硝基纖維素、聚酯、醇酸樹脂）。又，本發明中使用之低折射率層亦可爲由離輻射線交聯之含氟樹脂（以下亦稱爲「交聯脂」）之交聯而成之低折射率層。至於交聯前之含氟樹脂可列舉較佳者爲由單體與賦予交聯性基用之單體形成之含氟共聚氟乙烯基單體之具體例列舉爲例如氟烯烴類（烯、偏氟化乙烯、四氟乙烯、六氟乙烯、六類、噻噸酮酮化合物類類。苯乙酮苯乙酮、1-甲基-4-甲硫 4-嗎啉基苯醚、苯偶因爲二苯甲酮氯二苯甲酮苯基氧化膦層之塗佈液聚合反應（之塗佈液中氧乙烯、聚素、三乙醯藉由熱或電前之含氟樹含氟乙烯基物。上述含例如，氟乙氟丙烯、全 -169- 201213864 氟-2,2-二甲基-1，3-二氧雜環戊烯等）、（甲基）丙烯酸之部分或全部氟化烷酯衍生物類（例如，Biscote 6FM (大阪有機化學製造）或M-2020 ( DAIKIN製造）等）、完全或部分氟化乙烯基醚類等。賦予交聯性基用之單體列舉爲縮水甘油基甲基丙烯酸酯、或乙烯基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、乙烯基縮水甘油醚等分子內預先具有交聯性官能基之乙烯基單體，以及具有羧基或羥基、胺基、磺酸基等之乙烯基單體（例如，（甲基）丙烯酸、羥甲基（甲基）丙烯酸酯、（甲基）丙烯酸羥基烷基酯、丙烯酸烯丙酯、羥基烷基乙烯基醚、羥基烷基烯丙基醚等）。後者藉由於共聚合後添加具有至少一個以上與聚合物中之官能基反應之基之反應性基之化合物，而可導入交聯構造，係記載於特開平1 0-253 8 8號、特開平10-147739號中。交聯性基之例列舉爲丙烯醯基、甲基丙烯醯基、異氰酸酯基’、環氧基、吖啶基、噁唑啉基、醛、羰基、聯胺、羧基、羥甲基及活性亞甲基等。含氟共聚物藉由以加熱而反應之交聯基、或乙烯性不飽和基與熱自由基產生劑’或環氧基與熱酸產生劑等之組合，於藉由加熱交聯時’爲熱硬化型，藉由使乙烯性不飽和基與光自由基產生劑，或環氧基與光酸產生劑等之組合，於藉由光（較好爲紫外線 '電子束等）之照射而交聯時，爲電離輻射線硬化型。且除上述單體以外，倂用含氟乙烯基單體及賦予交聯性用之單體以外之單體形成之含氟共聚物亦可使用作爲交 -170- 201213864 聯前之含氟樹脂。可倂用之單體並無特別限制，可列舉爲例如烯烴類（乙烯、丙烯、異戊間二烯、氯化乙烯、偏氯化乙烯等）、丙烯酸酯類（丙烯酸甲酯、丙烯酸乙酯、丙烯酸2-乙基己酯）、甲基丙烯酸酯類（甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、乙二醇二甲基丙烯酸酯等）、苯乙烯衍生物（苯乙烯、二乙烯基苯、乙烯基甲苯、α-甲基苯乙烯等）、乙烯基醚類（甲基乙烯基醚等） | 、乙烯基酯類（乙酸乙烯酯、丙酸乙烯酯、桂皮酸乙烯酯等）、丙烯醯胺類（N-第三丁基丙烯醯胺、N-環己基丙烯醯胺等）、甲基丙烯醯胺類、丙烯腈衍生物等。另外，含氟聚合物中’爲了賦予潤滑性、防污性，亦較好導入聚有機矽氧烷骨架、或全氟聚醚骨架。該等係藉由例如於末端具有丙烯酸基、甲基丙烯酸酯、乙烯基醚基、苯乙烯基等之聚有機矽氧烷或全氟聚醚與上述之單體聚合、由末端具有自由基產生基之聚有機矽氧烷或全氟聚醚之上述單體之 φ 聚合、具有官能基之聚有機矽氧烷或全氟聚醚與含氟共聚物之反應等而獲得。用以形成交聯前之含氟共聚物之上述各單體之使用比例’含氟乙烯基單體較好爲20-70莫耳％，更好爲40〜70莫耳％ ’用以賦予交聯性基之單體較好爲1〜2〇莫耳％，更好爲5〜20莫耳％ ’所倂用之其他單體較好爲10〜70莫耳％，更好爲1 0〜5 0莫耳％之比例。含氟共聚物可藉由使該等單體在自由基聚合起始劑存在下’利用溶液聚合、塊狀聚合、乳化聚合、懸浮聚合法 -171 - 201213864 等手段聚合而獲得。交聯前之含氟樹脂可使用市售品。市售之交聯前之含氟樹脂列舉爲CYTOP (旭硝子製造）、TEFLON (註冊商標）AF ( DUPON製造）、聚偏氟化乙烯、LUMIFLON (旭硝子製造）、〇PSTAR(JSR製造）等。以經交聯之含氟樹脂作爲構成成分之低折射率層之動摩擦係數較好爲0.03 ~0.15之範圍，對水之接觸角較好爲 90〜120度之範圍。本發明中使用之低折射率層可藉由浸漬塗佈法、空氣刮刀塗佈法、簾流式塗佈法、輥塗佈法、線塗佈法、凹版塗佈法或擠出塗佈法（美國專利268 1 294號），利用塗佈而形成。又，亦可同時塗佈兩層以上之層。同時塗佈之方法記載於美國專利第2,761，791號、美國專利第2,941，898 號、美國專利第3,508,947號、美國專利第3,526,52 8號及原崎勇次著，塗佈工學，2H頁，朝倉書店（19 73 )中。本發明中使用之低折射率層之膜厚較好爲50~200nm，更好爲60~ 1 5 Onm。〈高折射率層及中折射率層〉本發明中，爲降低反射率，較好在硬質塗層與低折射率層之間設置高折射率層。或更好在硬塗層與高折射率層之間設置中折射率層。高折射率層之折射率較好爲1 ·55~ 2.30，更好爲1.57〜2.20。中折射率層之折射率係以成爲支撐體之折射率與高折射率層之折射率之中間之値之方式調 -172- 201213864 整。中折射率層之折射率較好爲1 . 5 5〜1 . 8 0。高折射率層及中折射率層之厚度較好爲5nm〜Ιμιη，更好爲10ηιη~0.2μιη ’ 最好爲30nm~l OOnm。高折射率層及中折射率層之濁度較好爲5%以下，更好爲3%以下，最好爲1%以下。高折射率層及中折射率層之強度以1 kg荷重之鉛筆硬度計較好爲Η以上，更好爲2Η以上，最好爲3Η以上。本發明中所用之高折射率層較好爲塗佈含有以下述一 | 般式（9)表示之有機鈦化合物之單體、寡聚物或該等之水解物之塗佈液並經乾燥而形成之折射率1 . 5 5 ~ 2.5之層。 —般式（9) :1^(01^)4 式中’ R1爲碳數1〜8之脂肪族烴基即可，但較好爲碳數1〜4之脂肪族烴基。又，有機鈦化合物之單體、寡聚物或該等之水解物爲烷氧基經受水解，反應成如_Ti_〇_Ti_而作出交聯構造，形成硬化層。本發明中使用之有機鈦化合物之單體、寡聚物列舉較 φ 佳之例爲叫0(^ 3)4、Ti(〇C2H5)4、Ti(0_n_C3H7)4、Ti(0_i- C3H7)4、Ti(0-n-C4H9)4、Ti(〇-n_c3H7)4 之 2〜10 聚物，Ti(0-i-C3H7)4之2〜10聚物、Ti(〇-n-C4H9)4之2〜1〇聚物等。該等可單獨使用或組合兩種以上使用。其中，以Ti(0_n_C3H7)4 、Ti(0-i-C3H7)4、Ti(0-n-C4H9)4、Ti(〇_n_C3H7)4 之 2~1〇聚物、Ti(0-n-C4H9)4之2〜10聚物最佳。本發明中使用之高折射率層用塗佈液較好將上述有機鈦化合物添加於依序添加水與後述之有機溶劑而成之溶液中。於水之後添加時’水解/聚合無法均句進行，會產生 -173- 201213864 白濁，且膜強度降低。添加水與有機溶劑後，爲充分混^ 較好攪拌使之混合溶解。另外’作爲其他方法’以預先使有機鈦化合物與有機溶劑混合，將該混合溶液添加於上述水與混合溶劑之混合攪拌之溶液中亦爲較佳之樣態。又’水之量相對於有機鈦化合物1莫耳，較好爲〇25〜3 莫耳之範圍。未達0.25莫耳時，由於水解、聚合之進行不充分導致膜強度降低。超過3莫耳時水解、聚合過度進行 ’產生Ti〇2之粗大粒子而白濁故較不佳。據此，有必要將水量調整在上述範圍。且’水之含有率相對於塗佈液之總量較好未達1 0質量 %。使水之含有率相對於塗佈液之總量在1 〇質量％以上時 ’塗佈液之經時安定差而產生白濁故較不佳。本發明中使用之有機溶劑較好爲水混合性之有機溶劑。水混合性有機溶劑列舉爲例如醇類（例如，甲醇、乙醇、丙醇、異丙醇、丁醇、異丁醇、第二丁醇、第三丁醇、戊醇、己醇、環己醇、苄基醇等）、多價醇類（例如’乙二醇、二乙二醇、三乙二醇、聚乙二醇、丙二醇、二丙二醇、聚丙二醇、丁二醇、己二醇、戊二醇、丙三醇、己烷三醇、硫代二甘醇等）、多價醇醚類（例如，乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丁基醚、二乙二醇單甲基醚、二乙二醇單甲基醚、二乙二醇單丁基醚、丙二醇單甲基醚、丙二醇單丁基醚、乙二醇單甲基醚乙酸醋、三乙二醇單甲基醚、三乙二醇單乙基醚、乙二醇單苯基醚、丙 -174- 201213864 二醇單苯基醚等）、胺類（例如，乙醇胺、二乙醇胺、三乙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺、嗎啉、N-乙基嗎啉、乙二胺、二乙二胺、三伸乙基四胺、四伸乙基五胺、聚伸乙基亞胺、五甲基二伸乙基三胺、四甲基丙二胺等）、醯胺類（例如，甲醯胺、Ν,Ν-二甲基甲醯胺、ν,ν-二甲基乙醯胺等）、雜環類（例如，2 -吡咯烷酮、Ν_甲基-2 -吡咯烷酮、環己基吡咯烷酮、2 -噁唑酮、1，3 -二甲基-$ 2-咪唑啶酮等）、亞颯類（例如，二甲基亞颯等）、颯類 (例如，環丁碼等）、脲、乙腈、丙酮等，但最好爲醇類、多價醇類、多價醇醚類。該等有機溶劑之使用量係如前述，較好以水之含有率相對於塗佈液總量未達1 0質量％之方式調整水與有機溶劑之總使用量。本發明中使用之有機鈦化合物之單體、寡聚物或該等之水解物宜佔塗佈液中所含固體成分中之50.0質量％〜98.0 質量％。固體成分比率更好爲50質量％~90質量％，又更好 φ 爲5 5質量％〜90質量％。此外，塗佈組成物中亦較好添加有機鈦化合物之聚合物（預先進行有機鈦化合物之水解並經交聯者）或者氧化鈦微粒子。本發明中使用之高折射率層及中折射率層較好含有金屬氧化物作爲微粒子，更好含有黏合劑聚合物。以上述塗佈液調製法使水解/聚合之有機鈦化合物與金屬氧化物粒子組合時，可強固的接著金屬氧化物粒子與水解/聚合之有機鈦化合物，可獲得兼具粒子之硬度與均一之膜柔軟性之強固塗膜。 -175- 201213864 高折射率層及中折射率層中使用之金屬氧化物粒子之折射率較好爲1.80〜2.80，更好爲1.90~2.80。金屬氧化物粒子之一次粒子之重量平均直徑較好爲1〜150nm，更好爲 1〜100nm，最好爲1〜80nm。層中之金屬氧化物粒子之重量平均直徑較好爲1〜200nm，更好爲5~150nm，又更好爲 10〜lOOnm，最好爲l〇~80nm。金屬氧化物粒子之平均粒徑若在20〜30nm以上則以光散設法測定，若在20〜30nm以下則以電子顯微鏡照相測定。金屬氧化物粒子之比表面積以 BET法測定之値較好爲1〇〜400m2/g，更好爲20~200m2/g，最好爲30〜1 50m2/g »These fluorine-based surfactants are sold under the trade names of MEGAFAC, EF TOP, SURFLON, FTERGENT, UNIDYNE, FLORIDE, ZONYL, and the like. The preferred addition amount is 0. The solid content of the coating layer of the hard coating layer and the antireflection layer is 0. 01~3. 0%, better 0. 02~1. 0%. It can also be used with other surfactants, and it is also preferable to use an anionic surfactant such as a sulfonate, a sulfate or a phosphate ester, or an ether having a polyoxyethylene chain as a hydrophilic group. A nonionic surfactant such as a type or an ether ester type. The solvent for coating the hard coat layer of the present invention may be appropriately selected from, for example, hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents, or may be used in combination. A solvent containing 5% by mass or more, more preferably 5% by mass to 80% by mass or more of propylene glycol mono(C1~C4) alkyl ether or propylene glycol mono-149-201213864 (C1-C4) alkyl ether ester is preferably used. The coating method of the hard coating composition coating liquid can be coated with an air squeegee using a gravure coater, a spin coater, a wire coater, a roll coater, a reverse roll coater, and an extrusion coater. A conventional method such as a cloth, a spray applicator, or an inkjet method. The coating amount is suitably 5 μηι to 30 μπι in terms of wet film thickness, more preferably 10 μηη to 20 μηι. The coating speed is preferably from 10 μm/min to 200 m/min. After the anti-glare hard coating composition is applied and dried, it is preferably irradiated with an active energy ray such as an ultraviolet ray or an electron beam for hardening treatment, but the aforementioned active energy ray The irradiation time is preferably 0. 5 seconds to 5 minutes, it is more preferably 3 seconds to 2 minutes in terms of curing efficiency and work efficiency of the ultraviolet curable resin. [Anti-reflection layer] The anti-reflection layer used in the present invention may be composed only of a single layer of a low refractive index layer, but a refractive index layer provided with a plurality of layers is also preferable. The λ/4 plate has a hard coat layer, and the refractive index, the film thickness, the number of layers, the layer order, and the like can be considered to be laminated on the surface thereof by optically reducing the reflectance. The antireflection layer is formed by combining a high refractive index layer having a higher refractive index than the support and a low refractive index layer having a lower refractive index than the support, and is preferably an antireflection composed of three or more refractive index layers. The layer, and preferably the medium refractive index layer (the layer having a higher refractive index than the support or the anti-glare hard coat layer than the high refractive index layer) from the support side / high refractive index layer / The low refractive index layer is formed by laminating three layers having different refractive indices. Or, it is also preferable to use an anti-reflection layer composed of a layer of four or more layers in which two or more layers of a high refractive index layer and two or more layers of a low refractive index are alternately laminated. -150-201213864 An example of a preferred layer configuration is shown below. The / here indicates the laminate configuration. (λ/4 plate) / transparent hard coating / low refractive index layer (λ / 4 plate) / transparent hard coating / high refractive index layer / low refractive index layer (λ / 4 plate) / transparent hard coating / medium Refractive index layer / high refractive index layer / low refractive index layer (λ / 4 plate) / anti-glare hard coat / low refractive index layer (λ / 4 plate) / anti-glare hard coat / high refractive index layer / Low refractive index layer (λ/4 plate) / anti-glare hard coating / medium refractive index layer / high refractive index layer / low refractive index layer to make the stain or fingerprint wipe easy, can be at the lowest surface An antifouling layer is further provided on the refractive index layer. The antifouling layer is preferably a fluorine-containing organic compound. As long as the reflectance can be reduced by optical interference, there is no particular limitation on the layer configuration. Further, the above layer configuration may be appropriately provided with an intermediate layer 'preferably, for example, an antistatic which contains conductive polymer microparticles (for example, crosslinked cationic microparticles) or metal oxide microparticles (for example, S η Ο 2, I Τ , etc.). Layers, etc. <Low Refractive Index Layer> The low refractive index layer used in the present invention preferably uses the following hollow spherical ceria-based fine particles. -151 - 201213864 (Hollow-bulky cerium oxide-based fine particles) The hollow spherical fine particles are (I) composite particles composed of porous particles and a coating layer provided on the porous particles, or pores inside (Π) The contents are filled with pores of a solvent, a gas or a porous substance. Further, the low refractive index layer may contain either (Ϊ) composite particles or (Π) pore particles, or may contain both. Further, the pore particles are particles having pores inside, and the pores are surrounded by the particle walls. The inside of the hole is filled with the contents of a solvent, a gas, or a porous substance used for preparation. The average particle diameter of the hollow spherical fine particles is preferably from 5 to 300 nm, preferably from 10 to 200 nm. The hollow spherical microparticles to be used are appropriately selected depending on the thickness of the transparent film to be formed, and are preferably in the range of 2/3 to 1/10 of the thickness of the transparent film of the formed low refractive index layer or the like. These hollow spherical fine particles are preferably used in a state of being dispersed in a suitable medium in order to form a low refractive index layer. The dispersion medium is preferably water, an alcohol (for example, methanol, ethanol, isopropanol) and a ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), or a ketone alcohol (for example, diacetone alcohol). The thickness of the coating layer of the composite particles or the thickness of the particle walls of the pore particles is preferably in the range of 1 to 2 Onm, preferably 2 to 15 nm. In the case of the composite particles, when the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and the tannic acid monomer or the oligomer having a low degree of polymerization of the coating liquid component described later may easily enter the composite particles. The inside is reduced in the internal porosity, and the low refractive index effect cannot be sufficiently obtained. When the thickness of the coating layer exceeds 2 Onm, the tannic acid monomer or the oligomer cannot enter the inside, and the porosity (fine pore volume) of the composite particles is lowered, and the low refractive index -152 - 201213864 effect cannot be sufficiently obtained. Happening. Further, in the case of the pore particles, when the thickness of the particle wall is less than 1 nm, the shape of the particles may not be maintained, and when the thickness exceeds 20 nm, the effect of the low refractive index may not be sufficiently exhibited. The particle wall of the coating layer of the composite particles or the pore particles preferably has ruthenium dioxide as a main component. Further, the component other than cerium oxide may be specifically mentioned as Al2〇3, B2〇3, Ti02, Zr02, Sn02, Ce02, P203, Sb203, M〇03, Zn02, W03 and the like. The multi-I-well particles constituting the composite particles are exemplified by those composed of cerium oxide and composed of inorganic compounds other than cerium oxide and cerium oxide, and are composed of CaF2, NaF, NaAlF6, MgF or the like. Among them, the most suitable one is a porous particle composed of a composite oxide of an inorganic compound other than cerium oxide and cerium oxide. The inorganic compound other than cerium oxide may be one or more selected from the group consisting of ai2o3, b2o3, TiO2, Zr02, Sn02' Ce02, P2〇3' Sb203, Mo03, Zn02, and W03. The porous particle is preferably 0. The molar ratio MOx/SiO 2 is 0 when the inorganic ruthenium compound other than cerium oxide is represented by Si 〇 2 and oxidized by (MOx ). 000 1 ~1. 0, preferably 0. 001~0. The scope of 3. The molar ratio of the porous particles to M0x/Si02 is less than 0. It is difficult to obtain 000 1 , and even if the pore volume is small, particles having a low refractive index cannot be obtained. Moreover, the molar ratio of the porous particles to MOx/Si〇2 exceeds 1. When it is 0, since the ratio of cerium oxide is small, the pore volume becomes large, and it is difficult to obtain a case where the refractive index is low. The pore volume of the porous particle is preferably 0. 1~1. 5ml / g, preferably 〇 · 2 ~ l. A range of 5 ml/g. The pore volume is not up to 〇. When imi/g, particles with a sufficiently low refractive index cannot be obtained, exceeding one. At 5 ml/g, the particle strength is lowered -153-201213864, and the strength of the obtained film is lowered. Further, the pore volume of the porous particle can be pressed by mercury. Further, examples of the contents of the pore particles include a solvent, a gas, and a porous material in the case of particle preparation. The solvent also contains an unreacted material of the particle precursor used in the preparation of the pores, a catalyst to be used, and the like. The porous material is exemplified by the above-mentioned porous particles. The contents may be a mixture of a plurality of ingredients consisting of a single component. The method for producing such a hollow spherical fine particle is preferably a method for preparing a colloidal particle disclosed in paragraphs [1010] to [ [0033] of JP-A No. 7-133105. Specifically, when the composite particles are composed of an inorganic compound other than cerium or cerium oxide, hollow spherical fine particles are produced by the following third step. First step: preparation of the porous particle precursor is carried out in the first step, and an alkaline aqueous solution of the raw material of the inorganic compound other than the raw material of the cerium oxide or the inorganic compound is prepared in advance, or an inorganic compound raw material other than the dioxane and the cerium oxide is prepared. The mixed aqueous solution is a composite ratio of the desired composite oxide, and the aqueous solution is slowly added to an alkaline aqueous solution having a pH of 10 or more to prepare a porous precursor. As the ceria raw material, an alkali metal, ammonium or organic alkali salt is used. The alkali metal citrate is sodium citrate (water glass) or a sand organic base, and examples thereof include a quaternary ammonium salt such as a tetraethylammonium salt, an amine such as monoethanol octaethanolamine or triethanolamine. In addition, the ammonium citrate or the organic test method can be used as a combination of the hole particles, and the first to the oxidized bismuth oxide of the composite oxygen dioxide, and the potassium citrate according to the stirring of the particles can be used. .二二 - - -154- 201213864 The salt also contains an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide 'amine compound, etc., to a citric acid solution. Further, as the raw material of the inorganic compound other than cerium oxide, an alkali-soluble inorganic compound is used. Specifically, an oxoacid which is an element selected from A1, B, Ti, Zr, Sn, Ce, P, Sb, Mo, Zn, W or the like, an alkali metal salt or an alkaline earth of the oxyacid Metal-like salts, ammonium salts, and quaternary ammonium salts. More specifically, sodium aluminate 'sodium tetraborate, ammonium cerium carbonate, potassium citrate, potassium stannate, sodium aluminosilicate, sodium molybdate, ammonium nitrate, and sodium phosphate are suitable. The pH of the mixed aqueous solution is changed while the aqueous solution is added, but the operation of controlling the pH 在 within a specific range is not particularly required. The aqueous solution finally becomes a pH 决定 depending on the type of the inorganic oxide and the mixing ratio thereof. The rate of addition of the aqueous solution at this time is not particularly limited. Further, when the composite oxide particles are produced, a dispersion of the seed particles may be used as a starting material. The seed crystal particles are not particularly limited, and inorganic oxides such as si〇2, ai2o3, TiO2 or Zr02 or fine particles of the composite oxides can be used, and the sols are usually used. Further, the porous particle precursor dispersion obtained by the above production method can be used as a seed particle dispersion. When the seed particle dispersion is used, the pH of the seed particle dispersion is adjusted to 10 or more, and then an aqueous solution of the compound in the seed particle dispersion is added to the alkaline solution under stirring. In this case, it is not necessary to carry out the pH control of the necessary dispersion. When the seed particles are used in this manner, the particle diameter of the prepared porous particles is easily controlled, and the above-mentioned H oxidation can be obtained. The sand raw material and the inorganic compound raw material have a high solubility of -155 to 201213864 on the alkaline side. However, when the two are mixed in the pH region where the solubility is large, the solubility of the oxo acid ions such as citrate ions and aluminate ions is lowered, and the composites are precipitated to grow into fine particles or on the seed particles. Precipitation causes the particles to grow. From the above, when the fine particles are precipitated and grown, it is not always necessary to control the pH as in the past. The compounding ratio of the inorganic compound other than the cerium oxide and the cerium oxide in the first step is converted to the oxide (MOx) with respect to the inorganic compound of cerium oxide, and the molar ratio of MOx/SiO2 is preferably 0. 05~2. 0, preferably 0. 2~2. The range of 0. Within this range, the proportion of cerium oxide becomes small, and the pore volume of the porous particles increases. However, even if the molar ratio exceeds 2. 0, the pore volume of the porous particles hardly increased. On the other hand, Moerby has not reached 0. At 05 o'clock, the pore volume becomes smaller. When modulating the pore particles, the molar ratio of MOx/Si02 should be 〇. 25~2. Within the range of 0. Step 2: Removal of inorganic compound other than cerium oxide from porous particles The second step is to selectively remove inorganic compounds other than cerium oxide from the porous precursor of the porous precursor obtained in the first step (except for hydrazine and oxygen) At least a portion of the element is specifically removed by using an inorganic or organic acid to dissolve the inorganic compound in the precursor of the porous particle or by ion exchange with the cation exchange resin. Further, the porous particle precursor obtained in the first step is a particle of a mesh structure in which an element of an inorganic compound and an inorganic compound are oxygen-bonded. Thus, by removing the inorganic compound (the element other than cerium and oxygen) from the porous particle precursor, porous particles having a large pore volume are obtained in a porous form. And - -156- 201213864 If the amount of inorganic oxide (formation) removed from the porous particle precursor is increased, the pore particles can be prepared. Further, before the removal of the dioxo compound from the porous precursor of the porous particles, it is preferred to add a decane compound obtained by removing the alkali metal salt of cerium oxide into a fluorine-substituted alkyl group in the polydispersion obtained in the first step. An acid solution or a compound forms a cerium oxide protective film. The cerium oxide is 0. The thickness of 5~15nm can be used. Further, even if the protective film forming the dioxygen in the step is a porous film and the thickness is smaller than that of the pore-precursor precursor to remove the cerium oxide, the porous ceramium protective film can be removed from the porous precursor. The aforementioned ruthenium dioxide is used. Further, when the ceria coating layer described later is formed, it is not blocked by the coating layer, and therefore the ceria coating layer which is described in the pores is not formed. Further, the inorganicization of the removal is not necessarily required to be formed, and it is not necessary to form a film. When the pore particles are prepared, it is preferable to form a film in advance. When the pore particles are modulated, when the inorganic yttria protective film is removed and the porous particles composed of the lyotropic solid components in the cerium oxide protective film form a coating layer to be described later on the precursor, the formed wall The pore particles are formed. It is less preferable to add a protective film for forming the above-mentioned cerium oxide in a range in which the shape of the particles can be maintained. Inorganic pore-plasmid precursor other than bismuth and oxygen, which contains a hydrolyzable organic bismuth protective film, the thickness of the protective film is thin, so it can still be derived from a multi-inorganic compound. The shape of the particles, and the inorganic compound of the pores of the pores are reduced to form a reduced amount of the compound, and the ruthenium film is formed. The cerium oxide protective material is obtained by two doses, which are not dissolved, and the amount of the cerium oxide source is more than -157 - 201213864 when the pore particle coating layer becomes the source of the particulate cerium oxide, the cerium oxide protective film Since the thickness becomes too thick, there is a case where it is difficult to remove an inorganic compound other than cerium oxide from the porous particle precursor. As the hydrolyzable organic ruthenium compound used for the formation of the ruthenium dioxide protective film, a hydrocarbon group such as RnSi(OR')4-n [R, R': alkyl group, aryl group, vinyl group, or acryl group can be used. , alkoxydecane represented by n = 0, 1, 2 or 3]. In particular, a tetraalkyloxydecane such as a fluorine-substituted tetramethoxynonane, tetraethoxysilane or tetraisopropoxydecane is preferably used. The addition method is a method in which a small amount of a base or an acid as a catalyst is added to a mixed solution of the alkoxysilane, the pure water, and the alcohol, and the solution is added to the dispersion of the porous particles to form an alkoxydecane. The hydrolysis is carried out and the formed phthalic acid polymer is deposited on the surface of the inorganic oxide particles. In this case, an alkoxydecane, an alcohol, or a catalyst may be simultaneously added to the dispersion. As the base catalyst, ammonia, an alkali metal hydroxide or an amine can be used. Further, various inorganic acids and organic acids can be used as the acid catalyst. When the dispersion medium of the porous particle precursor is water alone or when the ratio of water to the organic solvent is high, the ceric acid solution may be used to form the cerium oxide protective film. When the citric acid solution is used, a specific amount may be added to the dispersion. The acid solution is simultaneously added with a base to deposit the citric acid on the surface of the porous particles. Further, a cerium oxide protective film can also be produced by using a citric acid solution and the above alkoxy decane. The third step: formation of the ceria coating layer in the third step is performed by adding a hydrolyzable organic hydrazine compound containing a fluorinated alkyl group-containing decane compound or a citric acid solution or the like to the porous layer prepared in the second step. In the case of the particle dispersion (in the case of the pore particles, the pore particle precursor dispersion), the surface of the particle is coated with a hydrolyzable organic hydrazine compound or a citric acid solution to form a cerium oxide coating layer. The hydrolyzable organic ruthenium compound used for the formation of the ruthenium dioxide coating layer may be a hydrocarbon group such as a general formula of RnSi(OR')4-n [R, R'.. alkyl, aryl, vinyl or acrylate. Alkoxydecane represented by n = 0, 1, 2 or 3]. In particular, tetraalkoxydecane such as tetramethoxynonane, tetraethoxysilane or tetraisopropoxydecane is preferably used. The addition method is a method in which a small amount of a base or an acid as a catalyst is added to a mixed solution of the alkoxysilane, the pure water, and the alcohol, and is added to the porous particles (the case of the pore particles is a pore particle precursor). In the dispersion of the material, the alkoxydecane is hydrolyzed and the resulting decanoic acid polymer is deposited on the surface of the porous particles (in the case of the pore particles, the pore particle precursor). At this time, an alkoxydecane, an alcohol, and a catalyst may be simultaneously added to the dispersion. As the base catalyst, ammonia, an alkali metal hydroxide or an amine can be used. Further, various acid acids and organic acids can be used as the acid catalyst. The dispersion medium of the porous particles (in the case of the pore particles, the pore particle precursor) is water alone or in a mixed solvent with an organic solvent, and in the case of a mixed solvent having a high ratio of water to an organic solvent, a tannic acid solution may also be used. A coating layer is formed. The citric acid solution is an aqueous solution of a low polymer of citric acid which is subjected to ion exchange treatment by an aqueous solution of an alkali metal ruthenate such as water glass. The citric acid solution is added to the dispersion of the porous particles (the pore particles are in the case of the pore particles), and the alkali is added to make the phthalic acid low polymer deposit on the porous particles (the pore particles are in the case of the pore particles precursor) On the surface. Further, a citric acid solution may be used for the formation of the coating layer in combination with the above alkoxy decane. The amount of the organic cerium compound used in the formation of the coating layer or the ceric acid solution of -159-201213864 is sufficient as long as the surface of the colloidal particles can be sufficiently coated so that the thickness of the finally obtained cerium oxide coating layer becomes l. The amount of ~20 nm is added to the dispersion of the porous particles (in the case of the pore particles, the pore particle precursor). Further, when the cerium oxide protective film is formed, an organic cerium compound or a ceric acid solution is added in an amount such that the total thickness of the SiO 2 protective layer and the SiO 2 coating layer is in the range of 1 to 20 nm. Next, the dispersion liquid in which the particles of the coating layer are formed is heat-treated. By the heat treatment, in the case of the porous particles, the cerium oxide coating layer coated with the porous particles can be densified to obtain a dispersion of the composite particles obtained by coating the porous particles with the cerium oxide coating layer. Further, in the case of the void particle precursor, the formed coating layer is densified into a pore particle wall, and a dispersion of pore particles having pores filled with a solvent, a gas or a porous solid component is obtained. The heat treatment temperature at this time is not particularly limited as long as it is a fine pore that can block the ceria coating layer, and is preferably in the range of 80 to 300 °C. When the heat treatment temperature is less than 80 °C, the pores of the ceria coating layer cannot be completely blocked and cannot be densified, and the treatment time may take a long time. Further, the heat treatment temperature exceeds 300 ° C, and when it is treated for a long period of time, it may become a dense particle, and a low refractive index effect may not be obtained. The refractive index of the inorganic microparticles thus obtained is as low as less than 1. 42. Such inorganic fine particles are presumed to have a low refractive index because they maintain the porosity inside the porous particles or have pores inside. The refractive index of the low refractive index layer used in the present invention is preferably 1. 30~1. 50, better for 1. 35~1. 