JP4770038B2 - Polymerizable liquid crystal compound and optical anisotropic body - Google Patents

Description

【００１２】
（式中、Ｘは（メタ）アクリレート基を表し、Ｙ₁，Ｙ₂及びＹ₅は同一又は異なって、単結合、−Ｃ_nＨ_2n−、−Ｃ_nＨ_2nＯ−、−ＯＣ_nＨ_2n−、−（Ｃ₂Ｈ₄Ｏ）_n−、−（ＯＣ₂Ｈ₄）_n−、−（Ｃ₃Ｈ₆Ｏ）_n−、又は−（ＯＣ₃Ｈ₆）_n−のいずれかを表し、ｎは１〜２０までの整数、環Ａ〜Ｃ及びＡ'〜Ｃ'は各々独立に、下記の環のいずれかを表し、
【００１３】
【化５】

【００１４】
a、ｂは０又は１の整数、Ｒ₁〜Ｒ₆は水素原子、ハロゲン原子、炭素原子数1〜２０のアルキル基、アルコキシ基、アルケニル基、アルケニルオキシ基、フルオロアルキル基、又はフルオロアルコキシ基を表し、Ｙ₃及びＹ₄は、それぞれ独立に、単結合、−ＣＨ₂ＣＨ₂−、−ＣＨ₂Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−、又は−ＣＦ＝ＣＦ−を表し、
ｃが１〜１０の整数を表す）
【００１５】
本発明の重合性液晶化合物は、特に、一般式（I）のＲ ₁ 〜Ｒ ₆ が水素原子、ハロゲン原子、炭素原子数1〜５のアルキル基、又は炭素原子数1〜５のアルコキシ基である重合性液晶化合物であり、更に一般式（I）のＹ₁、Ｙ₂及びＹ₅が同一又は異なって、−Ｃ_nＨ_2n−、−Ｃ_nＨ_2nＯ−、又は−ＯＣ_nＨ_2n−であり、ｎは１〜２０までの整数である重合性液晶化合物、一般式（I）のＹ₃及びＹ₄がそれぞれ独立的に、単結合、又は−Ｃ≡Ｃ−である重合性液晶化合物である。
【００１６】
また本発明の重合性液晶化合物は、特に、一般式（I）の環Ａ〜Ｃ及びＡ'〜Ｃ'の何れか一つ以上が、
【００１７】
【化６】

【００１８】
（式中のＦはフッ素原子、ｍは１〜３までの整数、ｐは１〜３までの整数を表す）で表される、いずれかの芳香族基である重合性液晶化合物である。
【００１９】
また本発明は、上記の重合性液晶化合物の1つ以上を含む重合性液晶組成物であり、更に上記の重合性液晶化合物の1つ以上と、それら以外の重合性化合物とを含む重合性液晶組成物、また該重合性液晶化合物の1つ以上と、それら以外の重合性液晶化合物とを含む重合性液晶組成物、更にこれらの重合性液晶化合物、もしくは重合性液晶組成物からなる光学異方体とを含むものである。
【００２０】
【発明の実施の形態】
本発明の重合性液晶化合物は、下記の一般式（I）で表される化合物である。一般式（I）
【００２１】
【化７】

【００２２】
（式中、Ｘは重合性基を表し、Ｙ₁，Ｙ₂及びＹ₅は同一又は異なって、単結合、−Ｃ_nＨ_2n−、−Ｃ_nＨ_2nＯ−、−ＯＣ_nＨ_2n−、−（Ｃ₂Ｈ₄Ｏ）_n−、−（ＯＣ₂Ｈ₄）_n−、−（Ｃ₃Ｈ₆Ｏ）_n−、−（ＯＣ₃Ｈ₆）_n−、−Ｃ_nＨ_2nＣＯＯ−、−ＯＯＣＣ_nＨ_2n−、−Ｃ_nＨ_2nＯＯＣ−、又は−ＣＯＯＣ_nＨ_2n−のいずれかを表し、ｎは１〜２０までの整数であり、環Ａ、Ｂ及びＣは、それぞれ独立に、下記の環のいずれかを表し、
【００２３】
【化８】

【００２４】
ａ、ｂは０〜２の整数、Ｒ₁〜Ｒ₆は水素原子、ハロゲン原子、シアノ基、炭素原子数1〜２０のアルキル基、アルコキシ基、アルケニル基、アルケニルオキシ基、フルオロアルキル基、又はフルオロアルコキシ基を表し、Ｙ₃及びＹ₄は、それぞれ独立に、単結合、−ＣＨ₂ＣＨ₂−、−ＣＨ₂Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−（ＣＨ₂）₄−、−（ＣＨ₂）₆−、−ＣＨ₂ＣＨ₂ＣＨ₂Ｏ−、又は−ＣＨ₂＝ＣＨＣＨ₂ＣＨ₂を表し、ｃが１〜１０の整数を表す）
【００２５】
ここで、一般式（I）で表される重合性液晶化合物のＸは、重合性基を表し、具体的には、（メタ）アクリル基、（メタ）アクリロイルフェニル基、２−クロロ（メタ）アクリレート基、アクリルアミド基、マレイミド基、ビニルエーテル基、チオール基、アリルエーテル基、エポキシ基、イタコン酸誘導体、スチレン誘導体、ケイ皮酸誘導体などの重合可能な残基を示し、より好ましくはラジカル重合可能な（メタ）アクリル基、（メタ）アクリロイルフェニル基、２−クロロ（メタ）アクリレートである。
【００２６】
一般式（I）のＹ₁，Ｙ₂及びＹ₅が同一又は異なって、単結合、−Ｃ_nＨ_2n−、−Ｃ_nＨ_2nＯ−、−ＯＣ_nＨ_2n−、−（Ｃ₂Ｈ₄Ｏ）_n−、−（ＯＣ₂Ｈ₄）_n−、−（Ｃ₃Ｈ₆Ｏ）_n−、−（ＯＣ₃Ｈ₆）_n−、−Ｃ_nＨ_2nＣＯＯ−、−ＯＯＣＣ_nＨ_2n−、−Ｃ_nＨ_2nＯＯＣ−、又は−ＣＯＯＣ_nＨ_2n−のいずれかを表し、ｎは１〜２０までの整数であり、より好ましくはｎが３〜１０である。
【００２７】
一般式（I）のｃは、１〜１０の整数であり、より好ましくは１〜４の整数である。一般式（I）の環Ａ〜Ｃ及びＡ'〜Ｃ'としては、例えば、ハロゲン原子、炭素数１〜５のアルキル基、炭素数１〜５のアルコキシ基で置換された芳香族基、及び脂肪族基であり、より好ましくは、
【００２８】
【化９】

【００２９】
（式中、ｍは１〜３の整数、ｐは１〜３の整数を表す）
のいずれかで表される置換基を何れか一つ以上有する芳香族基である。
【００３０】
本発明の重合性液晶化合物の特徴は、重合性基及び液晶性発現に寄与する液晶特有の剛直な液晶性骨格を各々２つ有し、その液晶性発現に寄与する液晶特有の剛直な液晶性骨格がシロキサン結合を介して連結していることである。剛直な液晶性骨格とは、例えば、６員環Ａ及び環Ｂ、三重結合、環Ｃからなる骨格を挙げることが出来る。このような特徴から、本発明に係わる重合性化合物は高い複屈折率差を有し、且つ、１００℃以下での低い温度で液晶相を示すことが可能となり、これを用いた光学異方体は１２０℃以上の高温域においても良好な分子配向の維持が可能となる。
【００３１】
本発明の一般式（I）で表される化合物は、下記のように合成できる。
例えば、一般式（I）においてＸがアクリレート基、Ｙ₁、Ｙ₂がそれぞれ−（ＣＨ₂）₃Ｏ−、−Ｏ（ＣＨ₂）₃−であり、Ｙ₅が−（ＣＨ₂）₃−であり、Ｙ₃が単結合、Ｙ₄がエステル結合、環Ａ、Ｂ及びＡ'、Ｂ'がそれぞれ芳香族基を表し、環Ｃ、Ｃ'がメチル基で置換された芳香族基を表し、ｃが２の整数で、
【００３２】
【化１０】

【００３３】
で表される重合性液晶化合物の場合は、３，４−ジヒドロ−２Ｈ−ピランと４−ヒドロキシ−４'−ビフェニルカルボン酸とを当量仕込み、ｐ−トルエンスルホン酸を触媒として低温で反応させ水酸基を保護した中間体１を得る。
【００３４】
次いで、１，１，３，３，５，５−ヘキサメチルトリシロキサン１当量に対し、４−アリル−２−メチルフェノール２当量を加えて白金触媒下で加熱してシロキサンが付加した中間体２を得る。
【００３５】
この中間体１と中間体２をジシクロヘキシルカルボジイミド及びＮ−メチルアミノピリジンの存在下で加熱して反応させ、更にその反応物を希塩酸／メタノール溶液で撹拌することによりシロキサン結合を導入したビスビフェノール誘導体を得ることが出来る。
【００３６】
このビスビフェノール誘導体と３−ブロモプロピルアクリレートとを炭酸カリウム存在下において８０〜１００℃で加熱することにより、目的の重合性液晶化合物を得ることが出来る。反応温度が１１０℃以上だとアクリル基同士が重合する恐れがあるので好ましくない。
【００３７】
また、一般式（I）においてＸがアクリレート基、Ｙ₁、Ｙ₂がそれぞれ−（ＣＨ₂）₄Ｏ−、−Ｏ（ＣＨ₂）₄−であり、Ｙ₅が−（ＣＨ₂）₂−であり、ｎが０であり、Ｙ₄が−Ｃ≡Ｃ−であり、環Ｂ、Ｂ'、Ｃ、Ｃ'が芳香族基を表し、ｃが２の整数である、
【００３８】
【化１１】

