JP7024458B2 - Anisotropic dye film forming composition, anisotropic dye film and polarizing element - Google Patents

Anisotropic dye film forming composition, anisotropic dye film and polarizing element Download PDF

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JP7024458B2
JP7024458B2 JP2018015847A JP2018015847A JP7024458B2 JP 7024458 B2 JP7024458 B2 JP 7024458B2 JP 2018015847 A JP2018015847 A JP 2018015847A JP 2018015847 A JP2018015847 A JP 2018015847A JP 7024458 B2 JP7024458 B2 JP 7024458B2
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祐三 金子
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Mitsubishi Chemical Corp
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Description

本発明は、湿式成膜法により形成される異方性色素膜、特に、調光素子、液晶素子（ＬＣＤ）及び有機エレクトロルミネッセンス素子（ＯＬＥＤ）の表示素子に具備される偏光膜等に有用な高い二色性を示す異方性色素膜形成用組成物、異方性色素膜及び偏光素子に関するものである。 INDUSTRIAL APPLICABILITY The present invention is useful for an anisotropic dye film formed by a wet film forming method, particularly a polarizing film provided in a display element of a dimming element, a liquid crystal element (LCD) and an organic electroluminescence element (OLED). The present invention relates to a composition for forming an anisotropic dye film, an anisotropic dye film and a polarizing element, which exhibit high dichroism.

ＬＣＤでは、表示における旋光性や複屈折性を制御するために直線偏光膜及び円偏光膜が用いられている。ＯＬＥＤにおいても、外光の反射防止のために円偏光膜が使用されている。
従来、これらの偏光膜にはヨウ素が二色性物質として広く使用されてきた。しかしながら、ヨウ素は昇華性が大きいために、偏光膜を用いた偏光素子として使用した場合、その耐熱性や耐光性が十分ではなかった。また、その消光色が深い青色となるため、全可視スペクトル領域に亘って、理想的な無彩色の偏光素子とは言えなかった。 In the LCD, a linear polarizing film and a circular polarizing film are used to control the optical rotation and birefringence in the display. Also in the OLED, a circular polarizing film is used to prevent reflection of external light.
Conventionally, iodine has been widely used as a dichroic substance in these polarizing films. However, since iodine has a high sublimation property, its heat resistance and light resistance are not sufficient when it is used as a polarizing element using a polarizing film. Further, since the quenching color is deep blue, it cannot be said that it is an ideal achromatic polarizing element over the entire visible spectrum region.

理想的な無彩色の偏光素子を得るために、有機系の色素を二色性物質に使用する異方性色素膜が検討されている。有機系の色素を使用する異方性色素膜としては、従来のポリマーに有機系の色素を含浸させた膜、基板等の上に有機系の色素を塗布することで膜を得る方法（湿式成膜法）を用いて形成させた膜等が挙げられる。
従来のポリマーに有機系の色素を含浸させた異方性色素膜を用いる場合、該異方性色素膜に接着層を設け、接着層の保護フィルムを貼り合わせ、該保護フィルムを貼り合せた偏光膜をディスプレイ製造ラインに移送し、ディスプレイ製造ラインで保護フィルムを剥がし、異方性色素膜を基板等に貼合するというプロセスが取られている。これをガラスや透明フィルム等の基板上に、湿式成膜法を用いて異方性色素膜を形成する方法に置き換えれば、前記の従来のポリマーに有機系の色素を含浸させた異方性色素膜を用いる方法と比較して、製造プロセスを簡略化でき、生産性向上に寄与するものと考えられる。 In order to obtain an ideal achromatic polarizing element, an anisotropic dye film using an organic dye as a dichroic substance has been studied. As an anisotropic dye film using an organic dye, a method of obtaining a film by applying an organic dye on a conventional polymer impregnated with an organic dye, a substrate, or the like (wet formation). Examples thereof include a membrane formed by using the membrane method).
When an anisotropic dye film obtained by impregnating a conventional polymer with an organic dye is used, an adhesive layer is provided on the anisotropic dye film, a protective film of the adhesive layer is attached, and the polarizing film to which the protective film is attached is attached. A process is taken in which the film is transferred to a display manufacturing line, the protective film is peeled off at the display manufacturing line, and the anisotropic dye film is attached to a substrate or the like. If this is replaced with a method of forming an anisotropic dye film on a substrate such as glass or a transparent film by using a wet film forming method, the anisotropic dye obtained by impregnating the above-mentioned conventional polymer with an organic dye. Compared with the method using a membrane, the manufacturing process can be simplified and it is considered that it contributes to the improvement of productivity.

特許文献１には二色比の高い異方性色素膜を得るための、トリスアゾ色素を含む異方性色素膜形成用組成物が示されている。
また、異方性色素膜の高い二色比を得るために、特定の色素を組み合わせて用いることが示されている。例えば、アントラキノン環を有するアゾ化合物と、ナフタレン環を有するジスアゾ色素とを含む異方性色素膜形成用組成物（特許文献２）、ジスアゾ色素とモノアゾ化合物とを含む異方性色素膜形成用組成物（特許文献３）、ジスアゾ色素を２種組み合わせて用いて異方性色素膜を得たことも示されている（特許文献４及び５）。 Patent Document 1 discloses an anisotropic dye film forming composition containing a trisazo dye for obtaining an anisotropic dye film having a high two-color ratio.
It has also been shown that specific dyes are used in combination in order to obtain a high two-color ratio of the anisotropic dye film. For example, an anisotropic dye film forming composition containing an azo compound having an anthraquinone ring and a disuazo dye having a naphthalene ring (Patent Document 2), and an anisotropic dye film forming composition containing a disazo dye and a monoazo compound. It is also shown that an anisotropic dye film was obtained by using a compound (Patent Document 3) and two kinds of disazo dyes in combination (Patent Documents 4 and 5).

異方性色素膜の性能を向上させるため、添加材の開発が同時に進められている。例えば、二色性の向上や耐熱性の向上を目的としてアミノ酸などを添加する組成物が開発されている（特許文献６）。また、アミノ酸以外にも、界面活性剤の添加により塗布時の基板への濡れ性を向上させると同時に、乾燥過程で界面活性剤が気液界面に集積することで色素の異方性を阻害せずに、二色比が向上する検討がなされている（特許文献７）。 In order to improve the performance of the anisotropic dye film, the development of additives is being promoted at the same time. For example, a composition to which an amino acid or the like is added has been developed for the purpose of improving dichroism and heat resistance (Patent Document 6). In addition to amino acids, the addition of a surfactant improves the wettability to the substrate during coating, and at the same time, the surfactant accumulates at the gas-liquid interface during the drying process, thereby inhibiting the anisotropy of the dye. Instead, studies have been made to improve the two-color ratio (Patent Document 7).

特開２０１０－１６８５７０号公報Japanese Unexamined Patent Publication No. 2010-168570 特開２００８－１０１１５４号公報Japanese Unexamined Patent Publication No. 2008-101154 特開２０１２－１９４３５７号公報Japanese Unexamined Patent Publication No. 2012-194357 特開２００７－１２６６２８号公報Japanese Unexamined Patent Publication No. 2007-126628 国際公開第２０１５／０８７９７８号International Publication No. 2015/087798 国際公開第２００５／０６９０４８号International Publication No. 2005/069048 特開２００９－１８０９７５号公報Japanese Unexamined Patent Publication No. 2009-180975

一方、化合物を添加することにより発生する耐湿性低下に対して、色素と特定の高分子化合物を含む異方性色素膜形成用組成物を用いることで、耐湿性の問題を解決できることが示されている（特願２０１７－２４３２６４号）。 On the other hand, it has been shown that the problem of moisture resistance can be solved by using a composition for forming an anisotropic dye film containing a dye and a specific polymer compound against the decrease in moisture resistance caused by the addition of the compound. (Japanese Patent Application No. 2017-243264).

本発明者達は、特願２０１７－２４３２６４号等に記載の高分子化合物を含む異方性色素膜形成用組成物用いて異方性色素膜を形成する場合、高分子化合物の添加により、吸湿により発生する膜欠陥を抑制し、膜硬度が高くなることを見出した。一方、高分子化合物の添加により、粘度増加が発生し、塗布膜厚が不均一化する場合があることも見出した。具体的には、塗布装置にバーコーター等を用いる場合、塗布時に形成される塗布スジにより塗布膜の均一性が不足する場合があった。量産性向上のためロールツーロール方式等を用いる場合、高い塗布速度を維持するためにはバーコーター等が有用であり、上記問題を含む場合には生産性において問題となる。
また、特許文献７等に記載の界面活性剤を添加すると、異方性色素膜形成用組成物の粘度変動、異方性色素の会合及び配向状態への影響が無視できず、異方性色素膜形成用組成物を塗布する際の量産性向上と異方性色素膜の二色比維持を両立させることが困難であった。
さらに、量産時においては異方性色素膜形成用組成物の保管安定性が高いことも求められる。
本発明は、上記の方法で得られる効果と課題を両立させる異方性色素膜形成用組成物及び異方性色素膜を提供するものである。具体的には、保管安定性に優れ、均一塗布が可能である異方性色素膜形成用組成物、並びに、耐湿性に優れることで経時での膜欠陥を抑制し、膜硬度が高く、さらに二色比に優れた異方性色素膜を提供することを課題とする。 When the present inventors form an anisotropic dye film by using the composition for forming an anisotropic dye film containing the polymer compound described in Japanese Patent Application No. 2017-243264, the present inventors absorb moisture by adding the polymer compound. It has been found that the film defects generated by the above are suppressed and the film hardness is increased. On the other hand, it has also been found that the addition of the polymer compound causes an increase in viscosity and the coating film thickness may become non-uniform. Specifically, when a bar coater or the like is used as the coating device, the uniformity of the coating film may be insufficient due to the coating streaks formed at the time of coating. When a roll-to-roll method or the like is used to improve mass productivity, a bar coater or the like is useful for maintaining a high coating speed, and when the above problems are included, there is a problem in productivity.
Further, when the surfactant described in Patent Document 7 or the like is added, the influence on the viscosity fluctuation of the anisotropic dye film forming composition, the association of the anisotropic dye and the orientation state cannot be ignored, and the anisotropic dye cannot be ignored. It has been difficult to improve mass productivity when applying the film-forming composition and maintain the two-color ratio of the anisotropic dye film at the same time.
Further, at the time of mass production, it is also required that the composition for forming an anisotropic dye film has high storage stability.
The present invention provides a composition for forming an anisotropic dye film and an anisotropic dye film that achieve both the effects obtained by the above method and the problems. Specifically, the composition for forming an anisotropic dye film having excellent storage stability and being able to be uniformly applied, and the excellent moisture resistance suppresses film defects over time, has high film hardness, and further. An object of the present invention is to provide an anisotropic dye film having an excellent two-color ratio.

本発明者らは、色素と特定の高分子化合物、並びに特定の水溶性有機化合物を含む異方性色素膜形成用組成物を用いることにより、前記課題を解決できることを見出した。
すなわち、本発明は以下を要旨とする。 The present inventors have found that the above problems can be solved by using a composition for forming an anisotropic dye film containing a dye, a specific polymer compound, and a specific water-soluble organic compound.
That is, the gist of the present invention is as follows.

［１］色素、酸性基及び塩基性基を有する高分子化合物、並びに水溶性有機化合物を含むものである、異方性色素膜形成用組成物。
［２］前記塩基性基がアミノ基を含むものである、［１］に記載の異方性色素膜形成用組成物。
［３］前記酸性基がスルホ基を含むものである、［１］又は［２］に記載の異方性色素膜形成用組成物。
［４］前記酸性基の少なくとも一部が塩型の酸性基であり、前記塩型の酸性基の対カチオンが、リチウムイオン及び／又はナトリウムイオンである、［１］～［３］のいずれか１項に記載の異方性色素膜形成用組成物。
［５］前記塩基性基及び／又は前記酸性基が、芳香族性の部分構造を有さないものである、［１］～［４］のいずれか１項に記載の異方性色素膜形成用組成物。
［６］前記水溶性有機化合物が親水基及び疎水基を有するものである、［１］～［５］のいずれか１項に記載の異方性色素膜形成用組成物。
［７］色素、酸性基及び塩基性基を有する高分子化合物、並びに水溶性有機化合物を含むものである、異方性色素膜。
［８］［７］に記載の異方性色素膜を含む、偏光素子。 [1] A composition for forming an anisotropic dye film, which comprises a dye, a polymer compound having an acidic group and a basic group, and a water-soluble organic compound.
[2] The composition for forming an anisotropic dye film according to [1], wherein the basic group contains an amino group.
[3] The composition for forming an anisotropic dye film according to [1] or [2], wherein the acidic group contains a sulfo group.
[4] Any of [1] to [3], wherein at least a part of the acidic group is a salt-type acidic group, and the counter cation of the salt-type acidic group is a lithium ion and / or a sodium ion. Item 2. The composition for forming an anisotropic dye film according to Item 1.
[5] The anisotropic dye film formation according to any one of [1] to [4], wherein the basic group and / or the acidic group does not have an aromatic partial structure. Composition for.
[6] The composition for forming an anisotropic dye film according to any one of [1] to [5], wherein the water-soluble organic compound has a hydrophilic group and a hydrophobic group.
[7] An anisotropic dye film containing a dye, a polymer compound having an acidic group and a basic group, and a water-soluble organic compound.
[8] A polarizing element including the anisotropic dye film according to [7].

本発明は、保管安定性に優れ、均一塗布が可能である異方性色素膜形成用組成物を提供するものである。また、耐湿性に優れることで経時での膜欠陥を抑制し、膜硬度が高く、さらに二色比に優れた異方性色素膜を提供するものである。
具体的には、水溶性有機化合物を含有する本発明の異方性色素膜形成用組成物を用いることにより、形成された異方性色素膜の耐湿性及び硬度の向上、経時での膜欠陥の抑制が期待できる。また、製造時における保管環境に対するマージンの向上により安定製造に寄与するほか、保管環境の安価化が図れるものである。さらに、異方性色素膜組成物を塗布する際の膜厚分布により形成される塗布膜の不均一性を抑制し、量産性に優れた異方性色素膜を形成するものである。 The present invention provides a composition for forming an anisotropic dye film, which has excellent storage stability and can be uniformly applied. Further, the present invention provides an anisotropic dye film having excellent moisture resistance, suppressing film defects over time, having high film hardness, and having an excellent two-color ratio.
Specifically, by using the composition for forming an anisotropic dye film of the present invention containing a water-soluble organic compound, the moisture resistance and hardness of the formed anisotropic dye film are improved, and film defects over time are achieved. Can be expected to be suppressed. In addition, it contributes to stable manufacturing by improving the margin for the storage environment at the time of manufacturing, and also makes it possible to reduce the cost of the storage environment. Further, it suppresses the non-uniformity of the coating film formed by the film thickness distribution when the anisotropic dye film composition is applied, and forms an anisotropic dye film having excellent mass productivity.

以下、本発明の実施の形態を具体的に説明するが、本発明は、以下の実施の形態に限定されるものではなく、その要旨の範囲内で種々に変更して実施することができる。 Hereinafter, embodiments of the present invention will be specifically described, but the present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.

本発明でいう異方性色素膜とは、異方性色素膜の厚み方向及び任意の直交する面内２方向の立体座標系における合計３方向から選ばれる、任意の２方向における電磁気学的性質に異方性を有する色素膜である。電磁気学的性質としては、吸収、屈折等の光学的性質、抵抗、容量等の電気的性質等が挙げられる。
吸収、屈折等の光学的異方性を有する膜としては、例えば、直線偏光膜、円偏光膜等の偏光膜、位相差膜、導電異方性色素膜等がある。本発明の異方性色素膜は、偏光膜、位相差膜及び導電異方性色素膜に用いられることが好ましく、偏光膜に用いられることがより好ましい。 The anisotropic dye film as used in the present invention is an electromagnetic property in any two directions selected from a total of three directions in a three-dimensional coordinate system in the thickness direction of the anisotropic dye film and two directions in any orthogonal plane. It is a dye film having anisotropy. Examples of electromagnetic properties include optical properties such as absorption and refraction, and electrical properties such as resistance and capacitance.
Examples of the film having optical anisotropy such as absorption and refraction include a linear polarizing film, a polarizing film such as a circular polarizing film, a retardation film, and a conductive anisotropic dye film. The anisotropic dye film of the present invention is preferably used for a polarizing film, a retardation film, and a conductive anisotropic dye film, and more preferably used for a polarizing film.

