201033658 六、發明說明： 【發明所屬之技術領域】 本發明係關於可作爲構成液晶顯示裝置之偏光板的構 件加以使用之偏光膜之製法。 【先前技術】 液晶顯示裝置（LCD )在其開發初期係在電子計算機 及手錶等小型機器中被加以使用，但近年來則在筆記型個 人電腦、液晶監視器、液晶彩色投影機、液晶電視、車載 用導航系統、行動電話、室內外使用的量測機器等廣泛範 圍內加以使用。另一方面，尤其在液晶電視等用途中，係 逐漸圖求顯示品質的提升，例如對比的提升，對於作爲LCD 之構件之一的偏光板，亦強烈要求偏光性能的提升。 以往一般所使用的偏光板係具有對由聚乙烯醇（以下 有時稱爲PVA)所構成的生膜材料施行單軸延伸、藉由碘 或雙色性染料所爲之染色處理、藉由硼化合物所爲之固定 處理等，在所得偏光膜的單面或雙面貼合三醋酸纖維素膜 或醋酸-丁酸纖維素膜等保護膜而成的構成。以使如上所示 之偏光板的偏光性能提升的手法而言，已提案有將作爲原 料的PVA的構造加以改良的手法、控制PVA膜之物性的方 法、在偏光板的製造條件設法的方法等各種手法，有助於 LCD的對比提升。 例如在專利文獻1中，係記載由具有2 5 0 0以上、最好 爲6000〜10000之聚合度的PVA所構成的偏光膜的光學特 性優異。使用聚合度高的PVA雖係有利於提升偏光性能的 手法，但是在工業上的實施乃極其困難。 201033658 此外，以使偏光性能提升的其他方法而言，例如在專 • 利文獻2中，係記載一種使用在熱水中的完全溶解溫度（X) 與平衡膨潤度（Y)的關係如下式所示之範圍的PV A系膜 作爲生膜材料之偏光膜之製法。 Y > -0.0667X + 6.73 ...... (I) X ^ 65 ...... (II) 但是，上述發明所使用的PVA的聚合度較佳爲3 5 00 〜5000的範圍，即使將該製法直接應用在高聚合度PVA， 〇 亦如後述之比較例所示，可知所得之偏光膜的偏光性能並 不足夠。亦即，在工業上製造由高聚合度的PVA所構成之 偏光膜時，必須全方位考量關於PVA的結構、PVA薄膜的 物性等資訊，而找出最適當之原料條件。 (先前技術文獻） (專利文獻） 專利文獻1 日本特開平1 -1 05204號公報 φ 專利文獻2 日本特開平7-1 2061 6號公報 【發明內容】 (發明所欲解決之課題） 因此，本發明之目的在提供一種可將由高聚合度的 PVA所構成的膜加工成具有高偏光性能之偏光膜的偏光膜 之製法。 (解決課題之手段） • 發明人等將關於PVA的構造及PVA膜的物性、甚至偏 光膜的製造條件等之所知以最大限度加以活用而進行檢 -4- 201033658 討。結果，發現一種偏光膜之製法，係包含將聚合度爲5000 以上之PVA予以製膜所得之膨潤度爲A ( % )的生膜材料 濕式延伸爲2.0〜2.9倍，以製得膨潤度爲B ( % )之延伸 膜的步驟，其中上述A與B滿足下式（1)及（2)，藉此呈現 本發明之效果： 200 ^ A ^ 240 (1) A + 20 ^ B ^ A + 35 (2)。 此時，較佳爲將前述生膜材料在碘-碘化鉀水溶液中作 ^濕式延伸。 此外，前述生膜材料較佳爲在製膜後以115〜130 °C予 以熱處理所得者。 此外，較佳爲在前述濕式延伸的步驟之後，包含將所 得延伸膜另外在硼酸水溶液中延伸爲3倍以下的步驟。 本發明亦包含一種偏光膜，其係藉由上述製法所得， 透過率爲43.0%以上且偏光度爲99.97%以上。 φ (發明之效果） 藉由本發明之製法，可將由高聚合度的PVA所構成的 膜加工成具有高偏光性能之偏光膜，使得具有高偏光性能 之偏光膜可在工業上生產。 【實施方式】 (實施發明之形態） 以下詳加說明本發明。 ' 在本發明中所使用之PVA的聚合度係爲了對應於作爲 本發明之目的的良好偏光性能，因此必須爲5 000以上’較 201033658 佳爲5500以上’更佳爲6000以上。若PVA的聚合度低於 5000’難以呈現高偏光性能。以PVA的聚合度的上限而言， 雖未特別有所限制，但是愈爲高聚合度，PVA的生產性愈 爲降低，因此由工業上的觀點來看，較佳爲10000以下。 其中’本發明中所稱之PVA的聚合度意指按照後述之實施 例所記載的方法所測定出的聚合度（黏度平均聚合度）。 此外，PVA的皂化度較佳爲99莫耳％以上，更佳爲99.8 ^ 莫耳％以上。若PVA的皂化度低於99莫耳％，在後述之偏 ❹ 光膜之製造步驟中，PV A容易溶析，所溶析的VA會附著 在膜上而有使偏光膜的性能降低之虞。 在本發明中所使用的PV A係可藉由將乙烯酯聚合所得 之聚乙烯酯系聚合物加以皂化予以製造。以乙烯酯而言， 可例示：乙酸乙烯酯、甲酸乙烯酯、丙酸乙烯酯、丁酸乙 烯酯、三甲基乙酸乙烯酯、叔碳酸乙烯酯（vinyl versatate )、月桂酸乙烯酯、硬脂酸乙烯酯、苯甲酸乙烯 Q 酯等，由該等之中選擇1種或2種以上。由取得容易性、 PVA製造容易性、成本等方面來看，在該等之中，較適於 使用乙酸乙烯酯。聚合溫度雖未特別有所限制，但是在使 用甲醇作爲聚合溶媒時，聚合溫度較佳爲甲醇之沸點附近 的6 0 °C前後。 只要未損及本發明之效果，PVA則未限定於乙烯酯之 單獨聚合物的皂化物。例如亦可爲在PVA將不飽和羧酸或 • 其衍生物、不飽和磺酸或其衍生物、碳數2〜30的^^ -烯烴 等，以低於5莫耳％的比例作接枝共聚合而成的改質PVA ; 201033658 將乙烯酯 '不飽和羧酸或其衍生物、不飽和磺酸或其衍生 物、碳數2〜30的α -烯烴等，以低於15莫耳％的比例共聚 合的改質聚乙烯酯的皂化物；以甲醛水、丁醛、苯甲酵等 醛類將PVA之羥基的一部分交聯而成的聚乙烯縮醒系聚合 物等。 藉由將上述PVA予以製膜而得生膜材料。以製膜方法 而言，除了將含水PVA進行熔融押出的方法以外，另外可 採用流延製膜法、濕式製膜法（排出至不良溶媒中）、凝 響 膠製膜法（在將PVA水溶液暫時冷卻凝膠化之後，將溶媒 予以抽出去除）、鑄型製膜法（將PVA水溶液在基盤上流 動、乾燥）、及藉由該等組合所得之方法等。在該等之中， 以熔融押出製膜法及流延製膜法可得良好的PVA膜（生膜 材料），故較爲理想。 以上述製膜時所使用的溶劑而言，列舉例如：二甲基 亞砸、二甲基甲醯胺、二甲基乙醯胺、Ν-甲基咯烷酮、乙 _ 二醇、甘油、丙二醇、二乙二醇、三乙二醇、四乙二醇、 三甲基醇丙烷、乙二胺、二伸乙三胺、水等，可使用該等 之中的1種或2種以上。在該等之中，亦較適於使用水、 二甲基亞碾、及該等之混合溶媒。 主要由PVA與溶劑所構成之製膜原液的揮發分率係依 製膜方法或PVA的分子量而產生變化，但以50〜95質量％ 爲佳，以6 0〜9 5質量％爲較佳，以7 0〜9 5質量％爲更佳。 若揮發分率低於50質量％，製膜原液的黏度會變得過高， 調製時的過濾或消泡會變得較爲困難，而會有難以獲得沒 201033658 有異物或缺點的生膜材料之虞。此外，若揮發分率超過95 質量％，則製膜原液的黏度會變得過低，會有難以製造具 有目的厚度或厚度精度的生膜材料之虞。 在製造生膜材料時，亦可使用可塑劑。以可塑劑而言， 列舉甘油、二甘油、乙二醇等，但是並非限定於此。可塑 劑的使用量亦未特別有所限制，但是通常在相對PVA1 00 質量份爲1〇〜15質量份的範圍內。 I 以製膜後之生膜材料的乾燥方法而言，列舉例如藉由 熱風所爲之乾燥、或使用加熱輥的接觸乾燥、或藉由紅外 線加熱器所爲之乾燥等。可單獨使用該等方法中的1種， 亦可組合2種以上加以使用。關於乾燥溫度雖未特別有所 限制，但是以50〜70 °C的範圍內爲佳。此外，此時的乾燥 時間亦依製膜原液的濃度或製膜條件而異，但是大槪爲45 〜75分鐘。 乾燥後的生膜材料係以進行熱處理爲佳，俾以將其膨 ^ 潤度控制在後述之預定範圍內。以製膜後之原膜材料的熱 處理方法而言，列舉例如藉由熱風所爲之方法、或使生膜 材料接觸加熱輥的方法等。可單獨使用該等方法中的1 種，亦可組合2種以上加以使用。關於熱處理溫度雖未特 別有所限制，但是以1 1 5〜1 30°c的範圍內爲佳。此外，此 時的熱處理時間係以5分鐘以內爲佳。 如此所得之生膜材料的厚度係以20〜120；am爲佳，以 20〜80 yin爲較佳，以20〜40ym爲更佳。若厚度低於20 #rn，會有在後述之延伸步驟中容易發生膜斷裂之虞。此 201033658 外，若厚度超過120/zm，則在延伸時施加於 大，而會有難以充分延伸之虞。 生膜材料的膨潤度A必須爲200〜240 %， 爲佳，以2 1 0〜23 0%爲較佳。若膨潤度A低;! 伸時的張力會變得過大，而會難以進行充分 若膨潤度A超過240%，由於吸水性較高，在 之製造步驟中，容易在膜發生皺痕或端部捲 ^ 伸時斷裂的原因。爲了將膨潤度A控制在預 ❺ 例如在將製膜後的生膜材料進行熱處理時的 以調整即可。生膜材料的膨潤度A係在實施 藉由後述方法加以測定。 接著，敘述使用上述生膜材料之本發明 法。偏光膜之製造步驟係可包含水分調整、 色調整等步驟。此時，必須進行生膜材料的 進行延伸膜之膨潤度B的調整。此外，亦可 φ 述濕式延伸的步驟之後，將所得延伸膜另外 中延伸。此外，亦可視需要，例如在含有硼 水溶液中進行色調整且予以乾燥，而製造偏 生膜材料的水分調整係以浸漬在純水或 爲佳。以此時的溫度而言，以20〜40°C爲fi °C爲較佳，以2 7〜3 3 °C爲更佳。若溫度低於 ' 料的含水率會變低，在之後作延伸時施加於 高，而會有難以調整延伸膜之膨潤度B之虞 度超過40°C，生膜材料的吸水性會變高，在 膜的應力會變 以 20 5 〜23 5% 令2 0 0 %，則延 延伸。此外， 後述之偏光膜 曲，而造成延 定範圍內，若 溫度或時間加 例之項目中可 之偏光膜之製 染色、延伸、 濕式延伸，而 視需要，在上 在硼酸水溶液 酸及碘化鉀的 光膜。 蒸餾水中進行 i，以 2 5〜3 5 2〇°C，生膜材 膜的張力會變 。此外，若溫 之後的步驟中 201033658 容易在膜發生皺痕或端部捲曲，而有造成延伸時斷裂的原 因之虞。另一方面，以浸漬生膜材料的時間而言，大槪在 • 30〜120秒鐘的範圍內。 生膜材料的染色係在例如碘-碘化鉀水溶液中進行。此 時以碘的濃度爲0.01〜0.1質量％，碘化鉀的濃度爲1〜10 質量％爲佳，以碘濃度0.0 2〜0.0 8質量％，碘化鉀濃度2〜 8質量％爲較佳，以碘濃度0.03〜0.06質量％，碘化鉀濃度 3〜6質量％爲更佳。關於水溶液的溫度雖未特別有所限 制，但以25〜40°C爲佳。 生膜材料的濕式延伸亦可作爲有別於上述的水分調整 或染色的步驟來進行，但是以在上述之水分調整用的水 中、或在染色用的水溶液中進行在效率上較爲理想，在染 色用的水溶液，亦即碘-碘化鉀水溶液中進行爲更佳。生膜 材料之濕式延伸時，爲了將延伸後的膜的膨潤度B調整爲 後述之預定範圍，以延伸前後之膜的長度的比所表示的延 q 伸倍率係必須設爲2.0〜2.9倍，以2 · 2〜2.8倍爲佳，以2 · 4 〜2.8倍爲較佳。若延伸倍率超過2.9倍，PVA分子鏈進行 配向而促進結晶化，變得難以將膨潤度B調整爲預定範 圍。此外，若延伸倍率低於2.0倍，提高膨潤度B的效果 會不足。 以在將生膜材料作濕式延伸時的溫度而言，由於變得 較爲容易將延伸膜的膨潤度B調整爲後述的範圍，因此以 20〜40 °C爲佳，以25〜40 °C爲較佳，以25〜35 °C爲更佳， 以2 7〜3 3 °C爲特佳。 -10- 201033658 上述延伸膜的膨潤度B係必須滿足下述式（2)，以滿足 下述式（2’）爲佳，以滿足下述式（2，，）爲較佳。 Α + 20 Β Α + 3 5 (2) Α + 20 Β Α + 3 3 (2，） Α + 20 Β Α + 30 (2’’） 藉由控制延伸倍率而使偏光性能提升的理由雖不明 確’但是預測如以下所示。亦即，若延伸倍率過低時，微 結晶不會破壞而殘留在延伸膜中。此時，B變得小於A + 20， ❹ 在之後的延伸中無法提升延伸倍率，所得偏光膜的偏光性 能會變低》此外，在延伸倍率過高時，由於PVA的配向結 晶化會進展’因此仍然B變得小於A + 20，在之後的延伸中 無法提升延伸倍率，所得偏光膜的偏光性能會變低。另— 方面，例如作延伸時之浴的溫度過高時，B會變得大於 A + 35。此時，膜內的結晶破壞在延伸中進行，難以在之後 的延伸中施加充分的張力來作延伸，所得偏光膜的偏光性 ❿ 能會變低。 其中，延伸膜的膨潤度B係以230〜265 %爲佳。爲了 將膨潤度B控制在所希望的範圍，若如上所述調整延伸倍 率或在作濕式延伸時的水或水溶液的溫度即可。延伸膜的 膨潤度B在實施例的項目中可藉由後述方法加以測定。 如前所述，亦可在將生膜材料作濕式延伸的步驟之 後，將所得延伸膜另外在硼酸水溶液中延伸。此時的延伸 倍率係以3倍以下爲佳，以1.2〜3倍爲較佳，以1.3〜2.9 倍爲更佳，以1·4〜2.8倍爲最佳。若延伸倍率超過3倍， -11- 201033658 在延伸中會發生多起膜斷裂，而會有難以穩定製造偏光膜 之虞。 此時之水溶液中的硼酸濃度係以2〜6質量％爲佳，以 2〜5質量％爲較佳，以2〜4質量％爲更佳。若硼酸的濃度 低於2質量％，會有在所得偏光膜色斑變多之虞。此外， 若硼酸的濃度超過6質量％，藉由硼酸所爲之PVA的交聯 變成過剩，而會有難以將膜以高倍率作延伸之虞。 I 此外，爲了將偏光膜的色相接近於中性灰，亦以在硼 酸水溶液添加碘化鉀爲佳。碘化鉀的濃度以3〜1 0質量％ 爲佳，以4〜8質量％爲較隹。若碘化鉀的濃度低於3質量 %，會有所得偏光偏的藍色程度變強之虞。另一方面，若 碘化鉀的濃度超過10質量％，則有所得偏光偏的紅色程度 變強之虞。硼酸水溶液亦可含有例如鐵、鉻等金屬化合物 作爲其他成分。 在上述延伸中，水溶液的溫度並未特別有所限制，但 φ 以50〜60°C爲佳，以55〜60°C爲較佳，以57〜60°C爲更 佳。若延伸溫度低於50°C，會有難以將膜延伸至高倍率之 虞。此外，若延伸溫度超過6(TC，則會有所得偏光膜的透 過度降低之虞。 延伸後的色調整係以在含有硼酸與碘化鉀的水溶液中 進行爲佳。此時，亦可在水溶液中添加氯化鋅、碘化鋅等 金屬化合物。爲了防止偏光性能降低，水溶液的溫度以低 於延伸溫度爲佳，具體而言以20〜50°C爲佳，以30〜40 °C爲較佳。關於色調整的時間，並未特別有所限制。 -12- 201033658 所得偏光膜的乾燥係可使用各種乾燥機，而以批次 式、連續浮動式、連續滾筒上接觸式等方法來進行。以乾 燥溫度而言，爲了防止來自偏光膜之碘的昇華，而且爲了 抑制與PVA交聯之硼酸的脫離反應，以40〜8(TC進行爲 佳，以45〜70 °C爲較佳，以50〜60 °C爲更佳。關於乾燥時 間並未特別有所限制，雖依裝置或乾燥溫度而異，但是例 如在3〜6分鐘的範圍內。 ^ 如此所得之偏光膜係以具有優異偏光性能爲佳，俾以 供作偏光板等的用途。亦即，偏光膜的透過率較佳爲43.0% 以上，偏光度較佳爲99.97%以上（更佳爲99.98%以上）。 (實施例） 以下藉由實施例等，具體說明本發明，惟本發明並非 因以下實施例而有所限定。在實施例等中，PVA的黏度平 均聚合度P、生膜材料的膨潤度A、延伸膜的膨潤度B、偏 光膜的透過率Y及偏光度V係以下列方法加以評估。 φ (l)PVA的黏度平均聚合度P的測定 將PVA〇.28g、蒸餾水70g、及攪拌子投入在lOOmL標 準磨口接頭三角燒瓶。在95 °C的恒溫槽浸漬已加上栓塞的 上述三角燒瓶，一面以攪拌子攪拌，一面將PVA溶解，而 製作出0.4% PVA水溶液。將該PVA水溶液以布赫納漏斗 (Buechner funnel )型玻璃過濾器3G加以過濾，在30°C • 的恒溫水槽中冷卻，形成爲聚合度測定用試樣。