1379891 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種塗布液及使用其之偏光膜。 【先前技術】 在液晶顯示器中，為了控制通過液晶之光線的旋光性或 雙折射性而使用偏光板或相位差板。又，在有機EL顯示器 中’為了防止外光之反射而使用圓偏光板。先前，該等偏 光板中’將聚乙稀醇等之樹脂膜以填或二色性有機色素進 行染色，並利用將膜在一個方向上延伸之方法（延伸法）來 使色素專之分子配向而獲得之偏光元件得到廣泛使用。但 是，利用延伸法而製造之偏光元件存在根據所使用之色素 或高分子材料，耐熱性或耐光性並不充分之問題。又，隨 著顯示面板之大型化，寬幅之膜的延伸成為必須，因此製 膜裝置大型化亦成為問題。 針對此’已知有在由玻璃板或樹脂膜等形成之基板上， 塗布含有溶致液晶化合物與水之塗布液而形成塗膜，使塗 膜内之溶致液晶化合物配向而形成偏光膜的方法（專利文 獻1)。本說明書中，將此種偏光膜稱為「溶致液晶化合物 之偏光膜」。溶致液晶化合物之偏光膜無須延伸，並無由 延伸所引起的寬度方向之收縮，故而容易獲得寬度方向寬 之偏光膜。但是，習知的溶致液晶化合物之偏光膜存在與 藉由延伸法而製造之偏光元件相比，偏光特性（單體穿透 率或偏光度）差之問題。 [專利文獻1]曰本專利特開2007-178993號公報 134316-1011009.doc 1379891 【發明内容】 [發明所欲解決之問題] 本發明之目的在於提供一種用以獲得單體穿透率以及偏 光度高的溶致液晶化合物之偏光膜的塗布液之製造方法、 以及使用上述塗布液之偏光獏之製造方法。 [解決問題之技術手段]1379891 IX. Description of the Invention: [Technical Field] The present invention relates to a coating liquid and a polarizing film using the same. [Prior Art] In a liquid crystal display, a polarizing plate or a phase difference plate is used in order to control the optical rotation or birefringence of light passing through a liquid crystal. Further, in the organic EL display, a circularly polarizing plate is used in order to prevent reflection of external light. Previously, in the polarizing plates, a resin film such as polyethylene glycol was dyed with a filled or dichroic organic dye, and a method of stretching the film in one direction (extension method) was used to align the molecules of the dye. The obtained polarizing element is widely used. However, the polarizing element manufactured by the stretching method has a problem that heat resistance or light resistance is insufficient depending on the dye or polymer material to be used. Further, as the size of the display panel increases, the extension of the wide film becomes necessary, and therefore the size of the film forming apparatus becomes a problem. In view of the above, it is known that a coating liquid containing a lyotropic liquid crystal compound and water is applied onto a substrate formed of a glass plate or a resin film to form a coating film, and a lyotropic liquid crystal compound in the coating film is aligned to form a polarizing film. Method (Patent Document 1). In the present specification, such a polarizing film is referred to as "a polarizing film of a lyotropic liquid crystal compound". The polarizing film of the lyotropic liquid crystal compound does not have to be stretched, and there is no shrinkage in the width direction caused by the stretching, so that it is easy to obtain a polarizing film having a wide width direction. However, the polarizing film of the conventional lyotropic liquid crystal compound has a problem that the polarization characteristics (monomer transmittance or polarization degree) are inferior to those of the polarizing element produced by the stretching method. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2007-178993 No. 134316-1011009.doc 1379891 [Disclosure of the Invention] [Problem to be Solved by the Invention] An object of the present invention is to provide a monomer transmittance and polarized light. A method for producing a coating liquid of a polarizing film having a high degree of lyotropic liquid crystal compound, and a method for producing a polarizing film using the above coating liquid. [Technical means to solve the problem]