［異方性色素膜形成用組成物］
まず、本発明の異方性色素膜形成用組成物について説明する。
本発明の異方性色素膜形成用組成物は、色素、酸性基及び塩基性基を有する高分子化合物、並びに水溶性有機化合物を含むものである。
本発明の異方性色素膜形成用組成物が効果を奏する理由は定かではないが、以下が考えられる。
本発明の異方性色素膜形成用組成物及び異方性色素膜中において、色素はその異方性を発現するため、ある程度の大きさを有する集合体を形成する。特許文献６に記載のアミノ酸等の化合物は、この色素集合体をつなぎ、固定していると推定される。
本発明の異方性色素膜形成用組成物が含む高分子化合物が有する酸性基又は塩基性基は、水分子との相性が良く、吸湿性を持つため、異方性色素膜は水分を吸着しやすい性質がある。前記色素集合体のつなぎとなっているアミノ酸などの化合物同士は弱い水素結合で結ばれており、吸湿によりその会合力が弱くなる。つまり、吸湿により、色素集合体の固定が緩和され、析出やひび割れが起こってしまうと推定される。
一方で、本発明の高分子化合物を用いることにより、アミノ酸などの化合物同士の弱い水素結合のネットワークの一部を強固な原子結合に置き換えることになる。つまり、吸湿しても、色素の集合体の固定状態を維持できると推定される。従って、耐湿性に優れた、吸湿による経時での膜欠陥の発生が抑制される。
また、色素単独で形成する異方性色素膜は脆くなる傾向にあるため硬度が低くなるが、本願発明の高分子化合物を添加することで可塑剤的な効果により脆さが解消され、硬度が向上すると推定される。
一方、上記高分子化合物を含む異方性色素膜形成用組成物用は、高分子添加による粘度増加により塗布膜厚が不均一化し、生産性において大きな問題となる傾向にある。
本発明では、異方性色素膜形成用組成物に水溶性有機化合物を含むことで、高分子化合物を含むことにより得られる効果を損なうことなく、上記課題を解決する。具体的には、異方性色素膜形成用組成物の粘度や表面張力を最適化し、塗布特性を向上しながらも異方性色素の会合及び配向状態も最適な状態とすることが可能となる。さらに具体的には、水溶性有機化合物を添加することで、保管安定性が向上し、基板への濡れ性改善、粘度や表面張力低下による塗布膜厚不均一化を解消しながらも、得られた塗布膜の二色比は高い状態となる。 [Composition for forming an anisotropic dye film]
First, the composition for forming an anisotropic dye film of the present invention will be described.
The composition for forming an anisotropic dye film of the present invention contains a dye, a polymer compound having an acidic group and a basic group, and a water-soluble organic compound.
The reason why the composition for forming an anisotropic dye film of the present invention is effective is not clear, but the following can be considered.
In the composition for forming an anisotropic dye film and the anisotropic dye film of the present invention, the dye exhibits the anisotropy and thus forms an aggregate having a certain size. It is presumed that the compounds such as amino acids described in Patent Document 6 connect and fix the dye aggregates.
Since the acidic group or the basic group contained in the polymer compound contained in the composition for forming an anisotropic dye film of the present invention has good compatibility with water molecules and has hygroscopicity, the anisotropic dye film adsorbs water. It has the property of being easy to do. Compounds such as amino acids that are the linking dye aggregates are bound by weak hydrogen bonds, and their associative power is weakened by moisture absorption. That is, it is presumed that the moisture absorption relaxes the fixation of the dye aggregate and causes precipitation and cracking.
On the other hand, by using the polymer compound of the present invention, a part of the network of weak hydrogen bonds between compounds such as amino acids is replaced with strong atomic bonds. That is, it is presumed that the fixed state of the dye aggregate can be maintained even if moisture is absorbed. Therefore, the occurrence of film defects over time due to moisture absorption, which is excellent in moisture resistance, is suppressed.
Further, the anisotropic dye film formed by the dye alone tends to be brittle, so that the hardness is low. However, by adding the polymer compound of the present invention, the brittleness is eliminated by the effect of a plasticizer and the hardness is reduced. It is estimated that it will improve.
On the other hand, in the composition for forming an anisotropic dye film containing the above polymer compound, the coating film thickness becomes non-uniform due to the increase in viscosity due to the addition of the polymer, which tends to cause a big problem in productivity.
In the present invention, by including the water-soluble organic compound in the composition for forming an anisotropic dye film, the above-mentioned problems are solved without impairing the effect obtained by containing the polymer compound. Specifically, it is possible to optimize the viscosity and surface tension of the composition for forming an anisotropic dye film, and to optimize the association and orientation of the anisotropic dye while improving the coating characteristics. .. More specifically, by adding a water-soluble organic compound, storage stability is improved, wettability to the substrate is improved, and non-uniform coating film thickness due to a decrease in viscosity and surface tension is eliminated. The two-color ratio of the coated film is high.

上記異方性色素膜形成用組成物の態様としては、上記の高分子化合物、水溶性有機化合物及び色素を含めば特に限定されない。異方性色素膜形成用組成物が相分離を引き起こさない状態であれば、溶液であっても、液晶であっても、分散状態であってもよいが、異方性色素膜形成用組成物として液晶相の状態であることが、溶剤が蒸発した後に形成される異方性色素膜が高配向度に形成される観点から好ましい。なお、本実施の形態において、液晶相の状態であるとは、具体的には、『液晶の基礎と応用』（松本正一・角田市良著、１９９１）の１～１６ページに記載されているように、液体と結晶の双方の性質を示す液晶状態であり、ネマティック相、コレステリック相、スメクティック相又はディスコティック相であることをいう。特に、溶液中での秩序性が低く、粘度が低い傾向にあるため、液晶相はネマティック相が好ましい。 The embodiment of the composition for forming an anisotropic dye film is not particularly limited as long as the above-mentioned polymer compound, water-soluble organic compound and dye are included. As long as the composition for forming an anisotropic dye film does not cause phase separation, it may be a solution, a liquid crystal, or a dispersed state, but the composition for forming an anisotropic dye film may be in a dispersed state. The liquid crystal phase is preferable from the viewpoint that the anisotropic dye film formed after the solvent evaporates is formed with a high degree of orientation. In this embodiment, the state of the liquid crystal phase is specifically described on pages 1 to 16 of "Fundamentals and Applications of Liquid Crystals" (Shoichi Matsumoto and Ichiyoshi Tsunoda, 1991). As described above, it is a liquid crystal state exhibiting the properties of both a liquid and a crystal, and is a nematic phase, a cholesteric phase, a smectic phase, or a discotic phase. In particular, the liquid crystal phase is preferably a nematic phase because the order in the solution is low and the viscosity tends to be low.

（高分子化合物）
本発明の異方性色素膜形成用組成物に用いることができる高分子化合物は、酸性基及び塩基性基を有する高分子化合物（以下、本明細書において「高分子化合物」と表すことがある。）である。 (Polymer compound)
The polymer compound that can be used in the composition for forming an anisotropic dye film of the present invention may be referred to as a polymer compound having an acidic group and a basic group (hereinafter, referred to as “polymer compound” in the present specification. .).

本発明の異方性色素膜形成用組成物に含まれる高分子化合物が有する置換基については、以下のように説明できる。
本発明の異方性色素膜を形成するには、相分離を起こさない液晶性の組成物を形成する事が好ましい。そのためには、色素と高分子化合物が会合体を形成し、且つ、色素同士が積層した色素集合体が形成されることが必要である。後述するが、色素は、水溶性を発現させるために、酸性基又は塩基性基を有する場合がある。塩基性基は通常正電荷又はカチオン性を、酸性基は通常負電荷又はアニオン性を有する。そのため、色素と高分子化合物が会合対を形成するためには、高分子化合物は酸性基又は塩基性基を有する必要がある。このとき、高分子化合物が酸性基又は塩基性基のどちらか一方の基のみを有する場合、色素と強く会合するか、強く反発を引き起こすかのいずれかが起こると推定される。前者の場合、高分子化合物を介して色素会合体同士が架橋され、均一な液晶相の形成が困難となる。一方後者の場合、同じ電荷を有するが故に色素と高分子化合物がそれぞれ独自の凝集体を形成し、相分離状態となってしまうと推定される。そのため、高分子化合物は酸性基と塩基性基を同時に有することが好ましい。 Substituents contained in the polymer compound contained in the composition for forming an anisotropic dye film of the present invention can be described as follows.
In order to form the anisotropic dye film of the present invention, it is preferable to form a liquid crystal composition that does not cause phase separation. For that purpose, it is necessary that the dye and the polymer compound form an aggregate, and a dye aggregate in which the dyes are laminated is formed. As will be described later, the dye may have an acidic group or a basic group in order to develop water solubility. Basic groups are usually positively charged or cationic, and acidic groups are usually negatively charged or anionic. Therefore, in order for the dye and the polymer compound to form an association pair, the polymer compound needs to have an acidic group or a basic group. At this time, when the polymer compound has only one of the acidic group and the basic group, it is presumed that either the dye strongly associates with the dye or the strong repulsion is caused. In the former case, the dye aggregates are crosslinked with each other via the polymer compound, making it difficult to form a uniform liquid crystal phase. On the other hand, in the latter case, it is presumed that the dye and the polymer compound each form their own aggregates because they have the same charge, resulting in a phase-separated state. Therefore, it is preferable that the polymer compound has an acidic group and a basic group at the same time.

高分子化合物が有する酸性基及び塩基性基は、以下の通りである。
酸性基及び塩基性基とは、それぞれ、酸性基は７未満、塩基性基は７以上のｐＫａを有する官能基のことである。なお、ｐＫａとは、濃度酸解離定数Ｋａの逆数の対数値、すなわち－ｌｏｇ Ｋａである。 The acidic and basic groups of the polymer compound are as follows.
The acidic group and the basic group are functional groups having a pKa of less than 7 as an acidic group and 7 or more as a basic group, respectively. Note that pKa is the logarithm of the reciprocal of the concentration acid dissociation constant Ka, that is, -log Ka.

高分子化合物が有する酸性基としては、例えば、スルホ基、カルボキシル基、リン酸基などが挙げられる。これらの中でも、色素の積層崩壊を抑制するため、酸性基は、芳香族性の部分構造を有しないことが好ましい。また、水溶性の維持と秩序性の向上の観点では、酸性基はスルホ基を含むことが好ましく、とりわけスルホ基が望ましい。 Examples of the acidic group contained in the polymer compound include a sulfo group, a carboxyl group, and a phosphoric acid group. Among these, it is preferable that the acidic group does not have an aromatic partial structure in order to suppress the layered disintegration of the dye. Further, from the viewpoint of maintaining water solubility and improving orderability, the acidic group preferably contains a sulfo group, and a sulfo group is particularly preferable.

塩基性基としては、含窒素塩基性基（電子供与性の窒素原子を含み、該窒素原子が正電荷又はカチオン性を有しやすい性質を持つものが好ましい。）が挙げられ、アミノ基、アルキルアミノ基（メチルアミノ基、エチルアミノ基等）、ピロリル基、３-ピロリニル基、ピロリジニル基、ピラゾーリル基、２－ピラゾリニル基、ピラゾリジニル基、イミダゾリル基、１，２，３－トリアゾリル基、１，２，４－トリアゾリル基、ピリジニル基、ピリダジニル基、ピペリジニル基、ピラジニル基、ピペラジニル基、ピリミジニル基、トリアジニル基等が挙げられる。これらの中でも、色素の積層崩壊を抑制するため、塩基性基は、芳香族性の部分構造を有しないことが好ましく、特にアミノ基を含むことが好ましく、とりわけアミノ基が望ましい。 Examples of the basic group include a nitrogen-containing basic group (preferably one containing an electron-donating nitrogen atom and having a property that the nitrogen atom tends to have a positive charge or a cationic property), and an amino group and an alkyl group. Amino group (methylamino group, ethylamino group, etc.), pyrrolyl group, 3-pyrrolinyl group, pyrrolidinyl group, pyrazolyl group, 2-pyrazolinyl group, pyrazoridinyl group, imidazolyl group, 1,2,3-triazolyl group, 1,2 , 4-Triazolyl group, pyridinyl group, pyridadinyl group, piperidinyl group, pyrazinyl group, piperazinyl group, pyrimidinyl group, triazinyl group and the like. Among these, in order to suppress the layered disintegration of the dye, the basic group preferably does not have an aromatic partial structure, and particularly preferably contains an amino group, and particularly preferably an amino group.

高分子化合物に含まれる酸性基と塩基性基は、それぞれその一部または全部が塩型をとってもよい。
酸性基の少なくとも一部は塩型の酸性基であってもよく、酸性基の対カチオンとしては、ナトリウム、リチウム、カリウム等のアルカリ金属、アルキル基もしくはヒドロキシアルキル基で置換されていてもよいアンモニウム、有機アミン等が挙げられる。有機アミンの例として、炭素数１以上、６以下の低級アルキルアミン、ヒドロキシ置換された炭素数１以上、６以下の低級アルキルアミン、カルボキシ置換された炭素数１以上、６以下の低級アルキルアミン等が挙げられる。これらの塩型の場合、その種類は１種類に限られず、複数種混在していてもよい。溶解性の観点から、イオン化傾向が高いアルカリ金属の塩が望ましい。特に、リチウム及び／又はナトリウムが好ましく、色素と高分子化合物とを含む組成物の相分離を抑制し、溶解性を向上する観点から、リチウムが特に好ましい。また、色素と高分子化合物とを含む組成物からなる膜の二色比を高める観点からも、リチウムが特に好ましい。
塩基性基の少なくとも一部は塩型の塩基性基であってもよく、塩基性基の塩型としては、例えば、塩酸、硫酸等の無機酸の塩、酢酸、ギ酸等の有機酸の塩が挙げられる。 The acidic group and the basic group contained in the polymer compound may be partially or wholly salted.
At least a part of the acidic group may be a salt-type acidic group, and the counter cation of the acidic group may be an alkali metal such as sodium, lithium or potassium, or ammonium which may be substituted with an alkyl group or a hydroxyalkyl group. , Organic amines and the like. Examples of organic amines include lower alkylamines having 1 or more carbon atoms and 6 or less carbon atoms, hydroxy-substituted lower alkylamines having 1 or more carbon atoms and 6 or less carbon atoms, and carboxy-substituted lower alkylamines having 1 or more carbon atoms and 6 or less carbon atoms. Can be mentioned. In the case of these salt types, the type is not limited to one type, and a plurality of types may be mixed. From the viewpoint of solubility, an alkali metal salt having a high ionization tendency is desirable. In particular, lithium and / or sodium are preferable, and lithium is particularly preferable from the viewpoint of suppressing phase separation of the composition containing the dye and the polymer compound and improving the solubility. In addition, lithium is particularly preferable from the viewpoint of increasing the bicolor ratio of the film composed of the composition containing the dye and the polymer compound.
At least a part of the basic group may be a salt-type basic group, and the salt type of the basic group includes, for example, a salt of an inorganic acid such as hydrochloric acid or sulfuric acid, or a salt of an organic acid such as acetic acid or formic acid. Can be mentioned.

高分子化合物の分子量（重量平均分子量）としては、通常８００以上が好ましく、１０００以上がさらに好ましく、１４００以上が特に好ましい。また、通常１００００以下が好ましく、７０００以下がさらに好ましく、５０００以下が特に好ましい。例えば、８００以上１００００以下が好ましく、１０００以上７０００以下がより好ましく、１４００以上５０００以下がさらに好ましい。分子量が上記下限値以上であることで耐湿性が得られる傾向にあり、分子量が上記上限値以下であることで溶解性が得られる傾向にある。 The molecular weight (weight average molecular weight) of the polymer compound is usually preferably 800 or more, more preferably 1000 or more, and particularly preferably 1400 or more. Further, usually 10,000 or less is preferable, 7,000 or less is more preferable, and 5,000 or less is particularly preferable. For example, 800 or more and 10000 or less are preferable, 1000 or more and 7000 or less are more preferable, and 1400 or more and 5000 or less are further preferable. Moisture resistance tends to be obtained when the molecular weight is at least the above lower limit value, and solubility tends to be obtained when the molecular weight is at least the above upper limit value.

高分子化合物の主鎖は、特に限定されるものではないが、後述する色素の相性から、アミド結合、エステル結合、エーテル結合、－ＮＲ1－基（Ｒ1は、水素原子、メチル基又はエチル基を表す。）及びスルホニル基からなる群から選ばれる少なくとも１つを含む炭素鎖、飽和結合のみからなる炭素鎖等が好ましく、特に、飽和結合のみからなる炭素鎖、アミド結合及び／又は－ＮＲ1－基を含む炭素鎖の構造を有することが望ましい。なお、主鎖は、上記結合又は上記基を複数有していてもよい。
一方で、不飽和結合やフェニレンのような芳香族性を有する部分構造を有さない方が望ましい。不飽和結合や芳香族性を有する部分構造を有さないことで、不飽和結合部が色素のπ-πスタックを阻害することを抑制し、異方性色素膜形成用組成物が液晶性を得て、異方性色素膜の偏光度を向上できる傾向にある。 The main chain of the polymer compound is not particularly limited, but from the compatibility of the dye described later, an amide bond, an ester bond, an ether bond, and a -NR 1- group (R 1 is a hydrogen atom, a methyl group or an ethyl). A carbon chain containing at least one selected from the group consisting of a group and a sulfonyl group, a carbon chain consisting of only a saturated bond, and the like are preferable, and in particular, a carbon chain consisting of only a saturated bond, an amide bond and / or -NR It is desirable to have a carbon chain structure containing 1 -group. The main chain may have the above-mentioned bond or the above-mentioned group.
On the other hand, it is desirable not to have a partial structure having aromaticity such as unsaturated bond or phenylene. By not having an unsaturated bond or a partial structure having aromaticity, the unsaturated bond portion suppresses the inhibition of the π-π stack of the dye, and the composition for forming an anisotropic dye film has a liquid crystallinity. As a result, the degree of polarization of the unsaturated dye film tends to be improved.

高分子化合物の側鎖に関しても、主鎖と同様に特に限定されるものではないが、主鎖同様、後述する色素との相性から、アミド結合、エステル結合、エーテル結合、－ＮＲ1－基（Ｒ1は、水素原子、メチル基又はエチル基を表す。）及びスルホニル基からなる群から選ばれる少なくとも１つを含む炭素鎖、飽和結合のみからなる炭素鎖等が望ましい。特に、飽和結合のみからなる炭素鎖、アミド結合及び－ＮＲ1－基からなる群から選ばれる少なくとも１つを含む炭素鎖を有することが望ましい。
一方で、不飽和結合やフェニレンのような芳香族性を有する部分構造を有さない方が望ましい。不飽和結合やフェニレンのような芳香族性を有する部分構造を有さないことで、色素のπ-πスタックを阻害することを抑制し、異方性色素膜形成用組成物が液晶性を得て、異方性色素膜の偏光度を向上できる傾向にある。
同様に、側鎖の鎖長は短い方が好ましい。側鎖が短いことで、色素の会合を阻害することを抑制できる傾向にある。そのため、側鎖は、最も主鎖から離れた原子（Ｈ原子を除く）までの原子数が２以上、１０以下であることが好ましく、より好ましくは８以下である。 The side chain of the polymer compound is not particularly limited as in the main chain, but like the main chain, it has an amide bond, an ester bond, an ether bond, and a -NR 1- group (as in the case of the main chain, due to its compatibility with the dye described later. R 1 represents a hydrogen atom, a methyl group or an ethyl group), a carbon chain containing at least one selected from the group consisting of a sulfonyl group, a carbon chain consisting of only a saturated bond, and the like are desirable. In particular, it is desirable to have a carbon chain containing only a saturated bond, an amide bond and a carbon chain containing at least one selected from the group consisting of -NR 1 -groups.
On the other hand, it is desirable not to have a partial structure having aromaticity such as unsaturated bond or phenylene. By not having an unsaturated bond or a partial structure having aromaticity such as phenylene, it is possible to suppress the inhibition of the π-π stack of the dye, and the composition for forming an anisotropic dye film obtains liquid crystallinity. Therefore, the degree of polarization of the anisotropic dye film tends to be improved.
Similarly, the chain length of the side chain is preferably short. Short side chains tend to suppress inhibition of dye association. Therefore, the side chain preferably has 2 or more and 10 or less atoms up to the atom farthest from the main chain (excluding H atom), and more preferably 8 or less.

