1281991 玖、發明說明 .................A··-·'· ；，- (發明說明應敘明：發明所屬之技術領域、先前技術、內容、實施方式及圖式簡單說明) (一） 發明所屬之技術領域 本發明係有關一種長偏光板，而由此以高良率獲致具有絕 佳偏光性能的偏光板；此偏光板之製造方法及液晶顯示器。 (二） 先前技術 因爲液晶顯不器（以下稱爲「L C D」）的流行，使得對偏光 板的需求急遽地增加。一般而言，偏光板係包括一具有偏光 性之偏光層以及一透過黏著層黏貼於該偏光層之一個或兩 個表面上的保護膜。 用於偏光膜的材料主要是聚乙烯醇（以下稱爲「PVA」）。 令PVA膜作單軸伸展然後以碘或二色性染料加以染色，或是 染色之後再進行伸展，且進一步使此薄膜與硼化合物進行交 聯以形成用於偏光層的偏光膜。 對保護膜而言，主要使用的是三醋酸酯纖維素，因爲此膜 係呈光學透明的且其雙折射性很小。該偏光膜通常係沿著延 伸方向（縱軸方向）使連續薄膜作單軸伸展而製成的，因此該 偏光膜的吸收軸通常是幾乎平行於縱軸方向。 在習知LCD中，偏光板的配置方式是使其吸收軸相對於畫 像平面的垂直或橫軸方向傾斜4 5 °，必須在打孔步驟中沿著 相對於捲軸之縱軸方向的45 °方向爲製作成捲軸形式的偏 光板打孔。 不過，假如沿著45 °方向爲偏光板打孔，則會在捲軸邊緣 -7- 1281991 附近產生不能使用的部分，特別是在大尺寸偏光板的例子裡 ，其良率會降低，結果不利地增加了其耗損。 爲了防止著色作用或是啓動諸如擴大視角之類光學補償 -作用的目的，也會藉由將之黏貼在用以形成LCD的偏光板之 、 類上而用到相差膜，且要求將其定向軸設定在相對於該偏光 板之透射軸方向的各個角度上。習知地，使用的是一種從沿 著縱軸方向作單軸伸展之薄膜切割出相差膜的方法，係藉由 剪除周緣使得其定向軸相對於其側邊夾一預定傾角，且類似 於偏光板存在有良率減低的問題。 此外，當黏貼有另一光學構件例如1 / 4波板時，必須在每 一個面板上黏貼此種構件且其程序很麻煩。除此之外，需要 一種層壓複數個薄膜而嚴格控制其角度的製造方法，且會肇 因於角度的滑動而產生漏光現象而造成黑色部位的顏色顯 示變成黃色或藍色。因此，必需進行捲軸對捲軸的黏貼作用 〇 爲了解決上述問題，已提出的數種方法係使聚合物之定向 軸相對於薄膜輸送方向（縱軸方向）傾斜一必要角度。 曰本專利申請案第JP-A- 20 00 - 9 9 1 2號（此中「JP-A」意指 「曰本未審查而公開之專利申請案」）文件中說明了 一種沿 著橫軸或縱軸方向使塑膠薄膜作單軸伸展技術，係藉由改變 該伸展方向上右邊與左邊之間的伸展速率，令薄膜沿著不同 於上述伸展方向的縱軸或橫軸方向作抗張性伸展。不過，根 據這種方法在使用例如張布機系統的例子裡，必須改變右邊 與左邊之間的輸送速率且這會造成拉扯、起皺或薄膜滑動現 -8 - 1281991 象，結果很難得到必要的傾角（與偏光板4 5。角）。爲了減小 右邊與左邊之間的速率差異，必須拖長伸展步驟且會大幅增 加設備的成本。 日本專利申請案第JP-A- 3 - 1 8270 1號文件中揭示了一種 薄膜製造方法，係藉由使用一種機構使其伸展軸落在相對於 薄膜延伸方向的任意角度Θ上，其中係將各相對於薄膜延伸 方向夾有角度Θ的複數個橫向的成對薄膜支持點設置在一 連續薄膜的兩側邊緣上，且每一對支持點都能隨著薄膜的延 伸使薄膜朝Θ方向伸展。同時在這種方法中，由於薄膜的行 進速率在其右邊與左邊之間有差異，故會在薄膜上產生拉扯 或起皺現象，且爲了舒緩這種現象必須拖長其伸展步驟而產 生增加設備成本的問題。 日本專利申請案第J P - A - 2 - 1 1 3 9 2 0號文件中揭示了一種 薄膜製造方法，係藉由延伸薄膜而在沿著兩列對齊之叉柱間 抓住其兩個邊緣而使之沿著所配置之各張布機軌道延伸下 ，令薄膜沿著機器方向呈斜角對角方向伸展，使得各叉柱會 在各預定延伸區段內延伸不同的距離。同時在這種方法中， 會在斜角伸展作用上產生拉扯或起皺現象，而這是不利於光 學薄膜的。 韓國未審查之專利公告案第P-2001-005184號文件中所 揭示的一種偏光板係藉由摩擦處理使其透射軸出現傾斜。不 過如同一般所熟知的，藉由摩擦調整其定向的作用只有在從 薄膜表面到最多奈米等級部分的區域內是有效的’且無法依 令人滿意的方式爲諸如碘或二色性染料之類的偏光器進行 -9- 1281991 定位，結果不利的是其偏光性能很差。 在沿著捲軸之縱軸方向伸展薄膜的習知方法中，隨著薄膜 伸展寛度的變大，當以高伸展倍率伸展薄膜時薄膜邊緣會捲 曲得愈厲害。這會造成薄膜出現破裂之類現象且很難在伸展 步驟中進行操作，此外，利用多階段伸展方法進行伸展的作 業會在諸如對捲軸之旋軸速率的控制或是對捲軸式薄膜之 邊緣部分上之收縮及彎折現的控制之類操縱作業上遭遇到 困難。 (三）發明內容 本發明的目的是提供一種包括作斜角伸展之偏光性薄膜 的長捲軸式偏光板，而能夠在打孔取出偏光板的步驟中改良 其良率。 本發明的另一目的是提供一種高品質而價廉的捲軸式偏 光板，係具有絕佳平坦度且很難肇因於外來光而受到破壞。 本發明的又一目的是提供一種高等級而價廉的長偏光板 ，係具有650毫米或更大的工作寬度（有效寬度），其中包括 能夠在打孔取出偏光板的步驟中改良其良率的斜角伸展式 偏光性薄膜。 本發明的再一目的是提供一種用於製造上述偏光板的方 法，以及使用該偏光板的液晶顯示器。 在對用以達成上述目的之機制進行密集硏究的結果，本發 明的發明人發現一種在不產生拉扯、起皺或薄膜滑動之類現 象下獲致斜角定向的方法，因此可製備了一種長形偏光板且 能夠製作出一種捲軸形式的偏光板。在將此長形偏光板捲成 -1 0 - 1281991 的角度。 根據本發明之偏光板也具有的另一特徵爲在5 5 0奈米的 單板透射率是等於或大35%且在5 50奈米的偏光程度是等於 或大於80%。較佳的是其單板透射率是等於或大於40%且其 偏光程度是等於或大於95.0%，更佳的是其偏光程度是等於 或大於99%，特別較佳的是其偏光程度是等於或大於99.9% 。根據本發明的偏光板具有絕佳的單板透射率及偏光板程度 ，且因此當使用液晶顯示器時可有利地提高其反差。 吾人能夠藉由說明如下的方法很容易地得到根據本發明 的斜角定向偏光板。也就是說，係藉由伸展一聚合物膜獲致 斜角定向作用，且在此同時設計出在薄膜伸展作業上揮發性 內含物的百分比、在薄膜收縮作業中的收縮百分比以及薄膜 在進行伸展之前的彈性模量。同時較佳的是，控制在進行伸 展之前黏貼於該薄膜上的異物量額。 吾人可在各種應用中使用根據本發的偏光板，不過因爲其 定向軸係相對於縱軸方向呈傾斜之特徵性質的優點，特別較 佳的是使用其定向軸相對於縱軸方向的傾角爲從40 °到5 0。 的偏光膜當作LCD(具有諸如TN、STN、OCB、ROCB、ECB、CPA 、IPS及VA之類所有液晶模式）用的偏光板或是抗反射式有 機電發光顯示器用的旋轉偏光板。 此外，根據本發明之偏光板也適於結合各種光學構件一起 使用，這類光學構件有例如諸如1 / 4波板及1 / 2波板之類相 差模、視角放大膜、抗眩目膜及硬式塗膜。 本發明中，假如捲軸長度等於或大於1米且其圈數等於或 -16- 1281991 大於三則其捲軸形式是充分的。較佳的是具有更大長度，不 過假如其長度太大則會過度增加捲軸的重量。因此，較佳的 是其長度等於或小於1 0，〇 〇 〇米。較佳的是具有更大圈數例 如等於或大於1 0圈。當捲軸內徑變得比較小時，其捲數會 變得更大。不過，較佳的是寧可其內徑不是過小因爲會產生 捲曲行爲。較佳的是其內徑等於或大於1英吋。其寬度並未 特別受限，但是假如其寬度太小則破壞了其捲軸形式。因此 ’較佳的是其寬度等於或大於5厘米。 在捲軸的形成作業中，可以使用一核心結構。該核心結構 的建造材料並未特別受限，且可以使用諸如紙張、鐵和鋁之 類工業上常用的任何材料。 本發明中’重要的是在形成捲軸時增加其縱軸方向的長度 。爲了這個目的，重要的是進行下列控制：控制其在薄膜伸 展作業中的揮發性內含物百分比，控制其在薄膜收縮作業中 的收縮百分比，控制其縱軸方向的輸送速率，控制薄膜的乾 燥點’控制在進行伸展之前黏貼於該薄膜上的異物量額，在 薄膜伸展作業中控制其溫度和溼度，以及在乾燥作業中控制 其乾燥溫度以減少其揮發性內含物。其薄膜伸展方法將說明 如下，其中個別地說明其中的重要部分。 本發明中所用的「肇因於儲存期間之外來光受到的破壞」 一詞意指其偏光程度在曝露於儲存條件的光下例如當曝露 在螢光燈、白熱燈之類的光下的起伏。一般而言，易於在曝 露於光下時增加其偏光程度。 在根據本發明第二實施例的偏光板中，垂直於縱軸方向的 -17- 1281991 工作寬度會等於或大於650毫米，較佳的是等於或大於 1，3 00毫米。 吾人能夠藉由說明如下的方法很容易地獲致根據本發明 第二實施例具斜角定向的偏光板。也就是說，藉由伸展一聚 合物膜獲致斜角定向，使伸展作業中之偏光膜用聚合物膜沿 著縱軸方向的張力以及伸展作業中的環境溼度最佳化，也使 染色作業中之偏光膜用聚合物膜的含水量百分比最佳化，並 使在伸展及染色作業之後的膨脹百分比低於伸展作業之前 的膨脹百分比。同時較佳的是控制在進行伸展之前黏貼於該 薄膜上的異物量額，在染色步驟中，可同時執行薄膜的染色 及硬化作業。 爲了在本發明中得到工作寬度等於或大於6 50毫米的寬 偏光板，特別重要的是使下列條件最佳化：染色作業之後的 含水量百分比，薄膜在伸展作業中沿著縱軸方向的張力及環 境溼度，以及在伸展作業之後的膨脹百分比。個別的的重要 部分將說明如下。 <工作寬度> 本發明中所用的工作寬度意指在垂直於捲軸形式偏光板 縱軸方向之方向上的寬度，該捲軸形式偏光板係藉由對偏光 膜用聚合物膜進行伸展和乾燥得到的，通常會黏貼一保護膜 然後再切除邊緣以便進行接合。令偏光膜用聚合物膜與各張 布機夾接合，且在各薄膜邊緣連續地保留未伸展的接合寬度 。該接合寬度部分不僅不具有偏光性能同時使之無法黏貼保 護膜。因此切除此接合寬度部分，但是此例中隨著所切除邊 - 1 8 - 1281991 緣的寬度變得愈大，會進一步減小可當作偏光板的工作寬度 。本發明中，較佳的是所切除邊緣的寬度等於或小於伸展作 業之後薄膜寬度的1 0%，更佳的是使之等於或小於5%，又更 佳的是使之等於或小於3%。 本發明之偏光板的工作寬度係等於或大於6 50毫米且較 佳的是等於或大於1 3 00毫米，因此可減小所切除邊緣寬度 的百分比使之落在上述範圍內，增加該偏光膜用聚合物膜內 可用部分的百分比並降低該偏光板的成本。 <伸展作業中的溼度> 假如伸展作業中的溼度不足，不僅無法對薄膜進行伸展而 且會造成張布機的故障。另一方面，當伸展作業中的溼度很 高時，不致發生諸如偏光性能受到破壞之類的現象且易於進 行伸展，因此這是非常有效的。同時在對含有水分當作（揮 發分）諸如聚乙烯醇及丙烯酸酯纖維素之類揮發性內含物的 薄膜進行伸展的例子裡，當然可在高溼度調節大氣內爲薄膜 進行伸展。在聚乙烯醇的例子裡，較佳的是其溼度等於或大 於5 0%，更佳的是其溼度等於或大於80%，或是又更佳的是 其溼度等於或大於90%。 <縱軸方向的張力> 在對薄膜進行接合、伸展及乾燥的步驟中，必項沿著縱軸 方向連續地施加張力。假如在進行接合時的張力不足，則其 接合寬度會減小且薄膜會在伸展期間從支持機制上脫落下 來’因此假如其張力太強，不僅薄膜無法騎乘在各支持機制 上且無法接合，而且其接合寬度部分會不利地在與薄膜接合 -19- 1281991 之後發生捲曲。本發明中，較佳的是在沿著薄膜之縱軸方向 施加定常張力時對薄膜進行伸展及乾燥並取出薄膜。本發明 中，較佳的是當藉由支持機制支持薄膜的兩側邊緣時將薄膜 保持在緊緻狀態內以利其支持作用。本方法的特定實施例包 含利用張力控制器沿著縱軸方向施加張力使薄膜受張力作 用的方法。該張力會取決於聚合物膜的種類以及沿著薄膜之 縱軸方向的輸送速率而改變。較佳張力指的是一種能夠提供 在接合之前瞬間落在輸送捲軸上的薄膜邊緣會重複與薄膜 接觸或提起之狀態的張力。較佳的是此張力爲從100到500 牛頓/米，更佳的是該張力爲從350到450牛頓/米。 <揮發性內含物百分比〉 當在伸展步驟中左邊和右邊的路徑變得不相同時，薄膜會 產生起皺及滑動現象。爲了解決這些問題，極佳的是本發明 係藉由允許在進行伸展之前出現等於或大於5%之揮發性內 含物以保持其支撐性質下對聚合物膜進行伸展，然後再收縮 薄膜以降低其揮發性內含物百分比。本發明中所用的揮發性 內含物百分比意指每單位容積之薄膜內所含揮發性成分的 容積且指的是將揮發性成分的容積除以薄膜容積得到的數 値。 本發明中，較佳的是在對偏光膜用聚合物膜進行伸展之前 提供至少一個用以結合揮發性內含物的步驟。結合揮發性內 含物的步驟係例如藉由對薄膜進行鑄造並結合以溶劑或水 ’或者藉由於溶劑或水內或是以溶劑或水進行浸漬、塗覆或 噴濺作業而執行的。染色步驟或是稍後將在 <染色配方/方法 - 2 0 _ 1281991 >及 <硬化劑及金屬鹽的添加 >章節內加以說明之添加硬化劑 的步驟都可以扮演著結合揮發性內含物步驟的角色。在染色 步驟同時扮演著結合揮發性內含物步驟之角色的例子裡，較 佳的是在進行伸展之前或之後提供該染色步驟。當在進行伸 展之前提供該染色步驟時，可同時執行該染色步驟及伸展步 驟。 較佳的揮發性內含物百分比會取決於聚合物膜的種類而 改變。揮發性內含物百分比的最大値可能是任意數値只要該 聚合物膜能夠保持其支撐性質即可。較佳的是其揮發性內含 物百分比，對聚乙烯醇而言爲從1 0到1 00%且對丙烯酸酯纖 維素而言爲從10到200%。 <揮發性成分內含物的分佈> 在藉由一中間步驟製作一很長特別是捲軸形式之偏光板 的例子裡，必要的是未出現任何不均勻的染色作用或是未染 到色的點。例如薄膜內的揮發性成分在進行伸展之前具有不 均勻的分布（揮發性成分的量額取決於在薄膜平面內之位置 所出現的差異），則會造成不均勻的染色作用或是出現未到 染色的點。據此，較佳的是使薄膜內在進行伸展之前之揮發 性成分含量的分布是比較小的，且較佳的是其分布爲至少等 於或小於5 %。揮發性成分含量的分布指的是，其揮發性內 含物百分比之最大値或最小値與平均揮發性內含物百分比 之間差異中較大的差異，相對於定義如上之揮發性內含物百 分比之平均揮發性內含物百分比的比例。爲了減小揮發性成 分含量的分布，可以使用一種以均勻空氣對薄膜的前方或背 -21 - 1281991 膜接受乾燥作用。較佳的是在進行伸展之後的瞬間其含水量 百分比係等於或小於5 0%且更佳的是使其含水量百分比具 有更高的減低速率。然後對偏光膜進行乾燥並黏貼以保護膜 ，且此時較佳的是其含水量百分比係等於或小於1 0 %且更佳 的是其含水量百分比係等於或小於5%。本發明中所用的含 水量百分比意指每單位容積之薄膜內所含含水量的容積且 指的是將含水量的容積除以薄膜容積得到的數値。 本發明中所用之含水量百分比分布指的是其含水量百分 比之最大値或最小値與平均含水量百分比之間差異中較大 的差異，相對於沿著捲軸形式薄膜之對角方向的平均含水量 百分比的比例。例如，當在薄膜兩側邊緣上的含水量百分比 之最小値爲44.0%且其最大値爲44. 5%時，其含水量百分比 分布爲0.5%。本發明中，較佳的是其含水量百分比分布等 於或小於20%，更佳的是其含水量百分比分布等於或小於 1 0 %，又更佳的是其含水量百分比分布等於或小於5 %。較佳 的是，在對本發明的偏光器及硬化劑施行了染色步驟之後， 可使該聚合物膜的含水量百分比分布變得比較小，因爲假如 其含水量百分比分布很大則會產生不均勻度及斑紋。 <中間步驟> 本發明中，較佳的是提供用以收縮經伸展的聚合物膜以降 低其揮發性內含物百分比的乾燥步驟，以及在乾燥作業之後 或期間將保護膜黏貼於該偏光板的至少一個表面上之後的 薄膜後熱步驟。黏貼保護膜用方法的特定實例包含一種保持 偏光膜的兩側邊緣於在乾燥步驟期間受到支持的狀態下使用 1281991 黏著劑將一保護膜黏貼於該偏光膜上然後再切除其兩側邊 緣的方法，以及一種在進行乾燥、切除薄膜兩側邊緣並將保 護膜黏貼其上之後從兩側的邊緣支持部分使偏光膜脫模的 方法。爲了切除各邊緣可使用一種通用技術，例如利用諸如 含緣工具之類切割器切除邊緣的方法或是利用雷射的方法 。較佳的是，爲該組合薄膜施行後熱作用以便使黏著劑乾燥 並改良其偏光性能。該後熱作用條件會取決於黏著劑而改變 ’但是在水性黏著劑的例子裡較佳的是加熱溫度等於或大於 3 0 °C，更佳的是其加熱溫度爲從4 0到1 0 0 °C，又更佳的是 從5 0到8 0 °C。較佳的是在性能及生產效率的觀點下於中間 生產線內執行這些步驟。 在本發明的偏光膜製造方法中，吾人能夠藉由說明如下的 方法很容易地得到根據本發明的斜角定向偏光板。也就是說 ，係藉由伸展一聚合物膜獲致斜角定向作用，且在此同時設 計出在進行薄膜伸展作業之前的揮發性內含物分布及揮發 性內含物百分比，且在進行伸展作業時諸如伸展溫度及伸展 溼度之類的伸展大氣。同時較佳的是，控制在進行伸展之前 黏貼於該薄膜上的異物量額。藉由這些，即使作斜角伸展時 ，也可在未於已伸展薄膜上造成拉扯或起皺現象下獲致一高 ，等級而價廉的長偏光板。 在本發明的偏光膜製造方法中，係藉由支持機制支持偏光 膜用薄膜的兩側邊緣，且因此很難使薄膜在如同平常偏光板 製造機制的溶液內進行伸展。據此，較佳的是在將薄膜浸漬 於染色溶液、硬化溶液或同時浸漬於兩者內之後在施加有溼 -24- 1281991 度下爲薄膜進行伸展。較佳的是其伸展大氣的伸展溫度i 〇 到1 00 C且其淫度等於或大於7〇%，更佳的是其伸展溫度4〇 到50t且其溼度等於或大於80%。 不過在這類條件下’會在進行伸展之前的薄膜表面上出現 過里Itc色溶液或硬化彳谷液的分布。這種分布會偏光膜在伸展 之後產生不均句度。爲了防止產生這種不均句度，重要的是 本發明提供一種狀態使得薄膜內在進行伸展之前的染色溶 液或硬化溶液亦即薄膜內揮發性成分的含量分布等於或小 於5%。 其伸展方法將說明如下，且之後將說明其個別的重要項目 <伸展方法> 第1和2圖係用以顯示一種用以使根據本發明之聚合物膜 作斜角伸展之方法實例的平面示意圖。 本發明之伸展方法係包括··（ a )沿著箭號（i )方向引進有機 薄膜的步驟；（b )沿著對角方向伸展薄膜的步驟·，（ c )沿著箭 號（i i )方向將已伸展薄膜輸送到下一步驟的步驟。以下「伸 展步驟」一詞指的是含有步驟（a )到（c )的步驟且用以標示出 用以執行本發明之伸展方法的完整步驟。 連續地從（i )方向引進薄膜且一開始係藉由落在從上游看 到之左側上的支持機制支持在點B 1上。在這一點上，薄膜 的另一側並未受到支持且並未沿著對角方向產生張力。換句 話說，點B1指的並非實質上開始支持的點（以下稱之爲「實 質支持起始點」）。 -25- 1281991 本發明中，係將該實質的支持起始點定義成薄膜兩側邊緣 一開始受到支持的點。該實質的支持起始點係包含兩個點， 也就是說落在較下游側的支持起始點A 1以及在引進側上依 幾乎垂直於薄膜之中心線1 1 (第1圖）或2 1 (第2圖）的方式 從點A 1畫出之直線與相對側之支持機制的軌跡1 3 (第1圖） 或23(第2圖）相交的點C1。 從這些點開始，當藉由落在兩側邊緣上的支持機制以實質 上相等的速率輸送薄膜時，點A 1會在每個單位時間移向點 A2 ' A3、…An，同樣地點C1會移向點C2、C3、…Cn。也就 是說，用以連接當作基底之各支持機制同時通過的點An和 Cn的直線指的是該時刻的伸展方向。 在本發明的方法中如第1和2圖所示，點An會逐漸地自 點C η出現延遲且因此其伸展方向會逐漸地從垂直於輸送方 向的方向傾斜出來。本發明中，係藉由兩個點定義出實質上 脫離支持的點（以下稱作「實質支持脫離點」），這兩個點中 一個點指的是薄膜在更上游側脫離支持機制的點Cx，另一 個點指的是從點Cx依幾乎垂直於被輸送到下一步驟之薄膜 中心線1 2 (第1圖）或2 2 (第2圖）的方式畫出之直線與相對 側之支持機制的軌跡1 4 (第1圖）或2 4 (第2圖）相交的點Ay 〇 薄fl吴之最後伸展方向的角度係藉由落在伸展步驟之實質 端點（實質的支持脫離點）上的左邊及右邊支持機制之間的 路徑差異Ay-Αχ(亦即| L1-L2 | )對各實質支持脫離點之間 距離W (亦即Cx與Ay之間的距離）的比例而定出的。據此， -26- 1281991 其伸展方向相對於輸送到下一步驟之輸送方向的傾角0會 滿足下列關係·· t an 0 =W / ( Ay - Αχ )，亦即 t an 0 =W/ I LI-L2 | 落在第1和2圖上邊的薄膜邊緣會受到支持直到點i 8 (第 1圖）或28(第2圖）甚至到點Ay之後爲止，不過由於另一邊 緣並未受到支持，故不致沿著對角方向產生新的伸展作用。 因此’點1 8和28並不是實質的支持脫離點。 本發明中’出現在薄膜兩側邊緣上的實質支持起始點指的 並不是薄膜上只與各左邊及右邊支持機制接合的點。爲了對 本發明中定義如上的兩個實質支持起始點作更嚴謹的說明 ，係將這些點定義成使用以連接左邊或右邊支持點以及另一 支持點與被引進薄膜支持步驟之薄膜中心線幾乎呈正交的 點，且指的是定位在最上游的兩個支持點。 同樣地，本發明中係將兩個實質支持脫離點定義成使用以 連接左邊或右邊支持點以及另一支持點與被輸送到下一步 驟之薄膜中心線幾乎呈正交的點，且指的是定位在最下游的 兩個支持點。 此中使用的「幾乎呈正交」一詞意指該薄膜的中心線會與 用以連接左邊或右邊之實質支持起始點或實質支持脫離點 的直線夾90±0 . 5 °的角度。 在藉由如同本發明之張布系統伸展機以給定左邊與右邊 路徑差的例子裡，會肇因於諸如軌道長度之類的機械限制而 在和各支持機制接合的點與該實質支持起始點之間或是和各 -27- 1281991 藉由在薄膜進行一次伸展之後提供一薄膜收縮步驟使 I Ll -L2 | 變大。 較佳的是其伸展比例爲1 . 1到1 〇 . 〇倍，更佳的是其伸展 -· 比例爲2到1 0倍。較佳的是在那之後的收縮百分比係等於 _ · 或大於1 0%。此外如第4圖所示，同時較佳的是重複多次伸 展-收縮作業，因爲可使I Ll -L2 |變大。 從使用於伸展步驟之設備成本最小化的觀點，較佳的是使 各支持機制軌跡內的彎折數目以及其彎折角度變得比較小 0 。依這種觀點如第2、3和5圖所示，較佳的是在保持薄膜 兩側邊緣受到支持的狀態下使薄膜行進方向出現彎折，以致 能夠使支持薄膜兩側邊緣的步驟出口上的薄膜行進方向與 薄膜的實質伸展方向所夾的角度傾斜2 0到7 0 °。 本發明中，較佳的是藉由在支持雨側邊緣下施加張力的薄 膜伸展裝置指的是一種如第1到5圖所示的張布機。除了習 知的二維張布機之外，也可以使用如第6圖所示的伸展步驟 在兩側邊緣的各抓握機制之間給出螺旋式路徑差。 · 在很多例子裡，該張布式伸展機的結構是具有沿著軌道走 的固夾式鏈條。不過，當如同本發明使用的是垂直式非均伸 展方法時，則如第1如2圖所示某一軌道的端點端子會在伸 展步驟的入口和出口上從一軌道的端點端子錯置開，且無法 同時在左和右側邊緣之間發生接合及解連作業。此例中，實 質的路徑長度L 1和L2並不是單純的接合到解連距離，但是 如同已說明如上述地指的是用以支持薄膜兩側邊緣之各支 持機制間的路徑長度。 -29- 1281991 假如落在伸展步驟出口之左側和右側邊緣之間的薄膜行 進速率是不同的，則會發生起皺或滑動現象。因此，需要左 側和右側的薄膜夾持機制以便依實質上相同的速率輸送薄 膜。較佳的是其速率差等於或小於1 %，更佳的是其速率差 等於或小於0.5%，且最佳的是其速率差等於或小於0.05% 。此中使用的速率意指每一個左側和右側支持機制每分鐘行 進軌跡之長度。在一般的張布伸展機之類機器內，會根據用 以驅動鏈條之扣鏈齒輪的週期及驅動馬達的頻率之類，在速 率上產生等於或小於數秒等級的不均勻度且經常會產生等 於或小於數個％的不均勻度，但是這並不包括在本發明所指 的速率差之下。 <縱軸方向的輸送速率> 在對分派有硬化劑之聚乙烯醇薄膜進行伸展的例子裡，會 隨著伸展時間的消逝進行薄膜的硬化作業。因此，較佳的是 沿著聚合物膜之縱軸方向的輸送速率係等於或大於1米/分 鐘。在生產率的觀點下，較佳的是具有更高的縱軸輸送速率 。在任意例子裡，其縱軸輸送速率的上限會取決於該已伸展 薄膜以及伸展機器而改變。 <收縮作用> 可於伸展期間或之後爲已伸展之聚合物膜執行收縮作用 。假如能夠排除聚合物膜在斜角方向上的定向作用所產生的 起皺現象則其收縮作用已足夠。爲了對薄膜進行收縮。可使 用一種薄膜加熱法且因此移除其揮發性成分，不過假如能夠 使薄膜收縮則可使用任意機制。較佳的是使薄膜的收縮倍率 -30- 1281991 等於或大於1 / s i η θ，其中0指的是一相對於縱軸方向的定 向角。較佳的是其收縮百分比等於或大於1 〇%。 <揮發性內含物百分比> 當左側和右側路徑變得不相同時，會使薄膜產生起皺或滑 動現象。爲了解決這類問題，本發明的特徵係在保持其支撐 性質且允許出現5%或更多揮發性內含物下對聚合物膜進行 伸展然後再進行收縮以降低其揮發性內含物百分比。本發明 中所用的揮發性內含物百分比意指每單位容積之薄膜內所 含揮發性成分的容積且指的是將揮發性成分的容積除以薄 膜容積得到的數値。結合揮發性內含物的方法實例係包含一 種對薄膜進行鑄造並結合以溶劑或水的方法，一種在進行伸 展之前於溶劑或水內或是以溶劑或水進行浸漬、塗覆或噴濺 作業的方法，以及一種於進行伸展期間以溶劑或水進行塗覆 的方法。可藉由在高溼大氣中進行溼度調節之後對薄膜進行 伸展或是藉由在高溼度條件下對薄膜進行伸展，使於高溫高 溼大氣中的諸如含水聚乙烯醇之類親水性聚合物膜結合有 揮發性內含物。除了這些方法之外，假如能夠使聚合物膜之 揮發性內含物等於或大於5%則可使用任意機制。 較佳的揮發性內含物百分比會取決於聚合物膜的種類而 改變。只要能夠保持其支撐性質則其揮發性內含物百分比的 最大値可以是任意數値。較佳的是對聚乙靖醇而言其揮發性 內含物百分比爲從1 0到1 0 0 %，而對丙烯酸酯纖維素而言其 揮發性內含物百分比爲從10到200%。 <彈性模量> - 3 1 _ 1281991 至於該聚合物膜在進行伸展之前的物理性質，假如其彈性 模量太低，則其於伸展期間或之後的收縮百分比會減小而很 難使其起皺現象消失；而假如其彈性模量過高則會在進行伸 展時施加極大的張力，結果必須增加用以支持薄膜兩側邊緣 之部分的強度且增加了機器上的負載。本發明中，較佳的是 該聚合物膜在進行伸展之前的彈性模量（以楊氏模量表出） 爲從0.1到5 00Mpa，更佳的是該彈性模量爲從1到lOOMpa 〇 <從產生起皴現象到消失的距離> 假如能夠在本發明中所指的實質支持脫離點之前使聚合 物膜因斜角方向上的定向作用所產生的起皺現象消失就足 夠了。不過，假如從產生起皺現象到消失所花費的時間太長 ，則可能在伸展方向上產生色散。因此，較佳的是在量離開 產生起皺現象的點儘可能愈短愈好的行進距離內使起皺現 象消失。爲了此一目的，例如可以使用一種用以增加其揮發 性內含物之揮發速率的方法。 〈異物> 本發明中假如在進行伸展之前有異物黏貼於該聚合物膜 上則其表面會變粗糙。因此，較佳的是將異物移除掉。假如 存在有異物，則特別是在製造偏光板時這些異物會造成色彩 /光學上的不均勻度。同時重要的是異物不會在結合有保護 膜之前黏貼於該聚合物膜上。因此，較佳的是在儘可能減少 其懸浮灰塵的環境內製造偏光板。本發明中所用的異物量額 指的是藉由將黏貼於薄膜表面上的異物重量除以其表面積 1281991 所得到的數値且係表爲每平方米上的公克數。較佳的是其異 物量額係等於或小於1公克/平方米，更佳的是其異物量額 係等於或小於0 · 5公克/平方米。更佳的是具有更小的異物 量額。 用以移除異物的方法並未特別受限，只要能夠在不致對進 行伸展之前的薄膜造成有害影響下移除異物便可以使用任 意一種方法。其實例包含一種藉由噴射水流以掃除異物的方 法，一種藉由氣體噴射作用以掃除異物的方法，以及一種使 用由布或橡膠之類製成的刮刀掃除異物的方法。 <乾燥作用：乾燥速率及乾燥點> 爲了製造一種長形特別是捲軸形式偏光板必須在減少其 揮發性內含物的狀態下黏貼一保護膜。較佳的是該聚合物膜 具有一落在脫離對兩側邊緣的支持之前的乾燥點。更佳的是 ’可調整該乾燥點使得在獲致必要定向角之後的行進距離愈 小愈好。該乾燥點意指該薄膜的表面溫度變成等於環境中之 大氣溫度的點。同時爲了這個理由，較佳的是其乾燥速率愈 高愈好。 <乾燥溫度> 必須使聚合物膜保持乾燥直到與保護膜結合爲止，在使用 聚乙烯醇薄膜製備偏光板的例子裡，較佳的是其乾燥溫度爲 從20到100 °C ’更佳的是其乾燥溫度爲從40到90 °C，又更 佳的是其乾燥溫度爲從6 0到8 5 °C。 <膨脹百分比> 本發明中’當該聚合物膜係一種聚乙烯醇薄膜且使用硬化 1281991 是較佳的是其施加程度係用以使薄膜不致鬆脫。 <伸展作業的溫度> 本發明中，假如在進行伸展時的環境溫度至少高於薄膜內 所含揮發性內含物的皂化點便足夠了。在該薄膜係一種聚乙 烯醇薄膜的例子裡，較佳的是其環境溫度等於或大於25 。在對浸漬於碘/硼酸內之聚乙烯醇薄膜進行伸展以便製造 偏光膜的例子裡，較佳的是其環境溫度爲從3 0到9 0 °C，更 佳的是其環境溫度爲從40到9 (TC。 <伸展作業的溼度> 在對含有水以當作揮發性內含物之薄膜進行伸展的例子 裡，較佳的是在具有溼度調節的大氣中對薄膜進行伸展。特 別是在已分派有硬化劑的例子裡，假如減少所含的水份量額 ，則薄膜會持續硬化而變得很難對薄膜進行伸展。據此，較 佳的是其溼度等於或大於50%，更佳的是其溼度等於或大於 8 0%，又更佳的是其溼度等於或大於90%。 <偏光膜用聚合物膜〉 本發明中，將要進行伸展的薄膜並未特別受限且可以使用 一種包括具有適當熱塑性聚合物的薄膜。該聚合物的實例包 含PVA、聚羰酸酯、丙烯酸酯纖維素及聚磺酸酯。 薄膜在進行伸展之前的厚度並未特別受限，在薄膜支持作 業之穩定度及伸展作業之均勻度的觀點下，較佳的是其厚度 爲從1微米到1毫米，更佳的是其厚度爲從20到200微米 較佳的是該偏光膜用聚合物膜係一種聚醋酸乙酯（PVA )。 1281991 PVA通常係藉由使聚醋酸乙烯酯皂化而得到的，但是可能含 有一種諸如不飽和羧酸、不飽和磺酸、烯烴及乙烯醚之類與 醋酸乙烯酯共聚化的成分。同時也可以使用含有3 -氧丁醯 基、磺酸基、羧基或烯氧基之類的PVA。 PVA的皂化程度並未特別受限，但是在溶解度之類的觀點 下’較佳的是其島化程度爲從8 0到1 0 0莫爾％>，更佳的是其 皂化程度爲從90到100莫爾％。同時PVA的聚合化程度並未 特別受限，但是較佳的是其聚合化程度爲從1，000到10, 〇〇〇 ，更佳的是其聚合化程度爲從1，500到5,000。 <染色配方/方法> 該偏光膜係藉由對PVA進行染色而得到的且其染色步驟 係藉由氣相或液相吸收作用而執行的。至於液相染色法的實 例，當使用碘時係藉由將PVA膜浸漬於水性碘-碘化鉀溶液 內而執行染色的。較佳的是其碘含量爲從〇 . 1到2 0公克/ 公升，較佳的是其碘化鉀含量爲從1到20 0公克/公升且較 佳的是其碘和碘化鉀的重量比例爲從1到200。較佳的是其 染色時間爲從1 0到5 0 0 0秒，且較佳的是其液體溫度爲從5 到60t。其染色方法並非只受限於浸漬法而可使用諸如塗 覆或噴濺碘或染色溶液之類的任意一種機制。該染色步驟可 設置在本發明的伸展步驟之前或之後，不過較佳的是在該伸 展步驟之前以液相執行染色，因爲薄膜會適當地膨脹而有利 於伸展作業。 <硬化劑（交聯）及金屬鹽的添加作業> 在藉由伸展PVA膜而製造偏光模的程序中，較佳的是使用 -36- 1281991 能夠使PVA產生交聯的添加物。特別是當使用本發明的斜角 伸展方法時，假如未在伸展步驟的出口上使PV A充分硬化時 ，則PVA的定向方向可能肇因於步驟中的張力而出現平移。 因此，較佳的是在伸展之前的步驟中或是在伸展步驟中藉由 將PVA膜浸漬於交聯試劑溶液內或是藉由塗覆該溶液使交 聯試劑結合於PVA內。將交聯試劑分派到PVA膜上的機制並 未特別受限，且可以使用諸如於溶劑或水內或是以溶劑或水 進行浸漬、塗覆或噴濺作業之類的任意一種方法，不過較佳 的是浸漬及塗覆法。至於塗覆機制，可以使用諸如捲軸塗覆 器、鑄模塗覆器、桿狀塗覆器、滑動塗覆器及簾幕塗覆器之 類任意一種常用的已知機制。同時較佳的是使用一種帶進蘊 藏有溶液的布、棉或多孔材料使之與薄膜接觸的方法。至於 交聯試劑，可以使用美國專利申請案第US Re23 2897號文件 中所說明的那些交聯試劑，較佳的是實際應用中的硼酸及硼 砂。除此之外也可依組合方式使用諸如鋅、鈷、锆、鐵、鎳 及錳之類的金屬鹽。 在添加了硬化試劑之後，可提供一淸洗/水洗步驟。 可在將薄膜接合到伸展機上之前或之後分派硬化試劑。這 可在如第1和2圖所示之實施例中直到步驟（b )之終點亦即 實質上完成對角方向之伸展作業爲止任一步驟中執行。 <偏光器> 除了碘之外，較佳的是以二色性染料對薄膜進行染色。該 二色性染料的特定實例包含諸如偶氮基染料、芪基染料、吡 唑啉酮基染料、三苯基甲烷基染料、喹啉基染料、噁嗪基染 -37- 1281991 料、噻啶基染料及蒽醌基染料之類的染料型化合物。較佳的 是使用可溶於水的化合物，但是本發明並不受限於此。同時 較佳的是將諸如磺酸基、氨基及羥基之類的親水性取代物引 進這類二色性分子內。該二色性分子的特定實例包含c ·工· 正黃 12、C.I.正橘 39、C.I.正橘 72、C.I.正紅 39、C.I· 正紅 7 9、C · I ·正紅 8 1、C · I ·正紅 8 3、C · I ·正紅 8 9、C · I · 正紫 48、C.I.正藍 67、C.I.正藍 90、C.I.正緣 59、C.I· 酸紅37以及專利申請案第：ίΡ-Α· 62 - 7 0802號、第 JP-A- 1 - 1 6 1 202 號、第；FP-A- 1 72906 號、第 JP-A- 1 - 1 72907 號、第；ΙΡ-Α- 1 - 1 8 3 602 號、第 JP-A- 1 - 248 1 05 號、第 JP-A-1-265205號及第〗Ρ-Α-7 - 261024號文件中所揭示的染 料。使用的有像游離酸、鹼金屬鹽、銨鹽及胺鹽這類二色性 分子。藉由摻合兩種或更多種這類二色性分子，可製造出具 有各種顏色的偏光器。較佳的是藉摻合有在各偏光角呈正交 交叉時用以提供黑色或是摻合有各種二色性分子以提供黑 色之化合物（染料）的偏光裝置或偏光板，因爲同時具有絕佳 之單板透射率及偏光程度的緣故。本發明中除非另外標示， 透射率一詞意指單板透射率。 同時較佳的是將本發明的伸展方法用於所謂聚乙烯撐基 偏光膜的製作，其中係將PVA或聚氯乙烯脫水或去氯以形成 一多烯結構並藉由共軛雙鍵獲致其偏光作用。 <保護膜> 本發明所製造的偏光膜係在將保護膜黏貼於該偏光膜之 一個或兩個表面上之後被用來當作偏光板。該保護膜的種類 - 38- 1281991 並未特別受限，且例如能夠使用諸如醋酸酯纖維素和醋酸酯 丁酸醋纖維素之類的丙烯酸酯纖維素、聚羰酸酯、聚烯烴、 聚苯乙烯及聚酯類。必要的是該偏光板的保護膜具有諸如透 明、適當的透溼性、低雙折射性及適當的剛性之類的性質’ 且從整體觀點較佳的是一種丙烯酸酯纖維素膜且更佳的是 一種醋酸酯纖維素膜。 該保護膜通常係依捲軸形式饋入，且較佳的是連續地黏貼 於長形偏光板上使得其縱軸方向能夠配合。這裡，該保護膜 的定向軸（相位落後軸）可能朝任意方向延伸，但是在簡單及 操作容易度的觀點下較佳的是使該保護膜的定向軸平行於 縱軸方向。 該保護膜的相位落後軸（定向軸）與該偏光膜的吸收軸（伸 展軸）所夾的角度也未特別受限，且可根據偏光板的目的作 適當地設定。本發明之長形偏光板的吸收軸並非平行於縱軸 方向，因此當該保護膜具有平行於縱軸方向的定向軸且係連 續地黏貼於本發明的長形偏光板上時，可獲致一種其偏光膜 的吸收軸和其保護膜的定向軸並非相互平行的偏光板。其偏 光膜及保護膜之結合方式是使偏光膜的吸收軸和保護膜的 定向軸並非相互平行的偏光板具有絕佳的尺度穩定性。特別 有利的是會在將偏光板用於液晶顯示器時發揮這種性能。較 佳的是該保護膜的相位落後軸與該偏光膜的吸收軸所夾的 角度爲從1 0 °到小於9 0 °，更佳的是該保護膜的相位落後軸 與該偏光膜的吸收軸所夾的角度爲從40 °到小於50 °。以這 種角度，可發揮極高的尺度穩定效應。 一 3 9 - 1281991 該保護膜可根據使用端具有任意物理性質數値，且以下將 要說明一種使用正常透射式LCD用保護膜的代表性較佳數 値。在操縱性及持久性的觀點下，較佳的是其薄膜厚度爲從 5到500微米，更佳的是其薄膜厚度爲從20到200微米， 又更佳的是其薄膜厚度爲從20到100微米。較佳的是在 632.8奈米的延遲數値爲從0到150奈米，更佳的是其延遲 數値爲從0到20奈米，又更佳的是其延遲數値爲從0到1 0 奈米，特別較佳的是其延遲數値爲從0到5奈米。從避免其 線性偏極化形成橢圓偏極化，較佳的是該保護膜的相位落後 軸的實質走向係平行或正交於該偏光膜的吸收軸。不過，當 該保護膜分派有諸如相差板之類改變偏光性質的功能時這 是不適用的，且該偏光板的吸收軸可與該保護膜的相位落後 軸夾任意的角度。 較佳的是其可見光透射率等於或大於60%，更佳的是其可 見光透射率等於或大於90%。在以90t處理達120小時之後 ，較佳的是其尺度減小了 〇 . 3到0 . 0 1 %，更佳的是其尺度減 小了 0 . 1 5到0 . 0 1 %。較佳的是在薄膜抗拉測試的抗拉強度 爲50到lOOOMPa，更佳的是其抗拉強度爲100到300Mpa。 較佳的是該薄膜的透溼性爲從100到800公克/平方米•天 ，更佳的是其透溼性爲從300到600公克/平方米•天。 當然，本發明並不受限於這些數値。 以下詳細說明較佳的是以丙烯酸酯纖維素當作該保護膜 。在一種較佳丙烯酸酯纖維素中，其纖維素羥基取代程度會 滿足以下所有的公式（I )到（I V ): 1281991 2.6^ A + B^ 3 . 0 (I) 2·0 S AS 3.0 (II) 0 . 8 (III) 1 · 9<A-B (IV) 其中A和B各代表著用以取代纖維素之羥基的醯基取代程 度，A指的是乙醯基取代程度而B指的是含有3到5個碳原 子之醯基的取代程度。含有落在一個葡萄糖單位內的三個羥 基以及顯示如上數値之纖維素的羥基取代程度的爲3 · 0且 其最大取代程度爲3.0。三醋酸酯纖維素中，一般而言取代 程度A爲從2 . 6到3 . 0 (此例中，未被取代的羥基最大爲 0 . 4 ) B 則爲 0。 用來當作偏光板之保護膜的丙烯酸酯纖維素，較佳的是其 醯基全部都是乙醯基的三醋酸酯纖維素，或是其乙醯基等於 或大於2 . 0、其含3到5個碳原子之醯基等於或小於〇 . 8且 其未被取代之羥基等於或小於0.4的丙烯酸酯纖維素。在物 理性質的觀點下，較佳的是其含3到5個碳原子之醯基等於 或小於〇 . 3。其取代程度可藉著對用以取代纖維素之羥基的 醋酸以及含3到5個碳原子之脂肪酸的量測鍵結程度進行計 算而得到。該量測作業則可藉由根據ASTM D - 8 1 7 - 9 1文件中 的方法加以執行。 除了乙醯基之外，含3到5個碳原子之醯基包含：丙醯基 (CMCO - ) ; 丁醯基（dCO -)及其正-和異-型同分異構物 ;戊醯基（dCO -)及其正_ 、異-、另-、特-型同分異 構物。這當中，在所形成薄膜之機械強度及易於溶解之類白勺 一 41 一 1281991 觀點下，較佳的是正-型取代基且更佳的是正-丙醯基。例 如乙醯基的取代程度很低，則其機械強度及耐溼和耐熱度會 降低。當含3到5個碳原子之醯基的取代程度很高時可強化 其於有機溶劑內的溶解性質，但是當個別的取代程度落在上 述範圍之內時可得到良好的物理性質。 較佳的是丙烯酸酯纖維素的聚合程度（黏度平均）爲從 200到7〇〇，更佳的是其聚合程度爲從250到550。該黏度 平均聚合程度可藉由〇 s t w a 1 d黏度計量測得。由量測得的丙 烯酸酯纖維素內特性黏度[Θ ]，可根據下列公式定出其聚合 程度： DP=[ 7? ] /Km 其中DP指的是其黏度平均聚合程度而Km指的是等於6x 1 (Γ4的常數。 用以當作丙燒酸酯纖維素原料的纖維素包含棉滅和木質 紙槳，但是吾人可以使用得自任何原料纖維素的丙烯酸酯纖 維素同時也可以使用其混合物。 丙烯酸酯纖維素通常係藉由一種溶劑鑄造法製成的。該溶 劑鑄造法中，係將丙烯酸酯纖維素及各種添加物溶解於溶劑 內以製備一濃稠溶液（以下稱爲「膠液」）且在諸如之類無止 境的鼓或帶狀物上進行鑄造並將溶劑蒸發掉以形成薄膜。較 佳的是調整膠液使之具有10到40重量％的固體內含物濃度 。較佳的是修飾該鼓或帶狀物使之具有面鏡表面。該溶劑鑄 造法中的鑄造及乾燥方法可參見美國專利申請案第 2,336,310號、第 2,367,603號、第 2,492,977號、第 1281991 2,492,978 號、第 2,607,704 號、第 2,7 3 9,06 9 號和第 2，7 3 9，070號文件，英國專利申請案第640，731號和第 736,892號文件，以及日本專利申請案第〗P-B-45-4554號 、第 JP-B- 49 - 56 1 4 號、第；FP-A- 60 - 1 7 683 4 號、第 JP-A- 60 - 203430 號、第 JP-A- 62 - 1 1 5 0 3 5 號文件中的說明。 同時較佳的是使用一種用以鑄造兩層或更多層膠液的方 法。在對多層膠液進行鑄造的例子裡’可藉由對含有分別來 自沿著支撐走向之各間隔上所設置複數個鑄造埠之膠液的 溶液進行鑄造使之相互堆疊製成薄膜’且可應用日本專利申 請案第 JP-A-61-158414 號、第 JP-A-1-122419 號、第 JP-A-11-198285號文件中所說明的方法。同時可藉由對來 自兩個鑄造埠之丙烯酸酯纖維素溶液製成薄膜’且這可藉由 日本專利申請案第 1P-B- 60 - 27 5 62號、第】P-A- 6 1 - 94724 號、第 JP-A-61-947245 號、第 JP-A-61-104813 號、第 JP-A- 6 1 - 1 5 84 1 3號和第JP-A- 6 - 1 3493 3號文件中所說明的 方法施行。此外，較佳的是也可以使用日本專利申請案第 JP-A-56-162617號文件中所說明的方法，其中係令高黏度 膠液流包裹有低黏度膠液並同時射出該高黏度及低黏度膠 液。 用以溶解丙烯酸酯纖維素的有機溶劑實例係包含：烴類（ 例如苯和甲苯）；鹵化烴（例如二氯甲烷和氯苯）；醇類（例如 甲醇、乙醇和二甘醇）；酮類（例如丙酮）；酯類（例如乙基乙 酸酯和丙基乙酸酯）；醚類（例如四氫呋喃和甲基溶纖劑）。這 當中，較佳的是含有1到7個碳原子的鹵化烴，且最佳的二 1281991 氯甲烷。在丙烯酸酯纖維素溶解度、支架上可剝除性以及諸 如機械強度及光學性質之類物理性質的觀點下，較佳的是除 了二氯甲烷之外混合有一種或多種含有1到5個碳原子的醇 類。較佳的是在以溶劑爲整體的基礎下其醇‘類含量爲從2 到2 5重量％，更佳的是其醇類含量爲從5到2 0重量％。較佳 的是該醇類的特定實例包含：甲醇；乙醇；正-丙醇；異― 丙醇；和正-丁醇。這當中，較佳的是甲醇、乙醇、正-丁 醇及其混合物。 除了丙烯酸酯纖維素之外，該膠液可能含有任意組成，至 於在乾燥之後變成固體內含物的成分可能是塑化劑、紫外線 吸收劑、無機微細粒子、諸如驗土族金屬鹽（例如錦和鎂） 之類的熱安定劑、抗靜電試劑、阻燃劑、潤滑劑、油劑、支 架脫模催速劑和丙烯酸酯纖維素用水解禁制劑之類。 較佳的是所添加的塑化劑爲磷酸酯或羧酸酯。磷酸酯的實 例包含：三苯基磷酸酯（TPP);三甲苯基磷酸酯（TCP);甲苯 基二苯基磷酸酯；辛基二苯基磷酸酯；二苯基雙苯基磷酸酯 :三辛基磷酸酯；和三丁基磷酸酯。羧酸酯的代表性實例包 含：酞酸酯和檸檬酸酯。酞酸酯的實例包含：二甲基酞酸酯 (DMP);二乙基酞酸酯（EDP);二丁基酞酸酯（DBP);二辛基 酞酸酯（DOP);二苯基酞酸酯（DPP);二乙基己基酞酸酯（DEHP) 。