JP4324333B2 - Optical information recording medium - Google Patents

Description

【０００９】
(式中R¹、R²およびR⁴はそれぞれ独立に置換および無置換のアルキル基、置換および無置換のアルケニル基、置換および無置換のアルキニル基、置換および無置換のアリール基、およびヘテロ環基から選ばれる基を表す。R⁵は置換基を表し、hは0〜4の整数を表し、hが２以上の整数のとき、複数個のR⁵はそれぞれ同一でも異なってもよく、また互いに連結して環を形成してもよい。R⁶は二つのベンゼン環上の置換基を表し、jは0〜6の整数を表し、jが２以上の整数のとき、複数個のR⁶はそれぞれ同一でも異なってもよく、また互いに連結して環を形成してもよい。R⁷はNに結合したベンゼン環上の置換基を表し、iは0〜10の整数を表し、iが２以上の整数のとき、複数個のR⁷はそれぞれ同一でも異なってもよく、また互いに連結して環を形成してもよい。R⁸はメチン基上の置換基を表し、pは0〜2の整数を表し、pが２のとき複数個のR⁸はそれぞれ同一でも異なってもよく、また互いに連結して環を形成してもよい。mは0〜5の整数を表す。X^Y-はY価の有機もしくは無機アニオンを表し、Yは1〜5の整数を表す。)
一般式（２）
【００１０】
【化２】

【００１１】
(式中R¹、R²、R⁴およびR⁹はそれぞれ独立に置換および無置換のアルキル基、置換および無置換のアルケニル基、置換および無置換のアルキニル基、置換および無置換のアリール基、およびヘテロ環基から選ばれる基を表す。R⁵およびR¹⁰は置換基を表し、hおよびkはそれぞれ独立に0〜4の整数を表し、hおよびkが2以上の整数のとき、複数個のR⁵およびR¹⁰はそれぞれ同一でも異なってもよく、また互いに連結して環を形成してもよい。R⁶は置換基を表し、jは0 〜6の整数を表し、jが２以上の整数のとき、複数個のR⁶はそれぞれ同一でも異なってもよく、また互いに連結して環を形成してもよい。mおよびnはそれぞれ独立に0〜5の整数を表し、R¹¹およびR¹²はそれぞれメチン基上の置換基を表し、sおよびtはそれぞれ独立に0〜2の整数を表し、sおよびtが２のとき複数のR¹¹およびR¹²はそれぞれ同一でも異なってもよく、また互いに連結して環を形成してもよい。X^Y-はY価の有機もしくは無機アニオンを表し、Yは1〜5の整数を表す。
一般式（３）
【００１２】
【化３】

【００１３】
(式中R¹は置換および無置換のアルキル基、置換および無置換のアルケニル基、置換および無置換のアルキニル基、置換および無置換のアリール基、およびヘテロ環基から選ばれる基を表す。R¹³およびR¹⁴はそれぞれ独立に置換および無置換のアルキル基、置換および無置換のアルケニル基、置換および無置換のアルキニル基、置換および無置換のアリール基、およびヘテロ環基から選ばれる基を表す。R⁵は置換基を表し、hは0〜4の整数を表し、hが２以上の整数のとき、複数個のR⁵はそれぞれ同一でも異なってもよく、また互いに連結して環を形成してもよい。R⁶は置換基を表し、jは0〜6の整数を表し、jが２以上の整数のとき、複数個のR⁶はそれぞれ同一でも異なってもよく、また互いに連結して環を形成してもよい。R⁸はメチン基上の置換基を表し、pは0〜2mの整数を表し、pが2以上のとき複数個のR⁸はそれぞれ同一でも異なってもよく、また互いに連結して環を形成してもよい。mは0〜5の整数を表す。)
一般式（４）
【００１４】
【化４】

【００１５】
(式中R¹は置換および無置換のアルキル基、置換および無置換のアルケニル基・置換および無置換のアルキニル基、置換および無置換のアリール基、およびヘテロ環基から選ばれる基を表す。R⁵およびR¹⁰は置換基を表し、hおよびkはそれぞれ独立に0〜4の整数を表し、hおよびkが2以上の整数のとき、複数個のR⁵およびR¹⁰はそれぞれ同一でも異なってもよく、また互いに連結して環を形成してもよい。R⁶は置換基を表し、jは0〜6の整数を表し、jが2以上の整数のとき、複数個のR⁶はそれぞれ同一でも異なってもよく、また互いに連結して環を形成してもよい。mおよびnはそれぞれ独立に0〜5の整数を表し、R¹¹ およびR¹²は置換基を表し、sおよびtはそれぞれ独立に0〜2n、0〜2mの整数を表し、sおよびtが2以上のとき複数のR¹¹およびR¹²はそれぞれ同一でも異なってもよく、また互いに連結して環を形成してもよい。)
一般式（５）
【００１６】
【化５】

【００１７】
(式中R¹³およびR¹⁴はそれぞれ独立に置換および無置換のアルキル基、置換および無置換のアルケニル基、置換および無置換のアルキニル基、置換および無置換のアリール基、およびヘテロ環基から選ばれる基を表す。R⁶は置換基を表し、jは0〜6の整数を表し、jが2以上の整数のとき、複数個のR⁶はそれぞれ同一でも異なってもよく、また互いに連結して環を形成してもよい。R⁸はメチン基上の置換基を表し、pは0〜2mの整数を表し、pが2以上のとき複数個のR⁸はそれぞれ同一でも異なってもよく、また互いに連結して環を形成してもよい。mは0〜5 の整数を表す。R¹⁵は置換または無置換のヘテロ環基を表す。)
【００１８】
以下に２光子吸化合物の具体例を挙げるが、本発明の範囲はこれらのみにて限定されるものではない。
【００１９】
【化６】

