TWI356212B

TWI356212B - Optical compensation film, liquid crystal display

Info

Publication number: TWI356212B
Application number: TW093126123A
Authority: TW
Inventors: Junichi Hirakata; Mitsuyoshi Ichihashi; Tadashi Ito
Original assignee: Fujifilm Corp
Priority date: 2003-09-01
Filing date: 2004-08-31
Publication date: 2012-01-11
Also published as: KR101006043B1; KR20050024210A; TW200512496A

Description

1356212 九、發明說明：【發明所屬之技術領域】本發明係關於一種具有偏光膜'及夾持該偏光膜之一對保護膜之偏光板，及使用其之液晶顯示裝置。另外，本發明也關於有助於改善液晶顯示裝置之視野角特性等之光學補償膜。【先前技術】液晶顯示裝置通常是具有液晶胞（liquid crystal cell) 和偏光板。「偏光板j是由保護膜和偏光膜所構成，將由聚乙烯醇薄膜所構成的偏光膜以碘染色，並加以延伸後將其兩面以保護膜積層即可製得。在「透射型」液晶顯示裝置，則將該偏光板裝設在液晶胞兩側，也有再進一步配置 —片以上的光學補償膜之情形。在「反射型」液晶顯示裝置，則以反射板 '液晶胞、一片以上之光學補償膜 '偏光板之順序配置。「液晶胞」是由液晶性分子、用以封入其之兩片基板、及用以對液晶性分子外加電壓之電極層所構成。液晶胞係根據液晶性分子的配向狀態之差異來作開啓 •關閉（ON . OFF )顯示，且對於透射及反射型中任一種皆可適用。其顯示模式包括例如：TN (扭轉向列）型、 IPS (面內切換）型、OCB (光學補償彎曲）型、VA (垂直配向）型、ECB (電控雙折射）型。「光學補償膜」是爲消除影像著色，或擴大視野角而使用在各種液晶顯示裝置。光學補償膜傳統上是使用延伸雙折射聚合物薄膜。另外’也有一種取代由延伸雙折射薄膜 1356212 所構成的光學補償膜，而使用在透明支撐體上具有由低分子或高分子液晶性分子所形成之光學異β方向性層（ optically anisotropic layer)的光學補償膜之提案》由於液晶性分子具有多種不同的配向形態，使用液晶性分子即可實現以傳統的延伸雙折射聚合物薄膜所不能製得之光學性質。此外，也有一種藉由對偏光板之保護膜附加雙折射性來兼作保護膜與光學補償膜之提案。光學補償膜之光學性質，係根據液晶胞之光學性質；具體而言，係取決於如上所述之顯示模式之差異而定。若使用液晶性分子時，則可製造具有可對應於液晶胞之各種顯示模式之各種光學性質的光學補償膜。使用液晶性分子之光學補償膜，早就有能對應於各種顯示模式者之提案。例如在「TN模式」之液晶胞方面，則邊以施加電壓來消除液晶分子之扭轉結構，邊由經固定傾斜於基板面的配向狀態所構成的光學補償膜來作光學補償，以藉由防止黑色顯示時的斜向漏光來改善對比之視角特性（請參閱日本國專利特開平第6_214,116號公報）。另外，對於「平行配向」液晶胞用光學補償膜，則已在未施加電壓狀態之黑色顯示時’作平行配向於基板面的液晶性分子之光學補償，及兼作爲偏光板之正交透射率的視野角特性之改善方面有所記載（請參閱日本國專利特開平第9-292,5 22號公報）。在「IPS模式」之液晶胞方面，則在未施加電壓狀態之黑色顯示時，以由平行配向於基板面的液晶分子所構成的光學補償膜來作光學補償’同時該膜片又兼作爲偏光板之正交 1356212 透射率的視野角特性之改善（請參閱日本國專利特開平第 - 10-54,9 82號公報）。另外，在「OCB模式j之液晶胞方面、，液晶層中央部之液晶分子則因施加電壓而呈垂直配向，在基板界面附近則將傾斜配向之液晶層以光學補償膜來加以光學補償，以改善黑色顯示之視野角特性（請參閱美國專利第5,805,253號）。在「VA模式」之液晶胞方面，貝!| 將在未施加電壓狀態下液晶分子係對於基板面成垂直配向狀態的黒色顯示之視野角特性，以光學補償膜來加以改善 (請參閱美國專利第2,866,372號公報）。 ® 【發明內容】發明所欲解決之課顆傳統的TN模式液晶胞用光學補償膜，係僅取代延伸雙折射聚合物薄膜，而使用由液晶性分子所構成的薄膜，即可實現比傳統者可更正確地以光學方式來補償液晶胞。然而，即使使用液晶性分子，如欲在無問題下以光學方式完全補償液晶胞，則仍舊是非常困難。例如，茲就先前所提議之光學補償膜而言，在黑色顯示時仍可看得到來自偏光 β 板之斜方向的漏光，可知目前視野角並未獲得充分的擴大 (至理論上可期待的程度）。同樣地，在傳統的IPS、OCB 、VA模式之液晶胞用光學補償膜也可看得到漏光。再者，在IPS與VA模式之液晶胞用光學補償膜，由於其係僅由延伸雙折射聚合物薄膜來作光學補償，因此必須使用數片薄膜’其結果導致光學補償膜之厚度增加，因此不利於顯示裝置之薄型化。此外，因爲延伸薄膜之積層必須使用黏 1356212 合層’以致黏合層會因溫濕度之變化而收縮並造成薄膜之間的剝離或翹曲等缺陷。本發明係基於上述各問題所達成，亦即，係以提供一種簡單的結構，且不僅是顯示品質，也能顯著地改善視野角之液晶顯示裝置’特別是「VA型」液晶顯示裝置與「IPS 型」之「液晶顯示裝置」爲其課題。另外，本發明也提供 —種不僅是具有偏光機能，也有助於擴大液晶顯示裝置之視野角，且可容易地製造之「偏光板」爲其課題。再者，本發明也提供一種有助於改善液晶顯示裝置，特別是IPS 型或VA型之液晶顯示裝置的視野角特性之「光學補償膜 J ° 解決課顆之方法本發明之課題係藉由如下所述之第（1)項及第（2)項之「光學補償膜」、如下所述之第（3)項至第（6)項之「液晶顯示裝置」、及如下所述之第（7)至第（9)項之「偏光板」所達成。 (1)—種光學補償膜，其係使用於具有：至少在—方具有電極之對向配置的一對基板，夾持在該基板之間的液晶層’及配置在該液晶層外側之至少一偏光膜，且該液晶層之厚度d(微米）與折射率異方向性 △ π的乘積Δη·(1爲0.1 ~ 1.〇微米之液晶顯示裝置者；且由接於該偏光膜之保護膜，與具有碟狀（discotic) 結構單元之化合物所構成的光學補償層所構成；且 1356212 該保護膜係在可見光域之任何波長λ符合下列條件 -30 (奈米）各{ (nx - ny) X d2 } S 50 (奈米 )，及 -5 0 (奈米）S〔 { (nx + ny) / 2 - nz } x d2〕S 300 (奈米），式中，d2(奈米）是保護膜之厚度，nx和ny (但是 ny < nx)是面內之主平均折射率，nz是厚度方向之主平均折射率，nx、ny和nz係各自呈互相正交；並且，該光學補償層之配向控制方向與該保護膜之遲相軸 (retardation axis )，係對於該偏光膜之吸收軸（ absorption axis)配置成大致平行。 (2) —種光學補償膜，其係使用於具有：至少在一方具有電極之對向配置的一對基板，由夾持在該基板之間且配向成未施加電壓時對於該一對基板表面大致平行之向列型液晶材料之液晶層所構成的液晶胞’ 及分別配置在該液晶胞外側之第一偏光膜和第二偏光膜之液晶顯示裝置者；且該保護膜係在可見光域之任何波長λ符合下列條件 -30 (奈米）忘{ (nx - ny) X d2 } S 50 (奈米 )，及 -50 (奈米）各〔{ (nx + ny) / 2 - nz } X 6〕$ -10- 1356212 300 (奈米），式中，d2(奈米）是保護膜之厚度，nx和ny (但是 ny < nx)是面內之主平均折射率，nz是厚度方向之主平均折射率，nx、ny和nz係各自呈互相正交；該光學補償層是由具有碟狀結構單元之化合物的分子所構成，該碟狀面係對於膜面大致呈垂直配向；且該光學補償層之配向控制方向，與該保護膜之遲相軸，及該第二偏光膜之吸收軸係各自呈大致平行。 (3)—種液晶顯示裝置，其係具有：至少在一方具有電極之對向配置的一對基板、夾持在該基板之間的液晶層、及配置在該液晶層外側之第一偏光板者；且該液晶層之厚度d (微米）與折射率異方向性Δη的乘積Δη· d爲0.1〜1.0微米；該第一偏光板具有偏光膜、及夾持該偏光膜之一對保護膜；該一對保護膜中至少一方，具有與膜面之平均折射率會成爲最大之方向實質的相符之遲相軸，且該液晶層的近側之保護膜之遲相軸與該偏光膜之吸收軸係成交叉；該一對保護膜中之配置於液晶層的近側之保護膜，係厚度爲（^ (奈米），在各自呈互相正交之x、y和 2軸方向具有三平均折射率nx、ny和nz，設若平行於該液晶層表面的面內之主平均折射率爲nx和ny 1356212 (但是ny<nx)，該液晶層的厚度方向之主平均折射率爲nz時，則在可見光域之任何波長λ符合下列條件= • 30(奈米）$ { (nx - ny) X di } ^ 50 (奈米 )，及 -50(奈米）$〔{ (nx + ny) / 2 - nz } x di ) ^ 300 (奈米）。在第（3)項之液晶顯示裝置中，其偏光板係使用一對保護膜中至少一方的面內之遲相軸係與偏光膜之吸收軸成交叉的偏光板。該偏光板不僅是偏光機能，也有助於擴大顯示裝置之視野角，因此可提供一種以簡單的結構，且不僅是顯示品質，也可顯著地改善視野角之液晶顯示裝置，特別是VA (垂直配向 )型和IPS (面內切換）型液晶顯示襞置。上述偏光板係使用以「斜向延伸法」所製得之偏光膜，將一對保護膜及該偏光膜之合計3種高分子薄膜等以捲裝進出方式加以積層即可容易地製得.，因此，也有助於提高液晶顯示裝置之生產性。另外，上述偏光板之保護膜，也可用於光學補償層，因此，此等態樣即可以更簡單的結構製得具有優越的顯示品質之液晶顯示裝置。而且，第（3 )項之液晶顯示裝置，其夾持液晶層所配置之偏光板的偏光膜之吸收軸係呈正交，因此，偏光板透射率低，可在屬於正常黑色顯示模式（ -12- 1356212 NBM; Normally Black Mode )之液晶顯示裝置態樣 · ，獲得高對比。 Λ (4 )如第（3 )項之液晶顯示裝置，其中該液晶層含有向列型液晶材料，在黑色顯示時，該向列型液晶材料之液晶分子係對該一對基板之表面大致呈垂直配向〇 . 第（4 )項之液晶顯示裝置，雖然係屬於液晶材料在，黑色顯示時係呈大致垂直配向之態樣，但是能減輕以此種態樣就會成問題的由斜向觀看時之漏光。另肇外’本態樣可爲在未施加電壓狀態下，液晶胞中液晶分子係呈大致垂直配向之VA型，也可爲在施加高電壓狀態下，液晶分子係垂直配向之OCB型、 ECB型、或丁>^型》第（4)項之液晶顯示裝置，係屬於液晶分子因施加電壓而會對基板法線傾斜之VA 型態樣，由於其液晶分子係朝單方向傾斜，亮度及色調將相依於視野角而產生偏差現象，因此將一畫像素以初始配向狀態互相不同的2區以上（較佳爲 · 4或8區以上）之液晶區來構成，以加以平均化，即可減輕該現象。 (5 ).如第（3 )項之液晶顯示裝置，其中該液晶層含有向列型液晶材料，在黑色顯示時，該向列型液晶材料之液晶分子係對該一對基板之表面大致呈平行配向〇第（5)項之液晶顯示裝置，由於上述偏光板之保護 -13- 1356212 設置於接近該第二偏光板之偏光膜液晶胞的面之保護膜，係在可見光域之任何波長λ符合下列條件： • 30(奈米）S { (nx - ny) X d2 } $ 50 (奈米 )，及 -50 (奈米）S〔 { (nx + ny) / 2 - nz } x d2〕S 300 (奈米），式中，d2(奈米）是保護膜之厚度，nx和ny (但是 ny < nx)是面內之主平均折射率，nz是厚度方向之主平均折射率，nx、ny和nz係各自呈互相正交；該光學補償層是由具有碟狀結構單元之化合物所構成，且該化合物之碟狀面係對該基板面大致垂直配向；並且該光學補償層之配向控制方向，與設在接近該第二偏光板之偏光膜液晶胞的面之該保護膜之遲相軸，及該第二偏光膜之吸收軸係各自呈大致平行。在第（6)項之液晶顯示裝置，只要是上下偏光板之保護膜的延遲値設定爲非對稱，即可有助於大幅度地防止由斜向觀看時之漏光。尤其是將配置在上下偏光板之液晶胞與偏光膜之間的保護膜之延遲値設定爲非對稱時，則可有效地減少在上下偏光板之吸收軸成正交的態樣中之斜向漏光。第（6)項之液晶顯示裝置，係屬於在黑色顯示時，液晶分子將大致平行配向之態樣，其係包括例如在未施加電壓狀態下，使液晶分子對基板面平行配向 -15- 1356212 ’以作黑色顯示之IPS型。在該等模式，上述偏光板也有助於擴大視野角。在本態樣時，配置在上述保護膜及保護膜與液晶胞之間的光學異方向性層之延遲値較佳爲設定在液晶層之Δη· d値的2倍以下〇第（6)項之液晶顯示裝置，也可進一步在上述第一和/或第二偏光板，與由上述一對基板及上述液晶層所構成的液晶胞之間，具有由至少一片高分子薄膜或至少一層液晶化合物所構成的光學異方向性層（但是該保護膜也可爲可兼作爲該光學補償層之結構 )° 在該態樣之液晶顯示裝置，由於包括具有光學補償能之高分子薄膜或光學異方向性層，因此與上述效果同時具有優越的視野角擴大及改善顯示特性。 (7) —種偏光板，其係具有偏光膜、及夾持該偏光膜所配置具有折射性之一對保護膜；該保護膜係厚度爲幻（奈米），在各自呈互相正交之x'y和z軸方向具有三平均折射率nx、ny和nz，設若平行於面內之主平均折射率爲ηχ和nyC但是ny < nx) ’厚度方向之主平均折射率爲nz時’則在可見光域之任何波長λ符合下列條件： -30 (奈米）^ { (nx - ny) X di } S 50 (奈米 )，及 -50(奈米）S〔{ (nx + ny)/2-nz } X d!〕客 1356212 300 (奈米）。第（7)項之偏光板，其特徵爲：一對保護膜中至少 —方係具有特定的面內之延遲（Re)、或厚度方向之延遲（Rth)，同時上述保護膜中任一方之遲相軸與上述偏光膜之吸收軸係實質地成平行或正交。該偏光板不僅是偏光機能，也有助於擴大液晶顯示裝置，特別是VA (垂直配向）型、IPS (面內切換）型液晶顯示裝置之視野角。另外，上述偏光板係使用以斜向延伸法所製得之偏光膜，將一對保護膜及該偏光膜之合計三種高分子薄膜等以捲裝進出方式加以積層即可容易地製得，因此也有助於改善液晶顯示裝置之生產性。另外，上述偏光板之保護膜，也可具有光學補償層之機能，因此以此態樣，不僅是有助於擴大液晶顯示裝置之視野角，也有助於光學補償。 (8) 如第（7)項之偏光板，其中該偏光板之保護膜中任一方之遲相軸與該偏光膜之吸收軸係成交叉。在第（8)項之偏光板中，由於其偏光板所具有的偏光膜之吸收軸，與保護膜（液晶層的遠側之保護膜 )之遲相軸係成正交，因此加上上述效果，也能提高例如防止偏光板之尺寸變化或捲曲等機械上的可靠性。另外，若液晶層的近側之保護膜之遲相軸與偏光膜之吸收軸成正交時，即可減輕在黒色顯示時 ‘來自斜方向之漏光。此外，若在液晶層與保護膜之 -17- 1356212 間，將光學異方向性配置成使其遲相軸與偏光膜之 · 吸收軸成交叉時，則不需要使保護膜之遲相軸與偏，光膜之吸收軸一定要交叉。此時，光學異方向性層無論是塗佈型薄膜或延伸薄膜也能獲得相同效果，但是較佳爲大於保護膜之延遲値。並且，雙方之保護膜係具有雙折射性，同時該液晶 ‘ 層近側之保護膜的遲相軸係互相實質地成正交。在 _ 遲相軸互相正交的態樣，藉由互相消除各保護膜之雙折射，即可減少液晶顯示裝置在垂直入射時之光 β 學特性劣化。相對地，在遲相軸互相平行的態樣，液晶層若有殘留相位差時，則可以保護膜之雙折射性來補償該相位差。再者，在此所謂「保護膜之遲相軸與上述偏光膜之吸收軸係成交叉」，係意謂偏光膜之吸收軸並非平行於保護膜之遲相軸。偏光膜之.吸收軸與保護膜之遲相軸所形成的角度（與偏光膜之切斷前或後無關係）係以1〇°~ 90°爲佳，較佳爲20°~ 70°與80°〜90° ® ，更佳爲 40°~ 50°與 90° ’ 特佳爲 43°~ 47°與 87 。〜90。。此外，也可使用2片保護膜，並將任一方的遲相軸與偏光膜之吸收軸成交叉。此時’ 2片保護膜可以黏合層或接合層來貼合β (9) 如第（7)或第（8)項之偏光板’其中具有配置於該—對保護膜中至少一方的表面之「光學補償層」 -18 - 1356212 ，該光學補償層是由具有碟狀結構單元之化合物所 - 構成，且該化合物之碟狀面係對該偏光膜大致呈垂 t 直配向，並且該光學補償層之配向控制方向，與接於該光學補償層的保護膜之遲相軸，及該偏光膜之吸收軸係各自呈大致平行。在第（9)項之偏光板，由於偏光板所具有一對保護 _ 膜之上述遲相軸之方向一致，加上上述效果，也可 · 獲得提高偏光板之機械性的穩定性、或光學性能均勻化之效果。 β 在本發明說明書中所謂「45°」、「平行」或「正交」，係意謂爲小於嚴格的角度±5°之範圍內。與嚴格的角度之誤差較佳爲小於4°，更佳爲小於3°。另外，關於角度，「+ 」係意謂順時鐘方向，「-」係意謂反時鐘方向。「遲相軸」係意謂折射率會變得最大之方向。「可見光域」係意謂 3 80奈米~ 780奈米》此外，折射率之測定波長係除非另有加註以外，乃是可見光域之λ = 550奈米時之値。在本說明書中所謂「偏光板」，除非另有加註以外，係 β 以包括長尺寸之偏光板及切斷（在本說明書中「切斷」一詞係也包括「沖壓」及「沖裁」等）成可供組配於液晶顯示裝置的大小之偏光板兩者之意思來使用。另外，在本說明書，則將「偏光膜」及「偏光板」加以區別來使用，但是「偏光板」係意謂在「偏光膜」之至少單面具有用以保護該偏光膜的透明保護膜之積層體。發明之效果 -19- 1356212 本發明人之硏究結果，終於藉由調節偏光膜、保護膜及液晶胞之材料及其製造方法成功地製得具有與傳統的液晶，顯示裝置相同結構’同時具有以光學方式補償液晶胞的機能之橢圓偏光板。並且’將該偏光板搭配於VA型、IPS型液晶胞以使用於液晶顯示裝置，結果不僅是顯示品質，連同視野角也獲得顯著的改善。並且，也可不再需要如同傳統慣用的將1片或數片之相位差薄膜與偏光板的角度邊嚴格地加以調整 '邊進行積層之製程，可實現以「捲裝進出」方式之偏光板製造方法。另外，若根據本發明，其係可 ® 提供一種不僅具有偏光機能，也有助於液晶顯示裝置之視野角擴大，且可容易地製造之偏光板。發明之實施形態茲就本發明液晶顯示裝置一實施形態之結構構件依序說明如下。第1圖及第2圖係本發明液晶顯示裝置之一實施形態之示意模式圖。〔液晶顯示裝置〕首先，如第1圖所示之液晶顯示裝置，係具有液晶胞（5 ® ~ 8)，及夾持液晶胞所配置之上側偏光膜1與下側偏光膜 14。偏光膜1和14是由一對透明保護膜3和3a、及.12和 1 2a所夾持。液晶胞5 ~ 8是由液晶胞上側基板5和液晶胞下側基板8、及爲該等所夾持之液晶分子7所構成’液晶分子7是由施加在基板5和8的對向面之摩擦處理方向或配向膜材料來控制其配向方向。上側偏光板是由一對透明保護膜3a和3、及由該#所夾 -20- 1356212 持之偏光膜1所構成（假設透明保護膜3係配置在液晶胞 -(第1圖中之5~8)的近側）。偏光膜1之吸收軸2係與 t 透明保護膜3之遲相軸4交叉。具體而言，偏光膜丨之吸收軸2與透明保護膜3之遲相軸4所形成的角度α係以10。 ~ 90°爲佳，較佳爲20。~ 70°，更佳爲40。~ 50。，特佳爲43。 ~ 47°。關於另一方的透明保護膜3a (係配置在液晶胞5 ~ ' 8的遠側）之遲相軸與偏光膜1之吸收軸2所形成的角度 · ’雖然並無特殊的限制，但是與上述α之較佳範圍相同。另外，下側偏光膜14之吸收軸15與配置在液晶胞的近側 # 之保護膜12之遲相軸13之關係，也是以相同範圍爲佳。一對透明保護膜3a和3之各遲相軸，係以實質地互相平行爲佳。一對透明保護膜之遲相軸若爲平行時，則將可獲得提高偏光板之機械性的穩定性、或光學性能均勻化之效果，因此較佳。另外，若配置在液晶胞的遠側之透明保護膜之遲相軸與偏光膜之吸收軸是實質地爲平行時，則將可提高例如偏光板之尺寸變化或防止捲曲等機械性的可靠性。配置在液晶胞的遠側之透明保護膜之遲相軸，與偏光膜 ® 之吸收軸成正交時也能獲得相同效果，並且若透明保護膜之厚度或剛性足夠時，則一對保護膜之遲相軸即使各自以不同角度交叉時，也能獲得相同效果。此外，也可將配置在液晶層的近側之保護膜製成爲2片，且使得一方的保護膜之遲相軸與偏光膜之吸收軸成交叉。在第1圖中，上側偏光板和下側偏光扳之偏光膜’1和偏光膜14之液晶胞的近側之保護膜3和12之遲相軸4和13 -21 - 1356212 ，係以實質地互相平行或成正交爲佳。若透明保護膜3和 12之遲相軸4和13是互相交叉時，則藉由互相消除各保護膜之雙折射，即可減少垂直入射於液晶顯示裝置的光之光學特性劣化。另外，在遲相軸4和13互相平行之模式時，若液晶層有殘留相位差時，則可以保護膜之雙折射來補償該相位差。配置在上側偏光膜1之液晶胞側的保護膜3或配置在下側偏光膜14之液晶胞側的保護膜12,係在可見光域之任何波長λ符合如下所述條件之光學特性： -30 (奈米）各{ (nx - ny) x d2 } ^ 50 (奈米），及 -50 (奈米）蕊〔{ (nx + ny) / 2 - nz } x d2 ] έ 300 (奈米）。然而，在該式中，d2 (奈米）是保護膜之厚度，nx和ny (但是ny<nx)是面內之主平均折射率，nz是厚度方向之主平均折射率.，nx、ny和nz係各自呈互相正交。在本發明中，係將會顯現此光學特性之保護膜，藉由使其遲相軸如上所述加以配置成與偏光膜之偏光軸成交叉，以使得該保護膜具有液晶胞之光學補償功能。關於保護膜之製造方法、材料等之細節則容後說明。「液晶胞」是由上側基板5和下側基板8、及由夾持在該等中之液晶分子7所形成的液晶層所構成。在與基板5 和8相接觸之液晶分子7的表面（在下文中也稱爲「內面」之情形）形成配向膜（未圖示），並藉由施加在配向膜上的摩擦處理或配向膜材料等來控制在未施加電壓狀態或 -22- 1356212 低施加狀態的液晶分子7之配向。另外，在基板5和8之內面，則形成用以對於由液晶分子7所構成的液晶層施加電壓之透明電極（未圖示）。關於「液晶層j之顯示模式並無特殊的限制，可爲VA 模式' IPS模式、ECB模式、TN模式及OCB模式等任一種顯示模式之液晶層。在本發明中，液晶層之厚度d (微米 )與折射率異方向性Δη的乘積Δη·(1爲0.1〜1.0微米。 △ n_ d之最適値是視顯示模式Μ不同。在透射模式，在未具有扭轉結構之VA型或IPS型、ECB型則爲0.2〜0.4微米之範圍，TN型雖然也會相依於扭轉角度之大小，但是以 0.2 ~ 0· 5微米之範圍，在OCB型則以0.6 ~ 1.0微米爲其最適値。由於在該等之範圍的白色顯示亮度高，黑色顯示亮度小，因此能獲得明亮且高對比之顯示裝置。此外，在第1圖雖然展示具有上側偏光板及下側偏光板的透.射型顯示裝置之態樣，但是本發明也可爲僅具一偏光板之反射型模式之態樣，在此情況下，液晶胞內光路將變爲2倍，因此Δη· d之最適値將爲上述之約1/2之値。關於偏光膜1和14之吸收軸2和15，保護膜3和12之遲相軸方向4和13，及液晶分子7之配向方向，可按照用在各構件之材料、顯示模式、構件之積層結構等加以調整成最適範圍。例如在VA型或IPS型之屬於正常黑色顯示模式的液晶顯示裝置之態樣，如欲獲得高對比，則將偏光膜1和14之吸收軸2和15配置成互相實質地成正交。但是本發明之液晶顯示裝置並不受限於此結構。 •23- 1356212 其次，使用第1圖，茲就「VA模式」之液晶顯示裝置的實施形態說明其驅動原理如下。在本實施形態中，作爲「場效應型j液晶則以使用具有負介電異方向性的向列型液晶來作主動驅動之實例加以說明。第1圖所示之液晶顯示裝置係在未對於各液晶胞基板 5和8之透明電極（未圖示）施加驅動電壓的非驅動狀態，則其液晶層中之液晶分子7係對基板5和8之面大致呈垂直配向，其結果使得所通過的光之偏光狀態幾乎都不會變化。由於吸收軸2和15係呈正交，因此經由下側（例如背面電極）所入射之光，將爲偏光膜14所偏光，並在仍然維持偏光狀態下通過液晶胞5 ~ 8,然後即由偏光膜1來加以遮斷。換言之，第1圖之液晶顯示裝置可在非驅動狀態時實現理想的黑色顯示。與此相對，在對於透明電極（未圖示）施加驅動電壓的驅動狀態時，液晶分子7將朝對於基板5和8之面成平行方向傾斜，使得所通過之光因如此傾斜的液晶分子7而使其偏光狀態變化。因此從下側（例如背面電極）所入射之光，將爲偏光膜14所偏光，再通過液晶胞5 ~ 8，以使偏光狀態變化，然後通過偏光膜1。換言之，第1圖所示之液晶顯示裝置，係在驅動狀態能獲得白色顯示。在此，由於電場係施加在上下基板5和8之間，因此應使用如液晶分子7會垂直於電場方向作響應（response)般的介電常數異方向性爲負之液晶材料。另外，若將電極僅形成在基板5和8中任一方，使電場僅能施加於平行於基 -24- 1356212 板面之橫方向時，則液晶材料即可使用具有正介電常數異方向性者。「VA模式」之特徵爲高速響應和高對比。然而，傳統的 .V A模式液晶顯示裝置，則有對比在正面雖然高，但是在斜方向卻將變差之難題。在黑色顯示時，由於液晶分子7係垂直配向於基板5和8之面，從正面觀察時，因爲液晶分子7幾乎都無雙折射、透射率低，因此可獲得高對比。然而，由斜向觀察時，液晶分子7就會產生雙折射。並且，上下之偏光膜1和14之吸收軸2和15之交叉角，在正面雖然爲90°之正交，但是由斜向看時將變成大於90。。由於該等兩項原因，在斜向就會產生漏光，使得對比降低。在第1圖之液晶顯不裝置中’其係在偏光膜1之液晶胞的近側配置將會顯現特定光學特性之透明保護膜3，使其遲相軸4與偏光膜1之吸收軸2交叉，或在偏光膜14之液晶胞的近側配置將會顯現特定光學特性之透明保護膜12，使其遲相軸13與偏光膜14之吸收軸15交叉，藉以改善在黑色顯示時的透射率之視野角特性，以達成廣視野角化。另外’液晶分子7在白色顯示時係傾斜，因此在傾斜方向與其反方向，雖然由斜向觀察時之液晶分子7的雙折射大小就不相同，使得亮度與色調會產生差異，但是若構成爲將液晶顯示裝置的一畫像素加以分割成數個領域之所謂「多域結構（multi-domain structure )」時，即可改善亮度或色調之視野角特性，因此較爲理想。具體而言，以液晶分子之初始配向狀態互不相同的兩個（較佳爲四個或八 -25- 1356212 個）以上之領域來構成各畫像素，以使其平均化，藉此即 · 可減少相依於視野角的亮度或色調之偏差。此外，以在電，壓施加狀態液晶分子之配向方向會連續地變化之互不相同的兩個以上之領域來構成各畫像素也能獲得相同效果。如欲在一畫像素內形成數個液晶分子7之配向方向不同的領域，則可利用例如在電極設置細縫（slit )、或設置突 ’ 起、或改變電場方向、或使電場密度具有偏差等方法。如 · 欲在全方向獲得均勻視野角，則將該分割數增加即可，但是設定爲4分割或8分割以上，即可獲得大致均勻的視野 ® 角。特別是8分割時，即可將偏光板吸收軸設定爲任何角度，因此較爲理想》在各區塊（domain)之領域邊界，·液晶分子7則有難以進行響應之傾向。在VA模式等之正常白色顯示模式（ NWM ； Normally White Mode)，由於會維持黑色顯示，亮度下降將成爲問題。因此，可在液晶材料添加對掌劑（ chiral agent)以使區塊之間的邊界領域變小。與此相對，在正常黑色顯示模式，由於會維持白色顯示狀態，正面對 β 比將下降。因此，設置用以覆蓋該領域的黑色矩陣（遮光層）（black matrix)等之遮光層即可。液晶顯示裝置有「主動矩陣型」和「被動矩陣型」之兩種驅動方式，使用於筆記型個人電腦之液晶顯示裝置，一般使用主動矩陣型之薄膜電晶體。偏光膜1和14之吸收軸 2和15,若將對朝主動矩陣型的薄膜電晶體送電氣信號之配.線實質地以45°交叉時，則視野角特性將變成左右對稱之 -26- 1356212 結構，因此較爲理想。不僅是VA模式，在TN及OCB模式也是相同。偏光膜之吸收軸若對液晶胞基板長邊成平行或垂直時，則雖然需要考慮及信號線與吸收軸所形成之交叉角來作配線，但是如第1圖所示之方式，若使偏光板之吸收軸原先就使其對液晶胞基板長邊以45°交叉，並以僅使信號線對液晶胞基板長邊成平行或垂直之方式來設計，即可獲得左右對稱之視野角。從如此之觀點來考量，則第1 圖中偏光膜1和14之吸收軸2和15，應以對液晶胞基板5 和8之長邊以+ 45°、或以-45°交叉爲理想。但是若也考慮及信號線並非爲直線之情形而言，則以45°±10°、或以-45°±10°交叉爲佳。 VA模式之「液晶胞」，例如在上下基板5和8之間注入介電異方向性爲負，且Δη = 0.0813、△ ε = - 4.6左右之向列型液晶材料等，並藉由摩擦配向處理，並設定表示液晶分子之配向方向的「指向角（director)」，即所謂的「傾斜角（tilt angle)」爲約89°即可製得。關於液晶層之厚度d雖然並無特殊的限制，但是使用上述範圍之特性的液晶時，則可設定爲約3.5微米。由於白色顯示時之亮度會因厚度d與折射率異方向性Δη的乘積Δη· d之大小而變化，因此如欲獲得最大亮度，△ η · d則較佳爲設定在0.2 〜0.5微米之範圍。另外，在VA模式之液晶顯示裝置，添加在TN模式液晶顯示裝置一般使用的對掌（chiral)材料之措施，因會導致動態響應特性劣化之故而很少使用，但是也有爲減輕配向不良而添加之情形。另外，如上所述使 -27- 1356212 用多域結構時，則對於調整各區塊之間的邊界領域之液晶 . 分子配向上是有利》 _ 如上所述係在上述各種液晶顯示模式中，在未施加電壓或施加低電壓時爲黑色顯示，在施加高電壓時則變成白色顯示的方式，即所謂「正常黑色顯示模式j中，針對於VA 模式加以說明，但是本發明並不受限於此，其他也屬於正 ’ 常黑色顯示模式的利用IPS模式之態樣也可。另外，也可爲利用在未施加電壓或施加低電壓時爲白色顯示，在施加高電壓時則變成黑色顯示的「正常白色顯示模式」之態樣鲁 ’可使用OCB模式、ECB模式、或TN模式之液晶胞。另外，也可使用在黑色顯示時，向列型液晶材料之液晶分子將對基板表面大致平行配向之液晶胞；具體而言，也可使用在未施加電壓狀態下，使液晶分子對基板面平行配向而作黑色顯示的IPS模式或ECB模式之液晶胞。但是在此態樣如欲獲得視野角改善效果，則偏光板之保護膜的（nx -ny) X ch之値，較佳爲設定在液晶層之約△!!·(!之値。本發明之液晶顯示裝置並不受限於如第1圖所示之結構 ® ，也可包括其他構件。例如，在液晶胞與偏光膜之間也可配置彩色濾光片。而且，如後所述也可在液晶胞與偏光板之間另外配置光學補償膜。此外，當用於「透射型」時，也可將以冷陰極或熱陰極螢光管、或發光二極體、場致發射元件、電激發光元件爲光源的背光配置於背面。此外，本發明之液晶顯示裝置也可爲「反射型」，在此情況下，偏光板即可僅在觀察側設置一片，且將反射膜設 -28- 1356212 置於液晶胞背面或液晶胞下側基板之內面。當然也可將使《用上述光源之正面光（front light )設置於液晶胞觀察側。：本發明之液晶顯示裝置係包括：影像直視型、影像投影型 '光調制型。本發明係以適用於如同TFT (薄膜電晶體 )或MIM (金屬-絕緣體-金屬）方式般使用三端子或二端子半導體元件之主動矩陣型液晶顯示裝置之態樣爲特別有 _ 效。當然適用於被稱爲「時分割驅動」的以超扭轉向列型 · (STN )爲代表之被動矩陣型液晶顯示裝置之態樣也是有效。本發明雖然係藉由將偏光板的透明保護膜之遲相軸，與偏光膜之吸收軸設定成特定關係以意圖改善液晶顯示裝置之視野角者，但是若進一步在偏光板與液晶胞之間配置光學補償膜時’則可更進一步地改善視野角，因此較爲理想。關於光學浦償膜，並無特殊的限制，只要是具有光學補償能，則任何結構皆可使用。例如，可使用雙折射性之高分子薄膜’或由透明支撐體與形成在該透明支撐體上之液晶分子所構成的光學異方向性層之積層體等。在後者之態 β 樣，其偏光板之液晶層的近側之透明保護膜3和12也可兼作上述光學異方向性層之支撐體《爲改善VA模式之視野角，有一種使用具有正折射率異方向性的相位差板，與具有負折射率異方向性的相位差板之方法，已記載於日本國專利特開平第10- 153,802號公報 ’本發明也可適用該方法。相位差板係具有在互相正交的 X ' y和ζ軸方向具有三平均折射率nx、ny和ηζ，且設若 -29- 1356212 面內之平均折射率爲nx和ny、厚度方向之平均折射率爲 - nz時，則有將各成爲nx、ny = nz、nx > ny之相位差板（ ^ 在下文中稱爲「光學異方向性層A」），與將成爲nx = ny 、nz、nx > nz之相位差板（在下文中稱爲「光學異方向性層B」）。若將該光學異方向性層A和該光學異方向性層 B之積層體用作爲光學補償膜時，則可防止VA模式之黒 ‘ 色顯示由斜方向所觀察時之漏光。另外，如上所述，若使 · 上側偏光膜1與下側偏光膜14之吸收軸2和15係正交配置時，則有由斜向觀察時交叉角度將由直角偏移，以致漏 · 光會增加之問題。已知該漏光係藉由使用經積層該光學異方向性層A和該光學異方向性層B所形成之積層體，即可加以減少（請參閱日本國專利特開第2001 -350,022號公報 )。如欲獲得在VA模式所垂直配向的液晶分子之視野角光學補償，雖然以該光學異方向性層B爲有效，但是如欲改善上述之偏光板視野角，則該光學異方向性層A也是需要。因此’若將該光學異方向性層A及該光學異方向性層 B之積層體用作爲光學補償膜時，則有利於改善對於在VA · 模式所垂直配向的液晶分子之視野角之光學補償、及偏光板視野角。再者’本發明之液晶顯示裝置也可具有組合上述光學異方向性層A和上述光學異方向性層B之光學補償膜。視液晶層之Δπ· d的大小、積層配置位置 '偏光板之保護膜的光學性能而有各種不同的組合態樣。例如，偏光板的保護膜（第1圖中之3或12)之Re値 -30- 1356212 配置於偏光板之液晶胞的近側之透明保護膜，係可兼作. 學異方向性層之支撐體。因此，也可製成爲依照透明保護膜、偏光膜、透明保護膜（兼作爲透明支撐體）及光學異方向性層之順序積層之一體型偏光板而搭配於液晶顯示裝 ' 置內。另外，也可邊依序作積層、邊製造液晶顯示裝置。在液晶顯示裝置內則較佳爲從裝置外側（液晶胞的遠側），以透明保護膜、偏光膜 '透明保護膜（兼作爲光學異方 . 向性層之透明支撐體）及光學異方向性層之順序積層。其次，將本發明液晶顯示裝置之其他實施形態示意模式 φ 圖展示於第2圖。本實施形態中之液晶顯示裝置係在第1 圖所示之液晶顯示裝置，再組合倂用「光學補償層1 〇」之結構。第2圖中，對於與第1圖相同構件則附以相同代表符號並省略說明。另外，在第2圖則將上側偏光膜1及下側偏光膜14的一對保護膜中，省略配置在外側之保護膜。第2圖所示之液晶顯示裝置，其保護膜12之光學特性係在可見光域之任何波長λ符合如下所述之條件： -30 (奈米）$ { (nx - ny) x d2 } ^ 50 (奈米），及 β -50 (奈米）S〔 { (nx + ny) / 2 - nz } x d2〕^ 300 (奈米）。 .式中各代號之定義係如上所述。另外，第2圖之液晶顯示裝置係在第1圖之液晶顯示裝置之結構構件，再加上鄰接於保護膜12所配置成之光學補償層1〇者。光學補償層 10是由具有碟狀結構單元之化合物所構成，且該碟狀面係對於上述基板面大致呈垂直配向所構成的膜。並且，上述 -32- 1356212 光學補償膜之配向控制方向（例如，在藉由摩擦處理之配向膜所配向控制之情形時即爲「摩擦軸」）與保護膜12之遲相軸1 3，係配置成對於上側偏光膜之吸收軸大致平行。在本態樣係藉由將自上下偏光膜直至液晶胞光將通過的層 (偏光膜所含有之保護膜）之延遲値設定成爲非對稱來改善由斜向所觀察時之漏光防止。尤其是在本態樣中，可有效地對於減少在上偏光板1A和下偏光板14A之吸收軸係呈正交之態樣中的斜方向漏光。下偏光板14A係將偏光膜14、保護膜12及光學補償層 1〇 —體形成所製得者。製成爲如此之結構，藉此保護膜12 即可兼作光學補償層10之支撐體，有助於液晶顯示裝置之輕量化和薄型化。另外、在本實施形態中，由於將光學補償層10之配向控制方向11與保護膜12之遲相軸13配置成對於偏光膜14之吸收軸15大致平行，因此在製造一體型偏光板時，在可容易作軸的對準上也是有利。關於本實施形態中之液晶胞（5 ~ 8 )之驅動模式，雖然也並無特殊的限制，但是較佳爲IPS模式之液晶胞。在第3圖展示「IPS模式」液晶胞之模式側截面圖。在 IPS模式之液晶胞，通常因矩陣狀之電極而具有數個畫像素，但是第3圖只是表示其一畫像素之一部份。其係在透明的一對基板5、8之內側形成線狀電極16，並在其上面形成配向控制膜（未圖示）。夾持在基板5、8之間的棒狀液晶性分子7係配置成在未施加電壓時對於線狀電極〗6之長度方向具有些角度。另外，在此情況下的液晶之介電常 -33 - 1356212 數異方向性係假設爲正之情形。因此一施加電場，液晶性分子7就對電場方向改變其方向。使偏光膜1A及14A夾持IPS模式之液晶胞而配置成特定角度，藉此即可改變光透射率。另外，電場方向對基板 8之表面所形成的角度’較佳爲20度以下，更佳爲10度以下’換言之'以實質地成平行爲佳。以下，在本發明則將屬於20度以下者總稱爲「平行電場」來表達。再者，將電極16分成於上下基板而形成，抑或僅形成於一方之基板，其效果不會改變。液晶材料LC係使用介電常數異方向性△ e爲正的向列型液晶。液晶層之厚度（間隙）係設定爲大於2.8微米、小於4.5微米。如此，若將延遲値△ η · d設定爲大於0.25 微米、小於0.32微米時，則可更容易地製得在可見光範圍內幾乎並無波長相依性之透射率特性。藉由如後所述之配向膜與偏光板之組合，液晶性分子由摩擦方向朝電場方向回轉45度時’即可獲得最大透射率。另外，液晶層之厚度 (間隙）係以聚合物珠狀物（bead )來加以控制。當然玻璃珠或纖維、樹脂製之柱狀間隔物（spacer )也可製得相同之間隙。另外，液晶材料LC只要其是向列型液晶，則並無特殊的限制。介電常數異方向性△ £係其値爲大者，即能減低驅動電壓，折射率異方向性△ n係愈小，即能使液晶層之厚度（間隙）增厚，可縮短封入液晶所需之時間 ’且可使間隙之變異性減少。也可使包含在上述液晶層的向列型液晶材料由配向狀態 1356212 不同的兩種以上之領域來構成。如上所述，本實施形態中之液晶顯示裝置的顯示模式並無特殊的限制’但是以ECB模式、IPS模式爲適合使用。在本實施形態中’其液晶層之厚度d(微米）與折射率異方向性△!!的乘積Δη.ά，較佳爲設定成0.2 ~ 1.2微米。 △n· d之最適値爲0.2 ~ 0.5徵米。在該等之範圍時，白色顯示亮度高、黑色顯示亮度小’因此能獲得明亮且高對比之顯示裝置。另外’該等最適値係透射模式之値，在反射模式則因液晶胞內的光路將變爲2倍，因此Δη. d之最適値將變爲上述之約1/2之値。可使用於本實施形態之液晶顯示裝置’不僅是上述顯示模式，適用於VA型、OCB模式、TN模式、HAN (混合配向向列型）模式、及STN模式之態樣也是有效。茲就可供使用於本發明液晶顯示裝置的各種構件所使用之材料，及其製造方法詳加說明如下。〔偏光板〕偏光板一般是由偏光膜'及夾持該偏光膜之一對保護膜所構成。本發明之偏光板，其偏光膜之一對保護膜中至少形成於配置在液晶胞的更近側之面的保護膜，係會顯現出如後所述之特定的光學特性。本發明偏光板之一態樣是貼附由液晶性化合物所形成之光學補償層（在下文中也稱爲「光學異方向性層」之情形），且同時具有光學補償能之偏光板。另外，一種以由具有特定光學特性之高分子薄膜或液晶性化合物所形成之光學補償層作爲保護膜之偏光板 1356212 ，同時也會具有光學補償機能之情形，此種結構之偏光板 * 也可使用。光學補償層較佳爲在偏光膜或偏光板之保護膜的表面上，直接由液晶性分子來形成，抑或藉由配向膜由 « 液晶性分子所形成。具體而言，將光學異方向性層用塗佈液塗佈在偏光膜之表面或該偏光膜之保護膜的表面，即可形成光學異方向性層。前者之態樣係在偏光板之保護膜與 ‘ 光學異方向性層之間，可在不必使用聚合物薄膜下，製得 . 隨著偏光膜的尺寸變化之應力（應變 X截面積 X彈性模數）小的薄偏光板。若將根據本發明之偏光板安裝在大型 Φ 液晶顯示裝置時，即可在不致於產生漏光等問題下，顯示出高顯示品質之影像。偏光膜較佳爲以Optiva Inc.爲其代表之塗佈型偏光膜，或是由「黏結劑（binder )」與碘系或二色性色素所構成的偏光膜。碘系及二色性色素，係在黏結劑中加以配向即可顯現出偏向性能。碘系及二色性色素較佳爲沿著黏結劑加以配向，或使二色性色素藉由如同液晶般的自組織化來配向成單方向。 φ 目gij市售商品級之偏光膜’ 一般將經延伸的聚合物浸漬在浴槽中之碘系或二色性色素的溶液中，以在黏結劑中使碘系或二色性色素滲透於黏結劑中所製得。另外，市售商品級之偏光膜，其碘系或二色性色素係分佈於距自聚合物表面約4微米（兩側合計爲約8微米），因此如欲獲得足夠的偏光性能，則至少需要10微米之厚度。滲透度係可藉由碘系或二色性色素的溶液濃度、同浴槽 -36- 之溫度、同浸漬時間來加以控制。如上所述，黏結劑厚度之下限較佳爲10微米。至於厚度之上限’則從將偏光板用在液晶顯示裝置時所產生的漏光現象之觀點來考慮，則以愈薄愈佳。以目前市售商品級之偏光板（約爲30微米）以下爲佳，較佳爲25微米以下，更佳爲20微米以下。若爲20微米以下時，則在17英寸之液晶顯示裝置即不會觀察到漏光現象。偏光膜之黏結劑也可爲經交聯化者。偏光膜之黏結劑也可使用其本身即可交聯性聚合物。也可在具有官能基之聚合物，或在聚合物導入官能基所製得之聚合物’施加光、熱或pH變化，使官能基反應以使得聚合物之間交聯化，以形成偏光膜。此外，也可以交聯劑將交聯結構導入聚合物中。交聯係一般在透明支撐體上塗佈含有可交聯性聚合物、或聚合物與交聯劑之混合物的塗佈液後’加以加熱即可實施。由於只要是在最終商品之階段能確保耐久性即可，因此施加交聯化之處理，也可在直至獲得最終之偏光板之前的任何階段實施。偏光膜之黏結劑係可使用其本身爲可交聯性聚合物、或可藉由交聯劑交聯之聚合物中任一者。聚合物之實例係包括與可利用於如後所述之配向膜的製造者相同之聚合物。其中以聚乙烯醇及改質聚乙烯醇爲最佳》關於改質聚乙烯醇，則已記載於日本國專利特開平第8-338,9 1 3號、同第 9-152,509號及同第9-316,127號之各公報中。聚乙烯醇及改質聚乙烯醇係可倂用兩種以上。 -37- 1356212 黏結劑的交聯劑之添加量係以相對於黏結劑爲〇. 1 ~ 20 · 質量％爲佳。如此偏光元件之配向性'偏光膜之耐濕熱性 — 將變得良好。偏光膜係在結束交聯反應後，也含有某一程度的未經反應之交聯劑》但是所殘留的交聯劑量，則較佳爲在配向膜中爲1.0質量％以下，更佳爲0.5質量％以下。設定爲如上 · 所誠時，即使將偏光膜搭配於液晶顯示裝置，並經長期使 · 用，或長期放置在高溫高濕之周圍環境下時，也不致於導致偏光度下降。 Φ 關於交聯劑，則在美國再發行專利第23,297號說明書有所記載。另外，硼化合物（例如硼酸、.硼砂）也可用作爲交聯劑。「二色性色素」係可使用：偶氮系色素、二苯乙烯系色素 '二氫吡唑酮系色素、三苯基甲烷系色素、喹啉系色素、噁井系色素、噻井系色素、或蒽醌系色素。二色性色素較佳爲水溶性者。二色性色素較佳爲具有親水性取代基（例如，磺酸基、胺基、羥基）。二色性色素之實例係包括 β 例如在發明協會公開技術方法，公技號碼200 1-1745號，第58頁（發行日期2001年3月15日）所記載之化合物。爲提高液晶顯示裝置之對比，偏光板之透射率則以高者爲佳，偏光度也以高者爲佳。偏光板之「透射率」係在波長爲550奈米之光，較佳爲30 ~ 50 %之範圍，更佳爲35 ~ 50 %之範圍，且最佳爲4〇 ~ 50 %之範圍。「偏光度」係在波長爲550奈米之光，較佳爲90 ~ 100 %之範圍，更佳爲 -38- 1356212 95 ~ 1 00 %之範圍，且最佳爲99 ~ 1 00 %>之範圍。 - 也可將偏光膜與光學補償層、偏光板之保護膜與光學異方向性層、或偏光膜與形成光學異方向性層所使用之配向膜，藉由黏合劑（adhesive)來黏合。「黏合劑」係可使用聚乙烯醇系樹脂（包括藉由乙醯乙醯基、磺酸基、羧基、氧化烯基之改質聚乙烯醇）或硼系化合物水溶液。其中較 ’ 佳爲聚乙烯醇系樹脂。黏合劑層之厚度經乾燥後較佳爲 · 0.01 ~ 10微米之範圍，且特佳爲0.05 ~ 5微米之範圍。〔偏光膜之製造〕 ® 若從生產良率之觀點來考慮，偏光膜則較佳爲使黏結劑在對於偏光膜長度方向（MD方向）傾斜10〜80度下實施延伸（延伸法），或是經摩擦（摩擦法）後，以碘系、二色性色素加以染色。「傾斜角度」較佳爲以符合貼合於構成LCD的液晶單元兩側之兩片偏光板的透射軸與液晶單元之縱或橫方向所形成的角度之方式加以延伸。通常之傾斜角度爲45 °。然而，最近卻在透射型、反射型及半透射型 LCD中開發出並非一定爲45°之裝置，因此延伸方向應以 Φ 可根據LCD設計而任意加以調整者爲宜。在延伸法之情形下，「延伸倍率」較佳爲2.5〜30.0倍 ’更佳爲3.0至10.0倍。延伸係可以在空氣中實施之乾延伸法。另外’也可在浸漬於水的狀態下實施之濕延伸法。「乾延伸」之延伸倍率較佳爲2_5 ~ 5.0倍，「濕延伸」之延伸倍率則以3·0 ~ 10.0倍爲佳。延伸製程係包括斜向延伸在內也可分成數次進行。分成爲數次，藉此即使爲高倍 -39- 1356212 率延伸也可更均勻地施加延伸。在進行斜向延伸前，也可朝橫向或朝縱向實施數次延伸（能防止寬度方向收縮之程度）。延伸可藉由將雙軸向延伸中的拉幅延伸以左右不同之步驟來進行即可實施。該雙軸向延伸係與在通常薄膜製膜過程所使用之延伸方法相同。在雙軸向延伸，由於以左右不相同之速度下進行延伸，因此延伸前的黏結劑薄膜之厚度必須使其左右不相同。在流延製膜法，則對於模頭附加錐形，即可對於黏結劑溶液之流量賦予左右差異。藉由如上所述方法，即可製得對於偏光膜MD方向斜向延伸成10至80度之黏結劑薄膜（binder film )。在摩擦法中，則可應用作爲LCD液晶配向處理步驟所廣泛使用之摩擦處理方法。換言之，使.用紙或紗布、毛氈布、橡膠或耐綸、聚酯纖維將膜表面朝一定方向摩擦即可獲得配向。一般使用均勻地將長度和粗細度均勻的纖維植毛所形成之布來施加左右摩擦數次即可達成。較佳爲使用輥本身之真圓度、圓筒度、徑向擺動（偏心）均爲30微米以下之摩擦輥來實施。對於摩擦輥的薄膜之摩擦角（lap angle)較佳爲Ο.Γ~ 90°。但是，例如日本國專利特開平第 8- 1 60,430號公報所記載，捲取360°以上，藉此也可獲得穩定的摩擦處理。將長尺寸薄膜加以摩擦處理時，則較佳爲使用搬送裝置在一定的張力狀態下以1 ~ 100公尺/分鐘之速率來搬送薄膜。爲設定任何摩擦角度，摩擦輥較佳爲對於薄膜行進方向可朝水平方向自由回轉。較佳爲可在0°〜60°之範圍選擇 -40- 1356212 適當的摩擦角度。使用於液晶顯示裝置時，則較佳爲40° ~ 50°，且特佳爲45°。較佳爲在偏光膜之與光學異方向性層相反側的表面配置用以保護偏光膜之聚合物薄膜（光學各向異性層/偏光膜/ 聚合物薄膜之配置）。聚合物薄膜也可爲其最表面是具有防污性及耐擦傷性之反射防止膜。〔保護膜〕本發明之偏光板係在偏光膜兩面積層一對保護膜者。保護膜之種類並無特殊的限制，可使用纖維素醋酸酯、纖維素醋酸-丁酸酯、纖維素丙酸酯等之纖維素酯類，聚碳酸酯、聚烯烴、聚苯乙烯、及聚酯等。保護膜通常係以捲筒形態所供應，因此對於長尺寸之偏光膜，較佳爲以能使長度方向成爲一致之方式來作連續貼合。然而，保護膜之配向軸（遲相軸）可爲任何方向，但是從操作上的簡便性之觀點來考慮，則保護膜之配向軸較佳爲平行於長度方向。在本發明中，關於夾持偏光膜之一對保護膜中至少一方，則使用具有與膜'面之平均折射率會成爲最大之方向實質的符合之遲相軸者。換言之，至少一方之保護膜，係由在各自呈互相正交的X、y和Z軸方向具有三平均折射率nx 、ny和nz，且假設面內之主平均折射率爲nx和ny，厚度方向之主平均折射率爲nz時，則.nx、ny = nz、nx > ny之關係會成立之薄膜；nx = ny、nz、nx > nz會成立之薄膜所構成。亦即，由具有作爲如上所述之光學異方向性層A或 1356212 光學異方向性層B的光學特性之薄膜所構成。如上所述，如欲對保護膜賦予光學補償能，則較佳爲以在可見光域之任何波長λ能符合下列條件： -30 (奈米）S { (nx - ny) x d2 } ^ 50 (奈米），及 -50 (奈米）S〔 { (nx + ny) / 2 - nz } x d2〕S 300 (奈米）。另一方面，在不使用保護膜作爲光學補償層之態樣中，則較佳爲透明保護膜之延遲低，在偏光膜之吸收軸與透明保護膜之配向軸並非爲平行之態樣，尤其是若透明保護膜之延遲値爲一定値以上時，則由於偏光軸與透明保護膜之配向軸（遲相軸）係向斜向偏移，使得直線偏光變化成橢圓偏光，因此係視爲不理想。因此，透明保護膜之延遲，係例如在632.8奈米則較佳爲1〇奈米以下，且更佳爲5奈米以下。延遲較低之高分子薄膜，則包括例如：纖維素醋酸酯’ ZEONEX、ZEONOA (皆爲日本Zeon公司（股）製 )’ ARTON (JSR公司（股）製）之聚烯烴類可適合使用。其他例如在日本國專利特開平第8- 1 10,402號公報或特開平第U-293，116號公報所記載之非雙折射性光學樹脂材料也適合使用。在進行貼合保護膜與偏光膜時，宜以至少使一方的保護膜（組配液晶顯示裝置時，配置在液晶胞的近側之保護膜 )之遲相軸（配向軸），能與上述偏光膜之吸收軸（延伸軸）成交叉之方式’而將保護膜與偏光膜積層。具體而言 ’偏光膜之吸收軸與上述保護膜之遲相軸所形成的角度， -42- 1356212 係以10°〜90°爲佳，較佳爲2(Γ~ 70°，更佳爲40°~ 50°，且特佳爲43°~47°。對於另一方的保護膜之遲相軸與偏光膜之吸收軸的角度，並無特殊的限制，可視偏光板之目的而加以適當地設定，但是仍以在上述範圍爲佳，且以使一對保護膜之遲相軸成一致爲佳》另外，若保護膜之遲相軸與偏光膜之吸收軸互相平行時，則可提高防止偏光板的尺寸變化或捲曲等偏光膜之機械性上的穩定性。若偏光膜及一對保護膜之合計3個薄膜之至少2個軸，一方的保護膜之遲相軸與偏光膜之吸收軸，或2片保護膜之遲相軸等實質地爲成平行，則可獲得相同效果》另外，若將上下偏光板之保護膜的延遲値設定爲「非對稱」時，即可有助於大幅度地防止由斜方向所觀察時之漏光。尤其是將配置於上下偏光板之液晶胞與偏光膜之間的延遲値設定爲非對稱時，則可有效地降低在上下偏光板之吸收軸成正交的態樣之斜方向漏光。爲使延遲設定成非對稱，則應在上偏光板之一對保護膜中至少一方及下偏光板之一對保護膜中至少一方，分別使用{(nx-ny) X (11}或{ (nx + ny) / 2 - nz } X di之値不相同者◊相對地，若爲在液晶胞之上下偏光板配置同一結構之偏光板之模式，亦即上下偏光板之一對保護膜的延遲爲相同時，則可藉由該等保護膜，或另外組配的光學補償膜來作液晶胞之光學補償〇〈黏合劑〉偏光膜與保護膜之黏合劑雖然並無特殊的限制，然而較 1356212 佳爲PVA (聚乙烯醇）系樹脂（包括乙醯乙醯基、磺酸基、羧基、氧化烯等之改質PVA)、或硼化合物水溶液等，其中較佳爲PVA系樹脂。黏合劑層之厚度經乾燥後較佳爲在0.01〜10微米之範圍，特佳爲在〇.〇5 ~ 5微米之範圍。〈偏光膜與透明保護膜之一貫製程〉本發明之偏光板，係將偏光膜用薄膜加以延伸後，雖然具有使其收縮並使揮發分率降低之乾燥步驟，但是較佳爲在乾燥後或在乾燥時在單面貼合透明保護膜後，具有後加熱步驟。在上述透明保護膜也兼用作爲光學補償層的光學異方向性層之支撐體的態樣，則較佳爲在單面貼合透明保護膜，在相反側貼合具有光學異方向性層之透明支撐體後，施加後加熱。具體的貼合方法，係在薄膜乾燥步驟中，在保持著兩端的狀態下使用黏合劑在偏光膜貼合透明保護膜，然後切除兩端邊緣，或是經乾燥後，由兩端保持部解除偏光膜用薄膜，並切斷薄膜兩端邊緣後，貼合透明保護膜等之方法。切斷邊緣之方法可使用以刀刃等切刀來切斷之方法，使用雷射之方法等一般性技術。貼合後，爲乾燥黏合劑，並使偏光性能良化，較佳爲加熱。加熱條件雖因黏合劑而不同，但是若爲水系時，則以30°C以上爲佳，更佳爲40°C以上、100°C以下，特佳爲50°C以上、90°C以下。該等步驟從性能及生產效率之觀點來考慮，則以一貫性的生產線來製造爲佳。〈偏光板之性能〉本發明之由透明保護膜、偏光膜、透明支撐體所構成的 -44 - 1356212 偏光板的光學性質及耐久性（在短期、長期之保存性），係以具有與市售商品級之超高對比商品（例如Sanritz公司 (股）製HLC 2-5618等）同等以上的性能爲佳。具體而言，可見光透射率爲42.5 %以上，偏光度{ ( Tp · Tc ) / ( Tp + Tc) }1/2 2 0.9995 )(但是，Τρ爲「平行透射率」，[Technical Field] The present invention relates to a polarizing plate having a polarizing film 'and a pair of protective film for holding the polarizing film, and a liquid crystal display device using the same. Further, the present invention relates to an optical compensation film which contributes to improvement of viewing angle characteristics and the like of a liquid crystal display device. [Prior Art] A liquid crystal display device usually has a liquid crystal cell and a polarizing plate. "The polarizing plate j is composed of a protective film and a polarizing film, and a polarizing film made of a polyvinyl alcohol film is dyed with iodine, and is stretched, and then both surfaces are laminated with a protective film. In the "transmissive" liquid crystal In the display device, the polarizing plate is mounted on both sides of the liquid crystal cell, and there is a case where the optical compensation film is further disposed. In the "reflective" liquid crystal display device, the reflection plate 'liquid crystal cell, one or more optical compensation film' polarizing plates are arranged in this order. The "liquid crystal cell" is composed of a liquid crystal molecule, two substrates for encapsulating the substrate, and an electrode layer for applying a voltage to the liquid crystal molecules. The liquid crystal cell system is turned on according to the difference in the alignment state of the liquid crystal molecules. The display is turned off (ON. OFF) and is applicable to either of the transmissive and reflective types. The display modes include, for example, TN (twisted nematic) type, IPS (in-plane switching) type, OCB (optical compensation bending) type, VA (vertical alignment) type, and ECB (electrically controlled birefringence) type. The "optical compensation film" is used in various liquid crystal display devices to eliminate image coloration or to widen the viewing angle. Optical compensation films have traditionally used extended birefringent polymer films. In addition, there is also an optical compensation film composed of an extended birefringent film 1356212, and an optically anisotropic layer formed of a low molecular or high molecular liquid crystalline molecule on a transparent support. Proposal for Optical Compensation Films Since liquid crystal molecules have a plurality of different alignment forms, optical properties which cannot be obtained by conventional extended birefringence polymer films can be realized by using liquid crystal molecules. Further, there has been proposed a combination of a protective film and an optical compensation film by adding birefringence to a protective film of a polarizing plate. The optical properties of the optical compensation film are based on the optical properties of the liquid crystal cell; in particular, depending on the difference in display modes as described above. When a liquid crystalline molecule is used, an optical compensation film having various optical properties which can correspond to various display modes of liquid crystal cells can be produced. The use of an optical compensation film of a liquid crystal molecule has long been possible in response to various display modes. For example, in the case of the liquid crystal cell of the "TN mode", the twisted structure of the liquid crystal molecules is removed by applying a voltage, and the optical compensation film formed by the alignment state fixed to the substrate surface is optically compensated to prevent The oblique light leakage in the black display is used to improve the viewing angle characteristics of the contrast (refer to Japanese Patent Laid-Open No. Hei 6-214, No. 116). In addition, in the "parallel alignment" liquid crystal cell optical compensation film, when the black display is not applied, the optical compensation of the liquid crystal molecules parallel to the substrate surface is performed, and the orthogonal transmittance of the polarizing plate is also used. The improvement of the viewing angle characteristics has been described (see Japanese Patent Laid-Open No. Hei 9-292, No. 5-22). In the liquid crystal cell of the "IPS mode", when the black display is not applied, the optical compensation film composed of liquid crystal molecules aligned in parallel to the substrate surface is optically compensated, and the film also serves as a polarizing light. Improvement of the viewing angle characteristic of the transmittance of the plate Orthogonal 1356212 (refer to Japanese Patent Laid-Open No. 10-54, No. 9 82). Further, in the liquid crystal cell of the OCB mode j, the liquid crystal molecules in the central portion of the liquid crystal layer are vertically aligned by application of a voltage, and the liquid crystal layer of the oblique alignment is optically compensated by an optical compensation film in the vicinity of the substrate interface. Improve the viewing angle characteristics of the black display (refer to U.S. Patent No. 5,805,253). In the "VA mode" of the liquid crystal cell, the liquid crystal molecule will be displayed in a vertical alignment state with respect to the substrate surface in the state where no voltage is applied. The viewing angle characteristics are improved by an optical compensation film (see U.S. Patent No. 2,866,372). ® [Summary of the Invention] The conventional TN mode liquid crystal cell optical compensation film which is to be solved by the invention is only a substitute for the extended birefringent polymer film, and a film composed of liquid crystal molecules can be used to achieve a more conventional method. The liquid crystal cell can be compensated optically more correctly. However, even if liquid crystal molecules are used, it is still very difficult to optically compensate the liquid crystal cells without problems. For example, in the optical compensation film previously proposed, the light leakage from the oblique direction of the polarizing beta plate can still be seen in the black display, and it is understood that the current viewing angle is not sufficiently enlarged (to a theoretically predictable degree). ). Similarly, light leakage can be seen in the conventional IPS, OCB, and VA mode liquid crystal cell optical compensation films. Furthermore, in the IPS and VA mode liquid crystal cell optical compensation film, since it is optically compensated only by the extended birefringent polymer film, it is necessary to use a plurality of films, which results in an increase in the thickness of the optical compensation film. It is not conducive to the thinning of the display device. In addition, since the laminate of the stretched film must use the adhesive layer 1356212, the adhesive layer shrinks due to changes in temperature and humidity and causes defects such as peeling or warpage between the films. The present invention has been made in view of the above problems, that is, to provide a simple structure, and not only display quality, but also a liquid crystal display device which can significantly improve the viewing angle, particularly a "VA type" liquid crystal display device and " The "IPS type" "liquid crystal display device" is a problem. Further, the present invention provides a "polarizing plate" which is not only a polarizing function but also contributes to an increase in the viewing angle of the liquid crystal display device, and can be easily manufactured. Furthermore, the present invention also provides a method for improving the viewing angle characteristics of a liquid crystal display device, particularly an IPS type or VA type liquid crystal display device, by the method of the present invention. The "optical compensation film" of items (1) and (2), the "liquid crystal display device" of items (3) to (6) below, and the following (7) To the "polarizer" of item (9). (1) An optical compensation film for use in a pair of substrates having an electrode disposed at least in opposite directions, a liquid crystal layer sandwiched between the substrates, and at least disposed outside the liquid crystal layer a polarizing film, and the thickness d (micrometer) of the liquid crystal layer and the product of the refractive index anisotropy Δπ Δη·(1 is a liquid crystal display device of 0.1 to 1. μm; and protected by the polarizing film a film, which is composed of an optical compensation layer composed of a compound having a discotic structural unit; and 1356212, the protective film is at any wavelength λ in the visible light region, meeting the following conditions -30 (nano) each { (nx - ny ) X d2 } S 50 (nano), and -5 0 (nano) S[ { (nx + ny) / 2 - nz } x d2]S 300 (nano), where d2 (nano) Is the thickness of the protective film, nx and ny (but ny < nx) is the main average refractive index in the plane, nz is the main average refractive index in the thickness direction, and nx, ny, and nz are each orthogonal to each other; and, the alignment control direction of the optical compensation layer and the protective film The retardation axis is arranged substantially parallel to the absorption axis of the polarizing film. (2) An optical compensation film for use in a pair of substrates having an electrode disposed at least in opposite directions, sandwiched between the substrates and aligned to a surface of the pair of substrates when no voltage is applied a liquid crystal cell composed of a liquid crystal layer of a substantially parallel nematic liquid crystal material, and a liquid crystal display device respectively disposed on the first polarizing film and the second polarizing film outside the liquid crystal cell; and the protective film is in the visible light region Any wavelength λ meets the following conditions -30 (nano) forget { (nx - ny) X d2 } S 50 (nano), and -50 (nano) each [{ (nx + ny) / 2 - nz } X 6]$ -10- 1356212 300 (nano), where d2 (nano) is the thickness of the protective film, nx and ny (but ny < nx) is the main average refractive index in the plane, nz is the main average refractive index in the thickness direction, and nx, ny, and nz are each orthogonal to each other; the optical compensation layer is a molecule of a compound having a dish-like structural unit The disc surface is substantially perpendicularly aligned with respect to the film surface; and the alignment control direction of the optical compensation layer is substantially parallel to the retardation axis of the protective film and the absorption axis of the second polarizing film. (3) A liquid crystal display device comprising: a pair of substrates having at least one of the electrodes disposed opposite to each other; a liquid crystal layer sandwiched between the substrates; and a first polarizing plate disposed outside the liquid crystal layer And the product Δη·d of the thickness d (micrometer) of the liquid crystal layer and the refractive index anisotropy Δη is 0.1 to 1.0 μm; the first polarizing plate has a polarizing film, and the protective film is sandwiched between the polarizing film and the polarizing film And at least one of the pair of protective films has a late phase axis substantially corresponding to a direction in which an average refractive index of the film surface becomes maximum, and a retardation axis of the protective film on the near side of the liquid crystal layer and the polarizing film The absorption axis is crossed; the protective film disposed on the near side of the liquid crystal layer of the pair of protective films has a thickness of (^ (nano), and has three in the x, y, and 2 axis directions orthogonal to each other The average refractive indices nx, ny, and nz are set such that the principal average refractive indices in the plane parallel to the surface of the liquid crystal layer are nx and ny 1356212 (but ny <nx), when the main average refractive index of the liquid crystal layer in the thickness direction is nz, any wavelength λ in the visible