檸檬酸酯的實例包含：三乙基·〇_乙醯基檸檬酸酯（0ACTE ) ;三丁基- ο-乙醯基檸檬酸酯（OACTB);乙醯基三乙基檸檬酸 酯；和乙醯基三丁基檸檬酸酯。 其他羧酸酯的實例包含：丁基油酸酯；甲基乙醯基（順） 一 4 4 一 1281991 蓖麻酸酯；二丁基癸二酸酯；和諸如三甲基徧苯三酸酯之類 的徧苯三酸酯。乙醇酸酯的實例包含：甘油三醋酸酯；甘油 三丁酸酯；丁基酞醯丁基乙醇酸酯；乙基酞醯乙基乙醇酸酯 ;和甲基酞醯乙基乙醇酸酯。 這些塑化劑當中，較佳的是三苯基憐酸酯、雙苯基二苯基 磷酸酯、三甲苯基磷酸酯、甲苯基二苯基磷酸酯、三丁基磷 酸酯、二甲基酞酸酯、二乙基酞酸酯、二丁基酞酸酯、二辛 基酞酸酯、二乙基己基酞酸酯、甘油三醋酸酯、乙基酞醯乙 基乙醇酸酯、和三甲基徧苯三酸酯’更佳的是三苯基磷酸酯 、雙苯基二苯基磷酸酯、二乙基酞酸酯、乙基酞醯乙基乙醇 酸醇、和三甲基徧苯三酸酯。這些塑化劑可單獨使用或是結 合其中兩種或更多種一起使用。較佳的是以丙烯酸酯纖維素 爲基礎的塑化劑添加量額爲從5到30重量％，更佳的是其塑 化劑添加量額爲從8到1 6重量％。可在製備丙稀酸酯纖維素 溶液的同時或是於製備製備期間或之後，將這類化合物與丙 烯酸酯纖維素或溶劑加在一起。 紫外線吸收劑可根據目的自由地選用例如水楊酸酯基 '二 苯甲酮基、苯並三唑基、苯甲酸酯基、氰基丙烯酸酯基及鎳 錯鹽基之類吸收劑。這當中，較佳的是二苯甲酮基、苯並三 唑基和水楊酸酯基之類吸收劑。二苯甲酮基紫外線吸收劑的 實例包含：2,4 -二羥基二苯甲酮；2 -羥基乙醯氧基二苯 甲酮；2 -羥基-4-乙羥氧基二苯甲酮；2 -羥基-4-甲醯氧基二 苯甲酮；2，2，-二羥基-4-甲醯氧基二苯甲酮；2，2’-二羥基 -4, 4’·甲醯氧基二苯甲酮；2 -羥基-4-正辛醯氧基二苯甲酮 -45- 1281991 ;2 -經基-4-十二碳醯氧基二苯甲酮；和2 -經基- 4- (2 -經基 -3 -甲基丙烯氧基）丙氧基二苯甲酮。苯並三唑基紫外線吸收 劑的實例包含：2 - ( 2 ’ -羥基_ 3 ’ -特丁基_ 5，-甲基苯基）_ 5 _氯 苯並三唑；2-(2’-羥基- 5’-特丁基苯基卜苯並三唑；2_(2，_ 淫基- 3’，5’-二特戊基苯基）-苯並三哩；2-(2，-經基-3，5， 二特丁基苯基）-5 -氯苯並三哩；和2-(2，-經基- 5，-特辛基苯 基）-苯並三π坐。水楊酸酯基紫外線吸收劑的眚例包含··苯基 水楊酸酯；對辛基苯基水楊酸酯；和對特丁基苯基水楊酸酯 。這些紫外線吸收劑當中，較佳的是2 -羥基-4 -甲醯氧基二 苯甲酮；2,2’-二羥基-4-甲醯氧基二苯甲酮；2-(2，經基-3，_ 特丁基-5、甲基苯基）-5 -氯苯並三唑；2_(2，·經基。、特丁 基苯基）-苯並三唑；2-(2’_羥基-3’，5，-二特戊基苯基）_苯 並三唑，·和2-(2，-羥基-3’，5’-二特丁基苯基）_5_氯苯並三 口坐0 較佳的是結合複數個具有不同吸收波長的吸收劑一起使 用，因爲如是可跨越很寬的波長範圍得到高防護效應。較佳 的是以丙！1¾酸醋纖維素爲基礎的紫外線吸收劑量額爲從 0 . 0 1到5重量％，更佳的是其紫外線吸收劑量額爲從〇 .丨到 3重量％。吾人可在溶解丙烯酸酯纖維素的同時或是在溶解 之後，將紫外線吸收劑加到膠液內。特別較佳的是，有一種 形式係在進行鑄造之前瞬間使用靜電攪伴器之類將紫外線 吸收劑加到膠液內。 加到丙烯酸酯纖維素內的無機微細粒子，可根據目的自由 地選擇包含下列各項的實例：矽石；高嶺土；滑石；矽藻土 _ 4 6 - 1281991 ;石英；碳酸鈣；硫酸鋇；氧化鈦；和礬土。較佳的是在加 到膠液內之前藉由諸如高速攪拌器、球磨機、磨碎機和超音 波分散器之類任意機制使無機微細粒子分散於黏結劑溶液 內。同時較佳的是，無機微細粒子係連同諸如紫外線吸收劑 之類其他添加物一起分散的。吾人可以使用任意的分散溶劑 但是較佳的是其組成接近膠液溶劑的分散溶劑。較佳的是所 分散粒子的數値平均粒子尺寸爲從0 . 0 1到1 00微米，更佳 的是其數値平均粒子尺寸爲從0 . 1到1 〇微米。吾人可以在 施行用以溶解丙烯酸酯纖維素之步驟的同時加入該分散溶 液或者可在任意步驟中將之加到該膠液內，不過類似於紫外 線吸收劑地較佳的是一種在利用靜電攪拌器進行鑄造之前 瞬間添加分散溶液的形式。 至於支架脫模催速劑，有效的是使用一種界面活性劑，此 界面活性劑並未特別受限且其實例包含磷酸基、磺酸基、羧 酸基、非離子式及陽離子式的界面活性劑。這類界面活性劑 可參見日本專利申請案第JP-A- 6 1 - 243 83 7號文件中所說明 的。 在將丙烯酸酯纖維素膜用於保護膜的例子裡，較佳的是藉 由皂化作用、電暈處理、火焰處理、輝光放電處理及鹼皂化 處理之類處理法將親水性分派到薄膜表面上以便強化PVA 型樹脂上的黏著性質。同時吾人也能夠將親水性樹脂分散到 對丙烯酸酯纖維素具有親和性的溶劑內並塗覆該溶液以形 成一薄層。這類機制當中，較佳的是進行皂化處理因爲此機 制不致妨礙薄膜的平坦度及物理性質。吾人係藉由將薄膜浸 -47 - 1281991 漬於諸如荷性鹼之類的鹼性水溶液內而執行皂化處理。在該 處理之後，較佳的是以低濃度的酸進行中和並以水進行完整 的淸洗以移除過剩的鹼液。 特別將當作丙烯酸酯纖維素薄膜之較佳表面處理所用的 鹼皂化處理說明如下。較佳的是這種處理係藉由一種將該丙 烯酸酯纖維薄膜表面浸漬於鹼性溶液內、以酸性溶液進行中 和、進行水洗然後再爲薄膜進行乾燥的循環而執行的。該鹼 性溶液的實例包含氫氧化鉀溶液及氫氧化鈉溶液。較佳的是 該氫氧離子的當量濃度爲從0.1到3. ON，更佳的是其當量 濃度爲從0 · 5到2 . 0N。較佳的是該鹼性溶液的溫度爲從室 溫到9 0 °C，更佳的是其溫度爲從4 0到7 0 °C。然後一般而言 以水進行淸洗且在通過一酸性水溶液之後再次以水進行淸 洗以獲致經表面處理的丙烯酸酯纖維素薄膜。這裡所用酸類 的實例包含氫氯酸、硝酸、硫酸、醋酸、蟻酸、氯化醋酸和 早酸。較佳的是該等酸類的濃度爲從〇·〇1到3.0N，更佳的 是其濃度爲從0.05到2·0Ν°在使用丙烯酸酯纖維素薄膜當 作偏光板之透明保護膜的例子裡，較佳的是在偏光膜之黏著 性的觀點下執行酸處理及鹼處理亦即用於丙稀酸酯纖維素 的皂化處理。 如Realize Sha於「潤溼法的基礎及應用（Basis and1281991 发明, invention description....................A··-·'· ;,- (The description of the invention should be stated: the technical field, prior art, content, BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a long polarizing plate, thereby obtaining a polarizing plate having excellent polarizing performance at a high yield; a method of manufacturing the polarizing plate and a liquid crystal display . (2) Prior art The popularity of liquid crystal display devices (hereinafter referred to as "L C D") has drastically increased the demand for polarizing plates. In general, the polarizing plate comprises a polarizing layer having a polarizing property and a protective film adhered to one or both surfaces of the polarizing layer through an adhesive layer. The material used for the polarizing film is mainly polyvinyl alcohol (hereinafter referred to as "PVA"). The PVA film is uniaxially stretched and then dyed with iodine or a dichroic dye, or stretched after dyeing, and the film is further crosslinked with a boron compound to form a polarizing film for the polarizing layer. For the protective film, triacetate cellulose is mainly used because the film is optically transparent and has low birefringence. The polarizing film is usually formed by uniaxially stretching a continuous film in the extending direction (longitudinal axis direction), and therefore the absorption axis of the polarizing film is usually almost parallel to the longitudinal axis direction. In the conventional LCD, the polarizing plate is arranged such that its absorption axis is inclined by 45° with respect to the vertical or horizontal axis of the image plane, and must be in the direction of 45° with respect to the longitudinal axis of the reel in the punching step. A hole is made for making a polarizing plate in the form of a reel. However, if the polarizing plate is perforated along the 45° direction, an unusable portion will be produced near the edge of the reel -7-1281991, especially in the case of a large-sized polarizing plate, the yield is lowered, and the result is disadvantageously Increased its wear and tear. In order to prevent the coloring effect or to initiate the optical compensation-effect such as widening the viewing angle, the phase difference film is also used by sticking it to the polarizing plate for forming the LCD, and the orientation axis is required. It is set at various angles with respect to the transmission axis direction of the polarizing plate. Conventionally, a method of cutting a phase difference film from a film that is uniaxially stretched along the longitudinal axis is used, by cutting the circumference such that its orientation axis is at a predetermined inclination angle with respect to its side, and is similar to polarized light. There is a problem with the yield reduction of the board. Further, when another optical member such as a 1/4 wave plate is pasted, such a member must be attached to each of the panels and the procedure is troublesome. In addition to this, there is a need for a manufacturing method in which a plurality of films are laminated and the angle thereof is strictly controlled, and light leakage due to the sliding of the angle causes the color of the black portion to become yellow or blue. Therefore, it is necessary to perform the reel-to-reel adhesion. 〇 In order to solve the above problems, several methods have been proposed in which the orientation axis of the polymer is inclined by a necessary angle with respect to the film conveyance direction (longitudinal axis direction). The patent application No. JP-A- 20 00 - 9 9 1 2 (where "JP-A" means "unpublished patent application") describes a kind of horizontal axis along the horizontal axis. Or the uniaxial stretching technique of the plastic film in the longitudinal direction, by changing the stretching rate between the right side and the left side in the extending direction, so that the film is tensile in the direction of the longitudinal or transverse axis different from the above extending direction stretch. However, according to this method, in the case of using, for example, a cloth machine system, it is necessary to change the conveying speed between the right side and the left side and this may cause pulling, wrinkling or film sliding, and it is difficult to obtain the necessary Inclination (with polarizer 4 5 . angle). In order to reduce the rate difference between the right and left sides, the stretching step must be lengthened and the cost of the equipment can be greatly increased. A film manufacturing method is disclosed in Japanese Patent Application Laid-Open No. JP-A-A No. No. 8-8270, by using a mechanism to cause the stretching axis to fall at any angle with respect to the direction in which the film extends. A plurality of transverse pair of film support points each having an angle Θ with respect to the extending direction of the film are disposed on both side edges of a continuous film, and each pair of support points can extend the film toward the 随着 direction as the film extends . At the same time, in this method, since the traveling speed of the film differs between the right side and the left side, pulling or wrinkling may occur on the film, and in order to relieve this phenomenon, the stretching step must be lengthened to increase the device. The problem of cost. Japanese Patent Application Laid-Open No. JP-A-2 - 1 1 3 9 2 0 discloses a film manufacturing method in which a film is stretched to grasp its two edges between two aligned columns of forks. Extending along the track of each of the deployed cloth machines, the film is stretched diagonally in the machine direction so that the forks extend a different distance within each predetermined extension. At the same time, in this method, pulling or wrinkling occurs in the oblique stretching action, which is disadvantageous to the optical film. A polarizing plate disclosed in Korean Unexamined Patent Publication No. P-2001-005184 has a tilting of its transmission axis by a rubbing treatment. However, as is well known, the effect of adjusting its orientation by friction is only effective in the region from the surface of the film to the portion of the most nano-scale portion and cannot be satisfactorily such as iodine or dichroic dyes. The class of polarizers performs the -9-1281991 positioning, and the result is unfavorable in that the polarization performance is poor. In the conventional method of stretching the film in the direction of the longitudinal axis of the reel, as the stretching strength of the film becomes larger, the edge of the film wraps more when the film is stretched at a high stretching ratio. This causes the film to rupture and is difficult to operate in the stretching step. In addition, the stretching operation using the multi-stage stretching method can be performed on the edge of the reel such as the control of the reel or on the edge portion of the reel film. Difficulties encountered in manipulating operations such as shrinkage and bending control. (III) SUMMARY OF THE INVENTION An object of the present invention is to provide a long-sleeve polarizing plate comprising a polarizing film which is obliquely stretched, and which can improve the yield in the step of punching out the polarizing plate. Another object of the present invention is to provide a high quality and inexpensive scroll type polarizing plate which has excellent flatness and is hard to be damaged by external light. It is still another object of the present invention to provide a high-grade and inexpensive long polarizing plate having a working width (effective width) of 650 mm or more, including the ability to improve the yield in the step of punching out the polarizing plate. An obliquely stretched polarizing film. A further object of the present invention is to provide a method for manufacturing the above polarizing plate, and a liquid crystal display using the same. As a result of intensive research on the mechanism for achieving the above object, the inventors of the present invention have found a method of obtaining oblique angle orientation without causing pulling, wrinkling or film sliding, and thus a long length can be prepared. The polarizing plate is shaped and a polarizing plate in the form of a reel can be produced. The elongated polarizing plate was rolled at an angle of -1 0 - 1281991. Another feature of the polarizing plate according to the present invention is that the transmittance of the veneer at 550 nm is equal to or greater than 35% and the degree of polarization at 550 nm is equal to or greater than 80%. Preferably, the veneer transmittance is equal to or greater than 40% and the degree of polarization is equal to or greater than 95.0%, more preferably the degree of polarization is equal to or greater than 99%, and particularly preferably the degree of polarization is equal to Or greater than 99.9%. The polarizing plate according to the present invention has excellent veneer transmittance and degree of polarizing plate, and thus the contrast can be advantageously improved when a liquid crystal display is used. The angled directional polarizing plate according to the present invention can be easily obtained by a person by the following method. That is, the oblique orientation is achieved by stretching a polymer film, and at the same time, the percentage of volatile inclusions in the film stretching operation, the percentage of shrinkage during film shrinkage operation, and the stretching of the film are designed. The previous modulus of elasticity. It is also preferred to control the amount of foreign matter adhered to the film prior to stretching. The polarizing plate according to the present invention can be used in various applications, but because of the advantageous property of its directional axis being inclined with respect to the longitudinal axis direction, it is particularly preferable to use the inclination angle of the orientation axis with respect to the longitudinal axis direction. From 40 ° to 50. The polarizing film is used as a polarizing plate for an LCD (having all liquid crystal modes such as TN, STN, OCB, ROCB, ECB, CPA, IPS, and VA) or a rotating polarizing plate for an anti-reflective electromechanical display. Further, the polarizing plate according to the present invention is also suitable for use in combination with various optical members such as a phase difference mode such as a 1/4 wave plate and a 1/2 wave plate, a viewing angle magnifying film, an anti-glare film, and Hard coating. In the present invention, the reel form is sufficient if the length of the reel is equal to or greater than 1 m and the number of turns is equal to or -16-1281991 is greater than three. It is preferred to have a larger length, but if the length is too large, the weight of the reel is excessively increased. Therefore, it is preferable that the length thereof is equal to or less than 10, 〇 〇 〇. It is preferable to have a larger number of turns such as equal to or greater than 10 turns. As the inner diameter of the reel becomes smaller, the number of rolls becomes larger. However, it is preferred that the inner diameter is not too small because of the curling behavior. Preferably, the inner diameter is equal to or greater than 1 inch. The width is not particularly limited, but if its width is too small, its reel form is destroyed. Therefore, it is preferable that the width is equal to or greater than 5 cm. In the forming operation of the reel, a core structure can be used. The construction material of the core structure is not particularly limited, and any material commonly used in the industry such as paper, iron, and aluminum can be used. In the present invention, it is important to increase the length in the longitudinal direction of the reel when forming the reel. For this purpose, it is important to control the percentage of volatile inclusions in the film stretching operation, control the percentage of shrinkage during film shrinkage, control the rate of transport in the direction of the longitudinal axis, and control the drying of the film. The point 'controls the amount of foreign matter adhered to the film before stretching, controls its temperature and humidity during film stretching, and controls its drying temperature during drying to reduce its volatile content. The film stretching method will be explained below, in which important portions are individually explained. The term "destruction of light due to light outside the storage period" as used in the present invention means the degree of polarization of the undulation under the light exposed to the storage conditions, for example, when exposed to light such as a fluorescent lamp or a white heat lamp. . In general, it is easy to increase the degree of polarization when exposed to light. In the polarizing plate according to the second embodiment of the present invention, the working width of -17 - 1281991 perpendicular to the longitudinal axis direction is equal to or greater than 650 mm, preferably equal to or greater than 1,300 mm. It is possible to easily obtain a polarizing plate having an oblique angle according to the second embodiment of the present invention by explaining the following method. That is to say, by stretching a polymer film to obtain an oblique angle orientation, the tension of the polymer film for the polarizing film in the stretching operation along the longitudinal axis direction and the environmental humidity during the stretching operation are optimized, and the dyeing operation is also performed. The percentage of water content of the polymer film for the polarizing film is optimized, and the percentage of expansion after the stretching and dyeing operation is lower than the percentage of expansion before the stretching operation. At the same time, it is preferred to control the amount of foreign matter adhered to the film before stretching, and in the dyeing step, the dyeing and hardening of the film can be performed simultaneously. In order to obtain a wide polarizing plate having a working width equal to or greater than 65 mm in the present invention, it is particularly important to optimize the following conditions: the percentage of water content after the dyeing operation, and the tension of the film along the longitudinal axis during the stretching operation. And ambient humidity, as well as the percentage of expansion after stretching. The important parts of the individual will be explained below. <Working Width> The working width used in the present invention means a width in a direction perpendicular to the longitudinal direction of the polarizing plate in the form of a reel which is stretched and dried by a polymer film for a polarizing film. As a result, a protective film is usually adhered and then the edges are cut to join. The polymer film for polarizing film was bonded to each of the sheets, and the unstretched joint width was continuously retained at the edges of the films. The joint width portion has not only the polarizing property but also the inability to adhere to the protective film. Therefore, the joint width portion is cut, but in this example, as the width of the edge of the cut edge - 18 - 1281991 becomes larger, the working width which can be regarded as the polarizing plate is further reduced. In the present invention, it is preferred that the width of the cut edge is equal to or less than 10% of the film width after the stretching operation, more preferably equal to or less than 5%, and more preferably equal to or less than 3%. . The working width of the polarizing plate of the present invention is equal to or greater than 650 mm and preferably equal to or greater than 1300 mm, so that the percentage of the width of the cut edge can be reduced to fall within the above range, and the polarizing film is increased. The percentage of the portion available in the polymer film is used and the cost of the polarizing