JP2005208415A - Reverse wavelength dispersion retardation film, and polarizing plate and display apparatus using the same - Google Patents

Reverse wavelength dispersion retardation film, and polarizing plate and display apparatus using the same Download PDF

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JP2005208415A
JP2005208415A JP2004016008A JP2004016008A JP2005208415A JP 2005208415 A JP2005208415 A JP 2005208415A JP 2004016008 A JP2004016008 A JP 2004016008A JP 2004016008 A JP2004016008 A JP 2004016008A JP 2005208415 A JP2005208415 A JP 2005208415A
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wavelength dispersion
film
reverse wavelength
retardation film
polarizing plate
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Yutaka Omori
裕 大森
Shusaku Nakano
秀作 中野
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Nitto Denko Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate

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Abstract

<P>PROBLEM TO BE SOLVED: To provide a reverse wavelength dispersion retardation film which can be easily manufactured and shows satisfactory reverse wavelength dispersion characteristics for its thickness. <P>SOLUTION: A liquid crystal monomer has, in its molecule: an aromatic skeleton constituted of at least one aromatic ring; principal chain mesogene combining with the aromatic skeleton and having a polymerization group at its terminal; and side chain mesogene combining with the aromatic skeleton. The reverse wavelength dispersion retardation film is obtained by immobilizing the liquid crystal monomer while maintaining such an orientation that the optical axes of the principal chain mesogene and side chain mesogene cross each other. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、逆波長分散位相差フィルム及び該逆波長分散位相差フィルムを用いた偏光板等に関する。   The present invention relates to a reverse wavelength dispersion retardation film, a polarizing plate using the reverse wavelength dispersion retardation film, and the like.

従来、逆波長分散位相差フィルムを得る方法としては、複屈折光の位相差が１／４波長である１／４波長板と複屈折光の位相差が１／２波長である１／２波長板とを光軸を交差させて積層する方法（特許文献１）、波長分散の異なる位相差フィルムの光軸を交差させて積層する方法（特許文献２）、正の屈折率異方性を有する高分子のモノマー単位と負の屈折率異方性を有する高分子のモノマー単位とからなる高分子フィルムを延伸する方法（特許文献３）が知られている。   Conventionally, as a method for obtaining a reverse wavelength dispersion retardation film, a quarter wavelength plate in which the phase difference of birefringent light is ¼ wavelength and a half wavelength in which the phase difference of birefringent light is ½ wavelength. A method of laminating plates with crossed optical axes (Patent Document 1), a method of laminating optical axes of retardation films having different wavelength dispersions (Patent Document 2), and having positive refractive index anisotropy A method of stretching a polymer film composed of a polymer monomer unit and a polymer monomer unit having negative refractive index anisotropy (Patent Document 3) is known.

特許文献１及び２の方法では、位相差フィルム等を積層させる工程が必要であり、積層させる際に異物が混入したり光軸がずれたりする等、製造が煩雑であるという問題を有している。
特許文献３の方法では、積層工程が不要で、一層で逆波長分散位相差フィルムが得られるが、該フィルムの膜厚を数十μｍと厚くしないと十分な逆波長分散特性が得られないという問題を有している。 In the methods of Patent Documents 1 and 2, a step of laminating a retardation film or the like is necessary, and there is a problem in that the production is complicated, such as mixing foreign substances or shifting the optical axis when laminating. Yes.
In the method of Patent Document 3, a lamination step is not required, and a reverse wavelength dispersion retardation film can be obtained in one layer, but sufficient reverse wavelength dispersion characteristics cannot be obtained unless the film thickness is increased to several tens of μm. Have a problem.

一方、液晶モノマーを配向させた状態で紫外線照射等により固定化させて作製される位相差フィルムは、数μｍと非常に薄いことが知られている（特許文献４）。
しかし、液晶モノマーを配向させた状態で固定化させて作製される位相差フィルムで逆波長分散特性を示すものは、未だに知られていないのが現状である。 On the other hand, it is known that a retardation film produced by fixing a liquid crystal monomer by ultraviolet irradiation or the like in an aligned state is as thin as several μm (Patent Document 4).
However, the phase difference film produced by fixing the liquid crystal monomer in an aligned state and showing reverse wavelength dispersion characteristics is not yet known.

特開平１０−６８８１６号公報JP-A-10-68816 特開平５−２７１１８号公報JP-A-5-27118 特許第３３２５５６０号公報Japanese Patent No. 3325560 特開平７−２９４７３５号公報JP-A-7-294735

本発明は、簡便に製造でき、しかも、膜厚の割に十分な逆波長分散特性を示す逆波長分散位相差フィルムを提供することを課題とする。   This invention makes it a subject to provide the reverse wavelength dispersion phase-difference film which can be manufactured simply and shows the reverse wavelength dispersion characteristic sufficient for the film thickness.

本発明者らは、上記課題を解決するために鋭意検討した結果、分子中に２種類のメソゲンを有する液晶モノマーを、各メソゲンの光軸が交わるように配向させた状態で固定化させることにより、膜厚の薄い逆波長分散特性を示す逆波長分散位相差フィルムが得られることを見いだし、本発明を完成するに至った。   As a result of intensive studies to solve the above-mentioned problems, the present inventors have fixed a liquid crystal monomer having two types of mesogens in the molecule so that the optical axes of the mesogens are aligned with each other. The inventors have found that a reverse wavelength dispersion retardation film having a thin reverse wavelength dispersion characteristic can be obtained, and have completed the present invention.

