JP3865547B2 - 光記録媒体および光記録媒体の製造方法 - Google Patents

光記録媒体および光記録媒体の製造方法 Download PDF

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JP3865547B2
JP3865547B2 JP32328199A JP32328199A JP3865547B2 JP 3865547 B2 JP3865547 B2 JP 3865547B2 JP 32328199 A JP32328199 A JP 32328199A JP 32328199 A JP32328199 A JP 32328199A JP 3865547 B2 JP3865547 B2 JP 3865547B2
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layer
recording medium
optical recording
light
groove
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JP32328199A
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JP2001138635A (ja
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徹 八代
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Ricoh Co Ltd
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Ricoh Co Ltd
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Priority to JP32328199A priority Critical patent/JP3865547B2/ja
Priority to TW089124009A priority patent/TW546205B/zh
Publication of JP2001138635A publication Critical patent/JP2001138635A/ja
Priority to US10/293,185 priority patent/US20030059712A1/en
Priority to US10/979,066 priority patent/US20050058802A1/en
Priority to US11/245,690 priority patent/US20060029886A1/en
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    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/257—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers
    • G11B7/2578—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of inorganic materials
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/258—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of reflective layers
    • G11B7/2595—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of reflective layers based on gold
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/26—Apparatus or processes specially adapted for the manufacture of record carriers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)

Description

【０００１】
【発明の属する技術分野】
本発明は、光記録媒体およびその製造方法に関するものであり、特に高速のＣＤ−Ｒ、ＣＤ−ＲＷにも好適に応用される光記録技術に関するものである。
【０００２】
【従来の技術】
近年、読み出し専用のＣＤ（コンパクトディスク）などの光記録媒体に加えて、記録可能なＣＤ（ＣＤ−Ｒ、ＣＤ−ＲＷ）が実用化されている。ＣＤ−Ｒ、ＣＤ−ＲＷは、従来のＣＤと異なりユーザが情報を記録することが可能で且つ記録後の信号は、従来のＣＤの規格を満足するため、市販ＣＤプレーヤで再生可能であるという特徴を持つ。
このようなメディアを実現する方法の１つとしては、例えばＣＤ−Ｒでは特開平２−４２６５２号公報において、基板上に色素をスピンコーティングして光吸収層を設け、その背後に金属反射層を設けることが提案されている。
このような光吸収層の材料としては、主としてシアニン色素系材料が用いられてきたが、このタイプの色素は吸収係数が大きいという点で光学特性に優れるが、耐光性が悪いという欠点があった。そこで、耐光性に優れたフタロシアニン系色素材料を用いることが、特開平３−６２８７８号公報などで提案されている。
【０００３】
一方、記録用ドライブは、従来の等速度（約１．３ｍ／ｓ）記録よりも記録速度の速いモデルが商品化され、処理速度の速さから、一般ユーザーに普及してきた。記録速度としては、４倍速度（約５．２ｍ／ｓ）記録モデルが主流であるが、さらに、６倍速・８倍速のドライブも市販されている。
【０００４】
ところが、従来のＣＤ−Ｒメディアは４倍速以上の高速度で記録した場合、等速度記録に比べ、信号品質が劣っていた。すなわち、高速度で記録再生する場合は、記録パワーに対するマージンが狭く、さらにウォブルグルーブに記録されたアドレス情報の再生特性が低下する。記録機と再生機の組み合わせによっては、再生エラーが発生するという問題があった。
【０００５】
【発明が解決しようとする課題】
本発明の目的は、これらの問題点を解消し、高速記録条件での信頼性が高く、耐久性に優れた光記録媒体を提供することである。
【０００６】
【課題を解決するための手段】
本発明の光記録媒体は、一般式（Ｉ）で表わされるフタロシアニン材料を記録層に使用し、ウォブルグルーブのトラックピッチが１．５〜１．７μｍ、グルーブの半値幅が０．５８〜０．７５μｍ、グルーブの深さが１２００〜１７００Åの範囲にあることにより、高速記録条件にて良好な信号品質・耐久性が得られる。
高速度記録条件での信号品質について検討した結果、一般式（Ｉ）で表わされるフタロシアニン材料記録層およびウォブルグルーブの溝幅により、高速記録での記録パワーマージンが大きくなり、さらにウォブルグルーブに記録されたアドレス情報の再生特性が向上することを見出し、本発明に至った。
一般式（Ｉ）で表わされるフタロシアニン化合物は次のようなものである。
【０００７】
【化２】
Figure 0003865547
（式中、Ｍ及びＡ1〜Ａ8は、それぞれ以下のものを表わす。
Ｍ：２価の金属原子、置換３価金属原子、２置換４価金属原子又はオキシ金属、Ａ1とＡ2、Ａ3とＡ4、Ａ5とＡ6及びＡ7とＡ8：それぞれのどちらか一方は、それぞれ独立に−Ｏ−Ｃ（Ｒ1）（Ｒ3）−Ｒ2、他方は水素原子、
Ｒ1、Ｒ3：アルキル基、フッ素置換されたアルキル基又は水素原子、
Ｒ2：アルキル基置換されたフェニル基又は未置換のフェニル基。）
【０００８】