以參照試 料而言，在其他l〇〇mL標準磨口接頭三角燒瓶放入70g蒸 餾水且加栓，然後浸漬在3 0 °C的恒溫水槽。 -13- 201033658 將以1 05°C的乾燥機加熱1小時後的蒸發皿，以保乾 器（desiccator)冷卻30分鐘，測定出蒸發皿的質量a(g)。 在該蒸發皿以全吸管（whole pipette)使聚合度測定用試 樣10mL移動，將其以105 °C的乾燥機乾燥16小時後，以 保乾器冷卻30分鐘，測定出質量b ( g)。聚合度測定用試 樣的濃度c(g/L)係藉由下式予以算出。 c=1000x ( b-a) /10 A 將聚合度測定用試樣或蒸餾水以全吸管投入在奧士華 ❿ 黏度計（Ostwald viscosimeter)，在30 °C的恒溫水槽中使 其安定1 5分鐘。測定所投入的聚合度測定用試樣的落下秒 數“（s)與蒸餾水的落下秒數U(s)，藉由下式，計算出 黏度平均聚合度P。 7? r = ti/ t〇 〔η〕=2.3 03xLog ( η r / c)[Technical Field] The present invention relates to a method of producing a polarizing film which can be used as a member constituting a polarizing plate of a liquid crystal display device. [Prior Art] Liquid crystal display devices (LCDs) were used in small computers such as electronic computers and watches in the early days of development, but in recent years, notebook personal computers, LCD monitors, liquid crystal color projectors, and LCD TVs have been used. It is widely used in a wide range of navigation systems for vehicles, mobile phones, and measuring devices for indoor and outdoor use. On the other hand, in particular, in applications such as liquid crystal televisions, the display quality is gradually improved, for example, the improvement of contrast, and the polarizing plate which is one of the components of the LCD is also strongly required to have an improvement in polarization performance. A polarizing plate generally used in the prior art has a uniaxial stretching of a green film material composed of polyvinyl alcohol (hereinafter sometimes referred to as PVA), a dyeing treatment by iodine or a dichroic dye, and a boron compound. For the fixation treatment or the like, a protective film such as a cellulose triacetate film or a cellulose acetate butyrate film is bonded to one surface or both surfaces of the obtained polarizing film. In order to improve the polarizing performance of the polarizing plate as described above, a method of improving the structure of the PVA as a raw material, a method of controlling the physical properties of the PVA film, a method of controlling the manufacturing conditions of the polarizing plate, and the like have been proposed. Various methods help to improve the contrast of the LCD. For example, Patent Document 1 discloses that a polarizing film comprising a PVA having a polymerization degree of 2,500 or more, preferably 6,000 to 10,000, is excellent in optical characteristics. The use of PVA having a high degree of polymerization is advantageous for improving the polarizing performance, but it is extremely difficult to implement in the industry. Further, in order to improve the polarizing performance, for example, in Patent Document 2, the relationship between the complete dissolution temperature (X) used in hot water and the equilibrium swelling degree (Y) is described as follows. The PV A film of the range shown is a method for producing a polarizing film of a green film material. Y > -0.0667X + 6.73 (I) X ^ 65 (II) However, the degree of polymerization of the PVA used in the above invention is preferably in the range of 3 5 00 to 5000. Even if this method was directly applied to a high polymerization degree PVA, as shown in the comparative example described later, it was found that the polarizing performance of the obtained polarizing film was not sufficient. That is, in the industrial production of a polarizing film composed of a PVA having a high degree of polymerization, it is necessary to comprehensively consider information on the structure of the PVA, the physical properties of the PVA film, and the like, and to find the most suitable raw material conditions. (Prior Art Document) (Patent Document 1) Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION An object of the invention is to provide a method for producing a polarizing film which can process a film composed of a PVA having a high degree of polymerization into a polarizing film having high polarizing properties. (Means for Solving the Problem) The inventors have examined the structure of the PVA, the physical properties of the PVA film, and the manufacturing conditions of the polarizing film, etc., to the maximum extent, and to examine it. As a result, a method for producing a polarizing film comprising a wet film having a degree of swelling of A (%) obtained by forming a film having a degree of polymerization of 5,000 or more and having a degree of swelling of A (%) of 2.0 to 2.9 times was obtained to obtain a degree of swelling. B (%) of the step of stretching the film, wherein the above A and B satisfy the following formulas (1) and (2), thereby exhibiting the effects of the present invention: 200 ^ A ^ 240 (1) A + 20 ^ B ^ A + 35 (2). In this case, it is preferred that the green film material is wet-extruded in an aqueous iodine-potassium iodide solution. Further, the above-mentioned green film material is preferably obtained by heat-treating at 115 to 130 ° C after film formation. Further, it is preferred to include a step of extending the obtained stretched film in the aqueous boric acid solution by a factor of 3 or less after the step of the wet stretching. The present invention also encompasses a polarizing film obtained by the above-described production method, having a transmittance of 43.0% or more and a degree of polarization of 99.97% or more. φ (Effect of the Invention) By the process of the present invention, a film composed of a PVA having a high degree of polymerization can be processed into a polarizing film having high polarizing properties, so that a polarizing film having high polarizing properties can be industrially produced. [Embodiment] (Mode for Carrying Out the Invention) The present invention will be described in detail below. The degree of polymerization of the PVA used in the present invention is preferably 5,000 or more in order to correspond to the good polarizing performance as the object of the present invention, and more preferably 5,000 or more in terms of 201033658 or more preferably 6,000 or more. If the degree of polymerization of PVA is less than 5000', it is difficult to exhibit high polarization performance. The upper limit of the degree of polymerization of the PVA is not particularly limited, but the higher the degree of polymerization, the more the productivity of PVA is lowered. Therefore, from the industrial viewpoint, it is preferably 10,000 or less. The degree of polymerization of the PVA referred to in the present invention means the degree of polymerization (viscosity average degree of polymerization) measured by the method described in the examples below. Further, the degree of