plate is reduced. <Humidity in stretching operation> If the humidity in the stretching operation is insufficient, it is not possible to stretch the film and cause malfunction of the cloth machine. On the other hand, when the humidity in the stretching operation is high, the phenomenon such as the deterioration of the polarizing performance is not caused and the stretching is easy, so this is very effective. At the same time, in the case of stretching a film containing moisture as a volatile component such as polyvinyl alcohol and acrylate cellulose, it is of course possible to stretch the film in a high humidity-conditioned atmosphere. In the case of polyvinyl alcohol, it is preferred that the humidity is equal to or greater than 50%, more preferably the humidity is equal to or greater than 80%, or even more preferably, the humidity is equal to or greater than 90%. <Tensile in the direction of the longitudinal axis> In the step of joining, stretching, and drying the film, tension is continuously applied along the longitudinal axis direction. If the tension at the time of joining is insufficient, the joint width is reduced and the film is detached from the support mechanism during stretching. Therefore, if the tension is too strong, not only the film cannot ride on the support mechanisms but also cannot be joined. Moreover, the joint width portion may disadvantageously curl after bonding to the film -19-1281991. In the present invention, it is preferred to stretch and dry the film and take out the film while applying a constant tension along the longitudinal axis of the film. In the present invention, it is preferred to maintain the film in a compact state when supporting the both side edges of the film by a support mechanism to facilitate its support. A particular embodiment of the method includes a method of applying tension to the longitudinal axis of the tension controller to subject the film to tension. This tension will vary depending on the type of polymer film and the rate of transport along the longitudinal axis of the film. The preferred tension refers to a tension which provides a state in which the edge of the film which is dropped on the transport reel immediately before joining is repeatedly brought into contact with or lifted up by the film. Preferably, the tension is from 100 to 500 Newtons/meter, and more preferably the tension is from 350 to 450 Newtons/meter. <Percent Volatile Contents> When the paths on the left and right sides become different in the stretching step, the film wrinkles and slips. In order to solve these problems, it is an excellent aspect of the present invention to reduce the polymer film by allowing a volatile inclusion equal to or greater than 5% to occur before stretching to maintain its supporting properties, and then shrink the film to reduce Its percentage of volatile inclusions. The percentage of volatile content used in the present invention means the volume of the volatile component contained in the film per unit volume and refers to the number obtained by dividing the volume of the volatile component by the volume of the film. In the present invention, it is preferred to provide at least one step for bonding a volatile inclusion before stretching the polymer film for a polarizing film. The step of combining the volatile contents is carried out, for example, by casting the film and combining it with a solvent or water' or by dipping, coating or spraying in a solvent or water or in a solvent or water. The staining step will be later <Staining Formulation/Method - 2 0 _ 1281991 > and <Addition of Hardener and Metal Salt > The step of adding a hardener described in the section can play a role in the step of combining the volatile inclusions. In the case where the dyeing step simultaneously plays the role of the step of incorporating the volatile inclusions, it is preferred to provide the dyeing step before or after stretching. The dyeing step and the stretching step can be performed simultaneously when the dyeing step is provided before the stretching is performed. The preferred percentage of volatile inclusions will vary depending on the type of polymeric film. The maximum enthalpy of the percentage of volatile inclusions may be any number as long as the polymer film retains its supporting properties. Preferably, the percentage of volatile content is from 10 to 100% for polyvinyl alcohol and from 10 to 200% for acrylate cellulose. <Distribution of Volatile Component Contents> In an example in which a long, particularly reel-shaped, polarizing plate is produced by an intermediate step, it is necessary that no uneven dyeing or undyed color occurs. Point. For example, the volatile components in the film have an uneven distribution before the stretching (the amount of volatile components depends on the difference in the position in the plane of the film), which may cause uneven dyeing or unsuccessful The point of staining. Accordingly, it is preferred that the distribution of the volatile component content before the film is internally stretched is relatively small, and it is preferred that the distribution be at least equal to or less than 5%. The distribution of the volatile component content refers to the difference between the maximum or minimum enthalpy of the volatile content percentage and the percentage of the average volatile content, relative to the volatile inclusions defined above. Percentage of the percentage of the average volatile content of the percentage. In order to reduce the distribution of the volatile component content, it is possible to use a uniform air to the front or back -21 - 1281991 film of the film to be dried. Preferably, the moisture content percentage is equal to or less than 50% at the instant after stretching, and more preferably, the water content percentage has a higher reduction rate. The polarizing film is then dried and pasted to protect the film, and at this time, it is preferred that the percentage of water content is equal to or less than 10% and more preferably the percentage of water content thereof is equal to or less than 5%. The percentage of water content used in the present invention means the volume of water contained in the film per unit volume and refers to the number obtained by dividing the volume of the water content by the volume of the film. The percent water content distribution used in the present invention refers to the difference between the maximum or minimum enthalpy of the percentage of water content and the percentage of the average water content, relative to the average of the diagonal direction of the film along the reel form. The percentage of water percentage. For example, when the minimum enthalpy of the water content on both sides of the film is 44.0% and the maximum enthalpy is 44.5%, the water content percentage distribution is 0.5%. In the present invention, it is preferred that the water content percentage distribution is equal to or less than 20%, more preferably, the water content percentage distribution is equal to or less than 10%, and more preferably, the water content percentage distribution is equal to or less than 5%. . Preferably, after the dyeing step of the polarizer and the hardener of the present invention is performed, the percentage distribution of the water content of the polymer film can be made relatively small, because if the water content percentage distribution is large, unevenness is generated. Degree and marking. <Intermediate Step> In the present invention, it is preferred to provide a drying step for shrinking the stretched polymer film to reduce the percentage of its volatile content, and to adhere the protective film to the film after or during the drying operation a post-film thermal step after at least one surface of the polarizing plate. A specific example of the method for adhering the protective film includes a method of adhering a protective film to the polarizing film and then cutting both side edges thereof using a 1281991 adhesive while maintaining both side edges of the polarizing film in a state of being supported during the drying step. And a method of demolding the polarizing film from the edge supporting portions on both sides after drying, cutting both sides of the film and adhering the protective film thereto. In order to cut off the edges, a general technique can be used, such as a method of cutting an edge using a cutter such as a edge cutter or a method using a laser. Preferably, the composite film is subjected to post-heating to dry the adhesive and improve its polarizing properties. The post-heating condition will vary depending on the adhesive', but in the case of the aqueous adhesive, it is preferred that the heating temperature is equal to or greater than 30 ° C, and more preferably the heating temperature is from 40 to 100. °C, and more preferably from 50 to 80 °C. It is preferred to perform these steps in an intermediate production line from the standpoint of performance and production efficiency. In the method for producing a polarizing film of the present invention, it is possible to easily obtain the bevel-oriented polarizing plate according to the present invention by explaining the following method. That is, the oblique orientation is achieved by stretching a polymer film, and at the same time, the volatile inclusion distribution and the percentage of volatile inclusions before the film stretching operation are designed, and the stretching operation is performed. Stretching the atmosphere such as stretching temperature and stretching humidity. It is also preferred to control the amount of foreign matter adhered to the film prior to stretching. With these, even when the bevel is stretched, a long, graded and inexpensive long polarizing plate can be obtained without causing pulling or wrinkling on the stretched film. In the method for producing a polarizing film of the present invention, both side edges of the film for a polarizing film are supported by a supporting mechanism, and thus it is difficult to stretch the film in a solution as in the usual polarizing plate manufacturing mechanism. Accordingly, it is preferred to stretch the film at a wet application temperature of -24 to 128, 1991 after the film is immersed in the dyeing solution, the hardening solution, or both. Preferably, the stretching temperature of the stretching atmosphere is 〇 00 C and the degree of lust is equal to or greater than 7 %, more preferably the stretching temperature is 4 Torr to 50 t and the humidity is 80% or more. However, under such conditions, the distribution of the Itc color solution or the hardened solution solution may occur on the surface of the film before stretching. This distribution causes the polarizing film to produce an unevenness after stretching. In order to prevent such unevenness, it is important that the present invention provides a state in which the content of the dyeing solution or the hardening solution, i.e., the volatile component in the film, before the stretching of the film is equal to or less than 5%. The method of stretching will be explained as follows, and the individual important items will be explained later. <Extension Method> Figs. 1 and 2 are schematic plan views showing an example of a method for obliquely stretching a polymer film according to the present invention. The stretching method of the present invention comprises the steps of: (a) introducing an organic film in the direction of the arrow (i); (b) the step of stretching the film in a diagonal direction, (c) along the arrow (ii) The direction transports the stretched film to the next step. The term "extension step" below refers to the steps comprising steps (a) through (c) and is used to indicate the complete steps for performing the stretching method of the present invention. The film is continuously introduced from the (i) direction and is initially supported at point B1 by a support mechanism that falls on the left side as seen from the upstream. At this point, the other side of the film is not supported and does not create tension in the diagonal direction. In other words, point B1 refers to a point that is not essentially supported (hereafter referred to as "physical support starting point"). -25- 1281991 In the present invention, the substantial support starting point is defined as the point at which the edges of the film are initially supported. The substantial starting point of support comprises two points, that is to say, the support starting point A 1 falling on the downstream side and the center line 1 1 (Fig. 1) or 2 on the introduction side which is almost perpendicular to the film. 1 (Fig. 2) The point C1 at which the straight line drawn from point A1 intersects the trajectory 1 3 (Fig. 1) or 23 (Fig. 2) of the supporting mechanism on the opposite side. From these points, when the film is transported at a substantially equal rate by the support mechanism falling on the side edges, point A 1 will move to point A2 'A3, ... An every unit time, and the same location C1 will Move to points C2, C3, ... Cn. That is to say, the straight line connecting the points An and Cn which are simultaneously passed by the respective support mechanisms as the base refers to the extending direction at that moment. In the method of the present invention, as shown in Figs. 1 and 2, the point An gradually appears to be delayed from the point C η and thus its extending direction is gradually inclined from the direction perpendicular to the conveying direction. In the present invention, a point substantially deviated from support is defined by two points (hereinafter referred to as "substantial support disengagement point"), and one of the two points refers to a point at which the film is separated from the support mechanism on the more upstream side. Cx, another point refers to the straight line and the opposite side drawn from the point Cx in a manner almost perpendicular to the film center line 1 2 (Fig. 1) or 2 2 (Fig. 2) being transported to the next step. The trajectory of the support mechanism 1 4 (Fig. 1) or 2 4 (Fig. 2) intersects the point Ay. The angle of the final extension direction of the fl. Wu is by the substantial endpoint of the stretching step (substantial support disengagement point) The path difference between the left and right support mechanisms Ay-Αχ (ie | L1-L2 | ) depends on the ratio of the distance W between the substantial support points (ie the distance between Cx and Ay) Out. Accordingly, the inclination angle 0 of the extension direction of -26-1281991 with respect to the conveying direction to the next step satisfies the following relationship: t an 0 = W / ( Ay - Αχ ), that is, t an 0 = W / I LI-L2 | The edge of the film that falls on the top of Figures 1 and 2 will be supported until point i 8 (Fig. 1) or 28 (Fig. 2) or even after point Ay, but the other edge is not supported. Therefore, it does not create a new stretching effect in the diagonal direction. Therefore, 'points 18 and 28 are not substantial support points for disengagement. The substantial support starting point appearing on both sides of the film in the present invention refers to the point on the film that only engages the respective left and right support mechanisms. For a more rigorous description of the two substantial support starting points defined above in the present invention, these points are defined to be used to connect the left or right support point and another support point to the film centerline of the introduced film support step. An orthogonal point and refers to two support points positioned at the most upstream. Similarly, in the present invention, two substantial support detachment points are defined to be used to connect the left or right support point and another support point is substantially orthogonal to the film center line being transported to the next step, and refers to It is the two support points that are positioned at the most downstream. The term "almost orthogonal" as used herein means that the centerline of the film is at an angle of 90 ± 0.5 ° with a straight clip for connecting the left or right substantial support starting point or the substantial support breaking point. In the example of giving the left and right path differences by the stretching system of the present invention, the point of engagement with the support mechanisms and the substantial support will be due to mechanical constraints such as the length of the track. I Ll - L2 | is made larger between the starting points or with each of -27-1281991 by providing a film shrinking step after the film is stretched once. Preferably, the stretching ratio is from 1.1 to 1 〇. 