JP3590863B2 - Liquid crystalline compound having a photosensitive part, liquid crystal additive and optical recording medium - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は液晶性化合物、光記録媒体及び液晶組成物に関する。
【０００２】
【従来の技術】
フルカラーを記録することが可能で書き換えが不可能な記録材料としてはカラー写真やカラーコピーが知られている。書き換えが可能でフルカラーではない記録材料としては、ベヘン酸等の長鎖アルキルカルボン酸誘導体を含む感熱記録材料やスピロピラン誘導体等のフォトクロミック化合物を利用した光記録材料、その他、磁気や光磁気等のメモリー材料が知られている。また、最近では書き換え可能フルカラー感熱記録材料として玉置らが分子量２０００以下でガラス転移温度が３５℃以上のコレステリック液晶性化合物を用いる方法を示している（Ｎ．Ｔａｍａｏｋｉ ｅｔ ａ１．，Ａｄｖａｎｃｅｄ Ｍａｔｅｒｉａｌｓ，９（１４），１１０２（１９９７））。そこでは、コレステリック反射色が液晶温度からの急冷却操作によりガラス状固体中に保存される。さらに玉置らは、光モードでの書き換え可能なフルカラー記録材料及び画像形成方法を分子量２０００以下でガラス転移温度が３５℃以上のコレステリック液晶性化合物にアゾベンゼン誘導体等のフォトクロミック化合物を添加した組成物に光照射することにより実現している。コレステリック液晶温度での光照射により光照射部の反射色が光照射量に依存して連続的に変化し、その後のガラス転移温度以下への急冷操作で、反射色をガラス状固体中でも維持できるという特性を有するものである。
【０００３】
玉置らは分子量２０００以下でガラス転移温度が３５℃以上のコレステリック液晶性化合物にフォトクロミック化合物を添加した混合物からなる光による書き換え可能なカラー記録材料を提案している。しかしながら、このカラー記録材料の場合、その光応答性を高めるべくフォトクロミック化合物を１０重量％以上添加すれば、色固定後の結晶化が促進されるため、室温における固定色の安定保存に問題のあることが判明した。
【０００４】
【発明が解決しようとする課題】
本発明は、良好な光応答性を有し、さらに、色固定後の室温で保持しても結晶化が促進されず、固定色の保存安定性にすぐれたコレステリック液晶性化合物、該液晶性化合物からなる光記録媒体及び該液晶性化合物を含む液晶組成物を提供することをその課題とする。
【０００５】
【課題を解決するための手段】
本発明者らは、前記課題を解決すべく鋭意研究を重ねた結果、本発明を完成するに至った。
即ち、本発明によれば、以下に示す液晶性化合物、光記録媒体及び液晶組成物が提供される。
（１）下記一般式（１）
【化３】
Ｚ−Ｏ−ＣＯ−Ｒ−ＣＯ−Ｏ−Ｙ−Ａ （１）
（式中、Ａは水素原子又は炭素数１〜２０の有機基、Ｙはアゾベンゼン基、Ｚはコレステリル基、Ｒは炭素数２から３０の鎖状の飽和もしくは不飽和の２価脂肪族炭化水素基を示す）
で表され、その分子量が３０００以下でガラス転移温度が３５℃以上の液晶性化合物。
（２）前記（１）の液晶性化合物の単独からなる光記録媒体。
（３）前記（１）の液晶性化合物を少なくとも２種類混合した組成物を用いた光記録媒体。
（４）前記（１）請求項１以外の分子量が２０００以下でガラス転移温度が３５℃以上のコレステリック液晶性化合物もしくはそれらの混合物に前記（１）の化合物を少なくとも１種類以上添加して得られる液晶組成物。
【０００６】
【発明の実施の形態】
本発明の液晶性化合物は、前記一般式（１）で表されるジエステル化合物である。
【０００７】
前記一般式（１）において、Ａは水素原子又は炭素数１〜２０の有機基を示す。この場合の有機基には、炭素数１〜２０、好ましくは１〜１２の脂肪族基、炭素数６〜２０、好ましくは６〜１２の芳香族基又は炭素数１〜２０、好ましくは１〜１２の炭化水素基を有する炭化水素オキシ基を示す。
【０００８】
脂肪族基には、鎖状及び環状の飽和又は不飽和脂肪族基が包含される。その鎖状脂肪族基には、アルキル基、及びアルケニル基が包含される。その具体例としては、例えば、メチル、エチル、プロピル、ブチル、ヘキシル、プロペニル、ヘキセニル等の炭素数１〜６の低級アルキル基又はアルケニル基；へプチル、オクチル、デシル、オクチニル、デセニル等の炭素数７〜１１の中級アルキル基又はアルケニル基；ドデシル、オクタデシル、ベヘニル、ドデセニル、オクタデセニル等の炭素数１２〜２０の高級アルキル基又はアルケニル基が挙げられる。環状脂肪族基には、シクロアルキル基及びシクロアルケニル基が包含される。その炭素数は、５〜２０、好ましくは６〜１２である。その具体例を示すと、例えば、シクロヘキシル、シクロヘキセニル、シクロオクチル、シクロヘキシルメチル、シクロヘキシルオクチル等が挙げられる。
【０００９】
芳香族基には、ベンゼン環の他、ナフタレン環やアントラセン環等の縮合多環芳香族環、及びビフェニル、ターフェニル等の鎖状多環芳香族環を有するものが包含される。その具体例としては、フェニル、トリル、キシリル、ナフチル、メチルナフチル等のアリール基；ベンジル、フェネチル、ナフチルメチル、ナフチルエチル等のアルキルアリール基を挙げることができる。
