201234058 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種用於製造使用於液晶顯示裝置之偏光 板之偏光膜之製造方法。 本專利申請案係主張基於曰本專利申請案第2010-141429號（2010年6月22日申請）之巴黎條約上之優先權，此 處將上述申請所揭示之全部内容以引用之方式併入本說明 書。 【先前技術】 自先前以來’作為偏光膜係使用使二色性色素定向吸附 於聚乙烯醇系膜上而成者。即，已知有以硬為二色性色素 之碘系偏光膜、或以二色性染料為二色性色素之染料系偏 光膜等。該等偏光膜通常係於其至少單面上、較佳為兩面 上經由包含聚乙烯醇系樹脂之水溶液之黏著劑貼合三乙酸 從而形成偏光板，作為液晶顯示裝置 纖維素等之保護膜 (CD Liquid Crystal Display)，例如使用於液晶電視、電 腦顯示器、手機之顯示晝面等。 將聚乙烯醇系膜浸潰於水中使其膨潤之201234058 SUMMARY OF THE INVENTION Technical Field The present invention relates to a method for producing a polarizing film for use in manufacturing a polarizing plate for a liquid crystal display device. This patent application claims priority to the Parisian Patent Application Serial No. 2010- 141 429, filed on Jun. 22, 2010, the entire disclosure of which is hereby incorporated by reference. This manual. [Prior Art] Since the prior art has been used as a polarizing film system, a dichroic dye is oriented and adsorbed on a polyvinyl alcohol film. Namely, an iodine-based polarizing film which is a hard dichroic dye or a dye-based polarizing film which uses a dichroic dye as a dichroic dye is known. The polarizing film is usually laminated on at least one surface thereof, preferably on both surfaces, via an adhesive containing an aqueous solution of a polyvinyl alcohol resin to form a polarizing plate, and is used as a protective film for cellulose or the like of a liquid crystal display device. CD Liquid Crystal Display), for example, for LCD TVs, computer monitors, display screens for mobile phones, etc. The polyvinyl alcohol film is immersed in water to swell
膜向處理液之導入、 自處理液之取出。 之後， 對處理浴前後之夾輥賦予周速差 輕改變膜之搬送方向，從而進行 作為偏光膜之製造方法， 導輥，將聚乙嫌醇条瞄、袁d 已知有如下方法：使用爽輥、 以上述 ’繼而為了使碘固定於 理（交聯處理），進而於 5 157074.doc 201234058 ^近年來，伴隨液晶顯示裝置之大型化、功能及亮度 挺幵而要求使用於其之偏光膜之大型化，並且要求光 子特性及面内均勻性之提昇。然而為獲得大型之偏光 膜必為對寬幅之达材薄膜進行均勻地單轴延伸，所獲得 之偏光膜之光線吸收轴（以下，有時稱為吸收抽）會產生偏 差存在光予特性惡化之傾向。進而，於面内之光學特性 偏差之情形時，形成圖像顯示裝置時會產生顯示色斑。 另方面於專利文獻1中揭示有如下内容：於硼酸處 理步驟及/或其之前之步驟中進行翠轴延伸之偏光膜的製 造方法中，為獲得瑕症或褶敵更少、且無折痕之偏光膜’ 而使用擴幅辕作為處理液中之至少一個導辕。然而，於專 利文獻1所揭示之方法中’例如在染色槽中使用擴幅輥， 進行累計延伸料i.6倍以上线伸之情料，吸收輛會 產生偏差’存在所得之偏光膜之光學特性較低之問題。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2005_227650號公報 【發明内容】 [發明所欲解決之問題] 本發明之課題在於提供—種光學特性優異之偏光 造方法。 、表 [解決問題之技術手段] 本發明者等人為解決上述課題而進行銳意研究，結 現如下新的事實：於一方面以擴幅輥進行擴幅—方面進行 157074.do, 201234058 累什延伸倍率κ6倍以上之單轴延伸時，藉由使擴 擴幅方向為特定之方向，而可抑制獲得之偏光膜之吸收軸 之偏差，從而可獲得具有良好之光學特性之偏光膜，最終 完成本發明。 即’本發明之偏光膜之製造方法包含以下構成。 ㈣光臈之製造方法，其包含對聚W料膜依序進 订知潤處理、染色處理、硕酸處理及清洗處理之步驟，且 於其ΓΓ一之步驟前或步驟中，利用2個夾輥間之周速差 而進仃早軸延伸，該偏光膜之製造方法包含於上述2個夾 親間設置至少1個擴幅轉而進行擴幅及單轴延伸之擴幅延 伸步驟’且包含擴幅延伸步驟在内之直至擴幅延伸步驟為 止的累計延伸倍率（其中，於直至擴幅延伸步驟為止而無The film is introduced into the treatment liquid and taken out from the treatment liquid. After that, the nip roller before and after the treatment bath is given a difference in the circumferential speed to change the direction in which the film is conveyed, thereby performing a method of producing a polarizing film. The guide roller is used to illuminate the polyethyl alcohol, and the following method is known: In order to fix the iodine to the chemistry (cross-linking treatment), the roller is required to be used in the polarizing film of the liquid crystal display device in accordance with the increase in size, function, and brightness of the liquid crystal display device. It is enlarged and requires an increase in photon characteristics and in-plane uniformity. However, in order to obtain a large polarizing film, it is necessary to uniformly uniaxially extend the wide film, and the light absorption axis (hereinafter, sometimes referred to as absorption pumping) of the polarizing film obtained may be deviated, and the light characteristic deteriorates. The tendency. Further, in the case where the optical characteristics in the plane are deviated, a display stain is generated when the image display device is formed. On the other hand, Patent Document 1 discloses that in the method for producing a polarizing film in which the emerald axis is extended in the boric acid treatment step and/or the preceding step, in order to obtain snoring or less entanglement, and no crease The polarizing film 'is used as the at least one guide in the treatment liquid. However, in the method disclosed in Patent Document 1, 'for example, in the dyeing tank, a widening roll is used to carry out the cumulative stretching of i. 6 times or more, and the absorption of the vehicle may cause a deviation. The optical characteristics of the obtained polarizing film are present. Lower question. [Prior Art] [Patent Document 1] [Patent Document 1] JP-A-2005-227650 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] An object of the present invention is to provide a polarizing method which is excellent in optical characteristics. Table [Technical means for solving the problem] The inventors of the present invention conducted intensive studies to solve the above problems, and the following new facts were realized: on the one hand, expansion is carried out by a wide-rolling roll - 157074.do, 201234058 When the uniaxial stretching of the magnification κ is 6 times or more, the deviation of the absorption axis of the obtained polarizing film can be suppressed by making the direction of the expansion and expansion direction a specific direction, and a polarizing film having good optical characteristics can be obtained, and finally the present invention can be obtained. invention. That is, the method for producing a polarizing film of the present invention comprises the following constitution. (4) A method for manufacturing a ray, comprising the steps of sequentially ordering a smudge treatment, a dyeing treatment, a sonication treatment, and a cleaning treatment on a poly-W film, and using two clamps before or in the step of the first step The circumferential speed difference between the rolls is extended to the early axis. The method for producing the polarizing film includes at least one expansion and expansion step of expanding and uniaxially extending between the two members. The cumulative stretching ratio from the expansion stretching step to the expansion stretching step (wherein, until the expansion stretching step