【００３９】
で表される重合性液晶化合物の場合は、１，１，３，３，５，５−ヘキサメチルトリシロキサン１当量に対し、４−ブロモスチレン２当量を加えて白金触媒下で加熱してシロキサンが付加した中間体３を得る。
【００４０】
更に、２−（４−ブロモ−フェノキシ）テトラヒドロ−２Ｈ−ピランと３−メチル−１−ブチン−３−オールとを当量仕込み、パラジウム／ヨウ化銅触媒下で加熱し、更にその反応液を水酸化カリウム存在下でトルエン還流を行い、アセチレン誘導体を得る。
【００４１】
次いで得られたアセチレン誘導体２当量と上記の中間体３の１当量とをパラジウム／ヨウ化銅触媒下で加熱して反応させた後に、この反応物を希塩酸／メタノール溶液で撹拌することにより、シロキサン結合及びトラン骨格を有するフェノール誘導体の中間体４を得る。
【００４２】
このフェノール誘導体とブロモブチルアクリレートとを炭酸カリウム存在下において８０〜１００℃で加熱することにより、目的の重合性液晶化合物を得ることが出来る。反応温度が１１０℃以上だとアクリル基同士が重合する恐れがあるので好ましくない。
【００４３】
本発明で使用する重合性液晶化合物は、上記の方法などで容易に合成することができる。次に該重合性液晶化合物を用いた光学異方体の製造方法について説明する。
【００４４】
本発明の重合性液晶組成物は、一般式（I）で表される化合物を一種類以上、又は、他の重合性化合物、もしくは他の液晶成分、あるいは他の重合性液晶化合物との混合物の形で用いることができ、本発明の重合性液晶化合物の単独及び／又は２種以上を混合した組成物に、本発明の液晶性、重合性、光学異方体等の特性を低下させない範囲で、本発明以外の重合性液晶化合物、非液晶性の重合性化合物及び非重合性の液晶化合物を配合しても良い。
【００４５】
重合性官能基を有していない液晶化合物としては、ネマチック液晶化合物、スメクチック液晶化合物、コレステリック液晶化合物等の通常この分野で液晶と認識されるものが挙げられ、特に制限なく使用できる。また、非液晶性の重合性化合物としては、重合性基を有するアクリルモノマー、重合性基を有するウレタンオリゴマー、ポリエステルオリゴマー、エポキシアクリレートオリゴマー等が挙げられる。
【００４６】
これらの重合性化合物又は液晶化合物は適宜選択して組み合わせて添加してよいが、光学異方体の配向、機械的強度及び得られる重合性液晶組成物の液晶性が失われないように、各成分の添加量を調整することが必要である。
【００４７】
本発明の重合性液晶化合物、及び重合性液晶組成物の重合手段としては、熱、及び／又は紫外線等のエネルギー線を用いることができる。熱重合の場合は、重合開始剤として熱重合開始剤を用いることが好ましい。熱重合開始剤としては公知慣用の熱重合開始剤をいずれも特に限定なく用いることが出来る。
【００４８】
それらの熱重合開始剤としては、例えば、ベンゾイルパーオキサイド、２，４−ジクロロベンゾイルパーオキサイド、１，１−ジ（ターシャリーブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、ｎ−ブチル−４，４’−ジ（ターシャリーブチルパーオキシ）バレレート、ジクミルパーオキサイドの如き過酸化物類；７−アゾビスイソブチルニトリルの如きアゾ化合物類；テトラメチルチウラムジスルフィド等が挙げられる。
【００４９】
また、重合手段としてエネルギー線を用いる方法は、製造工程が容易であり好ましい。エネルギー線として紫外線を用いる場合には、重合開始剤として光重合開始剤を重合性液晶組成物中に添加することが好ましい。光重合開始剤としては、ラジカル重合用光開始剤とカチオン重合用光開始剤の２種に大別できる。
【００５０】
前者の例としては、ジエトキシアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、ベンジルジメチルケタール、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、２−メチル−２−モルホリノ（４−チオメチルフェニル）プロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノン等のアセトフェノン系；
【００５１】
ベンゾイン、ベンゾインイソブチルエーテル等のベンゾイン系；２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド等のアシルホスフィンオキサイド系；ベンゾフェノン、ο−ベンゾイル安息香酸メチル、４−フェニルベンゾフェノン、４，４′−ジクロロベンゾフェノン、４−ベンゾイル−４′−メチル−ジフェニルサルファイド、アクリル化ベンゾフェノン、３，３′，４，４′−テトラ（ｔ−ブチルパーオキシカルボニル）ベンゾフェノン、３，３′−ジメチル−４−メトキシベンゾフェノン等のベンゾフェノン系；
【００５２】
２−イソプロピルチオキサントン、２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、４，４′−ジエチルアミノベンゾフェノン等のアミノベンゾフェノン系；１０−ブチル−２−クロロアクリドン、２−エチルアンスラキノン、９，１０−フェナンスレンキノン、カンファーキノン等が挙げられる。
【００５３】
後者としては、鉄アレーン錯体、アリールスルホニウム塩、アリールヨードニウム塩などが挙げられる。重合開始剤の添加量は、重合性液晶化合物及び／又は重合性液晶組成物中に０．０１〜１０重量％、好ましくは１〜５重量％である。
本発明の重合性液晶化合物及び／又は重合性液晶組成物にラジカル重合型光開始剤を添加した場合、上記のラジカル重合型光開始剤の添加だけでも硬化するが、硬化性をより向上させるために、光増感剤を併用することが好ましい。
【００５４】
かかる光増感剤としては、トリエタノールアミン、メチルジエタノールアミン、トリイソプロパノールアミン、４−ジメチルアミノ安息香酸メチル、４−ジメチルアミノ安息香酸エチル、４−ジメチルアミノ安息香酸イソアミル、安息香酸（２−ジメチルアミノ）エチル、４−ジメチルアミノ安息香酸（ｎ−ブトキシ）エチル、４−ジメチルアミノ安息香酸２−エチルヘキシル等のアミン類が挙げられる。光増感剤の配合量は、重合性液晶化合物及び／又は重合性液晶組成物中に０．０１〜１０重量％、好ましくは０．０５〜５重量％である。
【００５５】
また、本発明の重合性液晶化合物の重合性基としてマレイミド基を用いた場合は、光重合開始剤の無添加又は極少量の添加でも十分硬化が可能である。
【００５６】
また、本発明で用いる重合性液晶化合物及び／又は重合性液晶組成物には、光学異方体中にねじれネマチック配向、又はコレステリック配向の螺旋構造を導入する目的で、光学活性化合物を添加してもよい。ここで使用することができる光学活性化合物は、それ自体が液晶性を示す必要がなく、また重合性基を有していても、有していなくてもよい。またねじれの向きは使用する目的によって適宜選択することができる。
【００５７】
これらの光学活性化合物としては、例えば、光学活性基としてコレステリル基を有するペラルゴン酸コレステロール、ステアリン酸コレステロール、光学活性基として２−メチルブチル基を有する「ＣＢ−１５」、「Ｃ−１５」（以上、ＢＤＨ社製）、「Ｓ１０８２」（メルク社製）、「ＣＭ−１９」、「ＣＭ−２０」、「ＣＭ」（以上チッソ社製）、光学活性基として１−メチルヘプチル基を有する「Ｓ−８１１」（メルク社製）、「ＣＭ−２１」、「ＣＭ−２２」（以上、チッソ社製）等を挙げることができる。
【００５８】
光学活性化合物の好ましい添加量は、光学異方体の用途により異なる。カイラルネマチック配向、又はコレステリック配向の螺旋構造を導入し、例えば液晶表示素子の視覚補償板として用いる場合には、コレステリック構造に由来する選択反射光の波長が可視光領域から外れるように、螺旋構造のピッチ（Ｐ）を０．２５μｍ以下もしくは０．５μｍ以上になるように調整することが好ましく、例えば特定波長の反射板として用いる場合には、選択反射光の波長が可視光領域にあるように螺旋構造のピッチが０．２５〜０．５μｍになるように調整するのが好ましい。
【００５９】
次に、本発明の重合性液晶化合物、又はそれらを含む重合性液晶組成物の重合により得られる光学異方体の製造方法について説明する。
配向手段を有する基板上に本発明の重合性液晶化合物、又はそれらを含む重合性液晶組成物を塗布するか、あるいは少なくとも一方が配向手段を有する２枚の基板間に、該重合性液晶化合物又は重合性液晶組成物を介在させ、配向した状態のまま、熱及び／又は光照射により重合させて得ることができる。
【００６０】
配向手段としては、基板表面を布等でラビングしたものや紫外線照射したもの、あるいは基板表面へのＳｉＯ₂を斜方蒸着したのもを用いれば達成することができる。また、このような配向処理を施した基板を用いない場合には、電場又は磁場を利用する方法を挙げることができる。これらの配向手段は単独でも、また組み合わせて用いてもよい。その中でも、基板表面を布等でラビング処理した基板を用いる方法や基板に紫外線照射した方法は、その簡便性から好ましい。
【００６１】
このとき使用することができる基板は、有機材料、無機材料を問わずに用いることができる。具体的には、例えばポリエチレンテレフタレート、ポリカーボネート、ポリイミド、ポリメタクリル酸メチル、ポリエチレン、ポリエーテルスルホン、ポリテトラフルオロエチレンなどの有機材料や、シリコン、ガラス等の無機材料が挙げられる。
【００６２】
また、偏光フィルムを基板として用いると、偏光フィルムに直接光学異方体を取り込むことが可能であり、このようにして得られる光学異方体は楕円偏光フィルムとして、液晶ディスプレイの構成部品として好適に用いることができる。
これらの基板を布等でラビングすることによって適当な配向性を得られないときは、公知の方法に従ってポリイミド薄膜又はポリビニルアルコール薄膜等を基板表面上に形成し、これを布等でラビングしても良い。
【００６３】
本発明の重合性液晶化合物の重合方法としては、低温硬化及び迅速な重合が期待されることからエネルギー線を照射することにより重合させる方法が望ましい。エネルギー線とは、紫外線、電子線、α線、β線、γ線のような電離放射線、可視光線、マイクロ波、高周波等をいうが、ラジカル性活性種を生成させうるならば、いかなるエネルギー種でもかまわない。
【００６４】
紫外線を発生するものとしては、例えば超高圧水銀ランプ、高圧水銀ランプ、低圧水銀ランプ、メタルハライドランプ、ケミカルランプ、ブラックライトランプ、水銀−キセノンランプ、ショートアーク灯等が挙げられ、ラジカル性活性種を発生させる化合物の吸収波長を考慮して選択すればよい。
【００６５】
特に、光重合、中でも紫外線による重合方法は製造面からより好ましい。本発明の重合性液晶化合物、又はそれを含む重合性液晶組成物を塗布した基板面又は塗布していない基板面のどちらから照射してもよいが、塗布していない基板面に照射する場合、用いる基板は透明性を有していなければならない。また、本発明によって作製される光学異方体は、基板から剥離して用いても、また剥離せずに基板に担持させたまま用いてもよい。
【００６６】
【実施例】
以下に、本発明の実施例を示し、本発明を更に具体的に説明する。しかしながら、本発明はこれらの実施例に限定されるものではない。なお、以下の実施例において「部」は特に断りのない限り「重量部」を表す。また、紫外線照度は、ウシオ電機社製の受光器「ＵＶＤ−３６５ＰＤ」付きユニメータＵＩＴ−１５０」を用いて測定した。
【００６７】
耐熱性試験は、顕微鏡用冷却加熱装置ＬＫ−６００ＰＭ（リンカム社製）を使用して顕微ラマン分光ＲＭ−２０００（レニショウ社製）を使用して室温及び１２０℃での１６００及び２２００ｃｍ^{― 1}の偏光ラマン散乱光の測定により評価した。
【００６８】
（実施例１）
ジムロート還流管、温度計を取り付けた４つ口フラスコに４−ブロモスチレン２５ｇ、ヘキサクロロ白金酸六水和物を５００ｐｐｍ、トルエン５０ｍｌを仕込み８０℃に加熱した。次いで１，１，３，３−テトラメチルジシロキサン８．７ｇを滴下した。滴下終了後フラスコを１００℃に保ち３時間撹拌した。反応終了後、飽和食塩水で反応液を洗浄し硫酸ナトリウムで乾燥させ溶媒を溜去し中間体（ａ）を得た。
【００６９】
ジムロート還流管、温度計を取り付けた４つ口フラスコに中間体（ａ）１０ｇ３−メチル−１−ブチン−３オール４ｇ、テトラキストリフェニルフォスフィンパラジウム５５０ｍｇ、ヨウ化銅１８０ｍｇ、トリエチルアミン１０ｍｌ、ジメチルホルムアミド（以下、ＤＭＦ）５０ｍｌを仕込み撹拌した。次いでフラスコを９０℃に加熱し３時間反応させた。反応終了後、飽和食塩水で反応液を洗浄し硫酸ナトリウムで乾燥させ溶媒を溜去して、シリカゲルカラムにより精製して中間体（ｂ）を４．５ｇ得た。
【００７０】
次いで、ディーンスターク、温度計を取り付けた４つ口フラスコ内に上記で合成した中間体（ｂ）３．５ｇ、トルエン５０ｍｌ、水酸化カリウム４４ｍｇを仕込み、フラスコを１２０℃に加熱しトルエンを３時間還流させた。その後、反応液を濾過し濾液を飽和食塩水で洗浄し硫酸ナトリウムで乾燥させ溶媒を溜去し、シリカゲルカラムにより精製し中間体（ｃ）を２．６ｇ得た。
【００７１】
ジムロート還流管、温度計を取り付けた４つ口フラスコ内に中間体（ｃ）２．６ｇ、２−（４―ブロモ−２−フルオロフェノキシ）テトラヒドロ２Ｈ−ピラン３．７ｇ、テトラキストリフェニルフォスフィンパラジウム１５０ｍｇ、ヨウ化銅５１ｍｇ、トリエチルアミン１０ｍｌ、ＤＭＦ３０ｍｌを仕込み撹拌した。
次いでフラスコを９０℃に加熱し４時間反応させた。反応終了後、飽和食塩水で反応液を洗浄し硫酸ナトリウムで乾燥させ溶媒を溜去して、シリカゲルカラムにより精製し中間体（ｄ）を４．２ｇ得た。
【００７２】
次いで滴下ロートを取り付けたナスフラスコに中間体（ｄ）４．２ｇ、テトラヒドロフラン２０ｍｌを仕込み撹拌した。次いで１／１０Ｎ塩酸水溶液を１ｍｌ滴下し３０分撹拌した。反応液に酢酸エチル１００ｍｌを加え、純水、飽和食塩水で洗浄し硫酸ナトリウムで乾燥させ溶媒を溜去して、シリカゲルカラムにより精製を行い、シロキサン結合及びトラン結合を有する中間体（ｅ）２ｇを得た。
【００７３】
更にジムロート還流管、滴下ロート、温度計を取り付けた４つ口フラスコ内に中間体（ｅ）１．０ｇ、炭酸カリウム１．３ｇ、ＤＭＦ３０ｍｌを仕込み、２５℃で１時間撹拌した。次いで６−ブロヘキシルアクリレート０．８ｇのＤＭＦ溶液を滴下した。滴下終了後、フラスコを１００℃に保ち４時間撹拌させ反応を完結させた。反応終了後、純水、飽和食塩水で洗浄し有機層を無水硫酸ナトリウムで乾燥させ溶媒を溜去して、シリカゲルカラムにより精製し、下式で表される白色結晶の重合性液晶化合物（Ａ−１）を０．９ｇ得た。
【００７４】
【化１２】