【００２０】
【化７】

【００２１】
【化８】

【００２２】
【化９】

【００２３】
【化１０】

【００２４】
２光子吸収断面積の大きい化合物は２光子励起状態になりやすいが、その励起エネルギーを目的に応じて利用しやすくする工夫が必要である。例えば２光子励起により重合を開始しようとする場合に、２光子吸収断面積の大きな化合物が励起されてできる励起状態が重合を開始する能力が低ければ、重合開始効率が低くなってしまう。そこで２光子吸収断面積の大きな化合物自身が励起されると高い重合開始能力を持つように設計するか、あるいは２光子吸収断面積の大きな化合物が励起されてできる励起状態のエネルギーを受容して励起される化合物に、高い重合開始能力を付与するなどの工夫が必要である。また適当な高分子バインダ、溶剤、可塑剤などを併用して２光子吸収化合物の性状、例えば液体であるか固体であるか、あるいは粘度の調節をしてもよい。したがって本発明の２光子吸収式光学的情報記録媒体の好ましい態様において、種々の機能性化合物を２光子吸収断面積の大きな化合物と組み合わせて用い得る。
【００２５】
本発明に用いられる蛍光消光剤は、２光子吸収化合物の励起状態を何らかの機構により失活させる化合物である。例えば(1)２光子吸収化合物の励起状態からのエネルギー移動により励起されるが、実質的に蛍光を発しない化合物、(2)２光子吸収化合物の励起状態に電子を注入することにより励起電子が光を発して元に戻るのを阻害する化合物、あるいは(3)２光子吸収化合物の励起状態から電子を受容することにより励起電子が光を発して元に戻るのを阻害する化合物などが挙げられる。(1)において、２光子吸収化合物の励起状態からのエネルギー移動により励起されるには、いわゆるFoelster型エネルギー移動が起こるための要件である、該２光子吸収化合物の蛍光スペクトルと該可視蛍光を発する化合物の吸収スペクトルがある波長域において重なること、が満たされることが好ましく、これらの化合物の１光子励起エネルギーが２光子吸収化合物の１光子励起エネルギーより小さいことが必要である。(2)において、２光子吸収化合物の励起状態に電子を注入できるためには、２光子吸収化合物の最高被占軌道のエネルギー準位よりも高エネルギーの被占軌道を有することが好ましい。(3)において、２光子吸収化合物の励起状態から電子を受容できるためには、２光子吸収化合物の最低空軌道のエネルギー準位よりも低エネルギーの空軌道を有することが好ましい。
単独では蛍光を発する化合物でも組み合わせることによって実質的に有害の蛍光を発しない状況を作ることができる。例えば、Foelster型エネルギー移動が起こるための要件を満たす化合物を組み合わせて多段階のエネルギー移動を繰り返し、エネルギー移動の連鎖の最終段階で励起される化合物が本２光子吸収式光学的情報記録媒体の機能上実質的に支障の無い波長領域に蛍光を発するようにすれば、実質的な無蛍光状態を達成できる。
【００２６】
本発明に用いられる蛍光消光剤としては、種々のものを用いることができる。該２光子吸収化合物の励起エネルギーを受容し得る化合物としては、いわゆるFoelster型エネルギー移動が起こるための要件である、該２光子吸収化合物の蛍光スペクトルと該可視蛍光を発する化合物の吸収スペクトルがある波長域において重なること、を満たす化合物であることが好ましい。エネルギー移動の結果生じる励起1重項が速やかに、励起三重項に変化するか、あるいは電子移動などの化学的変化を起こす化合物が好ましいが、不要な化学変化を起こさない点で前者がより好ましい。蛍光消光剤としては種々の化合物群を挙げることができるが、代表例としては、強い電子受容性の化合物群（例えばニトロ化合物、キノン類、テトラシアノキノジメタン類、アミニウム類、ジインモニウム類）、強い電子供与性化合物群（例えばヒドラジン類、ヒドラジド類、ヒドロキシルアミン類、ハイドロキノン類、四置換ホウ素陰イオン類）、重金属錯体のような高周期元素を含有する化合物群（例えばフェロセンなどのメタロセン類、ビス（１，２−ベンゼンジチオラト）ニッケル類、アゾ色素の重金属錯体類、フォルマザン重金属錯体、ジピロメテン金属錯体類、ポルフィリン重金属錯体類、重金属フタロシアニン類、重金属ナフタロシアニン類）などを挙げることができる。
【００２７】
蛍光消光剤の例を挙げるが、本発明の範囲はこれらのみにて限定されるものではない。
【００２８】
【化１１】