中心金属Ｍとしては、上記のように前記２価の金属原子、１置換３価金属原子、２置換４価金属原子またはオキシ金属が挙げられるが、具体的にはＺｎ、Ｎｉ、Ｃｕ、Ｐｄ、ＶＯ、ＴｉＯから選ばれる１つの金属原子または金属酸化物が好ましい。これらのＭは光吸収層の複素屈折率が良好であり、高反射率を得やすいためである。
【０００９】
（２価の金属）
Ｃｕ2+、Ｚｎ2+、Ｆｅ2+、Ｃｏ2+、Ｎｉ2+、Ｒｕ2+、Ｒｈ2+、Ｐｄ2+、Ｐｔ2+、Ｍｎ2+、Ｍｇ2+、Ｔｉ2+、Ｂｅ2+、Ｃａ2+、Ｂａ2+、Ｃｄ2+、Ｈｇ2+、Ｐｂ2+、Ｓｎ2+など。
【００１０】
（１置換３価金属）
Ａｌ−Ｃｌ、Ａｌ−Ｂｒ、Ａｌ−Ｆ、Ａｌ−Ｉ、Ｇａ−Ｃｌ、Ｇａ−Ｆ、Ｇａ−Ｉ、Ｇａ−Ｂｒ、Ｉｎ−Ｃｌ、Ｉｎ−Ｂｒ、Ｉｎ−Ｉ、Ｉｎ−Ｆ、Ｔｌ−Ｃｌ、Ｔｌ−Ｂｒ、Ｔｌ−Ｉ、Ｔｌ−Ｆ、Ａｌ−Ｃ6Ｈ5、Ａｌ−Ｃ6Ｈ4（ＣＨ3）、Ｉｎ−Ｃ6Ｈ5、Ｉｎ−Ｃ6Ｈ4（ＣＨ3）、Ｉｎ−Ｃ10Ｈ7、Ｍｎ（ＯＨ）、Ｍｎ（ＯＣ6Ｈ5）、Ｍｎ〔ＯＳｉ（ＣＨ3）3〕、ＦｅＣｌ、ＲｕＣｌなど。
【００１１】
（２置換４価金属）
ＣｒＣl2、ＳｉＣ12、ＳｉＢｒ2、ＳｉＦ2、ＳｉＩ2、ＺｒＣｌ2、ＧｅＣｌ2、ＧｅＢｒ2、ＧｅＩ2、ＧｅＦ2、ＳｎＣｌ2、ＳｎＢｒ2、ＳｎＩ2、ＳｎＦ2、ＴｉＣｌ2、ＴｉＢｒ2、ＴｉＦ2、Ｓｉ（ＯＨ）2、Ｇｅ（ＯＨ）2、Ｚｒ（ＯＨ）2、Ｍｎ（ＯＨ）2、Ｓｎ（ＯＨ）2、ＴｉＲ2、ＣｒＲ2、ＳｉＲ2、ＳｎＲ2、ＧｅＲ2（Ｒはアルキル基、フェニル基、ナフチル基及びその誘導体を表わす）、Ｓｉ（ＯＲ’）2、Ｓｎ（ＯＲ’）2、Ｇｅ（ＯＲ’）2、Ｔｉ（ＯＲ’）2、Ｃｒ（ＯＲ’）2（Ｒ’はアルキル基、フェニル基、ナフチル基、トリアルキルシリル基、ジアルキルアルコキシシリル基及びその誘導体を表わす）、Ｓｎ（ＳＲ”）2、Ｇｅ（ＳＲ”）2（Ｒ”はアルキル基、フェニル基、ナフチル基及びその誘導体を表わす）など。
【００１２】
（オキシ置換）
ＶＯ、ＭｎＯ、ＴｉＯなど。
【００１３】
Ｒ1、Ｒ3の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ−プロピル基、ブチル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、−ＣＦ3、−Ｃ2Ｆ5、−ＣＦ（ＣＦ3）2、水素原子などを挙げることができる。
特に、置換基Ｒ1、Ｒ3がともに−ＣＦ3であることが好ましい。
−ＣＦ3基により、熱分解温度が低下し、記録感度が向上する。
【００１４】
Ｒ2の具体例としては、フェニル基、ナフチル基、２−メチルフェニル基、２，４−ジメチルフェニル基、２，４，６−トリメチルフェニル基、２−イソプロピルフェニル基、２，５−ジメチルフェニル基、２，６−ジメチルフェニル基、２−エチルフェニル基などが挙げられる。
フェニル基に付与されるアルキル基の炭素数は１〜４が好ましい。炭素数がこれより大きくなると光吸収層の単位膜厚当たりの吸光度が低下しやすく、良好な複素屈折率を得にくくなるためである。
前記一般式（Ｉ）で示されるフタロシアニン化合物は、対応するフタロニトリル混合物の環化反応などにより容易に合成することができる。即ち、下記式（II）のフタロニトリルを、例えば１，８−ジアザビシクロ（５，４，０）−７−ウンデセンの存在下、金属誘導体とアルコール中加熱反応させることにより容易に合成できる。
【００１５】
【化３】
Figure 0003865547
【００１６】
前記フタロシアニン化合物（Ｉ）からなる光吸収層は、化合物を溶媒に溶解し、塗布液として基板上にコートすることにより容易に得られる。更に、中心金属ＭがＦｅ2+、Ｃｏ2+、Ｚｎ2+、Ｃｄ2+、Ｍｎ2+である場合は、アミノ化合物を添加することが好ましい。Ｍがこれらの金属である場合は、アミノ化合物がＭに配位しやすく、配位により溶媒への溶解性、塗布成膜性が向上するためである。アミノ化合物としては、以下のような化合物を挙げることができるが、これらに限定されるものではない。これらの中で、フタロシアニン系化合物の会合を防ぐ効果が高く、且つ耐久性（耐熱性、耐光性）に優れているという点から、Ｎ原子を複素環に含む化合物が好ましい。更に、光吸収層の熱安定性を維持するという点から、アミノ化合物は、融点が１５０℃以上のものであることが好ましい。融点が１５０℃未満の場合には、高温高湿環境下で光吸収層の特性（特に光学特性）が変化しやすいためである。中でも特に好ましいのは、イミダゾール、ベンズイミダゾール及びチアゾール誘導体である。