本發明者們對習知的溶致液晶化合物之偏光膜之偏光度 低的原因進行了研究’結果發現原因在於，溶致液晶化合 物之合成反應中的雜質包含於塗布液中。溶致液晶化合物 係利用無機鹽進行鹽析而自粗產物中單離。因此，著眼於 鹽析時所產生之雜質即氣化物離子，減小其濃度，可獲得 與習知的溶致液晶化合物之偏光膜相比，偏光特性（單體 穿透率以及偏光度）極其優異之偏光膜。再者，氯化物離 子之濃度係將氣化物離子/溶致液晶化合物之重量比以 PPm表示。又，為防止看錯指數而將1〇n記作1〇卜卜The inventors of the present invention have studied the reason why the polarizing film of the conventional lyotropic liquid crystal compound has a low degree of polarization. As a result, it has been found that impurities in the synthesis reaction of the lyotropic liquid crystal compound are contained in the coating liquid. The lyotropic liquid crystal compound is isolated from the crude product by salting out using an inorganic salt. Therefore, focusing on the impurity ions generated during salting out, that is, the vaporized ions, the concentration thereof is reduced, and the polarizing characteristics (monomer transmittance and polarization degree) are extremely high as compared with the polarizing film of the conventional lyotropic liquid crystal compound. Excellent polarizing film. Further, the concentration of the chloride ions is expressed by the weight ratio of the vaporized ion/lyotropic liquid crystal compound in terms of PPm. Also, in order to prevent misreading the index, 1〇n is recorded as 1 〇卜卜
本發明之主旨如下。 本發明之塗布液之製造方法係包含如下步驟： ⑷自溶致液晶化合物合成後之反應溶液中，藉由鹽析而單 離出溶致液晶化合物； ⑻將單㈣之溶致液晶化合物與溶劑混合而獲得混合液； ==交換樹脂及膜之任一者或兩者，將上述混合液 、上述混合液之氯化物離子的濃 ppm以下。 l’j [發明之效果] 134316-101J009.doc 1379891 根據本發明之製造方法，可獲得用以獲得單體穿透率以 及偏光度高的溶致液晶化合物之偏光膜的塗布液、以及偏 光膜。 【實施方式】 [塗布液] 藉由本發明之製造方法所製造之塗布液含有藉由鹽析而 單離之溶致液晶化合物與溶劑。藉由本發明之製造方法所 製造之塗布液可含有其他的任意者。例如可含有並不藉由 鹽析而單離之溶致液晶化合物。又，亦可含有鹼劑、界面 活性劑、抗氧化劑等任意添加劑。 藉由本發明之製造方法所製造之塗布液之總固形分濃度 較好的是1重量％~5 0重量％。 若總固形分濃度為上述範圍，則可獲得目標厚度（例如 0.4 μιη左右）之偏光膜。 較好的是’藉由本發明之製造方法所製造之塗布液於23 °C下’總固形分濃度為i重量％〜3〇重量％之範圍内的至少 一部分表現出液晶性。藉由總固形分濃度為1重量〇重 量之範圍内的至少一部分表現出液晶性，溶致液晶化合 物良好地進行配向，故而可獲得偏光度高之偏光膜。 藉由本發明之製造方法所製造之塗布液之氯化物離子濃 度為3xl0[4] ppm以下。塗布液可藉由減小氯化物離子濃 度而提高偏光度。氣化物離子濃度較好的是2Xi〇[4] ppm 以下’更好的是1.5χ10[4] ppm以下，進而好的是lxi〇[4] ppm以下《氣化物離子濃度越小越好，亦可實質上為零。 134316-1011009.doc 1379891 所謂實質上為零，包括使用離子層析裝置（例如DIONEX公 司製造之DX-320)而測定之值為0.01 x 1〇[4] ppm以下的情 .況》 [溶致液晶化合物] 本發明中所使用之溶致液晶化合物係自該溶致液晶化合 物之合成反應中的反應粗產物中藉由鹽析而單離出者β於 本說明書中所謂「鹽析」，係指在含有親水性化合物之溶 • 液中，若添加大量鹽類（通常為氯化鈉或者氯化鋰），則進 行水合之水分子被奪’親水性化合物凝集而沈澱。 於本說明書中所謂「溶致液晶化合物」，係指具有藉由 在溶液狀態下使該溶致液晶化合物之濃.度變化而產生等向 相-液晶相之相轉變的性質的液晶化合物。對所表現出之 液晶相並無限制，可列舉向列液晶相、層列液晶相、膽固 醇液晶相等。該等液晶相係根據以偏光顯微鏡觀察到之光 學情況來確認、識別。 • 溶致液晶化合物較好的是分子之長軸方向之躍遷矩大於 短軸方向、或者短轴方向之躍遷矩大於長軸方向者。如 此，若長軸與短轴的躍遷矩大小不同，則表現吸收二色 性。又，溶致液晶化合物較好的是在可見光區域（波長為 3 80 nm〜780 nm)之某一處表現最大吸收。 相對於溶劑H)() g，溶致液晶化合物對溶劑之溶解度較 好的是毫莫耳〜〇.15莫耳’更好的是5毫莫耳〜5〇毫莫 耳。若溶解度為上述範圍，則獲得表現出穩定之液晶相的 塗布液。溶致液晶化合物較好的是水溶性。溶致液晶化合 134316-1011009.doc 1379891 物為了賦予水溶性，較好的是具有親水性基。親水性基較 好的是選自由-COOM、-S03M、·Ρ03Μ、·〇Η、-NH2所組 成之群中的至少一種取代基β M表示陽離子，較好的是氫 離子或如Li、Na、Κ、Cs之第一族金屬之離子或者銨離 子。 本發明中所使用之溶致液晶化合物較好的是偶氮系化合 物、蒽酿i系化合物、茈系化合物、嗜狄酿j系化合物、萘職 系化合物或者部花青系化合物。此種化合物在溶液狀態下 可表現溶致液晶性，且可表現吸收二色性。其中尤其好的 是偶氮系化合物。 偶氮系化合物較好的是由下述通式⑴所表示之化合物。 [化1]The gist of the present invention is as follows. The method for producing a coating liquid of the present invention comprises the following steps: (4) separating a lyotropic liquid crystal compound by salting out in a reaction solution after synthesis of a liquid crystal compound; (8) dissolving a liquid crystal compound of a single (four) with a solvent The mixed liquid is obtained by mixing; == either or both of the exchange resin and the film, and the concentration of the chloride ions of the mixed liquid and the mixed liquid is equal to or less than the ppm. L'j [Effects of the Invention] 134316-101J009.doc 1379891 According to the production method of the present invention, a coating liquid for obtaining a polarizing film of a lyotropic liquid crystal compound having a monomer transmittance and a high degree of polarization, and a polarizing film can be obtained. . [Embodiment] [Coating liquid] The coating liquid produced by the production method of the present invention contains a lyotropic liquid crystal compound and a solvent which are separated by salting out. The coating liquid produced by the production method of the present invention may contain any other one. For example, it may contain a lyotropic liquid crystal compound which is not separated by salting out. Further, it may contain any additives such as an alkali agent, a surfactant, and an antioxidant. The total solid content of the coating liquid produced by the production method of the present invention is