【００２９】
【化１２】

【００３０】
【化１３】

【００３１】
本発明の２光子吸収式光学的情報記録媒体は、更に高分子バインダや微量の溶剤を含有していても良い。溶剤の例としては、酢酸ブチル、乳酸エチル、セロソルブアセテートなどのエステル類;メチルエチルケトン、シクロヘキサノン、メチルイソブチルケトンなどのケトン類;ジクロルメタン、1,2一ジクロルエタン、クロロホルムなどのハロゲン化炭化水素類;N,N-ジメチルホルムアミドなどのアミド類;ジメチススルホキシドなどのスルホキシド類、スルホランなどのスルホン類、シクロヘキサン、トルエンなどの炭化水素類;テトラヒドロフラン、エチルエーテル、ジオキサン、などのエーテル類;エタノール、n−ブロパノール、イソプロパノール、n−ブタノール、ジアセトンアルコールなどのアルコール類;2,2,3,3-テトラフロロブロパノールなどのフツ素系溶剤; エチレングリコールモノメチルエーテル、エチレンングリコールモノエチルエーテル、ブロピレンングリコールモノメチルエーテルなどのグリコールエーテル類などを挙げることができる。上記溶剤は使用する化合物の溶解性を考慮して単独または二種以上組み合わせて用いることができる。本発明の２光子吸収式光学的情報記録媒体中にはさらに酸化防止剤、UV吸収剤、可塑剤などの各種の添加剤を目的に応じて添加してもよい。
【００３２】
光学的情報記録媒体の記録層の材料として高分子バインダを併用する場合に、高分子バインダの使用量は、２光子吸収化合物に対して一般に0.01〜50倍量(質量比)の範囲にあり、好ましくは0.1〜5倍量(質量比)の範囲にある。このようにして調製される組成物中の２光子吸収化合物の濃度は一般に0.01〜10質量%の範囲にあり、好ましくは0.1〜5質量%の範囲にある。
【００３３】
本発明の２光子吸収式光学的情報記録媒体に使用されるバインダ−としては従来公知の熱可塑性樹脂、熱硬化性樹脂、反応型樹脂、電子線硬化型樹脂、紫外線硬化型樹脂、可視光線硬化型樹脂やこれらの混合物が使用される。熱可塑性樹脂としては軟化温度が１５０℃以下、平均分子量が１００００〜３０００００、重合度が約５０〜２０００程度のものでより好ましくは２００〜７００程度であり、例えば塩化ビニル酢酸ビニル共重合体、塩化ビニル共重合体、塩化ビニル酢酸ビニルビニルアルコール共重合体、塩化ビニルビニルアルコール共重合体、塩化ビニル塩化ビニリデン共重合体、塩化ビニルアクリロニトリル共重合体、アクリル酸エステルアクリロニトリル共重合体、アクリル酸エステル塩化ビニリデン共重合体、アクリル酸エステルスチレン共重合体、メタクリル酸エステルアクリロニトリル共重合体、メタクリル酸エステル塩化ビニリデン共重合体、メタクリル酸エステルスチレン共重合体、ウレタンエラストマ−、ナイロン−シリコン系樹脂、ニトロセルロ−ス−ポリアミド樹脂、ポリフッカビニル、塩化ビニリデンアクリロニトリル共重合体、ブタジエンアクリロニトリル共重合体、ポリアミド樹脂、ポリビニルブチラ−ル、セルロ−ス誘導体（セルロ−スアセテ−トブチレ−ト、セルロ−スダイアセテ−ト、セルロ−ストリアセテ−ト、セルロ−スプロピオネ−ト、ニトロセルロ−ス、エチルセルロ−ス、メチルセルロ−ス、プロピルセルロ−ス、メチルエチルセルロ−ス、カルボキシメチルセルロ−ス、アセチルセルロ−ス等）、スチレンブタジエン共重合体、ポリエステル樹脂、ポリカーボネート樹脂、クロロビニルエ−テルアクリル酸エステル共重合体、アミノ樹脂、各種の合成ゴム系の熱可塑性樹脂及びこれらの混合物等が使用される。
【００３４】
また熱硬化性樹脂又は反応型樹脂としては塗布液の状態では２０００００以下の分子量であり、塗布、乾燥後に加熱加湿することにより、縮合、付加等の反応により分子量は無限大のものとなる。又、これらの樹脂のなかで、樹脂が熱分解するまでの間に軟化又は溶融しないものが好ましい。具体的には例えばフェノ−ル樹脂、フェノキシ樹脂、エポキシ樹脂、ポリウレタン樹脂、ポリエステル樹脂、ポリウレタンポリカーボネート樹脂、尿素樹脂、メラミン樹脂、アルキッド樹脂、シリコン樹脂、アクリル系反応樹脂（電子線硬化樹脂）、エポキシ−ポリアミド樹脂、ニトロセルロ−スメラミン樹脂、高分子量ポリエステル樹脂とイソシアネ−トプレポリマ−の混合物、メタクリル酸塩共重合体とジイソシアネ−トプレポリマ−の混合物、ポリエステルポリオ−ルとポリイソシアネ−トとの混合物、尿素ホルムアルデヒド樹脂、低分子量グリコ−ル／高分子量ジオ−ル／トリフェニルメタントリイソシアネ−トの混合物、ポリアミン樹脂、ポリイミン樹脂及びこれらの混合物等である。これらの熱可塑、熱硬化性樹脂、反応型樹脂は、主たる官能基以外に官能基としてカルボン酸（ＣＯＯＭ）、スルフィン酸、スルフェン酸、スルホン酸（ＳＯ₃Ｍ）、燐酸（ＰＯ（ＯＭ）（ＯＭ））、ホスホン酸、硫酸（ＯＳＯ₃Ｍ）、及びこれらのエステル基等の酸性基（ＭはＨ、アルカリ金属、アルカリ土類金属、炭化水素基）、アミノ酸類、アミノスルホン酸類、アミノアルコ−ルの硫酸または燐酸エステル類、スルフォベタイン、ホスホベタイン、アルキルベタイン型等の両性類基、アミノ基、イミノ基、イミド基、アミド基等また、水酸基、アルコキシル基、チオ−ル基、アルキルチオ基、ハロゲン基（Ｆ、Ｃｌ、Ｂｒ、Ｉ）、シリル基、シロキサン基、エポキシ基、イソシアナト基、シアノ基、ニトリル基、オキソ基、アクリル基、フォスフィン基を通常１種以上６種以内含み、各々の官能基は樹脂１ｇあたり１×１０^-6ｅｑ〜１×１０^-2ｅｑ含む事が好ましい。
これらのバインダーの単独又は組合わされたものが使われ、ほかに添加剤が加えられる。本発明の２光子吸収式光学的情報記録媒体とバインダーとの混合割合は質量比で２光子吸収式光学的情報記録媒体の１００質量部に対してバインダー５〜５００００質量部の範囲で使用されることが好ましい。添加剤として分散剤、潤滑剤、帯電防止剤、酸化防止剤、防黴剤、着色剤、溶剤等を必要に応じて添加してもよい。
【００３５】
好ましい高分子バインダの一例としては、特開平11-221963および特開2000-48411にも記載されている、シクロヘキサンジメタノール系ポリエステルポリウレタン樹脂が挙げられる。
【００３６】
２光子吸収式光学的情報記録媒体中には架橋剤を添加して高分子バインダを架橋して形態安定性あるいは支持体への固着性を高めることが好ましい。架橋剤としては、高分子バインダ中の水酸基、アミノ基、あるいはカルボキシル基などの活性水素原子を有する官能基を複数有する化合物が好ましい。たとえばポリアルデヒド、ポリ酸ハライド、ポリ酸無水物、ポリビニルスルホン、シアヌル酸クロライド誘導体、ポリイソシアネートなどが挙げられる。これらのうち特に好ましいポリイソシアネ−トとしては、トリレンジイソシアネ−ト、４、４’−ジフェニルメタンジイソシアネ−ト、ヘキサメチレンジイソシアネ−ト、キシリレンジイソシアネ−ト、ナフチレン−１、５−ジイソシアネ−ト、ｏ−トルイジンジイソシアネ−ト、イソホロンジイソシアネ−ト、トリフェニルメタントリイソシアネ−ト、イソホロンジイソシアネ−ト等のイソシアネ−ト類、又当該イソシアネ−ト類とポリアルコ−ルとの生成物、又イソシアネ−ト類の縮合に依って生成した２〜１０量体のポリイソシアネ−ト、又ポリイソシアネートとポリウレタンとの生成物で末端官能基がイソシアネートであるもの等を使用することができる。これらポリイソシアネ−ト類の平均分子量は１００〜２００００のものが好適である。これらポリイソシアネ−トの市販されている商品名としては、コロネ−トＬ、コロネ−トＨＬ、コロネ−ト２０３０、コロネ−ト２０３１、ミリオネ−トＭＲ、ミリオネ−トＭＴＬ（日本ポリウレタン株製）、タケネ−トＤ−１０２、タケネ−トＤ−１１０Ｎ、タケネ−トＤ−２００、タケネ−トＤ−２０２、タケネ−ト３００Ｓ、タケネ−ト５００（武田薬品株製）、スミジュ−ルＴ−８０、スミジュ−ル４４Ｓ、スミジュ−ルＰＦ、スミジュ−ルＬ、スミジュ−ルＮデスモジュ−ルＬ、デスモジュ−ルＩＬ、デスモジュ−ルＮ、デスモジュ−ルＨＬ、デスモジュ−ルＴ６５、デスモジュ−ル１５、デスモジュ−ルＲ、デスモジュ−ルＲＦ、デスモジュ−ルＳＬ、デスモジュ−ルＺ４２７３（住友バイエル社製）等があり、これらを単独若しくは硬化反応性の差を利用して二つ若しくはそれ以上の組み合わせによって使用することができる。又、硬化反応を促進する目的で、水酸基（ブタンジオ−ル、ヘキサンジオ−ル、分子量が１０００〜１００００のポリウレタン、水等）、アミノ基（モノメチルアミン、ジメチルアミン、トリメチルアミン等）を有する化合物や金属酸化物の触媒や鉄アセチルアセトネート等の触媒を併用する事も出来る。これらの水酸基やアミノ基を有する化合物は多官能である事が望ましい。これらポリイソシアネ−トは２光子吸収式光学的情報記録媒体中の高分子バインダとポリイソシアネ−トの総量１００質量部あたり２〜７０質量部で使用することが好ましく、よりこのましくは５〜５０質量部である。
【００３７】
【実施例】
以下に本発明を実施例により更に具体的に説明する。ここに示す成分、割合、操作順序等は本発明の精神から逸脱しない範囲において変更しうるものであることは本業界に携わるものにとつては容易に理解されることである。従って、本発明は、下記の実施例にて制限されるべきではない。なお、実施例中の部は質量部を表す。
【００３８】
〔実施例１〕
光学的情報記録媒体の例
２光子吸収化合物（１４）１部
蛍光消光剤（Q5） １０部
バインダ（日本ゼオン製ＭＲ１１０Ｔ）２００部
バインダ（東洋紡製ＵＲ−５５００ ３０％）２８０部
希釈剤（メチルエチルケトン／シクロヘキサノン＝２／１）５０００部
架橋剤（コロネート３０４１ ５０％）１００部
以上を混合し均一透明な液状組成物を得た。この組成物をガラス板に塗布し乾燥して光学的情報記録媒体を作成した。この記録媒体は780nm周辺の近赤外域に吸収帯を持たなかった。
これに波長780nm、平均パワー１０ｍＷ尖頭パワー5kw、パルス幅100fs、繰り返し周波数48MHzのレーザーを照射したところ照射部において屈折率の変化が観測された。すなわち近赤外レーザー光の吸収により変化が起こったことがわかる。この塗布物に紫外線ランプを照射したが、比較例２ほどの著しい蛍光色は認められなかった。
【００３９】
〔実施例２〕
実施例1において２光子吸収化合物（１４）の代わりに２光子吸収化合物（１６）を用い、蛍光消光剤（Q5）の代わりに蛍光消光剤（Q6）を用いる他は実施例１と同様にして光学的情報記録媒体を作成した。この記録媒体は780nm周辺の近赤外域に吸収帯を持たなかった。
これに波長780nm、平均パワー１０ｍＷ尖頭パワー5kw、パルス幅100fs、繰り返し周波数48MHzのレーザーを照射したところ照射部において屈折率の変化が観測された。すなわち近赤外レーザー光の吸収により変化が起こったことがわかる。この塗布物に紫外線ランプを照射したが、比較例２ほどの著しい蛍光色は認められなかった。
〔比較例１〕
実施例１において２光子吸収化合物（１４）を添加しない他は実施例１と同様にして液状組成物を得た。これを実施例１と同様にガラス板に塗布し乾燥し、レーザーを照射したが、照射部における屈折率の変化は観測されず、近赤外レーザー光を変化を起こすほど充分には吸収しないことがわかる。この塗布物に紫外線ランプを照射したが、比較例２ほどの著しい蛍光色は認められなかった。
【００４０】
〔比較例２〕
実施例1において蛍光消光剤を添加しない他は実施例1と同様にして液状組成物を得た。これを実施例１と同様にガラス板に塗布し乾燥し、レーザーを照射したが、照射部における屈折率の変化は観測されたが、紫外線ランプを照射すると塗布膜全体が蛍光色に輝くことが肉眼で観測された。
【００４１】
【発明の効果】
本発明の２光子吸収式光学的情報記録媒体は２光子吸収により変化を起こすと同時に蛍光の発生が著しく抑制されるという好ましい効果を有することがわかる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a two-photon absorption optical information recording medium containing a compound having a large two-photon absorption cross-section excited only by intense light.
[0002]
[Prior art]
Normally, a substance is excited by absorbing one photon of energy corresponding to the excitation energy, and a photon having an energy less than this energy is not absorbed. However, when the intensity of light is very strong, two photons whose sum of photon energies corresponds to excitation energy may be absorbed simultaneously. If this property is used, a light reaction can be caused only near the focal point where the light is narrowed by a lens, and an excited state can be created by selecting an arbitrary position in space. However, since two-photon absorption is usually very difficult to occur, a substance having high two-photon excitation efficiency has been demanded. Although two-photon absorption cross-section showing the likelihood of occurrence of two-photon absorption is usually very small 1GM (although ^{1GM = 1 × 10 -50 cm 4} s molecule -1 photon -1) order, in recent years hundreds to thousands Substances having a relatively large two-photon absorption cross section of the order of GM have also been found.
Examples of compounds having a relatively large two-photon absorption cross section are described in, for example, the following documents. That is, Reinhardt et al., Chemistry of Materials, 1998, 10 volumes, 1863, M. Albota et al., Science, 1998, 281, 1653, M. Rumi et al. Journal of the American Chemical Society, 2000, 122, 9500, JD Bhawalkar et al., Optics Communications, 1996, 124, 33, SGHe et al., Applied Physics Letters 1995, 67, 2433, PN Prasad et al., Nonlinear Optics, 1999, 21, 39, GS He et al., Journal of Applied Physics, 1997, 81, 2529, S.-J. Chung et al., Journal of Physical Chemistry B, 1999, 103, 10741, SG He et al., Optics Letters, 1995, 20 Vol. 435, JW Perry et al., Nonlinear Optics, 1999, 21, 225.
