JP2004195765A - Optical information recording medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical information recording medium employing coloring matter, which especially can improve light resistance. <P>SOLUTION: This optical information recording medium has an optical interference layer made of a coloring matter layer including a substitution polymethine compound, in which a substituent such as that of an organic metal complex or a metallocene represented by formula 1 is introduced. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【化２】

（但し、Ａは
【化３】

を表わし、Ｂは
【化４】

を表わし、Ａ’は
【化５】

を表わし、Ｂ’は
【化６】

を表わし、Ａ、Ｂ、Ａ’及びＢ’のそれぞれが芳香族環を有する場合には単数又は複数の置換基としてハロゲン原子、アルキル基、アルコキシ基又はアリール基を有してもよく、Ｒはアルキル基又はスルホン化されたアルキル基を表わし、（Ａ、Ｂ）、（Ａ’、Ｂ’）のそれぞれの各組において互いに同じでも異なってもよく、Ｘは陰イオンを表わし（上記のスルホン化されたアルキル基はＸを有してもよく）、Ａ、Ａ’のそれぞれのＸが結合しているＮは陽イオンを表わすが、ＸはＢ、Ｂ’のそれぞれのＲが結合しているＮが陽イオンのときはこれに結合してもよく、その場合Ａ、Ａ’のそれぞれのＮはＲのみが結合する非イオンとなり、Ｒ’は水素原子又はカルボアルキル基を表わし、Ｒ’’は水素原子又はアルキル基を表わし、Ｒ’、Ｒ’’は同じでも異なってもよく、相互に入れ替わってもよく、中央の連結鎖のポリメチン鎖のｎは０を含む正の整数を表わす。）
（７）、シアニン系化合物が下記一般式〔化７〕で表されるシアニン系化合物である上記（５）又は（６）の光情報記録媒体、
【化７】

（但し、Ａ１、Ａ２は置換又は非置換のベンゼン環又はナフタレン環を表わし、Ｙ、Ｙ’はＣ、−ＣＨ＝ＣＨ−、Ｏ、Ｓ、Ｓｅ又はＮＨを表わし、同じでも異なってもく、置換基を有することができるときはその置換基はアルキル基であってもよく、Ｙ、Ｙ’は両方又はいずれか一方がＣであってその少なくとも一方のＣがスピロ縮合環を有し、その一方のみがスピロ縮合環を有するときは他方のＣの置換基はジアルキル基であってもよく、Ｒ₁ 、Ｒ₂ はアルキル基又はスルホン化されたアルキル基を表わし、Ｘはハロゲン原子、ＰＦ₆ ^- 、過塩素酸、ホウフッ化水素酸、リン酸、ベンゼンスルホン酸、ＳｂＦ₆ ^- 、トルエンスルホン酸、アルキルスルホン酸、ベンゼンカルボン酸、アルキルカルボン酸、トリフルオロメチルカルボン酸、過ヨウ素酸、ＳＣＮ^- 、テトラフェニルホウ酸及びタングステン酸の陰イオンの群のなかから選択される陰イオンを表わし（上記のスルホン化されたアルキル基はＸを有してもよく）、Ｘが結合している一方の複素環のＮは陽イオンを表わすが、Ｘは他方の複素環のＲ₂ が結合しているＮが陽イオンのときはこれに結合してもよく、その場合は上記の一方の複素環のＮはＲ₁ のみが結合する非イオンとなり、中央の連結鎖のポリメチン鎖のｎは０を含む正の整数を表わし、該ポリメチン鎖には置換基を有してもよく、複数の炭素間にわたる環状側鎖を有していてもよい。）、（８）、上記一般式〔化７〕のカチオン成分にメタロセン系化合物の置換基を有する置換基を導入して置換シアニン系化合物とし、該置換シアニン系化合物が下記一般式〔化８〕で表される複素環の芳香族環にメタロセン系化合物の置換基を有する置換基を導入した置換シアニン系化合物である上記（７）の光情報記録媒体、
【化８】

（但し、Ｘ^- はジチオール錯体、メタロセン系化合物等の有機金属錯体に陰イオン基を導入して得られる１価又は２価の陰イオンであってもよいこと及びＲ₃ 、Ｒ₄ 以外の各記号等は上記一般式〔化７〕のものと同じものを表わし、Ｒ₃ 、Ｒ₄ は両方が水素原子、これらの両方又はいずれか一方がメタロセン系化合物の置換基を有する置換基を表わし、その両方のときは同じでも異なってもよく、そのいずれか一方のときは他方は水素原子又はメタロセン系化合物の置換基を有する置換基以外の有機の置換基を表わし、Ｒ₃ 、Ｒ₄ はそれぞれにおいて水素原子、メタロセン系化合物の置換基を有する置換基及びメタロセン系化合物の置換基を有する置換基以外の有機の置換基から選択された同一又は異なる複数の置換基（置換できるいずれの位置でもよい）でもよい。）、（９）、上記一般式〔化７〕のカチオン成分にメタロセン系化合物の置換基を有する置換基を導入して置換シアニン系化合物とし、該置換シアニン系化合物が下記一般式〔化９〕で表される複素環のＮにメタロセン系化合物の置換基を有する置換基を導入したシアニン系化合物である上記（７）の光情報記録媒体、
【化９】

（但し、Ｒ₃ 、Ｒ₄ は両方が水素原子であってもよいこと及びＲ₁ −Ｍ₁ 、Ｒ₂ −Ｍ₂ 以外は各記号等は上記一般式〔化８〕のものと同じものを表わし、Ｍ₁ 、Ｍ₂ はメタロセン系化合物の置換基又は水素原子を表わし、Ｒ₁ −Ｍ₁ 、Ｒ₂ −Ｍ₂ は少なくとも一方はメタロセン系化合物の置換基で置換した他の置換基を有してもよい置換又は他の置換基を有しない非置換のアルキル基、アルコキシル基、カルボキシル基、アルコキシカルボニル基、アルキルカルボキシル基、ハロゲン化アルキル基、アルキルヒドロキシル基、アラルキル基、アルケニル基、アルキルアミド基、アルキルアミノ基、アルキルスルホンアミド基、アルキルカルバモイル基、アルキルスルファモイル基、水酸基、ハロゲン原子、アルキルアルコキシル基、アルキルスルホニル基、金属イオン若しくはアルキル基と結合したアルキルカルボキシル基若しくはアルキルスルホニル基、フェニル基、ベンジル基、アルキルフェニル基及びフェノキシアルキル基（ベンゼン環部分及び／又はアルキル部分の水素原子をアルキル基、カルボキシル基、水酸基、ハロゲン原子等の金属イオン以外の置換基で置換してもよく、前記フェニル基、ベンジル基、アルキルフェニル基の該当部分についても同様である。）の群から選択される置換基を表わし、その両方がメタロセン系化合物の置換基で置換した置換基を有するときは同種でも異種でもよく、その一方のみがメタロセン系の化合物の置換基で置換した置換基を有するときは他方は該メタロセン系の化合物の置換基以外の置換又は非置換のアルキル基、アルコキシル基、カルボキシル基、アルコキシカルボニル基、アルキルカルボキシル基、ハロゲン化アルキル基、アルキルヒドロキシル基、アラルキル基、アルケニル基、アルキルアミド基、アルキルアミノ基、アルキルスルホンアミド基、アルキルカルバモイル基、アルキルスルファモイル基、水酸基、ハロゲン原子、アルキルアルコキシル基、アルキルスルホニル基、金属イオン若しくはアルキル基と結合したアルキルカルボキシル基若しくはアルキルスルホニル基、フェニル基、ベンジル基、アルキルフェニル基及びフェノキシアルキル基（ベンゼン環部分及び／又はアルキル部分の水素原子をアルキル基、カルボキシル基、水酸基、ハロゲン原子等の金属イオン以外の置換基で置換してもよく、前記フェニル基、ベンジル基、アルキルフェニル基の該当部分についても同様である。）の群から選択される置換基を表わす。）、（１０）、上記一般式〔化９〕で表される複素環のＮにメタロセン系化合物の置換基を有する置換基を導入した置換シアニン系化合物が下記一般式〔化１０〕で表されるスピロ縮合環を導入した置換シアニン系化合物である上記（９）の光情報記録媒体、
【化１０】

（但し、Ｎ⁺ Ｘ^- 、Ｃ１、Ｃ２以外は各記号等は上記一般式〔化９〕のものと同じものを表わし、Ｎ⁺ Ｘ^- はＮ−Ｘと同じものを別の表示法で表わし、Ｃ１、Ｃ２は両方又はいずれか一方がスピロ縮合環を表わし、そのいずれか一方がスピロ縮合環を表わすときは他方はジメチルを表わし、Ｘ^- はハロゲン原子、ＰＦ₆ ^- 、過塩素酸、ホウフッ化水素酸、リン酸、ベンゼンスルホン酸、ＳｂＦ₆ ^- 、トルエンスルホン酸、アルキルスルホン酸、ベンゼンカルボン酸、アルキルカルボン酸、トリフルオロメチルカルボン酸、過ヨウ素酸、ＳＣＮ^- 、テトラフェニルホウ酸及びタングステン酸の陰イオン、及びジチオール錯体、メタロセン系化合物等の金属錯体を陰イオン化して得られる陰イオンの群のなかから選択される陰イオンを表わす。）、（１１）、Ｒ₁ 及びＲ₂ はＣ_n Ｈ_2n、ｎは０〜８であり、同じでも異なってもよい上記（９）又は（１０）の光情報記録媒体、（１２）、Ｒ₁ −Ｍ₁ 及びＲ₂ −Ｍ₂ の少なくとも一方は分岐した側鎖を有する上記（１０）又は（１１）の光情報記録媒体、（１３）、Ｘ^- がＣｌＯ₄ ^- 、ＰＦ₆ ^- 、ＢＦ₄ ^- 又はメタロセン系化合物を陰イオン化して得られる陰イオンである上記（９）ないし（１２）のいずれかの光情報記録媒体、（１４）、メタロセン系化合物が下記一般式〔化１５〕で表される化合物である上記（２）ないし（１３）のいずれかの光情報記録媒体、
【化１５】

（Ｍは金属原子を表わし、Ｒ¹ 、Ｒ² は置換基を表わす。）、（１５）、ＭはＦｅ、Ｔｉ、Ｖ、Ｍｎ、Ｃｒ、Ｃｏ、Ｎｉ、Ｍｏ、Ｒｕ、Ｒｈ、Ｚｒ、Ｌｕ、Ｗ、Ｏｓ又はＩｒであり、Ｒ¹ 、Ｒ² は水素原子、炭素数１〜１０のアルキル基若しくはそのハロゲン化アルキル基、炭素数２〜１０のアシル基、炭素数６〜１０のアリール基、炭素数７〜１０のアロイル基、炭素数１〜１０のアルデヒド基、炭素数１〜１０のアルコキシ基、炭素数０〜１０のアミノ基、ヒドロキシル基、ハロゲン原子、ホウ酸基、ベンゾイル基、低級アルケニル基を含む炭素数２〜１０のアルケニ基、ヒドロキシアルキル基、アセチル基、脂肪族環状基又はアルコキシカルボニル基を表わし（それぞれは置換基を有してもよい。）、同一で異なってもよい上記（１４）の光情報記録媒体、（１６）、光干渉層が３５０ｎｍ前後〜８３０ｎｍの波長領域から選ばれたレーザー光により記録及び再生が可能である上記（１）ないし（１５）のいずれかの光情報記録媒体を提供するものである。
【０００８】
本発明において、光干渉層は３５０ｎｍ前後〜８３０ｎｍの波長領域から選ばれたレーザー光により記録及び再生が可能になるように形成されるが、これはこの光干渉層を約６４０ｎｍ〜６８０ｎｍの範囲のレーザー光に対してはＤＶＤ−Ｒ用、約７７０ｎｍ〜８３０ｎｍの範囲のレーザー光に対してはＣＤ−Ｒ用に使用可能にすることにある。また、将来的には、４００ｎｍ前後のレーザー対応のいわゆるブルーレーザー対応のメディアに対しても応用可能となる。
上記光干渉層とは、有機色素材料からなる色素層その他の有機材料あるいは無機材料からなる層から構成され、レーザー光照射でピット形成可能な単一層又は複数層の色素層を含む記録層や、この記録層以外に光情報記録媒体の光学的物性を調整する目的で屈折率、膜厚を調整した例えば樹脂材料からなるエンハンス層、さらには基板と色素層、色素層が複数の場合にはその間に設ける中間層等も含まれ、これらを総称したものである。なお、「有機色素材料からなる色素層」は「有機材料を含有する記録層」としてもよく、有機材料は有機色素材料に限らず着色してない材料を用いてもよく、色素層も着色していなくてもよいが、便宜上この着色してない場合を含めて色素層ということがある。
【０００９】
上記の色素層に含有させる、ポリメチン系化合物に有機金属錯体の置換基を有する置換基を導入した置換ポリメチン系化合物としては、そのポリメチン系化合物がポリメチン系色素としても知られているように、カチオン成分とアニオン成分の結合された化合物であるが、そのカチオン成分にその有機金属錯体の置換基を有する置換基を導入した化合物は知られていない。この場合にはアニオン成分は従来使用されているものは有機金属錯体のアニオンを含めて使用できるが、アニオン成分には例えばシアニン系色素の場合には耐光性を向上させるためにクエンチャーアニオンとして使用されている有機金属錯体のアニオンもあるので、アニオン成分にのみその有機金属錯体の置換基を有する置換基を導入する場合にはその有機金属錯体はメタロセン系化合物に限定される。
有機金属錯体の置換基を有する置換基の分子量はこれを導入するポリメチン系化合物の分子量より小さくすることが好ましいが、これは溶剤に対する溶解性や吸光度等を損なわない等のためにも好ましく、特にメタロセン系化合物は有機金属錯体の内でも分子量が比較的小さいので好ましい。
【００１０】
ポリメチン系化合物としては、上記一般式〔１〕で表されるシアニン系化合物、上記一般式〔化２〕で表されるメロシアニン系化合物が挙げられ、これらに属する少なくとも１種を用いることが好ましいが、シアニン系化合物としては上記一般式〔化７〕で表される化合物がより好ましい。これらの一般式〔化１〕、〔化２〕、〔化７〕において、メタロセン系化合物の置換基で置換した置換基を導入した置換シアニン系化合物が好ましいが、その置換位置は置換できる位置であればいずれでもよく、その数も種類も問わないが、上記一般式〔化８〕、〔化９〕の置換シアニン系化合物が挙げられる。
【００１１】
上記一般式〔化８〕に属する置換シアニン系化合物としては、下記一般式〔化１１〕、下記一般式〔化１２〕で表わされる化合物が挙げられる。
【化１１】