【００１０】
炭化水素オキシ基には、脂肪族基及び芳香族基を有するものが包含される。その具体例としては、メトキシ、エトキシ、プロポキシ、オクチルオキシ、ドデシルオキシ、フェノキシ、ベンジルオキシ等が挙げられる。
【００１１】
Ｙはアゾベンゼン基を示す。このアゾベンゼン基は下記式（３）で表される。
【化４】
【００１２】
Ｒは炭素数２〜３０、好ましくは８〜２４の２価有機基を示す。この場合の二価有機基には、脂肪族基及び芳香族基が包含される。また、脂肪族基には、鎖状又は環状の飽和もしくは不飽和の二価脂肪族炭化水素基が包含され、その炭素数は２〜３０、好ましくは８〜２４である。不飽和脂肪族基には、２重結合や３重結合を持ったものが包含される。二価芳香族基には、１つのベンゼン環を有する単環芳香族炭化水素（ベンゼン、トルエン、キシレン等）から誘導される二価炭化水素基及び２つ以上、通常、２〜４個のベンゼン環を有する多環芳香族炭化水素（ナフタレン、ビフェニル、ターフェニル等）から誘導される二価炭化水素基が包含される。
【００１３】
前記二価有機基Ｒは、下記一般式（２）の不飽和脂肪族基であるのが好ましい。
【化５】
−（ＣＨ２）ｍ−Ｃ≡Ｃ−Ｃ≡Ｃ−（ＣＨ２）ｎ− （２）
前記式中、ｍ及びｎは独立して１以上の整数であり、そのｍとｎとの合計は２６以下、好ましくは２０以下であり、その下限値は４程度である。Ｚはコレステロールから水酸基を（ＯＨ）を除いた残基であるコレステリル基を示す。
【００１４】
本発明による好ましい液晶性化合物の具体例を例示すると、以下の通りである。
【化６】
【化７】
【化８】
【００１５】
本発明の化合物は、コレステロールと、相当するジカルボン酸化合物と、相当するヒドロキシアゾベンゼン化合物とを、ジシクロヘキシルカルボジイミド、４−ジメチルアミノピリジンの存在下、塩化メチレンの中で、室温下で撹拌し、得られた反応生成物から沈殿物をフィルターで分離後、溶液とシリカゲル（展開溶媒は塩化メチレンとヘキサンとの体積比３：２の混合物）のカラムクロマトグラフィーで精製することにより得ることができる。
【００１６】
本発明の光記録媒体は、前記一般式（１）で表される液晶性化合物からなる。この場合、その液晶性化合物において、その分子量は３０００以下、好ましくは２０００以下であり、その下限値は７００程度である。そのガラス転移温度は３５℃以上、好ましくは５０℃以上であり、その上限値は９０℃程度である。
【００１７】
本発明の光記録媒体は、前記液晶性化合物の単独又は混合物からなる他、他のコレステリック液晶性化合物を含有させることができる。このような液晶性化合物としては、例えば、下記一般式（８）で表される化合物を挙げることができる。
【化９】
Ｚ−Ｏ−ＣＯ−Ｒ−ＣＯ−Ｏ−Ｙ （８）
前記式中、Ｚ及びＹはそれぞれ独立してコレステリル基、水素原子又はアルキル基を示し、Ｒは炭素数２〜３０の２価有機基を示し、Ｚ及びＹの少なくとも一方はコレステリル基を示す。Ｒの具体例としては、前記一般式（１）に関して示したものを挙げることができる。
前記一般式（８）で表されるコレステリック液晶性化合物の含有量は、全液晶性化合物中、重量比率で、１〜９９％、好ましくは５０〜９８％である。
【００１８】
本発明の光記録媒体の形態は、従来公知の形態であることができる。例えば、本発明の光記録媒体は、少なくとも一方が透明である２つの基板の間に、本発明による前記液晶性化合物又はそれを含む混合物をはさんだものであることができる。この場合、基板としては、通常、薄いガラス板等が用いられるが、高分子薄膜や金属板などでもよい。二枚のうち一枚は少なくとも一部の光が透過するような透明性が必要である。液晶性化合物又は混合物を二枚の基板間にはさむ方法としては、まず液晶性化合物又は混合物を溶融状態かもしくは液晶状態の温度に加熱し、一方の基板に添加後もう一方の基板をのせるか、平行に保たれた二枚の基板間に減圧やキャピラリー現象を利用して添加する方法がある。基板間の間隔は特に限定されるものではないが数ミクロンから１００ミクロン程度が望ましい。本媒体に対する部分的もしくは全体的な加熱はサーマルヘッド、加熱ロール、レーザー光線などあらゆる方法が可能である。また液晶温度範囲への温度コントロールが必要な加熱は、サーマルヘッドや加熱ロール等の温度をコントロールするかレーザー光線の強度やスポット径を調節すること、もしくは全体を一定の温度まで加熱した後でイメージ状の平らな金属板やゴム板で必要な温度まで降温することで可能である。本発明による感光性液晶化合物を光反応させるための光源は、水銀灯、キセノンランプ、タングステンランプ、レーザーなど化合物の吸収波長に合わせて選択できる。ガラス転移以下への急冷は試料全体を冷媒もしくは冷却された雰囲気の中に浸せきする方法、試料の一部を冷却されたヘッドに接触させる方法等がある。
【００１９】
本発明による光記録媒体は、短時間の光照射により記録することのできる書き換え可能なカラー画像記録媒体である。このものを用いて画像を形成するには、基板間にはさんだ液晶性化合物又はその混合物に対して、その透明基板側から、その液晶性化合物又はその混合物が本発明の液晶性化合物を含む液晶相を示す温度下で光照射し、その後ガラス転移温度以下まで急冷することにより画像情報を書き込み、保存することが可能となる。また、特に前記本発明の液晶性化合物を含む混合物においては、混入する化合物、混入される化合物との間に分子量、官能基等の共通性があり、ガラス状態の混合による熱的不安定化が抑制され、保存された画像情報の室温での長期保存も可能となる。