However, this size is not practical because it still requires a very high power laser. In addition, in order to make the excitation energy easy to use according to the purpose, it is necessary to devise a combination of various functional substances. In addition, the compounds having a relatively large two-photon absorption cross section reported so far emit strong fluorescence, which is inconvenient for some applications. For example, when information is recorded by causing a change in the state of the recording layer by light irradiation, and this change is read by a change in absorption or reflection of light, it is used in a so-called optical information recording medium. And signal light are difficult to distinguish, causing noise. Therefore, a two-photon absorption optical information recording medium that does not substantially emit fluorescence has been demanded.
[0003]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to provide a high-sensitivity two-photon absorption optical information recording medium that can induce two-photon absorption using a relatively low power laser. It is to provide a two-photon absorption type optical information recording medium for facilitating connection of the resulting excited state energy to a physical and chemical change, and in particular, two-photon absorption type optical information that does not substantially emit fluorescence. It is to provide a recording medium.
[0004]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have paid attention to the fact that it is important to use a compound in which two-photon absorption is efficiently performed and a compound having a function for effectively using the excitation energy. It has been found that the problem is solved by the following two-photon absorption optical information recording medium.
(1) It has a recording layer containing a two-photon absorption compound having a two-photon absorption cross section of 10 ² GM (where 1GM = 1 × 10 ⁻⁵⁰ cm ⁴ s molecule ⁻¹ photon ⁻¹ ) or more and a fluorescence quencher A two-photon absorption type optical information recording medium.
(2) The two-photon absorption optical information recording medium according to (1), wherein the recording layer contains a polymer binder.
(3) The two-photon absorption optical information recording medium according to (1) or (2), wherein the polymer binder is crosslinked with a crosslinking agent.
(4) The two-photon absorbing compound according to any one of (1) to (3), wherein the two-photon absorbing compound is at least one of compounds represented by the following general formulas (1) to (5) Absorption type optical information recording medium.
(5) The two-photon absorption optical system according to any one of (1) to (4), wherein the fluorescence quencher is at least one compound selected from the group of strong electron-accepting compounds Information recording medium.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The embodiment of the two-photon absorption optical information recording medium of the present invention will be described in detail below.
The working principle of the composition that functions in response to only strong light used in the two-photon absorption optical information recording medium of the present invention will be described. When light hits a substance, energy equivalent to one photon is usually absorbed. Even for light having a wavelength at which this one-photon absorption does not occur, if the intensity is very strong, two photons in which the sum of the photon energies corresponds to the excitation energy may be absorbed simultaneously. The two-photon absorption cross-section indicating the ease of two-photon absorption is usually very small, about 1GM (however, 1GM = 1 × 10 ^-50 cm ⁴ smol cule ^-1 photon ^-1 ). A substance having a relatively large two-photon absorption cross section of about 1,000 GM has also been found. When such a substance is used, even light in a wavelength region having no light absorption band absorbs energy of two photons if a light source having a very strong intensity such as a high power laser is used. For example, an absorption maximum wavelength of one photon is shown at 400 nm, and a compound having no absorption band at 800 nm is irradiated with a high power laser with a wavelength of 800 nm, so that an excited state close to the excited state generated when 400 nm light is irradiated is obtained. Can be made. If this compound is excited with 400 nm light, for example, it emits 430 nm fluorescence, it will also emit 430 nm fluorescence when it absorbs 800 nm light. Furthermore, if a compound that absorbs 430 nm light and emits 460 nm fluorescence coexists, it emits 460 nm fluorescence when irradiated with an 800 nm high power laser. If the laser beam is squeezed with a lens and irradiates, the entire optical path does not emit light, but it has a feature that a three-dimensional position selection system can be provided in which fluorescence is emitted only near the focal point where the photon density is high. If a polymerization initiator and a polymerizable monomer or oligomer are mixed and used instead of the fluorescent compound, polymerization can occur only in the vicinity of the focal point, so that a solid polymer having an arbitrary shape can be produced. Further, since the intensity of the focused laser beam decreases as the distance from the center of the beam decreases, the portion having a light intensity sufficient to cause two-photon excitation is smaller than the beam diameter, approximately 1 / √2 times, that is, about 0.7. Double. Therefore, there is an advantage that only a region finer than the minimum value of the beam diameter determined by the wavelength of light can be excited. Thus, the composition used for this invention exhibits a function.
[0006]
However, in order for two-photon absorption to occur more efficiently than the two-photon absorption of a coexisting material such as a binder and a support so as to meet the object of the present invention, the two-photon absorption cross section is GM (Goeppert-Mayers) for convenience. When the unit, that is, 1 × 10 ⁻⁵⁰ cm ⁴ s molecule ⁻¹ photon ⁻¹ ) is expressed as a unit, it is desirably 100 GM or more (preferably 1,000,000,000 GM or less), and more preferably 1,000 GM or more. Particularly preferred is 100,000 GM to 1,000,000,000 GM.
[0007]
Examples of the two-photon absorption compound used in the present invention include compounds represented by the following general formulas (1) to (5) in addition to those described in the literature cited in the above-mentioned conventional technique.
General formula (1)
[0008]
[Chemical 1]