其他延伸步驟之情形時為擴幅延伸步驟之延伸倍率）為U 倍以上’於擴幅延伸步驟中擴幅輥之擴幅方向相對於自擴 幅輥所搬出之上述膜之搬出方向之角度為-40。〜70。(苴中， 將自左向右觀察膜之移動方向時之膜自擴幅輥之搬出方向 設為〇。1自該搬出方向為順時針方向之角度設為-，逆 時針方向之角度設為+)。 ⑺如⑴之偏光膜之製造方法，其包含2個^射 步驟。 ⑺如⑴或⑺之偏光膜之製造方法，其中將擴幅延伸步驟 之擴幅輥配置於空氣中。 (4)如⑴至（3)中任-項之偏光膜之製造方法，其中擴幅延 伸步驟之擴幅輥為海綿橡膠輥，該海綿之硬度以In the case of the other extension step, the stretching ratio of the expansion stretching step is U times or more. The angle of the expansion direction of the expansion roller in the expansion stretching step is opposite to the direction in which the film is carried out by the self-expanding roller. -40. ~70. (In the middle, the direction in which the film is moved from the left to the right when the film is moved is set to 〇. The angle from the direction of the movement in the clockwise direction is -, and the angle in the counterclockwise direction is set to +). (7) A method for producing a polarizing film according to (1), which comprises two steps. (7) A method of producing a polarizing film according to (1) or (7), wherein the expanding roller of the expanding step is disposed in the air. (4) The method for producing a polarizing film according to any one of (1) to (3), wherein the expanding roller of the expanded stretching step is a sponge rubber roller, and the hardness of the sponge is
157074.doc S 201234058 · JIS(Japanese Industrial Standards，日本工業標準）簫氏 (sh〇re)C標度計為20〜60度，密度為〇 4〜〇 6 g/cm3及表面粗 糙度為10〜30 S。 (5) 如（1)至（4)中任一項之偏光膜之製造方法其中擴幅延 伸步驟之延伸係藉由濕式延伸而進行，且所使用之液體溫 度為 20°C~40°C。 (6) 如（1)至（5)中任一項之偏光膜之製造方法其中直至擴 幅延伸步驟為止之累計延伸倍率（其中，於直至該步驟為 止而無其他延伸步驟之情形時為該步驟之延伸倍率）為2倍 以上。 [發明之效果] 根據本發明之偏光膜之製造方法，實現可抑制獲得之偏 光膜之吸收軸之偏差，從而製造光學特性優異之偏光膜。 【實施方式】 ' (偏光膜之製造方法） _形成本發明之聚乙烯醇系膜之聚乙稀醇系樹脂通常可例 不使聚醋酸乙烯®旨系樹脂皂化而成者。4化度通常為約85 。莫耳％以上，較佳為約9〇莫耳％以上，更佳為約99莫耳 %〜100莫耳％。作為聚醋酸乙烯酯系樹脂，除列舉作為醋 酸乙烯酯之均聚物之聚醋酸乙烯酯之外，還可列舉醋酸乙 稀^與能與其共聚之其他單體之共聚物，例如乙稀㈣乙 婦知等。作為可共聚之其他單體，可列舉例如不餘和叛酸 類烯L類、乙烯醚類、不飽和磺酸類等。聚乙烯醇系樹 月曰之聚合度通常為約1000〜10000，較佳為約1500〜5000左 157074.doc 201234058 右。 亦可對該等聚乙烯醇系樹脂進行改質，例如，亦可使用 以搭類進行改質而得之聚乙稀曱酿、聚乙缔縮醒、聚乙婦 丁醛等。通常，作為偏光膜製造之起始材料，係使用厚度 為約20 μπι〜100 μηι、較佳約3〇 μιη〜8〇 μιη之聚乙烯醇系二 脂膜之未經延伸之膜。就工業上而言，膜之實用寬度為約 1500 mm~6000 mm 〇 對該未經延伸之膜依序進行膨潤處理、染色處理、侧酸 處理(交聯處理)、水洗處理，最後乾燥而得之聚乙烯醇系 偏光臈之厚度為例如約5〜5〇 μιη左右。 作為使二色性色素定向吸附之聚乙稀醇系單軸延伸膜之 偏光臈，-般而言，可藉由如下方式獲得：使未經延伸之 聚乙婦醇系膜於水溶液中以膨潤處理、染色處理、_酸處 理及水洗處理之順序進行溶液處理，於蝴酸處理步驟中及 若需要則於其之前之步驟中，以濕式或乾式進行單抽延 伸’最後進行乾燥。 本發明之單轴延料僅於-個㈣延伸㈣巾進行，亦 可於2個以上之㈣t進行。於2個以上之步驟中進行之情 形時’除至少包含—個擴幅延伸步驟以外，可採用周知^ 延伸方法。作為周知之延伸方法，有如曰本專 2731813號公報揭示之熱輥延伸法、拉幅機延伸法 利用於搬送膜之2個夾輥間設置周速差而進行輥間延伸。 當然，亦可進行複數次之擴幅延伸步驟。又，基本上步驟 之順序為如上所述’而關於處理浴之次數或處理條件等則 157074.doc 201234058 無限制。 又’顯然’亦可因其他目的而插人上述步驟中未記載之 步驟。作為該步驟之例可列舉於硼酸處理後，利用不 酸之硬化物水溶液之浸潰處理（魏物處理）步驟或利用含 有不含硼酸之氯化辞等之水溶液之浸潰處理（鋅處理）步戰 等。 膨潤步驟之目的在於除去膜表面之雜質'除去膜中之塑 化劑、賦予後續步驟中之易染色性、及膜之可塑化等。處 理條件係於可達成該等目的之範圍，且不會產生基材膜之 極端溶解、失料不良狀狀範_決定。於使預先在氣 體中經延伸之膜膨潤之情形時，將膜浸潰於例如約 2(TC〜7(TC ’較佳為約3(rc〜6(rc之水溶液中而進行。膜之 浸潰時間較佳為約30秒〜300秒，進而較佳為約6〇秒〜24〇秒 左右。於使未預先延伸之坯材薄膜膨潤之情形時，係將膜 浸潰於例如約HTC〜50。(：，較佳為約2(rc〜4(rc之水溶液中 進行。膜之浸潰時間較佳為約30秒〜3〇〇秒，進而較佳為約 60秒〜240秒左右。 再者，於對聚乙烯醇系膜進行膨潤、染色、硼酸處理之 情形時，亦可於膨潤步驟中進行單軸延伸，作為該情形之 延伸倍率通常為I.2〜3倍，較佳為1>3〜2.5倍。 於膨潤處理步驟中，使膜於寬度方向進行膨潤而容易出 現於膜上產生褶皺等問題，因此較佳為一面藉由擴幅輥 (寬度擴展輥）、螺旋輥、冠狀輥（crown r〇Uer)、導布器 (cloth guider)、彎曲桿 '拉幅夾（tenter cUp)等周知之擴幅 157074.doc 201234058 裝置除去膜之褶H搬送臈。為了使浴中之膜之搬送 穩定化，以水中淋浴控制膨潤浴中之水流，或併用Epc裝 置（Edge Positicm c。—裝置：檢測膜之端部防止膜之 婉蜒之裝置）等亦有用。於本步驟中，亦於膜之移動方向 對膜進行膨潤擴大，因此於不對膜進行積極地延伸之情形 時為/肖除搬送方向之膜之鬆弛，較佳為採取例如控制處 理槽則後之搬送輥之速度等手段。又，於所使用之膨潤處 理浴中，除純水以外，亦可使用在約〇 〇1重量％〜1〇重量％ 之範圍内添加硼酸（揭示於日本專利特開平1〇_1537〇9號公 報）、氯化物（揭示於曰本專利特開平〇6 281816號公報）、 無機g文、無機鹽、水溶性有機溶劑、乙醇類等而製成之水 溶液。 利用二色性色素之染色步驟係為了使二色性色素於膜上 吸附、且定向等而進行。處理條件係於可達成該等目的之 範圍内，且不會產生基材膜之極端溶解、失透等不良狀況 之範圍内決定。於使用碘作為二色性色素之情形時，於例 如約HTC〜45°c，較佳為約20°c〜35°c之溫度下，且以重量 比計艰/KI/水=約〇.003〜〇.2/約〇 υοηοο之濃度，進行約 30秒〜600秒、較佳約60秒〜3〇〇秒的浸潰處理。亦可使用其 他蛾化物、例如碘化鋅等代替碘化鉀。又，亦可將其他之 蛾化物與峨化鉀併用。又，亦可使碘化物以外之化合物例 如棚酸、氯化辞、氯化鈷等共存。於添加硼酸之情形時， 係於包含碘方面區別於下述硼酸處理。只要相對於水1〇〇 重量部，包含約0.003重量部以上之碘則視為染色槽。 157074.doc 3 -9- 201234058 於使用水溶性二色性染料作為二色性色素之情形時，於 例如約20。(：〜80。(：，較佳為約30t： 〜7(rc之溫度下且以重 量比計二色性染料/水=約〇.0〇1〜〇1/1〇〇之濃度，進行約％ 秒〜600秒、較佳約6〇秒〜3〇〇秒的浸潰處理。使用之二色性 染料之水溶液，可包含染色助劑等，亦可含有例如硫酸納 等之無機鹽、界面活性劑等。二色性染料可單獨使用，亦 可同時使用2種以上之二色性染料。 ' 於對聚乙烯醇系膜依序進行膨潤處理、染色處理、删酸 處理之情形時，通常，於染色槽中進行膜之延伸。直至染 色處理為止之累計延伸倍率（於直至該步驟為止而無延二 步驟之情形時為該步驟之延伸倍率）通常為1 6〜4 5倍，較 佳為1.8〜4倍。又，於直至染色處理為止之累計之延伸倍 率為未達1.6倍之情形時，膜之斷裂之頻率變高，有良率 惡化之傾向。 延伸係以使染色槽之前後之夾輥具有周速差等方法而進 仃。又，以與膨潤步驟相同之方式，亦可將擴幅輕（寬度 擴展輥）' 螺旋輥、冠狀輥、導布器、彎 色浴中及，或染色浴之出口、入口。再者，本發明：單二 延伸可使用於膨潤步驟、染色步驟、棚酸處理步驟及清洗 步驟中之任一步驟。 硼酸處理係於相對於水丨〇 〇重量部含有硼酸約丨〜丨〇重量 Ρ之水冷液中’次潰以二色性色素進行染色之聚乙稀醇系 膜而進行。於二色性色素為填之情形時，較佳為含有峨化 物約1〜30重量部。 157074.doc 201234058 作為峨化物可列舉破化卸、蛾化辞等。&，亦可使埃化 物以外之化合物’例如氯化鋅、氣化鈷、氣化锆、硫代硫 酸鈉、亞硫酸舒、硫酸納等共存。 該硼酸處理係為了利用交聯之耐水化或色相調整（防止 帶有藍色等)等而實施。於用於利用交聯之耐水化之情形 時，依據需I，除㈣酸以外，或者亦可將爛酸與乙二路、 戊二醛等交聯劑同時使用。 再者，亦存在將用於耐水化之硼酸處理以耐水化處理、 交聯處理、固定化處理等名稱稱呼的情形。又，亦存在將 用於色相調整之處理以補色處理、再染色處理等名稱 稱呼之情形。 關於該硼酸處理，依據其目的，可適當改變硼酸及碘化 物之濃度、處理浴之溫度而進行。 用於耐水化之硼酸處理與用於色相調整之硼酸處理無特 別區分之處，以下述條件實施。 於對坯材薄膜進行膨潤、染色、硼酸處理之情形時，當 硼酸處理之目的為利用交聯之耐水化時，使用相對於水 100重量部含有硼酸約3〜10重量部、碘化物約卜20重量部 之硼酸處理浴，且通常於約50»c〜70。0，較佳為約 53°C〜65°C之溫度下進行。浸潰時間通常為約1〇〜6〇〇秒左 右，較佳為20〜300秒，更佳為2〇〜200秒》 再者，於對預先經延伸之膜進行染色、進行硼酸處理之 情形時’硼酸處理浴之溫度通常為約5(rc〜85〇c，較佳為 約 55°C 〜80°C。