200923017 九、發明說明： 【發明所属之技術範圍3 技術範圍 本發明係有關於將含有黃色色素及藍色色素之溶致液 5 晶性混合物製膜而成的偏光膜，及具有該偏光膜之液晶顯 示裝置。 背景技術 偏光膜係例如，液晶顯示裝置所使用之重要構造構件 10 的1種。 以往，將吸附有蛾之聚乙烯醇薄膜延伸而成的二色性 PVA延伸薄膜作為偏光膜使用。該偏光膜於製造時必須進 行延伸處理，此外，吸收軸僅於特定方向（延伸方向）產生。 又，該偏光膜係由延伸薄膜構成，故於形成薄膜狀方面有 5所限制。 A又’專利文獻1中，揭示了藉於基材塗布含有混合色素 液所形成的塗膜構成之偏光膜，且該混合色素係混合 =複數色素(例如，藍色色素'紅色色素、及黃色色素)者。 二偏光膜可形成薄膜狀，此外，於可見光之範圍内具有吸 1欠二色性。 【專利文獻1】日本專利申請公開平9_23〇142號公報 【聲明内容;3 發明揭示 〜而，别述含有複數色素之偏光膜有可見光範圍之吸 5 200923017 收二色性小的問題。該吸收二色性之下降，於可見光範圍 之短波長側特別顯著。 本毛月之目的係提供一種於可見光之廣大範圍中具有 高吸收二色性的偏光膜。 〃本毛月人等針對於含有複數色素之偏光膜中 ，可見光 I巳圍之短波長側之吸收二色性變小方面專心致力於研究。 、口果&現吸收—色性下降之原因係黃色色素與藍色色素 妨礙互相之配向。為進行改善，本發明人等研究了使用以 ’8伸不甲醯基_ι，2’_料咪唾衍生物作為黃色色素，並將 10其混合於藍色色素的方法。 s本發明之偏光膜含有溶致液晶性混合物，且該溶致液 曰曰!·生此σ物含有.黃色色素，係於波長挪〜伽⑽範圍 之任-波長中顯示最大吸收者；及藍色色素，係於波長 580mn〜_細範圍之任一波長中顯示最大吸收者且前述 15黃色色素係认伸萘甲醯基_1，，2，-苯并味唾衍生物。 前述偏光膜於可見光之廣大範圍中具有高吸收二色 !生又’則述偏光膜亦可藉塗布含有前述溶致液晶性混合 物之/合液形成。因此，前述偏光膜可形成薄膜狀。這些， 係本發明人等首次發現之事項，可達到未預期之優異效果。 2〇 树明之偏光膜於可見光之廣大範圍具有高吸收二色 !·生的理由’可由以下⑴及⑺推測而知。⑴因前述Μ·伸萘 曱醯基·1’，2’_苯并·衍生物本身係具高度配向，故於短波 長範圍之吸收二色性變大。⑺藍色色素因前述伸蔡甲 醯基·Γ，2，.苯并咪销生物之存在而具高度配向，故長波長 200923017 範圍之吸收二色性亦變大。因此，依據本發明，可提供一 種於可見光之廣大範圍中具有高吸收二色性的偏光膜。此 種偏光膜之偏光特性優異，且特別適用於液晶顯示裝置。 又，由另一面來看，本發明係提供一種具有前述偏光 5 膜之液晶顯示裝置。 I：實施方式3 實施發明之最佳形態 (本發明偏光膜之概要） 本發明之偏光膜係將含有溶致液晶性混合物之形成材 10 料形成為膜狀的薄膜，且前述溶致液晶性混合物含有：1,8-伸萘甲醯基-Γ,2’-苯并咪哇衍生物（黃色色素），係於波長 380nm〜480nm範圍之任一波長中顯示最大吸收者、及藍色 色素，係於波長580nm〜680nm範圍之任一波長中顯示最大 吸收者。 15 此種偏光膜於可見光之廣大範圍中具有高吸收二色 性。 本發明中，「吸收二色性」係指選擇性地吸收丨個振動 方向之光（幾未吸收與其吸收之光的振動方向垂直的振動 方向之光）的性質。可以垂直透射率評價偏光膜之吸收二色 20 性。垂直透射率低之偏光膜係吸收二色性高之偏光膜。 另外，垂直透射率（％)係由]^與]^2之積求得。前述1^表 示於偏光膜射入直線偏光時，最大透射率方向之透射率， 前述k2表示於偏光膜射入直線偏光時，與前述最大透射率 方向垂直之方向的透射率。前述1^及1^2可以下述實施例記載 200923017 之方法冽定。200923017 IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a polarizing film formed by forming a five-crystal mixture of a lyotropic liquid containing a yellow pigment and a blue pigment, and a polarizing film. Liquid crystal display device. Background Art A polarizing film is, for example, one type of important structural member 10 used in a liquid crystal display device. Conventionally, a dichroic PVA stretched film obtained by stretching a moth-resistant polyvinyl alcohol film has been used as a polarizing film. The polarizing film must be stretched at the time of manufacture, and the absorption axis is generated only in a specific direction (extension direction). Further, since the polarizing film is composed of a stretched film, there are five limitations in forming a film. In addition, in Patent Document 1, a polarizing film comprising a coating film formed by mixing a dye liquid is applied to a substrate, and the mixed dye is mixed = a plurality of pigments (for example, a blue pigment 'red pigment, and yellow Pigment). The dichroic film can be formed into a film shape, and further has a dichroic property in the range of visible light. [Patent Document 1] Japanese Patent Application Laid-Open Publication No. Hei 9-23 No. 142. [Description of Contents; 3 Disclosure of Invention] The polarizing film containing a plurality of dyes has a problem of absorption in the visible light range. 5 200923017 The problem of small dichroism is small. This decrease in absorption dichroism is particularly remarkable on the short wavelength side of the visible light range. The purpose of this month is to provide a polarizing film having high absorption dichroism in a wide range of visible light. In the polarizing film containing a plurality of pigments, the 毛本毛月人 and others focus on research on the absorption dichroism of the short-wavelength side of the visible light I. , the fruit of the mouth & the current absorption - color decline is caused by the yellow pigment and the blue pigment hinder the mutual alignment. In order to improve the present invention, the inventors of the present invention have studied a method of using a yellow pigment as a yellow pigment and a mixture of 10 and a blue pigment. The polarizing film of the present invention contains a lyotropic liquid crystal mixture, and the lyotropic liquid contains a yellow pigment which exhibits maximum absorption in any wavelength range of wavelength shift to gamma (10); The blue coloring matter exhibits a maximum absorption in any wavelength of a wavelength of 580 nm to _ and the above-mentioned 15 yellow pigment is a naphthylmethylidene-1,2,-benzopyran derivative. The polarizing film has a high absorption of two colors in a wide range of visible light. The polarizing film can also be formed by applying a liquid/liquid containing the lyotropic liquid crystal mixture. Therefore, the aforementioned polarizing film can be formed into a film shape. These are the first findings of the present inventors, and can achieve unexpectedly excellent effects. 2 〇 The bright film of Shuming has a high absorption of two colors in a wide range of visible light. The reason for the birth can be estimated by the following (1) and (7). (1) Since the above-mentioned Μ·Naphthylquinone·1', 2'-benzo-derivative itself is highly aligned, the absorption dichroism in the short wavelength range becomes large. (7) The blue pigment has a high degree of alignment due to the presence of the above-mentioned scorpion Γ Γ Γ, 2, benzopyrene, and the absorption dichroism of the long wavelength 200923017 range also becomes large. Therefore, according to the present invention, it is possible to provide a polarizing film having high absorption dichroism in a wide range of visible light. Such a polarizing film is excellent in polarizing characteristics and is particularly suitable for use in a liquid crystal display device. Further, from the other side, the present invention provides a liquid crystal display device having the above-described polarizing film. I: Embodiment 3 The best mode for carrying out the invention (summary of the polarizing film of the present invention) The polarizing film of the present invention is a film in which a material 10 containing a lyotropic liquid crystal mixture is formed into a film, and the lyotropic liquid crystal property The mixture contains: 1,8-naphthoquinone-indole, 2'-benzimide derivative (yellow pigment), which exhibits maximum absorption and blue pigment at any wavelength ranging from 380 nm to 480 nm. The maximum absorption is shown in any of the wavelengths ranging from 580 nm to 680 nm. 15 Such a polarizing film has high absorption dichroism in a wide range of visible light. In the present invention, "absorbing dichroism" means a property of selectively absorbing light in a direction of vibration (a light which does not absorb a direction of vibration perpendicular to the direction of vibration of the light absorbed therein). The absorption of the two-color film of the polarizing film can be evaluated by the vertical transmittance. A polarizing film having a low vertical transmittance absorbs a polarizing film having high dichroism. In addition, the vertical transmittance (%) is obtained from the product of ^^ and ^^2. The above is shown in the transmittance in the maximum transmittance direction when the polarizing film is incident on the linearly polarized light, and k2 is the transmittance in the direction perpendicular to the direction of the maximum transmittance when the polarizing film is incident on the linearly polarized light. The above 1 and 1 and 2 can be determined by the method of 200923017 described in the following embodiments.