【００７５】
赤外線吸収スペクトルより３２００〜３６００ｃｍ^-1のフェノール性水酸基の吸収が消失しており、完全にエーテル化されていることを確認した。
【００７６】
（物性値）
¹Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：7.32(4H),7.16(2H),7.08(6H),6.79(2H),6.27(2H),6.03(2H),5.73(2H),4.07(4H),3.94(4H),2.59-2.53(4H),1.79-1.74(4H),1.74-1.70(4H),1.48-1.36(8H),0.80(4H),0.00
【００７７】
¹³Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ；165.9,158,131.1,130.1,128.2,127.5,114.4,88.3,68.8,64.8,29.0,28.6,28.1,25.3,25.2,19.6
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）ｃｍ^-1：2937,2860，2215,1916,1726,
1635,1606,1197,817,807.5
元素分析：C=70.2％(70.56),H=6.9％(7.02)
【００７８】
得られた重合性液晶化合物（Ａ−１）は、毎分２℃の降温状態において、８２℃で等方相液体状態からネマチック相へ相転移し、７５℃にて結晶相に相転移した。また、非重合性の液晶化合物「ＲＯ−５７１」（大日本インキ化学社製）に対して本発明の重合性液晶化合物（Ａ−１）を５重量％及び１０重量％添加した組成物の複屈折率差（Δｎ）をアッペ屈折率計（アタゴ社製）で測定し、重合性液晶化合物（Ａ−１）のΔｎを外挿したところ、０．２０と高い値を示した。また１２０℃の耐熱試験後も、何ら変化は認められなかった。
【００７９】
（実施例２）
ジムロート還流管、温度計を取り付けた４つ口フラスコ内に（実施例１）の中間体（ｃ）４．２ｇ、２−（４―ブロモフェニル−４'−フェノキシ）テトラヒドロ２Ｈ−ピラン７．２ｇ、テトラキストリフェニルフォスフィンパラジウム２５０ｍｇ、ヨウ化銅８２ｍｇ、トリエチルアミン１５ｍｌ、ＤＭＦ５０ｍｌを仕込み撹拌した。次いでフラスコを９０℃に加熱し４時間反応させた。反応終了後、飽和食塩水で反応液を洗浄し硫酸ナトリウムで乾燥させ溶媒を溜去し、シリカゲルカラムにより精製し中間体（ｆ）を８ｇ得た。
【００８０】
次いで、滴下ロートを取り付けたナスフラスコに中間体（ｆ）４．０ｇ、テトラヒドロフラン２０ｍｌを仕込み撹拌した。次いで１／１０Ｎ塩酸水溶液を１ｍｌ滴下し３０分撹拌した。反応液に酢酸エチル１００ｍｌを加え、純水、飽和食塩水で洗浄し硫酸ナトリウムで乾燥させ溶媒を溜去して、シリカゲルカラムにより精製を行い、シロキサン結合及びトラン骨格を有する中間体（ｇ）を２．８ｇ得た。
【００８１】
更にジムロート還流管、滴下ロート、温度計を取り付けた４つ口フラスコ内に中間体（ｇ）２．８ｇ、炭酸カリウム３．４ｇ、ＤＭＦ５０ｍｌを仕込み、２５℃で１時間撹拌した。次いで６−ブロヘキシルアクリレート１．９ｇのＤＭＦ溶液を滴下した。滴下終了後、フラスコを１００℃に保ち４時間撹拌させ反応を完結させた。反応終了後、純水、飽和食塩水で洗浄し有機層を無水硫酸ナトリウムで乾燥させ溶媒を溜去し、シリカゲルカラムにより精製し、下式で表される白色結晶の重合性液晶化合物（Ａ−２）を３．０ｇ得た。
【００８２】
【化１３】

【００８３】
赤外線吸収スペクトルより３２００〜３６００ｃｍ^-1のフェノール性水酸基の吸収が消失しており、完全にエーテル化されていることを確認した。
【００８４】
（物性値）
¹Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：7.46-7.30(16H),7.06(4H),6.82(4H),6.32(2H),6.03(2H),5.72(2H),4.07(4H),3.94(4H),2.59-2.49(4H),1.76-1.72(4H),1.69-1.66(4H),1.44-1.36(8H),0.80(4H),0.00
【００８５】
¹³Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：165.8,158.5,145,139.131.1,130.1,128.2,127.5,114.4,88.3,68.8,64.8,29.0,28.6,28.1,25.3,25.2,19.6
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）ｃｍ^-1：2937,2860，2215,1916,1726,
1635,1606,1197,817,807.5
元素分析：C=78.2％(79.00),H=7.2％(7.43)
【００８６】
得られた重合性液晶化合物（Ａ−２）は、毎分２℃の降温状態において、１８９℃で等方相液体状態からスメクチック相へ相転移を行い、８８℃にて結晶相に相転移した。また、非重合性の液晶化合物「ＲＯ−５７１」（大日本インキ化学社製）に対して本発明の重合性液晶化合物（Ａ−２）を５重量％及び１０重量％添加した組成物の複屈折率差（Δｎ）をアッペ屈折率計（アタゴ社製）で測定し、重合性液晶化合物（Ａ−２）のΔｎを外挿したところ、０．３０と高い値を示した。また１２０℃の耐熱試験後も何ら変化は認められなかった。
【００８７】
（実施例３）
ジムロート還流管、温度計を取り付けた４つ口フラスコに４−ブロモスチレン２７．６ｇ、ヘキサクロロ白金酸六水和物を８４ｍｇ、トルエン５０ｍｌを仕込み８０℃に加熱した。次いで１，１，３，３，５，５−ヘキサメチルトリシロキサン１５ｇを滴下した。滴下終了後フラスコを１００℃に保ち３時間撹拌した。反応終了後、飽和食塩水で反応液を洗浄し硫酸ナトリウムで乾燥させ溶媒を溜去し中間体（ｈ）を得た。
【００８８】
ジムロート還流管、温度計を取り付けた４つ口フラスコに中間体（ｈ）１０ｇ３−メチル−１−ブチン−３オール３．２ｇ、テトラキストリフェニルフォスフィンパラジウム４４０ｍｇ、ヨウ化銅１４０ｍｇ、トリエチルアミン１０ｍｌ、ＤＭＦ５０ｍｌを仕込み撹拌した。次いでフラスコを９０℃に加熱し３時間反応させた。反応終了後、飽和食塩水で反応液を洗浄し硫酸ナトリウムで乾燥させ溶媒を溜去して、シリカゲルカラムにより精製して中間体（ｉ）を６ｇ得た。
【００８９】
次いで、ディーンスターク、温度計を取り付けた４つ口フラスコ内に上記で合成した中間体（ｉ）５．４ｇ、トルエン５０ｍｌ、水酸化カリウム２００ｍｇを仕込み、フラスコを１２０℃に加熱しトルエンを３時間還流させた。その後、反応液を濾過し濾液を飽和食塩水で洗浄し硫酸ナトリウムで乾燥させ溶媒を溜去して、シリカゲルカラムにより精製しアセチレン基を有する中間体（ｊ）を２．２ｇ得た。
【００９０】
ジムロート還流管、温度計を取り付けた４つ口フラスコ内に中間体（ｊ）２．２ｇ、２−（４―ブロモ−２−フルオロフェニル−４'−フェノキシ）テトラヒドロ２Ｈ−ピラン３．４ｇ、テトラキストリフェニルフォスフィンパラジウム１１０ｍｇ、ヨウ化銅３６ｍｇ、トリエチルアミン１０ｍｌ、ＤＭＦ３０ｍｌを仕込み撹拌した。次いでフラスコを９０℃に加熱し４時間反応させた。反応終了後、塩酸飽和食塩水で反応液を洗浄し硫酸ナトリウムで乾燥させ溶媒を溜去し、シリカゲルカラムにより精製して中間体（ｋ）を５ｇ得た。
【００９１】
次いで、滴下ロートを取り付けたナスフラスコに中間体（ｋ）５ｇ、テトラヒドロフラン２０ｍｌを仕込み撹拌した。次いで１／１０Ｎ塩酸水溶液を１ｍｌ滴下し３０分撹拌した。反応液に酢酸エチル１００ｍｌを加え、純水、飽和食塩水で洗浄し硫酸ナトリウムで乾燥させ溶媒を溜去して、シリカゲルカラムにより精製し、シロキサン結合及びトラン骨格を有する中間体（ｌ）を３ｇ得た。
【００９２】
更にジムロート還流管、滴下ロート、温度計を取り付けた４つ口フラスコ内に中間体（ｌ）３．０ｇ、炭酸カリウム３ｇ、ＤＭＦ３０ｍｌを仕込み、２５℃で１時間撹拌した。次いで６−ブロヘキシルアクリレート１．８ｇのＤＭＦ溶液を滴下した。滴下終了後、フラスコを１００℃に保ち４時間撹拌させ反応を完結させた。反応終了後、純水、飽和食塩水で洗浄し有機層を無水硫酸ナトリウムで乾燥させ溶媒を溜去して、シリカゲルカラムにより精製し、下式で表される白色結晶の重合性液晶化合物（Ａ−３）を２．２ｇ得た。
【００９３】
【化１４】

【００９４】
また、赤外線吸収スペクトルより３２００〜３６００ｃｍ^-1のフェノール性水酸基の吸収が消失しており、完全にエーテル化されていることを確認した。
【００９５】
（物性値）
¹Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：7.38-7.33(8H),7.28-7.17(6H),7.06(4H),6.85(4H),6.30(2H),6.01(2H),5.68(2H),4.06(4H),3.88(2H), 2.55(4H),1.70(4H),1.58(4H),1.42-1.33(8H),0.8(4H)
【００９６】
¹³Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：166.0,136.2,130.0,127.7,120,114.3,67.6,64.3,28.9, 28.3,25.8
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）ｃｍ^-1：2932,2860，2215,1734,
1634,1606,1197,817,807.5
元素分析：C=70.1％(71.3),H=6.86％(6.70)
【００９７】
得られた重合性液晶化合物（Ａ−３）は、毎分２℃の降温状態において、１１８℃で等方相液体状態からネマチック相へ相転移を行い、１０８℃にてネマチック相状態からスメクチック相に相転移を行い、７２℃にて結晶相に相転移した。また、非重合性の液晶化合物「ＲＯ−５７１」（大日本インキ化学社製）に対して本発明の重合性液晶化合物（Ａ−３）を５重量％及び１０重量％添加した組成物の複屈折率差（Δｎ）をアッペ屈折率計（アタゴ社製）で測定し、重合性液晶化合物（Ａ−３）のΔｎを外挿したところ、０．３１と高い値を示した。また１２０℃の耐熱試験後も、何ら変化は認められなかった。
【００９８】
（実施例４）
ジムロート還流管、温度計を取り付けた４つ口フラスコに４−アリル−２−メトキシフェノール２４．８ｇ、ヘキサクロロ白金酸六水和物を８４ｍｇ、トルエン５０ｍｌを仕込み８０℃に加熱した。次いで１，１，３，３，５，５−ヘキサメチルトリシロキサン１５ｇを滴下した。滴下終了後フラスコを１００℃に保ち３時間撹拌した。反応終了後、飽和食塩水で反応液を洗浄し硫酸ナトリウムで乾燥させ溶媒を溜去して中間体（ｍ）を得た。
【００９９】
エステル合成用環流管、温度計を取り付けた４つ口フラスコに、アクリル酸２７ｇ、２−（４−ヒドロキシフェニル）エチルアルコール４０ｇ、ｐ−トルエンスルホン酸１．３ｇ、ハイドロキノン１００ｍｇ、トルエン１５０ｍｌを仕込み、８０℃にて均一に溶解させた。その後、フラスコを９０℃に加熱して真空ポンプで３５０ｍｍＨｇに減圧し４時間反応させた。更にフラスコを１００℃に加熱後、減圧度を１００ｍｍＨｇして反応を完結させた。反応終了後、純水、飽和食塩水で反応液を洗浄し硫酸ナトリウムで乾燥させ溶媒を溜去し、シリカゲルカラムにより精製して中間体（ｎ）を２４ｇ得た。
【０１００】
ジムロート還流管、温度計を取り付けた４つ口フラスコ内にトランス１，４−シクロヘキサンカルボン酸１２．８ｇ、ドータイトＷＳＣ（同仁化学研究所製）１５．３ｇ、ジメチルアミノピリジン１．０ｇ、ジクロロメタン３５０ｍｌを仕込み撹拌した。フラスコを５℃以下に保ち、中間体（ｎ）１５ｇのジクロロメタン溶液を滴下した。滴下終了後にフラスコを室温に戻して６時間撹拌して反応を終了した。反応液を１／１０Ｎ塩酸溶液及び飽和食塩水で反応液を洗浄し硫酸ナトリウムで乾燥させ溶媒を溜去して、シリカゲルカラムにより精製しアクリル基とカルボキシル基を有する中間体（ｏ）を２４ｇ得た。
【０１０１】
ジムロート還流管と温度計を取り付けた４つ口フラスコ内に中間体（ｍ）１０．７ｇ、ドータイトＷＳＣ（同仁化学研究所製）７．７ｇ、ジメチルアミノピリジン０．５ｇ、ジクロロメタン２５０ｍｌを仕込み撹拌した。フラスコを５℃以下に保ち、中間体（ｏ）１３．８ｇのジクロロメタン溶液を滴下した。滴下終了後にフラスコを室温に戻して６時間撹拌して反応を終了した。反応液を１／１０Ｎ塩酸溶液及び飽和食塩水で反応液を洗浄し硫酸ナトリウムで乾燥させ溶媒を溜去し、シリカゲルカラムにより精製し、下式で表される白色結晶の重合性液晶化合物（Ａ−４）を８．２ｇ得た。
【０１０２】
【化１５】