【化１２】

（但し、Ｒ₁ 、Ｒ₂ 、Ｘ^- 及びｎは上記一般式〔化８〕のものと同じものを表わし、ＭはＦｅ、Ｎｉ又はＣｏの金属を表わす。）
上記化合物のほか、上記〔化１２〕においてそのアニオン成分の代わりに上記〔化１１〕におけるアニオン成分を用いた化合物、上記〔化１１〕においてそのアニオン成分のまま又はそのの代わりにＸ^- を用い、片方のナフタレン環にメタロセン系化合物の置換基を有する化合物も例示できる。
これらの化合物は耐光性を改善できる効果が得られるとともに、上記〔化１１〕の化合物はシアニン系化合物のカチオン成分を適宜変えて使用できるメリットがある。
【００１２】
また、上記一般式〔化９〕に属する置換シアニン系化合物としては、下記一般式〔化１３〕、下記一般式〔１４〕で表わされる化合物が挙げられる。
【化１３】

【化１４】

（但し、ｎは０、１又は２を表わし、ｍ、ｍ’は１〜８であって同一でも異なってもよく、Ｘ^- はＣｌＯ₄ ^- 、ＰＦ₆ ^- 、ＢＦ₄ ^- 又はＳｂＦ₆ ^- を表わし、ＭはＦｅ、Ｎｉ又はＣｏの金属を表わし、Ｒ₅ 、Ｒ₆ は低級アルキル基等のアルキル基を表わし、同一でも異なってもよく、Ｒ₇ 、Ｒ₈ は水素原子又は低級アルキル基等のアルキル基を表わし、同一でも異なってもよい。）
上記〔化１３〕、〔化１４〕の化合物は、耐光性を改善することができるほかに、上記〔化１３〕の化合物はｍ、ｍ’が１〜８であることによりアルキル基の長さを最適化することにより、溶剤に対する溶解性を向上させることができ、特にｎが２の場合のペンタメチン（ＣＤ−Ｒ用色素）、ＭがＦｅである場合にはその溶解性の向上効果が大きい。また、上記〔１４〕の化合物は、分岐構造のアルキル鎖を持たせることでレーザー光を照射したときの分解性を向上させることができ、記録層に用いたときの感度を改善することができ、特にｎが１の場合のトリメチン（ＤＶＤ−Ｒ用色素）、ＭがＦｅである場合にはその分解性の向上効果が大きい。
【００１３】
上記一般式〔化９〕に属する上記一般式〔化１０〕に属する化合物は、スピロ縮合環を導入した置換シアニン系化合物（スピロ縮合環導入型置換シアニン系化合物）である。スピロ縮合環とは、１個の炭素を共有する二環性化合物スピランにおいては分子不斉による立体異性体の光学活性体を生じるが、シアニン系化合物の環状基を一方にし、その環状基を構成する炭素を他方の環状基を構成する炭素として共有するその他方の環状基（スピロ環構造体）のことを言い、このスピロ縮合環導入型シアニン系化合物は分子不斉による立体異性体の光学活性体である。
上記一般式〔化１０〕中、Ｃ１、Ｃ２は、そのいずれか一方がスピロ縮合環を表わし、他方がジメチルを表わす場合がレーザー光に対する感度等の点で好ましいが、その両方がスピロ縮合環を表わす場合でもよく、そのスピロ縮合環は同種又は異種のいずれでもよい。スピロ縮合環としては、６員環（Ｃ（炭素）が６個の環状体、以下これに準じる）、５員環、３員環が挙げられる。また、上記一般式〔化１〕、〔化２〕、〔化７〕〜〔化９〕においても同様であるが、ｎが０の場合はモノメチン系シアニン色素、ｎが１の場合はトリメチン系シアニン色素、ｎが２の場合はペンタメチン系シアニン色素であり、ＤＶＤ−Ｒ用、ＣＤ−Ｒ用等の色素として単独又は他の色素と併用して用いることができるが、特にペンタメチン系シアニン色素はＣＤ−Ｒ用の色素として、また、トリメチン系シアニン色素等はＤＶＤ−Ｒ用の色素として好ましく用いられる。
【００１４】
スピロ縮合環導入型シアニン系化合物は、上記した分子不斉による立体異性体の構造により、例えばこの一般式〔化１０〕で表される化合物の場合には、両方にスピロ縮合環を導入した場合は左右対称構造とすることができ、その場合には、この一般式〔化１０〕中、Ｒ₁ −Ｍ₁ 、Ｒ₂ −Ｍ₂ は同種であり、本発明はこの場合も含むが、このＲ₁ −Ｍ₁ 、Ｒ₂ −Ｍ₂ が異種である場合は勿論のこと、これが同種であっても片方にのみスピロ縮合環を導入した場合には左右非対称構造とすることができる。このような左右非対称型構造のスピロ縮合環導入型シアニン系化合物は、溶剤に対する溶解性及び成膜性の点で好ましい。
一般式〔化１０〕中のＲ₁ −Ｍ₁ 、Ｒ₂ −Ｍ₂ については具体的には、上記〔化１３〕、〔化１４〕の化合物における対応する置換基が挙げられ、それぞれ上記したように溶剤に対する溶解性を向上させ、レーザー光に対する分解性を向上させることができ、特に前者に対してはペンタメチン（ＣＤ−Ｒ用色素）、ＭがＦｅである場合、後者に対してはトリメチン（ＤＶＤ−Ｒ用色素）、ＭがＦｅである場合にそれぞれの向上効果を大きくすることができる。なお、一般式〔化１０〕において、Ｒ₃ 、Ｒ₄ 、Ｎ⁺ 置換基、Ｎ置換基、Ｘ^- について、上述した上記〔化１１〕、〔化１２〕の化合物及びこれらの類似物の対応する置換基を有する具体的化合物も挙げることができ、同様のメリットを有することができる。
【００１５】
上記のスピロ縮合環導入型シアニン系化合物を含有する記録層においては感度、すなわち与えられたエネルギーに対する反応性、例えば熱分解性が高くなるが、その理由は、例えば上記一般式〔化１０〕の化合物の場合には、分子構造として不安定なスピロ環構造体をシアニン色素の末端複素環に直接導入することで上記した分子不斉による立体異性体の構造を生じさせ、シアニン分子全体を不安定構造（非平面構造）にすることができることにより、例えばスピロ縮合環の導入による立体化により分子に歪みが生じ、熱等に対して分解等の変化を起こし易くなるためと考えられる。
上記一般式〔化１０〕に属する化合物について、スピロ縮合環が６員環の場合のみならず、その他の上記した環状基の場合も、分子シミュレーションにおける構造最適化計算を行なって、スピロ環構造体と分子の安定性の関係を求めたところ、上記したスピロ縮合環導入型シアニン色素を含有する記録層に与えられたエネルギーに対する反応性の特性は、スピロ縮合環が６員環の場合等についてこれまでに行った実際の特性評価とは一致するものであった。
【００１６】
このように、有機色素についてその分子構造の点から熱分解性を高め、その熱分解温度を低下させてレーザー光に対する反応性を高め、いわゆる感度を向上させることができると、ＣＤ−Ｒ、ＤＶＤ−Ｒ等の色素層にこの有機色素を用いることにより、レーザー光による記録の感度をレーザー光に対する反射率、すなわち再生の感度に影響を与えることなく向上させることができる。このことは、レーザー光に対する反射率が優れるシアニン色素についてスピロ縮合環を導入すれば、その反射率を損なわずに記録の感度を向上させることができ易くなり、高速記録材料の選択幅を広げることができる。これに対し、従来の有機色素を用いた光情報記録媒体においては、高速記録に対応した記録材料を考える場合には記録波長において、より良い吸収を持つ材料を選択することになるが、レーザー波長域での光吸収量を向上させるために吸収のピーク（λ_max ) が長波長側の材料を選択する場合には、再生波長において吸収が増大し反射率が確保できなくなり、再生の感度を向上させることができないという問題を生じる。本発明はこの問題を容易に解決することができるというメリットもある。
なお、上記一般式〔化１０〕に属する化合物であって、Ｒ₁ −Ｍ₁ 、Ｒ₂ −Ｍ₂ におけるＭ₁ 、Ｍ₂ が水素原子である具体的化合物については、その製造及び同定が行われている。
【００１７】
上記一般式〔化１〕、〔化２〕、〔化７〕〜〔化１０〕において、それぞれの一般式の説明の際に、メタロセン系化合物の置換基を有する置換基については述べたものもあるが、「メタロセン系化合物の置換基を有する置換基」とはメタロセン系化合物の置換基そのものでもよく、いずれにしてもそのメタロセン系化合物としては、上記一般式〔化１５〕で表される化合物を挙げることができる。この一般式中、Ｍは金属、特に上記のＦｅ等の金属を表わすが、その内でも常温ではいうまでもなく、レーザーを照射して比較的高温になった場合にも、熱的に安定なフェロセン（Ｆｅビスシクロベンタジエニル錯体）、ルテノセン、オスモセン、ニッケロセン及びチタノセン等や、これらの誘導体はレーザー照射により記録した場合に、形成したピット形状の均一化が図られ、ピットエッジ形状がピット中心に対して前後対称となり、非常に良好であるだけでなく、各化合物を含有する記録層を有する光情報記録媒体の耐久性の点からも非常に良好である。また、Ｒ¹ 、Ｒ² が具体的なメタロセン系化合物としては例えば金属がＦｅの場合には、下記〔化１６〕のそれぞれのフェロセン系化合物を挙げることができる。その内でも、アルキル基、アシル基、ベンゾイル基置換のメタロセン系化合物は溶解性、耐昇華性の観点からも好ましい。なお、これらのフェロセン系化合物を置換基とするときは、その置換位置はフェロセン核そのものであってもよく、その置換基であってもよく、その他のメタロセン系化合物においても同様である。
【００１８】
【化１６】

【００１９】
メタロセン系化合物の置換基を有する置換基で置換した化合物を得るには、例えばそのシアニン系化合物としては、例えば下記反応式〔化１７〕、〔化１８〕によって製造することができるが、上記一般式〔化１〕、〔化２〕、〔化７〕〜〔化１０〕のそれぞれに属する化合物もこれに準じて製造することができる。
【００２０】
【化１７】

【００２１】
【化１８】

【００２２】
反応式中、（ａ）、（ｂ）は公知の方法により製造でき、これらから加熱により（ｃ）を製造することができ、この（ｃ）とジフェニルホルムアミジンとから加熱により（ｄ）を製造することができ、この（ｄ）をＡｃ₂ Ｏ（無水酢酸）によりアセチル化して（ｅ）を製造し、ついで、トリエチルアミン存在下に（ａ）を反応させて（ｆ）を製造することができ、最後に所望のアニオン成分にするために例えばＨＰＦ₆ によりアニオン成分の種類の変換を行って目的物（ｇ）を得ることができる。この反応式から、（ａ）と（ｂ）とから（ｃ）〜（ｇ）を既存物質を用いて製造できることがわかるが、（ａ）を再度反応させて（ｆ）を得る際に、その（ａ）の代わりに（ｃ）を用いれば、（ｆ）においてメチン鎖の両側のＮ置換基を同じにすることができ、その際（ｃ）の代わりに、（ｂ）のヨウ化アルキル基のアルキル基の長さを変えたフェロセン誘導体と（ａ）を用いて得られるこの（ｃ）に対応する化合物を用いれば、（ｆ）においてメチン鎖の両側のＮ置換基のアルキル基の長さが異なる化合物が得られる。また、同様に、（ｃ）の代わりに、（ｂ）のヨウ化アルキル基のアルキル基に分岐したアルキル基を用いたフェロセン誘導体と（ａ）を用いて得られたこの（ｃ）に対応する化合物を用いれば、（ｆ）においてメチン鎖の両側のＮ置換基にアルキル基が分岐した化合物が得られる。また、（ａ）〜（ｇ）において、芳香環に例えば（ｂ）のようなハロゲン化アルキル基置換フェロセンを反応させる等によりフェロセン置換基を有する置換基あるいはフェロセンの置換基を導入することができる。その際、（ｂ）成分としてハロゲン化アルキルを用いれば（ｆ）、（ｇ）はメチン鎖の両側のＮ置換基をアルキル基とすることができる。また、２度反応させる（ａ）成分としてその一方又は両方にスピロ縮合環を有するものを用いれば、（ｆ）、（ｇ）においてメチン鎖の一方又は両側にスピロ縮合環を有する化合物を得ることができる。また、（ｇ）を得る際に、ＨＰＦ₆ の代わりにフェロセンの置換基を有する置換基を導入したアニオン成分の化合物を用いることにより、（ｇ）においてフェロセンの置換基を有する置換基を導入したアニオン成分を有する化合物を得ることができる。このように、上記の各反応を利用してフェロセンの置換基を有する置換基をメチン鎖の両側のＮ置換基の少なくとも一方、カチオン成分のメチン鎖の両側の芳香環の少なくとも一方、あるいはアニオン成分に導入することができ、これらを組み合わせた多種多様な化合物を得ることができる。
【００２３】
上記に準じてメタロセンの置換基を有する置換基で置換できるシアニン系化合物あるいはメロシアニン系化合物としては下記〔化１９〕〜〔化２４〕の化合物も挙げることができる。
【化１９】

【００２４】
【化２０】

【００２５】
【化２１】

【００２６】
【化２２】

【００２７】
【化２３】

【００２８】
【化２４】

ここで、例えば〔化１９〕の第１番目の化合物については、メチン鎖の両側の少なくとも一方のＮ置換基のエチル基にメタロセン系化合物の置換基を有する場合、メチン鎖の両側の少なくとも一方のベンゼン環にメタロセン系化合物の置換基又はその置換基を有する置換基を有する場合、Ｂｒの代わりにメタロセン系化合物の置換基又はその置換基を有する置換基で置換したアニオン成分を有する場合の少なくとも１つの場合が挙げられる。その他の化合物についてもこれに準じる。
具体的には、後述の実施例に示すもののほかに下記〔化２５〕〜〔化３５〕を挙げることができる。
【００２９】
【化２５】

