JP3594258B2 - Optical information recording medium - Google Patents

Description

〔式中、Ｍ、Ｘ¹〜Ｘ⁴、Ｒ¹〜Ｒ⁴及びｋ〜ｎは、それぞれ以下のものを表わす。
Ｍ：２個の水素原子、ハロゲン原子若しくは酸素原子を有してもよい金属原子、又は−（ＯＲ⁵）p 基若しくは−（ＯＳｉＲ⁶Ｒ⁷Ｒ⁸）q 基を有してもよい金属原子、
Ｒ⁵〜Ｒ⁸：それぞれ独立に水素原子、置換若しくは未置換の１価の脂肪族炭化水素基、置換若しくは未置換の１価の芳香族炭化水素基、又は置換若しくは未置換の１価の芳香族複素環基、
ｐ、ｑ：０〜２の整数、
Ｘ¹〜Ｘ⁴：それぞれ独立に酸素原子又は硫黄原子、
Ｒ¹〜Ｒ⁴：それぞれ独立に、塩素原子、臭素原子、メチル基のいずれか置換のアダマンタン残基、又はアダマンタン置換メチル残基、
ｋ、ｌ、ｍ、ｎ：それぞれ独立に０〜４の整数、但し全部が同時に０になることはなく、ｋ、ｌ、ｍ、ｎが３以下の場合ベンゼン環の他の置換基は水素原子又はハロゲン原子である。〕
【００１０】
また、本発明によれば、前記記録層上に金属反射層を設け、更にその上に保護層を設けてなり、ＣＤフォーマット信号の記録を行なう追記コンパクトディスク型の記録媒体であることを特徴とする前記光情報記録媒体が提供される。更に、前記一般式（Ｉ）において、ｋ＝ｌ＝ｍ＝ｎ＝１又は２であり、置換位置が式中１又は／及び４であり、その他の置換基は水素原子又はハロゲン原子である前記光情報記録媒体が、また前記ハロゲン原子が臭素原子である前記光情報記録媒体がそれぞれ提供される。
【００１１】
以下、本発明を詳しく説明する。
まず、記録媒体の構成について述べる。
図１は、本発明の記録媒体に適用し得る層構成例を示す図で、基板１の上に、必要に応じて下引き層３を介して、記録層２を設け、更に必要に応じ保護層４が設けられる。
図２は、本発明の記録媒体に適用し得る別のタイプの層構成例を示す図で、図１の構成の記録層２の上に金属反射層５が設けられている。
【００１２】
本発明の記録媒体は、図１及び図２に示した構成の記録層（有機薄膜層）を内側にして、他の基板と空間を介して密封したエアーサンドイッチ構造にしてもよく、また保護層を介して接着した貼合せ構造にしてもよい。
【００１３】
次に、構成各層の必要特性及びその構成材料について述べる。
１）基板
基板の必要特性としては、基板側より記録再生を行なう場合には使用レーザー光に対して透明でなければならないが、記録層側から記録再生を行なう場合は透明である必要はない。基板材料としては、例えばポリエステル、アクリル樹脂、ポリアミド、ポリカーボネート樹脂、ポリオレフィン樹脂、フェノール樹脂、エポキシ樹脂、ポリイミドなどのプラスチック、ガラス、セラミックあるいは金属などを用いることができる。なお、基板の表面にトラッキング用の案内溝や案内ピット、更にアドレス信号などのプレフォーマットが形成されていてもよい。
【００１４】
２）記録層
記録層はレーザー光の照射により何らかの光学的変化を生じさせその変化により情報を記録できるものであって、この記録層中には前記一般式（Ｉ）のフタロシアニン化合物が含有されている必要がある。記録層の形成に当っては、本発明の化合物を１種又は２種以上組み合わせて用いてもよい。更に、本発明の化合物は他の染料、例えばポリメチン色素、ナフタロシアニン系、スクアリリウム系、クロコニウム系、ピリリウム系、ナフトキノン系、アントラキノン（インダンスレン）系、キサンテン系、トリフェニルメタン系、アズレン系、テトラヒドロコリン系、フェナンスレン系、トリフェノチアジン系染料、あるいは金属錯体化合物などと組み合わせて用いてもよい。この場合、上記の染料は単独で用いでもよいし、２種以上の組み合わせにしてもよい。
【００１５】
また、本発明の化合物は金属、金属化合物、例えばＩｎ、Ａｌ、Ｔｅ、Ｂｉ、Ａｌ、Ｂｅ、ＴｅＯ_２、ＳｎＯ、Ａｓ、Ｃｄなどを分散混合あるいは積層の形態で用いることもできる。更に、本発明の化合物中に高分子材料、例えばアイオノマー樹脂、ポリアミド系樹脂、ビニル系樹脂、天然高分子、シリコーン、液状ゴムなどの種々の材料若しくはシランカップリング剤などを分散混合して用いてもよく、あるいは特性改良の目的で安定剤（例えば、遷移金属錯体）、分散剤、難燃剤、滑剤、帯電防止剤、界面活性剤、可塑剤などと一緒に用いることができる。
【００１６】
記録層の形成は蒸着、スパッタリング、ＣＶＤ又は溶剤塗布などの通常の手段によって行なうことができる。塗布法を用いる場合には、上記化合物などを有機溶剤に溶解して、スプレー、ローラー塗布、ディッピング又はスピナー塗布などの慣用の塗布方法で行なう。有機溶剤としては、一般にメタノール、エタノール、イソプロパノールなどアルコール類、アセトン、メチルエチルケトン、シクロヘキサノンなどのケトン類、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミドなどのアミド類、ジメチルスルホキシドなどのスルホキシド類、テトラヒドロフラン、ジオキサン、ジエチルエーテル、エチレングリコールモノメチルエーテルなどのエーテル類、酢酸メチル、酢酸エチルなどのエステル類、クロロホルム、塩化メチレン、ジクロロエタン、四塩化炭素、トリクロロエタンなどの脂肪族ハロゲン化炭素類、ベンゼン、キシレン、モノクロロベンゼン、ジクロロベンゼンなどの芳香族類、あるいはメチルセルソルブ、エチルセルソルブなどのセルソルブ類、ヘキサン、ペンタン、シクロヘキサン、メチルシクロヘキサンなどの炭化水素類などを用いることができる。
記録層の膜厚は、図１のような媒体構成の場合は、１００Å〜１０μｍ、好ましくは２００Å〜１０００Åが適当であり、図２のような媒体構成の場合は、３００Å〜５μｍ、好ましくは５００Å〜２０００Åが適当である。
【００１７】
３）下引き層
下引き層は、（ａ）接着性の向上、（ｂ）水又はガスなどに対するバリヤー
、（ｃ）記録層の保存安定性の向上、（ｄ）反射率の向上、（ｅ）溶剤からの基板の保護、（ｆ）案内溝、案内ピット、プレフォーマットの形成などを目的として使用される。（ａ）の目的に対しては高分子、例えばアイオノマー樹脂、ポリアミド、ビニル系樹脂、天然樹脂、天然高分子、シリコーン、液状ゴムなどの種々の高分子物質及びシランカップリング剤などを用いることができ、（ｂ）及び（ｃ）の目的に対しては、上記高分子材料以外に無機化合物、例えばＳｉＯ_２、ＭｇＦ_２、ＳｉＯ、ＴｉＯ_２、ＺｎＯ、ＴｉＮ、ＳｉＮ、及びＺｎ、Ｃｕ、Ｎｉ、Ｃｒ、Ｇｅ、Ｓｅ、Ａｕ、Ａｇ、Ａｌなどの金属又は半金属などを用いることができる。また、（ｂ）の目的に対しては、金属、例えばＡｌ、Ａｇなどや、金属光沢を有する有機薄膜、例えばメチン染料、キサンテン系染料などを用いることができ、（ｅ）及び（ｆ）の目的に対しては、紫外線硬化樹脂、熱硬化樹脂、熱可塑性樹脂などを用いることができる。下引き層の膜厚は０．０１〜３０μｍ、好ましくは０．０５〜１０μｍが適当である。
【００１８】
４）金属反射層
金属反射層は単体で高反射率の得られる腐食されにくい金属、半金属などが使用できる。具体的材料としては、Ａｕ、Ａｇ、Ｃｕ、Ａｌ、Ｃｒ、Ｎｉなどが挙げられ、好ましくはＡｕ、Ａｌがよい。これらの金属、半金属は単独で使用してもよく、２種以上の合金としてもよい。膜形成法としては蒸着、スパッタリングなどが挙げられ、膜厚としては５０〜３０００Å、好ましくは１００〜１０００Åである。
【００１９】
５）保護層、基板表面ハードコート層
保護層又は基板表面ハードコート層は、（ａ）記録層を傷、埃、汚れなどから保護する、（ｂ）記録層の保存安定性の向上、（ｃ）反射率の向上などを目的として使用される。これらの目的に対しては、前記の下引き層に示した材料を用いることができる。また無機材料としてＳｉＯ、ＳｉＯ_２なども用いることもでき、有機材料としてアクリル樹脂、ポリカーボネート、エポキシ樹脂、ポリスチレン、ポリエステル樹脂、ビニル樹脂、セルロース、脂肪族炭化水素樹脂、芳香族炭化水素樹脂、天然ゴム、スチレン−ブタジエン樹脂、クロロプレンゴム、ワックス、アルキッド樹脂、乾性油、ロジンなどの熱軟化性、熱溶融性樹脂も用いることができる。上記材料のうち保護層又は基板表面ハードコート層に最も好ましいものは、生産性に優れた紫外線硬化樹脂である。保護層又は基板表面ハードコート層の膜厚は０．０１〜３０μｍ、好ましくは０．０５〜１０μｍが適当である。
本発明において、前記の下引き層及び保護層には記録層の場合と同様に、安定剤、分散剤、難燃剤、滑剤、帯電防止剤、界面活性剤、可塑剤などを含有させることができる。
【００２０】
本発明においては、前述したように、下記一般式（Ｉ）で示されるフタロシアニン化合物が記録層に含有される。
【化１】