酸性基及び塩基性基の同一主鎖中の比率は、特に限定されない。液晶性を維持する観点からは、塩基性基／（塩基性基＋酸性基）の数値が０．０５より大きいことが好ましく、より好ましくは０．１以上、さらに好ましくは０．２以上であり、０．８以下が好ましく、０．７以下がより好ましく、０．６以下がさらに好ましく、０．５以下がよりさらに好ましく、０．４以下がことさら好ましい。例えば、０．０５より大きく０．８以下が好ましく、０．１以上０．７以下がより好ましく、０．２以上０．６以下がさらに好ましく、０．２以上０．５以下がよりさらに好ましく、０．２以上０．４以下がことさら好ましい。上記下限値以上とすることで、色素と高分子化合物との相溶性が向上する傾向にある。上記上限値以下とすることで、色素と高分子化合物との会合より色素間の積層が進み、組成物の液晶性が向上し、異方性色素膜の偏光度が向上する傾向にある。 The ratio of the acidic group and the basic group in the same main chain is not particularly limited. From the viewpoint of maintaining liquidity, the value of basic group / (basic group + acidic group) is preferably greater than 0.05, more preferably 0.1 or more, still more preferably 0.2 or more. , 0.8 or less is preferable, 0.7 or less is more preferable, 0.6 or less is further preferable, 0.5 or less is further preferable, and 0.4 or less is particularly preferable. For example, it is more preferably greater than 0.05 and less than 0.8, more preferably 0.1 or more and 0.7 or less, further preferably 0.2 or more and 0.6 or less, and even more preferably 0.2 or more and 0.5 or less. , 0.2 or more and 0.4 or less is particularly preferable. By setting the value to the above lower limit or higher, the compatibility between the dye and the polymer compound tends to be improved. When the value is not more than the above upper limit, the lamination between the dyes proceeds due to the association between the dye and the polymer compound, the liquid crystal property of the composition is improved, and the degree of polarization of the anisotropic dye film tends to be improved.

高分子化合物が有する酸性基及び塩基性基の種類の組合せも特に限定されない。塩基性基がアミノ基であり、酸性基がスルホ基、カルボキシ基及び／又はリン酸基であることが好ましい。さらに、塩基性基がアミノ基であり、酸性基がスルホ基であることが好ましい。塩基性基としては、骨格が小さく、カチオン化した場合にＨＳＡＢ則における堅いカチオンが発生するアミノ基は、色素との相互作用が強くなり、相分離を起こしにくくなる。色素と静電反発し、色素と高分子化合物の過度な相互作用による相分離を抑制する観点から、酸性基はスルホ基又はリン酸基が好ましい。
なお、本発明の高分子化合物が、複数の種類の酸性基及び塩基性基を有する場合、二つ以上の基は、同一の基であっても異なる基であってもよい。 The combination of the types of acidic groups and basic groups of the polymer compound is not particularly limited. It is preferable that the basic group is an amino group and the acidic group is a sulfo group, a carboxy group and / or a phosphoric acid group. Further, it is preferable that the basic group is an amino group and the acidic group is a sulfo group. As a basic group, an amino group having a small skeleton and generating a hard cation according to the HSAB rule when cationized has a strong interaction with a dye and is less likely to cause phase separation. The acidic group is preferably a sulfo group or a phosphoric acid group from the viewpoint of electrostatically repelling the dye and suppressing phase separation due to excessive interaction between the dye and the polymer compound.
When the polymer compound of the present invention has a plurality of types of acidic groups and basic groups, the two or more groups may be the same group or different groups.

本発明の高分子化合物は、ランダム構造であってもブロック構造であってもよく、特にランダム構造であることが好ましい。ランダム構造であることで、高分子化合物及び色素の相溶性が高くなる傾向にある。また線状の高分子であっても、分岐状の高分子であってもよい。 The polymer compound of the present invention may have a random structure or a block structure, and is particularly preferably a random structure. The random structure tends to increase the compatibility of the polymer compound and the dye. Further, it may be a linear polymer or a branched polymer.

高分子化合物の具体例としては、特開２００４－０２７１６２号公報、特開２００２－２９３８４２号公報、特開昭５２－１０１２９１号公報、特公平０３－０２０１２７号公報、特開２００４－１１５６７５号公報等に記載の高分子化合物が挙げられ、また、上記公報記載の方法で製造することができる。
高分子化合物の例示化合物を下記に示すが、下記構造に限定されるものではない。なお、すべて対カチオンがプロトン体での記載だが、対カチオンがアルカリ金属等の上述した対カチオンであるものも含まれる。また、プロトン体と塩型が混合していてもよいし、塩型が複数含まれていてもよい。下記例示化合物中のｌ、ｍ、ｎ及びｐは任意の整数を表す。 Specific examples of the polymer compound include JP-A-2004-021762, JP-A-2002-293842, JP-A-52-102911, JP-A-03-020127, JP-A-2004-115675 and the like. The polymer compound described in the above is mentioned, and it can also be produced by the method described in the above-mentioned publication.
Examples of the polymer compound are shown below, but the structure is not limited to the following. In addition, although all the descriptions are based on the protons of the counter cations, those in which the counter cations are the above-mentioned counter cations such as alkali metals are also included. Further, the proton form and the salt type may be mixed, or a plurality of salt types may be contained. In the following exemplified compounds, l, m, n and p represent arbitrary integers.

Figure 0007024458000001
Figure 0007024458000001

Figure 0007024458000002
Figure 0007024458000002

高分子化合物の含有量（全固形分中の重量％）は特に制限されない。高分子化合物は異方性色素膜形成用組成物中の全固形分に対して、９０質量部以下が好ましく、８０質量部以下であることがより好ましく、７０質量部以下であることがさらに好ましく、６０質量部以下であることが特に好ましい。一方、０．１質量部以上が好ましく、１質量部以上がより好ましく、３質量部以上がさらに好ましく、５質量部以上がより好ましく、１０質量部以上がより好ましく、２０質量部以上がより好ましく、３０質量部以上がとりわけ好ましく、４０質量部以上がことさら好ましい。例えば、０．１重量％以上９０重量％以下が好ましく、１重量％以上９０重量％以下がより好ましく、５重量％以上８０重量％以下がさらに好ましく、１０重量％以上７０重量％以下がよりさらに好ましく、２０重量％以上６０重量％以下がことさら好ましく、３０重量％以上６０重量％以下がよりことさら好ましく、４０重量％以上６０重量％以下がさらにことさら好ましい。上記上限値以下とすることで、異方性色素膜の偏光度が高くなる傾向がある。上記下限値以上とすることで、異方性色素膜の脆さを抑制し、硬度を向上し、反射率を低減する傾向がある。上記範囲であることで、耐湿性に優れる傾向にある。 The content of the polymer compound (% by weight in the total solid content) is not particularly limited. The polymer compound is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 70 parts by mass or less with respect to the total solid content in the composition for forming an anisotropic dye film. , 60 parts by mass or less is particularly preferable. On the other hand, 0.1 part by mass or more is preferable, 1 part by mass or more is more preferable, 3 parts by mass or more is further preferable, 5 parts by mass or more is more preferable, 10 parts by mass or more is more preferable, and 20 parts by mass or more is more preferable. , 30 parts by mass or more is particularly preferable, and 40 parts by mass or more is particularly preferable. For example, 0.1% by weight or more and 90% by weight or less is preferable, 1% by weight or more and 90% by weight or less is more preferable, 5% by weight or more and 80% by weight or less is further preferable, and 10% by weight or more and 70% by weight or less is further preferable. It is preferably 20% by weight or more and 60% by weight or less, more preferably 30% by weight or more and 60% by weight or less, and even more preferably 40% by weight or more and 60% by weight or less. By setting the value to the upper limit or less, the degree of polarization of the anisotropic dye film tends to increase. By setting the value to the above lower limit or more, the brittleness of the anisotropic dye film tends to be suppressed, the hardness tends to be improved, and the reflectance tends to be reduced. Within the above range, the moisture resistance tends to be excellent.

本発明の異方性色素膜形成用組成物における高分子化合物と色素の配合比は特に制限されない。色素：高分子化合物＝１０：９０～９９．９：０．１であることが好ましい。さらに２０：８０～９０：１０であることがより好ましく、２５：７５～８０：２０であることがさらに好ましく、３０：７０～６０：４０であることが特に好ましい。上記範囲であることで、異方性色素膜は偏光性、耐湿性に優れ、さらに異方性色素膜の脆さを抑制し、硬度を向上する傾向にある。 The compounding ratio of the polymer compound and the dye in the composition for forming an anisotropic dye film of the present invention is not particularly limited. Dye: Polymer compound = 10: 90 to 99.9: 0.1 is preferable. Further, it is more preferably 20:80 to 90:10, further preferably 25:75 to 80:20, and particularly preferably 30:70 to 60:40. Within the above range, the anisotropic dye film is excellent in polarization property and moisture resistance, further suppresses brittleness of the anisotropic dye film, and tends to improve hardness.

（水溶性有機化合物）
本発明の異方性色素膜形成用組成物に用いることができる水溶性有機化合物としては、後述の色素（配合用色素を使用する場合、配合用色素を含む。）を除いた化合物であることが好ましい。
水溶性有機化合物は特に限定されないが、異方性色素膜形成用組成物の塗膜の気液界面に集積しやすく、その表面張力を均一化させる作用のある化合物であることが好ましい。異方性色素膜形成用組成物の塗膜の膜厚を均一化するため、レベリング作用のある化合物を用いることができる。
なお、本発明において水溶性とは、水中で水和して分散する分子状態となることをいう。 (Water-soluble organic compound)
The water-soluble organic compound that can be used in the composition for forming an anisotropic dye film of the present invention is a compound excluding the dyes described below (including the dyes for blending when the dyes for blending are used). Is preferable.
The water-soluble organic compound is not particularly limited, but is preferably a compound that easily accumulates at the gas-liquid interface of the coating film of the anisotropic dye film forming composition and has an effect of equalizing the surface tension thereof. In order to make the film thickness of the coating film of the anisotropic dye film forming composition uniform, a compound having a leveling action can be used.
In the present invention, water-soluble means a molecular state in which water is hydrated and dispersed in water.

水溶性有機化合物は特に限定されないが、親水基及び疎水基の両基を有することが好ましい。水溶性有機化合物が親水基と疎水基を有することで、異方性色素膜形成用組成物の塗膜乾燥時に水溶性有機化合物の疎水基部分が膜界面側に、親水基部分が膜中側に集まることにより、水溶性有機化合物が気液界面に集積する傾向にある。この結果、異方性色素膜形成用組成物の状態では異方性色素と混合していたが、塗布時には異方性色素の層と水溶性有機化合物層に相分離を生じて、基板側に集積した異方性色素の秩序性を損なうことなく、高分子化合物等を添加しない場合と同等にその二色比を維持させることができる。
加えて、異方性色素膜形成用組成物の塗膜乾燥後に表面に緻密に集積した水溶性有機化合物が、異方性色素膜内部への水の浸入を防ぎ、耐湿性を向上させる傾向にあるとともに、表面張力を下げる。これらの結果から、従来不可能であった異方性色素膜形成用組成物を塗布する際の量産性の向上と異方性色素膜の二色比の維持を両立させることができる。 The water-soluble organic compound is not particularly limited, but preferably has both a hydrophilic group and a hydrophobic group. Since the water-soluble organic compound has a hydrophilic group and a hydrophobic group, the hydrophobic group portion of the water-soluble organic compound is on the interface side of the film and the hydrophilic group portion is on the middle side of the film when the coating film of the composition for forming an anisotropic dye film is dried. Water-soluble organic compounds tend to accumulate at the gas-liquid interface. As a result, in the state of the composition for forming an anisotropic dye film, it was mixed with the anisotropic dye, but at the time of coating, phase separation occurred between the anisotropic dye layer and the water-soluble organic compound layer, and the substrate side The two-color ratio can be maintained in the same manner as when no polymer compound or the like is added, without impairing the order of the accumulated anisotropic dye.
In addition, the water-soluble organic compound densely accumulated on the surface of the composition for forming an anisotropic dye film after drying the coating film tends to prevent water from entering the inside of the anisotropic dye film and improve the moisture resistance. At the same time, it lowers the surface tension. From these results, it is possible to achieve both improvement in mass productivity when applying the composition for forming an anisotropic dye film, which was impossible in the past, and maintenance of the two-color ratio of the anisotropic dye film.

親水基としては、ノニオン性基及びイオン性基が挙げられる。
ノニオン性基は、ヒドロキシ基、炭素数が１～４のアルキルオキシ基、ポリエチレンオキシ基、ポリプロピレンオキシ基等が挙げられる。
イオン性基は、アミノ基、モノアルキルアミノ基、ジアルキルアミノ基、カルボキシ基、スルホ基、ピリジニウム基、第４級アンモニウム基、リン酸基、ポリエチレンイミノ基等が挙げられる。
疎水基としては、直鎖アルキル基、分岐鎖アルキル基、置換基を有していても良いフェニルアルキル基、パープロピレンオキサイド、ポリオルガノシロキシ基、パーフルオロアルキル基等が挙げられる。 Examples of the hydrophilic group include a nonionic group and an ionic group.
Examples of the nonionic group include a hydroxy group, an alkyloxy group having 1 to 4 carbon atoms, a polyethyleneoxy group, a polypropyleneoxy group and the like.
Examples of the ionic group include an amino group, a monoalkylamino group, a dialkylamino group, a carboxy group, a sulfo group, a pyridinium group, a quaternary ammonium group, a phosphoric acid group, a polyethylene imino group and the like.
Examples of the hydrophobic group include a linear alkyl group, a branched chain alkyl group, a phenylalkyl group which may have a substituent, a perpropylene oxide, a polyorganosyloxy group, a perfluoroalkyl group and the like.

水溶性有機化合物としては、シリコーン系、フッ素系、アクリル系、ビニル系化合物等が挙げられる。異方性色素膜形成用組成物の気液界面に素早く物質移動して集積しやすくするため、一般的に比較的低分子量であり、且つ、高極性の物質が、レベリング作用が大きくなるため好ましい。気液界面に集積し、塗膜均一性を向上する観点で、特にシリコーン系、フッ素系化合物が好ましい。
水溶性有機化合物の分子量は特に限定されないが、１００００以下であることが好ましく、５０００以下であることがより好ましく、２０００以下であることがさらに好ましい。また、下限は特に限定されない。 Examples of the water-soluble organic compound include silicone-based, fluorine-based, acrylic-based, and vinyl-based compounds. Generally, a substance having a relatively low molecular weight and a high polarity is preferable because a substance having a relatively low molecular weight and having a large leveling action is preferable because the substance quickly moves to the gas-liquid interface of the composition for forming an anisotropic dye film and facilitates accumulation. .. Silicone-based and fluorine-based compounds are particularly preferable from the viewpoint of accumulating at the gas-liquid interface and improving the uniformity of the coating film.
The molecular weight of the water-soluble organic compound is not particularly limited, but is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 2,000 or less. Further, the lower limit is not particularly limited.

水溶性有機化合物は具体的には以下が挙げられる。
シリコーン系化合物は、化合物中にＳｉ原子を含むものであり、具体的にはポリジメチルシロキサン、ポリエーテル変性ポリジメチルシロキサン、ポリメチルアルキルシロキサン、変性ポリシロキサン、反応性シリコーン、シリコーン系界面活性剤等が挙げられる。 Specific examples of the water-soluble organic compound include the following.
The silicone-based compound contains a Si atom in the compound, and specifically, polydimethylsiloxane, polyether-modified polydimethylsiloxane, polymethylalkylsiloxane, modified polysiloxane, reactive silicone, silicone-based surfactant, and the like. Can be mentioned.

フッ素系化合物は、化合物中にＦ原子を含むものであり、具体的には、フッ素基含有オリゴマーまたはポリマー、パーフルオロ基含有オリゴマーまたはポリマー、パーフルオロアルキル基含有カルボン酸塩、パーフルオロアルキル基・リン酸含有リン酸エステル、フッ素基およびカルボキシル基含有オリゴマー等が挙げられる。また、熱やＵＶにより反応する反応性基を含むものも挙げられる。 The fluorine-based compound contains an F atom in the compound, and specifically, a fluorine group-containing oligomer or polymer, a perfluoro group-containing oligomer or polymer, a perfluoroalkyl group-containing carboxylate, a perfluoroalkyl group, and the like. Examples thereof include a phosphoric acid-containing phosphoric acid ester, a fluorine group-containing and a carboxyl group-containing oligomer. In addition, those containing a reactive group that reacts with heat or UV can also be mentioned.

アクリル系化合物は、アクリレートやメタクリレートなどのアクリルを骨格としたオリゴマーまたはポリマーで、側鎖カルボキシ基の水素原子を他の官能基と置換したアクリル酸エステルである。側鎖カルボキシ基の水素原子を置換した他の官能基は、アルキル基、ポリエチレンオキシエチル基、ポリエステル基、アミノ基、水酸基などの反応基などが挙げられる。 The acrylic compound is an oligomer or polymer having an acrylic skeleton such as acrylate or methacrylate, and is an acrylic acid ester in which the hydrogen atom of the side chain carboxy group is replaced with another functional group. Examples of other functional groups in which the hydrogen atom of the side chain carboxy group is substituted include an alkyl group, a polyethyleneoxyethyl group, a polyester group, an amino group, a reactive group such as a hydroxyl group, and the like.