【００３０】
【化２６】

【００３１】
【化２７】

【００３２】
【化２８】

【００３３】
【化２９】

【００３４】
【化３０】

【００３５】
【化３１】

【００３６】
【化３２】

【００３７】
【化３３】

【００３８】
【化３４】

【００３９】
【化３５】

【００４０】
なお、上記化合物についてトリメチンのものをペンタメチンにし、ペンタメチンのものをトリメチンにしたものも挙げられる。
本発明における光干渉層には、上記一般式〔化１〕、〔化２〕、〔化７〕〜〔化１０〕、上記化合物〔化１１〕〜〔化１４〕、上記反応式〔化１７〕、〔化１８〕で得られる（ｆ）、（ｇ）やこれに準じる他の化合物及びこの反応式に準じて得られる上記〔化１９〕〜〔化２４〕の化合物にメタロセン系化合物の置換基を有する置換基を導入したそれぞれに属する化合物とともに、それぞれのメタロセン系化合物の置換基を有する置換基を導入した化合物を除く、すなわちその置換基の代わりに水素原子等の置換基を有する化合物その他の化合物あるいは色素の１種又は複数種を同一の色素層あるいは他の色素層を設けて併用してもよく、全化合物中あるいは全色素中メタロセン系化合物の置換基を有する置換基を導入した化合物を少なくとも５０重量％、すなわち５０重量％以上使用すると、レーザーによる記録の感度が向上する等メタロセン系化合物を導入した化合物あるいは色素を使用することによる上述の効果をより良く奏することができる。この際、メチン鎖の数が同じもの同士混合すれば、例えばトリメチン鎖の化合物の場合にはＤＶＤ−Ｒ用、ペンタメチン鎖の化合物の場合にはＣＤ−Ｒ用に好ましいがこれに限らない。
上記のその他の化合物あるいは色素としては、下記一般式〔化３６〕で表されるシアニン化合物（シアニン色素）を全化合物中あるいは全色素中多くても５０重量％、すなわち５０重量％以下使用してもよい。
【００４１】
【化３６】

〔ただし、Ａは下記一般式〔化３７〕ないし〔化３９〕のいずれかを表わし、
【化３７】

、
【化３８】

、
【化３９】

、
Ａ’は下記一般式〔化４０〕ないし〔化４２〕のいずれかを表わし、
【化４０】

、
【化４１】

、
【化４２】

、
ＡとＡ’は同種であっても異種であってもよく（ただし、Ｄ₁ 、Ｄ₂ はそれぞれ水素原子、アルキル基、アルコキシル基、水酸基、ハロゲン原子、カルボキシル基、アルコキシカルボニル基、アルキルカルボキシル基、アルキルヒドロキシル基、アラルキル基、アルケニル基、アルキルアミド基、アルキルアミノ基、アルキルスルホンアミド基、アルキルカルバモイル基、アルキルスルファモイル基、アルキルスルホニル基、フェニル基、シアノ基、エステル基、ニトロ基、アシル基、アリル基、アリール基、アリールオキシ基、アルキルチオ基、アリールチオ基、フェニルアゾ基、ピリジノアゾ基、アルキルカルボニルアミノ基、スルホンアミド基、アミノ基、アルキルスルホン基、チオシアノ基、メルカプト基、クロロスルホン基、アルキルアゾメチン基、アルキルアミノスルホン基、ビニル基及びスルホン基の群のなかから選択される置換基を表わし、同種であっても異種であってもよく、ｐ、ｑは置換基の数であってそれぞれ１又は複数の整数を表わす。）、Ｒ₃ 、Ｒ₄ は置換又は非置換のアルキル基、カルボキシル基、アルコキシカルボニル基、アルキルカルボキシル基、アルコキシル基、アルキルヒドロキシル基、アラルキル基、アルケニル基、アルキルアミド基、アルキルアミノ基、アルキルスルホンアミド基、アルキルカルバモイル基、アルキルスルファモイル基、水酸基、ハロゲン原子、アルキルアルコキシル基、ハロゲン化アルキル基、アルキルスルホニル基、金属イオン若しくはアルキル基と結合したアルキルカルボキシル基若しくはアルキルスルホリニル基、フェニル基、ベンジル基、アルキルフェニル基及びフェノキシアルキル基（ベンゼン環部分及び／又はアルキル部分の水素原子をアルキル基、カルボキシル基、水酸基、ハロゲン原子等の金属イオン以外の置換基で置換してもよく、前記フェニル基、ベンジル基、アルキルフェニル基の該当部分についても同様である。）の群から選択される置換基を表わし、同種でも異種でもよく、Ｘ^- 、ｎは上記一般式〔化１〕のものと同じものを表わす。〕
上記一般式〔化３６〕においてＡが上記一般式〔化３７〕〜〔化３９〕の一般式から任意に選択され、Ａ’が上記一般式〔化４０〕〜〔化４２〕の一般式から任意に選択され、両者のその選択したそれぞれの個々の全ての組み合わせの化合物が挙げられる。例えば一般式〔化３７〕と一般式〔化４０〕〜〔化４２〕のそれぞれとの組み合わせが挙げられるが、その他の一般式〔化３８〕、〔化３９〕のそれぞれについても同様である。Ａ、Ａ’の置換基（Ｄ₁ ）ｐ、（Ｄ₂ ）ｑのｐ、ｑは少なくとも１であるが、複数の整数、すなわち２以上の整数である。
なお、色素の合成法としては、Ｔｈｅ Ｃｈｅｍｉｓｔｒｙ ｏｆ Ｓｙｎｔｈｅｔｉｃ Ｄｙｅｓ Ｖｏｌ１４に記載されている方法を利用できる。
【００４２】
上記一般式〔化１〕、〔化２〕、〔化７〕〜〔化１０〕、上記〔化１１〕〜〔化１４〕の化合物において、特に上記一般式〔化７〕〜〔化１０〕、上記〔化１１〕〜〔化１４〕及び上記反応式〔化１７〕、〔化１８〕で得られる（ｆ）、（ｇ）やこれに準じる他の化合物、この反応式に準じて得られる上記〔化１９〕〜〔化２４〕の化合物、上記〔化２５〕〜〔化３５〕や後述の実施例で用いる化合物においてそれぞれに属する化合物を単独で用いる場合や、さらにそれぞれメタロセン系化合物の置換基を有する置換基を導入した化合物を除くその他の化合物あるいは色素の１種又は複数種を同一の色素層あるいは他の色素層を設けて併用する場合に、これらの化合物あるいは色素のみで用いてもよいが、耐光性を向上させるために、光安定化剤を色素層に含有させ、あるいは他の層に含有させて用いてもよい。
このような光安定化剤としては金属錯体が挙げられ、この金属錯体としては、下記一般式〔化４３〕で表わされる化合物を挙げることができる。
【００４３】
【化４３】

〔ただし、Ｒ¹ 、Ｒ² はそれぞれハロゲン原子、フェニル基、アルキル基、シアノ基、チオアルキル基、アルキルスルホニル基、ｒ、ｓは１〜４の整数を表わし、Ｒ⁴ はアルキル基、ＹはＮ又はＰ、ＭはＣｕ、Ｃｏ又はＮｉ等の金属を表わす。〕
【００４４】
上記一般式〔化４１〕に属する具体的化合物としては、下記〔化４４〕、〔化４５〕の化合物を挙げることができる。
【００４５】
【化４４】

【００４６】
【化４５】

【００４７】
また、光安定化剤としてはアミニウム系及びジイモニウム系安定化剤を挙げることができる。具体的化合物としては、下記〔化４６〕、〔化４７〕で表される化合物を挙げることができる。
これらの光安定化剤は少なくとも１種、すなわち単独又は複数併用することができる。
【００４８】
【化４６】

【００４９】
【化４７】

【００５０】
本発明の光情報記録媒体を製造するには、上記有機金属錯体の置換基を有する置換基を導入したポリメチン系化合物、例えば上記一般式〔化１〕で示される化合物、あるいはこれとその他のシアニン系化合物等を溶解した混合色素（前者を５０重量％以上混合することが好ましい）、あるいはこれらのそれぞれに上記一般式〔化４３〕で示される金属錯体その他の光安定化剤を溶解した溶液を調製し、透光性の基板に塗布する。これらの色素溶液にはクロロホルム、ジクロロエタン、フッ素化アルコール等のフッ素系溶剤、メチルエチルケトン、ジメチルホルムアミド、メタノール、トルエン、シクロヘキサノン、アセチルアセトン、ジアセトンアルコール、メチルセロソルブ等のセロソルブ類、ジオキサン等を用いることができ、これらは複数を併用してもよい。これらの場合のシアニン色素の混合割合は１重量％〜１０重量％が好ましい。
また、本発明に用いられる基板には、ガラスや、エポキシ樹脂、メタクリル樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリ塩化ビニル樹脂、ポリオレフィン樹脂等のプラスチックスが例示される。この基板にはトラック溝あるいはピットが形成されていてもよく、また、アドレス信号に必要な信号を有するものでもよい。
また、上記シアニン色素溶液を基板に塗布するにはスピンコート法を用いることが好ましい。
また、本発明における光干渉層には上記の金属錯体以外の一重項酸素クエンチャー、光吸収剤、ラジカルスカベンジャー（捕捉剤）等の他の化合物を含んでもよい。
【００５１】
上記の光干渉層のほかに反射層を設けてもよく、また、その反射層の上に保護層、さらには基板面（レーザー光の入射側）に保護層を有する場合でよい。
反射層としては、蒸着、スパッタリング等により形成したＡｕ、Ａｌ、Ａｇ、Ｃｕ、Ｐｔ、これらの各々その他の合金、さらにはこれら以外の微量成分が添加された合金等の金属膜等の高反射率材料膜が挙げられ、保護層としては光情報記録媒体の保護と耐候性の向上等の目的で紫外線硬化型樹脂等の放射線硬化型樹脂の溶液をスピンコート法等により塗布し、放射線硬化させた塗布層が挙げられる。
【００５２】
このようにして基板の上に色素層を含む光干渉層、反射層を設け、さらには保護層などが設けられた光ディスクが得られる。その光干渉層を少なくとも有した他の同様な構成あるいは別の構成の光ディスクを貼り合わせたり、あるいは基板そのものを対向させて貼り合わせたりしてもよい。
この貼り合わせのための材料、方法としては、紫外線硬化樹脂、カチオン性硬化樹脂、両面粘着シート、ホットメルト法、スピンコート法、ディスペンス法（押し出し法）、スクリーン印刷法、ロールコート方式等が用いられる。
【００５３】
【発明の実施の形態】
詳細は以下の実施例により説明するが、トラックピッチ長が０．７４μｍ（０．８０μｍでもよい）で、ｗｏｂｂｌｅ信号のみを持つ（プレピット信号も併せ持ってもよい）ポリカーボネート基板を用い、光干渉層の記録層を、▲１▼ 上記一般式〔化１１〕、〔化１２〕に属する化合物であって、ｎが１又は２、ＭがＦｅであり、Ｒ₁ 、Ｒ₂ が同種又は異種の低級アルキル基（炭素数５以下（少なくとも炭素数５）のアルキル基、以下同様）である化合物、▲２▼ 上記一般式〔化１３〕に属する化合物であって、ｎが１又は２であり、ｍ、ｍ’が１〜５で同一又は異なり、Ｃ_m Ｈ_2m 、Ｃ_m'Ｈ_2m' が同種又は異種の低級アルキレン基である化合物、又はその化合物においてＣ_m Ｈ_2m 、Ｃ_m'Ｈ_2m' のいずれか一方はその末端のフェロセン基が水素原子である低級アルキル基である化合物、▲３▼ 上記一般式〔化１４〕に属する化合物であって、ｎが１又は２であり、Ｒ₇ 、Ｒ₈ は水素原子であり、Ｒ₅ 、Ｒ₆ は同一又は異なる低級アルキル基であり、ｍ、ｍ’が５以下（少なくとも５）で同一又は異なり、Ｃ_m Ｈ_2m 、Ｃ_m'Ｈ_2m' が同種又は異種の低級アルキレン基である化合物、又はその化合物においてＣ_m Ｈ_2m 、Ｃ_m'Ｈ_2m' のいずれか一方はその末端のフェロセン基が水素原子である低級アルキル基であり、フェロセン基を除くＮ置換基の炭素数が２〜８である化合物、▲４▼ 上記一般式〔化１０〕に属する化合物であって、Ｃ１が脂環基（６員環、５員環、３員環等）、Ｃ２がＣ１と同種又は異種の脂環基又はジメチルであり、そのほかは、（ａ）上記▲１▼と同様の化合物（Ｒ₁ −Ｍ₁ 、Ｒ₂ −Ｍ₂ はそれぞれ上記一般式〔化１１〕、〔化１２〕のＲ₁ 、Ｒ₂ に該当し、Ａ１、Ａ２はナフタレン環、Ｒ₃ は水素原子、Ｒ₄ は水素原子又はフェロセン基、Ｘ^- はＰＦ₆ ^- 又は一般式〔化１１〕のアニオン成分である）、（ｂ）上記▲２▼と同様の化合物（Ｒ₁ −Ｍ₁ 、Ｒ₂ −Ｍ₂ はそれぞれ上記一般式〔化１３〕のＮ⁺ 置換基、Ｎ置換基に該当し、Ａ１、Ａ２はナフタレン環、Ｒ₃ 、Ｒ₄ は水素原子である）、（ｃ）上記▲３▼と同様の化合物（Ｒ₁ −Ｍ₁ 、Ｒ₂ −Ｍ₂ はそれぞれ上記一般式〔化１４〕のＮ⁺ 置換基、Ｎ置換基に該当し、Ａ１、Ａ２はナフタレン環、Ｒ₃ 、Ｒ₄ は水素原子である）であり、これら▲１▼〜▲４▼においてＸ^- が上記一般式〔化１１〕のアニオン成分、ＣｌＯ₄ ^- 、ＰＦ₆ ^- 又はＢＦ₄ ^- である置換シアニン系化合物について、それぞれの化合物（色素）の溶液、その各化合物とアミニウム系光安定化剤を加えた溶液、また、これらにさらに、▲５▼ 上記一般式〔化３８〕と一般式〔化４１〕の組み合わせからなる上記一般式〔化３６〕の化合物、その中で、▲６▼ 特にＤ₁ 、Ｄ₂ が共に水素である化合物、▲７▼ Ｒ₃ 、Ｒ₄ が同種又は異種であって、炭素数１〜４等の低級アルキル基である化合物、さらにその中でも▲７▼ 特にＸ^- がＣｌＯ₄ ^- 、ＰＦ₆ ^- 又はＢＦ₄ ^- の陰イオンである化合物のそれぞれのインドレニン系のシアニン色素（ｎは▲１▼〜▲４▼の各化合物のｎと一致させることが好ましい）について、これらの▲５▼〜▲７▼の各々に属する色素を加え、上記の▲１▼〜▲４▼の各々に属する色素を色素全体の５０〜１００重量％比率を占める色素溶液を調製し、これらの各々の溶液を用いてスピンコート法により乾燥膜厚が５０〜１５０ｎｍとなるように形成する。
その後、スパッタリングによるＡｕ又はＡｌの反射層を設け、その上に紫外線硬化樹脂からなる保護層をスピンコート法により形成し、さらにポリカーボネート基板をスピンコート法による紫外線硬化樹脂からなる接着剤層により貼り合わせ、貼り合わせ型光ディスクを得る。
このようにして得られる光ディスクは耐光性に優れるとともに、例えば６６０ｎｍ〜６８０ｎｍのレーザー光を照射して記録を行うと、例えば上記一般式〔化１０〕に属するスピロ縮合環を導入したトリメチン系シアニン化合物を使用したときは、感度、変調度、ジッター等の特性を向上し、上記一般式〔化１０〕に属する化合物を使用せず、その代わりに上記の一般式〔化３６〕で表されるトリメチン系シアニン化合物を使用したこと以外は同様にして得られた光ディスクに比べて、記録パワーをより小さくすることができる。
上記はスピロ縮合環を導入したトリメチン系シアニン化合物を使用したが、ＣＤ−Ｒ用途の場合、上記一般式〔化１０〕に属するスピロ縮合環を導入したペンタメチン系シアニン化合物についても、上記に準じて使用することができ、上記に準じた結果を得ることができる。
【００５４】
【実施例】
次に本発明の実施例を説明する。
実施例１
表面に幅０．５μｍ、深さ２００ｎｍ、ピッチ１．６μｍのスパイラル状のグルーブが形成された厚さ１．２ｍｍ、外径（直径）１２０ｍｍφのポリカーボネートからなる透明な基板を射出成形法により成形した。
次に、下記〔化４８〕のペンタメチン系の置換シアニン系化合物０．３ｇをジアセトンアルコール１０ｍｌに溶解し、その溶液を上記の基板の表面にスピンコート法（回転数２０００ｒｐｍ）で塗布し、膜厚７０ｎｍの感光記録層からなる光干渉層を形成した。
【００５５】
【化４８】