157074.doc S 201234058 · JIS (Japanese Industrial Standards) The Sh〇re C scale is 20~60 degrees, the density is 〇4~〇6 g/cm3 and the surface roughness is 10~ 30 S. (5) The method for producing a polarizing film according to any one of (1) to (4) wherein the stretching step is performed by wet stretching, and the liquid temperature used is 20 ° C to 40 ° C. (6) The method for producing a polarizing film according to any one of (1) to (5), wherein the cumulative stretching ratio up to the expansion stretching step (wherein, in the case where there is no other stretching step up to the step) The step magnification of the step is more than 2 times. [Effects of the Invention] According to the method for producing a polarizing film of the present invention, it is possible to produce a polarizing film which is excellent in optical characteristics by suppressing variation in the absorption axis of the obtained polarizing film. [Embodiment] The method of producing a polyvinyl alcohol-based film of the present invention can be exemplified by not saponifying a polyvinyl acetate® resin. The degree of 4 is usually about 85. More than 5% by mole, preferably about 9 〇 mol% or more, more preferably about 99 mol% to 100 mol%. As the polyvinyl acetate-based resin, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, a copolymer of ethyl acetate and another monomer copolymerizable therewith may be mentioned, for example, ethylene (tetra) Women know. Examples of the other monomer copolymerizable include, for example, a group of alkaloids, a vinyl ether, an unsaturated sulfonic acid, and the like. The degree of polymerization of the polyvinyl alcohol tree is usually from about 1000 to 10,000, preferably from about 1,500 to 5,000. 157074.doc 201234058 Right. These polyvinyl alcohol-based resins may be modified, and for example, polyethylene smelting, polyethylene condensing, and polybutyroyl aldehyde may be used. In general, as a starting material for the production of a polarizing film, an unstretched film of a polyvinyl alcohol-based diester film having a thickness of about 20 μm to 100 μm, preferably about 3 μm to 8 μm is used. Industrially, the practical width of the membrane is about 1500 mm to 6000 mm. The unstretched membrane is sequentially subjected to swelling treatment, dyeing treatment, side acid treatment (crosslinking treatment), water washing treatment, and finally drying. The thickness of the polyvinyl alcohol-based polarizing iridium is, for example, about 5 to 5 Å μηη. The polarizing enthalpy of the polyethylene uniaxially stretched film which is oriented to adsorb the dichroic dye can be generally obtained by swelling the unstretched polyethyl alcohol film in an aqueous solution. The treatment, the dyeing treatment, the _acid treatment, and the water washing treatment are carried out in the order of the solution, and in the palmitic acid treatment step and, if necessary, in the previous step, the single-extraction is carried out in a wet or dry manner, and finally dried. The uniaxially extending material of the present invention is carried out only for one (four) extended (four) towels, and may be carried out for two or more (four) t. In the case of performing in two or more steps, the method of extending the extension may be employed in addition to at least one step of expanding. As a well-known extension method, the hot roll stretching method and the tenter stretching method disclosed in Japanese Patent Publication No. 2731813 are used to form a circumferential speed difference between two nip rolls of a transfer film to extend between rolls. Of course, a plurality of expansion and extension steps can also be performed. Further, the order of the basic steps is as described above, and the number of times of processing the bath or the processing conditions, etc. 157074.doc 201234058 is not limited. It is also apparent that the steps not described in the above steps may be inserted for other purposes. As an example of this step, after the boric acid treatment, the impregnation treatment (wealth treatment) step using an aqueous solution of a hard acid-free hardened material or the impregnation treatment (zinc treatment) using an aqueous solution containing a boric acid-free chlorination or the like is used. Step by step and so on. The purpose of the swelling step is to remove impurities on the surface of the film 'removing the plasticizer in the film, imparting dyeability in the subsequent step, and plasticizing the film. The treatment conditions are within the range in which such a purpose can be achieved, and there is no such a problem that the substrate film is extremely dissolved and the material is undesired. In the case where the film which has been previously stretched in the gas is swollen, the film is immersed in, for example, about 2 (TC~7 (TC' is preferably about 3 (rc~6) in an aqueous solution of rc. The collapse time is preferably from about 30 seconds to 300 seconds, and more preferably from about 6 seconds to about 24 seconds. When the unextended material film is swollen, the film is impregnated, for example, to about HTC~ 50. (:, preferably about 2 (rc~4) is carried out in an aqueous solution of rc. The film impregnation time is preferably about 30 seconds to 3 seconds, and more preferably about 60 seconds to 240 seconds. Further, when the polyvinyl alcohol-based film is subjected to swelling, dyeing or boric acid treatment, uniaxial stretching may be carried out in the swelling step, and the stretching ratio in this case is usually from 1.2 to 3 times, preferably 1> 3 to 2.5 times. In the swelling treatment step, the film is swollen in the width direction and is likely to cause wrinkles on the film. Therefore, it is preferable to use a widening roll (width expanding roll), a spiral roll, Coronal roll (crown r〇Uer), cloth guider, curved rod 'tenter cUp' and other well-known expansion 157074.doc 201234058 The device removes the pleats of the film H. In order to stabilize the film transfer in the bath, the water in the swelling bath is controlled by a shower in the water, or the Epc device is used in combination (Edge Positicm c-device: the film at the end of the detection film) In the present