ビニル系は、ビニル基を含む化合物を重合したオリゴマーまたはポリマーであり、具体的には酢酸ビニルが挙げられる。 The vinyl type is an oligomer or polymer obtained by polymerizing a compound containing a vinyl group, and specific examples thereof include vinyl acetate.

水溶性有機化合物の異方性色素膜形成用組成物中の濃度は本発明の効果を著しく損なわない範囲であれば特に限定されない。好ましくは０．００１質量％以上であり、より好ましくは０．００３質量％以上である。また、好ましくは０．１質量％以下であり、より好ましくは０．０５質量％以下である。例えば、０．００１質量％以上０．１質量％以下が好ましく、０．００３質量％以上０．０５質量％以下がより好ましい。この範囲であることで、レベリング作用効果が得られ、且つ、色素分子の配向を阻害しない傾向にある。 The concentration of the water-soluble organic compound in the composition for forming an anisotropic dye film is not particularly limited as long as it does not significantly impair the effects of the present invention. It is preferably 0.001% by mass or more, and more preferably 0.003% by mass or more. Further, it is preferably 0.1% by mass or less, and more preferably 0.05% by mass or less. For example, 0.001% by mass or more and 0.1% by mass or less is preferable, and 0.003% by mass or more and 0.05% by mass or less is more preferable. Within this range, a leveling effect can be obtained, and the orientation of the dye molecule tends not to be inhibited.

本発明の異方性色素膜形成用組成物における水溶性有機化合物と色素の配合比は特に制限されない。色素と水溶性有機化合物の配合比（色素に対する水溶性有機化合物の重量比）が、好ましくは０．００００１以上、より好ましくは０．０００１以上、さらに好ましくは０．０００５以上である。また好ましくは０．５以下、より好ましくは０．１以下、さらに好ましくは０．０１以下、よりさらに好ましくは０．００５以下である。例えば、０．００００１以上０．５以下が好ましく、０．００００１以上０．１以下がより好ましく、０．０００１以上０．０１以下がさらに好ましく、０．０００５以上０．００５以下がよりさらに好ましい。上記範囲であることでレベリング作用効果が得られ、且つ、色素分子の配向を阻害しない傾向にある。 The compounding ratio of the water-soluble organic compound and the dye in the composition for forming an anisotropic dye film of the present invention is not particularly limited. The compounding ratio of the dye and the water-soluble organic compound (weight ratio of the water-soluble organic compound to the dye) is preferably 0.00001 or more, more preferably 0.0001 or more, still more preferably 0.0005 or more. Further, it is preferably 0.5 or less, more preferably 0.1 or less, still more preferably 0.01 or less, still more preferably 0.005 or less. For example, 0.00001 or more and 0.5 or less are preferable, 0.00001 or more and 0.1 or less are more preferable, 0.0001 or more and 0.01 or less are further preferable, and 0.0005 or more and 0.005 or less are further preferable. Within the above range, a leveling effect can be obtained, and the orientation of the dye molecule tends not to be inhibited.

（色素）
本明細書において色素とは、可視光領域の波長の少なくとも一部を吸収する物質又は化合物を意味する。
本発明の異方性色素膜形成用組成物に用いることができる色素としては、水溶性有機色素又は二色性色素が用いられる。また、色素は、配向制御のため液晶性を有する色素であることが好ましい。ここで、液晶性を有する色素とは、溶剤中でリオトロピック液晶性を示す色素を意味する。
本発明で用いられるリオトロピック液晶性を示す色素としては、塗布により異方性色素膜を形成するために、水又は有機溶媒に可溶であることが好ましい。さらに好ましいものは、「有機概念図－基礎と応用」（甲田善生著、三共出版、１９８４年）で定義される無機性値が有機性値よりも小さな化合物である。なお、水溶性とは、室温で色素が水に、通常０．１重量％以上、好ましくは１重量％以上溶解することをいう。 (Dye)
As used herein, the term dye means a substance or compound that absorbs at least a part of wavelengths in the visible light region.
As the dye that can be used in the composition for forming an anisotropic dye film of the present invention, a water-soluble organic dye or a dichroic dye is used. Further, the dye is preferably a dye having a liquid crystal property for orientation control. Here, the dye having liquid crystallinity means a dye showing liquid crystallinity in a solvent.
The dye having lyotropic liquid crystallinity used in the present invention is preferably soluble in water or an organic solvent in order to form an anisotropic dye film by coating. Further preferred are compounds having an inorganic value smaller than the organic value as defined in "Organic Conceptual Diagram-Basics and Applications" (Yoshio Koda, Sankyo Publishing, 1984). The term "water-soluble" means that the dye dissolves in water at room temperature in an amount of usually 0.1% by weight or more, preferably 1% by weight or more.

色素は、塩型をとらない遊離の状態で、その分子量が２００以上であるのが好ましく、３００以上であるのが特に好ましい。また、１５００以下であるのが好ましく、１２００以下であるのが特に好ましい。例えば、２００以上１５００以下であるのが好ましく、３００以上１２００以下であるのが特に好ましい。
また、色素は、１種のみを用いてもよいし、２種以上を組み合わせて用いてもよい。 The dye is preferably in a free state without taking a salt form and has a molecular weight of 200 or more, and particularly preferably 300 or more. Further, it is preferably 1500 or less, and particularly preferably 1200 or less. For example, it is preferably 200 or more and 1500 or less, and particularly preferably 300 or more and 1200 or less.
Further, as the dye, only one kind may be used, or two or more kinds may be used in combination.

色素として、具体的には、アゾ系色素（以下、単に「アゾ色素」とも言う。）、スチルベン系色素、シアニン系色素、フタロシアニン系色素、縮合多環系色素（ペリレン系、オキサジン系）等が挙げられる。これら色素の中でも、異方性色素膜中で高い分子配列を取り得るアゾ系色素が好ましい。アゾ系色素とは、アゾ基を少なくとも１個以上持つ色素をいう。その一分子中のアゾ基の数は、色調及び製造面の観点から、２以上が好ましく、６以下が好ましく、４以下がより好ましく、３以下がさらに好ましい。特にアゾ色素において、スルホ基、カルボキシル基、ホスホ基及びホスフィン酸基からなる群より選ばれる少なくとも１つの基を有することが、異方性色素膜の水への溶解、脱落、割れ等の発生を抑制し、さらに光学特性の劣化を小さくする効果を得ることができる傾向にある。これらの中でも、アゾ色素がスルホ基を有することが特に好ましい。 Specific examples of the dye include azo dyes (hereinafter, also simply referred to as "azo dyes"), stilbene dyes, cyanine dyes, phthalocyanine dyes, condensed polycyclic dyes (perylene type, oxazine type) and the like. Can be mentioned. Among these dyes, azo dyes capable of having a high molecular arrangement in the anisotropic dye film are preferable. The azo dye refers to a dye having at least one azo group. The number of azo groups in one molecule is preferably 2 or more, preferably 6 or less, more preferably 4 or less, still more preferably 3 or less, from the viewpoint of color tone and production. In particular, in the azo dye, having at least one group selected from the group consisting of a sulfo group, a carboxyl group, a phospho group and a phosphinic acid group causes the anisotropic dye film to dissolve in water, fall off, crack, etc. There is a tendency to obtain the effect of suppressing and further reducing the deterioration of optical characteristics. Among these, it is particularly preferable that the azo dye has a sulfo group.

本発明に用いることができる色素は特に限定されず、公知の色素を用いることができる。
色素としては、例えば、特開２００６－０７９０３０号公報、特開２０１０－１６８５７０号公報、特開２００７－３０２８０７号公報、特開２００８－０８１７００号公報、特開平０９－２３０１４２号公報、特開２００７－２７２２１１号公報、特開２００７－１８６４２８号公報、特開２００８－６９３００号公報、特開２００９－１６９３４１号公報、特開２００９－１６１７２２号公報、特開２００９－１７３８４９号公報、特開２０１０－０３９１５４号公報、特開２０１０－１８０３１４号公報、特開２０１０－２６６７６９号公報、特開２０１０－０３１２６８号公報、特開２０１１－０１２１５２号公報、特開２０１１―０１６９２２号公報、特開２０１０－１０００５９号公報、特開２０１１－１４１３３１号公報、特開２０１１－１９０３１３号公報、特表平０８－５１１１０９号公報、特表２００１－５０４２３８号公報、特開２００６－４８０７８号公報、特開２００６－９８９２７号公報、特開２００６－１９３７２２号公報、特開２００６－２０６８７８号公報、特開２００５－２５５８４６号公報、特開２００７－１４５９９５号公報、特開２００７－１２６６２８号公報、特開２００８－１０２４１７号公報、特開２０１２－１９４３５７号公報、特開２０１２－１９４２９７号公報、特開２０１１－０３４０６１号公報、特開２００９－１１０９０２号公報、特開２０１１－１０００５９号公報、特開２０１２－１９４３６５号公報、特開２０１１－０１６９２０号公報等に記載の色素が挙げられる。 The dye that can be used in the present invention is not particularly limited, and known dyes can be used.
Examples of the dye include JP-A-2006-0793030, JP-A-2010-168570, JP-A-2007-302807, JP-A-2008-081700, JP-A-09-230142, JP-A-2007- 272221, 2007-186428, 2008-69300, 2009-169341, 2009-161722, 2009-173849, 2010-039154. Japanese Patent Laid-Open No. 2010-180314, Japanese Patent Application Laid-Open No. 2010-266769, Japanese Patent Application Laid-Open No. 2010-031268, Japanese Patent Application Laid-Open No. 2011-012152, Japanese Patent Application Laid-Open No. 2011-016922, Japanese Patent Application Laid-Open No. 2010-100059, JP-A-2011-141331, JP-A-2011-190313, JP-A-08-511109, JP-A-2001-504238, JP-A-2006-48078, JP-A-2006-98927, Japanese Patent Laid-Open No. Kai 2006-193722, JP-A-2006-206878, JP-A-2005-255846, JP-A-2007-145995, JP-A-2007-126628, JP-A-2008-102417, JP-A-2012 -194357, 2012-194297, 2011-034061, 2009-11902, 2011-100059, 2012-194365, 2011-016920 Examples thereof include the dyes described in the publications and the like.

本発明に用いられる色素は、遊離酸の形のまま使用してもよく、酸基の一部が塩型を取っているものであってもよい。また、塩型の色素と遊離酸型の色素が混在していてもよい。
製造時に色素が塩型で得られた場合はそのまま使用してもよいし、所望の塩型に変換（塩交換）してもよい。塩交換の方法としては、公知の方法を任意に用いることができ、例えば以下の方法が挙げられる。 The dye used in the present invention may be used in the form of a free acid, or a part of the acid group may be in the salt form. Further, a salt-type dye and a free acid-type dye may be mixed.
When the dye is obtained in a salt form at the time of production, it may be used as it is, or it may be converted into a desired salt form (salt exchange). As a method of salt exchange, a known method can be arbitrarily used, and examples thereof include the following methods.

１）塩型で得られた色素の水溶液に塩酸等の強酸を添加し、色素を遊離酸の形で酸析せしめた後、所望の対イオンを有するアルカリ溶液（例えば水酸化リチウム水溶液）で色素酸性基を中和し塩交換する方法。
２）塩型で得られた色素の水溶液に、所望の対イオンを有する大過剰の中性塩（例えば、塩化リチウム）を添加し、塩析ケーキの形で塩交換する方法。
３）塩型で得られた色素の水溶液を、強酸性陽イオン交換樹脂で処理し、色素を遊離酸の形で酸析せしめた後、所望の対イオンを有するアルカリ溶液（例えば水酸化リチウム水溶液）で色素酸性基を中和し塩交換する方法。
４）予め所望の対イオンを有するアルカリ溶液（例えば水酸化リチウム水溶液）で処理した強酸性陽イオン交換樹脂に、塩型で得られた色素の水溶液を作用させ、塩交換する方法。 1) A strong acid such as hydrochloric acid is added to the aqueous solution of the dye obtained in the salt mold, the dye is acidified in the form of free acid, and then the dye is prepared with an alkaline solution having a desired counter ion (for example, an aqueous solution of lithium hydroxide). A method of neutralizing acidic groups and exchanging salts.
2) A method in which a large excess neutral salt having a desired counterion (for example, lithium chloride) is added to an aqueous solution of a dye obtained in a salt mold, and the salt is exchanged in the form of a salting out cake.
3) The aqueous solution of the dye obtained in the salt mold is treated with a strongly acidic cation exchange resin, the dye is acidified in the form of a free acid, and then an alkaline solution having a desired counterion (for example, an aqueous solution of lithium hydroxide). ) To neutralize the acidic group of the dye and exchange the salt.
4) A method in which an aqueous solution of a dye obtained in a salt mold is allowed to act on a strongly acidic cation exchange resin previously treated with an alkaline solution having a desired counterion (for example, an aqueous solution of lithium hydroxide) to exchange salts.

また、色素が有する酸性基が、遊離酸型となるか塩型となるかは、色素のｐＫａと色素水溶液のｐＨに依存する。前記の塩型の例としては、ナトリウム、リチウム、カリウム等のアルカリ金属の塩、アルキル基又はヒドロキシアルキル基で置換されていてもよいアンモニウムの塩、有機アミンの塩等が挙げられる。
有機アミンの例として、炭素数１～６の低級アルキルアミン、ヒドロキシ置換された炭素数１～６の低級アルキルアミン、カルボキシ置換された炭素数１～６の低級アルキルアミン等が挙げられる。
これらの塩型の場合、その種類は１種類に限らず複数種混在していてもよい。また、本発明において、色素は単独で使用することができるが、これらの２種以上を併用してもよく、また、配向を低下させない程度に前記例示色素以外の色素を配合して用いることもできる。これにより各種の色相を有する異方性色素膜を製造することができる。 Whether the acidic group of the dye is a free acid type or a salt type depends on the pH of the dye pKa and the dye aqueous solution. Examples of the above-mentioned salt type include salts of alkali metals such as sodium, lithium and potassium, salts of ammonium which may be substituted with an alkyl group or a hydroxyalkyl group, salts of organic amines and the like.
Examples of the organic amine include a lower alkylamine having 1 to 6 carbon atoms, a hydroxy-substituted lower alkylamine having 1 to 6 carbon atoms, a carboxy-substituted lower alkylamine having 1 to 6 carbon atoms, and the like.
In the case of these salt types, the type is not limited to one type, and a plurality of types may be mixed. Further, in the present invention, the dye can be used alone, but two or more of these may be used in combination, or a dye other than the above-mentioned exemplified dye may be blended and used to the extent that the orientation is not deteriorated. can. This makes it possible to produce anisotropic dye films having various hues.

他の色素を配合する場合の配合用色素（「配合用色素」とも言う。）の例としては、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｙｅｌｌｏｗ １２、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｙｅｌｌｏｗ ３４、Ｃ．Ｉ．ＤｉｒｅｃｔＹｅｌｌｏｗ ８６、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｙｅｌｌｏｗ １４２、Ｃ．Ｉ．ＤｉｒｅｃｔＹｅｌｌｏｗ １３２、Ｃ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ ９、Ｃ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ ２５、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｏｒａｎｇｅ ３９、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｏｒａｎｇｅ ７２、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｏｒａｎｇｅ ７９、Ｃ．Ｉ．Ａｃｉｄ Ｏｒａｎｇｅ ２８、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ３９、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ７９、Ｃ．Ｉ．ＤｉｒｅｃｔＲｅｄ
８１、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ８３、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ８９、Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ３７、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｖｉｏｌｅｔ ９、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｖｉｏｌｅｔ ３５、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｖｉｏｌｅｔ ４８、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｖｉｏｌｅｔ ５７、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ １、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ ６７、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ ８３、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ ９０、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｇｒｅｅｎ ４２、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｇｒｅｅｎ ５１、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｇｒｅｅｎ ５９、特許５０９２３４５号公報等に記載の色素等が挙げられる。 Examples of compounding dyes (also referred to as "blending dyes") when blending other dyes include C.I. I. Direct Yellow 12, C.I. I. Direct Yellow 34, C.I. I. DirectYellow 86, C.I. I. Direct Yellow 142, C.I. I. DirectYellow 132, C.I. I. Acid Yellow 9, C.I. I. Acid Yellow 25, C.I. I. Direct Orange 39, C.I. I. Direct Orange 72, C.I. I. Direct Orange 79, C.I. I. Acid Orange 28, C.I. I. Direct Red 39, C.I. I. Direct Red 79, C.I. I. DirectRed
81, C.I. I. Direct Red 83, C.I. I. Direct Red89, C.I. I. Acid Red 37, C.I. I. Direct Violet 9, C.I. I. Direct Violet 35, C.I. I. Direct Violet 48, C.I. I. Direct Violet 57, C.I. I. Direct Blue 1, C.I. I. Direct Blue 67, C.I. I. Direct Blue 83, C.I. I. Direct Blue 90, C.I. I. Direct Green 42, C.I. I. Direct Green 51, C.I. I. Examples thereof include dyes and the like described in Direct Green 59, Japanese Patent No. 5092345, and the like.