〔式中、Ｍ、Ｘ¹〜Ｘ⁴、Ｒ¹〜Ｒ⁴及びｋ〜ｎは、それぞれ以下のものを表わす。
Ｍ：２個の水素原子、ハロゲン原子若しくは酸素原子を有してもよい金属原子、又は−（ＯＲ⁵）p 基若しくは−（ＯＳｉＲ⁶Ｒ⁷Ｒ⁸）q 基を有してもよい金属原子、
Ｒ⁵〜Ｒ⁸：それぞれ独立に水素原子、置換若しくは未置換の１価の脂肪族炭化水素基、置換若しくは未置換の１価の芳香族炭化水素基、又は置換若しくは未置換の１価の芳香族複素環基、
ｐ、ｑ：０〜２の整数、
Ｘ¹〜Ｘ⁴：それぞれ独立に酸素原子又は硫黄原子、
Ｒ¹〜Ｒ⁴：それぞれ独立に、塩素原子、臭素原子、メチル基のいずれか置換のアダマンタン残基、又はアダマンタン置換メチル残基、
ｋ、ｌ、ｍ、ｎ：それぞれ独立に０〜４の整数、但し全部が同時に０になることはなく、ｋ、ｌ、ｍ、ｎが３以下の場合ベンゼン環の他の置換基は水素原子又はハロゲン原子である。〕
【００２１】
上記一般式（Ｉ）において、Ｍで表わされる金属原子としては、Ａｌ，Ｓｉ，Ｃａ，Ｃｄ，Ｔｉ，Ｖ，Ｍｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｚｎ，Ｇｅ，Ｍｏ，Ｒｕ，Ｒｈ，Ｐｄ，Ｉｎ，Ｓｎ，Ｐｔ，Ｐｂ等が挙げられる。また、上記Ｒ^５〜Ｒ^８の定義中、１価の脂肪族炭化水素基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、アミル基、ヘキシル基、オクチル基、デシル基、ドデシル基、オクタデシル基等のアルキル基や、ビニル基、アリル基、イソプロペニル基、１−ブテニル基、２−ブテニル基、２−ペンテニル基等のアルケニル基などが挙げられる。１価の芳香族炭化水素基としては、フェニル基、ベンジル基などが挙げられる。また、それらの置換基としては、フッ素、塩素、臭素などのハロゲン原子、三フッ化炭素基、シアノ基、エステル基などが挙げられる。
【００２２】
また、前記一般式（Ｉ）において、Ｒ¹〜Ｒ⁴は、塩素原子、臭素原子、メチル基のいずれか置換のアダマンタン残基、又はアダマンタン置換メチル残基を表わすが、その具体例としては、下記表１に示される残基が挙げられる。尚、表１中、（１）及び（２）は参考例である。
【表１】