preferably from 1% by weight to 50% by weight. When the total solid content concentration is in the above range, a polarizing film having a target thickness (for example, about 0.4 μηη) can be obtained. It is preferred that at least a part of the coating liquid produced by the production method of the present invention at a total solid content concentration of from i% by weight to 3% by weight at 23 ° C exhibits liquid crystallinity. At least a part of the range of the total solid content concentration of 1 part by weight of the ruthenium exhibits liquid crystallinity, and the lyotropic liquid crystal compound is well aligned, so that a polarizing film having a high degree of polarization can be obtained. The coating liquid produced by the production method of the present invention has a chloride ion concentration of 3 x 10 [4] ppm or less. The coating liquid can increase the degree of polarization by reducing the concentration of chloride ions. The concentration of vapor ions is preferably 2Xi〇[4] ppm or less, and more preferably 1.5χ10[4] ppm or less, and further preferably lxi〇[4] ppm or less. The smaller the vapor ion concentration, the better. Can be substantially zero. 134316-1011009.doc 1379891 is essentially zero, including the use of an ion chromatography device (such as DX-320 manufactured by DIONEX) to determine a value of 0.01 x 1 〇 [4] ppm or less. Liquid crystal compound] The lyotropic liquid crystal compound used in the present invention is a so-called "salting out" in the present specification by salting out from the crude reaction product in the synthesis reaction of the lyotropic liquid crystal compound. When a large amount of a salt (usually sodium chloride or lithium chloride) is added to a solution containing a hydrophilic compound, the water molecule to be hydrated is agglomerated and precipitated by the hydrophilic compound. The term "lyotropic liquid crystal compound" as used herein means a liquid crystal compound having a property of causing a phase transition of an isotropic phase-liquid crystal phase by changing the concentration of the lyotropic liquid crystal compound in a solution state. There is no limitation on the liquid crystal phase to be exhibited, and examples thereof include a nematic liquid crystal phase, a smectic liquid crystal phase, and a cholesteric liquid crystal. These liquid crystal phases are confirmed and recognized based on the optical condition observed by a polarizing microscope. • The lyotropic liquid crystal compound is preferably such that the transition moment of the long axis direction of the molecule is larger than the short axis direction, or the transition moment of the short axis direction is larger than the long axis direction. Thus, if the transition axes of the major axis and the minor axis are different in magnitude, the absorption dichroism is exhibited. Further, the lyotropic liquid crystal compound preferably exhibits maximum absorption in a visible light region (wavelength of 380 nm to 780 nm). The solubility of the lyotropic liquid crystal compound with respect to the solvent is preferably from 1 mm to about 15 mol%, more preferably from 5 mg to 5 μm. When the solubility is in the above range, a coating liquid exhibiting a stable liquid crystal phase is obtained. The lyotropic liquid crystal compound is preferably water soluble. Lyotropic liquid crystal compound 134316-1011009.doc 1379891 In order to impart water solubility, it is preferred to have a hydrophilic group. The hydrophilic group is preferably at least one substituent selected from the group consisting of -COOM, -S03M, Ρ03Μ, 〇Η, -NH2, and represents a cation, preferably a hydrogen ion or a Li or Na such as Li or Na. , Κ, the first group of metal ions or ammonium ions of Cs. The lyotropic liquid crystal compound used in the present invention is preferably an azo compound, an i-based compound, an anthraquinone compound, a zeolitic compound, a naphthalene compound or a merocyanine compound. Such a compound exhibits lyotropic liquid crystallinity in a solution state and exhibits absorption dichroism. Among them, an azo compound is particularly preferable. The azo compound is preferably a compound represented by the following formula (1). [Chemical 1]