【００２０】
本発明で得られる画像情報は一度記録した後、全体をもしくは一部分を液晶性化合物もしくはその混合物の融点以上に加熱すれば何度でも消去が可能であり、さらに新しい画像情報を前記の方法で光記録できる。本発明による液晶性化合物を用いれば、その化合物が光異性化反応を起こす程度の弱い光をマスクを介して液晶状態で照射するだけで部分的な光学的性質を変化させることにより画像情報を書きこみ、急冷操作でその光学的性質を固定化することにより画像情報を保存できる。例えば、可視域の光を反射する光学的性質を有するコレステリック液晶状態で光照射を行えば、未照射部の反射色はそのままで、光照射部は光照射量に依存して未照射部より短波長の光を反射するようになるため、少なくとも２色のカラー画像情報を記録できる。また、赤外域に反射を有するコレステリック液晶状態に光照射を行えば、未照射部は可視域の光は反射しないため透明で、光照射部は光照射量に依存して未照射部より短波長の光、つまり可視域の光を反射するようになるため、背景が透明のカラー画像情報を記録できる。また光照射量を増加させることで相転移を起こし、光照射部が等方性液体状態になり、これを急冷すれば結晶状態になるため、光散乱状態と光反射状態でコントラストを有する画像情報も記録できる。さらに液晶状態はコレステリック液晶相に限定されず、ネマティック、スメクティック相でも光照射部のみの光学的性質が変化するため、光照射部と未照射部でコントラストが発生することによる画像情報を記録することができる。
【００２１】
【実施例】
次に本発明を実施例によりさらに詳細に説明する。
【００２２】
実施例１
下記構造式の液晶性化合物の合成
【化１０】
【００２３】
１０，１２−ドコサジインジカルボン酸１．９０ｇ、ジシクロヘキシルカルボジイミド２．１４ｇ、４−ジメチルアミノピリジン０．１２ｇを塩化メチレン３０ｍ１に溶解した溶液に４−ヒドロキシアゾベンゼン２．００ｇ、コレステロール１．０３ｇを塩化メチレン４０ｍ１に溶解した溶液をゆっくり滴下し、室温で６時間攪拌。反応混合物中の不溶物を濾過後、溶液を塩化メチレンとｎ−ヘキサンの混合溶媒（体積比＝３：２）を展開溶媒とするカラムクロマトグラフィーで分離精製後、溶媒を減圧下で除去し、目的化合物０．１８ｇを得た。分子量：９１１、等方相→液晶相：７９℃、液晶相→結晶：２６℃、ガラス転移温度：４７℃１Ｈ−ＮＭＲデータ（ＣＤＣｌ３）
０．６５〜２．６０（ｍ，７５Ｈ），４．６０（ｍ，１Ｈ），５．３４（ｍ，１Ｈ），７．２２（ｄ，２Ｈ），７．４８（ｍ，３Ｈ），７．９１（ｍ，４Ｈ）
【００２４】
実施例２
下記構造式の液晶性化合物の合成
【化１１】
【００２５】
ドコサジカルボン酸１．８７ｇ、ジシクロヘキシルカルボジイミド２．０８ｇ、４−ジメチルアミノピリジン０．０９ｇを塩化メチレン６０ｍ１に溶解した溶液に４−ヒドロキシアゾベンゼン１．００ｇ、コレステロール１．９５ｇを塩化メチレン１１０ｍｌに溶解した溶液をゆっくり滴下し、室温で１５時間攪拌。反応混合物中の不溶物を濾過後、溶液を塩化メチレンとｎ−ヘキサンの混合溶媒（体積比＝３：２）にを展開溶媒とするカラムクロマトグラフィーで分離精製後、溶媒を減圧下で除去し、目的化合物０．２５ｇを得た。分子量：９１９、等方相→液晶相：１０１℃、液晶相→結晶：８１℃、ガラス転移温度：６０℃
１Ｈ−ＮＭＲデータ（ＣＤＣｌ３）
０．６５〜２．６２（ｍ，８３Ｈ），４．６０（ｍ，１Ｈ），５．３７（ｍ，１Ｈ），７．２３（ｄ，２Ｈ），７．５１（ｍ，３Ｈ），７．９３（ｍ，４Ｈ）
【００２６】
実施例３
下記構造式の液晶性化合物の合成
【化１２】
【００２７】
１０，１２−ドコサジインジカルボン酸１．８７ｇ、ジシクロヘキシルカルボジイミド２、０８ｇ、４−ジメチルアミノピリジン０．０９ｇを塩化メチレン５０ｍｌに溶解した溶液に４−ヒドロキシ−４’ヘプチルアゾベンゼン１．４９ｇ、コレステロール１．９５ｇを塩化メチレン１００ｍｌ液を塩化メチレンを展開溶媒とするカラムクロマトグラフィーで分離後、ヘキサンで再結晶を行い、ろ別したろ液から溶媒を除去し粗結晶を得た。さらにエーテルで再結晶を行い、目的化合物０．３０ｇを得た。分子量：１０１０、等方相→液晶相：１１１℃・液晶相→結晶：３３℃、ガラス転移温度：４７℃
１Ｈ−ＮＭＲデータ（ＣＤＣｌ３）
０．６７〜２．６８（ｍ，９０Ｈ），４．６５（ｍ，１Ｈ），５．３９（ｍ，１Ｈ），７．２３（ｄ，２Ｈ），７，３１（ｄ，２Ｈ），７．８３（ｄ，２Ｈ），７．９３（ｄ，２Ｈ）
【００２８】
実施例４
実施例１の化合物９を厚さ０．１８ｍｍの二枚のガラス板間にはさみ、全体を９５℃に加熱して溶融し、試料部の厚さが約１０ミクロンとなるように調整した。次に７０℃に保たれたホットステージ上にサンプルをのせると全体が緑の反射色を呈した。そこにマスクを介して水銀灯からの紫外線を部分的に１５秒間照射すると照射部が青色に変化し、未照射部は緑色のままであった。紫外線照射後、試料を氷水の中に浸漬して０℃まで急冷すると色が固定された。固定された色は２日以上室温で安定であった。