【００２３】
なお、本発明の前記一般式（Ｉ）で示されるフタロシアニン化合物の中でも、特にｋ＝ｌ＝ｍ＝ｎ＝１又は２であり、且つ置換位置が式中１又は／及び４である置換体であって、しかもその他の置換基が水素原子又はハロゲン原子（特に臭素原子）であるものは、吸収波長の制御が容易であり、また会合を阻止し、膜の屈折率を高め、反射率を向上できるという点で特に優れている。
【００２４】
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化合物若しくはジイミノイソインドリン化合物と、有機溶媒中で金属若しくは金属誘導体を反応させることによって製造することができる。詳しく言うと、上記フタロニトリル化合物又は上記ジイミノイソインドリン化合物と、Ａｌ，Ｓｉ，Ｃａ，Ｃｄ，Ｔｉ，Ｖ，Ｍｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｚｎ，Ｇｅ，Ｍｏ，Ｒｕ，Ｒｈ，Ｐｄ，Ｉｎ，Ｓｎ，Ｐｔ，Ｐｂ等から選ばれる少なくとも１種の金属又はそれらのハロゲン化物、カルボン酸誘導体、硫酸塩、硝酸塩、カルボニル化合物、酸化物若しくは錯体等から選ばれた誘導体とを有機溶媒中で反応させることによって得られる。
また、前記一般式（Ｉ）においてＭが２個の水素原子である場合には、対応するフタロニトリル化合物若しくはジイミノイソインドリン化合物に、有機溶媒中でリチウム若しくはナトリウムを作用させることによって得られる。
【００２５】
前記一般式（Ｉ）で示されるフタロシアニン化合物の具体例としては、例えば表２に示すものが挙げられる。尚、表２中、化合物Ｎｏ．１〜Ｎｏ．４、Ｎｏ．６〜Ｎｏ．１１、Ｎｏ．１３〜Ｎｏ．１７、Ｎｏ．２０及びＮｏ．２１は参考のための化合物である。
【００２６】
【表２−（１）】

【００２７】
【表２−（２）】

【００２８】
【表２−（３）】

【００２９】
【実施例】
以下実施例について本発明を説明するが、本発明これらに限定されるものではない。
【００３０】
実施例１（参考例）
厚さ１．２μｍのポリメチルメタアクリレート板上にフォトポリマーにて、深さ１０００Å、半値幅０．４μｍ、トラックピッチ１．４μｍの案内溝を形成した基板上に、表２の化合物Ｎｏ．１の１，２−ジクロロエタン溶液をスピナー塗布し、厚さ８００Åの記録層を設けて記録媒体とした。
【００３１】
実施例２〜６（実施例２、３及び６は参考例）
実施例１において、表２の化合物Ｎｏ．１の代わりに、それぞれ同表の化合物Ｎｏ．６、Ｎｏ．１０、Ｎｏ．１２、Ｎｏ．１８、Ｎｏ．２０を用いたこと以外は、実施例１と同様にして実施例２〜６の記録媒体を得た。
【００３２】
比較例１
実施例１において、表２の化合物Ｎｏ．１の代わりに下記式（ＩＩ）で示される化合物を用いたこと以外は、実施例１と同様にして比較例１の記録媒体を得た。
【化２】