light region satisfies the following condition = • 30 (nano) $ { (nx - ny) X di } ^ 50 (nano), and -50 (nano) $[{ (nx + ny) / 2 - nz } x di ) ^ 300 (nano). In the liquid crystal display device of the item (3), the polarizing plate is a polarizing plate in which the retardation axis in the in-plane of at least one of the pair of protective films and the absorption axis of the polarizing film intersect. The polarizing plate is not only a polarizing function, but also contributes to widening the viewing angle of the display device, thereby providing a liquid crystal display device with a simple structure and not only display quality but also significantly improving the viewing angle, especially VA (vertical Alignment type and IPS (in-plane switching) type liquid crystal display. The polarizing plate is formed by using a polarizing film obtained by the "oblique stretching method", and a plurality of protective films and a total of three kinds of polymer films of the polarizing film are laminated in a roll-to-roll manner. Therefore, it also contributes to improving the productivity of the liquid crystal display device. Further, since the protective film of the above polarizing plate can also be used for the optical compensation layer, it is possible to obtain a liquid crystal display device having superior display quality with a simpler structure. Further, in the liquid crystal display device of the item (3), the absorption axis of the polarizing film sandwiching the polarizing plate disposed in the liquid crystal layer is orthogonal, and therefore, the polarizing plate has a low transmittance and can be in a normal black display mode ( 12- 1356212 NBM; Normally Black Mode) The liquid crystal display device has a high contrast. (4) The liquid crystal display device of (3), wherein the liquid crystal layer contains a nematic liquid crystal material, and when displayed in black, the liquid crystal molecules of the nematic liquid crystal material are substantially the surface of the pair of substrates Vertical alignment 〇. The liquid crystal display device of item (4), although belonging to the liquid crystal material, is in a substantially vertical alignment when displayed in black, but can reduce the oblique viewing in such a situation. Light leaks. In addition, the present aspect may be a VA type in which the liquid crystal molecules in the liquid crystal cell are substantially vertically aligned in a state where no voltage is applied, or an OCB type or an ECB type in which the liquid crystal molecules are vertically aligned under application of a high voltage state. Or the liquid crystal display device of the item (4), which belongs to the VA type in which the liquid crystal molecules are inclined to the normal line of the substrate by applying a voltage, and the liquid crystal molecules are inclined in one direction, and the brightness and Since the color tone will vary depending on the viewing angle, a pixel is formed by arranging the liquid crystal regions of two or more regions (preferably 4 or more regions or more) which are different from each other in the initial alignment state, and can be averaged. Alleviate this phenomenon. (5) The liquid crystal display device of item (3), wherein the liquid crystal layer contains a nematic liquid crystal material, and when displayed in black, the liquid crystal molecules of the nematic liquid crystal material are substantially the surface of the pair of substrates Parallel alignment 〇 (5) of the liquid crystal display device, because the protection of the polarizing plate-13-1356212 is disposed on a protective film close to the surface of the polarizing film liquid crystal cell of the second polarizing plate, at any wavelength in the visible light region λ The following conditions are met: • 30 (nano) S { (nx - ny) X d2 } $ 50 (nano), and -50 (nano) S[ { (nx + ny) / 2 - nz } x d2] S 300 (nano), where d2 (nano) is the thickness of the protective film, nx and ny (but ny < nx) is the main average refractive index in the plane, nz is the main average refractive index in the thickness direction, and nx, ny, and nz are each orthogonal to each other; the optical compensation layer is composed of a compound having a dish structure unit And the disc surface of the compound is substantially perpendicularly aligned to the surface of the substrate; and the alignment control direction of the optical compensation layer is delayed from the protective film disposed on the surface of the liquid crystal cell of the polarizing film adjacent to the second polarizing plate The shaft, and the absorption axis of the second polarizing film are each substantially parallel. In the liquid crystal display device of the item (6), if the retardation 値 of the protective film of the upper and lower polarizing plates is set to be asymmetrical, it is possible to contribute to greatly preventing light leakage when viewed obliquely. In particular, when the retardation 値 of the protective film disposed between the liquid crystal cell of the upper and lower polarizing plates and the polarizing film is set to be asymmetrical, the oblique direction in the state in which the absorption axes of the upper and lower polarizing plates are orthogonal can be effectively reduced. Light leaks. The liquid crystal display device of item (6) belongs to a state in which liquid crystal molecules will be substantially parallel aligned when displayed in black, which includes, for example, in a state where no voltage is applied, the liquid crystal molecules are aligned parallel to the substrate surface -15 - 1356212 'The IPS type for black display. In these modes, the polarizing plate described above also contributes to an increase in the viewing angle. In this aspect, the retardation 値 of the optically anisotropic layer disposed between the protective film and the protective film and the liquid crystal cell is preferably set to be less than twice the Δη·d値 of the liquid crystal layer, and (6) The liquid crystal display device may further include at least one polymer film or at least one liquid crystal compound between the first and/or second polarizing plates and the liquid crystal cell composed of the pair of substrates and the liquid crystal layer. The optically anisotropic layer (but the protective film may also be a structure that can also serve as the optical compensation layer). In this aspect, the liquid crystal display device includes a polymer film having optical compensation energy or optical anisotropy. The layer thus has superior viewing angle expansion and improved display characteristics at the same time as the above effects. (7) A polarizing plate having a polarizing film and a pair of refractive films disposed to sandwich the polarizing film; the protective film has a thickness of illusion (nano), which are mutually orthogonal The x'y and z-axis directions have three average refractive indices nx, ny, and nz, and the main average refractive index parallel to the in-plane is ηχ and nyC but ny < nx) 'When the main average refractive index in the thickness direction is nz', then any wavelength λ in the visible light region satisfies the following conditions: -30 (nano)^ { (nx - ny) X di } S 50 (nano) , and -50 (nano) S [{ (nx + ny)/2-nz } X d!] guest 1356212 300 (nano). The polarizing plate of item (7), wherein at least one of the pair of protective films has a specific in-plane retardation (Re) or a thickness direction retardation (Rth), and at least one of the protective films The slow phase axis is substantially parallel or orthogonal to the absorption axis of the polarizing film. This polarizing plate is not only a polarizing function, but also contributes to an increase in the viewing angle of a liquid crystal display device, particularly a VA (Vertical Alignment) type or IPS (In-Plane Switching) type liquid crystal display device. Further, the polarizing plate is formed by using a polarizing film obtained by a diagonal stretching method, and a plurality of protective films and a total of three polymer films of the polarizing film are laminated in a roll-to-roll manner, thereby being easily produced. It also contributes to improving the productivity of the liquid crystal display device. Further, since the protective film of the above polarizing plate can also have the function of an optical compensation layer, it is possible to contribute not only to the expansion of the viewing angle of the liquid crystal display device but also to optical compensation. (8) The polarizing plate of item (7), wherein a retardation axis of either one of the protective films of the polarizing plate intersects with an absorption axis of the polarizing film. In the polarizing plate of the item (8), since the absorption axis of the polarizing film of the polarizing plate is orthogonal to the retardation axis of the protective film (the protective film on the far side of the liquid crystal layer), the above-described addition is added. As a result, it is also possible to improve mechanical reliability such as prevention of dimensional change or curling of the polarizing plate. Further, when the retardation axis of the protective film on the near side of the liquid crystal layer is orthogonal to the absorption axis of the polarizing film, light leakage from the oblique direction in the case of the black display can be alleviated. Further, when the optical anisotropy is arranged between the liquid crystal layer and the protective film -17-1356212 so that the slow axis thereof crosses the absorption axis of the polarizing film, the retardation axis of the protective film does not need to be The absorption axis of the film must be crossed. At this time, the optically anisotropic layer can obtain the same effect regardless of the coated film or the stretched film, but is preferably larger than the retardation of the protective film. Further, both of the protective films have birefringence, and the retardation axes of the protective films on the near side of the liquid crystal layer are substantially orthogonal to each other. In the case where the _ the retardation axes are orthogonal to each other, by eliminating the birefringence of each of the protective films, the deterioration of the optical β-characteristics of the liquid crystal display device at the time of normal incidence can be reduced. In contrast, in the case where the retardation axes are parallel to each other, if the liquid crystal layer has a residual phase difference, the birefringence of the film can be protected to compensate for the phase difference. Here, the term "the retardation axis of the protective film is crossed with the absorption axis of the polarizing film" means that the absorption axis of the polarizing film is not parallel to the retardation axis of the protective film. The angle formed by the absorption axis of the polarizing film and the retardation axis of the protective film (not related to before or after the cutting of the polarizing film) is preferably 1 〇 ° ~ 90 °, preferably 20 ° ~ 70 ° 80° to 90° ® , more preferably 40° to 50° and 90° ' Especially good for 43° to 47° and 87. ~90. . Alternatively, two protective films may be used, and one of the slow axises may be crossed with the absorption axis of the polarizing film. At this time, the two protective films may be bonded to the bonding layer or the bonding layer to bind β (9). The polarizing plate of the item (7) or (8) has a surface disposed on at least one of the protective film. "Optical compensation layer" -18 - 1356212, the optical compensation layer is composed of a compound having a dish-like structural unit, and the dish-like surface of the compound is substantially perpendicularly aligned with the polarizing film, and the optical compensation The alignment control direction of the layer is substantially parallel to the retardation axis of the protective film attached to the optical compensation layer and the absorption axis of the polarizing film. In the polarizing plate of the item (9), since the direction of the retardation axis of the pair of protective films is the same as that of the polarizing plate, the above effects can be obtained, and the mechanical stability or optical of the polarizing plate can be improved. The effect of uniformity of performance. β In the specification of the present invention, "45°", "parallel" or "orthogonal" means within a range of less than a strict angle of ±5°. The difference from the strict angle is preferably less than 4°, more preferably less than 3°. In addition, regarding the angle, "+" means clockwise direction, and "-" means counterclockwise direction. The "late phase axis" means the direction in which the refractive index will become the largest. The "visible light field" means 3 80 nm to 780 nm. In addition, the measurement wavelength of the refractive index is λ = 550 nm in the visible light region unless otherwise noted. In the present specification, the term "polarizing plate" is used to include a long-length polarizing plate and cutting unless otherwise noted (in the present specification, the term "cutting" also includes "stamping" and "punching". It is used in the sense that it can be combined with a polarizing plate of the size of a liquid crystal display device. In addition, in the present specification, the "polarizing film" and the "polarizing plate" are used separately, but the "polarizing plate" means that a transparent protective film for protecting the polarizing film is provided on at least one side of the "polarizing film". The layered body. Effect of the Invention -19- 1356212 The inventors of the present invention finally succeeded in producing the same structure as the conventional liquid crystal display device by adjusting the material of the polarizing film, the protective film, and the liquid crystal cell, and the manufacturing method thereof. An elliptically polarizing plate that optically compensates for the function of the liquid crystal cell. Further, the polarizing plate was used in combination with a VA type or IPS type liquid crystal cell for use in a liquid crystal display device, and as a result, not only the display quality but also the viewing angle was significantly improved. Further, it is also possible to manufacture a polarizing plate in a "roll-in" manner by eliminating the need to strictly adjust the angle of one or a plurality of retardation films and the polarizing plate as conventionally used. method. Further, according to the present invention, it is possible to provide a polarizing plate which not only has a polarizing function but also contributes to an increase in the viewing angle of the liquid crystal display device and can be easily manufactured. BEST MODE FOR CARRYING OUT THE INVENTION A structural member of an embodiment of a liquid crystal display device of the present invention will be described below in order. Fig. 1 and Fig. 2 are schematic schematic views showing an embodiment of a liquid crystal display device of the present invention. [Liquid Crystal Display Device] First, the liquid crystal display device shown in Fig. 1 has liquid crystal cells (5 ® to 8), and the upper polarizing film 1 and the lower polarizing film 14 are disposed to sandwich the liquid crystal cells. The polarizing films 1 and 14 are sandwiched by a pair of transparent protective films 3 and 3a, and .12 and 12a. The liquid crystal cells 5 to 8 are composed of the liquid crystal cell upper substrate 5 and the liquid crystal cell lower substrate 8, and the liquid crystal molecules 7 sandwiched therebetween. The liquid crystal molecules 7 are applied to the opposite faces of the substrates 5 and 8. Rub the treatment direction or alignment film material to control its alignment direction. The upper polarizing plate is composed of a pair of transparent protective films 3a and 3, and a polarizing film 1 held by the #-20-1356212 (assuming that the transparent protective film 3 is disposed in the liquid crystal cell - (5 in FIG. 1) Near side of ~8). The absorption axis 2 of the polarizing film 1 crosses the late phase axis 4 of the t transparent protective film 3. Specifically, the angle α formed by the absorption axis 2 of the polarizing film 与 and the retardation axis 4 of the transparent protective film 3 is 10. It is preferably 90 °, preferably 20. ~ 70°, more preferably 40. ~ 50. , especially good for 43. ~ 47°. The angle formed by the retardation axis of the other transparent protective film 3a (which is disposed on the far side of the liquid crystal cell 5 to '8) and the absorption axis 2 of the polarizing film 1 is not particularly limited, but is as described above. The preferred range of α is the same. Further, the relationship between the absorption axis 15 of the lower polarizing film 14 and the retardation axis 13 of the protective film 12 disposed on the near side of the liquid crystal cell is preferably in the same range. The respective retardation axes of the pair of transparent protective films 3a and 3 are substantially flat to each other. When the retardation axes of the pair of transparent protective films are parallel, the effect of improving the mechanical stability of the polarizing plate or the uniformity of optical properties can be obtained, which is preferable. Further, if the retardation axis of the transparent protective film disposed on the far side of the liquid crystal cell is substantially parallel to the absorption axis of the polarizing film, mechanical reliability such as dimensional change of the polarizing plate or prevention of curling can be improved. . The retardation axis of the transparent protective film disposed on the far side of the liquid crystal cell can also obtain the same effect when orthogonal to the absorption axis of the polarizing film®, and if the thickness or rigidity of the transparent protective film is sufficient, a pair of protective films The late phase axes can achieve the same effect even if they each intersect at different angles. Further, the protective film disposed on the near side of the liquid crystal layer may be formed into two sheets, and the slow axis of one of the protective films may be crossed with the absorption axis of the polarizing film. In Fig. 1, the retardation film '1 of the upper polarizing plate and the polarizing film '1 of the lower polarizing plate and the retardation axes 4 and 13-21 - 1356212 of the protective films 3 and 12 on the near side of the liquid crystal cell of the polarizing film 14 are substantially It is preferred that the grounds are parallel or orthogonal to each other. When the retardation axes 4 and 13 of the transparent protective films 3 and 12 cross each other, the optical characteristics of the light perpendicularly incident on the liquid crystal display device can be reduced by eliminating the birefringence of each of the protective films. Further, when the retardation axes 4 and 13 are parallel to each other, if the liquid crystal layer has a residual phase difference, the birefringence of the film can be protected to compensate for the phase difference. The protective film 3 disposed on the liquid crystal cell side of the upper polarizing film 1 or the protective film 12 disposed on the liquid crystal cell side of the lower polarizing film 14 is optically characterized at any wavelength λ in the visible light region to satisfy the following conditions: -30 ( Nano) { {nx - ny) x d2 } ^ 50 (nano), and -50 (nano) core [{ (nx + ny) / 2 - nz } x d2 ] έ 300 (nano). However, in this formula, d2 (nano) is the thickness of the protective film, nx and ny (but ny <nx) is the main average refractive index in the plane, and nz is the main average refractive index in the thickness direction. The nx, ny, and nz lines are each orthogonal to each other. In the present invention, a protective film which exhibits such optical characteristics is formed by having its retardation axis disposed as described above to intersect the polarization axis of the polarizing film, so that the protective film has an optical compensation function of the liquid crystal cell. . Details of the manufacturing method and materials of the protective film will be described later. The "liquid crystal cell" is composed of the upper substrate 5 and the lower substrate 8, and a liquid crystal layer formed of the liquid crystal molecules 7 sandwiched therebetween. An alignment film (not shown) is formed on the surface of the liquid crystal molecules 7 in contact with the substrates 5 and 8 (hereinafter also referred to as "inner surface"), and is applied by rubbing treatment or alignment film on the alignment film. A material or the like is used to control the alignment of the liquid crystal molecules 7 in a state where no voltage is applied or a low applied state of -22 - 1356212. Further, on the inner surfaces of the substrates 5 and 8, a transparent electrode (not shown) for applying a voltage to the liquid crystal layer composed of the liquid crystal molecules 7 is formed. The display mode of the liquid crystal layer j is not particularly limited, and may be a liquid crystal layer of any display mode such as VA mode 'IPS mode, ECB mode, TN mode, and OCB mode. In the present invention, the thickness d of the liquid crystal layer ( The product of the micron) and the refractive index anisotropy Δη Δη·(1 is 0. 1~1. 0 micron. The optimum △ n_ d is different depending on the display mode. In the transmission mode, the VA type or the IPS type and the ECB type which have no torsion structure are 0. 2~0. In the range of 4 micrometers, the TN type will depend on the magnitude of the torsion angle, but it will be 0. 2 ~ 0 · 5 microns range, in the OCB type is 0. 6 ~ 1. 0 micron is the most suitable. Since the white display brightness in the range is high and the black display brightness is small, a bright and high contrast display device can be obtained. In addition, in Figure 1, the display shows the upper polarizer and the lower polarizer. The aspect of the radiation type display device, but the present invention can also be a reflection mode having only one polarizing plate. In this case, the intracellular optical path of the liquid crystal will be doubled, so the optimum of Δη·d will be It is about 1/2 of the above. Regarding the absorption axes 2 and 15 of the polarizing films 1 and 14, the retardation axis directions 4 and 13 of the protective films 3 and 12, and the alignment direction of the liquid crystal molecules 7 can be laminated according to the materials, display modes, and members used for the respective members. Structures, etc. are adjusted to the optimum range. For example, in the case of a liquid crystal display device of the VA type or the IPS type which belongs to the normal black display mode, if high contrast is to be obtained, the absorption axes 2 and 15 of the polarizing films 1 and 14 are arranged to be substantially orthogonal to each other. However, the liquid crystal display device of the present invention is not limited to this structure. • 23- 1356212 Next, using Fig. 1, the driving principle of the "VA mode" liquid crystal display device will be described below. In the present embodiment, a description will be given of an example in which a field effect type j liquid crystal is actively driven by using a nematic liquid crystal having a negative dielectric anisotropy. The liquid crystal display device shown in Fig. 1 is not When a transparent electrode (not shown) of each of the liquid crystal cell substrates 5 and 8 is applied in a non-driving state of a driving voltage, the liquid crystal molecules 7 in the liquid crystal layer are substantially vertically aligned with respect to the faces of the substrates 5 and 8, and as a result, the pass is made. The polarization state of the light hardly changes. Since the absorption axes 2 and 15 are orthogonal, the light incident through the lower side (for example, the back electrode) will be polarized by the polarizing film 14 and still maintain the polarization state. Passing through the liquid crystal cells 5 to 8, and then being blocked by the polarizing film 1. In other words, the liquid crystal display device of Fig. 1 can achieve an ideal black display in a non-driving state. In contrast, for a transparent electrode (not In the driving state in which the driving voltage is applied, the liquid crystal molecules 7 are inclined in a direction parallel to the faces of the substrates 5 and 8, so that the passing light is changed in polarization state by the liquid crystal molecules 7 thus inclined. Therefore, the light incident from the lower side (for example, the back electrode) will be polarized by the polarizing film 14, and then passed through the liquid crystal cells 5 to 8, so that the polarization state is changed, and then passed through the polarizing film 1. In other words, Fig. 1 The liquid crystal display device shown in the present invention can obtain a white display in a driving state. Here, since an electric field is applied between the upper and lower substrates 5 and 8, it is necessary to use, for example, liquid crystal molecules 7 to respond perpendicularly to the direction of the electric field. A liquid crystal material having a negative dielectric constant is a negative liquid crystal material. Further, if an electrode is formed only on one of the substrates 5 and 8, so that an electric field can be applied only in a lateral direction parallel to the surface of the base - 24 - 156212, the liquid crystal The material can be used with a positive dielectric constant anisotropy. The "VA mode" is characterized by high speed response and high contrast. However, traditional. In the V A mode liquid crystal display device, there is a problem that the contrast is high in the front side but will be deteriorated in the oblique direction. In the case of black display, since the liquid crystal molecules 7 are vertically aligned to the faces of the substrates 5 and 8, when viewed from the front, since the liquid crystal molecules 7 are almost free of birefringence and the transmittance is low, high contrast can be obtained. However, when observed obliquely, the liquid crystal molecules 7 generate birefringence. Further, the intersection angles of the absorption axes 2 and 15 of the upper and lower polarizing films 1 and 14 are orthogonal to 90° on the front side, but become larger than 90 when viewed obliquely. . For these two reasons, light leakage occurs in the oblique direction, which reduces the contrast. In the liquid crystal display device of Fig. 1, the transparent protective film 3 which exhibits specific optical characteristics is disposed on the vicinity of the liquid crystal cell of the polarizing film 1 so that the slow axis 4 and the absorption axis 2 of the polarizing film 1 are The transparent protective film 12 which will exhibit specific optical characteristics is disposed on the near side of the liquid crystal cell of the polarizing film 14 such that the slow axis 13 intersects the absorption axis 15 of the polarizing film 14 to improve transmission in black display. The viewing angle characteristics of the rate to achieve wide viewing angle. In addition, the liquid crystal molecules 7 are inclined when displayed in white, so that in the oblique direction and the opposite direction, although the birefringence of the liquid crystal molecules 7 when viewed obliquely is different, the brightness and the hue are different, but if the composition is When a pixel of a liquid crystal display device is divided into a plurality of fields called "multi-domain structure", it is preferable to improve the viewing angle characteristics of luminance or hue. Specifically, each of the pixels is formed by averaging two pixels (i.e., four or eight-25 to 1356212) or more in which the initial alignment states of the liquid crystal molecules are different from each other, thereby arranging The deviation of the brightness or hue depending on the viewing angle can be reduced. Further, the same effect can be obtained by constituting each pixel in two or more fields which are different from each other in the direction in which the alignment direction of the liquid crystal molecules is continuously changed in the state where the voltage is applied. If a plurality of fields in which the alignment directions of the liquid crystal molecules 7 are different are formed in one pixel, for example, it is possible to provide a slit at the electrode, or to set a protrusion, or to change the direction of the electric field, or to bias the electric field density. And other methods. For example, if you want to obtain a uniform viewing angle in all directions, you can increase the number of divisions. However, if you set it to 4 or more, you can get a roughly uniform field of view ® angle. In particular, in the case of eight divisions, the absorption axis of the polarizing plate can be set to any angle. Therefore, it is preferable that the liquid crystal molecules 7 have a tendency to respond to the boundary of the domain of each domain. In the normal white display mode (NWM; Normally White Mode) such as VA mode, the brightness drop will become a problem because the black display will be maintained. Therefore, a chiral agent can be added to the liquid crystal material to make the boundary area between the blocks small. On the other hand, in the normal black display mode, since the white display state is maintained, the front-to-beta ratio will decrease. Therefore, a light shielding layer for covering a black matrix (black matrix) or the like in the field may be provided. The liquid crystal display device has two driving modes of "active matrix type" and "passive matrix type", and is used for a liquid crystal display device of a notebook type personal computer, and an active matrix type thin film transistor is generally used. The absorption axes 2 and 15 of the polarizing films 1 and 14 are to be supplied with an electrical signal to the active matrix type thin film transistor. When the line substantially intersects at 45°, the viewing angle characteristic becomes a bilaterally symmetrical -26-1356212 structure, which is preferable. Not only the VA mode, but also the TN and OCB modes. When the absorption axis of the polarizing film is parallel or perpendicular to the long side of the liquid crystal cell substrate, it is necessary to consider the intersection angle between the signal line and the absorption axis for wiring. However, as shown in Fig. 1, if the polarization is made, The absorption axis of the board is originally designed to cross the long side of the liquid crystal cell substrate at 45°, and the signal line is designed to be parallel or perpendicular to the long side of the liquid crystal cell substrate, so that the viewing angle of the left and right symmetry can be obtained. From this point of view, the absorption axes 2 and 15 of the polarizing films 1 and 14 in Fig. 1 should preferably be +45° or -45° with respect to the long sides of the liquid crystal cell substrates 5 and 8. However, if it is also considered that the signal line is not a straight line, it is preferable to cross at 45 ° ± 10 ° or - 45 ° ± 10 °. In the "liquid crystal cell" of the VA mode, for example, the dielectric anisotropy is negative between the upper and lower substrates 5 and 8, and Δη = 0. 0813, △ ε = - 4. 6 or so nematic liquid crystal materials, etc., and by rubbing alignment treatment, and setting a "director" indicating the alignment direction of the liquid crystal molecules, that is, the so-called "tilt angle" is about 89°. Can be made. The thickness d of the liquid crystal layer is not particularly limited, but when the liquid crystal having the characteristics of the above range is used, it can be set to about 3. 5 microns. Since the brightness in the white display varies depending on the product of the thickness d and the refractive index anisotropy Δη, Δη·d, Δη·d is preferably set at 0. 