…⑴ 式中’Qi表示苯基或者萘基（該等基可具有取代基），（^2及 Q3分別獨立表示伸苯基或者伸萘基（該等基可具有取代 基）’ R表示氫原子、碳數為1〜3之烷基、乙醯基、苯曱醯 基或者苯基（該等基可具有取代基），k表示0〜4之整數、1表 示0〜4之整數（其中，k+i$ 4)，m表示0〜2之整數，η表示 〇〜2之整數，μ表示上述陽離子。Wherein 'Qi denotes a phenyl group or a naphthyl group (these groups may have a substituent), and (^2 and Q3 each independently represent a phenyl or a naphthyl group (the groups may have a substituent)' R represents hydrogen An atom, an alkyl group having a carbon number of 1 to 3, an ethyl fluorenyl group, a phenyl fluorenyl group or a phenyl group (the groups may have a substituent), k represents an integer of 0 to 4, and 1 represents an integer of 0 to 4 (wherein , k + i$ 4), m represents an integer of 0 to 2, η represents an integer of 〇 〜 2, and μ represents the above cation.
Qi較好的是具有1個或者2個選自由硝基、氰基、羥基、 胺基 '卣素基、碳數為id之鹵化烷基、碳數為1〜3之烷氧 134316-1011009.doc • 10- 1379891 錢組成之群中之取代基的苯基eQ3較好的是具有i個或 者2個選自由碳數為卜3之炫基、碳數為卜3之烧氧基經 • 基、磺酸基所組成之群中之取代基的伸萘基。 由通式（I)所表示之偶氮系化合物可根據細田豐著「理論 製造染料化學」（1968年7月15日，技法堂發行，第5版， 第135頁〜第152頁），例如使分別具有胺基之2種化合物進 行二偶氮化以及偶合反應而獲得。再者，以偶氮鍵連結之 φ 取代基Q2之數量可藉由反覆進行二偶氮化以及偶合反應而 使其增加。 [溶劑] 本發明中所使用之溶劑係將溶致液晶化合物均句溶解 者’較好的是不含氯化物離子者、或者氯化物離子濃度小 者。溶劑較好的是親水性溶劑。作為親水性溶劑，例如可 列舉水、醇類、溶纖劑類《亦可於水中添加醇類、喊類、 溶纖劑類、二曱亞砜、二曱基曱醯胺等水溶性溶劑。又， • 亦可添加甘油、乙二醇等水溶性化合物。該等添加物可用 於調整水溶性液晶化合物之易溶性或水溶液之乾燥速度。 相對於水溶液中之水100重量份，該等溶劑之添加量較好 的是100重量份以下。 [塗布液之製法] 藉由本發明之製造方法所製造之塗布液例如可利用包括 如下步驟（1)以及步驟（2)之製造方法而獲得。 步驟（1):自溶致液晶化合物合成後之反應溶液中，_ 由鹽析而單離出溶致液晶化合物。 134316-101I009.doc •11· 1379891 步驟（2):將步驟（i)中所單離出之溶致液晶化合物與溶 劑混合而獲得混合液，對該混合液使用離子交換樹脂來純 化處理成氯化物離子之濃度為3X1 〇[4] ppm以下，而獲得 塗布液。 塗布液中之氯化物離子之濃度除了可利用離子交換樹脂 以外’亦可利用膜來減小。使氣化物離子之濃度降低的該 等方法可將複數種加以組合來使用。 [偏光膜] 於本發明之偏光臈之製造方法中係將上述塗布液流延成 為薄膜狀’且使溶致液晶化合物配向。藉由本發明之製造 方法所製造之偏光膜較好的是在380 nm〜780 nm之波長域 的至少一部分，尤其在550 nm之波長下表現吸收二色性。 本發明之偏光膜的二色比在550 nm之波長下，較好的是2〇 以上，更好的是30以上。本發明之偏光膜的單體穿透率在 550 nm之波長下，較好的是30%〜50%。藉由本發明之製造 方法所製造之偏光膜的偏光度在550 nm之波長下，較好的 是90%以上，更好的是95%以上。 [流延] 藉由本發明之製造方法所製造之塗布液例如可藉由在基 板上流延而形成薄膜狀。流延方法若為將塗布液均勻流延 者，則無特別限制，係採用使用適當塗布機之流延方法。 作為流延裝置，可列舉：滑動塗布機、狹縫擠壓式塗布 機、棒塗布機、桿式塗布機 '輥塗布機、柔版印刷機、網 版印刷機、簾幕式塗布機、喷霧塗布機、旋轉塗布機等。 134316-1011009.doc •12· [基板] 對基板並無限制，可為單層者，亦可為複數層（例如包 含配向膜）之積層冑。作A具體之基板，可列舉玻璃板或 樹脂膜。於基板包含配向膜之情形時，配向膜較好的是實 施有配向處理者。作為包含配向膜之基板，例如可列舉在 玻璃板上塗布有聚醯亞胺臈之基板。該聚醯亞胺膜係藉由 公知方法，例如向一定方向進行摩擦等的機械性配向處 理、或光配向處理等的化學性配向處理而經賦予配向性。 關於基板之配向處理，可利用「液晶便覽」（丸善股份有 限公司，2000年1〇月30日發行）第226頁〜第2；39頁等中所記 載之公知方法。 基板之玻璃板較好的是液晶單元中所使用者，例如可列 舉無鹼玻璃。將樹脂膜用作基板之情形時，可使基板具有 可撓性，故而適用於要求可撓性之用途中。樹脂膜之表面 亦可藉由摩擦等而進行配向處理。或者亦可於樹脂膜之表 面形成含有其他素材之配向膜。作為基板中所使用之樹脂 膜的素材，若為具有膜形成性之樹脂，則無特別限定，可 例示·苯乙烯系樹脂、（曱基）丙烯酸系樹脂、聚酯系樹 月曰、聚烯烴系樹脂、降蒱烯系樹脂、聚醯亞胺系樹脂、纖 維素系樹脂、聚乙烯醇系樹脂、聚碳酸酯系樹脂β基板之 厚度除了根據用途以外，並無特別限定，通常為1 μηι〜1000 μιη之範圍。 [配向] 本發明中所使用之溶致液晶化合物若在液晶狀態下施加 1343l6-10liOQ9.doc •13- 1379891 剪應力，則可藉由流動來使其配向。溶致液晶化合物在液 晶狀態下形成超分子缔合體，若對含有其之塗布液施加剪 應力而使其流動，則超分子料體之妹方向配向為流動 方向。配向方法除了剪應力以外，亦可將摩擦處理或光配 向處理等配向處理、利用磁場或電場之配向等加以詛合來 使用。 ‘ [乾燥] 藉由本發明之製造方法所製造之塗布液可於流延成為薄 膜狀之後進行乾燥。對乾燥方法並無限制，例如可使用自 然乾燥、減壓乾燥、加熱乾燥、減壓加熱乾燥#。作為加 熱乾燥方法，係利用使用有空氣循環式乾燥烘箱或熱輥等 任意之乾燥裝置的乾燥方法。加熱乾燥時之乾燥溫度較好 的是50°C〜120°C，更好的是8〇°C〜1〇〇。〇。 [偏光膜之用途] 藉由本發明之製造方法所製造之偏光膜係有效利用光學 各向異性而用於各種光學元件中，尤其可適合用作偏光板 以及相位差板《偏光膜之用途例如可列舉：個人電腦顯示 器、筆s己本電月b、影印機等〇A(office automation，辦公事 務）機器；行動電話、鐘錶、數位攝影機、個人數位助理 (PDA’ Personal Digital Assistant)、行動遊戲機等行動機 器；攝影機、電視、電子爐等家庭用機器；後台監視器、 汽車導航、汽車音響等車載用機器；店鋪用監視器等展示 機器；監視用監視器等警備機器；看護用監視器；醫療用 監視器等的液晶顯示裝置。偏光膜可自基板上剝離而使 134316-1011009.doc • 14 - 1379891 於以積層狀態用於光 可見光之波長區域為 較好的是積層於其他 用，亦可以與基板積層之狀態使用。 學用途中之情形時，基板較好的是在 透明者。於自基板上剝離之情形時， 支持體或光學元件上而使用。 [實施例] 利用下述⑷〜⑷來合成由結構式（11)所表示之偶氣系化 合物。 φ ⑷由對甲氧苯胺與8-胺基·2_萘橫酸經，利用常法經過二 偶氮化'偶合步驟而獲得單偶氮化合物。 (b) 利用常法將所獲得之單偶氮化合物進行二偶氮化，與7_ 胺基-1-萘酚-3,6-二磺酸鋰進行偶合反應。 (c) 於含有所得粗產物之反應溶液中添加氯化鋰來進行鹽 析’單離出由結構式（II)所表示之偶氮系化合物。 [化2]Qi preferably has one or two selected from the group consisting of a nitro group, a cyano group, a hydroxyl group, an amine group, a halogen group, a halogenated alkyl group having a carbon number of id, and an alkoxy group having a carbon number of 1 to 3, 134316-1011009. Doc • 10- 1379891 The phenyl eQ3 of the substituent in the group consisting of money preferably has one or two alkoxy groups selected from the group consisting of a carbon number of 3 and a carbon number of 3 And a naphthyl group of a substituent in the group consisting of sulfonic acid groups. The azo compound represented by the general formula (I) can be "manufactured by the theory of dye chemistry" according to Hosoda (July 15, 1968, Technical Law, 5th edition, pp. 135 - 152), for example Two compounds each having an amine group are obtained by diazotization and a coupling reaction. Further, the number of φ substituents Q2 linked by an azo bond can be increased by repeating diazotization and coupling reaction. [Solvent] The solvent used in the present invention is a method in which a lyotropic liquid crystal compound is uniformly dissolved. It is preferred that the chloride ion is not contained or the chloride ion concentration is small. The solvent is preferably a hydrophilic solvent. Examples of the hydrophilic solvent include water, alcohols, and cellosolve. A water-soluble solvent such as an alcohol, a shim, a cellosolve, a disulfoxide or a dimethyl decylamine may be added to water. Also, • Water-soluble compounds such as glycerin and ethylene glycol may be added. These additives can be used to adjust the solubility of the water-soluble liquid crystal compound or the drying speed of the aqueous solution. The amount of the solvent added is preferably 100 parts by weight or less based on 100 parts by weight of the water in the aqueous solution. [Method for Producing Coating Liquid] The coating liquid produced by the production method of the present invention can be obtained, for example, by a production method including the following steps (1) and (2). Step (1): In the reaction solution after synthesis of the lyotropic liquid crystal compound, _ is separated from the lyotropic liquid crystal compound by salting out. 134316-101I009.doc •11· 1379891 Step (2): mixing the lyotropic liquid crystal compound separated from the step (i) with a solvent to obtain a mixed liquid, and purifying the mixture into chlorine using an ion exchange resin The concentration of the compound ions was 3×1 〇 [4] ppm or less to obtain a coating liquid. The concentration of the chloride ions in the coating liquid can be reduced by using a film other than the ion exchange resin. These methods of lowering the concentration of the vaporized ions can be used in combination of plural kinds. [Polarizing film] In the method for producing a polarizing film of the present invention, the coating liquid is cast into a film form and the lyotropic liquid crystal compound is aligned. The polarizing film produced by the manufacturing method of the present invention preferably exhibits absorption dichroism at least a part of a wavelength range of 380 nm to 780 nm, particularly at a wavelength of 550 nm. The dichroic ratio of the polarizing film of the present invention is preferably 2 Å or more, more preferably 30 or more, at a wavelength of 550 nm. The polarizing film of the present invention has a monomer transmittance of 550 nm, preferably 30% to 50%. The polarizing film produced by the production method of the present invention has a degree of polarization at a wavelength of 550 nm, preferably 90% or more, more preferably 95% or more. [Casting] The coating liquid produced by the production method of the present invention can be formed into