【０１０３】
また、赤外線吸収スペクトルより３２００〜３６００ｃｍ^-1のフェノール性水酸基の吸収が消失しており、完全にエステル化されていることを確認した。
【０１０４】
（物性値）
¹Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：7.26(8H),7.17(2H),7.02(4H),6.45(2H),6.1(2H),5.8(2H),4.36(4H),3.80(6H),2.98(4H),2.58(4H), 2.55(4H),2.27(8H),1.70-1.58(12H),0.8(4H)
【０１０５】
¹³Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：166.0,154.0,136.2,130.0,128.3,127.7,120,114.3,67.6,64.3,42.3,34.4,28.9, 28.3,25.8
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）ｃｍ^-1：2935,2862,1734,1634,1606,1199,817,808
元素分析：C=63.1％(64.4),H=6.99％(7.09)
【０１０６】
得られた重合性液晶化合物（Ａ−４）は、毎分２℃の降温状態において、１０５℃で等方相液体状態からネマチック相へ相転移を行い、７０℃にて結晶相に相転移した。また、非重合性の液晶化合物「ＲＯ−５７１」（大日本インキ化学社製）に対して本発明の重合性液晶化合物（Ａ−４）を５重量％及び１０重量％添加した組成物の複屈折率差（Δｎ）をアッペ屈折率計（アタゴ社製）で測定し、重合性液晶化合物（Ａ−４）のΔｎを外挿したところ、０．１７を示した。また１２０℃の耐熱試験後も、何ら変化は認められなかった。
【０１０７】
（比較例１）
環流管を取り付けた４つ口フラスコに、ヒドロキノン１５．２ｇ、炭酸カリウム５７ｇ、ＤＭＦ３００ｍｌを入れ室温で１時間撹拌した。次いで、６−ブロモ１−ヘキサノール２５ｇのＤＭＦ溶液を滴下した。滴下終了後フラスコを１００℃に保ち５時間撹拌させ反応を終了させた。反応液に塩化メチレンを加え、純水、飽和食塩水で反応液を洗浄し硫酸ナトリウムで乾燥させ溶媒を溜去して、シリカゲルカラムにより精製し中間体（ｐ）を３０ｇ得た。
【０１０８】
エステル合成用環流管を取り付けた４つ口フラスコに、アクリル酸５．７g、中間体（ｐ）１１ｇ、触媒としてｐ−トルエンスルホン酸０．３ｇ、重合禁止剤としてハイドロキノン １０ｍｇ、トルエン２５０ｍｌを仕込み、８０℃で均一に溶解させた。その後、フラスコを９０℃に加熱して真空ポンプで３５０ｍｍＨｇに減圧し４時間反応させた。更にフラスコを１００℃に加熱後、減圧度を１００ｍｍＨｇして反応を完結させた。終了後、純水、飽和食塩水で反応液を洗浄し硫酸ナトリウムで乾燥させ溶媒を溜去して、シリカゲルカラムにより精製して中間体（ｑ）を６ｇ得た。
【０１０９】
ジムロート還流管、温度計を取り付けた４つ口フラスコ内にトランス−１，４−シクロヘキサンカルボン酸２．０ｇ、ドータイトＷＳＣ（同仁化学研究所製）５ｇ、ジメチルアミノピリジン０．３ｇ、ジクロロメタン２５０ｍｌを仕込み撹拌した。フラスコを５℃以下に保ち、中間体（ｑ）６ｇのジクロロメタン溶液を滴下した。滴下終了後にフラスコを室温に戻し６時間撹拌して反応を終了した。反応液を１／１０Ｎ塩酸溶液及び飽和食塩水で反応液を洗浄し硫酸ナトリウムで乾燥させ溶媒を溜去して、シリカゲルカラムにより精製し、下式で表される白色結晶の重合性液晶化合物（Ｂ−１）を１０ｇ得た。
【０１１０】
【化１６】

【０１１１】
赤外線吸収スペクトルより３２００〜３６００ｃｍ^-1のフェノール性水酸基の吸収が消失しており、完全にエステル化されていることを確認した。
【０１１２】
（物性値）
¹Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ； 6.9(4H),6.8(4H),6.3(2H),6.0(2H),5.8(2H),4.26(4H),3.90(4H),2.5(2H),2.3(4H), 1.86-1.67(4H),1.50-1.40(10H)
【０１１３】
¹³Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：166.0,153.1,130.0,128.7,120,72.0,68.9,64.6,29.0,28.6,25.8,23
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）ｃｍ^-1：2930,2870,1746,1716,1635,1508,810
元素分析：C=67.9％(68.6),H=7.20％(7.28)
【０１１４】
得られた重合性液晶化合物（Ｂ−１）は、毎分２℃の降温状態において、１２４℃で等方相液体状態からネマチック相へ相転移を行い、１１３℃にてネマチック相状態からスメクチック相に相転移を行い、１０２℃にて結晶相に相転移した。また非重合性の液晶化合物「ＲＯ−５７１」（大日本インキ化学社製）に対して本発明の重合性液晶化合物（Ｂ−１）を５重量％及び１０重量％添加した組成物の複屈折率差（Δｎ）をアッペ屈折率計（アタゴ社製）で測定し、重合性液晶化合物（Ｂ−１）のΔｎを外挿したところ、０．１５を示した。
【０１１５】
（実施例５）
実施例２で得た重合性液晶化合物（Ａ−２）３０部、本発明以外の重合性液晶化合物として、４６℃で等方相液体からネマチック相へ相転移を行い５℃で結晶相に相転移し、複屈折率差が０．１５であり
【０１１６】
【化１７】

【０１１７】
で表される液晶混合物「ＵＣＬ−００１」（大日本インキ化学社製）を７０部、及び重合開始剤として「イルガキュアー６５１」（チバスペシャリティーケミカル社製）２重量部を混合した重合性液晶組成物を調整した。この組成物は毎分２℃の降温状態において、７４℃で等方相液体状態からネマチック相へ相転移を行い２０℃にてネマチック相状態からスメクチック相に相転移を行い１０℃にて結晶相に相転移した。複屈折率差（Δｎ）をアッペ屈折率計（アタゴ社製）で測定したところ０．１９を示した。
【０１１８】
次にホモジニアス配向処理を施されたポリイミド配向膜が形成されている厚さ２０μｍのガラスセルに、上記重合性組成物を等方相状態で注入後、４００Ｗ／ｍ²の紫外線を室温で６０秒照射して光学異方体を作製した。ラマン散乱測定による配向度の測定により、この光学異方体は均一なホモジニアス配向を維持しており１２０℃での耐熱性試験でも何ら問題がなかった。
【０１１９】
（実施例６）
実施例３で得た重合性液晶化合物（Ａ−３）３０部、本発明以外の重合性液晶化合物「ＵＣＬ−００１」（大日本インキ化学社製）７０部、及び重合開始剤として「イルガキュアー６５１」（チバスペシャリティーケミカル社製）２重量部を混合した重合性液晶組成物を調製した。この組成物は毎分２℃の降温状態において、６２℃で等方相液体状態からネマチック相へ相転移を行い１０℃にてネマチック相状態からスメクチック相に相転移を行い０℃にて結晶相に相転移した。複屈折率差（Δｎ）をアッペ屈折率計（アタゴ社製）で測定したところ０．２０を示した。
【０１２０】
次にホモジニアス配向処理を施されたポリイミド配向膜が形成されている厚さ２０μｍのガラスセルに、上記重合性組成物を等方相状態で注入後、４００Ｗ／ｍ²の紫外線を室温で６０秒照射して光学異方体を作製した。ラマン散乱測定による配向度の測定により、この光学異方体は均一なホモジニアス配向を維持しており、１２０℃での耐熱性試験でも何ら問題がなかった。
【０１２１】
（実施例７）
実施例３で得た重合性液晶化合物（Ａ−３）５０部、非重合性化合物として、６４℃で等方相液体からネマチック相へ相転移を行い−１０℃で結晶相に相転移し、複屈折率差が０．２２であり、
【０１２２】
【化１８】

【０１２３】
で表されるシアノ系液晶組成物「ＲＯ−５７１」（大日本インキ化学社製）５０部、及び重合開始剤として「イルガキュアー６５１」（チバスペシャリティーケミカル社製）２重量部を混合した重合性液晶組成物を調製した。この組成物は毎分２℃の降温状態において、８０℃で等方相液体状態からネマチック相へ相転移を行い７℃にて結晶相に相転移した。複屈折率差（Δｎ）をアッペ屈折率計（アタゴ社製）で測定したところ０．２６を示した。
【０１２４】
次にホモジニアス配向処理を施されたポリイミド配向膜が形成されている厚さ２０μｍのガラスセルに、上記重合性組成物を等方相状態で注入後、４００Ｗ／ｍ²の紫外線を室温で６０秒照射して光学異方体を作製した。ラマン散乱測定による配向度の測定により、この光学異方体は均一なホモジニアス配向を維持していた。
【０１２５】
（比較例２）
比較例１で得た重合性液晶化合物（Ｂ−１）３０部、本発明以外の重合性液晶化合物「ＵＣＬ−００１」（大日本インキ化学社製）７０部、及び重合開始剤として「イルガキュアー６５１」（チバスペシャリティーケミカル社製）２重量部を混合したが、溶解させることが出来なかった。
【０１２６】
（比較例３）
本発明以外の重合性液晶化合物「ＵＣＬ−００１」（大日本インキ化学社製）５０部、非重合性のシアノ系液晶混合物「ＲＯ−５７１」（大日本インキ化学社製）５０部、及び重合開始剤として「イルガキュアー６５１」（チバスペシャリティーケミカル社製）２重量部を混合した重合性液晶組成物を調製した。この組成物は毎分２℃の降温状態において、４５℃で等方相液体状態からネマチック相へ相転移を行い０℃にて結晶相に相転移した。複屈折率差（Δｎ）をアッペ屈折率計（アタゴ社製）で測定したところ０．１８を示した。
【０１２７】
次にホモジニアス配向処理を施されたポリイミド配向膜が形成されている厚さ２０μｍのガラスセルに、上記重合性組成物を等方相状態で注入後、４００Ｗ／ｍ²の紫外線を室温で６０秒照射して光学異方体を作製した。この光学異方体はラマン散乱測定により配向が大きく低下し、白く散乱した硬化膜であった。
【０１２８】
【発明の効果】
本発明は、１００℃以下の低い温度で液晶性を示し、熱安定性が優れると共に良好な溶解性、大きな複屈折率差を有する新規な重合性液晶化合物、該重合性液晶化合物を含む重合性組成物、及びそれらを用いた光学異方体を提供する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel polymerizable liquid crystal compound, a polymerizable liquid crystal composition containing the polymerizable liquid crystal compound, and a liquid crystal composition useful as a liquid crystal display, an optical compensator for a liquid crystal display, a polarizing prism, and other various light modulation materials. It relates to the optical anisotropic body used.
[0002]
[Prior art]
In recent years, due to the demand for both improvement in display quality and weight reduction of liquid crystal display elements, a polymer film in which the alignment structure of internal molecules is controlled is required as a compensation plate. (Kaihei 3-28822, JP-A-4-55813, JP-A-5-27235) have been reported.
[0003]
In the method using these liquid crystalline polymers, a desired orientation is obtained by applying a polymer compound solution exhibiting a thermotropic liquid crystal property to an alignment-treated substrate and then heat-treating the polymer liquid crystals at a temperature at which the liquid crystal phase exhibits a liquid crystal phase. After obtaining the orientation, the orientation is fixed by keeping the polymer compound in a glass state.
[0004]
However, these polymer films have a drawback that the use temperature is limited by the glass transition point because the alignment state is destroyed at a temperature exceeding the glass transition point of the liquid crystalline polymer. Further, when applying a liquid crystalline polymer to a substrate subjected to an alignment treatment, it cannot be used for a substrate having poor solvent resistance such as some plastics because it is dissolved in a solvent and applied.
[0005]
As a means for solving these problems, a method for producing an optically anisotropic material using a low-molecular bifunctional liquid crystalline acrylate compound has been reported (JP-A-3-14029). This is a method in which a low molecular bifunctional liquid crystal acrylate compound or composition is twisted nematically aligned and then photopolymerized to fix the alignment state.
[0006]
In order to use these optically anisotropic materials in polymer films, various optically anisotropic materials, liquid crystal displays, etc. with controlled internal orientation structure, good chemical stability, heat resistance, solvent and low molecular weight It must have solubility in liquid crystals and stability against electric fields.
[0007]
However, the conventional technology can be aligned in a short time, but the workability is poor because the temperature of the liquid crystal phase is higher than 100 ° C., and unintentional thermal polymerization is induced to fix in a non-uniform alignment state. There have been drawbacks such as the loss of optical anisotropy at high temperatures and poor solubility in solvents and liquid crystals. Furthermore, when optical modulation is performed using these conventional optically anisotropic materials having a small difference in birefringence, the optical modulation performance is caused by the thickness of the optical anisotropic body and the difference in birefringence. I had to increase the thickness of my body.
[0008]
A polymer material with controlled orientation structure that has good workability, heat resistance, and high birefringence anisotropy has not been known so far. Also, when using an optical anisotropic body with high birefringence anisotropy as a light modulation material such as an optical waveguide or an optical compensator, the wavelength of light with the minimum film thickness of the optical anisotropic body is reduced. Since it can be converted, it can be thin and lightweight. Therefore, development of an optical anisotropic body and an optical element having a birefringence difference as large as possible has been demanded.
[0009]
[Problems to be solved by the invention]
A problem to be solved by the present invention is a polymerizable liquid crystal compound exhibiting liquid crystallinity at a temperature of 100 ° C. or less, excellent in thermal stability, and having a large birefringence difference, and a polymerizable liquid crystal containing the polymerizable liquid crystal compound It is in providing the composition and the optically anisotropic body formed by polymerizing these.
[0010]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors have repeated the production search for a novel polymerizable liquid crystal compound, and as a result, the present invention has been completed.
That is, the present invention is a polymerizable liquid crystal compound represented by the following general formula (I).
Formula (I)
[0011]
[Formula 4]