step, the film is also swollen and expanded in the moving direction of the film. Therefore, when the film is not actively extended, the film is loosened in the direction of the transfer. For example, it is preferable to use a method such as controlling the speed of the transfer roller after the treatment tank, and in the swelling treatment bath to be used, in addition to the pure water, it may be used in the range of about 1% by weight to 1% by weight. Boric acid is added (disclosed in Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 6 281816), inorganic g, inorganic salt, water-soluble organic solvent, and ethanol. An aqueous solution prepared by using a dichroic dye is carried out in order to adsorb, orient, orient the dichroic dye on the film. The treatment conditions are within the range in which the objects can be achieved. In the case where iodine is used as the dichroic dye, it is determined to be, for example, about HTC to 45 ° C, preferably about 20 ° C, in the case where no adverse effect such as extreme dissolution or devitrification of the base film occurs. At a temperature of ～35°c, and in a weight ratio of //KI/water=about 003.003~〇.2/about 〇υοηοο, for about 30 seconds to 600 seconds, preferably about 60 seconds to 3 〇. Immersion treatment of leap seconds. Other molybdenum compounds such as zinc iodide may be used instead of potassium iodide. Alternatively, other moth compounds may be used together with potassium telluride. Further, compounds other than iodide such as linoleic acid may also be used. , chlorination, cobalt chloride and the like coexist. In the case of adding boric acid, it is distinguished from the following boric acid treatment in that it contains iodine. As long as it contains about 0.003 part by weight or more of iodine with respect to the weight of the water, it is regarded as a dyeing tank. 157074.doc 3 -9- 201234058 When a water-soluble dichroic dye is used as the dichroic dye, for example, about 20. (:~80. (:, preferably about 30t: 〜7 (at a temperature of rc and by weight ratio of dichroic dye/water = about 〇.0〇1~〇1/1〇〇, carry out The dipping treatment of about 2 seconds to 600 seconds, preferably about 6 seconds to 3 seconds. The aqueous solution of the dichroic dye used may contain a dyeing aid or the like, and may contain an inorganic salt such as sodium sulfate. A dichroic dye can be used alone or two or more kinds of dichroic dyes can be used at the same time. 'When the polyvinyl alcohol-based film is sequentially subjected to swelling treatment, dyeing treatment, or acid removal treatment, Usually, the extension of the film is carried out in the dyeing tank. The cumulative stretching ratio until the dyeing treatment (the stretching ratio of the step up to the step without the second step) is usually 16 to 45 times. In addition, when the cumulative stretching ratio until the dyeing treatment is less than 1.6 times, the frequency of breakage of the film becomes high, and the yield tends to be deteriorated. The front and rear nip rolls have a method of peripheral speed difference, etc. In the same way, it is also possible to expand the width (width expansion roll) 'screw roll, crown roll, guide cloth, curved bath and or the entrance and entrance of the dye bath. Furthermore, the present invention: single extension It is used in any of the swelling step, the dyeing step, the sulphonic acid treatment step and the washing step. The boric acid treatment is carried out in a water-cooled liquid containing boric acid of about 丨 丨〇 丨〇 Ρ 相对 relative to the weight of the leeches. The dichroic dye is dyed in the form of a polyethylene film. When the dichroic dye is filled, it preferably contains about 1 to 30 parts by weight of the telluride. 157074.doc 201234058 Decomposition, moth, etc. &, can also make compounds other than the adducts such as zinc chloride, cobalt hydride, zirconium hydride, sodium thiosulfate, sulfite, sodium sulphate, etc. coexistence. In order to utilize the water resistance of the cross-linking or the hue adjustment (preventing the presence of blue, etc.), etc., in the case of utilizing the water resistance of cross-linking, depending on the demand I, in addition to the (tetra) acid, or may be rotten Acid and cross-linking agent such as ethylene two-way, glutaraldehyde In addition, there is also a case where the boric acid treatment for water resistance is referred to as a water-resistant treatment, a cross-linking treatment, an immobilization treatment, etc. Further, there is also a treatment for color adjustment to complement color treatment, and then The name of the dyeing treatment is called. The boric acid treatment can be carried out by appropriately changing the concentration of boric acid and iodide and the temperature of the treatment bath according to the purpose. The boric acid treatment for hydration resistance and the boric acid treatment for hue adjustment are not performed. In particular, it is carried out under the following conditions: In the case of swelling, dyeing, or boric acid treatment of the raw material film, when the purpose of the boric acid treatment is to resist hydration by crosslinking, the use of boric acid is contained in about 100 parts by weight of water. The boric acid treatment bath of 3 to 10 parts by weight and iodide is 20 parts by weight, and is usually carried out at a temperature of about 50»c to 70. 0, preferably about 53 to 65 °C. The immersion time is usually about 1 〇 to 6 〇〇 seconds, preferably 20 to 300 seconds, more preferably 2 〇 to 200 seconds. Further, in the case of dyeing the previously stretched film and performing boric acid treatment The temperature of the boric acid treatment bath is usually about 5 (rc to 85 ° C, preferably about 55 ° C to 80 ° C).