【００１７】
（アミノ化合物）
ｎ−ブチルアミン、ｎ−ヘキシルアミン、ｔｅｒｔ−ブチルアミン、ピロール、ピロリジン、ピリジン、ピペリジン、プリン、イミダゾール、ベンズイミダゾール、５，６−ジメチルベンズイミダゾール、２，５，６−トリメチルベンズイミダゾール、ナフトイミダゾール、２−メチルナフトイミダゾール、キノリン、イソキノリン、キノキサリン、ベンズキノリン、フェナンスリジン、インドリン、カルバゾール、ノルハルマン、チアゾール、ベンズチアゾール、ベンズオキサゾール、ベンズトリアゾール、７−アザインドール、テトラヒドロキノリン、トリフェニルイミダゾール、フタルイミド、ベンゾイソキノリン−５，１０−ジオン、トリアジン、ペリミジン、５−クロロトリアゾール、エチレンジアミン、アゾベンゼン、トリメチルアミン、Ｎ，Ｎ−ジメチルホルムアミド、１（２Ｈ）フタラジノン、フタルヒドラジド、１，３−ジイミノイソインドリン、オキサゾール、ポリイミダゾール、ポリベンズイミダゾール、ポリチアゾール等。
【００１８】
ウォブルグルーブは通常のＣＤで使用されるトラックピッチ１．５〜１．７μｍの範囲にて、グルーブの半値幅は０．４〜０．７５μｍの範囲にある。グルーブ幅はＡＦＭ回折光測定機などで測定できるが、好ましくは、ＡＦＭによる測定がよい。回折光測定では、溝深さの影響が避けられず、測定誤差が大きいためである。グルーブ幅が０．７５μｍよりも広い場合は、レーザー光記録により形成するピットが幅方向に広がり易く、記録パワーに対するマージンが狭くなる。
また、グルーブ幅が０．７５μｍよりも狭い場合は、隣接トラックのウォブル干渉（クロストーク）が抑えられるので、ウォブルグルーブに記録されたアドレス情報（ＡＴＩＰ）の信号品質低下が小さく、再生特性が向上する。
一方、０．４μｍ未満では、記録ピットが形成しにくく、記録感度・信号変調度を得にくい。
【００１９】
本発明では、グルーブの深さは８００〜２０００Åの範囲にある。
好ましくは、１２００〜１７００Åがよい。
溝深さがこの範囲から外れると適正なトラック信号（ＰＰＡ）、シーク信号（ＲＣｂ）を得にくい。
【００２０】
光吸収材料としては、前記フタロシアニン系化合物（Ｉ）に加えて、従来より情報記録媒体の記録材料として知られている任意の色素を混合して用いることができる。このような色素としては、例えばシアニン系色素、ピリリウム系・チオピリリウム系色素、アズレニウム系色素、スクワリリウム系色素、Ｎｉ、Ｃｒなどの金属錯塩系色素、ナフトキノン系・アントラキノン系色素、インドフェノール系色素、インドアニリン系色素、トリフェニルメタン系色素、トリアリルメタン系色素、アミニウム系・ジインモニウム系色素及びニトロソ化合物を挙げることができる。更に、必要に応じて他の第３成分、例えばバインダー、安定剤等を含有させることができる。なお、光吸収層の膜厚は、１００〜５０００Åが好ましく、特に５００〜３０００Åが望ましい。光吸収層の膜厚が、この範囲より薄くなると記録感度が低下し、また厚くなると反射率が低下するからである。
【００２１】
本発明において使用する基板は、従来の情報記録媒体の基板として用いられている各種の材料から任意に選択することができる。基板材料の例としては、ポリメチルメタクリレートのようなアクリル樹脂、ポリ塩化ビニル、塩化ビニル共重合体等の塩化ビニル系樹脂、エポキシ樹脂、ポリカーボネート樹脂、アモルファスポリオレフィン、ポリエステル、ソーダ石灰ガラス等のガラス及びセラミックスを挙げることができる。特に寸法安定性、透明性及び平面性などの点から、ポリメチルメタクリレート、ポリカーボネート樹脂、エポキシ樹脂、アモルファスポリオレフィン、ポリエステル及びガラスなどを挙げることができる。