（異方性色素膜形成用組成物中の色素濃度）
異方性色素膜形成用組成物中の色素（配合用色素を使用する場合、配合用色素を含む。）の濃度としては、異方性色素膜の成膜条件にもよるが、好ましくは０．０１重量％以上、さらに好ましくは０．１重量％以上であり、好ましくは５０重量％以下、さらに好ましくは３０重量％以下である。例えば、０．０１重量％以上５０重量％以下が好ましく、０．１重量％以上３０重量％以下がより好ましい。色素濃度が前記範囲であることで、均一な薄膜塗布ができる異方性色素膜形成用組成物の粘度が得られ、且つ、色素が析出しない傾向にある。また、異方性色素膜において十分な二色比等の異方性を得られる傾向にある。 (Dye concentration in the composition for forming an anisotropic dye film)
The concentration of the dye (including the compounding dye when the compounding dye is used) in the composition for forming the anisotropic dye film depends on the film forming conditions of the anisotropic dye film, but is preferably 0. It is 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 50% by weight or less, still more preferably 30% by weight or less. For example, 0.01% by weight or more and 50% by weight or less is preferable, and 0.1% by weight or more and 30% by weight or less is more preferable. When the dye concentration is in the above range, the viscosity of the anisotropic dye film forming composition capable of uniformly applying a thin film can be obtained, and the dye tends not to precipitate. In addition, there is a tendency to obtain anisotropy such as a sufficient two-color ratio in the anisotropic dye film.

（異方性色素膜形成用組成物の溶剤）
溶剤としては、水、水混和性のある有機溶剤又はこれらの混合物が適している。有機溶剤の具体例としては、メチルアルコール、エチルアルコール、イソプロピルアルコール、グリセリン等のアルコール類、エチレングリコール、ジエチレングリコール等のグリコール類、メチルセロソルブ、エチルセロソルブ等のセロソルブ類等が挙げられる。これらは、単独で用いても、２種以上を混合して用いてもよい。
上記溶剤を用いた場合、異方性色素膜形成用組成物の全固形分濃度は好ましくは５質量％以上、より好ましくは１０質量％以上、さらに好ましくは１５質量％以上、また、好ましくは５０質量％以下、より好ましくは４０質量％以下、さらに好ましくは３０質量％以下、特に好ましくは２５質量％以下、例えば、好ましくは５質量％以上５０質量％以下、より好ましくは１０質量％以上４０質量％以下、さらに好ましくは１５質量％以上３０質量％以下、よりさらに好ましくは１５質量％以上２５質量％以下となるように調液して使用される。前記下限値以上とすることで所望の膜厚の異方性色素膜を形成できる傾向があり、また、前記上限値以下とすることで異方性色素膜の膜厚均一性が向上する傾向がある。 (Solvent of composition for forming anisotropic dye film)
As the solvent, water, a water-miscible organic solvent, or a mixture thereof is suitable. Specific examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and glycerin, glycols such as ethylene glycol and diethylene glycol, and cellosolves such as methyl cellosolve and ethyl cellosolve. These may be used alone or in combination of two or more.
When the above solvent is used, the total solid content concentration of the composition for forming an anisotropic dye film is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 50% by mass or more. Mass% or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, particularly preferably 25% by mass or less, for example, preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass. % Or less, more preferably 15% by mass or more and 30% by mass or less, and even more preferably 15% by mass or more and 25% by mass or less. When it is set to the lower limit value or more, an anisotropic dye film having a desired film thickness tends to be formed, and when it is set to the upper limit value or less, the film thickness uniformity of the anisotropic dye film tends to be improved. be.

本発明の異方性色素膜形成用組成物は、リオトロピック液晶相の発現有無は問わないが、リオトロピック液晶相を発現していない場合において、異方性色素膜形成用組成物中の溶剤量のみを変更することでリオトロピック液晶相が発現することが好ましい。リオトロピック液晶相が発現することで、異方性色素膜中で色素が高い配向度を発現し、高い二色性の異方性色素膜が得られる傾向にあるため好ましい。
異方性色素膜形成用組成物がリオトロピック液晶相を発現していれば、より異方性色素膜中での高い配向が得られる傾向にあるため、さらに好ましい。 The composition for forming an anisotropic dye film of the present invention may or may not have a lyotropic liquid crystal phase, but when the lyotropic liquid crystal phase is not expressed, only the amount of the solvent in the composition for forming an anisotropic dye film is present. It is preferable that the lyotropic liquid crystal phase is expressed by changing the above. The expression of the lyotropic liquid crystal phase is preferable because the dye exhibits a high degree of orientation in the anisotropic dye film and tends to obtain a highly dichroic anisotropic dye film.
It is more preferable that the composition for forming an anisotropic dye film expresses a lyotropic liquid crystal phase because a higher orientation in the anisotropic dye film tends to be obtained.

（異方性色素膜形成用組成物のｐＨ）
異方性色素膜形成用組成物のｐＨは、特に限定されるものではないが、好ましくは、４．０以上、さらに好ましくは５．０以上、最も好ましくは５．５以上である。また、好ましくは１２以下、さらに好ましくは１１以下、最も好ましくは１０以下である。ｐＨの数値が上記上限値以下であることで、高分子化合物の塩基性基がカチオン化され、色素との相溶性が向上し、相分離（析出）を抑制する傾向にある。また、ｐＨの数値が上記下限値以上であることで、酸性基がアニオン化され、異方性色素膜形成用組成物中において、色素と高分子化合物の過度な相互作用による相分離を抑制できる傾向にある。 (PH of composition for forming anisotropic dye film)
The pH of the composition for forming an anisotropic dye film is not particularly limited, but is preferably 4.0 or higher, more preferably 5.0 or higher, and most preferably 5.5 or higher. Further, it is preferably 12 or less, more preferably 11 or less, and most preferably 10 or less. When the value of pH is not more than the above upper limit value, the basic group of the polymer compound is cationized, the compatibility with the dye is improved, and the phase separation (precipitation) tends to be suppressed. Further, when the value of pH is at least the above lower limit value, the acidic group is anionized, and phase separation due to excessive interaction between the dye and the polymer compound can be suppressed in the composition for forming an anisotropic dye film. There is a tendency.

（異方性色素膜形成用組成物の添加剤）
異方性色素膜形成用組成物には、さらに必要に応じて、界面活性剤、レベリング剤、カップリング剤、ｐＨ調整剤、アラニン、バリン、ロイシン、イソロイシン、グリシン、グリシルグリシン、グリシルグリシルグリシン、セリン、プロリン、システイン、シスチン、グルタミン、６－アミノヘキサン酸、国際公開第２００５／０６９０４８号公報に記載のアミノ酸、３－アミノ－１－プロパンスルホン酸、タウリン等の酸性基及び塩基性基を有する低分子化合物等の添加剤を配合することができる。添加剤により、濡れ性、塗布性、異方性色素膜形成用組成物の安定性等を向上させ得る場合がある。
界面活性剤としては、アニオン性、カチオン性及びノニオン性のいずれも使用可能である。その添加濃度は、特に限定されるものではないが、異方性色素膜形成用組成物中の濃度として、好ましくは０．００１質量％以上、より好ましくは０．０１質量％以上、さらに好ましくは０．０５質量％以上である。また、好ましくは０．８質量％以下であり、より好ましくは０．５質量％以下である。例えば、０．００１質量％以上０．８質量％以下が好ましく、０．０１質量％以上０．５質量％以下がより好ましく、０．０５質量％以上０．５質量％以下がさらに好ましい。この範囲であることで、界面活性剤の添加効果が得られ、且つ、色素分子の配向を阻害しない傾向にある。
異方性色素膜形成用組成物中での異方性材料の造塩や凝集等の不安定性を抑制する等の目的のために、公知の酸／アルカリ等のｐＨ調整剤等を、異方性色素膜形成用組成物の構成成分の混合の前後或いは混合中のいずれかで添加してもよい。なお、前記以外の添加剤として“Ａｄｄｉｔｉｖｅ ｆｏｒ Ｃｏａｔｉｎｇ”，Ｅｄｉｔｅｄ ｂｙ Ｊ．Ｂｉｅｌｅｍａｎ，Ｗｉｌｌｅｙ－ＶＣＨ（２０００）に記載の公知の添加剤を用いることもできる。 (Additive for composition for forming anisotropic dye film)
Further, if necessary, the composition for forming an anisotropic dye film includes a surfactant, a leveling agent, a coupling agent, a pH adjuster, alanine, valine, leucine, isoleucine, glycine, glycylglycine, and glycylglycyl. Acidic and basic groups such as glycine, serine, proline, cysteine, cystine, glutamine, 6-aminohexanoic acid, amino acids described in International Publication No. 2005/069048, 3-amino-1-propanesulfonic acid, taurine and the like. Additives such as low molecular weight compounds having the above can be blended. The additive may improve wettability, coatability, stability of the composition for forming an anisotropic dye film, and the like.
As the surfactant, any of anionic, cationic and nonionic surfactants can be used. The addition concentration is not particularly limited, but is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.01% by mass or more, as a concentration in the composition for forming an anisotropic dye film. It is 0.05% by mass or more. Further, it is preferably 0.8% by mass or less, and more preferably 0.5% by mass or less. For example, 0.001% by mass or more and 0.8% by mass or less is preferable, 0.01% by mass or more and 0.5% by mass or less is more preferable, and 0.05% by mass or more and 0.5% by mass or less is further preferable. Within this range, the effect of adding the surfactant can be obtained, and the orientation of the dye molecule tends not to be hindered.
For the purpose of suppressing instability such as salt formation and aggregation of anisotropic materials in the composition for forming an anisotropic dye film, a known pH adjuster such as acid / alkali is used. It may be added before or after mixing the constituents of the composition for forming a sex dye film or during mixing. In addition, as an additive other than the above, "Additive for Coating", Edited by J. Mol. Known additives described in Bieleman, Willey-VCH (2000) can also be used.

［異方性色素膜形成用組成物の製造方法］
本発明の異方性色素膜形成用組成物の製造方法は特に限定されない。例えば、色素、その他の添加剤及び溶剤等を混合し、０～１００℃で撹拌、振盪して色素を溶解する。難溶性の場合は、ホモジナイザー、ビーズミル分散機等を用いてもよい。
本発明の異方性色素膜形成用組成物の製造方法として、組成物中の異物等を除去する目的でろ過工程を有していてもよい。ろ過以外の組成物中の異物等を除去する方法としては、特開２０１２－５３３８８号公報に記載の遠心分離を用いる方法もある。 [Method for producing a composition for forming an anisotropic dye film]
The method for producing the composition for forming an anisotropic dye film of the present invention is not particularly limited. For example, a dye, other additives, a solvent and the like are mixed, and the dye is dissolved by stirring and shaking at 0 to 100 ° C. In the case of poor solubility, a homogenizer, a bead mill disperser, or the like may be used.
As a method for producing an anisotropic dye film forming composition of the present invention, a filtration step may be provided for the purpose of removing foreign substances and the like in the composition. As a method for removing foreign substances and the like in the composition other than filtration, there is also a method using centrifugation described in JP-A-2012-53388.

［異方性色素膜の形成方法］
本発明の異方性色素膜は、湿式成膜法により作製することが好ましい。
本発明でいう湿式成膜法とは、異方性色素膜形成用組成物を基板上に何らかの手法により付与し、溶剤が乾燥する過程を経て色素等を基板上で配向・積層させる方法である。湿式成膜法では、異方性色素膜形成用組成物を基板上に付与すると、すでに異方性色素膜形成用組成物中で、又は溶剤が乾燥する過程で、色素自体が自己会合することにより微小面積での配向が起こる。この状態に外場を与えることにより、マクロな領域で一定方向に配向させ、所望の性能を有する異方性色素膜を得ることができる。この点で、いわゆるポリビニルアルコール（ＰＶＡ）フィルム等を、色素を含む溶液で染色して延伸し、延伸工程だけで色素を配向させることを原理とする方法とは異なる。なお、ここで外場とは、あらかじめ基板上に施された配向処理層の影響、せん断力、磁場等が挙げられ、これらを単独で用いてもよく、複数組み合わせて用いてもよい。 [Method for forming anisotropic dye film]
The anisotropic dye film of the present invention is preferably produced by a wet film forming method.
The wet film forming method referred to in the present invention is a method in which a composition for forming an anisotropic dye film is applied onto a substrate by some method, and the dye or the like is oriented and laminated on the substrate through a process in which the solvent dries. .. In the wet film forming method, when the composition for forming an anisotropic dye film is applied onto a substrate, the dye itself self-associates in the composition for forming an anisotropic dye film or in the process of drying the solvent. Causes orientation in a small area. By giving an external field to this state, it is possible to obtain an anisotropic dye film having desired performance by orienting in a certain direction in a macroscopic region. In this respect, it is different from the method in which a so-called polyvinyl alcohol (PVA) film or the like is dyed with a solution containing a dye, stretched, and the dye is oriented only in the stretching step. Here, the external field includes the influence of the alignment treatment layer previously applied on the substrate, the shearing force, the magnetic field, and the like, and these may be used alone or in combination of two or more.

また、異方性色素膜形成用組成物を基板上に付与し成膜する過程、外場を与えて配向させる過程、溶剤を乾燥させる過程は、逐次行ってもよいし、同時に行ってもよい。
湿式成膜法における異方性色素膜形成用組成物を基板上へ付与する方法としては、例えば、塗布法、ディップコート法、ＬＢ膜形成法、公知の印刷法等が挙げられる。またこのようにして得た異方性色素膜を別の基板に転写する方法もある。これらの中でも、本発明は塗布法を用いることが好ましい。
異方性色素膜の配向方向は、通常、塗布方向と一致するが、塗布方向と異なっていてもよい。なお、本実施の形態において異方性色素膜の配向方向とは、例えば、偏光膜であれば、偏光の透過軸又は吸収軸であり、位相差膜であれば、進相軸又は遅相軸のことである。 Further, the process of applying the anisotropic dye film forming composition on the substrate to form a film, the process of applying an external field to align the composition, and the process of drying the solvent may be sequentially performed or may be performed at the same time. ..
Examples of the method for applying the anisotropic dye film forming composition on the substrate in the wet film forming method include a coating method, a dip coating method, an LB film forming method, and a known printing method. There is also a method of transferring the anisotropic dye film thus obtained to another substrate. Among these, it is preferable to use the coating method in the present invention.
The orientation direction of the anisotropic dye film usually coincides with the coating direction, but may be different from the coating direction. In the present embodiment, the orientation direction of the anisotropic dye film is, for example, the transmission axis or absorption axis of polarization in the case of a polarizing film, and the phase advance axis or slow phase axis in the case of a retardation film. That is.

そして、本実施の形態における異方性色素膜は、光吸収の異方性を利用し直線偏光、円偏光、楕円偏光等を得る偏光膜又は位相差膜として機能する他、膜形成プロセスと基板や有機化合物（色素や透明材料）を含有する組成物の選択により、屈折異方性や伝導異方性等の各種異方性色素膜として機能化が可能である。 The anisotropic dye film in the present embodiment functions as a polarizing film or a retardation film that obtains linearly polarized light, circularly polarized light, elliptically polarized light, etc. by utilizing the anisotropy of light absorption, as well as a film forming process and a substrate. By selecting a composition containing an organic compound (dye or transparent material), it can be functionalized as various anisotropic dye films such as refractive anisotropy and conduction anisotropy.

異方性色素膜形成用組成物を塗布し、異方性色素膜を得る方法としては、特に限定されないが、例えば、原崎勇次著「コーティング工学」（株式会社朝倉書店、１９７１年３月２０日発行）２５３頁～２７７頁に記載の方法、市村國宏監修「分子協調材料の創製と応用」（株式会社シーエムシー出版、１９９８年３月３日発行）１１８頁～１４９頁に記載の方法、段差構造を有する基板（予め配向処理を施してもよい）上にスロットダイコート法、スピンコート法、スプレーコート法、バーコート法、ロールコート法、ブレードコート法、カーテンコート法、ファウンテン法、ディップ法等で塗布する方法が挙げられる。中でも、スロットダイコート法を採用すると、均一性の高い異方性色素膜が得られるため好適である。
スロットダイコート法に用いるダイコーターは、一般的に塗布液を吐出する塗布機、いわゆるスリットダイを備えている。該スリットダイは、例えば、特開平2-164480号公報、特開平6-154687号公報、特開平9-131559号公報、「分散・塗布・乾燥の基礎と応用」（2014年、株式会社テクノシステ、ISBN9784924728707 C 305）、「ディスプレイ・光学部材における湿式コーティング技術」（2007年、情報機構、ISBN9784901677752）、「エレクトロニクス分野における精密塗布・乾燥技術」（2007年、技術情報教会、ISBN9784861041389）等に開示されている。これら公知のスリットダイは、フィルムやテープなどの可撓性を有した部材やガラス基板のような硬い部材であっても塗布が実施できる。
本発明の異方性色素膜形成用組成物は、塗布装置への給液が容易であり、スロットダイコート法での塗布を行う場合にも、実用に耐える塗布速度で塗布することができ、生産性の高い異方性色素膜製造プロセスを構築することができる。一方で近年、設備投資やメンテナンスに関して低コストで、かつ高速塗布により生産性の向上を両立できる方法として、バーコーターによる塗布プロセスの構築が課題となっており、本発明の異方性色素膜形成用組成物はバーコーターにも好適に用いることができる。 The method for applying the composition for forming an anisotropic dye film to obtain an anisotropic dye film is not particularly limited, but for example, "Coating Engineering" by Yuji Harasaki (Asakura Shoten Co., Ltd., March 20, 1971). (Published) The method described on pages 253 to 277, "Creation and application of molecularly coordinated materials" supervised by Kunihiro Ichimura (CMC Publishing Co., Ltd., published March 3, 1998) The method described on pages 118 to 149, Slot die coating method, spin coating method, spray coating method, bar coating method, roll coating method, blade coating method, curtain coating method, fountain method, dip method on a substrate having a stepped structure (may be pre-aligned). The method of applying by the above can be mentioned. Above all, the slot die coat method is preferable because an anisotropic dye film having high uniformity can be obtained.
The die coater used in the slot die coating method generally includes a coating machine that discharges a coating liquid, a so-called slit die. The slit die is used, for example, in JP-A 2-164480, JP-A-6-154687, JP-A-9-131559, "Basics and Applications of Dispersion / Coating / Drying" (2014, Technosystem Co., Ltd.). , ISBN9784924728707 C 305), "Wet coating technology for displays and optical components" (2007, Information Organization, ISBN9784901677752), "Precision coating and drying technology in the field of electronics" (2007, Technical Information Church, ISBN9784861041389), etc. ing. These known slit dies can be applied even to a flexible member such as a film or tape or a hard member such as a glass substrate.
The composition for forming an anisotropic dye film of the present invention can be easily supplied to a coating device, and even when coated by the slot die coating method, it can be coated at a coating speed that can withstand practical use, and is produced. It is possible to construct a highly anisotropic dye film manufacturing process. On the other hand, in recent years, as a method of achieving both low cost in terms of capital investment and maintenance and improvement of productivity by high-speed coating, construction of a coating process by a bar coater has become an issue, and the formation of an anisotropic dye film of the present invention has become an issue. The composition for use can also be suitably used for a bar coater.