〇 times, and more preferably, the stretching - the ratio is from 2 to 10 times. Preferably, the percent shrinkage after that is equal to _ · or greater than 10%. Further, as shown in Fig. 4, it is preferable to repeat the stretching-contracting operation a plurality of times because I Ll - L2 | can be made larger. From the standpoint of minimizing the cost of equipment used in the stretching step, it is preferable to make the number of bends in the support mechanism trajectories and the bending angle thereof smaller. According to this point of view, as shown in Figures 2, 3 and 5, it is preferred to bend the film in the direction in which the edges of the film are supported, so that the step of supporting the both sides of the film can be exited. The angle between the direction of travel of the film and the substantial direction of extension of the film is inclined by 20 to 70 degrees. In the present invention, it is preferable that the film stretching device which applies tension under the side edge supporting the rain refers to a cloth stretching machine as shown in Figs. In addition to the conventional two-dimensional cloth stretching machine, a stretching step as shown in Fig. 6 can also be used to give a spiral path difference between the gripping mechanisms of the both side edges. • In many cases, the stretcher is constructed with a solid clip chain that runs along the track. However, when a vertical non-uniform stretching method is used as in the present invention, the end terminal of a track as shown in Fig. 1 is offset from the end terminal of a track at the entrance and exit of the stretching step. It is opened and it is not possible to engage and disengage between the left and right edges at the same time. In this example, the substantial path lengths L 1 and L2 are not simply joined to the disengagement distance, but as explained above, the path length between the support mechanisms for supporting the two sides of the film is as described above. -29- 1281991 Wrinkles or slippage may occur if the film travel rate between the left and right edges of the exit of the stretching step is different. Therefore, a film clamping mechanism on the left and right sides is required to transport the film at substantially the same rate. Preferably, the rate difference is equal to or less than 1%, more preferably the rate difference is equal to or less than 0.5%, and most preferably, the rate difference is equal to or less than 0.05%. The rate used here means the length of the trajectory per minute for each of the left and right support mechanisms. In a machine such as a general stretcher, depending on the period of the sprocket to drive the chain and the frequency of the drive motor, a rate equal to or less than a few seconds is generated in rate and often equals Or less than a few percent unevenness, but this is not included under the rate difference referred to in the present invention. <Transport rate in the direction of the longitudinal axis> In the case of stretching the polyvinyl alcohol film to which the curing agent is dispensed, the film hardening operation proceeds as the stretching time elapses. Therefore, it is preferred that the conveying rate along the longitudinal axis of the polymer film is equal to or greater than 1 m/min. From a productivity point of view, it is preferred to have a higher vertical axis transport rate. In any case, the upper limit of the vertical axis transport rate will vary depending on the stretched film and the stretching machine. <Shrinkage> The shrinkage action can be performed on the stretched polymer film during or after stretching. The shrinkage effect is sufficient if the wrinkling phenomenon caused by the orientation of the polymer film in the oblique direction can be excluded. In order to shrink the film. A film heating method can be used and thus its volatile components can be removed, but any mechanism can be used if the film can be shrunk. It is preferable that the shrinkage ratio of the film -30 - 1281991 is equal to or greater than 1 / s i η θ, where 0 means a directional angle with respect to the longitudinal axis direction. It is preferred that the percentage of shrinkage is equal to or greater than 1%. <Percent Volatile Content > When the left and right paths become different, the film may wrinkle or slip. In order to solve such problems, the present invention is characterized in that the polymer film is stretched and then shrunk to reduce its volatile content percentage while maintaining its supporting properties and allowing 5% or more of volatile inclusions to occur. The percentage of volatile inclusions used in the present invention means the volume of volatile components contained in the film per unit volume and refers to the number obtained by dividing the volume of the volatile component by the volume of the film. An example of a method of combining volatile inclusions comprises a method of casting a film and combining it with a solvent or water, a method of impregnating, coating or spraying in a solvent or water or in a solvent or water prior to stretching. And a method of coating with solvent or water during stretching. A hydrophilic polymer film such as aqueous polyvinyl alcohol in a high-temperature and high-humidity atmosphere can be stretched by humidity adjustment in a high-humidity atmosphere or by stretching the film under high humidity conditions. Combined with volatile inclusions. In addition to these methods, any mechanism can be used if the volatile content of the polymer film can be made equal to or greater than 5%. The preferred percentage of volatile inclusions will vary depending on the type of polymeric film. The maximum enthalpy of the percentage of volatile inclusions can be any number as long as it can maintain its supporting properties. Preferably, the percentage of volatile inclusions is from 10 to 100% for polyethene alcohol and from 10 to 200% for acrylate cellulose. <Elastic Modulus> - 3 1 _ 1281991 As for the physical properties of the polymer film before stretching, if its elastic modulus is too low, the percentage of shrinkage during or after stretching is reduced and it is difficult to make The wrinkling phenomenon disappears; and if the elastic modulus is too high, a great tension is applied during stretching, and as a result, the strength for supporting the portions on both side edges of the film must be increased and the load on the machine is increased. In the present invention, it is preferred that the elastic modulus (expressed in Young's modulus) of the polymer film before stretching is from 0.1 to 500 MPa, and more preferably the elastic modulus is from 1 to 100 MPa. <Distance from the occurrence of the creping phenomenon to the disappearance> It is sufficient if the wrinkle phenomenon caused by the orientation action in the oblique direction of the polymer film before the point of substantially supporting the break point in the present invention can be eliminated. However, if the time taken from the occurrence of the wrinkling phenomenon to the disappearance is too long, dispersion may occur in the stretching direction. Therefore, it is preferable that the wrinkles disappear in the traveling distance where the amount is as short as possible from the point at which wrinkles occur. For this purpose, for example, a method for increasing the rate of volatilization of its volatile contents can be used. < Foreign matter> In the present invention, if foreign matter adheres to the polymer film before stretching, the surface thereof becomes rough. Therefore, it is preferred to remove the foreign matter. If foreign matter is present, these foreign matter may cause color/optical unevenness particularly when the polarizing plate is manufactured. It is also important that foreign matter does not adhere to the polymer film prior to bonding with the protective film. Therefore, it is preferred to manufacture the polarizing plate in an environment where the suspended dust is minimized. The amount of the foreign matter used in the present invention refers to the number obtained by dividing the weight of the foreign matter adhered to the surface of the film by the surface area of 1281991 and is expressed in grams per square meter. Preferably, the amount of foreign matter is equal to or less than 1 g/m2, and more preferably, the amount of foreign matter is equal to or less than 0.5 g/m2. More preferably, it has a smaller amount of foreign matter. The method for removing foreign matter is not particularly limited as long as it can remove foreign matter without causing harmful effects on the film before stretching. Examples thereof include a method of sweeping a foreign matter by spraying a water stream, a method of sweeping a foreign matter by a gas jet, and a method of sweeping a foreign matter using a doctor blade made of cloth or rubber. <Drying action: drying rate and drying point> In order to manufacture an elongated shape, particularly a reel type, the polarizing plate must be adhered to a protective film while reducing its volatile content. Preferably, the polymeric film has a drying point that falls before the support is removed from the edges on both sides. More preferably, the dry point can be adjusted such that the smaller the travel distance after obtaining the necessary orientation angle, the better. The drying point means a point at which the surface temperature of the film becomes equal to the atmospheric temperature in the environment. Also for this reason, it is preferred that the drying rate is as high as possible. <Drying Temperature> The polymer film must be kept dry until it is combined with the protective film. In the case of preparing a polarizing plate using a polyvinyl alcohol film, it is preferred that the drying temperature is from 20 to 100 ° C. The drying temperature is from 40 to 90 ° C, and more preferably the drying temperature is from 60 to 85 ° C. <Percent expansion> In the present invention, when the polymer film is a polyvinyl alcohol film and hardening 1281991 is used, it is preferable that the degree of application is such that the film is not released. <Temperature of stretching operation> In the present invention, it is sufficient if the ambient temperature at the time of stretching is at least higher than the saponification point of the volatile content contained in the film. In the case where the film is a polyvinyl alcohol film, it is preferred that the ambient temperature is equal to or greater than 25. In the case of stretching a polyvinyl alcohol film immersed in iodine/boric acid to produce a polarizing film, it is preferred that the ambient temperature is from 30 to 90 ° C, and more preferably, the ambient temperature is from 40. To 9 (TC. <Humidity of Stretching Operation> In the case of stretching a film containing water as a volatile inclusion, it is preferred to stretch the film in an atmosphere having humidity adjustment. In particular, in the case where a hardener has been assigned, if the amount of water contained is reduced, the film will continue to harden and it becomes difficult to stretch the film. Accordingly, it is preferable that the humidity is equal to or greater than 50%, more preferably, the humidity is equal to or greater than 80%, and more preferably, the humidity is equal to or greater than 90%. <Polymer film for polarizing film> In the present invention, the film to be stretched is not particularly limited and a film comprising a suitable thermoplastic polymer can be used. Examples of the polymer include PVA, polycarboxylate, acrylate cellulose, and polysulfonate. The thickness of the film before stretching is not particularly limited, and from the viewpoint of the stability of the film supporting operation and the uniformity of the stretching operation, it is preferably from 1 μm to 1 mm in thickness, more preferably in the thickness thereof. It is preferable that the polymer film for a polarizing film is a polyvinyl acetate (PVA) from 20 to 200 μm. 1281991 PVA is usually obtained by saponifying polyvinyl acetate, but may contain a component copolymerized with vinyl acetate such as an unsaturated carboxylic acid, an unsaturated sulfonic acid, an olefin, and a vinyl ether. PVA containing a 3-oxetinyl group, a sulfonic acid group, a carboxyl group or an alkenyloxy group can also be used. The degree of saponification of PVA is not particularly limited, but in terms of solubility, etc., it is preferable that the degree of islanding is from 80 to 100% by mole, and more preferably, the degree of saponification is from 90 to 100% of Moore. Meanwhile, the degree of polymerization of PVA is not particularly limited, but it is preferred that the degree of polymerization is from 1,000 to 10, 〇〇〇, and more preferably, the degree of polymerization is from 1,500 to 5,000. <Staining Formulation/Method> The polarizing film is obtained by dyeing PVA and the dyeing step is carried out by gas phase or liquid phase absorption. As an example of the liquid phase dyeing method, when iodine is used, dyeing is performed by immersing the PVA film in an aqueous iodine-potassium iodide solution. Preferably, the iodine content is from 0.1 to 20 g/liter, preferably the potassium iodide content is from 1 to 20 g/l and preferably the weight ratio of iodine and potassium iodide is from 1 To 200. Preferably, the dyeing time is from 10 to 5,000 seconds, and preferably the liquid temperature is from 5 to 60 tons. The dyeing method is not limited to the dipping method, and any mechanism such as coating or spraying iodine or a dyeing solution can be used. The dyeing step may be provided before or after the stretching step of the present invention, but it is preferred to perform the dyeing in the liquid phase before the stretching step because the film will properly expand to facilitate the stretching operation. <Addition of Hardener (Crosslinking) and Metal Salt> In the procedure for producing a polarizing dies by stretching a PVA film, it is preferred to use P-36-1281991 to produce a crosslinked additive. Particularly when the bevel stretching method of the present invention is used, if the PV A is not sufficiently hardened at the exit of the stretching step, the orientation direction of the PVA may be shifted due to the tension in the step. Therefore, it is preferred to incorporate the crosslinking agent into the PVA by immersing the PVA film in the crosslinking reagent solution or by coating the solution in the step before stretching or in the stretching step. The mechanism for assigning the crosslinking reagent to the PVA film is not particularly limited, and any method such as dipping, coating or spraying in a solvent or water or in a solvent or water may be used, but Preferred are the impregnation and coating methods. As for the coating mechanism, any of the commonly known known mechanisms such as a reel coater, a mold applicator, a rod coater, a slide coater, and a curtain coater can be used. It is also preferred to use a method of bringing the cloth, cotton or porous material containing the solution into contact with the film. As the crosslinking reagent, those which are described in U.S. Patent Application Publication No. US Re 23 2897, which is preferably a boric acid and a borax in practical use, can be used. In addition to this, metal salts such as zinc, cobalt, zirconium, iron, nickel and manganese may also be used in combination. After the addition of the hardening agent, a rinse/water wash step can be provided. The hardening agent can be dispensed before or after the film is bonded to the stretcher. This can be performed in any of the steps as in the embodiment shown in Figures 1 and 2 up to the end of step (b), i.e., substantially completing the stretching operation in the diagonal direction. <Polarizer> In addition to iodine, it is preferred to dye the film with a dichroic dye. Specific examples of the dichroic dye include, for example, an azo dye, a mercapto dye, a pyrazolone dye, a triphenylmethylalkyl dye, a quinolyl dye, an oxazin dye-37-1281991 material, a thiene Dye-type compounds such as base dyes and mercapto dyes. It is preferred to use a water-soluble compound, but the present invention is not limited thereto. It is also preferred to introduce hydrophilic substituents such as sulfonic acid groups, amino groups and hydroxyl groups into such dichroic molecules. Specific examples of the dichroic molecule include c·工·正黄12, CI正橘39, CI正橘72, CI Zhenghong39, CI·正红7 9、C·I·正红8 1、C· I · Zhenghong 8 3, C · I · Zhenghong 8 9 , C · I · Zheng Zi 48, CI Zheng Lan 67, CI Zheng Lan 90, CI Zheng Yuan 59, CI · Acid Red 37 and Patent Application No.: Ρ Α 62 62 - 7 0802, JP-A-1 - 1 6 1 202, FP-A- 1 72906, JP-A-1 - 1 72907, ΙΡ-Α- Dyes disclosed in documents 1 - 1 8 3 602, JP-A- 1 - 248 1 05, JP-A-1-265205, and pp. Α-Α-7-261024. Dichromatic molecules such as free acids, alkali metal salts, ammonium salts and amine salts are used. By blending two or more such dichroic molecules, polarizers having various colors can be produced. It is preferred to incorporate a polarizing device or a polarizing plate for providing a black compound or a mixture of various dichroic molecules to provide a black compound (dye) when the polarization angles are orthogonally crossed, because at the same time The reason for the transmittance and polarization of the good veneer. In the present invention, unless otherwise indicated, the term transmissivity means veneer transmittance. At the same time, it is preferred to use the stretching method of the present invention for the production of a so-called polyethylene-based polarizing film in which PVA or polyvinyl chloride is dehydrated or dechlorinated to form a polyene structure and is obtained by conjugated double bonds. Polarization effect. <Protective film> The polarizing film produced by the present invention is used as a polarizing plate after the protective film is adhered to one or both surfaces of the polarizing film. The type of the protective film - 38-1281991 is not particularly limited, and for example, acrylate cellulose such as cellulose acetate and acetate butyrate cellulose acetate, polycarboxylate, polyolefin, polyphenyl can be used. Ethylene and polyester. It is necessary that the protective film of the polarizing plate has properties such as transparency, appropriate moisture permeability, low birefringence, and appropriate rigidity', and from the overall viewpoint, an acrylate cellulose film is preferable and more preferable. It is an acetate cellulose film. The protective film is usually fed in the form of a reel, and is preferably continuously adhered to the elongated polarizing plate so that its longitudinal axis direction can be matched. Here, the orientation axis (phase backward axis) of the protective film may extend in any direction, but it is preferable to make the orientation axis of the protective film parallel to the longitudinal axis direction from the viewpoint of simplicity and ease of handling. The angle between the phase backward axis (orientation axis) of the protective film and the absorption axis (extension axis) of the polarizing film is also not particularly limited, and can be appropriately set according to the purpose of the polarizing plate. The absorption axis of the elongated polarizing plate of the present invention is not parallel to the longitudinal axis direction, so when the protective film has an orientation axis parallel to the longitudinal axis direction and is continuously adhered to the elongated polarizing plate of the present invention, a kind of The absorption axis of the polarizing film and the orientation axis of the protective film are not mutually parallel polarizing plates. The polarizing film and the protective film are combined in such a manner that the polarizing plate in which the absorption axis of the polarizing film and the orientation axis of the protective film are not parallel to each other has excellent dimensional stability. It is particularly advantageous to exert this performance when a polarizing plate is used for a liquid crystal display. Preferably, the angle between the phase backward axis of the protective film and the absorption axis of the polarizing film is from 10 ° to less than 90 °, more preferably the phase behind the protective film and the absorption of the polarizing film. The axes are angled from 40 ° to less than 50 °. In this way, a very high dimensional stability effect can be exerted. A 3 9 - 1281991 The protective film may have any physical property number depending on the use end, and a representative preferred number of the protective film for a normal transmissive LCD will be described below. In terms of maneuverability and durability, it is preferred that the film has a thickness of from 5 to 500 μm, more preferably a film thickness of from 20 to 200 μm, and even more preferably a film thickness of from 20 to 20 100 microns. Preferably, the retardation number at 632.8 nm is from 0 to 150 nm, more preferably the delay number is from 0 to 20 nm, and more preferably the delay number is from 0 to 1. 