saponification of PVA is preferably 99 mol% or more, more preferably 99.8 mmol% or more. When the degree of saponification of PVA is less than 99 mol%, PV A is easily eluted in the production step of the bismuth film described later, and the eluted VA adheres to the film to lower the performance of the polarizing film. . The PV A system used in the present invention can be produced by saponifying a polyvinyl ester polymer obtained by polymerizing a vinyl ester. Examples of the vinyl esters include vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, trimethyl vinyl acetate, vinyl versatate, vinyl laurate, and stearic acid. One or two or more kinds of these are selected from the group consisting of vinyl acetate and benzoic acid ethylene ester. Among these, from the viewpoints of easiness of acquisition, ease of production of PVA, cost, and the like, among them, vinyl acetate is preferably used. Although the polymerization temperature is not particularly limited, when methanol is used as the polymerization solvent, the polymerization temperature is preferably about 60 ° C around the boiling point of methanol. The PVA is not limited to the saponified product of the individual polymer of the vinyl ester as long as the effect of the present invention is not impaired. For example, it is also possible to graft an unsaturated carboxylic acid or a derivative thereof, an unsaturated sulfonic acid or a derivative thereof, a carbon number of 2 to 30, and the like in PVA at a ratio of less than 5 mol%. Copolymerized modified PVA; 201033658 A vinyl ester 'unsaturated carboxylic acid or a derivative thereof, an unsaturated sulfonic acid or a derivative thereof, an α-olefin having a carbon number of 2 to 30, etc., to less than 15 mol% A saponified product of a modified polyvinyl ester which is copolymerized in a ratio; a polyethylene awake polymer obtained by crosslinking a part of a hydroxyl group of PVA with an aldehyde such as formal water, butyraldehyde or benzaldehyde. A green film material is obtained by forming the above PVA into a film. In the film forming method, in addition to the method of melting and pouring the aqueous PVA, a casting film forming method, a wet film forming method (discharging into a poor solvent), and a condensed rubber film forming method (in the PVA) may be employed. After the aqueous solution is temporarily cooled and gelled, the solvent is removed and removed, a mold forming method (flowing and drying of the PVA aqueous solution on the substrate), and a method obtained by the combination are used. Among these, a PVA film (film material) which is excellent by a melt extrusion film forming method and a casting film forming method is preferable. Examples of the solvent used in the film formation include dimethyl hydrazine, dimethylformamide, dimethyl acetamide, hydrazine-methyl rolosterone, ethylene glycol, and glycerin. One or two or more of these may be used, such as propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, ethylenediamine, diethylenetriamine, and water. Among these, water, dimethyl sub-grinding, and such mixed solvents are also preferred. The volatile matter ratio of the film-forming stock solution mainly composed of PVA and a solvent varies depending on the film formation method or the molecular weight of the PVA, but is preferably 50 to 95% by mass, more preferably 60 to 9.55% by mass. It is preferably 7 to 9 mass%. If the volatile fraction is less than 50% by mass, the viscosity of the film-forming stock solution becomes too high, and it becomes difficult to filter or defoam during preparation, and it is difficult to obtain a film-forming material having foreign matter or defects without 201033658. After that. Further, when the volatile matter ratio exceeds 95% by mass, the viscosity of the film forming stock solution becomes too low, and it is difficult to produce a green film material having a desired thickness or thickness precision. A plasticizer can also be used in the production of the green film material. Examples of the plasticizer include glycerin, diglycerin, ethylene glycol, and the like, but are not limited thereto. The amount of the plasticizer to be used is also not particularly limited, but it is usually in the range of 1 Torr to 15 parts by mass relative to 1 part by mass of the PVA. I The method for drying the green film material after film formation is, for example, drying by hot air, contact drying using a heating roll, or drying by an infrared heater. One type of these methods may be used alone, or two or more types may be used in combination. Although the drying temperature is not particularly limited, it is preferably in the range of 50 to 70 °C. Further, the drying time at this time varies depending on the concentration of the film stock solution or the film forming conditions, but the large enthalpy is 45 to 75 minutes. It is preferred that the green film material after drying is subjected to heat treatment so as to control the swelling degree within a predetermined range described later. The heat treatment method of the original film material after film formation includes, for example, a method by hot air or a method in which a green film is brought into contact with a heating roll. One of these methods may be used alone, or two or more of them may be used in combination. Although the heat treatment temperature is not particularly limited, it is preferably in the range of 1 1 5 to 1 30 °c. Further, the heat treatment time at this time is preferably within 5 minutes. The thickness of the green film material thus obtained is preferably 20 to 120; am is preferably 20 to 80 yin, more preferably 20 to 40 μm. If the thickness is less than 20 #rn, there is a possibility that film breakage easily occurs in the stretching step described later. When the thickness exceeds 120/zm outside of 201033658, it is applied to a large extent when it is extended, and there is a possibility that it is difficult to fully extend. The swelling degree A of the green film material must be 200 to 240%, preferably 2 to 30% to 25%. If the degree of swelling A is low; the tension at the time of stretching becomes too large, and it may be difficult to carry out if the degree of swelling A exceeds 240%, and the water absorption is high, and wrinkles or ends are likely to occur in the film during the manufacturing step. The reason why the roll is broken when stretched. In order to control the degree of swelling A, it may be adjusted, for example, when heat-treating the film-forming material after film formation. The swelling degree A of the green film material