本発明の異方性色素膜形成に使用される基板として、ガラスやトリアセテート、アクリル、ポリエステル、ポリイミド、トリアセチルセルロース又はウレタン系のフィルム等が挙げられる。また、この基板表面には、色素の配向方向を制御するために、「液晶便覧」丸善株式会社、平成１２年１０月３０日発行、２２６頁から２３９頁等に記載の公知の方法により、配向処理層（配向膜）を施していてもよい。配向処理層を設けた場合、配向処理層の配向処理の影響と塗布時に異方性色素膜形成用組成物にかかるせん断力とによって色素が配向すると考えられる。 Examples of the substrate used for forming the anisotropic dye film of the present invention include glass, triacetate, acrylic, polyester, polyimide, triacetyl cellulose, urethane-based film and the like. Further, in order to control the orientation direction of the dye, the surface of the substrate is oriented by a known method described in "LCD Handbook" Maruzen Co., Ltd., published on October 30, 2000, pp. 226 to 239. A treated layer (alignment film) may be applied. When the alignment treatment layer is provided, it is considered that the dye is oriented due to the influence of the alignment treatment of the alignment treatment layer and the shearing force applied to the composition for forming an anisotropic dye film at the time of coating.

異方性色素膜形成用組成物を塗布する際の、異方性色素膜形成用組成物の供給方法、供給間隔は特に限定されない。塗布液の供給操作が繁雑になったり、塗布液の開始時と停止時に塗布膜厚の変動を生じてしまったりする場合があるため、異方性色素膜の膜厚が薄い時には、連続的に異方性色素膜形成用組成物を供給しながら塗布することが望ましい。 When the composition for forming an anisotropic dye film is applied, the method of supplying the composition for forming an anisotropic dye film and the supply interval are not particularly limited. Since the operation of supplying the coating liquid may become complicated or the coating film thickness may fluctuate at the start and stop of the coating liquid, the anisotropic dye film may be continuously thin. It is desirable to apply the composition for forming an anisotropic dye film while supplying it.

異方性色素膜形成用組成物を塗布する速度としては、通常１ｍｍ／秒以上であり、好ましくは５ｍｍ／秒以上である。また、通常１０００ｍｍ／秒以下であり、好ましくは２００ｍｍ／秒以下である。塗布速度が適当な範囲であることで、異方性色素膜の異方性が得られ、均一に塗布できる傾向にある。
なお、異方性色素膜形成用組成物の塗布温度としては、通常０℃以上８０℃以下、好ましくは４０℃以下である。また、異方性色素膜形成用組成物の塗布時の湿度は、好ましくは１０％ＲＨ以上、さらに好ましくは３０％ＲＨ以上であり、好ましくは８０％ＲＨ以下である。 The speed at which the anisotropic dye film forming composition is applied is usually 1 mm / sec or more, preferably 5 mm / sec or more. Further, it is usually 1000 mm / sec or less, preferably 200 mm / sec or less. When the coating speed is in an appropriate range, the anisotropy of the anisotropic dye film can be obtained, and the coating tends to be uniform.
The coating temperature of the composition for forming an anisotropic dye film is usually 0 ° C. or higher and 80 ° C. or lower, preferably 40 ° C. or lower. The humidity at the time of coating the composition for forming an anisotropic dye film is preferably 10% RH or more, more preferably 30% RH or more, and preferably 80% RH or less.

異方性色素膜の膜厚は、乾燥膜厚として、好ましくは１０ｎｍ以上、さらに好ましくは５０ｎｍ以上である。一方、好ましくは３０μｍ以下、さらに好ましくは１μｍ以下である。異方性色素膜の膜厚が適当な範囲にあることで、膜内で色素の均一な配向及び均一な膜厚を得られる傾向にある。 The thickness of the anisotropic dye film is preferably 10 nm or more, more preferably 50 nm or more as a dry film thickness. On the other hand, it is preferably 30 μm or less, more preferably 1 μm or less. When the thickness of the anisotropic dye film is in an appropriate range, it tends to be possible to obtain a uniform orientation and a uniform film thickness of the dye in the film.

異方性色素膜には、不溶化処理を行ってもよい。不溶化とは、異方性色素膜中の化合物の溶解性を低下させることにより、該化合物の異方性色素膜からの溶出を制御し、膜の安定性を高める処理工程を意味する。
具体的には、例えば少ない価数のイオンを、それより大きい価数のイオンに置き換える（例えば、１価のイオンを多価のイオンに置き換える）処理や、イオン基を複数有する有機分子やポリマーに置き換える処理が挙げられる。このような処理方法としては、例えば、細田豊著「理論製造 染色化学」（技報堂、１９５７年）４３５～４３７頁等に記載されている処理工程等の公知の方法を用いることができる。
これらの中でも、得られた異方性色素膜を特開２００７－２４１２６７号公報等に記載の方法で処理し、水に対して不溶性の異方性色素膜とすることが、後工程の容易さ、耐久性等の点から好ましい。 The anisotropic dye film may be insolubilized. The insolubilization means a treatment step of controlling the elution of the compound from the anisotropic dye film by reducing the solubility of the compound in the anisotropic dye film and enhancing the stability of the film.
Specifically, for example, a process of replacing a low valence ion with a higher valence ion (for example, replacing a monovalent ion with a polyvalent ion), or an organic molecule or polymer having a plurality of ionic groups. The process of replacement can be mentioned. As such a treatment method, for example, a known method such as the treatment step described in "Theoretical Manufacturing Dyeing Chemistry" (Gihodo, 1957), pp. 435-437 by Yutaka Hosoda can be used.
Among these, it is easier to carry out the subsequent step by treating the obtained anisotropic dye film by the method described in JP-A-2007-241267 to obtain an anisotropic dye film insoluble in water. , Preferable from the viewpoint of durability and the like.

［異方性色素膜］
本発明の異方性色素膜は、本発明の異方性色素膜形成用組成物を用いて形成することができる。
また、本発明の異方性色素膜は、色素、酸性基及び塩基性基を有する高分子化合物、並びに、水溶性有機化合物を含むものであってもよい。
本発明の異方性色素膜を液晶ディスプレイ用の偏光素子として使う場合は、異方性色素膜の配向特性は二色比を用いて表すことができる。二色比は８以上あれば偏光素子として機能するが、１５以上が好ましく、２０以上がさらに好ましく、２５以上がさらに好ましく、３０以上が特に好ましい。また、二色比は高いほど好ましい。二色比が特定値以上であることで、後述する光学素子、特に偏光素子として有用である。 [Anisotropy dye film]
The anisotropic dye film of the present invention can be formed by using the composition for forming an anisotropic dye film of the present invention.
Further, the anisotropic dye film of the present invention may contain a dye, a polymer compound having an acidic group and a basic group, and a water-soluble organic compound.
When the anisotropic dye film of the present invention is used as a polarizing element for a liquid crystal display, the orientation characteristics of the anisotropic dye film can be expressed by using a two-color ratio. When the two-color ratio is 8 or more, it functions as a polarizing element, but 15 or more is preferable, 20 or more is further preferable, 25 or more is further preferable, and 30 or more is particularly preferable. Further, the higher the two-color ratio, the more preferable. When the two-color ratio is equal to or higher than a specific value, it is useful as an optical element described later, particularly a polarizing element.

本発明で言う二色比（Ｄ）とは、色素が一様に配向している場合、以下の式で表される。
Ｄ＝Ａｚ／Ａｙ
ここで、Ａｚは異方性色素膜に入射した光の偏光方向が色素の配向方向に平行な場合に観測される吸光度であり、Ａｙはその偏光方向が垂直な場合に観測される吸光度である。それぞれの吸光度は同じ波長のものを用いれば特に制限なく、目的によっていずれの波長を選択してもよいが、異方性色素膜の配向の度合を表す場合は、異方性色素膜の極大吸収波長における値を用いることが好ましい。 The two-color ratio (D) referred to in the present invention is expressed by the following formula when the dyes are uniformly oriented.
D = Az / Ay
Here, Az is the absorbance observed when the polarization direction of the light incident on the anisotropic dye film is parallel to the orientation direction of the dye, and Ay is the absorbance observed when the polarization direction is vertical. .. The absorbance of each of them is not particularly limited as long as it has the same wavelength, and any wavelength may be selected depending on the purpose. However, when expressing the degree of orientation of the anisotropic dye film, the maximum absorption of the anisotropic dye film is used. It is preferable to use the value at the wavelength.

また、本発明の異方性色素膜の可視光波長域における透過率は、好ましくは２５％以上である。３５％以上がさらに好ましく、４０％以上が特に好ましい。また、透過率は用途に応じた上限であればよい。
例えば、偏光度を高くする場合には、透過率は５０％以下であることが好ましい。透過率が特定範囲であることで、下記の光学素子として有用であり、特にカラー表示に用いる液晶ディスプレイ用の光学素子として有用である。 Further, the transmittance of the anisotropic dye film of the present invention in the visible light wavelength range is preferably 25% or more. 35% or more is more preferable, and 40% or more is particularly preferable. Further, the transmittance may be an upper limit according to the application.
For example, when the degree of polarization is increased, the transmittance is preferably 50% or less. Having a specific range of transmittance makes it useful as the following optical element, and particularly useful as an optical element for a liquid crystal display used for color display.

［光学素子］
本発明の光学素子は、本発明の異方性色素膜を含む。
本発明において、光学素子は、光吸収の異方性を利用し直線偏光、円偏光、楕円偏光等を得る偏光素子、位相差素子、屈折異方性や伝導異方性等の機能を有する素子を表す。これらの機能は、異方性色素膜形成プロセスと基板や有機化合物（色素や透明材料）を含有する組成物の選択により、適宜調整することができる。本発明では、偏光素子として用いることが最も好ましい。 [Optical element]
The optical device of the present invention includes the anisotropic dye film of the present invention.
In the present invention, the optical element is a polarizing element that obtains linear polarization, circular polarization, elliptically polarized light, etc. by utilizing the anisotropy of light absorption, a retardation element, and an element having functions such as refraction anisotropy and conduction anisotropy. Represents. These functions can be appropriately adjusted by the anisotropic dye film forming process and the selection of the substrate and the composition containing the organic compound (dye or transparent material). In the present invention, it is most preferable to use it as a polarizing element.

［偏光素子］
本発明の偏光素子は、本発明の異方性色素膜を含む。
本発明の偏光素子は、本発明の異方性色素膜を有するものであれば他の如何なる膜（層）を有するものであってもよい。例えば、基板上に配向膜を設け、該配向膜の表面に、異方性色素膜を形成することにより製造することができる。
また、偏光素子は異方性色素膜だけに限らず、偏光性能を向上させる、機械的強度を向上させる等の機能を有するオーバーコート層；粘着層又は反射防止層；配向膜；位相差フィルムとしての機能、輝度向上フィルムとしての機能、反射又は反射防止フィルムとしての機能、半透過反射フィルムとしての機能、拡散フィルムとしての機能などの光学機能を有する層；等、と組み合わせて使用してもよい。具体的には、前述の様々な機能を有する層を塗布や貼合等により積層形成し、積層体として使用してもよい。
これらの層は、製造プロセス、特性及び機能に合わせ適宜設けることができ、その積層の位置、順番等は特に限定されない。例えば、上記各層を形成する位置は、異方性色素膜の上に形成してもよく、また、異方性色素膜を設けた基板の反対面に形成してもよい。一方、上記各層を形成する順番は、異方性色素膜を形成する前でも形成した後でもよい。 [Polarizing element]
The polarizing element of the present invention includes the anisotropic dye film of the present invention.
The polarizing element of the present invention may have any other film (layer) as long as it has the anisotropic dye film of the present invention. For example, it can be manufactured by providing an alignment film on a substrate and forming an anisotropic dye film on the surface of the alignment film.
Further, the polarizing element is not limited to the anisotropic dye film, but as an overcoat layer having functions such as improving polarization performance and mechanical strength; an adhesive layer or an antireflection layer; an alignment film; a retardation film. It may be used in combination with a layer having optical functions such as a function as a brightness improving film, a function as a reflection or antireflection film, a function as a transflective reflective film, and a function as a diffusion film; .. Specifically, the above-mentioned layers having various functions may be laminated and formed by coating, bonding, or the like, and used as a laminated body.
These layers can be appropriately provided according to the manufacturing process, characteristics, and functions, and the position, order, and the like of the layers are not particularly limited. For example, the position where each of the above layers is formed may be formed on the anisotropic dye film, or may be formed on the opposite surface of the substrate provided with the anisotropic dye film. On the other hand, the order of forming each of the above layers may be before or after forming the anisotropic dye film.

これら光学機能を有する層は、以下の様な方法により形成することができる。
位相差フィルムとしての機能を有する層は、以下のような方法で得られた位相差フィルムを、偏光素子を構成する他の層に貼合等を行うことにより、形成することができる。
位相差フィルムは、例えば、特開平２－５９７０３号公報、特開平４－２３０７０４号公報等に記載の延伸処理を施したり、特開平７－２３０００７号公報等に記載された処理を施したりすることにより形成することができる。 The layer having these optical functions can be formed by the following method.
The layer having a function as a retardation film can be formed by laminating a retardation film obtained by the following method to another layer constituting the polarizing element.
The retardation film may be subjected to, for example, the stretching treatment described in JP-A-2-59703, JP-A-4-230704, etc., or the treatment described in JP-A-7-230007. Can be formed by

輝度向上フィルムとしての機能を有する層は、以下のような方法で得られた輝度向上フィルムを、偏光素子を構成する他の層に貼合等を行うことにより、形成することができる。
輝度向上フィルムは、例えば、特開２００２－１６９０２５号公報及び特開２００３－２９０３０号公報に記載されるような方法で微細孔を形成すること、又は、選択反射の中心波長が異なる２層以上のコレステリック液晶層を重畳することにより形成することができる。 The layer having a function as a luminance improving film can be formed by laminating a luminance improving film obtained by the following method to another layer constituting the polarizing element.
The luminance-improving film has, for example, two or more layers in which micropores are formed by the methods described in JP-A-2002-1690.25 and JP-A-2003-29030, or the center wavelength of selective reflection is different. It can be formed by superimposing a cholesteric liquid crystal layer.

反射フィルムまたは半透過反射フィルムとしての機能を有する層は、例えば、蒸着やスパッタリングなどで得られた金属薄膜を、偏光素子を構成する他の層に貼合等を行うことにより、形成することができる。
拡散フィルムとしての機能を有する層は、例えば、偏光素子を構成する他の層に微粒子を含む樹脂溶液をコーティングすることにより、形成することができる。 The layer having a function as a reflective film or a transflective reflective film can be formed, for example, by laminating a metal thin film obtained by vapor deposition or sputtering to another layer constituting the polarizing element. can.
The layer having a function as a diffusion film can be formed, for example, by coating another layer constituting the polarizing element with a resin solution containing fine particles.

また、位相差フィルムや光学補償フィルムとしての機能を有する層は、ディスコティック液晶性化合物、ネマティック液晶性化合物等の液晶性化合物を、偏光素子を構成する他の層に塗布して配向させることにより形成することができる。 Further, the layer having a function as a retardation film or an optical compensation film is formed by applying a liquid crystal compound such as a discotic liquid crystal compound or a nematic liquid crystal compound to another layer constituting the polarizing element and aligning the layer. Can be formed.

本実施の形態における異方性色素膜をＬＣＤやＯＬＥＤ等の各種の表示素子に異方性色素膜等として用いる場合には、これらの表示素子を構成する電極基板等の表面に直接異方性色素膜を形成したり、異方性色素膜を形成した基板をこれら表示素子の構成部材として用いたりすることができる。
本発明の光学素子は、基板上に塗布などにより異方性色素膜を形成することで偏光素子を得ることができるという点から、フレキシブルディスプレイ等の用途にも好適に使用することができる。 When the anisotropic dye film in the present embodiment is used as an anisotropic dye film or the like for various display elements such as LCDs and OLEDs, it is directly anisotropic to the surface of the electrode substrate or the like constituting these display elements. A dye film can be formed, or a substrate on which an anisotropic dye film is formed can be used as a constituent member of these display elements.
The optical element of the present invention can be suitably used for applications such as flexible displays because a polarizing element can be obtained by forming an anisotropic dye film on a substrate by coating or the like.

実施例により本発明をさらに具体的に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。
なお、下記の実施例における物性、製造条件および評価結果等の各種数値は、本発明の実施態様における上限または下限の好ましい値としての意味を持つものであり、好ましい範囲は前記した上限または下限の値と下記実施例の値との組合せまたは実施例同士の値の組合せで規定される範囲であってもよい。
以下の記載において、「部」は「質量部」を示し、「％」は「重量％」を示す。 The present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.
In addition, various numerical values such as physical properties, manufacturing conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-mentioned upper limit or the lower limit. It may be in the range specified by the combination of the value and the value of the following examples or the combination of the values of the examples.
In the following description, "parts" indicates "parts by mass" and "%" indicates "% by weight".