44. -160- 201213864 The above-mentioned Si〇2 fine particles which are commercially available can be used in the present invention. Specific examples of the commercially available particles are P-4 manufactured by Catalyst Chemical Industries, Ltd., and the like. The content (mass) of the hollow spherical cerium oxide microparticles A having a shell layer and a porous or porous inner portion in the coating liquid of the low refractive index layer is preferably from 10 to 80% by mass, more preferably from 20 to 60% by mass. . (Tetraalkoxydecane compound or hydrolyzate thereof) The low refractive index layer used in the present invention preferably contains a tetraalkoxydecane compound or a hydrolyzate thereof as a sol-gel material. The material for the low refractive index layer used in the present invention is also preferably a cerium oxide having an organic group other than the above inorganic cerium oxide. These are commonly referred to as lyogel materials, but metal alkoxides, organoalkoxy metal compounds, and hydrolyzates thereof can be used. In particular, alkoxydecane, organoalkoxydecane and hydrolyzate thereof are preferred. Examples of such examples include tetraalkoxydecane (tetramethoxydecane, tetraethoxydecane, etc.), alkyltrialkoxydecane (methyltrimethoxydecane, ethyltrimethoxydecane, etc.). An aryltrialkoxydecane (phenyltrimethoxydecane, etc.), a dialkyldialkoxydecane, a diaryldialkoxydecane, or the like. Most preferred are tetraalkoxydecane and its hydrolyzate. And 'organic alkoxy decane having various functional groups (vinyl trialkoxy decane, methyl vinyl dialkoxy decane, γ-glycidoxypropyl trialkoxy decane, γ) is also preferably used. - glycidoxypropylmethylditoxy decane, β-(3,4-epoxydicyclohexyl)ethyltrialkoxydecane' γ-methacryloxypropyltrialkyloxy Baseline, γ-aminopropyltrialkoxydecane, γ-mercaptopropyltrialkoxydecane, γ-chloropropyltrialkoxide-161 - 201213864 decane, etc.), containing perfluoroalkyl group a decane compound (for example, (pentadecafluoro-1,1,2,2-tetradecyl)triethoxydecane, 3,3,3-trifluoropropyltrimethoxydecane, etc.). In particular, a fluorine-containing decane compound is preferred in terms of low refractive index of the layer and imparting water repellency and oil repellency. When the above tetraalkoxydecane is hydrolyzed, it is preferred to mix the inorganic fine particles to increase the film strength. The low refractive index layer used in the present invention preferably contains the above cerium oxide and a decane coupling agent described below. Specific examples of the decane coupling agent are exemplified by methyltrimethoxydecane, methyltriethoxydecane, methyltrimethoxyethoxydecane, methyltriethoxydecane, and methyltributoxy. Decane, ethyltrimethoxydecane, ethyltriethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, vinyltriethoxydecane,vinyltrimethoxyethoxydecane , phenyl trimethoxy decane, phenyl triethoxy decane, phenyl triethoxy decane, γ-chloropropyl trimethoxy decane, γ-chloropropyl triethoxy decane, γ-chloropropyl Triethyl decyloxydecane, 3,3,3-trifluoropropyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, Γ-(β-glycidoxyethoxy)propyltrimethoxy sand, β-(3,4-epoxycyclohexyl)ethyltrimethoxy sand, β-(3,4_ ring Oxycyclohexyl)ethyltriethoxylate, γ-propenyloxypropyltrimethoxydecane, γ-methylpropenyloxypropyltrimethoxylate, γ-aminopropyl Trimethoxy sand, γ-aminopropyl triethoxy oxime, γ-mercaptopropyltrimethoxydecane, γ-mercaptopropyltriethoxy decane, Ν-β-(aminoethyl )-γ-Aminopropyltrimethoxydecane and β·cyano-162- 201213864 Ethyltriethoxydecane. Further, examples of the decane coupling agent having a 2-substituted alkyl group are dimethyl dimethoxy decane, phenylmethyl dimethoxy decane, dimethyl diethoxy decane, and phenyl group. Diethoxy decane, γ-glycidoxypropylmethyldiethoxy decane, γ-glycidoxypropylmethyldimethoxydecane, γ-glycidoxypropyl phenyl Ethoxy decane, γ-chloropropylmethyldiethoxy decane, dimethyldiethoxydecane, γ-acryloxypropylmethyldimethoxydecane, γ-acryloxyloxy Propylmethyldiethoxydecane, γ-methacryloxypropylmethyldimethoxydecane, γ-methylpropenyloxypropylmethyldiethoxydecane, γ-mercapto Propylmethyldimethoxydecane, γ-mercaptopropylmethyldiethoxydecane, γ-aminopropylmethyldimethoxydecane, γ-aminopropylmethyldiethoxy Decane, methylvinyldimethoxydecane and methylvinyldiethoxydecane. Among these, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl triethoxy decane, vinyl trimethoxy ethoxy decane, γ-propylene having a double bond in the molecule are preferred.醯-methoxypropyltrimethoxydecane and γ-methacryloxypropyltrimethoxydecane, γ-acryloxypropylmethyldimethoxydecane having a 2-substituted alkyl group , γ-propylene methoxypropyl methyl diethoxy decane, γ-methyl propylene methoxy propyl methyl dimethoxy decane, γ-methyl propylene methoxy propyl methyl di ethoxy Base decane, methyl vinyl dimethoxy decane and methyl vinyl diethoxy decane, preferably γ-propylene methoxypropyl trimethoxy decane and γ-methyl propylene methoxy propyl trimethyl Oxydecane, γ-propylene methoxypropyl methyl dimethoxy decane, γ-propylene methoxy propyl methyl diethoxy decane, γ-methyl propyl-163- 201213864 olefinic oxypropyl Methyl dimethoxy decane and γ-methyl propylene methoxy propyl methyl diethoxy decane. Specific examples of the decane coupling agent are ΚΒΜ-3 03, ΚΒΜ-403, ΚΒΜ-402, ΚΒΜ-403, ΚΒΜ-1 403, ΚΒΜ-502, ΚΒΜ-503, ΚΒΕ-5 02 manufactured by Shin-Etsu Chemical Co., Ltd. 'ΚΒΕ-503, ΚΒΜ-603 'ΚΒΕ-603, ΚΒΜ-903 'ΚΒΕ-903, ΚΒΕ-9103, ΚΒΜ-802, ΚΒΜ-803, etc. It is also possible to use two or more coupling agents. In addition to the decane coupling agents listed above, other decane coupling agents may also be used. Other decane coupling agents are listed as alkyl phthalic acid esters (for example, methyl ortho phthalate, ethyl ortho phthalate, n-propyl decanoate, isopropyl ortho phthalate, n-butyl decanoate, orthoquinone The acid second butyl ester, the tert-butyl phthalate and its hydrolyzate. The specific method of surface treatment using a coupling agent is as follows. The decane coupling agents are preferably hydrolyzed in advance with a necessary amount of water. When the oxime coupling agent is hydrolyzed, the surface of the above cerium oxide particles and the cerium oxide having an organic group is easily reacted to form a stronger film. Further, a hydrolyzed decane coupling agent may be added to the coating liquid in advance. Further, the low refractive index layer may also contain a polymer in an amount of 5 to 50% by mass. The polymer has a function of allowing the fine particles to follow and maintaining the structure of the low refractive index layer containing the pores. The amount of polymer used is adjusted to maintain the strength of the low refractive index layer without filling the pores. The amount of the polymer is preferably from 10 to 30% by mass based on the total amount of the low refractive index layer. In order to polymerize the microparticles, it is preferred to (1) bind the polymer to the surface treatment agent of the microparticles, or (2) to form a polymer shell around the microparticles, or (3) use a polymer for - 164- 201213864 is a binder between microparticles. The polymer bonded to the surface treating agent in (1) is preferably a shell polymer of (2) or a binder polymer of (3). The polymer of (2) is preferably formed by a polymerization reaction around the fine particles before the coating liquid of the low refractive index layer is prepared. The polymer of (3) is preferably formed by adding a monomer to a coating liquid of a low refractive index layer, and simultaneously or after coating the low refractive index layer, by a polymerization reaction. Preferably, the combination of two or more of the above (1) to (3) is carried out, and it is preferably carried out by a combination of (1) and (3) or a combination of all of (1) to (3). The surface treatment of (1), (2) shell and (3) binder are described in order. (1) Surface treatment The fine particles (especially inorganic fine particles) are preferably subjected to surface treatment to improve affinity with the polymer. The surface treatment can be classified into physical surface treatment such as plasma discharge treatment or corona discharge treatment, and chemical surface treatment using a coupling agent. It is preferred to carry out only chemical surface treatment or a combination of physical surface treatment and chemical surface treatment. As the coupling agent, an organoalkoxydecane compound (e.g., a titanium coupling agent, a decane coupling agent) is preferably used. When the microparticles are composed of SiO 2 , the surface treatment with the decane coupling agent is particularly effective, and the surface treatment with the coupling agent is carried out by adding a coupling agent to the dispersion of the microparticles, and the dispersion is at room temperature to 60 ° C. It is carried out at a temperature for several hours to 10 days. In order to promote the surface treatment reaction, a mineral acid (for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, protoporic acid, phosphoric acid, carbonic acid) or an organic acid (for example, acetic acid,) may be added to the dispersion. Polyacrylic acid, benzenesulfonic acid, phenol, polyglutamine), or such salts (-165-201213864, for example, metal salts, ammonium salts). (2) The shell-forming shell polymer preferably has a saturated hydrocarbon as a main component. It is preferably a polymer containing a fluorine atom in a main chain or a side chain, and a polymer containing a fluorine atom in the chain. Preferred are polyacrylate acrylates, preferably fluorine-substituted alcohols and polyacrylic acid or polymethyl esters. The refractive index of the shell polymer decreases with the fluorine atoms in the polymer. In order to lower the refractive index of the low refractive index layer, the shell has a fluorine atom of 35 to 80% by mass, more preferably 45 to 75 mass. The polymer containing a fluorine atom is preferably synthesized by a polymerization reaction of a monomer containing a fluorine atom. Examples of the fluorine atom-containing vinyl compound are exemplified as fluoroolefins (for example, vinyl fluoride, vinylidene fluoride, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-diox, fluorinated vinyl) The polymer in which the ether and the fluorine-substituted alcohol form a shell with an acrylic acid or a methyl group may also be a polymer composed of a repeating unit of a fluorine atom containing a fluorine atom. The fluorine-free unit is preferably a fluorine-free atom. Obtained as an ethylenically unsaturated monomer. Examples of hydrocarbons containing no fluorine atomic ethylenically unsaturated monomer (for example, ethylene, propylene, isoprene, ethyl chloride), acrylate (for example, acrylic acid) Ester, 2-ethylhexyl acrylate (meth) methacrylate (eg, methyl ester, ethyl methacrylate, butyl methacrylate, ethoxylate), styrene and its derivatives (eg The polymer of the styrene chain is more preferably added to the side or the content of the polymethyl propyl acrylate. Preferably, the fluorine atom is a fluorine atom, the ethylenic unsaturated unsaturated monounsole, the tetraheterocycle, the acrylic acid. The polymerization of the ester complex unit and the non-atomic repeat, enumerated Enene, ethyl hexanoate, dimethyl propyl propyl acrylate, divinyl-166- 201213864 benzene, vinyl toluene, α-methyl styrene, vinyl ether (eg, methyl vinyl) Ether), vinyl ester (eg, vinyl acetate, ethyl propionate, vinyl cinnamate), acrylamide (eg, N-t-butyl butyl decylamine, N-cyclohexyl acrylamide), Methyl acrylamide and acrylonitrile. When the binder polymer (3) described later is used, a crosslinkable functional group may be introduced into the shell polymer, and the shell polymer and the binder polymer may be crosslinked to be chemically bonded. The shell polymer may also have crystallinity. When the glass transition temperature (Tg) of the shell polymer is higher than the temperature at which the low refractive index layer is formed, it is easy to maintain micropores in the low refractive index layer. However, when the Tg is higher than the temperature at which the low refractive index layer is formed, the fine particles are not melted, and the low refractive index layer cannot be formed into a continuous layer (resulting in a decrease in strength). In this case, it is preferable to use the binder polymer (3) described later, and it is preferable to form the low refractive index layer into a continuous layer by the binder polymer. A polymer shell is formed around the microparticles to obtain core microparticles. The core formed by the inorganic fine particles in the core particles preferably contains 5 to 90% by volume, more preferably 15 to 80% by volume. It is also possible to use more than two kinds of core particles. Further, inorganic particles and core particles having no shell can be used. (3) Adhesive The binder polymer is preferably a polymer having a saturated hydrocarbon or a polyether as a main chain, more preferably a polymer having a saturated hydrocarbon as a main chain. The binder polymer is preferably crosslinked. A polymer having a saturated hydrocarbon as a main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder polymer, a monomer having two or more ethylenically unsaturated groups is preferably used. Examples of the monomer having two or more ethylenically unsaturated groups are exemplified by -167 to 201213864 esters of polyvalent alcohols and (meth)acrylic acid (for example, ethylene glycol acrylate, 1,4-cyclohexane Acrylate, pentaerythritol acrylate, pentaerythritol tri(meth)acrylate, tris(meth)acrylate, trimethylolethane tris(methyl, dipentaerythritol tetra(meth)acrylate, dipentaerythritol) Acrylate, pentaerythritol hexa(meth) acrylate, alkyl tetramethacrylate, polyurethane acrylate acrylate, vinyl benzene and its derivatives (for example, 1,4-' 4- Vinylbenzoic acid-2-propenylethyl ester, i,4-dione), vinyl anthracene (eg, divinylanthracene), propylene, methylenebis acrylamide, and methacrylamide . The polymer having a chain is preferably synthesized by using a polyfunctional epoxy compound. Instead of having two or more ethylenically unsaturated groups, it is also possible to crosslink the copolymer polymer by the reaction of a crosslinkable group. Examples of the crosslinkable functional group are an iso-epoxy group, an acridinyl group, an oxazolinyl group, an aldehyde group, a carbonyl group, a hydroxymethyl group, and an active methylene group. Vinylsulfonic acid, an acid anhydride, an ester derivative, a melamine, an etherified methylol group, an ester, and an amine group are used as a monomer introduced into a crosslinked structure. A functional group such as an alkyl group which exhibits crosslinkability as a result of a decomposition reaction can also be used. Further, it is not limited to the above compounds, and may be one which exhibits reactivity with the above functional groups. The polymerization reaction of the binder polymer and the crosslinking of the polymerization initiator are carried out using a thermal polymerization initiator or photopolymerization as a photopolymerization initiator. An example of a photopolymerization initiator is phenethyl bis(methyl)tetrakis(methyl) hydroxymethylpropane) acrylate alcohol penta-5 (methyl 1,2,3-cyclohexyl, polyester polydivinylstyrene) Cyclohexylamine (for example, a polyether is used as a monomer for the main ring polymerization reaction or is introduced into a mucyanate group, an amine group, a carboxycyanopropyl phthalate or a isocyanate, and the crosslinked group is decomposed. As a result, the initiator was used in the reaction, but more ketones, benzophenone-168-201213864, benzophenones, phosphine oxides, ketals, anthraquinones, azo compounds, peroxides, 2, Examples of 3-dialkyldi-disulfide compounds, fluoroamine compounds or aromatic oximes are 2,2-diethoxyacetophenone and p-dimethylhydroxydimethyl ketone. , 1-hydroxycyclohexyl phenyl ketone, 2-yl-2-morpholinylpropiophenone, and 2-benzyl-2-dimethylamino-1-(yl)-butanone. Examples of benzoin classes It is benzoin methyl ethyl ether and benzoin propyl ether. Examples of benzophenones, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and - The examples of phosphine oxides are listed as 2, The 4,6-trimethylbenzhydryl hydrazine binder polymer preferably adds the monomer to the low refractive index, and further crosslinks the reaction while coating the low refractive index layer or after coating. The low refractive index layer may also be added with a small amount of a polymer (for example, polyvinyl alcohol, poly φ methyl methacrylate, polymethyl acrylate, diethyl ketone cellulose, nitrocellulose, polyester, alcohol). Further, the low refractive index layer used in the present invention may be a low refractive index layer obtained by crosslinking a fluorine-containing resin (hereinafter also referred to as "crosslinked fat") which is crosslinked by radiation. The fluorine-containing resin before crosslinking may be exemplified by a fluorine-containing copolymerized fluorovinyl monomer which is preferably a monomer and a monomer for imparting a crosslinkable group, for example, a fluoroolefin (alkene, partial Fluorinated ethylene, tetrafluoroethylene, hexafluoroethylene, six, thioxanthone compounds, acetophenone acetophenone, 1-methyl-4-methylthio 4-morpholinyl phenyl ether, benzene couple Polymerization of a coating solution of a benzophenone chlorobenzophenone phenyl phosphine oxide layer (oxygen B in a coating liquid) , a polyfluorinated or a trifluoroanthracene fluoride-containing fluorovinyl group by heat or electricity. The above contains, for example, fluoroethylfluoropropene, all-169-201213864 fluoro-2,2-dimethyl-1,3 -dioxol or the like, or a part or all of a fluorinated alkyl ester derivative of (meth)acrylic acid (for example, Biscote 6FM (manufactured by Osaka Organic Chemical Co., Ltd.) or M-2020 (manufactured by DAIKIN), etc.) Partially fluorinated vinyl ethers, etc. The monomer used to impart a crosslinkable group is exemplified by glycidyl methacrylate, or vinyl trimethoxy decane, γ-methyl propylene methoxy propyl trimethoxy decane. a vinyl monomer having a crosslinkable functional group in the molecule such as a vinyl glycidyl ether, and a vinyl monomer having a carboxyl group or a hydroxyl group, an amine group, a sulfonic acid group or the like (for example, (meth)acrylic acid, hydroxy group Methyl (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, etc.). The latter can be introduced into a crosslinked structure by adding a compound having at least one reactive group which reacts with a functional group in a polymer after copolymerization, and is described in JP-A No. 10-253 8 8 No. 10-147739. Examples of the crosslinkable group are propylene fluorenyl group, methacryl fluorenyl group, isocyanate group ', epoxy group, acridinyl group, oxazolinyl group, aldehyde, carbonyl group, hydrazine, carboxyl group, hydroxymethyl group and active subunit. Methyl and the like. The fluorinated copolymer is crosslinked by heating, or a combination of an ethylenically unsaturated group and a thermal radical generator, or an epoxy group and a thermal acid generator, etc., when crosslinked by heating The thermosetting type is obtained by irradiating light (preferably ultraviolet 'electron beam, etc.) by combining an ethylenically unsaturated group with a photoradical generator, or an epoxy group with a photoacid generator or the like. When it is connected, it is hardened by ionizing radiation. Further, in addition to the above monomers, a fluorine-containing copolymer formed by using a fluorine-containing vinyl monomer and a monomer other than the monomer for crosslinking may be used as the fluorine-containing resin before the crosslinking of -170-201213864. The monomer which can be used is not particularly limited, and examples thereof include olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), and acrylates (methyl acrylate, ethyl acrylate). , 2-ethylhexyl acrylate), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives ( Styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl vinyl ether, etc.) |, vinyl esters (vinyl acetate, vinyl propionate, cinnamon) Acetate, etc.), acrylamide (N-t-butyl butyl decylamine, N-cyclohexyl acrylamide, etc.), methacrylamide, acrylonitrile derivative, etc. Further, in the fluorine-containing polymer, in order to impart lubricity and antifouling properties, it is also preferred to introduce a polyorganosiloxane skeleton or a perfluoropolyether skeleton. These are obtained by, for example, polymerizing a polyorganosiloxane or a perfluoropolyether having an acrylic group, a methacrylate, a vinyl ether group, a styryl group or the like at the terminal end with the above monomer, and having a radical generated from the terminal. The φ polymerization of the above-mentioned monomer of the polyorganosiloxane or the perfluoropolyether, the reaction of a polyorganosiloxane having a functional group or a perfluoropolyether with a fluorinated copolymer, and the like are obtained. The proportion of the above-mentioned respective monomers used for forming the fluorinated copolymer before crosslinking is preferably from 20 to 70 mol%, more preferably from 40 to 70 mol%, of the fluorine-containing vinyl monomer. The monomer of the linking group is preferably from 1 to 2 mol%, more preferably from 5 to 20 mol%, and the other monomers used are preferably from 10 to 70 mol%, more preferably 1 0~ The ratio of 50% of the moles. The fluorinated copolymer can be obtained by polymerizing such monomers in the presence of a radical polymerization initiator, by solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, -171 - 201213864. A commercially available product can be used as the fluorine-containing resin before crosslinking. The fluororesin before the cross-linking which is commercially available is exemplified by CYTOP (manufactured by Asahi Glass Co., Ltd.), TEFLON (registered trademark) AF (manufactured by DUPON), polyvinylidene fluoride, LUMIFLON (manufactured by Asahi Glass Co., Ltd.), and 〇PSTAR (manufactured by JSR). The dynamic refractive index of the low refractive index layer having the crosslinked fluorine-containing resin as a constituent component is preferably 0. 03 ~ 0. In the range of 15, the contact angle to water is preferably in the range of 90 to 120 degrees. The low refractive index layer used in the present invention may be subjected to dip coating, air knife coating, curtain flow coating, roll coating, wire coating, gravure coating or extrusion coating. (U.S. Patent No. 2,681,294), which is formed by coating. Further, it is also possible to apply two or more layers at the same time. At the same time, the method of coating is described in U.S. Patent No. 2,761,791, U.S. Patent No. 2,941,898, U.S. Patent No. 3,508,947, U.S. Patent No. 3,526,52, and U.S. Patent, Coating Engineering, 2H, In the Asakura Bookstore (19 73). The film thickness of the low refractive index layer used in the present invention is preferably from 50 to 200 nm, more preferably from 60 to 15 onm. <High refractive index layer and medium refractive index layer> In the present invention, in order to reduce the reflectance, it is preferred to provide a high refractive index layer between the hard coat layer and the low refractive index layer. Or better, a medium refractive index layer is provided between the hard coat layer and the high refractive index layer. The refractive index of the high refractive index layer is preferably from 1.55 to 2. 30, better for 1. 57~2. 20. The refractive index of the medium refractive index layer is adjusted in such a manner that it becomes the middle of the refractive index of the support and the refractive index of the high refractive index layer -172 - 201213864. The refractive index of the medium refractive index layer is preferably 1. 5 5~1. 8 0. The thickness of the high refractive index layer and the medium refractive index layer is preferably 5 nm to Ιμιη, more preferably 10 ηιη to 0. 2μιη ’ is preferably 30 nm to 10000 nm. The turbidity of the high refractive index layer and the medium refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The strength of the high refractive index layer and the medium refractive index layer is preferably Η or more, more preferably 2 Å or more, and most preferably 3 Å or more in terms of a pencil hardness of 1 kg load. The high refractive index layer used in the present invention is preferably coated with a coating liquid containing a monomer, an oligomer or a hydrolyzate of the organotitanium compound represented by the following formula (9) and dried. Formed refractive index 1 . 5 5 ~ 2. 5 layers. In the formula, R1 is an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Further, the monomer, the oligomer or the hydrolyzate of the organotitanium compound is subjected to hydrolysis by alkoxy group, and is reacted to form a crosslinked structure such as _Ti_〇_Ti_ to form a hardened layer. The monomers and oligomers of the organotitanium compound used in the present invention are preferably φ(^3)4, Ti(〇C2H5)4, Ti(0_n_C3H7)4, Ti(0_i-C3H7)4, etc. Ti(0-n-C4H9)4, 2~10 polymer of Ti(〇-n_c3H7)4, 2~10 polymer of Ti(0-i-C3H7)4, Ti(〇-n-C4H9)4 2~1 〇polymer and the like. These may be used singly or in combination of two or more. Among them, Ti(0_n_C3H7)4, Ti(0-i-C3H7)4, Ti(0-n-C4H9)4, Ti(〇_n_C3H7)4, 2~1 〇polymer, Ti(0-n- C4H9) 4 is preferably 2 to 10 polymers. In the coating liquid for a high refractive index layer used in the present invention, the organic titanium compound is preferably added to a solution obtained by sequentially adding water and an organic solvent to be described later. When added after water, 'hydrolysis/polymerization cannot be performed uniformly, and -173-201213864 is produced, and the film strength is lowered. After adding water and an organic solvent, it is well mixed and stirred well to be dissolved. Further, as another method, it is preferable to mix the organotitanium compound with an organic solvent in advance, and to add the mixed solution to the mixed solution of the water and the mixed solvent. Further, the amount of water is preferably in the range of 25 to 3 moles per mole of the organotitanium compound. Not up to 0. At 25 mol, the film strength was lowered due to insufficient hydrolysis and polymerization. When it exceeds 3 moles, it is hydrolyzed and the polymerization is excessively carried out. The coarse particles of Ti〇2 are produced and white turbidity is less preferable. Accordingly, it is necessary to adjust the amount of water to the above range. Further, the water content is preferably less than 10% by mass based on the total amount of the coating liquid. When the water content is more than 1% by mass based on the total amount of the coating liquid, the coating liquid has poor stability over time and is white turbid, which is not preferable. The organic solvent used in the present invention is preferably a water-miscible organic solvent. The water-miscible organic solvent is exemplified by, for example, an alcohol (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, second butanol, third butanol, pentanol, hexanol, cyclohexanol). , benzyl alcohol, etc.), polyvalent alcohols (eg 'ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butanediol, hexanediol, pentane Glycol, glycerol, hexane triol, thiodiglycol, etc.), polyvalent alcohol ethers (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl Ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate vinegar , triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether, C-174-201213864 glycol monophenyl ether, etc.), amines (eg, ethanolamine, diethanolamine) , triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, tri-ethyltetramine, tetraethylidene , polyethylenimine, pentamethyldiethyltriamine, tetramethylpropanediamine, etc.), guanamines (for example, formamidine, hydrazine, hydrazine-dimethylformamide, ν, Ν-dimethylacetamide, etc.), heterocyclics (for example, 2-pyrrolidone, Ν-methyl-2-pyrrolidone, cyclohexylpyrrolidone, 2-oxazolone, 1,3 -dimethyl-$ 2 -imidazolidinone, etc.), anthracene (for example, dimethyl hydrazine, etc.), anthracene (for example, cyclobutyl, etc.), urea, acetonitrile, acetone, etc., but preferably an alcohol or a polyvalent alcohol , multivalent alcohol ethers. The amount of the organic solvent used is as described above, and it is preferred to adjust the total amount of water and the organic solvent to be used in such a manner that the water content is less than 10% by mass based on the total amount of the coating liquid. The monomer, the oligomer or the hydrolyzate of the organotitanium compound used in the present invention preferably accounts for 50% of the solid content contained in the coating liquid. 0% by mass to 98. 0 mass%. The solid content ratio is more preferably 50% by mass to 90% by mass, and more preferably φ is 55% by mass to 90% by mass. Further, a polymer of an organic titanium compound (hydrolyzed by an organic titanium compound and crosslinked) or titanium oxide fine particles is preferably added to the coating composition. The high refractive index layer and the medium refractive index layer used in the present invention preferably contain a metal oxide as fine particles, and more preferably a binder polymer. When the hydrolyzed/polymerized organotitanium compound is combined with the metal oxide particles by the above coating liquid preparation method, the metal oxide particles and the hydrolyzed/polymerized organotitanium compound can be strongly adhered to obtain the hardness and uniformity of the particles. A strong solid film for film softness. -175- 201213864 The metal oxide particles used in the high refractive index layer and the medium refractive index layer preferably have a refractive index of 1. 80~2. 80, better to 1. 90~2. 80. The weight average diameter of the primary particles of the metal oxide particles is preferably from 1 to 150 nm, more preferably from 1 to 100 nm, most preferably from 1 to 80 nm. The weight average of the metal oxide particles in the layer is preferably from 1 to 200 nm, more preferably from 5 to 150 nm, still more preferably from 10 to 100 nm, most preferably from 10 to 80 nm. The average particle diameter of the metal oxide particles is measured by light scattering when it is 20 to 30 nm or more, and is measured by electron microscopy when it is 20 to 30 nm or less. The specific surface area of the metal oxide particles is preferably from 1 to 400 m2/g, more preferably from 20 to 200 m2/g, more preferably from 30 to 1 50 m2/g, as measured by the BET method.