本發明中，「、v? A 化，產k 洛致液晶性」係指藉使溫度或溶液濃度變 生等向相_液晶相之相轉移的性質。前述液晶相 特別限制，可兴加1 牛彳如，向列型液晶相、層列型液晶相、膽 口醇型液晶相等。 + 通專液晶相可精由偏光顯微鏡所觀察之 液曰曰相的光學圖案確認、辨識。 t發明中，「偏光膜」係指具有可使來自偏光或自然光 之特疋直線偏錢射功能的光學構件。 10 15 、/發Θ之偏_可藉由例如’將前述溶致液晶性混合 勿哈解或77散於適合之溶劑所得的溶液，塗布於適合之基 ^乾燥為塗膜而形成。依據如此之溶液塗布法，可形 成薄膜狀之偏光膜。具體而言，本發明偏光膜之厚度係例 如，ο.ίμιη〜5μιη，以0.3μηι〜3μΠ1為佳。 本發明之偏光膜於可見光範圍（波長38〇nm 〜780nm)之 任—者中具有吸收二色性。該偏光膜以於波長540nm中具有 吸收二色性為佳。本發明偏光膜之二色比於波長54〇nm中， 以20以上為佳。該偏光膜之二色比可以下述實施例中記載 之方法測定。又，該偏光膜之平均透射率以3〇%以上為佳， 較佳者是40%以上。 本發明偏光膜於波長420nm(短波長側）之垂直透射率 (Tc[420])以30%以下為佳，較佳者是1〇%〜30% ,特佳者為 15%〜25%。又，本發明偏光膜於波長600nm(長波長側）之垂 直透射率（Tc[600])以20%以下為佳，較佳者是5%〜20%，特 佳者為5%〜15%。 200923017 依據本發明，可提供短波長範圍之吸收二色性及長波 長範圍之吸收一色性均咼之偏光膜。依據本發明，可提供 波長420ηηι之垂直透射率（TC[420])與波長600nm之垂直透 射率（TC[600])差的絕對值（17^42(^^60(^1)係例如，15% 5以下的偏光膜。 (溶致液晶性混合物） 本發明之溶致液晶性混合物，含有波長38〇nm〜48〇nm 範圍之任一波長中顯示最大吸收的1,8-伸萘甲醯基_ι，，2，-苯并咪唑衍生物（黃色色素），與於波長58〇11111〜68〇11〇1範圍之 10任一波長中顯示最大吸收的藍色色素。本發明之溶致液晶 性混合物只要含有前述黃色色素與藍色色素即可，此外， 亦可含有其他化合物。 前述溶致液晶性混合物於溶液狀態下，各色素會顯現 液晶相。含有前述溶致液晶性混合物之溶液可顯現穩定的 15液晶相，因此，藉於基材塗布前述溶液，各色素會高度地 配=。因此，藉由塗布溶液，可得於可見光之広大範圍中 具高吸收二色性的偏光膜。 (黃色色素） 本發明中使用之黃色色素係於波長38〇nm〜48〇nm範圍 2〇之任—波長中顯示最大吸收的1，M申萘甲醯基_Γ,2，_苯并 咪唑衍生物。 本發明中，黃色声辛之^ , 、巴巴畜之汽色」係包含黃綠色或橙色 等廣義的黃色之意。 月J述η色色素藉其自身之高度配向’具有增強短波長 9 200923017 範圍之吸收二色性的作用、及提高與該黃色色素混合在一 起之藍色色素的配向之作用（即，增助藍色色素之配向的作 用）。藉由高度配向藍色色素，可增強長波長範圍之吸收二 色性。因此，含有前述黃色色素之偏光膜的短波長範圍之 5 吸收二色性及長波長範圍之吸收二色性均高。 習知技術中，為形成有短波長範圍及長波長範圍之吸 收二色性均高的偏光膜，需混合黃色色素及藍色色素以外 之補色色素且使該等色素配向。依據本發明，至少混合有 前述黃色色素及藍色色素，藉此可得可見光之廣大範圍中 10 具高吸收二色性的偏光膜。 前述黃色色素之含有量，於前述溶致液晶性混合物100 質量份中，以1質量份〜90質量份為佳，較佳者是1質量份〜50 質量份，特佳者為5質量份〜50質量份。 前述1,8-伸萘甲醯基-1’,2’-苯并咪唑衍生物以下述通 15 式（I)表示之化合物為佳。 【化1】In the present invention, ", v? A, and k-induced liquid crystallinity" means a property of shifting to a phase of a phase-liquid crystal phase by a change in temperature or a solution concentration. The liquid crystal phase is particularly limited, and it is possible to add 1 burdock, for example, a nematic liquid crystal phase, a smectic liquid crystal phase, or a cholesteric liquid crystal. + The special liquid crystal phase can be confirmed and identified by the optical pattern of the liquid helium phase observed by a polarizing microscope. In the invention, the "polarizing film" means an optical member having a function of linearly biasing a characteristic from polarized light or natural light. 10 15 / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / According to such a solution coating method, a film-shaped polarizing film can be formed. Specifically, the thickness of the polarizing film of the present invention is, for example, ο. ίμιη to 5 μιη, preferably 0.3 μηι to 3 μΠ1. The polarizing film of the present invention has absorption dichroism in any of the visible light range (wavelength: 38 Å to 780 nm). The polarizing film preferably has absorption dichroism at a wavelength of 540 nm. The dichroic film of the present invention has a dichroic ratio of more than 20 in a wavelength of 54 〇 nm. The dichroic ratio of the polarizing film can be measured by the method described in the following examples. Further, the average transmittance of the polarizing film is preferably 3% or more, and more preferably 40% or more. The polarizing film of the present invention has a vertical transmittance (Tc [420]) at a wavelength of 420 nm (short wavelength side) of preferably 30% or less, preferably 1% to 30%, and particularly preferably 15% to 25%. Further, the polarizing film of the present invention has a vertical transmittance (Tc [600]) at a wavelength of 600 nm (long wavelength side) of preferably 20% or less, preferably 5% to 20%, and particularly preferably 5% to 15%. . According to the present invention, it is possible to provide a polarizing film which absorbs dichroism in a short wavelength range and has uniform absorption and uniformity in a long wavelength range. According to the present invention, the absolute value of the difference between the vertical transmittance (TC [420]) of the wavelength 420 ηηι and the vertical transmittance (TC [600]) of the wavelength of 600 nm can be provided (17^42 (^^60(^1) is, for example, 15% or less of a polarizing film. (Liquidotropic liquid crystal mixture) The lyotropic liquid crystal mixture of the present invention contains 1,8-extension naphthene which exhibits maximum absorption at any wavelength ranging from 38 〇 nm to 48 〇 nm. A thiol-, 2,-benzimidazole derivative (yellow pigment) having a maximum absorption of blue pigment at any wavelength of 10 in the range of 58 〇 11111 to 68 〇 11 〇 1 . The liquid crystal mixture may contain the yellow pigment and the blue pigment, and may contain other compounds. The lyotropic liquid crystal mixture may exhibit a liquid crystal phase in a solution state, and the lyotropic liquid crystal mixture may be contained. The solution can exhibit a stable liquid crystal phase of 15 liquids. Therefore, by coating the above solution on the substrate, each pigment is highly matched. Therefore, by coating the solution, polarized light having high absorption dichroism in a wide range of visible light can be obtained. Film (yellow pigment) in the present invention The yellow pigment used is a 1,M-naphthylmethylidene- 2,-benzimidazole derivative exhibiting maximum absorption in a wavelength range of 38 〇 nm to 48 〇 nm. In the present invention, The yellow sound of Xin, and the steam color of the Baba animal contain the general meaning of yellow, such as yellow-green or orange. The η-color pigment of the moon is by its own height, the absorption two-color with the enhanced short wavelength 9 200923017 range. The role of the scent and the effect of the alignment of the blue pigment mixed with the yellow pigment (ie, the effect of assisting the alignment of the blue pigment). The absorption of the long wavelength range can be enhanced by the highly aligned blue pigment. Therefore, the polarizing film containing the yellow pigment has a high absorption dichroism in the short wavelength range and a high absorption dichroism in the long wavelength range. In the prior art, a short wavelength range and a long wavelength range are formed. In order to absorb a polarizing film having a high dichroism, it is necessary to mix a yellow coloring matter and a complementary coloring matter other than the blue pigment to align the pigments. According to the present invention, at least the yellow pigment and the blue pigment are mixed, thereby being visible. The polarizing film having a high absorption dichroic property in a wide range of light. The content of the yellow pigment is preferably from 1 part by mass to 90 parts by mass per 100 parts by mass of the lyotropic liquid crystalline mixture, preferably 1 part by mass to 50 parts by mass, particularly preferably 5 parts by mass to 50 parts by mass. The above 1,8-naphthoquinone-1',2'-benzimidazole derivative has the following formula (I) The compound represented is preferred.