Ｄｙｅ－１の合成
４－アミノベンズアミド５．４５質量部、および水２００質量部に塩酸酸性条件下、亜硝酸ナトリウム３．００質量部を加えてジアゾ化し、水２４０質量部に溶解した８－アミノ－２－ナフタレンスルホン酸（１，７－クレーブ酸）８．９３質量部とｐＨ＝２～３でカップリングを行った後、中和、塩析して析出固体を濾過分離し、モノアゾ化合物のウエットケーキを得た。
このモノアゾ化合物のウエットケーキをＮ－メチルピロリドン２２０質量部、および水１１０質量部に溶解し、塩酸酸性条件下、亜硝酸ナトリウム３．００質量部を加えてジアゾ化し、水２００質量部に溶解した８－アミノ－２－ナフタレンスルホン酸（１，７－クレーブ酸）８．９３質量部とｐＨ＝２～３でカップリングを行った後、塩析して析出物を取り出した。水に溶解して水酸化ナトリウムで中和し、イソプロピルアルコールを加えて析出固体を濾過分離し、得られたウエットケーキを乾燥することにより、下記式（Ｉ－１）で表されるアゾ色素のナトリウム塩３１．１質量部を得た。 Synthesis of Dye-1 To 5.45 parts by mass of 4-aminobenzamide and 200 parts by mass of water under acidic hydrochloric acid conditions, 3.00 parts by mass of sodium nitrite was added to diazotize, and 8-amino was dissolved in 240 parts by mass of water. After coupling with 8.93 parts by mass of -2-naphthalene sulfonic acid (1,7-clave acid) at pH = 2-3, neutralization and salting out were performed to separate the precipitated solid by filtration to separate the monoazo compound. I got a wet cake.
The wet cake of this monoazo compound was dissolved in 220 parts by mass of N-methylpyrrolidone and 110 parts by mass of water, and under acidic hydrochloric acid conditions, 3.00 parts by mass of sodium nitrite was added to diazotize and dissolved in 200 parts by mass of water. After coupling with 8.93 parts by mass of 8-amino-2-naphthalene sulfonic acid (1,7-clave acid) at pH = 2 to 3, the precipitate was removed by salting out. The azo dye represented by the following formula (I-1) is obtained by dissolving it in water, neutralizing it with sodium hydroxide, adding isopropyl alcohol, filtering and separating the precipitated solid, and drying the obtained wet cake. 31.1 parts by mass of sodium salt was obtained.

Figure 0007024458000003
Figure 0007024458000003

式（Ｉ－１）で表されるアゾ色素のナトリウム塩３１．３質量部をＮ－メチルピロリドン２００質量部、及び水２６０質量部に溶解した。塩酸酸性条件下、さらに、亜硝酸ナトリウム３．０４質量部を加えてジアゾ化し、水４００質量部に溶解した７－アミノ－１－ナフトール－３，６－ジスルホン酸（ＲＲ酸）（純度：６５．５％）１９．５質量部とｐＨ＝９～１０でカップリングを行った。反応後、析出固体を濾過分離し、下記で表される（Ｉ－２）のナトリウム塩を得た。 31.3 parts by mass of the sodium salt of the azo dye represented by the formula (I-1) was dissolved in 200 parts by mass of N-methylpyrrolidone and 260 parts by mass of water. Under acidic hydrochloric acid conditions, 3.04 parts by mass of sodium nitrite was further added to diazotize, and 7-amino-1-naphthol-3,6-disulfonic acid (RR acid) dissolved in 400 parts by mass of water (purity: 65). Coupling was performed with 19.5 parts by mass and pH = 9-10. After the reaction, the precipitated solid was separated by filtration to obtain the sodium salt (I-2) represented below.

Figure 0007024458000004
Figure 0007024458000004

式（Ｉ－２）で表されるトリスアゾ色素のナトリウム塩の水溶液を陽イオン交換樹脂（三菱ケミカル社製ＳＫ１ＢＨ）に通し、遊離酸の水溶液とした後、水酸化リチウム水溶液で中和、濃縮乾燥することにより、下記Ｄｙｅ－１で表されるトリスアゾ色素のリチウム塩を得た。 An aqueous solution of the sodium salt of the trisazo dye represented by the formula (I-2) is passed through a cation exchange resin (SK1BH manufactured by Mitsubishi Chemical Corporation) to prepare an aqueous solution of free acid, then neutralized with an aqueous solution of lithium hydroxide and concentrated and dried. By doing so, a lithium salt of the trisazo dye represented by the following Dye-1 was obtained.

Figure 0007024458000005
Figure 0007024458000005

[比較例１]
Ｄｙｅ－１とアリルアミンとアリルスルホン酸が４：６のモル比で含まれる共重合体の対カチオンをリチウムに塩交換して得られた酸性基及び塩基性基を有する高分子化合物（ポリマーＡ）（質量平均分子量：１７００）を６０：４０の質量比率で混ぜ、固形分濃度が１８％の溶液になるように水を添加した。その後、８０℃で９０分攪拌して完全に溶解させ、異方性色素膜形成用組成物１を作製した。
偏光顕微鏡を用いて常温（２５℃）にて液晶性の確認をしたところ、均一な液晶状態であることが確認できた。昇温させた時の等方相出現温度は５１．３℃であった。また、常温の粘度をＥ型粘度計で測定したところ、ローター回転数１０ｒｐｍの条件で１１６ｃＰであった。
なお、合成したポリマーの対カチオンのリチウム塩への交換は、ナトリウム塩体のポリマー水溶液を陽イオン交換樹脂（三菱ケミカル社製ＳＫ１ＢＨ）に通し、遊離酸の水溶液とした後、水酸化リチウム水溶液でｐＨが７．０になるまで中和し、濃縮乾燥することにより実施した。 [Comparative Example 1]
Polymer compound (polymer A) having an acidic group and a basic group obtained by salt exchanging the counter cation of a copolymer containing Dye-1, allylamine and allylsulfonic acid in a molar ratio of 4: 6 with lithium. (Mass average molecular weight: 1700) was mixed at a mass ratio of 60:40, and water was added so that the solution had a solid content concentration of 18%. Then, the mixture was stirred at 80 ° C. for 90 minutes to completely dissolve the composition 1 for forming an anisotropic dye film.
When the liquid crystal property was confirmed at room temperature (25 ° C.) using a polarizing microscope, it was confirmed that the liquid crystal state was uniform. The temperature at which the isotropic phase appeared when the temperature was raised was 51.3 ° C. Moreover, when the viscosity at room temperature was measured with an E-type viscometer, it was 116 cP under the condition of a rotor rotation speed of 10 rpm.
To exchange the synthesized polymer with a lithium salt for the cation, pass the aqueous polymer solution of the sodium salt through a cation exchange resin (SK1BH manufactured by Mitsubishi Chemical Corporation) to make an aqueous solution of free acid, and then use an aqueous solution of lithium hydroxide. This was carried out by neutralizing until the pH reached 7.0 and concentrating and drying.

[比較例２]
比較例１において、固形分濃度が１７％の溶液になるように水を混ぜた以外は比較例１と同様に、異方性色素膜形成用組成物２を作製した。
偏光顕微鏡を用いて常温（２５℃）にて液晶性の確認をしたところ、均一な液晶状態であることが確認できた。昇温させた時の等方相出現温度は４６．４℃であった。また常温の粘度をＥ型粘度計で測定したところ、ローター回転数１０ｒｐｍの条件で１１１ｃＰであった。 [Comparative Example 2]
In Comparative Example 1, an anisotropic dye film forming composition 2 was prepared in the same manner as in Comparative Example 1 except that water was mixed so as to obtain a solution having a solid content concentration of 17%.
When the liquid crystal property was confirmed at room temperature (25 ° C.) using a polarizing microscope, it was confirmed that the liquid crystal state was uniform. The temperature at which the isotropic phase appeared when the temperature was raised was 46.4 ° C. Moreover, when the viscosity at room temperature was measured with an E-type viscometer, it was 111 cP under the condition of a rotor rotation speed of 10 rpm.

[比較例３]
比較例２において、Ｄｙｅ－１とポリマーＡを３０：７０の質量比率で混ぜた以外は比較例２と同様に、固形分濃度が１７％の異方性色素膜形成用組成物３を作製した。
偏光顕微鏡を用いて常温（２５℃）にて液晶性の確認をしたところ、均一な液晶状態であることが確認できた。昇温させた時の等方相出現温度は２９．７℃であった。また常温の粘度をＥ型粘度計で測定したところ、ローター回転数１０ｒｐｍの条件で１３９ｃＰであった。 [Comparative Example 3]
In Comparative Example 2, an anisotropic dye film forming composition 3 having a solid content concentration of 17% was prepared in the same manner as in Comparative Example 2 except that Dye-1 and Polymer A were mixed at a mass ratio of 30:70. ..
When the liquid crystal property was confirmed at room temperature (25 ° C.) using a polarizing microscope, it was confirmed that the liquid crystal state was uniform. The temperature at which the isotropic phase appeared when the temperature was raised was 29.7 ° C. Moreover, when the viscosity at room temperature was measured with an E-type viscometer, it was 139 cP under the condition of a rotor rotation speed of 10 rpm.

[実施例１]
比較例１において、異方性色素膜形成用組成物の固形分に対して０．０２％のフッ素系水溶性有機化合物（ＤＩＣ株式会社製メガファックＦ－４４４。親水基としてエチレンオキサイド基を有し、疎水基としてパーフルオロアルキルを有する。）をさらに添加した以外は比較例１と同様に、固形分濃度が１８％の異方性色素膜形成用組成物４を作製した。
偏光顕微鏡を用いて常温（２５℃）にて液晶性の確認をしたところ、均一な液晶状態であることが確認できた。昇温させた時の等方相出現温度は６５．２℃であった。また常温の粘度をＥ型粘度計で測定したところ、ローター回転数１０ｒｐｍの条件で１１５ｃＰであった。 [Example 1]
In Comparative Example 1, a fluorine-based water-soluble organic compound (Megafuck F-444 manufactured by DIC Corporation) having 0.02% of the solid content of the composition for forming an anisotropic dye film has an ethylene oxide group as a hydrophilic group. The composition 4 for forming an anisotropic dye film having a solid content concentration of 18% was prepared in the same manner as in Comparative Example 1 except that (perfluoroalkyl as a hydrophobic group) was further added.
When the liquid crystal property was confirmed at room temperature (25 ° C.) using a polarizing microscope, it was confirmed that the liquid crystal state was uniform. The temperature at which the isotropic phase appeared when the temperature was raised was 65.2 ° C. Moreover, when the viscosity at room temperature was measured with an E-type viscometer, it was 115 cP under the condition of a rotor rotation speed of 10 rpm.

[実施例２]
比較例１において、異方性色素膜形成用組成物の固形分に対して０．０２％のフッ素系水溶性有機化合物（ＤＩＣ株式会社製メガファックＦ－４７７。親水基を有し、疎水基としてフッ素基を有する。）をさらに添加した以外は比較例１と同様に、固形分濃度が１８％の異方性色素膜形成用組成物５を作製した。
偏光顕微鏡を用いて常温（２５℃）にて液晶性の確認をしたところ、均一な液晶状態であることが確認できた。昇温させた時の等方相出現温度は４８．３℃であった。また常温の粘度をＥ型粘度計で測定したところ、ローター回転数１０ｒｐｍの条件で１１２ｃＰであった。 [Example 2]
In Comparative Example 1, a fluorine-based water-soluble organic compound (Megafuck F-477 manufactured by DIC Corporation, which has a hydrophilic group and a hydrophobic group) of 0.02% with respect to the solid content of the composition for forming an anisotropic dye film. The composition 5 for forming an anisotropic dye film having a solid content concentration of 18% was prepared in the same manner as in Comparative Example 1 except that a fluorine group was further added.
When the liquid crystal property was confirmed at room temperature (25 ° C.) using a polarizing microscope, it was confirmed that the liquid crystal state was uniform. The temperature at which the isotropic phase appeared when the temperature was raised was 48.3 ° C. Moreover, when the viscosity at room temperature was measured with an E-type viscometer, it was 112 cP under the condition of a rotor rotation speed of 10 rpm.

[実施例３]
比較例１において、異方性色素膜形成用組成物の固形分に対して０．０２％のフッ素系水溶性有機化合物（ＤＩＣ株式会社製メガファックＦ－５５３。親水基を有し、疎水基としてフッ素基を有する。）をさらに添加した以外は比較例１と同様に、固形分濃度が１８％の異方性色素膜形成用組成物６を作製した。
偏光顕微鏡を用いて常温（２５℃）にて液晶性の確認をしたところ、均一な液晶状態であることが確認できた。昇温させた時の等方相出現温度は５６．８℃であった。また常温の粘度をＥ型粘度計で測定したところ、ローター回転数１０ｒｐｍの条件で１０８ｃＰであった。 [Example 3]
In Comparative Example 1, a fluorine-based water-soluble organic compound (Megafuck F-553 manufactured by DIC Corporation, which has a hydrophilic group and a hydrophobic group) of 0.02% with respect to the solid content of the composition for forming an anisotropic dye film. A composition 6 for forming an anisotropic dye film having a solid content concentration of 18% was prepared in the same manner as in Comparative Example 1 except that a fluorine group was further added.
When the liquid crystal property was confirmed at room temperature (25 ° C.) using a polarizing microscope, it was confirmed that the liquid crystal state was uniform. The temperature at which the isotropic phase appeared when the temperature was raised was 56.8 ° C. Moreover, when the viscosity at room temperature was measured with an E-type viscometer, it was 108 cP under the condition of a rotor rotation speed of 10 rpm.

[実施例４]
比較例１において、異方性色素膜形成用組成物の固形分に対して０．０２％のフッ素系水溶性有機化合物（ＤＩＣ株式会社製メガファックＦ－５５６。親水基を有し、疎水基としてフッ素基を有する。）をさらに添加した以外は比較例１と同様に、固形分濃度が１８％の異方性色素膜形成用組成物７を作製した。
偏光顕微鏡を用いて常温（２５℃）にて液晶性の確認をしたところ、均一な液晶状態であることが確認できた。昇温させた時の等方相出現温度は４９．８℃であった。また常温の粘度をＥ型粘度計で測定したところ、ローター回転数１０ｒｐｍの条件で１０８ｃＰであった。 [Example 4]
In Comparative Example 1, a fluorine-based water-soluble organic compound (Megafuck F-556 manufactured by DIC Corporation, which has a hydrophilic group and a hydrophobic group) of 0.02% with respect to the solid content of the composition for forming an anisotropic dye film. A composition 7 for forming an anisotropic dye film having a solid content concentration of 18% was prepared in the same manner as in Comparative Example 1 except that a fluorine group was further added.
When the liquid crystal property was confirmed at room temperature (25 ° C.) using a polarizing microscope, it was confirmed that the liquid crystal state was uniform. The temperature at which the isotropic phase appeared when the temperature was raised was 49.8 ° C. Moreover, when the viscosity at room temperature was measured with an E-type viscometer, it was 108 cP under the condition of a rotor rotation speed of 10 rpm.

[実施例５]
比較例１において、異方性色素膜形成用組成物の固形分に対して０．０２％のシリコーン系水溶性有機化合物（ビックケミー社製ＢＹＫ－３４８。親水基としてポリエーテル基を有し、疎水基としてシロキサン基を有する。）をさらに添加した以外は比較例１と同様に、固形分濃度が１８％の異方性色素膜形成用組成物８を作製した。
偏光顕微鏡を用いて常温（２５℃）にて液晶性の確認をしたところ、均一な液晶状態であることが確認できた。昇温させた時の等方相出現温度は５１．２℃であった。また常温の粘度をＥ型粘度計で測定したところ、ローター回転数１０ｒｐｍの条件で１１２ｃＰであった。 [Example 5]
In Comparative Example 1, a silicone-based water-soluble organic compound (BYK-348 manufactured by Big Chemie Co., Ltd.) having 0.02% of the solid content of the composition for forming an anisotropic dye film has a polyether group as a hydrophilic group and is hydrophobic. A composition 8 for forming an anisotropic dye film having a solid content concentration of 18% was prepared in the same manner as in Comparative Example 1 except that a siloxane group was further added as a group.
When the liquid crystal property was confirmed at room temperature (25 ° C.) using a polarizing microscope, it was confirmed that the liquid crystal state was uniform. The temperature at which the isotropic phase appeared when the temperature was raised was 51.2 ° C. Moreover, when the viscosity at room temperature was measured with an E-type viscometer, it was 112 cP under the condition of a rotor rotation speed of 10 rpm.

[実施例６]
比較例１において、異方性色素膜形成用組成物の固形分に対して０．０２％のシリコーン系水溶性有機化合物（ビックケミー社製ＢＹＫ－３４９。親水基としてポリエーテル基を有し、疎水基としてシロキサン基を有する。）をさらに添加した以外は比較例１と同様に、固形分濃度が１８％の異方性色素膜形成用組成物９を作製した。
偏光顕微鏡を用いて常温（２５℃）にて液晶性の確認をしたところ、均一な液晶状態であることが確認できた。昇温させた時の等方相出現温度は５１．５℃であった。また常温の粘度をＥ型粘度計で測定したところ、ローター回転数１０ｒｐｍの条件で１０３ｃＰであった。 [Example 6]
In Comparative Example 1, a silicone-based water-soluble organic compound (BYK-349 manufactured by Big Chemie Co., Ltd.) having 0.02% of the solid content of the composition for forming an anisotropic dye film has a polyether group as a hydrophilic group and is hydrophobic. A composition 9 for forming an anisotropic dye film having a solid content concentration of 18% was prepared in the same manner as in Comparative Example 1 except that a siloxane group was further added as a group.
When the liquid crystal property was confirmed at room temperature (25 ° C.) using a polarizing microscope, it was confirmed that the liquid crystal state was uniform. The temperature at which the isotropic phase appeared when the temperature was raised was 51.5 ° C. Moreover, when the viscosity at room temperature was measured with an E-type viscometer, it was 103 cP under the condition of a rotor rotation speed of 10 rpm.