金屬氧化物粒子之例爲具有由Ti、Zr、Sn、Sb、Cu、 Fe、Μη、Pb、Cd、As、Cr、Hg、Zn、Al、Mg、Si、P及 S 選出之至少一種元素之金屬氧化物，具體而言列舉爲二氧化鈦（例如，金紅石、金紅石/銳鈦礦之混晶、銳鈦礦、非晶構造）、氧化錫、氧化銦、氧化鋅、及氧化锆。其中 ’以氧化鈦、氧化錫及氧化銦最好。金屬氧化物粒子係以該等金屬之氧化物作爲主成分，進而可含有其他元素。所謂主成分意指構成粒子之成分中含量（質量％ )最多之成分。其他元素之例列舉爲Ti、Zr、Sn、Sb、Cu、Fe、Μη 、Pb、Cd、As、Cr、Hg、Zn、Al、Mg、Si、P及 S等。金屬氧化物粒子較好經表面處理。表面處理可使用無機化合物或有機化合物實施。表面處理中使用之無機化合物之例較好爲氧化鋁、二氧化矽、氧化锆及氧化鐵。其中較好爲氧化鋁及二氧化矽。表面處理所用之有機化合物之 -176- 201213864 例列舉爲多元醇、烷醇胺、硬脂酸、矽烷偶合劑及鈦酸酯偶合劑。其中，以前述矽烷偶合劑最好。亦可倂用兩種以上之偶合劑，除前述矽烷偶合劑以外，亦可使用其他矽烷偶合劑。其他矽烷偶合劑列舉爲原矽酸之烷酯（例如，原矽酸甲酯、原矽酸乙酯、原矽酸正丙酯、原矽酸異丙酯、原矽酸正丁酯、原矽酸第二丁酯、原矽酸第三丁酯）及其水解物。 $ 利用偶合劑進行表面處理係藉由將偶合劑添加於微粒子之分散物中，將分散物在室溫至60°C之溫度下，放置數小時至10天而實施。爲了促進表面處理反應，亦可於分散物中添加無機酸（例如，硫酸、鹽酸、硝酸、鉻酸、次亞氯酸、硼酸、原矽酸、磷酸、碳酸）、有機酸（例如，乙酸、聚丙烯酸、苯磺酸、酚、聚穀胺酸）、或該等之鹽（例如，金屬鹽、銨鹽）。該等砂焼偶合劑較好預先以必要量之水進行水解。若 φ 使矽烷偶合劑水解，則使前述之有機鈦化合物及金屬氧化物粒子之表面容易反應’形成更強固之膜。另外，將經水解之矽烷偶合劑預先添加於塗佈液中亦較佳。該水解中使用之水亦可使用於有機鈦化合物之水解/聚合中。本發明中組合兩種以上之表面處理進行處理亦無妨。金屬氧化物粒子之形狀較好爲米粒狀、球形狀、立方體狀、紡錘形狀或不定形狀。亦可於高折射率層及中折射率層中倂用兩種以上之金屬氧化物粒子。高折射率層及中折射率層中之金屬氧化物粒子之比例 -177- 201213864 較好爲5〜65體積％，更好爲10〜60體積％，又更好爲20~55 體積％。上述金屬氧化物粒子係以分散於介質中之分散體狀態供給於形成高折射率層及中折射率層用之塗佈液中。金屬氧化物粒子之分散介質較好使用沸點爲60~ 170°C之液體。分散溶劑之具體例列舉爲水、醇類（例如，甲醇、乙醇、異丙醇、丁醇、苄醇）、酮類（例如，丙酮、甲基乙基酮、甲基異丁基酮、環己酮）、酯類（例如，乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酸丁酯）、脂肪族烴（例如，己烷、環己烷）、鹵化烴（例如，二氯甲烷、氯仿、四氯化碳）、芳香族烴（例如，苯、甲苯、二甲苯）、醯胺（例如，二甲基甲醯胺、二甲基乙醯胺、N_甲基吡咯烷酮）、醚類（例如，二乙醚、二噁烷、四氫呋喃）、醚醇（例如，1-甲氧基-2-丙醇）。其中，以甲苯、二甲苯、甲基乙基酮、甲基異丁基酮、環己酮及丁醇最好。 .又金屬氧化物粒子可使用分散機分散於介質中。分散機之例列舉爲砂磨機（例如，加裝鰭片之珠粒硏磨機）、高速螺旋槳硏磨機、班伯里硏磨機、滾筒硏磨機、攪動機及膠體硏磨機。最好爲砂磨機及高速螺旋槳硏磨機。另外，亦可實施預分散處理。預分散處理中使用之分散機之例列舉爲球磨機、三輥硏磨機、捏合機及擠出機。本發明中使用之高折射率層及中折射率層較好使用具有交聯構造之聚合物（以下亦稱爲交聯聚合物）作爲黏合 -178- 201213864 劑聚合物。交聯聚合物之例列舉爲聚烯烴等之具有飽和烴鏈之聚合物（以下總稱爲聚烯烴）、聚醚、聚脲、聚胺基甲酸酯、聚酯、聚胺、聚醯胺及三聚氰胺樹脂等之交聯物。其中’以聚烯烴、聚醚及聚胺基甲酸酯之交聯物較佳，更好爲聚烯烴及聚醚之交聯物，最好爲聚烯烴之交聯物。又’交聯聚合物更好具有陰離子性基。陰離子性基具有維持無機微粒^之分散狀態之功能，且交聯構造具有對聚合物賦予皮膜形成能而強化皮膜之功能。上述陰離子性基亦可直接鍵結於聚合物鏈上，亦可透過連結基鍵結於聚合物鏈，但較好透過連結基作爲側鏈鍵結於主鏈上。陰離子性基之例列舉爲羧酸基（羧基）、磺酸基（磺基）及磷酸基（磷醯基）。其中，以磺酸基及磷酸基較佳。此處，陰離子性基亦可爲鹽之狀態。與陰離子性基形成鹽之陽離子較^好爲鹼金屬離子。又，陰離子性基之質子亦可經解離。使陰離子性基與聚合物鏈鍵結之連結基較好爲由_C0_、-0_、伸烷基、伸芳基、及該等之組合選出之二價基。較佳之黏合劑聚合物的交聯聚合物較好含有具有陰離子性基之重複單位與具有交聯構造之重複單位之共聚物。該情況下，共聚物中之具有陰離子性基之重複單位之比例較好爲2〜96質量％，更好爲4〜94質量％，最好爲6〜92質量％。重複單位亦可具有兩個以上之陰離子性基。位其有單。具複} 及重位位他單單其複複有重重含之之可造基亦構銨物聯級合交四聚有或聯具基交不胺之亦有基基具性性爲子子好離離較陰陰位有有單具具複不重 ( 他 -179- 201213864 苯環之重複單位。胺基或四級銨基與陰離子性基同樣，具有維持無機微粒子之分散狀態之功能。苯環爲具有提高高折射率層之折射率之功能。又，胺基、四級銨基及苯環包含於具有陰離子性基之重複單位或具有交聯構造之重複單位中，亦可獲得同樣之效果。上述含有具有胺基或四級銨基之重複單位作爲構成單位之交聯聚合物中，胺基或四基銨基可直接鍵結於聚合物鏈上，或者亦可透過連結基作爲側鏈鍵結於聚合物鏈上，但後者更佳。胺基或四級銨基較好爲二級銨基、三級銨基或四級銨基，更好爲三級胺基或四級銨基。至於鍵結於二級胺基、三級胺基或四級銨基之氮原子上之基以烷基較佳，更好爲碳數1〜12之烷基，又更好爲碳數1〜6之烷基。四級銨基之相對離子較好爲鹵化物離子。使胺基或四級銨基與聚合物鏈鍵結之連結基較好爲由-CO-、-NH-、-0-、伸烷基、伸芳基、及該等之組合選出之二價基。交聯聚合物含有具有胺基或四級銨基之重複單位時，其比例較好爲 0·06〜32質量％，更好爲0.08~30質量％，最好爲0.1〜28質量 %。交聯聚合物較好藉由調配用以生成交聯聚合物之單體而調製高折射率層及中折射率層形成用之塗佈液，在塗佈塗佈液之同時或塗佈後，藉由聚合反應而生成。與交聯聚合物之生成同時形成各層。具有陰離子性基之單體在塗佈液中係作爲無機微粒子之分散劑之功能。具有陰離子性基之單體相對於無機微粒子，較好使用1〜5 0質量％，更好使 -180- 201213864 用5〜4〇質量％，又更好使用10〜3〇質量。/。。且，具有胺基或四級銨基之單體在塗佈液中係作爲分散助劑之功能。具有胺基或四級銨基之單體相對於具有陰離子性基之單體，較好使用3〜3 3質量％。與塗佈塗佈液之同時或塗佈之後，藉由利用聚合反應生成交聯聚合物之方法，在塗佈塗佈液之前’可使該等單體有效地發揮功能。本發明中使用之單體最好爲具有兩個以上之乙烯性不 • 飽和基之單體’其例列舉爲多價醇與（甲基）丙烯酸之酯 (例如，乙二醇二（甲基）丙烯酸酯、i，4-環己烷二丙烯酸酯、季戊四醇四（甲基）丙烯酸酯、季戊四醇三（甲基 )丙烯酸酯、三羥甲基丙烷三（甲基）丙烯酸酯、三羥甲基乙烷三（甲基）丙烯酸酯、二季戊四醇四（甲基）丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯、季戊四醇六（甲基）丙烯酸酯、1，2,3 -環己烷四甲基丙烯酸酯、聚胺基甲酸酯聚丙烯酸酯、聚酯聚丙烯酸酯）、乙烯基苯及其衍生 φ 物（例如，1，4-二乙烯基苯、4-乙烯基苯甲酸-2-丙烯醯基乙基酯、1，4-二乙烯基環己酮）、乙烯基楓（例如，二乙烯基礪）、丙烯醯胺（例如，亞甲基雙丙烯醯胺）及甲基丙烯醯胺等。具有陰離子性基之單體、及具有胺基或四級銨基之單體亦可使用市售之單體。較佳使用之市售之具有陰離子性基之單體列舉爲KAYAMARP M-21、PM-2 (日本化藥（股）製造）、Antox MS-60、MS-2N、MS-NH4 (日本乳化劑（股）製造）、ARONIX M-5000、M-6000、M-8〇〇〇系列（東亞合成（股）製造）、Biscote #2000系列（ -181 - 201213864 大阪有機化學工業（股）製造）、Newfrontiea GX-8289 ( 第一工業製藥（股）製造）、NK Ester CB-1、A-SA (新中村化學工業（股）製造）、AR-100、MR-100、MR-200 (第八化學工業（股）製造）等。又，較好使用之市售之具有胺基或四級銨基之單體列舉爲DMMA (大阪有機化學工業（股）製造）、DMAEA、DMAPAA (興人（股）製造 )、Blanmer-QA (日本油脂（股）製造）、NewFrontiea C-1615(第一工業製藥（股）製造）等。聚合物之聚合反應可使用光聚合反應或熱聚合反應》最好爲光聚合反應。爲了聚合反應較好使用聚合起始劑》列舉爲例如形成防眩性硬質塗層之黏合劑聚合物用之後述熱聚合起始劑，及光聚合起始劑。聚合起始劑亦可使用市售之聚合起始劑。除聚合起始劑以外，亦可使用聚合促進劑。聚合起始劑ιέ聚合促進劑之添加量較好爲單體總量之0.2~10質量％之範圍。加熱塗佈液（含有單體之無機粒子之分散液）液，亦可促進單體 (或寡聚物）之聚合。且，於塗佈後之光聚合反應之後加熱’亦可對形成之聚合物之熱硬化反應進行追加處理。中折射率層及高折射率層較好使用較高折射率之聚合物。折射率較高之聚合物之例列舉爲聚苯乙烯、苯乙烯共聚物、聚碳酸酯、三聚氰胺樹脂、酚樹脂、環氧樹脂及環狀（脂環式或芳香族）異氰酸酯與多元醇之反應獲得之聚胺基甲酸酯。其他具有環狀（芳香族、雜環式、脂環式）基之聚合物，或具有以氟以外之鹵素原子作爲取代基之聚 -182- 201213864 合物亦可用以提高折射率。抗反射層之各層或其塗佈液中，除前述成分（金屬氧化物粒子、聚合物、分散介質、聚合起始劑、聚合促進劑 )以外’亦可添加聚合抑制劑、平流劑、增黏劑、抗著色劑、紫外線吸收劑、矽烷偶合劑、抗靜電劑或黏著賦予劑 0 本發明之中〜高折射率層及低折射率層之塗設後，爲 Φ 了促進含有金屬烷氧化物之組成物之水解或硬化，較好照射活性能量線。更好於每次塗設各層時照射活性能量線。本發明中使用之活性能量線只要是以紫外線、電子束、γ射線等’使化合物活性化之能量源即無特別限制，但較好爲紫外線、電子束，尤其是就操作簡易且容易獲得高能量方面而言以紫外線較佳。至於使紫外線反應性化合物先聚合之紫外線之光源只要是產生紫外線之光源均可使用。例如’可使用低壓水銀燈、中壓水銀燈、高壓水銀燈、 φ 超高壓水銀燈、碳弧燈、金屬鹵素燈、氙氣燈等。又，亦可使用ArF準分子雷射、KrF準分子雷射、準分子燈或同步輻射光等。照射條件隨著各燈而不同，但照射光量較好爲 2〇mJ/cm2~l〇,〇〇〇mJ/cm2，更好爲 100mJ/cm2〜2,000mJ/cm2 ，最好爲 400mJ/cm2〜2,000mJ/cm2。使用紫外線時，多層之抗反射層可每一層照射，亦可層合後照射。就生產性之觀點而言，較好於層合多層後照射紫外線。又’同樣亦可使用電子束。電子束可列舉爲Cockcroft- -183- 201213864Examples of the metal oxide particles are at least one element selected from the group consisting of Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. The metal oxide is specifically exemplified by titanium dioxide (for example, rutile, rutile/anatite mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, and zirconium oxide. Among them, titanium oxide, tin oxide and indium oxide are preferred. The metal oxide particles are mainly composed of oxides of the metals, and may further contain other elements. The term "main component" means the component which constitutes the most content (% by mass) of the components of the particle. Examples of other elements are Ti, Zr, Sn, Sb, Cu, Fe, Μη, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. The metal oxide particles are preferably surface treated. The surface treatment can be carried out using an inorganic compound or an organic compound. Examples of the inorganic compound used in the surface treatment are preferably alumina, ceria, zirconia and iron oxide. Among them, alumina and cerium oxide are preferred. The organic compound used for the surface treatment -176-201213864 is exemplified by a polyol, an alkanolamine, a stearic acid, a decane coupling agent, and a titanate coupling agent. Among them, the above decane coupling agent is preferred. It is also possible to use two or more coupling agents, and other decane coupling agents may be used in addition to the above decane coupling agents. Other decane coupling agents are listed as alkyl phthalic acid esters (for example, methyl ortho phthalate, ethyl ortho phthalate, n-propyl decanoate, isopropyl ortho phthalate, n-butyl decanoate, orthoquinone Second butyl acid ester, tert-butyl phthalate and its hydrolyzate. The surface treatment with a coupling agent is carried out by adding a coupling agent to the dispersion of fine particles, and allowing the dispersion to stand at a temperature of from room temperature to 60 ° C for several hours to 10 days. In order to promote the surface treatment reaction, a mineral acid (for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, protoporic acid, phosphoric acid, carbonic acid) or an organic acid (for example, acetic acid,) may be added to the dispersion. Polyacrylic acid, benzenesulfonic acid, phenol, polyglutamine), or such salts (for example, metal salts, ammonium salts). Preferably, the sand mash coupler is hydrolyzed in advance with a necessary amount of water. When φ is hydrolyzed by the decane coupling agent, the surface of the above-mentioned organotitanium compound and metal oxide particles is easily reacted to form a stronger film. Further, it is also preferred to add a hydrolyzed decane coupling agent to the coating liquid in advance. The water used in the hydrolysis can also be used in the hydrolysis/polymerization of an organotitanium compound. In the present invention, it is also possible to combine two or more kinds of surface treatments for treatment. The shape of the metal oxide particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape. Two or more kinds of metal oxide particles may be used in the high refractive index layer and the medium refractive index layer. The ratio of the metal oxide particles in the high refractive index layer and the medium refractive index layer is -177 to 201213864, preferably 5 to 65 % by volume, more preferably 10 to 60% by volume, still more preferably 20 to 55% by volume. The metal oxide particles are supplied to a coating liquid for forming a high refractive index layer and a medium refractive index layer in a dispersion state dispersed in a medium. The dispersion medium of the metal oxide particles is preferably a liquid having a boiling point of 60 to 170 °C. Specific examples of the dispersion solvent are water, alcohols (for example, methanol, ethanol, isopropanol, butanol, benzyl alcohol), and ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, and ring). Hexone), esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane) , cyclohexane), halogenated hydrocarbons (eg, dichloromethane, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene), decylamine (eg, dimethylformamide, two Methylacetamide, N-methylpyrrolidone), ethers (for example, diethyl ether, dioxane, tetrahydrofuran), ether alcohols (for example, 1-methoxy-2-propanol). Among them, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are preferred. Further, the metal oxide particles may be dispersed in the medium using a disperser. Examples of dispersing machines are listed as sanders (for example, bead honing machines with fins), high speed propeller honing machines, Banbury honing machines, drum honing machines, agitators and colloid honing machines. It is best to use a sand mill and a high speed propeller honing machine. In addition, a pre-dispersion treatment can also be carried out. Examples of the dispersing machine used in the pre-dispersion treatment are exemplified by a ball mill, a three-roll honing machine, a kneader, and an extruder. The high refractive index layer and the medium refractive index layer used in the present invention are preferably a polymer having a crosslinked structure (hereinafter also referred to as a crosslinked polymer) as a binder-178-201213864 agent polymer. Examples of the crosslinked polymer are a polymer having a saturated hydrocarbon chain such as a polyolefin (hereinafter collectively referred to as a polyolefin), a polyether, a polyurea, a polyurethane, a polyester, a polyamine, a polyamine, and A crosslinked product of melamine resin or the like. Among them, a crosslinked product of a polyolefin, a polyether and a polyurethane is preferred, and more preferably a crosslinked product of a polyolefin and a polyether, preferably a crosslinked product of a polyolefin. Further, the crosslinked polymer preferably has an anionic group. The anionic group has a function of maintaining the dispersed state of the inorganic fine particles, and the crosslinked structure has a function of imparting a film forming ability to the polymer and strengthening the film. The anionic group may be bonded directly to the polymer chain or may be bonded to the polymer chain through a linking group, but is preferably bonded to the main chain through a linking group as a side chain. Examples of the anionic group are a carboxylic acid group (carboxy group), a sulfonic acid group (sulfo group), and a phosphoric acid group (phosphonium group). Among them, a sulfonic acid group and a phosphoric acid group are preferred. Here, the anionic group may also be in the form of a salt. The cation forming a salt with an anionic group is preferably an alkali metal ion. Further, the protons of the anionic group can also be dissociated. The linking group which bonds the anionic group to the polymer chain is preferably a divalent group selected from the group consisting of _C0_, -0_, alkylene, aryl, and the combination thereof. The crosslinked polymer of the preferred binder polymer preferably contains a copolymer having a repeating unit of an anionic group and a repeating unit having a crosslinked structure. In this case, the ratio of the repeating unit having an anionic group in the copolymer is preferably from 2 to 96% by mass, more preferably from 4 to 94% by mass, most preferably from 6 to 92% by mass. The repeating unit may also have two or more anionic groups. It has a single. He has a complex and heavier position, and he has a complex basis, and he has a complex structure. He also has a combination of ammonium or quaternary tetramers. There is a single element that is not heavy (the -179-201213864 repeating unit of the benzene ring. The amine group or the quaternary ammonium group has the same function as the anionic group, and maintains the dispersion state of the inorganic fine particles. The function of increasing the refractive index of the high refractive index layer. Further, the amine group, the quaternary ammonium group and the benzene ring are contained in a repeating unit having an anionic group or a repeating unit having a crosslinked structure, and the same effect can be obtained. In the above crosslinked polymer having a repeating unit having an amine group or a quaternary ammonium group as a constituent unit, the amine group or the tetraammonium group may be directly bonded to the polymer chain, or may also pass through the linking group as a side chain. Bonded to the polymer chain, but the latter is more preferred. The amine or quaternary ammonium group is preferably a secondary ammonium group, a tertiary ammonium group or a quaternary ammonium group, more preferably a tertiary or quaternary ammonium group. As for the secondary amine group, the tertiary amine group or the quaternary ammonium group The group on the nitrogen atom is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. The relative ion of the quaternary ammonium group is preferably a halide ion. The linking group which bonds the amine group or the quaternary ammonium group to the polymer chain is preferably a divalent group selected from -CO-, -NH-, -0-, alkylene, aryl, and combinations thereof. When the crosslinked polymer contains a repeating unit having an amine group or a quaternary ammonium group, the proportion thereof is preferably from 0.06 to 32% by mass, more preferably from 0.08 to 30% by mass, most preferably from 0.1 to 28% by mass. Preferably, the crosslinked polymer is prepared by preparing a monomer for forming a crosslinked polymer to prepare a coating liquid for forming a high refractive index layer and a medium refractive index layer, simultaneously or after coating the coating liquid. It is produced by a polymerization reaction. The layers are formed simultaneously with the formation of the crosslinked polymer. The monomer having an anionic group functions as a dispersing agent for the inorganic fine particles in the coating liquid. The monomer having an anionic group is relative to The inorganic fine particles are preferably used in an amount of 1 to 50% by mass, more preferably -180 to 201213864 by 5 to 4% by mass, and more preferably 10 to 3 %. And the monomer having an amine group or a quaternary ammonium group functions as a dispersing aid in the coating liquid. A monomer having an amine group or a quaternary ammonium group is relatively simple with respect to an anionic group The amount of the coating liquid is preferably from 3 to 3% by mass. The monomer is effective to function. The monomer used in the present invention is preferably a monomer having two or more ethylenic non-saturated groups, and examples thereof are exemplified by esters of a polyvalent alcohol and (meth)acrylic acid (for example, Ethylene glycol di(meth)acrylate, i,4-cyclohexane diacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(methyl) Acrylate, trimethylolethane tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol hexa(meth)acrylate, 1,2, 3-cyclohexane tetramethacrylate, polyurethane Acrylate, polyester polyacrylate), vinylbenzene and derivatives thereof (for example, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-propenylethyl ester, 1,4- Divinylcyclohexanone), vinyl maple (for example, divinyl fluorene), acrylamide (for example, methylenebis acrylamide), methacrylamide, and the like. Commercially available monomers can also be used as the monomer having an anionic group and the monomer having an amine group or a quaternary ammonium group. Preferred commercially available monomers having anionic groups are listed as KAYAMARP M-21, PM-2 (manufactured by Nippon Kayaku Co., Ltd.), Antox MS-60, MS-2N, MS-NH4 (Japanese emulsifier) (manufacturing), ARONIX M-5000, M-6000, M-8〇〇〇 series (made by East Asia Synthetic Co., Ltd.), Biscote #2000 series (-181 - 201213864 Osaka Organic Chemical Industry Co., Ltd.), Newfrontiea GX-8289 (manufactured by Daiichi Pharmaceutical Co., Ltd.), NK Ester CB-1, A-SA (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), AR-100, MR-100, MR-200 (eighth chemical Industrial (stock) manufacturing) and so on. Further, commercially available monomers having an amine group or a quaternary ammonium group are exemplified by DMMA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), DMAEA, DMAPAA (manufactured by Xingren Co., Ltd.), and Brancher-QA ( Japanese fats and oils (manufactured by Japan), NewFrontiea C-1615 (manufactured by First Industrial Pharmaceutical Co., Ltd.), etc. The polymerization of the polymer may use photopolymerization or thermal polymerization, preferably photopolymerization. For the polymerization reaction, a polymerization initiator is preferably used, for example, as a binder polymer for forming an antiglare hard coat layer, a thermal polymerization initiator described later, and a photopolymerization initiator. As the polymerization initiator, a commercially available polymerization initiator can also be used. In addition to the polymerization initiator, a polymerization accelerator can also be used. The amount of the polymerization initiator ιέ polymerization accelerator added is preferably in the range of 0.2 to 10% by mass based on the total amount of the monomers. The heating of the coating liquid (the dispersion containing the inorganic particles of the monomer) can also promote the polymerization of the monomer (or oligomer). Further, heating may be carried out after the photopolymerization reaction after coating. The thermosetting reaction of the formed polymer may be additionally treated. The medium refractive index layer and the high refractive index layer are preferably polymers having a higher refractive index. Examples of polymers having a higher refractive index are exemplified by the reaction of polystyrene, styrene copolymer, polycarbonate, melamine resin, phenol resin, epoxy resin, and cyclic (alicyclic or aromatic) isocyanate with a polyhydric alcohol. The obtained polyurethane is obtained. Other polymers having a cyclic (aromatic, heterocyclic, alicyclic) group or a poly-182-201213864 having a halogen atom other than fluorine may also be used to increase the refractive index. In addition to the above components (metal oxide particles, polymer, dispersion medium, polymerization initiator, polymerization accelerator), each layer of the antireflection layer or the coating liquid thereof may be added with a polymerization inhibitor, a leveling agent, or a viscosity-increasing agent. Agent, anti-coloring agent, ultraviolet absorber, decane coupling agent, antistatic agent or adhesion-imparting agent 0 In the present invention, after the coating of the high-refractive-index layer and the low-refractive-index layer, Φ promotes the inclusion of metal alkoxide The composition is hydrolyzed or hardened, preferably irradiating the active energy ray. It is better to illuminate the active energy line each time each layer is applied. The active energy ray used in the present invention is not particularly limited as long as it is an energy source for activating the compound such as ultraviolet rays, electron beams, or gamma rays, but is preferably ultraviolet light or electron beam, and is particularly easy to handle and easy to obtain. In terms of energy, ultraviolet light is preferred. The light source for ultraviolet rays which polymerizes the ultraviolet ray reactive compound can be used as long as it is a light source that generates ultraviolet rays. For example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a φ ultra-high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. Further, an ArF excimer laser, a KrF excimer laser, an excimer lamp, or a synchrotron light can be used. The irradiation conditions vary depending on the lamps, but the amount of irradiation light is preferably 2 〇 mJ/cm 2 to 1 Torr, 〇〇〇 mJ/cm 2 , more preferably 100 mJ/cm 2 to 2,000 mJ/cm 2 , and most preferably 400 mJ/cm 2 〜 2,000mJ/cm2. When ultraviolet rays are used, the multilayer antireflection layer may be irradiated for each layer or may be irradiated after lamination. From the viewpoint of productivity, it is preferred to irradiate ultraviolet rays after laminating a plurality of layers. Also, an electron beam can be used. The electron beam can be cited as Cockcroft--183- 201213864