前述式⑴中，k表示0〜4之整數，1及m分別表示0〜3之整 數，η表示1〜4之整數(k、1、m及η滿足1 $ k+l+m+n $ 10)， X、Υ及Ζ分別獨立，並表示氫原子、取代或無取代之碳數 10 200923017 1〜5的烧基、取代或無取代之碳數i〜5的烷氧基、鹵素原子、 經基、或胺基，且Μ表示相對離子。另外，本發明中，「取 代或無取代」係具有取代基或未具有取代基之意。具有取 代基時’其取代基可舉例如，羥基' _s〇3M、_c〇〇M、苯 基、氟等鹵素基、胺基、硝基、炭數丨〜4之烷基等。 f 10 15 20 前述Μ以氫原子、鹼金屬原子、鹼土金屬原子、金屬 離子、或者取代或無取代之銨離子等為佳。前述金屬離子 可舉例如：Ni2+ ' Fe3+、Cu2+、Ag+、Zn2+、Al3+、Pd2+、Cd2+、 g j^2+ 广 2+ 〇 、Mn2+、Ce3+等。另外，例如，藉由溶液塗布形 ^本發明之偏光料，可使用具有提升對水之溶解之基的 ,、,式(I)之化合物作為前述M，於成膜後，為提高耐水性， Ί用於水具有不溶性或難溶性之基取代該式⑴之M。 顯八式(1)表示之化合物（黃色色素）因其自身單獨即可 色素，^性’故前述式⑴之化合物可相較於其他黃色 -波二ST述式⑴之化合物的偏光膜於 示之化合物提高與===此外，前述式⑴中表 因此，含有色色素的配向作用亦優異。 具有較高之。魏二4的偏輕於長波長範圍中， 甲二=甲醢基-1，，2、笨并心衍生物可藉萘二 得。又前:Γ與鄰笨二胺或其衍生物之縮合反應而 發煙硫酸等=蔡甲醯基_1’，2，-笨輪衍生物可藉以 而得。將丨，8·伸萘爾_ι，，η并咪讀生物確化 11 200923017 (藍色色素) 本發明所使用之藍色色素係於波長580nm〜680nm範圍 =壬-波長中顯示最大魏。前述藍色色素制以與前述 η色色素|§]作並形成於可見光之廣大範圍具高吸收 二色性的偏光膜，所需之色素。 本發明中，1色色素之「藍色」係包含藍紫色或藍綠 色等廣義的藍色之意。 則述藍色色素之含有量，於前述溶致液晶性混合物刚 質量份中，以職量份〜㈣量份為佳，較佳者是％質量份 月J述▲色色素並未特別限制，可使用任意之色素。藍 色色素可舉例如：C.I Di_muel、c.LDlrectBlue67、 C.I.DirectBlue83、ClDirectBiue9〇 等。 前述藍色色素以使用偶氮衍生物、或花衍生物為佳。 U藉由使關氮衍生物或紐生物，可得長波長範圍之吸收 二色性局的偏光膜。 前述偶氮衍生物以具有複數（例如，2〜4)之偶氮基 (ΝΑ)的偶氮化合物紐。較佳者是，前述缝衍生物; 下述通式（II)表示之化合物。 π 20 【化2】In the above formula (1), k represents an integer of 0 to 4, 1 and m each represent an integer of 0 to 3, and η represents an integer of 1 to 4 (k, 1, m, and η satisfy 1 $ k+l+m+n $ 10), X, Υ and Ζ are each independently, and represent a hydrogen atom, a substituted or unsubstituted carbon number 10 200923017 1 to 5, a substituted or unsubstituted alkoxy group having a carbon number i to 5, a halogen atom, A radical, or an amine group, and Μ represents a relative ion. Further, in the present invention, "substituted or unsubstituted" means having a substituent or having no substituent. When it has a substituent, the substituent may, for example, be a hydroxyl group such as a hydroxyl group _s〇3M, _c〇〇M, a phenyl group or a fluorine group, an amine group, a nitro group or an alkyl group having a carbon number of 丨4 or the like. f 10 15 20 The above hydrazine is preferably a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a metal ion, or a substituted or unsubstituted ammonium ion. Examples of the metal ion include Ni2+ 'Fe3+, Cu2+, Ag+, Zn2+, Al3+, Pd2+, Cd2+, gj^2+, 2+ 〇, Mn2+, Ce3+, and the like. Further, for example, by coating a polarizing material of the present invention by a solution, a compound having the group of the formula (I) having a substance which enhances dissolution of water can be used as the above-mentioned M, and after the film formation, in order to improve water resistance, The base of the formula (1) is substituted with a group in which water is insoluble or poorly soluble. The compound represented by the formula (1) (yellow pigment) can be colored by itself, so that the compound of the above formula (1) can be compared with the polarizing film of the compound of the other yellow-wave two ST formula (1). The compound is improved and === In addition, the above formula (1) is also excellent in the alignment action containing the coloring matter. Has a higher one. Wei II 4 is lighter in the long wavelength range, and the second two = formazan-1, 2, and stupid derivatives can be obtained by naphthalene. Further, the condensation reaction of hydrazine with o-p-diamine or a derivative thereof, fuming sulfuric acid, etc. = cyanohydrin-1', 2,-stray derivative can be obtained.丨,8·伸奈尔尔_ι,,η, and Mi Mi bio-determination 11 200923017 (blue pigment) The blue pigment used in the present invention is in the range of wavelengths 580 nm to 680 nm = maximum wavelength in 壬-wavelength. The blue dye is prepared by a polarizing film having a high absorption dichroic property in a wide range of visible light, which is formed by the above-mentioned η color pigment|§. In the present invention, the "blue" of the one-color dye contains a broad blue color such as blue-violet or blue-green. The content of the blue pigment is preferably in the range of parts to (four) parts by mass of the lyotropic liquid crystalline mixture, and preferably % by mass of the ▲ color pigment is not particularly limited. Any pigment can be used. The blue coloring matter may, for example, be C.I Di_muel, c.LDlrectBlue67, C.I.DirectBlue83, ClDirectBiue9〇 or the like. The blue dye is preferably an azo derivative or a flower derivative. By using a nitrogen derivative or a neoplasm, U can obtain a polarizing film that absorbs a dichroic region in a long wavelength range. The above azo derivative is an azo compound having a plurality of (for example, 2 to 4) azo groups. Preferably, the above slit derivative; a compound represented by the following formula (II). π 20 【化2】
前述式（II)中，Q,表示取代或無取代之 …（Π) 求基、或者取代 12 200923017 或無取代之萘基，Q 2及Q 3分別獨立，並表示取代或無取代 之聯苯基、或者取代或無取代之伸萘基，R表示氫原子、取 代或無取代炭數1〜3之烷基、乙醯基、取代或無取代之苯甲 酿基、或者取代或無取代之苯基，k及1表示〇〜4之整數Ο及1 5滿足〇^k+l$4)’ m表示0〜2之整數，η表示〇〜2之整數，且 Μ表示相對離子。 前述茈衍生物以下述通式(III)表示之化合物為佳。 【化3】In the above formula (II), Q represents a substituted or unsubstituted ... (Π), or substituted 12 200923017 or an unsubstituted naphthyl group, and Q 2 and Q 3 are each independently and represent a substituted or unsubstituted biphenyl. a substituted or naphthyl group, R represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, an ethyl fluorenyl group, a substituted or unsubstituted benzoyl group, or a substituted or unsubstituted group. Phenyl, k and 1 represent an integer 〇 of 〇~4 and 1 5 satisfy 〇^k+l$4)' m represents an integer of 0 to 2, η represents an integer of 〇~2, and Μ represents a relative ion. The above anthracene derivative is preferably a compound represented by the following formula (III). [化3]
前述式(III)中，Q4表示式(a)或(b)，L!、L2、L3及L4分 10別獨立，並表示取代或無取代之碳數1〜5的烷基、取代或無 取代之碳數1〜5的烷氧基、鹵素原子、羥基、或胺基，〇、P、 q及r分別表示0〜2之整數，S表示0〜4之整數(0、p、q、r及S 滿足0$〇+p+q+r+s$8)，Μ表示相對離子。式⑻中，Q5表 示取代或無取代之苯基、取代或無取代之苯烷基、或者取 15代或無喊之祕。S(b)巾，L5表示取代絲取代之碳數 1〜5的烧基、减或無取代之魏1肩錄基、㈣原子、 13 200923017 羥基、或胺基，且t表示0〜4之整數。 另外，前述式(II)及式(III)之Μ係與前述式⑴之Μ相同。 前述通式（Π)及（III)表示之化合物（藍色色素）因JL自身 單獨顯示溶致液晶性，故可相較於其他藍色色素高度配 5向。因此，可得長波長範圍之吸收二色性高的偏光膜。前 述通式（II)及(ΠΙ)表示之化合物，均可單獨使用1種、或混合 2種使用。 (其他化合物） 如前述，本發明中使用之溶致液晶性混合物，除了前 10述黃色色素及藍色色素以外，亦可含有其他化合物。前述 其他化合物可舉紅色色素、添加劑等為例。 刖述紅色色素並未特別限制，可舉例如：C I Direct Red 39 C.I.Direct Red 28 C.I.Direct Red 79 C.I.Direct Red 81 ^ C.I.Direct Red 83 ^ C.I.Direct Red 89 ^ C.I.Add Red 37# 〇 15 齡前述紅色色素時，該紅色色素之含有量，相對於 前述溶致液晶性混合物⑽f量份，以大於㈣量份、輝 量份以下為佳。 前述添加劑可舉例如：界面活性劑、抗氧化劑、抗靜 可塑劑、熱穩疋劑、光穩地劑、潤滑劑、抗酸化劑、 2〇紫外線吸收劑、滯焰劑、著色劑等。添加劑中，界面活性 齊!係用以提升3有，谷致液晶性混合物之溶液對基材表面的 “；m生或塗布ι±而添加。前述界面活性劑以使用非離子界 面活性劑為佳。 α月）述添加劑4，該添加劑之含有量，相對於前述 14 200923017 溶致液晶性混合物100質量份，以大於0質量份、10質量份 以下為佳。 (偏光膜之製法） 前述溶致液晶性混合物於溶液狀態下，會顯現良好之 5 液晶相。因此，藉於適合之基材塗布前述溶致液晶性混合 物之溶液，可簡易地形成薄膜狀之偏光膜。 本發明偏光膜可藉由例如，包含下述步驟Α〜C之製造 方法製造。 步驟A，係準備含有前述溶致液晶性混合物與溶劑之溶 10 液的步驟。 步驟B，係將前述步驟A所得之溶液塗布於適合之基材 上，並於該基材之配向固定力及/或該塗布時剪切應力的存 在下，形成配向有前述黃色色素及該藍色色素之塗膜的步 驟。 