0 nm, it is particularly preferred that the retardation number is from 0 to 5 nm. From the avoidance of its linear polarization to form an elliptical polarization, it is preferred that the phase of the film behind the axis is substantially parallel or orthogonal to the absorption axis of the polarizing film. However, this is not applicable when the protective film is assigned a function of changing the polarizing property such as a phase difference plate, and the absorption axis of the polarizing plate can be positioned at an arbitrary angle from the axis of the protective film. It is preferable that the visible light transmittance is equal to or greater than 60%, and more preferably, the visible light transmittance is equal to or greater than 90%. After treatment at 90t for 120 hours, it is preferred that the scale is reduced by 〇3 to 0.01%, and more preferably the scale is reduced by 0.15 to 0.11%. It is preferred that the tensile strength of the film is 50 to 100 MPa, and more preferably the tensile strength is 100 to 300 MPa. Preferably, the film has a moisture permeability of from 100 to 800 g/m 2 •day, and more preferably has a moisture permeability of from 300 to 600 g/m 2 •day. Of course, the invention is not limited by these numbers. As described in detail below, it is preferred to use acrylate cellulose as the protective film. In a preferred acrylate cellulose, the cellulose hydroxy substitution degree satisfies all of the following formulas (I) to (IV): 1281991 2.6^ A + B^ 3 . 0 (I) 2·0 S AS 3.0 ( II) 0 . 8 (III) 1 · 9 <AB (IV) wherein A and B each represent the degree of substitution of a thiol group for substituting a hydroxyl group of cellulose, A refers to the degree of substitution of acetyl group and B refers to a fluorenyl group having 3 to 5 carbon atoms. The degree of substitution. The degree of substitution with the three hydroxyl groups falling within one glucose unit and the cellulose having the above number of oxime was 3.0 and the maximum degree of substitution was 3.0. In the triacetate cellulose, the degree of substitution A is generally from 2.6 to 3.0 (in this case, the unsubstituted hydroxyl group is at most 0.4) and B is 0. The acrylate cellulose used as the protective film of the polarizing plate, preferably, the thiol group of the acetamino group is all ethylene glycol triacetate cellulose, or the acetamidine group is equal to or greater than 2.0. An acrylate cellulose having a fluorenyl group of 3 to 5 carbon atoms equal to or less than 〇.8 and an unsubstituted hydroxy group of 0.4 or less. From the viewpoint of physical properties, it is preferred that the fluorenyl group having 3 to 5 carbon atoms is equal to or less than 〇. The degree of substitution can be calculated by measuring the degree of bonding of acetic acid used to replace the hydroxyl group of cellulose and fatty acid having 3 to 5 carbon atoms. This measurement can be performed by the method in accordance with ASTM D - 8 1 7 - 9 1 file. In addition to the ethyl hydrazide group, the fluorenyl group having 3 to 5 carbon atoms includes: propyl ketone (CMCO - ); butyl fluorenyl (dCO -) and its normal- and hetero-isomers; pentamidine ( dCO -) and its positive _, iso-, another-, special-type isomers. Among them, in the viewpoint of mechanical strength and ease of dissolution of the formed film, a positive-type substituent is preferred and a n-propyl group is more preferred. For example, if the degree of substitution of the ethyl group is very low, the mechanical strength and moisture resistance and heat resistance will be lowered. When the degree of substitution of a mercapto group having 3 to 5 carbon atoms is high, the solubility property in an organic solvent can be enhanced, but good physical properties can be obtained when the degree of individual substitution falls within the above range. It is preferred that the degree of polymerization (viscosity average) of the acrylate cellulose is from 200 to 7 Å, and more preferably, the degree of polymerization is from 250 to 550. The average degree of polymerization of the viscosity can be measured by 〇 s t w a 1 d viscosity measurement. The measured intrinsic viscosity of acrylate cellulose [Θ] can be determined according to the following formula: DP=[ 7? ] /Km where DP refers to the average degree of polymerization of the viscosity and Km refers to 6x 1 (the constant of Γ4. The cellulose used as the raw material of the propionate cellulose contains cotton and wood pulp, but we can use acrylate cellulose from any raw cellulose and also use the mixture. Acrylate cellulose is usually produced by a solvent casting method in which acrylate cellulose and various additives are dissolved in a solvent to prepare a thick solution (hereinafter referred to as "glue". And casting on an endless drum or ribbon such as the ones and evaporating the solvent to form a film. It is preferred to adjust the glue to have a solids content of 10 to 40% by weight. Preferably, the drum or ribbon is modified to have a mirror surface. The casting and drying methods in the solvent casting process can be found in U.S. Patent Nos. 2,336,310, 2,367,603, 2,492,977, and 12,819. 91 2,492,978, 2,607,704, 2,7 3 9,06 9 and 2,7 3 9,070, British Patent Application Nos. 640,731 and 736,892, and Japanese Patent Applications PB-45-4554, JP-B-49-56 1 4, FP-A- 60 - 1 7 683 4, JP-A-60-203430, JP-A- 62 - 1 1 5 0 3 5 Description. It is also preferable to use a method for casting two or more layers of glue. In the case of casting a multilayer glue, 'by A film containing a plurality of casting slags disposed at intervals along the support direction is cast and stacked to form a film, and the Japanese Patent Application No. JP-A-61-158414, The method described in JP-A-1-122419, JP-A-11-198285. At the same time, a film can be formed by using an acrylate cellulose solution from two cast crucibles and this can be Japanese Patent Application No. 1P-B-60 - 27 5 62, No. PA- 6 1 - 94724, JP-A-61-947245, JP-A-61-104813, JP-A - 6 The method described in 1 - 1 5 84 1 3 and JP-A-6 - 1 3493 No. 3 is carried out. Further, it is preferable to use Japanese Patent Application No. JP-A-56-162617 The method described in the document is such that the high viscosity glue stream is wrapped with a low viscosity glue and simultaneously ejects the high viscosity and low viscosity glue. Examples of the organic solvent used to dissolve the acrylate cellulose include: hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as dichloromethane and chlorobenzene; alcohols such as methanol, ethanol and diethylene glycol; ketones (eg acetone); esters (eg ethyl acetate and propyl acetate); ethers (eg tetrahydrofuran and methyl cellosolve). Among them, preferred are halogenated hydrocarbons having 1 to 7 carbon atoms, and most preferably two 1281991 methyl chloride. From the viewpoints of acrylate cellulose solubility, scaffold extensibility, and physical properties such as mechanical strength and optical properties, it is preferred to mix one or more of 1 to 5 carbon atoms in addition to methylene chloride. Alcohols. It is preferred that the alcohol content is from 2 to 25 % by weight on the basis of the solvent as a whole, and more preferably the alcohol content is from 5 to 20 % by weight. It is preferred that specific examples of the alcohol include: methanol; ethanol; n-propanol; iso-propanol; and n-butanol. Among them, preferred are methanol, ethanol, n-butanol and mixtures thereof. In addition to acrylate cellulose, the glue may contain any composition, and the ingredients that become solid contents after drying may be plasticizers, ultraviolet absorbers, inorganic fine particles, such as soil-reducing metal salts (eg Jinhe) Thermal stabilizers such as magnesium), antistatic agents, flame retardants, lubricants, oils, stent release accelerators, and emulsification inhibitors for acrylate cellulose. It is preferred that the plasticizer added is a phosphate or a carboxylate. Examples of phosphates include: triphenyl phosphate (TPP); tricresyl phosphate (TCP); tolyl diphenyl phosphate; octyl diphenyl phosphate; diphenyl bisphenyl phosphate: three Octyl phosphate; and tributyl phosphate. Representative examples of carboxylic acid esters include: phthalic acid esters and citric acid esters. Examples of phthalic acid esters include: dimethyl phthalate (DMP); diethyl phthalate (EDP); dibutyl phthalate (DBP); dioctyl phthalate (DOP); diphenyl Phthalate ester (DPP); diethylhexyl decanoate (DEHP). Examples of citrate esters include: triethyl sulfonium citrate (0ACTE); tributyl-o-acetyl citrate (OACTB); ethyltriethyl citrate; Ethyltributyl citrate. Examples of other carboxylic acid esters include: butyl oleate; methyl ethyl sulfonyl (cis) a 4 4 - 1281991 ricinoleate; dibutyl sebacate; and such as trimethyl benzene phthalate A perylene trimester or the like. Examples of the glycolate include: triacetin; glyceryl tributyrate; butyl butyl butyl glycolate; ethyl hydrazine ethyl glycolate; and methyl hydrazine ethyl glycolate. Among these plasticizers, preferred are triphenyl pate ester, bisphenyl diphenyl phosphate, tricresyl phosphate, tolyl diphenyl phosphate, tributyl phosphate, dimethyl hydrazine. Acid ester, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diethyl hexyl phthalate, triacetin, ethyl hydrazine ethyl glycolate, and top three More preferably, it is triphenyl phosphate, bisphenyl diphenyl phosphate, diethyl phthalate, ethyl decyl glycol glycolate, and trimethyl benzene benzene. Acid ester. These plasticizers may be used singly or in combination of two or more of them. Preferably, the amount of the plasticizer added based on the acrylate cellulose is from 5 to 30% by weight, and more preferably, the amount of the plasticizer added is from 8 to 16% by weight. Such compounds may be added to the acrylate cellulose or solvent at the same time as the preparation of the acrylate cellulose solution or during or after the preparation. As the ultraviolet absorber, an absorbent such as a salicylate-benzophenone group, a benzotriazolyl group, a benzoate group, a cyanoacrylate group or a nickel-substituted salt group can be freely selected depending on the purpose. Among them, preferred are benzophenone-based, benzotriazolyl-based and salicylate-based absorbents. Examples of the benzophenone-based ultraviolet absorber include: 2,4-dihydroxybenzophenone; 2-hydroxyethyloxybenzophenone; 2-hydroxy-4-ethoxylated benzophenone; 2-hydroxy-4-methyloxybenzophenone; 2,2,-dihydroxy-4-methyloxybenzophenone; 2,2'-dihydroxy-4,4'-carbomethoxy Bis-benzophenone; 2-hydroxy-4-n-octyloxy benzophenone-45-1281991; 2-pyridyl-4-dodecyloxybenzophenone; and 2-carbyl- 4-(2-propionyl-3-methylpropenyloxy)propoxybenzophenone. Examples of the benzotriazole-based ultraviolet absorber include: 2-(2'-hydroxy-3'-tert-butyl-5,-methylphenyl)-5-chlorobenzotriazole; 2-(2'- Hydroxy-5'-t-butylphenyl benzotriazole; 2_(2,_ keto-3',5'-di-t-pentylphenyl)-benzotriazine; 2-(2,-jing a group of 3-,5, di-tert-butylphenyl)-5-chlorobenzotriazine; and 2-(2,-trans-yl-5,-tert-octylphenyl)-benzotriazine. Examples of the acid ester-based ultraviolet absorber include: phenyl salicylate; p-octylphenyl salicylate; and p-butylphenyl salicylate. Among these ultraviolet absorbents, preferred Is 2-hydroxy-4-methyloxybenzophenone; 2,2'-dihydroxy-4-methyloxybenzophenone; 2-(2, benzyl-3,-tert-butyl- 5. Methylphenyl)-5-chlorobenzotriazole; 2_(2,·trans)., tert-butylphenyl)-benzotriazole; 2-(2'-hydroxy-3',5, -di-t-amylphenyl)-benzotriazole, and 2-(2,-hydroxy-3',5'-di-tert-butylphenyl)_5-chlorobenzotriene are preferably combined a plurality of absorbents having different absorption wavelengths together Because it can achieve high protection effect across a wide range of wavelengths. It is preferred that the amount of ultraviolet absorption dose based on C!13⁄4 vinegar cellulose is from 0.01 to 5% by weight, and more preferably The amount of ultraviolet absorbing agent is from 〇.丨 to 3% by weight. We can add the ultraviolet absorbing agent to the glue while dissolving the acrylate cellulose or after dissolving. Particularly preferably, there is a form The ultraviolet absorber is added to the glue immediately before the casting, using an electrostatic stirrer or the like. The inorganic fine particles added to the acrylate cellulose can be freely selected according to the purpose including the following examples: vermiculite; Kaolin; talc; diatomaceous earth _ 4 6 - 1281991; quartz; calcium carbonate; barium sulfate; titanium oxide; and alumina, preferably by means of a high-speed stirrer, ball mill, grit before being added to the glue Any mechanism such as a machine and an ultrasonic disperser disperses the inorganic fine particles in the binder solution. It is also preferred that the inorganic fine particles are combined with other additives such as ultraviolet absorbers. Dispersed. We can use any dispersing solvent, but it is preferably a dispersing solvent whose composition is close to the colloidal solvent. It is preferred that the average particle size of the dispersed particles is from 0.01 to 100 μm. Preferably, the number average particle size is from 0.1 to 1 μm. We may add the dispersion solution while performing the step of dissolving the acrylate cellulose or may add it to the glue in any step. In the liquid, but similar to the ultraviolet absorber, it is preferably a form in which the dispersion solution is added instantaneously before casting by means of an electrostatic stirrer. As for the stent release accelerator, it is effective to use a surfactant, the interface activity The agent is not particularly limited and examples thereof include a phosphate group, a sulfonic acid group, a carboxylic acid group, a nonionic type, and a cationic type surfactant. Such a surfactant can be referred to in Japanese Patent Application Laid-Open No. JP-A-61-243-83. In the case where an acrylate cellulose film is used for the protective film, it is preferred to impart hydrophilicity to the surface of the film by a treatment such as saponification, corona treatment, flame treatment, glow discharge treatment, and alkali saponification treatment. In order to strengthen the adhesive properties on the PVA type resin. At the same time, it is also possible to disperse the hydrophilic resin into a solvent having affinity for acrylate cellulose and apply the solution to form a thin layer. Among such mechanisms, it is preferred to carry out the saponification treatment because the mechanism does not hinder the flatness and physical properties of the film. The saponification treatment is carried out by immersing the film in an alkaline aqueous solution such as a caustic alkali. After this treatment, it is preferred to neutralize with a low concentration of acid and perform a complete rinsing with water to remove excess lye. The alkali saponification treatment particularly used for the preferred surface treatment of the acrylate cellulose film is explained below. Preferably, the treatment is carried out by a cycle in which the surface of the acrylate fiber membrane is immersed in an alkaline solution, neutralized with an acidic solution, washed with water, and then dried for the film. Examples of the basic solution include a potassium hydroxide solution and a sodium hydroxide solution. Preferably, the hydroxide ion has an equivalent concentration of from 0.1 to 3. ON, more preferably an equivalent concentration of from 0.5 to 2.0N. Preferably, the alkaline solution has a temperature of from room temperature to 90 ° C, more preferably from 40 to 70 ° C. Then, it is generally rinsed with water and washed again with water after passing through an acidic aqueous solution to obtain a surface-treated acrylate cellulose film. Examples of the acid used herein include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, formic acid, chlorinated acetic acid, and early acid. Preferably, the concentration of the acids is from 〇·〇1 to 3.0N, more preferably from 0.05 to 2.0 Ν° in the case of using a acrylate cellulose film as a transparent protective film for a polarizing plate. Preferably, the acid treatment and the alkali treatment, that is, the saponification treatment of the acrylate cellulose, are carried out from the viewpoint of the adhesion of the polarizing film. Such as Realize Sha in "Basic and Application of Wetting Method (Basis and