was measured by the method described later. Next, the method of the present invention using the above-mentioned green film material will be described. The manufacturing steps of the polarizing film may include steps of moisture adjustment, color adjustment, and the like. At this time, it is necessary to adjust the swelling degree B of the stretched film of the green film material. Alternatively, the resulting stretched film may be additionally stretched after the step of wet stretching. Further, if necessary, for example, color adjustment is carried out in an aqueous solution containing boron and dried, and moisture adjustment for producing a polarizing film material is preferably performed by immersing in pure water. In terms of the temperature at this time, it is preferably 20 to 40 ° C for fi ° C, more preferably 2 7 to 3 3 ° C. If the temperature is lower than the water content of the material, the water content will be high, and it will be difficult to adjust the swelling degree of the stretched film B to more than 40 ° C. The water absorption of the green film material will become high. The stress in the film will change from 20 5 to 23 5% to 200%, and then the extension will be extended. In addition, the polarizing film described later is curved, resulting in dyeing, stretching, and wet stretching of the polarizing film in the temperature or time addition example, and if necessary, acid and potassium iodide in the boric acid solution. Light film. In distilled water, i, at 2 5~3 5 2 ° ° C, the tension of the green film will change. In addition, in the step after the temperature, 201033658 is prone to wrinkles or curls at the end of the film, and there is a cause of breakage during extension. On the other hand, in terms of the time of impregnating the green film material, the large enthalpy is in the range of 30 to 120 seconds. The dyeing of the green film material is carried out, for example, in an aqueous solution of iodine-potassium iodide. In this case, the concentration of iodine is 0.01 to 0.1% by mass, and the concentration of potassium iodide is preferably 1 to 10% by mass, and the concentration of iodine is 0.02 to 0.08% by mass, and the concentration of potassium iodide is preferably 2 to 8 mass%, preferably iodine concentration. 0.03 to 0.06 mass%, and potassium iodide concentration of 3 to 6 mass% is more preferable. Although the temperature of the aqueous solution is not particularly limited, it is preferably 25 to 40 °C. The wet stretching of the green film material may be carried out as a step different from the above-described water conditioning or dyeing, but it is preferably carried out in the above-mentioned water for water conditioning or in an aqueous solution for dyeing. It is more preferably carried out in an aqueous solution for dyeing, that is, an aqueous solution of iodine-potassium iodide. In the wet stretching of the green film material, in order to adjust the swelling degree B of the stretched film to a predetermined range to be described later, the stretching ratio of the ratio of the length of the film before and after the stretching is required to be 2.0 to 2.9 times. It is preferably 2 · 2 to 2.8 times, preferably 2 · 4 to 2.8 times. When the stretching ratio exceeds 2.9 times, the PVA molecular chain is aligned to promote crystallization, and it becomes difficult to adjust the swelling degree B to a predetermined range. Further, if the stretching ratio is less than 2.0 times, the effect of increasing the swelling degree B will be insufficient. In order to make it easier to adjust the swelling degree B of the stretched film to a range to be described later, it is preferable to use 20 to 40 ° C, preferably 25 to 40 °, in terms of the temperature at which the green film material is wet-stretched. C is preferred, preferably 25 to 35 ° C, and particularly preferably 2 7 to 3 3 ° C. -10-201033658 The swelling degree B of the above-mentioned stretched film must satisfy the following formula (2), and it is preferable to satisfy the following formula (2'), and it is preferable to satisfy the following formula (2,). Α + 20 Β Α + 3 5 (2) Α + 20 Β Α + 3 3 (2,) Α + 20 Β Α + 30 (2'') The reason for improving the polarization performance by controlling the stretching ratio is not clear. 'But the forecast is as shown below. That is, if the stretching ratio is too low, the microcrystals do not break and remain in the stretched film. At this time, B becomes smaller than A + 20, ❹ the stretching ratio cannot be increased in the subsequent stretching, and the polarizing performance of the obtained polarizing film becomes low. Further, when the stretching ratio is too high, the alignment crystallization of PVA progresses. Therefore, B becomes smaller than A + 20, and the stretching ratio cannot be increased in the subsequent stretching, and the polarizing performance of the obtained polarizing film becomes low. On the other hand, if the temperature of the bath for extension is too high, B will become larger than A + 35. At this time, the crystal breakage in the film proceeds during the stretching, and it is difficult to apply sufficient tension to extend in the subsequent stretching, and the polarizing ❿ of the obtained polarizing film can be lowered. Among them, the swelling degree B of the stretched film is preferably 230 to 265%. In order to control the degree of swelling B within a desired range, the stretching ratio or the temperature of water or an aqueous solution at the time of wet stretching may be adjusted as described above. The swelling degree B of the stretched film can be measured by the method described later in the items of the examples. As described above, the resulting stretched film may be additionally extended in an aqueous boric acid solution after the step of wet-extending the green film material. The stretching ratio at this time is preferably 3 times or less, preferably 1.2 to 3 times, more preferably 1.3 to 2.9 times, and most preferably 1.4 to 2.8 times. If the stretching ratio exceeds 3 times, -11-201033658 may cause multiple film breakage during stretching, and it may be difficult to stably manufacture a polarizing film. The concentration of boric acid in the aqueous solution at this time is preferably 2 to 6 mass%, more preferably 2 to 5 mass%, still more preferably 2 to 4 mass%. If the concentration of boric acid is less than 2% by mass, the color unevenness of the obtained polarizing film may increase. Further, when the concentration of the boric acid exceeds 6% by mass, the crosslinking of the PVA by the boric acid becomes excessive, and