2 ~ 0. A range of 5 microns. Further, in the liquid crystal display device of the VA mode, the measure of the chiral material generally used in the TN mode liquid crystal display device is rarely used because the dynamic response characteristics are deteriorated, but it is also added to reduce the misalignment. The situation. In addition, when the multi-domain structure is used for -27-1356212 as described above, it is for adjusting the liquid crystal in the boundary area between the blocks. Molecular matching is advantageous. _ As described above, in the above various liquid crystal display modes, black display is performed when no voltage is applied or low voltage is applied, and white display is displayed when high voltage is applied, that is, "normal black display" In the mode j, the VA mode will be described, but the present invention is not limited thereto, and other aspects of the IPS mode which are also in the normal black display mode may be used. When it is applied with a low voltage, it is displayed in white. When a high voltage is applied, the "normal white display mode" which turns black is displayed. The liquid crystal cell of the OCB mode, the ECB mode, or the TN mode can be used. In addition, when the black display is used, the liquid crystal molecules of the nematic liquid crystal material may be aligned with the liquid crystal cell substantially parallel to the surface of the substrate; specifically, the liquid crystal molecules may be parallel to the substrate surface without applying a voltage. A liquid crystal cell in IPS mode or ECB mode that is aligned for black display. However, in this case, if the viewing angle improvement effect is to be obtained, the (nx -ny) X ch of the protective film of the polarizing plate is preferably set to about Δ!! (!) of the liquid crystal layer. The liquid crystal display device is not limited to the structure® as shown in Fig. 1. Other members may be included. For example, a color filter may be disposed between the liquid crystal cell and the polarizing film. An optical compensation film may be additionally disposed between the liquid crystal cell and the polarizing plate. Further, when used for "transmissive type", a cold cathode or a hot cathode fluorescent tube, or a light emitting diode, a field emission element, or The backlight of the light source is disposed on the back surface of the light source. The liquid crystal display device of the present invention may also be a "reflective type". In this case, the polarizing plate may be provided only on the observation side, and the reflective film is provided - 28- 1356212 is placed on the inner surface of the liquid crystal cell or on the inner surface of the lower cell of the liquid crystal cell. Of course, the front light of the above light source may be disposed on the liquid crystal cell observation side. The liquid crystal display device of the present invention includes : Image direct view type, image projection type 'Light modulation type. The present invention is particularly applicable to an active matrix type liquid crystal display device which is suitable for use in a three-terminal or two-terminal semiconductor element like a TFT (Thin Film Transistor) or MIM (Metal-Insulator-Metal) method. It is also effective to apply to a passive matrix type liquid crystal display device represented by a super twisted nematic type (STN), which is called "time division driving". The present invention is made by using a polarizing plate. The retardation axis of the transparent protective film is set to a specific relationship with the absorption axis of the polarizing film to improve the viewing angle of the liquid crystal display device, but if the optical compensation film is further disposed between the polarizing plate and the liquid crystal cell, It is preferable to improve the viewing angle, and there is no particular limitation on the optical compensation film. Any structure can be used as long as it has optical compensation energy. For example, a birefringent polymer film can be used. a laminate of a transparent support and an optically anisotropic layer formed of liquid crystal molecules formed on the transparent support, etc. In the latter state, the polarizing plate is The transparent protective films 3 and 12 on the near side of the crystal layer may also serve as the support of the optically anisotropic layer. In order to improve the viewing angle of the VA mode, there is a phase difference plate having a positive refractive index anisotropy, and The method of the present invention is also applicable to the present invention. The phase difference plate has X'y and orthogonal to each other. The z-axis direction has three average refractive indices nx, ny, and ηζ, and if the average refractive index in the plane of -29- 1356212 is nx and ny, and the average refractive index in the thickness direction is -nz, then each becomes nx, ny = nz, nx > ny phase difference plate (^ is hereinafter referred to as "optical anisotropic layer A"), and a phase difference plate which will become nx = ny, nz, nx > nz (hereinafter referred to as " Optical anisotropic layer B"). When the laminated body of the optically anisotropic layer A and the optically anisotropic layer B is used as an optical compensation film, it is possible to prevent light leakage when viewed in an oblique direction in the VA mode. Further, as described above, when the absorption axes 2 and 15 of the upper polarizing film 1 and the lower polarizing film 14 are arranged orthogonally, the intersection angle will be shifted from the right angle when viewed obliquely, so that the light leakage will occur. Increase the problem. It is known that the light leakage can be reduced by using a laminate formed by laminating the optical anisotropic layer A and the optical anisotropic layer B (refer to Japanese Laid-Open Patent Publication No. 2001-350,022). . If the viewing angle optical compensation of the liquid crystal molecules vertically aligned in the VA mode is obtained, although the optical anisotropic layer B is effective, if the above-mentioned polarizing plate viewing angle is to be improved, the optical anisotropic layer A is also need. Therefore, when the laminated body of the optically anisotropic layer A and the optically anisotropic layer B is used as an optical compensation film, it is advantageous to improve the optical compensation of the viewing angle of the liquid crystal molecules vertically aligned in the VA mode. And the viewing angle of the polarizing plate. Further, the liquid crystal display device of the present invention may have an optical compensation film in which the optically isotropic layer A and the optically anisotropic layer B are combined. The size of Δπ·d of the liquid crystal layer and the position of the laminated layer are different from the optical properties of the protective film of the polarizing plate. For example, the protective film of the polarizing plate (3 or 12 in Fig. 1) of Re値 -30- 1356212 is disposed on the transparent protective film on the near side of the liquid crystal cell of the polarizing plate, and can be used as a double. Learn the support of the directional layer. Therefore, it can be incorporated in a liquid crystal display device in accordance with a transparent polarizing film, a polarizing film, a transparent protective film (also serving as a transparent support), and an optically isotropic layer. Further, it is also possible to manufacture a liquid crystal display device while sequentially laminating. In the liquid crystal display device, it is preferably from the outside of the device (the far side of the liquid crystal cell), and a transparent protective film and a polarizing film 'transparent protective film (also used as an optical anisotropy). The transparent support of the tropism layer and the optically anisotropic layer are laminated in sequence. Next, a schematic mode φ diagram of another embodiment of the liquid crystal display device of the present invention will be shown in Fig. 2. In the liquid crystal display device of the first embodiment, the liquid crystal display device of the first embodiment is combined with the "optical compensation layer 1". In the second embodiment, the same members as those in the first embodiment are denoted by the same reference numerals, and their description will be omitted. Further, in the second embodiment, the protective film disposed on the outer side of the pair of protective films of the upper polarizing film 1 and the lower polarizing film 14 is omitted. In the liquid crystal display device shown in Fig. 2, the optical property of the protective film 12 is at any wavelength λ in the visible light region in accordance with the following conditions: -30 (nano) $ { (nx - ny) x d2 } ^ 50 (nano), and β -50 (nano) S [ { (nx + ny) / 2 - nz } x d2] ^ 300 (nano). . The definitions of each code in the formula are as described above. Further, the liquid crystal display device of Fig. 2 is a structural member of the liquid crystal display device of Fig. 1, and an optical compensation layer 1 disposed adjacent to the protective film 12 is added. The optical compensation layer 10 is composed of a compound having a dish-shaped structural unit, and the dish-like surface is formed by a substantially vertical alignment of the substrate surface. Further, in the direction of the alignment control of the optical compensation film of the above -32 - 1356212 (for example, the "friction axis" in the case of the alignment control by the rubbing treatment of the alignment film) and the retardation axis 13 of the protective film 12, It is arranged to be substantially parallel to the absorption axis of the upper polarizing film. In this aspect, the retardation 値 from the upper and lower polarizing films until the layer through which the liquid crystal cell passes (the protective film contained in the polarizing film) is set to be asymmetrical to improve the light leakage prevention when viewed from the oblique direction. In particular, in this aspect, it is possible to effectively reduce the oblique light leakage in the aspect in which the absorption axis of the upper polarizing plate 1A and the lower polarizing plate 14A is orthogonal. The lower polarizing plate 14A is obtained by forming the polarizing film 14, the protective film 12, and the optical compensation layer 1 . With such a structure, the protective film 12 can serve as a support for the optical compensation layer 10, contributing to weight reduction and thinning of the liquid crystal display device. Further, in the present embodiment, since the alignment control direction 11 of the optical compensation layer 10 and the retardation axis 13 of the protective film 12 are arranged substantially parallel to the absorption axis 15 of the polarizing film 14, when the integrated polarizing plate is manufactured, It is also advantageous in that it can be easily aligned as a shaft. The driving mode of the liquid crystal cell (5 to 8) in the present embodiment is not particularly limited, but is preferably a liquid crystal cell of the IPS mode. In Fig. 3, a schematic side sectional view of the "IPS mode" liquid crystal cell is shown. The liquid crystal cells in the IPS mode usually have several portraits due to the matrix-shaped electrodes, but the third figure only shows a part of one of the pixels. The linear electrode 16 is formed inside the transparent pair of substrates 5, 8, and an alignment control film (not shown) is formed on the surface. The rod-like liquid crystal molecules 7 sandwiched between the substrates 5 and 8 are arranged such that they have a certain angle with respect to the longitudinal direction of the linear electrode 6 when no voltage is applied. In addition, the dielectric of the liquid crystal in this case is often assumed to be positive in the case of the directionality of the -33 - 1356212. Therefore, upon application of an electric field, the liquid crystalline molecules 7 change their direction with respect to the direction of the electric field. The polarizing films 1A and 14A are sandwiched between the liquid crystal cells of the IPS mode and arranged at a specific angle, whereby the light transmittance can be changed. Further, the angle ' formed by the direction of the electric field on the surface of the substrate 8 is preferably 20 degrees or less, more preferably 10 degrees or less. In other words, it is preferable to be substantially parallel. Hereinafter, in the present invention, those belonging to 20 degrees or less are collectively referred to as "parallel electric field". Further, the electrode 16 is formed by dividing the upper and lower substrates, or is formed only on one of the substrates, and the effect is not changed. The liquid crystal material LC is a nematic liquid crystal in which the dielectric constant anisotropy Δ e is positive. The thickness (gap) of the liquid crystal layer is set to be greater than 2. 8 microns, less than 4. 5 microns. Thus, if the delay 値 Δ η · d is set to be greater than 0. 25 microns, less than 0. At 32 μm, it is easier to obtain transmittance characteristics having almost no wavelength dependence in the visible light range. The maximum transmittance can be obtained by the combination of the alignment film and the polarizing plate as will be described later, when the liquid crystal molecules are rotated by 45 degrees from the rubbing direction toward the electric field. Further, the thickness (gap) of the liquid crystal layer is controlled by a polymer bead. Of course, glass beads or fibers, resin column spacers can also produce the same gap. Further, the liquid crystal material LC is not particularly limited as long as it is a nematic liquid crystal. The dielectric constant anisotropy Δ £ is the larger one, that is, the driving voltage can be reduced, and the refractive index anisotropy Δ n is smaller, that is, the thickness (gap) of the liquid crystal layer can be increased, and the liquid crystal can be shortened. The time required 'can reduce the variability of the gap. The nematic liquid crystal material contained in the liquid crystal layer may be composed of two or more different domains in the alignment state 1356212. As described above, the display mode of the liquid crystal display device of the present embodiment is not particularly limited, but the ECB mode and the IPS mode are suitable for use. In the present embodiment, the product Δη of the thickness d (micrometer) of the liquid crystal layer and the refractive index isotropic Δ!! ά, preferably set to 0. 2 ~ 1. 2 microns. The optimum △n·d is 0. 2 ~ 0. 5 yuan. In the range of the above, the white display brightness is high and the black display brightness is small', so that a bright and high contrast display device can be obtained. In addition, in the case of the most suitable transmission mode, in the reflection mode, the optical path in the liquid crystal cell will be doubled, so Δη. The optimum of d will become about 1/2 of the above. The liquid crystal display device of the present embodiment can be applied not only to the above display mode but also to the VA type, the OCB mode, the TN mode, the HAN (hybrid alignment nematic) mode, and the STN mode. Materials which can be used for various members of the liquid crystal display device of the present invention, and a method for producing the same, are explained in detail below. [Polarizing Plate] The polarizing plate is generally composed of a polarizing film 'and one of the polarizing films sandwiching the protective film. In the polarizing plate of the present invention, a protective film of at least one of the polarizing films formed on the surface of the protective film disposed on the side closer to the liquid crystal cell exhibits specific optical characteristics as will be described later. One aspect of the polarizing plate of the present invention is a polarizing plate which is attached with an optical compensation layer (hereinafter also referred to as "optical anisotropic layer") formed of a liquid crystalline compound and has optical compensation energy. In addition, a polarizing plate 1356212 having an optical compensation layer formed of a polymer film or a liquid crystal compound having a specific optical property as a protective film may also have an optical compensation function, and the polarizing plate* of such a structure may also be used. use. Preferably, the optical compensation layer is formed of a liquid crystal molecule directly on the surface of the protective film of the polarizing film or the polarizing plate, or is formed of a liquid crystal molecule by an alignment film. Specifically, an optically anisotropic layer can be formed by applying an optically isotropic layer coating liquid onto the surface of the polarizing film or the surface of the protective film of the polarizing film. The former is formed between the protective film of the polarizing plate and the 'optical anisotropic layer, and can be obtained without using a polymer film. A thin polarizing plate having a small stress (strain X cross-sectional area X elastic modulus) with a change in the size of the polarizing film. When the polarizing plate according to the present invention is mounted on a large Φ liquid crystal display device, an image of high display quality can be displayed without causing light leakage or the like. The polarizing film is preferably made by Optiva Inc. It is a coating type polarizing film represented by it, or a polarizing film composed of a "binder" and an iodine-based or dichroic dye. The iodine-based and dichroic dyes exhibit alignment properties by being aligned in the binder. The iodine-based and dichroic dyes are preferably aligned along the binder or the dichroic dyes are aligned in a single direction by self-organization like liquid crystal. φ 目 gij commercially available commercial grade polarizing film 'Generally, the extended polymer is immersed in a solution of iodine or dichroic dye in the bath to infiltrate the iodine or dichroic pigment in the binder. Made in the agent. In addition, commercially available commercial grade polarizing films have an iodine or dichroic dye distribution of about 4 micrometers from the surface of the polymer (a total of about 8 micrometers on both sides), so if sufficient polarizing properties are to be obtained, at least A thickness of 10 microns is required. The degree of permeability can be controlled by the solution concentration of the iodine or dichroic dye, the temperature of the same bath - 36 -, and the immersion time. As described above, the lower limit of the thickness of the binder is preferably 10 μm. As for the upper limit of the thickness, it is considered to be thinner from the viewpoint of the light leakage phenomenon when the polarizing plate is used in a liquid crystal display device. It is preferably a commercially available commercial grade polarizing plate (about 30 μm) or less, preferably 25 μm or less, more preferably 20 μm or less. If it is 20 μm or less, no light leakage is observed in the 17-inch liquid crystal display device. The binder of the polarizing film may also be a crosslinked person. The binder of the polarizing film can also be used as a crosslinkable polymer. It is also possible to apply a light, heat or pH change to a polymer having a functional group or a polymer obtained by introducing a functional group into a polymer to react a functional group to crosslink the polymer to form a polarizing film. . Further, a crosslinking agent may also introduce a crosslinked structure into the polymer. The crosslinking is generally carried out by applying a coating liquid containing a crosslinkable polymer or a mixture of a polymer and a crosslinking agent to a transparent support. Since the durability can be ensured at the stage of the final product, the treatment of applying the cross-linking can be carried out at any stage until the final polarizing plate is obtained. As the binder of the polarizing film, any of a polymer which is itself a crosslinkable polymer or which can be crosslinked by a crosslinking agent can be used. Examples of the polymer include the same polymers as those which can be used for the alignment film as described later. Among them, polyvinyl alcohol and modified polyvinyl alcohol are the best. Regarding the modified polyvinyl alcohol, it has been described in Japanese Patent Laid-Open No. 8-338, No. 9 1 3, the same as No. 9-152,509 and the same In the bulletins of 9-316, 127. Polyvinyl alcohol and modified polyvinyl alcohol may be used in combination of two or more. -37- 1356212 The amount of crosslinker added to the binder is based on the binder. 1 ~ 20 · Quality % is better. The alignment of the polarizing element is such that the heat resistance of the polarizing film is good. The polarizing film is also contained in the alignment film after the end of the crosslinking reaction, and also contains a certain amount of the unreacted crosslinking agent, but the amount of the crosslinking agent remaining is 1. 0% by mass or less, more preferably 0. 5 mass% or less. It is set as above. When it is used, even if the polarizing film is used in a liquid crystal display device and it is used for a long period of time, or when it is placed in a high temperature and high humidity environment for a long period of time, it does not cause a decrease in the degree of polarization. Φ Regarding the cross-linking agent, it is described in the specification of U.S. Reissue Patent No. 23,297. In addition, boron compounds (such as boric acid, Borax) can also be used as a crosslinking agent. "Dichroic dye" can be used: azo dye, stilbene dye, dihydropyrazolone dye, triphenylmethane dye, quinoline dye, caesarean dye, thiophene pigment Or lanthanide pigments. The dichroic dye is preferably water-soluble. The dichroic dye preferably has a hydrophilic substituent (for example, a sulfonic acid group, an amine group, or a hydroxyl group). Examples of dichroic pigments include, for example, the compounds described in the Inventive Society's published technical method, Public Technical No. 200 1-1745, page 58 (issued date, March 15, 2001). In order to improve the contrast of the liquid crystal display device, the transmittance of the polarizing plate is preferably higher, and the polarizing degree is preferably higher. The "transmittance" of the polarizing plate is light having a wavelength of 550 nm, preferably 30 to 50%, more preferably 35 to 50%, and most preferably 4 to 50%. The "polarization" is in the range of 550 nm, preferably in the range of 90 to 100%, more preferably in the range of -38 to 1356212 95 to 100%, and most preferably 99 to 100%. The scope. - The polarizing film and the optical compensation layer, the protective film of the polarizing plate and the optically isotropic layer, or the polarizing film and the alignment film used for forming the optically anisotropic layer may be bonded by an adhesive. As the "adhesive", a polyvinyl alcohol-based resin (including a modified polyvinyl alcohol having an ethyl acetate, a sulfonic acid group, a carboxyl group or an oxyalkylene group) or an aqueous solution of a boron-based compound can be used. Among them, it is preferably a polyvinyl alcohol resin. The thickness of the adhesive layer is preferably dried after drying. 01 ~ 10 microns range, and particularly good. 05 ~ 5 microns range. [Production of polarizing film] ® The polarizing film is preferably subjected to stretching (extension method) by tilting the bonding agent by 10 to 80 degrees in the longitudinal direction (MD direction) of the polarizing film, from the viewpoint of production yield, or After rubbing (friction method), it is dyed with an iodine-based or dichroic dye. The "inclination angle" is preferably extended so as to conform to the angle formed by the transmission axes of the two polarizing plates bonded to both sides of the liquid crystal cell constituting the LCD and the longitudinal or lateral direction of the liquid crystal cell. The usual tilt angle is 45 °. However, recently, devices that are not necessarily 45° have been developed in transmissive, reflective, and semi-transmissive LCDs. Therefore, it is preferable that the extending direction should be arbitrarily adjusted according to the LCD design. In the case of the extension method, the "stretching ratio" is preferably 2. 5~30. 0 times ‘more preferably 3. 0 to 10. 0 times. The extension is a dry extension method that can be carried out in air. Further, the wet stretching method can also be carried out in a state of being immersed in water. The extension ratio of "dry extension" is preferably 2_5 ~ 5. 0 times, the stretch ratio of "wet extension" is 3·0 ~ 10. 0 times is better. The extension process can also be divided into several times, including oblique extension. The fraction is divided into several times, whereby the extension can be applied more uniformly even if the rate is extended by a high magnification of -39 - 1356212. It is also possible to perform several extensions in the lateral direction or in the longitudinal direction before the oblique extension (to prevent the width from contracting in the width direction). The extension can be carried out by extending the tenter in the biaxial extension in steps which are different from left to right. This biaxial extension is the same as the extension method used in the usual film forming process. In the biaxial stretching, since the stretching is performed at a speed different from the left and right, the thickness of the adhesive film before stretching must be different from left to right. In the casting film forming method, the taper is added to the die to impart a left-right difference to the flow rate of the binder solution. By the method as described above, a binder film which is obliquely extended in the MD direction of the polarizing film to 10 to 80 degrees can be obtained. In the rubbing method, a rubbing treatment method which is widely used as an LCD liquid crystal alignment processing step can be applied. In other words, make. Orientation can be achieved by rubbing the surface of the film in a certain direction with paper or gauze, felt cloth, rubber or nylon or polyester fiber. It is generally achieved by applying a cloth formed of fiber hairs having a uniform length and a small thickness to apply left and right rubbing several times. It is preferably carried out using a friction roller having a roundness, a cylindricality, and a radial oscillating (eccentricity) of the roller itself of 30 μm or less. The lap angle of the film of the rubbing roller is preferably Ο. Γ~ 90°. For example, as described in Japanese Laid-Open Patent Publication No. 8-160-430, the winding is performed at 360° or more, whereby a stable rubbing treatment can be obtained. When the long film is rubbed, it is preferred to transport the film at a rate of 1 to 100 meters per minute under a constant tension using a transfer device. In order to set any friction angle, the rubbing roller is preferably free to rotate in the horizontal direction for the film traveling direction. It is preferred to select a suitable friction angle of -40 to 1356212 in the range of 0° to 60°. When used in a liquid crystal display device, it is preferably 40 to 50, and particularly preferably 45. Preferably, a polymer film (optical anisotropic layer/polarizing film/polymer film arrangement) for protecting the polarizing film is disposed on the surface of the polarizing film opposite to the optically anisotropic layer. The polymer film may also be an antireflection film having antifouling properties and scratch resistance on its outermost surface. [Protective film] The polarizing plate of the present invention is a pair of protective films on the two-layer layer of the polarizing film. The type of the protective film is not particularly limited, and cellulose esters such as cellulose acetate, cellulose acetate-butyrate, cellulose propionate, polycarbonate, polyolefin, polystyrene, and poly can be used. Ester and the like. Since the protective film is usually supplied in the form of a roll, it is preferable that the long-sized polarizing film is continuously bonded so that the longitudinal direction becomes uniform. However, the alignment axis (slow phase axis) of the protective film may be in any direction, but from the viewpoint of ease of handling, the alignment axis of the protective film is preferably parallel to the longitudinal direction. In the present invention, at least one of the protective polarizing film is used, and at least one of the protective films has a retardation axis which is substantially coincident with the direction in which the average refractive index of the film 'surface is the largest. In other words, at least one of the protective films has three average refractive indices nx, ny, and nz in the mutually orthogonal X, y, and Z-axis directions, and assumes that the in-plane main average refractive index is nx and ny, and the thickness When the average refractive index of the direction is nz, then. Nx, ny = nz, nx > ny relationship will form a film; nx = ny, nz, nx > nz will form a film. That is, it is composed of a film having optical characteristics as the optically anisotropic layer A or the 1356212 optically anisotropic layer B as described above. As described above, if optical compensation energy is to be imparted to the protective film, it is preferable to satisfy the following conditions at any wavelength λ in the visible light region: -30 (nano) S { (nx - ny) x d2 } ^ 50 ( Nano), and -50 (nano) S[ { (nx + ny) / 2 - nz } x d2]S 300 (nano). On the other hand, in the case where the protective film is not used as the optical compensation layer, it is preferable that the retardation of the transparent protective film is low, and the alignment axis of the absorption axis of the polarizing film and the transparent protective film are not parallel, in particular When the retardation 値 of the transparent protective film is not more than 値, the alignment axis (slow phase axis) of the polarizing film and the transparent protective film are obliquely shifted, and the linearly polarized light is changed into elliptically polarized light, so that it is regarded as not ideal. Therefore, the delay of the transparent protective film is, for example, at 632. The 8 nm is preferably 1 nm or less, and more preferably 5 nm or less. The polymer film having a low retardation includes, for example, cellulose acetate ZEONEX and ZEONOA (all manufactured by Zeon Co., Ltd.). The polyolefin of ARTON (manufactured by JSR Co., Ltd.) can be suitably used. Other non-birefringent optical resin materials described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. When the protective film and the polarizing film are bonded together, it is preferable to have a retardation axis (alignment axis) of at least one of the protective films (the protective film disposed on the vicinity of the liquid crystal cell when the liquid crystal display device is assembled) The absorption axis (extension axis) of the polarizing film is crossed to form a protective film and a polarizing film. Specifically, the angle formed by the absorption axis of the polarizing film and the retardation axis of the protective film is preferably -10 to 1356212, preferably 2 (Γ~70°, more preferably 40). °~ 50°, and particularly preferably 43° to 47°. There is no particular limitation on the angle of the retardation axis of the other protective film and the absorption axis of the polarizing film, and it is appropriately set for the purpose of the polarizing plate. However, it is preferable that the above range is preferable, and it is preferable to make the retardation axes of the pair of protective films uniform. Further, if the retardation axis of the protective film and the absorption axis of the polarizing film are parallel to each other, the polarization prevention can be improved. The dimensional stability of the plate or the mechanical stability of the polarizing film such as curling. If the polarizing film and the pair of protective films total at least two axes of the three films, the retardation axis of one of the protective films and the absorption axis of the polarizing film , or the retardation axes of the two protective films are substantially parallel, the same effect can be obtained. In addition, if the retardation 値 of the protective film of the upper and lower polarizing plates is set to "asymmetry", it can contribute to the large Amplitude prevents light leakage when viewed in an oblique direction. Especially when it is placed on When the retardation 値 between the liquid crystal cell and the polarizing film of the lower polarizing plate is set to be asymmetrical, the light leakage in the oblique direction in which the absorption axes of the upper and lower polarizing plates are orthogonal can be effectively reduced. To set the delay to be asymmetric Then, at least one of the protective film and one of the lower polarizing plates should be used in at least one of the protective film and {(nx-ny) X (11} or { (nx + ny) / 2 - Nz } X di is not the same as the above, if the polarizing plate of the same structure is disposed on the polarizing plate above the liquid crystal cell, that is, the retardation of one of the upper and lower polarizing plates is the same, The optical compensation of the liquid crystal cell by the protective film or the optical compensation film additionally combined 〇 <Binder> Although the adhesive of the polarizing film and the protective film is not particularly limited, it is preferably PVA (polyethylene) than 1356212. An alcohol) resin (including a modified PVA such as an ethyl acetonitrile group, a sulfonic acid group, a carboxyl group or an alkylene oxide), or an aqueous solution of a boron compound, etc., wherein a PVA resin is preferred. The thickness of the adhesive layer is dried. Good is at 0. 01~10 microns range, especially good for 〇. 〇 5 ~ 5 microns range. <Consistent Process of Polarizing Film and Transparent Protective Film> The polarizing plate of the present invention has a drying step of stretching the film for a polarizing film, and has a drying step of shrinking and lowering the volatilization rate, but preferably after drying or After the transparent protective film is attached to one side at the time of drying, there is a post-heating step. In the aspect in which the transparent protective film also serves as a support for the optically anisotropic layer as the optical compensation layer, it is preferable to bond the transparent protective film on one side and the transparent transparent layer on the opposite side. After the support, it is heated after application. The specific bonding method is to adhere the transparent protective film on the polarizing film with the adhesive while maintaining the both ends in the film drying step, and then cut off the edges of both ends, or after drying, the two ends are removed. A film for a polarizing film, and a method of bonding a transparent protective film or the like after cutting the both end edges of the film. The method of cutting the edge can be performed by a method of cutting with a cutter such as a blade, and a general technique such as a laser method. After the bonding, the adhesive is dried and the polarizing performance is improved, and heating is preferred. The heating condition is different depending on the binder, but in the case of a water system, it is preferably 30 ° C or more, more preferably 40 ° C or more and 100 ° C or less, and particularly preferably 50 ° C or more and 90 ° C or less. These steps are considered to be manufactured from a consistent production line from the viewpoint of performance and production efficiency. <Performance of Polarizing Plate> The optical properties and durability (in the short-term and long-term storage) of the -44 - 1356212 polarizing plate composed of a transparent protective film, a polarizing film, and a transparent support of the present invention are Super-high-contrast products (such as HLB 2-5618 manufactured by Sanritz Co., Ltd.) sold at the commercial level are preferably equal or higher. Specifically, the visible light transmittance is 42. More than 5 %, the degree of polarization { ( Tp · Tc ) / ( Tp + Tc) } 1/2 2 0. 9995 ) (However, Τ ρ is "parallel transmittance",