【００５６】
この光干渉層について可視紫外分光光度計／Ｕ−４０００（（株）日立製作所製）による吸収スペクトル〔吸光度（Ａｂｓ）の波長４００〜８００ｎｍ範囲の波長依存性〕を測定したところ、図１に示す吸収スペクトル（吸光強度（Ａｂｓｏｒｂａｎｃｅ）の波長（Ｗａｖｅｌｅｎｇｔｈ）（ｎｍ）に対する変化）が得られた。
この光干渉層上にスパッタリング法により膜厚１００ｎｍのＡｇ膜を成膜し、反射層を形成した。
また、この反射層の上に紫外線硬化樹脂ＳＤ−２１１（大日本インキ化学工業社製）をスピンコートし、その塗膜に紫外線を照射して硬化させ、膜厚５μｍの保護膜を形成した。
【００５７】
このようにして作製された光ディスクに、ＮＡ（開口率（ｎｕｍｅｒｉｃａｌａｐｅｒｔｕｒｅ））＝０．５３、レーザー波長＝７８０ｎｍのＤＤＵ−１０００（パルステック社の記録機）により、線速１９．２ｍ／秒で記録したところ、レーザーパワーは２６ｍＷ（記録感度、以下同様）であった。その後、同装置を用いてレーザー出力を０．７ｍＷにして信号を再生し、反射率、変調度、エラーレート及びジッターを測定した結果、いずれも良好な値を示した。
また、耐光性試験をキセノンランプを用いて行ったところ、良好であった。
【００５８】
比較例１
上記実施例１において、上記〔化４８〕の化合物の代わりに、この化合物のＮ⁺ 置換基、Ｎ置換基をそれぞれ同種のメチル基（ＣＨ₃ ）にした化合物（ａ１）、さらにスピロ縮合環をジメチル基にした化合物（ｂ１）をそれぞれ用いたこと以外は同様にして光ディスクを作製し、実施例１と同様に測定したところ、レーザーパワーは順に２５．５ｍＷ、２８ｍＷであった。その後、同装置を用いてレーザー出力を０．７ｍＷにして信号を再生し、反射率、変調度、エラーレート及びジッターを測定した結果、いずれも良好な値を示した。
また、上記実施例１と同様に耐光性試験を行ったところ、化合物（ａ１）、化合物（ｂ１）を用いたものはいずれも十分なレベルに達しなかった。
なお、実施例１と同様に光干渉層について吸収スペクトルを測定したところ、化合物（ａ１）の場合には図２、化合物（ｂ１）の場合には図３に示す吸収スペクトルが得られた。
【００５９】
実施例２
表面に幅０．３２μｍ、深さ１００ｎｍ、ピッチ０．７４μｍのスパイラル状のグルーブが形成された厚さ１．２ｍｍ、外径（直径）１２０ｍｍφのポリカーボネートからなる透明な基板を射出成形法により成形した。
上記実施例１において、この基板を用いたこと、また、上記〔化４８〕の化合物の代わりに、下記〔化４９〕のトリメチン系の置換シアニン系化合物を用いたこと以外は同様にして光干渉層、反射層及び保護膜を形成し、さらにこの基板の保護膜及びその保護膜が形成されていない光干渉層の上に紫外線硬化樹脂ＳＤ−３１８（大日本インキ化学工業社製）を滴下した後、上記と同様に成形した他の基板（同じ材質、寸法）をその上に置き、その間隙にスピンコート法により樹脂を均一に拡散させた後、再度紫外線を重ねた基板側から照射して硬化させ、当初からの基板の３２ｍｍφから１２０ｍｍφの領域に樹脂からなる厚さ２５μｍの接着層を形成することにより重ねた基板を貼り合わせ、貼り合わせ型の光ディスクを作製した。
このようにして作製された光ディスクに、ＮＡ（開口率（ｎｕｍｅｒｉｃａｌａｐｅｒｔｕｒｅ））＝０．６５、レーザー波長＝６６０ｎｍのＤＤＵ−１０００（パルステック社の記録機）により、線速３．５ｍ／秒で記録したところ、レーザーパワーは７．０ｍＷ（記録感度、以下同様）であった。その後、同装置を用いてレーザー出力を０．７ｍＷにして信号を再生し、反射率、変調度、エラーレート及びジッターを測定した結果、いずれも良好な値を示した。
また、上記実施例１と同様に耐光性試験を行ったところ良好であった。
なお、実施例１と同様に光干渉層について吸収スペクトルを測定したところ、図４に示す吸収スペクトルが得られた。
【００６０】
【化４９】