[0009]
Wherein R ¹ , R ² and R ⁴ are each independently a substituted and unsubstituted alkyl group, a substituted and unsubstituted alkenyl group, a substituted and unsubstituted alkynyl group, a substituted and unsubstituted aryl group, and a heterocyclic ring R ⁵ represents a substituent, h represents an integer of 0 to 4, and when h is an integer of 2 or more, a plurality of R ⁵ may be the same or different, and R ⁶ represents a substituent on two benzene rings, j represents an integer of 0 to 6, and when j is an integer of 2 or more, a plurality of R ⁶ May be the same or different, and may be linked to each other to form a ring, R ⁷ represents a substituent on the benzene ring bonded to N, i represents an integer of 0 to 10, and i represents When the integer is 2 or more, a plurality of R ⁷ may be the same or different, and may be connected to each other to form a ring. R ⁸ represents a substituent on the methine group, p represents an integer of 0 to 2, and when p is 2, a plurality of R ⁸ may be the same or different, and may be connected to each other to form a ring. (M represents an integer of 0 to 5. X ^Y- represents a Y-valent organic or inorganic anion, and Y represents an integer of 1 to 5.)
General formula (2)
[0010]
[Chemical formula 2]

[0011]
Wherein R ¹ , R ² , R ⁴ and R ⁹ are each independently a substituted and unsubstituted alkyl group, a substituted and unsubstituted alkenyl group, a substituted and unsubstituted alkynyl group, a substituted and unsubstituted aryl group, And R ⁵ and R ¹⁰ each represents a substituent, h and k each independently represents an integer of 0 to 4, and when h and k are integers of 2 or more, R ⁵ and R ¹⁰ may be the same as or different from each other, and may be bonded to each other to form a ring, R ⁶ represents a substituent, j represents an integer of 0 to 6, and j is 2 or more when the integer, an integer of a plurality of R ⁶ 0 to 5 is good, also the respectively good .m and n may form a ring by linking each independently different and are each identical, R ¹¹ and R ¹² each represents a substituent on the methine group, s and t each independently represents an integer of 0 to 2, s and When t is 2, a plurality of R ¹¹ and R ¹² may be the same or different, and may be connected to each other to form a ring, X ^Y— represents a Y-valent organic or inorganic anion, and Y represents Represents an integer of 1-5.
General formula (3)
[0012]
[Chemical 3]

[0013]
(Wherein R ¹ represents a group selected from a substituted and unsubstituted alkyl group, a substituted and unsubstituted alkenyl group, a substituted and unsubstituted alkynyl group, a substituted and unsubstituted aryl group, and a heterocyclic group. ¹³ and R ¹⁴ each independently represent a substituted or unsubstituted alkyl groups, substituted and unsubstituted alkenyl group, substituted and unsubstituted alkynyl groups, substituted and unsubstituted aryl groups, and a group selected from a heterocyclic group R ⁵ represents a substituent, h represents an integer of 0 to 4, and when h is an integer of 2 or more, a plurality of R ⁵ may be the same or different, and are connected to each other to form a ring. R ⁶ represents a substituent, j represents an integer of 0 to 6, and when j is an integer of 2 or more, the plurality of R ⁶ may be the same or different, and are connected to each other. It may form a ring Te .R ⁸ of the substituent on the methine group The stands, p represents an integer of 0 to 2m, p is or different in each plurality of R ⁸ when two or more identical, also good .m be linked with each other to form a ring 0 (Represents an integer of 5.)
General formula (4)
[0014]
[Formula 4]

[0015]
(Wherein R ¹ represents a group selected from a substituted and unsubstituted alkyl group, a substituted and unsubstituted alkenyl group, a substituted and unsubstituted alkynyl group, a substituted and unsubstituted aryl group, and a heterocyclic group. ⁵ and R ¹⁰ represent a substituent, h and k each independently represent an integer of 0 to 4, and when h and k are integers of 2 or more, a plurality of R ⁵ and R ¹⁰ are the same or different. R ⁶ represents a substituent, j represents an integer of 0 to 6, and when j is an integer of 2 or more, a plurality of R ⁶ are each They may be the same or different, and may be linked together to form a ring, m and n each independently represents an integer of 0 to 5, R ¹¹ and R ¹² represent a substituent, and s and t are Each independently represents an integer of 0-2n, 0-2m, and when s and t are 2 or more, the plurality of R ¹¹ and R ¹² are the same And may be linked to each other to form a ring.)
General formula (5)
[0016]
[Chemical formula 5]