Tc爲「正交透射率」），在溫度爲60°C、相對濕度爲90 % RH之周圍環境下放置500小時，及在溫度爲80°C、乾周圍環境下放置500小時，其前後的光透射率之變化率以絕對値計則爲3 %以下，更佳爲1 %以下，偏光度之變化率以絕對値計則爲1 %以下，更佳爲0.1 %以下。在本發明所使用之偏光板，如上所述，也可具有光學補償層》該光學補償層是由具有碟狀結構單元之化合物所構成，該碟狀面較佳爲對於上述基板面呈大致垂直配向之光學補償層。關於上述光學補償層之材料及其製造方法之詳細且較佳的範圍，係與以下所說明之光學補償膜的一結構層之光學異方向性層相同。〔光學補償膜〕光學補償膜係用以消除影像著色、或擴大視野角。但是在本發明中’如上所述，光學補償膜並非爲不可或缺之構件’例如在將雙折射性附加於偏光板之一對保護膜之一方或雙方’以使其用作爲光學補償膜的模式等，則也有不再需要之情形。光學補償膜全體的面內之延遲（Re )，係以20〜200奈米爲佳。光學補償膜全體的厚度方向之延遲（Rth)，係以 -45- 1356212 50 ~ 500奈米爲佳。光學補償膜的面內之延遲（Re)和厚 . 度方向之延遲（Rth )係分別表示面內之延遲和厚度方向之 _ 延遲。Re係在KOBRA 2 1ADH (王子計測機器公司（股）製）使波長λ奈米之光入射於薄膜法線方向所測得.Rth . 係KOBRA 21 AD Η會根據該Re，將波長；I奈米之光從以面內之遲相軸（是由KOBRA 21ADH來判斷）作爲傾斜軸（ ^ 回轉軸）而對於薄膜法線方向傾斜 + 40°的方向入射所測 · 得之延遲値 '及以面內之遲相軸作爲傾斜軸（回轉軸）而對於薄膜法線方向傾斜-40°的方向入射所測得之延遲値 ® 總共3方向所測得之延遲値來計算得。在此，平均折射率之假定値可使用「高分子手冊j ( “Polymer Handbook”） (John Wiley & Sons, Inc.)、及各種光學薄膜商品型錄之値。對於平均折射率之値並非爲已知者，則可以阿貝（Tc is "orthogonal transmittance"), placed in a surrounding environment at a temperature of 60 ° C and a relative humidity of 90 % RH for 500 hours, and placed at a temperature of 80 ° C and a dry environment for 500 hours. The rate of change of the light transmittance is 3% or less, more preferably 1% or less in absolute enthalpy, and the rate of change in the degree of polarization is 1% or less, and more preferably 0.1% or less in absolute enthalpy. The polarizing plate used in the present invention may have an optical compensation layer as described above. The optical compensation layer is composed of a compound having a dish-like structural unit, and the dish surface is preferably substantially perpendicular to the substrate surface. An optical compensation layer for alignment. The detailed and preferable range of the material of the optical compensation layer and the method for producing the same is the same as the optically anisotropic layer of a structural layer of the optical compensation film described below. [Optical Compensation Film] The optical compensation film is used to eliminate image coloration or to increase the viewing angle. However, in the present invention, as described above, the optical compensation film is not an indispensable member, for example, by attaching birefringence to one or both of the protective films to use as an optical compensation film. Modes, etc., there are also situations that are no longer needed. The in-plane retardation (Re ) of the entire optical compensation film is preferably 20 to 200 nm. The retardation (Rth) in the thickness direction of the entire optical compensation film is preferably -45 to 1356212 50 to 500 nm. The in-plane retardation (Re) and the thickness retardation (Rth) of the optical compensation film indicate the retardation in the in-plane and the retardation in the thickness direction, respectively. Re is measured by KOBRA 2 1ADH (manufactured by Oji Scientific Instruments Co., Ltd.) to make the wavelength λ nm light incident on the normal direction of the film. Rth. KOBRA 21 AD Η will be based on the Re, the wavelength; The light of the meter is measured from the in-plane retardation axis (which is judged by KOBRA 21ADH) as the tilt axis (^ rotary axis) and the direction of the film normal direction tilt + 40°. The in-plane retardation axis is calculated as the tilt axis (rotary axis) and the delay 値 measured in the direction of the film normal direction tilted by -40°. Here, the assumption of the average refractive index can be used in the "Polymer Handbook" (John Wiley & Sons, Inc.), and various optical film catalogues. For the known person, you can Abe (