it is difficult to extend the film at a high magnification. Further, in order to bring the hue of the polarizing film close to neutral ash, it is preferred to add potassium iodide to the aqueous boric acid solution. The concentration of potassium iodide is preferably from 3 to 10% by mass, and more preferably from 4 to 8% by mass. If the concentration of potassium iodide is less than 3% by mass, the degree of blueness of the obtained polarization shift becomes strong. On the other hand, when the concentration of potassium iodide exceeds 10% by mass, the degree of redness of the obtained polarization shift becomes strong. The aqueous boric acid solution may contain a metal compound such as iron or chromium as another component. In the above extension, the temperature of the aqueous solution is not particularly limited, but φ is preferably 50 to 60 ° C, more preferably 55 to 60 ° C, and still more preferably 57 to 60 ° C. If the extension temperature is lower than 50 ° C, it may be difficult to extend the film to a high magnification. Further, when the stretching temperature exceeds 6 (TC, the transmittance of the obtained polarizing film is lowered. The color adjustment after stretching is preferably carried out in an aqueous solution containing boric acid and potassium iodide. In this case, it may also be in an aqueous solution. A metal compound such as zinc chloride or zinc iodide is added. In order to prevent a decrease in polarizing performance, the temperature of the aqueous solution is preferably lower than the elongation temperature, specifically 20 to 50 ° C, preferably 30 to 40 ° C. The time for color adjustment is not particularly limited. -12- 201033658 The drying of the obtained polarizing film can be carried out by a batch type, a continuous floating type, a continuous roll contact type or the like using various dryers. In order to prevent the sublimation of iodine from the polarizing film and to suppress the desorption reaction of boric acid cross-linked with PVA, the drying temperature is preferably 40 to 8 (preferably, TC is preferably 45 to 70 ° C, 50 to 60 ° C is more preferable. The drying time is not particularly limited, and it varies depending on the apparatus or drying temperature, but is, for example, in the range of 3 to 6 minutes. ^ The polarizing film thus obtained is excellent in polarizing light. Performance is good, The use of the polarizing film is preferably 43.0% or more, and the degree of polarization is preferably 99.97% or more (more preferably 99.98% or more). (Example) The present invention is specifically described by the following examples, but the present invention is not limited by the following examples. In the examples and the like, the viscosity average polymerization degree P of the PVA, the swelling degree A of the green film material, the swelling degree B of the stretched film, The transmittance Y and the degree of polarization V of the polarizing film were evaluated by the following methods. Φ (1) PVA viscosity average degree of polymerization P was measured by PVA 〇.28 g, distilled water 70 g, and stirrer in a 100 mL standard ground joint triangle. The flask was immersed in a constant temperature bath at 95 ° C, and the above-mentioned Erlenmeyer flask was stoppered, and the PVA was dissolved while stirring with a stirrer to prepare a 0.4% aqueous PVA solution. The PVA aqueous solution was used as a Bucherner funnel. The glass filter 3G was filtered and cooled in a constant temperature water bath at 30 ° C to form a sample for measuring the degree of polymerization. For the reference sample, 70 g of the other 1 mL mL standard ground joint flask was placed. Distilled water and tied Then, it was immersed in a constant temperature water tank at 30 ° C. -13- 201033658 The evaporating dish heated by a dryer at 1-5 ° C for 1 hour was cooled by a desiccator for 30 minutes to determine the mass of the evaporating dish. (g) The evaporating dish was moved to 10 mL of the polymerization degree measurement sample by a whole pipette, and dried in a dryer at 105 ° C for 16 hours, and then cooled by a dryer for 30 minutes to measure the mass. b (g) The concentration c (g/L) of the sample for measuring the degree of polymerization is calculated by the following formula: c = 1000x ( ba) /10 A The sample for measuring the degree of polymerization or distilled water is supplied as a full pipette. The Ostwald viscosimeter was allowed to settle for 15 minutes in a constant temperature water bath at 30 °C. The number of seconds of dropping ("s) and the number of seconds of dropping of distilled water U(s) of the sample for measurement of the degree of polymerization to be charged was measured, and the average degree of polymerization P of the viscosity was calculated by the following formula: 7? r = ti / t〇 [η]=2.3 03xLog ( η r / c)
Log ( P ) =1.613xLog ( [ η〕xl 〇4/ 8.29 ) φ (2)生膜材料的膨潤度A的測定 將生膜材料裁成5cmx5cm，在3〇t的蒸餾水1L中浸 漬4小時。將該生膜材料由蒸餾水中取出，以2枚濾紙包 夾而使表面的水滴吸收後，測定出質量D。此外，將該生 膜材料以l〇5°C的乾燥機乾燥16小時，以保乾器冷卻30 分鐘後，測定出質量E。藉由下式，計算出生膜材料的膨 潤度A。 A=100xD/E ( %) (3)延伸膜的膨潤度B的測定 -14- 201033658 以延伸方向l〇cmx寬幅方向5cm切取經濕式延伸的 膜，另外在碘〇. 〇 3質量％、碘化鉀3質量％的碘-碘化鉀水 溶液（3(TC )中浸漬4小時。將該延伸膜由碘-碘化鉀水溶 液中取出，以2枚濾紙包夾而使表面的水滴吸收後，測定 出質量F。將該延伸膜以105 °C的乾燥機乾燥16小時，以 保乾器冷卻30分鐘後，測定出質量G。藉由下式，計算出 延伸膜的膨潤度B。 _ B=100xF/ G ( % ) 〇 (4) 偏光膜之透過率Y的測定 由偏光膜之寬幅方向的中央部，採取2枚延伸方向4cra X寬幅方向4cm的正方形試樣，使用日立製作所製的分光光 度計U-4100C附屬積分球），依據JISZ8722C物體色的測 定方法），進行C光源、2°視野之可見光領域的視覺敏感 度修正，關於1枚偏光膜試樣，測定出對延伸軸方向呈45 °傾斜時之光的透過度與呈-45°傾斜時之光的透過度，求 Q 出該等的平均値Yl( %)。關於另一枚偏光膜試樣亦同樣地 測定出呈45°傾斜時之光的透過度與呈_45°傾斜時之光 的透過度，求出該等的平均値Υ2( %)。藉由下式，將Υ1 與Υ2平均，設爲偏光膜的透過率Υ( %)。 Y= ( Y 1 + Y2 ) / 2 (5) 偏光膜之偏光度V的測定 將以上述（4)所採取的2枚偏光膜，以其延伸方向呈平 行的方式相重疊時之光的透過率Y || ( % )、以延伸方向呈 正交的方式相重疊時之光的透過率Y丄（％)，與（4)所記載 -15- 201033658Log ( P ) = 1.613xLog ( [ η ] xl 〇 4 / 8.29 ) φ (2) Measurement of swelling degree A of the green film material The green film material was cut into 5 cm x 5 cm, and immersed in 1 liter of distilled water of 3 Torr for 4 hours. The green film material was taken out from distilled water, and the water droplets on the surface were absorbed by two filter papers, and the mass D was measured. Further, the film material was dried in a dryer at 10 ° C for 16 hours, and cooled by a dryer for 30 minutes, and then the mass E was measured. The swelling degree A of the raw film material was calculated by the following formula. A=100xD/E (%) (3) Determination of the swelling degree B of the stretched film-14- 201033658 The wet-stretched film was cut in the direction of extension l〇cmx 5 cm in width direction, in addition to iodine. 