[0017]
(Wherein R ¹³ and R ¹⁴ are each independently selected from substituted and unsubstituted alkyl groups, substituted and unsubstituted alkenyl groups, substituted and unsubstituted alkynyl groups, substituted and unsubstituted aryl groups, and heterocyclic groups. R ⁶ represents a substituent, j represents an integer of 0 to 6, and when j is an integer of 2 or more, a plurality of R ^{6 s} may be the same or different, and may be linked to each other. R ⁸ represents a substituent on the methine group, p represents an integer of 0 to 2 m, and when p is 2 or more, a plurality of R ⁸ may be the same or different. And may be linked to each other to form a ring, m represents an integer of 0 to 5. R ¹⁵ represents a substituted or unsubstituted heterocyclic group.)
[0018]
Specific examples of the two-photon absorption compound are given below, but the scope of the present invention is not limited to these.
[0019]
[Chemical 6]

[0020]
[Chemical 7]

[0021]
[Chemical 8]

[0022]
[Chemical 9]

[0023]
Embedded image

[0024]
A compound having a large two-photon absorption cross-section is likely to be in a two-photon excited state, but it is necessary to devise a method for easily using the excitation energy according to the purpose. For example, when the polymerization is to be started by two-photon excitation, if the excited state formed by exciting a compound having a large two-photon absorption cross-sectional area has a low ability to start polymerization, the polymerization initiation efficiency is lowered. Therefore, when the compound itself having a large two-photon absorption cross section is excited, it is designed to have a high polymerization initiating ability, or it is excited by receiving the excited state energy generated by exciting the compound having a large two-photon absorption cross section. It is necessary to devise such as imparting a high polymerization initiation ability to the compound to be produced. Further, the properties of the two-photon absorption compound, for example, liquid or solid, or viscosity may be adjusted by using an appropriate polymer binder, solvent, plasticizer and the like. Therefore, in the preferred embodiment of the two-photon absorption optical information recording medium of the present invention, various functional compounds can be used in combination with a compound having a large two-photon absorption cross section.
[0025]
The fluorescence quencher used in the present invention is a compound that deactivates the excited state of the two-photon absorption compound by some mechanism. For example, (1) a compound that is excited by energy transfer from the excited state of the two-photon absorption compound, but does not substantially fluoresce, (2) an excited electron is injected by injecting electrons into the excited state of the two-photon absorption compound Examples include compounds that inhibit light from returning to its original state, or (3) compounds that inhibit electrons from returning to their original state by accepting electrons from the excited state of the two-photon absorption compound. . In (1), in order to be excited by the energy transfer from the excited state of the two-photon absorption compound, the fluorescence spectrum of the two-photon absorption compound and the visible fluorescence are emitted, which is a requirement for the so-called Foelster type energy transfer. It is preferable that the absorption spectra of the compounds overlap in a certain wavelength region, and it is necessary that the one-photon excitation energy of these compounds is smaller than the one-photon excitation energy of the two-photon absorption compound. In (2), in order to inject electrons into the excited state of the two-photon absorption compound, it is preferable to have an occupied orbit having a higher energy than the energy level of the highest occupied orbit of the two-photon absorption compound. In (3), in order to accept electrons from the excited state of the two-photon absorption compound, it is preferable to have an empty orbit with energy lower than the energy level of the lowest empty orbit of the two-photon absorption compound.
By combining compounds that fluoresce alone, it is possible to create a situation in which substantially no harmful fluorescence is emitted. For example, a compound that satisfies the requirements for Foelster-type energy transfer is combined to repeat multi-stage energy transfer, and the compound excited in the final stage of the energy transfer chain is the function of this two-photon absorption optical information recording medium. If fluorescence is emitted in a wavelength region where there is substantially no trouble, a substantially non-fluorescent state can be achieved.
[0026]
Various fluorescent quenchers can be used in the present invention. The compound capable of receiving the excitation energy of the two-photon absorption compound has a wavelength having a fluorescence spectrum of the two-photon absorption compound and an absorption spectrum of the compound that emits visible fluorescence, which is a requirement for the so-called Foelster type energy transfer. It is preferable that the compound satisfies the overlapping in the region. A compound in which the excited singlet resulting from the energy transfer changes rapidly to an excited triplet or a chemical change such as electron transfer is preferred, but the former is more preferred in that it does not cause an unnecessary chemical change. As the fluorescence quencher, various compound groups can be exemplified, but representative examples include strong electron accepting compound groups (for example, nitro compounds, quinones, tetracyanoquinodimethanes, aminiums, diimmoniums), Strong electron-donating compounds (for example, hydrazines, hydrazides, hydroxylamines, hydroquinones, tetrasubstituted boron anions), compounds containing high-periodic elements such as heavy metal complexes (for example, metallocenes such as ferrocene, Bis (1,2-benzenedithiolato) nickel, heavy metal complexes of azo dyes, formazan heavy metal complexes, dipyrromethene metal complexes, porphyrin heavy metal complexes, heavy metal phthalocyanines, heavy metal naphthalocyanines).
[0027]
Examples of the fluorescence quencher are given, but the scope of the present invention is not limited to these examples.
[0028]
Embedded image