15 步驟C，係乾燥前述步驟B所得之塗膜，藉此得到偏光 膜的步驟。 <步驟A> 於步驟A，調製含有溶致液晶性混合物與溶劑的溶液。 如前述，溶致液晶性混合物至少含有於波長 20 380nm~480nm之任一波長中顯示最大吸收的黃色色素（1,8- 伸萘曱醯基-Γ,2’-苯并咪唑衍生物），與於波長 580nm〜680nm之任一波長中顯示最大吸收的藍色色素，亦 可視需要含有其他化合物。 溶劑並未特別限定，可使用習知眾所周知的溶劑。溶 15 200923017 劑以使用水系溶劑為佳。水系溶劑包含有：水、親水性溶 劑、水與親水性溶劑之混合溶劑。親水性溶劑係可與水均 勻溶解之溶劑。親水性溶劑可舉例如：曱醇、乙醇、乙二 醇等醇類；甲基賽路蘇、乙基賽路蘇等賽路蘇類；丙酮、 5 甲基乙基酮等酮類；乙酸乙酯等酯類等。前述溶劑以水、 或水與親水性溶劑之混合溶劑為佳。 前述黃色色素、藍色色素及視需要混合之其他化合物 混合於溶劑之順序並未特別限定。可為例如，將黃色色素、 藍色色素及其他化合物同時混合於溶劑中，亦可於將藍色 10 色素混合於溶劑後，再依黃色色素、其他化合物之順序混 合於溶劑中。又、亦可先將藍色色素與黃色色素分別混合 於不同之溶劑形成溶液，之後，再混合兩溶液。 前述溶液之溶致液晶性混合物的濃度，以調製成顯示 液晶相之濃度為佳。具體而言，溶液中之前述溶致液晶性 15 混合物的濃度，以1質量％〜30質量％為佳，較佳者是2質量 %〜20質量％。於此種濃度範圍之一部份，溶液可顯示良好 之液晶相。 又，前述溶液之pH，以調製成pH4〜10左右為佳，較佳 者是調製成pH6〜8左右。 20 前述溶液之黏度以調製成O.lmPa.s〜30mPa.s為佳，且， 以0.5mPa.s〜3mPa.s更佳。此外，前述黏度係以流變儀 (Rheometer)(Haake社製，製品名：卜才只卜b只600。測定條 件：雙錐感測器（double cone sensor)剪切速率1000(l/s))測定 之值。 16 200923017 〈步驟B> 於步驟B，藉在適合之基材上塗布前述溶液，形成配向 有前述黃色色素及藍色色素之塗膜。 前述基材係用以均勻展開前述溶液者。只要適合該目 5 的，基材之種類並未特別限定，可使用例如，合成樹脂薄 膜（包含一般稱之片材者）、玻璃板等。於較佳實施形態中， 基材係單獨之聚合物薄膜，於較佳之其他實施形態中，基 材係含有聚合物薄膜之積層體。含有該聚合物薄膜之積層 體，以於聚合物薄膜含有配向層為佳。 10 前述聚合物薄膜並未特別限定，但以透明性優異之薄 膜（例如，陰霾值(haze value)5%以下）為佳，且，以各向同 性之薄膜較佳。 前述聚合物薄膜之材料可舉例如：聚對苯二曱酸乙二 酯、聚萘二甲酸乙二酯等聚酯系；二乙醯纖維素、三乙醯 15 纖維素等纖維素系；聚碳酸酯系；聚甲基丙烯酸甲酯等丙 烯系；聚苯乙烯、丙烯腈·苯乙烯共聚物等苯乙稀系；聚乙 烯、聚丙浠、具有環狀或降冰片烯(norbornene)結構之聚豨 烴、乙烯·丙烯共聚物等烯烴系；氯乙烯系；耐綸、芳香族 聚醯胺等醯胺系；聚醯亞胺等醯亞胺系；聚醚颯系；聚醚 20 醚酮系；聚苯硫系；乙烯醇系；二氣亞乙烯系；乙烯丁醛 系；丙烯酸酯系；聚甲醛系；環氧系等。又，前述基材亦 可使用含有前述聚合物之2種以上混合物的聚合物薄膜 等。此外，前述基材亦可使用2個以上聚合物薄膜之積層 體。該等聚合物薄膜以使用延伸薄膜為佳。 17 200923017 ^述基材之厚度可依強度等適#地設計。由薄型輕量 2點來看’前述基材之厚度，以焉喊下為佳較 土疋5〜2〇〇μηι，特佳者為1〇〜1〇〇μιη。 5配向二述基材含有配向層時，該配向層以藉由於基材施行 理^理而形成者為佳。前述配向處理可舉例如，摩擦處 等寺^械性配向處理、光性配向處理等化學性配向處理 —藉於則述基材之配向面塗布溶液，可依據基材之配向 固疋使溶液中之各色素配向。 一機♦戒性配向處理可藉於基材之一面（或形成於基材之 此合塗布膜之__面），以布等於單向摩擦實施藉 可於基材之一面形成配向層。又，亦可使用經施行延 伸處理之延伸薄膜。進行前述摩擦處理等之基材或塗布 膜並未特別限定，可使用作為前述聚合物薄膜例示之聚 從色素之配向效率之點來看，配向層以醯亞胺系 15聚合物形成為佳。 、 化予性配向處理可藉於基材之一面形成含有配向劑之 光配向膜，並以光照射該光配向膜來實施。藉此，可於基 材之一面形成配向層。配向劑可舉例如，具有可產生光化 學反應（光異構化反應、光開閉環反應、光二聚合反應、光 2〇刀解反應、及光弗瑞斯重排反應(optical Fries rearrangement) 等）之光反應性官能基之聚合物等。將配向劑溶解於適用之 溶劑中使之成溶液狀’並將其塗布於基材，藉此可形成前 述光配向膜。 含有前述溶致液晶性混合物之溶液因固體含量濃度較 18 200923017 低，故流動性優異。且，前述溶液亦可簡易地進行塗布機（例 如塗布器等）之最適合塗布黏度範圍。因此，使用該溶液的 話’可於基材上形成薄膜狀且均勻之塗膜。 於基材之一面塗布含有前述溶致液晶性混合物之方 5法，可使用例如，使用適合之塗布器的塗布方法。該塗布 器可舉例如：反輥塗布器、正旋轉輥塗布器、凹板塗布器、 刀塗布器（knife coater)、桿式塗布器（r〇d c〇ater)、狹縫模具 式塗布器（slot die coater)、狹縫孔口式塗布器㈤的〇rifice coater)、簾幕式塗布器（curtain coater)、噴泉式塗布器 10 (fountain coater)、氣動式塗布器（air d〇ct〇r c〇ater)、吻合式 塗布器（kiss coater)、浸塗式塗布器、液滴式塗布器、刮刀 塗布器、塗鑄機(cast coater)、噴霧塗布器、旋轉塗布器、 擠壓塗布器、熱熔塗布器等。前述塗布器宜為例如，反輥 塗布器、正旋轉輥塗布器、凹板塗布器、桿式塗布器、狹 15縫模具式塗布器、狹缝孔口式塗布器、簾幕式塗布器、喷 泉式塗布器等。只要為使用該等塗布器之塗布方法，可施 加剪切力於溶液中所含之各色素。結果，可形成使該色素 咼度配向後之塗膜。如此，使用於塗布溶液時施加剪切力 之塗布方法，即使使用未具有配向層之基材，仍可使各色 20素配向。並且，即使如前述以施加剪切力之塗布方法塗布 溶液時’仍以使用具有配向層之基材為佳。 前述溶液之塗布速度並未特別限定，但以1〇〇mm/秒以 上為佳’較佳者是500mm/秒〜8000mm/秒，特佳者為800mm/ 秒〜600〇mm秒’最佳者係1000mm/秒〜4〇〇〇mm/秒以此種 19 200923017 塗布速度塗布含有溶致液晶性混合物之溶液時，可施加適 合該溶液中各色素配向之剪切力。因此，可形成於可見光 之廣大範圍中具高吸收二色性，且，厚度差異小之偏光膜。 又’亦可於塗布含有溶致液晶性混合物之溶液前，於 5 前述基材之溶液塗布面’施行親水化處理。親水化處理係 使水之接觸角下降的處理。藉由施行該親水化處理，可相 對溶液塗布面，提升溶液之濕潤性及塗布性。 前述親水化處理可使用任意適合之方法。前述親水化 處理，亦可使用例如，乾式處理或濕式處理。乾式處理係 10例如：電暈放電處理、電漿處理及輝光放電處理等放電處 理；火焰處理；臭氧處理；uv臭氧處理；紫外線處理及電 子線處理等電離活性線纽等。献處理係例如：使用水、 丙綱等洛劑之超音波處理；驗處理·，結合層處理等。該等 處理可單獨進行，亦可組合2種以上進行。 15 前述前述親水化處理宜為電暈放電處理、電漿處理、 驗I·生處理、或結合層處理。若為此種親水化處理，可形成 於可見光之廣大範圍中具高吸收二色性，且，厚度差異小 之偏光膜。 、 <步驟c> 20 於步驟C ’乾燥塗布於前述基材上之塗膜。 於乾燥塗膜時，可使用例如：循環熱風或冷風之空氣 循％式1^皿爐、利用微波或遠紅外線等加熱器、用以調節 狐度之、’、二加熱的輥、經加熱之熱管輥、或經加熱之金屬帶 等乾&機構。塗叙乾燥亦可為自㈣乞燥。 20 200923017 乾燥溫度係溶液之等向相轉移溫度以下，且㈣心 緩緩升至高溫乾燥為佳。前述乾燥溫度以贼〜啊為佳皿 更佳者為抓〜啊。若於如此之溫度範_，可 差異小之偏光膜。 5 ,㈣時間可依乾燥溫度與溶劑種類做適宜之選擇，為 形成厚度差異小之偏光膜，乾燥時間係例如丨分鐘〜如分 鐘，且以1分鐘〜10分鐘為佳。 前述塗膜藉由乾燥過程中濃度升高，固定塗膜内經配 向之各色素。乾燥後塗膜之殘留溶劑量以巧量。/。以下為 10佳，較佳者是〇.5質量％以下。 經乾燥之塗膜係本發明的偏光膜。 則述乾燥後之塗膜(偏光膜)係積層於前述基材上。本發 明之偏光膜可於積層於基材上之狀態下使用，亦可由基材 剝離使用。 15 〈步驟D> 此外’於前述乾燥後之塗膜表面(與基材積層面相反之 面）進行下述步驟D，亦可賦予塗膜耐水性。 步驟D係使含有化合物鹽之溶液接觸前述步驟c中經 〇乾燥之塗膜表面，該化合物鹽係選自於由銘鹽、鋇鹽、錯 骚、络鹽、總鹽、及分子内含有2個以上胺基之化合物鹽所 構成之群之至少1種者。 具體而言’係使化合物鹽接觸前述步驟c中所得之乾燥 支的塗膜表面藉使該溶液接觸塗膜表面，可於塗膜表面 %成化合物鹽之層。藉由形成前述化合物鹽之層，可使塗 21 200923017 膜表面不溶於水化或難溶於水化。 前述化合物鹽可舉例如：氣化鋁、氯化鋇、氣化鉛、 氯化鉻、氯化锶、4,4’-四甲基二胺二苯甲烷鹽酸鹽 (4,4,-tetramethyldiaminodiphenylmethane hydrochloride)、 5 2,2’-二°比°定基鹽酸鹽（2,2’- dipyridyl hydrochloride)、4,4’- 二吼咬基鹽酸鹽、三聚氰胺鹽酸鹽（melamine hydrochloride)、四胺》密咬鹽酸鹽 hydrochloride)等。 10 15 20 於含有前述化合物鹽之溶液中，該化合物鹽之濃度以3 貝里/〇〜40質置％為佳，較佳者是5質量質量〇/〇。 可使用任意方法作為使含有前述化合物鹽之溶液接觸 塗膜表面的方法。該方法可舉例如：於該塗膜之表面塗布 含有前述化合物鹽之溶㈣方法、及將該塗膜浸潰於含有 前述化合物紅溶㈣方法等。料賴等方法，則塗膜 表面宜以水或任意溶劑洗淨並乾燥。 Γ太1 步·，可叫纽«之偏光膜。 (本發明偏光膜之用途） 本發明之偏光膜，通常， 下使用。又+ ^ 積層於前述基材之狀 用又，本發明之偏光膜亦可In the above formula (III), Q4 represents the formula (a) or (b), and L!, L2, L3 and L4 are independently 10 and represent a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, substituted or absent. Substituting alkoxy group having 1 to 5 carbon atoms, halogen atom, hydroxyl group or amine group, 〇, P, q and r respectively represent an integer of 0 to 2, and S represents an integer of 0 to 4 (0, p, q, r and S satisfy 0$〇+p+q+r+s$8), and Μ denotes relative ions. In the formula (8), Q5 represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenylalkyl group, or a 15 generation or no screaming secret. S(b) towel, L5 represents a substituted alkyl group substituted with a carbon number of 1 to 5, a reduced or unsubstituted Wei 1 shoulder, a (iv) atom, a 13 200923017 hydroxyl group, or an amine group, and t represents 0 to 4 Integer. Further, the oxime of the above formula (II) and formula (III) is the same as that of the above formula (1). Since the compound (blue pigment) represented by the above formulas (Π) and (III) exhibits lyotropic liquid crystal properties by JL itself, it can be highly aligned with other blue pigments. Therefore, a polarizing film having a high dichroic absorption in a long wavelength range can be obtained. The compounds represented by the above formula (II) and (ΠΙ) may be used singly or in combination of two or more. (Other Compounds) As described above, the lyotropic liquid crystalline mixture used in the present invention may contain other compounds in addition to the yellow pigment and the blue pigment described in the above. The other compounds may be exemplified by red pigments, additives and the like. The red pigment is not particularly limited, for example: CI Direct Red 39 CIDirect Red 28 CIDirect Red 79 CIDirect Red 81 ^ CIDirect Red 83 ^ CIDirect Red 89 ^ CIAdd Red 37# 〇 15 Age Red In the case of a pigment, the content of the red pigment is preferably more than (four) parts by weight and less than the parts by weight of the lyotropic liquid crystalline mixture (10). The aforementioned additives may, for example, be surfactants, antioxidants, antistatic agents, thermal stabilizers, photostabilizers, lubricants, acidulants, UV absorbers, flame retardants, colorants and the like. In the additive, the interface activity is uniform; it is used to enhance the addition of the solution of the liquid crystal