（但し、式中ｔ−Ｂｕは２〜２′′′の位置と３〜３′′′の位置についたものの混合物である。
【００３３】
前記の実施例１〜６及び比較例１の記録媒体を用い、下記の記録条件で基板を介して記録し、その後記録位置を連続レーザー光で再生し、下記の条件でＣ／Ｎを測定した。また反射率も測定した。その結果を表３に示す。
記録条件：
線速 ２．１ｍ／ｓｅｃ
記録周波数 １．２５ＭＨｚ
レーザー発振波長 ６８０ｎｍ
ピックアップレンズ Ｎ．Ａ．０．５
再生条件：
スキャニングフィルター ３０ＫＨｚ
再生パワー ０．２５〜０．３ｍＷ
【００３４】
【表３】

【００３５】
実施例７（参考例）
深さ１０００Å、半値幅０．４５μｍ、トラックピッチ１．６μｍの案内溝を有する厚さ１．２ｍｍの射出成形ポリカーボネート基板上に、表２の化合物Ｎｏ．４の２−エトキシエタノール／１，２−ジクロロエタン／ＴＨＦ［＝８／１．５／０．５（重量比）］混合溶液をスピナー塗布し、厚さ１８００Åの記録層を設け、その上にＡｕを１２００Åの厚みで真空蒸着して反射層とし、更にその上にアクリル系フォトポリマーをスピナー塗布し、ＵＶ硬化処理して保護層を形成し、ＣＤ−Ｒ型の記録媒体とした。
【００３６】
実施例８〜１１（参考例）
実施例７において、表２の化合物Ｎｏ．４の代わりにそれぞれ同表の化合物Ｎｏ．１、Ｎｏ．２、Ｎｏ．９、Ｎｏ．２１を用いたこと以外は、実施例７と同様にして実施例８〜１１の記録媒体を得た。
【００３７】
比較例２
実施例７において、表２の化合物Ｎｏ．４の代わりに比較例１のフタロシアニンを用いたこと以外は、実施例７と同様にして比較例２の記録媒体を得た。
【００３８】
比較例３
実施例７において、表２の化合物Ｎｏ．４の代わりに下記式（ＩＩＩ）の化合物を用いたこと以外は、実施例７と同様にして比較例３の記録媒体を得た。
【化３】

【００３９】
比較例４
比較例３において、上記式（ＩＩＩ）の化合物に対して１０重量％の下記式（ＩＶ）のニッケル錯体化合物を添加した混合物を用いたこと以外は、比較例３と同様にして比較例４の記録媒体を得た。
【化４】

【００４０】
実施例７〜１１及び比較例２〜４の記録媒体を用い、レーザー発振波長７９０ｎｍ、線速１．４ｍ／ｓｅｃの記録条件でＥＦＭ信号を記録し、記録前及び光照射後の反射率及び最適パワーでのＣ_１エラー数を測定した。その結果を表４に示す。
【００４１】
【表４】

【００４２】
（評価）
本発明の光情報記録媒体は、波長６３０〜７２０ｎｍに高い光吸収能、光反射性を有し、６３０〜７２０ｎｍの半導体レーザーを用いたピックアップに適用できるし、また波長７７０〜８３０ｎｍに高い屈折率を示し、且つ高い安定性を有するため、高反射率で保存安定性及び再生安定性に優れたＣＤ−Ｒ媒体を提供できる。
【００４３】
【発明の効果】
請求項１及び２の光情報記録媒体は、前記一般式（Ｉ）で示されるフタロシアニン化合物を記録層中に含有してなるものとしたことから、次のような卓越した効果を奏する。
イ）波長６３０〜７２０ｎｍに高い光吸収能と光反射性を有しているため、高密度記録が可能な６３０〜７２０ｎｍの半導体レーザーを用いたピックアップに適応でき、現状の７７０〜８３０ｎｍの光記録媒体に比べ記録密度で１．６〜１．７倍の高密度化が可能となる。
ロ）波長７７０〜８３０ｎｍに高い屈折率を示し、且つ高い安定性を有するため、高反射率で保存安定性及び再生安定性に優れたＣＤ−Ｒ用記録媒体が提供できる。
【００４４】
請求項３の光情報記録媒体は、前記一般式（Ｉ）において、ｋ＝１＝ｍ＝ｎ＝１又は２であり、置換位置が式中１又は／及び４であり、その他の置換基は水素原子又はハロゲン原子であるフタロシアニン化合物を記録層に含有してなるものとしたことから、吸収波長の制御が容易であり、また会合阻止能力が更に向上し、膜の屈折率をより高め、反射率をより向上できるという効果が加わる。
【００４５】
請求項４の光情報記録媒体は、前記ハロゲン原子として臭素原子を選択したことから、反射率を更に向上できるという効果が加わる。
【図面の簡単な説明】
【図１】本発明の記録媒体に適用し得る層構成例を示す図である。
【図２】本発明の記録媒体に適用し得る他のタイプの層構成例を示す図である。
【符号の説明】
１ 基板
２ 記録層（有機色素層）
３ 下引き層
４ 保護層
５ 金属反射層[0001]
[Industrial applications]
The present invention relates to an optical information recording medium (hereinafter sometimes abbreviated as a recording medium) used for a computer memory, a memory for image and audio files, an optical card, and the like.
[0002]
[Prior art]
Among recording media having an organic dye thin film as a recording layer, those using a phthalocyanine compound for the organic dye thin film are known (JP-A-58-183296 and JP-A-58-37851). Phthalocyanine compounds have the feature of extremely high stability to heat and light, but have poor solubility in organic solvents, etc. , A high refractive index and a high reflectance cannot be obtained.
[0003]
On the other hand, recently, a semiconductor laser having an oscillation wavelength (up to 680 nm) in a wavelength shorter than the wavelength range used in conventional optical disks has been started to be used in order to increase the recording density. However, none of the conventional organic dye thin films has a light absorbing ability and a light reflecting ability in a wavelength region of 700 nm or less, and there is a limit in high-density recording properties in terms of material.
[0004]
Further, in a write-once compact disc (CD-R) recording medium in which an organic dye thin film, a metal reflective layer and a protective layer are sequentially laminated on a substrate, a high reflectance is required to satisfy the CD standard. Therefore, it is necessary to develop an organic dye material having a high refractive index in the reproduction wavelength region (700 to 830 nm) and high stability.
[0005]
Recently, attempts have been made to introduce a bulky alkoxy group at the α-position of phthalocyanine in order to prevent association of the phthalocyanine compound and achieve a high refractive index. -R recording media have been proposed (JP-A-3-62878, JP-A-3-215466, JP-A-4-348168, JP-A-4-226390, JP-A-4-15263-6, JP-A-5-17477, JP-A-5-86301, JP-A-5-25177, JP-A-5-25179, JP-A-5-17700, JP-A-5-1272, etc.).
[0006]
[Problems to be solved by the invention]
However, although these phthalocyanine compounds do provide an improvement in the refractive index and the like, they are not yet sufficiently satisfactory, and further improvements are desired.
[0007]
Accordingly, a first object of the present invention is to provide a recording medium using a phthalocyanine compound as a recording material, which has high solubility in an organic solvent, high productivity, and can be applied with a solvent, while utilizing the features of the phthalocyanine compound. Is to do.
A second object of the present invention is to provide a recording medium applicable to an optical pickup using a semiconductor laser of 630 to 720 nm capable of high-density recording. Further, a third object of the present invention is to provide a recording medium having a high refractive index in a wavelength range of 770 to 830 nm, and capable of achieving a high reflectivity CD-R medium excellent in storage stability and reproduction stability. To provide a medium.
[0008]
[Means for Solving the Problems]
The phthalocyanine compound is a macrocyclic planar compound, and has an extremely high associative property. Therefore, when the phthalocyanine compound is formed into a thin film, the absorption spectrum becomes broad and the reflectance (refractive index) decreases.
Then, the present invention introduces a substituent having a sterically bulky structure as a substituent to the phthalocyanine ring, prevents association, realizes a high absorption capacity and a high reflectance (refractive index), and achieves an organic compound. The solubility in a solvent is also improved.
[0009]
That is, according to the present invention, in an optical information recording medium having a recording layer provided on a substrate directly or via an undercoat layer, the recording layer contains a phthalocyanine compound represented by the following general formula (I). An optical information recording medium is provided.
Embedded image