[0029]
Embedded image

[0030]
Embedded image

[0031]
The two-photon absorption optical information recording medium of the present invention may further contain a polymer binder and a trace amount of solvent. Examples of solvents include esters such as butyl acetate, ethyl lactate and cellosolve acetate; ketones such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane and chloroform; N, Amides such as N-dimethylformamide; Sulfoxides such as dimethis sulfoxide; Sulfones such as sulfolane; Hydrocarbons such as cyclohexane and toluene; Ethers such as tetrahydrofuran, ethyl ether and dioxane; Ethanol, n-propanol, Alcohols such as isopropanol, n-butanol, diacetone alcohol; fluorine-based solvents such as 2,2,3,3-tetrafluorobropanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Such as glycol ethers such as bromide propylene glycol monomethyl ether. The said solvent can be used individually or in combination of 2 or more types in consideration of the solubility of the compound to be used. Various additives such as an antioxidant, a UV absorber, and a plasticizer may be further added to the two-photon absorption optical information recording medium of the present invention depending on the purpose.
[0032]
When a polymer binder is used in combination as the recording layer material of the optical information recording medium, the amount of the polymer binder used is generally in the range of 0.01 to 50 times (mass ratio) with respect to the two-photon absorption compound, Preferably it exists in the range of 0.1-5 times amount (mass ratio). The concentration of the two-photon absorption compound in the composition thus prepared is generally in the range of 0.01 to 10% by mass, preferably in the range of 0.1 to 5% by mass.
[0033]
Binders used in the two-photon absorption optical information recording medium of the present invention include conventionally known thermoplastic resins, thermosetting resins, reactive resins, electron beam curable resins, ultraviolet curable resins, and visible light curable resins. Mold resins and mixtures thereof are used. The thermoplastic resin has a softening temperature of 150 ° C. or lower, an average molecular weight of 10,000 to 300,000, and a degree of polymerization of about 50 to 2,000, more preferably about 200 to 700. For example, vinyl chloride vinyl acetate copolymer, chloride Vinyl copolymer, vinyl chloride vinyl acetate vinyl vinyl alcohol copolymer, vinyl chloride vinyl alcohol copolymer, vinyl chloride vinylidene chloride copolymer, vinyl acrylonitrile chloride copolymer, acrylate ester acrylonitrile copolymer, acrylate ester chloride Vinylidene copolymer, acrylate ester styrene copolymer, methacrylate ester acrylonitrile copolymer, methacrylate ester vinylidene chloride copolymer, methacrylate ester styrene copolymer, urethane elastomer, nylon-silicone resin, Loose-Rose-polyamide resin, Polyvinyl carbonate, Vinylidene acrylonitrile copolymer, Butadiene acrylonitrile copolymer, Polyamide resin, Polyvinyl butyral, Cellulose derivative (Cellulose acetate butyrate, Cellulose diacetate) , Cellulose triacetate, cellulose propionate, nitrocellulose, ethyl cellulose, methyl cellulose, propyl cellulose, methyl ethyl cellulose, carboxymethyl cellulose, acetyl cellulose, etc.) A styrene butadiene copolymer, a polyester resin, a polycarbonate resin, a chlorovinyl ether acrylate copolymer, an amino resin, various synthetic rubber thermoplastic resins, and a mixture thereof are used.
[0034]
Further, the thermosetting resin or the reactive resin has a molecular weight of 200,000 or less in the state of the coating liquid, and the molecular weight becomes infinite by reaction such as condensation and addition by heating and humidification after coating and drying. Of these resins, those that do not soften or melt until the resin is thermally decomposed are preferable. Specifically, for example, phenol resin, phenoxy resin, epoxy resin, polyurethane resin, polyester resin, polyurethane polycarbonate resin, urea resin, melamine resin, alkyd resin, silicone resin, acrylic reaction resin (electron beam curable resin), epoxy Polyamide resin, nitrocellulose melamine resin, mixture of high molecular weight polyester resin and isocyanate prepolymer, mixture of methacrylate copolymer and diisocyanate prepolymer, mixture of polyester polyol and polyisocyanate, urea formaldehyde resin A mixture of low molecular weight glycol / high molecular weight diol / triphenylmethane triisocyanate, polyamine resin, polyimine resin, and mixtures thereof. These thermoplastic and thermosetting resins and reactive resins have carboxylic acid (COOM), sulfinic acid, sulfenic acid, sulfonic acid (SO ₃ M), phosphoric acid (PO (OM) ( OM)), phosphonic acid, sulfuric acid (OSO ₃ M), and acidic groups such as these ester groups (M is H, alkali metal, alkaline earth metal, hydrocarbon group), amino acids, aminosulfonic acids, aminoalkoxy -Sulfuric acid or phosphoric acid esters, sulfobetaine, phosphobetaine, alkylbetaine type and the like amphoteric group, amino group, imino group, imide group, amide group, etc., hydroxyl group, alkoxyl group, thiol group, alkylthio group Group, halogen group (F, Cl, Br, I), silyl group, siloxane group, epoxy group, isocyanato group, cyano group, nitrile group, oxo group, acrylic Include phosphine groups usually within 1 or more six, it is preferred each functional group containing ^{1 × 10 -6 eq~1 × 10 -2} eq per resin 1g.
These binders are used alone or in combination, and other additives are added. The mixing ratio of the two-photon absorption optical information recording medium of the present invention and the binder is used in the range of 5 to 50000 parts by mass of the binder with respect to 100 parts by mass of the two-photon absorption optical information recording medium. It is preferable. A dispersant, lubricant, antistatic agent, antioxidant, antifungal agent, colorant, solvent and the like may be added as necessary.
[0035]
An example of a preferable polymer binder is a cyclohexanedimethanol-based polyester polyurethane resin described in JP-A-11-221963 and JP-A-2000-48411.
[0036]
It is preferable to add a cross-linking agent to the two-photon absorption optical information recording medium to cross-link the polymer binder to improve the form stability or the fixing property to the support. As the crosslinking agent, a compound having a plurality of functional groups having an active hydrogen atom such as a hydroxyl group, an amino group, or a carboxyl group in the polymer binder is preferable. For example, polyaldehyde, polyacid halide, polyacid anhydride, polyvinylsulfone, cyanuric acid chloride derivative, polyisocyanate and the like can be mentioned. Among these, particularly preferred polyisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, naphthylene-1, 5 -Isocyanates such as diisocyanate, o-toluidine diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, isophorone diisocyanate, and the like Products with polyalcohols, diisocyanate diisocyanates produced by condensation of isocyanates, products of polyisocyanates and polyurethanes with terminal functional groups being isocyanates, etc. Can be used. These polyisocyanates preferably have an average molecular weight of 100 to 20000. Commercially available product names of these polyisocyanates include Coronate L, Coronate HL, Coronate 2030, Coronate 2031, Millionate MR, Millionate MTL (manufactured by Nippon Polyurethane Co., Ltd.), Bamboo D-102, Bamboo D-110N, Bamboo D-200, Bamboo D-202, Bamboo 300S, Bamboo 500 (manufactured by Takeda Pharmaceutical Co., Ltd.), Sumidur T-80 , Sumi module 44S, Sumi module PF, Sumi module L, Sumi module N Death module L, Death module IL, Death module N, Death module HL, Death module T65, Death module 15, There are Death Module R, Death Module RF, Death Module SL, Death Module Z4273 (manufactured by Sumitomo Bayer), etc. Ku can be used by two or more thereof utilizing difference in curing reactivity. In addition, for the purpose of accelerating the curing reaction, a compound or metal oxide having a hydroxyl group (butanediol, hexanediol, polyurethane having a molecular weight of 1000 to 10,000, water, etc.), or an amino group (monomethylamine, dimethylamine, trimethylamine, etc.) A catalyst such as a product catalyst or iron acetylacetonate may be used in combination. These compounds having a hydroxyl group or an amino group are desirably polyfunctional. These polyisocyanates are preferably used in an amount of 2 to 70 parts by mass per 100 parts by mass of the total amount of polymer binder and polyisocyanate in the two-photon absorption optical information recording medium, more preferably 5 to 50 parts by mass. Part.
[0037]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. It will be readily understood by those skilled in the art that the components, ratios, operation order, and the like shown here can be changed without departing from the spirit of the present invention. Accordingly, the invention should not be limited by the following examples. In addition, the part in an Example represents a mass part.
[0038]
[Example 1]
Example of optical information recording medium 2 Photon absorbing compound (14) 1 part Fluorescence quencher (Q5) 10 parts binder (MR110T made by Nippon Zeon) 200 parts binder (UR-5500 30% made by Toyobo) 280 parts diluent (methyl ethyl ketone / Cyclohexanone = 2/1) 5000 parts crosslinker (Coronate 3041 50%) 100 parts or more were mixed to obtain a uniform transparent liquid composition. This composition was applied to a glass plate and dried to prepare an optical information recording medium. This recording medium had no absorption band in the near infrared region around 780 nm.
When this was irradiated with a laser having a wavelength of 780 nm, an average power of 10 mW, a peak power of 5 kw, a pulse width of 100 fs, and a repetition frequency of 48 MHz, a change in refractive index was observed in the irradiated portion. That is, it can be seen that a change has occurred due to absorption of near-infrared laser light. When this coated material was irradiated with an ultraviolet lamp, no remarkable fluorescent color as in Comparative Example 2 was observed.
[0039]
[Example 2]
In Example 1, the two-photon absorption compound (16) was used instead of the two-photon absorption compound (14), and the fluorescence quencher (Q6) was used instead of the fluorescence quencher (Q5). An optical information recording medium was prepared. This recording medium had no absorption band in the near infrared region around 780 nm.
When this was irradiated with a laser having a wavelength of 780 nm, an average power of 10 mW, a peak power of 5 kw, a pulse width of 100 fs, and a repetition frequency of 48 MHz, a change in refractive index was observed in the irradiated portion. That is, it can be seen that a change has occurred due to absorption of near-infrared laser light. When this coated material was irradiated with an ultraviolet lamp, no remarkable fluorescent color as in Comparative Example 2 was observed.
[Comparative Example 1]
A liquid composition was obtained in the same manner as in Example 1 except that the two-photon absorption compound (14) was not added. This was applied to a glass plate, dried, and irradiated with a laser in the same manner as in Example 1, but no change in the refractive index in the irradiated area was observed, and the near infrared laser light was not absorbed sufficiently to cause a change. I understand. The coated material was irradiated with an ultraviolet lamp, but no remarkable fluorescent color as in Comparative Example 2 was observed.
[0040]
[Comparative Example 2]
A liquid composition was obtained in the same manner as in Example 1 except that no fluorescence quencher was added in Example 1. This was applied to a glass plate in the same manner as in Example 1, dried, and irradiated with a laser, but a change in the refractive index in the irradiated part was observed, but when irradiated with an ultraviolet lamp, the entire coated film shined in a fluorescent color. Observed with the naked eye.
[0041]
【The invention's effect】
It can be seen that the two-photon absorption type optical information recording medium of the present invention has a preferable effect of causing a change due to two-photon absorption and at the same time suppressing the generation of fluorescence.