a film shape by, for example, casting on a substrate. The casting method is not particularly limited as long as the coating liquid is uniformly cast, and a casting method using a suitable coater is employed. Examples of the casting device include a slide coater, a slit press coater, a bar coater, a bar coater, a roll coater, a flexographic press, a screen printing machine, a curtain coater, and a spray. A mist coater, a spin coater, or the like. 134316-1011009.doc •12· [Substrate] The substrate is not limited, and may be a single layer or a laminate of a plurality of layers (for example, an alignment film). Examples of the substrate specific to A include a glass plate or a resin film. In the case where the substrate contains an alignment film, the alignment film is preferably an alignment processor. Examples of the substrate containing the alignment film include a substrate on which a polyimide plate is coated with polyimide. The polyimine film is imparted with an alignment property by a known method, for example, mechanical alignment treatment such as rubbing in a certain direction or chemical alignment treatment such as photo-alignment treatment. For the alignment processing of the substrate, a well-known method described in "Liquid Crystal Handbook" (Maruzen Co., Ltd., issued on January 30, 2000), page 226 to page 2; The glass plate of the substrate is preferably a user of the liquid crystal cell, and for example, an alkali-free glass can be listed. When a resin film is used as the substrate, the substrate can be made flexible, and thus it is suitable for applications requiring flexibility. The surface of the resin film can also be subjected to alignment treatment by friction or the like. Alternatively, an alignment film containing other materials may be formed on the surface of the resin film. The material of the resin film to be used in the substrate is not particularly limited, and examples thereof include a styrene resin, a (meth) acrylic resin, a polyester tree, and a polyolefin. The thickness of the resin, the norbornene-based resin, the polyimide-based resin, the cellulose-based resin, the polyvinyl alcohol-based resin, and the polycarbonate-based resin β substrate is not particularly limited, and is usually 1 μm. A range of ~1000 μιη. [Alignment] The lyotropic liquid crystal compound used in the present invention can be aligned by flow if it is subjected to a shear stress of 1343l6-10liOQ9.doc • 13-1379891 in a liquid crystal state. The lyotropic liquid crystal compound forms a supramolecular association in a liquid crystal state, and when a shear stress is applied to the coating liquid containing the same, the direction of the flow of the supramolecular material is the flow direction. In addition to the shear stress, the alignment method may be used by blending treatment such as rubbing treatment or photo-alignment treatment, and aligning with a magnetic field or an electric field. ‘[Drying] The coating liquid produced by the production method of the present invention can be dried after being cast into a film shape. The drying method is not limited, and for example, natural drying, reduced-pressure drying, heat drying, and drying under reduced pressure may be used. As the heating and drying method, a drying method using an air drying type drying oven or a heat roller or the like is used. The drying temperature at the time of heat drying is preferably from 50 ° C to 120 ° C, more preferably from 8 ° C to 1 Torr. Hey. [Application of Polarizing Film] The polarizing film produced by the production method of the present invention is effectively used for various optical elements by utilizing optical anisotropy, and is particularly suitable for use as a polarizing plate and a phase difference plate. List: PC monitors, pens, electric b, photocopying machines, etc. (office