【００２９】
実施例５
実施例４で得られた色固定を行ったサンプル全体を再び９５℃に加熱して溶融し、固定された色を消去した。次に７０℃に保たれたホットステージ上にサンプルをのせると全体が緑の反射色を呈した。そこにマスクを介して水銀灯からの紫外線を部分的に１分間照射すると照射部が透明に変化し（コレステリック液晶から等方性液体への変化）、未照射部は緑色のままであった。紫外線照射後、試料を氷水の中に浸漬して０℃まで急冷すると光照射部は光散乱状態の結晶、未照射部は緑色のままが色固定された。固定された色等は２日以上室温で安定であった。
【００３０】
実施例６
実施例２の化合物１０を厚さ０．１８ｍｍの二枚の石英板間にはさみ、全体を１１０℃に加熱して溶融し、試料部の厚さが約１０ミクロンとなるように調整した。次に９０℃に保たれたホットステージ上にサンプルをのせると全体が緑色を呈した。そこにマスクを介して水銀灯からの紫外線を部分的に１５秒照射すると照射部は青色に変化し、未照射部はもとのままであった。紫外線照射後、試料を氷水の中に浸漬して０℃まで急冷すると色が固定された。固定された色は３０日以上室温で安定であった。
【００３１】
実施例７
実施例１の化合物９と実施例２の化合物１０の混合物（重量で１：１の割合）を厚さ０．１８ｍｍの二枚の石英板間にはさみ、全体を１１０℃に加熱して溶融し、試料部の厚さが約１０ミクロンとなるように調整した。次に８０℃に保たれたホットステージ上にサンプルをのせると全体が黄緑色を呈した。そこにマスクを介して水銀灯からの紫外線を部分的に３０秒照射すると照射部は透明に変化し、未照射部はもとのままであった。紫外線照射後、試料を氷水の中に浸潰して０℃まで急冷すると光照射部は光散乱状態の結晶、未照射部は黄緑色のままが色固定された。固定された色等は３０日以上室温で安定であった。
【００３２】
実施例８
実施例１の化合物９をコレステリック液晶化合物である１０，１２−ドコサジインジコレステリルエステル（下記化合物１２）に１０重量％混合した混合物を厚さ０．１８ｍｍの二枚の石英板間にはさみ、全体を１３０℃に加熱してを溶融し、試料部の厚さが約１０ミクロンとなるように調整した。次に８５℃に保たれたホットステージ上にサンプルをのせると全体が緑色を呈した。そこにマスクを介して水銀灯からの紫外線を部分的に３０秒照射すると照射部は青色に変化し、未照射部はもとのままであった。紫外線照射後、試料を氷水の中に浸漬して０℃まで急冷すると色が固定された。照射部と未照射部の反射スペクトルを測定したところ反射ピークの極大波長は、それぞれ４９８ｎｍと５２３ｎｍであった。固定された色は３０日以上室温で安定であった。
【００３３】
【化１３】
【００３４】
実施例９
実施例１の化合物９をコレステリック液晶化合物である前記化合物１２に２０重量％混合した混合物を厚さ０．１８ｍｍの二枚の石英板間にはさみ、全体を１３０℃に加熱してを溶融し、試料部の厚さが約１０ミクロンとなるように調整した。次に７５℃に保たれたホットステージ上にサンプルをのせると全体が緑色を呈した。そこにマスクを介して水銀灯からの紫外線を部分的に３０秒照射すると照射部は青色に変化し、未照射部はもとのままであった。紫外線照射後、試料を氷水の中に浸漬して０℃まで急冷すると色が固定された。
【００３５】
実施例１０
実施例３の化合物１１をコレステリック液晶化合物である前記化合物１２に１０重量％混合した混合物を厚さ０．１８ｍｍの二枚の石英板間にはさみ、全体を１３０℃に加熱してを溶融し、試料部の厚さが約１０ミクロンとなるように調整した。次に９０℃に保たれたホットステージ上にサンプルをのせると全体が透明（赤外域に反射を有するコレステリック液晶）になった。そこにマスクを介して水銀灯からの紫外線を部分的に３０秒照射すると全光照射部は青色、光量２５％照射部は緑色に変化し、未照射部はもとの透明のままであった。紫外線照射後、試料を氷水の中に浸漬して０℃まで急冷すると未照射部は透明、照射部は青色、緑色のまま状態が固定された。固定された色は１０日以上室温で安定であった。
【００３６】
実施例１１
実施例３の化合物１１をコレステリック液晶化合物である前記化合物１２に２重量％混合した混合物を厚さ０．１８ｍｍの二枚の石英板間にはさみ、全体を１３０℃に加熱してを溶融し、試料部の厚さが約１０ミクロンとなるように調整した。次に８８℃に保たれたホットステージ上にサンプルをのせると全体がオレンジ色を呈した。そこにマスクを介して水銀灯からの紫外線を部分的に３０秒照射すると照射部は青色に変化し、未照射部はもとのままであった。紫外線照射後、試料を氷水の中に浸漬して０℃まで急冷すると色が固定された。固定された色は１０日以上室温で安定であった。
【００３７】
【発明の効果】
本発明の液晶性化合物を用いることにより、良好な光応答性を有し、さらに、色固定後の室温で保持しても結晶化が促進されず、固定色の保存安定性にすぐれた光記録媒体を得ることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a liquid crystal compound, an optical recording medium, and a liquid crystal composition .