S 157074.doc 201234058 亦可在用於耐水化之棚酸處理後，進行用於色相調整之 硼酸處理ϋ如於二色性染料為碘之情形時，為達成該目 的’使用相對於水100重量部含有硼酸約卜5重量部、碘化 物約3〜3G重量部之蝴酸處理浴，且通常於約⑺1〜价之 溫度下進行。浸潰時間通常為丨〜秒左右，較佳為2〜1〇〇 該等硼酸處理亦可進行複數次，通常大多㈣時係進行 W次。該情形時，使用之各硼酸處理槽之水溶液組成、 及溫度於上述範圍内既可相同’亦可不同。亦可於複數個 步驟中力別進行用於上料水化之顯處理、及用於色相 調整之硼酸處理。 本發明中偏光膜之延伸之最終累計延伸倍率通常為約 4.5〜7倍，較佳為約5〜6 5倍。 於硼ϋ夂處理後’進行水洗。水洗處理係藉由例如將為了 对水化及/或色相調整而經_處理之聚乙烯醇“於水 中浸潰，以水為喷水器進行錢，或者併用浸潰及喷霧而 進行。水洗處理中水之溫度，通常為約2〜4(TC左右，浸潰 時間為約2〜120秒左右即可。 其後’使聚乙歸醇系膜於乾燥爐中 進行乾燥、_〜咖秒，“顿得偏歧。 度 再者’於臂處理步驟及清洗處理步驟中，亦可使用擴 幅輥。 ' (擴幅延伸步驟） 於上述處理步驟中夕· Ar jt. tea, , 邵T之任一步驟、或與該等步驟不同之延 157074.doc •12- 201234058 伸步驟中’使膜於2個夾輥間進行單軸延伸。即，使膜之 搬送方向之下游側之夾輥的周速度大於上游側之夹輥之周 速度’從而賦予膜張力而進行延伸。 該情开々時，於本發明之延伸步驟中 於2個夾輥間設置至少1個擴幅輥，從而一面擴幅膜一面進 行單轴延伸（擴幅延伸步驟）。 直至設置有本發明之擴幅輥之擴幅延伸步驟為止之累計 延伸倍率（其中，於擴幅步驟之前無延伸步驟之情形時係 指擴幅延伸步驟之延伸倍率，以下均相同）為16倍以上， 較佳為2倍以上，又，通常為7倍以下，較佳為6 5倍以 下，藉此可充分發揮抑制吸收轴之偏差之效果。於直至擴 幅延伸步驟為止的累計延伸倍率為未達16倍之情形時， 有無法獲得充分之對吸收轴之偏差的抑制效果之虞，又， 如上所述，於直至進行延伸步驟之染色步驟為止的累計延 伸倍率為低於倍之情形時，有膜之斷裂頻率變高之傾 向。累計延伸倍率係對單軸延伸及擴幅延伸之倍率進行合 計而得之倍率，於里从 口 早軸延伸、及擴幅延伸分別進行複數次 之情形時為累計該等全部之倍率。 延伸可為乾式及渴式中 …、中之任一種，但較佳為將膜於特定 之各液中一面浸泡—面谁 "m 面進錢伸’即以所謂濕式延伸法進 灯。該濕式延伸法不易佶 故易於獲得必㈣心可充分地進行延伸， 高。 而之先學特性，與乾式延伸法相比偏光度較 以下，利用圖式 157074.doc 詳細地說明本發明之單軸延伸之實施 3 -13- 201234058 形態。圖1係表示本發明之擴幅延伸步驟之一實施形態之 說明圖，圖2係表示本發明之擴幅輥之一例之前視圖。 使圖1所示之處理槽1 〇中，充滿處理液4(例如碘、碘化 鉀水溶液），於通過其中之聚乙烯醇系膜丨之搬送方向之上 游側没置夾輥2，於下游側設置夾輥2,，於2個夾輥間設置 擴幅輥3、導輥5。如圖2所示，擴幅輥3具有彎曲之形狀。 於該擴幅延伸步驟中，將聚乙烯醇系膜丨浸潰於處理液4 中，進而一面經由擴幅輥3進行延伸，一面利用2個之夾輥 2、2·間之周速差進行延伸。再者，該情形時，擴幅輥3亦 可為複數個。 又，圖3(a)〜(c)係表示擴幅輥之擴幅方向M與膜 向之關係的說明圖 擴幅輥3之擴幅方向M於提高偏光膜之光學特性方面較 為重要相對於膜！之搬出方向，擴幅方向Μ之角度㊀ 為，。〜70。，更佳為_3〇。〜3〇。之範圍。其中，如圖3⑷〜⑷ 所示’將自左向右觀察膜!之移動方向時之膜ι之搬出方向 以〇°’自該㈣方向為順時針方向之角度設為_，逆時 針方向之角度认為+。圖3中分別表示擴幅輥之擴幅方向相 對於膜之搬出方向之角度為（輕、（_。、（eMQ。之情 形二於角度e超出上述範圍之情形時，偏光膜之吸收軸於 固疋方向（膜之搬送方向）將合 ^ ⑺將會不一致，故將引起膜之光學 特性降低之問題。 使用之擴幅輥3之曲率半徑較佳為胸〜5。刚酿更 佳為咖0〜麵0_，擴幅輥3之直徑d較佳為5〇〜遍 157074.doc 201234058 mm’更佳為75〜200 mm。 擴幅輥3可配置於空氣中（大氣中）、及液體中之任一 處’如圖1所示’於設置在空氣中之擴幅輥3使用本發明， 就可提高光學特性而言較植。 特別是，在利用膜之膨潤之寬度尺寸之變化較大的膨潤 步驟或染色步驟中，於設置有複數個擴幅輥之情形時，將 至少一個擴幅輥3設置於空氣中，藉由應用本發明而可抑 制褶敵之產生並提高光學特性。 於設置有複數個擴幅輥3之情形時，較佳為使用本發明 之擴幅輥3較多者，非常佳為對全部之擴幅輥3應用本發 明’即將全部之擴幅輥3設置於2個夾輥2、2,間。 作為本發明之製造步驟中之擴幅輥之素材較佳為可列舉 橡膠、海綿等，更佳為海綿橡膠較。》乙料系膜係利用 吸收浴液而於長度、寬度兩方向進行膨潤，特別是若在寬 度方向之膨潤尚未結束之狀態下施加張力，則於輥上容易 產生褶皺或折痕。若使用海綿橡膠輥作為擴幅輥，則基於 其表面高粗度之對膜之把持力較高，故可發揮充分之^幅 力’且亦可最大限度地發揮作為擴幅親之另—作用之婉挺 防止功能’從而減少褶皺，消除折痕。 作為本發明中所使用之海綿橡膠輥較佳為：海綿之硬度S 157074.doc 201234058 It is also possible to carry out boric acid treatment for hue adjustment after liquefied acid treatment for hydration, for example, when the dichroic dye is iodine, to achieve the purpose of 'using 100 weight relative to water The molybdenum treatment bath containing 5 parts by weight of boric acid and about 3 to 3 parts by weight of iodide is usually carried out at a temperature of about (7) 1 to a price. The immersion time is usually about 丨~sec, preferably 2~1 〇〇. The boric acid treatment can also be carried out plural times, and usually it is carried out W times in many (four) times. In this case, the aqueous solution composition and the temperature of each of the boric acid treatment tanks used may be the same or different. It is also possible to carry out the treatment for the hydration of the feed and the treatment of the boric acid for the hue adjustment in a plurality of steps. The final cumulative stretching ratio of the extension of the polarizing film in the present invention is usually about 4.5 to 7 times, preferably about 5 to 6 5 times. After the treatment with boron boring, water washing was carried out. The water washing treatment is carried out by, for example, impregnating polyvinyl alcohol which has been treated for hydration and/or hue adjustment in water, using water as a water sprayer, or using both impregnation and spraying. The temperature of the treated water is usually about 2 to 4 (about TC, and the impregnation time is about 2 to 120 seconds. Thereafter, the polyethyl alcohol film is dried in a drying oven, _~ coffee seconds , "Don't be distorted. Degree again" in the arm processing step and the cleaning process step, you can also use a widening roller. ' (Expansion and extension step) in the above processing steps ‧ Ar jt. tea, , Shao T Any step, or different from the steps 157074.doc •12-201234058 in the stretching step, the film is uniaxially stretched between the two nip rolls, that is, the nip roller on the downstream side of the film conveying direction The circumferential speed is greater than the circumferential speed of the nip roller on the upstream side to extend the film tension. In the extension step of the present invention, at least one expansion roller is disposed between the two nip rolls in the extension step of the present invention. The expanded film is uniaxially stretched on one side (expansion and extension step). The cumulative stretching ratio up to the expansion step of the expanded roll of the invention (wherein, in the case of no stretching step before the expanding step, the stretching ratio of the expansion stretching step, the same is the same) is 16 times or more, preferably It is twice or more, and is usually 7 times or less, preferably 6 5 times or less, whereby the effect of suppressing variations in the absorption axis can be sufficiently exhibited. The cumulative stretching ratio until the expansion and extension step is less than 16 times. In the case of the case, it is impossible to obtain a sufficient effect of suppressing the deviation of the absorption axis, and as described above, when the cumulative stretching ratio until the dyeing step of the stretching step is less than twice, there is a film. The tendency of the fracture frequency to become higher. The cumulative stretching ratio is a ratio obtained by summing the magnifications of the uniaxial extension and the expansion extension, and is accumulated when the extension is extended from the early axis of the mouth and the expansion is performed plural times. Such as the full magnification. The extension may be either dry or thirsty... or any of the above, but it is preferred to soak the film in one of the specific liquids - who is &#m face into the money The so-called wet extension method enters the lamp. The wet extension method is not easy to