Walton型、Van de Graaff型、共振變壓型、絕緣蕊變壓器型、直線型' Dynamitron型、高頻型等各種電子束加速器釋出之具有50~ 1 000keV，較好l〇〇~3 00keV能量之電子束。 (抗反射層之膜厚）構成抗反射層之各折射率層之膜厚較好各爲lnm~2 00 nm之範圍，更好爲5nm~l 50nm，但較好依據各層之折射率選擇各適當之膜厚。 (抗反射層之反射率）本發明中使用之各抗反射層在45 Onm〜65 Onm之平均反射率較好爲1%以下，最好爲0.5 %以下。且，該範圍內之最低反射率最好爲0.0 0 ~ 0.3 %。抗反射層之折射率與膜厚可由分光反射率之測定計算而算出。另外，製作之低反射薄膜之反射光學特性可使用分光光度計，以5度正反射之條件測定反射率。該測定法中，使未塗佈抗反射層之側之基板面粗糙化後，使用黑色之噴霧進行光吸收處理，防止薄膜背面之光反射，而測定反射率。測定時，於波長5 50nm之透射率係使用分光光度計，以空氣作爲參考進行測定。 (偏光板）利用本發明之λ/4板之偏光板爲依序設置有該λ/4板、 -184- 201213864 偏光子及光學薄膜之偏光板’該光學薄膜之特徵滿足下述要件（1 )或（2 )(參照圖5 )。 (1 )以下述式（I )定義之面內滯相値R〇 ( 590 )在 20〜150nm之範圍內，且以下述式（Π)定義之厚度方向之滯相値Rt( 590)在70〜400nm之範圍內。 (2 )以下述式（I )定義之面內滯相値R〇 ( 590 )在 0〜2nm之範圍內，且以下述式（Π)定義之厚度方向之滞相値Rt( 590)在-15〜15nm之範圍內。式（I) : Ro ( 5 9 0 ) = ( nx-ny) xd ( nm ) 式（II) : Rt ( 5 90 ) ={ ( nx + ny) /2-nz} xd ( nm ) [上式中，R〇( 590)表示於測定波長590 nm之薄膜內之面內滯相値，Rt ( 5 90 )表示於測定波長5 90nm之薄膜內之厚度方向之滞相値。且，d表示光學薄膜之厚度（nm) ，nx表示於測定波長590nm之薄膜之面內最大折射率，亦稱爲滞相軸方向之折射率。1^表示於測定波長590nm之薄膜面內之與滯相軸垂直方向之折射率，112表示於測定波長 590nm之厚度方向之薄膜折射率。且，測定係在23°C、 55%RH環境下進行]。本發明之偏光板可使用使經摻雜碘、或雙色性染料之聚乙烯醇經延伸者作爲偏光子，以λ/4板/偏光子/光學薄膜之構成貼合而製造。本發明之λ/4板係貼合於辨識側。〈偏光板用光學薄膜〉本發明中使用之光學薄膜可較好地使用在前述λ/4板 -185- 201213864 中使用之纖維素乙酸酯、可塑劑、紫外線吸收劑、抗氧化劑、滯相調整劑、消光劑、抗劣化劑、剝離助劑、界面活性劑等。對於偏光子貼合於與貼合前述λ/4板之面相反側之面上之光學薄膜，較好貼合以下述式定義之滯相値R〇、Rt分別爲20~150nm、70〜400nm之光學薄膜，或0nm$R〇S2nm ，且-15nm$RtS15nm之光學薄膜之任一種。式（i) : Ro= ( nx-ny) xd 式（ii ) : Rt= ( ( nx + ny ) /2-nz ) xd 式中，nx、ny、nz爲在 23°C、55%RH、590nm下之折射率nx (於薄膜面內之最大折射率，亦稱爲滯相軸方向之折射率）、ny (薄膜之面內與滯相軸垂直之方向的折射率）、nz (厚度方向之薄膜折射率），（1爲薄膜之厚度（11111) 〇上述光學薄膜由於滯相値R〇、Rt分別在20〜1 50nm、 70~400nm之範圍，尤其作爲具有VA模式之液晶胞之VA型液晶顯示裝置之光學補償薄膜使用時，R〇値較好設爲 30〜lOOnm ’ Rt値在VA型液晶顯示裝置中使用兩片光學補償薄膜時較好爲70~250nm，在VA型液晶顯示裝置中使用一片光學薄膜時，Rt値較好爲15〇~40〇11111。至於上述光學薄膜，列舉爲例如藉由將具有負的單軸性之化合物的滯相液晶性化合物擔持於支撐體上之方法（例如’參照特開平7-3 2522 1號公報）、於支撐支體上擔持使具有正的光學異向性之向列型高分子液晶性化合物朝深 -186- 201213864 度方向改變液晶分子之預傾角之經混合配向者之方法（例如’參照特開平10-186356號公報）、於支撐體上使具有正的光學異向性之向列型液晶性化合物藉由兩層之構成使各層之配向方向成爲約9 0 °，而賦予擬似負的類似單軸性之光學特性之方法（例如，參照特開平8 - 1 5 6 8 1號公報）等之於支撐體上設置光學異向性層之光學薄膜，或代替過去之TAC薄膜’藉由使纖維素衍生物薄膜延伸而展現相位 ^ 差，使該等經皂化處理並層合PVA偏光子而同時具有向位差薄膜之功能之光學薄膜（例如，參照特開2003-270442 號公報）、於纖維素酯薄膜中添加滯相調整劑，獲得相位差薄膜之方法（例如，參照特開2000-275434號公報、 2003-344655號公報）等之光學補償薄膜，但並不限於該等。該等光學薄膜較好爲聚合物薄膜，且較好製造容易、爲光學均勻性、爲光學透明性。只要具有該等性質則可爲 φ 任一種’可列舉爲例如纖維素酯系薄膜、聚酯系薄膜、聚碳酸酯係薄膜、聚芳酸酯系薄膜、聚颯（亦包含聚醚颯）系薄膜、聚對本一甲酸乙一醋、聚蔡二甲酸乙二醋等聚酯薄膜，聚乙烯薄膜、聚丙烯薄膜、玻璃紙（cell〇phane ) 、纖維素二乙酸酯薄膜、纖維素乙酸酯丁酸酯薄膜、聚偏氯化乙燃薄膜、聚乙燃醇薄膜、乙燃乙嫌醇薄膜、間規聚苯乙烯系薄膜、聚碳酸酯薄膜、降冰片烯樹脂系薄膜、聚甲基戊燏薄膜、聚酸酮薄膜、聚醚酮醯亞胺薄膜、聚釀胺薄膜 '氟樹脂薄膜、尼龍薄膜、環稀烴聚合物薄膜、聚乙 -187- 201213864 烯基乙縮醛系樹脂薄膜、聚甲基丙烯酸甲酯薄膜或丙烯酸薄膜等，但並不限於該等。該等薄膜較好使用以溶液澆鑄法或熔融法製膜而成之薄膜。該等中以纖維素酯薄膜、聚碳酸酯薄膜、聚颯（包含聚醚楓）、環烯烴聚合物薄膜較佳，本發明中，尤其以纖維素酯薄膜、環烯烴聚合物薄膜就製造面、成本面、透明性、均勻性、接著性等方面而言較佳。例如，市售纖維素酯薄膜較好使用KONIKA MINOLTA KC8UX 、 KC4UX 、 KC5UX 、 KC8UCR3 、 KC8UCR4 ' KC8UCR5 ' KC8UY 、 KC4UY 、 KC12UR 、 KC16UR、 KC4UE、 KC8UE、 KC4FR-1 、 KC4FR-2 (以上爲 KONIKA MINOLTA (股）製造）等。最佳之光學薄膜爲以拉幅機裝置等朝薄膜寬度方向延伸而成之纖維素酯薄膜。又，本發明中使用之光學薄膜亦可使用作爲橫電場切換模式型（亦稱爲IPS模式型）液晶顯示裝置中使用之偏光板保護薄膜。該情況下，滯相値較好爲0nmSR〇S2rim，且-15nmSRtS15nni之光學薄膜。該光學薄膜較好包含纖維素酯，且含有重量平均分子量爲500以上、30000以下之丙烯酸聚合物’其中較好爲使分子內不具有芳香環及親水性基之乙烯性不飽和單體Xa，與分子內不具有芳香環但具有親水性基之乙烯性不飽和單體Xb共聚合所得之重量平均分子量爲5000以上、3 0000以下之聚合物X，更好含有使分子內不具有芳香環與親水性基之乙烯性不飽和單體Xa與分子內不具有芳香環但具有親水性基之乙烯性不飽和單體Xb •188- 201213864 共聚合而得之重量平均分子量爲5 000以上' 300 〇〇以下之聚合物X，與使不具有芳香環之乙烯性不飽和單體Ya聚合所得之重量平均分子量500以上、3000以下之聚合物Y。 (聚合物X、聚合物Y) 本發明中使用之聚合物X爲使分子內不具有芳香環與親水性基之乙烯性不飽和單體Xa，與分子內不具有芳香環但具有親水性基之乙烯性不飽和單體Xb共聚合而得之重量平均分子量5000以上、30000以下之聚合物。較好，Xa爲分子內不具有芳香環與親水性基之丙烯酸或甲基丙烯酸單體，Xb爲分子內不具有芳香環但具有親水性基之丙烯酸或甲基丙烯酸單體。本發明所使用之聚合物X係以下述一般式（X )表示〇 —般式（X) : - (X a) m - (Xb) η - (X c) p- 更好爲以下述一般式（Χ-1)表示之聚合物。 —般式（X-1) ·· -[CH2-C(-Rt)(-C02R2)]m-[CH2-C(-R3)(- C02R4OH)-]n-[Xc]p- (式中，Ι^、_Ι13表示Η或CH3，112表示碳數1~12之烷基、環烷基，R4表示- CH2-、-C2H4·或- C3H6-，Xc表示可聚合於Xa、Xb上之單體單位，m、η及p表示莫耳組成，其中 m关0、 n^〇 ' k/0 、 m + n + p=l〇〇)'。構成本發明中使用之聚合物X之單體單位之單體列舉如下述，但並不限於該等。 -189- 201213864 χ中，所謂親水性基意指具有羥（羥基）、環氧乙烷鏈之基。分子內不具有芳香環與親水性基之乙烯性不飽和單體 Xa可列舉爲例如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯（異-、正·）、丙烯酸丁酯（正-、異-、第二·、第三-)、丙烯酸戊酯（正-、異-、第二-)、丙烯酸己酯（正-、異-)、丙烯酸庚酯（正-、異-)、丙烯酸辛酯（正-、異-) 、丙烯酸壬酯（正-、異-)、丙烯酸十四烷酯（正-、異-)、丙烯酸（2-乙基己酯）、丙烯酸（ε-己內酯）、丙烯酸（2-羥基乙酯）、丙烯酸（2-乙氧基乙酯）等，或將上述丙烯酸酯換成甲基丙烯酸酯者。其中，以丙烯酸甲酯、丙烯酸乙酯、’甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯（異-、正-)較佳。分子內不具有芳香環但具有親水性基之乙烯性不飽和單體Xb，作爲具有羥（羥基）之單體單位，可列舉較佳者爲丙烯酸或甲基丙烯酸酯，例如丙烯酸（2-羥基乙酯）、丙烯酸（2-羥基丙酯）、丙烯酸（3-羥基丙酯）、丙烯酸 (4-羥基丁酯）、丙烯酸（2-羥基丁酯），或將該等丙烯酸換成甲基丙烯酸而成者，較好爲丙烯酸（2 -羥基乙酯）及甲基丙烯酸（2 -羥基乙酯）、丙烯酸（2 -羥基丙酯）、丙烯酸（3-羥基丙酯）。至於Xc只要是Xa、Xb以外者且可共聚合之乙烯性不飽和單體即無特別限制’但較好爲不具有芳香環者。Various electron beam accelerators such as Walton type, Van de Graaff type, resonant transformer type, insulated core transformer type, linear type 'Dynamitron type, high frequency type, etc. have 50~ 1 000 keV, preferably l〇〇~3 00 keV energy. The electron beam. (Thickness of Antireflection Layer) The film thickness of each of the refractive index layers constituting the antireflection layer is preferably in the range of 1 nm to 200 nm, more preferably 5 nm to 150 nm, but it is preferred to select each of the refractive indices of the respective layers. Appropriate film thickness. (Reflectance of Antireflection Layer) The average reflectance of each of the antireflection layers used in the present invention at 45 Onm to 65 Onm is preferably 1% or less, preferably 0.5% or less. Also, the minimum reflectance in this range is preferably from 0.00 to 0.3%. The refractive index and film thickness of the antireflection layer can be calculated from the measurement of the spectral reflectance. Further, the reflection optical characteristics of the produced low-reflection film can be measured by a spectrophotometer under the condition of a positive reflection of 5 degrees. In this measurement method, the surface of the substrate on the side where the antireflection layer was not applied was roughened, and then light absorption treatment was performed using a black spray to prevent light reflection on the back surface of the film, and the reflectance was measured. For the measurement, the transmittance at a wavelength of 50 nm was measured using a spectrophotometer using air as a reference. (Polarizing Plate) The polarizing plate of the λ/4 plate of the present invention is provided with the λ/4 plate, the -184-201213864 polarizer and the polarizing plate of the optical film. The characteristics of the optical film satisfy the following requirements (1) ) or (2) (refer to Figure 5). (1) The in-plane retardation 値R〇(590) defined by the following formula (I) is in the range of 20 to 150 nm, and the stagnation phase 値Rt(590) in the thickness direction defined by the following formula (Π) is 70 ~400nm range. (2) The in-plane retardation 値R〇(590) defined by the following formula (I) is in the range of 0 to 2 nm, and the stagnation phase 値Rt(590) in the thickness direction defined by the following formula (Π) is at - Within the range of 15 to 15 nm. Formula (I) : Ro ( 5 9 0 ) = ( nx-ny ) xd ( nm ) Formula (II) : Rt ( 5 90 ) ={ ( nx + ny) /2-nz} xd ( nm ) [Top In the mean, R 〇 ( 590 ) represents the in-plane stagnation 値 in the film at a wavelength of 590 nm, and Rt ( 5 90 ) represents the lag phase in the thickness direction in the film having a wavelength of 5 90 nm. Further, d represents the thickness (nm) of the optical film, and nx represents the maximum refractive index in the plane of the film having a measurement wavelength of 590 nm, which is also referred to as the refractive index in the direction of the slow axis. 1 is a refractive index perpendicular to the slow axis in the plane of the film having a wavelength of 590 nm, and 112 is a refractive index of the film in the thickness direction of the measurement wavelength of 590 nm. Further, the measurement was carried out in an environment of 23 ° C and 55% RH]. The polarizing plate of the present invention can be produced by laminating a polyvinyl alcohol doped with iodine or a dichroic dye as a polarizer and a λ/4 plate/polarizer/optical film. The λ/4 plate of the present invention is attached to the identification side. <Optical Film for Polarizing Plate> The optical film used in the present invention can preferably use cellulose acetate, a plasticizer, an ultraviolet absorber, an antioxidant, and a slow phase used in the aforementioned λ/4 plate-185-201213864. Adjusting agent, matting agent, anti-deterioration agent, peeling aid, surfactant, and the like. For the optical film in which the polarizer is bonded to the surface opposite to the surface on which the λ/4 plate is bonded, it is preferable to laminate the stagnation phases R 〇 and R t defined by the following formula to be 20 to 150 nm and 70 to 400 nm, respectively. The optical film, or any of 0 nm $ R 〇 S 2 nm, and -15 nm $ RtS 15 nm optical film. Formula (i): Ro= ( nx-ny) xd Formula (ii ) : Rt= ( ( nx + ny ) /2-nz ) xd where nx, ny, nz are at 23 ° C, 55% RH, The refractive index nx at 590 nm (the maximum refractive index in the plane of the film, also known as the refractive index in the direction of the slow axis), ny (the refractive index in the direction perpendicular to the slow axis of the film), nz (thickness direction) (the refractive index of the film), (1 is the thickness of the film (11111) 〇 The above optical film has a retardation 値R〇, Rt in the range of 20 to 150 nm, 70 to 400 nm, respectively, especially as a VA having a VA mode liquid crystal cell When the optical compensation film of the liquid crystal display device is used, R 〇値 is preferably set to 30 to 100 nm ' Rt 时 when using two optical compensation films in the VA liquid crystal display device, preferably 70 to 250 nm, in the VA type liquid crystal display When an optical film is used in the apparatus, the Rt 値 is preferably from 15 〇 to 40 〇 11111. The optical film is exemplified by, for example, a phasing liquid crystal compound having a compound having a negative uniaxiality supported on a support. The above method (for example, 'Ref. Japanese Patent Publication No. 7-3 2522 1), which is supported on the support support to have positive optics A method of mixing an omnidirectional nematic polymer liquid crystal compound to a pre-tilt angle of a liquid crystal molecule in a direction of -186-201213864 (for example, see Japanese Patent Application Laid-Open No. Hei 10-186356) on a support A method in which a nematic liquid crystal compound having positive optical anisotropy is formed by two layers such that the alignment direction of each layer becomes about 90°, and imparts a pseudo-like uniaxial property (for example, reference) Japanese Laid-Open Patent Publication No. Hei 8 - 1 5 6 8 1), or an optical film in which an optically anisotropic layer is provided on a support, or in place of the conventional TAC film, which exhibits a phase difference by extending the cellulose derivative film. An optical film which is saponified and laminated with a PVA polarizer and has a function as a difference film (for example, JP-A-2003-270442), and a phase retarder is added to the cellulose ester film to obtain The optical compensation film such as the method of the retardation film (for example, JP-A-2000-275434, JP-A-2003-344655) is not limited thereto. The optical film is preferably a polymer film. Further, it is preferably easy to manufacture, optically uniform, and optically transparent. Any of these properties may be φ, and examples thereof include a cellulose ester film, a polyester film, a polycarbonate film, and a poly Aromatic ester film, polyfluorene (also including polyether fluorene) film, polyester film such as polyparaben methyl vinegar, polyethylene diacetate, polyethylene film, polypropylene film, cellophane ), cellulose diacetate film, cellulose acetate butyrate film, poly(ethylene fluorite) film, polyoxyethylene alcohol film, ethylene ethoxide film, syndiotactic polystyrene film, poly Carbonate film, norbornene resin film, polymethylammonium film, polyacid ketone film, polyether ketoximine film, poly urethane film 'fluoro resin film, nylon film, cycloaliphatic polymer film, Polyethylene-187-201213864 Alkenyl acetal resin film, polymethyl methacrylate film or acrylic film, etc., but is not limited thereto. These films are preferably films formed by a solution casting method or a melt method. Among these, a cellulose ester film, a polycarbonate film, a polyfluorene (including a polyether maple), and a cycloolefin polymer film are preferable. In the present invention, a cellulose ester film or a cycloolefin polymer film is especially used. It is preferable in terms of cost, transparency, uniformity, and adhesion. For example, commercially available cellulose ester films are preferably KONIKA MINOLTA KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4 'KC8UCR5 'KC8UY, KC4UY, KC12UR, KC16UR, KC4UE, KC8UE, KC4FR-1, KC4FR-2 (above KONIKA MINOLTA ( Share) manufacturing) and so on. The most preferred optical film is a cellulose ester film which is stretched in the width direction of the film by a tenter device or the like. Further, the optical film used in the present invention can also be used as a polarizing plate protective film used in a horizontal electric field switching mode type (also referred to as IPS mode type) liquid crystal display device. In this case, the retardation enthalpy is preferably an optical film of 0 nm SR 〇 S2 rim and -15 nm SRtS 15 nni. The optical film preferably contains a cellulose ester and contains an acrylic polymer having a weight average molecular weight of 500 or more and 30,000 or less. Among them, an ethylenically unsaturated monomer Xa having no aromatic ring and hydrophilic group in the molecule is preferable. a polymer X having a weight average molecular weight of 5,000 or more and 30,000 or less obtained by copolymerization of an ethylenically unsaturated monomer Xb having no aromatic ring in the molecule but having a hydrophilic group, and more preferably contains no aromatic ring in the molecule. The hydrophilic group of the ethylenically unsaturated monomer Xa and the ethylenically unsaturated monomer having no aromatic ring in the molecule but having a hydrophilic group Xb •188- 201213864 have a weight average molecular weight of 5,000 or more '300 〇 The following polymer X is a polymer Y having a weight average molecular weight of 500 or more and 3,000 or less obtained by polymerizing an ethylenically unsaturated monomer Ya having no aromatic ring. (Polymer X, Polymer Y) The polymer X used in the present invention is an ethylenically unsaturated monomer Xa having no aromatic ring and hydrophilic group in the molecule, and has no aromatic ring in the molecule but has a hydrophilic group. The polymer obtained by copolymerizing the ethylenically unsaturated monomer Xb and having a weight average molecular weight of 5,000 or more and 30,000 or less. Preferably, Xa is an acrylic or methacrylic monomer having no aromatic ring and hydrophilic group in the molecule, and Xb is an acrylic or methacrylic monomer having no aromatic ring in the molecule but having a hydrophilic group. The polymer X used in the present invention has the general formula (X) represented by the following general formula (X): - (X a) m - (Xb) η - (X c) p - is more preferably in the following general formula (Χ-1) indicates the polymer. - General formula (X-1) ··-[CH2-C(-Rt)(-C02R2)]m-[CH2-C(-R3)(- C02R4OH)-]n-[Xc]p- (wherein , Ι^, _Ι13 represents Η or CH3, 112 represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, R4 represents -CH2-, -C2H4. or -C3H6-, and Xc represents a single polymerizable on Xa, Xb. The body unit, m, η, and p represent the moir composition, where m is off 0, n^〇' k/0 , m + n + p=l〇〇)'. The monomers constituting the monomer unit of the polymer X used in the present invention are listed below, but are not limited thereto. -189- 201213864 In the sputum, the hydrophilic group means a group having a hydroxyl group (hydroxyl group) or an ethylene oxide chain. The ethylenically unsaturated monomer Xa having no aromatic ring and hydrophilic group in the molecule may, for example, be methyl acrylate, ethyl acrylate, propyl acrylate (iso-, n-) or butyl acrylate (positive-, iso-) , second, third-), amyl acrylate (positive-, iso-, second-), hexyl acrylate (positive-, iso-), heptyl acrylate (positive-, iso-), octyl acrylate (positive-, iso-), decyl acrylate (positive-, iso-), tetradecyl acrylate (positive-, iso-), acrylic acid (2-ethylhexyl), acrylic acid (ε-caprolactone) Acrylic acid (2-hydroxyethyl ester), acrylic acid (2-ethoxyethyl ester), etc., or the above acrylate is replaced by methacrylate. Among them, methyl acrylate, ethyl acrylate, 'methyl methacrylate, ethyl methacrylate, and propyl methacrylate (iso-, plus-) are preferred. The ethylenically unsaturated monomer Xb having no aromatic ring in the molecule but having a hydrophilic group, and as the monomer unit having a hydroxyl group (hydroxyl group), preferred is acrylic acid or methacrylic acid ester such as acrylic acid (2-hydroxyl group). Ethyl ester), acrylic acid (2-hydroxypropyl ester), acrylic acid (3-hydroxypropyl ester), acrylic acid (4-hydroxybutyl ester), acrylic acid (2-hydroxybutyl ester), or replacing the acrylic acid with methacrylic acid The composition is preferably acrylic acid (2-hydroxyethyl ester) and methacrylic acid (2-hydroxyethyl ester), acrylic acid (2-hydroxypropyl ester), or acrylic acid (3-hydroxypropyl ester). As long as Xc is an ethylenically unsaturated monomer which is copolymerizable other than Xa and Xb, it is not particularly limited, but it is preferred that it does not have an aromatic ring.