即ち、本発明は、分子中に少なくとも１つの芳香環からなる芳香族骨格と該芳香族骨格に結合し且つ末端に重合性基とを備える主鎖メソゲンと、前記芳香族骨格に結合した側鎖メソゲンとを有する液晶モノマーを、前記主鎖メソゲンと前記側鎖メソゲンとの光軸が交わるように配向させ、該配向を維持したまま固定化させた逆波長分散位相差フィルムを提供する。
なお、メソゲンとは、中間相（＝液晶相）形成分子とも称され、液晶性分子構造とほぼ同義である。 That is, the present invention provides an aromatic skeleton composed of at least one aromatic ring in a molecule, a main chain mesogen bonded to the aromatic skeleton and having a polymerizable group at a terminal, and a side chain bonded to the aromatic skeleton. Provided is a reverse wavelength dispersion retardation film in which a liquid crystal monomer having a mesogen is aligned so that the optical axes of the main chain mesogen and the side chain mesogen intersect, and fixed while maintaining the alignment.
The mesogen is also called an intermediate phase (= liquid crystal phase) -forming molecule, and is almost synonymous with the liquid crystal molecular structure.

本発明の逆波長分散位相差フィルムは、簡便に製造でき、しかも、膜厚の割に十分な逆波長分散特性を示すことができる。
更に、本発明の逆波長分散位相差フィルムは、使用する可視波長領域全体で略一様な位相差を発生する波長分散特性を示すことができる。 The reverse wavelength dispersion retardation film of the present invention can be easily produced, and can exhibit reverse wavelength dispersion characteristics sufficient for the film thickness.
Furthermore, the reverse wavelength dispersion retardation film of the present invention can exhibit wavelength dispersion characteristics that generate a substantially uniform retardation across the entire visible wavelength region to be used.

以下、本発明の逆波長分散位相差フィルムの実施形態について説明する。
本実施形態の逆波長分散位相差フィルムは、分子中に少なくとも１つの芳香環からなる芳香族骨格と該芳香族骨格に結合し且つ末端に重合性基とを備える主鎖メソゲンと、前記芳香族骨格に結合した側鎖メソゲンとを有する液晶モノマーを、前記主鎖メソゲンと前記側鎖メソゲンとの光軸が交わるように配向させ、該配向を維持したまま固定化させたものである。 Hereinafter, embodiments of the reverse wavelength dispersion retardation film of the present invention will be described.
The reverse wavelength dispersion retardation film of the present embodiment includes an aromatic skeleton composed of at least one aromatic ring in a molecule, a main chain mesogen bonded to the aromatic skeleton and having a polymerizable group at the terminal, and the aromatic A liquid crystal monomer having a side chain mesogen bonded to a skeleton is aligned so that the optical axes of the main chain mesogen and the side chain mesogen intersect, and fixed while maintaining the alignment.

前記液晶モノマーは、分子中に少なくとも１つの芳香環からなる芳香族骨格と該芳香族骨格に結合し且つ末端に重合性基とを備える主鎖メソゲンと前記芳香族骨格に結合した側鎖メソゲンとからなる。   The liquid crystal monomer comprises an aromatic skeleton composed of at least one aromatic ring in the molecule, a main chain mesogen bonded to the aromatic skeleton and having a polymerizable group at a terminal, and a side chain mesogen bonded to the aromatic skeleton. Consists of.

前記芳香環としては、（Ａ−１）〜（Ａ−９）から選ばれる環構造が挙げられる。   Examples of the aromatic ring include ring structures selected from (A-1) to (A-9).

前記芳香族骨格は、（Ａ−１）〜（Ａ−９）から選ばれる環構造が直接或いは結合基で２つ以上連結されていてもよい。
該結合基としては、（Ｂ−１）〜（Ｂ−１２）に示すものが挙げられる。 In the aromatic skeleton, two or more ring structures selected from (A-1) to (A-9) may be connected directly or via a bonding group.
Examples of the linking group include those shown in (B-1) to (B-12).

前記芳香族骨格としては、例えば、ビフェニル、フェニルオキシカルボニルフェニル、フェニルカルボニルオキシフェニル、フェニルカルボニルオキシカルボニルフェニル、フェニルオキシカルボニルフェニルカルボニルオキシフェニル等が挙げられる。   Examples of the aromatic skeleton include biphenyl, phenyloxycarbonylphenyl, phenylcarbonyloxyphenyl, phenylcarbonyloxycarbonylphenyl, phenyloxycarbonylphenylcarbonyloxyphenyl, and the like.

前記重合性基としては、メタアクリロイルオキシ基、アクリロイルオキシ基、エポキシ基、ビニルエーテル基などが挙げられる。中でもアクリロイルオキシ基が好ましい。
前記重合性基と前記芳香族骨格との間には、好ましくは、スペーサと呼ばれる柔軟な結合基が存在する。スペーサには、メチレン鎖が好ましく用いられる。メチレン鎖の炭素原子数は２〜１０が好ましく，２〜６がより好ましい。 Examples of the polymerizable group include a methacryloyloxy group, an acryloyloxy group, an epoxy group, and a vinyl ether group. Of these, an acryloyloxy group is preferred.
There is preferably a flexible bonding group called a spacer between the polymerizable group and the aromatic skeleton. As the spacer, a methylene chain is preferably used. 2-10 are preferable and, as for the carbon atom number of a methylene chain, 2-6 are more preferable.