【００２２】
光吸収層が設けられる側の基板表面には、平面性の改善、接着力の向上及び光吸収層の変質の防止の目的で、下塗層が設けられてもよい。下塗層の材料としては、例えばポリメチルメタクリレート、アクリル酸／メタクリル酸共重合体、スチレン／無水マレイン酸共重合体、ポリビニルアルコール、Ｎ−メチロールアクリルアミド、スチレン／スルホン酸共重合体、スチレン／ビニルトルエン共重合体、クロルスルホン化ポリエチレン、ニトロセルロース、ポリ塩化ビニル、塩素化ポリオレフィン、ポリエステル、ポリイミド、酢酸ビニル／塩化ビニル共重合体、エチレン／酢酸ビニル共重合体、ポリエチレン、ポリプロピレン、ポリカーボネート等の高分子物質：シランカップリング剤などの有機物質：及び無機酸化物（ＳｉＯ2、Ａｌ2Ｏ3等）、無機フッ化物（ＭｇＦ2）などの無機物質を挙げることができる。なお、下塗層の層厚は一般に０．００５〜２０μｍの範囲にあり、好ましくは０．０１〜１０μｍの範囲である。
【００２３】
また、基板（又は下塗層）上には、トラッキング用溝又はアドレス信号等の情報を表わす凹凸の形成の目的で、プレグループ層が設けられてもよい。プレグループ層の材料としては、アクリル酸のモノエステル、ジエステル、トリエステル及びテトラエステルのうちの少なくとも一種のモノマー（又はオリゴマー）と光重合開始剤との混合物を用いることができる。
【００２４】
更に、光吸収層の上には、Ｓ／Ｎ比、反射率の向上及び記録時における感度の向上の目的で、反射層が設けられてもよい。反射層の材料である光反射性物質はレーザー光に対する反射率が高い物質であり、その例としては、Ｍｇ、Ｓｅ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｒｅ、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｐｄ、Ｉｒ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ、Ｃｄ、Ａｌ、Ｃａ、Ｉｎ、Ｓｉ、Ｇｅ、Ｔｅ、Ｐｂ、Ｐｏ、Ｓｎ、Ｓｉなどの金属及び半金属を挙げることができる。これらのうちで好ましいものはＡｕ、Ａｌ及びＡｇである。これら物質は単独で用いてもよいし、あるいは二種以上の組合せで又は合金として用いてもよい。なお、反射層の層厚は一般に１００〜３０００Åの範囲にある。
また、光吸収層（又は反射層）の上には、光吸収層などを物理的及び化学的に保護する目的で保護層が設けられてもよい。この保護層は、基板の光吸収層が設けられていない側にも耐傷性、耐湿性を高める目的で設けられてもよい。保護層に用いられる材料の例としては、Ｓｉ、Ｏ、ＳｉＯ2、ＭｇＦ2、ＳｎＯ2等の無機物質、熱可塑性樹脂、熱硬化性樹脂、ＵＶ硬化性樹脂を挙げることができる。
なお、保護層の層厚は一般的には５００Å〜５０μｍの範囲にある。
【００２５】
次に、本発明の光記録媒体の製造方法について説明する。本発明の光記録媒体の製造方法は、表面にウォブルグルーブが形成されてなる基板上に、直接又は他の層を介して前記フタロシアニン系化合物（Ｉ）を主成分とする光吸収層を塗布成膜手段により設け、その上に直接又は他の層を介して光反射層を真空成膜手段により設け、更にその上に保護層を設けることを特徴とする。即ち、本発明の製造方法は、下記の工程からなる。
（イ）表面にウォブルグルーブが形成されている基板上に、直接又は他の層を介して前記フタロシアニン系化合物（Ｉ）を主成分とする光吸収層を塗布成膜手段により設ける工程、（ロ）光吸収層上に直接又は他の層を介して光反射層を真空成膜手段により設ける工程、及び（ハ）光吸収層上に保護層を設ける工程。
【００２６】
（光吸収層形成工程）