mixture of the valley to the surface of the substrate; the above surfactant is preferably a nonionic surfactant. In the case of the additive 4, the content of the additive is preferably more than 0 parts by mass and 10 parts by mass or less based on 100 parts by mass of the lyotropic liquid crystalline mixture of the above-mentioned 14 200923017. (Preparation method of polarizing film) When the liquid crystal mixture is in a solution state, a good liquid crystal phase is obtained. Therefore, a film-like polarizing film can be easily formed by applying a solution of the lyotropic liquid crystal mixture to a suitable substrate. For example, it is produced by the production method including the following steps Α to C. Step A is a step of preparing a solution containing the lyotropic liquid crystal mixture and a solvent. Step B, applying the solution obtained in the above step A to a suitable one. Forming a coating film having the yellow pigment and the blue pigment in the presence of the alignment fixing force of the substrate and/or the shear stress at the coating. Step C: The step of drying the coating film obtained in the above step B to obtain a polarizing film. <Step A> In Step A, a solution containing a lyotropic liquid crystal mixture and a solvent is prepared. The liquid crystal mixture contains at least a yellow pigment (1,8-naphthoquinone-anthracene, 2'-benzimidazole derivative) exhibiting maximum absorption at any wavelength of 20 380 nm to 480 nm, and a wavelength of 580 nm~ The blue pigment which exhibits maximum absorption at any wavelength of 680 nm may also contain other compounds as needed. The solvent is not particularly limited, and a well-known solvent can be used. It is preferred to use an aqueous solvent in the case of 200915. Water, a hydrophilic solvent, a mixed solvent of water and a hydrophilic solvent, and a hydrophilic solvent is a solvent which can be uniformly dissolved in water. Examples of the hydrophilic solvent include alcohols such as decyl alcohol, ethanol, and ethylene glycol; Lusu, ethyl 赛路苏, etc.; ketones such as acetone and 5 methyl ethyl ketone; esters such as ethyl acetate, etc. The solvent is preferably water or a mixed solvent of water and a hydrophilic solvent. . The order in which the yellow pigment, the blue dye, and other compounds to be mixed as needed is mixed in a solvent is not particularly limited. For example, a yellow dye, a blue dye, and other compounds may be simultaneously mixed in a solvent, or may be blue. 10 After mixing the pigment in the solvent, it is mixed with the solvent in the order of the yellow pigment and other compounds. Alternatively, the blue pigment and the yellow pigment may be separately mixed in different solvents to form a solution, and then the two solutions are mixed. The concentration of the lyotropic liquid crystal mixture of the solution is preferably adjusted to exhibit a concentration of the liquid crystal phase. Specifically, the concentration of the lyotropic liquid crystal 15 mixture in the solution is preferably from 1% by mass to 30% by mass. The best is 2% by mass to 20% by mass. In one part of this concentration range, the solution shows a good liquid crystal phase. Further, the pH of the solution is preferably adjusted to a pH of about 4 to 10, preferably to a pH of about 6 to 8. The viscosity of the above solution is preferably adjusted to O.lmPa.s to 30 mPa.s, and more preferably 0.5 mPa.s to 3 mPa.s. Further, the viscosity is a rheometer (manufactured by Haake Co., Ltd., product name: Bu Cai only b only 600. Measurement conditions: double cone sensor shear rate 1000 (l/s) The value of the measurement. 16 200923017 <Step B> In Step B, the coating solution is applied onto a suitable substrate to form a coating film having the yellow pigment and the blue pigment. The aforementioned substrate is used to uniformly spread the aforementioned solution. The type of the substrate is not particularly limited as long as it is suitable for the purpose, and for example, a synthetic resin film (including a generally called sheet), a glass plate, or the like can be used. In a preferred embodiment, the substrate is a separate polymeric film. In other preferred embodiments, the substrate comprises a laminate of polymeric films. The laminate containing the polymer film is preferably such that the polymer film contains an alignment layer. The polymer film is not particularly limited, but a film having excellent transparency (for example, a haze value of 5% or less) is preferred, and an isotropic film is preferred. The material of the polymer film may, for example, be a polyester such as polyethylene terephthalate or polyethylene naphthalate; a cellulose system such as diethyl phthalocyanine or triethylene sulfonate; Carbonate type; propylene type such as polymethyl methacrylate; styrene type such as polystyrene, acrylonitrile styrene copolymer; polyethylene, polypropylene, polyfluorene or norbornene structure Olefin such as terpene hydrocarbon, ethylene/propylene copolymer; vinyl chloride; guanamine such as nylon or aromatic polyamine; quinone imine such as polyamidene; polyether oxime; polyether 20 ether ketone Polyphenylene sulfide; vinyl alcohol; diethylene vinylene; ethylene butyraldehyde; acrylate; polyoxymethylene; Further, as the substrate, a polymer film containing two or more kinds of the above polymers may be used. Further, a laminate of two or more polymer films may be used as the substrate. These polymer films are preferably used as the stretch film. 17 200923017 ^The thickness of the substrate can be designed according to the strength. From the thin and light weight point of 2 points, the thickness of the above-mentioned substrate is better than that of the soil, 5~2〇〇μηι, and the best one is 1〇~1〇〇μιη. 