前記側鎖メソゲンも、通常、芳香環を有するものからなる。
該芳香環としては、（Ａ−１）〜（Ａ−９）に示す環構造の中から選ばれるものが挙げられる。該環構造が直接或いは前記結合基で２つ以上連結されていてもよい。
該側鎖メソゲンは、直接或いは前記結合基を介して前記芳香族骨格に結合している。
また、前記芳香族骨格と前記側鎖メソゲンとの結合距離は、長すぎると配向させた場合に主鎖メソゲンと側鎖メソゲンとが同一方向に配向して所望の波長分散特性が得られないため、原子数として１０個以下が好ましい。
尚、前記側鎖メソゲンを構成する芳香環が、例えば、アルコキシ基、ハロゲン基、シアノ基等の官能基を置換基として有していてもよい。 The side chain mesogen is also usually composed of an aromatic ring.
Examples of the aromatic ring include those selected from the ring structures shown in (A-1) to (A-9). Two or more of the ring structures may be connected directly or by the linking group.
The side chain mesogen is bonded to the aromatic skeleton directly or through the bonding group.
In addition, when the bond distance between the aromatic skeleton and the side chain mesogen is too long, the main chain mesogen and the side chain mesogen are aligned in the same direction and the desired wavelength dispersion characteristic cannot be obtained. The number of atoms is preferably 10 or less.
In addition, the aromatic ring which comprises the said side chain mesogen may have functional groups, such as an alkoxy group, a halogen group, a cyano group, as a substituent, for example.

本実施形態の液晶モノマーの具体例を（Ｃ−１）〜（Ｃ−３）に示す。
尚、本実施形態の液晶モノマーは、ネマチック相及び／又はスメクチック相を示す。 Specific examples of the liquid crystal monomer of this embodiment are shown in (C-1) to (C-3).
In addition, the liquid crystal monomer of this embodiment shows a nematic phase and / or a smectic phase.

本実施形態の液晶モノマーは、上記の通りであるが、次いで本実施形態の逆波長分散位相差フィルムの作製について説明する。
本実施形態の逆波長分散位相差フィルムは、基板上に前記液晶モノマーを塗布し、そして、それらを配向させ固定化させることにより製造できる。 The liquid crystal monomer of this embodiment is as described above. Next, production of the reverse wavelength dispersion retardation film of this embodiment will be described.
The reverse wavelength dispersion retardation film of this embodiment can be produced by coating the liquid crystal monomer on a substrate, and aligning and fixing them.

前記基板としては、一般的に、ポリエチレンテレフタレート・トリアセチルセルロース・ノルボルネン樹脂・ポリビニルアルコール・ポリイミド・ポリアクリレート・ポリカーボネート・ポリスルホン・ポリエーテルスルホン等のポリマーフィルム又はガラス板を用いうる。   As the substrate, generally, a polymer film such as polyethylene terephthalate, triacetyl cellulose, norbornene resin, polyvinyl alcohol, polyimide, polyacrylate, polycarbonate, polysulfone, polyethersulfone, or a glass plate can be used.

前記液晶モノマーは、一般的に、基板上に設けられた配向膜を用いて配向させる。
配向膜としては、従来知られているものを用いることができる。例えば、基板上にポリイミドやポリビニルアルコール等からなる薄膜、シンナメートやアゾベンゼンなどの光重合基を有するポリマー或いはポリイミドに偏光紫外線を照射した光配向膜、斜方蒸着膜、延伸フィルムなどを用いうる。
尚、配向膜としては、ポリイミド系配向膜及びポリビニルアルコール系配向膜が代表的である。
配向膜には、該配向膜上に液晶モノマーを塗工する前に予めラビング処理を行っておく。該ラビング処理は、前記配向膜の表面を紙や布で一定方向に数回こすることにより行う。
該ラビング処理により、液晶を配向させる方向を決める。 The liquid crystal monomer is generally aligned using an alignment film provided on a substrate.
As the alignment film, a conventionally known film can be used. For example, a thin film made of polyimide, polyvinyl alcohol, or the like on a substrate, a polymer having a photopolymerizable group such as cinnamate or azobenzene, or a photo-alignment film obtained by irradiating polarized ultraviolet rays on a polyimide film, an oblique deposition film, or a stretched film can be used.
Typical examples of the alignment film include a polyimide alignment film and a polyvinyl alcohol alignment film.
The alignment film is preliminarily rubbed before the liquid crystal monomer is applied onto the alignment film. The rubbing treatment is performed by rubbing the surface of the alignment film several times in a certain direction with paper or cloth.
The rubbing treatment determines the direction in which the liquid crystal is aligned.

液晶モノマーの前記配向膜上への塗工には、加熱溶融方式又は液晶モノマーを有機溶剤に溶解し溶液として配向膜上に塗工する方式がある。通常、液晶モノマーを有機溶剤に溶解し溶液として塗工する方式を用いうる。有機溶剤に溶解し溶液として塗工する場合、バーコーター・スピンコーター・ロールコーター等の適宜な塗工機を用いて行うことができる。
前記有機溶剤としては、液晶モノマーを溶解しうるものを特に制限なく用いることができる。例えば、メチルエチルケトン・シクロヘキサノン・テトラヒドロフラン等が好ましい。尚、生産性の点から高沸点の有機溶剤は好ましくない。 Application of the liquid crystal monomer onto the alignment film includes a heat melting method or a method in which the liquid crystal monomer is dissolved in an organic solvent and applied as a solution onto the alignment film. Usually, a method in which a liquid crystal monomer is dissolved in an organic solvent and applied as a solution can be used. When dissolved in an organic solvent and applied as a solution, it can be performed using an appropriate coating machine such as a bar coater, a spin coater, or a roll coater.
As the organic solvent, those capable of dissolving the liquid crystal monomer can be used without particular limitation. For example, methyl ethyl ketone, cyclohexanone, tetrahydrofuran and the like are preferable. A high boiling point organic solvent is not preferable from the viewpoint of productivity.