[0012]
(Where X is(Meth) acrylate groupY₁, Y₂And Y_FiveAre the same or different, single bond, -C_nH_2n-, -C_nH_2nO-, -OC_nH_2n-,-(C₂H_FourO)_n-,-(OC₂H_Four)_n-,-(C_ThreeH₆O)_n−,Or-(OC_ThreeH₆)_n−ofN represents an integer of 1 to 20, rings A to C and A ′ to C ′ each independently represent any of the following rings:
[0013]
[Chemical formula 5]

[0014]
a and b are 0Or 1Integer, R₁~ R₆Is a hydrogen atom or a halogen atom,Represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group, an alkenyloxy group, a fluoroalkyl group, or a fluoroalkoxy group;_ThreeAnd Y_FourEach independently represents a single bond, —CH₂CH₂-, -CH₂O—, —COO—, —OCO—, —C≡C—, —CH═CH—,Or-CF = CF-TheRepresent,
c represents an integer of 1 to 10)
[0015]
The polymerizable liquid crystal compound of the present invention particularly has the general formula (I)R ₁ ~ R ₆ Is a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atomsA polymerizable liquid crystal compound which is Y in the general formula (I)₁, Y₂And Y_FiveAre the same or different and -C_nH_2n-, -C_nH_2nO- or -OC_nH_2nA polymerizable liquid crystal compound in which n is an integer from 1 to 20, Y in the general formula (I)_ThreeAnd Y_FourAre each independently a single bond or a polymerizable liquid crystal compound of —C≡C—.
[0016]
In addition, the polymerizable liquid crystal compound of the present invention particularly has one or more of the rings A to C and A ′ to C ′ of the general formula (I),
[0017]
[Chemical 6]

[0018]
(Wherein F represents a fluorine atom, m represents an integer from 1 to 3, and p represents an integer from 1 to 3), which is a polymerizable liquid crystal compound that is any aromatic group.
[0019]
Further, the present invention is a polymerizable liquid crystal composition containing one or more of the above polymerizable liquid crystal compounds, and further includes a polymerizable liquid crystal containing one or more of the above polymerizable liquid crystal compounds and a polymerizable compound other than those. A composition, a polymerizable liquid crystal composition containing one or more of the polymerizable liquid crystal compounds and a polymerizable liquid crystal compound other than these, and an optically anisotropic composition comprising these polymerizable liquid crystal compounds or polymerizable liquid crystal compositions Including the body.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
The polymerizable liquid crystal compound of the present invention is a compound represented by the following general formula (I). Formula (I)
[0021]
[Chemical 7]

[0022]
(Wherein X represents a polymerizable group, Y₁, Y₂And Y_FiveAre the same or different, single bond, -C_nH_2n-, -C_nH_2nO-, -OC_nH_2n-,-(C₂H_FourO)_n-,-(OC₂H_Four)_n-,-(C_ThreeH₆O)_n-,-(OC_ThreeH₆)_n-, -C_nH_2nCOO-, -OOCC_nH_2n-, -C_nH_2nOOC- or -COOC_nH_2n-Represents one of the following, n is an integer of 1 to 20, and rings A, B and C each independently represent any of the following rings:
[0023]
[Chemical 8]

[0024]
a and b are integers of 0 to 2, R₁~ R₆Represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group, an alkenyloxy group, a fluoroalkyl group, or a fluoroalkoxy group;_ThreeAnd Y_FourEach independently represents a single bond, —CH₂CH₂-, -CH₂O—, —COO—, —OCO—, —C≡C—, —CH═CH—, —CF═CF—, — (CH₂)_Four-,-(CH₂)₆-, -CH₂CH₂CH₂O- or -CH₂= CHCH₂CH₂And c represents an integer of 1 to 10)
[0025]
Here, X of the polymerizable liquid crystal compound represented by the general formula (I) represents a polymerizable group, specifically, a (meth) acryl group, a (meth) acryloylphenyl group, 2-chloro (meth). Indicates a polymerizable residue such as an acrylate group, an acrylamide group, a maleimide group, a vinyl ether group, a thiol group, an allyl ether group, an epoxy group, an itaconic acid derivative, a styrene derivative, or a cinnamic acid derivative, and more preferably radical polymerization is possible. A (meth) acryl group, a (meth) acryloylphenyl group, and 2-chloro (meth) acrylate.
[0026]
Y in general formula (I)₁, Y₂And Y_FiveAre the same or different, a single bond, -C_nH_2n-, -C_nH_2nO-, -OC_nH_2n-,-(C₂H_FourO)_n-,-(OC₂H_Four)_n-,-(C_ThreeH₆O)_n-,-(OC_ThreeH₆)_n-, -C_nH_2nCOO-, -OOCC_nH_2n-, -C_nH_2nOOC- or -COOC_nH_2n-Represents any one, and n is an integer of 1 to 20, more preferably n is 3 to 10.
[0027]
C of general formula (I) is an integer of 1-10, More preferably, it is an integer of 1-4. Rings A to C and A ′ to C ′ in formula (I) include, for example, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an aromatic group substituted with an alkoxy group having 1 to 5 carbon atoms, and An aliphatic group, more preferably
[0028]
[Chemical 9]

[0029]
(In the formula, m represents an integer of 1 to 3, and p represents an integer of 1 to 3)
Or an aromatic group having one or more substituents represented by any of the above.
[0030]
The polymerizable liquid crystal compound of the present invention is characterized by having a polymerizable group and two rigid liquid crystalline skeletons specific to liquid crystals that contribute to the development of liquid crystallinity, and a rigid liquid crystal characteristic unique to liquid crystals that contributes to the expression of liquid crystallinity. The skeleton is linked through a siloxane bond. Examples of the rigid liquid crystalline skeleton include a skeleton composed of a 6-membered ring A and a ring B, a triple bond, and a ring C. From these characteristics, the polymerizable compound according to the present invention has a high birefringence difference and can exhibit a liquid crystal phase at a low temperature of 100 ° C. or less, and an optical anisotropic body using the same. Can maintain good molecular orientation even in a high temperature range of 120 ° C. or higher.
[0031]
The compound represented by the general formula (I) of the present invention can be synthesized as follows.
For example, in the general formula (I), X is an acrylate group, Y₁, Y₂Are-(CH₂)_ThreeO-, -O (CH₂)_Three-And Y_FiveIs-(CH₂)_Three-And Y_ThreeIs a single bond, Y_FourIs an ester bond, ring A, B and A ′, B ′ each represents an aromatic group, ring C, C ′ represents an aromatic group substituted with a methyl group, c is an integer of 2,
[0032]
[Chemical Formula 10]

[0033]
In the case of the polymerizable liquid crystal compound represented by the formula, 3,4-dihydro-2H-pyran and 4-hydroxy-4'-biphenylcarboxylic acid are charged in an equivalent amount, and reacted at a low temperature using p-toluenesulfonic acid as a catalyst. Intermediate 1 is protected.
[0034]
Subsequently, intermediate 2 in which siloxane was added by adding 2 equivalents of 4-allyl-2-methylphenol to 1 equivalent of 1,1,3,3,5,5-hexamethyltrisiloxane and heating under a platinum catalyst. Get.
[0035]
This intermediate 1 and intermediate 2 were reacted by heating in the presence of dicyclohexylcarbodiimide and N-methylaminopyridine, and the reaction product was further stirred with dilute hydrochloric acid / methanol solution to obtain a bisbiphenol derivative having a siloxane bond introduced. Can be obtained.
[0036]
The target polymerizable liquid crystal compound can be obtained by heating the bisbiphenol derivative and 3-bromopropyl acrylate at 80 to 100 ° C. in the presence of potassium carbonate. A reaction temperature of 110 ° C. or higher is not preferable because acrylic groups may be polymerized.
[0037]
In the general formula (I), X is an acrylate group, Y₁, Y₂Are-(CH₂)_FourO-, -O (CH₂)_Four-And Y_FiveIs-(CH₂)₂-, N is 0, and Y_FourIs —C≡C—, ring B, B ′, C, C ′ represents an aromatic group, and c is an integer of 2.
[0038]
Embedded image