〇3 mass% The iodine-potassium iodide aqueous solution (3 (TC) was immersed for 4 hours in a 3 mass% potassium iodide solution. The stretched film was taken out from the iodine-potassium iodide aqueous solution, and the surface water droplets were absorbed by two filter papers to measure the mass F. The stretched film was dried in a dryer at 105 ° C for 16 hours, and cooled by a dryer for 30 minutes, and then the mass G was measured. The swelling degree B of the stretched film was calculated by the following formula: _ B = 100 x F / G (%) 〇(4) Measurement of the transmittance Y of the polarizing film A square sample having a width of 4 cm in the direction of 4cra X and a width of 4 cm was used in the central portion in the width direction of the polarizing film, and a spectrophotometer manufactured by Hitachi, Ltd. was used. U-4100C auxiliary integrating sphere), according to the JISZ8722C object color measurement method, the visual sensitivity correction of the C light source and the visible field of the 2° field of view is performed. For one polarizing film sample, the direction of the extension axis is 45°. Transmittance of light when tilted and transmission of light when tilted at -45° Degree, ask Q to get the average 値Yl (%). Similarly, in another polarizing film sample, the transmittance of light when inclined at 45° and the transmittance of light when inclined at _45° were measured, and the average 値Υ 2 (%) of these was obtained. By averaging Υ1 and Υ2, the transmittance Υ(%) of the polarizing film is set by the following formula. Y=( Y 1 + Y2 ) / 2 (5) Measurement of the degree of polarization V of the polarizing film The transmission of light when the two polarizing films taken in the above (4) are overlapped in such a manner that their extending directions are parallel Rate Y || ( % ), transmittance Y丄(%) of light when the extension directions are orthogonal, and -15-201033658 as described in (4)
之透過率的情形相同地進行測定，藉由下式求出偏光度V (%)。 V={(Y|| -Y 丄）/ (Υ|| +Υ 丄）} 1/2χ100 〔實施例1〕 將含有聚合度5800、皂化度99.8莫耳％之PVA100質 量份、與作爲可塑劑的甘油1 2質量份的5.5質量％PVA水 溶液，在60°C的金屬軋輥上流延，乾燥60分鐘，獲得厚 度40# m的PVA膜。將該膜固定在金屬框，以120 °C進行 3分鐘熱處理，將熱處理後的生膜材料的膨潤度A以上述 (2)所記載的方法加以測定後爲23 0%。The transmittance was measured in the same manner as in the case of the transmittance, and the degree of polarization V (%) was obtained by the following formula. V={(Y|| -Y 丄)/ (Υ|| +Υ 丄)} 1/2χ100 [Example 1] 100 parts by mass of PVA containing a polymerization degree of 5800 and a saponification degree of 99.8 mol%, and a plasticizer The glycerin 12 parts by mass of a 5.5 mass% PVA aqueous solution was cast on a metal roll at 60 ° C and dried for 60 minutes to obtain a PVA film having a thickness of 40 # m. The film was fixed in a metal frame, and heat-treated at 120 ° C for 3 minutes, and the swelling degree A of the heat-treated green film material was measured by the method described in the above (2) to be 23%.
接著，將上述生膜材料以流動方向llcmx寬幅方向 10 cm作切剪，將流動方向作爲延伸方向而安裝在夾盤間 4cm的延伸夾具，在30°C純水中浸漬1分鐘，接著浸漬在 以碘爲〇·〇3質量％、碘化鉀爲3質量％的比例所含有的染 色液（溫度30°C )，以〇.13m/min的速度，延伸爲2·6倍， 使碘吸附。將該延伸膜的膨潤度Β以上述（3)所記載的方法 加以測定後爲260%。 接著，將該延伸膜浸漬在以硼酸爲4質量％、碘化鉀 爲6質量％的比例所含有的延伸液（溫度57.5 °C )’以0.13m /min的速度，延伸爲2.3倍後，將延伸方向固定而以50 °C乾燥4分鐘而得偏光膜。將該偏光膜的透過度及偏光度 以上述（4)及（5)所記載的方法加以測定後分別爲44.0%、 9 9.9 9 %，獲得偏光性能良好的偏光膜。 -16- 201033658 〔實施例2〕 將含有聚合度5800、皂化度99.8莫耳％之PVA100質 量份、與作爲可塑劑的甘油1 2質量份的5 .5質量％PVA水 溶液，在60 °C的金屬軋輥上流延，乾燥60分鐘，獲得厚 度40 μ m的PVA膜。將該膜固定在金屬框，以115°C進行 3分鐘熱處理，將熱處理後的生膜材料的膨潤度A以上述 (2)所記載的方法加以測定後爲240%。 接著，與實施例1相同地，一面將上述生膜材料延伸， ❹ 一面使碘吸附。將所得延伸膜的膨潤度B以上述（3)所記載 的方法加以測定後爲260%。 接著，與實施例1相同地獲得偏光膜。將該偏光膜的 透過度及偏光度以上述（4)及（5)所記載的方法加以測定後 分別爲44.0%、99.99%，獲得偏光性能良好的偏光膜。 〔實施例3〕Next, the above-mentioned green film material was cut in a flow direction of llcmx in a width direction of 10 cm, and the flow direction was set as an extending direction to be attached to an extension jig of 4 cm between the chucks, and immersed in pure water at 30 ° C for 1 minute, followed by dipping. The dyeing liquid (temperature: 30 ° C) contained in a ratio of iodine of 〇·〇3 mass% and potassium iodide of 3% by mass was extended to 2.6 times at a rate of 1313 m/min to adsorb iodine. The degree of swelling of the stretched film was measured by the method described in the above (3) to be 260%. Next, the stretched film was immersed in an extension liquid (temperature: 57.5 ° C) contained in a ratio of boric acid of 4% by mass and potassium iodide of 6% by mass to extend 2.3 times at a rate of 0.13 m /min, and then extended. The polarizing film was obtained by fixing in a direction and drying at 50 ° C for 4 minutes. The transmittance and the degree of polarization of the polarizing film were measured by the methods described in the above (4) and (5), and were 44.0% and 99.99%, respectively, to obtain a polarizing film having excellent polarizing performance. -16-201033658 [Example 2] 100 parts by mass of PVA having a polymerization degree of 5800 and a degree of saponification of 99.8 mol%, and a 5 mass% PVA aqueous solution of 12 parts by mass of glycerin as a plasticizer at 60 ° C The metal roll was cast and dried for 60 minutes to obtain a PVA film having a thickness of 40 μm. The film was fixed in a metal frame, and heat-treated at 115 ° C for 3 minutes, and the swelling degree A of the heat-treated green film material was measured by the method described in the above (2) to be 240%. Next, in the same manner as in Example 1, the above-mentioned green film material was stretched, and iodine was adsorbed while being immersed. The swelling degree B of the obtained stretched film was measured by the method described in the above (3) to be 260%. Next, a polarizing film was obtained in the same manner as in Example 1. The transmittance and the degree of polarization of the polarizing film were measured by the methods described in the above (4) and (5), and were 44.0% and 99.99%, respectively, and a polarizing film having excellent polarizing performance was obtained. [Example 3]