前記主鎖メソゲンと前記側鎖メソゲンとの光軸が交わるように配向させる方法としては、加熱して配向させる方法を用いることができる。加熱配向の温度は、一般的には、液晶性物質のＣｒ（結晶相）／Ｎ（ネマチック相）相転移温度以上、Ｎ（ネマチック相）／Ｉ（等方相）相転移温度以下で行う。
高温になると、熱重合反応が進行し配向を阻害する虞があるため、Ｃｒ／Ｎの相転移温度＋５０℃以下とするのが好ましい。加熱時間は、特に制限されないが、１０秒〜１０分程度の範囲が好ましい。 As a method of aligning so that the optical axes of the main chain mesogen and the side chain mesogen intersect, a method of aligning by heating can be used. In general, the temperature of the heating alignment is not less than the Cr (crystal phase) / N (nematic phase) phase transition temperature and not more than the N (nematic phase) / I (isotropic phase) phase transition temperature of the liquid crystalline material.
If the temperature is high, the thermal polymerization reaction may proceed and the orientation may be hindered. Therefore, the Cr / N phase transition temperature is preferably + 50 ° C. or lower. The heating time is not particularly limited, but is preferably in the range of about 10 seconds to 10 minutes.

前記固定化は、重合性基を反応させて硬化させることにより行うことができる。
前記重合性基が、アクリロイルオキシ基・メタアクリロイルオキシ基の場合の固定化方法としては、活性エネルギー線照射により行うことが好ましい。
活性エネルギー線としては、紫外線・電子線等が用いられるが、特に紫外線が好ましい。 紫外線を照射する場合には、光重合開始剤を液晶モノマーに添加することで硬化反応を迅速に進行させることができる。
光重合開始剤としては、特に限定されないが、例えば、ベンゾインエーテル類・ベンゾフェノン類・アセトフェノン類・ベンジルケタール類などが挙げられる。
光重合開始剤の添加量は、液晶モノマーに対して０．１〜１０重量％が好ましく、０．３〜５重量％がより好ましい。
尚、液晶モノマーによっては、加熱配向後にＣｒ／Ｎの相転移温度以下になっても結晶が析出せず配向状態を維持するものがあるので、この場合には室温で活性エネルギー線を照射することができる。また、温度が下がると結晶化しやすい場合は、Ｃｒ／Ｎの相転移温度以上の温度で活性エネルギー線を照射する。 The immobilization can be performed by reacting a polymerizable group and curing.
As the immobilization method when the polymerizable group is an acryloyloxy group / methacryloyloxy group, it is preferably performed by irradiation with active energy rays.
As the active energy rays, ultraviolet rays, electron beams, and the like are used, and ultraviolet rays are particularly preferable. In the case of irradiation with ultraviolet rays, the curing reaction can be rapidly advanced by adding a photopolymerization initiator to the liquid crystal monomer.
The photopolymerization initiator is not particularly limited, and examples thereof include benzoin ethers, benzophenones, acetophenones, and benzyl ketals.
The addition amount of the photopolymerization initiator is preferably 0.1 to 10% by weight, more preferably 0.3 to 5% by weight with respect to the liquid crystal monomer.
Depending on the liquid crystal monomer, there are those in which the crystal does not precipitate and maintains the alignment state even when the temperature falls below the Cr / N phase transition temperature after heating alignment. Can do. In the case where crystallization is likely to occur when the temperature is lowered, the active energy rays are irradiated at a temperature equal to or higher than the Cr / N phase transition temperature.

前記重合性基が、ビニルエーテル基やエポキシ基の場合は、光酸発生剤を液晶モノマーに添加することで、紫外線照射により速やかに硬化反応を促進させることができる。光酸発生剤の添加量は、液晶モノマー１００重量部に対して０．１〜２０重量部が好ましく、０．５〜１０重量部がより好ましい。
光酸発生剤としては、例えば、トリアジン類・芳香族スルホニウム塩類・芳香族ジアゾニウム塩類・シアン酸エステル類・芳香族スルホン酸エステル類・ニトロベンジルエステル類・芳香族スルファミド類などを用いることができる。これらの中でも特に、添加効果や配向性への影響の無さ等の点より、トリアジン類・芳香族スルホニウム塩類が好ましい。 When the polymerizable group is a vinyl ether group or an epoxy group, the curing reaction can be promptly accelerated by ultraviolet irradiation by adding a photoacid generator to the liquid crystal monomer. The addition amount of the photoacid generator is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the liquid crystal monomer.
As the photoacid generator, for example, triazines, aromatic sulfonium salts, aromatic diazonium salts, cyanate esters, aromatic sulfonate esters, nitrobenzyl esters, aromatic sulfamides, and the like can be used. Among these, triazines and aromatic sulfonium salts are particularly preferable from the viewpoints of the addition effect and the lack of influence on the orientation.