obtain, so it is easy to obtain the necessary (four) heart to fully extend and high. However, the pre-learning characteristic is lower than the dry extension method, and the pattern is 157074. The exemplification of the uniaxial stretching of the present invention is described in detail in the embodiment of the invention. FIG. 1 is an explanatory view showing an embodiment of the expansion stretching step of the present invention, and FIG. 2 is a view showing an example of the expanding roller of the present invention. The processing tank 1 shown in FIG. 1 is filled with the treatment liquid 4 (for example, iodine or potassium iodide aqueous solution), and the nip roller 2 is not placed on the upstream side of the transport direction of the polyvinyl alcohol-based membrane crucible therein. The nip roll 2 is provided on the downstream side, and the spreader roll 3 and the guide roll 5 are provided between the two nip rolls. As shown in Fig. 2, the spreader roll 3 has a curved shape. In the expansion and extension step, the polyvinyl alcohol-based film is immersed in the treatment liquid 4, and further stretched by the expansion rolls 3, and the circumferential speed difference between the two nip rolls 2 and 2 is used. extend. Further, in this case, the expansion rolls 3 may be plural. 3(a) to 3(c) are explanatory views showing the relationship between the expansion direction M of the widening roller and the film direction. The expansion direction M of the expansion roller 3 is important in terms of improving the optical characteristics of the polarizing film. membrane! The direction of the unloading direction is the angle of the expansion direction. ~70. More preferably _3〇. ~3〇. The scope. As shown in Fig. 3 (4) to (4), the angle of the film ι when the film is moved from the left to the right is 〇°', and the angle from the (four) direction is _, counterclockwise The angle is considered to be +. 3 shows the angle of the expansion direction of the expansion roller with respect to the direction in which the film is ejected (light, (_., (eMQ). When the angle e exceeds the above range, the absorption axis of the polarizing film is The direction of solidification (transport direction of the film) will be inconsistent, so it will cause the problem of lowering the optical properties of the film. The radius of curvature of the expanding roller 3 used is preferably ~5. 0~面0_, the diameter d of the expanding roller 3 is preferably 5 〇~pass 157074.doc 201234058 mm' is more preferably 75~200 mm. The expanding roller 3 can be disposed in the air (atmosphere) and in the liquid Any one of the 'expanding rolls 3 set in the air as shown in Fig. 1 can be improved in terms of optical characteristics by using the present invention. In particular, the variation in the width dimension of the film by the swelling is large. In the swelling step or the dyeing step, at the time of providing a plurality of expansion rolls, at least one of the expansion rolls 3 is disposed in the air, and by applying the present invention, generation of pleats and improvement of optical characteristics can be suppressed. When a plurality of expansion rolls 3 are provided, it is preferable to use the present In the case where there are a large number of expansion rolls 3, it is preferable to apply the present invention to all of the expansion rolls 3, that is, all of the expansion rolls 3 are disposed between the two nip rolls 2, 2, as in the manufacturing steps of the present invention. The material of the expansion roll is preferably rubber, sponge, etc., more preferably sponge rubber. The ethyl film is swelled in both the length and the width by the absorption bath, especially if it is swollen in the width direction. When the tension is applied in the unfinished state, wrinkles or creases are likely to occur on the roll. If a sponge rubber roll is used as the spreader roll, the holding force of the film is high based on the high surface roughness, so that it can be fully utilized. ^Amplitude' can also maximize the role of the expansion as a function of the other side to prevent the function', thereby reducing wrinkles and eliminating creases. As the sponge rubber roller used in the present invention, the hardness of the sponge is preferably:
以藉由—一By means of one
& 25〜50度’密度為約0.4〜0.6 g/cm3 ’及表面粗糙度以JIS 表示為 g/cm3 Β〇6(Π(表面粗糙度）之粗縫度曲線之局部頂部之平均間隔s 157074.doc -15- 201234058 來表示為約10〜30s，更佳為約15〜25Se 又’於上述擴幅延伸步驟之延伸為濕式延伸之情形時， /¾泡膜之溶液之溫度通常為2〜7(rc即可，特別是於 20 40 C，較佳為於在25〜35<>c之範圍之溫度經由擴幅輥進 仃延之伸情形時，最能不降低光學特性而進行延伸。 於擴巾田延伸步驟後之各個步驟中，亦可以膜之張力實質 上分別固定之方式進行張力控制。 於硼酸處理後，於進行上述碘化物處理或辞處理之情形 時’較佳為亦對該等步驟進行張力控制。 各個步驟之張力可相同，亦可不同。關於張力控制中對 膜之張力’並無特別限定’可於每單位寬度為約1 5〇 N/m~2000 N/m ’較佳為約6〇〇 N/m〜1500 N/m之範圍内適 當地進行設定^若張力低於約丨5〇 N/m，則於膜上容易產 生褶皺等。另一方面，若張力超出約2〇〇〇 N/m，則有時會 產生膜之斷裂或起因於轴承之磨耗之低壽命化等問題。 又’該每單位寬度之張力係根據該步驟之入口附近之膜寬 度及張力檢測器之張力值來進行計算。 再者，於進行張力控制之情形時，不可避免地會出現一 些延伸、收縮的情況’本發明中該情況不包含於延伸處理 中。 於如此所製造之偏光膜之至少單面上利用黏著劑貼合保 護膜，藉此可獲得偏光板。 作為保護膜可列舉例如：包含三乙酸纖維素或二醋酸纖 維素之類之醋酸纖維素系樹脂之膜，包含聚對苯二甲酸乙 157074.doc -16 · 201234058 二醇酯或聚萘二曱酸乙二醇酯、聚對苯二曱酸丁二醇酯之 類之聚酯系樹脂之膜，包含聚碳酸酯系樹脂之膜，包含環 烯系樹脂之膜’丙稀酸系樹脂膜’聚丙烯系樹脂膜。 為了提高黏著劑與偏光膜及/或保護膜之黏著性，亦可 對偏光膜及/或保護膜實施電暈處理、火焰處理、電漿處 理、紫外線照射、底塗處理、皂化處理等表面處理。 [實施例] 其次，列舉本發明之實施例而進行具體說明，但本發明 並不限定於該等實施例。 <吸收轴之測定方法> 將膜之寬度方向設為基準，相對於該基準軸自長度方向 50 mm、寬度方向為於整個寬度獲取帶狀膜片，進而使用 自動雙折射測量裝置（大塚電子公司製造，商品名 「RETS」），在將該膜片於寬度方向9等分之各處對吸收軸 角度進行測定。於所獲得之軸角度中，採用最大值與最小 值之差作為吸收軸之偏差。 [實施例1] 將厚度75 μιη之聚乙烯醇膜（Kuraray Vinyl〇n VF ps# 75〇0、聚合度2,4〇〇、皂化度99.9莫耳％以上）浸潰於3〇<>(：之 純水中且一面使膜充分膨潤，一面以13〇倍進行單轴延 伸0 其次，一面將膜浸潰於碘/碘化鉀/水之重量比計 0.02/2.0/100之30°C之染色槽中，一面使累計延伸倍率成為 2.80倍，以此方式進行如圖i所示之單軸延伸。