本発明の方法においては、先ず表面にウォブルグルーブが形成されている基板上に、直接又は他の層を介して、前記フタロシアニン系化合物（Ｉ）を主成分とする光吸収層が塗布成膜手段により設けられる。即ち、前記フタロシアニン系化合物（Ｉ）を溶媒に溶解し、液状の塗布液として基板上にコートすることにより、光吸収層が形成される。この塗布液を調整するための溶媒としては、公知の有機溶媒（例えばアルコール、セルソルブ、ハロゲン化炭素、ケトン、エーテル等）を使用することができる。また、コート方法としては、光吸収層の濃度、粘度、溶剤の乾燥温度を調節することにより層厚を制御できるため、スピンコート法が望ましい。
なお、光吸収層が設けられる側の基体表面に下塗層を設けることが、基板表面の平面性の改善や接着力の向上あるいは光吸収層の変質防止等の目的で、行なわれる。この場合の下塗層は、例えば前述した下塗層用物質を適当な溶剤に溶解又は分散して塗布液を調整したのち、この塗布液をスピンコート、ディップコート、エクストルージョンコートなどの塗布法により基板表面に塗布することにより形成することができる。
【００２７】
（光反射層形成工程）
本発明の方法においては、次に光吸収層上に直接又は他の層を介して光反射層が真空成膜手段により設けられる。即ち、前述した光反射性物質を、例えば蒸着、スパッタリング又はイオンプレーティングすることにより、光反射層が光吸収層の上に形成される。
【００２８】
（保護層形成工程）
本発明の方法においては、光反射層上に保護層が設けられる。即ち、前述した無機物質や種々の樹脂からなる保護層用材料を、真空成膜又は塗布成膜することにより形成される。特にＵＶ硬化性樹脂を用いるのが好ましく、該樹脂をスピンコート後、紫外線照射により硬化して形成される。
【００２９】
【実施例】
以下実施例について本発明を説明するが、本発明はこれらに限定されるものではない。
＜実施例１＞
直径１２０ｍｍ、厚さ１．２ｍｍの円板表面上に、トラックピッチ：１．５８μｍ、半値幅：０．６８μｍ、溝深さ：約１５００Åのウォブルグルーブ有する基板をポリカーボネイトの射出成形により作成した。
この基板に一般式（Ｉ）において、
Ｍ：ＶＯ、Ｒ1：ＣＦ3、Ｒ2：フェニル、Ｒ3：ＣＦ3で表わされるフタロシアニン色素光吸収層をテトラヒドロフラン、２−メトキシエタンノール、エチルシクロヘキサンからなる混合溶媒を塗布液としてスピンコートすることにより設けた。光吸収層の膜厚は約１５００Åであった。
【００３０】
次に、光吸収層の上にスパッタ法により金（Ａｕ）を約１０００Åの厚さに設け反射層とし、さらにその上面に紫外線硬化樹脂からなる保護層を約５μｍの厚さに設けて、本発明の光記録媒体Ｎｏ．１を作成した。
この媒体を光ディスク記録再生装置ＤＤＵ−１０００(パルステック社)にて、ＮＡ：０．５、波長：７９０ｎｍ、線速度：４．８ｍ／ｓの条件で記録し、信号特性を測定した。記録信号はＣＤ信号（ＥＦＭ）とし、記録ストラテジは（ｎ−１）Ｔとした。
ジッターメーター（ＬＡＥＤＥＲ社製 ＬＪＭ−１８５１）による、等速度再生３Ｔピットジッターの測定結果は図１のようであり、広い記録パワーレンジ（β）に対して良好（低い）なジッター特性が得られた。
【００３１】
＜実施例２＞
実施例１においてフタロシアニン色素として、Ｍ：ＴｉＯ、Ｒ1：ＣＦ3、Ｒ2：２−メチルフェニル、Ｒ3：Ｃ2Ｆ5を用いたこと以外同様にして本発明の光記録媒体Ｎｏ．２を作成し、ジッターを測定した。
ジッター値はβ＝−８％：２３ｎｓ β＝＋８％：２３ｎｓであり、実施例１同様、良好な結果が得られた。
【００３２】
＜実施例３＞
実施例１において、半値幅：０．５８μｍ、０．６１μｍ、０．７３μｍの溝基板を用いたこと以外同様にして本発明の光記録媒体Ｎｏ．３、４、５を作成し、Ｎｏ．１、３、４、５について復調後の４速度再生ＡＴＩＰ信号の最短ピットジッターをタイムインターバルアナライザー（ＨＥＷＬＥＴＴ ＰＡＣＫＡＲＤ社製 ５３７２Ａ）により測定した。