前記基板上に形成された逆波長分散位相差フィルムは、光学フィルムとして使用される。 該逆波長分散位相差フィルムは、基板との一体物としてそのまま光学フィルムに用いることもできるし、基板から剥離して他の光学フィルムと積層させて用いることもできる。
本実施形態の逆波長分散位相差フィルムの厚さは、通常、０．１〜２０μｍ程度である。 The reverse wavelength dispersion retardation film formed on the substrate is used as an optical film. The reverse wavelength dispersion retardation film can be used as an optical film as it is as an integral body with the substrate, or can be peeled off from the substrate and laminated with another optical film.
The thickness of the reverse wavelength dispersion retardation film of the present embodiment is usually about 0.1 to 20 μm.

本実施形態の逆波長分散位相差フィルムにおいては、前記液晶モノマーを主鎖メソゲンと側鎖メソゲンとを平行でない異なる方向に配向し、固定化させることで、前記主鎖メソゲンの光軸と前記側鎖メソゲンの光軸とが交わるようにする。
このとき、主鎖メソゲンの波長分散よりも側鎖メソゲンの波長分散が大きく、主鎖メソゲンの位相差の値よりも側鎖メソゲンの位相差の値のほうが小さいときに、△ｎｄ（４５０ｎｍ）／△ｎｄ（６５０ｎｍ）が１より小さくなり、いわゆる逆波長分散特性を示す。
尚、逆波長分散特性は、主鎖メソゲンや側鎖メソゲンの種類、連結基の長さ等によって適宜調整することができる。 In the reverse wavelength dispersion retardation film of the present embodiment, the liquid crystal monomer is oriented in a different direction that is not parallel to the main chain mesogen and the side chain mesogen, and fixed, whereby the optical axis and the side of the main chain mesogen are fixed. Make sure that the optical axis of the chain mesogen intersects.
At this time, when the wavelength dispersion of the side chain mesogen is larger than the wavelength dispersion of the main chain mesogen and the phase difference value of the side chain mesogen is smaller than the phase difference value of the main chain mesogen, Δnd (450 nm) / Δnd (650 nm) is smaller than 1, indicating so-called reverse wavelength dispersion characteristics.
The reverse wavelength dispersion characteristic can be appropriately adjusted depending on the kind of main chain mesogen and side chain mesogen, the length of the linking group, and the like.

本実施形態の逆波長分散位相差フィルムは、偏光に与える位相差が波長によりほぼ一定となるため、該逆波長分散位相差フィルムを出射した偏光の状態がほぼ等しくなる。
このような特性を有する逆波長分散位相差フィルムを偏光フィルムと貼り合わせた偏光板、即ち楕円偏光板はその位相差がλ／２やλ／４のときに特に有効である。
位相差がλ／２のときは、楕円偏光板を出射した偏光は該楕円偏光板を透過する前の偏光とは９０度偏光面が回転した偏光となる。
位相差がλ／４のときは、楕円偏光板を出射した偏光は円偏光となる。このときの楕円偏光板は、特に円偏光板と呼ばれる。
本実施形態の逆波長分散位相差フィルムにおいて、位相差がλ／４であるものを偏光フィルムと積層させることで得られる円偏光板が広帯域円偏光板となる。
ここで、位相差（△ｎｄ）は下記式で表される。下記式においてｎｘ、ｎｙは、それぞれフィルム中のＸ軸、Ｙ軸方向の屈折率を示し、ｄはフィルムの厚みを示す。
△ｎｄ＝（ｎｘ−ｎｙ）×ｄ
前記Ｘ軸方向とは、フィルム中の面内において最大の屈折率を示す軸方向を意味し、Ｙ軸方向とは、前記面内において前記Ｘ軸に対して垂直な軸方向を意味する。また、位相差（△ｎｄ）は、自動複屈折計KOBRA-21ADHを用いて測定した値である。
尚、前記偏光フィルムとしては、ヨウ素−ポリビニルアルコール（ＰＶＡ）系・染料−ポリビニルアルコール（ＰＶＡ）系等が用いられる。 In the reverse wavelength dispersion phase difference film of the present embodiment, the phase difference given to the polarized light is substantially constant depending on the wavelength, and therefore the state of the polarized light emitted from the reverse wavelength dispersion phase difference film is substantially equal.
A polarizing plate in which an inverse wavelength dispersion retardation film having such characteristics is bonded to a polarizing film, that is, an elliptical polarizing plate, is particularly effective when the retardation is λ / 2 or λ / 4.
When the phase difference is λ / 2, the polarized light emitted from the elliptically polarizing plate is a polarized light whose plane of polarization is rotated by 90 degrees from the polarized light before passing through the elliptically polarizing plate.
When the phase difference is λ / 4, the polarized light emitted from the elliptically polarizing plate is circularly polarized light. The elliptically polarizing plate at this time is particularly called a circularly polarizing plate.
In the reverse wavelength dispersion retardation film of this embodiment, a circularly polarizing plate obtained by laminating a film having a retardation of λ / 4 with a polarizing film is a broadband circularly polarizing plate.
Here, the phase difference (Δnd) is expressed by the following equation. In the following formula, nx and ny indicate the refractive indexes in the X-axis and Y-axis directions in the film, respectively, and d indicates the thickness of the film.
Δnd = (nx−ny) × d
The X-axis direction means an axial direction showing the maximum refractive index in the plane of the film, and the Y-axis direction means an axial direction perpendicular to the X-axis in the plane. The phase difference (Δnd) is a value measured using an automatic birefringence meter KOBRA-21ADH.
In addition, as the polarizing film, iodine-polyvinyl alcohol (PVA) system, dye-polyvinyl alcohol (PVA) system, or the like is used.