[0039]
In the case of the polymerizable liquid crystal compound represented by the formula, 2 equivalents of 4-bromostyrene are added to 1 equivalent of 1,1,3,3,5,5-hexamethyltrisiloxane and heated under a platinum catalyst to prepare siloxane. To obtain an intermediate 3.
[0040]
Further, 2- (4-bromo-phenoxy) tetrahydro-2H-pyran and 3-methyl-1-butyn-3-ol were charged in an equivalent amount and heated under a palladium / copper iodide catalyst. Refluxing with toluene in the presence of potassium oxide gives an acetylene derivative.
[0041]
Next, 2 equivalents of the obtained acetylene derivative and 1 equivalent of the above intermediate 3 were reacted with heating under a palladium / copper iodide catalyst, and then the reaction product was stirred with dilute hydrochloric acid / methanol solution to obtain siloxane. An intermediate 4 of a phenol derivative having a bond and a tolan skeleton is obtained.
[0042]
The target polymerizable liquid crystal compound can be obtained by heating the phenol derivative and bromobutyl acrylate in the presence of potassium carbonate at 80 to 100 ° C. A reaction temperature of 110 ° C. or higher is not preferable because acrylic groups may be polymerized.
[0043]
The polymerizable liquid crystal compound used in the present invention can be easily synthesized by the method described above. Next, a method for producing an optical anisotropic body using the polymerizable liquid crystal compound will be described.
[0044]
The polymerizable liquid crystal composition of the present invention comprises one or more compounds represented by the general formula (I), other polymerizable compounds, other liquid crystal components, or a mixture with other polymerizable liquid crystal compounds. As long as the properties of the liquid crystallinity, polymerizability, optical anisotropy, etc. of the present invention are not deteriorated, the composition of the present invention alone and / or a composition obtained by mixing two or more of the polymerizable liquid crystal compounds of the present invention may be used. A polymerizable liquid crystal compound other than the present invention, a non-liquid crystalline polymerizable compound, and a non-polymerizable liquid crystal compound may be blended.
[0045]
Examples of the liquid crystal compound having no polymerizable functional group include those that are generally recognized as liquid crystals in this field, such as nematic liquid crystal compounds, smectic liquid crystal compounds, and cholesteric liquid crystal compounds, and can be used without particular limitation. Examples of the non-liquid crystalline polymerizable compound include an acrylic monomer having a polymerizable group, a urethane oligomer having a polymerizable group, a polyester oligomer, and an epoxy acrylate oligomer.
[0046]
These polymerizable compounds or liquid crystal compounds may be appropriately selected and combined to be added, but in order not to lose the alignment of the optical anisotropic body, the mechanical strength, and the liquid crystallinity of the resulting polymerizable liquid crystal composition. It is necessary to adjust the amount of ingredients added.
[0047]
As a polymerization means of the polymerizable liquid crystal compound and the polymerizable liquid crystal composition of the present invention, heat and / or energy rays such as ultraviolet rays can be used. In the case of thermal polymerization, it is preferable to use a thermal polymerization initiator as the polymerization initiator. As the thermal polymerization initiator, any known and commonly used thermal polymerization initiator can be used without any particular limitation.
[0048]
Examples of these thermal polymerization initiators include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 1,1-di (tertiary butyl peroxy) -3,3,5-trimethylcyclohexane, n-butyl- Examples thereof include peroxides such as 4,4′-di (tertiary butyl peroxy) valerate and dicumyl peroxide; azo compounds such as 7-azobisisobutylnitrile; tetramethylthiuram disulfide and the like.
[0049]
Moreover, the method using an energy beam as a polymerization means is preferable because the production process is easy. When ultraviolet rays are used as energy rays, it is preferable to add a photopolymerization initiator as a polymerization initiator to the polymerizable liquid crystal composition. Photopolymerization initiators can be broadly classified into two types: radical polymerization photoinitiators and cationic polymerization photoinitiators.
[0050]
Examples of the former include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1 Acetophenone systems such as -one, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone;
[0051]
Benzoins such as benzoin and benzoin isobutyl ether; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; benzophenone, ο-benzoylmethyl benzoate, 4-phenylbenzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, etc. Benzophenone series;
[0052]
Aminobenzophenone series such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9, Examples thereof include 10-phenanthrenequinone and camphorquinone.
[0053]
Examples of the latter include iron arene complexes, arylsulfonium salts, aryliodonium salts and the like. The addition amount of the polymerization initiator is 0.01 to 10% by weight, preferably 1 to 5% by weight in the polymerizable liquid crystal compound and / or polymerizable liquid crystal composition.
When a radical polymerization type photoinitiator is added to the polymerizable liquid crystal compound and / or polymerizable liquid crystal composition of the present invention, it is cured only by the addition of the above radical polymerization type photoinitiator, in order to further improve the curability. In addition, it is preferable to use a photosensitizer in combination.
[0054]
Such photosensitizers include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, benzoic acid (2-dimethylamino). And amines such as ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, 2-dimethylhexyl 4-dimethylaminobenzoate, and the like. The compounding quantity of a photosensitizer is 0.01 to 10 weight% in a polymeric liquid crystal compound and / or polymeric liquid crystal composition, Preferably it is 0.05 to 5 weight%.
[0055]
Further, when a maleimide group is used as the polymerizable group of the polymerizable liquid crystal compound of the present invention, it can be cured sufficiently even without addition of a photopolymerization initiator or with a very small amount.
[0056]
In addition, an optically active compound is added to the polymerizable liquid crystal compound and / or polymerizable liquid crystal composition used in the present invention for the purpose of introducing a helical structure of twisted nematic alignment or cholesteric alignment into the optical anisotropic body. Also good. The optically active compound that can be used here does not need to exhibit liquid crystal properties per se, and may or may not have a polymerizable group. The direction of twisting can be appropriately selected depending on the purpose of use.
[0057]
These optically active compounds include, for example, cholesterol pelargonate having a cholesteryl group as an optically active group, cholesterol stearate, and “CB-15” and “C-15” having a 2-methylbutyl group as an optically active group (above, BDH), “S1082” (manufactured by Merck), “CM-19”, “CM-20”, “CM” (manufactured by Chisso), “S- having 1-methylheptyl group as an optically active group” 811 "(manufactured by Merck)," CM-21 "," CM-22 "(manufactured by Chisso Corporation), and the like.
[0058]
The preferable addition amount of the optically active compound varies depending on the use of the optical anisotropic body. When a spiral structure of chiral nematic orientation or cholesteric orientation is introduced and used as, for example, a visual compensator for a liquid crystal display element, the spiral structure is designed so that the wavelength of the selectively reflected light derived from the cholesteric structure is out of the visible light region. It is preferable to adjust the pitch (P) to be 0.25 μm or less or 0.5 μm or more. For example, when used as a reflector having a specific wavelength, the spiral is selected so that the wavelength of the selectively reflected light is in the visible light region. It is preferable to adjust the pitch of the structure to be 0.25 to 0.5 μm.
[0059]
Next, the manufacturing method of the optical anisotropic body obtained by superposition | polymerization of the polymeric liquid crystal compound of this invention or the polymeric liquid crystal composition containing them is demonstrated.
The polymerizable liquid crystal compound of the present invention or a polymerizable liquid crystal composition containing the same is applied onto a substrate having orientation means, or at least one of the polymerizable liquid crystal compound or It can be obtained by polymerizing by heat and / or light irradiation with the polymerizable liquid crystal composition interposed and in an aligned state.
[0060]
As the orientation means, the substrate surface is rubbed with a cloth or the like, irradiated with ultraviolet rays, or SiO on the substrate surface.₂This can be achieved by using an obliquely deposited layer. Moreover, when not using the board | substrate which performed such an orientation process, the method of utilizing an electric field or a magnetic field can be mentioned. These orientation means may be used alone or in combination. Among them, the method using a substrate whose surface is rubbed with a cloth or the like and the method of irradiating the substrate with ultraviolet rays are preferable from the viewpoint of simplicity.
[0061]
The substrate which can be used at this time can be used regardless of an organic material or an inorganic material. Specific examples include organic materials such as polyethylene terephthalate, polycarbonate, polyimide, polymethyl methacrylate, polyethylene, polyethersulfone, and polytetrafluoroethylene, and inorganic materials such as silicon and glass.
[0062]
Further, when a polarizing film is used as a substrate, it is possible to incorporate an optical anisotropic body directly into the polarizing film, and the optical anisotropic body thus obtained is suitable as an elliptically polarizing film as a component of a liquid crystal display. Can be used.
When appropriate orientation cannot be obtained by rubbing these substrates with a cloth or the like, a polyimide thin film or a polyvinyl alcohol thin film or the like is formed on the surface of the substrate according to a known method, and this may be rubbed with a cloth or the like. good.
[0063]
As a polymerization method of the polymerizable liquid crystal compound of the present invention, a method of polymerizing by irradiating energy rays is desirable because low temperature curing and rapid polymerization are expected. The energy rays are ionizing radiation such as ultraviolet rays, electron rays, α rays, β rays, γ rays, visible rays, microwaves, high frequencies, etc., but any energy species can be used as long as it can generate radically active species. But it doesn't matter.
[0064]
Examples of those that generate ultraviolet rays include ultra high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, metal halide lamps, chemical lamps, black light lamps, mercury-xenon lamps, short arc lamps, and the like. It may be selected in consideration of the absorption wavelength of the compound to be generated.
[0065]
In particular, photopolymerization, particularly polymerization method using ultraviolet rays is more preferable from the viewpoint of production. Irradiation may be from either the substrate surface to which the polymerizable liquid crystal compound of the present invention or the polymerizable liquid crystal composition containing it is applied or the substrate surface to which it is not applied. The substrate used must be transparent. Further, the optical anisotropic body produced by the present invention may be used after being peeled off from the substrate, or may be used while being carried on the substrate without being peeled off.
[0066]
【Example】
Examples of the present invention will be shown below, and the present invention will be described more specifically. However, the present invention is not limited to these examples. In the following examples, “parts” represents “parts by weight” unless otherwise specified. In addition, the ultraviolet illuminance was measured by using a unit “UID-150 with UVD-365PD” manufactured by USHIO INC.
[0067]
The heat resistance test was performed at 1600 and 2200 cm at room temperature and 120 ° C. using a microscopic Raman spectroscopic RM-2000 (manufactured by Renishaw) using a microscope cooling and heating device LK-600PM (manufactured by Linkham).^{- 1}Was evaluated by measurement of polarized Raman scattered light.
[0068]
Example 1
A 4-neck flask equipped with a Dimroth reflux tube and a thermometer was charged with 25 g of 4-bromostyrene, 500 ppm of hexachloroplatinic acid hexahydrate, and 50 ml of toluene, and heated to 80 ° C. Next, 8.7 g of 1,1,3,3-tetramethyldisiloxane was added dropwise. After dropping, the flask was kept at 100 ° C. and stirred for 3 hours. After completion of the reaction, the reaction solution was washed with saturated brine, dried over sodium sulfate, and the solvent was distilled off to obtain an intermediate (a).
[0069]
Dimroth reflux tube, 4-neck flask equipped with a thermometer, intermediate (a) 10 g 3-methyl-1-butyn-3ol 4 g, tetrakistriphenylphosphine palladium 550 mg, copper iodide 180 mg, triethylamine 10 ml, dimethylformamide ( Hereinafter, 50 ml of DMF) was charged and stirred. The flask was then heated to 90 ° C. and reacted for 3 hours. After completion of the reaction, the reaction solution was washed with saturated brine, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column to obtain 4.5 g of intermediate (b).
[0070]
Next, 3.5 g of the intermediate (b) synthesized above, 50 ml of toluene and 44 mg of potassium hydroxide were charged into a 4-neck flask equipped with Dean Stark and a thermometer, and the flask was heated to 120 ° C. and toluene was added for 3 hours. Refluxed. Thereafter, the reaction solution was filtered, and the filtrate was washed with saturated brine, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column to obtain 2.6 g of intermediate (c).
[0071]
In a four-necked flask equipped with a Dimroth reflux tube and a thermometer, 2.6 g of intermediate (c), 3.7 g of 2- (4-bromo-2-fluorophenoxy) tetrahydro-2H-pyran, tetrakistriphenylphosphine palladium 150 mg, copper iodide 51 mg, triethylamine 10 ml and DMF 30 ml were charged and stirred.
The flask was then heated to 90 ° C. and reacted for 4 hours. After completion of the reaction, the reaction mixture was washed with saturated brine, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column to obtain 4.2 g of intermediate (d).
[0072]
Next, 4.2 g of intermediate (d) and 20 ml of tetrahydrofuran were placed in an eggplant flask equipped with a dropping funnel and stirred. Subsequently, 1 ml of 1 / 10N hydrochloric acid aqueous solution was dropped and stirred for 30 minutes. 100 ml of ethyl acetate was added to the reaction solution, washed with pure water and saturated brine, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column to obtain 2 g of intermediate (e) having a siloxane bond and a tolan bond. Got.
[0073]
Furthermore, 1.0 g of intermediate (e), 1.3 g of potassium carbonate, and 30 ml of DMF were charged into a four-necked flask equipped with a Dimroth reflux tube, a dropping funnel, and a thermometer, and stirred at 25 ° C. for 1 hour. Next, a DMF solution of 0.8 g of 6-bromohexyl acrylate was added dropwise. After completion of dropping, the flask was kept at 100 ° C. and stirred for 4 hours to complete the reaction. After completion of the reaction, the mixture was washed with pure water and saturated brine, the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column, and a white crystalline polymerizable liquid crystal compound (A 0.9 g of -1) was obtained.
[0074]
Embedded image

[0075]
3200-3600cm from infrared absorption spectrum^-1It was confirmed that the absorption of the phenolic hydroxyl group disappeared and was completely etherified.
[0076]
(Physical property value)
¹H-NMR (solvent: deuterated chloroform): δ: 7.32 (4H), 7.16 (2H), 7.08 (6H), 6.79 (2H), 6.27 (2H), 6.03 (2H), 5.73 (2H), 4.07 (4H ), 3.94 (4H), 2.59-2.53 (4H), 1.79-1.74 (4H), 1.74-1.70 (4H), 1.48-1.36 (8H), 0.80 (4H), 0.00
[0077]
¹³C-NMR (solvent: deuterated chloroform): δ; 165.9,158,131.1,130.1,128.2,127.5,114.4,88.3,68.8,64.8,29.0,28.6,28.1,25.3,25.2,19.6
Infrared absorption spectrum (IR) (KBr) cm^-1: 2937, 2860, 2215, 1916, 1726,
1635,1606,1197,817,807.5
Elemental analysis: C = 70.2% (70.56), H = 6.9% (7.02)
[0078]
The obtained polymerizable liquid crystal compound (A-1) transitioned from an isotropic liquid state to a nematic phase at 82 ° C. in a temperature-decreasing state at 2 ° C. per minute and into a crystalline phase at 75 ° C. Further, a composite of a composition obtained by adding 5 wt% and 10 wt% of the polymerizable liquid crystal compound (A-1) of the present invention to the non-polymerizable liquid crystal compound “RO-571” (Dainippon Ink Chemical Co., Ltd.). When the refractive index difference (Δn) was measured with an Appe refractometer (manufactured by Atago Co., Ltd.) and Δn of the polymerizable liquid crystal compound (A-1) was extrapolated, it showed a high value of 0.20. Also, no change was observed after the 120 ° C. heat test.
[0079]
(Example 2)
In a four-necked flask equipped with a Dimroth reflux tube and a thermometer, 4.2 g of intermediate (c) of Example 1 and 7.2 g of 2- (4-bromophenyl-4′-phenoxy) tetrahydro 2H-pyran , Tetrakistriphenylphosphine palladium 250 mg, copper iodide 82 mg, triethylamine 15 ml, DMF 50 ml were charged and stirred. The flask was then heated to 90 ° C. and reacted for 4 hours. After completion of the reaction, the reaction solution was washed with saturated brine, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column to obtain 8 g of intermediate (f).
[0080]
Next, 4.0 g of intermediate (f) and 20 ml of tetrahydrofuran were placed in an eggplant flask equipped with a dropping funnel and stirred. Subsequently, 1 ml of 1 / 10N hydrochloric acid aqueous solution was dropped and stirred for 30 minutes. 100 ml of ethyl acetate was added to the reaction solution, washed with pure water and saturated brine, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column to obtain an intermediate (g) having a siloxane bond and a tolan skeleton. 2.8 g was obtained.
[0081]
Further, 2.8 g of intermediate (g), 3.4 g of potassium carbonate and 50 ml of DMF were charged into a four-necked flask equipped with a Dimroth reflux tube, a dropping funnel and a thermometer, and stirred at 25 ° C. for 1 hour. Next, a DMF solution of 1.9 g of 6-bromohexyl acrylate was added dropwise. After completion of dropping, the flask was kept at 100 ° C. and stirred for 4 hours to complete the reaction. After completion of the reaction, the reaction mixture was washed with pure water and saturated brine, the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, the residue was purified by a silica gel column, and a white crystalline polymerizable liquid crystal compound (A- 3.0 g of 2) was obtained.
[0082]
Embedded image