【００６１】
比較例２
上記実施例２において、上記〔化４９〕の化合物の代わりに、この化合物のＮ⁺ 置換基、Ｎ置換基をそれぞれメチル基（ＣＨ₃ ）とブチル基（Ｃ₄ Ｈ₉ ）にし、スピロ縮合環をジメチル基にした化合物（ｂ２）を用いたこと以外は同様にして貼り合わせ型の光ディスクを作製し、実施例１と同様に測定したところ、レーザーパワーは１１ｍＷであった。その後、同装置を用いてレーザー出力を０．７ｍＷにして信号を再生し、反射率、変調度、エラーレート及びジッターを測定した結果、いずれも良好な値を示した。
また、上記実施例１と同様に耐光性試験を行ったところ、実施例２のものに比べれば劣っていた。
なお、実施例１と同様に光干渉層について吸収スペクトルを測定したところ、図５にに示す吸収スペクトル（波線）が得られた。なお、同図中、実線はアセトン溶液中のものである。
【００６２】
【発明の効果】
本発明によれば、長期間に渡る保存時や繰り返し数の多い再生時の光劣化を防止でき、しかも記録及び再生の性能を損なわず、ヒートモードによる記録用化合物の光の吸収エネルギーそのものを減らしてその劣化を防止し、安定化ラジカルやクエンチャーその他の光安定化剤を添加しないでもよく、波長３５０ｎｍ前後〜８３０ｎｍの範囲から選択されるレーザー光に対して反応性がよく、記録感度が良好で、高速記録を行なうことができる光情報記録媒体を提供することができる。
また、溶剤に対する溶解性が良いとともに、成膜性が良い記録用化合物を用いることができる光情報記録媒体を提供することがてきる。
そして、ＣＲ−ＲやＤＶＤ−Ｒの従来の製造方法をその大きな変更なしにほぼ適用できる光情報記録媒体を提供することができる。
【図面の簡単な説明】
【図１】本発明に係わる上記一般式〔化１０〕に属する１例（上記〔化４８〕の化合物）の色素を含有する色素層からなる光干渉層の吸収スペクトルを示す図である。
【図２】その比較例の化合物の１例の色素を含有する色素層からなる光干渉層の吸収スペクトルを示す図である。
【図３】その比較例の化合物の他の１例の色素を含有する色素層からなる光干渉層の吸収スペクトルを示す図である。
【図４】本発明に係わる上記一般式〔化１０〕に属する他の１例（上記〔化４９〕の化合物）の色素を含有する色素層からなる光干渉層の吸収スペクトルを示す図である。
【図５】その比較例の化合物の他の１例の色素を含有する色素層からなる光干渉層の吸収スペクトルを示す図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a write-once type optical information recording medium in a heat mode capable of recording and reproducing with a laser beam of 350 to 830 nm, such as a CD-R and a DVD-R, wherein a recording layer has a substituent of a metallocene compound. The present invention relates to an optical information recording medium using a polymethine compound having a substituted substituent, and particularly having improved light resistance.
[0002]
[Prior art]
As means for recording and reproducing data such as characters, figures, and other images, video, and audio, for example, a pentamethine cyanine dye is contained as a recording material capable of recording and reproducing corresponding to a laser beam having a wavelength of 770 to 830 nm. An optical disk having a recording layer is known as a CD-R. A DVD-R (digital video disk) capable of high-density recording and reproduction with a red laser beam having a shorter wavelength than this laser beam, for example, 620 to 690 nm. A recordable or digital versatile disc-recordable) or the like has come to be used as a medium (optical information recording medium) that will replace the CD-R in the future era.
In such a CD-R or DVD-R, a pit is formed by thermal decomposition or the like in accordance with a signal of information to be recorded in response to a semiconductor laser having a wavelength of 600 to 800 nm. An organic dye compound which can be used for a recording layer is used to improve recording performance. In particular, cyanine dyes have advantages such as the ability to apply a high productivity method called spin coating, and the ability to form pits with sharp edges and dimensional stability with clear edges because of low thermal conductivity. In particular, they have attracted attention because they exhibit high absorption and reflection properties in the wavelength region of semiconductor lasers.
[0003]
However, these write-once optical information recording media such as CD-Rs and DVD-Rs generally use a cyanine dye as a recording layer, and this dye does not have sufficient light resistance. Easily deteriorated by sunlight, the recorded contents cannot be stored for a long period of time, or if the number of repetitions increases by irradiating a laser beam during playback, the deterioration easily occurs. However, there is a problem that the quality of the product may be easily damaged.
As a countermeasure, generally, a light stabilizer (quencher) such as a stabilizing radical is added to a main component of a cyanine dye having an absorption characteristic in a semiconductor oscillation wavelength region to cause the dye to fade. Improvement of the recording layer of the cyanine dye-containing layer of CD-R or DVD-R by changing singlet oxygen generated by sunlight to mild triplet oxygen by its oxidizing action has been performed. If the record of the contents is to be preserved for a long period of time, such as an encyclopedia, it is not enough, but the addition of such a light stabilizer reduces the characteristics of cyanine dyes that can be heated locally. This causes so-called thermal interference, which adversely affects the recording characteristics, and particularly causes deterioration of recording sensitivity and jitter.
In particular, in the future CD-R and DVD-R, in order to efficiently perform recording, it is necessary to enable high-speed recording even with an organic dye compound currently proposed as a dye for a recording layer. However, in order to perform such high-speed recording, it is necessary to irradiate the recording layer with a laser beam to perform writing at a high speed, and for that purpose, the scanning speed of the laser beam must be increased, As a result, the amount of energy per unit time required for the writing decreases, and if an attempt is made to form a good pit as a signal of the information to be written, a laser is irradiated to cover the reduction in the amount of energy. It is necessary to perform recording in which the pits are formed with so-called high power by increasing the power of the light. In such a case, the addition of the above-mentioned light stabilizer to the cyanine dye tends to cause the above-mentioned thermal interference and easily cause the above-mentioned problem. Therefore, a device for reducing the amount of the light stabilizer is required.
As an improvement measure, as disclosed in JP-A-4-25493, an anion of an organometallic complex having a light stabilizing action is added to a cation of a cyanine dye main body, and both are integrated by ionic bonding. One of the methods is to incorporate the light stabilizing component into the dye efficiently.
[0004]
[Patent Document 1]
JP-A-4-25493 (pp. 630-631)
[0005]
[Problems to be solved by the invention]
However, the molecules of the dye obtained by the integration become large, the ratio of the cyanine dye itself to the dye molecules becomes relatively small, and the molecular extinction coefficient decreases. Until now, it has been necessary for the anion molecule of the organometallic complex to be large in order to exhibit the light stabilizing effect better, but as the molecule becomes larger, the molecular extinction coefficient becomes more and more. It tends to decrease. As a result, it is still insufficient to solve the above-mentioned problems caused by thermal interference. In particular, the cyanine dye, azo dye or phthalocyanine compound currently used for the current CD-R and DVD-R cannot sufficiently cope with the above-mentioned high-speed recording. The unit of semiconductor laser that can form good pits even if the energy for writing is reduced in response to high-speed recording because the emission power of the semiconductor laser itself is limited, as well as possible. A so-called highly sensitive recording material having high reactivity per energy is demanded.
[0006]
A first object of the present invention is to provide an optical information recording medium that can prevent deterioration of photothermal interference during storage for a long period of time or during reproduction with a large number of repetitions, and that does not impair recording and reproduction performance.
A second object of the present invention is to provide an optical information recording medium which reduces the absorption energy itself of light of a recording compound in a heat mode to prevent its deterioration.
A third object of the present invention is to provide an optical information recording medium which does not require the addition of a stabilizing radical, a quencher or another light stabilizer.
A fourth object of the present invention is to provide an optical information recording medium using a recording compound having good reactivity to laser light selected from a wavelength range of about 350 nm to 830 nm.
A fifth object of the present invention is to provide an optical information recording medium having good recording sensitivity to laser light selected from a wavelength range of about 350 nm to 830 nm. A sixth object of the present invention is to provide an optical information recording medium capable of performing good high-speed recording with respect to laser light selected from a wavelength range of about 350 nm to 830 nm.
A seventh object of the present invention is to provide an optical information recording medium which can use a recording compound having good solubility in a solvent.
An eighth object of the present invention is to provide an optical information recording medium that can use a recording compound having good film-forming properties.
A ninth object of the present invention is to provide an optical information recording medium to which a conventional method of manufacturing a CR-R or a DVD-R can be substantially applied without major changes.
[0007]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, for example, a cyanine dye (metallocene-introduced cyanine dye) into which a substituent having a metallocene substituent has been introduced is excellent in light resistance and has a wavelength of about 350 nm. The dye layer containing the dye has high reactivity to 830 nm laser light, can form good pits, and the optical information recording medium provided with the light interference layer having the dye layer has the above object. It has been found that this has been achieved and the present invention has been made.
The present invention relates to (1) an optical information recording medium having an optical interference layer including a recording layer on a substrate, wherein the recording layer comprises a polymethine-based compound comprising a cation component and an anion component having a substituent having an organometallic complex substituent. It is an object of the present invention to provide an optical information recording medium containing a substituted polymethine compound introduced into the cation component of a compound.
The present invention also provides (2) the optical information recording medium of (1), wherein the molecular weight of the substituent having a substituent of the organometallic complex is smaller than the molecular weight of the polymethine compound; In the optical information recording medium of the above (1) or (2), which is a compound, (4), the optical information recording medium having an optical interference layer including a recording layer on a substrate, the recording layer has a substituent of a metallocene compound. An optical information recording medium containing a substituted polymethine compound in which a substituent having a cation component and an anion component is introduced into the anion component; (5) the polymethine compound is at least one of a cyanine compound and a merocyanine compound. The optical information recording medium according to any one of the above (1) to (4), (6), wherein the cyanine compound is a cyanine compound represented by the following general formula (1): An emission-based compound, a merocyanine-based compound is a merocyanine compound represented by the following general formula [2] The optical information recording medium of the above (5),
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(However, A is
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And B is
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Where A 'is
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And B ′ is
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In the case where each of A, B, A ′ and B ′ has an aromatic ring, it may have a halogen atom, an alkyl group, an alkoxy group or an aryl group as one or more substituents, and R is Represents an alkyl group or a sulfonated alkyl group, and may be the same or different from each other in each set of (A, B) and (A ', B'), and X represents an anion (see the above sulfonated group). Alkyl group may have X), N to which each X of A and A 'is bonded represents a cation, but X is bonded to each R of B and B' When N is a cation, it may be bonded to the cation. In this case, each N of A and A 'is a nonion to which only R is bonded, R' represents a hydrogen atom or a carboalkyl group, and R " Represents a hydrogen atom or an alkyl group; R ′, '' May be the same or different, may be interchanged, n of the polymethine chain of the central linking chain represents a positive integer including zero. )
(7) The optical information recording medium according to the above (5) or (6), wherein the cyanine compound is a cyanine compound represented by the following general formula [Formula 7]:
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(However, A1 and A2 represent a substituted or unsubstituted benzene ring or naphthalene ring, Y and Y 'represent C, -CH = CH-, O, S, Se or NH, which may be the same or different, When it can have a substituent, the substituent may be an alkyl group, and Y and Y ′ are both or any one of C and at least one C has a spiro fused ring, When only one has a spiro-fused ring, the other C substituent may be a dialkyl group;₁, R_TwoRepresents an alkyl group or a sulfonated alkyl group, X represents a halogen atom, PF₆ ^-, Perchloric acid, borofluoric acid, phosphoric acid, benzenesulfonic acid, SbF₆ ^-, Toluenesulfonic acid, alkylsulfonic acid, benzenecarboxylic acid, alkylcarboxylic acid, trifluoromethylcarboxylic acid, periodic acid, SCN^-, Represents an anion selected from the group of the anions of tetraphenylborate and tungstate (the above-mentioned sulfonated alkyl group may have X), one of which is bonded to X N in the heterocycle represents a cation, while X is R in the other heterocycle._TwoMay be bonded to a cation when N is bonded to the cation, in which case N of one of the above heterocyclic rings is R₁Only a non-ion to be bonded, n of the polymethine chain of the central connecting chain represents a positive integer including 0, and the polymethine chain may have a substituent, and may have a cyclic side chain extending between a plurality of carbon atoms. You may have. ), (8), a substituent having a substituent of a metallocene compound is introduced into the cation component of the general formula [Chemical formula 7] to obtain a substituted cyanine compound, and the substituted cyanine compound is represented by the following general formula [Chemical formula 8] The optical information recording medium according to the above (7), which is a substituted cyanine compound in which a substituent having a substituent of a metallocene compound is introduced into an aromatic ring of a heterocyclic ring represented by the formula:
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(However, X^-May be a monovalent or divalent anion obtained by introducing an anionic group into an organometallic complex such as a dithiol complex or a metallocene compound;_Three, R_FourAnd other symbols represent the same as those in the above general formula [Chemical formula 7]._Three, R_FourRepresents a hydrogen atom, both or one of them represents a substituent having a substituent of a metallocene compound, and when both are the same or different, the other is a hydrogen atom Or an organic substituent other than a substituent having a substituent of the metallocene compound,_Three, R_FourIs the same or different plural substituents selected from a hydrogen atom, a substituent having a substituent of a metallocene compound, and an organic substituent other than a substituent having a substituent of the metallocene compound (any position that can be substituted) Or may be). ), (9), a substituent having a substituent of a metallocene compound is introduced into the cation component of the general formula [Chemical formula 7] to form a substituted cyanine compound, and the substituted cyanine compound is represented by the following general formula [Chemical formula 9] The optical information recording medium according to the above (7), which is a cyanine compound in which a substituent having a substituent of a metallocene compound is introduced into N of the heterocyclic ring represented by
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(However, R_Three, R_FourIs that both may be hydrogen atoms and R₁-M₁, R_Two-M_TwoOther than that, each symbol represents the same as that of the above-mentioned general formula [Chemical formula 8].₁, M_TwoRepresents a substituent or a hydrogen atom of the metallocene compound;₁-M₁, R_Two-M_TwoIs an unsubstituted alkyl group, an alkoxyl group, a carboxyl group, an alkoxycarbonyl group, an alkylcarboxyl group, at least one of which may have another substituent substituted with a substituent of the metallocene compound and has no other substituent. Group, halogenated alkyl group, alkylhydroxyl group, aralkyl group, alkenyl group, alkylamide group, alkylamino group, alkylsulfonamide group, alkylcarbamoyl group, alkylsulfamoyl group, hydroxyl group, halogen atom, alkylalkoxyl group, alkyl An alkylcarboxyl group or an alkylsulfonyl group bonded to a sulfonyl group, a metal ion or an alkyl group, a phenyl group, a benzyl group, an alkylphenyl group, and a phenoxyalkyl group (a hydrogen atom in a benzene ring portion and / or an alkyl portion is May be substituted with a substituent other than a metal ion such as an alkyl group, a carboxyl group, a hydroxyl group, and a halogen atom, and the same applies to the above-mentioned phenyl group, benzyl group and alkylphenyl group.) When both have a substituent substituted with a substituent of a metallocene compound, they may be the same or different, and when only one of them has a substituent substituted with a substituent of the metallocene compound, The other is a substituted or unsubstituted alkyl group other than the substituent of the metallocene compound, an alkoxyl group, a carboxyl group, an alkoxycarbonyl group, an alkylcarboxyl group, a halogenated alkyl group, an alkylhydroxyl group, an aralkyl group, an alkenyl group, an alkyl group. Amido group, alkylamino group, alkylsulfonamide group, alkylcarba Yl group, alkylsulfamoyl group, hydroxyl group, halogen atom, alkylalkoxyl group, alkylsulfonyl group, alkylcarboxyl group or alkylsulfonyl group bonded to metal ion or alkyl group, phenyl group, benzyl group, alkylphenyl group and phenoxyalkyl Groups (the hydrogen atom of the benzene ring portion and / or the alkyl portion may be substituted with a substituent other than a metal ion such as an alkyl group, a carboxyl group, a hydroxyl group, or a halogen atom; The same applies to the corresponding portion.). ), (10), a substituted cyanine-based compound in which a substituent having a substituent of a metallocene-based compound is introduced into N of the heterocyclic ring represented by the above-mentioned general formula [Chemical formula 9], is represented by the following general formula [Chemical formula 10]. The optical information recording medium according to the above (9), which is a substituted cyanine-based compound into which a spiro fused ring has been introduced,
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(However, N⁺X^-, C1 and C2, each symbol is the same as that of the above-mentioned general formula [Chemical formula 9].⁺X^-Represents the same as NX in another notation, and C1 and C2 both or either represent a spiro-fused ring, and when either one represents a spiro-fused ring, the other represents dimethyl;^-Is a halogen atom, PF₆ ^-, Perchloric acid, borofluoric acid, phosphoric acid, benzenesulfonic acid, SbF₆ ^-, Toluenesulfonic acid, alkylsulfonic acid, benzenecarboxylic acid, alkylcarboxylic acid, trifluoromethylcarboxylic acid, periodic acid, SCN^-, Anions of tetraphenylboric acid and tungstate, and anions selected from the group of anions obtained by anionizing metal complexes such as dithiol complexes and metallocene compounds. ), (11), R₁And R_TwoIs C_nH_2n, N is from 0 to 8 and may be the same or different, and the optical information recording medium of (9) or (10), (12), R₁-M₁And R_Two-M_TwoAt least one of the optical information recording media according to the above (10) or (11), which has a branched side chain;^-Is ClO_Four ^-, PF₆ ^-, BF_Four ^-Alternatively, the optical information recording medium according to any one of the above (9) to (12), which is an anion obtained by anionizing a metallocene compound, (14), a metallocene compound represented by the following general formula [Formula 15] An optical information recording medium according to any one of the above (2) to (13),
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(M represents a metal atom;¹, R^TwoRepresents a substituent. ), (15), M is Fe, Ti, V, Mn, Cr, Co, Ni, Mo, Ru, Rh, Zr, Lu, W, Os or Ir;¹, R^TwoIs a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a halogenated alkyl group thereof, an acyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aroyl group having 7 to 10 carbon atoms, An aldehyde group having 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group having 0 to 10 carbon atoms, a hydroxyl group, a halogen atom, a boric acid group, a benzoyl group, an alkenyl group having 2 to 10 carbon atoms including a lower alkenyl group, An optical information recording medium according to the above (14), which represents a hydroxyalkyl group, an acetyl group, an aliphatic cyclic group or an alkoxycarbonyl group (each of which may have a substituent), and which may be the same and different; (1) The optical information recording according to any one of (1) to (15), wherein the optical interference layer is capable of recording and reproducing with a laser beam selected from a wavelength range of about 350 nm to 830 nm. It is intended to provide the body.
[0008]