[Wherein, M, X ^{1 to} X ⁴ , R ^{1 to} R ⁴ and k to n each represent the following.
M: 2 hydrogen atoms, optionally a metal atom which may have a halogen atom or oxygen atom, or - (OR ⁵⁾ p group or ^{- (OSiR 6 R 7 R 8} ) Good metal atom which may have a q group ,
R ^{5 to} R ⁸ each independently represent a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, or a substituted or unsubstituted monovalent aromatic group; Group heterocyclic group,
p, q: an integer of 0 to 2,
X ^{1 to} X ⁴ : independently an oxygen atom or a sulfur atom,
R ^{1 to} R ⁴ each independently represent an adamantane residue substituted with any of a chlorine atom, a bromine atom and a methyl group , or an adamantane-substituted methyl residue;
k, l, m, n: each independently an integer of 0 to 4; however, all of them are not simultaneously 0, and when k, l, m, and n are 3 or less, the other substituent of the benzene ring is a hydrogen atom Or a halogen atom. ]
[0010]
Further, according to the present invention, a write-once compact disc type recording medium for recording a CD format signal, comprising a metal reflective layer provided on the recording layer , and a protective layer further provided thereon. Is provided. Further, in the general formula (I), k = l = m = n = 1 or 2, the substitution position is 1 or / and 4 in the formula, and the other substituent is a hydrogen atom or a halogen atom. An optical information recording medium, and the optical information recording medium, wherein the halogen atom is a bromine atom, are provided.
[0011]
Hereinafter, the present invention will be described in detail.
First, the configuration of the recording medium will be described.
FIG. 1 is a diagram showing an example of a layer structure applicable to the recording medium of the present invention. A recording layer 2 is provided on a substrate 1 via an undercoat layer 3 as necessary, and further protected as necessary. Layer 4 is provided.
FIG. 2 is a diagram showing another example of a layer configuration applicable to the recording medium of the present invention. A metal reflection layer 5 is provided on the recording layer 2 having the configuration of FIG.
[0012]
The recording medium of the present invention may have an air sandwich structure in which the recording layer (organic thin film layer) having the structure shown in FIGS. A bonding structure may be used in which the bonding structure is adhered through the bonding.
[0013]
Next, the required characteristics of the constituent layers and the constituent materials thereof will be described.
1) Substrate As a necessary characteristic of the substrate, when recording / reproducing is performed from the substrate side, the substrate must be transparent to a laser beam to be used. As the substrate material, for example, a plastic such as polyester, acrylic resin, polyamide, polycarbonate resin, polyolefin resin, phenol resin, epoxy resin, polyimide, glass, ceramic or metal can be used. Note that a guide groove or guide pit for tracking, and a preformat such as an address signal may be formed on the surface of the substrate.
[0014]
2) Recording layer The recording layer is capable of causing some optical change by irradiation with laser light and recording information by the change. This recording layer contains the phthalocyanine compound of the general formula (I). Need to be. In forming the recording layer, the compounds of the present invention may be used alone or in combination of two or more. Further, the compound of the present invention may contain other dyes such as polymethine dyes, naphthalocyanine, squarylium, croconium, pyrylium, naphthoquinone, anthraquinone (indanthrene), xanthene, triphenylmethane, azulene, It may be used in combination with a tetrahydrocholine-based, phenanthrene-based, triphenothiazine-based dye, or a metal complex compound. In this case, the above dyes may be used alone or in combination of two or more.
[0015]
Further, the compound of the present invention can be used in the form of a metal, a metal compound, for example, In, Al, Te, Bi, Al, Be, TeO ₂ , SnO, As, Cd, etc., in a dispersed mixture or in a laminated form. Further, in the compound of the present invention, a polymer material, for example, an ionomer resin, a polyamide resin, a vinyl resin, a natural polymer, silicone, various materials such as a liquid rubber or a silane coupling agent or the like is used by dispersing and mixing. Or a stabilizer (for example, a transition metal complex), a dispersant, a flame retardant, a lubricant, an antistatic agent, a surfactant, a plasticizer, or the like for the purpose of improving properties.
[0016]
The recording layer can be formed by ordinary means such as vapor deposition, sputtering, CVD, or solvent application. When the coating method is used, the above compound or the like is dissolved in an organic solvent, and the coating is performed by a conventional coating method such as spraying, roller coating, dipping or spinner coating. As the organic solvent, generally, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, amides such as N, N-dimethylacetamide and N, N-dimethylformamide, sulfoxides such as dimethyl sulfoxide, Ethers such as tetrahydrofuran, dioxane, diethyl ether and ethylene glycol monomethyl ether; esters such as methyl acetate and ethyl acetate; aliphatic halogenated carbons such as chloroform, methylene chloride, dichloroethane, carbon tetrachloride and trichloroethane, benzene, xylene , Monochlorobenzene, aromatics such as dichlorobenzene, or cellosolves such as methylcellosolve and ethylcellosolve, hexane, pentane, cyclo Hexane, or the like can be used hydrocarbons such as methylcyclohexane.
The thickness of the recording layer is suitably 100 to 10 μm, preferably 200 to 1000 μm for the medium configuration as shown in FIG. 1, and 300 to 5 μm, preferably 500 μm for the medium configuration as shown in FIG. Å2000Å is appropriate.
[0017]
3) Undercoat Layer The undercoat layer comprises (a) an improvement in adhesiveness, (b) a barrier against water or gas, (c) an improvement in storage stability of the recording layer, (d) an improvement in reflectance, and (e). ) It is used for the purpose of protecting a substrate from a solvent, (f) forming a guide groove, a guide pit, a preformat, and the like. For the purpose of (a), it is possible to use various polymers such as ionomer resins, polyamides, vinyl resins, natural resins, natural polymers, silicones, liquid rubbers, and silane coupling agents. For the purposes (b) and (c), in addition to the above-mentioned polymer materials, inorganic compounds such as SiO ₂ , MgF ₂ , SiO, TiO ₂ , ZnO, TiN, SiN, and Zn, Cu, Ni, Metals such as Cr, Ge, Se, Au, Ag, and Al or semimetals can be used. For the purpose of (b), a metal such as Al or Ag or an organic thin film having a metallic luster such as a methine dye or a xanthene dye can be used. For the purpose, an ultraviolet curing resin, a thermosetting resin, a thermoplastic resin, or the like can be used. The thickness of the undercoat layer is suitably 0.01 to 30 μm, preferably 0.05 to 10 μm.
[0018]
4) Metal Reflection Layer As the metal reflection layer, a metal, a semi-metal, or the like, which can provide high reflectance by itself and is hardly corroded, can be used. Specific materials include Au, Ag, Cu, Al, Cr, Ni, and the like, and Au and Al are preferable. These metals and metalloids may be used alone or as an alloy of two or more. Examples of the film forming method include vapor deposition and sputtering, and the film thickness is 50 to 3000 °, preferably 100 to 1000 °.
[0019]
5) Protective layer, substrate surface hard coat layer The protective layer or substrate surface hard coat layer protects the recording layer from scratches, dust, dirt, etc., (b) improves the storage stability of the recording layer, (c) ) Used for the purpose of improving the reflectance. For these purposes, the materials shown in the undercoat layer can be used. Inorganic materials such as SiO and SiO ₂ can also be used. As organic materials, acrylic resin, polycarbonate, epoxy resin, polystyrene, polyester resin, vinyl resin, cellulose, aliphatic hydrocarbon resin, aromatic hydrocarbon resin, natural rubber , Styrene-butadiene resin, chloroprene rubber, wax, alkyd resin, drying oil, rosin and the like can be used. Among the above materials, the most preferable one for the protective layer or the hard coat layer on the substrate surface is an ultraviolet curable resin having excellent productivity. The thickness of the protective layer or the hard coat layer on the substrate surface is suitably 0.01 to 30 μm, preferably 0.05 to 10 μm.
In the present invention, the undercoat layer and the protective layer may contain a stabilizer, a dispersant, a flame retardant, a lubricant, an antistatic agent, a surfactant, a plasticizer, and the like as in the case of the recording layer. .
[0020]
In the present invention, as described above, the phthalocyanine compound represented by the following general formula (I) is contained in the recording layer.
Embedded image