5 When the alignment substrate comprises an alignment layer, the alignment layer is preferably formed by the treatment of the substrate. The alignment treatment may be, for example, a chemical alignment treatment such as rubbing or the like, or a photo-alignment treatment, and the alignment coating solution of the substrate may be used in the solution according to the alignment of the substrate. Each pigment is aligned. A machine can be treated by one side of the substrate (or the surface of the coating film formed on the substrate), and the cloth is formed by one side of the substrate to form an alignment layer. Further, an extended film subjected to elongation treatment may also be used. The substrate or the coating film which is subjected to the above-mentioned rubbing treatment or the like is not particularly limited, and the alignment layer may preferably be formed of a quinone imine 15 polymer as the alignment efficiency of the polydextrose exemplified as the polymer film. The chemical alignment treatment can be carried out by forming a photo-alignment film containing an alignment agent on one surface of the substrate and irradiating the photo-alignment film with light. Thereby, an alignment layer can be formed on one side of the substrate. The alignment agent may, for example, have a photochemical reaction (photoisomerization reaction, photo-opening-loop reaction, photo-dimerization reaction, photo 2 cleavage reaction, and optical Fries rearrangement). A polymer of a photoreactive functional group or the like. The above-mentioned photo-alignment film can be formed by dissolving the alignment agent in a suitable solvent to form a solution and applying it to a substrate. The solution containing the lyotropic liquid crystalline mixture is excellent in fluidity because the solid content concentration is lower than that of 18 200923017. Further, the solution can be easily subjected to a coating viscosity range of a coater (e.g., an applicator). Therefore, when the solution is used, a film-like and uniform coating film can be formed on the substrate. The method of coating the lyotropic liquid crystalline mixture described above is applied to one side of the substrate, and for example, a coating method using a suitable applicator can be used. The applicator may, for example, be a reverse roll coater, a positive roll coater, a gravure coater, a knife coater, a rod coater, or a slit die coater. Slot die coater), 〇rifice coater for slit orifice applicator (5), curtain coater, fountain coater 10, pneumatic coater (air d〇ct〇rc 〇ater), kiss coater, dip coater, drop coater, knife coater, cast coater, spray coater, spin coater, extrusion applicator, Hot melt applicator, etc. The aforementioned applicator is preferably, for example, a reverse roll coater, a positive roll coater, a gravure coater, a rod coater, a slit die coater, a slit orifice coater, a curtain coater, Fountain applicator, etc. As long as it is a coating method using these applicators, a shearing force can be applied to each of the pigments contained in the solution. As a result, a coating film obtained by aligning the pigment enthalpy can be formed. As described above, in the coating method for applying a shearing force when applying a solution, even if a substrate having no alignment layer is used, it is possible to align the respective colors. Further, even when the solution is applied by a coating method applying a shearing force as described above, it is preferable to use a substrate having an alignment layer. The coating speed of the above solution is not particularly limited, but preferably 1 〇〇mm/sec or more, preferably 500 mm/sec to 8000 mm/sec, and particularly preferably 800 mm/sec to 600 〇mm sec. When a solution containing a lyotropic liquid crystal mixture is applied at a coating speed of 1000 mm/sec to 4 mm/sec, the shearing force suitable for the alignment of the respective pigments in the solution can be applied. Therefore, it is possible to form a polarizing film having a high absorption dichroism in a wide range of visible light and having a small difference in thickness. Further, the hydrophilization treatment may be carried out on the solution-coated surface of the substrate of 5 before applying the solution containing the lyotropic liquid crystal mixture. The hydrophilization treatment is a treatment for lowering the contact angle of water. By carrying out the hydrophilization treatment, the surface can be coated with the solution to improve the wettability and coatability of the solution. Any suitable method can be used for the aforementioned hydrophilization treatment. For the hydrophilization treatment, for example, dry treatment or wet treatment can also be used. The dry treatment system 10 is, for example, a discharge treatment such as corona discharge treatment, plasma treatment, and glow discharge treatment; flame treatment; ozone treatment; uv ozone treatment; ultraviolet treatment and electron beam treatment, and the like. The treatment system is, for example, ultrasonic treatment using water, propyl or the like; treatment, combined layer treatment, and the like. These treatments may be carried out singly or in combination of two or more. The aforementioned hydrophilization treatment is preferably a corona discharge treatment, a plasma treatment, a test treatment, or a tie layer treatment. According to this hydrophilization treatment, a polarizing film having high absorption dichroism and a small difference in thickness can be formed in a wide range of visible light. <Step c> 20 The coating film coated on the substrate is dried in the step C'. When drying the coating film, for example, circulating hot air or cold air may be used to pass the heat of the type 1 furnace, using a heater such as microwave or far infrared ray, to adjust the fox's degree, the second heating roller, and the heating. Heat pipe, or heated metal belt and other dry & Drying can also be self-drying. 20 200923017 The drying temperature is below the isotropic phase transfer temperature of the solution, and (4) the heart is slowly raised to high temperature and dry. The aforementioned drying temperature is better for the thief ~ ah as a better dish for the ah ~ ah. If it is such a temperature range, a small polarizing film can be used. 5, (4) The time can be appropriately selected according to the drying temperature and the solvent type, and a polarizing film having a small difference in thickness is formed, and the drying time is, for example, 丨 minute to minute, and preferably 1 minute to 10 minutes. The coating film is fixed to the respective pigments in the coating film by an increase in concentration during drying. The amount of residual solvent of the coating film after drying is in abundance. /. The following are 10 best, preferably 〇.5% by mass or less. The dried coating film is the polarizing film of the present invention. The dried coating film (polarizing film) is laminated on the substrate. The polarizing film of the present invention can be used in a state of being laminated on a substrate, or can be used as a substrate. 