擴幅輥對 157074.doc •17- 201234058& 25~50 degrees 'density is about 0.4~0.6 g/cm3' and the surface roughness is expressed as JIS as g/cm3 Β〇6 (the average interval of the top part of the rough seam curve of Π(surface roughness) s 157074.doc -15- 201234058 is expressed as about 10~30s, more preferably about 15~25Se, and when the extension of the expansion step is wet extension, the temperature of the solution of the /3⁄4 bubble film is usually 2 to 7 (rc can be used, especially at 20 40 C, preferably at a temperature in the range of 25 to 35 <>c, which is most preferably not reduced in optical properties by a stretching roller. The stretching may be performed in a manner in which the tension of the film is substantially fixed separately in each step after the stretching step of the towel growing field. After the boric acid treatment, in the case of performing the above iodide treatment or word processing, it is preferable. In order to perform tension control on these steps, the tension of each step may be the same or different. The tension of the film in the tension control is not particularly limited, and may be about 15 〇N/m to 2000 per unit width. N/m' is preferably in the range of about 6 〇〇N/m to 1500 N/m. When the tension is less than about 〇5〇N/m, wrinkles and the like are likely to occur on the film. On the other hand, if the tension exceeds about 2〇〇〇N/m, the film may be broken or caused by The problem of low wear life of the bearing, etc. The 'tension per unit width is calculated based on the film width near the entrance of the step and the tension value of the tension detector. Further, in the case of tension control, Inevitably, some cases of stretching and shrinking may occur. This is not included in the stretching treatment in the present invention. The protective film is bonded to at least one side of the polarizing film thus produced by an adhesive, whereby a polarizing plate can be obtained. The protective film may, for example, be a film comprising a cellulose acetate resin such as cellulose triacetate or cellulose diacetate, and comprises polyethylene terephthalate 157074.doc -16 · 201234058 glycol ester or polynaphthalene A film of a polyester resin such as ethylene glycol phthalate or polybutylene terephthalate, which comprises a film of a polycarbonate resin, and a film of a cycloolefin resin, an acrylic resin film. 'Polypropylene resin In order to improve the adhesion between the adhesive and the polarizing film and/or the protective film, the polarizing film and/or the protective film may be subjected to corona treatment, flame treatment, plasma treatment, ultraviolet irradiation, primer treatment, saponification treatment, etc. [Examples] Next, the examples of the present invention will be specifically described, but the present invention is not limited to the examples. <Method for Measuring Absorption Shaft> The width direction of the film is used as a reference, and the relative The reference axis is obtained from the longitudinal direction of 50 mm and the width direction is a strip-shaped film over the entire width, and an automatic birefringence measuring device (manufactured by Otsuka Electronics Co., Ltd., trade name "RETS") is used, and the film is oriented in the width direction. The absorption axis angle was measured at 9 divisions. In the obtained shaft angle, the difference between the maximum value and the minimum value is used as the deviation of the absorption axis. [Example 1] A polyvinyl alcohol film (Kuraray Vinyl〇n VF ps# 75〇0, polymerization degree 2, 4 〇〇, saponification degree: 99.9 mol% or more) having a thickness of 75 μm was immersed in 3 〇<> (: in pure water, while fully swelling the film, uniaxially stretching at 13 〇 0. Next, the film was immersed in a weight ratio of iodine/potassium iodide/water of 0.02/2.0/100 at 30 ° C. In the dyeing tank, the cumulative stretching ratio is 2.80 times, and the uniaxial stretching as shown in Fig. i is performed in this manner. The expanding roller pair 157074.doc • 17- 201234058
於碘化鉀/硼酸/水之重量比計9/2 9/100之40它 繼而以5X：之純水清洗8秒鐘，進而於7(rc進行乾燥3分 '听化評/ί朋酸/水之重 一面進行單軸延伸直 為止’然後將膜浸潰 00之40°c水溶液中。 鐘，從而獲得偏光膜。獲得之偏光膜之吸收軸之偏差（最 大與最小之差）為0.04。。 [實施例2] 除將染色槽之擴幅輥之夾角設為3〇。以外，以與實施例1 相同之方式獲得偏光膜❶獲得之偏光膜之吸收軸之偏差 (最大與最小之差）為0.08。。 [實施例3] 除將染色槽之擴幅親之夾角設為60。以外，以與實施例1 相同之方式獲得偏光膜。獲得之偏光膜之吸收軸之偏差 (最大與最小之差）為0.12。。 [實施例4] 除將染色槽之擴幅親之夾角設為-30。以外，以與實施例 1相同之方式獲得偏光膜。獲得之偏光膜之吸收轴之偏差 (最大與最小之差）為〇.〇9。。 [實施例5] 157074.doc -18- 201234058 將厚度75 μιη之聚乙烯醇膜（Kuraray Vinylon VF-PS # 7500、聚合度2,400、息化度99 9莫耳％以上）浸潰於之 純水中一面使膜充分地膨潤，一面以1 · 3 〇倍進行單軸延 伸0 其-入， 面將膜&潰於峨/破化舒/水之重量比計 0.02/2.0/100之30 C之染色槽中，一面使累計延伸倍率成為 1.65倍，以此方式進行如圖1所示之單轴延伸。此時之擴 幅報以夾角為0。而進行搬送。其後，一面將膜浸潰於磁化 鉀/硼酸/水之重量比計11/3.5/100之53°C水溶液中，一面進 行單軸延伸直至整幅之累計延伸倍率成為5 8倍為止，然 後將膜浸潰於蛾化鉀/硼酸/水之重量比計11/35/1〇〇之4〇t>c 水溶液中。繼而，以5°C之純水清洗8秒鐘，進而於7〇〇c乾 燥3分鐘，從而獲得偏光膜》獲得之偏光膜之吸收軸之偏 差（最大與最小之差）為〇.1〇。。 [實施例6] 除將染色槽之擴幅輥之夾角設為30。以外，以與實施例5 相同之方式獲得偏光膜。獲得之偏光膜之吸收軸之偏差 (最大與最小之差）為0.13。。 [實施例7] 除將染色槽之擴幅輥之夾角設為6〇。以外，以與實施例5 相同之方式獲得偏光膜。獲得之偏光膜之吸收軸之偏差 (最大與最小之差）為0.15。。 [比較例1] 除將染色槽之擴幅輥之夾角設為90。以外，以與實施例i 157074.doc 5 •19· 201234058 相同之方式獲得偏光膜。獲得之偏光膜之吸收轴之偏差 (最大與最小之差）為0.23°。 [比較例2] 除將染色槽之擴幅輥之夾角設為90°以外，以與實施例5 相同之方式獲得偏光膜。獲得之偏光膜之吸收軸之偏差 (最大與最小之差）為0.24°。 於以下表示上述實施例1〜4及比較例1之結果。 [表1] 累計延伸倍率 (倍） 擴幅輥之夾角度 (°) 吸收軸之偏差 (最大-最小)(°) 實施例1 2.80 0 0.04 實施例2 ” 30 0.08 實施例3 II 60 0.12 實施例4 11 -30 0.09 實施例5 1.65 0 0.10 實施例6 " 30 0.13 實施例7 ” 60 0.15 比較例1 2.80 90 0.23 比較例2 1.65 90 0.24 根據表1，可知與比較例1、2相比較，實施例1〜7之吸收 軸之偏差（最大-最小之差）較小。 [實施例8] 於膨潤槽中，經由夾角設為0°之空氣中之擴幅輥，使延 伸倍率成為2.20倍，進行如圖1所示之單軸延伸，繼而於 染色槽中使累計延伸倍率成為2.80倍，進行如圖1所示之 157074.doc -20- 201234058 單轴延伸（染色槽之擴幅輥之夾角為〇。），除此以外以與實 施例1相同之方式獲得偏光膜。獲得之偏光膜之吸收轴之 偏差（最大與最小之差）為0.11。。 [比較例3] 除將膨潤槽之擴幅輥之夾角設為90。以外，以與實施例8 相同之方式獲得偏光膜。獲得之偏光膜之吸收轴之偏差 (最大與最小之差）為 0.34° 〇 於以下顯示上述實施例8及比較例3之結果。 [表2] 累計延伸倍率 (倍） 擴幅輥之夾角度 (。） 吸收軸之偏差 (最大-最小)(°) 實施例8 2.80 0 0.11 比較例3 2.80 90 0.34 根據表2，可知與比較例3相比，實施例8之吸收轴之偏 差（最大-最小之差）較小。 【圖式簡單說明】 圖1係表示言免置本發明之擴幅輥而進行擴幅及單轴延伸 之擴幅延伸步驟之一實施形態的說明圖。 圖2係表示本發明之擴幅輥之一例之前視圖。 圖3係表示擴幅輥之擴幅方向與膜之搬出方向之關係的 說明圖，且分別表示擴幅輥之擴幅方向相對於臈之搬出方 向的角度為（a)70。、（b)〇。、（c)_4〇。之情形。 