[0083]
3200-3600cm from infrared absorption spectrum^-1It was confirmed that the absorption of the phenolic hydroxyl group disappeared and was completely etherified.
[0084]
(Physical property value)
¹H-NMR (solvent: deuterated chloroform): δ: 7.46-7.30 (16H), 7.06 (4H), 6.82 (4H), 6.32 (2H), 6.03 (2H), 5.72 (2H), 4.07 (4H), 3.94 (4H), 2.59-2.49 (4H), 1.76-1.72 (4H), 1.69-1.66 (4H), 1.44-1.36 (8H), 0.80 (4H), 0.00
[0085]
¹³C-NMR (solvent: deuterated chloroform): δ: 165.8,158.5,145,139.131.1,130.1,128.2,127.5,114.4,88.3,68.8,64.8,29.0,28.6,28.1,25.3,25.2,19.6
Infrared absorption spectrum (IR) (KBr) cm^-1: 2937, 2860, 2215, 1916, 1726,
1635,1606,1197,817,807.5
Elemental analysis: C = 78.2% (79.00), H = 7.2% (7.43)
[0086]
The obtained polymerizable liquid crystal compound (A-2) undergoes a phase transition from an isotropic liquid state to a smectic phase at 189 ° C. in a temperature-decreasing state at 2 ° C. per minute and phase transition to a crystalline phase at 88 ° C. . Further, a composite of a composition obtained by adding 5 wt% and 10 wt% of the polymerizable liquid crystal compound (A-2) of the present invention to the non-polymerizable liquid crystal compound “RO-571” (Dainippon Ink Chemical Co., Ltd.). When the refractive index difference (Δn) was measured with an Appe refractometer (manufactured by Atago Co., Ltd.) and Δn of the polymerizable liquid crystal compound (A-2) was extrapolated, it showed a high value of 0.30. Also, no change was observed after the 120 ° C. heat test.
[0087]
(Example 3)
A 4-neck flask equipped with a Dimroth reflux tube and a thermometer was charged with 27.6 g of 4-bromostyrene, 84 mg of hexachloroplatinic acid hexahydrate, and 50 ml of toluene, and heated to 80 ° C. Next, 15 g of 1,1,3,3,5,5-hexamethyltrisiloxane was added dropwise. After dropping, the flask was kept at 100 ° C. and stirred for 3 hours. After completion of the reaction, the reaction solution was washed with saturated brine, dried over sodium sulfate, and the solvent was distilled off to obtain an intermediate (h).
[0088]
Dimroth reflux tube, 4-neck flask equipped with a thermometer, intermediate (h) 10 g 3-methyl-1-butyne-3ol 3.2 g, tetrakistriphenylphosphine palladium 440 mg, copper iodide 140 mg, triethylamine 10 ml, DMF 50 ml Was stirred. The flask was then heated to 90 ° C. and reacted for 3 hours. After completion of the reaction, the reaction solution was washed with saturated brine, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column to obtain 6 g of intermediate (i).
[0089]
Next, 5.4 g of the intermediate (i) synthesized above, 50 ml of toluene, and 200 mg of potassium hydroxide were charged into a four-necked flask equipped with Dean Stark and a thermometer, and the flask was heated to 120 ° C. and toluene was added for 3 hours. Refluxed. Then, the reaction solution was filtered, and the filtrate was washed with saturated brine, dried over sodium sulfate, the solvent was distilled off, and purified by a silica gel column to obtain 2.2 g of an intermediate (j) having an acetylene group.
[0090]
In a four-necked flask equipped with a Dimroth reflux tube and a thermometer, 2.2 g of intermediate (j), 3.4 g of 2- (4-bromo-2-fluorophenyl-4′-phenoxy) tetrahydro-2H-pyran, tetrakis 110 mg of triphenylphosphine palladium, 36 mg of copper iodide, 10 ml of triethylamine, and 30 ml of DMF were charged and stirred. The flask was then heated to 90 ° C. and reacted for 4 hours. After completion of the reaction, the reaction solution was washed with saturated aqueous hydrochloric acid, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column to obtain 5 g of intermediate (k).
[0091]
Next, 5 g of intermediate (k) and 20 ml of tetrahydrofuran were charged into an eggplant flask equipped with a dropping funnel and stirred. Subsequently, 1 ml of 1 / 10N hydrochloric acid aqueous solution was dropped and stirred for 30 minutes. 100 ml of ethyl acetate was added to the reaction solution, washed with pure water and saturated brine, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column to obtain 3 g of intermediate (l) having a siloxane bond and a tolan skeleton. Obtained.
[0092]
Further, 3.0 g of intermediate (l), 3 g of potassium carbonate, and 30 ml of DMF were charged into a four-necked flask equipped with a Dimroth reflux tube, a dropping funnel, and a thermometer, and stirred at 25 ° C. for 1 hour. Next, a DMF solution of 1.8 g of 6-bromohexyl acrylate was added dropwise. After completion of dropping, the flask was kept at 100 ° C. and stirred for 4 hours to complete the reaction. After completion of the reaction, the mixture was washed with pure water and saturated brine, the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column, and a white crystalline polymerizable liquid crystal compound (A -3) was obtained 2.2g.
[0093]
Embedded image

[0094]
Also, from 3200 to 3600 cm from infrared absorption spectrum^-1It was confirmed that the absorption of the phenolic hydroxyl group disappeared and was completely etherified.
[0095]
(Physical property value)
¹H-NMR (solvent: deuterated chloroform): δ: 7.38-7.33 (8H), 7.28-7.17 (6H), 7.06 (4H), 6.85 (4H), 6.30 (2H), 6.01 (2H), 5.68 (2H) , 4.06 (4H), 3.88 (2H), 2.55 (4H), 1.70 (4H), 1.58 (4H), 1.42-1.33 (8H), 0.8 (4H)
[0096]
¹³C-NMR (solvent: deuterated chloroform): δ: 166.0, 136.2, 130.0, 127.7, 120, 114.3, 67.6, 64.3, 28.9, 28.3, 25.8
Infrared absorption spectrum (IR) (KBr) cm^-1: 2932, 2860, 2215, 1734,
1634,1606,1197,817,807.5
Elemental analysis: C = 70.1% (71.3), H = 6.86% (6.70)
[0097]
The obtained polymerizable liquid crystal compound (A-3) undergoes a phase transition from an isotropic liquid state to a nematic phase at 118 ° C. in a temperature-decreasing state at 2 ° C. per minute, and from the nematic phase state to the smectic phase at 108 ° C. A phase transition was carried out at 72 ° C. to a crystal phase. Further, a composite of a composition obtained by adding 5% by weight and 10% by weight of the polymerizable liquid crystal compound (A-3) of the present invention to the non-polymerizable liquid crystal compound “RO-571” (manufactured by Dainippon Ink & Chemicals, Inc.). When the refractive index difference (Δn) was measured with an Appe refractometer (manufactured by Atago Co., Ltd.) and Δn of the polymerizable liquid crystal compound (A-3) was extrapolated, it showed a high value of 0.31. Also, no change was observed after the 120 ° C. heat test.
[0098]
Example 4
A 4-necked flask equipped with a Dimroth reflux tube and a thermometer was charged with 24.8 g of 4-allyl-2-methoxyphenol, 84 mg of hexachloroplatinic acid hexahydrate, and 50 ml of toluene, and heated to 80 ° C. Next, 15 g of 1,1,3,3,5,5-hexamethyltrisiloxane was added dropwise. After dropping, the flask was kept at 100 ° C. and stirred for 3 hours. After completion of the reaction, the reaction solution was washed with saturated brine, dried over sodium sulfate, and the solvent was distilled off to obtain an intermediate (m).
[0099]
A four-necked flask equipped with a reflux tube for ester synthesis and a thermometer was charged with 27 g of acrylic acid, 40 g of 2- (4-hydroxyphenyl) ethyl alcohol, 1.3 g of p-toluenesulfonic acid, 100 mg of hydroquinone, and 150 ml of toluene, It was uniformly dissolved at 80 ° C. Thereafter, the flask was heated to 90 ° C., and the pressure was reduced to 350 mmHg with a vacuum pump, followed by reaction for 4 hours. Further, after the flask was heated to 100 ° C., the degree of vacuum was 100 mmHg to complete the reaction. After completion of the reaction, the reaction solution was washed with pure water and saturated brine, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column to obtain 24 g of intermediate (n).
[0100]
In a four-necked flask equipped with a Dimroth reflux tube and a thermometer, 12.8 g of trans 1,4-cyclohexanecarboxylic acid, 15.3 g of Dotite WSC (manufactured by Dojin Chemical Laboratory), 1.0 g of dimethylaminopyridine, and 350 ml of dichloromethane were added. Charged and stirred. The flask was kept at 5 ° C. or lower, and a dichloromethane solution of 15 g of intermediate (n) was added dropwise. After completion of dropping, the flask was returned to room temperature and stirred for 6 hours to complete the reaction. The reaction solution was washed with 1/10 N hydrochloric acid solution and saturated brine, dried over sodium sulfate, the solvent was distilled off, and purified by a silica gel column to obtain 24 g of an intermediate (o) having an acrylic group and a carboxyl group. It was.
[0101]
Into a four-necked flask equipped with a Dimroth reflux tube and a thermometer, 10.7 g of intermediate (m), 7.7 g of Dotite WSC (manufactured by Dojin Chemical Laboratory), 0.5 g of dimethylaminopyridine, and 250 ml of dichloromethane were charged and stirred. . The flask was kept at 5 ° C. or lower, and 13.8 g of a solution of intermediate (o) in dichloromethane was added dropwise. After completion of dropping, the flask was returned to room temperature and stirred for 6 hours to complete the reaction. The reaction solution was washed with a 1/10 N hydrochloric acid solution and saturated brine, dried over sodium sulfate, the solvent was distilled off, the residue was purified by a silica gel column, and a white crystalline polymerizable liquid crystal compound (A -4) was obtained 8.2g.
[0102]
Embedded image