automation); mobile phones, clocks, digital cameras, personal digital assistants, mobile game consoles Such as mobile devices; home devices such as cameras, televisions, and electronic stoves; vehicle-mounted devices such as back-end monitors, car navigation, and car audio; display devices such as monitors for stores; guard devices such as monitors for surveillance; and monitors for care; A liquid crystal display device such as a medical monitor. The polarizing film can be peeled off from the substrate so that 134316-1011009.doc • 14 - 1379891 is used in a layered state for the wavelength region of light and visible light, and it is preferable to use it in other layers or in a state of being laminated with the substrate. In the case of learning use, the substrate is preferably transparent. When it is peeled off from the substrate, it is used on a support or an optical element. [Examples] The gas system compounds represented by Structural Formula (11) were synthesized by the following (4) to (4). φ (4) is obtained by p-methoxyaniline and 8-amino-2-naphthyl acid, and a monoazo compound is obtained by a diazotization coupling step by a usual method. (b) The obtained monoazo compound is diazotized by a usual method, and coupled with 7-amino-1-naphthol-3,6-disulfonic acid lithium. (c) Lithium chloride is added to the reaction solution containing the obtained crude product to carry out salting out. The azo compound represented by the structural formula (II) is isolated. [Chemical 2]
含有由結構式（II)所表示之偶氮系化合物與水之水溶液 的氯化物離子為42x1 〇[4] ppm左右，故而通過離子交換樹 脂（日本Rensui股份有限公司製造之DIAION AMP01)而純 化成氣化物離子濃度為O.lxl 0[4] ppm。經純化之水溶液的 總固形分濃度為0.9重量％左右，故而使用旋轉蒸發器，濃 縮成總固形分濃度為18重量％來製作塗布液。 134316-1011009.doc 1379891 繼而，於實施有摩擦處理以及電暈處理之環烯烴系樹脂 膜（曰本Zeon公司製造之Zeonor)的實施有摩擦處理以及電 暈處理之表面，使用線棒（支#丨.5)將塗布液流延成為薄膜 狀，使其自然乾燥約1分鐘，來製成厚度為0.4 μιη之偏光 膜。實施例之偏光膜係如表1所示，單體穿透率為39_2〇/〇， 較高’而且偏光度為98.2%，非常高，因此平衡性良好且 偏光特性優異。 [表1] 氣化物離子濃度 (ppm) 單體穿透率 (%) 偏光度 (%) 實施例 0.1xl0[41 39.2 98.2 比較例1 5xl0[41 46.4 57.3 比較例2 10xl0[4] 38.4 86.4 比較例3 20xl0[41 17.4 78.1 [比較例1] 除了縮短離子交換樹脂之處理時間，純化成氯化物離子 濃度為5X 10[4] ppm以外，以與實施例相同之方法來製作 塗布液以及偏光膜》比較例1之偏光膜係如表1所示，單體 穿透率為46.4%，非常高，但偏光度為57.3%，非常低。 [比較例2] 除了縮短離子交換樹脂之處理時間，純化成氯化物離子 濃度為1 Οχ 1 〇[4] ppm以外’以與實施例相同之方法來製作 塗布液以及偏光膜。比較例2之偏光膜係如表1所示，單體 穿透率為38.4%，較高，但偏光度為86.4%，較低。 [比較例3] 除了縮短離子交換樹脂之處理時間，純化成氯化物離子 i34316-1011009.doc -16- 1379891 濃度為20x10[4] ppm以外，以與實施例相同之方法來製作 塗布液以及偏光膜。比較例3之偏光膜係如表1所示，單體 穿透率為17.4%，非常低，且偏光度為78.1%，較低。 [評價] 如表1所示，實施例之偏光膜的單體穿透率與偏光度此 兩者均高，偏光特性優異。另一方面，比較例1、比較例2 之偏光膜的單體穿透率與偏光度中有一者較低，又，比較 例3之偏光膜的單體穿透率與偏光度此兩者均低，因此均 為偏光特性不良。一般認為，實施例之偏光膜的偏光特性 良好的原因在於減小了氯化物離子濃度。 [測定方法] 氯化物離子之定量方法如下。秤取試料（塗布液或者偏 光臈）約20 mg，包裹於Sn箔中，使用自動試料燃燒裝置來 使其燃燒，將所產生之氣體收集於吸收液（在純水中追加 有雙氧水30 ppm者）10 ml中。將該吸收液定容為15 m卜使 用離子層析裝置（例如DIONEX公司製造之DX-320)進行測 定。 二色比、單體穿透率、偏光度係使用具備葛蘭-湯普生 (Glan-Thompso)偏光元件之分光光度計（曰本分光公司製造 之V-7100) ’使測定波長之直線偏光之測定光射入，求出 下述1^及1^，利用下式算出。 二色比：logO/kJ/logG/k：】） 單體穿透率：（1^+1^)/2 偏光度：（ki-kzVA+kj) 134316-1011009.doc 1379891 其中，1^表示最大穿透率方向之直線偏光的穿透率，k2表 示與最大穿透率方向正交之方向的直線偏光之穿透率。The chloride ion containing the aqueous solution of the azo compound represented by the structural formula (II) and water is about 42×1 〇 [4] ppm, and thus purified by ion exchange resin (DIAION AMP01 manufactured by Rensu, Inc., Japan). The vapor ion concentration is O.lxl 0 [4] ppm. The purified aqueous solution had a total solid content concentration of about 0.9% by weight, and thus a coating liquid was prepared by using a rotary evaporator to concentrate to a total solid content of 18% by weight. 134316-1011009.doc 1379891 Then, the surface of the cycloolefin-based resin film (Zeonor manufactured by Sakamoto Zeon Co., Ltd.) which has a rubbing treatment and a corona treatment is subjected to a rubbing treatment and a corona treatment, and a wire rod is used. 5. 