Application of Wetting)」一書（1989 年 12 月 ι〇 日）中所 述’可藉由接觸角度法、潤溼加熱法或吸收法定出藉由這種 方法得到之固體的表面能量。這類方法當中，較佳的是使用 接觸角度法且其較佳接觸角爲從5到90。，H佳的是其接觸 - 4 8 - 1281991 角爲從5到70°。 可在本發明偏光板的保護膜上設置任意一種功能性層，這 類功能性層包含：用以補償LCD之視角的光學各向異性層； 用以改良顯示器之可見度的抗眩目層或抗反射層；日本專利 申請案第 JP-A- 4 - 229828號、第；[P-A-6-75115號及第 JP-A- 8 - 50206號文件中所說明的一種例如聚合物分散液晶 層及膽固醇型液晶層之類的層，係肇因於各向異性散射作用 或是各向異性光學干涉作用而具有PS波分離功能以改良 LCD的亮度；用以提高偏光板之耐刮性的硬式外罩層；用以 防止含水量或氧氣擴散的氣體阻擋層；用以提高偏光膜上之 黏著強度的易黏層；黏著層或壓敏黏著層以及用以分派滑動 性的層。 該功能性層可設置於該偏光膜一側內或是設置在該偏光 膜之相對一側的表面上。吾人可以根據目的適當地選擇將該 功能性層設置於那一側上。 可在本發明偏光膜的一個或兩個表面上直接黏貼各種功 能性薄膜當作保護膜。該功能性薄膜的實施例包含：諸如 1 / 4波板和1 / 2波板之類的相差膜；光漫射膜，塑膠單元， 係含有設置於該偏光板之相對一側表面上的導電層；亮度改 良用薄膜，係具有各向異性散射或是各向異性光學干涉功能 ;反射板；以及具有透射反射功能的反射板。 至於偏光板的保護膜，可使用一片如上所述的較佳保護膜 或是堆疊在一起的複數片較佳保護膜。可將相同的保護膜黏 貼於該偏光膜的雨側表面上，或者黏貼於兩側表面上的各保 - 49- 1281991 護膜可能的具有不同的功能以及互不相同的物理性質。同時 吾人能夠只將上述保護膜黏貼於一側表面上，且不在相對側 表面上黏貼保護膜而是直接在其上設置一壓敏黏著層以便 將一液晶單元直接黏貼其上。此例中，較佳的是於該壓敏黏 著層外側設置一可脫膜式分隔薄膜。 該保護膜通常係依捲軸形式饋入且較佳的是使之連續地 黏貼於一長形偏光板上使其縱軸方向相吻合。這裡，該保護 膜的定向軸可能沿著任意方向延伸，但是在簡單及易於操作 的觀點下較佳的是沿著縱軸方向係平行於其沿著縱軸方向。 該保護膜的相位落後軸（定向軸）與該偏光膜的吸收軸（伸 展軸）所夾的角度也未特別受限，且可根據偏光板的目的作 適當地設定。本發明之長形偏光板的吸收軸並非平行於縱軸 方向’因此當該保護膜具有平丫了於縱軸方向的定向軸且係連 續地黏貼於本發明的長形偏光板上時，可獲致一種其偏光膜 的吸收軸和其保護膜的定向軸並非相互平行的偏光板。其偏 光膜及保護膜之結合方式是使偏光膜的吸收軸和保護膜的 定向軸並非相互平行的偏光板具有絕佳的尺度穩定性。特別 有利的是會在將偏光板用於液晶顯示器時發揮這種性能。較 佳的是該保護膜的相位落後軸與該偏光膜的吸收軸所夾的 角度爲從1 〇到小於9 0 °，更佳的是其所夾的角度爲從2 0。到 小於80°。以這種角度，可發揮極高的尺度穩定效應。 <黏著劑> 用以結合偏光膜及保護膜的黏著劑並未特別受限，但是其 實例包含PVA-基樹脂（包含諸如3-氧丁醯基、磺酸基、羧基 1281991 及烯氧基之類的已改質PVA)以及硼化合物水溶液。這當中 ，較佳的是PVA樹脂。可將硼化合物、碘化鉀水溶液之類加 到PVA樹脂內。較佳的是在進行乾燥之後該黏著層的厚度爲 0.01到10微米，更佳的是其厚度爲0.05到5微米。 <壓敏黏性層> 本發明的偏光板中，可設置用來與其他液晶顯示器構件黏 貼在一起的壓敏黏性層。較佳的是在該壓敏黏性層表面上設 置一脫模薄膜。當然該壓敏黏性層係呈光學透明的且會同時 呈現出適當的黏稠度及黏著性。吾人可例如藉由形成並烘烤 薄膜以提供本發明中所用的壓敏黏性層，亦即藉由乾燥法、 化學烘烤法、加熱烘烤法、加熱熔融法或光電烘烤法等方法 ，利用由黏著劑或壓敏黏著劑構成的諸如丙烯酸基共聚物之 類聚合物、環氧基樹脂、聚胺甲酸酯、聚矽氧基聚合物、聚 醚類、丁醛基樹脂、聚醯胺基樹脂、聚乙烯醇基樹脂及合成 橡膠。這當中，較佳的是丙烯酸基共聚物，因爲其黏著性質 最容易控制且具有絕佳的透明度、氣候阻抗以及持久度。 <中間步驟> 本發明中，較佳的是提供用以收縮經伸展薄膜以降低其揮 發性內含物百分比的收縮用乾燥步驟，以及在乾燥步驟之後 或期間將保護膜黏貼於薄膜的至少一個表面上之後的薄膜 後加熱步驟。用於黏貼保護膜之方法的特定實例包含一種保 持偏光膜的兩側邊緣於在乾燥步驟期間受到支持的狀態下 使用黏著劑將一保護膜黏貼於該偏光膜上然後再切除其兩 側邊緣的方法，以及一種在進行乾燥、切除薄膜兩側邊緣並 -51- 1281991 將保護膜黏貼其上之後從兩側的邊緣支持部分使偏光膜脫 模的方法。爲了切除各邊緣可使用一種通用技術，例如利用 諸如含緣工具之類切割器切除邊緣的方法或是利用雷射的 方法。較佳的是，是該組合薄膜進行加熱以便使黏著劑乾燥 並改良其偏光性能。該加熱條件會取決於黏著劑而改變，但 是在水性黏著劑的例子裡較佳的是其加熱溫度等於或大於 3 0 °C，更佳的是其加熱溫度爲從40到100 °C，又更佳的是 從50到80°C較佳的是在性能及生產效率的觀點下於中間生 產線內執行這些步驟。 <打孔作業> 第7圖顯示的是一種對習知偏光板進行打孔的實例，而第 8圖顯示的是一種對本發明之偏光板進行打孔的實例。在如 第7圖所示的習知偏光板中其偏光板膜的吸收軸7 1亦即伸 展軸係與縱軸方向72吻合，而在如第8圖所示的本發明偏 光板中其偏光膜的吸收軸8 1亦即伸展軸係相對於其縱軸方 向82傾斜了 45°，且這個角度會與在LCD內黏貼有液晶單元 時該偏光板之吸收軸與液晶單元本身的垂直或橫軸方向之 間所夾的角度吻合。因此不需要在打孔步驟中進行斜角打孔 作業。此外如第8圖所示，由於本發明的偏光板係朝一沿著 縱軸方向的直線進行切割，故也能夠在未打穿該長形偏光板 而是沿著縱軸方向切縫下製作出實用的偏光板，結果可得到 明顯的高產量。 <揮發性成分含量分布〉 在藉由一中間步驟製作一很長特別是捲軸形式之偏光板 -52- 1281991 的例子裡，必要的是未出現任何不均勻的染色作用或是未染 色的點。假如薄膜內的揮發性成分在進行伸展之前具有不均 勻的分布（揮發性成分的量額取決於在薄膜平面內之位置所 出的差異），則會造成不均，勻的染色作用或是出現未染到色 的點。據此，較佳的是使薄膜內在進行伸展之前之揮發性成 分含量的分布是比較小的，且較佳的是其分布爲至少等於或 小於5%。本發明中所用的揮發性內含物百分比意指每單位 容積之薄膜內所含揮發性成分的容積且指的是將揮發性成 分的容積除以薄膜容積得到的數値。該揮發性成分含量的分 布指的是每平方米之揮發性內含物百分比的起伏寬度（其揮 發性內含物百分比之最大値或最小値與平均揮發性內含物 百分比之間差異中較大的差異，相對於其平均揮發性內含物 百分比的比例）。爲了減小揮發性成分含量的分布，可以使 用一種以均勻空氣對薄膜的前方或背部表面吹氣的方法，一 種以捏挾捲軸均勻地擠壓薄膜的方法，或是一種藉由擦拭器 (例如刮刀或海棉）擦除揮發性成分的方法，不過只要能夠使 分布變均勻可使用任意一種方法。 以下將參照各實例對本發明作更詳細的說明，不過本發明 並不受限於此。 [實例1] 以流速爲2公升/分鐘的離子交換處理過的水淸洗PVA薄 膜的兩側表面並藉由吹氣法甩掉表面上的水以移除異物。然 後將此薄膜浸漬於溫度爲25 °C而含有1.0公克/公升之碘及 60.0公克/公升之碘化鉀的水溶液內達90秒鐘，再進一步 -53- 1281991 將之浸漬於溫度爲25 °C而含有40公克/公升之硼酸及30公 克/公升之碘化鉀的水溶液內達1 20秒鐘。隨後，對薄膜的 兩側表面吹氣以移除過剩的含水量，並將薄膜內含水量百分 比的分布調整爲等於或小於2%，且在這種狀態下依如第丄 圖所示之形式將薄膜引進張布伸展機內。一次於40°C及95% 的大氣中使薄膜伸展6.4倍並以5米/分鐘的輸送速率傳遞 1 00米然後再收縮爲4 · 5倍。之後在保持定常寬度下以 6 0°C對薄膜進行乾燥並自張布機上移開。利用切割器切出對 角方向爲3厘米的邊緣，並令此薄膜黏貼有由富士相片公司 製造其型號爲Fuj i t ac的已皂化產品（三醋酸酯纖維素，延 遲値：3奈米），利用含有3%水溶性PVA (由Kura ray公司製 造其型號爲P V A - 1 1 7 Η的產品）溶液及4 %姚化鉀的水溶液當 作黏著劑，以60°C加熱30分鐘然後再圍繞外徑3英吋的紙 質核心取出。因此能夠在沒有任何麻煩下製造出寬度爲650 毫米而長度爲100米的捲軸形偏光板。 其乾燥點係落在c區的中點而PVA薄膜的含水量百分比在 啓動伸展時爲30%且在乾燥之後爲1 . 5%。 在右邊與左邊張布夾之間的輸送速率差小於0.05%，而所 引進薄膜之中心線和傳送到下一步驟之薄膜中心線所夾的 角度爲〇°。這裡，|L1-L2|爲〇·7米且W爲0.7米而建立 了 | L 1 - L 2 | =W的關係。在張布機的出口上並未觀測到薄膜 出現起皺及變形現象。 所獲致偏光板的吸收軸方向係相對於其縱軸方向傾斜了 4 5 °同時也相對於F u j 1 t a c的相位落後軸傾斜了 4 5 °。此偏光 - 54- 1281991 板在5 50奈米的透射率爲40 · 6%且其偏光程度爲99 · 53% ° 令偏光板捲軸在25°C、50%及2, 000 lux下儲存30天。 其外面兩圏的偏光程度減低了但是從第三圈起的偏光程度 並未減低。 此外，如第8圖所示將此偏光板切割成3 1 0x23 3毫米的尺 寸，結果可獲致區域效率爲9 1 · 5%且吸收軸相對於側邊傾斜 了 45°的偏光板。 [實例2 ] 以流速爲2公升/分鐘的離子交換處理過的水淸洗PVA薄 膜的兩側表面並藉由吹氣法甩掉表面上的水以移除異物。然 後將此薄膜浸漬於溫度爲4(TC而含有1.0公克/公升之碘及 120 . 0公克/公升之碘化鉀的水溶液內達90秒鐘，再進一步 將之浸漬於溫度爲40°C而含有40公克/公升之硼酸及30公 克/公升之碘化鉀的水溶液內達60秒鐘。隨後，對薄膜的兩 側表面吹氣以移除過剩的含水量，並將薄膜內含水量百分比 的分布調整爲等於或小於2%，且在這種狀態下依如第2圖 所示之形式將薄膜引進張布伸展機內。使薄膜伸展4 . 5倍並 以15米/分鐘的輸送速率傳遞5 00米，然後如第2圖所示使 張布機相對於伸展方向產生彎折。之後在保持定常寬度並對 薄膜進行收縮下於80 °C的大氣中對薄膜進行乾燥並自張布 機上移開。利用切割器切出對角方向爲3厘米的邊緣，並令 此薄膜黏貼有由富士相片公司製造其型號爲Fuj it ac的已 皂化產品（三醋酸酯纖維素，延遲値：3奈米），利用含有3 % 水溶性PVA(由Kuraray公司製造其型號爲pVA-i 17H的產品 1281991 )溶液及4%碘化鉀的水溶液當作黏著劑’以6 0 °C加熱3 0分 鐘然後再圍繞外徑3英吋的紙質核心取出’因此能夠在沒有 任何麻煩下製造出寬度爲650毫米而長度爲500米的捲軸形 偏光板。 其乾燥點係落在c區之1 / 3位置上而PVA薄膜的含水量百 分比在啓動伸展時爲32%且在乾燥之後爲1 · 5%。 在右邊與左邊張布夾之間的輸送速率差小於0.05%’而所 引進薄膜之中心線和傳送到下一步驟之薄膜中心線所夾的 角度爲46°。這裡，丨L1-L2I爲0.7米且W爲0.7米而建立 了 | LI -L2 | =W的關係。在張布機的出口上，實質的伸展方 向Ax - Cx會相對於傳送到下一步驟之薄膜中心線22傾斜 45°。並未在張布機的出口上觀測到薄膜出現起皺及變形現 象。 所獲致偏光板的吸收軸方向係相對於其縱軸方向傾斜了 45°。此偏光板在5 50奈米的透射率爲42.1 %且其偏光程度爲 99.97%。 令偏光板捲軸在25°C、50%及2,000 lux下儲存30天。 其外面兩圈的偏光程度減低了但是從第三圈起的偏光程度 並未減低。 此外，如第8圖所示將此偏光板切割成310x233毫米的尺 寸，結果可獲致區域效率爲9 1 · 5%且吸收軸相對於側邊傾斜 了 45°的偏光板。 [比較用實例1 ] 以流速爲2公升/分鐘的離子交換處理過的水淸洗PVA薄 1281991 膜的兩側表面藉由吹氣法甩掉表面上的水以便將黏貼在表 面上的異物減爲等於或小於0 · 5%。將此薄膜浸漬於溫度爲 40 °C而含有1.0公克/公升之碘及120.0公克/公升之碘化鉀 的水溶液內達90秒鐘，再進一步將之浸漬於溫度爲40°C而 含有40公克/公升之硼酸及30公克/公升之碘化鉀的水溶液 內達60秒鐘。隨後，在未對薄膜的兩側表面吹氣下且在薄 膜內含水量百分比的分布爲1 〇%的狀態下，依如第2圖所示 之形式將薄膜引進張布伸展機內使薄膜伸展4 . 5倍。如第2 圖所示使張布機相對於伸展方向產生彎折，在保持定常寬度 並對薄膜進行收縮下於30°C的大氣中對薄膜進行乾燥並自 張布機上移開。跨越薄膜的整個表面上產生了染色不均勻度 ，起鈹現象維持原狀，且肇因於粗糙表面故無法黏貼保護膜 ，而無法製成捲軸形偏光板。 [實例3] 使用實例2中所製備的碘-型偏光板9 1和92當作兩片偏 光板並於其間插入用於LCD的液晶單元9 3。如第9圖所示 ，係配置偏光板9 1當作顯示側的偏光板並透過黏著劑黏貼 於液晶單元93上以製造LCD。 如是製成的LCD會呈現出絕佳的亮度、視角性質及可見度 ，且即使在40 °C及3 0%RH下使用一個月之後其也不致破壞 其顯示等級。 (在5 50奈米上進行透射率及偏光程度的量測） 透射率係藉著由Shimadzu公司製造其型號爲UV2100的自 動記錄式光譜儀加以量測的。此外，可由兩個重疊偏光板之 - 57- 1281991 吸收軸相吻合時的透射率Η Ο ( % )及其吸收軸相互正交時的 透射率Η1 ( % )，藉著下列公式定出其偏光程度p ( % ): P=[ (HO-H1 ) / (HO + H1 ) ] 1/2 xlOO (延遲度的量測） 此量測係在6 3 2 . 8奈米利用由〇j i測試儀器公司製造其型 號爲K0BRA21DH的產品執行的。 [實例4 ] 將PVA薄膜浸漬於溫度爲40 °C而含有1.0公克/公升之碘 及120 . 0公克/公升之碘化鉀的水溶液內達90秒鐘，再進一 步將之浸漬於溫度爲40 °C而含有40公克/公升之硼酸及30 公克/公升之碘化鉀的水溶液內達1 20秒鐘。隨後，如第1 圖所示之形式將薄膜引進張布伸展機內，一次於溫度爲 6 2 °C及溼度爲9 6 %的大氣中使薄膜伸展7 . 0倍之後再施加 370牛頓/米的定常張力使之收縮爲5.3倍。之後在保持定 常寬度下以60°C對薄膜進行乾燥並自張布機上移開。 在啓.動伸展之前，該PVA薄膜的含水量百分比爲42 . 3%、 含水量百分比的分布爲3.8%且其膨脹百分比爲31.9%;經過 乾燥以後，該薄膜含水量百分比爲4 · 8 %、含水量百分比的 分布爲2.0 %。 在右邊與左邊張布夾之間的輸送速率差小於〇 〇5%，而所 引進薄膜之中心線和傳送到下一步驟之薄膜中心線所夾的 角度0。迨裡，I L1-L2I爲〇·7米且w爲〇.7米而建立了 I L 1 - L2 | 的關係。在張布機的出口上，並未觀測到薄膜 出現起皺及變形現象。 - 58 - 1281991 然後，令此PVA薄膜黏貼有由富士相片公司製造其型號爲 Fu j i t a c的已皂化產品（三醋酸纖維素，延遲値：3奈米）， 利用含有 3%水溶性PVA (由 Kura ray公司製造其型號爲 PVA - 1 1 7H的產品）溶液及4%碘化鉀的水溶液當作黏著劑，以 8 0°C進行乾燥以獲致工作寬度爲670毫米的偏光板。所獲致 偏光板的吸收軸方向係相對於其縱軸方向傾斜了 4 5 °同時也 相對於Fuj i t ac的相位落後軸傾斜了 45°。 此偏光板在5 5 0奈米的透射率爲43.0%且其偏光程度爲 99.94%° [實例5 ] 將PVA薄膜浸漬於溫度爲4(TC而含有1.0公克·/公升之碘 及120 .0公克/公升之碘化鉀的水溶液內達90秒鐘，再進一 步將之浸漬於溫度爲40 °C而含有40公克/公升之硼酸及30 公克/公升之碘化鉀的水溶液內達1 20秒鐘。隨後，如第1 圖所示之形式將薄膜引進張布伸展機內而使沿著薄膜的縱 軸方向的張力保持定常下，一次於溫度爲62 °C及溼度爲96% 的大氣中使薄膜伸展7.0倍之後再施加390牛頓/米的定常 張力使之收縮爲5 . 3倍。之後在保持定常寬度下以60°C對 薄膜進行乾燥並自張布機上移開。 在啓動伸展之前，該PVA薄膜的含水量百分比爲43 . 1%、 含水量百分比的分布爲4.0%且其膨脹百分比爲32.3%。在進 行乾燥之後，其含水量百分比爲4 . 2%且其膨脹百分比爲 1.9%° 在右邊與左邊張布之間的輸送速率差小於0 . 05%，而所引 - 59- 1281991 進薄膜之中心線和傳送到下一步驟之薄膜中心線所夾的角 度爲0。迨裡’ lLl-L2|爲〇·7米且W爲0.7米而建立了 | L· 1 - L2 | =W的關係。在張布機的出口上，並未觀測到薄膜 出現起皺及變形現象。 然後’令此PVA薄膜黏貼有由富士相片公司製造其型號爲 Fuj i tac的已皂化產品（三醋酸酯纖維素，延遲値：3奈米） ’利用含有3%水溶性PVA(由Kuraray公司製造其型號爲 PVA - 1 1 7H的產品）溶液及4%碘化鉀的水溶液當作黏著劑，以 80 °C進行乾燥以獲致工作寬度爲680毫米的偏光板。所獲致 光板的吸收軸方向係相對於其縱軸方向傾斜了 4 5。。此偏光 板在5 50奈米的透射率爲43 . 4%且其偏光程度爲99 . 9 3%。 [實例6] 以流速爲2公升/分鐘的離子交換水處理過的水淸洗PVA 薄膜並藉由吹氣法甩掉表面上的水以移除異物。將此薄膜浸 漬於溫度爲4(TC而含有1.0公克/公升之碘及60.0公克/公 升之碘化鉀的水溶液內達90秒鐘，再進一步將之浸漬於溫 度爲40 °C而含有40公克/公升之硼酸及30公克/公升之碘 化鉀的水溶液內達1 20秒鐘。隨後，以如第1 0圖所示之吹 氣裝置對薄膜吹氣以甩掉過剩的含水量。依如第1圖所示之 形式將薄膜引進張布伸展機內，並在一次於溫度爲64°C及 溼度爲91%的大氣中使薄膜伸展7 . 0倍之後再施加3 7 5牛頓 /米的定常張力使之收縮爲5 . 3倍。之後在保持定常寬度下 以6 0°C對薄膜進行乾燥並自張布機上移開。 在啓動伸展之前，該PVA薄膜的含水量百分比爲44 · 2%、 1281991 含水量百分比的分布爲4 · 3%且其膨脹百分比爲32 · 7%。在進 行乾燥之後，其含水量百分比爲3 . 9%且其膨脹百分比爲 1.8%。 在右邊與左邊張布夾之間的輸送速率差小於〇 · 〇 5 %，而所 引進薄膜之中心線和傳送到下一步驟之薄膜中心線所夾的 角度爲0°。這裡，|L1-L2|爲0.7米且W爲0.7米而建立 了 I L 1 - L2 | =W的關係。在張布機的出口上，並未觀測到薄 膜出現起皺及變形現象。 然後’令此PVA薄膜黏貼有由富士相片公司製造其型號爲 Fuj i tac的已皂化產品（三醋酸酯纖維素，延遲値：3奈米） ，利用含有3%水溶性？\^(由1(111^^7公司製造其型號爲 PVA - 1 17H的產品）溶液及4%碘化鉀的水溶液當作黏著劑’以 8 0°C進行乾燥以獲致工作寬度爲67 5毫米的偏光板。所獲致 偏光板的吸收軸方向係相對於其縱軸方向傾斜了 45° °此偏 光板在5 5 0奈米的透射率爲43.1%且其偏光程度爲9 9.9 8% 〇 [實例7] 以流速爲2公升/分鐘的離子交換處理過的水淸洗PVA薄 膜並藉由吹氣法甩掉表面上的水以移除異物。將此薄膜浸漬 於溫度爲而含有I·0公克/公升之碑及I20·0公克’公 升之碘鉀的水溶液內達9 0秒鐘，再進一步將之浸漬於溫度 爲40 °C而含有40公克/公升之硼酸及30公克/公升之碑化 鉀的水溶液內達1 2〇秒鐘。隨後’以如第1 1圖所示之捏挟 裝置對薄膜吹氣以甩掉過剩的含水量。依如第1圖所示之形 -61- 1281991 式將薄膜引進張布伸展機內而使沿著薄膜的縱軸方向的張 力保常定常下，並在一次於溫度爲57°C及溼度爲95%的大氣 中使薄膜伸展7 . 0倍之後再施加3 6 0牛頓/米的定常張力使 之收縮爲5 . 3倍。之後在保持定常寬度下以60°C對薄膜進 行乾燥並自張布機上移開。 在啓動伸展之前，該PVA薄膜的含水量百分比爲44 . 7%、 含水量百分比的分布爲4.4%且其膨脹百分比爲33.1%。在進 行乾燥之後，其含量水量百分比爲3 . 7%且其膨脹百分比爲 1.6%。 在右邊與左邊張布夾之間的輸送速率差小於0 . 0 5%，而所 引進薄膜之中心線和傳送到下一步驟之薄膜中心線所夾的 角度爲0°。這裡，|L1-L2|爲0.7米且W爲0.7米而建立 了 | L 1 - L2 | =W的關係。在張布機的出口上，並未觀測到薄 膜出現起皺及變形現象。 然後，令此PVA薄膜黏貼有由富士相片公司製造其型號爲 Fuj i tac的已皂化產品（三醋酸酯纖維素，延遲値：3奈米） ，利用含有3%水溶性PVA(由Kuraray公司製造其型號爲 PVA - 1 1 1 7H的產品）溶液當作黏著劑，以80°C進行乾燥以獲 致工作寬度爲685毫米的偏光板。所獲致偏光板的吸收軸方 向係相對於其縱軸方向傾斜了 45°。此偏光板在5 5 0奈米的 透射率爲43.9%且其偏光程度爲99.97%。 [實例8 :液晶顯示器的製造] 使用實例5中所製備的碘-型偏光板9 1和9 2當作兩片偏 光板並於其間插入用於LCD的液晶單元9 3。如第9圖所示 - 6 2 - 1281991 ，係配置偏光板91當作顯示側的偏光板並透過黏著劑黏貼 於液晶單元93上以製造LCD。 如是製成的LCD會呈現出絕佳的亮度、視角性質及可見度 ，且即使在40 °C及3 OMH下使用一個月之後其也不致破壞 其顯示等級。 [比較用實例2 ] 將PVA薄膜浸漬於溫度爲4(TC而含有1.0公克/公升之碘 及120.0公克/公升之碘化鉀的水溶液內達90秒鐘，再進一 步將之浸漬於溫度爲4(TC而含有40公克/公升之硼酸及30 公克/公升之碘化鉀的水溶液內達1 20秒鐘。隨後，依如第 1圖所示之形式將薄膜引進張布伸展機內，在一次於溫度爲 60°C及溼度爲45%的大氣中使薄膜伸展7.0倍之後再施加 3 3 0牛頓/米的定常張力使之收縮爲5 . 3倍。之後在保持定 常寬度下以60°C對薄膜進行乾燥並自張布機上移開。 在啓動伸展之前，該PVA薄膜的含水量百分比爲28.9%、 含水量百分比的分布爲7. 3 %且其膨脹百分比爲29.1 %。在進 行乾燥之後，其含水量百分比爲8 . 3%且其膨脹百分比爲 6.3%。 在右邊與左邊張布夾之間的輸送速率差小於0.05%，而所 引進薄膜之中心線和傳送到下一步驟之薄膜中心線所夾的 角度爲〇°。這裡，I Ll-L2|爲0.7米且W爲0.7米而建立 了 | L 1 - L2 | =W的關係。在張布機的出口上，雖則並未觀測 到薄膜出現起皺及變形現象，然而可觀測到極大數目的不均 勻部分。 - 63- 1281991 然後’令此PVA薄膜黏貼有由富士相片公司製造其型號爲 Fuj i t ac的已皂化產品（三醋酸酯纖維素，延遲値：3奈米） ，利用含有3%水溶性PVA (由Kura ray公司製造其型號爲 PVA - 1 1 7H的產品）溶液當作黏著劑，以80°C進行乾燥以獲致 工作寬度爲4 5 0毫米的偏光板。所獲致偏光板的吸收軸方向 係相對於其縱軸方向傾斜了 45°。此偏光板5 50奈米的透射 率爲40.1 %且其偏光程度爲96.3 8%。 (在5 5 0奈米上進行透射率及偏光程度的量測） 透射率係藉著由Shimadzu公司製造其型號爲UV2100的自 動記錄式光譜儀加以量測的。此外，可由兩個重疊偏光板之 吸收軸相吻合時的透射率H0 ( % )及其吸收軸相互正交時的 透射率Hl(%)，藉著下列公式定出其偏光程度P(%); P=[ (H0-H1 ) / (H0 + H1 ) ] 1/2χ100 從比較用實例2與實例4到6之間的比較可以淸楚地看出 ，可藉由對進行伸展時之溼度以及沿著薄膜縱軸方向之張力 作最佳化控制而獲致其工作寬度等於或大於650毫米的偏 光板。同時從實例4可以淸楚地看出，可藉由對進行伸展時 之溼度、沿著薄膜縱軸方向之張力以及在進行伸展之前和之 後進行伸展作最佳化控制而進一步增加其工作寬度。 [實例9 ] 將PVA薄膜浸漬於溫度爲25 °C而含有1 .0公克/公升之碘 及60 . 0公克/公升之碘化鉀的水溶液內達90秒鐘，再進一 步將之浸漬於溫度爲25 °C而含有40公克/公升之硼酸及30 公克/公升之碘化鉀的水溶液內達1 20秒鐘。使用如第1 0 - 64- 1281991 圖所示之吹氣機裝置對薄膜兩側表面進行吹氣，以去除薄膜 的多餘水分及降低水分百分比佈至2%或更少。在此狀態下 ’依如第1圖所示之形式將薄膜引進張布伸展機內，在一次 於溫度爲40 °C及溼度爲95%的大氣中使薄膜伸展6 . 4倍之後 再使之收縮爲4.5倍。之後在保持定常寬度下以6(TC對薄 膜進行乾燥並自張布機上移開。利用切割器切出對角方向爲 3厘米的邊緣，並令此薄膜黏貼有由富士相片公司製造其型 號爲Fuj i tac的已皂化產品（三醋酸酯纖維素，延遲値：3 奈米），利用含有3%水溶性PVA (由Kuraray公司製造其型號 爲PVA - 1 1 7H的產品）溶液及4%碘化鉀的水溶液當作黏著劑 ，以6 0 °C加熱3 0分鐘，因此能夠在沒有任何麻煩下製造出 工作寬度爲6 5 0毫米偏光板。 該PVA薄膜的含水量百分比在啓動伸展時爲30 %且在乾燥 之後爲1 . 5%。 在右邊與左邊張布夾之間的輸送速率差小於〇 . 〇 5 %，而所 引進薄膜之中心線和傳送到下一步驟之薄膜中心線所夾的 角度爲（Γ。這裡，|L1-L2|爲0.7米且W爲0.7米而建立 了 | L 1 - L 2 | = W的關係。在張布機的出口上，並未觀測到薄 膜出現起鈹及變形現象。 所獲致偏光板的吸收軸方向係相對於其縱軸方向傾斜了 45°同時也相對於Fuj i tac的相位落後軸傾斜了 45。。此偏光 板在5 50奈米的透射率爲40.2%且其偏光程度爲9 9.5 0%。此 偏光板具有良好的表面狀態且在目測情況下並未觀測到不 均勻度。 -65- 1281991 此外，如第8圖所示將此偏光板切割成310x233毫米的尺 寸，結果可獲致區域效率爲9 1 · 5%且吸收軸相對於側邊傾斜 了 45°的偏光板。 [實例1 〇 ] 將PVA薄膜浸漬於溫度爲30°而含有1 · 0公克/公升之碘及 120.0公克/公升之碘化鉀的水溶液內達90秒鐘’再進一步 將之浸漬於溫度爲30 °C而含有40公克/公升之硼酸及30公 克/公升之碘化鉀的水溶液內達60秒鐘。以如第1 1圖所示 之捏挾裝置對薄膜的兩側表面吹氣以甩掉過剩的含水量並 將其含水量百分比降爲等於或小於2%。在此狀態下，依如 第1圖所示之形式將薄膜引進張布伸展機內，使薄膜於溫度 爲60 °C及溼度爲95%的大氣中伸展4 . 5倍然後再如第2圖所 示使張布機相對於伸展方向產生彎折。之後在保持定常寬度 且對薄膜進行收縮下以8(TC對薄膜進行乾燥並自張布機上 移開。利用切割器切出對角方向爲3厘米的邊緣，並令此薄 膜黏貼有由富士相片公司製造其型號爲Fu jit ac的已皂化 產品（三醋酸酯纖維素，延遲値：3奈米），利用含有3%水溶 性PVA(由Kuraray公司製造其型號爲PVA-117H的產品）溶 液及4%碘化鉀的水溶液當作黏著劑，以60°C加熱30分鐘， 因此能夠在沒有任何麻煩下製造出工作寬度爲6 50毫米的 偏光板。 該PVA薄膜的含水量百分比在啓動伸展時爲32%且在乾燥 之後爲1 . 5%。 在右邊與左邊張布夾之間的輸送速率差小於0.05%，而所 - 6 6 - 1281991 引進薄膜之中心線和傳送到下一步驟之薄膜中心線所夾白勺 角度爲46。。這裡，I L卜L2|爲0.7米且W爲0·7米而建立 了 | L卜L2| =W的關係。在張布機的出口上，實質的伸展方 向Ax - Cx會相對於傳送到下一步驟之薄膜中心線22傾斜 4 5。。並未在張布機的出口上觀測到薄膜出現起皺及變形現 象。 所獲致偏光板的吸收軸方向係枏對於其縱軸方向傾斜了 45。。此偏光板在550奈米的透射率爲41.9%且其偏光程度爲 9 9 . 9 6 %。此偏光板具有良好的表面狀態且在目測情況下並未 觀測到不均勻度。 此外，如第8圖所示將此偏光板切割成3 1 0x2 3 3毫米的尺 寸，結果可獲致區域效率爲9 1 . 5%且吸收軸相對於側邊傾斜 了 45°的偏光板。 [比較用實例3 ] 將PVA薄膜浸漬於溫度爲30°C而含有1.0公克/公升之碘 及120 . 0公克/公升之碘化鉀的水溶液內達90秒鐘，再進一 步將之浸漬於溫度爲30°C而含有40公克/公升之硼酸及30 公克/公升之碘化鉀的水溶液內達60秒鐘。隨後，在未對薄 膜的兩側表面吹氣下且在薄膜內含水量百分比的分布爲 1 0%的狀態下，依如第2圖所示之形式將薄膜引進張布伸展 機內使薄膜伸展4 . 5倍。如第2圖所示使張布機相對於伸展 方向產生彎折，在保持定常寬度並對薄膜進行收縮下於 3 0 °C的大氣中對薄膜進行乾燥並自張布機上移開。跨越薄膜 的整個表面上產生了染色不均勻度，起皺現象維持原狀，且 -67- 1281991 肇因於粗糙表面故無法黏貼保護膜，而無法製成捲軸形偏光 板。 [實例11] 使用實例1 〇中製備的碘-型偏光板9 1和9 2當作兩片偏 光板並於其間插入用於LCD的液晶單元93。如第9圖所示 ，係配置偏光板9 1當作顯示側的偏光板並透過黏著劑黏貼 於液晶單元93上以製造LCD。 如是製成的LCD會呈現出絕佳的亮度、視角性質及可見度 、且即使在40 °C及3 0%RH下使用一個月之後其也不致破壞 其顯示等級。 (在550奈米上進行透射率及偏光程度的量測） 透射率係藉著由Shimadzu公司製造其型號爲UV2100的自 動紀錄式光譜儀加以量測的。此外，可由兩個重疊偏光板之 吸收軸相吻合時的透射率Η 0 ( % )及其吸收軸相互正交時的 透射率Hl(%)，藉著下列公式定出偏光裎度Ρ(%) Ρ=[ (Η0-Η1 ) / (Η0 + Η1 ) ] 1/2χ100 (延遲度的量測） 此量測係在63 2 . 8奈米利用由Oj i測試儀器公司製造其型 號爲K0BRA2 1DH的產品執行的。 工業應用 根據本發明獲致一種包括呈斜角伸展之偏光膜的長形捲 軸式的偏光板。這種長形捲軸式的偏光板可在進行打孔以形 成偏光板的步驟中提高良率且因此降低其成本。此外該偏光 板具有絕佳的儲存性及極高的性能。藉由這種偏光板，可以 1281991 低成本提供具有絕佳顯示等級的液晶顯示器。 (五）圖式簡單說明 第1圖係用以顯示一種用以使根據本發明之聚合物膜作 斜角伸展之方法實例的平面示意圖。 第2圖係用以顯示一種用以使根據本發明之聚合物膜作 斜角伸展之方法實例的平面示意圖。 第3圖係用以顯示一種用以使根據本發明之聚合物膜作 斜角伸展之方法實例的平面示意圖。 第4圖係用以顯示一種用以使根據本發明之聚合物膜作 斜角伸展之方法實例的平面示意圖。 第5圖係用以顯示一種用以使根據本發明之聚合物膜作 斜角伸展之方法實例的平面示意圖。 第6圖係用以顯示一種用以使根據本發明之聚合物膜作 斜角伸展之方法實例的平面示意圖。 第7圖係用以顯示一種對習知偏光板進行打孔之狀態的 平面示意圖。 第8圖係用以顯示一種對本發明之偏光板進行打孔之狀 態的平面示意圖。 第9圖係用以顯示實例5之液晶顯示器內層膜結構的平面 示意圖。 第1 0圖係用以顯示一種吹氣裝置的槪念圖示。 第11圖係用以顯示一種捏挾裝置的槪念圖示。 第1 2圖係用以顯示一種刀片裝置的槪念圖示。 主要元件符號說明 -69- 1281991 (11) (a) (b) (c ) A1 B1 ClThe surface energy of the solid obtained by this method can be determined by the contact angle method, the wetting heating method or the absorption method as described in the book "Application of Wetting" (December 1989). Among such methods, it is preferred to use a contact angle method and preferably have a contact angle of from 5 to 90. H is good for its contact - 4 8 - 1281991 The angle is from 5 to 70 °. Any functional layer may be disposed on the protective film of the polarizing plate of the present invention, such functional layer comprising: an optically anisotropic layer for compensating for the viewing angle of the LCD; an anti-glare layer or anti-reflection layer for improving the visibility of the display a reflective layer; for example, a polymer-dispersed liquid crystal layer and cholesterol as described in Japanese Patent Application Laid-Open No. JP-A-4-229828, No. [PA-6-75115, and JP-A-8-50206 A layer such as a liquid crystal layer having a PS wave separation function for improving the brightness of the LCD due to anisotropic scattering or anisotropic optical interference; and a hard outer layer for improving the scratch resistance of the polarizing plate a gas barrier layer for preventing moisture or oxygen diffusion; an easy-adhesive layer for improving the adhesion strength on the polarizing film; an adhesive layer or a pressure-sensitive adhesive layer; and a layer for imparting slidability. The functional layer may be disposed on one side of the polarizing film or on a surface on the opposite side of the polarizing film. We can appropriately select the functional layer on that side depending on the purpose. Various functional films can be directly adhered to one or both surfaces of the polarizing film of the present invention as a protective film. Embodiments of the functional film include: a phase difference film such as a 1/4 wave plate and a 1/2 wave plate; a light diffusing film, a plastic unit having conductive layers disposed on opposite side surfaces of the polarizing plate The film for brightness improvement has anisotropic scattering or anisotropic optical interference function; a reflecting plate; and a reflecting plate having a transflective function. As the protective film of the polarizing plate, a preferred protective film as described above or a plurality of preferred protective films stacked together may be used. The same protective film may be adhered to the rain side surface of the polarizing film, or each of the protective films adhered to the both sides may have different functions and different physical properties. At the same time, the adhesive film can be adhered to one side surface only, and the protective film is not adhered to the opposite side surface, but a pressure-sensitive adhesive layer is directly disposed thereon to directly adhere a liquid crystal cell thereto. In this case, it is preferred to provide a release film separating film on the outside of the pressure-sensitive adhesive layer. The protective film is usually fed in the form of a reel and is preferably adhered continuously to an elongated polarizing plate such that its longitudinal axis direction coincides. Here, the orientation axis of the protective film may extend in any direction, but it is preferably parallel to the longitudinal axis direction along the longitudinal axis from the viewpoint of simplicity and ease of handling. The angle between the phase backward axis (orientation axis) of the protective film and the absorption axis (extension axis) of the polarizing film is also not particularly limited, and can be appropriately set according to the purpose of the polarizing plate. The absorption axis of the elongated polarizing plate of the present invention is not parallel to the longitudinal axis direction. Therefore, when the protective film has an orientation axis that is flat with respect to the longitudinal axis direction and is continuously adhered to the elongated polarizing plate of the present invention, A polarizing plate is obtained in which the absorption axis of the polarizing film and the orientation axis of the protective film are not parallel to each other. The polarizing film and the protective film are combined in such a manner that the polarizing plate in which the absorption axis of the polarizing film and the orientation axis of the protective film are not parallel to each other has excellent dimensional stability. It is particularly advantageous to exert this performance when a polarizing plate is used for a liquid crystal display. Preferably, the phase of the retardation axis of the protective film and the absorption axis of the polarizing film are from 1 〇 to less than 90 °, and more preferably the angle is from 20 to 50. To less than 80°. In this way, a very high dimensional stability effect can be exerted. <Adhesive> The adhesive for bonding the polarizing film and the protective film is not particularly limited, but examples thereof include a PVA-based resin (including, for example, 3-oxetyl sulfonate, sulfonic acid group, carboxyl group 1281991, and alkenyloxy group) A modified PVA of the class) and an aqueous solution of a boron compound. Among them, preferred is a PVA resin. A boron compound, an aqueous solution of potassium iodide or the like can be added to the PVA resin. Preferably, the adhesive layer has a thickness of 0.01 to 10 μm after drying, and more preferably 0.05 to 5 μm. <Pressure-sensitive adhesive layer> In the polarizing plate of the present invention, a pressure-sensitive adhesive layer for adhering to other liquid crystal display members may be provided. Preferably, a release film is provided on the surface of the pressure-sensitive adhesive layer. Of course, the pressure sensitive adhesive layer is optically clear and exhibits both proper adhesion and adhesion. The pressure sensitive adhesive layer used in the present invention can be provided, for example, by forming and baking a film, that is, by a drying method, a chemical baking method, a heating baking method, a heating melting method, or a photoelectric baking method. , using a polymer such as an acrylic-based copolymer composed of an adhesive or a pressure-sensitive adhesive, an epoxy resin, a polyurethane, a polyoxyl polymer, a polyether, a butyral-based resin, a polyamine Base resin, polyvinyl alcohol based resin and synthetic rubber. Among them, acrylic-based copolymers are preferred because of their adhesion properties being the most controllable and having excellent transparency, weather resistance and durability. <Intermediate Step> In the present invention, it is preferred to provide a shrinking drying step for shrinking the stretched film to reduce the percentage of its volatile content, and to adhere the protective film to the film after or during the drying step. A film post-heating