[0103]
Also, from 3200 to 3600 cm from infrared absorption spectrum^-1It was confirmed that the absorption of the phenolic hydroxyl group disappeared and was completely esterified.
[0104]
(Physical property value)
¹H-NMR (solvent: deuterated chloroform): δ: 7.26 (8H), 7.17 (2H), 7.02 (4H), 6.45 (2H), 6.1 (2H), 5.8 (2H), 4.36 (4H), 3.80 (6H ), 2.98 (4H), 2.58 (4H), 2.55 (4H), 2.27 (8H), 1.70-1.58 (12H), 0.8 (4H)
[0105]
¹³C-NMR (solvent: deuterated chloroform): δ: 166.0, 154.0, 136.2, 130.0, 128.3, 127.7, 120, 114.3, 67.6, 64.3,42.3, 34.4, 28.9, 28.3, 25.8
Infrared absorption spectrum (IR) (KBr) cm^-1: 2935,2862,1734,1634,1606,1199,817,808
Elemental analysis: C = 63.1% (64.4), H = 6.99% (7.09)
[0106]
The obtained polymerizable liquid crystal compound (A-4) undergoes a phase transition from an isotropic liquid state to a nematic phase at 105 ° C. in a temperature-decreasing state at 2 ° C. per minute and phase transition to a crystalline phase at 70 ° C. . Further, a composite of a composition obtained by adding 5% by weight and 10% by weight of the polymerizable liquid crystal compound (A-4) of the present invention to the non-polymerizable liquid crystal compound “RO-571” (manufactured by Dainippon Ink & Chemicals, Inc.). The refractive index difference (Δn) was measured with an Appe refractometer (manufactured by Atago Co., Ltd.), and Δn of the polymerizable liquid crystal compound (A-4) was extrapolated to show 0.17. Also, no change was observed after the 120 ° C. heat test.
[0107]
(Comparative Example 1)
In a four-necked flask equipped with a reflux tube, 15.2 g of hydroquinone, 57 g of potassium carbonate, and 300 ml of DMF were placed and stirred at room temperature for 1 hour. Then, a DMF solution of 25 g of 6-bromo-1-hexanol was dropped. After completion of dropping, the flask was kept at 100 ° C. and stirred for 5 hours to complete the reaction. Methylene chloride was added to the reaction solution, the reaction solution was washed with pure water and saturated brine, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column to obtain 30 g of intermediate (p).
[0108]
A four-necked flask equipped with a reflux tube for ester synthesis was charged with 5.7 g of acrylic acid, 11 g of intermediate (p), 0.3 g of p-toluenesulfonic acid as a catalyst, 10 mg of hydroquinone as a polymerization inhibitor, and 250 ml of toluene. It was uniformly dissolved at 80 ° C. Thereafter, the flask was heated to 90 ° C., and the pressure was reduced to 350 mmHg with a vacuum pump, followed by reaction for 4 hours. Further, after the flask was heated to 100 ° C., the degree of vacuum was 100 mmHg to complete the reaction. After completion, the reaction solution was washed with pure water and saturated brine, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column to obtain 6 g of intermediate (q).
[0109]
A four-necked flask equipped with a Dimroth reflux tube and a thermometer was charged with 2.0 g of trans-1,4-cyclohexanecarboxylic acid, 5 g of Dotite WSC (manufactured by Dojin Chemical Laboratories), 0.3 g of dimethylaminopyridine, and 250 ml of dichloromethane. Stir. The flask was kept at 5 ° C. or lower, and a dichloromethane solution of 6 g of intermediate (q) was added dropwise. After completion of the dropping, the flask was returned to room temperature and stirred for 6 hours to complete the reaction. The reaction solution was washed with a 1 / 10N hydrochloric acid solution and saturated brine, dried over sodium sulfate, the solvent was distilled off, the residue was purified by a silica gel column, and a white crystalline polymerizable liquid crystal compound represented by the following formula ( 10 g of B-1) was obtained.
[0110]
Embedded image

[0111]
3200-3600cm from infrared absorption spectrum^-1It was confirmed that the absorption of the phenolic hydroxyl group disappeared and was completely esterified.
[0112]
(Physical property value)
¹H-NMR (solvent: deuterated chloroform): δ; 6.9 (4H), 6.8 (4H), 6.3 (2H), 6.0 (2H), 5.8 (2H), 4.26 (4H), 3.90 (4H), 2.5 (2H ), 2.3 (4H), 1.86-1.67 (4H), 1.50-1.40 (10H)
[0113]
¹³C-NMR (solvent: deuterated chloroform): δ: 166.0, 153.1, 130.0, 128.7, 120, 72.0, 68.9, 64.6, 29.0, 28.6, 25.8, 23
Infrared absorption spectrum (IR) (KBr) cm^-1: 2930, 2870, 1746, 1716, 1635, 1508, 810
Elemental analysis: C = 67.9% (68.6), H = 7.20% (7.28)
[0114]
The obtained polymerizable liquid crystal compound (B-1) undergoes a phase transition from an isotropic liquid state to a nematic phase at 124 ° C. in a temperature-decreasing state at 2 ° C. per minute, and from the nematic phase state to the smectic phase at 113 ° C. A phase transition was carried out at 102 ° C. Further, birefringence of a composition obtained by adding 5 wt% and 10 wt% of the polymerizable liquid crystal compound (B-1) of the present invention to the non-polymerizable liquid crystal compound “RO-571” (manufactured by Dainippon Ink & Chemicals, Inc.). When the rate difference (Δn) was measured with an Appe refractometer (manufactured by Atago Co., Ltd.) and Δn of the polymerizable liquid crystal compound (B-1) was extrapolated, 0.15 was shown.
[0115]
(Example 5)
As a polymerizable liquid crystal compound other than the present invention, 30 parts of the polymerizable liquid crystal compound (A-2) obtained in Example 2, a phase transition from an isotropic liquid to a nematic phase is performed at 46 ° C., and a phase is changed to a crystalline phase at 5 ° C. The birefringence difference is 0.15
[0116]
Embedded image

[0117]
A polymerizable liquid crystal in which 70 parts of a liquid crystal mixture “UCL-001” (manufactured by Dainippon Ink Chemical Co., Ltd.) and 2 parts by weight of “Irgacure 651” (manufactured by Ciba Specialty Chemicals) are mixed as a polymerization initiator. The composition was adjusted. This composition undergoes a phase transition from an isotropic liquid state to a nematic phase at 74 ° C. at a temperature drop of 2 ° C. per minute, phase transition from a nematic phase state to a smectic phase at 20 ° C., and a crystalline phase at 10 ° C. Phase transition. The birefringence difference (Δn) was measured by an Appe refractometer (manufactured by Atago Co., Ltd.) and found to be 0.19.
[0118]
Next, after injecting the polymerizable composition in an isotropic phase state into a glass cell having a thickness of 20 μm on which a polyimide alignment film subjected to a homogeneous alignment treatment has been formed, 400 W / m²Were irradiated for 60 seconds at room temperature to prepare an optical anisotropic body. As a result of measuring the degree of orientation by Raman scattering measurement, this optical anisotropic body maintained a uniform homogeneous orientation, and there was no problem in the heat resistance test at 120 ° C.
[0119]
(Example 6)
30 parts of the polymerizable liquid crystal compound (A-3) obtained in Example 3, 70 parts of a polymerizable liquid crystal compound “UCL-001” (manufactured by Dainippon Ink & Chemicals) other than the present invention, and “Irgacure as a polymerization initiator” A polymerizable liquid crystal composition in which 2 parts by weight of “651” (manufactured by Ciba Specialty Chemicals) was mixed was prepared. This composition undergoes a phase transition from an isotropic liquid state to a nematic phase at 62 ° C. at a temperature drop of 2 ° C. per minute, undergoes a phase transition from a nematic phase state to a smectic phase at 10 ° C., and crystallizes at 0 ° C. Phase transition. The birefringence difference (Δn) was measured by an Appe refractometer (manufactured by Atago Co., Ltd.) and found to be 0.20.
[0120]
Next, after injecting the polymerizable composition in an isotropic phase state into a glass cell having a thickness of 20 μm on which a polyimide alignment film subjected to a homogeneous alignment treatment has been formed, 400 W / m²Were irradiated for 60 seconds at room temperature to prepare an optical anisotropic body. As a result of measurement of the degree of orientation by Raman scattering measurement, this optical anisotropic body maintained a uniform homogeneous orientation, and there was no problem even in a heat resistance test at 120 ° C.
[0121]
(Example 7)
As a non-polymerizable compound, 50 parts of the polymerizable liquid crystal compound (A-3) obtained in Example 3, a phase transition from an isotropic liquid to a nematic phase at 64 ° C. and a phase transition at −10 ° C. The birefringence difference is 0.22,
[0122]
Embedded image

[0123]
Polymerization in which 50 parts of a cyano-based liquid crystal composition “RO-571” (Dainippon Ink Chemical Co., Ltd.) represented by the formula, and 2 parts by weight of “Irgacure 651” (Ciba Specialty Chemical Co., Ltd.) as a polymerization initiator were mixed. Liquid crystalline composition was prepared. This composition undergoes a phase transition from an isotropic liquid state to a nematic phase at 80 ° C. in a temperature-decreasing state at 2 ° C. per minute, and transitions to a crystalline phase at 7 ° C. The birefringence difference (Δn) was measured by an Appe refractometer (manufactured by Atago Co., Ltd.) and found to be 0.26.
[0124]
Next, after injecting the polymerizable composition in an isotropic phase state into a glass cell having a thickness of 20 μm on which a polyimide alignment film subjected to a homogeneous alignment treatment has been formed, 400 W / m²Were irradiated for 60 seconds at room temperature to prepare an optical anisotropic body. By measuring the degree of orientation by Raman scattering measurement, the optical anisotropic body maintained a uniform homogeneous orientation.
[0125]
(Comparative Example 2)
30 parts of the polymerizable liquid crystal compound (B-1) obtained in Comparative Example 1, 70 parts of the polymerizable liquid crystal compound “UCL-001” (manufactured by Dainippon Ink & Chemicals) other than the present invention, and “Irgacure as a polymerization initiator” 651 "(manufactured by Ciba Specialty Chemicals) was mixed with 2 parts by weight, but could not be dissolved.
[0126]
(Comparative Example 3)
Polymeric liquid crystal compound “UCL-001” (Dainippon Ink Chemical Co., Ltd.) 50 parts other than the present invention, non-polymerizable cyano liquid crystal mixture “RO-571” (Dainippon Ink Chemical Co., Ltd.) 50 parts, and polymerization A polymerizable liquid crystal composition in which 2 parts by weight of “Irgacure 651” (manufactured by Ciba Specialty Chemicals) was mixed as an initiator was prepared. This composition transitioned from an isotropic liquid state to a nematic phase at 45 ° C. in a temperature-decreasing state of 2 ° C. per minute, and transitioned to a crystalline phase at 0 ° C. The birefringence difference (Δn) was measured by an Appe refractometer (manufactured by Atago Co., Ltd.) and found to be 0.18.
[0127]
Next, after injecting the polymerizable composition in an isotropic phase state into a glass cell having a thickness of 20 μm on which a polyimide alignment film subjected to a homogeneous alignment treatment has been formed, 400 W / m²Were irradiated for 60 seconds at room temperature to prepare an optical anisotropic body. This optically anisotropic body was a cured film which had a significantly lowered orientation and was scattered white by Raman scattering measurement.
[0128]
【The invention's effect】
The present invention is a novel polymerizable liquid crystal compound that exhibits liquid crystallinity at a low temperature of 100 ° C. or lower, has excellent thermal stability, has good solubility, and has a large difference in birefringence, and polymerizability including the polymerizable liquid crystal compound Compositions and optical anisotropic bodies using them are provided.

Claims (10)

A polymerizable liquid crystal compound represented by the following general formula (I). Formula (I)

(In the formula, X represents a (meth) acrylate group , and Y ₁ , Y ₂ and Y ₅ are the same or different, and are a single bond, —C _n H _2n —, —C _n H _2n O—, —OC _n H. _{2n -, - (C 2 H} 4 O) n -, - (OC 2 H 4) n -, - (C 3 H 6 O) n -, or _{- (OC 3 H 6) n} - represents one of the , N is an integer from 1 to 20, rings A to C and A ′ to C ′ each independently represent any of the following rings:

a and b are integers of 0 or 1 ,
R _{1 to} R ₆ represent a hydrogen atom, a halogen atom , an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group, an alkenyloxy group, a fluoroalkyl group, or a fluoroalkoxy group, and Y ₃ and Y ₄ are each independently represent a single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - COO -, - OCO -, - C≡C -, - CH = CH-, or an -CF = CF-,
c represents an integer of 1 to 10) The polymerizable liquid crystal according to claim 1, wherein R _{1 to} R _{6 in} the general formula (I) are a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. Compound. Y ₁ , Y ₂ and Y _{5 in the} general formula (I) are the same or different and are —C _n H _2n —, —C _n H _2n O—, —OC _n H _2n —, and n is 1 to 20 The polymerizable liquid crystal compound according to claim 1, which is an integer of The polymerizable liquid crystal compound according to claim 1, wherein Y ₃ and Y _{4 in} the general formula (I) are each independently a single bond or —C≡C—. Any one or more of the rings A to C and A ′ to C ′ in the general formula (I)

(Wherein F represents a fluorine atom, m represents an integer from 1 to 3, and p represents an integer from 1 to 3). The polymerizable liquid crystal compound according to one.  A polymerizable liquid crystal composition comprising one or more polymerizable liquid crystal compounds according to claim 1.  A polymerizable liquid crystal composition comprising one or more polymerizable liquid crystal compounds according to claim 1 and a polymerizable compound other than the polymerizable liquid crystal compounds.  A polymerizable liquid crystal composition comprising one or more polymerizable liquid crystal compounds according to claim 1 and a polymerizable liquid crystal compound other than those.  An optical anisotropic body comprising the polymerizable liquid crystal compound according to claim 1.  An optical anisotropic body comprising the polymerizable liquid crystal composition according to any one of claims 6 to 8.