Xa、Xb及Xc之莫耳組成以m: η爲99: 1〜65: 35之範 -190- 201213864 圍較佳，更好爲95: 5〜75·· 25之範圍，Xc之卩爲0~10。Xc 亦可爲複數單體單位。The molar composition of Xa, Xb and Xc is m: η is 99: 1~65: 35-190-201213864 is better, more preferably 95: 5~75·· 25 range, Xc is 0 ~10. Xc can also be a plurality of monomer units.

Xa之莫耳組成較多時與纖維素酯之相溶性優良但薄膜厚度方向之滯相値Rt變大。Xb之莫耳組成比較多時上述相溶性變差，但提高使Rt減低之效果。且’ Xb之莫耳組成比超過上述範圍時，在製膜時有出現霧濁之傾向，較好決定實現到該等最適化之Xa、Xb之莫耳組成比。 0 聚合物X之分子量爲重量平均分子量在5000以上、 3 0000以下，更好爲8000以上、25000以下。藉由使重量平均分子量爲5000以上，而使纖維素酯薄膜在高溫高濕下之尺寸變化較少，獲得作爲偏光板保護薄膜之捲曲較少等之優點故較佳。重量平均分子量在30000 以內時，與纖維素酯之相溶性更提高，且抑制在高溫高濕下之滲出進而抑制剛製膜後之霧濁發生。本發明中使用之聚合物X之重量平均分子量可以習知 φ 之分子量調節方法調整。該分子量調節方法列舉爲例如添加四氯化碳、月桂基硫醇、硫代乙醇酸辛酯等鏈轉移劑之方法等。且，以使聚合溫度通常在室溫至1 3 (TC，較好在 5 0°C至100°C進行，但可調整該溫度或聚合反應時間。重量平均分子量之測定方法可藉由以下方法進行。 (重量平均分子量之測定方法）重量平均分子量Mw係使用凝膠滲透層析儀測定。測定條件如下。 -191 - 201213864 溶劑：二氯甲烷管柱：使 Shodex K806、K805、K803G (昭和電工（股）製造）三根串聯使用）管柱溫度：25°C 試料濃度：0.1質量％偵測器：RI型號504 ( GL Science公司製造）泵：L6000 (日立製作所（股）製造）流量：1 · Oml/min 校正曲線：使用利用標準聚苯乙烯STK standard聚苯乙烯（TOSOH (股）製造）Mw=1000000〜500之13個樣品獲得之校正曲線。1 3個樣品以幾乎等間隔使用。本發明中使用之聚合物Y爲使不具有芳香環之乙烯性不飽和單體Ya聚合所得之重量平均分子量500以上、3000 以下之聚合物。於重量平均分子量500以上使聚合物之殘留單體減少而較佳。又，爲3〇〇〇以下時，由於可維持滯相値Rt降低性能故較佳。Ya較好爲不具有芳香環之丙烯酸或甲基丙烯酸單體。本發明中使用之聚合物Y係以下述一般式（Y)表示〇 —般式（Y ) ： -(Ya)k-(Yb)q- 更好爲以下述一般式（Y-1)表示之聚合物。 —般式（Y-l) : -[CH2-C(-R5)(-C02R6)]k-[Yb]q' (式中，Rs表示Η或CH3，r6表示碳數卜12之烷基或環烷基，Yb表示可與Ya共聚合之單體單位，k及q表示莫耳 -192- 201213864 組成，但 k#0、k + q=100 )。When the molar composition of Xa is large, the compatibility with the cellulose ester is excellent, but the retardation 値Rt of the film thickness direction becomes large. When the composition of the Mob of Xb is relatively large, the above-mentioned compatibility is deteriorated, but the effect of lowering Rt is improved. Further, when the molar composition ratio of Xb exceeds the above range, fogging tends to occur during film formation, and it is preferable to determine the molar composition ratio of Xa and Xb which are optimized. The molecular weight of the polymer X is 5,000 or more and 30,000 or less, more preferably 8,000 or more and 25,000 or less. When the weight average molecular weight is 5,000 or more, the dimensional change of the cellulose ester film under high temperature and high humidity is small, and the advantage of being less curling as a protective film for a polarizing plate is obtained. When the weight average molecular weight is within 30,000, the compatibility with the cellulose ester is further improved, and the bleeding under high temperature and high humidity is suppressed to suppress the occurrence of haze after the film formation. The weight average molecular weight of the polymer X used in the present invention can be adjusted by a conventional molecular weight adjustment method of φ. The molecular weight adjusting method is exemplified by a method of adding a chain transfer agent such as carbon tetrachloride, lauryl mercaptan or octyl thioglycolate. Further, the polymerization temperature is usually carried out at room temperature to 13 (TC, preferably 50 ° C to 100 ° C, but the temperature or polymerization time can be adjusted. The method for measuring the weight average molecular weight can be determined by the following method (Measurement method of weight average molecular weight) The weight average molecular weight Mw is measured using a gel permeation chromatograph. The measurement conditions are as follows: -191 - 201213864 Solvent: dichloromethane column: Shodex K806, K805, K803G (Showa Denko (manufacturing) (three) used in series) Column temperature: 25 °C Sample concentration: 0.1% by mass Detector: RI model 504 (manufactured by GL Science) Pump: L6000 (manufactured by Hitachi, Ltd.) Flow rate: 1 Oml/min calibration curve: A calibration curve obtained using 13 samples of standard polystyrene STK standard polystyrene (manufactured by TOSOH) Mw = 1000000 to 500 was used. 1 3 samples were used at almost equal intervals. The polymer Y used in the present invention is a polymer having a weight average molecular weight of 500 or more and 3,000 or less obtained by polymerizing the ethylenically unsaturated monomer Ya having no aromatic ring. It is preferred to reduce the residual monomer of the polymer by a weight average molecular weight of 500 or more. Further, when it is 3 Torr or less, it is preferable because the retardation 値Rt can be maintained. Ya is preferably an acrylic or methacrylic monomer having no aromatic ring. The polymer Y used in the present invention is represented by the following general formula (Y): (Y): -(Ya)k-(Yb)q- is more preferably represented by the following general formula (Y-1) polymer. - General formula (Yl): -[CH2-C(-R5)(-C02R6)]k-[Yb]q' (wherein Rs represents hydrazine or CH3, and r6 represents an alkyl group or a cycloalkane of carbon number 12 Base, Yb represents a monomer unit copolymerizable with Ya, and k and q represent a composition of Mo-192-201213864, but k#0, k + q=100).

Yb只要是可與Ya共聚合之乙烯性不飽和單體即無特別限制。Yb亦可爲複數。k + q= l〇〇，q較好爲〇〜30。構成使不具有芳香環之乙烯性不飽和單體聚合所得之聚合物Y之乙烯性不飽和單體Ya，作爲丙烯酸酯，列舉爲例如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯（異-、正-) 、丙烯酸丁酯（正-、異-、第二-、第三-)、丙烯酸戊酯 (正-、異-、第二-)、丙烯酸己酯（正-、異-)、丙烯酸庚酯（正-、異-)、丙烯酸辛酯（正-、異-)、丙烯酸壬酯（正-、異-)、丙烯酸十四烷酯（正-、異-)、丙烯酸環己酯、丙烯酸（2-乙基己酯）、丙烯酸（ε-己內酯）、丙烯酸（2-羥基乙酯）、丙烯酸（2-羥基丙酯）、丙烯酸 (3-羥基丙酯）、丙烯酸（4-羥基丁酯）、丙烯酸（2-羥基丁酯）：作爲甲基丙烯酸酯，係將上述丙烯酸酯換成甲基丙烯酸酯者；作爲不飽和酸，列舉爲例如丙烯酸、甲基丙烯酸 '馬來酸酐、巴豆酸 '衣康酸等。Yb is not particularly limited as long as it is an ethylenically unsaturated monomer copolymerizable with Ya. Yb can also be plural. k + q = l〇〇, q is preferably 〇~30. An ethylenically unsaturated monomer Ya constituting the polymer Y obtained by polymerizing an ethylenically unsaturated monomer having no aromatic ring, and examples of the acrylate include methyl acrylate, ethyl acrylate, and propyl acrylate (iso-, Ortho-), butyl acrylate (positive-, iso-, second-, third-), amyl acrylate (positive-, iso-, second-), hexyl acrylate (positive-, iso-), acrylic acid Heptyl ester (positive-, iso-), octyl acrylate (n-, iso-), decyl acrylate (n-, iso-), tetradecyl acrylate (n-, iso-), cyclohexyl acrylate, Acrylic (2-ethylhexyl), acrylic acid (ε-caprolactone), acrylic acid (2-hydroxyethyl ester), acrylic acid (2-hydroxypropyl ester), acrylic acid (3-hydroxypropyl ester), acrylic acid (4- Hydroxybutyl ester), acrylic acid (2-hydroxybutyl ester): as a methacrylate, the above acrylate is replaced by a methacrylate; as an unsaturated acid, for example, acrylic acid, methacrylic acid 'maleic anhydride , crotonic acid, itaconic acid, and the like.