前記広帯域偏光板は、円偏光モードの液晶ディスプレイ装置や各種ディスプレイ装置の反射防止フィルムとして用いられる。特に、有機ＥＬディスプレイ装置においては、広帯域偏光板は金属電極の反射を抑える反射防止フィルムとして用いられ、明所コントラスト比を著しく向上させる。   The broadband polarizing plate is used as an antireflection film for a circularly polarized liquid crystal display device and various display devices. In particular, in an organic EL display device, a broadband polarizing plate is used as an antireflection film that suppresses reflection of a metal electrode, and remarkably improves a bright place contrast ratio.

以下、実施例により本発明を詳細に説明するが、本発明はこれらに限定されるものではない。   EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

＜波長分散（位相差）の測定＞
王子計測機器株式会社製：自動複屈折計KOBRA-21ADHを用いて測定した。 <Measurement of wavelength dispersion (phase difference)>
Oji Scientific Instruments Co., Ltd .: Measured using an automatic birefringence meter KOBRA-21ADH.

（化合物１の合成）
3,5-ジブロモ-4-ヒドロキシ安息香酸(15.0g(50.7mmol))、2,2,2-トリクロロエタノール(0.76g(0.51mmol))、濃硫酸(2ml)の混合溶液を120℃で12時間攪拌した。反応混合物を水に注ぎ入れ、水層を酢酸エチルで３回抽出した。有機層を飽和炭酸ナトリウム水溶液、水、飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥後、溶媒を減圧下で留去した。
溶媒を完全に除去した後、再び酢酸エチルに溶解し、ヘキサンに滴下し、析出した固体を濾別、乾燥して化合物１(15.6g)を得た。 (Synthesis of Compound 1)
A mixed solution of 3,5-dibromo-4-hydroxybenzoic acid (15.0 g (50.7 mmol)), 2,2,2-trichloroethanol (0.76 g (0.51 mmol)) and concentrated sulfuric acid (2 ml) was added at 120 ° C. at 12 ° C. Stir for hours. The reaction mixture was poured into water and the aqueous layer was extracted three times with ethyl acetate. The organic layer was washed with a saturated aqueous sodium carbonate solution, water and saturated brine, and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure.
After completely removing the solvent, it was dissolved again in ethyl acetate and added dropwise to hexane. The precipitated solid was filtered off and dried to obtain Compound 1 (15.6 g).

（化合物２の合成）
4-(6-アクリロイルオキシヘキシルオキシ)安息香酸(12.8g(43.8mmol))、塩化チオニル(16.0ml(0.22mol))の混合物にDMF（ジメチルホルムアミド）を少量加え、窒素気流下、70℃で2時間攪拌した。
減圧下で過剰の塩化チオニルを除いた後、ジクロロメタン(100ml)、化合物１(15.6g(36.5mmol))、少量のBHT（ジ-n-ブチルヒドロキシトルエン）を加えた。
反応容器を水浴に浸して、トリエチルアミン(8.0ml(54.8mmol)）をゆっくり滴下し、その後40℃、6時間攪拌した。反応終了後1N塩酸を加え、ジクロロメタンで抽出を行った。 有機層を飽和食塩水で洗浄した後、無水硫酸マグネシウムで乾燥した。溶媒を減圧下で留去した後、粗生成物をシリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン／酢酸エチル＝１０／１）で精製し、化合物２(11.0g)を得た。 (Synthesis of Compound 2)
Add a small amount of DMF (dimethylformamide) to a mixture of 4- (6-acryloyloxyhexyloxy) benzoic acid (12.8 g (43.8 mmol)) and thionyl chloride (16.0 ml (0.22 mol)) at 70 ° C under a nitrogen stream. Stir for 2 hours.
Excess thionyl chloride was removed under reduced pressure, and then dichloromethane (100 ml), compound 1 (15.6 g (36.5 mmol)) and a small amount of BHT (di-n-butylhydroxytoluene) were added.
The reaction vessel was immersed in a water bath, and triethylamine (8.0 ml (54.8 mmol)) was slowly added dropwise, followed by stirring at 40 ° C. for 6 hours. After completion of the reaction, 1N hydrochloric acid was added and extracted with dichloromethane. The organic layer was washed with saturated brine and then dried over anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, the crude product was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 10/1) to obtain Compound 2 (11.0 g).

（化合物３の合成）
化合物２(11.0g(15.7mmol))、ＴＨＦ（テトラヒドロフラン）(30ml)、酢酸(3ml)、蒸留水(3ml)の混合溶液に亜鉛粉末(3.60g(55.0mmol))を0℃で30分かけて加えた。0℃で2時間攪拌した後、室温で5時間攪拌した。水、酢酸エチルを加えて抽出し、有機層を飽和食塩水で洗浄した。有機層を無水硫酸マグネシウムで乾燥し、溶媒を減圧下で留去した。粗生成物をシリカゲルカラムクロマトグラフィー（展開溶媒：ジクロロメタン／メタノール＝９／１）で精製し、化合物３(3.2g)を得た。 (Synthesis of Compound 3)
Zinc powder (3.60 g (55.0 mmol)) was added to a mixed solution of Compound 2 (11.0 g (15.7 mmol)), THF (tetrahydrofuran) (30 ml), acetic acid (3 ml), and distilled water (3 ml) at 0 ° C. for 30 minutes. Added. After stirring at 0 ° C. for 2 hours, the mixture was stirred at room temperature for 5 hours. Water and ethyl acetate were added for extraction, and the organic layer was washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The crude product was purified by silica gel column chromatography (developing solvent: dichloromethane / methanol = 9/1) to obtain Compound 3 (3.2 g).