[0002]
[Prior art]
Color photographs and color copies are known as recording materials that can record full color and cannot be rewritten. Non-full-color rewritable recording materials include thermosensitive recording materials containing long-chain alkyl carboxylic acid derivatives such as behenic acid, optical recording materials using photochromic compounds such as spiropyran derivatives, and other memories such as magnetism and magneto-optics. Materials are known. Recently, Tamaki et al. Have shown a method of using a cholesteric liquid crystalline compound having a molecular weight of 2000 or less and a glass transition temperature of 35 ° C. or more as a rewritable full-color thermal recording material (N. Tamaki et al., Advanced Materials, 9 ( 14), 1102 (1997)). There, the cholesteric reflection color is preserved in the glassy solid by a rapid cooling operation from the liquid crystal temperature. Further, Tamaki et al. Applied a full-color recording material capable of rewritable in an optical mode and an image forming method to a cholesteric liquid crystal compound having a molecular weight of 2,000 or less and a glass transition temperature of 35 ° C. or more to a composition in which a photochromic compound such as an azobenzene derivative was added. This is achieved by irradiation. It is said that the reflection color of the light irradiation part changes continuously depending on the light irradiation amount by light irradiation at the cholesteric liquid crystal temperature, and the reflection color can be maintained even in the glassy solid by the subsequent quenching operation below the glass transition temperature. It has characteristics.
[0003]
Tamaki et al. Have proposed a light-rewritable color recording material comprising a mixture of a cholesteric liquid crystalline compound having a molecular weight of 2000 or less and a glass transition temperature of 35 ° C. or more and a photochromic compound added thereto. However, in the case of this color recording material, if a photochromic compound is added in an amount of 10% by weight or more to enhance the photoresponsiveness, crystallization after color fixation is promoted, and there is a problem in stable storage of fixed colors at room temperature. it has been determine Akira.
[0004]
[Problems to be solved by the invention]
The present invention has good photoresponsiveness, furthermore, crystallization is not promoted even when kept at room temperature after color fixation , and cholesteric liquid crystal compound excellent in storage stability of fixed color, the liquid crystal compound It is an object of the present invention to provide an optical recording medium comprising: and a liquid crystal composition containing the liquid crystal compound .
[0005]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above problems, and as a result, completed the present invention.
That is, according to the present invention, the following liquid crystal compound, optical recording medium, and liquid crystal composition are provided.
(1) The following general formula (1)
Embedded image
ZO-CO-R-CO-OYA (1)
(In the formula, A is a hydrogen atom or an organic group having 1 to 20 carbon atoms, Y is an azobenzene group, Z is a cholesteryl group, and R is a linear saturated or unsaturated divalent aliphatic hydrocarbon having 2 to 30 carbon atoms. Indicates a group )
A liquid crystalline compound having a molecular weight of 3000 or less and a glass transition temperature of 35 ° C. or more.
(2) An optical recording medium comprising the liquid crystalline compound of (1) alone.
(3) An optical recording medium using a composition obtained by mixing at least two types of the liquid crystal compound of the above (1).
(4) The (1) cholesteric liquid crystalline compound having a molecular weight of 2,000 or less and a glass transition temperature of 35 ° C. or more, or a mixture thereof, obtained by adding at least one compound of the above (1) other than the above (1). Liquid crystal composition.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
The liquid crystal compound of the present invention is a diester compound represented by the general formula (1).
[0007]
In the general formula (1), A represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. In this case, the organic group includes an aliphatic group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, or 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. A hydrocarbon oxy group having 12 hydrocarbon groups is shown.
[0008]
Aliphatic groups include linear and cyclic saturated or unsaturated aliphatic groups. The chain aliphatic group includes an alkyl group and an alkenyl group. Specific examples thereof include lower alkyl or alkenyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl, propenyl and hexenyl; and carbon numbers such as heptyl, octyl, decyl, octynyl and decenyl. 7 to 11 middle alkyl or alkenyl groups; higher alkyl or alkenyl groups having 12 to 20 carbon atoms such as dodecyl, octadecyl, behenyl, dodecenyl, octadecenyl and the like. The cycloaliphatic group includes a cycloalkyl group and a cycloalkenyl group. Its carbon number is 5-20, preferably 6-12. Specific examples thereof include, for example, cyclohexyl, cyclohexenyl, cyclooctyl, cyclohexylmethyl, cyclohexyloctyl and the like.
[0009]
Examples of the aromatic group include those having a condensed polycyclic aromatic ring such as a naphthalene ring and an anthracene ring, and a chain polycyclic aromatic ring such as biphenyl and terphenyl in addition to a benzene ring. Specific examples thereof include aryl groups such as phenyl, tolyl, xylyl, naphthyl, and methylnaphthyl; and alkylaryl groups such as benzyl, phenethyl, naphthylmethyl, and naphthylethyl.
[0010]
The hydrocarbonoxy group includes those having an aliphatic group and an aromatic group. Specific examples thereof include methoxy, ethoxy, propoxy, octyloxy, dodecyloxy, phenoxy, benzyloxy and the like.
[0011]
Y represents an azobenzene group. This azobenzene group is represented by the following formula (3).
Embedded image
[0012]
R represents a divalent organic group having 2 to 30, preferably 8 to 24 carbon atoms. In this case, the divalent organic group includes an aliphatic group and an aromatic group. The aliphatic group includes a linear or cyclic saturated or unsaturated divalent aliphatic hydrocarbon group, and has 2 to 30, preferably 8 to 24 carbon atoms. Unsaturated aliphatic groups include those having a double bond or a triple bond. The divalent aromatic group includes a divalent hydrocarbon group derived from a monocyclic aromatic hydrocarbon having one benzene ring (benzene, toluene, xylene, etc.) and two or more, usually two to four benzene groups. A divalent hydrocarbon group derived from a polycyclic aromatic hydrocarbon having a ring (naphthalene, biphenyl, terphenyl, etc.) is included.
[0013]
The divalent organic group R is preferably an unsaturated aliphatic group represented by the following general formula (2).