Yb只要是可與Ya共聚合之乙烯性不飽和單體即無特別限制，但作爲乙烯酯較好爲例如乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、戊酸乙烯酯、特戊酸乙烯酯、己酸乙烯酯、癸酸乙烯酯、月桂酸乙烯酯、肉豆蔻酸乙烯酯、棕櫚酸乙烯酯、硬脂酸乙烯酯、環己烷羧酸乙烯酯、辛酸乙烯酯、甲基丙烯酸乙烯酯、巴豆酸乙烯酯、山梨酸乙烯酯、桂皮酸乙烯酯等。Yb亦可爲複數。合成聚合物X、Y時，藉由一般之聚合難以控制分子 -193- 201213864 量’僅可藉不使分子量過度增大之方法，宜使用可使分子量整齊之方法。該聚合方法爲使用如枯烯過氧化物或第三丁基過氧化物之過氧化物聚合起始劑之方法，比一般聚合使用更多量聚合起始劑之方法，除聚合起始劑以外亦使用硫醇化合物或四氯化碳等鏈轉移劑之方法，除聚合起始劑以外亦使用如苯醌或二硝基苯之聚合終止劑之方法，以及特開2000-128911號或特開2000-344823號之具有一個硫醇基與二級羥（羥基）之化合物，或倂用該化合物與有機金屬化合物且使用聚合觸媒之塊狀聚合之方法等，任一種均可較好地使用於本發明之羥（羥基），但聚合物Y較好使用分子中具有硫醇基與二級羥（羥基）之化合物作爲鏈轉移劑之聚合方法。該情況下，聚合物Y之末端成爲起因於聚合觸媒及鏈轉移劑之羥（羥基）、硫醚。藉由該末端基，可調整Y與纖維素酯之相溶性。聚合物X及Y之羥（羥基）價較好爲30〜150[mgKOH/g] (羥（羥基）價之測定方法）該測定係依據JIS K 0070 ( 1 992 )。該羥（羥基）價定義爲使試料lg乙醯基化時，使與羥（羥基）鍵結之乙酸中和所需之氫氧化鉀之mg數。具體而言，係將試料Xg ( 約1 g )精秤於燒瓶中，於其中精確添加乙醯化試藥（於乙酸酐2 0ml中添加吡啶成爲400ml者）20ml。於燒瓶口上裝置空氣冷卻管，以95〜1 00°C之甘油浴加熱。1小時30分鐘 -194- 201213864 後，經冷卻，自空氣冷卻管添加純水1 ml，使乙酸酐分解成乙酸。接著使用電位差滴定裝置，以〇.5mol/L氫氧化鉀乙醇溶液進行滴定，以所得滴定曲線之彎曲點作爲終點。另外作爲空白試驗，於未放入試料下進行滴定，求得滴定曲線之彎曲點。以下述式算出羥（羥基）價。羥（羥基）價={(B-C)xfx28.05/X}+D (式中，B爲空白試驗中使用之0.5mol/L之氫氧化鉀乙醇溶液之量（ml) ，C爲滴定中所用之〇.5mol/L之氫氧化鉀乙醇溶液之量（ml) ，f爲〇.5mol/L之氫氧化鉀乙醇溶液之係數，D爲酸價’又28.05表示氫氧化鉀之lmol量之 56.11之 1/2 )。上述聚合物X與聚合物Y與纖維素酯之相溶性均優異，不蒸發亦不揮發而生產性優異，作爲偏光板用保護薄膜之保留性良好，透濕度小，且尺寸安定性優異。聚合物X與聚合物γ在纖維素酯薄膜中之含量較好爲滿足下述式（i)、式（Π)之範圍。以聚合物X之含量作爲Xg (質量％ =聚合物X之質量/纖維素酯之質量χΐ00)、以聚合物Υ之含量作爲Yg (質量％ )時，式（i) 5 彡 Xg + YgS35 (質量％) 式（ii) 0.05 ^Yg/ ( Xg + Yg ) ^0.4 式（i)之較佳範圍爲10〜25質量％。聚合物X與聚合物Y若總量爲5質量％以上，則對滯相値Rt之降低具有充分作用。且，若總量爲3 5質量。/。以下’ 則與聚乙烯醇系之偏光子之接著性良好。 -195- 201213864 聚合物χ與聚合物γ可作爲構成摻雜液之材料直接添加、溶解，或者可預先溶解於溶解有纖維素酯之有機溶齊[| 中之後添加於摻雜液中。本發明之偏光板中較好使用之偏光子，列舉爲聚乙稀醇系偏光薄膜，該等有對聚乙烯醇系薄膜以碘染色而成者及以雙色性染料染色而成者。至於聚乙烯醇系薄膜較好使用以乙烯改質之改質聚乙烯醇系薄膜。偏光子係使用使聚乙烯醇水溶液予以製膜，使其經單軸延伸並染色，或染色後經單軸延伸後，較好以硼化合物進行耐久性處理者。延伸係於薄膜製膜方向進行單軸延伸，或較好與前述λ/4板同樣對於薄膜製膜方向成45°方向延伸。偏光子之膜厚爲5〜40μιη，較好爲5〜30μηι，最好爲 5~20μιη。於該偏光子之面上貼合本發明之λ/4板、及偏光子保護薄膜Β之單面而形成偏光板。偏光板可藉一般方法製作。經鹼皂化處理之本發明之 λ/4板較好於使聚乙烯醇系薄膜在碘溶液中浸漬延伸而製作之偏光子之至少一面上，使用完全皂化型聚乙烯醇水溶液予以貼合。另一面上較好貼合前述偏光板保護膜Β。偏光板可進而於該偏光板之一面上貼合保護膜，於相反面貼合隔離膜而構成。保護膜及隔離膜在偏光板出貨時、製品檢査時等中用於保護偏光板。作板光偏之明發本合貼上面之側識 >辨置之裝胞示晶顯液晶於液由 <藉 -196- 201213864 成液晶顯示裝置，即使通過偏光太陽眼鏡等具有偏光作用之光學構件觀察時，仍可降低顯示圖像依據偏光軸方向而難以看見之情況，可製作相對於使用環境耐久性更高之本發明之液晶顯示裝置。本發明之偏光板較好以反射型、透射型、半透射型LCD或TN型、STN型、OCB型、HAN型、 VA型（PVA型、MVA型）、IPS型等各種驅動方式之LCD 使用。 (液晶胞之驅動模式）液晶胞之驅動模式只要可獲得本發明效果即可採用任意適當之驅動模式。驅動模式之具體例列舉爲超扭轉向列型（STN )模式、扭轉向列型（TN )模式、電控制雙折射 (ECB :電控制雙折射）模式、共平面切換（in Piane Switching ) (IPS)模式、垂直配向（VA)模式、彎曲向列（OCB :光學對準雙折射）模式及混合配向（HAN :混 0 合對準向列）模式。較好爲ECB模式。本發明中，尤其可獲得對比性與視角特性之均衡優異之立體影像顯示裝置。又，ECB模式係利用液晶之雙折射性者，係藉由對液晶分子施加電壓而改變滯相，藉由與相位差薄膜之組合而控制透射不透射者。 (立體影像顯示裝置）本發明之立體影像顯示裝置爲由顯示裝置與液晶快門型眼鏡所組成之立體影像顯示裝置，於該顯示裝置，係自 -197- 201213864 辨識側依序設置λ/4板及偏光子，該液晶快門型眼鏡係自辨識側依序設置偏光子、液晶胞及λ/4板，其特徵係所有光學補償層之厚度方向相位差Rt之合計(其中η表示整數）與液晶胞之厚度方向之向位差Rtc滿足前述式（1 ) 〇本發明中，藉由上述之樣態、構成，可降低立體（3 D )影相觀賞時自斜方向觀看顯示裝置時之串訊或亮度降低及色調變化，可確保對使用環境優異之辨識性，可成爲對使用環境耐久性更高之立體影像顯示裝置。 [實施例] 以下針對本發明列舉實施例加以說明，但本發明並不受限於該等。實施例1 <λ/4板1之製作> 〈微粒子分散液1〉微粒子（Aerosil R972V日本Aerosil (股）製造） 1 1質量份乙醇 89質量份以溶解機携泮混合以上成分5〇分鐘後’以均質機進行分散。〈微粒子添加液1〉 -198- 201213864 邊對加入二氯甲烷之溶解槽充分攪拌，邊緩慢添加微粒子分散液1。接著’使二次粒子之粒徑成爲特定大小之方式’以攪動機進行分散。使該等經日本精線（股）製造之FINEMET NF過濾，調製微粒子添加液卜二氯甲烷 99質量份微粒子分散液1 5質量份調製下述組成之主摻雜液。首先將二氯甲烷及乙醇添加於加壓溶解槽中。邊攪拌邊將纖維素乙酸酯投入裝進有溶劑之加壓溶解槽中。使之加熱，邊攪拌邊完全溶解。使用安積濾紙（股）製造之安積濾紙No. 2 44過濾該溶液，調製主摻雜液。〈主摻雜液之組成〉二氯甲烷 340質量份乙醇 . 64質量份Yb is not particularly limited as long as it is an ethylenically unsaturated monomer copolymerizable with Ya, but as the vinyl ester, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, pivalic acid is preferable. Vinyl ester, vinyl hexanoate, vinyl decanoate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, vinyl octanoate, methacrylic acid Vinyl ester, vinyl crotonate, vinyl sorbate, vinyl cinnamate, and the like. Yb can also be plural. In the case of synthesizing the polymers X and Y, it is difficult to control the molecular amount by the usual polymerization - 193 - 201213864. The method of arranging the molecular weight should be used only by a method which does not excessively increase the molecular weight. The polymerization method is a method using a peroxide polymerization initiator such as cumene peroxide or a third butyl peroxide, and a method of using a larger amount of a polymerization initiator than usual polymerization, except for the polymerization initiator A method of using a chain transfer agent such as a thiol compound or carbon tetrachloride, a polymerization terminator such as phenylhydrazine or dinitrobenzene, and a method of using a polymerization terminator such as phenylhydrazine or dinitrobenzene, and the special opening of 2000-128911 or special opening A compound having a thiol group and a secondary hydroxyl group (hydroxyl group) of 2000-344823, or a method of using the compound and an organometallic compound and using a bulk polymerization of a polymerization catalyst, etc., can be preferably used. In the hydroxy group (hydroxyl group) of the present invention, the polymer Y preferably uses a polymerization method of a compound having a thiol group and a secondary hydroxy group (hydroxyl group) in the molecule as a chain transfer agent. In this case, the terminal of the polymer Y is a hydroxyl group (hydroxyl group) or a thioether which is caused by a polymerization catalyst and a chain transfer agent. By virtue of the terminal group, the compatibility of Y with the cellulose ester can be adjusted. The hydroxy (hydroxyl) valence of the polymers X and Y is preferably from 30 to 150 [mgKOH/g] (Method for measuring hydroxy (hydroxyl) valence) The measurement is based on JIS K 0070 (1992). The hydroxy (hydroxyl) valence is defined as the number of mg of potassium hydroxide required to neutralize the hydroxy (hydroxy)-bonded acetic acid when the sample is lg-acetylated. Specifically, a sample Xg (about 1 g) was weighed into a flask, and 20 ml of an acetamidine reagent (addition of pyridine to 400 ml in 20 ml of acetic anhydride) was precisely added thereto. An air cooling tube was placed on the mouth of the flask and heated in a glycerin bath at 95 to 100 °C. After 1 hour 30 minutes -194-201213864, 1 ml of pure water was added from the air cooling tube after cooling to decompose acetic anhydride into acetic acid. Next, titration was carried out using a potentiometric titration apparatus in a solution of mol.5 mol/L of potassium hydroxide ethanol, and the bending point of the obtained titration curve was used as an end point. Further, as a blank test, titration was carried out without placing a sample, and the bending point of the titration curve was obtained. The hydroxy (hydroxy) valence was calculated by the following formula. Hydroxy (hydroxy) valence = {(BC) xfx28.05/X} + D (where B is the amount of 0.5 mol/L potassium hydroxide ethanol solution used in the blank test (ml), C is used in the titration Then, the amount of 5 mol / L potassium hydroxide ethanol solution (ml), f is the coefficient of 氢氧化. 5mol / L potassium hydroxide ethanol solution, D is the acid value 'and 28.05 means the amount of potassium hydroxide is 56.11 1/2). The polymer X is excellent in compatibility with the polymer Y and the cellulose ester, and is excellent in productivity without evaporating or volatilizing, and has good retention properties as a protective film for a polarizing plate, low moisture permeability, and excellent dimensional stability. The content of the polymer X and the polymer γ in the cellulose ester film is preferably in the range satisfying the following formula (i) and formula (Π). When the content of the polymer X is Xg (% by mass = mass of the polymer X / mass of the cellulose ester χΐ 00), and the content of the polymer yt is Yg (% by mass), the formula (i) 5 彡 Xg + YgS35 ( Mass%) Formula (ii) 0.05 ^Yg/ ( Xg + Yg ) ^0.4 The preferred range of the formula (i) is 10 to 25% by mass. When the total amount of the polymer X and the polymer Y is 5% by mass or more, the effect of the retardation 値Rt is sufficiently reduced. And, if the total amount is 35 mass. /. The following is good in adhesion to a polyvinyl alcohol-based polarizer. -195- 201213864 The polymer ruthenium and the polymer γ may be directly added or dissolved as a material constituting the doping liquid, or may be previously dissolved in the doping liquid after being dissolved in the organic solvent in which the cellulose ester is dissolved. The polarizer which is preferably used in the polarizing plate of the present invention is exemplified by a polyethylene-based polarizing film, which is obtained by dyeing a polyvinyl alcohol-based film with iodine and dyeing with a dichroic dye. As the polyvinyl alcohol-based film, a modified polyvinyl alcohol-based film which is modified with ethylene is preferred. The polarizer is formed by forming a film of a polyvinyl alcohol aqueous solution to be uniaxially stretched and dyed, or by uniaxially stretching after dyeing, preferably after durability treatment with a boron compound. The stretching is uniaxially stretched in the film forming direction, or preferably in the direction of 45° in the film forming direction as in the case of the above λ/4 plate. The film thickness of the polarizer is 5 to 40 μm, preferably 5 to 30 μm, preferably 5 to 20 μm. A polarizing plate is formed by laminating one side of the λ/4 plate and the polarizing protective film 本 of the present invention on the surface of the polarizer. The polarizing plate can be produced by a general method. The λ/4 plate of the present invention which has been subjected to alkali saponification is preferably laminated on at least one side of a polarizer prepared by immersing and stretching a polyvinyl alcohol-based film in an iodine solution, using a completely saponified polyvinyl alcohol aqueous solution. On the other hand, the polarizing plate protective film 较好 is preferably attached. The polarizing plate may be further formed by laminating a protective film on one surface of the polarizing plate and bonding the separator on the opposite side. The protective film and the separator are used to protect the polarizing plate when the polarizing plate is shipped, when the product is inspected, and the like. The light-emitting surface of the plate is affixed to the side of the above-mentioned side. The liquid crystal display device is formed by the liquid crystal display device, which has a polarizing effect even by polarized sunglasses. When the optical member is observed, the display image can be made difficult to see depending on the direction of the polarization axis, and the liquid crystal display device of the present invention having higher durability with respect to the use environment can be produced. The polarizing plate of the present invention is preferably used in a reflective, transmissive, semi-transmissive LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type, and the like. . (Drive Mode of Liquid Crystal Cell) The driving mode of the liquid crystal cell can adopt any appropriate driving mode as long as the effect of the present invention can be obtained. Specific examples of the driving mode are listed as a super twisted nematic (STN) mode, a twisted nematic (TN) mode, an electrically controlled birefringence (ECB: electrically controlled birefringence) mode, and an in-plane switching (in Piane Switching) (IPS). Mode, Vertical Alignment (VA) mode, Curved Nematic (OCB: Optical Alignment Birefringence) mode, and Mixed Alignment (HAN: Mixed 0 Alignment Nematic) mode. It is preferably ECB mode. In the present invention, in particular, a stereoscopic image display device excellent in balance between contrast and viewing angle characteristics can be obtained. Further, in the ECB mode, the birefringence of the liquid crystal is used to change the stagnation phase by applying a voltage to the liquid crystal molecules, and the transmission non-transmission is controlled by the combination with the retardation film. (Stereoscopic image display device) The stereoscopic image display device of the present invention is a stereoscopic image display device composed of a display device and liquid crystal shutter type glasses, and the display device is sequentially provided with a λ/4 plate from the identification side of -197-201213864 And a polarizer, the liquid crystal shutter type glasses are provided with a polarizer, a liquid crystal cell and a λ/4 plate in sequence from the identification side, and are characterized by a total of thickness direction phase differences Rt of all optical compensation layers (where η represents an integer) and liquid crystal The lateral difference Rtc of the cell thickness satisfies the above formula (1). In the present invention, the above-described configuration and configuration can reduce the crosstalk when viewing the display device from the oblique direction during stereoscopic (3D) viewing. In addition, the brightness is reduced and the color tone is changed, and the visibility of the use environment is ensured, and the stereoscopic image display device having higher durability to the use environment can be obtained. [Examples] Hereinafter, examples of the invention will be described, but the invention is not limited thereto. Example 1 <Production of λ/4 plate 1> <Microparticle dispersion 1> Microparticles (manufactured by Aerosil R972V Japan Aerosil Co., Ltd.) 1 part by mass of ethanol 89 parts by mass, and the above components were mixed for 5 minutes in a dissolving machine. After 'distribution with a homogenizer. <Microparticle-added liquid 1> -198- 201213864 The microparticle dispersion 1 was slowly added while stirring the dissolution tank to which methylene chloride was added. Then, 'the size of the secondary particles is made to have a specific size' is dispersed by an agitator. The FINEMET NF manufactured by Nippon Seisakusho Co., Ltd. was filtered to prepare a fine particle-added liquid, methylene chloride, 99 parts by mass, and a fine particle dispersion, 15 parts by mass, to prepare a main dope having the following composition. First, dichloromethane and ethanol were added to the pressure dissolution tank. The cellulose acetate was charged into a pressurized dissolution tank having a solvent while stirring. Heat it and dissolve completely with stirring. The solution was filtered using a filter paper No. 2 44 made of a filter paper (strand) to prepare a main dope. <Composition of main doping liquid> Dichloromethane 340 parts by mass Ethanol. 64 parts by mass

乙醯基取代度2.1之纖維素乙酸酯 1〇〇質量份糖酯化合物1-22 10.0質量份聚酯（a ) 2.5質量份紫外線吸收劑（Tinuvin 928 (日本BASF (股）製造） 2.3質量份微粒子添加液1 1質量份將以上成分倒入密閉容器中，邊攪拌邊溶解而調製摻雜液。接著，使用環狀輸送帶澆鑄裝置，將摻雜液均勻的澆鑄在溫度33 t、2000mm寬之不銹鋼輸送帶支撐體上。不 -199- 201213864 銹鋼輸送帶之溫度控制在3 (TC。在不銹鋼輸送帶支撐體上，蒸發溶劑直至澆鑄（cast )薄膜中殘留之溶劑量成爲75%爲止，接著以剝離張力 13 0N/m，自不銹鋼輸送帶支撐體上剝離。隨後，使剝離部分之張力，於使切斷之部分（輥）與隨後施加之輸送張力之部分（輥）有速度差之狀態，在 170°C下邊以與澆鑄方向平行之方向延伸1.6倍邊進行輸送。接著在設定成130 °C之乾燥區中輸送30分鐘進行乾燥，製作寬度1 5 00mm，且於端部具有寬度lcm、高度8μιη之滾花之膜厚40μηι之λ/4板1。 λ/4板 1 之 Θ爲 0°，Ro爲 138nm，Rt爲 80nm ’ Ro ( 550). Ro ( 450 )爲 4nm » 又，製作各種λ/4板時使用之聚酯（a)之合成方法如下。 <聚酯（a)之合成> 在氮氣氛圍下，混合2,6-萘二羧酸二甲酯19.2g、1，2_ 丙二醇14.9g、鈦酸四異丙酯2 Omg，邊餾除生成之甲醇邊在165t下進行攪拌1小時。接著在185°C下進行攪拌1小時後，升溫至195°C且進行攪拌18小時。接著，降溫至170°c ，藉由減壓餾除未反應物之1，2-丙二醇，獲得聚酯多元醇 (a) 〇酸價：〇·2 數平均分子量：1020 -200- 201213864 分散度：1.6 分子量300〜1 800之成分含有率：48% 羥（羥基）價：11 〇羥基含量：100% 由1 H-NMR，確認於末端無甲酯殘基。 (硬質塗層之塗設）接著，於上述λ/4板1之一面上設置下述硬質塗層，製作 λ / 4 板 1 h c。《硬質塗層之塗佈》 . 以塗佈寬度1.4m模嘴塗佈下述硬質塗層塗佈液，# 8〇°C乾燥後，以高壓水銀燈照射120mJ/cm2之紫外線使硬化後之膜厚成爲6μηι之方式設置透明硬質塗層。 (硬質塗層用塗佈液）丙酮 45質量份乙酸乙酯 45質量份丙二醇單甲基醚 1〇質量份季戊四醇三丙烯酸酯 3 〇質量份季戊四醇四丙烯酸酯 45質量份Cellulose acetate with a degree of substitution of 2.1. 1 part by mass of a sugar ester compound 1-22 10.0 parts by mass of a polyester (a) 2.5 parts by mass of a UV absorber (Tinuvin 928 (manufactured by BASF, Japan) 2.3 Quality 1 part by mass of the microparticle-added liquid, the above components were poured into a sealed container, and dissolved while stirring to prepare a dope. Then, using a ring-shaped conveyor casting apparatus, the doping liquid was uniformly cast at a temperature of 33 t, 2000 mm. Wide stainless steel conveyor belt support. Not-199- 201213864 The temperature of the stainless steel conveyor belt is controlled at 3 (TC. On the stainless steel conveyor belt support, the solvent is evaporated until the amount of solvent remaining in the cast film becomes 75%. Then, it is peeled off from the stainless steel conveyor belt support body at a peeling tension of 13 0 N/m. Subsequently, the tension of the peeling portion is made to have a speed at which the cut portion (roller) and the portion of the transport tension (roller) to be applied subsequently have a speed. In the poor state, it was conveyed at 170 ° C in a direction parallel to the casting direction by 1.6 times, and then dried in a drying zone set at 130 ° C for 30 minutes to make a width of 1 500 mm. And at the end portion having a width of 1 cm and a height of 8 μm, the thickness of the knurling film is 40 μm of λ/4 plate 1. The λ/4 plate 1 has a Θ of 0°, Ro is 138 nm, and Rt is 80 nm ' Ro (550). Ro ( 450) 4 nm » Further, the synthesis method of the polyester (a) used in the production of various λ/4 plates is as follows. <Synthesis of Polyester (a)> 2,6-naphthalenedicarboxylate is mixed under a nitrogen atmosphere. 19.2 g of dimethyl acid, 14.9 g of 1,2-propylene glycol, and 2 mg of tetraisopropyl titanate were stirred at 165 t for 1 hour while distilling off the formed methanol, followed by stirring at 185 ° C for 1 hour. The temperature was raised to 195 ° C and stirred for 18 hours. Then, the temperature was lowered to 170 ° C, and the unreacted 1,2-propanediol was distilled off under reduced pressure to obtain a polyester polyol (a) phthalic acid: 〇·2 Number average molecular weight: 1020 -200- 201213864 Dispersity: 1.6 Molecular weight 300~1 800 Component content: 48% Hydroxy (hydroxyl) Price: 11 Hydrazine hydroxyl content: 100% Confirmed by 1 H-NMR, no methyl ester at the end Residue. (Coating of Hard Coating) Next, the following hard coating layer is provided on one surface of the above λ/4 plate 1 to prepare a λ / 4 plate 1 hc. The following hard coating liquid was applied to a die having a coating width of 1.4 m, dried at # 8 ° ° C, and then irradiated with a high-pressure mercury lamp to irradiate ultraviolet rays of 120 mJ/cm 2 so that the film thickness after hardening became 6 μm. Hard coating (coating liquid for hard coating) acetone 45 parts by mass ethyl acetate 45 parts by mass propylene glycol monomethyl ether 1 part by mass pentaerythritol triacrylate 3 parts by mass pentaerythritol tetraacrylate 45 parts by mass

胺基甲酸酯丙烯酸酯（商品名U-4H Α新中村化學工業公司製造） 25質量份 1-羥基-環己基-苯基-酮（Irgacure 184，日本BASF& -201 - 201213864 司製造） 5質量份 2 -甲基- l- [4_(甲硫基）苯基]-2 -嗎啉基丙-i_酮（ Irgacure 907，日本BASF公司製造） 3質量份 BYK-331 (矽氧界面活性劑，日本BYK (股）製造）〇·5質量份於製作之硬質塗層上進而設置下述抗反射層，獲得 λ/4板 1。《抗反射層之塗佈》 (中折射率層之塗佈）於硬質塗層上模嘴塗佈下述之中折射率層塗佈液，在 80°C乾燥後，以高壓水銀燈照射120mJ/cm2之紫外線，以使硬化後之膜厚成爲1 1 〇nm之方式設置中折射率層。折射率爲1.60 » 〈中折射率層塗佈液〉〈粒子分散液A之調製〉邊攪拌異丙醇12. Okg邊緩慢添加於甲醇分散銻複合氧化物膠體（固體成分60%，日產化學工業（股）製造之銻酸鋅溶膠，商品名：CELNAX CX-Z61 0M-F2 ) 6.0kg，調製粒子分散液A。 PGME (丙二醇單甲基醚） 4 0質量份異丙醇 25質量份甲基乙基酮 25質量份 -202- 201213864 季戊四醇三丙餘酸醋 0.9質量份季戊四醇四丙烧酸醋 1.0質量份胺基甲酸酯丙烯酸酯（商品名：U-4H A新中村化學工業公司製造） 0.6質量份粒子分散液A 2 0質量份 1-羥基-環己基-苯基-酮（Irgacure 184，日本BASF公司製造） 0.4質量份 φ 2 -甲基-l-[4-(甲硫基）苯基]-2-嗎啉基丙-1-酮（Urethane acrylate (trade name U-4H, manufactured by Shin-Nakamura Chemical Co., Ltd.) 25 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by BASF & -201 - 201213864, Japan) 5 Parts by mass 2-methyl-l-[4-(methylthio)phenyl]-2-morpholinylpropan-i-one (Irgacure 907, manufactured by BASF, Japan) 3 parts by mass of BYK-331 (oxygen interface activity) Agent, manufactured by BYK Co., Ltd., Japan. 5 parts by mass of the hard coating layer produced was further provided with the following antireflection layer to obtain λ/4 plate 1. <<Coating of Antireflection Layer>> (Application of Medium Refractive Index Layer) The following refractive index layer coating liquid was applied onto a hard coat layer, and dried at 80 ° C, and then irradiated with a high pressure mercury lamp at 120 mJ/ The ultraviolet ray of cm2 is provided with a medium refractive index layer so that the film thickness after hardening becomes 1 1 〇 nm. The refractive index is 1.60 » <Medium refractive index layer coating liquid> <Preparation of particle dispersion A> While stirring isopropanol 12. Okg is slowly added to the methanol dispersion 锑 composite oxide colloid (solid content 60%, Nissan Chemical Industry) Zinc silicate sol manufactured by the company (trade name: CELNAX CX-Z61 0M-F2) 6.0 kg, and a particle dispersion A was prepared. PGME (propylene glycol monomethyl ether) 40 parts by mass isopropanol 25 parts by mass methyl ethyl ketone 25 parts by mass - 202 - 201213864 pentaerythritol tripropyl vinegar 0.9 parts by mass pentaerythritol tetrapropyl sulphuric acid vinegar 1.0 parts by mass of amine group Formate acrylate (trade name: U-4H A, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.6 parts by mass of the particle dispersion A 2 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by BASF Corporation, Japan) 0.4 parts by mass of φ 2 -methyl-l-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one (