（化合物４の合成）
化合物３(3.2g(5.7mmol))、塩化チオニル(2.1ml(28.3mmol))の混合物にＤＭＦを少量加え、窒素気流下、70℃で2時間攪拌した。減圧下で過剰の塩化チオニルを除いた後、ジクロロメタン(100ml)、4-(6-アクリロイルオキシヘキシルオキシ)フェノール(1.79g(6.8mmol))、少量のBHTを加えた。
反応容器を水浴に浸して、トリエチルアミン(1.2ml(8.6mmol)）をゆっくり滴下し、その後40℃、6時間攪拌した。反応終了後1N塩酸を加え、ジクロロメタンで抽出を行った。 有機層を飽和食塩水で洗浄した後、該有機層を無水硫酸マグネシウムで乾燥した。溶媒を減圧下で留去した後、粗生成物をシリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン／酢酸エチル／ジクロロメタン＝８／１／１）で精製し、化合物４(2.63g)を得た。 (Synthesis of Compound 4)
A small amount of DMF was added to a mixture of compound 3 (3.2 g (5.7 mmol)) and thionyl chloride (2.1 ml (28.3 mmol)), and the mixture was stirred at 70 ° C. for 2 hours under a nitrogen stream. Excess thionyl chloride was removed under reduced pressure, and then dichloromethane (100 ml), 4- (6-acryloyloxyhexyloxy) phenol (1.79 g (6.8 mmol)) and a small amount of BHT were added.
The reaction vessel was immersed in a water bath, triethylamine (1.2 ml (8.6 mmol)) was slowly added dropwise, and then stirred at 40 ° C. for 6 hours. After completion of the reaction, 1N hydrochloric acid was added and extracted with dichloromethane. The organic layer was washed with saturated brine, and then the organic layer was dried over anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, the crude product was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate / dichloromethane = 8/1/1) to obtain Compound 4 (2.63 g).

（化合物５の合成）
化合物４(2.63g(3.2mmol))、フェニルアセチレン(0.98g(9.6mmol))、Pd(dba)2(49.2mg(0.16mmol))、トリ(t-ブチル)ホスフィン(0.13g(0.65mmol))、BHT(少量)、トリエチルアミン(1.4ml(9.6mmol))、THF(10ml)の混合溶液を70℃で12時間攪拌した。
反応終了後、１Ｎ塩酸を加え、ジクロロメタンで抽出を行った。
有機層を飽和食塩水で洗浄した後、該有機層を無水硫酸マグネシウムで乾燥した。
粗生成物をシリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン／酢酸エチル／ジクロロメタン＝８／１／１）で精製し、化合物５(1.11g)を得た。
得られた化合物５が、液晶性を示す液晶モノマーであることを偏光顕微鏡観察にて確認した。
相転移温度は、Ｃｒ 130 Ｎ 145 Ｉ であった。 (Synthesis of Compound 5)
Compound 4 (2.63 g (3.2 mmol)), phenylacetylene (0.98 g (9.6 mmol)), Pd (dba) 2 (49.2 mg (0.16 mmol)), tri (t-butyl) phosphine (0.13 g (0.65 mmol) ), BHT (small amount), triethylamine (1.4 ml (9.6 mmol)) and THF (10 ml) were stirred at 70 ° C. for 12 hours.
1N hydrochloric acid was added after completion | finish of reaction, and the dichloromethane extracted.
The organic layer was washed with saturated brine, and then the organic layer was dried over anhydrous magnesium sulfate.
The crude product was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate / dichloromethane = 8/1/1) to obtain Compound 5 (1.11 g).
It was confirmed by polarizing microscope observation that the obtained compound 5 was a liquid crystal monomer exhibiting liquid crystallinity.
The phase transition temperature was Cr 130 N 145 I.

＜位相差フィルムの作製＞
（実施例１）
得られた化合物５をテトラクロロエタンに溶解し30重量%溶液とし、化合物５に対して3重量%のイルガキュア907（チバ・スペシャルティー・ケミカルズ社製：光重合開始剤）を添加した。ガラス板上に形成したポリビニルアルコールラビング配向膜上にスピンコート後、140℃に加熱して配向させた。その後、高圧水銀ランプにて紫外線を100mJ/cm2照射して配向を固定した。得られた配向フィルムは、3μｍで、He-Neレーザを用いたセナルモン法で求めた位相差は、340nmであった。
位相差測定装置を用いて波長分散性を測定したところ、△nd(450nm)／△nd(650nm)＝0.90と１より小さく、逆波長分散位相差フィルムであることを確認した。この逆波長分散位相差フィルムを透過軸を直交させた２枚の偏光板の間に挟んで観察したところ、着色がほとんどなかった。 <Production of retardation film>
(Example 1)
The obtained compound 5 was dissolved in tetrachloroethane to form a 30 wt% solution, and 3 wt% of Irgacure 907 (Ciba Specialty Chemicals, Inc .: photopolymerization initiator) was added to the compound 5. After spin coating on a polyvinyl alcohol rubbing alignment film formed on a glass plate, the film was aligned by heating to 140 ° C. Thereafter, the orientation was fixed by irradiating ultraviolet rays at 100 mJ / cm 2 with a high-pressure mercury lamp. The obtained oriented film was 3 μm, and the phase difference determined by the Senarmon method using a He—Ne laser was 340 nm.
When the wavelength dispersion was measured using a phase difference measuring apparatus, Δnd (450 nm) / Δnd (650 nm) = 0.90, which was smaller than 1, confirming that the film was a reverse wavelength dispersion retardation film. When this reverse wavelength dispersion phase difference film was observed between two polarizing plates having transmission axes orthogonal to each other, there was almost no coloring.