Embedded image
- (CH 2) m-C≡C -C≡C- (CH 2) n- (2)
In the above formula, m and n are each independently an integer of 1 or more, and the sum of m and n is 26 or less, preferably 20 or less, and the lower limit thereof is about 4. Z represents a cholesteryl group which is a residue obtained by removing a hydroxyl group (OH) from cholesterol.
[0014]
Specific examples of preferred liquid crystalline compounds according to the present invention are as follows.
Embedded image
Embedded image
Embedded image
[0015]
The compound of the present invention is obtained by stirring cholesterol, the corresponding dicarboxylic acid compound, and the corresponding hydroxyazobenzene compound in methylene chloride in the presence of dicyclohexylcarbodiimide and 4-dimethylaminopyridine at room temperature. The precipitate can be obtained by separating the precipitate from the reaction product obtained by a filter, and purifying the solution by column chromatography on silica gel (developing solvent is a mixture of methylene chloride and hexane in a volume ratio of 3: 2).
[0016]
The optical recording medium of the present invention comprises a liquid crystalline compound represented by the general formula (1). In this case, the molecular weight of the liquid crystal compound is 3000 or less, preferably 2000 or less, and its lower limit is about 700. Its glass transition temperature is 35 ° C. or higher, preferably 50 ° C. or higher, and its upper limit is about 90 ° C.
[0017]
The optical recording medium of the present invention may contain another cholesteric liquid crystal compound in addition to a single or a mixture of the above liquid crystal compounds. Examples of such a liquid crystal compound include a compound represented by the following general formula (8).
Embedded image
ZO-CO-R-CO-OY (8)
In the above formula, Z and Y each independently represent a cholesteryl group, a hydrogen atom or an alkyl group, R represents a divalent organic group having 2 to 30 carbon atoms, and at least one of Z and Y represents a cholesteryl group. Specific examples of R include those described for the general formula (1).
The content of the cholesteric liquid crystal compound represented by the general formula (8) is 1 to 99%, preferably 50 to 98% by weight of all the liquid crystal compounds.
[0018]
The form of the optical recording medium of the present invention can be a conventionally known form. For example, the optical recording medium of the present invention can have the liquid crystalline compound according to the present invention or a mixture containing the same interposed between two substrates at least one of which is transparent. In this case, a thin glass plate or the like is usually used as the substrate, but a polymer thin film or a metal plate may be used. One of the two sheets needs to be transparent so that at least a part of the light is transmitted. As a method of sandwiching a liquid crystal compound or a mixture between two substrates, first, the liquid crystal compound or the mixture is heated to a temperature of a molten state or a liquid crystal state, and then added to one substrate and then placed on the other substrate. There is a method of adding the pressure between two substrates kept in parallel by utilizing a reduced pressure or a capillary phenomenon. The distance between the substrates is not particularly limited, but is preferably about several microns to 100 microns. The partial or total heating of the medium can be performed by any method such as a thermal head, a heating roll, and a laser beam. Heating that requires temperature control to the liquid crystal temperature range can be achieved by controlling the temperature of the thermal head or heating roll, adjusting the intensity or spot diameter of the laser beam, or by heating the whole to a certain temperature and then imaging it. It is possible by lowering the temperature to the required temperature with a flat metal plate or rubber plate. The light source for photoreacting the photosensitive liquid crystal compound according to the present invention can be selected according to the absorption wavelength of the compound, such as a mercury lamp, a xenon lamp, a tungsten lamp, and a laser. The rapid cooling to the glass transition temperature or lower includes a method of immersing the entire sample in a refrigerant or a cooled atmosphere, a method of bringing a part of the sample into contact with a cooled head, and the like.
[0019]
The optical recording medium according to the present invention is a rewritable color image recording medium that can be recorded by light irradiation for a short time. In order to form an image using this, a liquid crystal compound or a mixture thereof sandwiched between substrates, from the transparent substrate side, the liquid crystal compound or a mixture thereof contains a liquid crystal containing the liquid crystal compound of the present invention. By irradiating light at a temperature indicating a phase and then rapidly cooling to a temperature lower than the glass transition temperature, image information can be written and stored. Particularly, in the mixture containing the liquid crystal compound of the present invention, the compound to be mixed, the compound to be mixed, have a common molecular weight, a functional group, and the like, and the thermal instability due to the mixing of the glass state. It is also possible to suppress the stored image information for a long time at room temperature.
[0020]
The image information obtained by the present invention can be erased as many times as it is once recorded, and can be erased as many times as the whole or a part is heated to a temperature higher than the melting point of the liquid crystal compound or a mixture thereof. Can be recorded. When the liquid crystalline compound according to the present invention is used, image information is written by changing partial optical properties only by irradiating the compound in a liquid crystal state through a mask with light weak enough to cause a photoisomerization reaction. In this case, image information can be stored by fixing the optical properties by a quenching operation. For example, if light irradiation is performed in a cholesteric liquid crystal state having an optical property of reflecting light in the visible region, the reflection color of the non-irradiated portion remains unchanged, and the light-irradiated portion is shorter than the unirradiated portion depending on the amount of light irradiation. Since light of a wavelength is reflected, color image information of at least two colors can be recorded. If light is irradiated to the cholesteric liquid crystal state having reflection in the infrared region, the unirradiated portion is transparent because it does not reflect visible region light, and the light irradiated portion has a shorter wavelength than the unirradiated portion depending on the amount of light irradiation. , That is, light in the visible range, so that color image information with a transparent background can be recorded. Also, by increasing the amount of light irradiation, a phase transition occurs, and the light irradiation part becomes an isotropic liquid state, and when it is rapidly cooled, it becomes a crystalline state. Therefore, image information having a contrast between the light scattering state and the light reflection state. Can also be recorded. Furthermore, the liquid crystal state is not limited to the cholesteric liquid crystal phase, and since the optical properties of only the light-irradiated part change in the nematic and smectic phases, image information due to the contrast between the light-irradiated part and the non-irradiated part must be recorded. Can be.