Claims (2)

It has a recording layer containing a two-photon absorption compound having a two-photon absorption cross-section of 10 ² GM (where 1GM = 1 × 10 ⁻⁵⁰ cm ⁴ s molecule ⁻¹ photon ⁻¹ ) or more and a fluorescence quencher. A two-photon absorption optical information recording medium. The two-photon absorption optical information recording medium according to claim 1, wherein the two-photon absorption compound is at least one of compounds represented by the following general formulas (1) to (5).
General formula (1)

Wherein R ¹ , R ² and R ⁴ are each independently a substituted and unsubstituted alkyl group, a substituted and unsubstituted alkenyl group, a substituted and unsubstituted alkynyl group, a substituted and unsubstituted aryl group, and a heterocyclic ring R ⁵ represents a substituent, h represents an integer of 0 to 4, and when h is an integer of 2 or more, a plurality of R ⁵ may be the same or different, and R ⁶ represents a substituent on two benzene rings, j represents an integer of 0 to 6, and when j is an integer of 2 or more, a plurality of R ⁶ May be the same or different, and may be linked to each other to form a ring, R ⁷ represents a substituent on the benzene ring bonded to N, i represents an integer of 0 to 10, and i represents When the integer is 2 or more, a plurality of R ⁷ may be the same or different, and may be connected to each other to form a ring. R ⁸ represents a substituent on the methine group, p represents an integer of 0 to 2, and when p is 2, a plurality of R ⁸ may be the same or different, and may be connected to each other to form a ring. (M represents an integer of 0 to 5. X ^Y- represents a Y-valent organic or inorganic anion, and Y represents an integer of 1 to 5.)
General formula (2)

Wherein R ¹ , R ² , R ⁴ and R ⁹ are each independently a substituted and unsubstituted alkyl group, a substituted and unsubstituted alkenyl group, a substituted and unsubstituted alkynyl group, a substituted and unsubstituted aryl group, And R ⁵ and R ¹⁰ each represents a substituent, h and k each independently represents an integer of 0 to 4, and when h and k are integers of 2 or more, R ⁵ and R ¹⁰ may be the same as or different from each other, and may be bonded to each other to form a ring, R ⁶ represents a substituent, j represents an integer of 0 to 6, and j is 2 or more when the integer, an integer of a plurality of R ⁶ 0 to 5 is good, also the respectively good .m and n may form a ring by linking each independently different and are each identical, R ¹¹ and R ¹² each represents a substituent on the methine group, s and t each independently represents an integer of 0 to 2, s and When t is 2, a plurality of R ¹¹ and R ¹² may be the same or different, and may be connected to each other to form a ring, X ^Y— represents a Y-valent organic or inorganic anion, and Y represents Represents an integer of 1-5.
General formula (3)

(Wherein R ¹ represents a group selected from a substituted and unsubstituted alkyl group, a substituted and unsubstituted alkenyl group, a substituted and unsubstituted alkynyl group, a substituted and unsubstituted aryl group, and a heterocyclic group. ¹³ and R ¹⁴ each independently represent a substituted or unsubstituted alkyl groups, substituted and unsubstituted alkenyl group, substituted and unsubstituted alkynyl groups, substituted and unsubstituted aryl groups, and a group selected from a heterocyclic group R ⁵ represents a substituent, h represents an integer of 0 to 4, and when h is an integer of 2 or more, a plurality of R ⁵ may be the same or different, and are connected to each other to form a ring. R ⁶ represents a substituent, j represents an integer of 0 to 6, and when j is an integer of 2 or more, the plurality of R ⁶ may be the same or different, and are connected to each other. It may form a ring Te .R ⁸ of the substituent on the methine group The stands, p represents an integer of 0 to 2m, p is or different in each plurality of R ⁸ when two or more identical, also good .m be linked with each other to form a ring 0 (Represents an integer of 5.)
General formula (4)

(Wherein R ¹ represents a group selected from a substituted and unsubstituted alkyl group, a substituted and unsubstituted alkenyl group, a substituted and unsubstituted alkynyl group, a substituted and unsubstituted aryl group, and a heterocyclic group. ⁵ and R ¹⁰ represent a substituent, h and k each independently represent an integer of 0 to 4, and when h and k are integers of 2 or more, a plurality of R ⁵ and R ¹⁰ are the same or different. R ⁶ represents a substituent, j represents an integer of 0 to 6, and when j is an integer of 2 or more, a plurality of R ⁶ are each They may be the same or different, and may be linked together to form a ring, m and n each independently represents an integer of 0 to 5, R ¹¹ and R ¹² represent a substituent, and s and t are Each independently represents an integer of 0-2n, 0-2m, and when s and t are 2 or more, the plurality of R ¹¹ and R ¹² are the same And may be linked to each other to form a ring.)
General formula (5)

(Wherein R ¹³ and R ¹⁴ are each independently selected from substituted and unsubstituted alkyl groups, substituted and unsubstituted alkenyl groups, substituted and unsubstituted alkynyl groups, substituted and unsubstituted aryl groups, and heterocyclic groups. R ⁶ represents a substituent, j represents an integer of 0 to 6, and when j is an integer of 2 or more, a plurality of R ^{6 s} may be the same or different, and may be linked to each other. R ⁸ represents a substituent on the methine group, p represents an integer of 0 to 2 m, and when p is 2 or more, a plurality of R ⁸ may be the same or different. And may be linked to each other to form a ring, m represents an integer of 0 to 5. R ¹⁵ represents a substituted or unsubstituted heterocyclic group.)