（実施例２）
テトラクロロエタン溶液中の化合物５の濃度を15重量%に変えた以外は、実施例１と同様にして配向フィルムを作製した。得られた配向フィルムの位相差は138nmであった。 これを配向フィルムの配向方向と偏光板の延伸軸とが45度になるように、該配向フィルムと該偏光板とを貼り合わせて円偏光板を作製した。作製した円偏光板を鏡の上に置いたところ、黒状態になり、広帯域円偏光板として機能していることが確認された。 (Example 2)
An oriented film was produced in the same manner as in Example 1 except that the concentration of Compound 5 in the tetrachloroethane solution was changed to 15% by weight. The phase difference of the obtained oriented film was 138 nm. The alignment film and the polarizing plate were bonded to each other so that the alignment direction of the alignment film and the stretching axis of the polarizing plate were 45 degrees to prepare a circularly polarizing plate. When the produced circularly polarizing plate was placed on a mirror, it became black and it was confirmed that it functions as a broadband circularly polarizing plate.

（比較例１）
化合物５に変えて（Ｄ−１）に示す液晶モノマーを用いた以外は、実施例１と同様にして位相差を有する配向フィルムを作製した。
この配向フィルムを透過軸を直交させた２枚の偏光板の間に挟んで観察したところ、青く着色していた。 (Comparative Example 1)
An alignment film having a retardation was produced in the same manner as in Example 1 except that the liquid crystal monomer shown in (D-1) was used instead of the compound 5.
When this oriented film was observed between two polarizing plates having transmission axes orthogonal to each other, it was colored blue.

化合物５に変えて比較例１の液晶モノマーを用いた以外は、実施例２と同様にして位相差を有する配向フィルムを作製した。実施例２と同様にして円偏光板を作製し、作製した円偏光板を鏡の上に置いたところ、紫色であり、広帯域円偏光板ではなかった。   An alignment film having a retardation was produced in the same manner as in Example 2 except that the liquid crystal monomer of Comparative Example 1 was used instead of Compound 5. When a circularly polarizing plate was produced in the same manner as in Example 2 and the produced circularly polarizing plate was placed on a mirror, it was purple and was not a broadband circularly polarizing plate.

実施例１より逆波長分散特性を示す位相差フィルムを得ることができた。
実施例２より逆波長分散特性を示す位相差フィルムと偏光板とを貼り合わせて得られた円偏光板が、広帯域円偏光板として機能していることが判明した。
From Example 1, a retardation film showing reverse wavelength dispersion characteristics could be obtained.
From Example 2, it was found that a circularly polarizing plate obtained by laminating a retardation film showing reverse wavelength dispersion characteristics and a polarizing plate functions as a broadband circularly polarizing plate.

Claims (5)

分子中に少なくとも１つの芳香環からなる芳香族骨格と該芳香族骨格に結合し且つ末端に重合性基とを備える主鎖メソゲンと、
前記芳香族骨格に結合した側鎖メソゲンとを有する液晶モノマーを、
前記主鎖メソゲンと前記側鎖メソゲンとの光軸が交わるように配向させ、該配向を維持したまま固定化させたことを特徴とする逆波長分散位相差フィルム。 A main chain mesogen having an aromatic skeleton composed of at least one aromatic ring in the molecule and a polymerizable group bonded to the aromatic skeleton and a terminal;
A liquid crystal monomer having a side chain mesogen bonded to the aromatic skeleton,
An inverse wavelength dispersion retardation film, wherein the main-chain mesogen and the side-chain mesogen are aligned so that the optical axes intersect with each other and are fixed while maintaining the alignment. 波長４５０ｎｍで測定した位相差△ｎｄ（４５０ｎｍ）と、
波長６５０ｎｍで測定した位相差△ｎｄ（６５０ｎｍ）とが、
下記式（１）を満たす請求項１記載の逆波長分散位相差フィルム。
△ｎｄ（４５０ｎｍ）／ △ｎｄ（６５０ｎｍ）＜１ （１） A phase difference Δnd (450 nm) measured at a wavelength of 450 nm;
The phase difference Δnd (650 nm) measured at a wavelength of 650 nm is
The reverse wavelength dispersion phase difference film of Claim 1 which satisfy | fills following formula (1).
Δnd (450 nm) / Δnd (650 nm) <1 (1) 請求項１又は２に記載の逆波長分散位相差フィルムと偏光フィルムとを積層したことを特徴とする偏光板。   A polarizing plate, wherein the reverse wavelength dispersion retardation film according to claim 1 or 2 and a polarizing film are laminated. 前記逆波長分散位相差フィルムの位相差が、λ／４である請求項３記載の偏光板。   The polarizing plate according to claim 3, wherein the retardation of the reverse wavelength dispersion retardation film is λ / 4. 請求項１又は２に記載の逆波長分散位相差フィルム或いは請求項３又は４に記載の偏光板を用いたディスプレイ装置。   A display device using the reverse wavelength dispersion retardation film according to claim 1 or 2 or the polarizing plate according to claim 3 or 4.
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