Irgacure907，日本BASF公司製造） 0.2質量份 10%FZ-2 2 07 >丙二醇單甲基醚溶液（日本Unica公司製造） 0.4質量份 (低折射率層之塗佈）於上述中折射率層上，模嘴塗佈下述之低折射率層塗佈液，在80°C乾燥後，以高壓水銀燈照射120mJ/cm2之紫 % 外線，以使膜厚成爲92nm之方式設置低折射率層，製作抗反射層。折射率爲1.38。 (低折射率層塗佈液）〈四乙氧基矽烷水解物A之調製〉混合四乙氧基矽烷23 0g (商品名：KBE04，信越化學工業公司製造）與乙醇44〇g，於其中添加2%乙酸水溶液 l2〇g後，於室溫（25°C )攪拌26小時，調製四乙氧基矽烷水解物A。 -203- 201213864 43 0質量份 430質量份 120質量份丙二醇單甲基醚異丙醇Irgacure 907, manufactured by BASF Corporation, Japan) 0.2 parts by mass of 10% FZ-2 2 07 > propylene glycol monomethyl ether solution (manufactured by Unica, Japan) 0.4 parts by mass (coating of low refractive index layer) on the above-mentioned medium refractive index layer The nozzle was coated with the low refractive index layer coating liquid described below, and after drying at 80 ° C, the ultraviolet % outer line of 120 mJ/cm 2 was irradiated with a high pressure mercury lamp, and a low refractive index layer was formed so that the film thickness became 92 nm. Anti-reflective layer. The refractive index is 1.38. (Low-refractive-index layer coating liquid) <Preparation of tetraethoxy decane hydrolysate A> Mixed tetraethoxy decane 23 0 g (trade name: KBE04, manufactured by Shin-Etsu Chemical Co., Ltd.) and 44 g of ethanol were added thereto. After 2% of aqueous acetic acid solution was stirred at room temperature (25 ° C) for 26 hours, tetraethoxydecan hydrolyzate A was prepared. -203- 201213864 43 0 parts by mass 430 parts by mass 120 parts by weight Propylene glycol monomethyl ether Isopropanol

四乙氧基矽烷水解物A γ -甲基丙烯醯氧基丙基三甲氧基矽烷（商品名： ΚΒΜ503，信越化學工業公司製造） 3.0質量份異丙醇分散之中空二氧化矽溶膠（固體成分2 0%，觸媒化成工業公司製造之二氧化矽溶膠，商品名：ELCOM V-8209 ) 40質量份乙基乙醯基乙酸鋁·二異丙酸酯（川硏精密化學公司製造） 3.0質量份 10%FZ-2 207 >丙二醇單甲基醚溶液（日本Unica公司製造） 3.0質量份 (光學薄膜201之製作）〈微粒子分散液1〉微粒子（Aerosil R972V日本Aerosil (股）製造） 1 1質量份乙醇 89質量份以溶解機攪拌混合以上成分50分鐘後，以均質機進行分散。〈微粒子添加液1〉邊對加入二氯甲烷之溶解槽充分攪拌，邊緩慢添加微粒子分散液1。接著，使二次粒子之粒徑成爲特定大小之 -204- 201213864 方式，以攪動機進行分散。使其經日本精線（股）製造之 FINEMET NF過濾，調製微粒子添加液1。二氯甲烷 99質量份微粒子分散液1 5質量份調製下列組成之主摻雜液。首先將二氯甲烷及乙醇添加於加壓溶解槽中，邊攪拌邊將纖維素乙酸酯倒入裝入有溶劑之加壓溶解槽中。使之加熱，邊攪拌邊完全溶解。使用安積濾紙（股）製造之安積濾紙No. 2 44使之過濾，而調製主摻雜液。〈主摻雜液之組成〉二氯甲烷 340質量份乙醇 64質量份乙醯基取代度2.4之纖維素乙酸酯 1〇〇質量份糖酯化合物1-23 10.0質量份Tetraethoxy decane hydrolyzate A γ-methyl propylene methoxy propyl trimethoxy decane (trade name: ΚΒΜ 503, manufactured by Shin-Etsu Chemical Co., Ltd.) 3.0 parts by mass of isopropyl alcohol dispersed hollow cerium oxide sol (solid content) 20%, cerium oxide sol manufactured by Catalyst Chemical Industries, Ltd., trade name: ELCOM V-8209) 40 parts by mass of ethyl ethyl acetoxyacetate and diisopropyl ester (manufactured by Chuanxi Precision Chemical Co., Ltd.) 3.0 Quality 10% FZ-2 207 > Propylene glycol monomethyl ether solution (manufactured by Unica, Japan) 3.0 parts by mass (Production of optical film 201) <Microparticle dispersion 1> Microparticles (Aerosil R972V manufactured by Japan Aerosil Co., Ltd.) 1 1 89 parts by mass of ethanol was mixed with the above ingredients in a dissolving machine for 50 minutes, and then dispersed by a homogenizer. <Microparticle-added liquid 1> The microparticle dispersion 1 was slowly added while stirring the dissolution tank to which methylene chloride was added. Next, the particle size of the secondary particles is made into a specific size -204-201213864, and dispersed by an agitator. The fine particle addition liquid 1 was prepared by filtering it through FINEMET NF manufactured by Nippon Seisaku Co., Ltd. Methylene chloride 99 parts by mass Microparticle dispersion 15 parts by mass The main dope of the following composition was prepared. First, dichloromethane and ethanol were added to the pressure-dissolving tank, and the cellulose acetate was poured into a pressure-dissolving tank filled with a solvent while stirring. Heat it and dissolve completely with stirring. The main dope was prepared by filtering the filter paper No. 2 44 made of the filter paper (strand). <Composition of main doping liquid> Dichloromethane 340 parts by mass Ethanol 64 parts by mass Ethylene oxime substitution degree 2.4 cellulose acetate 1 〇〇 parts by mass Sugar ester compound 1-23 10.0 parts by mass

聚酯（a ) 2.5質量份紫外線吸收劑（Tinuvin 928 (日本BASF (股）製造） 2.3質量份微粒子添加液1 1質量份將以上組成物投入密閉容器中，邊攪拌邊溶解調製摻雜液。接著，使用環狀輸送帶澆鑄裝置，將摻雜液均勻澆鑄在溫度33 °C、2000mm寬之不錄鋼輸送帶支撐體上。不錄鋼輸送帶之溫度控制在30°C。在不绣鋼輸送帶支撐體上，蒸發溶劑直至澆鑄（cast -205- 201213864 )薄膜中殘留之溶劑量成爲7 5 %爲止’接著以剝離張力 130N/m，自不鍵鋼輸送帶支撐體上剝離。隨後以設定成17〇 °C之拉幅機對寬度方向進行1.4倍之延伸，接著在設定成130 °C之乾燥區中輸送30分鐘進行乾燥，製作寬度2m’且於端部具有寬度lcm、高度8μιη之滾花之膜厚40μηι之光學薄膜201 ’以5000m捲取。光學薄膜201之滯相値R〇( 590) 、Rt( 590)分別爲 5 Onm、 13 Onm 〇 <偏光板1之製作> 單軸延伸（溫度1 10°c ’延伸倍率5倍）厚度120μιη之聚乙烯醇薄膜。使該等浸漬於由碘〇.〇75g、碘化鉀5g、水100g組成之水溶液中60秒，接著浸漬於由碘化鉀6g、硼酸7.5g、水 l〇〇g組成之68 °C水溶液中。使之經水洗、乾燥，獲得偏光子。接著，依循下列步驟1〜5使偏光子與NIKON Minolta公司製造之TAC薄膜4UY貼合，及於背面貼合光學薄膜201製作偏光板。Polyester (a) 2.5 parts by mass of a UV absorber (Tinuvin 928 (manufactured by BASF Co., Ltd.) 2.3 parts by mass of fine particle-added liquid 1 part by mass The above composition was placed in a sealed container, and the dope was dissolved while stirring. Then, using a ring-shaped conveyor belt casting device, the doping liquid is uniformly cast on the non-recording steel belt support body at a temperature of 33 ° C and 2000 mm wide. The temperature of the non-recording steel conveyor belt is controlled at 30 ° C. On the steel conveyor belt support, the solvent was evaporated until the amount of solvent remaining in the cast (cast-205-201213864) film became 75%. Then, the peeling tension was 130 N/m, and the support was peeled off from the unbonded steel belt support. The width direction was extended by 1.4 times with a tenter set at 17 ° C, and then dried in a drying zone set to 130 ° C for 30 minutes to make a width of 2 m' and a width of 1 cm at the end. 8μιη knurled film thickness 40μηι optical film 201 'rolled at 5000m. Optical film 201 lag phase 〇R 〇 ( 590), Rt ( 590) are 5 Onm, 13 Onm 〇 < Polaroid 1 production > uniaxial extension (temperature 1 10°c '5 times extension ratio> Polyvinyl alcohol film having a thickness of 120 μm. These were immersed in an aqueous solution of 75 g of iodine, 75 g, 5 g of potassium iodide and 100 g of water, followed by immersion in 6 g of potassium iodide, boric acid. 7.5 g, water l〇〇g consisting of a 68 ° C aqueous solution, which was washed with water and dried to obtain a polarizer. Next, follow the following steps 1 to 5 to bond the polarizer to the TAC film 4UY manufactured by NIKON Minolta Co., Ltd. A polarizing plate is formed by bonding the optical film 201 to the back surface.

步驟1 :浸漬於60°C之2mol/L之氫氧化鈉溶液中90秒，接著經水洗並乾燥，獲得與偏光子貼合側經皂化之TAC 薄膜。步驟2:將前述偏光子浸漬於固體成分2質量％之聚乙烯醇接著劑槽中1〜2秒。 -206- 201213864 步驟3:輕輕擦拭去除步驟2中附著於偏光子上之過量接著劑，將其配置於步驟1中處理之TAC薄膜上。步驟4 :以壓力20〜30N/cm2、輸送速度約2m/分鐘將於步驟3中層合之TAC薄膜與偏光子及光學薄膜201予以貼合〇步驟5:在80 °C之乾燥機中乾燥於步驟4中製作之使偏光子與TAC薄膜及光學薄膜201貼合之試料2分鐘，製作偏光板。以使λ/4板之滯相軸與偏光子之吸收軸成45°之方式，於所得偏光板之4UY側上以薄片貼合λ/4板1，獲得偏光板1 此次使用之TAC薄膜4UY爲膜厚40μιη、Ro爲Onm，Rt 爲 3 0 n m。顯示裝置1之製作剝離SONY製之40型顯示器BRAVIA LX900之預先貼合之前面板，去除面板前面之偏光板與前面板之間之塡充劑，且剝離預先貼合之面板前側之偏光板，將上述製作之偏光板1貼合於液晶胞之玻璃面之前面。此時，該偏光板之貼合方向，係以使本發明之λ/4薄膜之面成爲辨識側，且使吸收軸朝向與預先貼合之偏光板相同之方向之方式進行，製作顯示裝置1。吸收軸、滯相軸成爲如圖6所示之方向。 -207- 201213864 偏光板1 〇 1之製作 <偏光板101之製作> 單軸延伸（溫度1 l〇°C，延伸倍率5倍）厚度120μπι之聚乙烯醇薄膜。使該薄膜浸漬於由碘〇.〇75g、碘化鉀5g '水100g組成之水溶液中60秒，接著浸漬於由碘化鉀6g、硼酸7.5g、水 1 〇〇g組成之68 °C水溶液中。使之經水洗、乾燥’獲得偏光子。接著，依循下列步驟1〜5使偏光子與NIKON Minolta公司製造之TAC薄膜4UY貼合，於背面亦貼合NIKON Minolta 公司製造之TAC薄膜4UY而製作偏光板。步驟1 :浸漬於60°C之2mol/L之氫氧化鈉溶液中90秒，接著經水洗並乾燥，獲得與偏光子貼合側經皂化之TAC 薄膜。步驟2:將前述偏光子浸漬於固體成分2質量％之聚乙烯醇接著劑槽中1〜2秒。步驟3:輕輕擦拭去除步驟2中附著於偏光子上之過量接著劑，且將其配置於步驟1中處理之TAC薄膜上。步驟4 :以壓力20~30N/cm2、輸送速度約2m/分鐘使步驟3中層合之TAC薄膜與偏光子及TAC薄膜予以貼合。步驟5:在80 °C之乾燥機中使步驟4中製作之貼合偏光子與TAC薄膜及TAC薄膜之試料乾燥2分鐘，製作偏光板。液晶快門型眼鏡1之製作 -208- 201213864 剝離ECB模式之液晶快門型眼鏡之光學薄膜、偏光板 ’於辨識側貼合偏光板1 0 1，於相反側貼合λ/4板1，製作液晶快門型眼鏡1。吸收軸、滞相軸係成爲圖6所示之方向。此次使用之液晶快門型眼鏡用之ECB胞之快門在關閉狀態時之R〇爲Onm，Rt爲- 300nm。立體影像顯示裝置1 以由液晶快門型眼鏡1與顯示裝置1所組成之立體影像顯示裝置作爲立體影像顯示裝置1。實施例2 λ/4板2之製作自不銹鋼輸送帶支撐體剝離之前，均與λ/4板1同樣製作，剝離後，以拉幅機於180 t朝TD方向延伸1.5倍，製作 λ/4板2。膜厚爲80μιη。偏光板2之製作除將λ/4板1變更爲λ/4板2以外，餘與偏光板1同樣製作偏光板2。顯示裝置2之製作除將偏光板1變更爲偏光板2以外，餘與顯示裝置1同樣製作顯示裝置2。 -209- 201213864 立體影像顯示裝置2 以由液晶快門型眼鏡1與顯示裝置2所組成之立體影像顯示裝置作爲立體影像顯示裝置2。實施例3 λ/4板3之製作除延伸溫度、延伸倍率、膜厚變更如表1以外，與λ/4 板2同樣製作λ/4板3。偏光板3之製作除將λ/4板1變更爲λΜ板3以外，與偏光板1同樣製作偏光板^ 顯示裝置3之製作除將偏光板1變更爲偏光板3以外，與顯示裝置丨同樣製作顯示裝置3。 AL體影像顯不裝置3 以由液晶快門型眼鏡1與顯示裝置3所組成之立體影像顯示裝置作爲立體影像顯示裝置3» 實施例4 λ/4板4之製作 -210- 201213864 自不銹鋼輸送帶支撐體剝離之前，均與λ/4板1同樣製作’剝離後，使用特開2009-2 1 444 1號公報之實施例1中所述之裝置（延伸機Α:圖11)，在溫度1701，以倍率1.5倍 ’使滯相軸與薄膜寬度方向成爲45。之斜方向進行延伸。接著，以多數輥輸送過乾燥區一邊結束乾燥。乾燥溫度爲130°C，輸送張力爲10 0N/m。如上述，獲得乾燥膜厚40μιη之λ/4板4。偏光板4之製作（顯示裝置用偏光板） <偏光板4之製作> 單軸延伸（溫度1 1 0°C，延伸倍率5倍）厚度12〇μιη之聚乙烯醇薄膜。使該薄膜浸漬於由碘0.075g、碘化鉀5g、水100g組成之水溶液中60秒，接著浸漬於由碘化鉀6g、硼酸7.5g、水 l〇〇g組成之68 °C水溶液中。使之經水洗、乾燥，獲得偏光子。接著，依據下列步驟1〜5使偏光子與前述λ/4板4貼合，且於背面側貼合光學薄膜20 1製作偏光板4。步驟1 :浸漬於60°C之2mol/L之氫氧化鈉溶液中90秒 ’接著經水洗並乾燥，獲得與偏光子貼合側經皂化之λ/4 板4。步驟2:將前述偏光子浸漬於固體成分2質量％之聚乙烯醇接著劑槽中1~2秒。步驟3:輕輕擦拭去除步驟2中附著於偏光子上之過量 •211 - 201213864 接著劑，將其配置於步驟1中處理之λ/4板4上。步驟4 :以壓力20~30N/cm2、輸送速度約2m/分鐘使步驟3中層合之λ/4板4與偏光子及光學薄膜201予以貼合。步驟5 :在80°C之乾燥機中使步驟4中製作之貼合偏光子與λ/4板4及光學薄膜201之試料乾燥2分鐘，製作偏光板 4 〇顯示裝置4之製作除將偏光板1變更爲偏光板4以外，與顯示裝置1同樣製作顯示裝置4。立體影像顯示裝置4 以由液晶快門型眼鏡1與顯示裝置4所組成之立體影像顯示裝置作爲立體影像顯示裝置4。實施例5 λ/4板5之製作除延伸溫度、延伸倍率、膜厚變更如表1所示以外，與λ/4板2同樣製作λ/4板5。偏光板5之製作除將λ/4板1變更爲λ/4板5以外’與偏光板1同樣製作偏光板5 » -212- 201213864 顯示裝置5之製作除將偏光板1變更爲偏光板5以外’與顯示裝置1同樣製作顯示裝置5。立體影像顯示裝置5 以由液晶快門型眼鏡1與顯示裝置5所組成之立體影像顯示裝置作爲立體影像顯示裝置5。實施例6 λ/4板6之製作除延伸溫度、延伸倍率、膜厚變更如表1所示以外，與λΜ板1同樣製作λ/4板6。偏光板6之製作Step 1: Immersion in a 2 mol/L sodium hydroxide solution at 60 ° C for 90 seconds, followed by washing with water and drying to obtain a TAC film which was saponified to the side of the polarizer. Step 2: The aforementioned polarizer was immersed in a polyethylene glycol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds. -206-201213864 Step 3: Gently wipe away excess excess agent attached to the polarizer in step 2, and dispose it on the TAC film processed in step 1. Step 4: The TAC film laminated in step 3 is bonded to the polarizer and the optical film 201 at a pressure of 20 to 30 N/cm 2 and a conveying speed of about 2 m/min. Step 5: Drying in a dryer at 80 ° C The sample prepared by bonding the polarizer to the TAC film and the optical film 201 in the step 4 was prepared for 2 minutes to prepare a polarizing plate. The λ/4 plate 1 is laminated on the 4UY side of the obtained polarizing plate so that the slow axis of the λ/4 plate and the absorption axis of the polarizer are 45°, and the polarizing plate 1 is used. 4UY is a film thickness of 40 μm, Ro is Onm, and Rt is 30 nm. Production of the display device 1 peels off the front panel of the BRAVIA LX900 of the 40-type display made by SONY, removes the squeezing agent between the polarizing plate and the front panel in front of the panel, and peels off the polarizing plate on the front side of the pre-bonded panel. The polarizing plate 1 produced as described above is bonded to the front surface of the glass surface of the liquid crystal cell. In this case, the bonding direction of the polarizing plate is such that the surface of the λ/4 film of the present invention is the identification side, and the absorption axis is oriented in the same direction as the polarizing plate to be bonded in advance, thereby producing the display device 1. . The absorption axis and the slow axis form a direction as shown in Fig. 6. -207- 201213864 Production of polarizing plate 1 〇 1 <Production of polarizing plate 101> A uniaxially stretched (temperature 1 l 〇 ° C, 5 times extension ratio) polyvinyl alcohol film having a thickness of 120 μm. The film was immersed in an aqueous solution composed of 75 g of iodonium ruthenium and 5 g of potassium iodide as water for 60 seconds, and then immersed in an aqueous solution of 68 ° C composed of 6 g of potassium iodide, 7.5 g of boric acid, and 1 g of water. It is washed with water and dried to obtain a polarizer. Then, the polarizer was bonded to the TAC film 4UY manufactured by NIKON Minolta Co., Ltd. in the following steps 1 to 5, and the polarizing plate was produced by bonding the TAC film 4UY manufactured by NIKON Minolta Co., Ltd. on the back side. Step 1: Immersion in a 2 mol/L sodium hydroxide solution at 60 ° C for 90 seconds, followed by washing with water and drying to obtain a TAC film which was saponified to the side of the polarizer. Step 2: The aforementioned polarizer was immersed in a polyethylene glycol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds. Step 3: Gently wipe away excess excess agent attached to the polarizer in step 2, and dispose it on the TAC film processed in step 1. Step 4: The TAC film laminated in step 3 is bonded to the polarizer and the TAC film at a pressure of 20 to 30 N/cm 2 and a conveying speed of about 2 m/min. Step 5: The bonded polarizer prepared in the step 4 and the sample of the TAC film and the TAC film were dried in a dryer at 80 ° C for 2 minutes to prepare a polarizing plate. Production of the liquid crystal shutter type glasses 1 - 208 - 201213864 The optical film and the polarizing plate of the liquid crystal shutter type glasses of the peeling ECB mode are attached to the polarizing plate 1 0 on the identification side, and the λ/4 plate 1 is bonded to the opposite side to produce a liquid crystal. Shutter type glasses 1. The absorption axis and the slow axis system are oriented as shown in Fig. 6. The shutter of the ECB cell for the liquid crystal shutter type glasses used in this time has an Rm of Onm and an Rt of -300 nm in the off state. The stereoscopic image display device 1 is a stereoscopic image display device 1 comprising a stereoscopic image display device composed of liquid crystal shutter glasses 1 and a display device 1. Example 2 The λ/4 plate 2 was produced in the same manner as the λ/4 plate 1 before being peeled off from the stainless steel conveyor belt support, and after being peeled off, it was stretched 1.5 times in the TD direction by a tenter at 180 t to produce λ/4. Board 2. The film thickness was 80 μm. Production of Polarizing Plate 2 A polarizing plate 2 was produced in the same manner as the polarizing plate 1 except that the λ/4 plate 1 was changed to the λ/4 plate 2. Production of Display Device 2 Except that the polarizing plate 1 is changed to the polarizing plate 2, the display device 2 is produced in the same manner as the display device 1. -209-201213864 Stereoscopic image display device 2 A stereoscopic image display device 2 composed of liquid crystal shutter glasses 1 and a display device 2 is used as the stereoscopic image display device 2. Example 3 Production of λ/4 plate 3 A λ/4 plate 3 was produced in the same manner as in the λ/4 plate 2 except that the stretching temperature, the stretching ratio, and the film thickness were changed as shown in Table 1. In the production of the polarizing plate 3, a polarizing plate is produced in the same manner as the polarizing plate 1 except that the λ/4 plate 1 is changed to the λ plate 3. The display device 3 is produced in the same manner as the display device 除 except that the polarizing plate 1 is changed to the polarizing plate 3. A display device 3 is produced. The AL image display device 3 is a stereoscopic image display device composed of the liquid crystal shutter glasses 1 and the display device 3 as a stereoscopic image display device. 3»Example 4 λ/4 plate 4 production -210-201213864 From stainless steel conveyor belt Before the support was peeled off, the same as that of the λ/4 plate 1 was produced. After the peeling, the apparatus described in Example 1 of the Japanese Patent Publication No. 2009-2 1 444 1 (extension machine: Fig. 11) was used at a temperature of 1701. At a magnification of 1.5 times, the retardation axis and the film width direction were set to 45. It extends in an oblique direction. Next, drying is carried out while conveying the drying zone with a plurality of rolls. The drying temperature was 130 ° C and the conveying tension was 10 0 N/m. As described above, a λ/4 plate 4 having a dry film thickness of 40 μm was obtained. Production of polarizing plate 4 (polarizing plate for display device) <Production of polarizing plate 4> A polyvinyl alcohol film having a thickness of 12 μm uniaxially stretched (temperature: 1 0 ° C, extension magnification: 5 times). The film was immersed in an aqueous solution containing 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C composed of 6 g of potassium iodide, 7.5 g of boric acid, and water. It is washed with water and dried to obtain a polarizer. Next, the polarizer is bonded to the λ/4 plate 4 in accordance with the following steps 1 to 5, and the polarizing plate 4 is formed by laminating the optical film 20 1 on the back side. Step 1: It was immersed in a 2 mol/L sodium hydroxide solution at 60 ° C for 90 seconds. Then, it was washed with water and dried to obtain a saponified λ/4 plate 4 which was bonded to the polarizer. Step 2: The aforementioned polarizer was immersed in a polyethylene glycol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds. Step 3: Gently wipe away the excess 211 - 201213864 attached to the polarizer in step 2, and arrange it on the λ/4 plate 4 processed in step 1. Step 4: The laminated λ/4 plate 4 in step 3 is bonded to the polarizer and the optical film 201 at a pressure of 20 to 30 N/cm 2 and a conveying speed of about 2 m/min. Step 5: The sample of the bonded polarizer and the λ/4 plate 4 and the optical film 201 produced in the step 4 was dried in a dryer at 80 ° C for 2 minutes to prepare a polarizing plate 4 . The display device 4 is produced in the same manner as the display device 1 except that the panel 1 is changed to the polarizing plate 4. The stereoscopic image display device 4 uses a stereoscopic image display device composed of the liquid crystal shutter glasses 1 and the display device 4 as the stereoscopic image display device 4. Example 5 Production of λ/4 plate 5 A λ/4 plate 5 was produced in the same manner as in the λ/4 plate 2 except that the stretching temperature, the stretching ratio, and the film thickness were changed as shown in Table 1. In the production of the polarizing plate 5, except that the λ/4 plate 1 is changed to the λ/4 plate 5, a polarizing plate 5 is produced in the same manner as the polarizing plate 1. » 212-201213864 Creation of the display device 5 In addition to changing the polarizing plate 1 to the polarizing plate 5 The display device 5 is produced in the same manner as the display device 1. The stereoscopic image display device 5 is a stereoscopic image display device 5 having a stereoscopic image display device composed of liquid crystal shutter glasses 1 and a display device 5. Example 6 Production of λ/4 plate 6 A λ/4 plate 6 was produced in the same manner as the λ plate 1 except that the extension temperature, the stretching ratio, and the film thickness were changed as shown in Table 1. Production of polarizing plate 6