Abbe )折射計來測定。茲將主要光學薄膜之平均折射率之値例示如下：醯化纖維素（1.48)、環烯烴聚合物（1.52) 、聚碳酸酯（1.59)、聚甲基丙烯酸甲酯（1.49)、聚苯乙烯（1.59)。將該等平均折射率之假定値與膜厚値輸入’ ® 反0811八21八011貝[1可計算出1^'1^和1^。光學補償膜雖然有由延伸雙折射聚合物薄膜所構成的光學補償膜、及在透明支撐體上具有由低分子或高分子液晶性化合物所形成的光學異方向性層之光學補償膜’但是在本發明中則可使用任一者。也可使用上述光學異方向性層 A和光學異方向性層B之積層體，及塗佈型之積層體結構之光學補償膜。關於積層結構之光學補償膜’若加以考慮 -46- 1356212 厚度，則與由高分子延伸薄膜之積層體所構成的光學補償膜相比較，則較佳爲由塗佈型之積層體所構成的光學補償膜。可作爲光學補償膜使用之高分子薄膜，也可爲經延伸之高分子薄膜，或爲塗佈型高分子層與高分子薄膜之組合倂用。高分子薄膜之材料一般使用合成高分子（例如，聚碳酸酯、聚楓、聚醚碾'聚丙烯酸酯、聚甲基丙烯酸酯、降伯烯樹脂、三乙醯基纖維素。其次，就具有由液晶性化合物所構成的光學異方向性層的光學補償膜詳加說明如下。〔液晶性化合物所構成的光學異方向性層〕由於液晶性化合物具有各種不同的配向形態，由液晶性化合物所構成的光學異方向性層，係以單層或以數層之積層·體，即能顯現出吾所欲得之光學性質。換言之，光學補償膜也可爲.由支撐體與形成於該支撐體上的一個以上之光學異方向性層所構成的態樣。此種態樣之光學補償膜全體之延遲，即可由光學異方向性層的光學異方向性來加以調整。「液晶性化合物」可由其形狀來分類成「棒狀液晶性化合物」與「圓盤狀（disco tic )化合物」。並且，各分別也有低分子型和高分子型，但是任何者皆可使用。使用於本發明之由液晶性化合物所構成的光學異方向性層，其液晶性化合物較佳爲使用棒狀液晶性化合物、或圓盤狀化合物，更佳爲使用具有聚合性基之棒狀液晶性化合物、或具有聚合性基之圓盤狀化合物。 -47- 1356212 (棒狀液晶性化合物）棒狀（Rod-like )液晶性化合物，較佳爲使用：偶氮甲鹼類、氧化偶氮類、氰基聯苯類''氰基聯苯酯類、苯甲酸酯類、環己烷甲酸苯酯類、氰基苯基環己烷類、經氰基取代之苯基嘧啶類、經烷氧基取代之苯基嘧啶類、苯基二噁烷類、二苯基乙炔類、及烯基環己基苯甲腈類。另外，棒狀液晶性分子也包括金屬錯合物。此外，將棒狀液晶性分子包含在重複單元中的液晶聚合物，也可作爲棒狀液晶性分子來使用。換言之，棒狀液晶性分子也可與 (液晶）聚合物鍵結。關於棒狀液晶性化合物，在季刊化學總說，第22冊，「液晶之化學」（1994 )日本化學學會編著之第4章、第7 章和第11章，及「液晶裝置手冊」日本學術振興會第142 次委員會編著之第3章中有所記載^ 棒狀液晶性化合物之雙折射率，較佳爲0.001 ~ 0.7之範圍。棒狀液晶性化合物較佳爲具有聚合性基，以使其可固定成配向狀態。聚合性基較佳爲自由基聚合性不飽和基或陽離子聚合性基，具體而言，其係包括例如在日本國專利特開第2002-62,427號公報專利說明書中記載於段落〔〇〇64 〕~〔 0086〕之聚合性基及聚合性液晶性化合物。 (圓盤狀化合物）使用「圓盤狀化合物」作爲用以形成上述光學異方向性層之液晶性化合物也是較佳的。圓盤狀化合物較佳爲加以 -48- 1356212 配向成對於聚合物薄膜實質地成垂直（平均傾斜角爲.在50 ~ 90度之範圍）。圓盤狀化合物係已記載於各種文獻（C. Destrade 等人：Mol. Crysr. Liq. Cryst.，第 71 冊、第 111 頁（1981年）；日本化學會編：季刊化學總說，第22期，「液晶之化學d ，第5章 '第1 〇章第2節（1 994年） > B. Kohne 等人：Angew. Chem. Soc. Chem. Comm.，第 1,794 頁（1 985 年）；J. Zhang 等人：J. Am. Chem. Soc.，第116冊、第2,655頁（1994年）〕。關於圓盤狀化合物之聚合係已記載於日本國專利特開平第8-27,284號公報。圓盤狀化合物較佳爲具有聚合性基，以使其可藉由聚合加以固定。例如，可使用一種使聚合性基作爲取代基而鍵結於圓盤狀化合物的圓盤狀芯之結構，但是若使聚合性基直接鍵結於圓盤狀芯時，則在聚合反應中將難以保持配向狀態。因此，較佳爲在圓盤狀芯與聚合性基之間具有連結基（linking group )。換言之，具有聚合性基之圓盤狀化合物，較佳爲以如下所示通式（III)所表示之化合物：通式（III) : D_ ( — L — P) n 式中，D是圓盤狀芯，L是二價連結基，Ρ是聚合性基，η 是4至12之整數。上述式（III)中之圓盤狀芯（D)、二價連結基（L)及聚合性基（Ρ )之較佳實例係分別記載於日本國專利特開第 200 1 -4,837 號公報之（D1 ) ~ ( D15 ) 、( LI ) ~ ( L25 )、 (Ρ1)〜（Ρ18)，且該公報所記載之內容係適用於本發明 -49- 1356212 (液晶性化合物之配向）該等液晶性化合物在光學異方向性層中較佳爲實質地配向成均勻，且更佳爲實質地在均勻配向的狀態下加以固定，同時最佳爲液晶性化合物係藉由聚合反應加以固定。在具有聚合性基的棒狀液晶性化合物之情形時，較佳爲實質地加以固定化成水平（均勻）配向。所謂「實質地爲水平」係意謂棒狀液晶性化合物之長軸方向與光學異方向性層的面之平均角度（平均傾斜角）爲在0°~ 40°之範圍內。棒狀液晶性化合物也可使其作「傾斜配向」，也可使其傾斜角慢慢地變化（「混成配向」）。在傾斜配向或混成配向之情形時，平均傾斜角也是較佳爲〇°~ 40°。藉由固定成此種配向的棒狀液晶性化合物所形成之光學異方向性層，也可將其搭配於VA模式、IPS模式之液晶顯示裝置中，如此即可用以有助於改善液晶顯示裝置之視野角特性的光學補償層。在具有聚合性基的圓盤狀液晶性化合物之情形時，較佳爲實質地加以固定化成垂直配向。所謂「實質地爲水平」係意謂圓盤狀液晶性化合物之圓盤面與光學異方向性層的面之平均角度（平均傾斜角）爲在50。~ 90。之範圍內。圓盤狀液晶性化合物也可使其作傾斜配向，也可使其傾斜角慢慢地變化（混成配向）。在傾斜配向或混成配向之情形時’平均傾斜角也是較佳爲50。〜90。。藉由固定成此種配向的圓盤狀液晶性化合物所形成之光學異方向性層，也可將其搭配於、VA模式' IPS模式之液晶顯示裝置中，如此即 -50- 1356212 可用以有助於改善液晶顯示裝置視野角特性的光學補償層 0 光學異方向性層較佳爲藉由將含有液晶性化合物、及下述聚合引發劑、或其他添加劑之塗佈液塗佈在配向膜上所形成者。使用於調製塗佈液之溶劑較佳爲使用有機溶劑。有機溶劑之使用實例係包括：醯胺類（例如N, N-二甲基甲醯胺）、亞碾類（例如二甲基亞颯）、雜環化合物（例如吡啶）、碳氫化合物（例如苯、己烷）、烷基鹵化物（例如氯仿、二氯甲烷、四氯乙烷）、酯類（例如醋酸甲酯、醋酸丁酯）、酮類（例如丙酮 '甲基乙基酮）、醚類（例如四氫呋喃、1，2 -二甲氧基乙烷）。其中較佳爲烷基鹵化物及酮類。也可併用兩種以上之有機溶劑。塗佈液之塗佈，係可由傳統方法（例如，線棒塗佈法、擠壓塗佈法、直接凹版輪轉塗佈法、反向凹版輪轉塗佈法、模頭塗佈法）來實施。 (液晶性化合物配向狀態之固定化）經配向之液晶性化合物，較佳爲在維持其配向狀態下加以固定。固定化較佳爲以導入於液晶性化合物的聚合性基之聚合反應來實施。聚合反應係包括：使用熱聚合引發劑之熱聚合反應、及使用光聚合引發劑之光聚合反應。但是較佳爲光聚合反應。光聚合引發劑之實例包括：α-羰基化合物（揭示於美國專利第2,367,661號、同第2,3 67，670號之各說明書）、偶姻醚（揭示於美國專利第2,448,828號說明書）、α -碳氫化合物取代之芳香族偶姻化合物（揭示於 -51 - 1356212 美國專利第2,722,5 1 2號說明書）、多核醌化合物（揭示於美國專利第3,046,127號、同第2,951,758號之各說明書）、三芳基咪唑二聚物與對-胺基苯基酮）之組合（揭示於美國專利第3,549,367號說明書）、吖啶及啡井化合物（揭示於日本國專利特開昭第60 - 105,667號公報、美國專利第 4,239,850號之說明書）及氧二氮唑（揭示於美國專利第 4,212,970號說明書）。光聚合引發劑之使用量，較佳爲在塗佈液的固態份之 0.01 ~ 20質量％之範圍，且更佳爲在0.5 ~ 5質量％之範圍。聚合液晶性化合物所需之光照射，較佳爲使用紫外線。照射能量較佳爲20 mJ/cm2 ~ 50 mJ/cm2，且更佳爲1〇〇 ~ 8 00 mJ/cm2。欲能促進光聚合反應，也可在加熱條件下實施光照射。光學異方向性層之厚度較佳爲0.1〜10微米，且更佳爲〇.5~5微米。 (配向膜）在形成光學異方向性層時爲使液晶性化合物配向，則較佳爲使用配向膜。配向膜可以例如以有機化合物（較佳爲聚合物）之摩擦處理、無機化合物之傾斜蒸鍍、具有密紋的層之形成、或利用 LB膜（Langmuir-Blodgett film)之有機化合物〔例如ω-二十三酸、氯化雙十八基甲基銨、硬脂酸甲酯〕的累積之方法來設置。另外，有一種藉由施加電場、施加磁場 '或光照射即可產生配向機能之配向膜，也是眾所皆知。但是以利用聚合物之摩擦處理所形成之配向膜爲特別佳。摩擦處理係以紙或布向一定方向摩擦聚合 -52- 1356212 層表面之方法來實施。·可供使用於配向膜之聚合物種類，可根據液晶性化合物之配向（特別是平均傾斜角）來作決定。例如，如欲使液晶性化合物配向成水平配向，則應使用不會降低配向膜表面能量之聚合物（通常之配向用聚合物）。關於具體的聚合物種類，係揭述於有關液晶胞或光學補償片之各種文獻。任何一種配向膜較佳爲以改善液晶化合物與透明支撐體之貼緊性爲目的而具有聚合性基。聚合性基係可在側鏈導入重複單元，或可作爲環狀基之取代基而導入。更佳爲使用在界面可與液晶性化合物形成化學鍵結之配向膜，此種配向膜已記載於日本國專利特開平第 9-152,509 號 ° 配向膜厚度係以0.01 ~ 5微米爲佳，以〇·〇5 ~ 1微米爲更佳。另外，也可經使用配向膜使液晶性化合物配向後，仍在其配向狀態下固定液晶性化合物以形成光學異方向性層，然後，僅使光學異方向性層轉印於聚合物薄膜（或透明支撐體）上。〔垂直配向膜〕爲使液晶性化合物在配向膜側配向成垂直，重要的是必須降低配向膜之表面能量。具體而言，藉由聚合物之官能基使配向膜之表面能量降低，以使液晶性化合物成爲豎立狀態。可便配向膜之表面能量降低之官能基，係以氟原子及碳原子數爲10以上之烴基爲有效。爲使氟原子或烴基存在於配向膜表面，較佳爲並非將氟原子或烴基導入於聚合 -53- 1356212 物之主鏈，而是導入於側鏈。含氟聚合物之氟原子含量較佳爲0.05 ~ 80重量％之比率，更佳爲〇· 1 ~ 70重量％之比率，且特佳爲0.5 ~ 65重量％之比率。烴基就是脂肪族基、芳香族基或其等之組合。脂肪族基係可爲環狀、分枝狀或直鏈狀中之任一者。脂肪族基較佳爲烷基（也可爲環烷基）或烯基（也可爲環烯基）。烴基也可具有如同鹵原子 ‘ 般之不會顯現強烈親水性之取代基。烴基之碳原子數較佳 · 爲10 ~ 100，更佳爲10 ~ 60，且最佳爲10〜40。聚合物之主鏈較佳爲具有聚醯亞胺結構或聚乙烯醇結構。 Φ 聚醯亞肢一般藉由四羧酸與二胺之縮合反應來合成。也可使用兩種以上之四羧酸或兩種以上之二胺來合成相當於共聚合物之聚醯亞胺》氟原子或烴基，係也可使其存在於四羧酸之重複單元’也可使其存在於源於二胺之重複單元，也可使其存在於兩者之重複單元。若在聚醯亞胺導入烴基時’則特佳爲在聚醯亞胺之主鏈或側鏈形成「類固醇（ steroid )」結構。存在於側鏈之類固醇結構係相當於碳原子數爲10以上之烴基’且具有可使液晶性化合物配向成垂 Φ 直之機能。在本說明書所謂之「類固醇結構」係意謂環戊烷并氫菲環結構或其環之一部份以脂肪族環之範圍（不會形成芳香族環之範圍）成爲雙鍵之環結構。另外，使液晶性化合物配向成垂直之方法，可使用將有機酸混合於聚乙烯醇或聚醯亞胺的髙分子之方法。可供混合之酸可使用羧酸或磺酸、胺基酸。也可使用如後所述之空氣界面配向劑中會顯現酸性者。其混合量較佳爲相對於 -54- 1356212 高分子爲0.1重量％至20重量％，更佳爲自0.5重量％至l〇重量％。對於碟狀液晶性化合物之均勻配向，則將垂直配向膜加以摩擦處理，以控制配向方向。摩擦處理係以紙或布朝一定方向擦拭聚合物層表面數次，藉以實施。相對地，對於棒狀液晶性化合物之配向則以不實施摩擦處理爲佳。對於任一種配向膜，較佳爲以改善液晶化合物與透明支撐體的· 貼緊性爲目的而使配向膜具有聚合性基。聚合性基可以在側鏈導入具有聚合性基的重複單元之方式，或以作爲環狀基的取代基之方式來導入。更佳爲在界面能與液晶性化合物形成化學鍵結之配向膜，如此之配向膜則已記載於曰本國專利特開平第9-152,509號公報。配向膜厚度較佳爲 0.01〜5微米，更佳爲0.05 ~ 1微米。此外，也可使用配向膜使液晶性化合物配向後，仍在其配向狀態下使液晶性化合物固定，以形成相位差層，然後只使相位差層轉印到聚合物薄膜（或透明支撐體）上。〔空氣界面配向劑〕通常液晶性化合物係具有在空氣界面側會傾斜而配向之性質，因此如欲獲得均勻地垂直配向的狀態，則必須在空氣界面側也將液晶性化合物控制成垂直配向。爲達成此目的，則將會不均勻地偏在空氣界面側，且具有會因其排除體積效應或靜電性效應來使液晶性化合物垂直配向的作用之化合物混合於液晶塗佈液。使液晶性化合物垂直配向之作用，在碟狀液晶性化合物係相當於使其「指向角（ -55- 1356212 director)」之傾斜角度，即指向角與塗佈液晶空氣界面所形成的角度加以減少的作用。可使碟狀液晶性分子的指向角之傾斜角度減少之化合物’則較佳爲使用如下所述之爲要偏在於空氣界面側而使F原子鍵結數個者，或對於已鍵結擴醯基或羧基者’再使能對液晶性分子賦予垂直配向的排除體積效應之剛直性結構單元鍵結之化合物。 • ·!« ： · . ·· , >0 (CH2) nCinF2B+l H〇3S~(CH2) n_CfflF2m+l (n = l〜8、m=3 〜16) H〇3S-Abbe) Refractometer to determine. The average refractive index of the main optical film is exemplified as follows: deuterated cellulose (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), polystyrene (1.59). The assumption of the average refractive index and the film thickness 値 input '® anti-0811 eight 21 eight 011 shells [1 can be calculated 1^'1^ and 1^. The optical compensation film has an optical compensation film composed of an extended birefringent polymer film and an optical compensation film having an optically anisotropic layer formed of a low molecular or high molecular liquid crystalline compound on a transparent support. Any of the present invention can be used. It is also possible to use a laminate of the above-described optical anisotropic layer A and optically anisotropic layer B, and an optical compensation film of a coating type laminate structure. Regarding the optical compensation film of the laminated structure, considering the thickness of -46 to 1356212, it is preferably composed of a coating type laminated body as compared with the optical compensation film composed of the laminated body of the polymer-extended film. Optical compensation film. The polymer film which can be used as an optical compensation film may be an extended polymer film or a combination of a coating polymer layer and a polymer film. As the material of the polymer film, a synthetic polymer (for example, polycarbonate, poly maple, polyether mill polyacrylate, polymethacrylate, urethane resin, triacetyl cellulose) is used. The optical compensation film of the optically anisotropic layer composed of a liquid crystal compound is described in detail below. [Optical anisotropic layer composed of a liquid crystal compound] The liquid crystal compound has various alignment forms, and is composed of a liquid crystal compound. The optically anisotropic layer is formed by a single layer or a plurality of layers, which can reveal the optical properties that I want. In other words, the optical compensation film can also be formed by the support and the support. A state in which one or more optically anisotropic layers are formed on the body. The retardation of the entire optical compensation film of such a state can be adjusted by the optical anisotropy of the optical anisotropic layer. It can be classified into a "rod-like liquid crystalline compound" and a "disc tic compound" by its shape, and each has a low molecular type and a high molecular type, respectively. Any of the optically anisotropic layers composed of the liquid crystalline compound of the present invention, preferably a liquid crystalline compound using a rod-like liquid crystalline compound or a disk-shaped compound, more preferably used A rod-like liquid crystal compound having a polymerizable group or a discotic compound having a polymerizable group. -47 - 1356212 (rod-like liquid crystalline compound) Rod-like liquid crystal compound, preferably used: azo Methyl bases, oxidized azos, cyanobiphenyls, 'cyanobiphenyl esters, benzoic acid esters, phenyl cyclohexanecarboxylates, cyanophenyl cyclohexanes, substituted by cyano Phenylpyrimidines, phenylpyrimidines substituted with alkoxy groups, phenyldioxanes, diphenylacetylenes, and alkenylcyclohexylbenzonitriles. In addition, rod-like liquid crystalline molecules also include metal Further, a liquid crystal polymer containing a rod-like liquid crystalline molecule in a repeating unit may be used as a rod-like liquid crystalline molecule. In other words, a rod-like liquid crystalline molecule may be bonded to a (liquid crystal) polymer. About rod-like liquid crystalline compounds, in the season Journal of Chemistry, Volume 22, "Chemistry of Liquid Crystals" (1994) Chapters 4, 7 and 11 of the Japanese Chemical Society, and "The Handbook of Liquid Crystal Devices" edited by the 142nd Committee of the Japan Society for the Promotion of Science It is described in Chapter 3 that the birefringence of the rod-like liquid crystalline compound is preferably in the range of 0.001 to 0.7. The rod-like liquid crystalline compound preferably has a polymerizable group so that it can be immobilized in an aligned state. The radical group is preferably a radical polymerizable unsaturated group or a cationically polymerizable group, and specifically, it is described in paragraph [〇〇64] in the patent specification of Japanese Patent Laid-Open Publication No. 2002-62,427. Polymerizable group and polymerizable liquid crystal compound of [0086] (Disc type compound) It is also preferable to use a "disk-shaped compound" as the liquid crystalline compound for forming the optically anisotropic layer. Preferably, the discotic compound is oriented to -48 - 1356212 to be substantially perpendicular to the polymer film (average tilt angle in the range of 50 to 90 degrees). Discotic compounds have been described in various literatures (C. Destrade et al.: Mol. Crysr. Liq. Cryst., Vol. 71, p. 111 (1981); Japanese Chemical Society: Quarterly Chemistry General, No. 22 Period, "Chemical D in Liquid Crystals, Chapter 5 'Chapter 1 Section 2 (1 994) > B. Kohne et al.: Angew. Chem. Soc. Chem. Comm., p. 1, 794 (1 985) J. Zhang et al.: J. Am. Chem. Soc., vol. 116, p. 2, 655 (1994). The polymerization of disc-shaped compounds is described in Japanese Patent Laid-Open No. 8-27,284. The discotic compound preferably has a polymerizable group so that it can be fixed by polymerization. For example, a disc-shaped core in which a polymerizable group is used as a substituent and bonded to a discotic compound can be used. However, when the polymerizable group is directly bonded to the disk-shaped core, it is difficult to maintain the alignment state in the polymerization reaction. Therefore, it is preferred to have a linking group between the disk-shaped core and the polymerizable group ( Linking group ). In other words, a discotic compound having a polymerizable group is preferably as shown below A compound represented by the formula (III): a formula (III): D_(- L - P) n wherein D is a discotic core, L is a divalent linking group, Ρ is a polymerizable group, and η is 4 to An integer of 12. The preferred examples of the disc-shaped core (D), the divalent linking group (L), and the polymerizable group (Ρ) in the above formula (III) are respectively described in Japanese Patent Laid-Open No. 2001- (D1) ~ (D15), (LI) ~ (L25), (Ρ1)~(Ρ18) of the Japanese Patent Publication No. 4,837, and the contents described in the publication are applicable to the present invention -49- 1356212 (Alignment of liquid crystal compounds) Preferably, the liquid crystalline compounds are substantially uniformly aligned in the optically anisotropic layer, and more preferably are substantially fixed in a uniformly aligned state, and preferably the liquid crystalline compound is polymerized. In the case of a rod-like liquid crystalline compound having a polymerizable group, it is preferably substantially immobilized to a horizontal (uniform) alignment. The term "substantially horizontal" means the long axis direction of the rod-like liquid crystalline compound. The average angle (average tilt angle) of the face with the optical anisotropic layer is between 0° and 40° Within the range of °, the rod-like liquid crystalline compound can also be made to "tilt alignment", or the inclination angle thereof can be gradually changed ("mixed alignment"). In the case of oblique alignment or blending alignment, the average tilt angle It is also preferably 〇° to 40°. The optically anisotropic layer formed by fixing the aligned linear liquid crystalline compound can also be used in a VA mode or IPS mode liquid crystal display device. It can be used as an optical compensation layer which contributes to the improvement of the viewing angle characteristics of the liquid crystal display device. In the case of a discotic liquid crystalline compound having a polymerizable group, it is preferably substantially immobilized in a vertical alignment. The term "substantially horizontal" means that the average angle (average inclination angle) of the disk surface of the discotic liquid crystalline compound and the surface of the optically anisotropic layer is 50. ~ 90. Within the scope. The disc-shaped liquid crystal compound can also be tilt-aligned, or the tilt angle thereof can be gradually changed (mixed alignment). The average tilt angle is also preferably 50 in the case of oblique alignment or blending alignment. ~90. . The optically anisotropic layer formed by fixing the aligned discotic liquid crystalline compound can also be used in a liquid crystal display device of the VA mode 'IPS mode, so that the -50-1356212 can be used. The optical compensation layer 0 which contributes to the improvement of the viewing angle characteristic of the liquid crystal display device is preferably coated on the alignment film by a coating liquid containing a liquid crystal compound, a polymerization initiator described below, or other additives. Formed by. The solvent used for preparing the coating liquid is preferably an organic solvent. Examples of the use of the organic solvent include: guanamines (for example, N,N-dimethylformamide), submillings (for example, dimethylammonium), heterocyclic compounds (for example, pyridine), hydrocarbons (for example). Benzene, hexane), alkyl halides (such as chloroform, dichloromethane, tetrachloroethane), esters (such as methyl acetate, butyl acetate), ketones (such as acetone 'methyl ethyl ketone), Ethers (e.g., tetrahydrofuran, 1,2-dimethoxyethane). Among them, preferred are alkyl halides and ketones. It is also possible to use two or more organic solvents in combination. The coating of the coating liquid can be carried out by a conventional method (e.g., bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method). (Immobilization of alignment state of liquid crystal compound) The alignment liquid crystal compound is preferably fixed while maintaining its alignment state. The immobilization is preferably carried out by a polymerization reaction of a polymerizable group introduced into the liquid crystalline compound. The polymerization reaction includes thermal polymerization using a thermal polymerization initiator and photopolymerization using a photopolymerization initiator. However, photopolymerization is preferred. Examples of the photopolymerization initiator include: an α-carbonyl compound (disclosed in the specification of U.S. Patent No. 2,367,661, the entire disclosure of which is incorporated herein by reference) - a hydrocarbon-substituted aromatic cryptic compound (disclosed in the specification of -51 - 1356212, U.S. Patent No. 2,722, 5, 1 2), a polynuclear ruthenium compound (disclosed in the specification of U.S. Patent No. 3,046,127, the same as No. 2,951,758) , a combination of a triaryl imidazole dimer and a p-aminophenyl ketone (disclosed in U.S. Patent No. 3,549,367), acridine and a porphyrin compound (disclosed in Japanese Patent Laid-Open No. 60-105,667) And the specification of U.S. Patent No. 4,239,850, and oxadiazole (disclosed in U.S. Patent No. 4,212,970). The amount of the photopolymerization initiator to be used is preferably in the range of 0.01 to 20% by mass, and more preferably in the range of 0.5 to 5% by mass, based on the solid portion of the coating liquid. It is preferred to use ultraviolet rays for light irradiation required for polymerizing a liquid crystal compound. The irradiation energy is preferably from 20 mJ/cm 2 to 50 mJ/cm 2 , and more preferably from 1 〇〇 to 8 00 mJ/cm 2 . In order to promote photopolymerization, light irradiation can also be carried out under heating. The thickness of the optically anisotropic layer is preferably from 0.1 to 10 μm, and more preferably from 5 to 5 μm. (Alignment film) When the optically anisotropic layer is formed, it is preferred to use an alignment film in order to align the liquid crystal compound. The alignment film may be, for example, a rubbing treatment with an organic compound (preferably a polymer), a tilt evaporation of an inorganic compound, a formation of a dense layer, or an organic compound using a LB film (Langmuir-Blodgett film) [for example, ω- The method of accumulating the triacyl acid, dioctadecylmethylammonium chloride, and methyl stearate] is set. In addition, it is known that an alignment film which produces an alignment function by applying an electric field, applying a magnetic field or light irradiation is also known. However, an alignment film formed by rubbing treatment with a polymer is particularly preferable. The rubbing treatment is carried out by rubbing a paper or cloth in a certain direction by rubbing the surface of the polymer layer -52 - 1356212. • The type of polymer that can be used in the alignment film can be determined based on the alignment of the liquid crystal compound (especially the average tilt angle). For example, if the liquid crystal compound is to be aligned to a horizontal alignment, a polymer (usually a polymer for alignment) which does not lower the surface energy of the alignment film should be used. Regarding specific polymer types, various documents relating to liquid crystal cells or optical compensation sheets are disclosed. Any of the alignment films preferably has a polymerizable group for the purpose of improving the adhesion between the liquid crystal compound and the transparent support. The polymerizable group may be introduced into the repeating unit in the side chain or may be introduced as a substituent of the cyclic group. More preferably, it is an alignment film which can form a chemical bond with a liquid crystal compound at the interface. Such an alignment film is described in Japanese Patent Laid-Open No. 9-152,509. The thickness of the alignment film is preferably 0.01 to 5 μm. · 〇 5 ~ 1 micron is better. Further, after the liquid crystal compound is aligned by using the alignment film, the liquid crystal compound is fixed in the alignment state to form the optical anisotropic layer, and then only the optical anisotropic layer is transferred to the polymer film (or Transparent support). [Vertical alignment film] In order to make the liquid crystal compound perpendicular to the alignment film side, it is important to lower the surface energy of the alignment film. Specifically, the surface energy of the alignment film is lowered by the functional group of the polymer to bring the liquid crystal compound into an erect state. The functional group having a reduced surface energy of the alignment film is effective in a fluorine atom and a hydrocarbon group having 10 or more carbon atoms. In order to allow a fluorine atom or a hydrocarbon group to exist on the surface of the alignment film, it is preferred that the fluorine atom or the hydrocarbon group is not introduced into the main chain of the polymerization -53 - 1356212, but is introduced into the side chain. The fluorine atom content of the fluoropolymer is preferably from 0.05 to 80% by weight, more preferably from 1.7 to 70% by weight, and particularly preferably from 0.5 to 65 % by weight. The hydrocarbon group is an aliphatic group, an aromatic group or a combination thereof. The aliphatic group may be either cyclic, branched or linear. The aliphatic group is preferably an alkyl group (which may also be a cycloalkyl group) or an alkenyl group (which may also be a cycloalkenyl group). The hydrocarbon group may also have a substituent such as a halogen atom which does not exhibit strong hydrophilicity. The hydrocarbon group preferably has a carbon number of from 10 to 100, more preferably from 10 to 60, and most preferably from 10 to 40. The main chain of the polymer preferably has a polyimine structure or a polyvinyl alcohol structure. The Φ polythene limb is generally synthesized by a condensation reaction of a tetracarboxylic acid and a diamine. It is also possible to use two or more kinds of tetracarboxylic acids or two or more kinds of diamines to synthesize a polyfluoride atom or a hydrocarbon group corresponding to a copolymer, which may also be present in a repeating unit of a tetracarboxylic acid. It may be present in a repeating unit derived from a diamine, or it may be present in a repeating unit of both. When a polyalkylene imine is introduced into a hydrocarbon group, it is particularly preferable to form a "steroid" structure in the main chain or side chain of the polyimine. The steroid structure present in the side chain corresponds to a hydrocarbon group having a carbon atom number of 10 or more and has a function of allowing the liquid crystal compound to be aligned to be perpendicular to Φ. The term "steroid structure" as used herein means a cyclopentanehydrophenanthrene ring structure or a ring structure in which a part of the ring is in the range of an aliphatic ring (which does not form an aromatic ring). Further, a method of aligning a liquid crystalline compound to a vertical direction may be carried out by a method of mixing an organic acid with a ruthenium molecule of polyvinyl alcohol or polyimine. As the acid to be mixed, a carboxylic acid or a sulfonic acid or an amino acid can be used. It is also possible to use an acid which appears in the air interface alignment agent as described later. The amount thereof is preferably from 0.1% by weight to 20% by weight, more preferably from 0.5% by weight to 100% by weight, based on the polymer of -54 to 1356212. For the uniform alignment of the discotic liquid crystalline compound, the vertical alignment film is subjected to a rubbing treatment to control the alignment direction. The rubbing treatment is carried out by wiping the surface of the polymer layer several times with paper or cloth in a certain direction. On the other hand, it is preferred that the alignment of the rod-like liquid crystal compound is not performed by rubbing treatment. For any of the alignment films, it is preferred that the alignment film has a polymerizable group for the purpose of improving the adhesion of the liquid crystal compound and the transparent support. The polymerizable group may be introduced as a repeating unit having a polymerizable group in a side chain or as a substituent of a cyclic group. More preferably, it is an alignment film capable of forming a chemical bond with a liquid crystal compound at the interface, and such an alignment film is disclosed in Japanese Laid-Open Patent Publication No. Hei 9-152,509. The thickness of the alignment film is preferably 0.01 to 5 μm, more preferably 0.05 to 1 μm. Further, after the alignment film is used to align the liquid crystal compound, the liquid crystal compound is fixed in the alignment state to form a retardation layer, and then only the retardation layer is transferred to the polymer film (or transparent support). on. [Air Interface Aligning Agent] Generally, the liquid crystal compound has a property of being inclined at the air interface side and being aligned. Therefore, in order to obtain a state of uniform vertical alignment, it is necessary to control the liquid crystal compound to be vertically aligned also on the air interface side. In order to achieve this, the compound which is unevenly biased toward the air interface side and which has a function of causing the liquid crystal compound to vertically align due to the elimination of the volume effect or the electrostatic effect is mixed with the liquid crystal coating liquid. The role of the liquid crystal compound in the alignment of the liquid crystal compound is equivalent to the angle of inclination of the "directivity angle (-55- 1356212 director)", that is, the angle formed by the directivity angle and the coating liquid crystal air interface. The role. The compound which can reduce the inclination angle of the directional angle of the discotic liquid crystalline molecules is preferably used as follows, in which the number of F atoms is bonded to the air interface side, or for the bonding. The group of the carboxyl group or the carboxyl group is a compound which is capable of imparting a vertical alignment of the liquid crystal molecules to the rigid-structured unit which excludes the volume effect. • ·!« : · . ·· , >0 (CH2) nCinF2B+l H〇3S~(CH2) n_CfflF2m+l (n = l~8, m=3 ~16) H〇3S-