[0021]
【Example】
Next, the present invention will be described in more detail with reference to examples.
[0022]
Example 1
Synthesis of liquid crystalline compound of the following structural formula
[0023]
In a solution of 1.90 g of 10,12-docosadiindicarboxylic acid, 2.14 g of dicyclohexylcarbodiimide and 0.12 g of 4-dimethylaminopyridine in 30 ml of methylene chloride, 2.00 g of 4-hydroxyazobenzene and 1.03 g of cholesterol were dissolved in methylene chloride. A solution dissolved in 40 ml was slowly added dropwise and stirred at room temperature for 6 hours. After filtering the insolubles in the reaction mixture, the solution was separated and purified by column chromatography using a mixed solvent of methylene chloride and n-hexane (volume ratio = 3: 2) as a developing solvent, and the solvent was removed under reduced pressure. 0.18 g of the target compound was obtained. Molecular weight: 911, isotropic phase → liquid crystal phase: 79 ° C., liquid crystal phase → crystal: 26 ° C., glass transition temperature: 47 ° C. 1 H-NMR data (CDCl 3 )
0.65 to 2.60 (m, 75H), 4.60 (m, 1H), 5.34 (m, 1H), 7.22 (d, 2H), 7.48 (m, 3H), 7 .91 (m, 4H)
[0024]
Example 2
Synthesis of liquid crystalline compound of the following structural formula
[0025]
A solution obtained by dissolving 1.87 g of docosadicarboxylic acid, 2.08 g of dicyclohexylcarbodiimide and 0.09 g of 4-dimethylaminopyridine in 60 ml of methylene chloride and 1.00 g of 4-hydroxyazobenzene and 1.95 g of cholesterol in 110 ml of methylene chloride. Was slowly added dropwise and stirred at room temperature for 15 hours. After filtering off the insolubles in the reaction mixture, the solution was separated and purified by column chromatography using a mixed solvent of methylene chloride and n-hexane (volume ratio = 3: 2) as a developing solvent, and the solvent was removed under reduced pressure. Thus, 0.25 g of the target compound was obtained. Molecular weight: 919, isotropic phase → liquid crystal phase: 101 ° C., liquid crystal phase → crystal: 81 ° C., glass transition temperature: 60 ° C.
1 H-NMR data (CDCl 3 )
0.65 to 2.62 (m, 83H), 4.60 (m, 1H), 5.37 (m, 1H), 7.23 (d, 2H), 7.51 (m, 3H), 7 .93 (m, 4H)
[0026]
Example 3
Synthesis of liquid crystalline compound of the following structural formula
[0027]
In a solution of 1.87 g of 10,12-docosadiindicarboxylic acid, 2,08 g of dicyclohexylcarbodiimide and 0.09 g of 4-dimethylaminopyridine in 50 ml of methylene chloride, 1.49 g of 4-hydroxy-4′heptylazobenzene, 1.49 g of cholesterol. 95 g of 100 ml of methylene chloride was separated by column chromatography using methylene chloride as a developing solvent, and then recrystallized with hexane. The solvent was removed from the filtered filtrate to obtain crude crystals. Further recrystallization from ether gave 0.30 g of the target compound. Molecular weight: 1010, isotropic phase → liquid crystal phase: 111 ° C., liquid crystal phase → crystal: 33 ° C., glass transition temperature: 47 ° C.
1 H-NMR data (CDCl 3 )
0.67 to 2.68 (m, 90H), 4.65 (m, 1H), 5.39 (m, 1H), 7.23 (d, 2H), 7, 31 (d, 2H), 7 .83 (d, 2H), 7.93 (d, 2H)
[0028]
Example 4
Compound 9 of Example 1 was sandwiched between two glass plates having a thickness of 0.18 mm, the whole was heated to 95 ° C. and melted, and the thickness of the sample portion was adjusted to about 10 μm. Next, when the sample was placed on a hot stage maintained at 70 ° C., the whole exhibited a green reflection color. When ultraviolet rays from a mercury lamp were partially irradiated therethrough for 15 seconds through a mask, the irradiated part turned blue and the unirradiated part remained green. After ultraviolet irradiation, the sample was immersed in ice water and rapidly cooled to 0 ° C., and the color was fixed. The fixed color was stable at room temperature for more than 2 days.
[0029]
Example 5
The entire color-fixed sample obtained in Example 4 was heated again to 95 ° C. and melted to erase the fixed color. Next, when the sample was placed on a hot stage maintained at 70 ° C., the whole exhibited a green reflection color. When UV light from a mercury lamp was partially irradiated for 1 minute therethrough via a mask, the irradiated portion changed to transparent (change from cholesteric liquid crystal to isotropic liquid), and the unirradiated portion remained green. After the UV irradiation, the sample was immersed in ice water and rapidly cooled to 0 ° C., whereupon the light-irradiated part was fixed in a light-scattering state and the unirradiated part was green, but the color was fixed. The fixed color etc. was stable at room temperature for more than 2 days.
[0030]
Example 6
The compound 10 of Example 2 was sandwiched between two quartz plates having a thickness of 0.18 mm, and the whole was heated to 110 ° C. and melted to adjust the thickness of the sample portion to about 10 μm. Next, when the sample was placed on a hot stage maintained at 90 ° C., the whole turned green. When ultraviolet rays from a mercury lamp were partially irradiated therethrough for 15 seconds through a mask, the irradiated part turned blue, and the unirradiated part remained unchanged. After ultraviolet irradiation, the sample was immersed in ice water and rapidly cooled to 0 ° C., and the color was fixed. The fixed color was stable at room temperature for more than 30 days.