將含有聚合度9100、皂化度99.8莫耳％之PVA100質 量份、與作爲可塑劑的甘油1 2質量份的5.5質量％PVA水 溶液，在6(TC的金屬軋輥上流延’乾燥60分鐘’獲得厚 度20/zm的PVA膜。將該膜固定在金屬框，以ll〇°C進行 3分鐘熱處理。將熱處理後的生膜材料的膨潤度A以上述 (2)所記載的方法加以測定後爲230%。 接著，除了將延伸倍率設爲2.5倍以外，與實施例1 相同地，一面將上述生膜材料延伸，一面使碘吸附。將所 得延伸膜的膨潤度B以上述（3)所記載的方法加以測定後爲 2 5 5%° -17- 201033658 接著，與實施例1相同地獲得偏光膜。將該偏光膜的 透過度及偏光度以上述（4)及（5)所記載的方法加以測定後 分別爲44.0%、99.99%，獲得偏光性能良好的偏光膜》 〔實施例4〕 將含有聚合度5200、皂化度99.8莫耳％之PVA100質 量份、與作爲可塑劑的甘油1 2質量份的5.5質量％PVA水 溶液，在60°C的金屬軋輥上流延，乾燥60分鐘，獲得厚 度40 v m的PVA膜。將該膜固定在金屬框，以1 10 °C進行 3分鐘熱處理。將熱處理後的生膜材料的膨潤度A以上述 (2)所記載的方法加以測定後爲205%。 接著，與實施例3相同地，一面將上述生膜材料延伸， 一面使碘吸附。將所得延伸膜的膨潤度B以上述（3)所記載 的方法加以測定後爲2 3 5 %。 接著，與實施例1相同地獲得偏光膜。將該偏光膜的 透過度及偏光度以上述（4)及（5)所記載的方法加以測定後 分別爲44.0%、99.98%，獲得偏光性能良好的偏光膜。 〔實施例5〕 將含有聚合度5500、皂化度99·8莫耳％之PVA100質 量份、與作爲可塑劑的甘油1 2質量份的5 · 5質量％PVA水 溶液，在60 °C的金屬軋輥上流延，乾燥60分鐘，獲得厚 度30/zm的PVA膜。將該膜固定在金屬框，以130t進行 3分鐘熱處理。將熱處理後的生膜材料的膨潤度A以上述 (2)所記載的方法加以測定後爲215%。 接著，與實施例1相同地，一面將上述生膜材料延伸， 201033658 一面使碘吸附。將所得延伸膜的膨潤度B以上述（3)所記載 的方法加以測定後爲23 5%。 接著，與實施例1相同地獲得偏光膜。將該偏光膜的 透過度及偏光度以上述（4)及（5)所記載的方法加以測定後 分別爲44.0%、99.99%，獲得偏光性能良好的偏光膜。 〔比較例1〕 將含有聚合度4800、巷化度99.8莫耳％之PVA100質 量份、與作爲可塑劑的甘油1 2質量份的6 · 5質量％PVA水 溶液，在60°C的金屬軋輥上流延，乾燥60分鐘，獲得厚 度40/zm的PVA膜。將該膜固定在金屬框，以120°C進行 3分鐘熱處理。將熱處理後的生膜材料的膨潤度A以上述 (2)所記載的方法加以測定後爲220%。 接著，除了將延伸倍率設爲2.7倍以外，與實施例1 相同地，一面將上述生膜材料延伸，一面使碘吸附。將所 得延伸膜的膨潤度B以上述（3)所記載的方法加以測定後爲 接著，與實施例1相同地獲得偏光膜。將該偏光膜的 透過度及偏光度以上述（4)及（5)所記載的方法加以測定後 分別爲44.0%、99.92%，偏光膜的偏光度稍微不足。 〔比較例2〕 將含有聚合度5 800、皂化度99.8莫耳％之PVA100質 量份、與作爲可塑劑的甘油1 2質量份的5.5質量％PVA水 溶液，在60°C的金屬軋輥上流延，乾燥60分鐘，獲得厚 度40/zm的PVA膜。將該膜固定在金屬框，以140°C進行 -19- 201033658 3分鐘熱處理。將熱處理後的生膜材料的膨潤度A以上述 (2)所記載的方法加以測定後爲195%。 接著，與實施例1相同地，一面將上述生膜材料延伸， 一面使碘吸附。將所得延伸膜的膨潤度B以上述（3)所記載 的方法加以測定後爲220%。 接著，與實施例1相同地獲得偏光膜。將該偏光膜的 透過度及偏光度以上述（4)及（5)所記載的方法加以測定後 分別爲44.0%、99.92%，偏光膜的偏光度稍微不足。 將含有聚合度5800、皂化度99.8莫耳％之PVA100質 量份、與作爲可塑劑的甘油12質量份的5.5質量％PVA水 溶液，在60°C的金屬乳輥上流延，乾燥60分鐘，獲得厚 度40/zm的PVA膜。將該膜固定在金屬框，以ll〇°C進行 3分鐘熱處理。將熱處理後的生膜材料的膨潤度A以上述 (2)所記載的方法加以測定後爲2 5 0 %。 接著，與實施例1相同地，一面將上述生膜材料延伸， 一面使碘吸附。將所得延伸膜的膨潤度B以上述（3)所記載 的方法加以測定後爲2 8 0%。 接著，與實施例1相同地獲得偏光膜。將該偏光膜的 透過度及偏光度以上述（4)及（5)所記載的方法加以測定後 分別爲44.0%、99.87%，偏光膜的偏光度稍微不足。 〔比較例4〕 關於在實施例1中所得之生膜材料，除了將延伸倍率 設爲1.7倍以外，與實施例1相同地，一面將上述生膜材 -20- 201033658 料延伸，一面使碘吸附。將所得延伸膜的膨潤度B以上述 (3) 所記載的方法加以測定後爲240%。 ' 接著，除了將延伸倍率設爲3.5倍以外，與實施例1 相同地獲得偏光膜。將該偏光膜的透過度及偏光度以上述 (4) 及（5)所記載的方法加以測定後分別爲44.0%、99.90%， 偏光膜的偏光度稍微不足。 〔比較例5〕 ^ 關於在實施例1中所得之生膜材料，除了將延伸倍率 ❹ 設爲4.2倍以外，與實施例1相同地，一面將上述生膜材 料延伸，一面使碘吸附。將所得延伸膜的膨潤度B以上述 (3) 所記載的方法加以測定後爲240%。 接著，除了將延伸倍率設爲1.4倍以外，與實施例1 相同地獲得偏光膜。將該偏光膜的透過度及偏光度以上述 (4) 及（5)所記載的方法加以測定後分別爲44.0%、99.80%， 偏光膜的偏光度稍微不足。 0 〔比較例6〕 關於在實施例1中所得之生膜材料，除了將延伸倍率 設爲1.2倍以外，與實施例1相同地，一面將上述·生膜材 料延伸，一面使碘吸附。將所得延伸膜的膨潤度B以上述 (3) 所記載的方法加以測定後爲23 0%。 接著，除了將延伸倍率設爲4.6倍以外，與實施例1 相同地獲得偏光膜。將該偏光膜的透過度及偏光度以上述 (4) 及（5)所記載的方法加以測定後分別爲44.0%、99.40%， 偏光膜的偏光度稍微不足。因此，爲了改善偏光度，將延 -21 - 201033658 伸倍率的目標値由4.6倍變更爲5.0倍後，會發生延伸切斷 而無法獲得偏光膜。 彙整上述結果且顯示於表1。100 parts by mass of PVA having a degree of polymerization of 9100, a degree of saponification of 99.8 mol%, and a 5.5% by mass of a PVA aqueous solution of glycerin as a plasticizer were cast on a metal roll of TC 'dry for 60 minutes' to obtain a thickness. 20/zm PVA film. The film was fixed in a metal frame and heat-treated at ll ° C for 3 minutes. The swelling degree A of the heat-treated green film material was measured by the method described in the above (2) and was 230. In the same manner as in Example 1, except that the stretching ratio was 2.5 times, iodine was adsorbed while extending the green film material. The swelling degree B of the obtained stretched film was as described in the above (3). After the measurement, it was 2 5 5% ° -17 - 201033658. Then, a polarizing film was obtained in the same manner as in Example 1. The transmittance and the degree of polarization of the polarizing film were determined by the methods described in the above (4) and (5). After the measurement, it was 44.0% and 99.99%, respectively, and a polarizing film having good polarizing performance was obtained. [Example 4] 100 parts by mass of PVA having a polymerization degree of 5,200, a degree of saponification of 99.8 mol%, and 12 parts by mass of glycerin as a plasticizer. 5.5 mass% PVA aqueous solution at 60 The metal roll of °C was cast and dried for 60 minutes to obtain a PVA film having a thickness of 40 vm. The film was fixed in a metal frame and heat-treated at 10 ° C for 3 minutes. The swelling degree of the heat-treated green film material was The method described in the above (2) was measured to be 205%. Then, in the same manner as in Example 3, the above-mentioned green film material was stretched while iodine was adsorbed. The swelling degree B of the obtained stretched film was as described above (3). The polarizing film was obtained in the same manner as in Example 1. The transmittance and the degree of polarization of the polarizing film were measured by the methods described in the above (4) and (5). After that, it was 44.0% and 99.98%, respectively, and a polarizing film having good polarizing performance was obtained. [Example 5] 100 parts by mass of PVA containing a polymerization degree of 5,500, a degree of saponification of 99. 8 mol%, and a mass of glycerol 12 as a plasticizer A 5 wt% PVA aqueous solution was cast on a metal roll at 60 ° C and dried for 60 minutes to obtain a PVA film having a thickness of 30 / zm. The film was fixed in a metal frame and heat-treated at 130 t for 3 minutes. The swelling degree A of the subsequent green film material is as described above (2) The method described was measured to be 215%. Then, in the same manner as in Example 1, the green film material was stretched, and iodine was adsorbed on 201033658. The swelling degree B of the obtained stretched film was as described above (3). The measured method was measured to be 235%. Then, a polarizing film was obtained in the same manner as in Example 1. The transmittance and the degree of polarization of the polarizing film were measured by the methods described in the above (4) and (5). A polarizing film having good polarizing performance was obtained at 44.0% and 99.99%, respectively. [Comparative Example 1] 100 parts by mass of PVA having a polymerization degree of 4800 and a degree of roadway of 99.8 mol% and a 5.6 mass% PVA aqueous solution of 12 parts by mass of glycerin as a plasticizer were flowed up at a metal roll of 60 °C. The film was dried and dried for 60 minutes to obtain a PVA film having a thickness of 40/zm. The film was fixed to a metal frame and heat-treated at 120 ° C for 3 minutes. The swelling degree A of the green film material after the heat treatment was measured by the method described in the above (2) to be 220%. Next, in the same manner as in Example 1, except that the stretching ratio was 2.7 times, iodine was adsorbed while extending the green film material. The swelling degree B of the obtained stretched film was measured by the method described in the above (3), and then a polarizing film was obtained in the same manner as in Example 1. The transmittance and the degree of polarization of the polarizing film were measured by the methods described in the above (4) and (5), and were 44.0% and 99.92%, respectively, and the degree of polarization of the polarizing film was slightly insufficient. [Comparative Example 2] 100 parts by mass of PVA having a polymerization degree of 5,800 and a degree of saponification of 99.8 mol%, and a 5.5% by mass aqueous solution of PVA, which is a plasticizer, were cast on a metal roll at 60 ° C, After drying for 60 minutes, a PVA film having a thickness of 40/zm was obtained. The film was fixed in a metal frame and heat-treated at 140 ° C for -19-201033658 for 3 minutes. The swelling degree A of the green film material after the heat treatment was measured by the method described in the above (2) to be 195%. Next, in the same manner as in Example 1, the above-mentioned green film material was stretched while iodine was adsorbed. The swelling degree B of the obtained stretched film was measured by the method described in the above (3) to be 220%. Next, a polarizing film was obtained in the same manner as in Example 1. The transmittance and the degree of polarization of the polarizing film were measured by the methods described in the above (4) and (5), and were 44.0% and 99.92%, respectively, and the degree of polarization of the polarizing film was slightly insufficient. 