step after at least one surface. A specific example of the method for adhering the protective film includes a method of adhering a protective film to the polarizing film and then cutting both side edges thereof while maintaining the both side edges of the polarizing film in a state of being supported during the drying step. The method, and a method of demolding the polarizing film from the edge supporting portions on both sides after drying, cutting both side edges of the film and attaching the protective film to -51-1281991. A general technique can be used to cut the edges, such as a method of cutting an edge with a cutter such as a rim-containing tool or a method using a laser. Preferably, the composite film is heated to dry the adhesive and improve its polarizing properties. The heating condition may vary depending on the adhesive, but in the case of the aqueous adhesive, it is preferred that the heating temperature is equal to or greater than 30 ° C, and more preferably, the heating temperature is from 40 to 100 ° C. More preferably, from 50 to 80 ° C, these steps are preferably carried out in an intermediate production line from the viewpoint of performance and production efficiency. <Punching Operation> Fig. 7 shows an example of punching a conventional polarizing plate, and Fig. 8 shows an example of punching a polarizing plate of the present invention. In the conventional polarizing plate as shown in Fig. 7, the absorption axis 71 of the polarizing plate film, that is, the stretching axis system coincides with the longitudinal axis direction 72, and the polarizing plate of the present invention as shown in Fig. 8 is polarized. The absorption axis 81 of the film, that is, the stretching axis is inclined by 45° with respect to the longitudinal axis direction 82 thereof, and this angle is perpendicular or perpendicular to the absorption axis of the polarizing plate and the liquid crystal cell itself when the liquid crystal cell is adhered to the LCD. The angle between the axes is the same. Therefore, it is not necessary to perform the bevel punching operation in the punching step. Further, as shown in Fig. 8, since the polarizing plate of the present invention is cut toward a straight line along the longitudinal axis direction, it can be produced without cutting through the elongated polarizing plate but along the longitudinal axis. A practical polarizing plate results in a significant high yield. <Distributed component content distribution> In the case of producing a long, particularly reel-shaped, polarizing plate-52-1281991 by an intermediate step, it is necessary that no uneven dyeing or undyed dots appear. . If the volatile components in the film have an uneven distribution before the stretching (the amount of volatile components depends on the difference in the position in the plane of the film), unevenness, uniform dyeing or appearance may occur. The point where the color is not dyed. Accordingly, it is preferred that the distribution of the volatile component content before the film is internally stretched is relatively small, and it is preferred that the distribution be at least equal to or less than 5%. The percentage of volatile content used in the present invention means the volume of the volatile component contained in the film per unit volume and refers to the number obtained by dividing the volume of the volatile component by the volume of the film. The distribution of the volatile component content refers to the width of the fluctuation of the percentage of volatile inclusions per square meter (the difference between the maximum or minimum percentage of volatile inclusions and the percentage of average volatile inclusions) Large difference, relative to the percentage of its average volatile inclusions). In order to reduce the distribution of the volatile component content, a method of blowing air to the front or back surface of the film with uniform air, a method of uniformly pressing the film with a pinch roll, or a wiper (for example, A scraper or sponge) is a method of erasing volatile components, but any method can be used as long as the distribution can be made uniform. The present invention will now be described in more detail with reference to examples, but the invention is not limited thereto. [Example 1] Both sides of the PVA film were rinsed with ion exchange treated water having a flow rate of 2 liters/min and the water on the surface was blown off by blowing to remove foreign matter. The film was then immersed in an aqueous solution containing 1.0 g/liter of iodine and 60.0 g/liter of potassium iodide at a temperature of 25 ° C for 90 seconds, and further immersed at a temperature of 25 ° C at -53-1281991. An aqueous solution containing 40 g/L of boric acid and 30 g/L of potassium iodide is allowed to reach for 20 seconds. Subsequently, both sides of the film are blown to remove excess water content, and the distribution of the percentage of water content in the film is adjusted to be equal to or less than 2%, and in this state, as shown in the figure The film was introduced into a stretcher. The film was stretched 6.4 times at 40 ° C and 95% atmosphere and delivered at 100 m/min at a transport rate of 100 m and then shrunk to 4.6 times. The film was then dried at 60 ° C while maintaining the constant width and removed from the spreader. The edge of the diagonal direction of 3 cm was cut out by a cutter, and the film was adhered to a saponified product (triacetate cellulose, delayed 値: 3 nm) manufactured by Fuji Photo Co., Ltd., model Fuj it ac. Using an aqueous solution containing 3% water-soluble PVA (manufactured by Kuraray Co., Ltd., model PVA - 1 17 Η) and 4% potassium sulphate as an adhesive, heating at 60 ° C for 30 minutes and then surrounding A 3 inch diameter paper core is removed. Therefore, it is possible to manufacture a reel-shaped polarizing plate having a width of 650 mm and a length of 100 m without any trouble. The drying point was at the midpoint of zone c and the percentage of water content of the PVA film was 30% at the start of stretching and 1.5% after drying. The difference in transport rate between the right and left tabs is less than 0.05%, and the centerline of the introduced film and the film centerline conveyed to the next step are at an angle of 〇°. Here, |L1-L2| is 〇·7 m and W is 0.7 m, and the relationship of | L 1 - L 2 | = W is established. No wrinkles and deformation of the film were observed at the exit of the cloth machine. The absorption axis direction of the obtained polarizing plate is inclined by 45 ° with respect to the longitudinal axis direction thereof and also inclined by 45 ° with respect to the phase of F u j 1 t a c. This polarized - 54- 1281991 plate has a transmittance of 40 · 6% at 5 50 nm and a degree of polarization of 99 · 53% °. The polarizer reel is stored at 25 ° C, 50% and 2,000 lux for 30 days. . The degree of polarization of the two outer sides is reduced, but the degree of polarization from the third circle is not reduced. Further, as shown in Fig. 8, the polarizing plate was cut into a size of 3 10 0 23 mm, and as a result, a polarizing plate having an area efficiency of 9 1 · 5% and an absorption axis inclined by 45° with respect to the side was obtained. [Example 2] Both sides of the PVA film were washed with ion-exchanged water having a flow rate of 2 liters/min and the water on the surface was blown off by blowing to remove foreign matter. The film was then immersed in an aqueous solution having a temperature of 4 (TC and containing 1.0 g/liter of iodine and 12.0 g/liter of potassium iodide for 90 seconds, and further immersed in a temperature of 40 ° C and containing 40 An aqueous solution of gram/liter of boric acid and 30 g/liter of potassium iodide for 60 seconds. Subsequently, both sides of the film are blown to remove excess water content, and the distribution of the percentage of water content in the film is adjusted to be equal to Or less than 2%, and in this state, the film is introduced into the stretcher in the form shown in Fig. 2. The film is stretched 4.5 times and delivered at a conveying rate of 15 m/min, 500 m. The spreader was then bent relative to the direction of extension as shown in Figure 2. The film was then dried and removed from the spreader at 80 ° C in the atmosphere while maintaining a constant width and shrinking the film. The edge of the diagonal direction of 3 cm was cut out by a cutter, and the film was adhered to a saponified product (triacetate cellulose, delayed 値: 3 nm) manufactured by Fuji Photo Co., Ltd., model Fuj it ac. Use 3% water soluble PVA (by Kuraray manufactures its model pVA-i 17H product 1281991) solution and 4% potassium iodide aqueous solution as an adhesive 'heated at 60 °C for 30 minutes and then taken out around a 3 inch outer diameter paper core' A reel-shaped polarizing plate having a width of 650 mm and a length of 500 m was produced without any trouble. The drying point was at a position of 1/3 of the c-zone and the percentage of water content of the PVA film was 32% at the time of starting the stretching. And after drying, it is 1 · 5%. The difference in conveying rate between the right and left sheet bundles is less than 0.05%' and the angle between the center line of the introduced film and the film center line conveyed to the next step is 46. °. Here, 丨L1-L2I is 0.7 m and W is 0.7 m and the relationship of | LI -L2 | = W is established. At the exit of the cloth machine, the substantial extension direction Ax - Cx will be transmitted to the lower side. The film center line 22 of one step was inclined by 45. The film was not wrinkled and deformed at the exit of the cloth machine. The absorption axis direction of the obtained polarizing plate was inclined by 45° with respect to the longitudinal direction thereof. The polarizing plate has a transmittance of 42.1% at 5 50 nm and The degree of polarization is 99.97%. The polarizer reel is stored at 25 ° C, 50% and 2,000 lux for 30 days. The degree of polarization of the outer two circles is reduced but the degree of polarization from the third circle is not reduced. The polarizing plate was cut into a size of 310 x 233 mm as shown in Fig. 8, and as a result, a polarizing plate having an area efficiency of 9 1 · 5% and an absorption axis inclined by 45° with respect to the side was obtained. [Comparative Example 1] 2 liter/min ion-exchanged water-washed PVA thin 1281991 Both sides of the film were blown off by water to remove foreign matter adhering to the surface to be equal to or less than 0 · 5% . The film was immersed in an aqueous solution containing 1.0 g/liter of iodine and 120.0 g/liter of potassium iodide at a temperature of 40 ° C for 90 seconds, and further immersed in a temperature of 40 ° C and containing 40 g / liter. The boric acid and 30 g / liter of potassium iodide in an aqueous solution for 60 seconds. Subsequently, the film is introduced into the stretcher of the cloth to stretch the film in a form as shown in Fig. 2, without blowing the both sides of the film and having a distribution of the percentage of water content in the film of 1% by volume. 4 . 5 times. The fabric was bent relative to the direction of extension as shown in Fig. 2, and the film was dried and removed from the spreader in an atmosphere of 30 ° C while maintaining a constant width and shrinking the film. Dyeing unevenness was generated across the entire surface of the film, and the creping phenomenon was maintained as it was, and the protective film was not adhered due to the rough surface, and the reel-shaped polarizing plate could not be formed. [Example 3] The iodine-type polarizing plates 9 1 and 92 prepared in Example 2 were used as two polarizing plates with a liquid crystal cell 9 3 for an LCD interposed therebetween. As shown in Fig. 9, a polarizing plate 9 1 is disposed as a polarizing plate on the display side and adhered to the liquid crystal cell 93 through an adhesive to manufacture an LCD. If the LCD is made, it will exhibit excellent brightness, viewing angle properties and visibility, and it will not destroy its display level even after being used for one month at 40 °C and 30% RH. (Measurement of Transmittance and Degree of Polarization on 5 50 nm) Transmittance was measured by an automatic recording spectrometer manufactured by Shimadzu Corporation under the model number UV2100. In addition, the transmittance Η Ο ( % ) when the absorption axes are matched by two overlapping polarizers - 57- 1281991 and the transmittance Η 1 ( % ) when the absorption axes are orthogonal to each other can be determined by the following formula Degree p (%): P=[ (HO-H1 ) / (HO + H1 ) ] 1/2 xlOO (measurement of retardation) This measurement system is used in 6 3 2 . 8 nm by the 〇ji test instrument The company manufactures its model K0BRA21DH. [Example 4] The PVA film was immersed in an aqueous solution containing 1.0 g/liter of iodine and 10.0 g/liter of potassium iodide at a temperature of 40 ° C for 90 seconds, and further immersed in a temperature of 40 ° C. An aqueous solution containing 40 g/L of boric acid and 30 g/L of potassium iodide was allowed to reach 1 20 seconds. Subsequently, the film was introduced into a stretcher as shown in Fig. 1, and the film was stretched by 7.0 times and then applied at 7000 Newtons/meter in an atmosphere having a temperature of 6 2 ° C and a humidity of 96%. The constant tension caused it to shrink to 5.3 times. The film was then dried at 60 ° C while maintaining the constant width and removed from the spreader. The moisture content of the PVA film is 42.3%, the water content percentage distribution is 3.8%, and the expansion percentage is 31.9%. After drying, the film moisture content percentage is 4 · 8 %. The water content percentage distribution is 2.0%. The difference in transport rate between the right and left tabs is less than 〇 〇 5%, and the centerline of the introduced film and the angle 0 of the film centerline delivered to the next step. In the case, I L1-L2I is 〇·7 m and w is 〇.7 m and the relationship of I L 1 - L2 | is established. At the exit of the cloth machine, no wrinkles and deformation of the film were observed. - 58 - 1281991 Then, this PVA film was adhered to a saponified product (Triacetate, delayed 値: 3 nm) manufactured by Fuji Photo Co., Ltd., model Fu Kitac, using 3% water-soluble PVA (by Kura) Ray produced a solution of its model PVA-1 17H) and an aqueous solution of 4% potassium iodide as an adhesive, which was dried at 80 ° C to obtain a polarizing plate with a working width of 670 mm. The absorption axis direction of the obtained polarizing plate is inclined by 45 ° with respect to the longitudinal axis direction thereof and also by 45° with respect to the phase of the Fuj i t ac. The polarizing plate had a transmittance of 43.0% at 550 nm and a degree of polarization of 99.94%. [Example 5] The PVA film was immersed at a temperature of 4 (TC and contained 1.0 g·· liter of iodine and 12.0 Å. The aqueous solution of gram/liter of potassium iodide was allowed to stand for 90 seconds, and further immersed in an aqueous solution containing 40 g/liter of boric acid and 30 g/liter of potassium iodide at a temperature of 40 ° C for 1 20 seconds. The film was introduced into the stretcher as shown in Fig. 1 so that the tension along the longitudinal axis of the film was kept constant, and the film was stretched 7.0 at a temperature of 62 ° C and a humidity of 96%. After the doubling, a constant tension of 390 N/m was applied to shrink it to 5.3 times. The film was then dried at 60 ° C and removed from the spreader while maintaining the constant width. The PVA was taken before the stretch was initiated. The film has a water content percentage of 43. 1%, a water content percentage distribution of 4.0% and a percent expansion of 32.3%. After drying, the water content percentage is 4.2% and its swelling percentage is 1.9%. The difference in transport rate between the right and left sheets is less than 0. 0 5%, and the angle between the center line of the film and the center line of the film transferred to the next step is 0. The ''lLl-L2| is 〇·7 meters and W is 0.7 meters. The relationship of | L· 1 - L2 | = W was established. At the exit of the cloth machine, no wrinkles and deformation of the film were observed. Then, the PVA film was adhered to the model made by Fuji Photo Co. Fuj i tac saponified product (triacetate cellulose, delayed 値: 3 nm) 'Using a solution containing 3% water-soluble PVA (manufactured by Kuraray, model PVA - 1 17H) and 4% potassium iodide The aqueous solution was used as an adhesive and dried at 80 ° C to obtain a polarizing plate having a working width of 680 mm. The absorption axis direction of the obtained light-emitting plate was inclined by 45 with respect to the longitudinal axis thereof. The polarizing plate was at 5 50. The transmittance of nanometer was 43.4% and the degree of polarization was 99.9%. [Example 6] The PVA film was washed with ion-exchanged water treated at a flow rate of 2 liters/min and was blown by blowing. Remove the water from the surface to remove foreign matter. Immerse the film at a temperature of 4 (TC and contain 1.0 g / g Iodine and 60.0 g/L of potassium iodide in an aqueous solution for 90 seconds, and further immersed in an aqueous solution containing 40 g/L of boric acid and 30 g/L of potassium iodide at a temperature of 40 ° C for 1 20 seconds. Then, the film is blown with a blowing device as shown in Fig. 10 to remove excess water content. The film is introduced into the stretcher in the form shown in Fig. 1 and once at a time. The film was stretched by 7.5 times in a temperature of 64 ° C and a humidity of 91%, and then a constant tension of 375 N/m was applied to shrink it to 5.3 times. The film was then dried at 60 ° C and removed from the spreader while maintaining a constant width. The PVA film had a water content percentage of 44. 2%, 1281991 water content percentage distribution of 4 · 3% and a percent expansion of 32 · 7% before starting the stretching. After drying, the water content percentage was 3.9% and its percent expansion was 1.8%. The difference in conveyance rate between the right and left sheet bundles is less than 〇 · 〇 5%, and the center line of the introduced film and the film center line conveyed to the next step are at an angle of 0°. Here, |L1-L2| is 0.7 m and W is 0.7 m to establish a relationship of I L 1 - L2 | = W. At the exit of the cloth machine, no wrinkles and deformation of the film were observed. Then, the PVA film was pasted with a saponified product (Triacetate Cellulose, Delayed 値: 3 nm) made by Fuji Photo Co., Ltd., model Fuj i tac, using 3% water-soluble? \^ (1 (111^^7 company made the model of PVA-1 17H) solution and 4% potassium iodide aqueous solution as an adhesive 'drying at 80 ° C to achieve a working width of 67 5 mm Polarizing plate. The absorption axis direction of the obtained polarizing plate is inclined by 45° with respect to the longitudinal axis direction. The transmittance of the polarizing plate at 550 nm is 43.1% and the degree of polarization is 9 9.9 8%. 