測定結果は図２のようであり、０．５８〜０．７３μｍの範囲で良好（低い）なジッター特性が得られた。また、溝幅が狭いほどジッター良好であった。
【００３３】
＜参考例１＞
実施例１おいて半値幅に：０．４５μｍの溝基板を用いたこと以外同様にして光記録媒体Ｎｏ．６を作成し、ジッターを測定した。
ジッター値はβ＝−８％：２１ｎｓ β＝−８％：２２ｎｓであり、実施例１同様、良好な結果が得られた。
【００３４】
＜比較例＞
実施例１においてフタロシアニン色素に変えて、下記一般式（IV）、（Ｖ)で表わされるシアニン色素を（IV）／（Ｖ）＝１／２の重量比率で混合し、２，２，３，３−テトラフロロプロパノールを塗布液としてスピンコートすることにより色素光吸収層を設け、溝幅０．８０μｍの基板を用いたこと以外同様にして、比較用の光記録媒体を作成し、ジッターを測定した。
ジッターメーター（ＬＡＥＤＥＲ ＬＪＭ−１８５１）による、３Ｔピットジッターの測定結果は図１のようであり、
ＣＤ規格値（３５ｎｓ以下）を満足することができなかった。
【００３５】
【化４】
Figure 0003865547
【００３６】
【化５】
Figure 0003865547
【００３７】
【発明の効果】
以上、詳細かつ具体的な説明から明らかなように、請求項１の光記録媒体は、グルーブの半値幅が０．５８〜０．７５μｍの範囲にあり、かつ色素記録層が一般式（Ｉ）で表わされるフタロシアニン化合物を含有しているので、高速度記録にて良好な記録再生特性を有し、耐久性に優れている。また、請求項２の光記録媒体は、フタロシアニン化合物の、中心金属ＭがＺｎ、Ｎｉ、Ｃｕ、Ｐｄ、ＶＯ、ＴｉＯから選ばれる１つの金属原子または金属酸化物であり、置換基Ｒ１、Ｒ３が−ＣＦ３であるので、特に、高速度記録にて良好な記録再生特性を有し、耐久性に優れている。また、請求項３の製造方法により、容易に、高速度記録にて良好な記録再生特性を有し、耐久性に優れるＣＤ−Ｒ媒体を製造することができるという優れた効果を奏するものである。
【図面の簡単な説明】
【図１】実施例１および比較例の記録パワーマージン（β）に対するジッタマージンを示す図である。
【図２】実施例３の復調後のＡＴＩＰ信号ジッターを示す図である。

Claims (3)

  1. 表面にウォブルグルーブが形成された基板上に色素記録層を形成し、さらにその上に金属反射層を形成した光情報記録媒体において、前記ウォブルグルーブのトラックピッチが１．５〜１．７μｍ、グルーブの半値幅が０．５８〜０．７５μｍ、グルーブの深さが１２００〜１７００Åの範囲にあり、かつ色素記録層が一般式（Ｉ）で表わされるフタロシアニン化合物を含有することを特徴とする光情報記録媒体。
    Figure 0003865547
    （式中、Ｍ及びＡ１〜Ａ８は、それぞれ以下のものを表わす。
    Ｍ：２価の金属原子、置換３価金属原子、２置換４価金属原子又はオキシ金属、Ａ１とＡ２、Ａ３とＡ４、Ａ５とＡ６及びＡ７とＡ８：それぞれのどちらか一方は、それぞれ独立に−Ｏ−Ｃ（Ｒ１）（Ｒ３）−Ｒ２、他方は水素原子、
    Ｒ１、Ｒ３：アルキル基、フッ素置換されたアルキル基又は水素原子、
    Ｒ２：アルキル基置換されたフェニル基又は未置換のフェニル基。）
  2. 前記フタロシアニン化合物の、中心金属ＭがＺｎ、Ｎｉ、Ｃｕ、Ｐｄ、ＶＯ、ＴｉＯから選ばれる１つの金属原子または金属酸化物であり、置換基Ｒ1、Ｒ3が−ＣＦ3であることを特徴とする請求項１に記載の光記録媒体。
  3. 表面にウォブルグルーブが形成されてなる基板上に、直接又は他の層を介して前記化合物（Ｉ）を主成分とする光吸収層を塗布成膜手段により設け、その上に直接または他の層を介して光反射層を真空成膜手段により設け、更にその上に保護層を設けることを特徴とする請求項１または２に記載の光記録媒体の製造方法。
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