除將λ/4板1變更爲λ/4板6以外，與偏光板1同樣製作偏光板6。顯示裝置6之製作除將偏光板1變更爲偏光板6以外’與顯示裝置1同樣製作顯示裝置6。液晶快門型眼鏡2之製作除於辨識側上貼合偏光板1 〇 1，於相反側貼合λ/4板6 以外，與液晶快門型眼鏡1同樣製作液晶快門型眼鏡2 ^ -213- 201213864 立體影像顯示裝置6 以由液晶快門型眼鏡2與顯示裝置6所組成之立體影像顯示裝置作爲立體影像顯示裝置6。實施例7 液晶快門型眼鏡3之製作除於辨識側上貼合偏光板1 〇 1，於相反側貼合λ/4板2 以外’與液晶快門型眼鏡1同樣製作液晶快門型眼鏡3。立體影像顯示裝置7 以由液晶快門型眼鏡3與顯示裝置2所組成之立體影像顯示裝置作爲立體影像顯示裝置7。實施例8 偏光板1 02之製作除將一方之TAC薄膜變更爲KONICA MINOLTA公司製造之TAC薄膜8UX以外，與偏光板1〇1同樣製作偏光板10^ 此次使用之TAC薄膜8UX之膜厚爲80μηι，R〇爲〇nm， Rt 爲 6 Onm 〇液晶快門型眼鏡4之製作除使液晶快門型眼鏡之液晶胞側成爲8UX之方式於辨識側上貼合偏光板1 02，且於相反側貼合λ/4板1以外，與 -214- 201213864 液晶快門型眼鏡1同樣製作液晶快門型眼鏡4。偏光板7之製作除將TAC薄膜4UY變更爲TAC薄膜8UX以外，與偏光板1同樣製作偏光板7。顯示裝置7之製作除將偏光板1變更爲偏光板7以外，與顯示裝置1同樣製作顯示裝置7。立體影像顯示裝置8 以由液晶快門型眼鏡4與顯示裝置7所組成之立體影像顯示裝置作爲立體影像顯示裝置8。實施例9 偏光板8之製作除將λ/4板1變更爲λ/4板2以外，與偏光板7同樣製作偏光板8。顯示裝置8之製作除將偏光板1變更爲偏光板8以外，與顯示裝置1同樣製作顯示裝置8。立體影像顯示裝置9 -215- 201213864 以由液晶快門型眼鏡4與顯示裝置8所組成之立體影像顯示裝置作爲立體影像顯示裝置9。實施例1 〇偏光板103之製作除將一方之TAC薄膜變更爲KONICA MINOLTA公司製造之TAC薄膜4UE以外，與偏光板101同樣製作偏光板103。此次使用之TAC薄膜4UE之膜厚爲40μιη，Ro爲Onm， R t 爲 0 n m。液晶快門型眼鏡5之製作除使液晶快門型眼鏡之液晶胞側成爲4UE之方式於辨識側上貼合偏光板1 03，且於相反側貼合λ/4板1以外，與液晶快門型眼鏡1同樣製作液晶快門型眼鏡5。偏光板9之製作除將TAC薄膜8UX變更爲TAC薄膜4UE以外，與偏光板 8同樣製作偏光板9。顯示裝置9之製作除將偏光板1變更爲偏光板9以外，與顯示裝置1同樣製作顯示裝置9。立體影像顯示裝置1 0 -216- 201213864 以由液晶快門型眼鏡5與顯示裝置9所組成之立體影像顯示裝置作爲立體影像顯示裝置1 〇。實施例11 λ/4板7之製作除延伸溫度、延伸倍率、膜厚變更如表1所示以外’ 與λ/4板4同樣製作λ/4板7。偏光板10之製作除將λ/4板4變更爲λ/4板7以外，與偏光板4同樣製作偏光板1 0。顯示裝置10之製作除將偏光板1變更爲偏光板1 〇以外，與顯示裝置1同樣製作顯示裝置1 0。立體影像顯示裝置11 以由液晶快門型眼鏡1與顯示裝置1 〇所組成之立體影像顯示裝置作爲立體影像顯示裝置11。實施例1 2 液晶快門型眼鏡6之製作除使用IP S胞作爲液晶胞以外，與液晶快門型眼鏡1同樣製作液晶快門型眼鏡6。 -217 201213864 此次使用之液晶快門型眼鏡用之IPS胞之^爲270nm， Rt爲 1 3 5nm 〇立體影像顯示裝’置1 2 以由液晶快門型眼鏡6與顯示裝置4所組成之立體影像顯不裝置作爲立體影像顯示裝置12。《3 D影像視聽時頭部傾斜時之串訊評價》在23°C、55%RH環境下，使各顯示裝置點亮之後，立隹即在顯示裝置之正面配戴液晶快門型眼鏡，在使液晶快門型眼鏡以25°傾斜之狀態將頭部傾斜之狀態對3D影像進行視聽，以下述基準評價串訊。 ◎:完全沒有串訊〇：看見極弱之串訊 △:看見弱的串訊 X :清楚看見串訊立體影像顯示裝置1〜12之任一個均爲©。 0 《自斜方向觀看3D影像視聽時之顯示裝置時之串訊抑制之評價》在23°C、55%RH之環境下，將各顯示裝置放置於地面上使背光點亮後’立即配戴在各液晶快門型眼鏡，距面板正面lm處，接著於右側錯開lm自高度1.8m之視點，對3D 影像進行視聽，以下列基準評價串訊。 -218- 201213864 ◎:完全沒有串訊〇：看見極弱之串訊 △:看見弱的串訊 X :清楚看見串訊《3D影像視聽時之色調變化之評價》在23°C、5 5%RH之環境暗室中，將各顯示裝置放置於地面上將背光點亮後，立即配戴各液晶快門型眼鏡，距離面板正面lm處，自高度0.5m之視點觀察黑色顯示（視點A )，接著於右側錯開lm自高度1.8m之視點觀察黑色顯示（視點B )，以下列基準評價色調變化。 ◎:色調完全沒有變化〇：可確認極弱之色調變化 △:確認弱的色調變化 X :可清楚確認色調變化上述各種λ/4板（1〜7 )之製造條件及性能示於表1。又，各種立體影像顯示裝置（1〜12)之評價結果示於表2。 [表1] λ/4板延伸延伸溫度 rc) 延伸倍率 (倍）膜厚 (μηι) Θ (。） Ro (nm) Rt (nm) Nz λ/4 板 1 MD 170 1.6 40 0 138 80 1.1 λ/4 板 2 TD 180 1.5 80 90 138 200 2.0 λ/4 板 3 TD 170 1.45 90 90 138 300 2.7 λ/4 板 4 斜向 170 1.5 40 45 138 80 1.1 λ/4 板 5 TD 160 1.4 100 90 138 400 3.4 λ/4 板 6 MD 165 1.5 50 0 138 140 1.5 λ/4 板 7 斜向 160 1.45 45 45 138 200 2.0 -219- 201213864 【3谳〕備註本發明本發明本發明比較例 |比較例本發明比較例本發明本發明本發明本發明比較例色調變化〇 ◎ 〇 < < 〇 < 〇 ◎ ◎ ◎ X m =, m £ 騷5 •n： f rfr ^ 〇 ◎ 〇 < < ◎ < ◎ 〇 ◎ ◎ X λ/4板之Nz 眼鏡側〇 <N 面板側 Ο (Ν 卜 CN 寸 c〇 in 〇 <N »—Η 〇〇 CN 〇 CS Η IRt 卜 n+Rtc Ο οο I Ο 140 -110 240 〇 160 〇 (Ν 1 100 〇 CS 1 〇 325 立體影像顯示裝置編號立體影像顯示裝置1 立體影像顯示裝置2 立體影像顯示裝置3 立體影像顯示裝置4 立體影像顯示裝置5 立體影像顯示裝置6 立體影像顯示裝置7 立體影像顯示裝置8 立體影像顯示裝置9 立體影像顯示裝置10 立體影像顯示裝置11 立體影像顯示裝置12 實施例編號實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 ! 實施例10 實施例11 實施例12 • · -220- 201213864 由表2所示之結果可知，本發明之立體影像顯示裝置自斜方向觀看3D影像視聽時之顯示裝置時完全沒有串訊及色調變化或極少之辨識性優異之立體影像顯示裝置》【圖式簡單說明】圖1爲以往之立體圖像辨識用眼鏡G之模式圖圖2爲以往之立體圖像顯示裝置之模式圖圖3爲以往之液晶快門S1及S2之模式圖圖4爲顯示λ/4板之製造中使用之延伸用之拉幅機之軌道配置之一例之圖圖5爲本發明之偏光板之模式圖圖6爲立體影像顯示裝置（眼鏡之偏光板爲一片之方式）之模式圖【主要元件符號說明】 C C :控制電路 LCD :液晶顯示器 G :立體圖像辨識用眼鏡 S 1 :右眼用液晶快門 S 2 :左眼用液晶快門 L :直線偏光之光 LC :液晶層 LI :左眼用圖像 RI :右眼用圖像 -221 - 201213864 p 1、p 2 :偏光板 DR1 :拉出方向 DR2 :捲起方向 θί:拉出角度（拉出方向與捲起方向之角度） CR、CL :夾具The polarizing plate 6 was produced in the same manner as the polarizing plate 1 except that the λ/4 plate 1 was changed to the λ/4 plate 6. Production of Display Device 6 The display device 6 is produced in the same manner as the display device 1 except that the polarizing plate 1 is changed to the polarizing plate 6. In the production of the liquid crystal shutter type glasses 2, the liquid crystal shutter type glasses are produced in the same manner as the liquid crystal shutter type glasses 2 except that the polarizing plate 1 〇1 is attached to the identification side and the λ/4 plate 6 is attached to the opposite side. 2 ^ -213- 201213864 The stereoscopic image display device 6 is a stereoscopic image display device 6 including a stereoscopic image display device composed of the liquid crystal shutter glasses 2 and the display device 6. (Example 7) Production of liquid crystal shutter type glasses 3 The liquid crystal shutter type glasses 3 were produced in the same manner as the liquid crystal shutter type glasses 1 except that the polarizing plate 1 〇 1 was bonded to the identification side and the λ/4 plate 2 was bonded to the opposite side. The stereoscopic image display device 7 uses a stereoscopic image display device composed of the liquid crystal shutter type glasses 3 and the display device 2 as the stereoscopic image display device 7. Example 8 Production of Polarizing Plate 012 In addition to changing one of the TAC films to the TAC film 8UX manufactured by KONICA MINOLTA Co., Ltd., a polarizing plate 10 was produced in the same manner as the polarizing plate 1〇1. The film thickness of the TAC film 8UX used this time was 80μηι, R〇 is 〇nm, Rt is 6 Onm 〇 Liquid crystal shutter type glasses 4 is produced by disposing the polarizing plate 102 on the identification side except that the liquid crystal cell side of the liquid crystal shutter glasses is 8UX, and is attached on the opposite side. The liquid crystal shutter glasses 4 were produced in the same manner as the -214-201213864 liquid crystal shutter glasses 1 except for the λ/4 plate 1. Production of Polarizing Plate 7 A polarizing plate 7 was produced in the same manner as the polarizing plate 1 except that the TAC film 4UY was changed to the TAC film 8UX. Production of Display Device 7 A display device 7 is produced in the same manner as the display device 1 except that the polarizing plate 1 is changed to the polarizing plate 7. The stereoscopic image display device 8 is a stereoscopic image display device 8 having a stereoscopic image display device composed of liquid crystal shutter glasses 4 and a display device 7. [Embodiment 9] Production of polarizing plate 8 A polarizing plate 8 was produced in the same manner as in the case of the polarizing plate 7, except that the λ/4 plate 1 was changed to the λ/4 plate 2. Production of Display Device 8 A display device 8 is produced in the same manner as the display device 1 except that the polarizing plate 1 is changed to the polarizing plate 8. The stereoscopic image display device 9-215-201213864 uses a stereoscopic image display device composed of the liquid crystal shutter glasses 4 and the display device 8 as the stereoscopic image display device 9. Example 1 Manufacture of the polarizing plate 103 A polarizing plate 103 was produced in the same manner as the polarizing plate 101 except that one of the TAC films was changed to the TAC film 4 UE manufactured by KONICA MINOLTA. The film thickness of the TAC film 4UE used this time was 40 μm, Ro was Onm, and R t was 0 n m. The production of the liquid crystal shutter glasses 5 is performed by attaching the polarizing plate 103 to the identification side and bonding the λ/4 plate 1 to the opposite side, in the manner of making the liquid crystal cell side of the liquid crystal shutter glasses 4UE, and the liquid crystal shutter type glasses. 1 Liquid crystal shutter glasses 5 are also produced. Production of Polarizing Plate 9 A polarizing plate 9 was produced in the same manner as the polarizing plate 8 except that the TAC film 8UX was changed to the TAC film 4UE. Production of Display Device 9 A display device 9 is produced in the same manner as the display device 1 except that the polarizing plate 1 is changed to the polarizing plate 9. The stereoscopic image display device 1 0 - 216 - 201213864 uses a stereoscopic image display device composed of the liquid crystal shutter glasses 5 and the display device 9 as a stereoscopic image display device 1 . Example 11 Production of λ/4 plate 7 The λ/4 plate 7 was produced in the same manner as the λ/4 plate 4 except that the extension temperature, the stretching ratio, and the film thickness were changed as shown in Table 1. Production of Polarizing Plate 10 A polarizing plate 10 was produced in the same manner as the polarizing plate 4 except that the λ/4 plate 4 was changed to the λ/4 plate 7. Production of Display Device 10 A display device 10 is produced in the same manner as the display device 1 except that the polarizing plate 1 is changed to the polarizing plate 1. The stereoscopic image display device 11 has a stereoscopic image display device 11 composed of a liquid crystal shutter type eyeglass 1 and a display device 1 as a stereoscopic image display device 11. [Embodiment 1] Production of liquid crystal shutter glasses 6 The liquid crystal shutter glasses 6 were produced in the same manner as the liquid crystal shutter glasses 1 except that the IP S cells were used as the liquid crystal cells. -217 201213864 The IPS cell used for the liquid crystal shutter glasses used in this time is 270 nm, Rt is 135 nm, and the stereoscopic image display device is set to 1 2 to form a stereoscopic image composed of the liquid crystal shutter glasses 6 and the display device 4. The display device is used as the stereoscopic image display device 12. "Evaluation of crosstalk when the head is tilted during 3D video viewing" In the 23 ° C, 55% RH environment, after each display device is turned on, the liquid crystal shutter glasses are worn on the front side of the display device. The state in which the liquid crystal shutter glasses were tilted at a state of 25° was observed on the 3D image, and the crosstalk was evaluated on the basis of the following criteria. ◎: There is no crosstalk at all. 〇: I saw a very weak crosstalk △: I saw a weak crosstalk X: I saw a clear crosstalk. Any one of the stereoscopic image display devices 1 to 12 is ©. 0 "Evaluation of crosstalk suppression when viewing a display device for 3D video viewing from an oblique direction" Place the display devices on the ground at 23 ° C and 55% RH to light the backlight and then wear it immediately In each of the liquid crystal shutter glasses, lm from the front side of the panel, and then on the right side, lm is viewed from a height of 1.8 m, and the 3D image is viewed, and the crosstalk is evaluated on the following basis. -218- 201213864 ◎: There is no crosstalk at all: I saw a very weak crosstalk △: I saw a weak crosstalk X: I clearly saw the crosstalk "Evaluation of the change in hue when viewing 3D images" at 23 ° C, 5 5% In the environmental darkroom of RH, place each display device on the ground and light the backlight. Immediately wear the liquid crystal shutter glasses. From the front side of the panel, observe the black display (view A) from the viewpoint of height 0.5m. The black display (view B) was observed from the viewpoint of the height of 1.8 m on the right side, and the hue change was evaluated on the following basis. ◎: The color tone is completely unchanged. 〇: The color tone change is extremely weak. Δ: The weak color tone change is confirmed. X: The color tone change can be clearly confirmed. The manufacturing conditions and performance of the above various λ/4 plates (1 to 7) are shown in Table 1. Further, the evaluation results of various stereoscopic image display devices (1 to 12) are shown in Table 2. [Table 1] λ/4 plate extension elongation temperature rc) Extension ratio (times) Film thickness (μηι) Θ (.) Ro (nm) Rt (nm) Nz λ/4 Plate 1 MD 170 1.6 40 0 138 80 1.1 λ /4 Board 2 TD 180 1.5 80 90 138 200 2.0 λ/4 board 3 TD 170 1.45 90 90 138 300 2.7 λ/4 board 4 Oblique 170 1.5 40 45 138 80 1.1 λ/4 board 5 TD 160 1.4 100 90 138 400 3.4 λ/4 plate 6 MD 165 1.5 50 0 138 140 1.5 λ/4 plate 7 oblique 160 1.45 45 45 138 200 2.0 -219- 201213864 [3谳] Remarks The present invention is a comparative example of the present invention|Comparative example BEST MODE FOR CARRYING OUT THE INVENTION The present invention is a color change of a comparative example of the present invention 〇 ◎ 〇 << 〇 < 〇 ◎ ◎ ◎ X m =, m £ 骚5 • n: f rfr ^ 〇 ◎ 〇 << ◎ < ◎ 〇 ◎ ◎ X λ / 4 plate Nz glasses side 〇 < N panel side Ο (Ν CN c〇in 〇 < N » - Η 〇CN 〇 CS Η IRt 卜 n + Rtc Ο Οο I Ο 140 -110 240 〇160 〇(Ν 1 100 〇CS 1 〇325 Stereoscopic image display device number Stereoscopic image display device 1 Stereoscopic image display device 2 Stereoscopic image Display device 3 stereoscopic image display device 4 stereoscopic image display device 5 stereoscopic image display device 6 stereoscopic image display device 7 stereoscopic image display device 8 stereoscopic image display device 9 stereoscopic image display device 10 stereoscopic image display device 11 stereoscopic image display device 12 Numbering Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 ! Example 10 Example 11 Example 12 • · -220- 201213864 As a result, it can be seen that the stereoscopic image display device of the present invention has no stereoscopic image display device with no crosstalk and color tone change or few excellent visibility when viewing the display device during viewing of the 3D image from the oblique direction. FIG. 2 is a schematic view of a conventional stereoscopic image display device. FIG. 3 is a schematic view of a conventional liquid crystal shutter S1 and S2. FIG. 4 is a view showing the manufacture of a λ/4 plate. FIG. 5 is a schematic diagram of a polarizing plate of the present invention. FIG. 6 is a stereoscopic image display device (eye) Mode of the polarizing plate is one piece] [Main component symbol description] CC: Control circuit LCD: Liquid crystal display G: Stereo image recognition glasses S 1 : Right eye liquid crystal shutter S 2 : Left eye liquid crystal shutter L : Linear polarized light LC : Liquid crystal layer LI : Image for left eye RI : Image for right eye -221 - 201213864 p 1 , p 2 : Polarizer DR1 : Pull-out direction DR2 : Roll-up direction θί: Pull-out angle (the angle between the pull-out direction and the winding direction) CR, CL: Fixture

Wo:延伸前之薄膜寬度 W:延伸後之薄膜寬度 A :液晶快門型眼鏡Wo: film width before stretching W: film width after stretching A: liquid crystal shutter glasses

A1、A 4 :偏光子 A 2 :液晶胞 A3 : λ/4 板 Β :液晶顯示裝置（例如電視（TV )) C :偏光板 C1 : λ/4板 C2 :偏光子A1, A 4 : polarizer A 2 : liquid crystal cell A3 : λ/4 plate Β : liquid crystal display device (for example, television (TV)) C : polarizing plate C1 : λ/4 plate C2 : polarized photon

C3 :光學薄膜 C4=偏光子保護薄膜 D :液晶胞 E :偏光板 F :背光板 HC :硬質塗層 A R :抗反射層 a :吸收軸 b :滞相軸 -222-C3: optical film C4=polarized photoprotective film D: liquid crystal cell E: polarizing plate F: backlight IC: hard coating A R : anti-reflection layer a : absorption axis b : slow axis -222-

Claims

201213864 VII. Patent Application Range: 1. A stereoscopic image display device, which is a stereoscopic image display device composed of a display device and a liquid crystal shutter type lens (Shutter Glasses), characterized in that the display device is driven from the visual recognition side. The λ/4 plate and the polarizer are arranged in the order, and the liquid crystal shutter type glasses are provided with polarized light 'child, liquid crystal cell and λ/4 plate from the visual identification side, and the thickness direction phase difference Rt of all the optical compensation layers. The total (where η represents an integer) and the phase difference Rtc in the thickness direction when the shutter of the liquid crystal cell is closed satisfy the following formula (1): (1): -l〇〇nm< (ERti 〜n+Rtc) < 150nm. 2. The stereoscopic image display device of claim 1, wherein the liquid crystal cell driving mode of the liquid crystal shutter type lens is an E C B mode. 3. The stereoscopic image display device of claim 1 or 2, wherein the Nz coefficient of at least one of the λ/4 plates is within a range of 〜4. 4. The stereoscopic image display device of any one of claims 1 to 3 wherein the Nz coefficient of the λ/4 plate of the aforementioned display device is larger than the Nz coefficient of the λ/4 plate of the liquid crystal shutter type lens. 5. The stereoscopic image display device according to any one of claims 1 to 4, wherein the λ/4 plate of the display device has a hard coat layer. 6 - as claimed in the claims 1-5 to 5 A three-dimensional image display device in which the λ/4 plate of the aforementioned display device contains a cellulose ester resin. -223-