5) The coating liquid was cast into a film shape, and allowed to naturally dry for about 1 minute to prepare a polarizing film having a thickness of 0.4 μm. As shown in Table 1, the polarizing film of the examples has a monomer permeability of 39 〇 / 〇, a high degree and a degree of polarization of 98.2%, which is very high, so that the balance is good and the polarizing characteristics are excellent. [Table 1] Vapor ion concentration (ppm) Monomer transmittance (%) Polarization (%) Example 0.1x10 [41 39.2 98.2 Comparative Example 1 5x10 [41 46.4 57.3 Comparative Example 2 10xl0 [4] 38.4 86.4 Comparison Example 3 20x10 [41 17.4 78.1 [Comparative Example 1] A coating liquid and a polarizing film were produced in the same manner as in the Example except that the treatment time of the ion exchange resin was shortened and the chloride ion concentration was 5×10 [4] ppm. The polarizing film of Comparative Example 1 is as shown in Table 1. The monomer transmittance was 46.4%, which was very high, but the degree of polarization was 57.3%, which was very low. [Comparative Example 2] A coating liquid and a polarizing film were produced in the same manner as in the Example except that the treatment time of the ion exchange resin was shortened and purified to a chloride ion concentration of 1 Οχ 1 〇 [4] ppm. As shown in Table 1, the polarizing film of Comparative Example 2 had a monomer transmittance of 38.4%, which was high, but the degree of polarization was 86.4%, which was low. [Comparative Example 3] A coating liquid and a polarizing film were produced in the same manner as in the Examples except that the treatment time of the ion exchange resin was shortened and purified to a chloride ion of i34316-1011009.doc -16 - 1379891 at a concentration of 20x10 [4] ppm. membrane. The polarizing film of Comparative Example 3 is as shown in Table 1, and the monomer transmittance was 17.4%, which was very low, and the degree of polarization was 78.1%, which was low. [Evaluation] As shown in Table 1, the polarizing film of the examples had both high monomer transmittance and polarization degree, and was excellent in polarizing characteristics. On the other hand, in the polarizing film of Comparative Example 1 and Comparative Example 2, one of the monomer transmittance and the degree of polarization was lower, and the monomer transmittance and the degree of polarization of the polarizing film of Comparative Example 3 were both lower. It is low and therefore has poor polarization characteristics. It is considered that the reason why the polarizing characteristics of the polarizing film of the embodiment is good is that the chloride ion concentration is reduced. [Measurement Method] The method for quantifying chloride ions is as follows. Weigh about 20 mg of the sample (coating solution or polarized iridium), wrap it in Sn foil, burn it with an automatic sample burning device, and collect the generated gas in the absorbing liquid (addition of hydrogen peroxide 30 ppm in pure water) ) 10 ml. The absorption liquid was made up to a volume of 15 m and measured using an ion chromatography apparatus (for example, DX-320 manufactured by DIONEX Co., Ltd.). The two-color ratio, the monomer transmittance, and the degree of polarization are measured by using a spectrophotometer (V-7100 manufactured by Sakamoto Seiki Co., Ltd.) having a Glan-Thompso polarizing element. The light was incident, and the following 1^ and 1^ were obtained and calculated by the following formula. Two-color ratio: logO/kJ/logG/k:]) Monomer transmittance: (1^+1^)/2 Polarization: (ki-kzVA+kj) 134316-1011009.doc 1379891 where 1^ indicates The transmittance of the linearly polarized light in the direction of the maximum transmittance, and k2 represents the transmittance of the linearly polarized light in the direction orthogonal to the direction of the maximum transmittance.
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