[Wherein, M, X ^{1 to} X ⁴ , R ^{1 to} R ⁴ and k to n each represent the following.
M: 2 hydrogen atoms, optionally a metal atom which may have a halogen atom or oxygen atom, or - (OR ⁵⁾ p group or ^{- (OSiR 6 R 7 R 8} ) Good metal atom which may have a q group ,
R ^{5 to} R ⁸ each independently represent a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group , a substituted or unsubstituted monovalent aromatic hydrocarbon group, or a substituted or unsubstituted monovalent aromatic group; Group heterocyclic group,
p, q: an integer of 0 to 2,
X ^{1 to} X ⁴ : independently an oxygen atom or a sulfur atom,
R ^{1 to} R ⁴ each independently represent an adamantane residue substituted with any of a chlorine atom, a bromine atom and a methyl group , or an adamantane-substituted methyl residue;
k, l, m, n: each independently an integer of 0 to 4; however, all of them are not simultaneously 0, and when k, l, m, and n are 3 or less, the other substituent of the benzene ring is a hydrogen atom Or a halogen atom. ]
[0021]
In the general formula (I), the metal atoms represented by M include Al, Si, Ca, Cd, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Mo, Ru, Rh, and Pd. , In, Sn, Pt, Pb and the like. In the definition of R ^{5 to} R ⁸ , the monovalent aliphatic hydrocarbon group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. , Amyl group, hexyl group, octyl group, decyl group, dodecyl group, alkyl group such as octadecyl group, vinyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 2-pentenyl group, etc. An alkenyl group and the like can be mentioned. Examples of the monovalent aromatic hydrocarbon group include a phenyl group and a benzyl group. Examples of the substituent include a halogen atom such as fluorine, chlorine, and bromine, a carbon trifluoride group, a cyano group, and an ester group.
[0022]
In the general formula (I), R ^{1 to} R ⁴ each represent an adamantane residue substituted with any of a chlorine atom, a bromine atom and a methyl group , or an adamantane-substituted methyl residue. The residues shown in Table 1 below are included. In Table 1, (1) and (2) are reference examples.
[Table 1]