15 <Step D> Further, the surface of the coating film after drying (the surface opposite to the surface layer of the substrate) is subjected to the following step D, and the water resistance of the coating film can be imparted. Step D is to contact the solution containing the compound salt with the surface of the coating film which has been dried by the above step c, and the salt of the compound is selected from the group consisting of the salt, the salt, the salt, the total salt, and the intramolecular content. At least one of the group consisting of the compound salts of the above amine groups. Specifically, the surface of the coating film of the dry branch obtained in the above step c is brought into contact with the surface of the coating film by the contact of the compound salt to form a layer of the compound salt on the surface of the coating film. By forming a layer of the aforementioned compound salt, the surface of the film 21 200923017 can be made insoluble or poorly soluble in hydration. The above compound salt may, for example, be aluminum hydride, barium chloride, lead gas, chromium chloride, barium chloride or 4,4'-tetramethyldiamine diphenylmethane hydrochloride (4,4,-tetramethyldiaminodiphenylmethane). Hydrochloride), 2,2'-dipyridyl hydrochloride, 4,4'-diguanidyl hydrochloride, melamine hydrochloride, four Amine, hydrogen chloride, etc. 10 15 20 In the solution containing the salt of the above compound, the concentration of the salt of the compound is preferably 3 Å / 〇 to 40% by mass, preferably 5 mass % 〇 / 〇. Any method can be used as a method of bringing a solution containing the salt of the aforementioned compound into contact with the surface of the coating film. In the method, for example, a method of dissolving the compound (4) containing the salt of the compound on the surface of the coating film, and a method of impregnating the coating film with red solution (4) containing the compound may be employed. If the method is used, the surface of the coating film should be washed with water or any solvent and dried. Γ too 1 step, can be called the neon's polarizing film. (Use of the polarizing film of the present invention) The polarizing film of the present invention is usually used as follows. Further, + ^ is laminated on the substrate, and the polarizing film of the present invention can also be used.
太恭了由則述基材剝離使用 本發明之偏光膜可單獨_ W 其他光學薄膜。或者，亦可視需要積 几千碍犋。刖述其他光學薄 备 薄膜箄為你I 1 、可舉保護薄膜、相位 顯寺為例。4於本發明偏 滞 構成偏光板。另外，呈積層卜之両側積層保護薄膜， 將該基材作為保護薄膜使用。：基材之狀態的偏光膜 ^此’藉僅於未積層前述 22 200923017 材側之偏光膜的面積層保護薄膜，可構成偏光板。 又，於積層相位差層時，亦可於未積層前述基材側之 偏光膜的面積層相位差薄膜。此外，亦可於前述偏光板其 中一面積層相位差薄膜。 5 另外，於本發明之偏光膜積層前述其他光學薄膜時， 於實用上，可於各層間設置任意適合之接著層。 本發明偏光膜之用途並未特別限定，但以圖像顯示裝 置的構成構件為佳。 前述圖像顯示裝置可舉例如：液晶顯示裝置、有機EL 10 顯示器、及電漿顯示器等，且以液晶顯示裝置為佳。前述 圖像顯示裝置之較佳用途係電視(特別是，畫面大小40吋以 上之大型電視）。若圖像顯示裝置為液晶顯示裝置，其較佳 用途為：電視、個人電腦螢幕、筆記型電腦、影印機等辦 公設備；手機、鐘錶、數位相機、個人數位助理(PDA)、可 15 攜式遊戲機等可攜式裝置；攝影機、微波爐等家庭用電氣 設備；倒車監視器、汽車導航系統用監視器、汽車音響等 汽車裝備；商店用資訊監視器等顯示裝置；監視用監視器 等保全設備；護理用監視器、醫療用監視器等護理、醫療 裝備等。 20 【實施例】 使用實施例及比較例更加說明本發明。另外，本發明 並不僅限於下述實施例。另外，實施例中使用之各分析方 法係如以下所述。 (1)液晶相之確認： 23 200923017 以2片載玻片挾持塗敷液，並使用偏光顯微鏡 (OLYMPUS(股）製，商品名「BX50」），一面使溫度變化一 面親察液晶相。 (2) 厚度之測定： 5 厚度之測定係剝離形成於薄膜上之偏光膜的一部份， 並使用三維非接觸表面形狀計測系統((股)Ry〇ka Systems 製，製品名「Micromap MM5200」），測定薄膜面與偏光膜 之南度差。 (3) 垂直透射率之測定方法： 10 使用具有格蘭-湯姆森偏光片之分光光度計（日本分光 (股)製’製品名「U-4100」）’使測定波長（波長42〇nm，波 長600nm)之直線偏光射入偏光膜，測定各透射率(匕及匕）。 垂直透射率(％)係由式：垂直透射率=klXk2算出。並且，前 述1^表示最大透射率方向直線偏光之透射率，k2表示與最大 15 透射率方向垂直之方向的直線偏光之透射率。 (4) 二色比(DR)之測定方法： 使用具有格蘭-湯姆森偏光片之分光光度計（曰本分光 (股）製’製品名「U-4100」），使波長540nm之直線偏光射 入偏光膜，測定各透射率（k!及k；2)。二色比（dr)係由式： 20 DRHogU/kJ/logG/k,)算出。二色比之測定方法的前述匕及 h係與前述垂直透射率之測定方法的1^及]^2同義。 (5) 最大吸收波長之測定方法： 使用具有格蘭-湯姆森偏光片之分光光度計（日本分光 (股）製’製品名「U-4100」）’測定波長380nm~780nm之各 24 200923017 透射率（1^及1^2)。另外，該1^及]^2係與前述(3)相同。 最大吸收波長係將波長380nm〜780nm之h及k2代入 式：（1^+1<;2)/2所求得之値中，成為最小値之測定波長。 [實施例] 5 使用下述式(IV)表示之1,8-伸萘甲醯基-l’，2’-苯并咪唑 衍生物(Optiva社製，商品名「Y105」）作為黃色色素，且該 1,8-伸萘曱醯基-Γ,2’-苯并咪唑衍生物於波長390nm中顯示 最大吸收。 使用下述式（V)表示之茈衍生物（Optiva社製，商品名 10 「Blue Optiva LCP dye」）作為藍色色素，且該花衍生物於 波長640nm中顯示最大吸收。 【化4】Too much to say that the substrate is peeled off. The polarizing film of the present invention can be used alone. Or, you can add thousands of obstacles as needed. Illustrate other optical thin films. For example, you can use I 1 , a protective film, and a phased temple. 4 The deflection of the present invention constitutes a polarizing plate. Further, a laminate protective film of a laminate layer was used, and the substrate was used as a protective film. The polarizing film in the state of the substrate can be formed as a polarizing plate by merely covering the area layer protective film of the polarizing film of the above-mentioned 22 200923017 material side. Further, in the case of laminating the retardation layer, the interlayer retardation film of the polarizing film on the substrate side may not be laminated. Further, a retardation film of one area may be used in the polarizing plate. Further, in the case where the above-mentioned other optical film is laminated on the polarizing film of the present invention, any suitable adhesive layer can be provided between the respective layers. The use of the polarizing film of the present invention is not particularly limited, but it is preferably a constituent member of the image display device. The image display device may, for example, be a liquid crystal display device, an organic EL 10 display, a plasma display or the like, and is preferably a liquid crystal display device. The preferred use of the aforementioned image display device is a television (in particular, a large television having a screen size of 40 吋 or more). If the image display device is a liquid crystal display device, the preferred uses are: television, personal computer screen, notebook computer, photocopying machine and other office equipment; mobile phone, clock, digital camera, personal digital assistant (PDA), portable Portable devices such as game consoles; household electrical equipment such as cameras and microwave ovens; reversing monitors, monitors for car navigation systems, car equipment such as car audio; display devices such as information monitors for stores; and security devices such as monitors for surveillance Care monitors, medical monitors, etc., medical equipment, etc. [Examples] The present invention will be further described by way of Examples and Comparative Examples. Further, the present invention is not limited to the following embodiments. Further, each analysis method used in the examples is as follows. (1) Confirmation of liquid crystal phase: 23 200923017 The coating liquid was held in two glass slides, and a liquid crystal phase was observed by a polarizing microscope (manufactured by OLYMPUS Co., Ltd., trade name "BX50"). (2) Measurement of thickness: 5 The thickness is measured by peeling off a part of the polarizing film formed on the film, and using a three-dimensional non-contact surface shape measuring system (manufactured by Ry〇ka Systems, product name "Micromap MM5200" ), the southness difference between the film surface and the polarizing film was measured. (3) Method for measuring the vertical transmittance: 10 Using a spectrophotometer (product name "U-4100" manufactured by JASCO Corporation) with a Glan-Thomson polarizer, the measurement wavelength (wavelength 42 〇 nm, A linearly polarized light having a wavelength of 