[実施例７]
比較例１において、異方性色素膜形成用組成物の固形分に対して０．０２％のシリコーン系水溶性有機化合物（信越化学工業株式会社製ＫＰ－１０４。親水基としてポリオール基を有し、疎水基としてシロキサン基を有する。）をさらに添加した以外は比較例１と同様に、固形分濃度が１８％の異方性色素膜形成用組成物１０を作製した。
偏光顕微鏡を用いて常温（２５℃）にて液晶性の確認をしたところ、均一な液晶状態であることが確認できた。昇温させた時の等方相出現温度は５１．０℃であった。また常温の粘度をＥ型粘度計で測定したところ、ローター回転数１０ｒｐｍの条件で１１６ｃＰであった。 [Example 7]
In Comparative Example 1, a silicone-based water-soluble organic compound (KP-104 manufactured by Shin-Etsu Chemical Co., Ltd.) having 0.02% with respect to the solid content of the composition for forming an anisotropic dye film, having a polyol group as a hydrophilic group. , Which has a siloxane group as a hydrophobic group) was further added to prepare an anisotropic dye film forming composition 10 having a solid content concentration of 18% in the same manner as in Comparative Example 1.
When the liquid crystal property was confirmed at room temperature (25 ° C.) using a polarizing microscope, it was confirmed that the liquid crystal state was uniform. The temperature at which the isotropic phase appeared when the temperature was raised was 51.0 ° C. Moreover, when the viscosity at room temperature was measured with an E-type viscometer, it was 116 cP under the condition of a rotor rotation speed of 10 rpm.

[実施例８]
比較例２において、異方性色素膜形成用組成物の固形分に対して０．０１％のシリコーン系水溶性有機化合物（ビックケミー社製ＢＹＫ－３４９。親水基としてポリエーテル基を有し、疎水基としてシロキサン基を有する。）をさらに添加した以外は比較例２と同様に、固形分濃度が１７％の異方性色素膜形成用組成物１１を作製した。
偏光顕微鏡を用いて常温（２５℃）にて液晶性の確認をしたところ、均一な液晶状態であることが確認できた。昇温させた時の等方相出現温度は４５．１℃であった。また常温の粘度をＥ型粘度計で測定したところ、ローター回転数１０ｒｐｍの条件で１１０ｃＰであった。 [Example 8]
In Comparative Example 2, a silicone-based water-soluble organic compound (BYK-349 manufactured by Big Chemie Co., Ltd.) having a polyether group as a hydrophilic group and hydrophobic with respect to the solid content of the composition for forming an anisotropic dye film was 0.01%. A composition 11 for forming an anisotropic dye film having a solid content concentration of 17% was prepared in the same manner as in Comparative Example 2 except that a siloxane group was further added as a group.
When the liquid crystal property was confirmed at room temperature (25 ° C.) using a polarizing microscope, it was confirmed that the liquid crystal state was uniform. The temperature at which the isotropic phase appeared when the temperature was raised was 45.1 ° C. Moreover, when the viscosity at room temperature was measured with an E-type viscometer, it was 110 cP under the condition of a rotor rotation speed of 10 rpm.

[実施例９]
比較例２において、異方性色素膜形成用組成物の固形分に対して０．０１％のアクリル系水溶性有機化合物（ビックケミー社製ＢＹＫ－３８０Ｎ。親水基及び疎水基を有し、これらをブロック構造で有する。）をさらに添加した以外は比較例２と同様に、固形分濃度が１７％の異方性色素膜形成用組成物１２を作製した。
偏光顕微鏡を用いて常温（２５℃）にて液晶性の確認をしたところ、均一な液晶状態であることが確認できた。昇温させた時の等方相出現温度は４５．５℃であった。また常温の粘度をＥ型粘度計で測定したところ、ローター回転数１０ｒｐｍの条件で１１１ｃＰであった。 [Example 9]
In Comparative Example 2, an acrylic water-soluble organic compound (BYK-380N manufactured by Big Chemie Co., Ltd., which has a hydrophilic group and a hydrophobic group, which is 0.01% with respect to the solid content of the composition for forming an anisotropic dye film, is used. A composition 12 for forming an anisotropic dye film having a solid content concentration of 17% was prepared in the same manner as in Comparative Example 2 except that (having a block structure) was further added.
When the liquid crystal property was confirmed at room temperature (25 ° C.) using a polarizing microscope, it was confirmed that the liquid crystal state was uniform. The temperature at which the isotropic phase appeared when the temperature was raised was 45.5 ° C. Moreover, when the viscosity at room temperature was measured with an E-type viscometer, it was 111 cP under the condition of a rotor rotation speed of 10 rpm.

[実施例１０]
比較例３において、異方性色素膜形成用組成物の固形分に対して０．００６％のシリコーン系水溶性有機化合物（ビックケミー社製ＢＹＫ－３４８。親水基としてポリエーテル基を有し、疎水基としてアルキル基を有する。）をさらに添加した以外は比較例３と同様に、固形分濃度が１７％の異方性色素膜形成用組成物１３を作製した。
偏光顕微鏡を用いて常温（２５℃）にて液晶性の確認をしたところ、均一な液晶状態であることが確認できた。昇温させた時の等方相出現温度は３０．７℃であった。また常温の粘度をＥ型粘度計で測定したところ、ローター回転数１０ｒｐｍの条件で１３４ｃＰであった。 [Example 10]
In Comparative Example 3, a silicone-based water-soluble organic compound (BYK-348 manufactured by Big Chemie Co., Ltd.) having 0.006% with respect to the solid content of the composition for forming an anisotropic dye film, having a polyether group as a hydrophilic group and hydrophobic. A composition 13 for forming an anisotropic dye film having a solid content concentration of 17% was prepared in the same manner as in Comparative Example 3 except that (having an alkyl group as a group) was further added.
When the liquid crystal property was confirmed at room temperature (25 ° C.) using a polarizing microscope, it was confirmed that the liquid crystal state was uniform. The temperature at which the isotropic phase appeared when the temperature was raised was 30.7 ° C. Moreover, when the viscosity at room temperature was measured with an E-type viscometer, it was 134 cP under the condition of a rotor rotation speed of 10 rpm.

[実施例１１]
比較例３において、異方性色素膜形成用組成物の固形分に対して０．００６％のシリコーン系水溶性有機化合物（ビックケミー社製ＢＹＫ－３４９。親水基としてポリエーテル基を有し、疎水基としてシロキサン基を有する。）をさらに添加した以外は比較例３と同様に、固形分濃度が１７％の異方性色素膜形成用組成物１４を作製した。
偏光顕微鏡を用いて常温（２５℃）にて液晶性の確認をしたところ、均一な液晶状態であることが確認できた。昇温させた時の等方相出現温度は３０．４℃であった。また常温の粘度をＥ型粘度計で測定したところ、ローター回転数１０ｒｐｍの条件で１３２ｃＰであった。 [Example 11]
In Comparative Example 3, a silicone-based water-soluble organic compound (BYK-349 manufactured by Big Chemie Co., Ltd.) having 0.006% with respect to the solid content of the composition for forming an anisotropic dye film, having a polyether group as a hydrophilic group and hydrophobic. A composition 14 for forming an anisotropic dye film having a solid content concentration of 17% was prepared in the same manner as in Comparative Example 3 except that a siloxane group was further added as a group.
When the liquid crystal property was confirmed at room temperature (25 ° C.) using a polarizing microscope, it was confirmed that the liquid crystal state was uniform. The temperature at which the isotropic phase appeared when the temperature was raised was 30.4 ° C. Moreover, when the viscosity at room temperature was measured with an E-type viscometer, it was 132 cP under the condition of a rotor rotation speed of 10 rpm.

[実施例１２]
比較例３において、異方性色素膜形成用組成物の固形分に対して０．００６％のアクリル系水溶性有機化合物（ビックケミー社製ＢＹＫ－３８０Ｎ。親水基及び疎水基を有し、これらをブロック構造で有する。）をさらに添加した以外は比較例３と同様に、固形分濃度が１７％の異方性色素膜形成用組成物１５を作製した。
偏光顕微鏡を用いて常温（２５℃）にて液晶性の確認をしたところ、均一な液晶状態であることが確認できた。昇温させた時の等方相出現温度は３２．０℃であった。また常温の粘度をＥ型粘度計で測定したところ、ローター回転数１０ｒｐｍの条件で１５８ｃＰであった。 [Example 12]
In Comparative Example 3, an acrylic water-soluble organic compound (BYK-380N manufactured by Big Chemie Co., Ltd., which has a hydrophilic group and a hydrophobic group, which is 0.006% with respect to the solid content of the composition for forming an anisotropic dye film, is used. A composition 15 for forming an anisotropic dye film having a solid content concentration of 17% was prepared in the same manner as in Comparative Example 3 except that (having a block structure) was further added.
When the liquid crystal property was confirmed at room temperature (25 ° C.) using a polarizing microscope, it was confirmed that the liquid crystal state was uniform. The temperature at which the isotropic phase appeared when the temperature was raised was 32.0 ° C. Further, when the viscosity at room temperature was measured with an E-type viscometer, it was 158 cP under the condition of a rotor rotation speed of 10 rpm.

［塗布試験］
実施例１～１２、比較例１～３で調製した異方性色素膜形成用組成物をそれぞれＵＶオゾン処理装置で６００秒間処理したガラス基板上にバーコーター（松尾産業製ＯＳＰシリーズ）を用いて速度４０ｍｍ/ｓの速度で機械塗布し、風乾して、異方性色素膜１～１５
を作製した。異方性色素膜を目視で観察し、バーによる塗布スジがみられない場合はＡ、塗布スジがみられる場合はＢと評価した。 [Applying test]
Using a bar coater (OSP series manufactured by Matsuo Sangyo) on a glass substrate obtained by treating the anisotropic dye film forming compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 3 with a UV ozone treatment device for 600 seconds, respectively. Mechanically applied at a speed of 40 mm / s, air-dried, and anisotropic dye films 1 to 15
Was produced. The anisotropic dye film was visually observed and evaluated as A when no coating streaks due to the bar were observed and B when coating streaks were observed.

［偏光性評価］
得られた各異方性色素膜について大塚電子製ＲＥＴＳ－ＴＳ１００を用いて、空気の透過率を１００％とした時の単体透過率（Ｔｓ）及び偏光度（Ｐｅ）を測定し、光学特性について評価した。
Ｔｓは２５％以上５０％以下であり、且つ、Ｐｅが１５以上であるものはＡ、Ｐｅが１５未満の場合をＢと評価した。 [Polarity evaluation]
For each of the obtained anisotropic dye films, the simple substance transmittance (Ts) and the degree of polarization (Pe) were measured when the air transmittance was 100% using Otsuka Electronics' RETS-TS100, and the optical characteristics were measured. evaluated.
When Ts was 25% or more and 50% or less and Pe was 15 or more, it was evaluated as A, and when Pe was less than 15, it was evaluated as B.

［フィルム転写試験］
温度２３℃、相対湿度７０％に調整した恒湿環境に、得られた各異方性色素膜を１日放置した。その後、３ｃｍ角にカットしたＰＥＴ製フィルムを塗膜の上に載せ、さらにそのフィルム上に直径２ｃｍの円柱状の２００ｇの錘を載せて１０秒間荷重を負荷した。フィルムをはがしてその裏移りを目視で評価し、異方性色素膜からの転写試験を実施した。フィルムへの転写が無い場合はＡ、フィルムに異方性色素膜の一部が転写する場合はＢとして、塗膜の機械特性を評価した。 [Film transfer test]
Each of the obtained anisotropic dye films was left for one day in a constant humidity environment adjusted to a temperature of 23 ° C. and a relative humidity of 70%. Then, a PET film cut into 3 cm squares was placed on the coating film, and a cylindrical 200 g weight having a diameter of 2 cm was placed on the film and loaded for 10 seconds. The film was peeled off, the set-off was visually evaluated, and a transfer test from the anisotropic dye film was carried out. The mechanical properties of the coating film were evaluated as A when there was no transfer to the film and B when a part of the anisotropic dye film was transferred to the film.

上記の評価結果から、色素及び特定の高分子化合物を含む比較例１～３、並びに、本発明の異方性色素膜形成用組成物は、いずれも常温で均一な液晶状態であり、耐湿性が改良されたものであった。
特に水溶性有機化合物を含む本発明の異方性色素膜形成用組成物は、塗布スジを有意に減少させ、また、フィルムへの転写性を有意に低下させた。さらに、粘度が大きく増加することなく、異方性色素膜形成用組成物の液晶性（等方相出現温度）や異方性色素膜の光学特性は維持されていた。これは塗布・乾燥の過程で水溶性有機化合物が塗膜表面に集積して表面張力を低下させると同時に、色素と酸性基及び塩基性基を有する高分子化合物からなる組成物の表面をカバーするためである。このことから、本発明の異方性色素膜形成用組成物は、塗膜の均一塗布化を実現し、さらにハンドリング性が高いことが示された。 From the above evaluation results, Comparative Examples 1 to 3 containing a dye and a specific polymer compound, and the composition for forming an anisotropic dye film of the present invention are all in a uniform liquid crystal state at room temperature and have moisture resistance. Was an improvement.
In particular, the composition for forming an anisotropic dye film of the present invention containing a water-soluble organic compound significantly reduced coating streaks and significantly reduced transferability to a film. Further, the liquid crystal property (isotropy appearance temperature) of the composition for forming an anisotropic dye film and the optical characteristics of the anisotropic dye film were maintained without significantly increasing the viscosity. This covers the surface of the composition composed of the dye and the polymer compound having an acidic group and a basic group at the same time as the water-soluble organic compound accumulates on the surface of the coating film in the process of coating and drying to reduce the surface tension. Because. From this, it was shown that the composition for forming an anisotropic dye film of the present invention realized uniform coating of a coating film and had high handleability.

Figure 0007024458000006
Figure 0007024458000006

Figure 0007024458000007
Figure 0007024458000007

Claims (11)

酸性基又は塩基性基を有する二色性色素、酸性基及び塩基性基を有する、線状又は分岐状の高分子化合物、並びに親水基及び疎水基を有する水溶性有機化合物を含み、前記二色性色素に対する前記水溶性有機化合物の重量比が０．００００１以上であり、前記高分子化合物は、繰り返し単位を有するポリマーである、異方性色素膜形成用組成物。 The two colors include a dichroic dye having an acidic group or a basic group, a linear or branched polymer compound having an acidic group and a basic group, and a water-soluble organic compound having a hydrophilic group and a hydrophobic group. A composition for forming an anisotropic dye film, wherein the weight ratio of the water-soluble organic compound to the sex dye is 0.00001 or more, and the polymer compound is a polymer having a repeating unit . 前記高分子化合物が有する前記塩基性基がアミノ基を含む、請求項１に記載の異方性色素膜形成用組成物。 The composition for forming an anisotropic dye film according to claim 1, wherein the basic group of the polymer compound contains an amino group. 前記高分子化合物が有する前記酸性基がスルホ基を含む、請求項１又は２に記載の異方性色素膜形成用組成物。 The composition for forming an anisotropic dye film according to claim 1 or 2, wherein the acidic group contained in the polymer compound contains a sulfo group. 前記高分子化合物が有する前記酸性基の少なくとも一部が塩型の酸性基であり、前記塩型の酸性基の対カチオンが、リチウムイオン及び／又はナトリウムイオンである、請求項１～３のいずれか１項に記載の異方性色素膜形成用組成物。 Any of claims 1 to 3, wherein at least a part of the acidic group contained in the polymer compound is a salt-type acidic group, and the counter cation of the salt-type acidic group is a lithium ion and / or a sodium ion. The composition for forming an anisotropic dye film according to Item 1. 前記高分子化合物が有する前記塩基性基及び／又は前記酸性基が、芳香族性の部分構造を有さない、請求項１～４のいずれか１項に記載の異方性色素膜形成用組成物。 The composition for forming an anisotropic dye film according to any one of claims 1 to 4, wherein the basic group and / or the acidic group of the polymer compound does not have an aromatic partial structure. thing. 前記高分子化合物が、不飽和結合及び芳香族性を有する部分構造のいずれをも主鎖に有さない、請求項１～５のいずれか一項に記載の異方性色素膜形成用組成物。 The composition for forming an anisotropic dye film according to any one of claims 1 to 5, wherein the polymer compound does not have either an unsaturated bond or a partial structure having an aromatic property in the main chain. .. 前記高分子化合物の重量平均分子量が１４００以上である、請求項１～６のいずれか一項に記載の異方性色素膜形成用組成物。 The composition for forming an anisotropic dye film according to any one of claims 1 to 6, wherein the polymer compound has a weight average molecular weight of 1400 or more. 前記高分子化合物における前記酸性基及び前記塩基性基の同一主鎖中の比率が、（塩基性基のモル数／（塩基性基のモル数＋酸性基のモル数））として０．０５より大きい、請求項１～７のいずれか一項に記載の異方性色素膜形成用組成物。 The ratio of the acidic group and the basic group in the same main chain of the polymer compound is 0.05 or more as (number of moles of basic group / (number of moles of basic group + number of moles of acidic group)). The large composition for forming an anisotropic dye film according to any one of claims 1 to 7. 前記高分子化合物が有する前記酸性基がスルホ基を含む、請求項１～８のいずれか一項に記載の異方性色素膜形成用組成物から形成されてなる、異方性色素膜。 An anisotropic dye film formed from the composition for forming an anisotropic dye film according to any one of claims 1 to 8 , wherein the acidic group contained in the polymer compound contains a sulfo group . 酸性基又は塩基性基を有する二色性色素、酸性基及び塩基性基を有する、線状又は分岐状の高分子化合物、並びに親水基及び疎水基を有する水溶性有機化合物を含み、前記二色性色素に対する前記水溶性有機化合物の重量比が０．００００１以上であり、前記高分子化合物は、繰り返し単位を有するポリマーであり、前記高分子化合物が有する前記酸性基がスルホ基を含む、異方性色素膜。 The two colors include a dichroic dye having an acidic group or a basic group, a linear or branched polymer compound having an acidic group and a basic group, and a water-soluble organic compound having a hydrophilic group and a hydrophobic group. The weight ratio of the water-soluble organic compound to the sex dye is 0.00001 or more, the polymer compound is a polymer having a repeating unit, and the acidic group of the polymer compound contains a sulfo group. Square pigment film. 請求項９又は１０に記載の異方性色素膜を含む、偏光素子。 A polarizing device comprising the anisotropic dye film according to claim 9 or 10.
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