[0023]
In addition, among the phthalocyanine compounds represented by the general formula (I) of the present invention, particularly, a substituted compound in which k = 1 = m = n = 1 or 2 and the substitution position is 1 or / and 4 in the formula In addition, when the other substituent is a hydrogen atom or a halogen atom (especially a bromine atom), the absorption wavelength can be easily controlled, the association is prevented, the refractive index of the film is increased, and the reflectance is improved. It is especially good at being able to do it.
[0024]
The phthalocyanine compound represented by the general formula (I) can be produced by reacting a corresponding phthalonitrile compound or diiminoisoindoline compound with a metal or a metal derivative in an organic solvent. More specifically, the phthalonitrile compound or the diiminoisoindoline compound is mixed with Al, Si, Ca, Cd, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Mo, Ru, Rh, Pd. , In, Sn, Pt, Pb and the like, and at least one metal selected from the group consisting of halides, carboxylic acid derivatives, sulfates, nitrates, carbonyl compounds, oxides and complexes in an organic solvent. By reacting with
When M is two hydrogen atoms in the general formula (I), the compound is obtained by allowing lithium or sodium to act on the corresponding phthalonitrile compound or diiminoisoindoline compound in an organic solvent.
[0025]
Specific examples of the phthalocyanine compound represented by the general formula (I) include, for example, those shown in Table 2. In Table 2, Compound No. 1 to No. 4, no. 6-No. 11, No. 13-No. 17, No. 20 and no. 21 is a compound for reference.
[0026]
[Table 2- (1)]

[0027]
[Table 2- (2)]

[0028]
[Table 2- (3)]

[0029]
【Example】
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
[0030]
Example 1 (Reference example)
Compound No. 2 of Table 2 was formed on a substrate having a guide groove having a depth of 1,000 mm, a half width of 0.4 μm, and a track pitch of 1.4 μm formed on a 1.2 μm-thick polymethyl methacrylate plate by photopolymer. 1, a 1,2-dichloroethane solution was applied by spinner, and a recording layer having a thickness of 800 ° was provided to obtain a recording medium.
[0031]
Examples 2 to 6 (Examples 2, 3 and 6 are reference examples)
In Example 1, the compound No. In place of Compound No. 1, each of Compound Nos. 6, no. 10, No. 12, No. 18, No. Except for using No. 20, recording media of Examples 2 to 6 were obtained in the same manner as in Example 1.
[0032]
Comparative Example 1
In Example 1, the compound No. A recording medium of Comparative Example 1 was obtained in the same manner as in Example 1, except that the compound represented by the following formula (II) was used instead of 1.
Embedded image

(Where t-Bu is a mixture of those at positions 2 to 2 '' and 3 to 3 ''''.
[0033]
Using the recording media of Examples 1 to 6 and Comparative Example 1, recording was performed via a substrate under the following recording conditions, and thereafter, the recording position was reproduced with a continuous laser beam, and C / N was measured under the following conditions. . The reflectance was also measured. Table 3 shows the results.
Recording conditions:
Linear velocity 2.1m / sec
Recording frequency 1.25MHz
Laser oscillation wavelength 680nm
Pickup lens N. A. 0.5
Play conditions:
Scanning filter 30KHz
Reproduction power 0.25-0.3mW
[0034]
[Table 3]