100 parts by mass of PVA having a degree of polymerization of 5800 and a degree of saponification of 99.8 mol%, and a 5.5% by mass aqueous solution of PVA, which is 12 parts by mass of glycerin as a plasticizer, were cast on a metal latex roll at 60 ° C and dried for 60 minutes to obtain a thickness. 40/zm PVA film. The film was fixed in a metal frame and heat-treated at ll ° C for 3 minutes. The swelling degree A of the green film material after the heat treatment was measured by the method described in the above (2) to be 2,500%. Next, in the same manner as in Example 1, the above-mentioned green film material was stretched while iodine was adsorbed. The swelling degree B of the obtained stretched film was measured by the method described in the above (3) to be 2,800%. Next, a polarizing film was obtained in the same manner as in Example 1. The transmittance and the degree of polarization of the polarizing film were measured by the methods described in the above (4) and (5), and were 44.0% and 98.77%, respectively, and the degree of polarization of the polarizing film was slightly insufficient. [Comparative Example 4] In the same manner as in Example 1, except that the growth ratio was 1.7 times, the raw material obtained in Example 1 was extended while the raw material -20-201033658 was extended. Adsorption. The swelling degree B of the obtained stretched film was measured by the method described in the above (3) to be 240%. Then, a polarizing film was obtained in the same manner as in Example 1 except that the stretching ratio was 3.5 times. The transmittance and the degree of polarization of the polarizing film were measured by the methods described in the above (4) and (5), and were 44.0% and 99.90%, respectively, and the degree of polarization of the polarizing film was slightly insufficient. [Comparative Example 5] The green film obtained in Example 1 was adsorbed with iodine while extending the green film material in the same manner as in Example 1 except that the stretching ratio ❹ was 4.2. The swelling degree B of the obtained stretched film was measured by the method described in the above (3) to be 240%. Next, a polarizing film was obtained in the same manner as in Example 1 except that the stretching ratio was 1.4 times. The transmittance and the degree of polarization of the polarizing film were measured by the methods described in the above (4) and (5), and were 44.0% and 99.80%, respectively, and the degree of polarization of the polarizing film was slightly insufficient. [Comparative Example 6] The green film obtained in Example 1 was adsorbed with iodine while extending the above-mentioned green film material in the same manner as in Example 1 except that the stretching ratio was 1.2 times. The swelling degree B of the obtained stretched film was measured by the method described in the above (3) to be 23%. Next, a polarizing film was obtained in the same manner as in Example 1 except that the stretching ratio was 4.6. The transmittance and the degree of polarization of the polarizing film were measured by the methods described in the above (4) and (5), and were 44.0% and 99.40%, respectively, and the degree of polarization of the polarizing film was slightly insufficient. Therefore, in order to improve the degree of polarization, the target 値 of the extension of -21 - 201033658 is changed from 4.6 times to 5.0 times, and then the elongation cut occurs, and the polarizing film cannot be obtained. The above results are summarized and shown in Table 1.
-22- 65【一撇】 3 03 1X 20.」 OG 偏光膜 偏光度 99.99 99.99 99.99 99.98 99.99 99.92 99.92 99.87 99.90 99.80 99.40 透過率 44.0 44.0 44.0 44.0 44.0 44.0 44.0 44.0 44.0 44.0 44.0 總延伸倍率 班 Ο 〇 00 00 ίο 〇 (N 〇 〇 〇 ON in 延伸倍率2 m oi cn (N m CN (N CS cn <N CN 寸 Ό I2-KI延伸膜 膨潤度B 260 260 255 235 235 I 245 220 280 240 240 230 延伸倍率I CN CN <N <N (N 0 01 2.6 oi 卜 (N 寸 <N 生膜材料 膨潤度A 230 _I 240 230 205 215 ^20 195 250 230 230 230 熱處理溫度 P 120 ll5 llO llO 130 ! 120 140 llO 120 120 120 厚度 β m 〇 寸 o 寸 o 〇 o o o o . o PVA 聚合度 5800 5800 9100 5200 5500 ^soT 5800 5800 5800 5800 5800 實施例l 實施例2 實施例3 實施例4 實施例5 比較例l 比較例2 比較例3 比較例4 比較例5 比較例6 _ίτ- 201033658 (產業上利用可能性） . 藉由本發明之製法所得之偏光膜係活用偏光性能高之 . 優異特性，可有效用在電子計算機、手錶、筆記型個人電 腦、液晶監視器、液晶彩色投影機、液晶電視、車載用導 航系統、行動電話、室內外使用的量測機器等屬於液晶顯 示裝置之構成零件的偏光板的製作。 【圖式簡單說明】 無。 ® 【主要元件符號說明】 無0-22- 65【一撇】 3 03 1X 20.” OG Polarizing Film Polarization 99.99 99.99 99.99 99.98 99.99 99.92 99.92 99.87 99.90 99.80 99.40 Transmittance 44.0 44.0 44.0 44.0 44.0 44.0 44.0 44.0 44.0 44.0 44.0 Total Stretch Ratio Ο00 00 ίο 〇(N 〇〇〇ON in extension ratio 2 m oi cn (N m CN (N CS cn <N CN inch Ό I2-KI stretch film swelling degree B 260 260 255 235 235 I 245 220 280 240 240 230 230 Extension ratio I CN CN <N <N (N 0 01 2.6 oi 卜 (N inch < N film material swelling degree A 230 _I 240 230 205 215 ^ 20 195 250 230 230 230 heat treatment temperature P 120 ll5 llO llO 130 ! 120 140 llO 120 120 120 Thickness β m 〇 inch o o ooooo . o PVA degree of polymerization 5800 5800 9100 5200 5500 ^soT 5800 5800 5800 5800 5800 Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 _ίτ- 201033658 (Industrial Applicability) The polarizing film obtained by the method of the present invention has high polarizing performance and excellent characteristics. Utility in electronic computing , a watch, a notebook personal computer, a liquid crystal monitor, a liquid crystal color projector, a liquid crystal television, a car navigation system, a mobile phone, a measuring device used indoors and outdoors, and the like, which are components of a liquid crystal display device. Simple description of the schema] None. ® [Main component symbol description] No 0
-24--twenty four-