[0031]
Example 7
A mixture of the compound 9 of Example 1 and the compound 10 of Example 2 (weight ratio of 1: 1) was sandwiched between two quartz plates having a thickness of 0.18 mm, and the whole was heated to 110 ° C. and melted. The thickness of the sample was adjusted to about 10 microns. Next, when the sample was placed on a hot stage maintained at 80 ° C., the whole turned yellow-green. When UV light from a mercury lamp was partially irradiated through the mask for 30 seconds, the irradiated portion changed to transparent, and the unirradiated portion remained unchanged. When the sample was immersed in ice water and rapidly cooled to 0 ° C. after ultraviolet irradiation, the light-irradiated portion was fixed in a light-scattering state, and the non-irradiated portion was fixed in yellow-green color. The fixed color etc. was stable at room temperature for 30 days or more.
[0032]
Example 8
A mixture obtained by mixing 10% by weight of the compound 9 of Example 1 with 10,12-docosadiindicholesteryl ester (compound 12 below), which is a cholesteric liquid crystal compound, was sandwiched between two quartz plates having a thickness of 0.18 mm. Was heated to 130 ° C. and melted to adjust the thickness of the sample portion to about 10 μm. Next, when the sample was placed on a hot stage maintained at 85 ° C., the whole turned green. When UV light from a mercury lamp was partially irradiated through the mask for 30 seconds, the irradiated portion turned blue, and the unirradiated portion remained unchanged. After ultraviolet irradiation, the sample was immersed in ice water and rapidly cooled to 0 ° C., and the color was fixed. When the reflection spectra of the irradiated part and the unirradiated part were measured, the maximum wavelength of the reflection peak was 498 nm and 523 nm, respectively. The fixed color was stable at room temperature for more than 30 days.
[0033]
Embedded image
[0034]
Example 9
A mixture obtained by mixing 20% by weight of the compound 9 of Example 1 with the compound 12 as a cholesteric liquid crystal compound was sandwiched between two quartz plates having a thickness of 0.18 mm, and the whole was heated to 130 ° C. to melt. The thickness of the sample portion was adjusted to be about 10 microns. Next, when the sample was placed on a hot stage maintained at 75 ° C., the whole was green. When UV light from a mercury lamp was partially irradiated through the mask for 30 seconds, the irradiated portion turned blue, and the unirradiated portion remained unchanged. After ultraviolet irradiation, the sample was immersed in ice water and rapidly cooled to 0 ° C., and the color was fixed.
[0035]
Example 10
A mixture obtained by mixing the compound 11 of Example 3 with the compound 12 which is a cholesteric liquid crystal compound at 10% by weight was sandwiched between two quartz plates having a thickness of 0.18 mm, and the whole was heated to 130 ° C. and melted. The thickness of the sample portion was adjusted to be about 10 microns. Next, when the sample was placed on a hot stage maintained at 90 ° C., the whole became transparent (cholesteric liquid crystal having reflection in an infrared region). When UV light from a mercury lamp was partially irradiated through the mask for 30 seconds, the light-irradiated portion changed to blue, the light-irradiated portion changed to green, and the non-irradiated portion remained transparent. After the ultraviolet irradiation, the sample was immersed in ice water and rapidly cooled to 0 ° C., whereupon the unirradiated portion was transparent, and the irradiated portion was fixed in blue and green. The fixed color was stable at room temperature for more than 10 days.
[0036]
Example 11
A mixture obtained by mixing 2% by weight of the compound 11 of Example 3 with the compound 12 as a cholesteric liquid crystal compound was sandwiched between two quartz plates having a thickness of 0.18 mm, and the whole was heated to 130 ° C. to melt. The thickness of the sample portion was adjusted to be about 10 microns. Next, when the sample was placed on a hot stage maintained at 88 ° C., the whole thereof turned orange. When UV light from a mercury lamp was partially irradiated through the mask for 30 seconds, the irradiated portion turned blue, and the unirradiated portion remained unchanged. After ultraviolet irradiation, the sample was immersed in ice water and rapidly cooled to 0 ° C., and the color was fixed. The fixed color was stable at room temperature for more than 10 days.
[0037]
【The invention's effect】
By using the liquid crystalline compound of the present invention, it has good photo-responsiveness, and furthermore, crystallization is not promoted even if it is kept at room temperature after color fixation, and optical recording with excellent storage stability of fixed color Medium can be obtained.
Claims (6)
【化１】
Ｚ−Ｏ−ＣＯ−Ｒ−ＣＯ−Ｏ−Ｙ−Ａ （１）
（式中、Ａは水素原子又は炭素数１〜２０の有機基、Ｙはアゾベンゼン基、Ｚはコレステリル基、Ｒは炭素数２から３０の鎖状の飽和もしくは不飽和の２価脂肪族炭化水素基を示す）
で表され、その分子量が３０００以下でガラス転移温度が３５℃以上の液晶性化合物。The following general formula (1)
Embedded image
ZO-CO-R-CO-OYA (1)
(In the formula, A is a hydrogen atom or an organic group having 1 to 20 carbon atoms, Y is an azobenzene group, Z is a cholesteryl group, and R is a linear saturated or unsaturated divalent aliphatic hydrocarbon having 2 to 30 carbon atoms. Indicates a group )
A liquid crystalline compound having a molecular weight of 3000 or less and a glass transition temperature of 35 ° C. or more.
【化２】
−（ＣＨ2）ｍ−Ｃ≡Ｃ−Ｃ≡Ｃ−（ＣＨ2）ｎ− （２）
（式中、ｍ及びｎはそれぞれ独立して１以上の整数であり、但しｍとｎの合計は２６以下である）
で表される基である請求項１の液晶性化合物。 R is the following formula (2)
Embedded image
- (CH 2) m-C≡C -C≡C- (CH 2) n- (2)
(Wherein, m and n are each independently an integer of 1 or more, provided that the sum of m and n is 26 or less)
The liquid crystal compound according to claim 1, which is a group represented by the formula:
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