600 nm was incident on the polarizing film, and each transmittance (匕 and 匕) was measured. The vertical transmittance (%) is calculated by the formula: vertical transmittance = klXk2. Further, the above 1^ indicates the transmittance of the linearly polarized light in the maximum transmittance direction, and k2 indicates the transmittance of the linearly polarized light in the direction perpendicular to the direction of the maximum 15 transmittance. (4) Measurement method of dichroic ratio (DR): Using a spectrophotometer with a Glan-Thomson polarizer (product name "U-4100" manufactured by Sakamoto Seiki Co., Ltd.), linearly polarizing a wavelength of 540 nm The polarizing film was injected, and the respective transmittances (k! and k; 2) were measured. The dichroic ratio (dr) is calculated by the formula: 20 DRHogU/kJ/logG/k,). The above-described enthalpy and h-system of the two-color ratio measuring method are synonymous with 1^ and 2^ of the above-described method for measuring the perpendicular transmittance. (5) Method for measuring the maximum absorption wavelength: Using a spectrophotometer with a Glan-Thomson polarizer (product name "U-4100" manufactured by JASCO Corporation), the wavelength of each wavelength is 380 nm to 780 nm. 200923017 Transmission Rate (1^ and 1^2). In addition, this 1 and the ^2 are the same as the above (3). The maximum absorption wavelength is obtained by substituting h and k2 of a wavelength of 380 nm to 780 nm into a formula obtained by (1^+1 <; 2)/2, which is the measurement wavelength of the minimum chirp. [Examples] 5 A 1,8-naphthoquinone-l',2'-benzimidazole derivative (trade name "Y105", manufactured by Optiva Co., Ltd.) represented by the following formula (IV) was used as a yellow pigment. And the 1,8-naphthoquinone-fluorene, 2'-benzimidazole derivative showed maximum absorption at a wavelength of 390 nm. An anthracene derivative (trade name: "Blue Optiva LCP dye", manufactured by Optiva Co., Ltd.) represented by the following formula (V) was used as a blue pigment, and the flower derivative showed maximum absorption at a wavelength of 640 nm. 【化4】
準備混合有前述黃色色素1.2質量份與前述藍色色素 15 10質量份之混合物（混合物100質量份中，黃色色素約為10.7 25 200923017 質量份，藍色色素約為89.3質量份）。將該混合物溶解於水 中調製固體含量濃度為10質量％之溶液。於偏光顯微鏡觀 察該溶液時，顯示向列型液晶相。 使用塗布棒（BUSCHMAN社製，商品名r mayer r〇t 5 HS1.5」），於剪切應力存在下，將含有前述各色素之溶液， 均勻塗布於經施行電暈放電處理的聚合物薄膜（日本 ΖΕΟΝ(股)製，商品名「ZE0N0R」）之電暈放電處理面，使 前述各色素配向。之後’藉於23°C之恆溫室内使其自然乾 燥，製作乾燥塗膜(偏光膜）。所得之偏光膜厚度係〇 4μ〇ι。 10 於表1顯示該偏光膜之光學特性。 【表1】 實施例 比較例1 一 垂直透射率(％) ~~ 二色比 灰長540nm 波長420nm 波長600nm 22 10 26 34 12 19 比較例2 Γ 33 15 10 [比較例1 ] 除了未使用黃色色素以外，與前述實施例同構地製作 偏光膜。 15 具體而言，僅將前述式(ν)表示之茈衍生物（藍色色素) 溶解於水，調製固體含量濃度10質量％之溶液。於偏光顯 微鏡觀察該溶液時，顯示向列型液晶相。 與前述實施例同様地，將該溶液塗布於聚合物薄膜之 電暈放電處理面，並乾燥。所得之偏光膜厚度飢4哗。於 20 表1顯示該偏光膜之光學特性。 [比較例2] 26 200923017 除了使用下述式(νι)表示之黃色色素（東京化成工業社 製，商品名「Brilliant Yellow」）8質量份，取代前述實施例 之黃色色素以外，與前述實施例同様地，製作偏光膜。 【化6】A mixture of 1.2 parts by mass of the yellow pigment and 10 parts by mass of the blue pigment 15 is prepared (in a mixture of 100 parts by mass, a yellow pigment is about 10.75 25 200923017 parts by mass, and a blue pigment is about 89.3 parts by mass). The mixture was dissolved in water to prepare a solution having a solid content concentration of 10% by mass. When the solution was observed under a polarizing microscope, a nematic liquid crystal phase was shown. Using a coating bar (manufactured by BUSCHMAN, trade name r mayer r〇t 5 HS1.5), the solution containing each of the above-mentioned dyes was uniformly applied to the polymer film subjected to corona discharge treatment in the presence of shear stress. The corona discharge treatment surface of the product (product name "ZE0N0R" manufactured by Nippon Co., Ltd.) is used to align the respective pigments. Thereafter, it was naturally dried by a constant temperature room at 23 ° C to prepare a dried coating film (polarizing film). The resulting polarizing film thickness was 〇 4 μ〇ι. 10 The optical characteristics of the polarizing film are shown in Table 1. [Table 1] Example Comparative Example 1 A vertical transmittance (%) ~~ Two-color ratio Gray length 540 nm Wavelength 420 nm Wavelength 600 nm 22 10 26 34 12 19 Comparative Example 2 Γ 33 15 10 [Comparative Example 1] Except that yellow was not used In addition to the pigment, a polarizing film was produced in the same manner as in the above examples. Specifically, only the anthracene derivative (blue pigment) represented by the above formula (ν) was dissolved in water to prepare a solution having a solid content concentration of 10% by mass. When the solution was observed by a polarizing microscope, a nematic liquid crystal phase was observed. In the same manner as the foregoing examples, the solution was applied to a corona discharge treated surface of a polymer film and dried. The resulting polarizing film is hungry. Table 20 shows the optical characteristics of the polarizing film. [Comparative Example 2] 26 200923017 In addition to the yellow pigment (manufactured by Tokyo Chemical Industry Co., Ltd., trade name "Brilliant Yellow"), which is represented by the following formula (νι), in place of the yellow pigment of the above-mentioned examples, the foregoing examples At the same time, a polarizing film is produced. 【化6】
…（VI 5 具體而言，混合前述式(VI)表示之黃色色素8質量份與 前述式（V)表示之茈衍生物（藍色色素）10質量份，並使該混 合物溶解於水中，調製固體含量濃度10質量％之溶液。於 偏光顯微鏡觀察該溶液時，顯示向列型液晶相。 與前述實施例同様地，將該溶液塗布於聚合物薄膜之 10 電暈放電處理面，並乾燥。所得之偏光膜厚度係〇·4μιη。於 表1顯示該偏光膜之光學特性。 如表1所示，實施例之偏光膜於波長420nm及波長 600nm中之垂直透射率較比較例1及比較例2低，且於短波長 側及長波長側具有高吸收二色性。又，實施例之偏光膜之 15 二色比亦較比較例1及比較例2優異。 【圖式簡單說明3 無 【主要元件符號說明】 益 27In particular, 8 parts by mass of the yellow pigment represented by the above formula (VI) and 10 parts by mass of the anthracene derivative (blue pigment) represented by the above formula (V) are mixed, and the mixture is dissolved in water to prepare A solution having a solid content concentration of 10% by mass. When the solution was observed under a polarizing microscope, a nematic liquid crystal phase was observed. As in the previous examples, the solution was applied to a 10 corona discharge treated surface of a polymer film, and dried. The obtained polarizing film thickness was 〇·4 μm. The optical characteristics of the polarizing film are shown in Table 1. As shown in Table 1, the polarizing films of the examples had vertical transmittances at a wavelength of 420 nm and a wavelength of 600 nm, compared with Comparative Example 1 and Comparative Example. 2 is low, and has high absorption dichroism on the short-wavelength side and the long-wavelength side. Moreover, the 15-color ratio of the polarizing film of the example is also superior to that of Comparative Example 1 and Comparative Example 2. [Simple description of the figure 3 No [ Main component symbol description] Benefit 27