In the present invention, the light interference layer is formed so that recording and reproduction can be performed by using a laser beam selected from a wavelength range of about 350 nm to 830 nm, and this light interference layer is formed in a range of about 640 nm to 680 nm. It is intended to be usable for DVD-R for laser light and for CD-R for laser light in the range of about 770 nm to 830 nm. Further, in the future, it will be applicable to so-called blue laser compatible media compatible with lasers of about 400 nm.
The light interference layer, a recording layer including a single layer or a plurality of dye layers capable of forming pits by laser light irradiation, comprising a dye layer formed of an organic dye material and a layer formed of another organic material or an inorganic material, In addition to this recording layer, for the purpose of adjusting the optical properties of the optical information recording medium, the refractive index, the thickness of which is adjusted, for example, an enhanced layer made of a resin material, furthermore, a substrate and a dye layer, and between a plurality of dye layers, And the like, and these are generic names. The “dye layer made of an organic dye material” may be a “recording layer containing an organic material”, and the organic material is not limited to the organic dye material and may be a material that is not colored. However, for convenience, the pigment layer may be referred to as a pigment layer including the case where the pigment is not colored.
[0009]
As the substituted polymethine compound in which a substituent having an organometallic complex substituent is introduced into the polymethine compound to be contained in the dye layer, the polymethine compound is known as a polymethine dye. A compound in which a component and an anion component are bonded, but a compound in which a substituent having a substituent of the organometallic complex is introduced into the cation component is not known. In this case, the anion component which has been conventionally used can be used including the anion of the organometallic complex, but the anion component is used as a quencher anion in order to improve light resistance in the case of, for example, a cyanine dye. There is also an anion of an organometallic complex that has been used, and when a substituent having a substituent of the organometallic complex is introduced only into the anion component, the organometallic complex is limited to a metallocene compound.
The molecular weight of the substituent having a substituent of the organometallic complex is preferably smaller than the molecular weight of the polymethine compound into which the substituent is introduced, but this is also preferable because the solubility in a solvent and the absorbance are not impaired. Metallocene compounds are preferred because of their relatively small molecular weight among the organometallic complexes.
[0010]
Examples of the polymethine compound include a cyanine compound represented by the above general formula [1] and a merocyanine compound represented by the above general formula [Chemical Formula 2], and it is preferable to use at least one member belonging to these. As the cyanine-based compound, a compound represented by the above general formula [Formula 7] is more preferable. In these general formulas [Chemical Formula 1], [Chemical Formula 2], and [Chemical Formula 7], a substituted cyanine-based compound in which a substituent substituted with a substituent of a metallocene-based compound is introduced is preferable. Any one may be used as long as it is present, and the number and the type are not limited. Examples thereof include the substituted cyanine compounds represented by the above-mentioned general formulas [Formula 8] and [Formula 9].
[0011]
Examples of the substituted cyanine-based compound belonging to the above general formula [Chemical formula 8] include compounds represented by the following general formula [Chemical formula 11] and the following general formula [Chemical formula 12].
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(However, R₁, R_Two, X^-And n are the same as those of the above general formula [Formula 8], and M is a metal of Fe, Ni or Co. )
In addition to the above compound, a compound using the anion component in the above [Chemical formula 11] in place of the anionic component in the above [Chemical formula 12], X in the above [Chemical formula 11] as it is or instead of the anionic component^-And a compound having a substituent of a metallocene compound on one of the naphthalene rings.
These compounds have the effect of improving the light fastness, and the compounds of the above [Chemical Formula 11] have the merit that they can be used by appropriately changing the cation component of the cyanine compound.
[0012]
Examples of the substituted cyanine-based compound belonging to the above general formula [Chemical formula 9] include compounds represented by the following general formula [Chemical formula 13] and the following general formula [14].
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(However, n represents 0, 1 or 2, m and m 'are 1 to 8 and may be the same or different, and X^-Is ClO_Four ^-, PF₆ ^-, BF_Four ^-Or SbF₆ ^-M represents a metal of Fe, Ni or Co;_Five, R₆Represents an alkyl group such as a lower alkyl group and may be the same or different;₇, R₈Represents a hydrogen atom or an alkyl group such as a lower alkyl group, and may be the same or different. )
The compounds of the above [Chemical formula 13] and [Chemical formula 14] can improve the light resistance, and the compounds of the above [Chemical formula 13] have m and m 'of 1 to 8 so that the length of the alkyl group can be improved. Is optimized, so that the solubility in a solvent can be improved. In particular, when n is 2, pentamethine (a dye for CD-R), and when M is Fe, the effect of improving the solubility is large. . Further, the compound of the above [14] can improve the decomposability when irradiated with laser light by having an alkyl chain having a branched structure, and can improve the sensitivity when used in the recording layer. In particular, when n is 1, trimethine (a dye for DVD-R), and when M is Fe, the effect of improving the decomposability is large.
[0013]
The compound belonging to the above general formula [Chemical formula 9] and belonging to the above general formula [Chemical formula 10] is a substituted cyanine compound into which a spiro condensed ring is introduced (a spiro condensed ring introduced type substituted cyanine compound). Spiro-fused rings are optically active stereoisomers due to molecular asymmetry in spirane, a bicyclic compound that shares one carbon atom. Refers to the other cyclic group (spirocyclic structure) that shares the carbon to be formed as the carbon constituting the other cyclic group. This spiro-fused ring-introduced cyanine compound has the optical activity of a stereoisomer due to molecular asymmetry. Body.
In the above general formula [Chemical Formula 10], it is preferable that one of C1 and C2 represents a spiro-condensed ring and the other represents dimethyl in terms of sensitivity to laser light, etc. And the spiro-fused rings may be the same or different. Examples of the spiro condensed ring include a 6-membered ring (a cyclic body having 6 C (carbon), which will be hereinafter referred to), a 5-membered ring, and a 3-membered ring. The same applies to the above general formulas [Chemical Formula 1], [Chemical Formula 2], and [Chemical Formula 7] to [Chemical Formula 9]. However, when n is 0, a monomethine cyanine dye is obtained, and when n is 1, a trimethine dye is obtained. The cyanine dye, when n is 2, is a pentamethine cyanine dye, and can be used alone or in combination with other dyes as a dye for DVD-R, CD-R, etc. As a dye for CD-R, a trimethine cyanine dye or the like is preferably used as a dye for DVD-R.
[0014]
The spiro-fused ring-introduced cyanine-based compound has a structure of a stereoisomer due to the above-described molecular asymmetry. For example, in the case of a compound represented by this general formula [Chemical Formula 10], when a spiro-fused ring is introduced into both of them. Can have a bilaterally symmetric structure. In this case, in the general formula [Chemical Formula 10], R₁-M₁, R_Two-M_TwoAre the same, and the present invention includes this case.₁-M₁, R_Two-M_TwoIs a heterogeneous structure, as a matter of course, and even if they are the same, when a spiro-condensed ring is introduced into only one of them, a left-right asymmetric structure can be obtained. Such a spiro-condensed ring-introduced cyanine compound having an asymmetric structure is preferred in terms of solubility in a solvent and film-forming properties.
R in the general formula [Chemical Formula 10]₁-M₁, R_Two-M_TwoSpecifically, the above-mentioned [Chemical Formula 13] and the corresponding substituents in the compound of [Chemical Formula 14] are mentioned, and as described above, the solubility in a solvent is improved and the decomposability to laser light is improved. In particular, when the former is pentamethine (a dye for CD-R) and M is Fe, the latter is a trimethine (a dye for DVD-R) and when M is Fe, the respective improving effects are obtained. Can be increased. In the general formula [Chemical Formula 10], R_Three, R_Four, N⁺Substituent, N substituent, X^-As for the above, specific compounds having the corresponding substituents of the above-mentioned compounds of the above [Chemical formula 11] and [Chemical formula 12] and analogs thereof can also be mentioned, and the same merit can be obtained.
[0015]
In the recording layer containing the above-mentioned spiro-fused ring-introduced cyanine-based compound, the sensitivity, that is, the reactivity to a given energy, for example, the thermal decomposability is increased. In the case of a compound, a spiro ring structure, which is unstable as a molecular structure, is directly introduced into the terminal heterocyclic ring of the cyanine dye, thereby causing the stereoisomer structure due to the above-described molecular asymmetry, thereby making the entire cyanine molecule unstable. It is considered that the structure (non-planar structure) can cause a molecule to be distorted due to, for example, steric formation due to the introduction of a spiro-condensed ring, thereby easily causing a change such as decomposition due to heat or the like.
Regarding the compound belonging to the above general formula [Chemical formula 10], not only when the spiro condensed ring is a 6-membered ring but also for the above-mentioned other cyclic groups, the structure optimization calculation in molecular simulation is performed to obtain a spiro ring structure. And the stability of the molecule, the reactivity of the recording layer containing the spiro-condensed ring-introduced cyanine dye described above with respect to the energy applied to the recording layer was determined for the case where the spiro-condensed ring was a 6-membered ring. This was consistent with the actual characteristic evaluation performed up to this point.
[0016]
As described above, it is possible to increase the thermal decomposability of an organic dye from the viewpoint of its molecular structure, lower the thermal decomposition temperature to increase the reactivity to laser light, and improve the so-called sensitivity. By using this organic dye for the dye layer such as -R, the sensitivity of recording by laser light can be improved without affecting the reflectance to laser light, that is, the sensitivity of reproduction. This means that by introducing spiro-condensed rings for cyanine dyes that have excellent reflectivity to laser light, it becomes easier to improve the recording sensitivity without impairing the reflectivity, and to broaden the choice of high-speed recording materials. Can be. On the other hand, in a conventional optical information recording medium using an organic dye, when a recording material corresponding to high-speed recording is considered, a material having better absorption at a recording wavelength is selected. Absorption peak (λ) to improve the amount of light absorption in the_max)), When a material having a longer wavelength is selected, there is a problem that the absorption increases at the reproduction wavelength, the reflectance cannot be secured, and the reproduction sensitivity cannot be improved. The present invention also has an advantage that this problem can be easily solved.
The compound belonging to the above general formula [Formula 10]₁-M₁, R_Two-M_TwoM in₁, M_TwoHas been produced and identified for a specific compound wherein is a hydrogen atom.
[0017]
In the above general formulas [Chemical formula 1], [Chemical formula 2], [Chemical formula 7] to [Chemical formula 10], when describing the general formulas, the substituents having the substituents of the metallocene compounds are also described. However, the “substituent having a substituent of the metallocene compound” may be the substituent itself of the metallocene compound, and in any case, the metallocene compound is a compound represented by the above general formula [Formula 15]. Can be mentioned. In this general formula, M represents a metal, particularly a metal such as Fe described above. Of course, even at room temperature, even when irradiated with a laser and heated to a relatively high temperature, M is thermally stable. Ferrocene (Fe biscyclobentadienyl complex), ruthenocene, osmocene, nickelocene, titanocene and the like, and their derivatives, when recorded by laser irradiation, make the formed pit shape uniform, and the pit edge shape becomes the pit center. Symmetrical with respect to the front and back, and is not only very good, but also very good in terms of durability of an optical information recording medium having a recording layer containing each compound. Also, R¹, R^TwoAs a specific metallocene compound, for example, when the metal is Fe, the following ferrocene compounds of the following [Formula 16] can be exemplified. Among them, an alkyl group, an acyl group, and a benzoyl group-substituted metallocene compound are preferable from the viewpoint of solubility and sublimation resistance. When these ferrocene compounds are substituted, the substitution position may be the ferrocene nucleus itself or the substituent, and the same applies to other metallocene compounds.
[0018]
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[0019]
In order to obtain a compound substituted with a substituent having a substituent of a metallocene compound, for example, the cyanine compound can be produced by the following reaction formulas [Chemical Formula 17] and [Chemical Formula 18]. Compounds belonging to each of the formulas [Chemical formula 1], [Chemical formula 2], [Chemical formula 7] to [Chemical formula 10] can also be produced according to the formula.
[0020]
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[0021]
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[0022]
In the reaction formulas, (a) and (b) can be produced by a known method, and from these, (c) can be produced by heating. From this (c) and diphenylformamidine, (d) can be produced by heating. This (d) can be performed by Ac_TwoAcetylation with O (acetic anhydride) produces (e), which can then be reacted with (a) in the presence of triethylamine to produce (f), and finally to give the desired anion component, for example HPF₆Can convert the type of the anion component to obtain the desired product (g). From this reaction formula, it can be seen that (c) to (g) can be produced from (a) and (b) using an existing substance, but when (a) is reacted again to obtain (f), If (c) is used instead of (a), the N substituents on both sides of the methine chain in (f) can be the same, and instead of (c), the alkyl iodide group of (b) By using a ferrocene derivative having a different length of the alkyl group of (a) and a compound corresponding to (c) obtained using (a), the length of the alkyl group of the N substituent on both sides of the methine chain in (f) can be obtained. Are obtained. Further, similarly, instead of (c), a ferrocene derivative using an alkyl group branched from the alkyl group of the alkyl iodide group in (b) and this (c) obtained using (a) When a compound is used, a compound in which an alkyl group is branched to N substituents on both sides of a methine chain in (f) is obtained. In (a) to (g), a substituent having a ferrocene substituent or a ferrocene substituent can be introduced by, for example, reacting a halogenated alkyl group-substituted ferrocene such as (b) with an aromatic ring. . In this case, if an alkyl halide is used as the component (b), (f) and (g) allow the N substituents on both sides of the methine chain to be alkyl groups. If a component having a spiro-condensed ring on one or both of the components is used as the component (a) to be reacted twice, a compound having a spiro-condensed ring on one or both sides of a methine chain in (f) and (g) can be obtained. Can be. When obtaining (g), the HPF₆By using a compound of an anion component having a substituent having a ferrocene substituent introduced therein instead of the compound (g), a compound having an anion component having a substituent having a ferrocene substituent introduced therein can be obtained. Thus, using the above-described reactions, a substituent having a substituent of ferrocene is substituted with at least one of N substituents on both sides of a methine chain, at least one of aromatic rings on both sides of a methine chain of a cation component, or an anion component. And a wide variety of compounds obtained by combining these can be obtained.
[0023]
Examples of the cyanine-based compound or merocyanine-based compound that can be substituted with a substituent having a metallocene substituent in accordance with the above include the following compounds [19] to [24].
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[0024]
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[0025]
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[0026]
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[0027]
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[0028]
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Here, for example, as for the first compound of [Chemical Formula 19], when the ethyl group of at least one N substituent on both sides of the methine chain has a metallocene-based compound substituent, at least one of both sides of the methine chain has When the benzene ring has a substituent of the metallocene compound or a substituent having the substituent, at least one of the substituents of the metallocene compound having an anion component substituted with the substituent of the metallocene compound or the substituent having the substituent in place of Br There are two cases. The same applies to other compounds.
Specifically, the following [Formula 25] to [Formula 35] can be mentioned in addition to those shown in Examples described later.
[0029]
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[0030]
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[0031]
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[0032]
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[0033]
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[0034]
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[0035]
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[0036]
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[0037]
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[0038]
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[0039]
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[0040]
In addition, about the said compound, the thing which made the thing of a trimethine into pentamethine, and made the thing of a pentamethine into trimethine is also mentioned.
In the light interference layer in the present invention, the above-mentioned general formulas [Chemical Formula 1], [Chemical Formula 2], [Chemical Formula 7] to [Chemical Formula 10], the compounds [Chemical Formula 11] to [Chemical Formula 14], and the reaction formula [Chemical Formula 17] ], (F) and (g) obtained by [Chemical Formula 18] and other compounds similar thereto, and the compounds of [Chemical Formula 19] to [Chemical Formula 24] obtained according to this reaction formula with a metallocene compound. Along with the compound belonging to each having a substituent having a group, the compound having a substituent having a substituent of each metallocene compound is excluded, that is, a compound having a substituent such as a hydrogen atom in place of the substituent, and the like. One or more of the above compounds or dyes may be used in combination by providing the same dye layer or another dye layer, and a compound having a substituent having a substituent of a metallocene compound in all compounds or in all dyes is introduced. At least 50 wt%, i.e. when using 50 wt% or more, it is possible to achieve better described effect by using a compound or dye etc. metallocene compound is introduced to the sensitivity of recording by laser is improved. At this time, if compounds having the same number of methine chains are mixed with each other, for example, a compound having a trimethine chain is preferable for a DVD-R, and a compound having a pentamethine chain is preferable for a CD-R, but is not limited thereto.
As the above other compound or dye, a cyanine compound (cyanine dye) represented by the following general formula [Chemical Formula 36] is used in all the compounds or in all the dyes at most 50% by weight, that is, 50% by weight or less. Is also good.
[0041]
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[However, A represents any of the following general formulas [Formula 37] to [Formula 39],
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,
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,