[0035]
Example 7 (Reference example)
Compound No. 1 of Table 2 was placed on a 1.2 mm thick injection molded polycarbonate substrate having a guide groove with a depth of 1000 °, a half width of 0.45 μm, and a track pitch of 1.6 μm. 4, a mixed solution of 2-ethoxyethanol / 1,2-dichloroethane / THF [= 8 / 1.5 / 0.5 (weight ratio)] was applied by spinner, and a recording layer having a thickness of 1800 ° was provided thereon. Was vacuum-deposited to a thickness of 1200 ° to form a reflective layer, and an acrylic photopolymer was spin-coated thereon and UV-cured to form a protective layer, thereby obtaining a CD-R type recording medium.
[0036]
Examples 8 to 11 (Reference Examples)
In Example 7, the compound No. In place of Compound No. 4 in the same table, respectively. 1, No. 2, No. 9, No. Recording media of Examples 8 to 11 were obtained in the same manner as in Example 7, except that Sample No. 21 was used.
[0037]
Comparative Example 2
In Example 7, the compound No. A recording medium of Comparative Example 2 was obtained in the same manner as in Example 7, except that the phthalocyanine of Comparative Example 1 was used instead of 4.
[0038]
Comparative Example 3
In Example 7, the compound No. A recording medium of Comparative Example 3 was obtained in the same manner as in Example 7, except that the compound of the following formula (III) was used instead of 4.
Embedded image

[0039]
Comparative Example 4
Comparative Example 4 was prepared in the same manner as in Comparative Example 3 except that a mixture in which 10% by weight of a nickel complex compound of the following formula (IV) was added to the compound of the above formula (III) was used. A recording medium was obtained.
Embedded image

[0040]
Using the recording media of Examples 7 to 11 and Comparative Examples 2 to 4, an EFM signal was recorded under recording conditions of a laser oscillation wavelength of 790 nm and a linear velocity of 1.4 m / sec. It was measured C ₁ number of errors in power. Table 4 shows the results.
[0041]
[Table 4]

[0042]
(Evaluation)
INDUSTRIAL APPLICABILITY The optical information recording medium of the present invention has high light absorption and light reflectivity at wavelengths of 630 to 720 nm, is applicable to a pickup using a semiconductor laser of 630 to 720 nm, and has a high refractive index at wavelengths of 770 to 830 nm. And a high stability, it is possible to provide a CD-R medium having a high reflectance and excellent storage stability and reproduction stability.
[0043]
【The invention's effect】
The optical information recording medium according to claims 1 and 2 has the following excellent effects because the recording layer contains the phthalocyanine compound represented by the general formula (I).
B) Since it has high light absorption and light reflectivity at wavelengths of 630 to 720 nm, it can be applied to a pickup using a semiconductor laser of 630 to 720 nm capable of high-density recording. The recording density can be 1.6 to 1.7 times higher than the recording medium.
B) Since it shows a high refractive index at a wavelength of 770 to 830 nm and has high stability, it is possible to provide a recording medium for CD-R having a high reflectance and excellent storage stability and reproduction stability.
[0044]
The optical information recording medium according to claim 3, wherein, in the general formula (I), k = 1 = m = n = 1 or 2, the substitution position is 1 or / and 4, and the other substituents are Since the recording layer contains a phthalocyanine compound that is a hydrogen atom or a halogen atom, it is easy to control the absorption wavelength, and the association blocking ability is further improved, the refractive index of the film is further increased, and the reflection is improved. The effect that the rate can be further improved is added.
[0045]
According to the optical information recording medium of the fourth aspect, since a bromine atom is selected as the halogen atom, an effect that the reflectance can be further improved is added.
[Brief description of the drawings]
FIG. 1 is a diagram illustrating an example of a layer configuration applicable to a recording medium of the present invention.
FIG. 2 is a diagram showing another example of a layer configuration applicable to the recording medium of the present invention.
[Explanation of symbols]
1 substrate 2 recording layer (organic dye layer)
3 Undercoat layer 4 Protective layer 5 Metal reflective layer

Claims (4)

An optical information recording medium having a recording layer provided directly on a substrate or via an undercoat layer, wherein the recording layer contains a phthalocyanine compound represented by the following general formula (I). Information recording medium.

[Wherein, M, X ^{1 to} X ⁴ , R ^{1 to} R ⁴ and k to n each represent the following.
M: 2 hydrogen atoms, optionally a metal atom which may have a halogen atom or oxygen atom, or - (OR ⁵⁾ p group or ^{- (OSiR 6 R 7 R 8} ) Good metal atom which may have a q group ,
R ^{5 to} R ⁸ each independently represent a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, or a substituted or unsubstituted monovalent aromatic group; Group heterocyclic group,
p, q: an integer of 0 to 2,
X ^{1 to} X ⁴ : independently an oxygen atom or a sulfur atom,
R ^{1 to} R ⁴ each independently represent an adamantane residue substituted with any of a chlorine atom, a bromine atom and a methyl group , or an adamantane-substituted methyl residue;
k, l, m, n: each independently an integer of 0 to 4; however, all of them are not simultaneously 0, and when k, l, m, and n are 3 or less, the other substituent of the benzene ring is a hydrogen atom Or a halogen atom. ] 2. The optical disc according to claim 1, wherein the recording medium is a write-once compact disc type recording medium in which a metal reflective layer is provided on the recording layer, and a protective layer is further provided thereon. Information recording medium. In the general formula (I), k = l = m = n = 1 or 2, the substitution position is 1 or / and 4 in the formula, and the other substituent is a hydrogen atom or a halogen atom. Or the optical information recording medium according to 2. The optical information recording medium according to claim 3, wherein the halogen atom is a bromine atom.

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