7] The PVA film was washed with ion-exchanged water having a flow rate of 2 liters/min and the water on the surface was removed by blowing to remove foreign matter. The film was immersed at a temperature of 1·0 g. / liter of the monument and I20 · 0 grams of 'liters of iodine potassium in an aqueous solution for 90 seconds, and further immersed in a temperature of 40 ° C containing 40 grams / liter of boric acid and 30 grams / liter of the monument The aqueous solution of potassium was allowed to reach 1 2 sec. Then, the film was blown by a kneading device as shown in Fig. 1 1 to remove excess water content. The shape as shown in Fig. 1 -61-1281991 Introduce the film into the stretcher to stretch the tension along the longitudinal axis of the film, and once at a temperature After stretching the film at 57 ° C and a humidity of 95% in the atmosphere, the film was stretched by 0.001 times and then subjected to a constant tension of 366 N/m to make it shrink to 5.3 times. After that, the film was kept at a constant width of 60 ° C. The film was dried and removed from the spreader. The PVA film had a water content percentage of 44.7%, a water content percentage distribution of 4.4% and a percent expansion of 33.1% before starting the stretching. The percentage of water content is 3.7% and the percentage of expansion is 1.6%. The difference in conveying rate between the right and left sheets is less than 0.05%, and the center line of the introduced film is transferred to the next. The angle of the film center line of the step is 0°. Here, |L1-L2| is 0.7 m and W is 0.7 m, and the relationship of | L 1 - L2 | = W is established. At the exit of the cloth machine, No wrinkles and deformation of the film were observed. Then, the PVA film was adhered to a saponified product (triacetate cellulose, delayed 値: 3 nm) manufactured by Fuji Photo Co., Ltd., model Fuji I tac. Made with 3% water-soluble PVA (manufactured by Kuraray, model PVA - 1 1 1 7H) The solution was used as an adhesive and dried at 80 ° C to obtain a polarizing plate having a working width of 685 mm. The absorption axis direction of the obtained polarizing plate was inclined by 45° with respect to the longitudinal axis thereof. The transmittance of 550 nm was 43.9% and the degree of polarization was 99.97%. [Example 8: Fabrication of Liquid Crystal Display] Using the iodine-type polarizing plates 9 1 and 9 2 prepared in Example 5 as two polarized lights The board is inserted with a liquid crystal cell 93 for an LCD therebetween. As shown in Fig. 9, - 6 2 - 1281991, a polarizing plate 91 is disposed as a polarizing plate on the display side and adhered to the liquid crystal cell 93 through an adhesive to manufacture an LCD. If the LCD is made, it will exhibit excellent brightness, viewing angle properties and visibility, and it will not destroy its display level even after being used for one month at 40 °C and 3 OMH. [Comparative Example 2] The PVA film was immersed in an aqueous solution having a temperature of 4 (TC and containing 1.0 g/liter of iodine and 120.0 g/liter of potassium iodide for 90 seconds, and further immersed in a temperature of 4 (TC). The aqueous solution containing 40 g/L of boric acid and 30 g/L of potassium iodide was allowed to reach for 20 seconds. Then, the film was introduced into the stretcher as shown in Fig. 1, once at a temperature of 60. The film was stretched 7.0 times in °C and 45% humidity, and then subjected to a steady tension of 3 3 Newtons/meter to shrink it to 5.3 times. Then the film was dried at 60 ° C while maintaining a constant width. And the moisture content of the PVA film is 28.9%, the water content percentage distribution is 7.3 %, and the expansion percentage thereof is 29.1%. After drying, it is contained. The water percentage is 8.3% and its expansion percentage is 6.3%. The difference in transport rate between the right and left tabs is less than 0.05%, and the center line of the introduced film and the film center line transferred to the next step The angle of the clip is 〇°. Here, I Ll-L2 | is 0.7 m and W is 0.7 m and the relationship of | L 1 - L2 | = W is established. Although the wrinkles and deformation of the film are not observed at the exit of the cloth machine, a great number can be observed. Uneven part. - 63- 1281991 Then 'This PVA film is pasted with a saponified product of its type Fuj it ac manufactured by Fuji Photo Co., Ltd. (triacetate cellulose, delayed 値: 3 nm), with 3 A solution of % water-soluble PVA (manufactured by Kuraray Co., Ltd., model PVA - 1 1 7H) was used as an adhesive and dried at 80 ° C to obtain a polarizing plate having a working width of 450 mm. The absorption axis direction is inclined by 45° with respect to the longitudinal axis direction thereof. The transmittance of the polarizing plate 5 50 nm is 40.1% and the degree of polarization is 96.3 8%. (Transmittance is performed at 550 nm and Measurement of the degree of polarization) The transmittance was measured by an automatic recording spectrometer manufactured by Shimadzu Corporation, model number UV2100. In addition, the transmittance H0 (%) when the absorption axes of two overlapping polarizers were matched Transmittance when its absorption axis is orthogonal to each other Hl (%), the degree of polarization P (%) is determined by the following formula; P = [(H0-H1) / (H0 + H1)] 1/2 χ 100 from comparison between example 2 and examples 4 to 6 It can be clearly seen that the polarizing plate having a working width equal to or greater than 650 mm can be obtained by optimizing the humidity during stretching and the tension along the longitudinal axis of the film. It is apparent that the working width can be further increased by optimizing the humidity during stretching, the tension along the longitudinal axis of the film, and the stretching before and after stretching. [Example 9] The PVA film was immersed in an aqueous solution containing 1.0 g/liter of iodine and 60 g/liter of potassium iodide at a temperature of 25 ° C for 90 seconds, and further immersed at a temperature of 25 In an aqueous solution containing 40 g/L of boric acid and 30 g/L of potassium iodide for 1 20 seconds. The sides of the film were blown using a blower device as shown in Figures 1 0-64-1281991 to remove excess moisture from the film and reduce the moisture percentage to 2% or less. In this state, the film is introduced into the stretcher in the form shown in Fig. 1, and the film is stretched 6.4 times in an atmosphere at a temperature of 40 ° C and a humidity of 95%. The shrinkage is 4.5 times. Then, while maintaining the constant width, the film was dried at 6 (TC) and removed from the spreader. The cutter was used to cut the edge of the diagonal direction of 3 cm, and the film was adhered to the model manufactured by Fuji Photo Co., Ltd. For the saponified product of Fuj i tac (triacetate cellulose, delayed 値: 3 nm), a solution containing 3% water-soluble PVA (manufactured by Kuraray, model PVA - 1 17H) and 4% The aqueous solution of potassium iodide is used as an adhesive and heated at 60 ° C for 30 minutes, so that a polarizing plate having a working width of 650 mm can be produced without any trouble. The percentage of water content of the PVA film is 30 at the time of starting stretching. % and after drying is 1.5%. The difference in conveying rate between the right and left tabs is less than 〇. 〇 5%, and the center line of the introduced film and the film center line transferred to the next step are sandwiched The angle is (Γ. Here, |L1-L2| is 0.7 m and W is 0.7 m and the relationship of | L 1 - L 2 | = W is established. At the exit of the machine, no film is observed. Lifting and deformation phenomenon. The absorption axis direction of the obtained polarizing plate It is inclined by 45° with respect to the direction of its longitudinal axis and is also inclined by 45 with respect to the phase behind the Fuj i tac. The polarizing plate has a transmittance of 50.2% at 5 50 nm and a degree of polarization of 9 9.5 0%. This polarizing plate has a good surface state and no unevenness is observed under visual conditions. -65- 1281991 In addition, as shown in Fig. 8, the polarizing plate is cut into a size of 310 x 233 mm, resulting in a region efficiency of 9 1 · 5% and a polarizing plate whose absorption axis is inclined by 45° with respect to the side. [Example 1 〇] The PVA film was immersed in iodine at a temperature of 30 ° and containing 1 · 0 g / liter and 120.0 g / liter In an aqueous solution of potassium iodide for 90 seconds', it was further immersed in an aqueous solution containing 40 g/liter of boric acid and 30 g/liter of potassium iodide at a temperature of 30 ° C for 60 seconds. The kneading device is shown to blow air on both sides of the film to remove excess water content and reduce the water content percentage to 2% or less. In this state, the film is formed in the form as shown in Fig. 1. Introduce the cloth stretcher to make the film at 60 °C The air is stretched 4.5 times in the atmosphere with a humidity of 95% and then bent as shown in Fig. 2 with respect to the stretching direction. Then, after maintaining the constant width and shrinking the film, the film is made of 8 (TC). Dry and remove from the machine. Use a cutter to cut the edge of the diagonal direction of 3 cm, and attach the film to a saponified product (Triacetate fiber) made by Fuji Photo Co., Ltd., model Fu jit ac , delayed 値: 3 nm), using an aqueous solution containing 3% water-soluble PVA (manufactured by Kuraray, model PVA-117H) and 4% potassium iodide as an adhesive, heated at 60 ° C for 30 minutes Therefore, it is possible to manufacture a polarizing plate having a working width of 65 mm without any trouble. The water content of the PVA film was 32% at the time of starting stretching and 1.5% after drying. The difference in transport rate between the right and left tabs is less than 0.05%, and the angle between the centerline of the film introduced into the film and the centerline of the film transferred to the next step is 46. . Here, I L b L2| is 0.7 m and W is 0·7 m to establish a relationship of | L b L2| = W. At the exit of the spreader, the substantial stretch direction Ax - Cx is inclined 4 5 relative to the film centerline 22 that is transferred to the next step. . No wrinkles and deformation of the film were observed at the exit of the cloth machine. The absorption axis direction of the obtained polarizing plate is inclined by 45 for its longitudinal axis direction. . The polarizing plate has a transmittance of 41.9% at 550 nm and a degree of polarization of 99.96 %. This polarizing plate had a good surface state and no unevenness was observed under visual conditions. Further, as shown in Fig. 8, the polarizing plate was cut into a size of 3 10 0 2 3 3 mm, and as a result, a polarizing plate having an area efficiency of 91.5% and an absorption axis inclined by 45° with respect to the side was obtained. [Comparative Example 3] The PVA film was immersed in an aqueous solution containing 1.0 g/liter of iodine and 12.0 g/liter of potassium iodide at a temperature of 30 ° C for 90 seconds, and further immersed in a temperature of 30 In an aqueous solution containing 40 g/liter of boric acid and 30 g/liter of potassium iodide for 60 seconds. Subsequently, the film is introduced into the stretcher of the cloth to stretch the film in a form as shown in Fig. 2, without blowing on both side surfaces of the film and having a distribution of the percentage of water content in the film of 10%. 4 . 5 times. As shown in Fig. 2, the cloth stretching machine was bent with respect to the stretching direction, and the film was dried and removed from the cloth machine in an atmosphere of 30 ° C while maintaining a constant width and shrinking the film. Dyeing unevenness was generated across the entire surface of the film, the wrinkle was maintained as it was, and -67-1281991 was unable to adhere to the protective film due to the rough surface, and it was impossible to form a reel-shaped polarizing plate. [Example 11] Using the iodine-type polarizing plates 9 1 and 9 prepared in 〇 1 as two polarizing plates and inserting a liquid crystal cell 93 for an LCD therebetween. As shown in Fig. 9, a polarizing plate 9 1 is disposed as a polarizing plate on the display side and adhered to the liquid crystal cell 93 through an adhesive to manufacture an LCD. In the case of a finished LCD, it exhibits excellent brightness, viewing angle properties, and visibility, and it does not deteriorate its display level even after being used for one month at 40 ° C and 30% RH. (Measurement of Transmittance and Degree of Polarization at 550 nm) Transmittance was measured by an automatic recording spectrometer manufactured by Shimadzu Corporation under the model number UV2100. Further, the transmittance Η 0 (%) when the absorption axes of the two overlapping polarizing plates are matched and the transmittance Hl (%) when the absorption axes are orthogonal to each other are determined by the following formula (%) ) Ρ = [ (Η0-Η1 ) / (Η0 + Η1 ) ] 1/2χ100 (Measurement of delay) This measurement is made at 63 2 . 8 nm using the model K0BRA2 1DH manufactured by Oj i Test Instruments The implementation of the product. Industrial Applicability According to the present invention, an elongated reel type polarizing plate comprising a polarizing film extending at an oblique angle is obtained. Such a long scroll type polarizing plate can increase the yield and thus the cost thereof in the step of performing punching to form a polarizing plate. In addition, the polarizer has excellent storage and high performance. With such a polarizing plate, a liquid crystal display having an excellent display level can be provided at a low cost of 1281991. (5) Brief Description of Drawings Fig. 1 is a plan view showing an example of a method for obliquely stretching a polymer film according to the present invention. Figure 2 is a schematic plan view showing an example of a method for obliquely stretching a polymer film according to the present invention. Fig. 3 is a schematic plan view showing an example of a method for obliquely stretching a polymer film according to the present invention. Fig. 4 is a plan view showing an example of a method for obliquely stretching a polymer film according to the present invention. Fig. 5 is a plan view showing an example of a method for obliquely stretching a polymer film according to the present invention. Fig. 6 is a plan view showing an example of a method for obliquely stretching a polymer film according to the present invention. Fig. 7 is a plan view showing a state in which a conventional polarizing plate is punched. Fig. 8 is a plan view showing a state in which the polarizing plate of the present invention is perforated. Fig. 9 is a plan view showing the structure of the inner film of the liquid crystal display of Example 5. Figure 10 is a diagram showing the mourning of an air blowing device. Figure 11 is a diagram showing the concept of a kneading device. Figure 12 is a schematic representation of a blade device. Explanation of main component symbols -69- 1281991 (11) (a) (b) (c) A1 B1 Cl
CxCx
Ay I LI -L2 I W Θ II 12 13 14 15 16 17,179 薄膜引進方向 輸送到下一步驟的方向 薄膜引進步驟 薄膜伸展步驟 將已伸展薄膜送到下一步1 薄膜與支持機制的接合位 起始位置（實質的支持起始 薄膜與支持機制的接合位濯 薄膜伸展的起始位置（實質 左邊） 薄膜伸展的脫離位置及最I 的支持脫離點：左邊） 薄膜伸展的最後基礎位置（ 點：右邊） 左邊和右邊薄膜支持機制之 薄膜伸展步驟終點的實質1 伸展方向和薄膜行進方向的 引進側薄膜的中心線 送到下一步驟之薄膜的中；I 薄膜支持機制的軌跡（左邊 薄膜支持機制的軌跡（右邊 引進側的薄膜 送到下一步驟的薄膜 開始支持（接合）薄膜之左全 -70- 的步驟 置及薄膜伸展的 貼：右邊） (左邊） 的支持起始點z I基礎位置（實質 實質的支持脫離 間的路徑差 度 夾角 線 及右邊的點 1281991 18,185 薄膜脫離支持之左邊及右邊的點 21 引進側薄膜的中心線 22 送到下一步驟之薄膜的中心線 23 薄膜支持機制的軌跡（左邊） 24 薄膜支持機制的軌跡（右邊） 25 引進側的薄膜 26 送到下一步驟的薄膜 27，27， 開始支持（接合）薄膜之左邊及右邊的點 28，28， 薄膜脫離支持之左邊及右邊的點 33,43,53,63 薄膜支持機制的軌跡（左邊） 34,44,54,64 薄膜支持機制的軌跡（右邊） 35,45,55,65 引進側的薄膜 36,46,56,66 送到下一步驟的薄膜 71 吸收軸（伸展軸） 72 縱軸 81 吸收軸（伸展軸） 82 縱軸方向 91，92 含碘式偏光膜（偏光層） 93 液晶單元 94 背光 101 吹氣裝置 111 捏挾裝置 121 刀片裝置 -71-Ay I LI -L2 IW Θ II 12 13 14 15 16 17,179 Film introduction direction to the next step direction Film introduction step Film stretching step sends the stretched film to the start position of the next film and support mechanism ( Substantial support for the initial film and support mechanism of the joint position of the film stretching start position (substantially left) film release position and the most I support disengagement point: left) the final base position of the film stretch (point: right) left And the film of the right film support mechanism at the end of the film stretching step 1 The direction of the extension and the direction of the film is introduced into the film of the next step; I track the trajectory of the film support mechanism (the trajectory of the left film support mechanism ( The film on the right side of the right side is sent to the next step. The film starts to support (join the film). The left full-70-step of the film and the film stretched paste: the right side (left) support starting point z I base position (substantial substance) Support for the difference between the path difference angle and the right point 1281991 18,185 film off the left side of the support and The point 21 of the edge introduces the center line 22 of the side film to the center line of the film of the next step. 23 The track of the film support mechanism (left side) 24 The path of the film support mechanism (right side) 25 The film 26 of the introduction side is sent to the next step. Films 27, 27, starting to support (join) the left and right points 28, 28 of the film, the left and right points of the film detachment support 33, 43, 53, 63 trajectory of the film support mechanism (left) 34, 44, 54,64 Trace of film support mechanism (right) 35,45,55,65 Film 36,46,56,66 on the introduction side Send to film 71 of the next step Absorption axis (extension axis) 72 Vertical axis 81 Absorption axis ( Extension axis) 82 Vertical axis direction 91, 92 Iodine-containing polarizing film (polarizing layer) 93 Liquid crystal unit 94 Backlight 101 Air blowing device 111 Kneading device 121 Blade device-71-