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,
A ′ represents any one of the following general formulas [Formula 40] to [Formula 42],
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,
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,
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,
A and A 'may be the same or different (however, D₁, D_TwoIs a hydrogen atom, an alkyl group, an alkoxyl group, a hydroxyl group, a halogen atom, a carboxyl group, an alkoxycarbonyl group, an alkylcarboxyl group, an alkylhydroxyl group, an aralkyl group, an alkenyl group, an alkylamide group, an alkylamino group, an alkylsulfonamide group, Alkylcarbamoyl, alkylsulfamoyl, alkylsulfonyl, phenyl, cyano, ester, nitro, acyl, allyl, aryl, aryloxy, alkylthio, arylthio, phenylazo, pyridinoazo , An alkylcarbonylamino group, a sulfonamide group, an amino group, an alkylsulfone group, a thiocyano group, a mercapto group, a chlorosulfone group, an alkylazomethine group, an alkylaminosulfone group, a vinyl group and a sulfo group Represents a substituent selected from among the group of radicals may be heterologous be homologous, p, q each represents 1 or more integer a number of substituents. ), R_Three, R_Four Is a substituted or unsubstituted alkyl group, carboxyl group, alkoxycarbonyl group, alkylcarboxyl group, alkoxyl group, alkylhydroxyl group, aralkyl group, alkenyl group, alkylamide group, alkylamino group, alkylsulfonamide group, alkylcarbamoyl group, Alkylsulfamoyl group, hydroxyl group, halogen atom, alkylalkoxyl group, halogenated alkyl group, alkylsulfonyl group, alkylcarboxyl group or alkylsulfolinyl group bonded to metal ion or alkyl group, phenyl group, benzyl group, alkylphenyl Groups and phenoxyalkyl groups (the hydrogen atom of the benzene ring and / or alkyl moiety may be substituted with a substituent other than a metal ion such as an alkyl group, a carboxyl group, a hydroxyl group, or a halogen atom. Phenyl group, a benzyl group, is the same for the corresponding portion of the alkyl phenyl group.) Represents a substituent selected from the group of may be the same or different, X^-, N represent the same as those of the above general formula [Chemical Formula 1]. ]
In the above general formula [Chemical formula 36], A is arbitrarily selected from the above general formulas [Chemical formula 37] to [Chemical formula 39], and A 'is selected from the general formulas [Chemical formula 40] to [Chemical formula 42]. Optionally selected, compounds of all combinations of each of the selected each of both are included. For example, a combination of each of the general formulas [Chemical Formula 37] and each of the general formulas [Chemical Formulas 40] to [Chemical Formula 42] can be mentioned, but the same applies to each of the other general formulas [Chemical Formula 38] and [Chemical Formula 39]. A and A ′ substituents (D₁) P, (D_TwoP) q of q is at least 1, but is a plurality of integers, that is, 2 or more integers.
As a method for synthesizing the dye, a method described in The Chemistry of Synthetic Dyes Vol. 14 can be used.
[0042]
In the compounds represented by the above general formulas [Chemical Formula 1], [Chemical Formula 2], [Chemical Formula 7] to [Chemical Formula 10], and the above [Chemical Formula 11] to [Chemical Formula 14], particularly, (F) and (g) obtained by the above [Chemical Formula 11] to [Chemical Formula 14] and the above reaction formulas [Chemical Formula 17] and [Chemical Formula 18] and other compounds similar thereto, and obtained according to this reaction formula. Compounds belonging to the above [Chemical Formula 19] to [Chemical Formula 24], the compounds used in the above [Chemical Formula 25] to [Chemical Formula 35] and the compounds used in Examples described below are used alone, and further, each metallocene compound is substituted. When one or more kinds of other compounds or dyes excluding the compound into which a substituent having a group is introduced are used in combination by providing the same dye layer or another dye layer, these compounds or dyes may be used alone. Good, but light-stable to improve lightfastness Agent may be used is contained in is contained in the dye layer or another layer, the.
Examples of such a light stabilizer include a metal complex, and examples of the metal complex include a compound represented by the following general formula [Formula 43].
[0043]
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[However, R¹, R^TwoRepresents a halogen atom, a phenyl group, an alkyl group, a cyano group, a thioalkyl group, an alkylsulfonyl group, r and s each represent an integer of 1 to 4,^FourRepresents an alkyl group, Y represents N or P, and M represents a metal such as Cu, Co or Ni. ]
[0044]
Specific compounds belonging to the above general formula [Chemical formula 41] include the following compounds [Chemical formula 44] and [Chemical formula 45].
[0045]
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[0046]
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[0047]
In addition, examples of the light stabilizer include aminium-based and diimonium-based stabilizers. As specific compounds, compounds represented by the following [Formula 46] and [Formula 47] can be exemplified.
These light stabilizers can be used alone or in combination of two or more.
[0048]
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[0049]
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[0050]
In order to manufacture the optical information recording medium of the present invention, a polymethine compound having a substituent having a substituent of the organometallic complex introduced therein, for example, a compound represented by the above general formula [Chemical Formula 1] or a compound thereof and another cyanine A mixed dye in which a system compound or the like is dissolved (the former is preferably mixed in an amount of 50% by weight or more), or a solution in which a metal complex represented by the above general formula [Formula 43] or other light stabilizer is dissolved in each of them. Prepare and apply to translucent substrate. In these dye solutions, fluorinated solvents such as chloroform, dichloroethane, and fluorinated alcohol, methyl ethyl ketone, dimethylformamide, methanol, toluene, cyclohexanone, acetylacetone, diacetone alcohol, cellosolves such as methyl cellosolve, dioxane, and the like can be used. These may be used in combination of two or more. In these cases, the mixing ratio of the cyanine dye is preferably 1% by weight to 10% by weight.
Examples of the substrate used in the present invention include glass and plastics such as epoxy resin, methacrylic resin, polycarbonate resin, polyester resin, polyvinyl chloride resin, and polyolefin resin. The substrate may have track grooves or pits formed thereon, or may have signals necessary for address signals.
Further, to apply the cyanine dye solution to the substrate, it is preferable to use a spin coating method.
Further, the light interference layer in the present invention may contain other compounds such as a singlet oxygen quencher, a light absorber, a radical scavenger (scavenger) other than the above metal complex.
[0051]
A reflective layer may be provided in addition to the above-described light interference layer, and a protective layer may be provided on the reflective layer, and a protective layer may be provided on the substrate surface (on the side where laser light is incident).
As the reflective layer, a high reflectance of a metal film such as Au, Al, Ag, Cu, Pt, each of these other alloys, and an alloy to which a trace component other than these is added, formed by vapor deposition, sputtering, etc. A material film is mentioned, and as a protective layer, a solution of a radiation-curable resin such as an ultraviolet-curable resin is applied by a spin coating method or the like for the purpose of protecting the optical information recording medium and improving weather resistance, and is cured by radiation. A coating layer is exemplified.
[0052]
In this way, an optical disc is obtained in which the light interference layer including the dye layer and the reflection layer are provided on the substrate, and further the protection layer and the like are provided. An optical disk having another similar configuration or another configuration having at least the light interference layer may be bonded, or the substrate itself may be opposed and bonded.
As a material and a method for this bonding, an ultraviolet curable resin, a cationic curable resin, a double-sided pressure-sensitive adhesive sheet, a hot melt method, a spin coat method, a dispensing method (extrusion method), a screen printing method, a roll coat method and the like are used. Can be
[0053]
BEST MODE FOR CARRYING OUT THE INVENTION
Details will be described with reference to the following examples. A polycarbonate substrate having a track pitch length of 0.74 μm (or 0.80 μm), having only a wobble signal (or having a pre-pit signal) may be used. The recording layer is made of a compound belonging to the following general formulas (1) and (2), wherein n is 1 or 2, M is Fe,₁, R_TwoIs a same or different lower alkyl group (an alkyl group having 5 or less carbon atoms (at least 5 carbon atoms, the same applies hereinafter)); (2) a compound belonging to the above general formula [Formula 13], wherein n is 1 Or 2, m and m ′ are the same or different from 1 to 5, and C_mH_2m  , C_{m '}H_{2m '}Is the same or different lower alkylene group, or C_mH_2m  , C_{m '}H_{2m '}Is a compound in which the terminal ferrocene group is a lower alkyl group having a hydrogen atom, (3) a compound belonging to the above general formula [Formula 14], wherein n is 1 or 2, and R is₇, R₈Is a hydrogen atom, and R_Five, R₆Are the same or different lower alkyl groups, m and m 'are 5 or less (at least 5) and are the same or different;_mH_2m  , C_{m '}H_{2m '}Is the same or different lower alkylene group, or C_mH_2m  , C_{m '}H_{2m '}Is a lower alkyl group in which the terminal ferrocene group is a hydrogen atom, and a compound having 2 to 8 carbon atoms in the N substituent excluding the ferrocene group; (4) a compound represented by the above general formula [Chemical Formula 10] C1 is an alicyclic group (such as a 6-membered ring, a 5-membered ring, or a 3-membered ring); C2 is an alicyclic group of the same or different type as C1; or dimethyl. Compound (R) similar to 1 ▼₁-M₁, R_Two-M_TwoIs a group represented by R in the above general formulas₁, R_TwoA1 and A2 represent a naphthalene ring, R_ThreeIs a hydrogen atom, R_FourIs a hydrogen atom or a ferrocene group, X^-Is PF₆ ^-Or (b) a compound (R) similar to the above (2)₁-M₁, R_Two-M_TwoIs N in the above general formula [Formula 13]⁺A1 and A2 correspond to a naphthalene ring, R_Three, R_FourIs a hydrogen atom), and (c) a compound (R₁-M₁, R_Two-M_TwoIs N in the above general formula [Formula 14]⁺A1 and A2 correspond to a naphthalene ring, R_Three, R_FourIs a hydrogen atom). In these (1) to (4), X^-Is the anion component of the above general formula [Chemical Formula 11], ClO_Four ^-, PF₆ ^-Or BF_Four ^-For each of the substituted cyanine-based compounds, a solution of each compound (dye), a solution obtained by adding each compound and an aminium-based light stabilizer, and (5) a compound represented by the above general formula [Chemical Formula 38] A compound of the above general formula [Chemical formula 36] comprising a combination of the formula [Chemical formula 41], wherein₁, D_TwoIs a compound in which both are hydrogen;_Three, R_FourAre the same or different and are a lower alkyl group having 1 to 4 carbon atoms, among which (7) especially X^-Is ClO_Four ^-, PF₆ ^-Or BF_Four ^-For each of the indolenine-based cyanine dyes (n is preferably made to coincide with n of each of the compounds (1) to (4)) of the compound which is the anion of (5) to (7), The dyes belonging to the above (1) to (4) are added to prepare a dye solution which accounts for 50 to 100% by weight of the total amount of the dyes, and each of these solutions is spin-coated using the respective solutions. The film is formed so as to have a dry film thickness of 50 to 150 nm.
After that, a reflective layer of Au or Al is provided by sputtering, a protective layer made of an ultraviolet curable resin is formed thereon by spin coating, and a polycarbonate substrate is bonded by an adhesive layer made of ultraviolet curable resin by spin coating. To obtain a bonded optical disk.
The optical disc obtained in this way has excellent light resistance, and when recording is performed by irradiating a laser beam of, for example, 660 nm to 680 nm, for example, a trimethine-based cyanine compound having a spiro condensed ring belonging to the above general formula [Chemical Formula 10] introduced When the compound is used, the characteristics such as sensitivity, degree of modulation, and jitter are improved, and the compound belonging to the above-mentioned general formula [Chemical Formula 10] is not used. The recording power can be made smaller than that of an optical disk obtained in the same manner except that a system cyanine compound is used.
In the above, a trimethine-based cyanine compound into which a spiro-condensed ring was introduced was used. Can be used, and a result similar to the above can be obtained.
[0054]
【Example】
Next, examples of the present invention will be described.
Example 1
A transparent substrate made of polycarbonate having a thickness of 1.2 mm and an outer diameter (diameter) of 120 mmφ, on which spiral grooves having a width of 0.5 μm, a depth of 200 nm, and a pitch of 1.6 μm were formed, was formed by injection molding. .
Next, 0.3 g of a pentamethine-based substituted cyanine-based compound of the following [Chemical Formula 48] is dissolved in 10 ml of diacetone alcohol, and the solution is applied to the surface of the substrate by a spin coating method (2,000 rpm). An optical interference layer consisting of a photosensitive recording layer having a thickness of 70 nm was formed.
[0055]
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[0056]
The absorption spectrum [wavelength dependence of the absorbance (Abs) in the wavelength range of 400 to 800 nm] of this light interference layer was measured using a visible ultraviolet spectrophotometer / U-4000 (manufactured by Hitachi, Ltd.). An absorption spectrum (change in absorption intensity (Absorbance) with respect to wavelength (Wavelength) (nm)) was obtained.
An Ag film having a thickness of 100 nm was formed on the light interference layer by a sputtering method to form a reflection layer.
In addition, an ultraviolet-curable resin SD-211 (manufactured by Dainippon Ink and Chemicals, Inc.) was spin-coated on the reflective layer, and the coating was irradiated with ultraviolet light and cured to form a 5 μm-thick protective film.
[0057]
The optical disk thus manufactured was recorded at a linear velocity of 19.2 m / sec by a DDU-1000 (recording machine manufactured by Pulstec) having an NA (numerical aperture) of 0.53 and a laser wavelength of 780 nm. As a result, the laser power was 26 mW (recording sensitivity, the same applies hereinafter). Thereafter, the signal was reproduced with the laser output set to 0.7 mW using the same apparatus, and the reflectance, the modulation, the error rate, and the jitter were measured, and all showed good values.
When the light resistance test was performed using a xenon lamp, the results were good.
[0058]
Comparative Example 1
In Example 1 above, instead of the compound of the above formula,⁺Substituent and N substituent are each the same type of methyl group (CH_Three)) And a compound (b1) having a spiro-condensed ring as a dimethyl group, respectively, and an optical disk was produced in the same manner as in Example 1. The measurement was performed in the same manner as in Example 1. They were 25.5 mW and 28 mW. Thereafter, the signal was reproduced with the laser output set to 0.7 mW using the same apparatus, and the reflectance, the modulation, the error rate, and the jitter were measured, and all showed good values.
When a light resistance test was conducted in the same manner as in Example 1, none of the compounds using the compound (a1) and the compound (b1) reached a sufficient level.
When the absorption spectrum of the light interference layer was measured in the same manner as in Example 1, the absorption spectrum shown in FIG. 2 was obtained for the compound (a1), and the absorption spectrum shown in FIG. 3 was obtained for the compound (b1).
[0059]
Example 2
A transparent substrate made of polycarbonate having a thickness of 1.2 mm and an outer diameter (diameter) of 120 mmφ, on which spiral grooves having a width of 0.32 μm, a depth of 100 nm, and a pitch of 0.74 μm were formed, was formed by injection molding. .
In Example 1 described above, this substrate was used, and instead of the compound of the above [Chemical Formula 48], the optical interference was similarly performed except that a trimethine-based substituted cyanine compound of the following [Chemical Formula 49] was used. A layer, a reflective layer and a protective film are formed, and an ultraviolet curable resin SD-318 (manufactured by Dainippon Ink and Chemicals, Inc.) is dropped on the protective film of the substrate and the light interference layer on which the protective film is not formed. Then, another substrate (same material and dimensions) molded in the same manner as above is placed thereon, and the resin is uniformly diffused in the gap by the spin coating method. The cured substrates were cured, and an adhesive layer of resin having a thickness of 25 μm was formed in a region of 32 mmφ to 120 mmφ of the substrate from the beginning, and the laminated substrates were laminated to produce a laminated optical disk.
Recording on the optical disk manufactured in this manner at a linear velocity of 3.5 m / sec by a DDU-1000 (recording machine of Pulstec) having NA (numerical aperture) = 0.65 and laser wavelength = 660 nm. As a result, the laser power was 7.0 mW (recording sensitivity, the same applies hereinafter). Thereafter, the signal was reproduced with the laser output set to 0.7 mW using the same apparatus, and the reflectance, the modulation, the error rate, and the jitter were measured, and all showed good values.
A light resistance test was conducted in the same manner as in Example 1 above, and the result was good.
When the absorption spectrum of the light interference layer was measured in the same manner as in Example 1, the absorption spectrum shown in FIG. 4 was obtained.
[0060]
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[0061]
Comparative Example 2
In Example 2 above, instead of the compound of the above formula,⁺Substituent and N substituent are each a methyl group (CH_Three) And a butyl group (C_FourH₉), And a laminated optical disk was prepared in the same manner except that the compound (b2) having a spiro-condensed ring as a dimethyl group was used, and the laser power was 11 mW when measured in the same manner as in Example 1. . Thereafter, the signal was reproduced with the laser output set to 0.7 mW using the same apparatus, and the reflectance, the modulation, the error rate, and the jitter were measured, and all showed good values.
When a light resistance test was performed in the same manner as in Example 1, the results were inferior to those in Example 2.
When the absorption spectrum of the light interference layer was measured in the same manner as in Example 1, the absorption spectrum (broken line) shown in FIG. 5 was obtained. In the figure, the solid line is that in the acetone solution.
[0062]
【The invention's effect】
According to the present invention, it is possible to prevent light deterioration during storage for a long period of time or during reproduction with a large number of repetitions, and to reduce the light absorption energy itself of the recording compound in the heat mode without impairing the recording and reproduction performance. It is not necessary to add a stabilizing radical, a quencher or other light stabilizers, and has good reactivity to laser light selected from the wavelength range of about 350 nm to 830 nm, and has good recording sensitivity. Thus, it is possible to provide an optical information recording medium capable of performing high-speed recording.
Further, an optical information recording medium which has good solubility in a solvent and can use a recording compound having a good film-forming property can be provided.
Further, it is possible to provide an optical information recording medium to which a conventional method of manufacturing a CR-R or a DVD-R can be substantially applied without major changes.
[Brief description of the drawings]
FIG. 1 is a graph showing an absorption spectrum of a light interference layer comprising a dye layer containing a dye of one example (compound of the above formula [48]) belonging to the above general formula [Formula 10] according to the present invention.
FIG. 2 is a diagram showing an absorption spectrum of a light interference layer composed of a dye layer containing a dye of one example of the compound of the comparative example.
FIG. 3 is a diagram showing an absorption spectrum of a light interference layer composed of a dye layer containing a dye of another example of the compound of the comparative example.
FIG. 4 is a view showing an absorption spectrum of a light interference layer comprising a dye layer containing a dye of another example (compound of the above formula [49]) belonging to the above general formula [Formula 10] according to the present invention. .
FIG. 5 is a diagram showing an absorption spectrum of a light interference layer composed of a dye layer containing a dye of another example of the compound of the comparative example.