(CH2)n(CF2)n CF2H 0(CH2)n(CF2)〇 CF2H (n = 1〜8、(CH2)n(CF2)n CF2H 0(CH2)n(CF2)〇 CF2H (n = 1~8,

:n= 3 〜1 6) (CH2) nCmF2ui+l 0 (CH2) nCmF2n+l :3 〜1 6):n= 3 ～1 6) (CH2) nCmF2ui+l 0 (CH2) nCmF2n+l :3 〜1 6)

l(CH2)n(CF2)〇 CF2H HOOCH -0(CH2)n(CF2)n CFsH (n=l〜8、m=3 〜16) HOaS-l(CH2)n(CF2)〇 CF2H HOOCH -0(CH2)n(CF2)n CFsH (n=l~8, m=3~16) HOaS-

(CH2)k〇(CH2)BCnF2n4] 0 (CH2) k〇 (CH2) oCnF2n+l (k^=l〜1 0、 0 〜.5、 3〜1 6) -56- 1356212(CH2)k〇(CH2)BCnF2n4] 0 (CH2) k〇 (CH2) oCnF2n+l (k^=l~1 0, 0~.5, 3~1 6) -56- 1356212

_ O(CH2)k〇(CH2)tt(CF2)i. CF2H HOaS-X V〇(CH2)k〇(CH2)m(CF2)n CF2H (k = l〜l〇、m=0〜5.、n：=3〜16) 除所例示之化合物以外，也可將日本國專利特開第 2002-20,363號公報、同特開第2002- 129,162號公報所記載之化合物作爲空氣界面配向劑來使用。此外，在特願第 2〇02-212，1〇〇號專利說明書段落碼0〇72 ~ 0076、特願第 2002-243,600號專利說明書段落碼0038 ~ 0040與0048〜 0049 '特願第 2002-262,239號專利說明書段落碼0037 ~ 0039、特願第 2003-9 1,752號專利說明書段落碼 007 1 ~ 0 078所記載之事項也可適用於本發明。對於液晶塗佈液之「空_界面配向劑」的使用量較佳爲 0.05重量％ ~ 5重量％。但是使用氟系飽和系空氣界面配向劑時，則較佳爲1重量％以下。關於用以支撐光學異方向性層之「支撐體」，則並無特殊的限制，可使用各種高分子薄膜。例如，三乙醯基纖維素、降伯烯樹脂等。另外，如上所述，偏光板之保護膜也可兼作光學異方向性層之支撐體。關於此種態樣的支撐體材料之具體實例，則與偏光板之保護膜材料的具體實例相同，如上所述者。 -57- 丄356212 【實施方式】實施例茲以實施例更具體說明本發明如下。以下之實施例所示材料、試劑、物質量及其比率 '操作等在未脫離本發明之精義範圍內皆可適當地加以變更。因此，本發明並不受限於以下之具體實例》〔例1〕製造第1圖所示結構之液晶顯示裝置。亦即，由觀察方向（上）依序積層上側偏光板（保護膜3a、偏光板1、保護膜3)，液晶胞（上基板5、液晶層7 '下基板8 )，下偏光板（保護膜12、偏光膜14'保護膜12a)，也配置背光光源（未圖示）。〈液晶胞之製造〉液晶胞係將基板之間的液晶胞之間隙設定爲3微米，並將具有負介電常數異方向性之液晶材料（「MLC 6680」，默克（Merk )公司製）滴下注入於基板之間後加以密封，以在基板之間形成液晶層所製得。將液晶層之延遲（亦即，液晶層厚度d(微米）與折射率異方向性Δη的乘積Δη • d)設定爲3 00奈米。另外，液晶材料係加以配向成垂直配向。〈上下偏光板之製造〉 (偏光膜之製造）將平均聚合度爲2,4〇0、膜厚爲100微米之PVA薄膜以 15〜17 °C之離子交換水洗淨爲期60秒鐘’以不銹鋼製葉 -58- 1356212 片扒除表面水份後，邊修正該PVA薄膜之濃度成爲一定' 邊浸漬於4 0°C、0.7克/公升之碘、60.0克/公升之碘化鉀的水溶液中爲期55秒鐘》然後，邊作濃度修正以使濃度成爲 —定，邊浸漬於40°C、42.5克/公升之硼酸、30克/公升之碘化鉀的水溶液中爲期90秒鐘，然後以不銹鋼製葉片扒除兩面之多餘水份，使薄膜中含水率之分佈成爲2 %以下的狀態下導入拉幅延伸機。將搬送速率設定爲4公尺/分鐘，送出100公尺，在60°C 、95 % RH之周圍環境下延伸5倍後，使拉幅機對於延伸方向彎曲，以後則保持一定寬度，邊使其收縮、邊在70°C 之周圍環境下乾燥後從拉幅機脫離。延伸開始前的PVA薄膜之含水率爲32 %，乾燥後之含水率爲1.5 %。左右的拉幅夾具之搬送速率差爲小於0.05 %，所導入的薄膜中心線與被送往下製程的薄膜中心線所形成的角度爲46°。在此| LI - L2|爲〇_7公尺，W爲0.7公尺，且有丨LI -. L2| = W之關係。在拉幅機出口之實質延伸方向Ax - Cx係對於被送往下製程的薄膜中心線傾斜45°。在拉幅機出口並未看到皺紋、薄膜變形。另外，經延伸、乾燥後之薄膜厚度爲 18微米。 (透明保護膜之貼合）對於藉由上述斜向延伸法所製得之偏光膜，使用切刀從寬度方向切斷3公分之兩端邊緣後，在其兩面以3 % PVA (可樂麗（Kuraray)公司（股）製PVA-117H)水溶液作爲黏合劑’以貼合表面經皂化處理之透明保護膜用纖維素 -59- 1356212 三醋酸酯薄膜（Re値 =30奈米、Rth値 ='130奈米），並且在70°C加熱爲期10分鐘，以製得在有效寬度之650 毫米之兩面具有纖維素三醋酸酯之長尺寸狀之偏光板。另外，該薄膜係具有與膜面之平均折射率會成爲最大之方向實質的相符之遲相軸。在貼合上側偏光板時，則將上側保護膜之遲相軸、偏光膜之吸收軸、及下側保護膜之遲相軸的軸角度，以顯示裝置水平方向爲基準而加以設定爲（0°、45"、0° )，且同樣地將下側偏光板的軸角度設定爲（〇°、 -45\(Γ)。由於藉由上述所製得偏光膜之吸收軸方向，係對於長度方向傾斜45°，因此加以切斷成尺寸爲310 _Χ 233毫米，即可以 91.5 %之面積效率製得吸收軸對邊傾斜45°之偏光板。另外，以目視並未看到褪色條紋。所製得偏光板之偏光性能，係可見光透射率爲43.5 %，偏光度爲_· { ( Tp - Tc ) / ( Tp + Tc ) } 1/2 ^ 0.9997 (式中，Tp是平均透射率、Tc是正交透射率）。在溫度爲 60t、相對濕度爲90 % RH之周圍環境下放置500小時，及在溫度爲80°C、乾周圍環境下放置500小時後，在其前後的光透射率之變化率以絕對値計爲1 %以下，偏光度之變化率以絕對値計爲〇.〇5 %以下。〈所製得液晶顯示裝置之漏光的測定〉測定藉由如上所述所製得液晶顯示裝置之漏光。結果由左方向60°所觀察時之漏光爲0.7 %。在液晶顯示裝置之視 -60- 1356212 野角特性中，對比爲5對1以上之視野角較佳爲左右上下各爲80°以上。所製得液晶顯示裝置，由於白色顯示能獲得約30 %之透射率，因此在視野角60°時，若黑色顯示之漏光能符合小於1 %之條件，則當可推測爲能獲得對比爲5 對1以上之視野角在左右上下各爲80°以上。〔例2〕〈液晶顯示裝置之製造〉在以例1所製得液晶顯示裝置中，除在製造上下偏光板時，保護膜則使用如下表1所示會顯現各種Re値和Rth値之降伯烯系薄膜以外’其餘則與例1同樣地製得液晶顯示裝置No. 1 ~ 24»此外，該等所使用之降伯烯系薄膜，其任一者皆具有與膜面之平均折射率會成爲最大之方向實質的相符之遲相軸。〈液晶顯示裝置之漏光的測定〉分別測定所製得液晶顯示裝置No · 1 ~ 24之由斜向60。所觀察時之漏光値。其結果展示於表1。表1 :在左右60°方向視野角之黑色顯示透射率（％ ) 表1 液晶顯示裝置號碼保f m 透射率 (%) 液晶顯示裝置號碼保護膜透射率 (%) 液晶顯示裝置號碼保讓透射率 (%) Re (nm) Rth (nm) Re (nm) Rth (nm) Re (nm) Rth (nm) 1 2 0 8.1 9 10 0 7.4 17 30 0 6.2 2 2 5 5.7 10 10 5 4.9 18 30 5 3.2 3 2 50 3.4 11 10 50 3.9 19 30 50 0.9 4 2 76 1.6 12 10 76 2.0 20 30 76 0.8 5 2 133 0.8 13 10 133 1.5 21 30 133 0.7 6 2 190 0.9 14 10 190 1.0 22 30 190 0.8 7 2 250 1.0 15 10 250 0.9 23 30 250 0.9 8 2 300 1.2 16 10 300 1.1 24 30 300 1.0 〔例3〕 1356212 其次，說明使用具有光學補償能的光學補償層之偏光板實施例。〈光學補償薄膜之製造〉 (偏光膜用透明保護膜兼光學補償層用透明支撐體之製造 ) 將下述組成物裝入混合槽，邊加熱、邊攪拌，使各成份溶解，以調製纖維素醋酸酯溶液。纖維素醋酸酯溶液之組成：醯化度爲60.7〜61.1 %之纖維素醋酸酯 100質量份磷酸三苯酯（塑化劑） 7.8質量份磷酸聯苯基二苯酯（塑化劑） 3.9質量份二氯甲烷（第1溶劑） 336質量份甲醇（第2溶劑） 29質量份 -62 1356212 在另一混合槽裝入16質量份之下述延遲上升劑，92質量份之二氯甲烷 '及8質量份之甲醇，邊加熱邊攪拌，以調製延遲上升劑溶液。將25質量份之延遲上升劑溶液與 474質量份之纖維素醋酸酯溶液混合，並充分攪拌以調製成塗佈液（dope) 。「延遲上升劑」之添加量相對於1〇〇質量份之纖維素醋酸酯爲3.5質量份。延遲上升劑：_ O(CH2)k〇(CH2)tt(CF2)i. CF2H HOaS-X V〇(CH2)k〇(CH2)m(CF2)n CF2H (k = l~l〇, m=0~5. And n:=3 to 16) In addition to the exemplified compounds, the compounds described in JP-A-2002-203, 163, and JP-A-2002-129,162 can be used as an air interface alignment agent. . In addition, in the special request No. 2 〇 02-212, 1 专利 patent specification paragraph code 0〇72 ~ 0076, special wish 2002-243, 600 patent specification paragraph code 0038 ~ 0040 and 0048 ~ 0049 'Special Wishes 2002- The matters described in paragraphs 007 1 to 0 078 of the patent specification No. 262,239, and the patent specification No. 2003-9 1,752, are also applicable to the present invention. The amount of the "empty-interface alignment agent" used for the liquid crystal coating liquid is preferably from 0.05% by weight to 5% by weight. However, when a fluorine-based saturated air interface interposer is used, it is preferably 1% by weight or less. There is no particular limitation on the "support" for supporting the optically anisotropic layer, and various polymer films can be used. For example, triethyl fluorenyl cellulose, methacrylic resin, and the like. Further, as described above, the protective film of the polarizing plate can also serve as a support for the optically anisotropic layer. Specific examples of the support material of such a state are the same as those of the protective film material of the polarizing plate, as described above. -57- 丄 356212 [Embodiment] Embodiments The present invention will be more specifically described by way of examples. The materials, reagents, masses, and ratios of the following examples can be appropriately changed without departing from the spirit and scope of the invention. Therefore, the present invention is not limited to the following specific examples [Example 1] A liquid crystal display device having the structure shown in Fig. 1 was produced. That is, the upper polarizing plate (protective film 3a, polarizing plate 1, protective film 3) is sequentially laminated from the observation direction (upper), the liquid crystal cell (upper substrate 5, liquid crystal layer 7' lower substrate 8), lower polarizing plate (protection) The film 12 and the polarizing film 14' protective film 12a) are also provided with a backlight source (not shown). <Production of Liquid Crystal Cell> The liquid crystal cell system has a liquid crystal cell gap of 3 μm between the substrates, and a liquid crystal material having a negative dielectric constant anisotropy ("MLC 6680", manufactured by Merck) It is prepared by dropping and injecting between the substrates and sealing them to form a liquid crystal layer between the substrates. The retardation of the liquid crystal layer (i.e., the product Δη • d) of the liquid crystal layer thickness d (micrometer) and the refractive index anisotropy Δη is set to 300 nm. Further, the liquid crystal material is aligned to be vertically aligned. <Manufacture of upper and lower polarizing plates> (Manufacture of polarizing film) A PVA film having an average degree of polymerization of 2,4 Å and a film thickness of 100 μm was washed with ion-exchanged water at 15 to 17 ° C for 60 seconds. After the surface water of the stainless steel leaf-58- 1356212 was removed, the concentration of the PVA film was corrected to be immersed in an aqueous solution of 40 ° C, 0.7 g / liter of iodine, and 60.0 g / liter of potassium iodide. For a period of 55 seconds, then the concentration is corrected to make the concentration constant, and immersed in an aqueous solution of 40 ° C, 42.5 g / liter of boric acid, 30 g / liter of potassium iodide for 90 seconds, and then The stainless steel blade is removed from the excess moisture on both sides, and is introduced into the tenter stretching machine in a state where the moisture content distribution in the film is 2% or less. Set the transfer rate to 4 meters per minute, send 100 meters, and extend the framer by 5 times in the ambient environment of 60 ° C and 95 % RH, then bend the tenter in the direction of extension, and then keep a certain width. It shrinks and detaches from the tenter after drying at 70 ° C. The water content of the PVA film before the start of the elongation was 32%, and the moisture content after drying was 1.5%. The difference in transport rate between the left and right tenter jigs is less than 0.05%, and the angle between the center line of the introduced film and the center line of the film fed to the lower process is 46°. Here | LI - L2| is 〇7 meters, W is 0.7 meters, and there is a relationship of 丨LI -. L2| = W. The substantial extension direction Ax - Cx at the exit of the tenter is inclined at 45° to the center line of the film sent to the lower process. No wrinkles or film deformation were observed at the exit of the tenter. Further, the film thickness after stretching and drying was 18 μm. (Adhesion of transparent protective film) For the polarizing film obtained by the above-described oblique stretching method, after cutting the edge of 3 cm from the width direction using a cutter, 3% of PVA is used on both sides thereof (Kuraray ( Kuraray) company PVA-117H) aqueous solution as a binder's cellulose-59- 1356212 triacetate film with a transparent protective film saponified on the surface (Re値=30 nm, Rth値=' 130 nm), and heated at 70 ° C for 10 minutes to obtain a long-length polarizing plate having cellulose triacetate on both sides of an effective width of 650 mm. Further, the film has a retardation axis which is substantially coincident with the direction in which the average refractive index of the film surface becomes maximum. When the upper polarizing plate is bonded, the axis angle of the slow phase axis of the upper protective film, the absorption axis of the polarizing film, and the slow axis of the lower protective film is set to (0) based on the horizontal direction of the display device. °, 45 ", 0°), and similarly set the axial angle of the lower polarizing plate to (〇°, -45\(Γ). Since the absorption axis direction of the polarizing film produced by the above is the length The direction is inclined by 45°, so that it is cut into a size of 310 _ Χ 233 mm, that is, a polarizing plate having an absorption axis inclined at 45° to the side can be obtained with an area efficiency of 91.5%. Further, no fading streaks are observed by visual observation. The polarizing performance of the polarizing plate is 43.5 %, and the degree of polarization is _· { ( Tp - Tc ) / ( Tp + Tc ) } 1/2 ^ 0.9997 (where Tp is the average transmittance, Tc is Orthogonal transmittance). It is placed in a surrounding environment at a temperature of 60t and a relative humidity of 90% RH for 500 hours, and after being placed at a temperature of 80 ° C for 500 hours in a dry environment, the light transmittance before and after it is The rate of change is less than 1% in absolute terms, and the rate of change in polarization is measured in absolute terms. 〇5 % or less. <Measurement of Light Leakage of Liquid Crystal Display Device Produced> The light leakage of the liquid crystal display device produced as described above was measured. As a result, the light leakage when viewed from the left direction of 60° was 0.7%. In the field characteristics of the display device, the viewing angle of 5 to 1 or more is preferably 80° or more in the upper and lower directions. The liquid crystal display device can obtain a transmittance of about 30% due to the white display. Therefore, when the viewing angle is 60°, if the light leakage of the black display can satisfy the condition of less than 1%, it can be presumed that the viewing angle of 5 to 1 or more can be obtained by 80° or more in the upper and lower directions. <Manufacturing of Liquid Crystal Display Device> In the liquid crystal display device produced in Example 1, in addition to the production of the upper and lower polarizing plates, the protective film was formed as shown in Table 1 below, and various Reoxi and Rth値 were found. Other than the film, the liquid crystal display devices No. 1 to 24 were obtained in the same manner as in Example 1. In addition, any of the primary urethane-based films used in the film had the largest average refractive index with respect to the film surface. The direction of the substance is consistent Phase axis. <Measurement of light leakage of liquid crystal display device> The light leakage 値 of the obtained liquid crystal display device No. 1 to 24 was observed in the oblique direction 60. The results are shown in Table 1. Table 1: Black showing transmittance in the 60° direction of view (%) Table 1 Liquid crystal display device number fm Transmittance (%) Liquid crystal display device number Protective film transmittance (%) Liquid crystal display device number Guaranteed transmittance (%) Re ( Nm) Rth (nm) Re (nm) Rth (nm) Re (nm) Rth (nm) 1 2 0 8.1 9 10 0 7.4 17 30 0 6.2 2 2 5 5.7 10 10 5 4.9 18 30 5 3.2 3 2 50 3.4 11 10 50 3.9 19 30 50 0.9 4 2 76 1.6 12 10 76 2.0 20 30 76 0.8 5 2 133 0.8 13 10 133 1.5 21 30 133 0.7 6 2 190 0.9 14 10 190 1.0 22 30 190 0.8 7 2 250 1.0 15 10 250 0.9 23 30 250 0.9 8 2 300 1.2 16 10 300 1.1 24 30 300 1.0 [Example 3] 1356212 Next, an embodiment of a polarizing plate using an optical compensation layer having optical compensation energy will be described. <Production of optical compensation film> (Production of transparent protective film for polarizing film and transparent support for optical compensation layer) The following composition was placed in a mixing tank, and heated and stirred to dissolve each component to prepare cellulose. Acetate solution. Composition of cellulose acetate solution: Cellulose acetate having a degree of deuteration of 60.7 to 61.1% 100 parts by mass of triphenyl phosphate (plasticizer) 7.8 parts by mass of biphenyl diphenyl phosphate (plasticizer) 3.9 mass Methylene chloride (first solvent) 336 parts by mass of methanol (second solvent) 29 parts by mass - 62 1356212 In another mixing tank, 16 parts by mass of the following retarding agent, 92 parts by mass of methylene chloride' and 8 parts by mass of methanol was stirred while heating to prepare a delayed riser solution. 25 parts by mass of the delayed riser solution was mixed with 474 parts by mass of the cellulose acetate solution, and thoroughly stirred to prepare a coating liquid (dope). The amount of the "delay riser" added was 3.5 parts by mass based on 1 part by mass of the cellulose acetate. Delay riser:

將所製得之塗佈液使用帶式流延機流延.。當帶上之膜面溫度達到40°C後，以70°C溫空氣乾燥1分鐘，並從帶以 140°C乾燥空氣將薄膜乾燥20分鐘，以製得殘留溶劑量爲 0.3質量％之纖維素醋酸酯薄膜（厚度：146微米）。對於所製得之纖維素醋酸酯薄膜（透明支撐體、透明保護膜），使用偏振光橢圓計（M-150，日本分光公司（股）製）測定在波長爲550奈米之Re延遲値和Rth延遲値。結果Re 爲2奈米（偏差±1奈米）、Rth爲190奈米（偏差 ±3奈米）。另外，在波長爲4〇〇奈米〜7〇〇奈米的各波長之Re 爲2 ±1奈米，在波長爲4〇〇奈米 ~ 700奈米的各波長之The prepared coating liquid was cast using a belt casting machine. After the film surface temperature of the belt reached 40 ° C, it was air-dried at 70 ° C for 1 minute, and the film was dried from the belt at 140 ° C for 20 minutes to obtain a fiber having a residual solvent content of 0.3% by mass. Acetate film (thickness: 146 microns). For the obtained cellulose acetate film (transparent support, transparent protective film), a retardation iridium at a wavelength of 550 nm was measured using a polarization ellipsometer (M-150, manufactured by JASCO Corporation). Rth delay 値. As a result, Re was 2 nm (deviation ± 1 nm) and Rth was 190 nm (deviation ± 3 nm). In addition, Re at each wavelength of 4 〇〇 nanometers ~ 7 〇〇 nanometers is 2 ± 1 nm, at wavelengths of 4 〇〇 nm to 700 nm.

Rth爲190 ±2奈米之範圍。將所製得之纖維素醋酸酯薄膜浸漬於2.0 N之氫氧化鉀溶液（25 °C )爲期2分鐘後，以硫酸中和，並以純水洗滌 1356212 ，然後將其乾.燥。以接觸法量測該纖維素醋酸酯薄膜之表面能量結果爲63 mN/m。以如上所述方式製得透明支撐體兼透明保護膜用之纖維素醋酸酯薄膜。所製得之薄膜具有與膜面之平均折射率會成爲最大之方向實質的相符之遲相軸。 (配向膜層之製造）在該纖維素醋酸酯薄膜上，使用# 16之線棒塗佈器以28 ml/m2塗佈下述組成之塗佈液。然後在25 t乾燥60秒鐘，在60°C之溫空氣乾燥60秒鐘，再在90°C之溫空氣乾燥 150秒鐘，乾燥後之配向膜厚度爲1.1微米。另外，以原子間力顯微鏡（AFM: Atomic Force Microscope，SPI 3800N ，精工（Seiko)儀器（股）公司製）測定配向膜之表面粗糙度結果爲1.147奈米。其次，在所形成之膜，對於纖維素醋酸酯薄膜之遲相軸（以波長632.8奈米測定）朝· 45° 方向施加摩擦處理。配向膜塗佈液之組成：下述之改質聚乙烯醇 20質量份水 3 6 1質量份甲醇 119質量份戊二醛（交聯劑） 0.5質量份 -64- 1356212 改質聚乙烯醇： _ (CH2-CH) 87. 8— (CH2-CH) 12. 0— (CH2~^H) 0,2一 d)H . 9 9 c=o CH3 文0 Λ 0(CH2)40C0CH=CH2 (光學異方向性層之製造）在上述配向膜上使用棒式塗佈器將下述組成之塗佈液連續地塗佈、乾燥、及加熱（配向熟成），並且照射紫外線以形成1.1微米厚度之水平配向的光學異方向性層（A)，以製得光學補償膜。結果該光學異方向性層係對於透明支撐體長度方向朝-45°方向具有遲相軸。在550奈米之Re 値爲1 3 0奈米。 3 8.1質量％ 0. 3 8質量％ 1. 1 4質量％ 0.1 9質量％ 0.04質量％光學異方向性層（A)用塗佈液之組成：下述之棒狀液晶性化合物1-2 下述之增感劑A 下述之光聚合引發劑B 配向控制劑C 戊二醛甲基乙基酮 6 0.1質量％ -65 1356212 棒狀液晶性化合物1-2Rth is in the range of 190 ± 2 nm. The obtained cellulose acetate film was immersed in a 2.0 N potassium hydroxide solution (25 ° C) for 2 minutes, neutralized with sulfuric acid, and washed 1356212 with pure water, and then dried and dried. The surface energy of the cellulose acetate film measured by the contact method was 63 mN/m. A cellulose acetate film for a transparent support and a transparent protective film was obtained in the same manner as described above. The resulting film has a late phase axis which is substantially consistent with the direction in which the average refractive index of the film surface becomes maximum. (Manufacture of alignment film layer) On the cellulose acetate film, a coating liquid of the following composition was applied at 28 ml/m 2 using a wire bar coater of #16. Then, it was dried at 25 t for 60 seconds, air-dried at 60 ° C for 60 seconds, and air-dried at 90 ° C for 150 seconds, and the film thickness after drying was 1.1 μm. Further, the surface roughness of the alignment film was measured by an atomic force microscope (AFM: Atomic Force Microscope, SPI 3800N, manufactured by Seiko Instruments Co., Ltd.) to be 1.147 nm. Next, in the formed film, a rubbing treatment was applied to the retardation axis (measured at a wavelength of 632.8 nm) of the cellulose acetate film in the direction of 45°. Composition of alignment film coating liquid: Modified polyvinyl alcohol 20 parts by mass of water 361 parts by mass of methanol 119 parts by mass of glutaraldehyde (crosslinking agent) 0.5 parts by mass - 64 - 1356212 Modified polyvinyl alcohol: _ (CH2-CH) 87. 8—(CH2-CH) 12. 0—(CH2~^H) 0,2-d)H. 9 9 c=o CH3 text 0 Λ 0(CH2)40C0CH=CH2 ( Production of optical anisotropic layer) The coating liquid of the following composition was continuously applied, dried, and heated (aligned aging) on the above-mentioned alignment film using a bar coater, and irradiated with ultraviolet rays to form a thickness of 1.1 μm. The optically oriented omotropic layer (A) is aligned horizontally to produce an optical compensation film. As a result, the optically anisotropic layer has a slow phase axis in the direction of -45° with respect to the longitudinal direction of the transparent support. At 550 nm, Re 値 is 1 300 nm. 3 8.1 mass% 0. 3 8 mass% 1. 1 4 mass% 0.1 9 mass% 0.04 mass% Composition of the coating liquid for the optical anisotropic layer (A): The following rod-like liquid crystal compound 1-2 The sensitizer A The photopolymerization initiator B described below is the alignment control agent C glutaraldehyde methyl ethyl ketone 6 0.1% by mass -65 1356212 rod-like liquid crystalline compound 1-2

增感劑ASensitizer A

光聚合引發劑BPhotopolymerization initiator B

配向控制劑COrientation control agent C

將所製得之由光學異方向性層與透明支撐體所構成的光學補償膜，在第1圖中下側偏光膜14與液晶胞用下側基板 8之間搭配成使其由纖維素醋酸酯薄膜所構成的透明支撐體（Re = 2奈米、Rth = 190奈米）接於偏光膜14。亦即 -66- 1356212 ，製造透明保護膜12係兼作爲具有光學補償能的光學異方向性層之透明支撐體的模式之液晶顯示裝置。其他結構則使其爲與例1相同。亦即，將上側偏光板之上側偏光膜之遲相軸、偏光膜之吸收軸、及下側保護膜之遲相軸的軸角度，以顯示裝置水式方向爲基準而加以設定爲（0°、45°、0 °)，同樣地將下側偏光板的軸角度設定爲（（T、 - 45°、0° )，且將光學異方向性層之遲相軸（摩擦方向）設定爲-45。。在製造光學補償膜時，除將由纖維素醋酸酯薄膜所構成透明支撐體之Re値和Rth値調整成爲如表2所示，以製造光學補償膜以外，其餘則與上述同樣方式製造液晶顯示裝置No. 25 ~ 40。另外，所使用之纖維素醋酸酯薄膜中任一者，皆具有與膜面之平均折射率會成爲最大之方向實質的相符之遲相軸。〈所製得之液晶顯示裝置之漏光的測定〉經測定以如此方式所製得液晶顯示裝置No. 25 ~ 40之由斜向60°所觀察時之漏光。其結果展示於表2。表2:在左右60方向視野角之黑色顯不透射率（％) 1356212 表2 液晶顯示裝置號碼 mm* ---- 透射率 (%) 液晶顯不裝置號碼保護膜* 透射率 (%) Ke (nm) Rth (nm) Re (nm) Rth (nm) 25 2 0 4.3 33 10 0 - 26 2 ---r~ 5 1.5 34 10 5 - 27 2 50 0.9 35 10 50 - 28 2 76 0.6 36 10 76 0.9 29 2 133 0.3 37 10 133 0.4 30 2 190 0.04 38 10 190 0.1 31 2 250 0.2 39 10 250 0.3 32 2 300 0.8 40 10 300 1.0 附註：*係表示兼用作爲光學異方向性層之透明支撐體之保護膜The optical compensation film formed of the optically anisotropic layer and the transparent support is blended between the lower polarizing film 14 and the liquid crystal cell lower substrate 8 in the first drawing so as to be made of cellulose acetate. A transparent support (Re = 2 nm, Rth = 190 nm) composed of an ester film was attached to the polarizing film 14. That is, -66- 1356212, a liquid crystal display device in which a transparent protective film 12 is used as a transparent support of an optically isotropic layer having optical compensation energy is produced. The other structure is the same as in Example 1. That is, the axis angle of the retardation axis of the upper polarizing film of the upper polarizing plate, the absorption axis of the polarizing film, and the slow axis of the lower protective film is set to (0°) based on the water direction of the display device. 45°, 0°), the axial angle of the lower polarizing plate is set to ((T, - 45°, 0°), and the retardation axis (friction direction) of the optical anisotropic layer is set to - 45. In the production of the optical compensation film, except that Re値 and Rth値 of the transparent support made of the cellulose acetate film were adjusted as shown in Table 2 to produce an optical compensation film, the rest was produced in the same manner as above. Liquid crystal display devices No. 25 to 40. Further, any of the cellulose acetate films used has a retardation axis which is substantially in accordance with the direction in which the average refractive index of the film surface is maximized. Measurement of Light Leakage of Liquid Crystal Display Device> Light leakage when observed by oblique observation at 60° of liquid crystal display devices No. 25 to 40 prepared in this manner was measured. The results are shown in Table 2. Table 2: 60 on the left and right Black apparent transmittance (%) of the viewing angle of the direction 135 6212 Table 2 Liquid crystal display device number mm* ---- Transmittance (%) Liquid crystal display device No. protective film * Transmittance (%) Ke (nm) Rth (nm) Re (nm) Rth (nm) 25 2 0 4.3 33 10 0 - 26 2 ---r~ 5 1.5 34 10 5 - 27 2 50 0.9 35 10 50 - 28 2 76 0.6 36 10 76 0.9 29 2 133 0.3 37 10 133 0.4 30 2 190 0.04 38 10 190 0.1 31 2 250 0.2 39 10 250 0.3 32 2 300 0.8 40 10 300 1.0 Note: * indicates a protective film that serves as a transparent support for the optically anisotropic layer.

〔例 4〕 - 〈光學補償薄膜之製造〉與在例3所製得由纖維素醋酸酯薄膜所構成透明支撐體之製造方法相同方法’製造調整爲Re値=1〇奈米、Rth 値=76奈米透明支撐體。該薄膜具有與膜面之平均折射率會成爲最大之方向實質的相符之遲相軸。並且，將該支捧體上加以皂化處理，並在其上塗佈在例3所使用之配向膜。然後’將其上再以對於長度方向朝45。方向施加摩擦處理，並使用棒式塗佈器將在例3所使用之光學異方向性層 (A)用塗佈液組成物連續地塗佈、乾燥、及加熱（配向熟成），並照射紫外線以形成厚度爲0.43微米之光學異方向性層。光學異方向性層係對於透明支撐體長度方向朝45°之 -68- 1356212 方向具有遲相軸。在550奈米之延遲値爲53奈米。將所製得之由光學異方向性層與透明支撐體所構成的光學補償膜，在第1圖中上側偏光膜1與液晶胞用上側基板 5之間搭配成使其由纖維素醋酸酯薄膜所構成的透明支撐體（Re = 10奈米、Rth = 176奈米）接於偏光膜1。亦即，製造環明保護膜3係兼作爲具有光學捕償能的光學異方向性層之透明支撐體的態樣之液晶顯示裝置。其他結構則製成爲與例1相同。亦即，將上側偏光板之上側偏光膜之遲相軸、偏光膜之吸收軸、及下側保護膜之遲相軸的軸角度，以顯示裝置水式方向爲基準而加以設定爲（0°、45°、0 °)，將光學異方向性層之遲相軸（摩擦方向）設定爲45° ，下側偏光板的軸角度設定爲（0°、 - 45°、0°)。在製造光學補償膜時，除將光學異方向性層之Re値調整成爲如表3所示，以製造光學補償膜以外，其餘則與上述同樣方式製造液晶顯示裝置No. 41~ 46。〈所製得之液晶顯示裝置之漏光的測定〉經測定以如此方式所製得液晶顯示裝置No. 41 ~ 46之由斜向60°所觀察時之漏光。其結果展示於表3。表3:在左右6 0·方向視野角之黑色顯示透射率（％) -69- ^_3 液晶顯示裝置號碼光學異方向性層 Re (nm) 透射率 (%) 41 0 2.0 42 20 0.7 43 53 0.4 44 80 0.6 45 150 0.9 46 200 1.2 〔例5〕 1356212 除上下偏光板之保護膜使用Re値爲0奈米、Rth値爲 133奈米之纖維素三醋酸酯薄膜之外，其餘則與例1同樣地製造液晶顯示裝置。亦即，將上側偏光板的上側偏光膜之遲相軸、偏光膜之吸收軸、及下側保護膜之遲相軸的軸角度，以顯示裝置水式方向爲基準而加以設定爲（〇°、45° 、0°)，同樣地將下側偏光板的軸角度設定爲（〇°、 - 45° 、〇°)。另外，所使用之纖維素醋酸酯薄膜中任一者，皆具有與膜面之平均折射率會成爲最大之方向實質的相符之遲相軸。除上下偏光板之保護膜係使用如下表4所示之會顯現各種不同的Re値和Rth値之纖維素三醋酸酯薄膜以外，其他則與上述同樣地製造液晶顯示裝置No. 47〜70。另外，所使用之纖維素三醋酸酯薄膜中任一者，皆具有與膜面之平均折射率會成爲最大之方向實質的相符之遲相軸。〈所製得液晶顯示裝置之漏光的測定〉經測定以如此方式所製得液晶顯示裝置No. 47 ~ 70之由 -70- 1356212 斜向6(Τ所觀察時之漏光。其結果展示於表表4:在左右60。方向視野角之黑色顯示透射率（％)表4 液晶顯示裝置號碼保護膜透射率 (%) 液晶顯示裝置號碼保纖透射率 (%) 液晶顯示裝置號碼 umm 透射率 (%) Re (nm) Rth (nm) Re (nm) Rth (nm) Re (nm) Rth (nm) 47 -5 0 8.1 55 0 0 4.5 63 5 0 6.5 48 -5 5 5.7 56 0 5 1.6 64 5 5 4.4 49 -5 50 3.4 57 0 50 1Ό 65 5 50 2.5 50 -5 76 1.6 58 0 76 0.9 66 5 76 1.4 51 -5 133 0.9 59 0 133 0.8 67 5 133 1.1 52 -5 190 0.9 60 0 190 0.85 68 5 190 0.9 53 -5 250 1.0 61 0 250 0.9 69 5 250 0.9 54 -5 300 1.1 62 0 300 1.1 70 5 300 1.1 〔例6〕在實施例1中將偏光膜之延伸方向設定爲對於薄膜長度方向爲90°。使用所謂通常之寬度方向單軸向延伸型拉幅延伸機，將原捲裝厚度爲100微米之PVA系薄膜以二色性物質染色槽進行染色，以塗佈裝置塗佈交聯劑溶液，然後使其咬入於拉幅延伸機》在溫度爲30°C ~ 80°C '相對濕度爲70 ~ 99 % RH之周圍環境下朝寬度方向施加單軸向延伸後，在保持大致一定寬度下加以乾燥，使揮發份充分消除後，脫離以製得厚度爲18微米之偏光膜。將上側保護膜之遲相軸、偏光膜之吸收軸、及下側保護膜之遲相軸的軸角度，以顯示裝置水平方向爲基準設定爲（〇°、90°、0°)，同樣地將下側偏光板的軸角度設定爲（90°、0°、90° )。其 -71 - 1356212 他結構則使用與實施例1相同者。然後測定藉由如上所述方式所製得液晶顯示裝置之漏光。結果由左方向60°所觀察時之漏光爲0.6 %。〔例7〕〈液晶胞之製造〉準備內側形成線狀電極，且在其上形成配向控制膜之透明的一對基板5。夾持在基板之間的棒狀液晶分子7係配向成在未施加電場時對於線狀電極之長度方向具有一些角度。另外，在此情況下，液晶之介電異方向性係假設爲正。當施加電場時，液晶分子7將朝電場方向改變其方向。因此將偏光膜1配置成特定角度，藉此即可改變光透射率。另外，電場方向對於基板5之表面所形成的角度，實際爲20度以下，但是較佳爲實質地成平行。以下，在本發明中，則將20度以下者統稱爲「平行電場」來表示。另外，即使將電極分成於上下基板來形成，或僅在一方之基板形成，其效果仍然不變。液晶材料係使用介電常數異方向性△ ε爲正且其値爲 13.2、折射率異方向性Δη爲〇081 (589奈米、20。(：）之向列型液晶。液晶層之厚度（間隙）則設定爲大於2.8微米、小於4.5微米。亦即，延遲値△ η · d設定爲大於0.25 微米、小於0.32微米時，即可製得在可見光範圍內幾乎不會有波長相依性之透射率特性。藉由組合如後所述之配向膜與偏光板，液晶分子由摩擦方向朝電場方向回轉45。時即可獲得最大透射率。當然以坡璃珠或纖維、樹脂製柱狀間 -72- 1356212 隔物也可形成出同樣之間隙。上下偏光板保護膜是由纖維素醋酸酯薄膜所構成，在液晶胞的遠側之上下偏光板用保護膜，則使用經皂化處理的市售商品級之纖維素醋酸酯薄膜（Fujitack TD80UF，富士照相軟片公司（股）製），並將Re値設定爲3奈米、Rth 値設定爲50奈米。此外，上下偏光板之液晶胞的近側之透明保護膜，係使用以下述方法所製造且施加皂化處理者。在上側偏光板之液晶層的近側之透明保護膜，則使用Re値爲10奈米、Rth値爲80奈米者，在下側偏光板之液晶層的近側之透明保護膜，則使用Re値爲3奈米' Rth値爲50 奈米者。然後，在上下偏光板偏光膜之液晶層的近側之透明保護膜上，則形成光學異方向性層，並配置在液晶胞與透明保護膜之間。將上側保護膜之遲相軸、偏光膜之吸收軸、及下側保護膜之遲相軸的軸角度，以顯示裝置水式方向爲基準而加以設定爲（0°、90°、0° )，同樣地將下側偏光板的軸角度設定爲（90°、0°、90°)。另外，使用於透明保護膜之纖維素醋酸酯薄膜係任一者皆具有與膜面之平均折射率會成爲最大之方向實質的相符之遲相軸。配置在上側偏光板之透明保護膜與液晶胞之間的光學異方向性層，係藉由將透明保護膜作爲支撐體，並將圓盤狀化合物使其圓盤面配向成垂直所形成。延遲値係設定爲 150奈米》配向控制方向與偏光膜之吸收軸之交叉角度係設定爲90°。測定以如此所製得液晶顯示裝置之漏光，結果由左方向60°所觀察之漏光爲0.1 %。 -73- 1356212 另外，此時即使將作爲接近液晶層的上偏光板之偏光板保護膜之配置製成爲相反，也能獲得相等之效果。〔例8〕在例7中，除將上下偏光板之吸收軸與遲相軸的軸角度設定爲使上側爲（〇。、〇°、〇。），同樣地使下侧爲（90°、 90°、90° )以外，其他結構則製成相同時，結果由左方向 60°所觀察之漏光爲0.2 %。〔例9〕在例8中，除將配置在上側偏光板之透明保護膜與液晶胞之間的光學異方向性層，從藉由圓盤狀化合物所形成之層取代爲聚烯烴系延伸薄膜（例如ARTON )(厚度：80微米、延遲：70奈米）以外，其他結構則製成爲相同，結果由左方向60°所觀察之漏光爲0.3 % » 〔例 1〇〕在例8中，並未配置光學異方向性層。結果由左方向60° 所觀察之漏光爲0.5 %。〔例 11〕製造第2圖所示結構之液晶顯示裝置。亦即，自觀察方向（上）積層由保護膜（未圖示）'上側偏光膜1、保護膜3所構成的上側偏光板1A，液晶胞（上基板5、液晶層 7、下基板8)，及由光學補償層1〇、保護膜12、下側偏光膜14、保護膜（未圖示）所構成的下側偏光板14A，並在下側偏光板14A之更下側配置使用冷陰極螢光燈之背光 (未圖示）。 -74- 1356212 以下說明所使用各構件之製造方法。 (IPS模式液晶胞之製造）在第3圖展示液晶顯示裝置之截面圖。在透明的一對基板之一方8，在該基板之內側形成由ITO (氧化銦錫）構成 (也可爲鉻或鋁等金屬）之線狀電極，並在其上形成配向控制膜（未圖不）。夾持在基板之間的棒狀液晶分子7，係配向成在未施加電場時，對於線狀電極之長度方向具有一些角度。另外，在此情況下，液晶之介電異方向性係假設爲正。當施加電場時液晶分子7將朝其電場方向改變方向。並且，將上述結構之上側偏光板1 A、及下側偏光板 14A配置成特定的角度。另外，電場方向對於基板8之表面所形成的角度，係設定爲平行電場。在此平行電場係意謂電場方向對於基板表面所形成的角度爲20度以下，較佳爲10度以下，更佳爲成平行。另外，即使將電極分成於上下基板而形成，或僅在一方之基板形成，其效果仍然不變〇液晶材料係使用介電常數異方向性△ ε爲正且其値爲 13.2、折射率異方向性Δη爲0.085 (589奈米、20度）之向列型液晶（默克公司製。MLC 9 100- 1 00 )。液晶層之厚度（間隙）則設定爲大於3.5微米。 (偏光板之製造）將下述組成物裝入混合槽，邊加熱邊攪拌，使各成份溶解，以調製具有下述組成之纖維素醋酸酯溶液。纖維素醋酸酯溶液之組成： •75- 1356212 醯化度爲 60.9 %之纖維素醋酸酯 100 質量份磷酸三苯酯（塑化劑 ) 7.8 質量份磷酸聯苯基二苯酯 ( 塑化劑） 3.9 質量份二氯甲院 (第 1溶劑 ) 300 質息里份甲醇 ( 第 2溶劑） 54 質量份 1-丁醇 ( 第3 溶劑 ) 11 質量份在另一混合槽裝入16質量份之下述延遲上升劑，80質量份之二氯甲烷及20質量份之甲醇，邊加熱邊攪拌，以調製延遲上升劑溶液。並且，將所製得7質量份之延遲上升劑溶液與487質量份之纖維素醋酸酯溶液混合，並充分攪拌以調製塗佈液。延遲上升劑：[Example 4] - <Production of optical compensation film> The same method as in the production method of the transparent support body made of the cellulose acetate film obtained in Example 3 was manufactured and adjusted to Re値=1〇N, Rth 値= 76 nm transparent support. The film has a slow phase axis that is substantially consistent with the direction in which the average refractive index of the film surface becomes maximum. Further, the support was subjected to saponification treatment, and the alignment film used in Example 3 was applied thereon. Then 'put it up again towards 45 for the length direction. The rubbing treatment was applied in the direction, and the coating composition for the optically anisotropic layer (A) used in Example 3 was continuously applied, dried, and heated (aligned aging) with a bar coater, and irradiated with ultraviolet rays. To form an optically anisotropic layer having a thickness of 0.43 microns. The optically anisotropic layer has a slow phase axis in the direction of -68 - 1356212 of 45° with respect to the longitudinal direction of the transparent support. The delay at 550 nm is 53 nm. The optical compensation film formed of the optically anisotropic layer and the transparent support is blended between the upper polarizing film 1 and the liquid crystal cell upper substrate 5 in FIG. 1 to form a cellulose acetate film. The transparent support (Re = 10 nm, Rth = 176 nm) was attached to the polarizing film 1. That is, the liquid crystal display device in which the ring-shaped protective film 3 is also used as a transparent support of an optically anisotropic layer having optical compensation energy is produced. The other structure was made in the same manner as in Example 1. That is, the axis angle of the retardation axis of the upper polarizing film of the upper polarizing plate, the absorption axis of the polarizing film, and the slow axis of the lower protective film is set to (0°) based on the water direction of the display device. 45°, 0°), the retardation axis (friction direction) of the optical anisotropic layer is set to 45°, and the axial angle of the lower polarizing plate is set to (0°, -45°, 0°). In the production of the optical compensation film, liquid crystal display devices No. 41 to 46 were produced in the same manner as described above except that Re 値 of the optically anisotropic layer was adjusted as shown in Table 3 to produce an optical compensation film. <Measurement of Light Leakage of Liquid Crystal Display Device Produced> Light leakage when observed by obliquely 60° of the liquid crystal display devices No. 41 to 46 obtained in this manner was measured. The results are shown in Table 3. Table 3: Transmittance in black in the left and right 60° direction of view (%) -69- ^_3 Liquid crystal display device number Optical anisotropic layer Re (nm) Transmittance (%) 41 0 2.0 42 20 0.7 43 53 0.4 44 80 0.6 45 150 0.9 46 200 1.2 [Example 5] 1356212 In addition to the cellulose triacetate film with Re値 of 0 nm and Rth値 of 133 nm, the protective film of the upper and lower polarizers is used. 1 A liquid crystal display device was produced in the same manner. In other words, the axis angle of the slow phase axis of the upper polarizing film of the upper polarizing plate, the absorption axis of the polarizing film, and the slow axis of the lower protective film is set to (〇°) based on the water direction of the display device. 45°, 0°), the shaft angle of the lower polarizing plate is similarly set to (〇°, -45°, 〇°). Further, any of the cellulose acetate films to be used has a retardation axis which is substantially in conformity with the direction in which the average refractive index of the film surface becomes maximum. The liquid crystal display devices No. 47 to 70 were produced in the same manner as described above, except that the protective film of the upper and lower polarizing plates was used, except that the cellulose triacetate film of various Re 値 and R 値显现 was used as shown in the following Table 4. Further, any of the cellulose triacetate films used has a phase axis which is substantially coincident with the direction in which the average refractive index of the film surface becomes the largest. <Measurement of Light Leakage of Liquid Crystal Display Device Produced> The liquid crystal display device No. 47 to 70 obtained in this manner was measured by -70- 1356212 obliquely 6 (light leakage when observed). The results are shown in the table. Table 4: Black display transmittance (%) in the right and left 60. Directional viewing angle Table 4 Liquid crystal display device number Protective film transmittance (%) Liquid crystal display device number Fiber transmission transmittance (%) Liquid crystal display device number umm Transmittance ( %) Re (nm) Rth (nm) Re (nm) Rth (nm) Re (nm) Rth (nm) 47 -5 0 8.1 55 0 0 4.5 63 5 0 6.5 48 -5 5 5.7 56 0 5 1.6 64 5 5 4.4 49 -5 50 3.4 57 0 50 1Ό 65 5 50 2.5 50 -5 76 1.6 58 0 76 0.9 66 5 76 1.4 51 -5 133 0.9 59 0 133 0.8 67 5 133 1.1 52 -5 190 0.9 60 0 190 0.85 68 5 190 0.9 53 -5 250 1.0 61 0 250 0.9 69 5 250 0.9 54 -5 300 1.1 62 0 300 1.1 70 5 300 1.1 [Example 6] In Example 1, the direction in which the polarizing film was extended was set to the length of the film. The direction is 90°. The PVA-based film with a thickness of 100 μm is packaged in two colors using a so-called general width-direction uniaxially stretched tenter stretching machine. The material dyeing tank is dyed, and the cross-linking agent solution is applied by a coating device, and then bitten into a tenter stretching machine at a temperature of 30 ° C to 80 ° C and a relative humidity of 70 to 99 % RH. After applying a uniaxial extension in the width direction, the film is dried while maintaining a substantially constant width, and the volatile matter is sufficiently removed, and then released to obtain a polarizing film having a thickness of 18 μm. The retardation film and the polarizing film of the upper protective film are obtained. The axis angle of the absorption axis and the slow phase axis of the lower protective film is set to (〇°, 90°, 0°) based on the horizontal direction of the display device, and the axis angle of the lower polarizing plate is similarly set to ( 90°, 0°, 90°). The structure of -71 - 1356212 was the same as that of Example 1. Then, the light leakage of the liquid crystal display device produced by the above method was measured. The result was 60° from the left direction. The light leakage at the time of observation is 0.6%. [Example 7] <Production of liquid crystal cell> A pair of transparent substrates 5 are formed on the inner side to form a linear electrode, and an alignment control film is formed thereon. The liquid crystal molecules 7 are aligned such that when no electric field is applied There are some angles for the length direction of the wire electrode. In addition, in this case, the dielectric anisotropy of the liquid crystal is assumed to be positive. When an electric field is applied, the liquid crystal molecules 7 will change their direction toward the direction of the electric field. Therefore, the polarizing film 1 is disposed at a specific angle, whereby the light transmittance can be changed. Further, the angle formed by the direction of the electric field with respect to the surface of the substrate 5 is actually 20 degrees or less, but is preferably substantially parallel. Hereinafter, in the present invention, those of 20 degrees or less are collectively referred to as "parallel electric field". Further, even if the electrodes are formed by dividing the upper and lower substrates, or only on one of the substrates, the effect remains unchanged. In the liquid crystal material, the dielectric constant anisotropy Δ ε is positive and the 値 is 13.2, and the refractive index anisotropy Δη is 〇 081 (589 nm, 20 (:) nematic liquid crystal. The thickness of the liquid crystal layer ( The gap is set to be larger than 2.8 μm and smaller than 4.5 μm. That is, when the delay 値 Δ η · d is set to be larger than 0.25 μm and smaller than 0.32 μm, transmission with almost no wavelength dependence in the visible light range can be obtained. By combining the alignment film and the polarizing plate as described later, the liquid crystal molecules are rotated 45 from the rubbing direction toward the electric field direction, and the maximum transmittance can be obtained. Of course, the glass beads or the fibers and the resin column-72 - 1356212 The spacer can also form the same gap. The upper and lower polarizer protective film is made of a cellulose acetate film, and the protective film for the polarizing plate is used on the far side of the liquid crystal cell, and the saponified commercial product is used. Grade cellulose acetate film (Fujitack TD80UF, manufactured by Fuji Photo Film Co., Ltd.), and set Re値 to 3 nm and Rth 値 to 50 nm. In addition, the liquid crystal cell of the upper and lower polarizers is near. The transparent protective film is manufactured by the following method and applied to the saponification process. The transparent protective film on the near side of the liquid crystal layer of the upper polarizing plate is 10 nm in Re値 and 80 nm in Rth値. In the transparent protective film on the near side of the liquid crystal layer of the lower polarizing plate, Re Re is 3 nm 'Rth値 is 50 nm. Then, the transparent protective film on the near side of the liquid crystal layer of the polarizing film of the upper and lower polarizing plates is used. Further, an optically anisotropic layer is formed and disposed between the liquid crystal cell and the transparent protective film, and the retardation axis of the upper protective film, the absorption axis of the polarizing film, and the axis angle of the slow phase axis of the lower protective film are The axis angle of the lower polarizing plate is set to (90°, 90°, 90°) based on the water direction of the display device, and is also used for (90°, 0°, 90°). Any one of the cellulose acetate film of the transparent protective film has a phase axis which is substantially coincident with the direction in which the average refractive index of the film surface becomes the largest. Between the transparent protective film of the upper polarizing plate and the liquid crystal cell Optically anisotropic layer The film was used as a support, and the disc-shaped compound was formed such that the disk surface was aligned vertically. The retardation system was set to 150 nm. The angle of intersection between the alignment control direction and the absorption axis of the polarizing film was set to 90°. The light leakage of the liquid crystal display device thus obtained was measured, and as a result, the light leakage observed from the left direction of 60° was 0.1%. -73- 1356212 Further, at this time, even as a polarizing plate protective film of the upper polarizing plate close to the liquid crystal layer [Example 8] In Example 7, the axis angles of the absorption axis and the slow axis of the upper and lower polarizing plates were set such that the upper side was (〇, 〇°, 〇. Similarly, when the lower side was (90°, 90°, 90°) and the other structures were made the same, the light leakage observed from the left direction of 60° was 0.2%. [Example 9] In Example 8, except for the optically anisotropic layer disposed between the transparent protective film of the upper polarizing plate and the liquid crystal cell, the layer formed by the discotic compound was replaced with the polyolefin-based extended film. Other structures (for example, ARTON) (thickness: 80 μm, retardation: 70 nm) were made the same, and the light leakage observed from the left direction of 60° was 0.3% » [Example 1〇] In Example 8, The optical anisotropic layer is not configured. As a result, the light leakage observed from the left direction of 60° was 0.5%. [Example 11] A liquid crystal display device having the structure shown in Fig. 2 was produced. In other words, the upper polarizing plate 1A composed of the protective film (not shown) from the upper polarizing film 1 and the protective film 3, and the liquid crystal cells (the upper substrate 5, the liquid crystal layer 7, and the lower substrate 8) are laminated from the observation direction (upper). And a lower polarizing plate 14A composed of an optical compensation layer 1A, a protective film 12, a lower polarizing film 14, and a protective film (not shown), and a cold cathode fluorescent lamp is disposed on the lower side of the lower polarizing plate 14A. Backlight of light (not shown). -74- 1356212 The following describes the manufacturing method of each member used. (Manufacture of IPS Mode Liquid Crystal Cell) A cross-sectional view of the liquid crystal display device is shown in FIG. On one side of a pair of transparent substrates, a linear electrode made of ITO (indium tin oxide) (which may also be a metal such as chromium or aluminum) is formed on the inside of the substrate, and an alignment control film is formed thereon (not shown). Do not). The rod-like liquid crystal molecules 7 sandwiched between the substrates are aligned so as to have some angle with respect to the longitudinal direction of the linear electrodes when no electric field is applied. Further, in this case, the dielectric anisotropy of the liquid crystal is assumed to be positive. When an electric field is applied, the liquid crystal molecules 7 will change toward the direction of their electric field. Further, the above-described structure upper polarizing plate 1 A and lower polarizing plate 14A are arranged at a specific angle. Further, the angle formed by the direction of the electric field with respect to the surface of the substrate 8 is set to be a parallel electric field. The parallel electric field means that the angle formed by the direction of the electric field on the surface of the substrate is 20 degrees or less, preferably 10 degrees or less, more preferably parallel. Further, even if the electrode is formed by dividing the upper and lower substrates or formed on only one of the substrates, the effect is not changed. The dielectric material has a dielectric constant anisotropy Δ ε of positive and a 値 of 13.2, and the refractive index is different. The nematic liquid crystal having a property Δη of 0.085 (589 nm, 20 deg.) (MMC 9 100-100). The thickness (gap) of the liquid crystal layer is set to be larger than 3.5 μm. (Production of polarizing plate) The following composition was placed in a mixing tank, stirred while heating, and the components were dissolved to prepare a cellulose acetate solution having the following composition. Composition of cellulose acetate solution: • 75- 1356212 Cellulose acetate with a degree of deuteration of 60.9 % 100 parts by weight of triphenyl phosphate (plasticizer) 7.8 parts by mass of biphenyl diphenyl phosphate (plasticizer) 3.9 parts by mass of dichlorocarbyl (first solvent) 300 mass of methanol (second solvent) 54 parts by mass of 1-butanol (third solvent) 11 parts by mass in another mixing tank under 16 parts by mass The retardation increasing agent, 80 parts by mass of dichloromethane and 20 parts by mass of methanol were stirred while heating to prepare a delayed rising agent solution. Further, 7 parts by mass of the delayed riser solution prepared was mixed with 487 parts by mass of the cellulose acetate solution, and sufficiently stirred to prepare a coating liquid. Delay riser:

將所製得之塗佈液使用帶式流延機流延。當帶上之膜面溫度達到4〇°C後’以60°C溫空氣乾燥1分鐘，然後從帶剝取薄膜。其次’以140°C乾燥空氣將薄膜乾燥10分鐘，以製得厚度爲微米之纖維素醋_酯薄膜。該纖維素醋酸酯薄膜之光學特性係使用自動雙折射率計 (KOBRA 21ADH，王子計測機器公司製）測定。其結果， -76- 1356212The obtained coating liquid was cast using a belt casting machine. When the film surface temperature on the belt reached 4 ° C, it was air-dried at 60 ° C for 1 minute, and then the film was peeled off from the belt. Next, the film was dried by dry air at 140 ° C for 10 minutes to prepare a cellulose vine acetate film having a thickness of micrometer. The optical properties of the cellulose acetate film were measured using an automatic birefringence meter (KOBRA 21ADH, manufactured by Oji Scientific Instruments Co., Ltd.). Results for -76- 1356212

Re = 10 (奈米）、Rth = 102 (奈米）。 (光學補償層之製造）將上述纖維素醋酸酯薄膜之表面加以皂化，並在其上以線棒塗佈器以20 ml/m2塗佈下述組成之配向膜塗佈液。然後，在60°C之溫空氣乾燥爲期60秒鐘，再在100°C之溫空氣乾燥爲期120秒鐘。然後，對於所形成之膜朝與薄膜之遲相軸方向成平行之方向施加摩擦處理。配向膜塗佈液之組成：下述之改質聚乙烯醇 15質量份水 334質量份甲醇】〇〇質量份戊二醛 1質量份對-甲苯磺酸 0.3質量份改質聚乙烯醇： -(CH2-CH) 87.8— (CH2-CH) 12. 〇— (CHr-^H) 〇. 2—Re = 10 (nano), Rth = 102 (nano). (Production of optical compensation layer) The surface of the above cellulose acetate film was saponified, and an alignment film coating liquid of the following composition was applied thereto at 20 ml/m2 by a wire bar coater. Then, it was dried at a temperature of 60 ° C for 60 seconds, and then air-dried at a temperature of 100 ° C for 120 seconds. Then, a rubbing treatment is applied to the formed film in a direction parallel to the direction of the retardation axis of the film. Composition of the alignment film coating liquid: The following modified polyvinyl alcohol 15 parts by mass of water 334 parts by mass of methanol] 〇〇 parts by mass of glutaraldehyde 1 part by mass of p-toluenesulfonic acid 0.3 parts by mass of modified polyvinyl alcohol: - (CH2-CH) 87.8—(CH2-CH) 12. 〇—(CHr-^H) 〇. 2—

c=o ch3 將0.9克下述之碟狀（discotic)液晶性化合物、0.2克之經氧化乙烯改質之三丙烯酸三羥甲基丙烷醋（V# 360，大阪有機化學工業公司（股）製）、〇.〇6克之光聚合引發劑（Irgacure 907，Ciba-Geigy 公司製）、0.02 克之增感劑 (Kayacure - DETX，日本化藥公司（股）製）、〇.〇1克之下述空氣界面側垂直配向劑，溶解於3.9克之甲基乙基酮 -77- 1356212 。將該溶液以# 3.4之線棒塗佈於上述配向膜上。並且，對其貼附金屬框且在125°C恆溫槽中加熱3分鐘，以使碟狀液晶性化合物配向。其次，在100 °C下使用120 W/cm高壓水銀燈照射紫外線30秒鐘，以使碟狀液晶性化合物交聯化。然後放冷至室溫。以如此方式製造光學補償層。.c=o ch3 0.9 g of the following discotic liquid crystal compound and 0.2 g of ethylene oxide-modified trimethylolpropane vinegar modified by ethylene oxide (V# 360, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 〇. 〇 6 g of photopolymerization initiator (Irgacure 907, manufactured by Ciba-Geigy Co., Ltd.), 0.02 g of sensitizer (Kayacure - DETX, manufactured by Nippon Kayaku Co., Ltd.), 〇. 〇 1 g of the following air interface The side vertical alignment agent was dissolved in 3.9 g of methyl ethyl ketone-77- 1356212. This solution was applied to the above alignment film with a wire bar of #3.4. Further, a metal frame was attached thereto and heated in a 125 ° C thermostat bath for 3 minutes to align the discotic liquid crystalline compound. Next, ultraviolet rays were irradiated for 30 seconds at 100 °C using a 120 W/cm high-pressure mercury lamp to crosslink the discotic liquid crystalline compound. Then let cool to room temperature. The optical compensation layer is fabricated in this manner. .

使用自動雙折射率計（KOBRA 2 1ADH，王子計測機器公司（股）製）測定光學補償層的Re之光入射角度相依性，並扣除預先所測定的纖維素醋酸酯薄膜之參與部份，以求出只有碟狀液晶層之光學特性，結果Re爲50奈米、Rth 爲-25奈米，液晶之平均傾斜角爲89.9度，因此得以確認碟狀液晶係對於薄膜面成垂直配向。另外，遲相軸之方向係與配向膜之摩擦方向（配向控制方向）成平行。將碘吸附在經延伸之聚乙烯醇薄膜以製得偏光膜。使用聚乙烯醇系黏合劑，在偏光膜之單側將所製得之光學補償膜貼附成使纖維素醋酸酯薄膜位於偏光膜側。並加以配置 -78- 1356212 成使偏光膜之透射軸與光學補償層之遲相軸能成爲平行。對於市售商品級之纖維素醋酸酯薄膜（Fujitack TD80UF，富士照相軟片公司製）施加皂化處理，並使用聚乙烯醇系黏合劑將其貼附在偏光膜之相反側。藉由如此方式製得下側偏光膜14A。然後，將其以使光學補償層光遲相軸與液晶胞之摩擦方向成爲平行，且使碟狀液晶塗佈面側位於液晶胞側之方式，貼附在藉由上述所製得之IPS模式液晶胞之一方。其次，將市售商品級之偏光板（HLC 2-5618， Sanritz公司（股）製），作爲上側偏光板1A且以正交尼科耳之配置來貼附，.以製得液晶顯示裝置。該偏光板之一對保護膜之Re爲3奈米、Rth爲38奈米。此外，將偏光膜之吸收軸的軸角度，以顯示裝置水平方向爲基準而加以設定爲〇度，將上側保護膜之遲相軸設定爲〇度，將液晶胞上基板之配向控制方向（摩擦方向）設定爲90度，同樣地將下側偏光板的軸角度設定爲90度，將下側光學補償膜之配向控制方向設定爲90度，將液晶胞下基板之配向控制方向（摩擦方向）設定爲270度，下側保護膜之遲相軸設定爲90度，將下側偏光膜之吸收軸設定爲90度。 (所製得液晶顯示裝置之漏光的測定）測定以如此方式所製得液晶顯示裝置之漏光。測定機係使用亮度計BM-5 ( Topucon公司製），並以光源亮度與漏光亮度之比作爲透射率。由左斜向7〇度所觀察時之漏光爲 0.28 %。另外，由下側觀察時也爲相同之漏光透射率。亦 -79- 1356212 即，將該結構以液晶胞爲中心而使上側與下側互換，也能 ’ 獲得相同效果。 \. 〔例 1 2〕在藉由實施例1所製得液晶顯示裝置中，將下側保護膜之遲相軸，以顯示裝置之水平方向爲基準而加以設定爲0 度。其他結構則製成爲與實施例1相同。由左斜向70度所 _ 觀察時之漏光爲0.35 %。 · 〔例 1 3〕在上述所製得之IPS模式液晶胞1之兩側將市售商品級 ® 之偏光板（HLC 2-5618，Sanritz公司（股）製）以正交尼科耳之配置貼附，以製得液晶顯示裝置。但是並未使用光學補償層。在上述液晶顯示裝置，則與實施例1同樣地以使上側偏光板之透射軸與液晶胞摩擦方向成爲平行之方式貼附偏光板。經測定以如此方式所製得液晶顯示裝置之漏光，結果由左斜向70度觀察時之漏光爲0.72 %。〔例 14〕以例1 3之結構，且上側偏光板使用以例1 1所使用之保 ® 護膜兼支撐體則使用TD80 ( Re爲3奈米、豕th爲38奈米 )，並且以與例1 1相同製法朝與支撐體遲相軸平行方向以摩擦處理形成光學補償層。將所製得附有光學補償層之保護膜以黏合劑在上述上側偏光板之液晶胞側保護膜貼合成互相之遲相軸會大致成垂直。結果，由左斜向70度所觀察時之漏光爲0.35 %。〔例 1 5〕 -80- 1356212 【主要元件符號說 :明 1 ] 1 上側偏光膜 ( 上 1 A 上側偏光板 2 上側偏光膜之吸 3 ' 3a 上側保護膜 ( 保 4 上側保護膜之遲 5 液晶胞上側基板 6 上側基板液晶配 7 液晶性分子 δ 液晶胞下側基板 9 下側基板液晶配 10 光學補償層 11 光學補償層之配 12 ' 12a 下側保護膜 ( 保 13 下側保護膜之遲 14 下側偏光膜 ( 偏 1 4A 下側偏光板 ( 下 15 下側偏光膜之吸 16 線狀電極偏光膜、偏光膜）收軸護膜、透明保護膜）相軸 (基板、上基板、上側基板）向用摩擦方向 (基板、下基板、下側基板）向用摩擦方向向控制方向護膜、透明保護膜）相軸（遲相軸）光膜）偏光膜）收軸 -82 -The incident angle dependence of Re of the optical compensation layer was measured using an automatic birefringence meter (KOBRA 2 1ADH, manufactured by Oji Scientific Instruments Co., Ltd.), and the participation portion of the previously determined cellulose acetate film was subtracted to The optical characteristics of only the disk-shaped liquid crystal layer were determined. As a result, Re was 50 nm, Rth was -25 nm, and the average tilt angle of the liquid crystal was 89.9 degrees. Therefore, it was confirmed that the disk-like liquid crystal system was vertically aligned with respect to the film surface. Further, the direction of the retardation axis is parallel to the rubbing direction (alignment control direction) of the alignment film. The iodine is adsorbed on the stretched polyvinyl alcohol film to prepare a polarizing film. The optical compensation film thus obtained was attached to one side of the polarizing film by using a polyvinyl alcohol-based adhesive so that the cellulose acetate film was positioned on the side of the polarizing film. And configured -78- 1356212 so that the transmission axis of the polarizing film and the retardation axis of the optical compensation layer can be parallel. A saponification treatment was applied to a commercially available cellulose acetate film (Fujitack TD80UF, manufactured by Fuji Photo Film Co., Ltd.), and attached to the opposite side of the polarizing film using a polyvinyl alcohol-based adhesive. The lower polarizing film 14A was obtained in this manner. Then, it is attached in the IPS mode prepared by the above, in such a manner that the optical retardation axis of the optical compensation layer is parallel to the rubbing direction of the liquid crystal cell, and the disc-like liquid crystal coated surface side is located on the liquid crystal cell side. One side of the liquid crystal cell. Next, a commercially available commercial grade polarizing plate (HLC 2-5618, manufactured by Sanritz Co., Ltd.) was attached as the upper polarizing plate 1A and arranged in a crossed Nicols to obtain a liquid crystal display device. One of the polarizing plates had a Re of 3 nm for the protective film and an Rth of 38 nm. Further, the axial angle of the absorption axis of the polarizing film is set to the temperature based on the horizontal direction of the display device, and the retardation axis of the upper protective film is set to the degree of twist, and the alignment direction of the liquid crystal cell substrate is controlled (friction) The direction is set to 90 degrees, and the axial angle of the lower polarizing plate is set to 90 degrees, and the alignment control direction of the lower optical compensation film is set to 90 degrees, and the alignment direction of the liquid crystal sub-substrate is controlled (friction direction). When it is set to 270 degrees, the slow phase axis of the lower protective film is set to 90 degrees, and the absorption axis of the lower polarizing film is set to 90 degrees. (Measurement of Light Leakage of Liquid Crystal Display Device Produced) Light leakage of the liquid crystal display device produced in this manner was measured. The measuring machine used was a luminance meter BM-5 (manufactured by Topucon Co., Ltd.), and the ratio of the light source luminance to the light leakage luminance was used as the transmittance. The light leakage observed from the left oblique direction to 7 〇 is 0.28 %. In addition, the same light transmittance was observed when viewed from the lower side. Also, -79- 1356212, that is, the structure is centered on the liquid crystal cell, and the upper side and the lower side are interchanged, and the same effect can be obtained. [Example 1 2] In the liquid crystal display device produced in Example 1, the slow phase axis of the lower protective film was set to 0 degree based on the horizontal direction of the display device. The other structure was made the same as in the first embodiment. From the left oblique to 70 degrees, the light leakage when observed is 0.35 %. [Example 1 3] A commercially available commercial grade® polarizing plate (HLC 2-5618, manufactured by Sanritz Co., Ltd.) was placed on both sides of the above-mentioned IPS mode liquid crystal cells 1 in a crossed Nicols configuration. Attached to produce a liquid crystal display device. However, the optical compensation layer is not used. In the liquid crystal display device, the polarizing plate is attached so that the transmission axis of the upper polarizing plate and the rubbing direction of the liquid crystal cell are parallel in the same manner as in the first embodiment. The light leakage of the liquid crystal display device produced in this manner was measured, and as a result, the light leakage when viewed from the left oblique direction of 70 degrees was 0.72%. [Example 14] With the structure of Example 13 and the upper polarizing plate using the protective film and support used in Example 11 using TD80 (Re is 3 nm, 豕th is 38 nm), and In the same manner as in Example 1 1, an optical compensation layer was formed by rubbing treatment in a direction parallel to the slow axis of the support. The protective film having the optical compensation layer prepared thereon is bonded to the liquid crystal cell side protective film of the upper polarizing plate by an adhesive to be substantially perpendicular to each other. As a result, the light leakage observed from the left oblique direction of 70 degrees was 0.35%. [Example 1 5] -80- 1356212 [Main component symbol: Ming 1] 1 Upper polarizing film (upper 1 A upper polarizing plate 2 upper polarizing film suction 3 ' 3a upper protective film (protected 4 upper protective film delayed 5 Liquid crystal cell upper side substrate 6 Upper side substrate liquid crystal matching 7 Liquid crystal molecules δ Liquid crystal cell lower side substrate 9 Lower side substrate liquid crystal 10 Optical compensation layer 11 Optical compensation layer 12' 12a Lower side protective film (Bao 13 lower side protective film Late 14 lower polarizing film (1 4A lower polarizing plate (lower 15 lower polarizing film suction 16 linear electrode polarizing film, polarizing film) retracting film, transparent protective film) phase axis (substrate, upper substrate, Upper substrate) In the rubbing direction (substrate, lower substrate, lower substrate), the direction of the film is controlled by the rubbing direction, and the transparent protective film). The phase axis (lattic phase axis) film) The polarizing film)

Claims

1356212 : GWI Amendment Amendment No. 93126123 "Optical Compensation Film, Liquid Crystal Display Device and Polarizing Plate" Patent Case (Amended on January 28, 2011) X. Patent Application Range: 1. A VA type liquid crystal display device, A VA type liquid crystal display device having a pair of substrates having opposite electrodes disposed at least one of the electrodes, a liquid crystal layer interposed between the substrates, and first and second polarizing plates disposed outside the liquid crystal layer; And the product Δ n·d of the thickness d (micrometer) of the liquid crystal layer and the refractive index anisotropy Δη is 0.1 to 1.0 μm; and the first and second polarizing plates each have a polarizing film, and the polarizing film is sandwiched a pair of protective films; at least one of the pair of protective films having a late phase axis substantially conforming to a direction in which an average refractive index of the film surface becomes maximum, and a retardation axis of the protective film on the near side of the liquid crystal layer The absorption axis of the polarizing film is intersected at an angle of 20° to 70°; and the protective film disposed on the near side of the liquid crystal layer in the pair of protective films has a thickness of ch (nano) and is orthogonal to each other. With x, y and z axis directions The average refractive indices nx, ny, and nz, when the average in-plane refractive index is nx and ny (but ny < nx), and the average refractive index in the thickness direction is nz, then any wavelength λ in the visible light region meets the following Conditions: 〇奈米< { (nx - ny) X di } S 50 nm, and 50 nm S[{(nx + ny)/2-nz} X di]' 300 nm 1356212 Revision 2. The VA type liquid crystal display device of claim 1, wherein the liquid crystal layer contains a nematic liquid crystal material, and the liquid crystal molecules of the nematic liquid crystal material are substantially vertically aligned with respect to a surface of the pair of substrates when displayed in black. 3. The VA type liquid crystal display device of claim 1 or 2, wherein the retardation axis of the protective film on the near side of the liquid crystal layer and the absorption axis of the polarizing film are 40 to 50. 4. The VA type liquid crystal display device of claim 1 or 2, wherein the protective film on the side of the liquid crystal layer of at least one of the first and second polarizing plates and the liquid crystal layer have a ny〒nz And nx > ny phase difference plate.