【主要元件符號說明】 1 聚乙烯醇臈 5 157074.doc -21 - 201234058 2 夾輥 2’ 夾輥 3 擴幅輥. 4 處理液 5 導輥 10 硼酸處理槽（延伸處理） d 擴幅輥3之直徑 Μ 擴幅方向 Θ 角度 157074.doc -22-In the weight ratio of potassium iodide / boric acid / water to 9 / 9 9 / 100 of it, it is then washed with 5X: pure water for 8 seconds, and then dried at 7 (rc for 3 minutes ' listening evaluation / 朋 酸 acid / water On the other hand, the uniaxial extension is straight until the film is immersed in a 40 ° C aqueous solution of 00 to obtain a polarizing film. The deviation of the absorption axis (the difference between the maximum and the minimum) of the obtained polarizing film is 0.04. [Example 2] The deviation of the absorption axis of the polarizing film obtained by the polarizing film ( (the difference between the maximum and the minimum) was obtained in the same manner as in Example 1 except that the angle between the stretching rolls of the dyeing tank was set to 3 Torr. [Example 3] A polarizing film was obtained in the same manner as in Example 1 except that the angle of the dyeing groove was set to 60. The deviation of the absorption axis of the obtained polarizing film (maximum and minimum) The difference was 0.12. [Example 4] A polarizing film was obtained in the same manner as in Example 1 except that the angle of the dyeing groove was set to -30. The deviation of the absorption axis of the obtained polarizing film was obtained. (The difference between the maximum and the minimum) is 〇.〇9. [Example 5] 157074.doc -18- 201234058 Will thickness 75 The polyvinyl alcohol film of μιη (Kuraray Vinylon VF-PS # 7500, degree of polymerization 2,400, degree of recombination 99 9 mol% or more) is impregnated in pure water to fully swell the film, and the surface is 1 · 3 〇 The uniaxially stretched 0-in, the surface of the film & 溃 峨 / 破 舒 / water weight ratio of 0.02 / 2.0 / 100 30 C dyeing tank, while the cumulative stretching ratio is 1.65 times, In this manner, the uniaxial stretching is carried out as shown in Fig. 1. At this time, the expansion is reported to be carried out at an angle of 0. Thereafter, the film is immersed in a weight ratio of magnetized potassium/boric acid/water 11/3.5. In a solution of /100 in a 53 ° C aqueous solution, uniaxially extending until the cumulative stretching ratio of the entire sheet became 58 times, and then the film was immersed in a molybdenum/boric acid/water weight ratio of 11/35/1 〇 4〇t>c in an aqueous solution. Then, it is washed with pure water at 5 ° C for 8 seconds, and then dried at 7 ° C for 3 minutes to obtain a deviation of the absorption axis of the polarizing film obtained by the polarizing film (maximum The difference from the minimum is 〇.1〇. [Example 6] In addition to the angle of the expansion roll of the dyeing tank set to 30, in comparison with Example 5 In the manner of obtaining a polarizing film, the deviation (maximum difference between the maximum and the minimum) of the absorption axis of the obtained polarizing film was 0.13. [Example 7] Except that the angle of the expansion roller of the dyeing tank was set to 6 〇, Example 5 A polarizing film was obtained in the same manner. The deviation (maximum difference between the maximum and the minimum) of the absorption axis of the obtained polarizing film was 0.15. [Comparative Example 1] The angle of the widening roller of the dyeing tank was set to 90. A polarizing film was obtained in the same manner as in Example i 157074.doc 5 •19·201234058. The deviation (maximum to minimum difference) of the absorption axis of the obtained polarizing film was 0.23°. [Comparative Example 2] A polarizing film was obtained in the same manner as in Example 5 except that the angle between the widening rolls of the dyeing tank was set to 90°. The deviation (maximum to minimum difference) of the absorption axis of the obtained polarizing film was 0.24°. The results of the above Examples 1 to 4 and Comparative Example 1 are shown below. [Table 1] Cumulative stretching ratio (times) The angle of the expansion roll (°) The deviation of the absorption axis (maximum-minimum) (°) Example 1 2.80 0 0.04 Example 2 ” 30 0.08 Example 3 II 60 0.12 Implementation Example 4 11 -30 0.09 Example 5 1.65 0 0.10 Example 6 " 30 0.13 Example 7 ” 60 0.15 Comparative Example 1 2.80 90 0.23 Comparative Example 2 1.65 90 0.24 According to Table 1, it is known that compared with Comparative Examples 1 and 2. The deviation (maximum-minimum difference) of the absorption axes of Examples 1 to 7 was small. [Example 8] In the swelling tank, the stretching ratio in the air having an angle of 0° was set to 2.20 times, and the uniaxial stretching as shown in Fig. 1 was carried out, and then the cumulative stretching was performed in the dyeing tank. The magnification was 2.80 times, and a polarizing film was obtained in the same manner as in Example 1 except that the 157074.doc -20-201234058 uniaxial stretching as shown in Fig. 1 (the angle of the widening roller of the dyeing tank was 〇) was performed. . The deviation (the difference between the maximum and the minimum) of the absorption axis of the obtained polarizing film was 0.11. . [Comparative Example 3] The angle between the expansion rolls of the swelling grooves was set to 90. A polarizing film was obtained in the same manner as in Example 8 except for the same. The deviation (maximum difference from the minimum) of the absorption axis of the obtained polarizing film was 0.34 °. The results of the above Example 8 and Comparative Example 3 are shown below. [Table 2] Cumulative stretching ratio (times) The angle of the expansion roller (.) The deviation of the absorption axis (maximum-minimum) (°) Example 8 2.80 0 0.11 Comparative Example 3 2.80 90 0.34 According to Table 2, the comparison and comparison are made. In Comparative Example 3, the deviation (maximum-minimum difference) of the absorption axis of Example 8 was small. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an explanatory view showing an embodiment of a step of expanding and expanding a uniaxially stretched extension roller without using the widening roller of the present invention. Fig. 2 is a front view showing an example of the widening roller of the present invention. Fig. 3 is an explanatory view showing the relationship between the expanding direction of the widening roller and the direction in which the film is ejected, and shows that the angle of the expanding direction of the expanding roller with respect to the direction in which the crucible is ejected is (a) 70. , (b) 〇. , (c) _4 〇. The situation. [Description of main components] 1 PVA 5 157074.doc -21 - 201234058 2 Pinch 2' Clamping roller 3 Expanding roller. 4 Treatment liquid 5 Guide roller 10 Boric acid treatment tank (extension treatment) d Expansion roller 3 Diameter Μ expansion direction Θ angle 157074.doc -22-