Claims (16)

In an optical information recording medium having an optical interference layer including a recording layer on a substrate, the recording layer has a substituent having a substituent of an organometallic complex introduced into the cation component of a polymethine compound composed of a cation component and an anion component. An optical information recording medium containing a substituted polymethine compound. The optical information recording medium according to claim 1, wherein the molecular weight of the substituent having a substituent of the organometallic complex is smaller than the molecular weight of the polymethine compound. 3. The optical information recording medium according to claim 1, wherein the organometallic complex is a metallocene compound. In an optical information recording medium having an optical interference layer including a recording layer on a substrate, the recording layer has a substituent having a substituent of a metallocene compound introduced into the anion component of a polymethine compound composed of a cation component and an anion component. An optical information recording medium containing a substituted polymethine compound. 5. The optical information recording medium according to claim 1, wherein the polymethine compound is at least one of a cyanine compound and a merocyanine compound. The optical information according to claim 5, wherein the cyanine-based compound is a cyanine-based compound represented by the following general formula [Formula 1], and the merocyanine-based compound is a merocyanine-based compound represented by the following general formula [Formula 2]. recoding media.

(However, A is

And B is

And A ′ is

And B ′ is

In the case where each of A, B, A ′ and B ′ has an aromatic ring, it may have a halogen atom, an alkyl group, an alkoxy group or an aryl group as one or more substituents, and R is Represents an alkyl group or a sulfonated alkyl group, and may be the same or different from each other in each set of (A, B) and (A ', B'), and X represents an anion (see the above sulfonated group). Alkyl group may have X), N to which each X of A and A 'is bonded represents a cation, but X is bonded to each R of B and B' When N is a cation, it may be bonded to the cation. In this case, each N of A and A 'is a nonion to which only R is bonded, R' represents a hydrogen atom or a carboalkyl group, and R " Represents a hydrogen atom or an alkyl group, and R 'and R''are the same or different. And n may be a positive integer including 0, in the polymethine chain of the central connecting chain. ) The optical information recording medium according to claim 5, wherein the cyanine-based compound is a cyanine-based compound represented by the following general formula (7).

(However, A1 and A2 represent a substituted or unsubstituted benzene ring or naphthalene ring, Y and Y 'represent C, -CH = CH-, O, S, Se or NH, which may be the same or different, When it can have a substituent, the substituent may be an alkyl group, and Y and Y ′ are both or any one of C and at least one C has a spiro fused ring, When only one has a spiro condensed ring, the other substituent of C may be a dialkyl group, R ₁ and R ₂ represent an alkyl group or a sulfonated alkyl group, X represents a halogen atom, PF ₆ ^-, perchlorate, fluoroboric acid, phosphoric acid, benzenesulfonic acid, SbF ₆ ^-, toluenesulfonic acid, alkylsulfonic acid, benzenesulfonic acid, alkyl carboxylic acids, trifluoromethyl carboxylic acid, periodic Acid, SCN ^-, represents an anion selected from among the group of anions tetraphenylborate and tungstate (alkyl group sulfonation of the may have X), X is bonded N in one heterocyclic ring represents a cation, and X may be bonded to N when the R ₂ of the other heterocyclic ring is a cation. N is a non-ion to which only R ₁ is bonded, n of the polymethine chain of the central connecting chain represents a positive integer including 0, and the polymethine chain may have a substituent. May have a cyclic side chain extending between carbons.) A substituent having a substituent of a metallocene compound is introduced into the cation component of the general formula [Chemical formula 7] to obtain a substituted cyanine compound, and the substituted cyanine compound is a heterocyclic compound represented by the following general formula [Chemical formula 8]. The optical information recording medium according to claim 7, which is a substituted cyanine compound in which a substituent having a substituent of a metallocene compound is introduced into the aromatic ring.

(However, X ^- dithiol complex, it may be a monovalent or divalent anion obtained by introducing an anionic group in the organic metal complex such as a metallocene compound and R _3, except R ₄ each Symbols and the like represent the same as those in the above general formula [Chemical formula 7], R ₃ and R ₄ both represent a hydrogen atom, and both or one of these represents a substituent having a substituent of a metallocene compound, In both cases, they may be the same or different, and in any case, the other represents a hydrogen atom or an organic substituent other than a substituent having a substituent of a metallocene compound, and R ₃ and R ₄ each represent A plurality of the same or different substituents selected from a hydrogen atom, a substituent having a substituent of a metallocene compound, and an organic substituent other than a substituent having a substituent of the metallocene compound (at any position capable of being substituted) But good) may be used.) A substituent having a substituent of a metallocene compound is introduced into the cation component of the general formula [Chemical formula 7] to form a substituted cyanine compound, and the substituted cyanine compound is a heterocyclic compound represented by the following general formula [Chemical formula 9]. 8. The optical information recording medium according to claim 7, wherein the N is a cyanine compound in which a substituent having a substituent of a metallocene compound is introduced.

(However, R ₃ and R ₄ may be both hydrogen atoms, and each symbol and the like other than R ₁ -M ₁ and R ₂ -M ₂ are the same as those in the above general formula [Chemical Formula 8]. And M ₁ and M _{2 each} represent a substituent of a metallocene compound or a hydrogen atom, and R ₁ -M ₁ and R ₂ -M ₂ have at least one other substituent substituted by a substituent of the metallocene compound. Unsubstituted unsubstituted alkyl group, alkoxyl group, carboxyl group, alkoxycarbonyl group, alkylcarboxyl group, halogenated alkyl group, alkylhydroxyl group, aralkyl group, alkenyl group, alkylamide Group, alkylamino group, alkylsulfonamide group, alkylcarbamoyl group, alkylsulfamoyl group, hydroxyl group, halogen atom, alkylalkoxyl group, alkyls group A honyl group, an alkylcarboxyl group or an alkylsulfonyl group bonded to a metal ion or an alkyl group, a phenyl group, a benzyl group, an alkylphenyl group, and a phenoxyalkyl group (a hydrogen atom of a benzene ring portion and / or an alkyl portion is an alkyl group, a carboxyl group , A hydroxyl group, a halogen atom or the like, and may be substituted with a substituent other than a metal ion, and the same applies to the corresponding portions of the phenyl group, benzyl group and alkylphenyl group). May be the same or different when both of them have a substituent substituted with a substituent of a metallocene compound, and when only one of them has a substituent substituted with a substituent of a metallocene compound, the other is the metallocene compound. A substituted or unsubstituted alkyl group or alkoxyl group other than the substituent of the compound of , A carboxyl group, an alkoxycarbonyl group, an alkylcarboxyl group, an alkyl halide group, an alkylhydroxyl group, an aralkyl group, an alkenyl group, an alkylamide group, an alkylamino group, an alkylsulfonamide group, an alkylcarbamoyl group, an alkylsulfamoyl group, A hydroxyl group, a halogen atom, an alkylalkoxyl group, an alkylsulfonyl group, an alkylcarboxyl group or an alkylsulfonyl group bonded to a metal ion or an alkyl group, a phenyl group, a benzyl group, an alkylphenyl group, and a phenoxyalkyl group (a benzene ring portion and / or an alkyl group) Part of the hydrogen atom may be substituted with a substituent other than a metal ion such as an alkyl group, a carboxyl group, a hydroxyl group, and a halogen atom, and the phenyl group, benzyl group, and alkylphenyl group may be substituted. The same is true for those parts. Represents a substituent selected from the group of). ) A substituted cyanine compound in which a substituent having a substituent of a metallocene compound is introduced into N of the heterocyclic ring represented by the above general formula [Chemical formula 9], a spiro condensed ring represented by the following general formula [Chemical formula 10] is introduced. The optical information recording medium according to claim 9, which is a substituted substituted cyanine compound.

^{(However, N + X -, C1,} C2 except the symbols and the like represent the same as those of the above general formula [9], N ⁺ X ^- represents the same as the N-X in a different notation , C1, C2 are both or either one represents a spiro fused rings, represents the other dimethyl when either one thereof represents a spiro fused ring, X ^- a halogen atom, PF ₆ is ^-, perchlorate, tetrafluoroborate Hydrofluoric acid, phosphoric acid, benzenesulfonic acid, SbF ₆ ⁻ , toluenesulfonic acid, alkylsulfonic acid, benzenecarboxylic acid, alkylcarboxylic acid, trifluoromethylcarboxylic acid, periodic acid, SCN ⁻ , tetraphenylboric acid and tungsten It represents an anion of an acid and an anion selected from a group of anions obtained by anionizing a metal complex such as a dithiol complex or a metallocene compound.) The optical information recording medium according to claim 9, wherein R ₁ and R ₂ are C _n H _2n and n is 0 to 8, and may be the same or different. 12. The optical information recording medium according to claim 10, wherein at least one of R ₁ -M ₁ and R ₂ -M ₂ has a branched side chain. 13. The optical information recording medium according to claim 9, wherein X ⁻ is ClO ₄ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ or an anion obtained by anionizing a metallocene compound. 14. The optical information recording medium according to claim 2, wherein the metallocene compound is a compound represented by the following general formula [Formula 15].

(M represents a metal atom, and R ¹ and R ² represent substituents.) M is Fe, Ti, V, Mn, Cr, Co, Ni, Mo, Ru, Rh, Zr, Lu, W, Os or Ir; R ¹ and R ² are a hydrogen atom, an alkyl having 1 to 10 carbon atoms; A group or a halogenated alkyl group thereof, an acyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aroyl group having 7 to 10 carbon atoms, an aldehyde group having 1 to 10 carbon atoms, and an aldehyde group having 1 to 10 carbon atoms Alkoxy group, C2-C10 amino group, hydroxyl group, halogen atom, boric acid group, benzoyl group, C2-C10 alkenyl group including lower alkenyl group, hydroxyalkyl group, acetyl group, aliphatic cyclic group 15. The optical information recording medium according to claim 14, which represents an alkoxycarbonyl group (each of which may have a substituent) and may be the same and different. The optical information recording medium according to any one of claims 1 to 15, wherein the optical interference layer is capable of recording and reproducing with a laser beam selected from a wavelength range of about 350 nm to 830 nm.

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